WO1994013771A1 - 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
WO1994013771A1
WO1994013771A1 PCT/EP1993/003428 EP9303428W WO9413771A1 WO 1994013771 A1 WO1994013771 A1 WO 1994013771A1 EP 9303428 W EP9303428 W EP 9303428W WO 9413771 A1 WO9413771 A1 WO 9413771A1
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WIPO (PCT)
Prior art keywords
weight
mixtures
alcohol sulfates
acid
sulfates
Prior art date
Application number
PCT/EP1993/003428
Other languages
German (de)
English (en)
Inventor
Monika Böcker
Peter Krings
Amerigo Pastura
Eduard Smulders
Birgit Stevermann
Horst Upadek
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to JP6513762A priority Critical patent/JPH08504458A/ja
Priority to EP94902691A priority patent/EP0674700B1/fr
Priority to DE59307518T priority patent/DE59307518D1/de
Priority to KR1019950702432A priority patent/KR950704464A/ko
Publication of WO1994013771A1 publication Critical patent/WO1994013771A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 cleaning agents which have both a high surfactant content and a high bulk density, and a process for their preparation.
  • EP 340 013 discloses granular agents with a bulk density of at least 650 g / l, 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 460925 describes granular detergents with bulk densities of at least 650 g / l, which contain 17 to 35% by weight of surfactants, of which 5 to 35% by weight are alkyl sulfates and / or alkylbenzenesulfonates and 0 to 10% by weight. % nonionic surfactants, 25 to 45 wt .-% zeolite and 0 to 20 wt .-% sodium carbonate.
  • alkyl sulfates in particular the fatty alkyl sulfates, are based on renewable oleochemical raw materials, it is known, on the other hand, that they are used in large amounts, ie in amounts of above 8% by weight, particularly in conventional spray technology for granular agents with a modern means of low bulk density and with an unacceptable dissolving behavior and especially in combination with nonionic surfactants can lead to unacceptable washing-in behavior.
  • the object of the invention was to develop granular detergents and cleaners 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 fat chemical raw materials , or contain anionic surfactants produced on a petrochemical basis, but which show a degradation behavior similar to that of 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 comprising 20 to 55% by weight of anionic and nonionic surfactants and optionally including soap contains and the content of the agents of C8-C22 alcohol sulfates, ethoxylated alcohol sulfates, ⁇ -sulfofatty acid esters and mixtures of these above 8% by weight, the weight ratio of these anionic sulfates and / or sulfofatty acid esters to nonionic surfactants 10: 1 to 1 : 2.5 and the bulk density is between 700 and 1200 g / 1.
  • the alcoholic sulfates are the sulfuric acid monoesters of the Ci2-Ciß fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or un - preferred those secondary alcohols of this chain length. Also preferred are alcohol sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis, but which have an analogous degradation behavior to that adequate compounds based on oleochemical raw materials. Cio-Cis alcohol sulfates are particularly preferred for washing technology reasons.
  • compositions therefore contain mixtures of short-chain and long-chain fatty alcohol sulfates, preferably mixtures of Ci2-Ci4-fatty alcohol sulfates, C] _2-Ci4-fatty alcohol sulfates or Ci2-Ci6-fatty alcohol sulfates with Ciö-Cis- Fatty alcohol sulfates.
  • saturated alcohol sulfates not only saturated alcohol sulfates but also unsaturated alcohol sulfates with an alkenyl chain length of CJ ⁇ to C22 are used.
  • Mixtures of saturated, predominantly consisting of (5) sulfated fatty alcohols and unsaturated, predominantly consisting of (3 existing sulfated fatty alcohols) are particularly preferred, for example those which are derived from solid or liquid fatty alcohol mixtures of the type HD-0cenol ( R ) (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, and 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 C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide or C2-Cig 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 by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono salts.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono salts.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C
  • ⁇ -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.
  • MES ⁇ -sulfofatty acids
  • 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 large-scale 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 with regard to the ⁇ -sulfofatty acid alkyl esters are always understood as 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 of MES, based on the agent, is at least 5% by weight.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 2% by weight.
  • Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Kosmic, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C], 8-fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the salts of the alkyl sulfoberstein are first acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which are 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 Cg to Cis fatty alcohol residues or mixtures thereof.
  • preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (for a description, see below).
  • sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, as they are in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the esterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palitic acid, stearic acid or behenic acid. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a known manner before the sulfonation, ie to harden them to iodine numbers less than 5, advantageously less than 2.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil 1, sunflower oil 1, cotton seed oil 1, peanut oil 1, linseed oil, lard oil or lard. Because of 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, such as it is specified in the international patent application WO 91/9009.
  • the sulfonation products are a complex mixture, the mono-, di- and triglyceride sulfonates with . ⁇ constant 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, the proportion of the oc-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • the agents can also contain Cg-Ci3-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. go out. Agents that do not contain alkylbenzenesulfonates are particularly preferred.
  • the anionic surfactants can be present 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 with 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 linear or preferably in 2 Position can be ethyl branched or can contain linear and ethyl branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cu alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2- Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-C14 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol holethoxylates have a narrow homolog distribution (narrow ranks 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),
  • 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. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO 92/06984.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from
  • 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 / 1 and in particular 740 to 900 g / 1. Surprisingly, the granules, despite the high bulk density, show good dissolving behavior 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 commercially available washing machine, for example with a zanussi washing-in trough.
  • Agents of which 100 g completely dissolve in 10 liters of water, are given the grade A. The number of liters of water required is appended to the A as a number.
  • the grades B and C indicate that there are residues. Residues of 1 to 10 g are given the marks B1 to BIO, residues of 11 g and above are designated Cll etc. and indicate poor detergent 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 washing-in behavior are below the B 8 rating.
  • 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 also colorants and fragrances, opacifiers or perluster.
  • 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 which is still moist from its production.
  • small additions can nonionic surfactants contain as stabilizers, for example 1 to 3 wt .-%, be ⁇ coated on zeolite, of ethoxylated C j 2-CI8 fatty alcohols having from 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 Na Si x ⁇ 2 ⁇ + ⁇ * yH2 ⁇ , 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 represents sodium and x assumes the values 2 or 3.
  • both .beta.- and ⁇ '-NA- triumdisilikate Na2S ⁇ ' 2 ⁇ 5 * yH2 ⁇ preferred, with ß-sodium bei ⁇ may be playing as obtained by the method described in the German patent application 39 39 919th
  • 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.
  • Layered silicates are preferably not more than 65% by weight and in particular not more than 60% by weight, in each case based on the composition.
  • 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), provided that 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 framework 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 up 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 polyolearbonic 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 polyolearbonic acids such as gluconic acid and / or glucoheptonic acid.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing H2O2, 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 which 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 Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 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 Ci8-C24 ⁇ f : fatty acids.
  • Suitable non-tensile foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, possibly silanized silica and paraffins,
  • Waxes microcrystalline waxes and their mixtures with silanized silica.
  • Mixtures of different foam inhibitors are also advantageously used, e.g. those made of silicone, paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or water-dispersible carrier substance.
  • Suitable enzymes are those from the class of proteases, lipases, aylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces 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 Hü11 substances to protect them against premature decomposition.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber 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 , used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) st -bene-2,2'-disulfonic acid or compounds of the same structure which react to ⁇ replace the morpholino group with a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • 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 prepared by any of the known methods which make it possible to provide non-adhesive granules rich in surfactants 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 with the addition of a plasticizer and / or lubricant at high pressures of at least 25 bar and cut to the predetermined granulate dimension 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 27323.0 .
  • the liquid nonionic surfactants being used intimately mixed with a structure breaker to improve the dissolution behavior of the extrudates.
  • ethoxylated Cs-Ci8 fatty alcohols with 20 to 45 EO 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 earlier German patent application P 42 03 031.5 is used, an additive from the group consisting of alkyl sulfates, olefin sulfonates, short-chain non-anionic surfactant alkylaromatic sulfonates and mixtures of these being used to improve the dissolving behavior after mixing the solid constituents is introduced into the process.
  • the addition of lower fatty alkyl sulfates such as Ci2-AHyl sulfate and mixtures of Ci2-Ci6-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, colorants and fragrances, but also bleach activators can be subsequently mixed into the granules and extrudates. It is preferred here to use the enzymes and the bleach activator in each case in compacted granular form, for example as extrudates produced separately, which have been 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.
  • the 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.
  • the 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
  • 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 layered silicates in amounts of about 30 to 45% by weight, and peroxy bleach 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 from 3 to 8% by weight.
  • 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 layered silicates in amounts of about 30 to 45% by weight, and peroxy bleach in amounts of 10 to 25% by weight, preferably in amounts of 15 to 20% by weight, and bleach activator, which was preferably added
  • the detergents contain 20 to 30% by weight of total surfactant, including soap, if any, 10 to 15% by weight of saturated C 12 -C 8 -fatty alcohol sulfates, preferably C 1 -C 8 -s 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 of ethoxylated Ci2-Ci8 fatty alcohols.
  • total surfactant including soap, if any, 10 to 15% by weight of saturated C 12 -C 8 -fatty alcohol sulfates, preferably C 1 -C 8 -s 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
  • 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% by weight, in each case based on the composition.
  • 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 bleaching agents or be free of bleaching agents. Examples
  • 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 were extruded in accordance with the teaching of older German patent application P 41 24701.9.
  • the enzyme and, if appropriate, the bleach activator in granular form were subsequently added to the extrudate.
  • the agents had a bulk density between 745 g / 1 and 850 g / 1.
  • the washing-in behavior of the agents was checked on a random basis.
  • Medium 1 was A4, medium 3 was B4 and medium 4 was B4.5.
  • Acrylic acid-maleic acid polymer (BASF commercial product)
  • Surfactant composition means in% by weight 7 8
  • Sulfopon (R) T55 CISS Cjs fatty alcohol paste
  • HD-Ocenol (R) 50/55 mixture of saturated and unsaturated fatty alcohol Cjö C j s fatty alcohol
  • 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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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

