EP0674700B1 - Detergents et nettoyants granulaires a haute teneur en tensioactifs - Google Patents

Detergents et nettoyants granulaires a haute teneur en tensioactifs Download PDF

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Publication number
EP0674700B1
EP0674700B1 EP94902691A EP94902691A EP0674700B1 EP 0674700 B1 EP0674700 B1 EP 0674700B1 EP 94902691 A EP94902691 A EP 94902691A EP 94902691 A EP94902691 A EP 94902691A EP 0674700 B1 EP0674700 B1 EP 0674700B1
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EP
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Prior art keywords
weight
alcohol sulfates
detergent
mixtures
anionic
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German (de)
English (en)
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EP0674700A1 (fr
Inventor
Monika Böcker
Peter Krings
Amerigo Pastura
Eduard Smulders
Birgit Stevermann
Horst Upadek
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to granular detergents and cleaners which have both a high surfactant content and a high bulk density, and a process for their preparation.
  • Granular washing and cleaning agents with high bulk densities and high surfactant contents are already known.
  • European patent applications 340 013, 352 892 and 460 925 are mentioned here.
  • EP 340 013 granular agents with a bulk density of at least 650 g / l are known, these agents containing 17 to 35% by weight of anionic and optionally nonionic surfactants and 28 to 45% by weight of zeolite (based on anhydrous active substance) and the ratio of zeolite to surfactant is between 0.9: 1 and 2.6: 1. These agents are obtained by a granulation process.
  • EP 352 892 also describes heavy granules which contain 30 to 50% by weight of anionic surfactants and 40 to 60% by weight of an inorganic builder substance and an optical brightener, but at least 5 to 25% by weight of an anionic surfactant in the form of the potassium salt or Contain 2 to 10 wt .-% potassium carbonate or potassium sulfate and small amounts of sodium chloride and polyethylene glycol.
  • the agents are first spray dried and then granulated and processed in a high speed mixer.
  • EP 460 925 describes granular detergents with bulk densities of at least 650 g / l, which contain 17 to 35% by weight of surfactants, 5 to 35% by weight of alkyl sulfates and / or alkylbenzenesulfonates and 0 to 10% by weight of nonionic surfactants , 25 to 45 wt .-% zeolite and 0 to 20 wt .-% sodium carbonate.
  • EP-A-0 200 953 discloses granules with a relatively low bulk density (400 to 700 g / l) containing 10 to 25% by weight of a combination of anionic surfactants of the sulfonate and / or sulfate type and nonionic surfactants. Agents which contain more than 8% by weight of alcohol sulfates or ⁇ -sulfofatty acid esters are not recommended. In addition, the compositions preferably have less than 20% by weight of surfactants.
  • alkylbenzene sulfonates and alkyl sulfates are usually mentioned as anionic surfactants.
  • alkylbenzenesulfonates have the disadvantage that they are obtained from petrochemical raw materials. While alkyl sulfates, especially fatty alkyl sulfates, are based on renewable oleochemical raw materials, on the other hand it is known that they are present in large amounts, i.e. in amounts of above 8% by weight, used in particular in conventional spray technology, can lead to granular compositions with a bulk density that is too low for modern compositions and with an unacceptable dissolving behavior and, in particular in combination with nonionic surfactants, can lead to unacceptable washing-in behavior.
  • the object of the invention was to develop granular washing and cleaning agents with a bulk density of 700 g / l or above, which have a high surfactant content and an acceptable dissolving behavior and mainly anionic surfactants based on renewable raw materials, in particular oleochemical raw materials, or on Anionic surfactants manufactured on the basis of petrochemicals, but which show a similar degradation behavior as the anionic surfactants based on renewable raw materials.
  • the invention therefore relates to a granular washing and cleaning agent with a high bulk density, which contains anionic and nonionic surfactants and optionally soap, the agent containing 20 to 55% by weight of anionic and nonionic surfactants and optionally including soap and the content of the agents of C 8 -C 22 alcohol sulfates, ethoxylated alcohol sulfates, ⁇ -sulfofatty acid esters and mixtures of these above 8% by weight, the weight ratio of these anionic surfactant sulfates and / or sulfofatty acid esters to nonionic surfactants is 10: 1 to 1: 2.5 and the bulk density is between 700 and 1200 g / l.
  • Preferred alcohol sulfates are the sulfuric acid monoesters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length. Also preferred are alcohol sulfates of the chain length mentioned which contain a synthetic, petrochemical-based, straight-chain alkyl radical, but which have an analogous behavior to that in which adequate compounds based on oleochemical raw materials. C 16 -C 18 alcohol sulfates are particularly preferred from the point of view of washing technology.
