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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/1233—Carbonates, e.g. calcite or dolomite

Definitions

• the invention relates to the use of cationic non-silicate layer compounds in detergent compositions and in particular in reduced phosphate detergents based on zeolite.
• non-silicate layer compounds as a builder component in detergent compositions is not known. Only EP-A 0 206 799 describes the use of mixed metal hydroxides to prevent dye transfer in washing processes.
• reduced phosphate means that detergent compositions contain at most 30% by weight sodium tripolyphosphate, but can also be completely phosphate-free.
• the object of the present invention was to provide new phosphate-reduced detergent compositions and to bring about a reduction in the deposition of tissue in conventional washing processes.
• Cationic layer connections are understood here to mean solids, the structure of which is derived from the layered magnesium hydroxide brucite in that some of the divalent metal ions are replaced by trivalent metal ions. The resulting positive excess charge of the metal hydroxide layers is compensated for by exchangeable anions between the layers. Hydrotalcite can be used as a model substance for this class of solids.
• Hydrotalcite is a naturally occurring mineral with an approximate composition Mg6Al2 (OH) 16CO3. 4H2O the ratio of Mg to Al and thus also the carbonate content can fluctuate within relatively wide limits. Instead of the carbonate, other anions can also be present.
• the layer structure with the ABAB ... layer sequence is characteristic of the substance, if A stands for a positively charged triple layer consisting of hydroxyl ions, metal cations and again hydroxyl ions. B means an intermediate layer of anions and water of crystallization. This layer structure becomes clear in the X-ray powder diagram, which can be used for characterization: ASTM card no. 30, 1.96, 1.53 and 1.50 ⁇ .
• hydrotalcite can generally be used to bind acidic components, for example impurities from catalytic processes (DE-OS 27 19 024) or undesirable dyes (DE-OS 29 29 991).
• acidic components for example impurities from catalytic processes (DE-OS 27 19 024) or undesirable dyes (DE-OS 29 29 991).
• Other possible uses are in the field of corrosion protection (DE-OS 31 28 716), the stabilization of plastics, in particular PVC (DE-PS 30 19 632), waste water treatment (JP-PS 79 24 993, JP-PS 58 214 388 ) and the production of color pigments (JP-PS 81 98 265).
• a further embodiment of the present invention consists in the use of cationic non-silicate layer compounds, wherein A in the general formula (I) stands for one equivalent of a carbonate ion.
• Another preferred embodiment of the present invention consists in the use of cationic non-silicate layer compounds of the general formula (I) in an amount of 1 to 15% by weight, based on the detergent composition.
• the phosphate content based on tripolyphosphate, is not critical in the sense of the present invention, it is preferred according to a further embodiment of the present invention that the phosphate content, calculated as sodium tripolyphosphate, is less than 30% by weight.
• Another preferred embodiment of the present invention is that the use of cationic non-silicate layer compounds is carried out in phosphate-free detergent compositions.
• the use of cationic non-silicate layer compounds is preferred if the detergent compositions contain 10 to 30% of zeolite A and 1 to 15% of the contain cationic non-silicate layer compounds.
• the layer compounds to be used according to the invention can be incorporated by conventional techniques for the production of detergents, e.g. by hot atomization together with other detergent components, by granulation together with solid and / or liquid detergent components or by subsequent application to solid detergent parts (e.g. spray powder, granules, zeolite, layered silicate).
• detergent compositions according to the invention can contain further builder substances, builder substances, surfactants, soaps, non-surfactant-like foam inhibitors and dirt carriers.
• Suitable organic and inorganic builder substances are weakly acidic, neutral or alkaline-reacting salts, in particular alkali salts, which are able to precipitate or bind calcium ions in a complex manner.
• alkali salts which are able to precipitate or bind calcium ions in a complex manner.
• the water-soluble alkali metal or alkali polyphosphates in particular pentasodium triphosphate, in addition to the alkali ortho- and alkali pyrophosphates, are of particular importance. All or part of these phosphates can be replaced by organic complexing agents for calcium ions.
• Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkanephosphonic acids, amino- and hydroxyalkanephosphonic acids and phosphonopolycarboxylic acids such as methane diphosphonic acid, dimethylaminomethane-1,1-diphosphonic acids, aminotrimethylene triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonicarboxylic acid , 2-phosphonobutane-1,2,4-tricarboxylic acid.
