EP0026529A1 - Reinigungsmittelzusammensetzungen - Google Patents

Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0026529A1
EP0026529A1 EP80200878A EP80200878A EP0026529A1 EP 0026529 A1 EP0026529 A1 EP 0026529A1 EP 80200878 A EP80200878 A EP 80200878A EP 80200878 A EP80200878 A EP 80200878A EP 0026529 A1 EP0026529 A1 EP 0026529A1
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Prior art keywords
alkyl
component
detergent composition
composition according
detergent
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English (en)
French (fr)
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EP0026529B1 (de
EP0026529B2 (de
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Gianfranco Luigi Spadini
Peter Norman Crisp
Allan Campbell Mcritchie
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
Procter and Gamble Co
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/65Mixtures of anionic with cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/40Monoamines or polyamines; Salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/001Softening compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds

Definitions

  • This invention relates to detergent compositions that clean well and also act as textile softeners.
  • organic textile softening compounds are cationic materials that are reactive towards the anionic surfactants used in conventional laundry detergents. If both types of material are formulated in a single product, they tend to interact on addition to a wash liquor and, although in some instances the resulting complex has useful textile softening properties, its formation normally depresses the cleaning performance of the formulation and is therefore generally considered undesirable.
  • compositions have been proposed that have sought to minimise the mutual reactivity of the anionic and cationic materials by the addition of compatibilising compounds such as the amido amines and fatty acids described in U.S. Patent Nos. 3,886,075 and 3,954,632.
  • compatibilising compounds such as the amido amines and fatty acids described in U.S. Patent Nos. 3,886,075 and 3,954,632.
  • An alternative approach has been to incorporate one of the reactant materials in a form that inhibits its contact with the other in the wash liquor and examples of this type of formulation are taught in U.S. Patent Nos. 3,936,537 and 3 , 644 ,2 03 .
  • the performance of these compositions is however sensitive to the washing conditions that are employed.
  • nonionic surfactants have been proposed in place of the conventional anionic surfactants and compositions of this type are described in e.g. British Patent Specification No. 1,079,388, German Auslegeschrift 1,220,956 and U.S. Patent No. 3,607,763.
  • levels of nonionic surfactant sufficient to provide good cleaning impair the softening of the cationic softener.
  • Another proposal to provide acceptable cleaning and textile softening by avoiding the surfactant-softener interaction has been made in British Patent Specification No. 1,514,276 which teaches the use of certain long chain tertiary amines that are nonionic in character at the wash liquor pH existing when a conventional laundry detergent is used.
  • detergent compositions containing smectite-type clays and certain cationic compounds can be formulated which have cleaning performance equivalent to that of commercially available heavy duty laundry detergents together with textile softening performance that approaches that of rinse added fabric softeners.
  • component (b) is a C 12 -C 14 alkyl tri C 1 -C 4 alkyl or C 1 -C 4 hydroxy alkyl ammonium salt and component (c) comprises a montmorillonite.
  • component (b) is added to preformed spray dried detergent granules comprising components (a), (c) and also a detergent builder salt component (d).
  • the invention comprises three components, namely the anionic surfactant component (a), the the water soluble cationic component (b), and the smectite type clay component (c).
  • anionic surfactants can be used in the compositions of the present invention.
  • Suitable anionic non-soap surfactants are water soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alphaolefin sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2- acyloxy-alkane-l-sulfonates, and beta-alkyloxy alkane sulfonates.
  • Soaps are also suitable anionic surfactants.
  • Especially preferred alkyl benzene sulfonates have about 9 to about 15 carbon atoms in'a linear or branched alkyl chain, more especially about 11 to about 13 carbon atoms.
  • Suitable alkyl sulfates have about 10 to about 22 carbon atoms in the alkyl chain, more especially from about 12 to about 18 carbon atoms.
  • Suitable alkyl polyethoxy ether sulfates have about 10 to about 18 carbon atoms in the alkyl chain and have an average of about 1 to about 12 - CH 2 CH 2 0- groups per molecule, especially about 10 to about 16 carbon atoms in the alkyl chain and an average of about 1 to about 6 -CH 2 CH 2 0- groups per molecule.
