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

Definitions

• the present invention relates to a fabric softening detergent, containing customary surfactants, usual builders, fabric softening sheet silicate of the smectite type with an addition of incrustation-inhibiting synthetic sheet silicates.
• washed textiles In many cases it is necessary to give washed textiles a soft, full feel.
• One way to improve the above-mentioned comfort of the textiles is to treat the washed textiles with textile softening agents in the last rinsing bath after washing.
• textile softening agents are allowed to act on the washed textiles, so that the textiles feel soft when the cationic compounds are taken up after drying.
• Another way of achieving this effect is to allow the textile softening agents to act on the textiles during the subsequent drying of the washed laundry in an automatic clothes dryer.
• Both methods for softening textiles have in common that the softening active ingredients must be allowed to act on the textiles separately from the detergent after the actual washing process.
• the clay-like materials mentioned adhere to the fibers of the textiles and, due to their layer-like crystal structure, have a softening effect when used during the actual textile washing.
• Layered silicates of this type have therefore been used in textile softening detergents for some time.
• a disadvantage of these softening layered silicates is that they accumulate on the textiles and can therefore contribute to an additional incrustation of the washed textiles under some conditions.
• the object of the present invention was therefore to provide a textile-softening detergent containing customary surfactants and customary builders and textile-softening layered silicate of the smectite type with a reduced tendency to incrustation. It has now surprisingly been found that detergents of this type are obtained if they contain an additional content of incrustation-inhibiting synthetic phyllosilicates with a smectite-like crystal phase and with the total oxide formula I MgO. a M2O. b Al2O3. c SiO2.
• Incrustation-inhibiting synthetic layered silicates with the total oxide formula (I) have been proposed in the older European patent application number 86 / 109717.8 as a constituent of washing and cleaning agents. These layered silicates have a limited swelling capacity and make little or no contribution as a textile softener. It is therefore all the more surprising to find that detergents composed according to the invention, with unchanged washing performance, have better softness performance than detergents which contain only the same amount of textile-softening layered silicate of the smectite type. In order to achieve the same softness performance as the detergents according to the invention, the proportion of textile-softening layered silicates of the smectite type would have to be increased significantly in conventional detergents. The increase in the softness of the detergents composed according to the invention by the addition of synthetic layered silicate is surprising because the synthetic layered silicate practically does not soften itself.
• the synthetic sheet silicates to be used according to the invention together with the fabric softening sheet silicates of the smectite type are the sheet silicates with a smectite-like crystal structure described in the earlier European Patent Application No. 86 / 109717.8, but with a comparatively significantly reduced swelling capacity in water.
• These layered silicates are synthetic, finely divided, water-insoluble layered silicates with a smectite-like crystal phase, but increased contents of bound alkali and silicate and one in comparison to pure sheet silicates of this type, significantly reduced swelling capacity in aqueous suspension with the oxide sum formula MgO. a M2O. b Al2O3. c SiO2.
• n H2O stands for the water bound in the crystal phase.
• These finely divided clay minerals are to be understood as layered silicates with structural features of mica-like layered silicates, but with a disorder in the connection of adjacent layers.
• 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. It can be assumed that 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 an inclusion is not right occurs regularly, but leads to disorder in the crystallites. Crystallographic characterization using lattice constants that describe an elementary cell is therefore not possible. Suitable synthetic smectites in the sense mentioned are saponite and hectorite-like phases due to the chosen chemical composition. The mixed crystal system should therefore have the structural formula 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.
• composition of the synthetic phyllosilicates which clearly differs from the pure smectites, and the combination of these Related disorder in the crystal composite leads to changes in a number of properties typical of layered silicates, in particular with regard to the swellability and thus the gel formation properties, but also in the exchange capacity.
• 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. coconut 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.
• polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule that are not or not completely water-soluble are also of interest, in particular when used 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 reduction 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. from 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 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.
• the inorganic salts 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. All or part of these phosphates can be replaced by organic complexing agents for calcium ions.
• These include compounds of the aminopolycarboxylic acid type, such as nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid and higher homologs.
• 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.
• 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-soluble salts of polyglyoxylic acid are also suitable.
