EP0010247B1 - Produit pour le lavage sans phosphates et procédé pour sa fabrication - Google Patents

Produit pour le lavage sans phosphates et procédé pour sa fabrication Download PDF

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Publication number
EP0010247B1
EP0010247B1 EP79103848A EP79103848A EP0010247B1 EP 0010247 B1 EP0010247 B1 EP 0010247B1 EP 79103848 A EP79103848 A EP 79103848A EP 79103848 A EP79103848 A EP 79103848A EP 0010247 B1 EP0010247 B1 EP 0010247B1
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EP
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Prior art keywords
powder
weight
water
detergent
component
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EP79103848A
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German (de)
English (en)
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EP0010247A1 (fr
Inventor
Markus Dr. Berg
Jochen Dr. Kaufmann
Dieter Dr. Jung
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE19782844455 external-priority patent/DE2844455A1/de
Priority claimed from DE19792908305 external-priority patent/DE2908305A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT79103848T priority Critical patent/ATE2848T1/de
Publication of EP0010247A1 publication Critical patent/EP0010247A1/fr
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    • 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
    • C11D3/08—Silicates
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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

  • the invention relates to a powdered laundry detergent which contains large amounts of water-insoluble, finely divided alkali metal alumosilicate cation exchangers and small amounts of certain water-soluble organic complexing agents, and an alkali silicate.
  • the invention also relates to a method for producing this powdery agent.
  • German Offenlegungsschrift 2540510 describes a detergent for cold and 60 ° C washing, which essentially contains 5-20% by weight of a cation-exchanging aluminosilicate, 4-12% by weight of a surfactant component made from paraffin sulfonate and olefin sulfonate and 12-30% by weight .-% of a sodium silicate of the composition Na 2 O ⁇ 1.6-2.8 Si0 2 , and preferably no soluble complexing agents, especially no detergent phosphates.
  • this detergent has an unsatisfactory primary and secondary washing ability at all washing temperatures. The properties of this detergent cannot be significantly improved either by adding an active oxygen compound and when used under the conditions of the hot wash.
  • German Offenlegungsschrift 2656009 which contains a phosphate-free detergent containing 12-25% by weight of a water-insoluble aluminosilicate zeolite, in particular of type 4A, 12-25% by weight sodium perborate or - leads to a similar result.
  • percarbonate 5-20% by weight of a sodium silicate of the composition Na 2 O. 1 -3.2 Si0 2
  • 5-25% by weight of a conventional alkylbenzenesulfonate surfactant According to the information in this reference, undesired deposits of the water-insoluble zeolite particles on the laundry are to be prevented by a detergent with this combination.
  • phosphorus-free organic and inorganic builders such as.
  • alkali carbonate, borax, sodium nitrilotriacetate, sodium citrate, etc. may be present.
  • a further phosphate-free textile detergent based on the finely divided water-insoluble aluminum silicate cation exchangers, as well as the so-called washing alkalis, in particular the alkali carbonates and the alkali silicates, the latter in amounts of at least 3% by weight as a conventional water glass, is more organic from German Offenlegungsschrift 2 547 389 Complexing salts from the group of alkali metal salts of phosphorus-free polymeric polycarboxylic acids and phcphonic acids, and a surfactant component consisting of nonionic surfactants and optionally anionic surfactants are known.
  • This detergent contains 0.1-2 parts by weight of the organic complexing agent per 1 part by weight of the water-insoluble aluminosilicate, based on the anhydrous compound.
  • Comparable washing results should also be obtained if, instead of the sodium triphosphate, other builder substances, such as.
  • other builder substances such as.
  • sodium pyrophosphate or sodium nitrifotriacetate specific polyphosphonates, such as. B. the alkali salts of ethane-1-hydroxy-1,1-diphosphonic acid or ethane-1,1,2-triphosphonic acid, or polyacetates, such as. B. sodium ethylenediaminetetraacetate and sodium nitrilotriacetate, carboxylates such as. 8. the alkali citrates, polycarboxylates, such as. B. polymeric compounds based on maleic acid, and inorganic salts such as alkali carbonates and bicarbonates, in amounts of 5-50, preferably 10-55 wt .-%, based on the total detergent, are used.
  • detergents containing water-insoluble aluminosilicate cation exchangers and alkali pyrophosphate are known as soluble framework substances. These agents contain an alkali silicate of the composition M 2 O.1.6-4 SiO 2 (M stands for sodium or potassium), which has been converted into a polymer with certain poorly soluble properties by dehydration. This measure ensures that when the wash liquor is prepared, the pyrophosphate first reacts with the hardness constituents of the water and this precipitates before the silicate polymer is split into a more soluble product by rehydration.
  • the polymeric, sparingly soluble alkali silicate can be contained in the known detergents in amounts of 1-30% by weight, the water-insoluble aluminosilicate in amounts of 1-40% by weight.
  • German Offenlegungsschrift 2711 375 describes a powder detergent which contains no tripolyphosphate and pyrophosphate builders.
  • this agent can contain 5-50% by weight of a water-insoluble aluminosilicate cation exchanger in combination with 4-40% by weight of a magnesium ion-insensitive surfactant and larger amounts (approximately 13-40% by weight) of a readily soluble alkali silicate Composition M 2 O ⁇ 1.4-2.7 SiO 2 (where M means sodium or potassium).
  • M means sodium or potassium
  • the magnesium ions in the wash solution are to be bound with this alkali silicate, which is used in larger quantities.
  • the constituents are mixed in an aqueous batch and preferably spray-dried.
  • the detergent of Example 1 of DE-OS 2 711 375 is produced in two parts.
  • compositions of this earlier patent application can additionally contain customary water-soluble sodium silicates of the composition Na 2 O.1-3.5 SiO 2 , in particular of the composition Na 2, in amounts of up to 7% by weight, preferably in amounts of 2-5% by weight O: SiO 2 as 1: 2 to 1: 3.35, as a corrosion inhibitor.
  • the alkali silicates and, in particular, the sodium silicates thereof perform a number of functions as detergent constituents.
  • the most important properties of alkali silicates include their effect as alkali carriers and buffer substances, the promotion of dirt detachment by means of the same electrostatic charge on the surfaces of the fibers and the dirt particles, the ability to emulsify and disperse the dirt, and the ability to trace heavy metals, especially iron and manganese to be removed from the wash water and thus to stabilize the perborate present, but also to bind the hardness formers of the water to a certain extent.
  • Another chemical property of great importance when using modern detergents is the effect of the alkali silicates as corrosion inhibitors on the metal parts of the washing machines.
  • Another important property of the alkali silicates in the production of detergent powders by the process of hot spray drying is the positive influence on the strength of the resulting hollow spherical particles.
  • the aim of the present invention is to further develop the use of the 'cation exchanging alkali metal alumosilicates in detergent compositions and to completely dispense with the usual detergent phosphates.