  • Suit.able paraffin sulfonates are essentially linear and contain from about 8 to about 24 carbon atoms, more especially from about 14 to about 18 carbon atoms.
  • Suitable alphaolefin sulfonates have about 10 to about 24 carbon atoms, more especially about 14 to about 16 carbon atoms; alphaolefin sulfonates can be made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulfonates.
  • Suitable alpha-sulfocarboxylates contain from about 6 to about 20 carbon atoms; included herein are not only the salts of alpha- sulfonated fatty acids but also their esters made from alcohols containing about 1 to about 14 carbon atoms.
  • Suitable alkyl glyceryl ether sulfates are ethers of alcohols having about 10 to about 18 carbon atoms, more especially those derived from coconut oil and tallow.
  • Suitable alkyl phenol polyethoxy ether sulfates have about 8 to about 12 carbon atoms in the alkyl chain and an average of about 1 to about 6-CH 2 CH 2 0- groups per molecule.
  • Suitable 2-acyloxy-alkane-l-sulfonates contain from about 2 to about 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane moiety.
  • Suitable beta-alkyloxy alkane sulfonates contain about 1 to about 3 carbon atoms in the alkyl group and about 8 to about 20 carbon atoms in the alkane moiety.
  • alkyl chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and alkyl sulfate having 12 to 18 carbon atoms in the alkyl group.
  • Suitable soaps contain about 8 to about 18 carbon atoms, more especially about 12 to about 18'carbon atoms.
  • Soaps can be made by direct saponification of natural fats and oils such as coconut oil, tallow and palm oil, or by the neutralization of free fatty acids obtained from either natural or synthetic sources.
  • the soap cation can be alkali metal, ammonium or alkanol-ammonium; sodium is preferred.
  • compositions contain from 3 to 40% of organic detergent, preferably from 4 to 15 of anionic detergent, more preferably 5-10% of anionic surfactant.
  • the second essential component of the compositions of the present invention is an organic nitrogenous compound capable of existing in cationic form in a 0.1% aqueous solution at pH 10.
  • This can be a compound of any of the following types;
  • R 7 is C 8 -C 16 alkyl
  • each of R 8 ,R 9 , and R 10 is independently selected from C 1 -C 4 alkyl, C 1 -C 4 hydroxy alkyl, benzyl, and -(C 2 H 4 O) x H where x has a value from 2 to 5, and X is an anion.
  • R 8 ,R 9 , and R 10 should be benzyl.
  • the preferred alkyl chain length for R 7 is C 12 -C 14 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohol synthesis.
  • Preferred groups for R 8 R 9 and R 10 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosul- phate, acetate and phosphate ions.
  • quaternary ammonium compounds are coconut trimethyl anunonium bromide - coconut methyl dihydroxyethyl ammonium bromide decyl triethyl ammonium chloride decyl dimethyl hydroxyethyl ammonium bromide myristyl trimethyl ammonium methyl sulphate lauryl dimethyl benzyl ammonium bromide lauryl methyl (ethenoxy) 4 ammonium bromide
  • R 11 is C 8 -C 14 alkyl
  • R 12 and R 13 are independently selected from hydrogen, C l -C 4 alkyl, C l -C 4 hydroxyalkyl, benzyl or -(C 2 H 4 O) x H where x has a value from 2 to 5, and the water soluble salts thereof.
  • Suitable amine salts can be the hydrohalide salts of primary, secondary, or tertiary amines, examples of such amines being:
  • compositions of the present invention combine good softening and cleaning performance and in order to maintain the latter it is essential that the overall surfactant character be anionic.
  • the molar ratio of the cationic component (b) to the anionic surfactant component (a) should therefore be less than 1:1 and desirably should be less than 1:1.5. In preferred - embodiments of the invention such as heavy duty laundry detergent formulations, the molar ratio should be less than 1:2.
  • the cationic compound will normally be present in an amount of from 0.5% to 1.5% by weight of the composition, preferably from 1% to 5% and most preferably from 1.5% to 3% by weight.
  • the third component of the invention is a smectite-type clay having a particle size which cannot be perceived tactilely.
