EP0647261B1 - Granule de lavage et de nettoyage - Google Patents

Granule de lavage et de nettoyage Download PDF

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Publication number
EP0647261B1
EP0647261B1 EP93912982A EP93912982A EP0647261B1 EP 0647261 B1 EP0647261 B1 EP 0647261B1 EP 93912982 A EP93912982 A EP 93912982A EP 93912982 A EP93912982 A EP 93912982A EP 0647261 B1 EP0647261 B1 EP 0647261B1
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EP
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Prior art keywords
weight
fatty acid
granular detergent
glycerol esters
acid glycerol
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EP93912982A
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German (de)
English (en)
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EP0647261A1 (fr
Inventor
Frank Wangemann
Brigitte Giesen
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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
    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • 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
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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 a granular washing and cleaning agent which contains anionic surfactants which are obtained entirely or at least to a large extent from renewable raw materials.
  • oleochemical surfactant compounds which are obtained from renewable vegetable and / or animal raw materials and which have high ecological compatibility
  • examples of such oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which are produced by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts, in particular the corresponding alkali metal salts, and the known ⁇ -sulfofatty acid alkyl esters (ester sulfonates), which are prepared by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with predominantly 10 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts, in particular the corresponding alkali salts , and their disalts obtainable by hydrolysis.
  • oleochemical surfactant compounds are sulfated fatty acid glycerol esters, for example sulfated unsaturated fatty acid glycerol esters as described in international patent application WO 91/6532, or sulfonation products of saturated fatty acid glycerol esters as described in international patent application WO 91/9009.
  • the anionic surfactant that is still economically most important today belongs to the surfactant class of alkylbenzenesulfonates.
  • a disadvantage of these alkylbenzenesulfonates is that they are obtained from petrochemical raw materials.
  • the object was therefore to create a washing and cleaning agent which contains anionic surfactants which either completely or at least form one high proportion consist of native, i.e. renewable, fat chemical raw materials. These anionic surfactants are said to be able to completely or at least partially replace alkylbenzenesulfonates in otherwise customary detergent and cleaning agent formulations without sacrificing washing performance.
  • the invention accordingly relates to a granular washing and cleaning agent containing anionic or anionic and nonionic surfactants, the surfactant content of the agents being from 5 to 45% by weight and the agents at least one anionic surfactant consisting of sulfonated fatty acid glycerol esters, and contain inorganic image substances selected from zeolites and crystalline layered silicates.
  • 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. If one starts from fats and oils, that is, natural mixtures of different fatty acid glycerol esters, their fatty acid components usually build up partly from saturated and partly from unsaturated fatty acids.
  • Suitable sulfonated fatty acid glycerol esters are, for example, the sulfonation products of the unsaturated fatty acid glycerol esters which are obtained on the basis of coriander oil, sunflower oil, cottonseed oil, olive oil, peanut oil, linseed oil, fish oil, lard or rape oil rich in oleic acid.
  • the sulfonation can take place in accordance with international patent application W0 91/6532.
  • 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. If one again starts from fats and oils, i.e. natural mixtures of different fatty acid glycerol esters, it is necessary in this case to largely saturate the starting products with hydrogen in a manner known per se, 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, sunflower oil, cottonseed oil, peanut oil, linseed oil, or lard oil 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 which contains 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.
  • sulfated fatty acid glycerol esters are understood to mean in each case this complex reaction mixture, including the unsulfated and non-washing-active components, but without aqueous components.
  • the total surfactant content of the granular washing and cleaning agents is preferably 5 to 40% by weight.
  • the granular agents preferably contain 2 to 25% by weight and in particular 5 to 20% by weight of sulfated fatty acid glycerol esters, sulfated fatty acid glycerol esters with iodine numbers less than 5, in particular less than 2, or mixtures of sulfated fatty acid glycerol esters with iodine numbers less than 5 and sulfated unsaturated fatty acid glycerol esters in a weight ratio of 10: 1 to 1: 1, in particular from 5: 1 to 2: 1, are preferred.
  • Granular agents which contain 0.1 to 5% by weight of sulfated unsaturated fatty acid glycerol esters have a lower foam volume in use than conventional granular agents with conventional surfactants.
  • surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and Hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids are also suitable.
  • esters of ⁇ -sulfo fatty acids which are produced by ⁇ -sulfonation of the alkyl 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 are suitable.
  • These are preferably the ⁇ -sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, and sulfonation products of unsaturated fatty acids, for example oleic acid, are also present in small amounts, preferably in amounts not above about 2 to 3% by weight could be.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfofatty acids (MES) 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. Mixtures of mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonate, are also preferred.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
  • Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed.
  • the proportion of fatty alkyl sulfates in the granular agents is preferably 2 to 20% by weight and in particular 5 to 15% by weight.
  • anionic surfactants 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).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a restricted homolog distribution, are particularly preferred.
  • preferred granular detergents and cleaning agents contain alkylbenzene sulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, as further anionic surfactants, the weight ratio of sulfated fatty acid glycerol esters, in particular sulfated fatty acid glycerol esters having iodine numbers less than 5, to alkylbenzenesulfonate and / or alkyl sulfate 1: : 1 and in particular 2: 5 to 2: 1.
  • granular agents are preferred which do not sulfate alkylbenzenesulfonate, but rather as anionic surfactants Contain fatty acid glycerol esters alone or in a mixture with the other anionic surfactants mentioned.
  • anionic surfactants Contain fatty acid glycerol esters alone or in a mixture with the other anionic surfactants mentioned.
  • granular detergents and cleaning agents which contain sulfonated fatty acid glycerol esters with iodine numbers less than 5 instead of alkylbenzenesulfonate to achieve the same or better values in terms of washing power than an agent which contains alkylbenzenesulfonate.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% 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.
  • 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.
  • the granular detergents and cleaning agents also contain nonionic surfactants in addition to the anionic surfactants, preferably in amounts of 1 to 15% by weight and in particular in amounts of 2 to 12% by weight.
  • the nonionic surfactants used are preferably liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position, or linear and May contain methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms such as, for example, coconut oil, tallow oil or oleyl alcohol, are particularly preferred.
  • 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 restricted homolog distribution (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • anionic surfactant sulfonated fatty acid glycerol esters especially the sulfonated fatty acid glycerol esters with iodine numbers less than 5, which essentially contain fatty acids with 8 to 22 carbon atoms, can not only at least partially replace other conventional anionic surfactants such as alkylbenzenesulfonate without the washing performance of the detergents being reduced , but that this effect also occurs when in agents with conventional anionic surfactants such as alkylbenzenesulfonate and / or fatty alkyl sulfate, which contain conventional ethoxylated C 8 -C 18 alcohols as nonionic surfactants, the latter at least partially, for example by 10 to 50% by weight, based on the amount of nonionic surfactant, to be replaced by sulfated fatty acid glycerol esters.
  • 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 aliphatic radical branched with methyl in the 2-position with 8 to 22, preferably 12 to 18 C atoms and G denotes 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.
  • the content of the granular detergents and cleaning agents in alkyl glycosides and in particular in alkyl glucosides is preferably 0.5 to 8% by weight and in particular 1 to 5% by weight.
  • the granular detergents and cleaning agents according to the invention preferably contain builder substances as further constituents, in particular in amounts of 10 to 65% by weight, it being important to note that they must contain inorganic image substances selected from zeolites and crystalline layered silicates.
  • Preferred inorganic builder substances are zeolites, crystalline layered silicates and phosphates, provided that the use of phosphates is not objectionable for ecological reasons.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it 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 granular agents is preferably 15 to 40% by weight and in particular 20 to 35% by weight (in each case based on anhydrous active substance).
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x 0 2x + 1 .yH 2 0, 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 of the formula 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 0 are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO91 / 08171.
  • 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 and mixtures of these.