  • the agents therefore contain mixtures of short-chain and long-chain fatty alcohol sulfates, preferably mixtures of C 12 -C 14 fatty alcohol sulfates or C 12 -C 16 fatty alcohol sulfates with C 16 -C 18 fatty alcohol sulfates.
  • saturated alcohol sulfates not only saturated alcohol sulfates but also unsaturated alcohol sulfates with an alkenyl chain length of C 16 to C 22 are used.
  • Mixtures of saturated sulfated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) .
  • Weight ratios of saturated alcohol sulfates to unsaturated alcohol sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.
  • the total content of alcohol sulfates in the compositions is preferably 10 to 35% by weight and in particular 10 to 25% by weight.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide or C 12 -C 18 - Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in washing agents for machine cleaning only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the esters of ⁇ -sulfo fatty acids (ester sulfonates), which are produced by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), which are produced by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), which are produced by ⁇ -sulfonation of the methyl esters of fatty acids of plant and
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the mono salts of the methyl esters of ⁇ -sulfofatty acids (MES) are used with particular advantage.
  • Further suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • the disalt content of such surfactants is usually less than 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.
  • the amounts given for the ⁇ -sulfofatty acid alkyl esters are always understood to be the sum of the amounts of the ⁇ -sulfofatty acid alkyl ester mono salt and the corresponding ⁇ -sulfofatty acid disalt.
  • the content of the agents in MES or in mixtures of MES and saturated and / or unsaturated fatty alcohol sulfates is in a preferred embodiment of the invention 10 to 35% by weight and in particular 10 to 25% by weight, the content of the mixtures in MES, based on the average, is at least 5 wt .-%.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 2% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 18 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • anionic surfactants which can be used in combination with the named ones, the first are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by 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.
  • fats and oils that is to say natural mixtures of different fatty acid glycerol esters
  • suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent application WO 91/9009 is specified.
  • the sulfonation products are a complex mixture, the mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • the agents can also contain C 9 -C 13 alkylbenzenesulfonates, which are usually referred to as dodecylbenzenesulfonates, but their content should not exceed about 3 to 5% by weight, preferably not more than 4% by weight, within the scope of the task. Agents that do not contain alkylbenzenesulfonates are particularly preferred.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut oil, tallow oil or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 EO or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol , which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • polyhydroxy fatty acid amides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from the glucose.
  • the content of nonionic surfactants in the agents is preferably 1 to 20% by weight and in particular 2 to 15% by weight, in the latter case with particular advantage only ethoxylated fatty alcohols or mixtures of ethoxylated fatty alcohols and alkyl glucosides in a ratio of 4: 1 to 1 : 2 can be used.
  • the weight ratio of the anionic surfactants to the nonionic surfactants in the agents according to the invention is 1: 2 to 6: 1, preferably 1: 1.5 to 3: 1.
  • the bulk density of the granules according to the invention is preferably up to 1000 g / l and in particular 740 to 900 g / l. Surprisingly, the granules, despite the high bulk density, show good dissolving and flushing behavior, especially when they are obtained by an extrusion process.
  • the washing-in behavior of the granules can be tested, for example, in a commercial washing machine, for example with a zanussi washing-in trough.
  • Agents, of which 100 g completely dissolve in 10 liters of water, are given grade A. The number of liters of water required is appended to A as a number.
  • Notes B and C indicate that there are residues. Residues of 1 to 10 g receive the grades B1 to B10, residues of 11 g and above are designated C11 etc. and indicate poor washing-in behavior.