  • Impalpable clays have particle sizes below about 50 microns; the clays used herein normally have a particle size range of from about 5 microns to about 50 microns.
  • the clay minerals can be described as expandable, three-layer clays, i.e., aluminosilicates and magnesium silicates, having an ion exchange capacity of at least 50 meq/100 g. of clay and preferably at least 60 meq/100 g. of clay.
  • expandable as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
  • the three-layer expandable clays used herein are those materials classified geologically as smectites.
  • the dioctahedral minerals are primarily trivalent metal ion-based clays and are comprised of the prototype pyrophyllite and the members montmorillonite (OH) 4 Si 4- y (Al 4-x Mg x )O 20 , nontronite (OH) 4 Si 8-y Al y (Al 4-x Fe x )O 20 , and volchonskoite (OH) 4 Si 8-y Al y (Al 4-x Cr x )O 20 , where x has a value of from 0 to about 4.0 and y-has a value of from O to about 2.0.
  • montmorillonites having exchange capacities greater than 50 meq/100 g. are suitable for the present invention and provide fabric softening softening
  • the trioctahedral minerals are primarily divalent metal ion based and comprise the prototype talc and the members hectorite (OH) 4 Si 8-y Al y (Mg 6-x Li x )O 20 , saponite (OH) 4 Si a- y Al y (Zn 6-y Al x )O 20 , vermiculite (OH) 4 Si 8-y Al y (Mg 6-x Fe x )O 20 , wherein y has a value of 0 to about 6.0.
  • Hectorite and saponite are the only minerals in this class that are of value in the present invention, the fabric softening performance being related to the type of exchangeable cationic as well as to the exchange capacity.
  • the range of the water of hydration in the above formulas can vary with the processing to which the clay has been subjected. This is immaterial to the use of the smectite clays in the present invention in that the expandable characteristics of the hydrated clays are dictated by the silicate lattice structure.
  • the clays employed in the compositions of the present invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed.
  • a sodium clay is one in which the absorbed cation is predominantly sodium.
  • Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
  • a typical exchange reaction involving a smectite-type clay is expressed by the following equation.
  • the cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice structure, and the like.
  • the ion exchange capacity of clays varies widely in the range from about 2 mcq/100 g. for kaolinites to about 150 meq/100 g., and greater, for certain smectite clays.
  • Illite clays although having a three layer structure, are of a non- expanding lattice type and have an ion exchange capacity somewhere in the lower-portion of the range, i.e., around 26 meq/100 g. for an average illite clay.
  • Attapulgites another class of clay minerals, have a spicular (i.e. needle-like) crystalline form with a low cation exchange capacity (25-30 meq/100 g.).
  • Their structure is composed of chains of silica tetrahedrons linked together by octahedral groups of oxygens and hydroxyls containing Al and Mg atoms.
  • smectite clays useful herein can be characterised as montmorillonite, hectorites, and saponite clay minerals having an ion exchange capacity of at least about 50 meq/100 g. and preferably at least 60 meq/100 g.
  • Most of the smectite clays useful in the compositions herein are commercially available under various trade names, for example, ThixogelNo.l and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Imvite K from Industrial Mineral Ventures; Volclay BC and Volclay 325, from American Colloid Co., Skokie Illinois; and Veegum F from R.T. Vanderbilt. It is to be recognised that such smectite minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
  • Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions.
  • Volclay BC which is a smectite clay mineral containing at least 3% of iron (expressed as Fe 2 0 3 ) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in detergent softening compositions. Imvite K is also very satisfactory.
  • Appropriate clay minerals for use herein can be selected by virtue of the fact that smectites exhibit a true 14A x-ray diffraction pattern.
  • This characteristic exchange pattern taken in combination with exchange capacity measurements performed in the manner noted above, provides a basis for selecting particular smectite-type minerals for use in the compositions disclosed herein.
  • the smectite clay minerals useful in the present invention are hydrophilic in nature, i.e., they display swelling characteristics in aqueous media.
  • the smectite clay is present in an amount of from 1.5% to 45% by weight of the composition, preferably from about 2% to 15%, especially from about 5% to about 12% Optional Ingredients
  • the detergent compositions of the present invention may of course include, as optional ingredients, components that are usually found in laundry detergents.
