WO2009115380A1 - Spray-dried washing or cleaning products - Google Patents

Spray-dried washing or cleaning products Download PDF

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Publication number
WO2009115380A1
WO2009115380A1 PCT/EP2009/051676 EP2009051676W WO2009115380A1 WO 2009115380 A1 WO2009115380 A1 WO 2009115380A1 EP 2009051676 W EP2009051676 W EP 2009051676W WO 2009115380 A1 WO2009115380 A1 WO 2009115380A1
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WIPO (PCT)
Prior art keywords
spray
weight
drying product
acid
product according
Prior art date
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PCT/EP2009/051676
Other languages
German (de)
French (fr)
Inventor
Bernhard Orlich
Stefan Hammelstein
Michael Dreja
Kathrin Schnepp-Hentrich
Ingrid Kraus
Original Assignee
Henkel Ag & Co. Kgaa
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Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to ES09722712.8T priority Critical patent/ES2499023T3/en
Priority to EP09722712.8A priority patent/EP2252676B1/en
Priority to PL09722712T priority patent/PL2252676T3/en
Publication of WO2009115380A1 publication Critical patent/WO2009115380A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/02Preparation in the form of powder by spray drying
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a specific spray-drying product comprising silicate (s), surfactant (s), carrier material. It further relates to detergents or cleaners comprising such a spray-drying product. It further relates to a spray-drying process and to a process for the preparation of laundry detergent or cleaning powder, and to the use of silicate (s) in spray-dried aqueous slurries to improve the grain stability of the spray-drying product.
  • Spray drying is useful in many important technologies, such as Food technology and biotechnology is one of the most important types of convection drying of, in particular, temperature-sensitive substances and has been associated with the production of a wide variety of goods, such as Dry milk, instant coffee or pharmaceutical preparations, proven many times over.
  • spray-drying is a well-established process in the preparation of powdered detergents.
  • spray drying has been suppressed by other technology, such as in particular mixing and extrusion technologies, there continues to be a great demand for suitable spray-drying products, especially in the detergent and cleaner industry.
  • a spray-drying product comprising silicate (s), surfactant (s), carrier material
  • the spray-drying product a) ⁇ 5 wt .-% of water-soluble polycarboxylate copolymers, in particular copolymers the basis of acrylic and maleic acid b)> 7% by weight of silicates, c) contains ⁇ 15 wt .-% anionic surfactant.
  • This spray-drying product is characterized in particular by the fact that it has a surprisingly good grain stability even with light bulk densities, reduced polycarboxylate copolymer content and reduced anionic surfactant content. Further advantages of this spray-drying product are its very good solubility in water, its storage stability and its good flow properties.
  • the surprisingly good grain stability can advantageously be ensured particularly well if the polycarboxylate copolymer content is further reduced, that is to say advantageously from 0.01% by weight to ⁇ 3% by weight, preferably ⁇ 1% by weight, more advantageously ⁇ 0.5 wt .-%, wt .-% based on the total spray-drying product, and in particular, when no water-soluble polycarboxylate copolymer is included.
  • Suitable polycarboxylate copolymers are especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid, e.g. Copolymers of acrylic acid with maleic acid containing from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid.
  • the molecular weights are generally in the range of 500 to 10,000 g / mol, preferably from 2000 to 6000 g / mol, and more preferably from 3000 to 5000 g / mol.
  • these molecular weights are weight average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard.
  • the molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • a further preferred embodiment of the invention is when the spray-drying product contains 8-30% by weight, preferably 8-25% by weight, advantageously 8-15% by weight of silicate (s).
  • silicate s
  • 10-12 wt .-% silicate (s) in the spray-drying product are suitable, wt .-% based on the total spray-drying product.
  • the products in question show the aforementioned advantages in a particularly clear manner.
  • silicates it is possible to use the salts, in particular the alkali salts, of the various silicas.
  • Particularly suitable are sodium silicates, preferably amorphous sodium silicates, for example, amorphous sodium silicate with a modulus of Na 2 O: SiO 2 of 1: 2 to 1: 3.3.
  • water glass may be contained as a silicate. This corresponds to a preferred embodiment of the invention.
  • the spray-drying product according to the invention is advantageously distinguished by the fact that it has surprisingly good grain stability despite the reduced anionic surfactant content.
  • a possible lower limit of the anionic surfactant content of the spray-drying product may be e.g. at 0.01 wt .-%, wt .-% based on the total spray-drying product.
  • the spray-drying product according to the invention contains anionic surfactant, advantageously comprising alkylbenzenesulfonate, such as preferably linear alkylbenzenesulfonate (LAS), advantageously in amounts of 0.01-14% by weight, more preferably 3-13% by weight, in particular in amounts of 5-10% by weight. 12 wt .-%, wt .-% based on the total spray-drying product, so is a preferred embodiment of the invention.
  • the proportion of (water-soluble) polycarboxylate homopolymers can also be reduced.
  • An inventive spray-drying product which contains 0-5 wt .-% (water-soluble) polycarboxylate homopolymers, in particular homopolymers based on acrylic acid, advantageously 0.01 wt .-% to ⁇ 3 wt .-%, preferably less than 1 wt %, and in particular contains no (water-soluble) polycarboxylate homopolymers, therefore corresponds to a preferred embodiment of the invention.
  • the indication wt .-% is based on the total spray-drying product.
  • Suitable polycarboxylate homopolymers are, for example, the sodium salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 10,000 g / mol, preferably from 2,000 to 6,000 g / mol and in particular from 3,000 to 5,000 g / mol.
  • these molecular weights are also 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, as described above.
  • Suitable carrier materials for the spray-drying product according to the invention are in particular those which are selected from carbonates, sulfates, zeolite, sodium tripolyphosphate, and / or chlorides.
  • carbonates are the Alkali carbonates such as in particular soda or eg sodium bicarbonate, with soda is particularly preferred.
  • Particularly preferred sulfates are the alkali metal sulfates, such as sodium sulfate, but also the alkaline earth sulfates, such as magnesium sulfate.
  • Particularly preferred chlorides are in particular the alkali metal chlorides, such as preferably the sodium chloride.
  • the content of carrier material in the spray-drying product according to the invention is 5-90% by weight, preferably> 50% by weight, in particular> 60% by weight, based on the total spray-drying product, then a preferred embodiment of the invention is present.
  • the spray-drying product according to the invention also contains complexing agents, in particular phosphonate, for example in amounts of> 0.01% by weight to 3% by weight, based on the total spray-drying product.
  • complexing agents in particular phosphonate, for example in amounts of> 0.01% by weight to 3% by weight, based on the total spray-drying product.
  • Other complexing agents useful in detergents or cleaners can also be used.
  • the presence of cellulose ethers and / or their salts in the spray-drying product according to the invention can also advantageously contribute to a further improvement of the grain stability. If the spray-dried product according to the invention therefore contains cellulose ethers and / or their salts, in particular carboxymethylcellulose, for example in amounts of> 0.01% by weight to 3% by weight, this corresponds to a preferred embodiment of the invention.
  • the spray-dried product according to the invention advantageously has a bulk density of ⁇ 500 g / L, in particular the bulk density is in the range 400-500 g / L.
  • the spray-drying product according to the invention can already be used as an independent washing or cleaning agent.
  • a further subject of the invention is therefore a washing or cleaning agent containing a spray-drying product according to the invention.
  • Possible ingredients which may preferably be present in a washing or cleaning agent according to the invention are described in more detail below.
  • Another object of the invention is a spray-drying process in which an aqueous slurry is used, containing
  • anionic surfactant in particular LAS
  • carrier material in particular soda and / or sulfate
  • the spray-drying as such can be carried out by the customary processes for the preparation of powdered detergents or cleaners.
  • the first step of a conventional spray-drying process is generally the preparation of an aqueous slurry of the detergent ingredients to be spray-dried, which advantageously neither volatilize nor decompose under the conditions of spray-drying.
  • This slurry usually comprises surfactants, builders and usually adjusting agents.
  • the slurry is then pumped into the spray tower and sprayed through nozzles located in the top of the tower. In this case, rising, hot air at a temperature of preferably 200 to 35O 0 C dries the slurry and evaporates the adhering water. At the outlet of the tower (temperature preferably 80-120 0 C) then fall dried, fine powder.
  • a further advantage is that the process according to the invention makes it possible to obtain surfactant-reduced and polymer-reduced spray-drying products which have very good grain stability without having to set very high bulk densities.
  • anionic surfactant in particular LAS
  • carrier material in particular soda and / or sulfate
  • Another object of the invention is the use of 4 wt .-% to 12 wt .-% silicate (s) in spray-dried aqueous slurries to improve the grain stability of the spray-drying product, wt .-% based on the total aqueous slurry.
  • washing or cleaning agents in the context of this invention includes in particular a) the laundry detergents, b) the textile aftertreatment agents (such as softeners) and c) the cleaners, in particular cleaners for hard surfaces (such as preferably automatic dishwashing detergents) and the cleaning auxiliaries.
  • Detergents or cleaning agents according to the invention may e.g. also in sachets or (preferably self-dissolving) sachets (pouches) be packaged, especially in Mehrcropouches.
  • Detergents or cleaners according to the invention can also be present as tablets, in particular multi-layered tablets.
  • washing or cleaning agents encompassed by the invention include in particular:
  • heavy duty detergent (preferably contains bleach, optical brighteners, enzymes, etc.)
  • color detergents (preferably containing discoloration inhibitors, cellulases, etc.)
  • Sensitive detergent preferably containing nourishing substances, e.g. Almond oil, aloe vera extract, etc.
  • nourishing substances e.g. Almond oil, aloe vera extract, etc.
  • An inventive washing or cleaning agent contains surfactants. It is particularly preferred for the washing or cleaning agent according to the invention to comprise anionic, nonionic and / or cationic surfactants, in particular a mixture of anionic and nonionic surfactants, the total composition preferably being 0.1% by weight to 50% by weight, contains in particular 10 wt .-% to 40 wt .-% surfactant. This corresponds to a preferred embodiment of the invention and enables optimum cleaning performance.
  • the washing or cleaning agent according to the invention comprises alkylbenzenesulfonate, preferably linear alkylbenzenesulfonate (LAS), advantageously in amounts of 0.1-25% by weight, more preferably 1-20% by weight, in particular in amounts of 5-15% by weight, based on the total agent.
  • alkylbenzenesulfonate preferably linear alkylbenzenesulfonate (LAS)
  • LAS linear alkylbenzenesulfonate
  • Particularly suitable anionic surfactants are also the alkyl sulfates, in particular the fatty alcohol sulfates (FAS), for example Ci 2 -C 8 fatty alcohol sulfate.
  • FOS fatty alcohol sulfates
  • C 6 -C 8 alkyl sulfates are used, particularly preferred are alkyl sulfate and d 3 Ci 3 .i 5 alkyl sulfate and C 13 _ 17 - alkyl sulfate, advantageously branched, in particular alkyl-branched C 3 .i 7 alkyl sulfate.
  • Particularly suitable fatty alcohol sulfates are derived from lauryl and myristyl alcohol, so are fatty alcohol sulfates with 12 or 14 carbon atoms.
  • the long-chain FAS types (Ci 6 to Ci 8 ) are very suitable for washing at higher temperatures.
  • Particularly preferred are alkyl sulfates which have a lower Krafft point, preferably less with Krafft point 45, 40, 30, or 2O 0 C.
  • Krafft point is the term for the temperature at which the solubility of surfactants due to the formation of micelles strongly increases.
  • the Krafft point is a triple point at which the solid or hydrated crystals of the surfactant are in equilibrium with its dissolved (hydrated) monomers and micelles.
  • the Krafft point is determined by a turbidity measurement according to DIN EN 13955: 2003-03.
  • the washing or cleaning agent according to the invention contains alkyl sulfate, in particular C 12 -C 18 -fatty alcohol sulfate, advantageously in amounts of 0.1-25% by weight, more preferably 1-20% by weight, in particular in amounts of 5-10% by weight. 15 wt .-%, based on the total agent, so is a preferred embodiment of the invention.
  • anionic surfactants which may also be used are e.g. Alkanesulfonates (eg C13-C18 secondary alkanesulfonate), methyl ester sulfonates (eg ⁇ -C12-C18 methyl ester sulfonate) and ⁇ -olefin sulfonates (eg ⁇ -C14-C18 olefin sulfonate) and alkyl ether sulfates (eg C12-C14 fatty alcohol 2EO ether sulfate) and / or soaps.
  • suitable anionic surfactants will be described below. However, FAS and / or LAS are particularly suitable.
  • the anionic surfactants may 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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • washing or cleaning agent according to the invention comprises nonionic surfactant, in particular alkoxylated fatty alcohol, in particular in amounts of from 0.01 to 30% by weight, based on the total agent, then again a preferred embodiment of the invention is present wherein the combined use of alkylbenzenesulfonate with nonionic surfactant is very particularly preferred.
  • nonionic surfactants are also alkylphenol polyglycol ethers (APEO), (ethoxylated) sorbitan fatty acid esters (sorbitans), alkylpolyglucosides (APG), fatty acid glucamides, fatty acid ethoxylates, amine oxides, ethylene oxide-propylene oxide block polymers, polyglycerol fatty acid esters and / or fatty acid alkanolamides.