  • Conventional heavy agents usually have a C.
  • the granules have a flushing behavior which can be assessed with a B value or even with an A value.
  • the values for the induction behavior are below the B 8 rating.
  • the agents can include, as further ingredients, the usual ingredients of detergents and cleaning agents, for example inorganic and organic builder substances, bleaching agents, foam inhibitors, salts of polycarboxylic acids, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, Contain opacifiers or pearlescent agents.
  • detergents and cleaning agents for example inorganic and organic builder substances, bleaching agents, foam inhibitors, salts of polycarboxylic acids, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, Contain opacifiers or pearlescent agents.
  • Particularly suitable builder substance is finely crystalline, synthetic and bound water-containing zeolite, in particular zeolite NaA in detergent quality.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups .
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water.
  • the zeolite content of the compositions can be 10 to 60% by weight. However, its content is preferably 15 to 50% by weight and in particular 18 to 45% by weight.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in German patent application 39 39 919.
  • the agents according to the invention can use the crystalline layered silicates as a replacement for zeolite in the amounts specified above for zeolite (based on anhydrous active substance) contain.
  • agents are preferred which contain zeolite and crystalline layered silicates in any mixture, the sum of zeolite (based on anhydrous active substance) and crystalline layered silicates preferably not more than 65% by weight and in particular not more than 60% by weight, each based on the mean.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these .
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the content of these preferred organic builder substances is preferably 2 to 20% by weight and in particular 5 to 15% by weight, in each case based on the composition.
  • polymeric polycarboxylates for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% by weight. % aqueous solutions are preferred.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 8% by weight and in particular 0.5 to 5% by weight. In a particularly preferred embodiment of the invention, however, the agents are free from (co) polymeric polycarboxylates.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • the agents are free from peroxy bleaching agents. This is particularly preferred for agents that are used as detergents for colored textiles.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, possibly silanized silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Uniform white granules can be obtained if, in addition to the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts. for example 10 -6 to 10 -3 wt .-%, preferably around 10 -5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux (R) (commercial product from Ciba-Geigy).
  • the agents according to the invention can be produced by any of the known methods which make it possible to provide non-adhesive, surfactant-rich granules with a bulk density between 700 and 1200 g / l.
  • a method is preferred in which the agents are obtained by an extrusion process in accordance with the teaching of international patent application W091 / 02047.
  • a homogeneous and free-flowing premix is extruded in the form of a strand with the addition of a plasticizer and / or lubricant at high pressures of at least 25 bar and cut to the predetermined size of the granulate immediately after it emerges from the hole shape.
  • anionic surfactants into the process either as an aqueous paste or as a solid or partly as an aqueous paste and partly as a solid.
  • the anionic surfactants in solid form can be used as finely divided powders, but preferably in the form of a granular compound obtained by traditional spray drying or granulation or in particular by fluidized bed granulation, for example in accordance with the earlier German patent application P 41 27 323.0.
  • the liquid nonionic surfactants being used in intimate mixing with a structure breaker to improve the dissolution behavior of the extrudates.
  • ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 E0 such as tallow alcohols with 30 and 40 EO and polyethylene glycols with a relative molecular weight between 200 and 2000 are preferred as structure breakers.
  • teaching of the older German patent application P 42 03 031.5 is followed, with an additive from the group consisting of alkyl sulfates, olefin sulfonates, short-chain non-anionic alkyl aromatic sulfonates and mixtures of these being mixed after the mixing to improve the dissolving behavior solid components are introduced into the process.
  • the addition of lower fatty alkyl sulfates such as C 12 alkyl sulfate and mixtures of C 12 -C 16 alkyl sulfate is particularly preferred at this point in the process.