  • a particular object of the present invention is to have the small amounts of alkali silicate required for corrosion inhibition present in the powder detergent in such a form that even when these agents are used under very critical washing conditions, residues such as those described below are found on the washed textiles of the prior art literature discussed above are not to be feared.
  • the teachings of the prior art which deal with the incorporation and functioning of alkali metal silicate in detergents containing aluminosilicate, could not provide any useful suggestions.
  • the phosphate-free detergent which is the subject of the older German patent application P 2 814 083.2.
  • P 2 814 083.2 To develop so that it not only has a good primary and secondary washing power, a good bleaching action and excellent fabric-protecting properties, but also in terms of residue formation is not inferior to the usual phosphate-containing detergents, which consist practically exclusively of water-soluble components.
  • the sodium silicate powder according to (iii) generally has a bulk density of 350-800 g / l, preferably 350 to 450 g / l and in particular approximately 400 g / l, its particle size distribution is in the range from 1 mm to 0.05 mm, wherein at least 80% of the particles are smaller than 0.5 mm.
  • Such readily water-soluble sodium silicate powder can be produced by spray drying or roller drying an aqueous 35-50% solution at a temperature of 100 to 120 ° C. in spray drying and 100 to 140 ° C. in roller drying.
  • Particularly preferred detergents contain a roller-dried sodium silicate, which has been prepared by drying a 40 to 50% strength aqueous solution on a heated roller at 100 to 140 ° C. to a residual water content of 15-23, in particular 18 to 21,% by weight .
  • Such a product is adjusted to a bulk density of 350-450 g / l, in particular about 400 g / l. It owns excellent solubility properties, so that after the solubility test given above it is already at least 99% dissolved in cold water at 20 ° C after 3 minutes.
  • a product with these properties is commercially available under the name Portil AW.
  • organic complexing agents from the group of substituted alkanedi- and triphosphonic acids - which also include heterocyclically substituted compounds - include in particular those alkanedi- and triphosphonic acids or their alkali and Erdafkalisalze, whose alkane group by the hydroxyl, amino, phenyl or is substituted by a phenyl group carrying hydroxyl, amino or halogen groups.
  • the alkane and triphosphonates from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 3-amino-1-hydroxypropane-1,1-diphosphonic acid, 1-amino are particularly preferred -1-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1-hydroxybutane-1 , 1-diphosphonic acid and aminotrimethylene triphosphonic acid in the form of their alkali metal salts, in particular the sodium salts.
  • the sodium and calcium salts of 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxybutane 1,1-diphosphonic acid and aminotrimethylene triphosphonic acid are particularly preferred.
  • the detergent in powder component A) preferably contains conventional optical brighteners in the usual amounts.
  • both the calcium and the mugneslumions of the washing water - which are generally present in the Ca: Mg ratio in the ratio Ca: Mg such as about 5: 1 - by the way Alumosilicate bound.
  • 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 detergents according to the invention which contain a surfactant component according to (ba), show an excellent foam regulation during the entire boil washing program and when rinsing out the washing liquor, particularly when used in drum washing machines.
  • Detergents containing mixtures of the surfactant components (ba) and (bb) are also preferred. Preference is also given to detergents whose surfactant content consists of a mixture of the surfactant component (ba) and a surfactant type (bb3), ie. H. Compounds of the formula I exist, the surfactant type (bb3) being able to make up 5-25% by weight of the surfactant mixture and preferably consisting of coconut fatty acid monoethanolamide.
  • the anionic surfactants of the sulfonate and / or sulfate type of the surfactant component (ba) preferably consist of alkylbenzenesulfonates and / or of alkanesulfonates.
  • the use of wash-active alkanesulfonates in the context of this surfactant component is particularly preferred in view of their rapid and complete biodegradation in the waste water and because of their low toxicity.
  • the foam security during washing and rinsing is also ensured if the stated amounts of alkylbenzenesulfonate and / or ' alkanesulfonate up to a third of their amount due to the more foaming anionic Surfactants of the ⁇ -sulfofatty acid ester, olefin sulfonate, fatty alcohol sulfate and fatty alcohol polyglycol ether sulfate type, which also have good biodegradability and low toxicity, are replaced.
  • the nonionic surfactants contained in the combinations (ba) and (bb) from the group of ethoxylated aliphatic C 10 -C 20 alcohols with a degree of ethoxylation of 2-20 preferably consist of binary mixtures of separately produced ethylene oxide addition products with average degrees of ethoxylation on the one hand of 2-7 and on the other hand from 8-20 mol EO and a ratio of the low ethoxylated to the higher ethoxylated compound from 3: 1 to 1: 3.
  • Preferred nonionic surfactants are those whose aliphatic group is derived from primary alkanols and alkenols and which come from natural and synthetic sources.
  • the ethoxylation products of natural ones are particularly preferred because of their good biodegradability in connection with the easy accessibility.
  • oxo alcohols which are obtained from olefins by hydroformylation and hydrogenation, and which are primary aliphatic alcohols with an ⁇ -methyl branch which does not impair biodegradability. If an ethoxylated fatty alcohol is replaced by an ethoxylated oxo alcohol with the same ratio of the hydrophobic and hydrophilic part of the molecule in the two surfactant components (ba) and (bb) defined above, the washability of hydrophobic dirt is improved with equivalent replacement.
  • the compounds (bb3) of the formula 1 contained in the surfactant component (bb) are the optionally still ethoxylated addition products of 1 mol of a low-molecular amine, in particular mono- or diethanolamine, ethylenediamine, diethylenetriamine or triethylenetetramine, on 1 mol of one end - Or internal C 8 -C 22 epoxyalkane, in particular C 10 -C 18 epoxyalkane.
  • These compounds of the formula I have already been described as detergent additives for detergents in German Offenlegungsschrift 2 703 020.
  • Compounds (bb3) of the formula 1 also include the ethanolamides of C 8 -C 18 fatty acids, preferably C 12 -C 14 fatty acids, and in particular the monoethanolamides, which are also particularly preferred. These compounds of the formula are therefore also to be regarded in the broadest sense as nonionic surfactants.
  • Ready-formulated compositions of the agents according to the invention generally contain in amounts of 1-50% by weight of further customary additives which improve the utility value, in particular a graying inhibitor, such as, for. B. carboxymethyl cellulose, enzymes, antimicrobials, optical brighteners, fabric softeners, dyes and fragrances, sodium sulfate as filler and water, which is bound in the crystals of the water-soluble salts and in particular in the aluminosilicates, and a proportion of about 2-18% by weight. % of the free-flowing detergent powder.
  • a graying inhibitor such as, for. B. carboxymethyl cellulose, enzymes, antimicrobials, optical brighteners, fabric softeners, dyes and fragrances, sodium sulfate as filler and water, which is bound in the crystals of the water-soluble salts and in particular in the aluminosilicates, and a proportion of about 2-18% by weight. % of the free-flowing detergent powder.
