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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2089—Ether acids-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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
• • 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

Definitions

• detergents containing synthetic, crystalline alkali alumosilicates are known which are suitable for completely or partially replacing the phosphate usually contained in detergents.
• the cation-exchanging aluminosilicates are advantageously used together with water-soluble complexing agents to improve and accelerate the washing process.
• Optimal results, in particular with regard to the secondary washing ability, are obtained if the proportion of polymer phosphate in the agents according to DE-AS 24 12 837 is above 15%, for example between 15 and 25%.
• problems can arise in hard water areas, since a lower phosphate content with frequently washed laundry can lead to an insufficient secondary washing effect, in particular to fiber incrustation.
• CMOS carboxymethyl oxysuccinate
• DE-OS 24 56 633 recommends the use of larger amounts of phosphate up to a ratio of CMOS to tripolyphosphate of 1: 1, which contradicts the aim of keeping the P content as low as possible.
• DE-AS 26 56 251 discloses detergents which contain both alkali alumosilicate and CMOS as framework salts and which, moreover, should preferably be phosphate-free.
• a comparative detergent is stated, which is said to have an improved whiteness and contains 17% alkali alumosilicates, 17% CMOS and 17.5% sodium tripolyphosphate (stated in% by weight).
• the P content of this mixture is undesirably high for the reasons mentioned, so that it is out of the question for the intended purpose.
• the inventors have set themselves the task of developing a framework substance mixture which can be used in detergents and cleaning agents and which, with the lowest possible phosphate content and in the absence of problematic complexing agents, has a favorable primary and in particular secondary washing power and thus avoids the disadvantages of the agents cited above.
• Another object of the invention is the use of the framework salt mixture defined above as a component of detergents and cleaning agents in proportions of 25 to 60 wt .-%, preferably in proportions of 30 to 50 wt .-%, with the proviso that the content of Detergent and cleaning agent on phosphate (component c) does not exceed 5% by weight. It was highly surprising that this comparative wise small amount of polyphosphate is completely sufficient for the desired goal, ie agents of the claimed composition not only have a high primary washing power, but also largely prevent the formation of tissue graying and incrustations even when used repeatedly.
• Suitable cation-exchanging alkali alumosilicates are in principle the crystalline products described in the above-mentioned DE-OS 24 12 837, which generally have particle sizes below 50 p, essentially below 40 p and mostly in the range from 20 to 0.1 show.
• crystalline sodium aluminosilicates of the composition 0.7-1.1 Na 2 O in the agents according to the invention.
• 1.3 - 2.4 SiO 2 which are also referred to as "zeolite NaA", and in particular those products of this composition and crystal structure, the manufacture of which has been ensured by suitable selection of the starting conditions that the resulting crystallites have rounded corners and edges and their particle size is below 30 pound and is at least 80% in the range of 8 to 0.01 ⁇ , and the average particle diameter is 3 to 6 ⁇ .
• Such aluminosilicates with rounded corners and edges are described in DE-OS 25 31 342. '
• both the calcium and the magnesium ions of the washing water are present - those which are generally present in a Ca: Mg ratio of about 5: 1 at average degrees of hardness are equally bound by the aluminosilicate.
• One per easy removal of calcium hardness and magnesium hardness is also achieved in artificially prepared hot wash liquors of 16 ° d and a ratio of calcium to magnesium ions of 1: 1.
• the Heinrich crystalline aluminosilicates may, for example, by reaction of water-soluble silicates with water-soluble aluminates in the "presence carried by water.
• aqueous solutions of the starting materials are mixed with each other or a present in a solid state component to the other, present as an aqueous solution component reacted
• the desired aluminosilicates are also obtained in the presence of water by mixing the two components present in the solid state, and aluminosilicates can also be prepared from Al (OH) 3 , Al 2 O 3 or Si0 2 by reaction with alkali silicate or aluminate solutions .
• Preferred aluminosilicates have a calcium binding capacity which is approximately in the range from 100 to 200 mg CaO / g AS, usually around 100 to 180 mg CaO / g AS; this is found above all in compounds of the composition 0.7 to 1.1 Na 2 O. Al 2 O 3 . 1.3 - 3.3 Sio 2 .
• This empirical formula comprises two types of different crystal structures, which also differ in their empirical formulas. They are:
• the alumosilicates which are initially still water-moist from their manufacture and which can be present as aqueous suspensions or moist filter cakes, can be converted into dry powders in the usual way by first removing part of the water mechanically and then drying them, for example at temperatures of 50-400 C. Depending on the drying conditions, the powder product contains 5-35% by weight of bound water. Expediently, drying does not exceed 200 ° C if the aluminosilicate is intended for use in detergents and cleaning agents. Drying can be saved if you use it according to the teaching of DE-OS 25 27 388 certain dispersants and water are converted into a stable suspension and used for further processing to form the framework salt mixtures according to the invention or detergents containing them. In addition to saving energy by eliminating the drying stage, this processing mode practically completely prevents agglomeration of the primary particles into undesirable larger particles (secondary particles), as is observed in conventional drying and therefore requires grinding and sieving measures.