• the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions which also include polymers containing carboxyl groups, are of particular importance. Suitable are e.g. Citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid.
• Polycarboxylic acids containing ether groups are also suitable, such as 2,2'-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, e.g.
• Biscarboxymethylethylengylkol carboxymethyloxysuccinic acid, carboxymethyltartronic acid and carboxymethylated or oxidized polysaccharides.
• Polymeric carboxylic acids with a molecular weight between 350 and about 1,500,000 in the form of water-soluble salts are also suitable.
• 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.
• These compounds include, for example, polyacrylic acid, polyhydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as vinyl methyl ether .
• the water-soluble salts of polyglyoxylic acid are also suitable.
• Suitable water-insoluble inorganic builders are those in DE-OS 24 12 837 as phosphate substitutes for Detergents and cleaning agents described in more detail finely divided, synthetic, bound water-containing sodium aluminosilicates of the zeolite A type.
• the cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, that is to say that they have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% of particles smaller than 10 ⁇ m.
• Your calcium binding capacity which is determined according to the details of DE-OS 24 12 837, is in the range of 100 to 200 mg CaO / g.
• Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.
• Suitable inorganic, non-complexing salts are the alkali salts of bicarbonates, carbonates, borates, sulfates and silicates - also referred to as "washing alkalis".
• alkali silicates the sodium silicates in which the Na2O: SiO2 ratio is between 1: 1 and 1: 3.5 are particularly preferred.
• builder substances that are mostly used in liquid agents because of their hydrotropic properties are the salts of the non-capillary-active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkanoic, 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 ureas are also suitable as solubilizers.
• Surfactants which can be contained as additional components in existing washing and cleaning agents, have in Molecule at least one hydrophobic organic residue and a water-solubilizing anionic, zwitterionic or nonionic group.
• the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 C atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 aliphatic C atoms.
• anionic surfactants e.g. Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids, can be used.
• Suitable synthetic anionic surfactants are those of the sulfate, sulfonate and synthetic carboxylate type.
• the surfactants of the sulfonate type include alkylbenzenesulfonates (C9 ⁇ 15 alkyl), olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C12 ⁇ 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, are considered.
• alkylbenzenesulfonates C9 ⁇ 15 alkyl
• olefin sulfonates i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C12 ⁇ 18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis
• alkanesulfonates which are obtainable from C12 ⁇ 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha-sulfofatty acids, e.g. 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 and synthetic origin, ie from fatty alcohols, such as, for example, coconut oil alcohols, tallow oil alcohols, oleyl alcohol, lauryl, myristyl, Palmityl or stearyl alcohol, or the C10 ⁇ 20 oxo alcohols, and those secondary alcohols of this chain length.
• the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
• Sulfated fatty acid alcoholamides and sulfated fatty acid monoglycerides are also suitable.
• anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.
• the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols and fatty acids can be used as nonionic surfactants.
• non-fully or not fully water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
• non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-polypropylene glycol and with alkylpolypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical.
• Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide.
• N-alkoxylated fatty acid amides are not to be understood as nonionic surfactants.
• the optionally used zwitterionic surfactants are preferably derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C8-C18 radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group.
• Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonium) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.
• a reduced foaming power which is desirable when working in machines, can be achieved, for example, by using soaps.
• soaps foam attenuation increases with the degree of saturation and the C number of the fatty acid ester; Soaps of saturated and unsaturated C12 ⁇ 24 fatty acids are therefore particularly suitable as foam suppressants.
• the non-surfactant-like foam inhibitors are generally water-insoluble, mostly aliphatic C8-C22-carbon-containing compounds.
• Suitable non-surfactant foam inhibitors are e.g. the N-alkylaminotriazines, i.e. Reaction products of 1 mol of cyanuric chloride with 2 to 3 mol of a mono- or dialkylamine with essentially 8 to 18 carbon atoms in the alkyl radical.
• Propoxylated and / or butoxylated aminotriazines e.g. the reaction products of 1 mole of melamine with 5 to 10 moles of propylene oxide and additionally 10 to 50 moles of butylene oxide and the aliphatic C18-C40 ketones, e.g.
• the fatty ketones made from hardened trans-fatty acid or tallow fatty acid, as well as the paraffins and halogen paraffins with melting points below 100 ° C and silicone oil emulsions based on polymeric organosilicon compounds.