  • the granular detergents and cleaning agents according to the invention preferably contain the polycarboxylates mentioned in amounts of 0.5 to 25% by weight, in particular in amounts of 1 to 20% by weight and with particular advantages in amounts of 5 to 15% by weight ,
  • the zeolite content of the agents preferably being about 20 to 35% by weight and in particular about 20 to 32% by weight (in each case based on anhydrous active substance).
  • Suitable polymeric polycarboxylates are, 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.
  • Their 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 content of (co) polymeric polycarboxylates in the agents is preferably 1 to 8% by weight.
  • 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.
  • Suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous or crystalline 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 2 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight.
  • the other constituents of the granular agents include bleaching agents and bleach activators, graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, textile-softening substances, colorants and fragrances, solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, and neutral salts in the form of sulfates and chlorine their sodium or potassium salts.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further 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.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred Bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Graying inhibitors do the job of the fiber. keep loosened dirt suspended in the liquor and thus prevent graying.
  • Water-soluble colloids mostly of an 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, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • carboxymethyl cellulose sodium salt
  • methyl cellulose methyl cellulose
  • hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose
  • polyvinylpyrrolidone for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps or, as indicated, by using sulfated unsaturated fatty acid glycerol esters.
  • soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt.
  • foam-inhibiting soaps Soaps of natural or synthetic origin which contain a high proportion of C 18 -C 24 fatty acids are therefore suitable as foam-inhibiting soaps.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and 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.
  • the salts of the polyphosphonic acids are usually used in amounts of 0.1 to 2.5% by weight, preferably up to 1.5% by weight.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • 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-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • 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.
  • customary amounts for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight.
  • small amounts for example 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye.
  • a particularly preferred dye is Tinolux (R) (commercial product from Ciba-Geigy).
  • the granular washing and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / l. Granules with a bulk density of between 600 and 1100 g / l are preferred.
  • the granular detergents and cleaning agents can be produced by any of the known processes.
  • the granules can be produced by spray drying an aqueous slurry and, if appropriate, then adding temperature-sensitive components.
  • the granular washing and cleaning agents can be produced by one of the known granulating or extruding processes.
  • the granules are produced by an extrusion process which is described in international patent application WO 91/2047.
  • the granular detergents and cleaning agents are produced by using the sulfated fatty acid glycerol esters in the form of a spray-dried or granulated compound as an additive component to other granular constituents of detergents and cleaning agents.
  • a continuous falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO 3 gassing, about 5 moles of a fatty acid glycerol ester with an iodine number less than 5 (see Table 1) at 80 ° C with about 15 moles of gaseous sulfur trioxide reacted.
  • the fatty acid glycerol ester was sprayed into the reactor through a nozzle with an opening of 0.2 cm in such a way that the starting material formed a continuous fine film with a layer thickness of less than 0.1 cm along the tube wall.
  • the sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 2% by volume with nitrogen and blown in at the side of the reactor head.
  • the crude sulfonation product was subjected to a post-reaction at 80 ° C. for 30 minutes.
  • the acidic sulfonation product was then continuously neutralized to pH 6.5 to 7.5 using aqueous 25% strength by weight sodium hydroxide solution.
  • compositions of the basic agents W1 and W2 were (data in% by weight):
  • the agents consisted of spray-dried granules, which were sprayed with ethoxylated C 12 -C 18 fatty alcohol and to which the temperature-sensitive components had been subsequently mixed.
  • the bulk density was 650 g / l or 670 g / l.
  • Example 1 Testing W1, dosage 80 g
  • Example 2 Testing W1, dosage 120 g
  • T 30 ° C medium % Remission when soiled SH-PBV W1 / V 69.8 W1 / 1 69.2 W1 / 3 68.9
  • Table 8 The results of the tests at 40 ° C and a dosage of 100 g are summarized in Table 8.
  • Table 8 medium % Remission when soiled SW-B SH-B SH-PBV SH-P R-BV T-BV MU-PBV W2 / V 56.0 67.1 66.7 72.8 55.7 65.1 65.5 W2 / 1 56.7 67.3 65.9 72.5 53.9 64.4 63.8 W2 / 2 58.1 --- --- --- 54.7 65.9 64.1