  • APEO alkylphenol polyglycol ethers
  • APG alkylpolyglucosides
  • fatty acid glucamides fatty acid ethoxylates
  • amine oxides amine oxides
  • ethylene oxide-propylene oxide block polymers polyglycerol fatty acid esters and / or fatty acid alkanolamides.
  • sugar-based nonionic surfactants such as APG in particular, are particularly preferred.
  • the washing or cleaning agent according to the invention comprises enzymes, preferably amylase, pectinase, carbonic anhydrase, tannase, lipase, mannanase, protease and / or cellulase, advantageously in amounts of from 0.0001 to 5% by weight, based on the total mean.
  • a suitable minimum amount may also be 0.001 wt% or 0.01 wt%, based on the total agent.
  • Preferably usable enzymes are described in more detail below.
  • the washing or cleaning agent according to the invention comprises a builder system, preferably a zeolite-containing builder system, preferably comprising zeolite in amounts of> 5% by weight, more preferably> 10% by weight, more preferably> 15% by weight, in particular> 20% by weight,% by weight, based on the total composition.
  • a reasonable upper limit of zeolite may be, for example, 60% by weight, 50% by weight or 40% by weight, based on the total agent. This corresponds to a preferred embodiment of the invention.
  • the term "builder system” also encompasses those “systems” which consist only of a single builder, such as e.g. Zeolite. It is preferred, however, that at least 2 substances with a builder effect be used, e.g. Zeolite in combination with soda, or similar.
  • the washing or cleaning agent according to the invention contains a soluble builder system, preferably comprising soda, silicate, citrate and / or polycarboxylates, advantageously in amounts of from 0.1 to 50% by weight, based on the total agent , This corresponds to a preferred embodiment of the invention.
  • a soluble builder system preferably comprising soda, silicate, citrate and / or polycarboxylates, advantageously in amounts of from 0.1 to 50% by weight, based on the total agent.
  • insoluble builders such as, in particular, zeolite, e.g. ⁇ 5 wt .-% to 0.1 wt .-% are included, especially in such a case, no insoluble builder is included.
  • the washing or cleaning agent according to the invention comprises a phosphate-containing builder system, in which case phosphate preferably being present in amounts of 1-40% by weight, in particular 5-30% by weight, based on the total Medium.
  • the washing or cleaning agent according to the invention is free of phosphates.
  • Preferred washing or cleaning agent according to the invention have a pH of> 7.5 as measured in a 5% solution of the composition in water at 2O 0 C.
  • the washing or cleaning agents according to the invention can, as already shown, in particular builders and surface-active surfactants, but also bleach, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, fluorescers, Ver inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, 10
  • Corrosion inhibitors antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts and UV absorbers, foam regulators and colorants and fragrances.
  • the washing or cleaning agents according to the invention preferably comprise, as already described, one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • surfactants in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • nonionic surfactants are preferably alkoxylated, preferably ethoxylated, especially 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 optionally used in which the alcohol radical is linear or preferably methyl branched in the 2-position may contain linear or methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 2 -C 4 -alcohols with 3 EO or 4 EO, C 9 -C 12 -alcohols with 7 EO, C 3 -C 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -Ci 4 alcohol with 3 EO and Ci 2 -Ci 8 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • TaIg fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • extremely 1 1 low-foam connections are used. These include preferably C 2 -C 18 -alkylpolyethylene glycol polypropylene glycol ethers having in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, C 2 -C 18 -alkylpolyethyleneglycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule as well as end-capped alkyl polyalkylene glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols as described in European Patent Application EP 0 300 305, so-called hydroxy mixed ethers.
  • 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 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a Glykoseiki with 5 or 6 C-atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4.
  • polyhydroxy fatty acid amides of the formula (III) in which R 1 is CO for 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 having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)
  • R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein dC 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with 12 is substituted at least two hydroxyl groups, or is alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is also obtained here preferably 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 be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • anionic surfactants have already been mentioned.
  • the anionic surfactants used are preferably those of the sulfonate and sulfates type.
  • Preferred surfactants of the sulfonate type are C9-13-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C12-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-i 8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • esters of .alpha.-sulfo fatty acids esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. 13
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myrilecyl, cetyl or stearyl alcohol or the C 10 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 -alcohols such as 2-methyl-branched C ⁇ -alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • 18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of from 1 to 5% by weight, as an option.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18- fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or 14
  • Triethanolamine Triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the washing or cleaning agent according to the invention may preferably comprise cationic surfactant, in particular quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.
  • quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group.
  • N-methyl-N- (2-hydroxyethyl) -N N- (ditallowacyloxyethyl) ammonium methosulfate or bis (palmitoyloxyethyl) -hydroxyethyl-methylammonium methosulfate.
  • a washing or cleaning agent according to the invention may preferably contain at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which may also contain small amounts of polyme
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) - 15 acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an alkylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical ,
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can also be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.
  • All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builders may be used according to a preferred embodiment of the invention and may, if desired, be present in amounts, for example, of up to 40% by weight, in particular up to 25% by weight and preferably from 1% to 8% by weight ,% By weight based on the total washing or cleaning agent
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali metal silicates alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetra sodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, can be used as water-insoluble, water-dispersible inorganic builder materials,% by weight, based on the total washing or cleaning agent.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Ratio of Na 2 OiSiO 2 from 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, known as the modulus, an integer of 1, 9 to 22, in particular 1, 9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • amorphous alkali silicates practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite), Na-SKS-2 (Na 2 Sii 4 0 29 x H 2 0, magadiite), Na-SKS-3 (Na 2 Si 8 Oi 7 XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 XH 2 O, makatite).
  • Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite)
  • Na-SKS-2 Na 2 Sii 4 0 29 x H 2 0, magadiite
  • Na-SKS-3 Na 2 Si 8 Oi 7 XH 2 O
  • Na-SKS-4 Na 2 Si 4 O 9 XH 2 O, makatite
  • Na-SKS-5 (X-Na 2 Si 2 O 5)
  • Na-SKS-7 (.beta.-Na 2 Si 2 0 5, natrosilite)
  • Na SKS-9 NaHSi 2 O 5 3H 2 O
  • Na-SKS-10 NaHSi 2 O 5 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 0 5
  • Na SKS-13 NaHSi 2 O 5
  • Na-SKS-6 5-Na 2 Si 2 O 5
  • Builder substances may preferably be present in the detergents or cleaners according to the invention in amounts of up to, for example, 75% by weight, in particular 5% by weight to 50 % by weight based on the total agent are suitable as bleaching agents suitable for use in detergents according to the invention, for example peroxygen compounds, in particular organ or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of dodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate such as caroate into consideration.
  • peroxygen compounds in particular organ or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of dodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts, which include perborate, percarbonate, per
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. If an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and also magnesium salts such as magnesium sulfate may be expedient. 17
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters
  • TAED
  • hydrophilic substituted acyl acetals and the acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-supplied bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.
  • Suitable enzymes which can be used in the washing or cleaning agents according to the invention are, in particular, those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases, pectinases, carbonic anhydrases, mannanases, tannases and peroxidases and mixtures thereof , Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents.
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humi
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They may be present in the detergents or cleaners according to the invention preferably in amounts of up to 5% by weight, in particular from 0.01% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be achieved by incorporating the two or more separate or 18 enzymes are prepared separately in a known manner or by two or more assembled together in a granule enzymes.
  • the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators may be used in the compositions of the invention in amounts of e.g. preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, may optionally be present.
  • Alkalis e.g. NaOH can be used.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents or cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellel, lilial and bourgeonal, to the ketones e.g.
  • the ionones isomethylionone and methyl cedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes and balsams.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • Useful soil release polymers also referred to as "anti-redeposition agents" include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30 weight percent and hydroxypropyl groups of 1 to 15 weight percent, respectively based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or of their 19
  • Derivatives in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
  • Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners may be added to laundry detergents or cleaners to eliminate graying and yellowing of the treated fabrics, which will attract the fiber and cause lightening and fake bleaching by exposing invisible ultraviolet radiation to visible convert longer wavelength light, the absorbed from sunlight ultraviolet light is radiated as a pale blue fluorescence and the yellow shade of the grayed or yellowed laundry pure white.
  • Suitable compounds originate for example from the substance classes of the 4,4 'diamino-2,2 stilbenedisulfonic acids (flavonic), 4,4 'biphenylene -Distyryl- be Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles.
  • Suitable (heavy metal) complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which in preferred detergents or cleaning agents in amounts of, for example, 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1, 5 % By weight are optionally included.
  • These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • the washing or cleaning agents may additionally be added e.g. contain neutral filler salts such as sodium sulfate.
  • a preferred heavy duty powder detergent according to the invention may preferably be e.g. Contain components that are selected from the following:
  • Anionic surfactants e.g. Alkyl benzene sulfonate, alkyl sulfate, in amounts of e.g. 0-40% by weight, advantageously 5-30% by weight, preferably 8-20% by weight,
  • Nonionic surfactants e.g. Fatty alcohol polyglycol ethers, alkylpolyglucoside, fatty acid glucamide, in amounts of e.g. 0-30% by weight, advantageously 0.1-20% by weight, preferably 2-15% by weight, in particular 6-11% by weight,
  • Builders e.g. Zeolite, polycarboxylate, sodium citrate, in amounts of e.g. 0-70% by weight, advantageously 5-60% by weight, preferably 10-55% by weight, in particular 15-40% by weight,
  • Alkalis e.g. Sodium carbonate
  • Alkalis e.g. Sodium carbonate
  • amounts of e.g. 0-35 wt .-% advantageously 1-30 wt .-%, preferably 2-25 wt .-%, in particular 5-20 wt .-%,
  • Bleaching agents e.g. Sodium perborate, sodium percarbonate, in amounts of e.g. 0-30% by weight, advantageously 5-25% by weight, preferably 10-20% by weight,
  • corrosion inhibitors e.g. sodium silicate
  • Stabilizers e.g. Phosphonates, advantageously 0-1% by weight
  • Foam inhibitor e.g. Soap, silicone oils, paraffins advantageously 0-4 wt.%, Preferably 0.2-3 wt.%, In particular 1-1 wt.
  • Enzymes e.g. Proteases, amylases, cellulases, lipases, advantageously 0-2% by weight, preferably 0.2-1% by weight, in particular 0.3-0.8% by weight,
  • - grayness inhibitor e.g. Carboxymethylcellulose, advantageously 0-1% by weight
  • Discoloration inhibitor e.g. Polyvinylpyrrolidone derivatives, advantageously 0-2% by weight,
  • optical brighteners e.g. Stilbene derivative, biphenyl derivative, advantageously 0.01-0.3% by weight, in particular 0.1-0.4% by weight,
  • Compositions A (Comparative Formulation) and B (Formulation of the Invention) were prepared in a conventional spray-drying process.
  • Comparative product A showed, compared with product B according to the invention, a markedly poorer grain stability, which is evident, for example, from It stated that the bulk density of product A significantly increased to values well above 600 g / L upon further mechanical stress, which was not the case with product B.

Abstract

The invention relates to special silicate-containing spray drying products which are suitable for use in and as washing and cleaning agents and to a method for the production thereof. Said spray drying products demonstrate a surprisingly good grain stability, an excellent water solubility and storage stability as well as good flow properties even at low bulk densities and reduced content of polycarboxylate copolymer and reduced content of anion surfactant. The invention also relates to a spray drying process allowing an increase of the throughput speed.

Description

12.02.2009 12.02.2009
Sprühgetrocknete Wasch- oder ReinigungsmittelprodukteSpray-dried detergents or cleaning products
Die vorliegende Erfindung betrifft ein spezifisches Sprühtrocknungsprodukt, umfassend Silicat(e), Tensid(e), Trägermaterial. Sie betrifft ferner Wasch- oder Reinigungsmittel, die ein solches Sprühtrocknungsprodukt umfassen. Sie betrifft ferner ein Sprühtrocknungsverfahren sowie ein Verfahren zur Herstellung von Wasch- oder Reinigungsmittelpulver sowie die Verwendung von Silicat(en) in sprühzutrocknenden wässrigen Aufschlämmungen zur Verbesserung der Kornstabilität des Sprühtrocknungsproduktes.The present invention relates to a specific spray-drying product comprising silicate (s), surfactant (s), carrier material. It further relates to detergents or cleaners comprising such a spray-drying product. It further relates to a spray-drying process and to a process for the preparation of laundry detergent or cleaning powder, and to the use of silicate (s) in spray-dried aqueous slurries to improve the grain stability of the spray-drying product.
Die Sprühtrocknung ist in vielen wichtigen Technologien, wie z.B. der Lebensmitteltechnologie und Biotechnologie eine der wichtigsten Arten der Konvektionstrocknung von insbesondere temperaturempfindlichen Stoffen und hat sich im Zusammenhang mit der Herstellung der unterschiedlichsten Güter, wie z.B. Trockenmilch, Instantkaffee oder pharmazeutische Präparate, vielfach bewährt.Spray drying is useful in many important technologies, such as Food technology and biotechnology is one of the most important types of convection drying of, in particular, temperature-sensitive substances and has been associated with the production of a wide variety of goods, such as Dry milk, instant coffee or pharmaceutical preparations, proven many times over.