• the aluminosilicates are expediently used in the preparation in the state in which they are still moist, for example as aqueous suspensions or as moist filter cakes, firstly, if appropriate with the addition of further water and a dispersant, in stable pumpable suspensions containing the Alumosilicate of 25 - 40 wt .-% - based on the anhydrous substance - and a content of 0.3 - 4 wt .-% of the dispersant transferred.
• Compounds which are themselves effective detergent constituents are suitable as dispersants, for example ethoxylated aliphatic C 10 -C 20 alcohols with an average degree of ethoxylation of 2-7 mol EO.
• ethoxylated alcohols such as tallow alcohol + 5 moles of ethylene oxide or fatty acid ethanolamides such as lauric acid monoethanolamide as dispersants
• ethoxylated adducts of epoxyalkanes and low molecular weight amines are also suitable as dispersants for aluminosilicate suspensions.
• the suspensions produced by mixing aluminosilicate, water and dispersant are notable for their high stability; they let themselves be Store at room temperature or at higher temperatures, transport them through pipelines, in tankers or in some other way before they are processed further into the agents according to the invention.
• aluminosilicates in the form of a varying amount of bound water-containing powder, optionally together with the other skeleton salts or also together with sodium perborate, as a solid carrier for liquid or viscous detergent components, for example nonionic surfactants , starts.
• These compounds are converted into free-flowing premixes by spraying their solutions or their melts onto the solid supports, which are then mixed in a conventional manner with the other powdery constituents of the detergent.
• Such premixes and their preparation are described in more detail in DE-OS 25 07 926.
• the calcium binding capacity for the aluminosilicate is calculated from this (30 - x). 10 mg .CaO / g AS.
• the particle sizes of the aluminosilicates can e.g. determine by means of sedimentation analysis.
• the aluminosilicate can be combined with the other skeletal salts and possibly further detergent components by simply mixing the powdery or granular individual components or premixes containing several components - preferably with simultaneous granulation - or by combining the individual components to form an aqueous, paste-like batch with subsequent spray drying.
• these agents can contain customary anionic, nonionic or zwitterionic surfactants, washing alkalis, detergent-enhancing additives, graying inhibitors, bleaching agents, optical brighteners, stabilizers and other auxiliaries and additives commonly used in such detergents .
• Suitable anionic surfactants are those of the sulfonate, sulfate and carboxylate type which have at least one hydrophobic hydrocarbon residue and one water-solubilizing anionic, amphoteric or zwitterionic or nonionic group in the molecule.
• Aliphatic hydrocarbon radicals are preferably straight-chain and contain 10 to 22, in particular 12 to 18, carbon atoms, alkylaromatic radicals having 8 to 16, preferably 9 to 12, carbon atoms in the linear aliphatic radical.
• Suitable surfactants of the sulfonate type are alkylbenzenesulfonates with C 9-15 -alkyl groups and the alkanesulfonates which are obtainable from C 12 -C 18 -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
• esters of a-sulfo fatty acids for example the a-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and also the olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates as made from them Monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• 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 fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
• fatty alcohols such as, for example, coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 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 1-6 mol ethylene oxide are also suitable.
• Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
• Suitable carboxylates are soaps, for example those of coconut or tallow fatty acids or of foam-suppressing, behenic acid-containing mixtures, and also ether carboxylic acids, such as the salts of carboxymethyl (C 10 -C 18 ) alkyl ethers.
• 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.
• the nonionic surfactants suitable according to the invention are the adducts of 2 to 20, preferably 3 to 15, moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols and carboxylic acids.
• examples of this are the adducts of 8 to 20 moles of ethylene oxide with primary alcohols, e.g. on coconut oil or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols of the corresponding chain lengths, or on corresponding secondary alcohols, and on mono- or dialkylphenols with 6 to 14 C atoms in the alkyl radicals.
• 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.
• the ethoxylation products of primary aliphatic: alkanols and alkenols are of particular practical interest because of their good biodegradability.
• EO ethylene oxide
• tallow fatty alcohol 5-EO oleyl / cetyl alcohol 5-EO (iodine number 30-50 )
• Tallow fatty alcohol 7-EO synthetic C12-C16 fatty alcohol 6-EO, C 11 -C 15 oxo alcohol 3-EO, C 14 / C 15
• Exemplary representatives of the nonionic surfactants with an average degree of ethoxylation of 8 to 20, in particular 9 to 15, are the compounds coconut fatty alcohol-12-EO, synthetic C 12 / C 14 fatty alcohol-9-EO, oleyl / cetyl alcohol-10 -EO, tallow fatty alcohol-14-EO, C 11 -C 15 -oxoalcohol-13-EO, C 15 -C 18 -oxoalcohol-15-EO, iC 15 -C 17 -alkanediol-9-EO, C 14 / C 15 -Oxoalcohol-11-EO, sec.-C 11 -C 15 -Alcohol-9-EO.
