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
  • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
• • 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
  • 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
  • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
• • 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
  • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/043—Liquid or thixotropic (gel) 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
  • C11D1/22—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
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• nonionic surfactants in detergents primarily serves to improve the washability of oily and greasy soiling.
• the amount of the generally liquid nonionic surfactants is limited by the ability of the solid detergent constituents to absorb liquid constituents.
• the free-flowing properties of the detergents usually deteriorate if you want to use a quantity of nonionic liquid surfactants which is desirable per se.
• the nonionic surfactants are difficult to process using the hot spray method widely used for the production of detergents.
• Detergents with a high content of nonionic surfactants can be produced without problems as liquid to pasty detergents - referred to in the context of this invention as liquid detergents.
• detergents contain builders that are essential for washing. Support the washing performance in various ways.
• builders are powders or granules, which tend to settle in liquid systems after prolonged storage.
• the solids are completely ground to very small particle sizes (below 10 microns) according to the teaching of DE-OS 28 25 218.
• EP-PS 34 387 such detergents for encryption is known rin g augmentation of settling of solids clays having chain structure to add.
• EP-OS 158 464 describes liquid detergents whose solids have a particle size of over Have 10 microns and their nonionic surfactants have a pour point of less than about 24 ° C.
• the known liquid detergents have the disadvantage that they contain constituents (ballast components) which are inert with regard to the washing performance or that their viscosity is unstable when stored, which generally leads to a deterioration in the dissolving rate under washing conditions.
• the long-term sedimentation stability of most products is unsatisfactory.
• Another disadvantage of the liquid detergents described so far is the poor storage stability of chemically sensitive components, such as. B. perborate, bleach activator and the enzymes used. The more or less pronounced degradation of these components leads to a significant loss in washing performance and causes the well-known "gassing" of some liquid detergents, inter alia, in airtight containers, e.g. B. in portion packs.
• the object of the present invention is therefore to provide a liquid detergent based on nonionic surfactants and builders which does not have the disadvantages of the known liquid detergents.
• the fatty alcohol of component a) can be straight or branched, it can contain an even or odd number of carbon atoms and it can be both saturated and unsaturated.
• branched alcohols are particularly suitable, in particular oxo alcohols.
• the term "practically anhydrous" means that the detergent contains at most 5 percent by weight of unbound water.
• the detergent can also contain bound water, i.e. H. e.g. B. water in the form of water of crystallization in inorganic salts or water which is adsorptively bound and can only be removed by vigorous heating to, for example, above 400 ° C. or water which is part of the raw materials used for the detergent according to the invention.
• Practically gas-free means that the detergent contains at most 5, preferably less than 3 percent by volume of gaseous components at room temperature.
• Practically gas-free, liquid detergents in the context of this invention have a viscosity behavior which has hardly changed even after prolonged storage and permit the setting of a specific, desired viscosity within wide limits more easily than detergents with a higher gas content. They have a high, constant density and represent the most compact form of supply for the recipe in question. The low gas content therefore promotes the production of stable, flowable and pumpable detergents. This also improves the dissolving speed of the detergents in the wash liquor.
• Suitable anionic surfactants of the sulfate and sulfonate type are alkylbenzenesulfonates with a Cq to C 15 alkyl radical, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 -C 18 monoolefins with terminal or internal ones Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• dialcan sulfonates which are obtainable from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha sulfo fatty acids, e.g. B. the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from fatty alcohols such as. B.
• coconut fatty alcohols coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols and the secondary alcohols of this chain length.
• the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
• Sulfated fatty acid alkanolamides and sulfated fatty acid ranoglycerides are also suitable.
• Suitable soaps in the context of this invention are the alkali metal salts of saturated or unsaturated fatty acids with 10 to 24 carbon atoms: soaps with a higher number of carbon atoms, in particular with 14 to 24 carbon atoms, are used to dampen the foam. Soaps of the saturated C 20 -C 24 fatty acids are particularly suitable as foam suppressants for detergents based on sodium triphosphate as builders, while in detergents containing predominantly zeolite, C 14 -C 18 soaps already show good foam inhibition, especially at low washing temperatures.
• Particulate builders are organic and inorganic substances, preferably alkaline salts, in particular alkali salts, which not only are able to precipitate or bind complex calcium ions, but also, if possible, bring about a synergistic increase in washing power and have dirt-carrying capacity.