Insbesondere ist die Sprühtrocknung ein wohletabliertes Verfahren bei der Herstellung von pulverförmigen Waschmitteln. Obschon in der modernen Waschmittelherstellung die Sprühtrocknung durch andere Technologie, wie insbesondere Misch- und Extrusionstechnologien, zurückgedrängt wurde, besteht insbesondere in der Wasch- und Reinigungsmittelindustrie weiterhin ein sehr großer Bedarf an geeigneten Sprühtrocknungsprodukten.In particular, spray-drying is a well-established process in the preparation of powdered detergents. Although in modern detergent production, spray drying has been suppressed by other technology, such as in particular mixing and extrusion technologies, there continues to be a great demand for suitable spray-drying products, especially in the detergent and cleaner industry.
Ein besonders wichtiges Qualitätsmerkmal von Sprühtrocknungsprodukten ist die Kornstabilität. Ist diese nicht ausreichend gewährleistet, kann es bei der Weiterverarbeitung der Sprühtrocknungsprodukte und auch bei der Lagerung der Sprühtrocknungsprodukte zu erheblichen Problemen kommen.An especially important quality feature of spray drying products is grain stability. If this is not sufficiently ensured, considerable problems may arise in the further processing of the spray-drying products and also in the storage of the spray-drying products.
Vor diesem Hintergrund war es die Aufgabe der vorliegenden Erfindung, ein Sprühtrocknungsprodukt bereitzustellen, welches sich durch eine gute Kornstabilität auszeichnet.Against this background, it was the object of the present invention to provide a spray-drying product, which is characterized by a good grain stability.
Überraschend wurde gefunden, dass diese Aufgabe vom Gegenstand der Erfindung gelöst wird, nämlich einem Sprühtrocknungsprodukt, umfassend Silicat(e), Tensid(e), Trägermaterial, wobei das Sprühtrocknungsprodukt a) < 5 Gew.-% wasserlösliche Polycarboxylat-Copolymere, insbesondere Copolymere auf der Basis von Acryl- und Maleinsäure b) > 7 Gew.-% Silicate, c) < 15 Gew.-% Aniontensid enthält.Surprisingly, it has been found that this object is achieved by the subject matter of the invention, namely a spray-drying product comprising silicate (s), surfactant (s), carrier material, wherein the spray-drying product a) <5 wt .-% of water-soluble polycarboxylate copolymers, in particular copolymers the basis of acrylic and maleic acid b)> 7% by weight of silicates, c) contains <15 wt .-% anionic surfactant.
Dieses Sprühtrocknungsprodukt zeichnet sich insbesondere dadurch in vorteilhafter Weise aus, dass es auch bei leichten Schüttgewichten, vermindertem Polycarboxylat-Copolymer-Gehalt und vermindertem Aniontensid-Gehalt eine überraschend gute Kornstabilität aufweist. Weitere Vorteile dieses Sprühtrocknungsproduktes liegen in seiner sehr guten Wasserlöslichkeit, seiner Lagerstabilität sowie seinen guten Fließeigenschaften.This spray-drying product is characterized in particular by the fact that it has a surprisingly good grain stability even with light bulk densities, reduced polycarboxylate copolymer content and reduced anionic surfactant content. Further advantages of this spray-drying product are its very good solubility in water, its storage stability and its good flow properties.
Die überraschend gute Kornstabilität kann vorteilhafterweise dann besonders gut gewährleistet werden, wenn der Polycarboxylat-Copolymer-Gehalt weiter vermindert ist, also vorteilhafterweise 0,01 Gew.-% bis < 3 Gew.-%, vorzugsweise < 1 Gew.-%, weiter vorteilhaft < 0,5 Gew.-% beträgt, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt, und insbesondere, wenn gar kein wasserlösliches Polycarboxylat-Copolymer enthalten ist. Dies entspricht einer bevorzugten Ausführungsform der Erfindung.The surprisingly good grain stability can advantageously be ensured particularly well if the polycarboxylate copolymer content is further reduced, that is to say advantageously from 0.01% by weight to <3% by weight, preferably <1% by weight, more advantageously <0.5 wt .-%, wt .-% based on the total spray-drying product, and in particular, when no water-soluble polycarboxylate copolymer is included. This corresponds to a preferred embodiment of the invention.
Geeignete Polycarboxylat-Copolymere sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure, z.B. Copolymere der Acrylsäure mit Maleinsäure, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Die relativen Molekülmasse liegen in der Regel im Bereich von 500 bis 10000 g/mol, bevorzugt von 2000 bis 6000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol. Bei diesen Molmassen handelt es sich im Sinne dieser Schrift um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde. Die Messung erfolgte dabei gegen einen externen Polyacrylsäure- Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden. Die gegen Polystyrolsulfonsäuren gemessenen Molmassen sind in der Regel deutlich höher als die in dieser Schrift angegebenen Molmassen.Suitable polycarboxylate copolymers are especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid, e.g. Copolymers of acrylic acid with maleic acid containing from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid. The molecular weights are generally in the range of 500 to 10,000 g / mol, preferably from 2000 to 6000 g / mol, and more preferably from 3000 to 5000 g / mol. For the purposes of this specification, these molecular weights are weight average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
Eine weitere bevorzugte Ausführungsform der Erfindung liegt vor, wenn das Sprühtrocknungsprodukt 8-30 Gew.-%, vorzugsweise 8-25 Gew.-%, vorteilhafterweise 8-15 Gew.- % Silicat(e) enthält. Insbesondere 10-12 Gew.-% Silicat(e) im Sprühtrocknungsprodukt sind geeignet, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt. Die betreffenden Produkte zeigen die vorgenannten Vorteile in besonders deutlicher Weise. Als Silicate können die Salze, insbesondere die Alkalisalze, der verschiedenen Kieselsäuren eingesetzt werden. Besonders geeignet sind Natriumsilicate, vorzugsweise amorphe Natriumsilicate, beispielsweise amorphes Natriumsilicat mit einem Modul Na2O : SiO2 von 1 : 2 bis 1 : 3,3. Insbesondere Wasserglas kann als Silicat enthalten sein. Dies entspricht einer bevorzugten Ausführungsform der Erfindung.A further preferred embodiment of the invention is when the spray-drying product contains 8-30% by weight, preferably 8-25% by weight, advantageously 8-15% by weight of silicate (s). In particular 10-12 wt .-% silicate (s) in the spray-drying product are suitable, wt .-% based on the total spray-drying product. The products in question show the aforementioned advantages in a particularly clear manner. As silicates it is possible to use the salts, in particular the alkali salts, of the various silicas. Particularly suitable are sodium silicates, preferably amorphous sodium silicates, for example, amorphous sodium silicate with a modulus of Na 2 O: SiO 2 of 1: 2 to 1: 3.3. In particular, water glass may be contained as a silicate. This corresponds to a preferred embodiment of the invention.
Wie schon dargestellt wurde, zeichnet sich das erfindungsgemäße Sprühtrocknungsprodukt vorteilhafterweise dadurch aus, dass es trotz vermindertem Aniontensid-Gehalt eine überraschend gute Kornstabilität aufweist. Eine mögliche Untergrenze des Aniontensid-Gehaltes des Sprühtrocknungsprodukt kann z.B. bei 0,01 Gew.-% liegen, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt. Wenn das erfindungsgemäße Sprühtrocknungsprodukt Aniontensid, vorteilhafterweise umfassend Alkylbenzolsulfonat, wie vorzugsweise lineares Alkylbenzolsulfonat (LAS), enthält, vorteilhafterweise in Mengen von 0,01 - 14 Gew. %, in weiter vorteilhafter Weise 3- 13 Gew-%, insbesondere in Mengen von 5-12 Gew.-%, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt, so liegt eine bevorzugte Ausführungsform der Erfindung vor.As already stated, the spray-drying product according to the invention is advantageously distinguished by the fact that it has surprisingly good grain stability despite the reduced anionic surfactant content. A possible lower limit of the anionic surfactant content of the spray-drying product may be e.g. at 0.01 wt .-%, wt .-% based on the total spray-drying product. If the spray-drying product according to the invention contains anionic surfactant, advantageously comprising alkylbenzenesulfonate, such as preferably linear alkylbenzenesulfonate (LAS), advantageously in amounts of 0.01-14% by weight, more preferably 3-13% by weight, in particular in amounts of 5-10% by weight. 12 wt .-%, wt .-% based on the total spray-drying product, so is a preferred embodiment of the invention.
Wie schon beschrieben wurde, kann eine überraschend gute Kornstabilität gewährleistet werden, obwohl der Polycarboxylat-Copolymer-Gehalt erheblich vermindert ist.As already described, surprisingly good grain stability can be ensured, although the polycarboxylate copolymer content is considerably reduced.
Vorteilhafterweise kann auch der Anteil (wasserlöslicher) Polycarboxylat-Homopolymere vermindert sein. Ein erfindungsgemäßes Sprühtrocknungsprodukt, welches 0-5 Gew.-% (wasserlösliche) Polycarboxylat-Homopolymere, wie insbesondere Homopolymere auf der Basis von Acrylsäure enthält, vorteilhafterweise 0,01 Gew.-% bis < 3 Gew.-%, vorzugsweise weniger als 1 Gew.-%, und insbesondere gar keine (wasserlösliche) Polycarboxylat-Homopolymere enthält, entspricht daher einer bevorzugten Ausführungsform der Erfindung. Die Angabe Gew.-% ist bezogen auf das gesamte Sprühtrocknungsprodukt.Advantageously, the proportion of (water-soluble) polycarboxylate homopolymers can also be reduced. An inventive spray-drying product which contains 0-5 wt .-% (water-soluble) polycarboxylate homopolymers, in particular homopolymers based on acrylic acid, advantageously 0.01 wt .-% to <3 wt .-%, preferably less than 1 wt %, and in particular contains no (water-soluble) polycarboxylate homopolymers, therefore corresponds to a preferred embodiment of the invention. The indication wt .-% is based on the total spray-drying product.
Geeignete Polycarboxylat-Homopolymere sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 10000 g/mol, vorzugsweise 2000 bis 6000 g/mol und insbesondere von 3000 bis 5000 g/mol. Auch bei diesen Molmassen handelt es sich im Sinne dieser Schrift um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde, wie zuvor beschrieben.Suitable polycarboxylate homopolymers are, for example, the sodium salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 10,000 g / mol, preferably from 2,000 to 6,000 g / mol and in particular from 3,000 to 5,000 g / mol. In the context of this document, these molecular weights are also 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, as described above.
Als Trägermaterialien kommen für das erfindungsgemäße Sprühtrocknungsprodukt insbesondere solche in Frage, welche ausgewählt sind aus Carbonaten, Sulfaten, Zeolith, Natriumtripolyphosphat, und/oder Chloriden. Bevorzugt einsetzbare Carbonate sind die Alkalicarbonate wie z.B. insbesondere Soda oder z.B. Natriumhydrogencarbonat, wobei Soda besonders bevorzugt ist. Besonders bevorzugte Sulfate sind die Alkalisulfate, wie z.B. Natriumsulfat, aber auch die Erdalkalisulfate, wie z.B. Magnesiumsulfat. Besonders bevorzugte Chloride sind insbesondere die Alkalichloride, wie vorzugsweise das Natriumchlorid.Suitable carrier materials for the spray-drying product according to the invention are in particular those which are selected from carbonates, sulfates, zeolite, sodium tripolyphosphate, and / or chlorides. Preferably used carbonates are the Alkali carbonates such as in particular soda or eg sodium bicarbonate, with soda is particularly preferred. Particularly preferred sulfates are the alkali metal sulfates, such as sodium sulfate, but also the alkaline earth sulfates, such as magnesium sulfate. Particularly preferred chlorides are in particular the alkali metal chlorides, such as preferably the sodium chloride.
Wenn der Gehalt an Trägermaterial in dem erfindungsgemäße Sprühtrocknungsprodukt 5-90 Gew.-%, vorzugsweise > 50 Gew.-%, insbesondere > 60 Gew.-% beträgt, bezogen auf das gesamte Sprühtrocknungsprodukt, so liegt eine bevorzugten Ausführungsform der Erfindung vor.If the content of carrier material in the spray-drying product according to the invention is 5-90% by weight, preferably> 50% by weight, in particular> 60% by weight, based on the total spray-drying product, then a preferred embodiment of the invention is present.
Vorteilhafterweise enthält das erfindungsgemäße Sprühtrocknungsprodukt auch Komplexbildner, wie insbesondere Phosphonat, beispielsweise in Mengen von > 0,01 Gew.-% bis 3 Gew.-%, Gew.- % bezogen auf das gesamte Sprühtrocknungsprodukt. Dies entspricht einer bevorzugten Ausführungsform der Erfindung. Auch andere in Wasch- oder Reinigungsmitteln brauchbare Komplexbildner können eingesetzt werden.Advantageously, the spray-drying product according to the invention also contains complexing agents, in particular phosphonate, for example in amounts of> 0.01% by weight to 3% by weight, based on the total spray-drying product. This corresponds to a preferred embodiment of the invention. Other complexing agents useful in detergents or cleaners can also be used.