  • An essential characteristic of the detergents according to the invention is their presence as a mixture of the powder components A and B defined above, wherein in the case of the detergents with bleaching action there is a further powder component C containing the peroxy bleach component in the mixture.
  • the invention therefore also relates to a method for producing the detergents defined above.
  • This method comprises in its most general form comprises preparing a powder component by H exertzerstäubungstrocknen an aqueous suspension, producing a further powder component by a variety of this method of drying method and mixing the powder components, optionally with the addition n a Peroxybieichkompone - te, especially the sodium perborate as a further Powder component, characterized in that the above-defined water-insoluble alkali alumosilicates according to (i) or a), the above-defined surfactant component according to (ii) or b), optionally without the or part of the nonionic surfactants, and optionally the water-soluble complexing builders slurried according to (iv) with water and converted into powder component A by hot atomization, that further the sodium silicate powder defined above according to (iii) or e) optionally with the powdery, water-soluble, complex-forming framework substances according to (iv) mixed
  • the process for the preparation of the cooking detergent defined above, which contains a stabilizer combination c) in the tower powder component A is further characterized in that the aluminosilicate a), the surfactant component b) and the stabilizer combination c), optionally without part of the nonionic surfactants from b ) and preferably optical brighteners and other additives such as graying inhibitors and sodium sulfate, slurried with water and converted into powder component A by hot atomization drying, that the sodium silicate powder defined above according to e) is optionally mixed with non-ionic surfactants sensitive to drying and optionally further hydrolysis and temperature-sensitive detergent components, and the resulting powder component B and the sodium perborate are mixed with the powder component A in a conventional manner, the proportions of A, B and C being chosen so that the constituents a) in the resulting mixture to e) are present in the quantitative ranges specified above for this detergent.
  • sodium perborate tetrahydrate (NaBO 2 .H 2 O 2 .3H 2 O) is of particular practical importance; the monohydrate compound (NaBO 2 .H 2 O 2 ) can also be used.
  • H 2 O 2 supplying borates are also useful, e.g. B. the perborax Na 2 B 4 O 7 .4 H 2 O 2 .
  • These compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxy hydrates, such as peroxycarbonates (Na 2 CO 3 .1.5 H 2 O 2 ).
  • Peroxypyrophosphates citrate perhydrates, urea-H 2 O 2 or melamine-H 2 0 2 compounds as well as peracid salts providing H 2 0 2 , such as e.g. B. Caroate (KHSOs), Perbenzoate or Peroxyphthala'te to be replaced.
  • KHSOs B. Caroate
  • the water-soluble stabilizers which are preferably present together with the water-insoluble ones, are the organic heavy metal complexing agents of the amino or iminopolycarboxylic acid type, such as, for. B. the ethylenediaminotetraacetic acid, the diethylenetriaminopentaacetic acid or the iminotriacetic acid and their alkali and / or alkaline earth metal salts into consideration.
  • the aluminosilicates are expediently used in their still moist state, for example as an aqueous suspension or as a moist filter cake, and preferably by first adding these moist aluminosilicates, optionally with the addition of further water and a dispersant stable pumpable suspensions with an aluminosilicate content of approx. 40% by weight and above - based on the anhydrous substance - and a content of 0.3-4% by weight of the dispersant.
  • preferred dispersants are those compounds which are themselves active detergent constituents, and in particular those which are already intended as components of the agent according to the invention.
  • Particularly preferred within the scope of the present invention as a stabilizing agent for aqueous Suspensione n 'of the aluminosilicates in the surfactant (ba) and (bb) contained ethoxylated aliphatic C 10 -C 20 alcohols with an average degree of ethoxylation of 2-7 mol of EO, or the compound of formula I present in combination (bb) as component (bb3).
  • 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 used in the process according to the invention for the preparation of powder component A).
  • the remaining constituents of powder component A) are introduced into the initially prepared suspensions of the aluminosilicate and the resulting aqueous, flowable mixture is subjected to spray drying.
  • the low ethoxylated aliphatic alcohols of the surfactant components and the compounds of the formula I of the surfactant component (bb) have not been used completely as suspension aids, their incorporation into the powder component B) is recommended, for example by spraying, because of their mostly liquid-viscous nature the silicate powder (iii).
  • the aluminosilicates to be used are synthetic crystalline products; Mixtures of crystalline and amorphous products or semi-crystalline products can of course also be used for the purposes of the invention.
  • the preparation of the 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 together or a solution in the solid state Component are 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.
  • Alurnosilicates can also be produced from Al (OH) 3 , Al 2 O 3 or SiO 2 by reaction with alkali silicate or aluminate solutions. The production can also be carried out by other known processes.
  • the aluminosilicates which are initially still moist from their manufacture and which can be present as aqueous suspensions or moist filter cakes, can be converted into dry powders in the customary manner by first mechanically removing part of the water and then drying them, e.g. B. at temperatures of 50-400 ° C. Depending on the drying conditions, the powder product, which looks dry on the outside, contains more or less, usually 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; such aluminosilicate powders have a water content of about 18-22% by weight.
  • the aluminosilicates do not need to be dried at all after their production if, according to the teaching of DE-OS 2 527 388, they are converted into a stable suspension with a certain dispersant and water and used for further processing into detergents.
  • this processing mode practically completely avoids 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 magnesium binding capacity is calculated as (30-x) 7.19 mg MgO / g AS.
  • the particle sizes of the aluminosilicates can e.g. B. determine by means of sedimentation analysis.
  • the surfactants contained in the agents according to the invention have at least one hydrophobic organic residue and one anionic, amphoteric or zwitterionic or nonionic group which makes water soluble.
  • the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8-26, preferably 10-22 and in particular 12-18 C atoms or an alkyl aromatic radical with 6-18, preferably 8-16 aliphatic C atoms.
  • Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are the alkylbenzenesulfonates with C 9-15 -alkyl groups and the alkanesulfonates which are obtainable from C 12 -C 13 -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralisates or by bisulfite addition to olefins Consider.
  • Other usable tonsides from the sulfant type are the esters of ⁇ -sulfo fatty acids, e.g. B.
  • the ⁇ -sulfated methyl or ethyl ester of coconut, palm kernel or tallow fatty acids as well as the olefin sulfonates, ie mixtures of alien and hydroxyalkanesulfonates and disulfonates, such as those obtained from monoolefin with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is obtained.