  • the washing and cleaning agents according to the invention can consist uniformly of granules, preferably of an extrudate, which have the above-mentioned ingredients.
  • the granules according to the invention and in particular the extrudates can, however, also represent only one component of a detergent and cleaning agent, which are processed with further constituents to form the detergent and cleaning agent.
  • the enzymes as well as dyes and fragrances, but also bleach activators can be subsequently added to the granules and extrudates. It is preferred to use the enzymes and the bleach activator in each case in compacted granular form, for example as extrudates produced separately, which were obtained by means of an extruder or via a pellet press.
  • the compositions contain 22 to 25% by weight of total surfactant including soap, of which about 12 to 14% by weight saturated fatty alcohol sulfates or mixtures of saturated and unsaturated fatty alcohol sulfates and 10 to 12% by weight ethoxylated nonionic surfactants, zeolite and / or crystalline layered silicates in amounts above 35% by weight, preferably above 40% by weight, but no bleaching agents.
  • soap of which about 12 to 14% by weight saturated fatty alcohol sulfates or mixtures of saturated and unsaturated fatty alcohol sulfates and 10 to 12% by weight ethoxylated nonionic surfactants, zeolite and / or crystalline layered silicates in amounts above 35% by weight, preferably above 40% by weight, but no bleaching agents.
  • compositions comprise 22 to 25% by weight of total surfactant including soap, of which about 12 to 14% by weight saturated fatty alcohol sulfates or mixtures of saturated and unsaturated fatty alcohol sulfates and 9 to 12% by weight ethoxylated nonionic surfactants , Zeolite and / or crystalline phyllosilicates in amounts of about 30 to 45% by weight, and peroxy bleaching agents in amounts of 10 to 25% by weight, preferably in amounts of 15 to 20% by weight, and bleach activator which was preferably added subsequently, in amounts of 3 to 8 wt .-%.
  • soap of which about 12 to 14% by weight saturated fatty alcohol sulfates or mixtures of saturated and unsaturated fatty alcohol sulfates and 9 to 12% by weight ethoxylated nonionic surfactants
  • Zeolite and / or crystalline phyllosilicates in amounts of about 30 to 45% by weight
  • peroxy bleaching agents in amounts of 10 to 25% by weight, preferably
  • the compositions contain 20 to 30% by weight of total surfactant including any soap present, of which 10 to 15% by weight of saturated C 12 -C 18 fatty alcohol sulfates, preferably C 16 -C 18 fatty alcohol sulfates, and 1.5 to 10% by weight, preferably 2 to 5% by weight of unsaturated fatty alcohol sulfates, in particular oleyl sulfate, and 2 to 15% by weight, preferably 4 to 13% by weight and in particular 5 to 10% by weight C 12 -C 18 ethoxylated fatty alcohols.
  • total surfactant including any soap present, of which 10 to 15% by weight of saturated C 12 -C 18 fatty alcohol sulfates, preferably C 16 -C 18 fatty alcohol sulfates, and 1.5 to 10% by weight, preferably 2 to 5% by weight of unsaturated fatty alcohol sulfates, in particular oleyl sulfate, and 2 to 15% by weight, preferably 4 to 13% by weight and in particular 5 to 10% by
  • compositions of the composition given above contain polycarboxylates, preferably salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids or mixtures thereof, preferably in amounts of 2 to 20% by weight and in particular in Amounts of 5 to 15 wt .-%, each based on the agent.
  • polycarboxylates preferably salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids or mixtures thereof, preferably in amounts of 2 to 20% by weight and in particular in Amounts of 5 to 15 wt .-%, each based on the agent.
  • the agents contain, as anionic surfactants, ⁇ -sulfofatty acid methyl esters or mixtures of ⁇ -sulfofatty acid methyl esters and saturated and / or unsaturated fatty alcohol sulfates, and also nonionic surfactants, builder substances, including the polycarboxylates, as indicated above.
  • the agents can contain bleaches or be free of bleaches.
  • Agents of the compositions given below were extruded in accordance with the teaching of international patent application W091 / 02047 and agents which contain a structure breaker in accordance with the teaching of older German patent application P 41 24 701.9.
  • the enzyme and optionally the bleach activator in granular form were subsequently added to the extrudate.
  • the agents had a bulk density between 745 g / l and 850 g / l.
  • the detergent behavior of the agents was checked on a random basis.
  • Medium 1 was A4, medium 3 was B4 and medium 4 was B4.5.
  • cellulase, lipase or amylase instead of the protease or with enzyme mixtures, for example from protease, amylase and / or cellulase or lipase, cellulase and / or amylase.