Es hat sich auch gezeigt, dass das Vorhandensein von Celluloseether und/oder deren Salzen in dem erfindungsgemäßen Sprühtrocknungsprodukt ebenfalls in vorteilhafter weise zu einer weiteren Verbesserung der Kornstabilität beitragen kann. Enthält das erfindungsgemäße Sprühtrocknungsprodukt daher Celluloseether und/oder deren Salze, wie insbesondere Carboxymethylcellulose, beispielsweise in Mengen von > 0,01 Gew.-% bis 3 Gew.-%, so entspricht dies einer bevorzugten Ausführungsform der Erfindung.It has also been found that the presence of cellulose ethers and / or their salts in the spray-drying product according to the invention can also advantageously contribute to a further improvement of the grain stability. If the spray-dried product according to the invention therefore contains cellulose ethers and / or their salts, in particular carboxymethylcellulose, for example in amounts of> 0.01% by weight to 3% by weight, this corresponds to a preferred embodiment of the invention.
Das erfindungsgemäße Sprühtrocknungsprodukt weist vorteilhafterweise ein Schüttgewicht von < 500 g/L auf, insbesondere liegt das Schüttgewicht im Bereich 400-500 g/L.The spray-dried product according to the invention advantageously has a bulk density of <500 g / L, in particular the bulk density is in the range 400-500 g / L.
Das erfindungsgemäße Sprühtrocknungsprodukt kann bereits als eigenständiges Wasch- oder Reinigungsmittel eingesetzt werden.The spray-drying product according to the invention can already be used as an independent washing or cleaning agent.
Ebenso gut ist es möglich, das erfindungsgemäße Sprühtrocknungsprodukt mit weiteren Komponenten abzumischen bzw. zu vermengen. Insbesondere ist es möglich, dem erfindungsgemäßen Sprühtrocknungsprodukt temperaturlabile Bestandteile, wie z.B. Bleichmittel oder Duftstoffe, nachträglich zuzumischen.It is equally possible to mix or mix the spray-dried product according to the invention with other components. In particular, it is possible to add to the spray-drying product of the invention temperature-labile components, such as e.g. Bleach or perfume, to be added later.
Ein weiterer Gegenstand der Erfindung ist daher ein Wasch- oder Reinigungsmittel, enthaltend ein erfindungsgemäße Sprühtrocknungsprodukt. Mögliche Inhaltsstoffe, welche in einem erfindungsgemäßen Wasch- oder Reinigungsmittel vorzugsweise enthalten sein können, werden weiter unten noch genauer beschrieben.A further subject of the invention is therefore a washing or cleaning agent containing a spray-drying product according to the invention. Possible ingredients which may preferably be present in a washing or cleaning agent according to the invention are described in more detail below.
Ein weiterer Gegenstand der Erfindung ist ein Sprühtrocknungsverfahren, bei welchem eine wässrige Aufschlämmung eingesetzt wird, enthaltendAnother object of the invention is a spray-drying process in which an aqueous slurry is used, containing
4 bis 12 Gew.-% Silicat(e),4 to 12% by weight of silicate (e),
5 bis 12 Gew.-% Aniontensid, insbesondere LAS,From 5 to 12% by weight of anionic surfactant, in particular LAS,
40 bis 60 Gew.-% Trägermaterial, insbesondere Soda und/oder Sulfat,From 40 to 60% by weight of carrier material, in particular soda and / or sulfate,
20 bis 60 Gew.-% Wasser, sowie weniger als 2 Gew.-% Polycarboxylat-Copolymere,20 to 60% by weight of water and less than 2% by weight of polycarboxylate copolymers,
Gew.-% bezogen auf die gesamte wässrige Aufschlämmung.Wt .-% based on the total aqueous slurry.
Die Sprühtrocknung als solche kann nach den üblichen Verfahren zur Herstellung von pulverförmigen Wasch- oder Reinigungsmitteln vollzogen werden. Der erste Schritt eines üblichen Sprühtrocknungsverfahrens ist im Regelfall die Herstellung einer wäßrigen Aufschlämmung (Slurry) der sprühzutrocknenden Waschmittelinhaltsstoffe, die sich unter den Bedingungen der Sprühtrocknung vorteilhafterweise weder verflüchtigen noch zersetzen. Dieser Slurry umfasst in der Regel Tenside, Gerüststoffe und üblicherweise Stellmittel. Anschließend wird der Slurry über Pumpen in den Sprühturm befördert und über im Kopf des Turms befindliche Düsen versprüht. Dabei trocknet aufsteigende, heiße Luft mit einer Temperatur von vorzugsweise 200 bis 35O0C den Slurry und verdampft das anhaftende Wasser. Am Auslaß des Turms (Temperatur vorzugsweise 80-1200C) fallen dann getrocknete, feine Pulver an.The spray-drying as such can be carried out by the customary processes for the preparation of powdered detergents or cleaners. The first step of a conventional spray-drying process is generally the preparation of an aqueous slurry of the detergent ingredients to be spray-dried, which advantageously neither volatilize nor decompose under the conditions of spray-drying. This slurry usually comprises surfactants, builders and usually adjusting agents. The slurry is then pumped into the spray tower and sprayed through nozzles located in the top of the tower. In this case, rising, hot air at a temperature of preferably 200 to 35O 0 C dries the slurry and evaporates the adhering water. At the outlet of the tower (temperature preferably 80-120 0 C) then fall dried, fine powder.
Ein allgemeines Problem bei der Sprühtrocknung liegt darin, dass hoheA common problem in spray-drying is that high
Durchsatzgeschwindigkeiten zu Pluming und Staubexplosionen führen können. Ein weiterer Vorteil unserer Erfindung liegt nun darin, dass im erfindungsgemäßen Fall die Leistung des Sprühturms, also die Durchsatzgeschwindigkeit, weiter gesteigert werden kann, ohne dass sich die angegebenen nachteiligen Effekte ergeben.Throughput rates can lead to pluming and dust explosions. Another advantage of our invention lies in the fact that in the case of the invention, the performance of the spray tower, ie the throughput rate, can be further increased without resulting in the specified adverse effects.
Ein weiterer Vorteil liegt darin, dass es das erfindungsgemäße Verfahren ermöglicht, Tensid- reduzierte und Polymer-reduzierte Sprühtrocknungsprodukte zu erhalten, die einen sehr gute Kornstabilität aufweisen, ohne sehr hohe Schüttgewichte einstellen zu müssen.A further advantage is that the process according to the invention makes it possible to obtain surfactant-reduced and polymer-reduced spray-drying products which have very good grain stability without having to set very high bulk densities.
Dies ist besonders vorteilhaft, weil eine größer werdende Anzahl von Verbrauchern den Wunsch hat, bei der Dosierung von Wasch- oder Reinigungsmitteln individueller agieren zu können. Ist nun aber das Wasch- oder Reinigungsmittel sehr hoch konzentriert, so ist der Dosierungsfreiraum des Verbrauchers mangels Menge des zu dosierenden Mittels eingeschränkter als bei weniger konzentrierten Mitteln. Der Verbraucher fragt daher immer häufiger Wasch- oder Reinigungsmittelpulver mit vermindertem Schüttgewicht nach, die aber dennoch eine gute Kornstabilität haben sollen. Diesem Wunsch wird genüge getan mit einem Verfahren zur Herstellung von Wasch- oder Reinigungsmittelpulver mit einem Schüttgewicht im Bereich von < 500 g/L durch Sprühtrocknung einer wässrigen Aufschlämmung enthaltendThis is particularly advantageous because an increasing number of consumers has the desire to be able to act more individually in the dosage of detergents or cleaners. If, however, the detergent or cleaning agent is very highly concentrated, the dosage space of the consumer is less limited because of the lack of the amount of the agent to be dosed concentrated means. Consumers are therefore increasingly asking for washing powder or detergent powder with reduced bulk density, which nevertheless should have good grain stability. This request is satisfied with a process for the preparation of detergent or cleaning powder having a bulk density in the range of <500 g / L by spray-drying an aqueous slurry containing
4 bis 12 Gew.-% Silicat(e),4 to 12% by weight of silicate (e),
5 bis 12 Gew.-% Aniontensid, insbesondere LAS,From 5 to 12% by weight of anionic surfactant, in particular LAS,
40 bis 60 Gew.-% Trägermaterial, insbesondere Soda und/oder Sulfat,From 40 to 60% by weight of carrier material, in particular soda and / or sulfate,
20 bis 60 Gew.-% Wasser, sowie weniger als 2 Gew.-% Polycarboxylat-Copolymere,20 to 60% by weight of water and less than 2% by weight of polycarboxylate copolymers,
Gew.-% bezogen auf die gesamte wässrige Aufschlämmung.Wt .-% based on the total aqueous slurry.
Ein weiterer Gegenstand der Erfindung liegt in der Verwendung von 4 Gew.-% bis 12 Gew.-% Silicat(en) in sprühzutrocknenden wässrigen Aufschlämmungen zur Verbesserung der Kornstabilität des Sprühtrocknungsproduktes, Gew.-% bezogen auf die gesamte wässrige Aufschlämmung.Another object of the invention is the use of 4 wt .-% to 12 wt .-% silicate (s) in spray-dried aqueous slurries to improve the grain stability of the spray-drying product, wt .-% based on the total aqueous slurry.
Unter den Begriff der Wasch- oder Reinigungsmittel im Sinne dieser Erfindung fallen insbesondere a) die Textilwaschmittel, b) die Textilnachbehandlungsmittel (wie vorzugsweise Weichspüler) sowie c) die Reinigungsmittel, wie insbesondere Reiniger für harte Oberflächen (wie vorzugsweise maschinelle Geschirrspülmittel) sowie die Reinigungshilfsmittel.The term washing or cleaning agents in the context of this invention includes in particular a) the laundry detergents, b) the textile aftertreatment agents (such as softeners) and c) the cleaners, in particular cleaners for hard surfaces (such as preferably automatic dishwashing detergents) and the cleaning auxiliaries.
Erfindungsgemäße Wasch- oder Reinigungsmittel können z.B. auch in Portions-Säckchen oder (vorzugsweise selbstauflösenden) Portionsbeuteln (pouches) abgepackt sein, insbesondere auch in Mehrkammerpouches. Erfindungsgemäße Wasch- oder Reinigungsmittel können auch als Tabletten, insbesondere mehrlagige Tabletten vorliegen.Detergents or cleaning agents according to the invention may e.g. also in sachets or (preferably self-dissolving) sachets (pouches) be packaged, especially in Mehrkammerpouches. Detergents or cleaners according to the invention can also be present as tablets, in particular multi-layered tablets.
Zu den von der Erfindung umfassten Wasch- oder Reinigungsmitteln zählen insbesondere:The washing or cleaning agents encompassed by the invention include in particular:
(a) Vollwaschmittel, (enthält vorzugsweise Bleichmittel, optische Aufheller, Enzyme usw.)(a) heavy duty detergent, (preferably contains bleach, optical brighteners, enzymes, etc.)
(b) Colorwaschmittel, (vorzugsweise enthaltend Verfärbungsinhibitoren, Cellulasen usw.)(b) color detergents, (preferably containing discoloration inhibitors, cellulases, etc.)
(c) Feinwaschmittel, (vorzugsweise geringere Alkalität),(c) mild detergent, (preferably lower alkalinity),
(d) „2 in 1 "-Waschmittel (d.h. weichmachendes Waschmittel)(d) "2 in 1" detergent (i.e., softening detergent)
(e) Spezialwaschmittel, wie z.B. insbesondere i) Wollwaschmittel, (vorzugsweise pH-neutral) ii) Gardinenwaschmittel, iii) Waschmittel für die Handwäsche, iv) Waschmittel mit Zusatznutzen, wie vorzugsweise(e) special detergents, such as in particular i) wool detergents, (preferably pH-neutral) ii) curtain detergents, iii) detergents for hand washing, iv) added-benefit detergent, as preferably
Waschmittel mit Geruchsabsorber - UV-Schutz-Waschmittel, Hygiene-Waschmittel, Bügelerleichterungswaschmittel, Spezialwaschmittel für schwarze oder weiße Wäsche,Detergent with Odor Absorber - UV protection detergent, hygiene detergent, easy-care laundry detergent, special detergent for black or white laundry,
Sensitiv-Waschmittel, vorzugsweise enthaltend pflegende Substanzen, wie z.B. Mandelöl, Aloe Vera Extrakt usw. Duftintensiv- bzw. Aroma-Waschmittel.Sensitive detergent, preferably containing nourishing substances, e.g. Almond oil, aloe vera extract, etc. Duftintensiv- or aroma detergent.
Ein erfindungsgemäßes Wasch- oder Reinigungsmittel enthält Tenside. Besonders bevorzugt ist es, wenn das erfindungsgemäße Wasch- oder Reinigungsmittel anionische, nichtionische und/oder kationische Tenside, insbesondere eine Mischung aus anionischen und nichtionischen Tensiden enthält, wobei das gesamte Mittel vorzugsweise 0,1 Gew.-% bis 50 Gew.-%, insbesondere 10 Gew.-% bis 40 Gew.-% Tensid enthält. Dies entspricht einer bevorzugten Ausführungsform der Erfindung und ermöglicht optimale Reinigungsleistungen.An inventive washing or cleaning agent contains surfactants. It is particularly preferred for the washing or cleaning agent according to the invention to comprise anionic, nonionic and / or cationic surfactants, in particular a mixture of anionic and nonionic surfactants, the total composition preferably being 0.1% by weight to 50% by weight, contains in particular 10 wt .-% to 40 wt .-% surfactant. This corresponds to a preferred embodiment of the invention and enables optimum cleaning performance.