  • 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 ethoxylated with 1-6 mol ethylene oxide or ethoxylated secondary alcohols or alkylphenols are also suitable.
  • Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
  • 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 1-40, preferably 2-20, moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, alkylphenols and carboxylic acids.
  • the addition products of 8-20 moles of ethylene oxide with primary alcohols such as, for. B. 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 6-14 C atoms in the alkyl radicals.
  • non-fully or not fully water-soluble polyglycol ethers with 2-7 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-EO, C 11 -C 15 oxo alcohol 3-EO, C 14 / C 15
  • Exemplary representatives for the nonionic surfactants with an average degree of ethoxylation of 8-20, in particular 9-15 are the compounds coconut fatty alcohol-12-EO, synthetic C 12 / C 14 fatty alcohol-9-EO, oleyl / cetytalcohol-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 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups with polypropylene glycol, alkylenediamine polypropylene glycol and with alkylpolypropylene glycols having 1-10 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.
  • Foam-suppressing soaps and non-surfactant foam inhibitors come into consideration as foam-inhibiting additives.
  • the foam-suppressing action of the soaps generally increases with the degree of saturation and the C number of the fatty acid residue, so that soaps of natural and synthetic origin are particularly suitable as foam-inhibiting soaps, which have a high proportion of C 18 -C 22 fatty acids, for example the derivatives of hydrogenated fish oil and rapeseed oils.
  • fatty acid mixtures with a chain length distribution of C, 2 to C 22 are mostly used, which consist of at least 50% by weight of C 18 -C 22 fatty acid salts (iodine number ⁇ 5).
  • foam-suppressing soaps of saturated C 12 -C 18 fatty acids in particular predominantly C 16 -C 18 fatty acids, for example the soap of hydrogenated tallow fatty acid.
  • the ratio of soap to non-surfactant-like foam inhibitor from 20: 1 to 5: 1 the soap mainly dampens foaming when rinsing out the wash liquor.
  • non-surfactant foam inhibitors optionally used in combination with the foam-inhibiting soaps are generally water-insoluble, mostly containing aliphatic C a -C 22 carbon radicals.
  • Suitable non-surfactant foam inhibitors are e.g. B. the N-alkylaminotriazines, ie reaction products of 1 mole of cyanuric chloride with 2-3 moles of a mono- or dialkylamine with essentially 8-18 carbon atoms in the alkyl radical.
  • propoxylated and / or butoxylated aminotriazines e.g. B.
  • the compounds of the formula I contained in the agents according to the invention with the surfactant combination (bb) are primarily compounds in the case of the hydroxyalkylamines (in formula 1, X is a ⁇ -hydroxyalkyl radical and A is a simple C - N bond) which were prepared in a 1-stage or 2-stage reaction from terminal or internal epoxyalkanes by first reacting with mono- or diethanolamine or mono- or diisopropanolamine, with ammonia, an alkylenediamine, polyalkylene polyamine or hydroxyalkyl polyamine and optionally ethoxylating these addition products in a second stage .
  • the epoxyalkanes used as starting materials are obtained in a manner known per se from the corresponding olefins or olefin mixtures.
  • terminal epoxyalkanes used were preferably those with chain lengths in the range of C 12 -C 18 for the preparation of the hydroxyalkylamines of the formula I.
  • the compounds of the formula I in the surfactant combination (bb) in the case of the fatty acid ethanolamides are preferably fatty acid monoethanolamides composed of individual fatty acids or fatty acid mixtures, in particular of the chain length range C 10 -C 18 , the natural ones or can be of synthetic origin.
  • the fatty acids can be saturated and unsaturated; Monoethanolamides of mixed fatty acids from natural sources, such as, for example, are particularly suitable.
  • fatty acid monoethanolamides examples include the compounds: lauric acid monoethanolamide, coconut fatty acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, tallow fatty acid monoethanolamide.
  • 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 as well as compounds of the same structure, which instead of the sulfamoyl group z.
  • B. carry the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group.
  • Polyamide brighteners which can also be used are the substituted aminocoumarins, for example 4-methyl-7-dimethylamino- or 4-methyl-7-diethylamino-coumarin.
  • the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethy) -2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl are also useful as polyamide brighteners.
  • the compounds are 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzox-azolyl) -naphtho [2,3-b] -thiophene and 1,2-di - (5-methyl-2-benzoxazolyl) ethylene suitable.
  • Brighteners of the substituted 4,4'-distyryldiphenyis 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 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.
  • Carboxymethylated cellulose or starch in the form of its sodium salts and / or methyl celluloses are preferred.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Recoloring inhibitors of the polyvinylpyrrolidone type can also be used.
  • a manufacturing specification for the aluminosilicates is given; other known methods for producing the aluminosilicates can also be used.
  • the sodium aluminate solution was placed in a vessel with 151 contents and the sodium silicate solution was added with vigorous stirring. Was stirred with a stirrer with a dispersing disc at 3000 revolutions / min. Both solutions were at room temperature.
  • An X-ray amorphous sodium aluminosilicate formed as the primary precipitation product under an exothermic reaction. After stirring for 10 minutes, the suspension of the precipitate was transferred to a crystallization container and heated to 80-130 ° C. for about 6 hours with stirring (250-500 revolutions / min) for the purpose of crystallization. After sucking off the lye from the crystal slurry and washing with deionized water up to a pH of approx.
  • the filter cake was either dried - e.g. B. 24 hours at 100 ° C - and then crushed into a fine powder, or an aqueous slurry, preferably an aqueous suspension of the aluminosilicate, was used to produce the detergents or cleaning agents. More precise information on the temperature, the duration of heating and the type of workup are given in the manufacturing instructions for the following individual representative aluminosilicate types.
  • the detergents in Table I were generally prepared in such a way that Surfactant component, aluminosilicate, CMC, brightener and sodium sulfate using a slurry batch produced a spray-dried powder component A and mixed it with the powder component B consisting of the sodium silicate and the phosphonate salt and the powder component C consisting of the perborate.
  • a mixture of the aluminosilicate, the surfactants, the constituents of the stabilizer combination and CMC, brightener and sodium sulfate was spray-dried as a slurry batch and this tower powder was mixed with the Sodium silicate and the perborate mixed. Enzymes and fragrances were added to these mixtures in the usual way.
  • the insoluble residue on a sieve was determined by dissolving the detergents in water after a certain dissolution time, or the visible residue on black wool was assessed after a delicate wash by hand. Comparably good washing and test results were also obtained if, in the detergent formulations in Tables I and II, the aluminosilicate used there was replaced by the other aluminosilicate types mentioned, or by alumosilicate types of the same composition but produced in a different way.

