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
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated

Definitions

• the present invention relates to a spray-dried layered silicate / sodium sulfate agglomerate which is suitable as a constituent of solid, free-flowing detergents and cleaning agents and, because of its porosity, is capable of absorbing additional liquid constituents of detergents and cleaning agents.
• n H2O stands for the water bound in the crystal phase.
• a structural formula as usually given in idealized form for clay minerals can only be established for the layered silicates according to the invention with additional assumptions.
• the chemical composition of the new compounds has more Na2O and SiO2 than the associated smectite saponite or hectorite.
• these layered silicates contain, in addition to the layered structure typical of mica-like compounds of this type, structural units of embedded sodium silicates.
• the crystallization of the layered silicates can presumably be understood as mixed crystal formation due to structural and synthetic aspects, in which sodium polysilicate is embedded in smectite. It can be seen from the X-ray diffraction diagrams that such embedding does not take place regularly, but leads to disorder in the crystallites.
• Crystallographic characterization using lattice constants that describe an elementary cell is therefore not possible.
• smectite in the sense mentioned, saponite and hectorite-like phases come into consideration due to the chosen chemical composition.
• the mixed crystal system should therefore have the structural formula [Na x + y (Mg 3-x Li x ) (Si 4-y Al y ) O10 (OH) 2].
• m [Na2Si z O 2z + 1 ].
• n H2O to be described the first part of the formula characterizing smectite and the second characterizing sodium polysilicate. Both components form a phase in which the smectite determines the structure.
• composition of the synthetic sheet silicates according to the invention which differs significantly from the pure smectites, and the associated disorder in the crystal composite leads to changes in a number of properties which are typical of sheet silicates per se, in particular with regard to the swellability and thus the gel formation properties, but also in the exchange capacity.
• layered silicates exert an incrustation-inhibiting effect in detergents which are usually composed. Unlike layered silicates of the smectite type, these synthetic layered silicates have no or no pronounced plasticizing ability. Because of its incrustation-inhibiting effect, this synthetic layered silicate, the production of which is described in the older European patent application mentioned, is a valuable component of modern washing and cleaning agents. This is all the more true since both the softening smectite clays and the alkali aluminosilicates of the zeolite A type described as a phosphate substitute are water-insoluble detergent components which, under certain conditions, can lead to tissue incrustation.
• Such tissue incrustations can be effectively suppressed with the synthetic layered silicates described in the earlier European patent application.
• the synthetic layered silicates are obtained in their production by the process described in the earlier European patent application mentioned as the aqueous suspension of a mixture of layered silicate and sodium sulfate.
• the sodium sulfate can be removed by washing out the filtered layered silicate Separate layered silicate;
• sodium sulfate itself is a detergent component present in most detergents, it is advisable to further process the layered silicate / sodium sulfate mixture together in the manufacture of detergents and cleaning agents.
• the further processing of the layered silicates containing sodium sulfate together with most of the other detergent components has already been described in the older European patent application mentioned; the disclosure content of this European patent application is therefore expressly part of the disclosure of the present patent application.
• the processing of the mixture of sodium sulfate and synthetic layered silicate to form layered silicate / sodium sulfate agglomerates and, if appropriate, their further processing into free-flowing detergents and cleaning agents is not yet known.
• the object that is achieved with the present invention is therefore to provide layered silicate / sodium sulfate agglomerate, in which the layered silicate is the synthetic layered silicate mentioned above.
• the solution to the problem consists in the provision of a porous layered silicate / sodium sulfate agglomerate, in which the layered silicate is a synthetic layered silicate with a smectite-like crystal phase, but with increased contents of bound alkali and silicate and with a significantly reduced swelling capacity in aqueous suspension and with the total oxide formula compared to pure smectites I. MgO .a M2O. b Al2O3. c SiO2.
• the ratio of synthetic layered silicate to sodium sulfate in the agglomerate according to the invention is not critical, but agglomerates with particularly valuable properties are obtained if the weight ratio of layered silicate to sodium sulfate is in the range from 3: 1 to 1: 3.
• the agglomerate according to the invention contains 0.5 to 15% by weight of water in addition to the water bound in the crystal phase, which, as stated above, contains 0.3 to 3 mol in the layered silicate of the total oxide formula I. , based on the total weight of the agglomerate.
• agglomerate of a layered silicate and sodium sulfate is known from German patent application DE 35 41 410 A1.
• the layered silicate of this patent application is a naturally occurring textile softening bentonite, as is known as a softening detergent component, for example from DE 23 34 899 A1.