Besonders günstig ist es, wenn das erfindungsgemäße Wasch- oder Reinigungsmittel Alkylbenzolsulfonat, vorzugsweise lineares Alkylbenzolsulfonat (LAS) enthält, vorteilhafterweise in Mengen von 0,1 - 25 Gew. %, in weiter vorteilhafter Weise 1- 20 Gew-%, insbesondere in Mengen von 5-15 Gew.-%, bezogen auf das gesamte Mittel. Dies entspricht einer bevorzugten Ausführungsform der Erfindung und ermöglicht ganz besonders vorteilhafte Reinigungsleistungen.It is particularly advantageous if the washing or cleaning agent according to the invention comprises alkylbenzenesulfonate, preferably linear alkylbenzenesulfonate (LAS), advantageously in amounts of 0.1-25% by weight, more preferably 1-20% by weight, in particular in amounts of 5-15% by weight, based on the total agent. This corresponds to a preferred embodiment of the invention and allows very particularly advantageous cleaning performance.
Besonders geeignete Aniontenside sind ferner die Alkylsulfate, insbesondere die Fettalkoholsulfate (FAS), z.B. Ci2-Ci8-Fettalkoholsulfat. Vorzugsweise können C8-Ci6-Alkylsulfate eingesetzt werden, besonders bevorzugt sind d3-Alkylsulfat sowie Ci3.i5-Alkylsulfat und C13_17- Alkylsulfat, vorteilhafterweise verzweigtes, insbesondere Alkyl-verzweigtes Ci3.i7-Alkylsulfat. Besonders geeignete Fettalkoholsulfate leiten sich vom Lauryl- und Myristylalkohol ab, sind also Fettalkoholsulfate mit 12 bzw. 14 Kohlenstoffatomen. Die langkettigen FAS-Typen (Ci6 bis Ci8) eignen sich sehr gut zum Waschen bei höheren Temperaturen. Besonders bevorzugt sind Alkylsulfate, die einen niedrigeren Krafft-Punkt aufweisen, vorzugsweise mit Krafft-Punkt kleiner 45, 40, 30 oder 2O0C. Krafft-Punkt ist die Bezeichnung für diejenige Temperatur, bei der die Löslichkeit von Tensiden infolge der Bildung von Micellen stark zunimmt. Der Krafft-Punkt ist ein Tripelpunkt, an dem sich der Festkörper oder hydratisierte Kristalle des Tensids mit dessen gelösten (hydratisierten) Monomeren und Micellen im Gleichgewicht befinden. Bestimmt wird der Krafft- Punkt über eine Trübungsmessung gemäß DIN EN 13955: 2003-03. Wenn das erfindungsgemäße Wasch- oder Reinigungsmittel Alkylsulfat, insbesondere C12-C18- Fettalkoholsulfat, enthält, vorteilhafterweise in Mengen von 0,1 - 25 Gew. %, in weiter vorteilhafter Weise 1- 20 Gew-%, insbesondere in Mengen von 5-15 Gew.-%, bezogen auf das gesamte Mittel, so liegt eine bevorzugte Ausführungsform der Erfindung vor.Particularly suitable anionic surfactants are also the alkyl sulfates, in particular the fatty alcohol sulfates (FAS), for example Ci 2 -C 8 fatty alcohol sulfate. Preferably, C 6 -C 8 alkyl sulfates are used, particularly preferred are alkyl sulfate and d 3 Ci 3 .i 5 alkyl sulfate and C 13 _ 17 - alkyl sulfate, advantageously branched, in particular alkyl-branched C 3 .i 7 alkyl sulfate. Particularly suitable fatty alcohol sulfates are derived from lauryl and myristyl alcohol, so are fatty alcohol sulfates with 12 or 14 carbon atoms. The long-chain FAS types (Ci 6 to Ci 8 ) are very suitable for washing at higher temperatures. Particularly preferred are alkyl sulfates which have a lower Krafft point, preferably less with Krafft point 45, 40, 30, or 2O 0 C. Krafft point is the term for the temperature at which the solubility of surfactants due to the formation of micelles strongly increases. The Krafft point is a triple point at which the solid or hydrated crystals of the surfactant are in equilibrium with its dissolved (hydrated) monomers and micelles. The Krafft point is determined by a turbidity measurement according to DIN EN 13955: 2003-03. When the washing or cleaning agent according to the invention contains alkyl sulfate, in particular C 12 -C 18 -fatty alcohol sulfate, advantageously in amounts of 0.1-25% by weight, more preferably 1-20% by weight, in particular in amounts of 5-10% by weight. 15 wt .-%, based on the total agent, so is a preferred embodiment of the invention.
Andere geeignete Aniontenside, die ebenfalls eingesetzt werden können sind z.B. Alkansulfonate (z.B. sekundäres C13-C18-Alkansulfonat), Methylestersulfonate (z.B. α-C12-C18- Methylestersulfonat) und α-Olefinsulfonate (z.B. α-C14-C18-Olefinsulfonat) und Alkylethersulfate (z.B. C12-C14-Fettalkohol-2EO-ethersulfat) und/oder Seifen. Weitere geeignete Aniontenside werden weiter unten noch beschrieben. Besonders geeignet sind aber FAS und/oder LAS.Other suitable anionic surfactants which may also be used are e.g. Alkanesulfonates (eg C13-C18 secondary alkanesulfonate), methyl ester sulfonates (eg α-C12-C18 methyl ester sulfonate) and α-olefin sulfonates (eg α-C14-C18 olefin sulfonate) and alkyl ether sulfates (eg C12-C14 fatty alcohol 2EO ether sulfate) and / or soaps. Further suitable anionic surfactants will be described below. However, FAS and / or LAS are particularly suitable.
Die anionischen Tenside, einschließlich der Seifen, können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants, including soaps, may 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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Wenn das erfindungsgemäße Wasch- oder Reinigungsmittel nichtionisches Tensid, insbesondere alkoxylierten Fettalkohol umfasst, insbesondere in Mengen von 0,01 - 30 Gew. %, bezogen auf das gesamte Mittel, so liegt wiederum eine bevorzugte Ausführungsform der Erfindung vor, wobei der kombinierte Einsatz von Alkylbenzolsulfonat mit nichtionischem Tensid ganz besonders bevorzugt ist.If the washing or cleaning agent according to the invention comprises nonionic surfactant, in particular alkoxylated fatty alcohol, in particular in amounts of from 0.01 to 30% by weight, based on the total agent, then again a preferred embodiment of the invention is present wherein the combined use of alkylbenzenesulfonate with nonionic surfactant is very particularly preferred.
Besonders geeignete Niotenside sind ferner Alkylphenolpolyglycolether (APEO), (ethoxylierte) Sorbitanfettsäureester (Sorbitane), Alkylpolyglucoside (APG), Fettsäureglucamide, Fettsäure- ethoxylate, Aminoxide, Ethylenoxid-Propylenoxid-Blockpolymere, Polyglycerolfettsäureester und/oder Fettsäurealkanolamide. Weitere geeignete Niotenside werden weiter unten noch beschrieben. Niotenside auf Zuckerbasis, wie insbesondere APG, sind besonders bevorzugt.Particularly suitable nonionic surfactants are also alkylphenol polyglycol ethers (APEO), (ethoxylated) sorbitan fatty acid esters (sorbitans), alkylpolyglucosides (APG), fatty acid glucamides, fatty acid ethoxylates, amine oxides, ethylene oxide-propylene oxide block polymers, polyglycerol fatty acid esters and / or fatty acid alkanolamides. Other suitable nonionic surfactants will be described below. Sugar-based nonionic surfactants, such as APG in particular, are particularly preferred.
Nach einer weiteren bevorzugten Ausführungsform der Erfindung umfasst das erfindungsgemäße Wasch- oder Reinigungsmittel Enzyme, vorzugsweise Amylase, Pektinase, Carboanhydrase, Tannase, Lipase, Mannanase, Protease und/oder Cellulase, vorteilhafterweise in Mengen von 0,0001 - 5 % Gew.-%, bezogen auf das gesamte Mittel. Eine geeignete Mindestmenge kann auch bei 0,001 Gew.-% oder 0,01 Gew.-% liegen, bezogen auf das gesamte Mittel. Bevorzugt einsetzbare Enzyme werden weiter unten noch genauer beschrieben.According to a further preferred embodiment of the invention, the washing or cleaning agent according to the invention comprises enzymes, preferably amylase, pectinase, carbonic anhydrase, tannase, lipase, mannanase, protease and / or cellulase, advantageously in amounts of from 0.0001 to 5% by weight, based on the total mean. A suitable minimum amount may also be 0.001 wt% or 0.01 wt%, based on the total agent. Preferably usable enzymes are described in more detail below.
Weiterhin ist es ganz besonders bevorzugt, dass das erfindungsgemäße Wasch- oder Reinigungsmittel ein Buildersystem enthält, vorzugsweise ein zeolithhaltiges Buildersystem, vorzugsweise umfassend Zeolith in Mengen > 5 Gew.-%, noch vorteilhafter > 10 Gew.-%, weiter vorteilhaft > 15 Gew.- %, insbesondere > 20 Gew.-% enthalten ist, Gew.-% bezogen auf das gesamte Mittel. Eine sinnvolle Obergrenze an Zeolith kann z.B. bei 60 Gew.-%, 50 Gew.-% oder 40 Gew.-% liegen, bezogen auf das gesamte Mittel. Dies entspricht einer bevorzugten Ausführungsform der Erfindung.Furthermore, it is very particularly preferred that the washing or cleaning agent according to the invention comprises a builder system, preferably a zeolite-containing builder system, preferably comprising zeolite in amounts of> 5% by weight, more preferably> 10% by weight, more preferably> 15% by weight, in particular> 20% by weight,% by weight, based on the total composition. A reasonable upper limit of zeolite may be, for example, 60% by weight, 50% by weight or 40% by weight, based on the total agent. This corresponds to a preferred embodiment of the invention.
Im Sinne der Erfindung umfasst der Begriff „Buildersystem" auch solche „Systeme" die nur aus einem einzigen Builder bestehen, wie z.B. Zeolith. Bevorzugt ist es aber, dass zumindest 2 Substanzen mit Builderwirkung zum Einsatz gelangen, z.B. Zeolith in Kombination mit Soda, oder ähnliches.For the purposes of the invention, the term "builder system" also encompasses those "systems" which consist only of a single builder, such as e.g. Zeolite. It is preferred, however, that at least 2 substances with a builder effect be used, e.g. Zeolite in combination with soda, or similar.
Ebenfalls ist es besonders bevorzugt, wenn das erfindungsgemäße Wasch- oder Reinigungsmittel ein lösliches Buildersystem, vorzugsweise umfassend Soda, Silikat, Citrat und/oder Polycarboxylate, enthält, vorteilhafterweise in Mengen von 0,1 - 50 Gew.-%, bezogen auf das gesamte Mittel. Dies entspricht einer bevorzugten Ausführungsform der Erfindung. Ist ein solches lösliches Buildersystem enthalten, so kann es überaus bevorzugt sein, wenn nur geringe Mengen unlöslicher Builder, wie insbesondere Zeolith, z.B. < 5 Gew.-% bis 0,1 Gew.-% enthalten sind, insbesondere in solchem Falle gar kein unlöslicher Builder enthalten ist.It is likewise particularly preferred if the washing or cleaning agent according to the invention contains a soluble builder system, preferably comprising soda, silicate, citrate and / or polycarboxylates, advantageously in amounts of from 0.1 to 50% by weight, based on the total agent , This corresponds to a preferred embodiment of the invention. If such a soluble builder system is included, it may be highly preferred to use only minor amounts of insoluble builders such as, in particular, zeolite, e.g. <5 wt .-% to 0.1 wt .-% are included, especially in such a case, no insoluble builder is included.
Ebenfalls ist es möglich, dass das erfindungsgemäße Wasch- oder Reinigungsmittel ein Phosphate enthaltendes Buildersystem enthält, wobei in solchem Fall Phosphat vorzugsweise in Mengen von 1-40 Gew.-%, insbesondere 5-30 Gew.-% enthalten ist, bezogen auf das gesamte Mittel. Nach einer anderen bevorzugten Ausführungsform ist das erfindungsgemäße Wasch- oder Reinigungsmittel jedoch frei von Phosphaten.It is likewise possible for the washing or cleaning agent according to the invention to comprise a phosphate-containing builder system, in which case phosphate preferably being present in amounts of 1-40% by weight, in particular 5-30% by weight, based on the total Medium. According to another preferred embodiment, however, the washing or cleaning agent according to the invention is free of phosphates.
Bevorzugt einsetzbare Builder bzw. Buildersysteme werden weiter unten noch genauer beschrieben.Preferred builders or builder systems will be described in more detail below.
Bevorzugte erfindungsgemäße Wasch- oder Reinigungsmittel weisen einen pH > 7,5 auf, gemessen in einer 5%-Lösung des Mittels in Wasser bei 2O0C.Preferred washing or cleaning agent according to the invention have a pH of> 7.5 as measured in a 5% solution of the composition in water at 2O 0 C.