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Claims (12)

1. Agent de lavage sans phosphate contenant un alumosilicate échangeur de cations insoluble dans l'eau, des tensioactifs, des substances builders complexantes solubles dans l'eau, un silicate alcalin éventuellement un percomposant de blanchiment, qui se compose d'au moins deux constituants pulvérulents parmi lesquels un contient l'alumosilicate et un tensioactif et l'autre partie le silicate alcalin, caractérisé en ce qu'il contient les constituants suivants:
(i) 20-65% en poids d'un aiumosilicate insoluble dans l'eau, finement divisé, préparé synthétiquement, cristallin et contenant de l'eau liée, de formule:
0,7-1,5 MezO . Al2O3 - 1,3-4,0 SiO2,

par rapport à la substance active anhydre, qui possèdent une cpacité de fixation du calcium déterminée à 22°C de 50-200, de préférence de 100-200 mg de CaO/g de substance active anhydre, dans cette formule Me signifiant du sodium ou du potassium,
(ii) 5-30% en poids d'un composant tensioactif consistant en au moins un tensioactif synthétique anionique, non ionique, amphotère ou ionique hybride, et éventuellement en des additifs inhibiteurs de mousse;
(iii) 1-7%, de préférence 2-5 et en particulier 2-3% en poids d'un silicate de sodium solide pulvérulent de composition molaire Na2O · 2,0-2,2 SiO2, qui présente une teneur en eau de 15-23. de préférence 18-21% en poids et dont la solubilité dans l'eau, lors de la préparation d'une solution aqueuse à 5% ― en ajoutant à 95 g d'eau préparée d'avance à 20°C sous agitation régulière à environ 180-200 tours/minutes en une fois 5 g du silicate de sodium - s'élève après 1 minute au moins à 75% en poids, de préférence au moins à 85% en poids, après 3 minutes au moins à 95% en poids et au plus tard après 25 minutes à 100% en poids, et
(iv) 0,05 - 0,75, de préférence 0,2 à 0,6% en poids d'un formateur de'complexe organique soluble dans l'eau appartenant au groupe des acides alcane-di- et -triphosphoniques substitués sous forme des sels alcalins ou alcalino-terreux,