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Claims (14)

  1. Produit de lavage et de nettoyage granulaire ayant une densité apparente élevée, contenant des agents tensioactifs anioniques et non-ioniques ainsi qu'éventuellement du savon,
    caractérisé en ce qu'
    il renferme de 20 à 55 % en poids d'agents tensioactifs anioniques et non ioniques ainsi qu'éventuellement inclusivement du savon, tandis que la teneur du produit en (alcool en C8 - C22) sulfates, en alcool sulfates éthoxylés, en esters d'acide gras α-sulfonique et en mélange de ceux-ci, s'élève à au-dessus de 8 % en poids, le rapport en poids de ces sulfates tensioactifs anioniques et/ou de ces esters d'acides gras sulfonique aux agents tensioactifs non ioniques s'élève de 10:1 à 1:2,5 et la densité apparente se situe entre 700 et 1200 g/l.
  2. Produit selon la revendication 1,
    caractérisé en ce qu'
    il renferme comme agents tensioactifs anioniques de 10 à 35 % en poids (d'alcool en C12 à C18) sulfates, de préférence de 10 à 25 % en poids (d'alcools gras en C16 à C18) sulfates ou de 10 à 35 % en poids, de préférence de 10 à 25 % en poids d'esters méthyliques d'acide gras α-sulfoné ou de 10 à 35 % en poids de préférence de 10 à 25 % en poids, de mélanges de sulfates d'alcool gras avec des esters méthyliques d'acide gras α-sulfoné, pour lesquels la teneur des mélanges en esters méthyliques d'acide gras α-sulfoné rapporté au produit, s'élève au moins à 5 % en poids, et de 1 à 20 % en poids, de préférence de 2 à 15 % en poids, en particulier 9 % en poids et au-dessus, d'agents tensioactifs non ioniques, pour lesquels le rapport en poids d'agent tensioactif anionique à l'agent tensioactif non ionique s'élève de 1:2 à 6:1, de préférence de 1:1,5 à 3:1.
  3. Produit selon la revendication 1 ou la revendication 2,
    caractérisé en ce qu'
    il renferme comme agents tensioactifs anioniques, des (alcools en C16-C18) sulfates en combinaison avec des agents tensioactifs à point de fusion inférieur et en particulier avec des agents tensioactifs anioniques qui possèdent un point de Kraft inférieur et qui montrent une tendance plus faible à la cristallisation aux températures de lavage allant de la température ambiante à 40°C.
  4. Produit selon l'une des revendications 1 à 3,
    caractérisé en ce qu'
    il renferme comme agent tensioactif anionique des mélanges à base d'(alcool gras en C12-C14) sulfates, des (alcools gras en C12-C14) sulfates ou des (alcools gras en C12-C16) sulfates et des alcools gras en C16-C18) sulfates.
  5. Produit selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    il renferme comme agents tensioactifs anioniques des mélanges à base d'(alcools sulfates saturés et non saturés), de préférence des mélanges à base d'(alcools gras en C16) sulfates saturés et d'(alcools gras en C16-C22) sulfates non saturés, en particulier à base d'(alcool gras en C18 sulfate non saturé d'une manière plus avantageuse dans un rapport en poids d'(alcools) sulfates saturés aux (alcools) sulfates non saturés de 10:1 à 1:2.
  6. Produit selon la revendication 1,
    caractérisé en ce qu'
    il renferme comme agents tensioactifs anioniques de 10 à 35 % en poids, de préférence de 10 à 25 % en poids d'esters méthyliques d'acide gras α-sulfoné ou des mélanges à base d'esters méthyliques d'acide gras α-sulfoné et d'(alcools gras saturés en C8 à C22 et/ou non saturés en C16-C22, sulfates pour lesquels la teneur des mélanges en esters méthyliques d'acide gras α-sulfoné, rapporté au produit, s'élève à au moins 5 % en poids.
