EP0011846B1 - Agent de lavage et de nettoyage, contenant un mélange de sels d'adjuvants ayant une faible teneur en phosphates - Google Patents

Agent de lavage et de nettoyage, contenant un mélange de sels d'adjuvants ayant une faible teneur en phosphates Download PDF

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Publication number
EP0011846B1
EP0011846B1 EP79104696A EP79104696A EP0011846B1 EP 0011846 B1 EP0011846 B1 EP 0011846B1 EP 79104696 A EP79104696 A EP 79104696A EP 79104696 A EP79104696 A EP 79104696A EP 0011846 B1 EP0011846 B1 EP 0011846B1
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EP
European Patent Office
Prior art keywords
washing
weight
salt mixture
sodium
builder salt
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79104696A
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German (de)
English (en)
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EP0011846A1 (fr
Inventor
Klaus Dr. Hachmann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0011846A1 publication Critical patent/EP0011846A1/fr
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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 2 412 837 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 2 456 633 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-OS 2 656 251 discloses detergents which contain both alkali alumosilicate and CMOS as framework salts and which, moreover, should preferably be phosphate-free.
  • Example 1 of this DE-OS describes a detergent which contains 17% alkali alumosilicate, 17% sodium CMOS and 35% sodium sulfate.
  • the whiteness of this mixture is further improved if one half of the sodium sulfate, i. H. 17.5%, replaced by sodium tripolyphosphate, if permitted by law.
  • the reservation of legal admissibility already shows that a phosphate content of 17.5% is regarded as critical, namely when the demand is made for low-phosphate agents.
  • This problem consists in developing a detergent which, on the one hand a satisfactory, d. H. has a secondary washing capacity comparable to that of a relatively phosphate-rich detergent, the phosphate content of which, on the other hand, is set so low that there is no longer any significant environmental impact.
  • the proportion of organic builder substance which also leads to wastewater pollution due to the oxygen requirement in biodegradation, should not be increased, but rather should be reduced compared to the agents known from DE-OS 2 656 251.
  • Suitable cation-exchanging alkali alumosilicates are in principle the crystalline products described in the above-mentioned DE-OS 2412837, which generally have particle sizes below 50 ⁇ , essentially below 40 ⁇ and mostly in the range from 20 to 0.1 ⁇ .
  • both the calcium and the magnesium ions of the washing water - which are generally present in the Ca: Mg ratio in a ratio of about 5: 1 at average degrees of hardness - equally bound by the aluminosilicate. Trouble-free 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 production of the crystalline aluminosilicates can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water.
  • aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
  • the desired aluminosilicates are also obtained by mixing the two components present in the solid state in the presence of water.
  • Alosilicate can also be produced from Al (OH) 3 , Al 2 O 3 or SiO 2 by reaction with alkali silicate or aluminate solutions.
  • the aluminosilicates which are initially still moist from their production 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 some of the water mechanically and then drying it, e.g. B. 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, according to the teaching of DE-OS 2 527 388, it is converted into a stable suspension with a certain dispersing agent and water and used for further processing to form the framework salt mixtures according to the invention or detergents containing them.
  • 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 Alumosilikats of 25 - 40 wt .-% - based on the anhydrous substance - and a content of 0.3-4 wt .-% transferred to the dispersant.
  • 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 B. tallow alcohol + 5 moles of ethylene oxide or fatty acid ethanolamides such.
  • B. lauric acid monoethanolamide as a dispersant are described in DE-OS 2527388 in more detail.
  • 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 can be stored at room temperature or at higher temperatures, transported through pipelines, in tankers or in some other way before they are processed further into the agents according to the invention.