  • nonionic and zwitterionic surfactants include nonionic and zwitterionic surfactants, builder salts, bleaching agents and organic precursors therefor, suds suppression agents, soil suspending and anti-redeposition agents, enzymes, optical brighteners, colouring agents and perfumes.
  • Nonionic and zwitterionic surfactants may be incorporated in amounts of up to 50% by weight of the total surfactant but normally are present in amounts of less than 30% of the total surfactant.
  • total surfactant is meant the sum of the anionic surfactant (a) cationic component (b) and any added nonionic and/or zwitterionic surfactant.
  • the incorporation of 15-25% nonionic surfactant based on the total surfactant weight (corresponding to 1-2% on a total composition basis) has been found to provide advantages in the removal of oily soils.
  • Suitable nonionics are water soluble ethoxylated materials of HLB 11.5-17.0 and include (but are not limited to) C 10 -C 20 primary and secondary alcohol ethoxylates and C 6 -C 10 alkylphenol ethoxylates.
  • C 14 -C 18 linear primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol are preferred, examples being C 14 - C 15 (EO) 7 , C 16 -C 18 ( EO ) 25 and especially C 16 -C 18 (EO) 11 .
  • Suitable zwitterionic surfactants include the C 12 -C 16 alkyl betaines and sultaines. These and other zwitterionic and nonionic surfactants are disclosed in Laughlin & Heuring USP 3,929,678.
  • Detergent builder salts are a preferred component (d) of the compositions of-the invention and can be inorganic or organic in character.
  • suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates. Specific examples of such salts.include the sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, penta-polyphosphates and hexametaphosphates. Sulphates are usually also present.
  • Suitable organic alkaline detergency builder salts are:
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in Canadian Patent No. 755,038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • a water-soluble material capable of forming a water- insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
  • Preferred water soluble builders are sodium tripolyphosphate and sodium silicate, and usually both are present.
  • a substantial proportion for instance from 3.% to 15% by weight of the composition of sodium silicate (solids) or ratio (weights ratio SiO 2 :Na 2 O) from l:l to 3.5:1 be employed.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium alumino silicates, particularly those described in Belgian Patent 814,874 issued November 12, 1974 incorporated herein by reference.
  • This patent discloses and claims detergent compositions containing sodium aluminosilicates of the formula . wherein z and y are integers equal to at least 6, the - molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1 and x is an integer from about 15 to about 264.
  • a preferred material is Na 12 (Si O2 AlO 2 ) 12 27H 2 O. If present, incorporation of about 5% to 25% by weight of aluminosilicate is suitable, partially replacing water-soluble builder salts, provided that sufficient water-soluble alkaline salts remain to provide the specified pH of the composition in aqueous solution.
  • the detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
  • Bleaching agents useful in the compositions of the invention include sodium perborate, sodium percarbonate and other perhydrates at levels of from 5% to 35% by weight of the composition.
  • Organic peroxy bleach precursors such as tetra acetyl ethylene diamine and tetra acetyl glycouril can also be included and these and other precursors are disclosed in Belgian Patent No. 859461 published April 6th, 1978
  • bleach stabilisers are also preferred components usually at levels of from 0.2% to 2% by weight of the composition.
  • the stabilisers may be organic in nature such as the previously mentioned amino polyacetates and amino polyphosphonates or may be inorganic such as magnesium silicate. In the latter case the material may be added to the formulation or formed in situ by the addition of a water-soluble magnesium salt to a slurried detergent mix containing an alkali metal silicate.
  • Suds controlling agents are often present. These include suds boosting or suds stabilising agents such as mono- or di-ethanolarnides of fatty acids. More often in modern detergent compositions, suds suppressing agents are required. Soaps especially those having > 18 carbon atoms, or the corresponding fatty acids, can act as effective suds suppressors if included in the anionic surfactant component of the present compositions. Usually about 1% to about 4% of such soap is effective as a suds suppressor. Very suitable soaps when suds suppression is a primary reason for their use, are those derived from Hyfac (C 18 -C 22 hardened marine oil fatty acids available from the Humko Corporation).