L'invention concerne des détergents et nettoyants granulaires ayant une masse volumique apparente de 700 g/l et plus, qui ont une teneur élevée en tensioactifs et contiennent des tensioactifs anioniques présentant une bonne biodégradabilité. Ces agents ont un meilleur comportement à la dissolution et au rinçage lorsqu'ils contiennent entre 20 et 55 % en poids de tensioactifs anioniques et non ioniques, y compris éventuellement des savons, la teneur desdits agents en sulfates d'alcool C8-C22, en sulfates d'alcool éthoxylés, en α-esters d'acide sulfonique d'alkyle et en mélanges desdits constituants s'élève à plus de 8 % en poids et le rapport du poids de ces sulfates tensioactifs anioniques et/ou des esters d'acide sulfonique d'alkyle aux tensioactifs non ioniques est de 10:1 à 1:1,25.
PCT/EP1993/003428 1992-12-15 1993-12-06 Detergents et nettoyants granulaires a haute teneur en tensioactifs WO1994013771A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP6513762A JPH08504458A (ja) 1992-12-15 1993-12-06 高い界面活性剤含量を有する顆粒洗剤
EP94902691A EP0674700B1 (fr) 1992-12-15 1993-12-06 Detergents et nettoyants granulaires a haute teneur en tensioactifs
DE59307518T DE59307518D1 (de) 1992-12-15 1993-12-06 Granulare wasch- und reinigungsmittel mit hohem tensidgehalt
KR1019950702432A KR950704464A (ko) 1992-12-15 1993-12-06 계면 활성제 함량이 높은 과립의 세제(granulated washing and cleaning agents with a high surfactant content)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4242185.3 1992-12-15
DE4242185A DE4242185A1 (de) 1992-12-15 1992-12-15 Granulare Wasch- und Reinigungsmittel mit hohem Tensidgehalt

