EP2252676B1 - Sprühgetrocknete wasch- oder reinigungsmittelprodukte - Google Patents

Sprühgetrocknete wasch- oder reinigungsmittelprodukte Download PDF

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Publication number
EP2252676B1
EP2252676B1 EP09722712.8A EP09722712A EP2252676B1 EP 2252676 B1 EP2252676 B1 EP 2252676B1 EP 09722712 A EP09722712 A EP 09722712A EP 2252676 B1 EP2252676 B1 EP 2252676B1
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EP
European Patent Office
Prior art keywords
spray
weight
dried product
acid
product according
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Application number
EP09722712.8A
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German (de)
English (en)
French (fr)
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EP2252676A1 (de
Inventor
Bernhard Orlich
Stefan Hammelstein
Michael Dreja
Kathrin Schnepp-Hentrich
Ingrid Kraus
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP14170937.8A priority Critical patent/EP2787064A3/de
Priority to PL09722712T priority patent/PL2252676T3/pl
Publication of EP2252676A1 publication Critical patent/EP2252676A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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.
  • 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, see US 4,075,117 ,
  • a particularly important quality feature of spray-drying products is their 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.
  • This spray-drying product is characterized in particular by the fact that it has a surprisingly good Komstabiltician 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 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.
  • 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) 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.
  • 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 Na 2 0: Si0 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 0.01-5 wt .-% (water-soluble) polycarboxylate homopolymers, in particular homopolymers based on acrylic acid, advantageously 0.01 wt .-% to ⁇ 3 wt .-%, preferably less than Contains 1 wt .-% (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 from ⁇ 0.01% by weight to 3% by weight, based on the total spray-drying product.
  • complexing agents in particular phosphonate
  • 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 salts thereof, 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.
  • 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 350 ° C dries the slurry and evaporates the adhering water. At the outlet of the tower (temperature preferably 80-120 ° C) then fall dried, fine powder.
  • a common problem in spray-drying is that high 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.
  • Another advantage is that it allows the process to obtain surfactant-reduced and polymer-reduced spray-drying products which have a very good grain stability without having to set very high bulk densities.
  • silicate (s) in spray-dried aqueous slurries to improve the grain stability of the spray-drying product, by weight of the total aqueous slurry.
  • 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.
  • 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 C 12 -C 18 fatty alcohol sulfate.
  • FOS fatty alcohol sulfates
  • 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 (C 16 to C 18 ) are very suitable for washing at higher temperatures.
  • Particular preference is given to alkyl sulfates which have a lower Krafft point, preferably with a Krafft point of less than 45, 40, 30 or 20 ° C.
  • Krafft point is the term for the temperature at which the solubility of surfactants greatly increases due to the formation of micelles.
  • 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 in accordance with 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 from 0.1 to 25% by weight, more preferably from 1 to 20% by weight, in particular in amounts of from 5 to 5% 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 agent.
  • 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 agents according to the invention have a pH> 7.5, measured in a 5% solution of the composition in water at 20 ° C.
  • the washing or cleaning agents according to the invention can, as has already been shown, in particular builder substances and surface-active surfactants, but also also bleaching agents, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, fluorescers, grayness inhibitors , Inlet preventer, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, Corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts and UV absorbers, foam regulators and colorants and fragrances.
  • bleaching agents bleach activators
  • water-miscible organic solvents enzymes
  • sequestering agents electrolytes
  • pH regulators and other auxiliaries such as optical brighteners, fluorescers, grayness inhibitors , Inlet preventer, anti-crease agents
  • 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 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • in means for use in mechanical processes can usually extremely low-foam connections are used. These include preferably C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule.
  • 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 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical 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) 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 C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain with at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [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 acidic hydrolysis of the Sutfon mecanics occur, into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -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.
  • 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, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 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.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
  • EO ethylene oxide
  • 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 Sufosuccinic 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 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- (ditalgacyloxyethyl) ammonium methosulfate or bis (palmitoyloxyethyl) hydroxyethyl-methyl-ammonium 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 also polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small
  • 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 or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content 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) acrylic acid from.
  • 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 allylsulfonic 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 builders may also be used in the form of aqueous solutions, preferably in the form of 30 to 50 weight percent 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, tetrasodium 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 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Ratio Na 2 O: SiO 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 of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 22, especially 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 from 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 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O , Makatit).
  • Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite)
  • Na-SKS 2 Na 2 Si 14 O 29 .xH 2 O, magadiite
  • Na-SKS-3 Na 2 Si 8 O 17 .xH 2 O
  • Na-SKS-4 Na 2 Si 4 O 9 .xH 2 O , Makatit).
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , Natrosilit
  • 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 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 ⁇ -Na 2 Si 2 O 5
  • composition according to the invention a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the above-mentioned (co-) polymeric polycarboxylic acid, or of alkali silicate and alkali metal carbonate, such as, for example, commercially available under the name Nabion® 15, is used .
  • 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.
  • Suitable bleaching agents for use in detergents or cleaners according to the invention are, for example, peroxygen compounds such as, in particular, organic peracids or persistent organic acid salts, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, including perborate, percarbonate, Persilicate and / or persulfate such as caroate are considered.
  • peroxygen compounds such as, in particular, organic peracids or persistent organic acid salts, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, including perborate, percarbonate, Persilicate and / or persulfate such as caroate are considered.
  • solid peroxygen compounds are to be used, they can
  • 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 phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • 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-producing 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 in a known manner separately prepared enzymes or by two or more together in a granule ready-made enzymes are performed.
  • compositions of the invention 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 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 can be added to the detergents or cleaning agents in order to eliminate graying and yellowing of the treated textile fabrics. These fabrics impinge on the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure yellow with the yellowed or yellowed wash White results.
  • Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole - And benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • the optical brighteners are usually used in amounts between e.g. 0% and 0.3 wt .-%, based on the finished composition, optionally 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.
  • 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 cleaners 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 wt .-% 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.
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP or DETP
  • the washing or cleaning agents may additionally be added e.g. contain neutral filler salts such as sodium sulfate.
  • 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.