  • non-soap suds suppressors are preferred in synthetic detergent based compositions of the invention since soap or fatty acid tends to give rise to a characteristic odour in these compositions.
  • Preferred suds suppressors comprise silicones.
  • these may be employed a particulate suds suppressor comprising silicone and silanated silica releasably enclosed in water soluble or dispersible substantially non-surface active detergent impermeable carrier.
  • Suds suppressing agent of this sort are dis-: closed in British patent specification 1,407,997.
  • a very suitable granular (prilled) suds suppressing product comprises 7% silica/silicone (15% by weight silanated silica, 85% silicone, obtained from Messrs. Dow Corning), 65% sodium tripolyphosphate, 25% Tallow alcohol condensed with 25 molar proportions of ethylene oxide, and 3% moisture.
  • silica/silicone suds suppressor employed depends upon the degree of suds suppression desired but it is often in the range from 0.01% to 0.5% by weight of the detergent composition.
  • Other suds suppressors which may be used are water insoluble, preferably microcrystalline, waxes having melting point in the range from 35 to 125°C and saponification value less than 100, as described in British patent specification 1,492,938.
  • suds suppressing systems are mixtures of hydrocarbon oil, a hydrocarbon wax and hydrophobic silica as described in European patent application 782000035 and, especially, particulate suds suppressing compositions comprising such mixtures, combined with a nonionic ethoxylate having hydrophilic lipophilic balance in the range from 14-19 and a compatibilising agent capable of forming inclusion compounds, such as urea.
  • a compatibilising agent capable of forming inclusion compounds such as urea.
  • Soil suspending agents are usually present at about 0.1 to 10%, such as water soluble salts of carboxymethyl cellulose, carboxyhydroxymethyl cellulose, polyethylene glycols of molecular weight from about 400 to 10000 and copolymers of methylvinylether and maleic anhydride or acid, available from the General Aniline and Film Corporation under the Trade Name Gantrez.
  • Proteolytic, amylolytic or lipolytic enzymes especially proteolytic, and optical brighteners, of anionic, cationic or nonionic types, especially the derivatives of sulphonated triazinyl diamino stilbene may be present.
  • a further useful additive is a photo- activated bleach comprising mixture of the tri- and tetra sulphonated derivatives of zinc phthalocyanine as described in B.P. Specification Nos. 1372035 and 1408144.
  • sodium salts have been referred to potassium, lithium or ammonium or amine salts may be used instead if their extra cost etc., are justified for special.reasons.
  • the detergent compositions may be prepared in any way, as appropriate to their physical form, as by mixing the components, co-agglomerating them or dispersing them in a liquid carrier.
  • the compositions are granular and incorporate a detergent builder salt and are prepared by spray drying an aqueous slurry of the non-heat-sensitive components, (a), (c) and the builder salt (d) to form spray dried granules into'iihich may be admixed the heat sensitive components such as persalts, enzymes, perfumes etc.
  • the water soluble cationic (b) may be included in the slurry for spray drying, or it may be incorporated by dissolving or dispersing the cationic component in water or another suitable volatile liquid and then spraying this solution or dispersion onto the spray dried granules before or after other heat sensitive solids have been dry mixed with them.
  • the cationic component (b) can be dry mixed together with the other heat sensitive solids.
  • the clay component may be added to the slurry for spray drying or may be dry mixed, as preferred for reasons unrelated to its softening effect, such as for optimum colour of the product.
  • compositions were made up The compositions were made by first forming designated ingredients (a) into spray dried base granules. A concentrated aqueous solution of the quaternary ammonium compound (b) was then made up and sprayed on to the base powder to give crisp free flowing granules into which were dry mixed the remaining ingredients (c).
  • compositions were then used to wash 81b soiled fabric loads in a Miele Model 422 Drum Automatic machine set to a prewash-mainwash cycle in which the mainwash was a boil wash.
  • the water hardness was 14° Clark (Ca:Mg molar ratio 2:1) and the product usage was 70g in the prewash and 140 g in the mainwash.