  7. Produit selon l'une des revendications 1 à 6,
    caractérisé en ce qu'
    il renferme du savon en quantités allant de 0,5 à 2 % en poids.
  8. Produit selon l'une des revendications 1 à 7,
    caractérisé en ce qu'
    il renferme des adjuvants comme la zéolite (rapportée à la substance active anhydre) et/ou des silicates lamellaires cristallins de formule générale NaMSixO2x+1.yH2O, dans laquelle M signifie du sodium ou de l'hydrogène, x est un nombre allant de 1,9 à 4 et y un nombre allant de 0 à 20, et les valeurs préférées pour x sont 2,3 ou 4, en quantités allant de 10 à 60 % en poids, de préférence de 15 à 50 % en poids et en particulier de 18 à 45 % en poids.
  9. Produit selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    il renferme un agent de blanchiment peroxydique, en quantités allant de 10 à 25 % en poids.
  10. Procédé de production d'un produit selon l'une des revendications 1 à 9,
    caractérisé en ce qu'
    on comprime un pré-mélange homogène et apte au ruissellement tout en ajoutant un agent de plastification et/ou de glissement, à des pressions élevées d'au moins 25 bars sous forme de filaments et directement après la sortie de la forme en trou, on les coupe à la dimension déterminée au préalable de granulé.
  11. Procédé selon la revendication 10,
    caractérisé en ce qu'
    on met en oeuvre les agents tensioactifs anioniques au moins partiellement sous forme d'un composé granulaire, qui a été obtenu par séchage traditionnel par pulvérisation ou par granulation ou en particulier par granulation en lit fluidisé.
  12. Procédé selon la revendication 10 ou la revendication 11,
    caractérisé en ce qu'
    on met en oeuvre pour l'amélioration du comportement à la dissolution des extrudats, les agents tensioactifs non ioniques liquides en mélange intime avec un agent qui rompt la structure, procédé dans lequel sont préférés, comme agent qui rompt la structure en particulier des alcools gras en C8-C18 éthoxylés ayant de 20 à 45 OE, comme les alcools de suif avec 30 et 40 OE ainsi que des polyéthylène-glycols avec une masse moléculaire relative comprise entre 200 et 2000.
  13. Procédé selon l'une des revendications 10 à 12,
    caractérisé en ce que
    pour l'amélioration du comportement à la dissolution on introduit un additif choisi parmi le groupe des alkyl gras sulfates, des oléfine-sulfonates, des sulfonates alkylaromatiques et des mélanges de ceux-ci, après le mélange des constituants solides, dans le processus.
  14. Procédé selon l'une des revendications 10 à 13,
    caractérisé en ce que
    les extrudats ainsi obtenus sont préparés avec des constituants supplémentaires de produits de lavage et de nettoyage sous forme compactée granulaire.
EP94902691A 1992-12-15 1993-12-06 Detergents et nettoyants granulaires a haute teneur en tensioactifs Revoked EP0674700B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4242185A DE4242185A1 (de) 1992-12-15 1992-12-15 Granulare Wasch- und Reinigungsmittel mit hohem Tensidgehalt
DE4242185 1992-12-15
PCT/EP1993/003428 WO1994013771A1 (fr) 1992-12-15 1993-12-06 Detergents et nettoyants granulaires a haute teneur en tensioactifs