l'agent de lavage représentant un mélange d'au moins deux constituants pulvérulents A) et B) parmi lesquels
A) est un constituant pulvérulent préparé par séchage à chaud d'une suspension aqueuse des constituants, qui contient l'alumosilicate alcalin insoluble dans l'eau selon (i), le composant tensioactif selon (ii), éventuellement sans ou avec une partie des tensioactifs non ioniques, de même qu'éventuellement les substances builders complexantes organiques solubles dans l'eau selon (iv), et
B) est un constituant pulvérulent qui contient la poudre de silicate de sodium selon (iii), éventuellement conjointement avec les substances builders complexantes organiques solubles dans l'eau selon (iv) et éventuellement conjointement avec des tensioactifs non ioniques sensibles au séchage à chaud de même qu'éventuellement avec d'autres additifs d'agents de lavage sensibles à l'hydrolyse et à la température.
2. Agent selon la revendication 1, caractérisé en ce que le silicate de sodium selon (iii) présente une densité apparente de 350 à 800 g/litre, de préférence de 350-450 g/litre et en particulier d'environ 400 g/litre et en ce que sa granulométrie se situe dans l'intervalle de 1 mm à 0,05 mm, au moins 80% des particules étant inférieures à 0,5 mm.
3. Agent selon les revendications 1 et 2, caractérisé en ce que le silicate de sodium du composant (iii) selon la revendication 1 a été fabriqué par séchage par pulvérisation ou par séchage sur cylindre d'une solution aqueuse à 35-50%, à une température de 100 à 120"C au cours du séchage par pulvérisation, et à 100 - 140° C au cours du séchage sur cylindre.
4. Agent selon les revendications 1 à 3, caractérisé en ce que le silicate de sodium du composant (iii) selon la revendication 1 a été fabriqué par séchage d'une solution aqueuse à 40 - 50% sur cylindre chauffé à 100 - 140°C jusqu'à une teneur en eau résiduelle de 15 à 23, en particulier de 18 à 21% en poids, qui présente une densité apparente de 350 à 450 g/litre, en particulier d'environ 400 g/litre et qui se dissout suivant le test indique à la revendication 1 apres 3 mirfutes à raison d'au moins 99%.
5. Agent selon les revendications 1 à 4, caractérisé en. ce qu'il consiste en les constituants pulvérulents A et B selon la revendication 1 et supplémentairement en un autre constituant pulvérulent C contenant le percomposé de blachiment, consistant particulièrement en du perborate de sodium.
6. Agent selon les revendications 1 à 5, contenant
a) 20 - 40% en poids d'un alumosilicate alcalin insoluble dans l'eau, finement divisé, préparé synthétiquement, 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 (SA) anhydre, qui possède une capacité de fixation du calcium de 50 à 200, de préférence de 100 à 200 mg de CaO/g de SA, avec Me qui signifie du sodium ou du potassium;
b) 5 - 20% en poids d'un composant tensioactif consistant en au moins un tensioactif anionique, non ionique, amphotère ou ionique hybride et éventuellement en des additifs inhibiteurs de mousse;
c) 0,05 - 0,75, de préférence 0,2 à 0,6% en poids d'un formateur de complexe organique du groupe des acides alcane-di- et -triphosphoniques substitués et de leurs sels alcalins;
d) 10 - 35% en poids d'un percomposé minéral; et
e) jusqu'à 7% en poids d'un silicate de sodium soluble dans l'eau de composition Na2O · 1 -3,5 SiO2,