• the detergents according to the invention can additionally contain bleaching agents and bleach activators.
• bleaching agents sodium perborate tetrahydrate (NaBO2. H2O2. 3H2O) and monohydrate (NaBO2. H2O2) are of particular importance.
• other borates which supply H2O2 are also useful, e.g. the perborax Na2B4O7. 4H2O2.
• These compounds can be partially or completely by other active oxygen carriers, in particular by peroxypyrophosphates, citrate perhydrates, urea / H2O2 or melamine / H2O2 compounds as well as by H2O2 delivering peracid salts such as e.g. Caroate (KHSO5), perbenzoate or peroxyphthalate can be replaced.
• KHSO5 Caroate
• perbenzoate or peroxyphthalate can be replaced.
• the detergents according to the invention are intended in particular for washing at low washing temperatures, ar preferably bleach components containing activator are incorporated into the detergents.
• Certain organic peracid-forming N-acrylic or O-acyl compounds serve as activators for per compounds which supply H2O2 in water.
• Compounds which can be used include N-diacylated and N, N ⁇ -tetraacylated amines, such as N, N, N ⁇ , N ⁇ -tetraacetyl-methylenediamine or -ethylenediamine or tetraacetylglycoluril.
• the washing and cleaning agents can contain dirt carriers, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
• water-soluble colloids usually of an organic nature, are suitable, such as, 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, such as degraded starch, aldehyde starches, etc.
• Polyvinylpyrrolidone can also be used.
• the magnesium aluminum hydroxocarbonate (hydrotalcite) used for example 1 with a structure similar to hydrotalcite was prepared in accordance with DE-OS 15 92 126 by adding a solution of 6.4 kg of Mg (NO3) 2. 6 H2O and 4.7 kg Al (NO3) 3. 6H2O in 17.5 kg of deionized water was added within 4 hours with stirring at room temperature to a solution of 7 kg of 50% strength by weight sodium hydroxide solution and 2.5 kg of sodium carbonate in 25 kg of deionized water. The reaction mixture was then stirred at 65 ° C. for a further 18 hours, the white precipitate was centrifuged off and washed with about 60 l of deionized water. The product was then dried at 110 ° C. in vacuo.
• the analytically determined ratio of Mg to Al is 2.08 to 1.
• EO stands for ethylene oxide
• the basic detergent A was dosed in a 90 ° C cooking program with 104 g in the prewash and 144 in the main wash (water hardness approx. 16 ° d). It was washed 19 times with 3.5 kg of normally soiled laundry in the presence of cotton fabrics. After 19 washes, the cotton fabrics were ashed. The result is shown in Table 1.
• Detergent B like basic detergent A, was dosed in a 90 ° C cooking program with 104 g in the prewash and 144 in the main wash (water hardness approx. 16 ° d). It was washed 19 times with 3.5 kg of normally soiled laundry in the presence of cotton fabrics. After 19 washes, the cotton fabrics were ashed. The result is shown in Table 1.
• Detergent C was, as described in the comparative examples, metered in a 90 ° C. hot-washing program with 104 g in the prewash and 144 in the main wash (water hardness approx. 16 ° d). It was washed 19 times with 3.5 kg of normally soiled laundry in the presence of cotton fabrics. After 19 washes, the cotton fabrics were ashed. Table 1 Example (detergent composition) % Ashes See 1 (A) 1.21 See 2 (B) 0.99 1 (C) 0.84

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• 1988
  • 1988-06-06 DE DE3819191A patent/DE3819191A1/de not_active Withdrawn
• 1989
  • 1989-05-29 US US07/623,947 patent/US5145599A/en not_active Expired - Fee Related
  • 1989-05-29 WO PCT/EP1989/000594 patent/WO1989012088A1/fr not_active Application Discontinuation
  • 1989-05-29 JP JP1505510A patent/JPH03504869A/ja active Pending
  • 1989-05-29 EP EP89906064A patent/EP0422020A1/fr active Pending
  • 1989-05-29 EP EP89109633A patent/EP0345587A1/fr not_active Withdrawn
  • 1989-05-29 KR KR1019900700237A patent/KR900701994A/ko not_active Application Discontinuation
• 1990
  • 1990-11-08 DK DK268290A patent/DK268290A/da not_active Application Discontinuation

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