Die erfindungsgemäßen Wasch- oder Reinigungsmittel können, wie schon gezeigt wurde, insbesondere Buildersubstanzen und oberflächenaktive Tenside, weiterhin aber auch Bleichmittel, Bleichaktivatoren, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Fluoreszenzmittel, Ver- grauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffe, Germizide, Fungizide, Antioxidantien, Konservierungsmittel, 10The washing or cleaning agents according to the invention can, as already shown, in particular builders and surface-active surfactants, but also bleach, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, fluorescers, Ver inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, 10
Korrosionsinhibitoren, Antistatika, Bittermittel, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel, neutrale Füllsalze sowie UV-Absorber, Schaum reg ulatoren sowie Färb- und Riechstoffe enthalten.Corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts and UV absorbers, foam regulators and colorants and fragrances.
Vorgenannte Inhaltsstoffe werden nun z.T. noch genauer beschrieben.The aforementioned ingredients are now partly. described in more detail.
Die erfindungsgemäßen Wasch- oder Reinigungsmittel enthalten vorzugsweise , wie schon beschrieben wurde, ein Tensid oder auch mehrere Tenside, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische, aber auch kationische, zwitterionische und amphotere Tenside in Frage kommen.The washing or cleaning agents according to the invention preferably comprise, as already described, one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
Einsetzbare nichtionische Tenside wurden bereits genannt. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkyl- glykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest brauchbar.Usable nonionic surfactants have already been mentioned. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol optional eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise Ci2-Ci4-Alkohole mit 3 EO oder 4 EO, C9-Ci i-Alkohole mit 7 EO, Ci3-Ci5-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, Ci2-Ci8-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus Ci2-Ci4-Alkohol mit 3 EO und Ci2-Ci8-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (TaIg-) Fettalkohole mit 14 EO, 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO. Insbesondere in Mitteln für den Einsatz in maschinellen Verfahren können üblicherweise extrem 1 1 schaumarme Verbindungen eingesetzt werden. Hierzu zählen vorzugsweise C-i2-C18-Alkylpolyethy- lenglykol-polypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel C-i2-C18-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül sowie endgruppenverschlossene Alkyl- polyalkylenglykolmischether. Besonders bevorzugt sind auch die hydroxylgruppen haltigen alkoxylierten Alkohole, wie sie in der europäischen Patentanmeldung EP 0 300 305 beschrieben sind, sogenannte Hydroxymischether. Zu den nichtionischen Tensiden zählen auch Alkylglykoside der allgemeinen Formel RO(G)x , in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl - die als analytisch zu bestimmende Größe auch gebrochene Werte annehmen kann - zwischen 1 und 10; vorzugsweise liegt x bei 1 ,2 bis 1 ,4. Ebenfalls geeignet sind Polyhydroxyfettsäureamide der Formel (IM), in der R1CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht:As nonionic surfactants are preferably alkoxylated, preferably ethoxylated, especially 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 optionally used in which the alcohol radical is linear or preferably methyl branched in the 2-position may contain linear or methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 2 -C 4 -alcohols with 3 EO or 4 EO, C 9 -C 12 -alcohols with 7 EO, C 3 -C 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -Ci 4 alcohol with 3 EO and Ci 2 -Ci 8 alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. In particular, in means for use in mechanical processes can usually extremely 1 1 low-foam connections are used. These include preferably C 2 -C 18 -alkylpolyethylene glycol polypropylene glycol ethers having in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule. However, it is also possible to use other known low-foam nonionic surfactants, such as, for example, C 2 -C 18 -alkylpolyethyleneglycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule as well as end-capped alkyl polyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European Patent Application EP 0 300 305, so-called hydroxy mixed ethers. 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 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a Glykoseeinheit with 5 or 6 C-atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4. Also suitable are polyhydroxy fatty acid amides of the formula (III) in which R 1 is CO for 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 having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
R2 R 2
II
R1-CO-N-[Z] (III)R 1 -CO-N- [Z] (III)
Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (IV),The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)
R4-O-R5 R 4 -OR 5
(IV)(IV)
R3-CO-N-[Z]R 3 -CO-N- [Z]
in der R3 für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R4 für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R5 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei d-C4-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit 12 mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt einsetzbarer nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden können, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein dC 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with 12 is substituted at least two hydroxyl groups, or is alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferred nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
Bevorzugt einsetzbare Aniontenside wurden bereits genannt. Als anionische Tenside werden vorzugsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-18- Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-i8-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α- sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren geeignet.Preferred anionic surfactants have already been mentioned. The anionic surfactants used are preferably those of the sulfonate and sulfates type. Preferred surfactants of the sulfonate type are C9-13-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C12-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates, which are obtained from C 12-i 8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure. 13Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. 13
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myri- styl-, Cetyl- oder Stearylalkohol oder der C10-C2o-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C12-C16-Alkyl- sulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche als Handelsprodukte der Shell OiI Company unter dem Namen DAN® erhalten werden können, sind geeignete Aniontenside.Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myrilecyl, cetyl or stearyl alcohol or the C 10 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From a washing-technical point of view, the C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates are preferred. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7.21-Alkohole, wie 2-Methyl-verzweigte C^-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12.18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, optional eingesetzt.Also, the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with 1 to 6 moles of ethylene oxide. 21 -alcohols, such as 2-methyl-branched C ^ -alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of from 1 to 5% by weight, as an option.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8.18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 . 18- fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Insbesondere bevorzugte anionische Tenside sind Seifen. Geeignet sind gesättigte und ungesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, (hydrierten) Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, Olivenöl- oder Taigfettsäuren, abgeleitete Seifengemische. Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder 14Particularly preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids. The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or 14
Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.Triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Das erfindungsgemäße Wasch- oder Reinigungsmittel kann vorzugsweise Kationtensid enthalten, insbesondere quaternäre Ammoniumverbindungen wie Monoalk(en)yltrimethylammonium- Verbindungen, Dialk(en)yldimethylammonium-Verbindungen, Mono-, Di- oder Triester von Fettsäuren mit Alkanolaminen. Besonders bevorzugt sind alkylierte quaternäre Ammoniumverbindungen, von denen mindestens eine Alkylkette durch eine Estergruppe und/oder Amidogruppe unterbrochen ist. Ganz besonders bevorzugt sind N-Methyl-N-(2-hydroxyethyl)-N,N- (ditalgacyloxyethyl)ammonium-methosulfat oder Bis-(palmitoyloxyethyl)-hydroxyethyl-methyl- ammonium-methosulfat.The washing or cleaning agent according to the invention may preferably comprise cationic surfactant, in particular quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines. Particularly preferred are alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group. Very particular preference is given to N-methyl-N- (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) ammonium methosulfate or bis (palmitoyloxyethyl) -hydroxyethyl-methylammonium methosulfate.
Ein erfindungsgemäßes Wasch- oder Reinigungsmittel kann vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder enthalten. Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, insbesondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamintetrakis(methylenphosphonsäure) und 1-Hydroxyethan-1 ,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden beziehungsweise Dextrinen zugänglichen Polycarboxyla- te, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymeri- siert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 3 000 und 200 000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 30 000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 30 000 bis 100 000 auf. Handelsübliche Produkte sind zum Beispiel Sokalan® CP 5, CP 10 und PA 30 der Firma BASF. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copoly- mere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethy- len, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder einem veresterten Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8- Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth)- 15 acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Al- lylsulfonsäure, die in 2-Stellung mit einem Alkyl- oder Arylrest substituiert ist, sein. Derartige Polymere weisen im Allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können auch in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50-ge- wichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt. Derartige organische Buildersubstanzen können gemäß einer bevorzugten Ausführungsform der Erfindung eingesetzt werden und können gewünschtenfalls in Mengen z.B. bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.-% enthalten sein, Gew.- % bezogen auf das gesamte Wasch- oder ReinigungsmittelA washing or cleaning agent according to the invention may preferably contain at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) - 15 acrylic acid. The second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an alkylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical , Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can also be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts. Such organic builders may be used according to a preferred embodiment of the invention and may, if desired, be present in amounts, for example, of up to 40% by weight, in particular up to 25% by weight and preferably from 1% to 8% by weight ,% By weight based on the total washing or cleaning agent
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkalisilikate, Alkalicarbonate und Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natriumoder Kaliumsalze vorliegen können, in Betracht. Beispiele hierfür sind Trinatriumphosphat, Tetra- natriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere 5 bis 50, sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen.Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetra sodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien können insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-%, eingesetzt werden, Gew.-% bezogen auf das gesamte Wasch- oder Reinigungsmittel. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, allein oder in Mischungen, beispielsweise in Form eines Co-Kristallisats aus den Zeolithen A und X (Vegobond® AX, ein Handelsprodukt der Condea Augusta S.p.A.), bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μm. Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den erfindungsgemäßen Mitteln als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1 :1 ,1 bis 1 :12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem mola- 16 ren Verhältnis Na2OiSiO2 von 1 :2 bis 1 :2,8. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+1 y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 22, insbesondere 1 ,9 bis 4 und y eine Zahl von 0 bis 33 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natrium- disilikate (Na2Si2O5 y H2O) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1 ,9 bis 2,1 bedeutet, können in erfindungsgemäßen Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1 ,9 bis 3,5 werden in einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel eingesetzt. Kristalline schichtförmige Silikate der oben angegebenen Formel (I) werden von der Fa. Clariant GmbH unter dem Handelsnamen Na-SKS vertrieben, z.B. Na-SKS-1 (Na2Si22O45XH2O, Kenyait), Na-SKS-2 (Na2Sii4029xH20, Magadiit), Na-SKS-3 (Na2Si8Oi7XH2O) oder Na-SKS-4 (Na2Si4O9XH2O, Makatit). Von diesen eignen sich vor allem Na-SKS-5 ((X-Na2Si2O5), Na-SKS-7 (ß-Na2Si205, Natrosilit), Na- SKS-9 (NaHSi2O53H2O), Na-SKS-10 (NaHSi2O53H2O, Kanemit), Na-SKS-11 (t-Na2Si205) und Na- SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (5-Na2Si2O5). In einer bevorzugten Ausgestaltung erfindungsgemäßer Mittel setzt man ein granuläres Compound aus kristallinem Schichtsilikat und Citrat, aus kristallinem Schichtsilikat und oben genannter (co-)polymerer Polycarbonsäure, oder aus Alkalisilikat und Alkalicarbonat ein, wie es beispielsweise unter dem Namen Nabion® 15 im Handel erhältlich ist. Buildersubstanzen können in den erfindungsgemäßen Wasch- oder Reinigungsmitteln vorzugsweise in Mengen bis zu z.B. 75 Gew.-%, insbesondere 5 Gew.-% bis 50 enthalten sein, Gew.-% bezogen auf das gesamte Mittel. Als für den Einsatz in erfindungsgemäßen Wasch- oder Reinigungsmitteln geeignete Bleichmittel kommen z.B. Persauerstoffverbindungen wie insbesondere organische Persäuren beziehungsweise persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Perbenzoesäure oder Salze der Diper- dodecandisäure, Wasserstoffperoxid und unter den Waschbedingungen Wasserstoffperoxid abgebende anorganische Salze, zu denen Perborat, Percarbonat, Persilikat und/oder Persulfat wie Caroat gehören, in Betracht. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Falls ein erfindungsgemäßes Mittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-%, vorhanden. Der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasili- katen sowie Magnesiumsalzen wie Magnesiumsulfat kann zweckdienlich sein. 17Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, can be used as water-insoluble, water-dispersible inorganic builder materials,% by weight, based on the total washing or cleaning agent. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA) , Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Ratio of Na 2 OiSiO 2 from 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, known as the modulus, an integer of 1, 9 to 22, in particular 1, 9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite), Na-SKS-2 (Na 2 Sii 4 0 29 x H 2 0, magadiite), Na-SKS-3 (Na 2 Si 8 Oi 7 XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 XH 2 O, makatite). Of these, especially Na-SKS-5 ((X-Na 2 Si 2 O 5), are Na-SKS-7 (.beta.-Na 2 Si 2 0 5, natrosilite), Na SKS-9 (NaHSi 2 O 5 3H 2 O), Na-SKS-10 (NaHSi 2 O 5 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 0 5) and Na SKS-13 (NaHSi 2 O 5) , but in particular Na-SKS-6 (5-Na 2 Si 2 O 5). In a preferred embodiment of inventive compositions, a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the above-mentioned (co) polymeric polycarboxylic acid, or from alkali silicate and alkali carbonate, as it is commercially available, for example, under the name Nabion® 15. Builder substances may preferably be present in the detergents or cleaners according to the invention in amounts of up to, for example, 75% by weight, in particular 5% by weight to 50 % by weight based on the total agent are suitable as bleaching agents suitable for use in detergents according to the invention, for example peroxygen compounds, in particular organ or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of dodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate such as caroate into consideration. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. If an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and also magnesium salts such as magnesium sulfate may be expedient. 17
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1 ,5- Diacetyl-2,4-dioxohexahydro-1 ,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso- NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N- Benzoylcaprolactam. Die hydrophil substituierten Acylacetale und die Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren können, insbesondere bei Anwesenheit obengenannter Wasserstoffperoxid-Iiefernder Bleichmittel, im üblichen Mengenbereich, vorzugsweise in Mengen von 0,5 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten sein, fehlen bei Einsatz von Percarbonsäure als alleinigem Bleichmittel jedoch vorzugsweise ganz.As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoyl-caprolactam. The hydrophilic substituted acyl acetals and the acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-supplied bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.