Publications (2)

Publication Number Publication Date
EP0674700A1 EP0674700A1 (fr) 1995-10-04
EP0674700B1 true EP0674700B1 (fr) 1997-10-08

Family

ID=6475255

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94902691A Revoked EP0674700B1 (fr) 1992-12-15 1993-12-06 Detergents et nettoyants granulaires a haute teneur en tensioactifs

Country Status (7)

Country Link
EP (1) EP0674700B1 (fr)
JP (1) JPH08504458A (fr)
KR (1) KR950704464A (fr)
AT (1) ATE159044T1 (fr)
DE (2) DE4242185A1 (fr)
ES (1) ES2109662T3 (fr)
WO (1) WO1994013771A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9324127D0 (en) * 1993-05-26 1994-01-12 Unilever Plc Detergent compositions
DE4329389A1 (de) * 1993-09-01 1995-03-02 Henkel Kgaa Sprühgetrocknetes Wasch- oder Reinigungsmittel oder Komponente hierfür
DE4403323A1 (de) * 1993-09-23 1995-08-10 Henkel Kgaa Extrudierte Wasch- oder Reinigungsmittel mit verbesserten Löseeigenschaften
DE4415369C1 (de) * 1994-05-02 1995-08-31 Henkel Kgaa Heterogene Tensidgranulate
US5972861A (en) * 1997-03-27 1999-10-26 Corporacion Cressida Laundry detergent bar containing soap, and methylester sulfonate surfactants
DE19722767A1 (de) * 1997-06-02 1998-12-03 Henkel Kgaa Wasch- oder Reinigungsmittel mit erhöhter Reinigungsleistung
WO1999010471A1 (fr) * 1997-08-25 1999-03-04 Cognis Deutschland Gmbh Detergents solides contenant des sulfates d'ester de polyglycol d'acide gras et adjuvants solides
EP1007613A1 (fr) * 1997-08-25 2000-06-14 Cognis Deutschland GmbH Procede de production de granules d'agents de surface anioniques exempts d'eau et de poussiere
US7820612B2 (en) * 2006-06-19 2010-10-26 The Procter & Gamble Company Laundry detergent containing methyl ester sulfonate
DE102015002877B4 (de) * 2015-03-09 2024-09-12 Henkel Ag & Co. Kgaa Wasch- oder reinigungsaktive Extrudate, deren Herstellung und Verwendung in granularen Wasch- oder Reinigungsmitteln
JP6624716B2 (ja) * 2015-06-18 2019-12-25 ライオン株式会社 α−スルホ脂肪酸エステル塩含有液

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3514364A1 (de) * 1985-04-20 1986-10-23 Henkel KGaA, 4000 Düsseldorf Koerniges waschmittel mit verbessertem reinigungsvermoegen
DE3926253A1 (de) * 1989-08-09 1991-02-14 Henkel Kgaa Verdichtete wasch- und reinigungsmittel in granulatform, verfahren zu ihrer herstellung und anwendung des verfahrens zur gewinnung lagerstabil rieselfaehiger waschmittel-konzentrate
DE4007601A1 (de) * 1990-03-09 1991-09-12 Henkel Kgaa Verfahren zum herstellen von granulaten eines wasch- oder reinigungsmittels

Also Published As

Publication number Publication date
ES2109662T3 (es) 1998-01-16
JPH08504458A (ja) 1996-05-14
EP0674700A1 (fr) 1995-10-04
KR950704464A (ko) 1995-11-20
WO1994013771A1 (fr) 1994-06-23
DE4242185A1 (de) 1994-06-16
ATE159044T1 (de) 1997-10-15
DE59307518D1 (de) 1997-11-13

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