• the agglomerate of the textile-softening sheet silicate and sodium sulfate is also described as a detergent component.
• the agglomerate according to the present invention has a significantly higher liquid absorption capacity than the agglomerate of DE 35 41 410 A 1.
• a further preferred embodiment of the present invention is therefore an agglomerate which has an additional in the pores Contains liquid component adsorbed in such quantities that the agglomerate is a free-flowing product that feels dry on the outside.
• the additional liquid component is expediently no further water, but rather a detergent or cleaning agent constituent which is liquid at room temperature or dissolved or dispersed in a liquid or liquefied by heating, in particular a nonionic surfactant.
• the agglomerate according to the invention absorbs, for example, 35% by weight or more of liquid nonionic surfactant, which is still a free-flowing agglomerate that feels dry on the outside.
• an agglomerate of sodium sulfate and layered silicate of the smectite type which has taken up 10% by weight of nonionic surfactant, is no longer free-flowing and feels moist.
• An agglomerate with an additional liquid component is therefore a further preferred subject of the present patent application, particularly if the agglomerate contains 2 to 50% by weight, based on the mixture of layered silicate and sodium sulfate, of adsorbed additional liquid component.
• the agglomerate according to the invention can be produced by any known technique for producing agglomerates, for example by granulating, by tableting, by compacting and in particular by spray drying.
• a homogenized suspension as obtained according to the earlier European Patent Application No. 86 / 109770.8, is sprayed in a spray tower with drying to a water content of 0.5 to 15% by weight, a product according to the invention being obtained, which can be used as such or after adsorption of one or more liquid detergent components as a detergent component.
• agglomerate as a component of solid, free-flowing detergents or cleaning agents is therefore also an object of the present invention, as are detergents containing such layered silicate / sodium sulfate agglomerates.
• the granules according to the invention can also be used, for example, as carriers for textile softeners, for possibly additional soil-improving carriers for fertilizers or Pesticides, or used as abrasives.
• detergents according to the invention contain customary surfactants, customary builders and other constituents customary in detergents.
• hydrophobic organic radical has at least one hydrophobic organic radical and one water-solubilizing anionic, zwitterionic or nonionic group in the molecule.
• the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 carbon atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 aliphatic carbon atoms.
• anionic surfactants such as Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids.
• Suitable synthetic anionic surfactants are those of the sulfonate, sulfate and synthetic carboxylate type.
• the surfactants of the sulfonate type are alkylbenzenesulfonates (C9- to C15-alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C12- to C18-monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
• alkylbenzenesulfonates C9- to C15-alkyl
• olefin sulfonates ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates
• alkanesulfonates which are obtainable from C12- to C18-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. B. the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, i.e. H. from fatty alcohols, such as. B. coco fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C10 to C20 oxo alcohols, and the 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 amino carboxylic acids or sulfonic acids, such as. B. 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, fatty acids, fatty amines, fatty acid amides or alkanesulfonamides 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, alkylene diamine polypropylene glycol and with alkyl polypropylene glycol with 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.
• the zwitterionic surfactants are preferably derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C8 to 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.
• the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a decrease can also be achieved by adding non-surfactant-like organic substances.
• a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. B. of sulfates and / or sulfonates with nonionic surfactants and / or with soaps.
• soaps foam attenuation increases with the degree of saturation and the number of carbon atoms in the fatty acid residue. Soaps of the saturated C 20-24 fatty acids are therefore particularly suitable as foam suppressants.
• the non-surfactant-like foam inhibitors are generally water-insoluble, mostly containing aliphatic C8 to C22 hydrocarbon compounds.
• Suitable non-surfactant foam inhibitors are e.g. the N-alkylamino triazines, d. H. Reaction products of 1 mole of cyanuric chloride with 2 to 3 moles of a mono- or dialkylamine with essentially 8 to 18 carbon atoms in the alkyl radical.
• propoxylated and / or butoxylated aminotriazines e.g. B.
• Suitable builders or builder substances are organic and inorganic, 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, are of particular importance in addition to the alkali ortho- and alkali pyrophosphates tung. All or part of these phosphates can be replaced by organic complexing agents for calcium ions.
• NTA nitrilotriacetic acid
• EDTA ethylenediaminetetraacetic acid
• Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids such as. B.
• methane diphosphonic acid dimethylaminomethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonoethane, 1,2-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.
• the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions are of particular importance.
• 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, for example biscarboxymethylethylene glycol, carboxymethyloxysuccinic acid, carboxymethyltartronic acid and carboxymethylated or oxidized polysaccharides.