caractérisé en ce qu'il contient comme composant e) 2 à 5, en particulier 2 à 3% en poids d'un silicate de sodium solide pulvérulent de composition molaire Na2O . 2,0--2,2 Si02, qui présente une teneur en eau de 15 à 23, de préférence de 18 à 21% en poids et dont la solubilité dans l'eau, lors de la préparation d'une solution aqueuse à 5% dans laquelle on ajoute en une fois à 95 g d'eau préparée d'avance à 20° C, sous agitation uniforme à environ 180 à 200 tours/minute, 5 g du silicate de sodium, après 3 minutes s'élève au moins à 99% en poids, selon le composant (iii) de la revendication 1, l'agent de lavage se présentant sous la forme d'un mélange des trois constituants pulvérulents A, B et C selon les revendications 1 à 5 et le composant (c) étant présent sous la forme de sel alcalin ou alcalino-terreux.
7. Agent selon les revendications 1 à 6, caractérisé en ce qu'il contient le phosphonate défini à la revendication 1 conjointement avec le silicate de sodium (iii) ou e) en tant que partie du constituant pulvérulent B) selon la revendication 1.
8. Agent selôn les revendications 1 à 5, caractérisé en ce qu'il présente la composition suivante:
a) 30 - 40% en poids d'un alumosilicate de sodium insoluble dans l'eau, finement divisé, fabriqué synthétiquement, cristallin et contenant de l'eau liée, du type de la zéolite NaA ayant une capacité de fixation du calcium de 100-200 mg de CaO/g de la substance anhydre, et une dimension de particule inférieure à 30 µm et avec au moins 80% allant de à 0,01 µm;
b) 10-20% en poids d'un composant tensioactif consistant en au moins un tensioactif anionique et/ou non ionique et éventuellement en des additifs inhibiteurs de mousse;
c) 1 - 2,55% en poids d'une combinaison de stabilisants consistant en:
cl) 0,05 - 0,75% en poids d'un formateur de complexe organique du groupe des acides alcan-di-et -triphosphoniques substitués qui se présentent sous la forme de leurs sels alcalins et/ou alcalino-terreux;
c2) 0,8 - 1,5% en poids de silicate de magnésium et
c3) 0,15-0,3% en poids d'éthylène-diamine-tétracétate de sodium, chaque fois par rapport à l'agent de lavage tout entier,
d) 18-22% en poids de perborate de sodium tétrahydraté et
e) 2 - 3% en poids d'un silicate de sodium solide pulvérulent de composition molaire Na2O· 2,0-2,2 SiO2, qui présente une teneur en eau de 15-23, de préférence de 18-21% en poids et dont la solubilité dans l'eau dans la préparation d'une solution aqueuse à 5% où l'on ajoute, 5 g d'eau introduite d'avance à 20°C sous une agitation régulière d'environ 180-200 tours/minute, en une fois 5 g du silicate de sodium, s'élève après 3 minutes à au moins 99% en poids.