  • a further variant for the preparation of the agents according to the invention consists in that the aluminosilicates are in the form of a powder containing varying amounts of bound water, 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 , begins. 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 2 507 926.
  • the residual hardness x of the filtrate is determined. From this, the calcium binding capacity for the aluminosilicate is calculated to be (30 - x) - 10 mg CaO / g AS.
  • the particle sizes of the aluminosilicates can e.g. B. determine by means of sedimentation analysis.
  • the aluminosilicate can be combined with the other skeletal salts and, if appropriate, further detergent constituents by simply mixing the powdery or granular individual constituents or premixes containing several components, preferably with simultaneous granulation, or by Combine the individual components into an aqueous, paste-like batch with subsequent spray drying.
  • the skeleton salt mixture according to the invention is also used in detergents and cleaning agents, the usual anionic, nonionic or zwitterionic surfactants, washing alkalis, detergent additives, graying inhibitors, bleaching agents, optical brighteners, stabilizers and other auxiliaries and additives commonly used in such agents can be used in these agents .
  • 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 10-22, in particular 12-18, carbon atoms, alkylaromatic radicals with 8-16, preferably 9-12, carbon atoms in the linear aliphatic radical.
  • Suitable surfactants of the sulfonate type alkylbenzenesulfonates with C 5-15 alkyl groups and the alkane sulfonates obtained from C 12-18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition onto olefins are available, into consideration.
  • Other useful surfactants of the sulfonate type are the esters of ⁇ -sulfofatty acids, e.g. B.
  • the cx-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids and the olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates as obtained from 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. B. 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 include the adducts of 8 to 20 moles of ethylene oxide with primary alcohols, such as. B. on coconut 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 carbon atoms in the alkyl radicals.
  • 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. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols and alkenols are of particular practical interest.
  • EO ethylene oxide
  • tallow fatty alcohol 5-EO oleyl / cetyl alcohol 5-EO (iodine number 30-50 )
  • Tallow fatty alcohol 7-EO synthetic C 12 -C 16 fatty alcohol 6-E0, C 11 -C 15 oxo alcohol
  • 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. B. 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. B. sulfated imidazoline derivatives.
  • Suitable washing alkalis are the carbonates, bicarbonates and silicates of potassium and in particular sodium, the ratio of Na 2 0: Si0 2 in the case of sodium silicates varying 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.
  • bleach come, for. B. perhydrates, such as perborate, percarbonate, perpyrophosphate, persilicate and urea perhydrate in question, sodium perborate tetrahydrate is preferably used.
  • Agents to be used at low washing temperatures can additionally contain known identical 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. Are suitable for.
  • Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and compounds of the same structure which instead of the sulfamoyl group z.
  • B. carry the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group.
  • Useful polyamide brighteners are also the substituted aminocoumarins, e.g. B. the 4-methyl-7-dimethylamino or the 4-methyl-7-diethylaminocoumarin.
  • the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can also be used as polyamide brighteners.
  • the brighteners for polyester and polyamide fibers are 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; e.g. B. 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 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 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.
  • 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 tests had the following composition (in% by weight): An aluminosilicate obtained according to the following manufacturing instructions was used.
  • 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.
  • the degree of whiteness determined by photometry is a measure of that Primary washing power, whereby the whitenesses listed in Table II represent mean values for all 3 textile types from 3 parallel tests each.
  • comparative tests A to L primary washing tests were not carried out, since the primary concern here is the demonstration of the insufficient secondary washing power and, in contrast, the likewise reduced primary washing power does not play a role.