Als in den erfindungsgemäßen Wasch- oder Reinigungsmitteln verwendbare Enzyme kommen vor allem solche aus der Klasse der Amylasen, Proteasen, Lipasen, Cutinasen, Pullulanasen, Hemicellulasen, Cellulasen, Oxidasen, Laccasen, Pektinasen, Carboanhydrasen, Mannanasen, Tannasen und Peroxidasen sowie deren Gemische in Frage. Besonders geeignet sind aus Pilzen oder Bakterien, wie Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia oder Coprinus cinereus gewonnene enzymatische Wirkstoffe. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige In- aktivierung zu schützen. Sie können in den erfindungsgemäßen Wasch- oder Reinigungsmitteln vorzugsweise in Mengen bis zu 5 Gew.-%, insbesondere von 0,01 Gew.-% bis 4 Gew.-%, enthalten sein. Falls das erfindungsgemäße Mittel Protease enthält, weist es vorzugsweise eine proteolytische Aktivität im Bereich von etwa 100 PE/g bis etwa 10 000 PE/g, insbesondere 300 PE/g bis 8000 PE/g auf. Falls mehrere Enzyme in dem erfindungsgemäßen Mittel eingesetzt werden sollen, kann dies durch Einarbeitung der zwei oder mehreren separaten beziehungsweise 18 in bekannter Weise separat konfektionierten Enzyme oder durch zwei oder mehrere gemeinsam in einem Granulat konfektionierte Enzyme durchgeführt werden.Suitable enzymes which can be used in the washing or cleaning agents according to the invention are, in particular, those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases, pectinases, carbonic anhydrases, mannanases, tannases and peroxidases and mixtures thereof , Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They may be present in the detergents or cleaners according to the invention preferably in amounts of up to 5% by weight, in particular from 0.01% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be achieved by incorporating the two or more separate or 18 enzymes are prepared separately in a known manner or by two or more assembled together in a granule enzymes.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel System- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren können in den erfindungsgemäßen Mitteln in Mengen von z.B. vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 ,2 Gew.-% bis 17 Gew.-%, optional enthalten sein. Ebenso können z.B. Alkalien wie z.B. NaOH eingesetzt werden.In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators may be used in the compositions of the invention in amounts of e.g. preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, may optionally be present. Likewise, e.g. Alkalis, e.g. NaOH can be used.
Um den ästhetischen Eindruck der Wasch- oder Reinigungsmittel zu verbessern, können sie mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Wasch- oder Reinigungsmittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasern, um diese nicht anzufärben.To improve the aesthetic impression of detergents or cleaners, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents or cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
Als Parfümöle können beispielsweise einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyciohexylacetat, Linalylacetat, Dimethylbenzylcarbinyl-acetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethyl-methylphenylglycinat, Allylcyciohexylpropionat, Styrallylpropionat und Benzyisalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8 -18 C-Atomen, Citral, Citronellal, Citronellyloxy- acetaldehyd, Cyclamenaldehyd, Hydroxycitronellel, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, Isomethylionon und Methyl-cedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylelkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene und Balsame. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen.As perfume oils, for example, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellel, lilial and bourgeonal, to the ketones e.g. the ionones, isomethylionone and methyl cedryl ketone; the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
Einsetzbare Soil-Release-Polymere, die auch als „Antiredepositionsmittel" bezeichnet werden, sind beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose mit einem Anteil an Methoxygruppen von 15 bis 30 Gew.-% und an Hydroxypropylgruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder Terephthalsäure bzw. von deren 19Useful soil release polymers, also referred to as "anti-redeposition agents", include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose having a methoxy group content of 15 to 30 weight percent and hydroxypropyl groups of 1 to 15 weight percent, respectively based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or of their 19
Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylen- und/oder Polypropylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Geeignete Derivate umfassen die sulfonierten Derivate der Phthalsäure- und Terephthalsäure-Polymere.Derivatives, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
Optische Aufheller (so genannte „Weißtöner") können den Wasch- oder Reinigungsmitteln zugesetzt werden, um Vergrauungen und Vergilbungen der behandelten Textilen Flächengebilden zu beseitigen. Diese Stoffe ziehen auf die Faser auf und bewirken eine Aufhellung und vorgetäuschte Bleichwirkung, indem sie unsichtbare Ultraviolettstrahlung in sichtbares längerwelliges Licht umwandeln, wobei das aus dem Sonnenlicht absorbierte ultraviolette Licht als schwach bläuliche Fluoreszenz abgestrahlt wird und mit dem Gelbton der vergrauten bzw. vergilbten Wäsche reines Weiß ergibt. Geeignete Verbindungen stammen beispielsweise aus den Substanzklassen der 4,4'-Diamino-2,2'-stilbendisulfonsäuren (Flavonsäuren), 4,4'-Distyryl- biphenylen, Methylumbelliferone, Cumarine, Dihydrochinolinone, 1 ,3-Diarylpyrazoline, Naphthalsäureimide, Benzoxazol-, Benzisoxazol- und Benzimidazol-Systeme sowie der durch Heterocyclen substituierten Pyrenderivate. Die optischen Aufheller werden üblicherweise in Mengen zwischen z.B. 0% und 0,3 Gew.-%, bezogen auf das fertige Mittel, optional eingesetzt.Optical brighteners (so-called "whiteners") may be added to laundry detergents or cleaners to eliminate graying and yellowing of the treated fabrics, which will attract the fiber and cause lightening and fake bleaching by exposing invisible ultraviolet radiation to visible convert longer wavelength light, the absorbed from sunlight ultraviolet light is radiated as a pale blue fluorescence and the yellow shade of the grayed or yellowed laundry pure white. Suitable compounds originate for example from the substance classes of the 4,4 'diamino-2,2 stilbenedisulfonic acids (flavonic), 4,4 'biphenylene -Distyryl- be Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles. the optical brighteners üblicherweis e in amounts between, for example, 0% and 0.3% by weight, based on the finished composition, are optionally used.
Um die durch Schwermetalle katalysierte Zersetzung bestimmter Waschmittel-Inhaltsstoffe zu vermeiden, können Stoffe eingesetzt werden, die Schwermetalle komplexieren. Geeignete (Schwer- metall-)Komplexbildner sind beispielsweise die Alkalisalze der Ethylendiamintetraessigsäure (EDTA) oder der Nitrilotriessigsäure (NTA) sowie Alkalimetallsalze von anionischen Polyelektrolyten wie Polymaleaten und Polysulfonaten.In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex heavy metals can be used. Suitable (heavy metal) complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
Eine bevorzugte Klasse von Komplexbildnern sind die Phosphonate, die in bevorzugten Waschoder Reinigungsmitteln in Mengen von z.B. 0,01 bis 2,5 Gew.-%, vorzugsweise 0,02 bis 2 Gew.-% und insbesondere von 0,03 bis 1 ,5 Gew.-% optional enthalten sind. Zu diesen bevorzugten Verbindungen zählen insbesondere Organophosphonate wie beispielsweise 1-Hydroxyethan-1 ,1- diphosphonsäure (HEDP), Aminotri(methylenphosphonsäure) (ATMP), Diethylentriamin-penta- (methylenphosphonsäure) (DTPMP bzw. DETPMP) sowie 2-Phosphonobutan-1 ,2,4-tricarbonsäure (PBS-AM), die zumeist in Form ihrer Ammonium- oder Alkalimetallsalze eingesetzt werden. 20A preferred class of complexing agents are the phosphonates, which in preferred detergents or cleaning agents in amounts of, for example, 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1, 5 % By weight are optionally included. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. 20
Die Wasch- oder Reinigungsmittel können zusätzlich z.B. noch neutrale Füllsalze wie Natriumsulfat enthalten.The washing or cleaning agents may additionally be added e.g. contain neutral filler salts such as sodium sulfate.
Ein bevorzugtes erfindungsgemäßes, pulverförmiges Vollwaschmittel kann vorzugsweise z.B. Komponenten enthalten, die ausgewählt sind aus den folgenden:A preferred heavy duty powder detergent according to the invention may preferably be e.g. Contain components that are selected from the following:
- Aniontenside, wie z.B. Alkylbenzolsulfonat, Alkylsulfat, in Mengen von z.B. 0-40 Gew.-%, vorteilhafterweise 5-30 Gew.-%, vorzugsweise 8-20 Gew.-%,Anionic surfactants, e.g. Alkyl benzene sulfonate, alkyl sulfate, in amounts of e.g. 0-40% by weight, advantageously 5-30% by weight, preferably 8-20% by weight,
- Nichtionische Tenside, wie z.B. Fettalkoholpolyglycolether, Alkylpolyglucosid, Fettsäureglucamid, in Mengen von z.B. 0-30 Gew.-%, vorteilhafterweise 0,1-20 Gew.-%, vorzugsweise 2-15 Gew.- %, insbesondere 6-11 Gew.-%,Nonionic surfactants, e.g. Fatty alcohol polyglycol ethers, alkylpolyglucoside, fatty acid glucamide, in amounts of e.g. 0-30% by weight, advantageously 0.1-20% by weight, preferably 2-15% by weight, in particular 6-11% by weight,
- Gerüststoffe, wie z.B. Zeolith, Polycarboxylat, Natriumeitrat, in Mengen von z.B. 0-70 Gew.-% , vorteilhafterweise 5-60 Gew.-%, vorzugsweise 10-55 Gew.-%, insbesondere 15-40 Gew.-%,Builders, e.g. Zeolite, polycarboxylate, sodium citrate, in amounts of e.g. 0-70% by weight, advantageously 5-60% by weight, preferably 10-55% by weight, in particular 15-40% by weight,
- Alkalien, wie z.B. Natriumcarbonat, in Mengen von z.B. 0-35 Gew.-% vorteilhafterweise 1-30 Gew.-%, vorzugsweise 2-25 Gew.-%, insbesondere 5-20 Gew.-%,Alkalis, e.g. Sodium carbonate, in amounts of e.g. 0-35 wt .-% advantageously 1-30 wt .-%, preferably 2-25 wt .-%, in particular 5-20 wt .-%,
- Bleichmittel, wie z.B. Natriumperborat, Natriumpercarbonat, in Mengen von z.B. 0-30 Gew.-% vorteilhafterweise 5-25 Gew.-%, vorzugsweise 10-20 Gew.-%,Bleaching agents, e.g. Sodium perborate, sodium percarbonate, in amounts of e.g. 0-30% by weight, advantageously 5-25% by weight, preferably 10-20% by weight,
- optional Korrosionsinhibitoren, wie z.B. Natriumsilicat,optionally corrosion inhibitors, e.g. sodium silicate,
- Stabilisatoren, z.B. Phosphonate, vorteilhafterweise 0-1 Gew.-%,Stabilizers, e.g. Phosphonates, advantageously 0-1% by weight,
- Schauminhibitor, z.B. Seife, Siliconöle, Paraffine vorteilhafterweise 0-4 Gew.-%, vorzugsweise 0,2-3 Gew.-%, insbesondere 1-1 Gew.-%,Foam inhibitor, e.g. Soap, silicone oils, paraffins advantageously 0-4 wt.%, Preferably 0.2-3 wt.%, In particular 1-1 wt.
- Enzyme, z.B. Proteasen, Amylasen, Cellulasen, Lipasen, vorteilhafterweise 0-2 Gew.-%, vorzugsweise 0,2-1 Gew.-%, insbesondere 0,3-0,8 Gew.-%,Enzymes, e.g. Proteases, amylases, cellulases, lipases, advantageously 0-2% by weight, preferably 0.2-1% by weight, in particular 0.3-0.8% by weight,
- Vergrauungsinhibitor, z.B. Carboxymethylcellulose, vorteilhafterweise 0-1 Gew.-%,- grayness inhibitor, e.g. Carboxymethylcellulose, advantageously 0-1% by weight,
- Verfärbungsinhibitor, z.B. Polyvinylpyrrolidon-Derivate, vorteilhafterweise 0-2 Gew.-%,Discoloration inhibitor, e.g. Polyvinylpyrrolidone derivatives, advantageously 0-2% by weight,
- Stellmittel, z.B. Natriumsulfat, vorteilhafterweise 0-20 Gew.-%,- Adjustment means, e.g. Sodium sulfate, advantageously 0-20% by weight,
- optional optische Aufheller, z.B. Stilben-Derivat, Biphenyl-Derivat, vorteilhafterweise 0,01-0,3 Gew.-%, insbesondere 0,1-0,4 Gew.-%,Optionally, optical brighteners, e.g. Stilbene derivative, biphenyl derivative, advantageously 0.01-0.3% by weight, in particular 0.1-0.4% by weight,
- optional Riechstoffe- Optional fragrances
- optional Wasser- optional water
- optional Seife- optional soap
- optional Bleichaktivatoren- optional bleach activators
- optional Cellulosderivate optional Schmutzabweiser, Gew.-% jeweils bezogen auf das gesamte Mittel. 21 Beispiele:- optional cellulosic derivatives optional soil deflector, wt .-% in each case based on the total agent. 21 examples:
Die Zusammensetzungen A (Vergleichsrezeptur) und B (erfindungsgemäße Rezeptur) wurden in einem konventionellen Sprühtrocknungsverfahren hergestellt.Compositions A (Comparative Formulation) and B (Formulation of the Invention) were prepared in a conventional spray-drying process.