Publications (1)

Publication Number Publication Date
WO1994013771A1 true WO1994013771A1 (fr) 1994-06-23

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PCT/EP1993/003428 WO1994013771A1 (fr) 1992-12-15 1993-12-06 Detergents et nettoyants granulaires a haute teneur en tensioactifs

Country Status (7)

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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)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995006706A1 (fr) * 1993-09-01 1995-03-09 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou de nettoyage seche par pulverisation, ou composant dudit produit
US5668100A (en) * 1993-09-23 1997-09-16 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures and detergents or cleaning formulations with improved dissolving properties
EP0700428B1 (fr) * 1993-05-26 1998-08-26 Unilever Plc Compositions detergentes
DE19722767A1 (de) * 1997-06-02 1998-12-03 Henkel Kgaa Wasch- oder Reinigungsmittel mit erhöhter Reinigungsleistung
WO2016142209A1 (fr) * 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Détergent ou produit de nettoyage granulaire à solubilité améliorée

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200953A2 (fr) * 1985-04-20 1986-11-12 Henkel Kommanditgesellschaft auf Aktien Détergent granulaire
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200953A2 (fr) * 1985-04-20 1986-11-12 Henkel Kommanditgesellschaft auf Aktien Détergent granulaire
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0700428B1 (fr) * 1993-05-26 1998-08-26 Unilever Plc Compositions detergentes
WO1995006706A1 (fr) * 1993-09-01 1995-03-09 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou de nettoyage seche par pulverisation, ou composant dudit produit
US5668100A (en) * 1993-09-23 1997-09-16 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures and detergents or cleaning formulations with improved dissolving properties
DE19722767A1 (de) * 1997-06-02 1998-12-03 Henkel Kgaa Wasch- oder Reinigungsmittel mit erhöhter Reinigungsleistung
WO1998055568A1 (fr) * 1997-06-02 1998-12-10 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage ou de nettoyage a pouvoir nettoyant eleve
WO2016142209A1 (fr) * 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Détergent ou produit de nettoyage granulaire à solubilité améliorée

Also Published As

Publication number Publication date
DE59307518D1 (de) 1997-11-13
DE4242185A1 (de) 1994-06-16
ES2109662T3 (es) 1998-01-16
KR950704464A (ko) 1995-11-20
ATE159044T1 (de) 1997-10-15
EP0674700A1 (fr) 1995-10-04
EP0674700B1 (fr) 1997-10-08
JPH08504458A (ja) 1996-05-14

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