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Inorganic Chemistry (AREA)
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Claims (14)

  1. Granulé de lavage et de nettoyage, contenant des tensioactifs anioniques ou anioniques et non ioniques, caractérisé en ce que la concentration des granulés en tensioactifs est comprise entre 5 et 45 % en poids, les granulés contenant au moins un surfactif anionique, qui est constitué de glycérides d'acides gras sulfurisés, ainsi que des substances adjuvantes inorganiques sélectionnées parmi les zéolithes et les silicates stratifiés cristallins.
  2. Granulé selon la revendication 1, caractérisé en ce qu'il renferme des glycérides d'acides gras sulfurisés, qui sont obtenus à partir de glycérides d'acides gras présentant un indice d'iode inférieur à 5, de préférence à partir de mono-, de di- et de triglycérides ou de mélanges de ceux-ci avec un indice d'iode inférieur à 5, qui renferment des acides gras comportant 6 à 22 atomes de carbone, par mise en réaction avec du trioxyde de soufre gazeux, suivie de neutralisation par des bases aqueuses.
  3. Granulé selon la revendication 1 ou 2, caractérisé en ce que la concentration du produit en tensioactifs atteint 5 à 40 % en poids et le contenu en substances adjuvantes est compris entre 10 et 65 % en poids, les granulés renfermant 2 à 25 % en poids de glycérides d'acides gras sulfurisés, 1 à 15 % en poids de tensioactifs non ioniques et comme substance adjuvante, de la zéolithe.
  4. Granulé selon une des revendications 1 à 3, caractérisé en ce que l'on met en oeuvre comme tensioactifs non ioniques, des alcools gras éthoxylés et/ou des alkylglycosides, la concentration des granulés en glycérides d'acides gras sulfurisés atteignant de préférence 5 à 20 % en poids et en tensioactifs non ioniques, de préférence 2 à 12 % en poids.
  5. Granulé selon une des revendications 1 à 4, caractérisé en ce qu'il renferme d'autres surfactifs anioniques appartenant au groupe des sulfonates, sulfates et savons.
  6. Granulé selon la revendication 5, caractérisé en ce qu'il renferme comme autres surfactifs anioniques, de l'alkylbenzènesulfonate et/ou de l'alkylsulfate, de préférence de l'alkylsulfate gras, le rapport pondéral entre les glycérides d'acides gras sulfurisés et l'alkylbenzènesulfonate et/ou l'alkylsulfate atteignant 1:9 à 4:1 et, en particulier, 2:5 à 2:1.
  7. Granulé selon une des revendications 1 ou 6, caractérisé en ce qu'il est exempt d'alkylbenzènesulfonates.
  8. Granulé selon une des revendications 1 à 7, caractérisé en ce qu'il présente une concentration en zéolithe de 15 à 40 % en poids (par rapport à la substance active anhydre).
  9. Granulé selon une des revendications 1 à 8, caractérisé en ce qu'il renferme comme substances adjuvantes organiques, des polycarboxylates, de préférence du citrate, du succinate, du tartrate, du glutarate, de l'adipate ou des mélanges de ceux-ci en proportions de 0,5 à 25 % en poids, de préférence de 1 à 20 % en poids et, en particulier, de 5 à 15 % en poids.
  10. Granulé selon une des revendications 1 à 9, caractérisé en ce qu'il renferme un mélange de glycérides d'acides gras sulfurisés présentant un indice d'iode inférieur à 5 et de glycérides d'acides gras insaturés sulfurisés, dans un rapport pondéral de 10:1 à 1:1, de préférence de 5:1 à 2:1.
  11. Granulé selon une des revendications 1 à 10, caractérisé en ce qu'il possède une densité en vrac située entre 600 et 1100 g/l.
  12. Procédé de fabrication d'un granulé de lavage et de nettoyage selon une des revendications 1 à 11, caractérisé en ce que le granulé est fabriqué par séchage par pulvérisation.
  13. Procédé de fabrication d'un granulé de lavage et de nettoyage selon une des revendications 1 à 11, caractérisé en ce que le granulé est fabriqué par un procédé de granulation ou d'extrusion.
  14. Procédé de fabrication d'un granulé de lavage et de nettoyage selon une des revendications 1 à 11, caractérisé en ce que les glycérides d'acides gras sulfurisés sont mis en oeuvre sous la forme d'un compound séché par pulvérisation ou granulé, comme composant d'addition à d'autres constituants granulaires de produits de lavage et de nettoyage.
EP93912982A 1992-06-22 1993-06-15 Granule de lavage et de nettoyage Expired - Lifetime EP0647261B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4220387A DE4220387A1 (de) 1992-06-22 1992-06-22 Granulares Wasch- und Reinigungsmittel
DE4220387 1992-06-22
PCT/EP1993/001515 WO1994000544A1 (fr) 1992-06-22 1993-06-15 Granule de lavage et de nettoyage

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EP0647261A1 EP0647261A1 (fr) 1995-04-12
EP0647261B1 true EP0647261B1 (fr) 1996-07-24

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EP (1) EP0647261B1 (fr)
JP (1) JPH07508055A (fr)
AT (1) ATE140724T1 (fr)
DE (2) DE4220387A1 (fr)
ES (1) ES2091011T3 (fr)
WO (1) WO1994000544A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022596A1 (fr) * 1994-02-18 1995-08-24 Henkel-Ecolab Gmbh & Co. Ohg Granule seche par pulverisation a haute densite apparente
US11767495B2 (en) 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules
US11499124B2 (en) 2020-03-13 2022-11-15 YFY Consumer Products, Co. Solid granules used for cleaning agents

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2243306A1 (de) * 1972-09-02 1974-03-21 Henkel & Cie Gmbh Schaumregulierte waschmittel, insbesondere fuer trommelwaschmaschinen
DE3941365A1 (de) * 1989-12-15 1991-06-20 Henkel Kgaa Verfahren zur herstellung von salzen sulfierter fettsaeureglycerinester

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JPH07508055A (ja) 1995-09-07
ES2091011T3 (es) 1996-10-16
ATE140724T1 (de) 1996-08-15
DE59303332D1 (de) 1996-08-29
EP0647261A1 (fr) 1995-04-12
WO1994000544A1 (fr) 1994-01-06
DE4220387A1 (de) 1993-12-23

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