• Suitable water-insoluble inorganic builders are the finely divided, synthetic, bound water-containing sodium aluminosilicates of the zeolite A 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 noncapillary-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 high swelling capacity which goes back to the ability of the class of layered silicates concerned here to be able to incorporate water and / or organic, cationic compounds into the crystal lattice by widening the layer spacings, always plays a decisive role here.
• Swellable layered silicates and especially montmorillonite, hectorite and saponite are deposited in the sodium form on textile fibers in a thin layer and thus influence the softness and the feel of the washed textiles. Combining washing and softening of textiles in one process is one of the subjects of the aforementioned DE OS 23 34 899.
• the swellable smectites with softening properties described there are also used in the detergents according to the invention in the present patent application.
• Detergents with particularly valuable properties contain the synthetic smectite-like layered silicate of the formula I and the textile-softening smectite in a weight ratio of 4: 1 to 1: 6. Within this range, detergents with particularly balanced properties with regard to their washing performance and softness performance can be produced. To formulate detergents with both good softening performance and low tendency to incrustation.
• the two sheet silicates of the detergents according to the invention are present in an intimate mixture.
• Such an intimate mixture can be produced, for example, by forming a premix containing an incrustation-inhibiting layered silicate of the formula I and a textile-softening layered silicate of the smectite type, preferably in a weight ratio of 4: 1 to 1: 6 and optionally auxiliaries and additives.
• the auxiliaries and additives can be used to give the intimate mixture of the two layered silicates special properties, such as giving a certain grain strength or a high dispersibility in the wash liquor.
• Corresponding premixes can be produced by known mixing and processing methods such as granulation or spray drying.
• a detergent premix containing the two layered silicates and a detergent containing such a premix are therefore further objects of the present invention.
• Detergents according to the invention contain in particular 2 to 12% by weight incrustation-inhibiting sheet silicate of the formula I and 3 to 15% by weight textile-softening sheet silicate of the smectite type. Detergents with optimized properties can be produced within this framework.
• 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 replaced by other active oxygen carriers, in particular by peroxypyrophosphates, citrate perhydrates, urea / H2O2 or melamine / H2O2 compounds, and by H2O2-delivering peracid salts, such as caroates (KHSO5), perbenzoates or peroxyphthalates.
• bleach components containing activator are preferably incorporated into the detergents.
• Usable connections include N-diacylated and N, N ⁇ -tetraacylated amines, e.g. 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 detergents according to the invention can be present not only in particulate form, ie generally by spray drying, spray cooling or by granulation, but also in liquid or pasty form.
• Organic solvents for example lower alcohols, ether alcohols or ketones having 1 to 6 carbon atoms, are additionally used in the production of liquid or pasty forms.
• 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.
• the dry product contained layered silicate and Na sulfate in a weight ratio of 1: 1.
• Test fabrics were washed 25 times with a detergent D of the following composition and then the fabric ash was determined: 8.0% by weight of alkylbenzenesulfonate Na salt 1.5% by weight of C 12/18 fatty alcohol + 5 moles of ethylene oxide C 12/14 fatty alcohol + 3 moles of ethylene oxide in a ratio of 80:20 0.5% by weight tallow alcohol + 14 moles of ethylene oxide 2.4% by weight tallow alcohol + 5 moles of ethylene oxide 0.8% by weight of C 12/18 fatty acid Na salt 2.75% by weight water glass 3.5: 1 20.0% by weight Na perborate tetrahydrate 1.5 wt% TAED 25.0% by weight of zeolite A 0.8% by weight Na carbonate 0.75 wt% CMC / MC 0.3% by weight phosphonate 4.0% by weight of synthetic layered silicate from example 1 8.0% by weight of natural montmorillonite (DTE) ("Dis-Thix-Extra" (R) ) Balance Na sulfate, water
• detergents which contained A no layered silicate and B only DTE, and C only synthetic layered silicate according to Example 1.
• the detergents were produced by spray drying and the layered silicates were then mixed in.
• test fabrics for checking the softening and the primary washing performance were also washed at 60 ° C. in the soapy water washing process.
• the softening was checked by sensory testing of 5 trained people, the washing performance by measuring the remission.
• product D The product rated most favorably in terms of washing performance, softening effect and ash formation was product D according to the invention, while the product rated worst in all respects was product A containing no layered silicate.

Landscapes

• 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)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=6319466

Family Applications (1)

Country Status (7)

Families Citing this family (2)

Family Cites Families (6)

• 1987
  • 1987-01-24 DE DE19873702067 patent/DE3702067A1/de not_active Withdrawn
• 1988
  • 1988-01-16 EP EP88100553A patent/EP0276706A3/fr not_active Withdrawn
  • 1988-01-21 NO NO880248A patent/NO880248L/no unknown
  • 1988-01-22 DK DK030088A patent/DK30088A/da not_active Application Discontinuation
  • 1988-01-22 US US07/146,991 patent/US4839066A/en not_active Expired - Fee Related
  • 1988-01-22 FI FI880272A patent/FI880272A7/fi not_active IP Right Cessation
  • 1988-01-25 JP JP63015715A patent/JPS63193992A/ja active Pending

Also Published As

Similar Documents

Legal Events