• 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.
• amphoteric surfactants are compounds which contain both an anionic and a cationic group in the same molecule. Suitable compounds are the derivatives of aliphatic C 8 -C 18 amines with a water-solubilizing group, such as the carboxy, sulfo or sulfato group. Typical representatives of the amphoteric surfactants are the sodium salts of 2-dodecylaminopropionic acid and 3-dodecylaminopropanesulfonic acid and similar compounds, such as sulfated imidazoline derivatives.
• Derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C 8 -C 18 radical and another contains an anionic water-solubilizing carboxy, sulfo or sulfato group are preferred as zwitterionic surfactants.
• Typical Representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylaminonio) 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-dihydro: ypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.
• the carbonates, bicarbonates and silicates of potassium and in particular sodium are suitable as washing alkalis, and in the case of sodium silicates the ratio Na 2 O: SiO 2 can vary between 1: 1 and 1: 3.5.
• the amount of washing alkalis is chosen so that the pH of the solution is between 8.5 and 13, preferably 9.5 and 11.5.
• bleaching agents come e.g. Perhydrates such as perborate, percarbonate, perpyrophosphate, persilicate and urea perhydrate are possible, sodium perborate tetrahydrate being used with preference.
• Agents to be used at low washing temperatures can additionally contain known bleach activators, for example tetraacetylethylene diamine or tetraacetylglycoluril. Active chlorine compounds, in particular potassium or sodium dichloroisocyanurates, are also suitable.
• the bleach activators or active chlorine compounds can be embedded in water-soluble coating substances or melting substances at the washing temperatures envisaged.
• the detergents can contain, as optical brighteners for cotton, in particular 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 the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
• Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and compounds of the same structure, which instead of the sulfamoyl group such as carrying the methoxycarbonyl, 2-methoxyethoxycarbonyl, the Acet y lamino- or the vinylsulfonyl group.
• Useful polyamide brighteners are also the substituted aminocoumarins, for example 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin.
• the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril are also useful as polyamide brighteners.
• the brighteners for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene and 1,2-di- ( 5-methyl-2-benzoxazolyl) ethylene suitable.
• Brighteners of the substituted 4,4'-distyryldiphenyl 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 preparations may also contain graying inhibitors, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
• graying inhibitors are suitable for this, 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 the cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups and polyvinylpyrrolidone are also suitable for this purpose.
• Carboxymethylated cellulose is preferably used in the form of its sodium salts.
• Suitable cellulose ethers are methyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and methyl carboxymethyl cellulose, the latter in the form of the sodium salt,
• auxiliaries and additives are neutral salts, especially sodium sulfate, enzymes, especially bacterial proteases, foam inhibitors, such as e.g. Silicone defoamers, grip-improving agents, biocides as well as colors and fragrances.
• the skeleton salt mixture according to the invention and the detergents and cleaning agents containing this mixture are not only distinguished by a low and therefore environmentally friendly phosphate content and a low or no content of organic N- or P-containing complexing agents, but have a highly effective despite these small amounts
• Builder salts have a high dirt dissolving power (primary washing power) as well as a high secondary washing power largely precluding the formation of tissue incrustations and tissue graying, which is on a par with the conventional detergent containing high amounts of phosphate.
• the detergent used for the experiments had the following composition (in% by weight):
• Precipitation batch 2.985 kg aluminate solution of the composition: 17.7% Na 2 0, 15, 8% Al 2 O 3 , 6 6 , 5% H 2 O; 0.150 kg of caustic soda, 9.420 kg of water and 2.445 kg of a 25.8% solution of a sodium silicate of the composition 1 Na 2 O. 6 Sio 2 ; freshly prepared from commercially available water glass and slightly alkali-soluble silica; Precipitation: Suspension of the amorphous precipitate was 10 min. stirred with an intensive stirrer (10,000 rpm); Crystallization: 6 hours at 90 ° C; Drying: 24 hours at 100 ° C; Composition: 0.9 Na 2 0. 1 Al 2 O 3 . 2.04 SiO 2 .
• TPP Tripolyphosphate
• CMOS CMOS
• Table I The composition of the framework salt mixture or of the comparison mixtures can be found in Table I. Two percentages are given in the table for each component, the first number relating to the proportion of the compound in the detergent, the second number (in parentheses) relating to the proportion of the compound in the skeleton salt mixture.
• 2 - 3 g of the textile sample are left in a climatic chamber for 12 hours after thorough loosening (by defibrating), weighed, treated with a 5% aqueous EDTA solution for 30 minutes at boiling temperature, rinsed three times with distilled water, dried, Air-conditioned for 12 hours and then weighed back.

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• 1978
  • 1978-12-02 DE DE19782852285 patent/DE2852285A1/de not_active Withdrawn
• 1979
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