l'agent de lavage se présentant à l'état de mélange des trois constituants pulvérulents A), B) et C), parmi lesquels
A) est un constituant pulvérulent fabriqué par séchage par pulvérisation à chaud d'une suspension aqueuse des constituants qui contient l'alumosilicate insoluble dans l'eau a, le composant tensioactif selon b), éventuellement sans une partie des tensioactifs non ioniques, ainsi que la combinaison de stabilisants selon c);
B) est un constituant pulverulent qui contient la poudre de silicate de sodium selon e), éventuellement conjoiiitement'avec des tensioactifs non ioniques sensibles au séchage à chaud de même qu'éventuellement d'autres additifs d'agents de lavage sensibles à l'hydrolyse et à la température, et
C) est le troisième autre constituant pulvérulent consistant en le percomposé de blanchiment: le perborate de sodium.
9. Agent selon la revendication 8, caractérisé en ce qu'il contient dans le constituant pulvérulent A) des éclaircissants optiques.
10. Procédé de fabrication des agents selon les revendications 1 à 7, comprenant la fabrication d'un composant pulvérulent par séchage à chaud d'une suspension aqueuse, la fabrication d'un autre composant pulvérulent par une méthode différente de la méthode de séchage à chaud et le mélange des deux composants pulvérulents, éventuellement avec addition d'un percomposant de blanchiment comme autre composant pulvérulent, caractérisé en ce qu'on met en suspension avec de l'eau les alumosilicates alcalins insolubles dans l'eau (i) selon la revendication 1, le composant tensioactif (ii) selon la revendication 1, éventuellement sans les tensioactifs anioniques ou une partie de ceux-ci, de même qu'éventuellement les substances builders formatrices de complexes solubles dans l'eau (iv) selon la revendication 1, et on les convertit par puivérisation-à chaud en le composant pulvérulent A, en ce qu'on mélange en outre la poudre de silicate de sodium (iii) selon la revendication 1 éventuellement avec des substances builders pulvérulentes, solubles dans l'eau et formatrices de complexes (iv) selon 1-a. revendication 1 et l'on ajoute à cette poudre éventuellement des tensioactifs non ioniques sensibles au séchage à chaud tout comme éventuellement d'autres constituants d'agents de lavage sensibles à l'hydrolyse et à la température et l'on mélange le composant pulvérulent 8 ainsi résultant avec le composant pulvérulent A de la manière usuelle, en choisissant les proportions de A et de 8 en sorte que dans le mélange résultant les constituants (i), (ii), (iii) et (iv) se présentent dans les intervalles de quantité indiqués à la revendication 1.
11. Procédé selon la revendication 10, caractérisé en ce qu'on prépare le composant pulvérulent B en mélangeant 20 à 50 parties en poids de la poudre de silicate de sodium (iii) avec 2 à 6 parties en poids d'un sel alcalin ou alcalino-terreux pulvérulent du formateur de complexe organique du groupe des acides alcane-di- et -triphosphoniques (iv), en ce qu'on ajoute éventuellement des tensioactifs non ioniques et l'on mélange la poudre résultante avec le composant pulvérulent A et éventuellement l'autre composant pulvérulent C, en réglant les proportions de manière correspondante aux agents selon les revendications 1 à 6.
12. Procédé de fabrication des agents selon les revendications 8 et 9, comprenant la fabrication d'un composant pulvérulent par séchage par pulvérisation à chaud d'une suspension aqueuse, la fabrication d'un autre composant pulvérulent par une méthode différente de cette méthode de séchage, et par mélange des composants pulvérulents avec addition du perborate de sodium comme autre composant pulvérulent, caractérisé en ce qu'on,met en suspension avec de l'eau les constituants a), b) et c), éventuellement en l'absence d'une partie des tensioactifs non ioniques et de préférence les é éclaircissants optiques et autres additifs comme des inhibiteurs de grisaillement et du sulfate de sodium et l'on convertit ceux-ci par séchage par pulvérisation en le composant pulvérulent A), en ce qu'en outre on mélange la poudre de silicate de sodium selon e) éventuellement avec des tensioactifs non ioniques sensibles au séchage à chaud de même qu'éventuellement d'autres constituants d'agents de lavage qui sont sensibles à l'hydrolyse et à la température, et l'on mélange le composant pulvérulent B) ainsi résultant ainsi que le perborate de sodium comme composant C) avec le composant pulvérulent A), en choisissant les proportions de A), B) et C) en.sorte que, dans le mélange résultant, les constituants a) à e) se présentent dans les intervalles de quantité indiqués à la revendication 8 pour l'agent de lavage.
EP79103848A 1978-10-12 1979-10-08 Produit pour le lavage sans phosphates et procédé pour sa fabrication Expired EP0010247B1 (fr)

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AT79103848T ATE2848T1 (de) 1978-10-12 1979-10-08 Phosphatfreies waschmittel und verfahren zu dessen herstellung.

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DE19782844455 DE2844455A1 (de) 1978-10-12 1978-10-12 Phosphatfreies waschmittel und verfahren zu dessen herstellung
DE2844455 1978-10-12
DE2908305 1979-03-03
DE19792908305 DE2908305A1 (de) 1979-03-03 1979-03-03 Phosphatfreies waschmittel und verfahren zu dessen herstellung

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2025151743A1 (fr) * 2024-01-12 2025-07-17 University Of Florida Research Foundation, Incorporated Nanoparticules lipidiques à base de dendrimère pour la transfection d'arnm sélectif d'organe

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DE3066202D1 (en) * 1979-11-03 1984-02-23 Procter & Gamble Granular laundry compositions
EP0061296B1 (fr) * 1981-03-20 1984-10-24 Unilever Plc Procédé pour la préparation de compositions détergentes contenant de l'aluminosilicate de sodium
DE3311368A1 (de) * 1982-04-08 1983-10-27 Colgate-Palmolive Co., 10022 New York, N.Y. Teilchenfoermiges, bleichendes und weichmachendes textilwaschmittel
GB8310698D0 (en) * 1983-04-20 1983-05-25 Procter & Gamble Detergent compositions
GB8609043D0 (en) * 1986-04-14 1986-05-21 Unilever Plc Detergent powders
DE3545947A1 (de) * 1985-12-23 1987-07-02 Henkel Kgaa Phosphatfreies, granulares waschmittel
CA1286563C (fr) * 1986-04-04 1991-07-23 Jan Hendrik Eertink Poudres detersives, et leur preparation
DE4106880A1 (de) * 1991-03-05 1992-09-10 Henkel Kgaa Waschmittel
DE4134914A1 (de) * 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
ES2598402T5 (es) * 2009-12-30 2019-10-09 Ecolab Inc Sustitutos de fosfato para composiciones de limpieza y/o de detergente compatibles con membranas

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FR2281979A1 (fr) * 1974-08-12 1976-03-12 Sifrance Ste Silicates Speciau Nouvelle composition detergente sous forme pulverulente et procede d'obtention
CA1102653A (fr) * 1976-03-25 1981-06-09 Tom H. Ohren Traduction non-disponible
AT352241B (de) * 1977-04-22 1979-09-10 Henkel Kgaa Pulverfoermiges, phosphatfreies textil- waschmittel
IT1160682B (it) * 1977-10-14 1987-03-11 Po Corp. Composizioni detergenti con coadiuvante di silano-zeolite

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025151743A1 (fr) * 2024-01-12 2025-07-17 University Of Florida Research Foundation, Incorporated Nanoparticules lipidiques à base de dendrimère pour la transfection d'arnm sélectif d'organe

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DE2965075D1 (en) 1983-04-28
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