• Polymeric carboxylic acids with a molecular weight of between 350 and 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, 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 vinyl methyl ether.
• the water is still suitable soluble salts of polyglyoxylic acid.
• Suitable water-insoluble inorganic builders are the finely divided, synthetic, bound water-containing sodium aluminosilicates of the zeolite Ak type described in DE-OS 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.e. H. they have practically no particles larger than 30 microns and preferably consist of at least 80% of particles smaller than 10 microns.
• Your calcium binding capacity which is determined according to the details of DE-OS 24 12 837, is in the range of 100-200 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 known 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 urea are also suitable as solubilizers.
• the washing and cleaning agents according to the present invention can contain dirt carriers which keep the dirt detached from the fiber 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, e.g. degraded starch, aldehyde starches, etc.
• Polyvinylpyrrolidone can also be used. In many cases, the addition of polyvinylpyrrolidone suppresses the undesired transfer of dyes that have been detached from heavily colored textiles to less strongly or undyed textiles.
• H2O2 sodium perborate tetrahydrate
• NaBO2. H2O2. 3 H2O sodium perborate tetrahydrate
• NaBO2. H2O2 monohydrate
• H2O2 supplying borates z. B. the Perborax Na2B4O7. 4 H2O2.
• 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 peroxyphthalate
• bleach components containing activator are preferably incorporated into the detergents.
• activators for water in H2O2 delivering compounds certain organic N-acyl or O-acyl compounds are used.
• Compounds which can be used include N-diacylated and N, Nac-tetraacylated amines, such as N, N, N ⁇ , N ⁇ -tetraacetyl-methylenediamine or -ethylenediamine, or the tetraacetylglycoluril.
• the detergents can additionally contain optical brighteners, for example for cotton or polyamide fibers.
• the suspension was then heated in a stirred autoclave to 190 ° C. in the course of 20 minutes and stirred at this temperature for 4 hours. After cooling to 100 ° C., the stirred autoclave was emptied and the layered silicate formed was filtered off from the mother liquor. The filter cake was washed with deionized water on the filter until no sulfate could be detected in the wash water. The filter cake was then dried in a forced-air drying cabinet at about 100 ° C.
• the X-ray diffraction pattern of the layered silicate shows broad reflections with maxima at d ( ⁇ ): 13.4; 4.5; 2.57 and 1.535.
• a nonionic surfactant consisting of a mixture of 80 parts of C 12/18 fatty alcohol + 5 moles of ethylene oxide and 20 parts of C 12/14 fatty alcohol + 3 moles of ethylene oxide, a product was obtained which felt dry on the outside and was easy to pour.
• Example 2 A different layered silicate batch than in Example 1, which contained 13.3% by weight of layered silicate of the type mentioned above, 14.2% by weight of sodium sulfate, the rest of water, was sprayed in the same manner as described in Example 1.
• a bright white, granular product was obtained with a residual water content of 7.0% by weight and a main sieve content of 81% by weight on a 0.2 mm sieve.
• the liter weight was 421 g. After spraying this product with 35% by weight of the nonionic surfactant from Example 1, again based on the weight of the spray product, a product which also felt dry on the outside and was free-flowing was obtained.
• a dark white, granular spray product was produced from a bentonite suspension with 13.3% by weight bentonite ("DIS THIX EXTRA", Schwegmann), 14.2% by weight sodium sulfate, the rest water. With a liter weight of 420 g, it had a main sieve content of 93% by weight on a 0.2 mm sieve. The residual water content was 9.9% by weight. While this spray product was free-flowing, a product sprayed with only 10% by weight of the previously described nonionic surfactant, again based on the weight of the spray product, clumped to form a mass consisting of coarse, moist particles which was no longer free-flowing.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
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• 1987
  • 1987-01-24 DE DE19873702111 patent/DE3702111A1/de not_active Withdrawn
• 1988
  • 1988-01-16 EP EP88100552A patent/EP0276705A3/fr not_active Withdrawn
  • 1988-01-21 NO NO880250A patent/NO880250L/no unknown
  • 1988-01-21 US US07/146,450 patent/US4861510A/en not_active Expired - Fee Related
  • 1988-01-22 DK DK029988A patent/DK29988A/da not_active Application Discontinuation
  • 1988-01-22 FI FI880274A patent/FI880274A/fi not_active IP Right Cessation
  • 1988-01-25 JP JP63015717A patent/JPS63195112A/ja active Pending

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