• alkaline salts in particular alkali salts
• the water-soluble alkali metaphosphates or Alkalipoly - phosphates, especially pentasodium triphosphate are still of particular importance.
• organic complexing agents for calcium ions and heavy metal ions can be present.
• Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphonic acids and phosphonopolycarboxylic acids, such as. B.
• methanediphosphonic acid dimethylaminomethane1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, ethylenediaminetetramethylene tetraphosphonic acid, diethylenetriaminepentamethylenepentaphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-i, 2,4-tricarboxylic acid
• the N- and P-free polycarboxylic acids forming calcium ion complex salts which also include polymers containing carboxyl groups, are of particular importance.
• Low molecular weight compounds such as citric acid, 2,2-oxydisuccinic acid or carboxymethyloxysuccinic acid are suitable.
• Suitable polymeric polycarboxylic acids have a molecular weight of 350 to about 1,500,000 in the form of the water-soluble salts.
• Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000, and in particular in the range from 10,000 to 100,000.
• polyacrylic acid poly-alpha hydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds, such as, for example, vinyl methyl ether.
• ethylenically unsaturated compounds such as, for example, vinyl methyl ether.
• the water-soluble salts of polyglyoxylic acid can also be used.
• Suitable water-insoluble inorganic builders are the finely divided synthetic zeolite A-type sodium aluminosilicates containing bound water described in German patent application DE 24 12 837 as phosphate substitutes for detergents and cleaning agents.
• the cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, i. H. they have practically no particles larger than 30 microns and preferably consist at least 80% of particles smaller than 10 microns.
• Their calcium binding capacity which is determined according to the information in DE 24 12 837, is in the range from 100 to 2DO mg CaO / g.
• the zeolite NaA can be used in particular, also the zeolite NaX and mixtures of zeolite NaA and NaX.
• Suitable inorganic, non-complexing salts are the - also referred to as "washing alkalis" - bicarbonates, carbonates, borates, sulfates or silicates of the alkalis; Of the alkali silicates, especially the sodium silicates with a Na 2 O: SiO 2 ratio of 1: 1 to 1: 3.5 can be used.
• salts of the non-capillary-active sulfonic acids carboxylic acids and sulfocarboxylic acids containing 2 to 9 carbon atoms, for example the alkali salts of alkane, benzene, toluene, xylene - Or cumene sulfonic acids, sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid.
• Acetamide and urea are also suitable as solubilizers.
• Detergents which have particularly favorable properties with regard to their cleaning ability, their foaming behavior and their water solubility contain, as component b), a sulfonate together with soap.
• the soap is in particular those alkali salts of fatty acids that have foam-suppressing properties, i.e. of fatty acids with 18 to 24 carbon atoms.
• particularly valuable detergents contain, as component a), nonionic surfactants which are addition products of 3 to 5 moles of ethylene oxide with one mole of fatty alcohol. Addition products to fatty alcohols with 12 to 18 C atoms and in particular mixtures of adducts with fatty alcohols with different chain length ranges give the detergents particularly valuable properties.
• particularly interesting compounds of component c) are polyethylene glycols with a mole weight of about 300 to 400, i.e. Compounds with about 7 to about 9 ethoxy units in the molecule.
• These hydrotropic liquid phase additives can, as usual, carry terminal hydroxyl groups or they can, e.g. B. with methyl residues, end groups.
• the ratio of components a), b) and c) to one another is particularly important for the detergents according to the invention.
• detergents which contain component a) in a ratio to component b) of 1.1: 1 to 1.5: 1 and contain component c) in an amount of 2 to 10 percent by weight are preferred.
• Particularly powerful detergents according to the invention contain components a), b) and c) in an amount of 25 to 40 percent by weight.
• detergents have two types of particulate constituents, namely a first, finely divided fraction with a particle size in the range from dust fineness to 30 microns and a second, coarser fraction with a particle size in the range from 200 to 2000 microns included.
• “Dust fineness” stands for particles with a size of more than 0.01 micron, in particular with a particle size of more than 0.1 micron.
• Particles with a size in the range of 200 to 2000 microns are mainly granules.
• certain detergent ingredients are added to the liquid detergents. These are detergent constituents, which are in granular form either for handling reasons, but above all to prevent their interaction with other detergent constituents. These include, for example, anti-graying substances, optical brighteners, enzymes, bleaching agents and bleach activators, foam inhibitors.