  • Artifically soiled cotton tracers and clean terry towelling tracers were added to each wash to permit evaluation of respectively, the cleaning and softening performance of the compositions. Following the wash each load was air dried at ambient temperatures before being assessed by an expert panel. No differences in cleaning performance were apparent between either of the formulations but the softness assessment was as follows.
  • composition B was rated better for softness than A by 1.62 panel score units with a least significant difference (LSD) of 0.39 psu at the 95% confidence level.
  • LSD least significant difference
  • compositios B in accordance with the invention is superior in fabric softening performance to the prior art composition A whilst being equivalent to or slightly better than Composition A in cleaning performance.
  • the C 14 alkyl trimethyl quaternary component may be replaced by lauryl methyl dihydroxyethyl ammonium bromide, lauryl primary amine, C 12 -C 14 alkyl dimethyl amine, coconut alkyl trimethyl ammonium bromide and. N-tallowyl propylene diamine diacetate, whilst the sodium montmorillonite may be replaced by calcium montmorillonite, sodium hectorite or sodium saponite.

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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)
  • Detergent Compositions (AREA)
EP19800200878 1979-09-29 1980-09-18 Reinigungsmittelzusammensetzungen Expired EP0026529B2 (de)

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GB7933870 1979-09-29

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EP0026529B1 EP0026529B1 (de) 1984-12-05
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Cited By (78)

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EP0087914A1 (de) * 1982-03-01 1983-09-07 The Procter & Gamble Company Detergenszusammensetzung
FR2524903A1 (fr) * 1982-04-08 1983-10-14 Colgate Palmolive Co Assouplissant particulaire pour tissus a base de bentonite, procede pour sa preparation et composition detergente le contenant
DE3311568A1 (de) * 1982-04-08 1983-10-20 Colgate Palmolive Co Teilchenfoermiges und weichmachendes grobwaschmittel fuer textilien
EP0121949A1 (de) * 1983-02-15 1984-10-17 THE PROCTER & GAMBLE COMPANY Anionisch/kationische Detergensmischung mit irregulärer Struktur
EP0123489A2 (de) * 1983-04-20 1984-10-31 The Procter & Gamble Company Detergenszusammensetzungen
EP0146289A2 (de) * 1983-11-29 1985-06-26 The Procter & Gamble Company Wäschewaschmittel
GB2151219A (en) * 1983-11-05 1985-07-17 Perchem Ltd Organoclay materials
EP0163910A1 (de) * 1984-05-04 1985-12-11 Hoechst Aktiengesellschaft Weichmacher enthaltende Waschmittel
EP0181508A2 (de) * 1984-10-15 1986-05-21 Süd-Chemie Ag Waschmittelzusatz
EP0192630A2 (de) * 1985-02-21 1986-08-27 Monsanto Europe S.A./N.V. Aminomethylenphosphonat-Zusammensetzungen
FR2585362A1 (fr) * 1985-07-25 1987-01-30 Colgate Palmolive Co Composition detergente antistatique de blanchissage et compositions assouplissantes la contenant
FR2593517A1 (fr) * 1986-01-27 1987-07-31 Colgate Palmolive Co Composition detergente et assouplissante particulaire pour tissus, procede pour la preparer et son application au lavage des tissus
EP0264615A1 (de) * 1986-09-22 1988-04-27 Henkel Kommanditgesellschaft auf Aktien Phosphatreduziertes Waschmittel enthaltend N-alkoxylierte Fettsäureamide
EP0277522A2 (de) * 1987-01-24 1988-08-10 Henkel Kommanditgesellschaft auf Aktien Textilien weichmachendes Waschmittel
FR2611213A1 (fr) * 1987-02-20 1988-08-26 Colgate Palmolive Co Compositions detergentes et assouplissantes solides sans phosphate pour le lavage du linge, contenant un compose diammonique
US4839075A (en) * 1987-02-02 1989-06-13 Henkel Kommanditgesellschaft Auf Aktien Fabric-softening detergent