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EP09722712.8A 2008-03-19 2009-02-13 Sprühgetrocknete wasch- oder reinigungsmittelprodukte Revoked EP2252676B1 (de)

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DE102014218807A1 (de) 2014-09-18 2016-03-24 Henkel Ag & Co. Kgaa Verfahren zur Herstellung von sprühgetrockneten Waschmittelpulvern mit erhöhtem Schüttgewicht
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US4075117A (en) * 1973-10-15 1978-02-21 Witco Chemical Corporation Built detergent compositions
GR81618B (pl) * 1983-06-15 1984-12-11 Procter & Gamble
GB8328017D0 (en) * 1983-10-19 1983-11-23 Unilever Plc Detergent powders
CA1275019A (en) * 1985-10-09 1990-10-09 The Procter & Gamble Company Granular detergent compositions having improved solubility
DE3723873A1 (de) 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
JPH06506716A (ja) * 1991-04-19 1994-07-28 ザ、プロクター、エンド、ギャンブル、カンパニー 改良された溶解度を有する粒状洗濯洗剤組成物
MX9202828A (es) * 1991-06-28 1992-12-01 Colgate Palmolive Co Composiciones detergentes secadas por rociado a base de zeolita y proceso para la preparacion de las mismas.
EP0753571A1 (en) * 1995-07-10 1997-01-15 The Procter & Gamble Company Process for making granular detergent composition
AU3659797A (en) 1997-07-11 1999-02-08 Procter & Gamble Company, The Alkaline detergent compositions comprising a specific cellulase
IN243977B (pl) * 1998-09-25 2010-11-19 Procter & Gamble

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PL2252676T3 (pl) 2014-12-31
EP2252676A1 (de) 2010-11-24

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