A BA B
CMC-Natriumsalz [Gew.%] 1 1CMC sodium salt [wt.%] 1 1
Phosphonat [Gew %] 1 1Phosphonate [wt%] 1 1
Soda [Gew %] 14,5 10Soda [% by weight] 14.5 10
LAS [Gew %] 10 10 NatriumsilicatLAS [% by weight] 10 10 Sodium silicate
(Modul Na2O : SiO2 [Gew %] 5,5 10,0 von 1 : 2)(Modulus Na 2 O: SiO 2 [wt%] 5.5 10.0 of 1: 2)
Natriumsulfat [Gew %] 56 56 Polyacrylat- HomopolymerSodium sulfate [wt%] 56 56 Polyacrylate homopolymer
Seife [Gew %] 1 1Soap [weight%] 1 1
Wasser [Gew %] 5 5Water [% by weight] 5 5
Rest [Gew %] 4 4Remainder [weight%] 4 4
Summe [Gew %] 100 100Sum [weight%] 100 100
Schüttdichte 510 g/L 410 g/LBulk density 510 g / L 410 g / L
Das Vergleichsprodukt A zeigte gegenüber dem erfindungsgemäßen Produkt B eine deutlich schlechtere Kornstabilität, die sich z.B. darin äußerte, dass die Schüttdichte von Produkt A bei weiterer mechanischer Beanspruchung in deutlicher Weise auf Werte weit über 600 g/L zunahm, was bei Produkt B nicht der Fall war. Comparative product A showed, compared with product B according to the invention, a markedly poorer grain stability, which is evident, for example, from It stated that the bulk density of product A significantly increased to values well above 600 g / L upon further mechanical stress, which was not the case with product B.

Claims

22 Patentansprüche: 22 claims:
1. Sprühtrocknungsprodukt, umfassend Silicat(e), Tensid(e), Trägermaterial, wobei das Sprühtrocknungsprodukt a) < 5 Gew.-% wasserlösliche Polycarboxylat-Copolymere, insbesondere Copolymere auf der Basis von Acryl- und Maleinsäure b) > 7 Gew.-% Silicate, c) < 15 Gew.-% Aniontensid enthält.A spray-drying product comprising silicate (s), surfactant (s), carrier material, the spray-drying product a) <5% by weight of water-soluble polycarboxylate copolymers, in particular copolymers based on acrylic and maleic acids b)> 7% by weight. % Silicates, c) contains <15% by weight of anionic surfactant.
2. Sprühtrocknungsprodukt nach Anspruch 1 , dadurch gekennzeichnet, dass es 0,01 Gew.-% bis < 3 Gew.-%, vorzugsweise < 1 Gew.-%, vorteilhafterweise < 0,5 Gew.-% und insbesondere gar keine wasserlösliche Polycarboxylat-Copolymere enthält, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt.2. spray-drying product according to claim 1, characterized in that it is 0.01 wt .-% to <3 wt .-%, preferably <1 wt .-%, advantageously <0.5 wt .-% and in particular no water-soluble polycarboxylate Contains copolymers, wt .-% based on the total spray-drying product.
3. Sprühtrocknungsprodukt nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass es 8-30 Gew.-%, vorzugsweise 8-25 Gew.-% , insbesondere 8-15 Gew.-% Silicat(e) enthält, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt.3. spray-drying product according to any one of claims 1 or 2, characterized in that it contains 8-30 wt .-%, preferably 8-25 wt .-%, in particular 8-15 wt .-% silicate (s), wt. % based on the total spray-drying product.
4. Sprühtrocknungsprodukt nach einem der Ansprüche 1-3, dadurch gekennzeichnet, dass als Silicat Wasserglas enthalten ist.4. spray drying product according to any one of claims 1-3, characterized in that is contained as silicate water glass.
5. Sprühtrocknungsprodukt nach einem der Ansprüche 1-4, dadurch gekennzeichnet, dass es Aniontensid, vorteilhafterweise umfassend Alkylbenzolsulfonat, enthält, vorteilhafterweise in Mengen von 0,01 - 14 Gew. %, in weiter vorteilhafter Weise 3-13 Gew-%, insbesondere in Mengen von 5-12 Gew.-%, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt.5. spray drying product according to any one of claims 1-4, characterized in that it contains anionic surfactant, advantageously comprising alkylbenzenesulfonate, advantageously in amounts of 0.01 to 14 wt.%, More preferably 3-13 wt%, in particular Quantities of 5-12 wt .-%, wt .-% based on the total spray-drying product.
6. Sprühtrocknungsprodukt nach einem der Ansprüche 1-5, dadurch gekennzeichnet, dass es 0-5 Gew.-% wasserlösliche Polycarboxylat-Homopolymere, insbesondere Homopolymere auf der Basis von Acrylsäure enthält, vorteilhafterweise 0,01 Gew.-% bis < 3 Gew.-%, vorzugsweise weniger als 1 Gew.-%, und insbesondere gar keine wasserlösliche Polycarboxylat-Homopolymere enthält, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt.6. spray drying product according to any one of claims 1-5, characterized in that it contains 0-5 wt .-% of water-soluble polycarboxylate homopolymers, in particular homopolymers based on acrylic acid, advantageously 0.01 wt .-% to <3 wt. %, preferably less than 1 wt .-%, and in particular contains no water-soluble polycarboxylate homopolymers, wt .-% based on the total spray-drying product.
7. Sprühtrocknungsprodukt nach einem der Ansprüche 1-6, dadurch gekennzeichnet, dass das Trägermaterial ausgewählt ist aus Carbonaten, Sulfaten, Zeolith, Tripolyphosphat und/oder Chloriden. 237. spray drying product according to any one of claims 1-6, characterized in that the carrier material is selected from carbonates, sulfates, zeolite, tripolyphosphate and / or chlorides. 23
8. Sprühtrocknungsprodukt nach einem der Ansprüche 1-7, dadurch gekennzeichnet, dass der Gehalt an Trägermaterial 5-90 Gew.-%, vorzugsweise > 50 Gew.-%, insbesondere > 60 Gew.-% beträgt, Gew.-% bezogen auf das gesamte Sprühtrocknungsprodukt.8. spray-drying product according to any one of claims 1-7, characterized in that the content of carrier material is 5-90 wt .-%, preferably> 50 wt .-%, in particular> 60 wt .-%, wt .-% based on the entire spray-drying product.
9. Sprühtrocknungsprodukt nach einem der Ansprüche 1-8, dadurch gekennzeichnet, dass es Komplexbildner, insbesondere Phosphonate enthält.9. spray-drying product according to any one of claims 1-8, characterized in that it contains complexing agents, in particular phosphonates.
10. Sprühtrocknungsprodukt nach einem der Ansprüche 1-9, dadurch gekennzeichnet, dass es Celluloseether und/oder deren Salze enthält, insbesondere Carboxymethylcellulose.10. Spray drying product according to any one of claims 1-9, characterized in that it contains cellulose ethers and / or their salts, in particular carboxymethylcellulose.
11. Sprühtrocknungsprodukt nach einem der Ansprüche 1-10, dadurch gekennzeichnet, dass es ein Schüttgewicht von < 500 g/L, insbesondere ein Schüttgewicht im Bereich 400-500 g/L aufweist.11. Spray drying product according to any one of claims 1-10, characterized in that it has a bulk density of <500 g / L, in particular a bulk density in the range 400-500 g / L.
12. Wasch- oder Reinigungsmittel, enthaltend ein Sprühtrocknungsprodukt nach einem der Ansprüche 1-11.12. washing or cleaning agent containing a spray-drying product according to any one of claims 1-11.
13. Sprühtrocknungsverfahren, gekennzeichnet durch Einsatz einer wässrigen Aufschlämmung enthaltend13. spray-drying process, characterized by using an aqueous slurry containing
4 bis 12 Gew.-% Silicat(e),4 to 12% by weight of silicate (e),
5 bis 15 Gew.-% Aniontensid, insbesondere LAS,From 5 to 15% by weight of anionic surfactant, in particular LAS,
40 bis 60 Gew.-% Trägermaterial, insbesondere Soda und/oder Sulfat,From 40 to 60% by weight of carrier material, in particular soda and / or sulfate,
20 bis 60 Gew.-% Wasser, sowie weniger als 2 Gew.-% Polycarboxylat-Copolymere,20 to 60% by weight of water and less than 2% by weight of polycarboxylate copolymers,
Gew.-% bezogen auf die gesamte wässrige Aufschlämmung.Wt .-% based on the total aqueous slurry.
14. Verfahren zur Herstellung von Wasch- oder Reinigungsmittelpulver mit einem Schüttgewicht im Bereich von < 500 g/L durch Sprühtrocknung einer wässrigen Aufschlämmung enthaltend14. A process for the preparation of detergent or cleaning agent powder having a bulk density in the range of <500 g / L by spray-drying an aqueous slurry containing
4 bis 12 Gew.-% Silicat(e),4 to 12% by weight of silicate (e),
5 bis 12 Gew.-% Aniontensid, insbesondere LAS,From 5 to 12% by weight of anionic surfactant, in particular LAS,
40 bis 60 Gew.-% Trägermaterial, insbesondere Soda und/oder Sulfat,From 40 to 60% by weight of carrier material, in particular soda and / or sulfate,
20 bis 60 Gew.-% Wasser, sowie weniger als 2 Gew.-% Polycarboxylat-Copolymere,20 to 60% by weight of water and less than 2% by weight of polycarboxylate copolymers,
Gew.-% bezogen auf die gesamte wässrige Aufschlämmung.Wt .-% based on the total aqueous slurry.
15. Verwendung von 4 Gew.-% bis 12 Gew.-% Silicat(en) in sprühzutrocknenden wässrigen Aufschlämmungen zur Verbesserung der Kornstabilität des Sprühtrocknungsproduktes, Gew.-% bezogen auf die gesamte wässrige Aufschlämmung. 15. Use of 4 wt .-% to 12 wt .-% silicate (s) in spray-dried aqueous slurries to improve the grain stability of the spray-drying product, wt .-% based on the total aqueous slurry.
PCT/EP2009/051676 2008-03-19 2009-02-13 Spray-dried washing or cleaning products WO2009115380A1 (en)

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DE102014218805A1 (en) 2014-09-18 2016-03-24 Henkel Ag & Co. Kgaa Process for the preparation of spray-dried detergent powders
DE102014218807A1 (en) 2014-09-18 2016-03-24 Henkel Ag & Co. Kgaa Process for the preparation of spray-dried detergent powders with increased bulk density

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EP0129276A2 (en) * 1983-06-15 1984-12-27 THE PROCTER &amp; GAMBLE COMPANY Granular detergent compositions containing sodium aluminosilicate or other phosphorus-free detergency builders
EP0139523A2 (en) * 1983-10-19 1985-05-02 Unilever Plc Detergent powders and processes for producing them
EP0220024A2 (en) * 1985-10-09 1987-04-29 The Procter & Gamble Company Granular detergent compositions having improved solubility
WO1992018596A1 (en) * 1991-04-19 1992-10-29 The Procter & Gamble Company Granular laundry detergent compositions having improved solubility
EP0520582A1 (en) * 1991-06-28 1992-12-30 Colgate-Palmolive Company Zeolite based spray-dried detergent compositions and process for preparing same
EP0753571A1 (en) * 1995-07-10 1997-01-15 The Procter & Gamble Company Process for making granular detergent composition
US6635610B1 (en) * 1998-09-25 2003-10-21 The Procter & Gamble Company Detergent granules

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CA2296559A1 (en) * 1997-07-11 1999-01-21 The Procter & Gamble Company Alkaline detergent compositions comprising a specific cellulase

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Publication number Priority date Publication date Assignee Title
US4075117A (en) * 1973-10-15 1978-02-21 Witco Chemical Corporation Built detergent compositions
EP0129276A2 (en) * 1983-06-15 1984-12-27 THE PROCTER &amp; GAMBLE COMPANY Granular detergent compositions containing sodium aluminosilicate or other phosphorus-free detergency builders
EP0139523A2 (en) * 1983-10-19 1985-05-02 Unilever Plc Detergent powders and processes for producing them
EP0220024A2 (en) * 1985-10-09 1987-04-29 The Procter & Gamble Company Granular detergent compositions having improved solubility
WO1992018596A1 (en) * 1991-04-19 1992-10-29 The Procter & Gamble Company Granular laundry detergent compositions having improved solubility
EP0520582A1 (en) * 1991-06-28 1992-12-30 Colgate-Palmolive Company Zeolite based spray-dried detergent compositions and process for preparing same
EP0753571A1 (en) * 1995-07-10 1997-01-15 The Procter & Gamble Company Process for making granular detergent composition
US6635610B1 (en) * 1998-09-25 2003-10-21 The Procter & Gamble Company Detergent granules

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EP2252676B1 (en) 2014-07-16
ES2499023T3 (en) 2014-09-26

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