US4851138A (en) * 1986-09-02 1989-07-25 Akzo, N.V. Fabric softening composition and detergent-composition comprising the same
WO1989009204A1 (en) * 1988-04-02 1989-10-05 Henkel Kommanditgesellschaft Auf Aktien Quaternary ammonium compounds
US4919845A (en) * 1987-05-21 1990-04-24 Henkel Kommanditgesellschaft Auf Aktien Phosphate-free detergent having a reduced tendency towards incrustation
EP0364881A2 (de) 1988-10-21 1990-04-25 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung von tensidhaltigen Granulaten
AT394203B (de) * 1982-04-08 1992-02-25 Colgate Palmolive Co Teilchenfoermiges, bleichendes und weichmachendes textilwaschmittel sowie verfahren zur herstellung agglomerierter bentonitteilchen
US5149455A (en) * 1988-04-15 1992-09-22 Henkel Kommanditgesellschaft Auf Aktien Process for increasing the density of spray dried, phosphate-reduced detergents
DE4306665A1 (de) * 1993-03-03 1994-09-08 Sued Chemie Ag Waschmittelzusatz für gewebeweichmachende Waschmittel
WO1995029217A1 (en) * 1994-04-25 1995-11-02 The Procter & Gamble Company Stable, aqueous laundry detergent composition having improved softening properties
WO1995029218A1 (en) * 1994-04-25 1995-11-02 The Procter & Gamble Company Stable, aqueous laundry detergent composition having improved softening properties
US5501810A (en) * 1992-04-08 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Process for increasing the apparent density of spray-dried detergents
WO1997043389A1 (en) * 1996-05-17 1997-11-20 The Procter & Gamble Company Detergent composition
WO1997044431A1 (en) * 1996-05-17 1997-11-27 The Procter & Gamble Company Detergent composition
US5767057A (en) * 1993-09-04 1998-06-16 Henkel-Ecolab Gmbh & Co. Ohg Spray-dried granules of high apparent density
US5880083A (en) * 1994-08-16 1999-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquid bleach-containing formulation for washing or cleaning
US5883066A (en) * 1993-06-28 1999-03-16 The Procter & Gamble Company Liquid detergent compositions containing cellulase and amine
DE19948670A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmittel
WO2001046088A2 (de) 1999-12-22 2001-06-28 Cognis Deutchland Gmbh & Co. Kg Mehrkomponentige wertstoffgemische in fester form zur anregung und förderung des wachstums von pflanzen
GB2366801A (en) * 2000-09-19 2002-03-20 Procter & Gamble Detergent compositions with clay fabric softeners
US6413929B1 (en) 1996-03-26 2002-07-02 Basf Aktiengesellschaft Bleaching efficiency boosters for bleach and textile detergent compositions
US6479452B2 (en) 2000-06-29 2002-11-12 Cognis Deutschland Gmbh & Co. Kg Surfactant granules with an improved dissolving rate comprising alky and alkenyl sulfates
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US6610752B1 (en) 1999-10-09 2003-08-26 Cognis Deutschland Gmbh Defoamer granules and processes for producing the same
US6616705B2 (en) 2000-09-08 2003-09-09 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
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US6881359B2 (en) 2000-01-26 2005-04-19 Cognis Deutschland Gmbh & Co. Kg Processes for the preparation of low dust, limited particle size distribution, surfactant granules
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US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
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WO2021115724A1 (en) 2019-12-11 2021-06-17 Unilever Ip Holdings B.V. Detergent composition
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DE10019405A1 (de) 2000-04-19 2001-10-25 Cognis Deutschland Gmbh Verfahren zur Herstellung von Waschmittelgranulaten
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EP0000416A1 (de) * 1977-07-18 1979-01-24 THE PROCTER & GAMBLE COMPANY Antistatischer und textilweichmachender Waschmittelzusatz