• Suitable graying inhibitors are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers are also suitable, in particular mixtures of carboxymethyl cellulose and methyl cellulose. Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi, such as bacillus substilis, bacillus lichenififormis and streptomyces griseus, are particularly suitable. In order to protect the enzymes against premature decomposition, they are usually embedded in coating substances.
• perhydrates and per compounds commonly used in detergents and bleaching agents are suitable as bleaching components.
• Perhydrates preferably include sodium perborate, the is used as a monohydrate or in particular as a tetrahydrate.
• the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea are also suitable. These perhydrates are preferably used together with bleach activators.
• Sodium perborate tetrahydrate and sodium perborate monohydrate in combination with bleach activators are preferred as bleaching components.
• the bleach activators include in particular N-acyl compounds and O-acyl compounds.
• N-acyl compounds are multiply acylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril.
• acylated glycolurils such as tetraacetylglycoluril.
• Further examples are Na-cyanamide, N-alkyl-N-sulfonylcarbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines.
• acylated sugars such as glucose pentaacetate are suitable as O-acyl compounds.
• Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.
• the bleach activators can also be used to avoid interactions with per compounds or other substances, e.g. B. with enzymes, coated with H-üllsubstanzen.
• Such detergent components used in the form of granules or granules coated with coating substances lead to products with particularly valuable properties.
• the special composition of the detergents and the presence of particulate constituents with two different particle size ranges result in detergents with particularly high viscosity stability and sedimentation stability.
• the agents according to the invention with a viscosity in the range of 10,000 to 1,000,000 mPas, measured using a Brookfield RVT viscometer Use of spindle 6 at 1 to 10 revolutions per minute and 20 ° C are particularly preferred detergents.
• Another object of the present invention is a method for producing a liquid detergent of the composition and properties described above.
• the liquid constituents of the detergent and those particulate constituents which do not interact chemically with one another and with the liquid constituents even after comminution are intimately mixed in a first mixing stage and the suspension thus obtained is subjected to wet grinding, so that the average grain diameter of these solid components in the suspension thus obtained after grinding is at most 30 microns, whereupon the suspension is degassed.
• the remaining particulate constituents with a particle size between 200 and 2000 microns are degassed in vacuo, this degassed solid mixture is mixed with the ground suspension of the first mixing stage in a second mixing stage with further degassing, and optionally added to this mixture in vacuo further auxiliaries such as fragrances, dyes or hydrotropic compounds or other compounds for setting the desired viscosity are added.
• the degassing of liquid and solid components has the effect that the liquid detergents according to the invention are practically gas-free, which results in a particularly stable viscosity behavior of the detergents.
• the average grain diameter of the solids of the finely ground suspension should be of the order of magnitude mean pore size of the coarse-particle solid recipe components incorporated under grain retention or below.
• a special handling advantage is obtained if the detergents are packed in portions in bags from a water-soluble film.
• Particularly preferred as a form of supply are detergents which are contained in bags made of film based on polyvinyl alcohol.
• the bags contain so much of the detergents according to the invention that they are sufficient for washing the amount of laundry in a washing machine filling.
• Suitable films are, for example, polyvinyl alcohol films with a film thickness of 65 microns, which are formed by heat or wet sealing into closed bags containing the detergent.
• a phosphate-free detergent of the following composition was prepared in a manner comparable to that described above:
• This detergent had a viscosity of 38,000 mPas.
• the dissolution behavior was as described in Example 1.
• the detergents from Examples 1 and 2 had excellent washing performance both against fat / pigment, enzymatic and against bleachable stains in hard and soft water. If the water hardness is high, up to 3 sachets of detergent were used, if the water hardness was low only one.

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• 1986
  • 1986-06-27 DE DE19863621536 patent/DE3621536A1/de not_active Withdrawn
• 1987
  • 1987-06-19 EP EP87108777A patent/EP0253151A3/fr not_active Ceased
  • 1987-06-26 DK DK330887A patent/DK330887A/da not_active Application Discontinuation
  • 1987-06-27 JP JP62160823A patent/JPS638495A/ja active Pending
• 1988
  • 1988-10-19 US US07/262,204 patent/US4929380A/en not_active Expired - Fee Related

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