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  • Chemical & Material Sciences (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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (3)

1. Agent de lavage et de nettoyage contenant 25 à 60% en poids d'un mélange salin adjuvant pauvre en phosphate, lequel mélange est constitué de
a) 45 à 75% en poids d'un alum(in)o silicate alcalin insoluble dans l'eau, finement divisé, préparé par voie de synthèse, cristallin et contenant de l'eau liée, de formule
0,7―1,5 Me2O · Al2O3 · 1,3―4,0 SiO2

(par rapport à la substance active exempte d'eau SA), qui possède un pouvoir de fixation de calcium de 50 à 200, de préférence 100 à 200 mg de CaO/g SA, Me signifiant sodium ou potassium,
b) 15 à 40% en Poids de carboxyméthyloxysuccinate de sodium ou de potassium
c) du tripolyphosphate de métal alcalin, caractérisé en ce que la teneur de l'agent de lavage et de nettoyage en tripolyphosphate de sodium et/ou de potassium ne dépasse pas 5% en poids et la teneur du mélange salin adjuvant se monte à 5 à 15% en poids en tripolyphosphate de sodium ou de potassium (par rapport au sel anhydre).
2. Agent de lavage et de nettoyage contenant un mélange salin adjuvant selon la revendication 1, caractérisé en ce que le mélange salin adjuvant contient à côté du constituant a) encore
20 à 30% en poids du constituant b)
8 à 15% en poids du constituant c)

chaquefois sous forme de sel sodique.
3. Agent selon les revendications 1 et 2, caractérisé en ce que sa teneur en mélange salin adjuvant se monte à 30 à 50% en poids.
EP79104696A 1978-12-02 1979-11-26 Agent de lavage et de nettoyage, contenant un mélange de sels d'adjuvants ayant une faible teneur en phosphates Expired EP0011846B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782852285 DE2852285A1 (de) 1978-12-02 1978-12-02 Phosphatarmes geruestsalzgemisch und dessen verwendung in wasch- und reinigungsmitteln
DE2852285 1978-12-02

Publications (2)

Publication Number Publication Date
EP0011846A1 EP0011846A1 (fr) 1980-06-11
EP0011846B1 true EP0011846B1 (fr) 1983-05-04

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ID=6056211

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79104696A Expired EP0011846B1 (fr) 1978-12-02 1979-11-26 Agent de lavage et de nettoyage, contenant un mélange de sels d'adjuvants ayant une faible teneur en phosphates

Country Status (4)

Country Link
US (1) US4392974A (fr)
EP (1) EP0011846B1 (fr)
JP (1) JPS5578099A (fr)
DE (2) DE2852285A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1124027B (it) * 1979-03-23 1986-05-07 Mira Lanza Spa Composizione detersiva a basso o nullo tenore di fosforo
IT1180819B (it) * 1984-09-12 1987-09-23 Mira Lanza Spa Metodo di neutralizzazione della zeolite a mediante trattamento con a cidi forti del panello di filtrazione addizionato con un fludificante
GB8504489D0 (en) * 1985-02-21 1985-03-27 Monsanto Europe Sa Aminomethylenephosphonate compositions
EP1045022A1 (fr) * 1999-04-15 2000-10-18 Greither, Peter Utilisation de gélatine en agent de lavage

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2656251A1 (de) * 1975-12-15 1977-06-16 Colgate Palmolive Co Waschmittel

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692685A (en) * 1968-05-24 1972-09-19 Lever Brothers Ltd Detergent compositions
AT330930B (de) * 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
US3990983A (en) * 1973-12-03 1976-11-09 Lever Brothers Company Builder compositions
US3965169A (en) * 1974-02-25 1976-06-22 Monsanto Company Crystalline trisodium carboxymethyloxysuccinate monohydrate
AT373276B (de) * 1974-02-25 1984-01-10 Henkel Kgaa Nichtionische tenside enthaltende schuettfaehige wasch- und reinigungsmittel
US4007124A (en) * 1975-02-14 1977-02-08 The Procter & Gamble Company Process for preparing a silicate-pyrophosphate detergent composition
DE2714604C3 (de) * 1977-04-01 1985-04-25 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Granulat auf Basis von polymerem Phosphat und ionenaustauschendem Alkalialumosilikat

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2656251A1 (de) * 1975-12-15 1977-06-16 Colgate Palmolive Co Waschmittel

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Publication number Publication date
DE2965326D1 (en) 1983-06-09
JPS5578099A (en) 1980-06-12
DE2852285A1 (de) 1980-06-12
US4392974A (en) 1983-07-12
EP0011846A1 (fr) 1980-06-11

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