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DE2648304A1 (de) * 1975-10-31 1977-05-05 Procter & Gamble Europ Fluessiges reinigungsmittel
EP0000416A1 (de) * 1977-07-18 1979-01-24 THE PROCTER & GAMBLE COMPANY Antistatischer und textilweichmachender Waschmittelzusatz
GB2020689A (en) * 1978-05-15 1979-11-21 Colgate Palmolive Co Detergent and softening compositions
EP0011340A1 (de) * 1978-11-20 1980-05-28 THE PROCTER & GAMBLE COMPANY Reinigungsmittelzusammensetzung mit Textil-Weichmachereigenschaften

Cited By (103)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0087914A1 (de) * 1982-03-01 1983-09-07 The Procter & Gamble Company Detergenszusammensetzung
FR2524903A1 (fr) * 1982-04-08 1983-10-14 Colgate Palmolive Co Assouplissant particulaire pour tissus a base de bentonite, procede pour sa preparation et composition detergente le contenant
DE3311568A1 (de) * 1982-04-08 1983-10-20 Colgate Palmolive Co Teilchenfoermiges und weichmachendes grobwaschmittel fuer textilien
AT394203B (de) * 1982-04-08 1992-02-25 Colgate Palmolive Co Teilchenfoermiges, bleichendes und weichmachendes textilwaschmittel sowie verfahren zur herstellung agglomerierter bentonitteilchen
EP0121949A1 (de) * 1983-02-15 1984-10-17 THE PROCTER & GAMBLE COMPANY Anionisch/kationische Detergensmischung mit irregulärer Struktur
EP0123489A2 (de) * 1983-04-20 1984-10-31 The Procter & Gamble Company Detergenszusammensetzungen
EP0123489A3 (en) * 1983-04-20 1987-05-20 The Procter & Gamble Company Detergent compositions
GB2151219A (en) * 1983-11-05 1985-07-17 Perchem Ltd Organoclay materials
EP0146289A2 (de) * 1983-11-29 1985-06-26 The Procter & Gamble Company Wäschewaschmittel
EP0146289A3 (en) * 1983-11-29 1988-01-13 The Procter & Gamble Company Laundry compositions
EP0163910A1 (de) * 1984-05-04 1985-12-11 Hoechst Aktiengesellschaft Weichmacher enthaltende Waschmittel
EP0181508A2 (de) * 1984-10-15 1986-05-21 Süd-Chemie Ag Waschmittelzusatz
EP0181508A3 (de) * 1984-10-15 1988-11-09 Süd-Chemie Ag Waschmittelzusatz
EP0192630A2 (de) * 1985-02-21 1986-08-27 Monsanto Europe S.A./N.V. Aminomethylenphosphonat-Zusammensetzungen
EP0192630A3 (en) * 1985-02-21 1988-09-07 Monsanto Europe S.A. Aminomethylenephosphonate compositions
FR2585362A1 (fr) * 1985-07-25 1987-01-30 Colgate Palmolive Co Composition detergente antistatique de blanchissage et compositions assouplissantes la contenant
BE1002175A5 (fr) * 1986-01-27 1990-10-02 Colgate Palmolive Co Composition detergente et assouplissante particulaire pour tissus, procede pour la preparer et son application au lavage des tissus.
FR2593517A1 (fr) * 1986-01-27 1987-07-31 Colgate Palmolive Co Composition detergente et assouplissante particulaire pour tissus, procede pour la preparer et son application au lavage des tissus
US4851138A (en) * 1986-09-02 1989-07-25 Akzo, N.V. Fabric softening composition and detergent-composition comprising the same
EP0264615A1 (de) * 1986-09-22 1988-04-27 Henkel Kommanditgesellschaft auf Aktien Phosphatreduziertes Waschmittel enthaltend N-alkoxylierte Fettsäureamide
EP0277522A2 (de) * 1987-01-24 1988-08-10 Henkel Kommanditgesellschaft auf Aktien Textilien weichmachendes Waschmittel
EP0277522A3 (de) * 1987-01-24 1990-03-14 Henkel Kommanditgesellschaft auf Aktien Textilien weichmachendes Waschmittel
US4839075A (en) * 1987-02-02 1989-06-13 Henkel Kommanditgesellschaft Auf Aktien Fabric-softening detergent
GR880100091A (en) * 1987-02-20 1988-12-16 Colgate Palmolive Co Smoothing detergent composition for fabrics not containing phosphorus
FR2611213A1 (fr) * 1987-02-20 1988-08-26 Colgate Palmolive Co Compositions detergentes et assouplissantes solides sans phosphate pour le lavage du linge, contenant un compose diammonique
BE1003069A4 (fr) * 1987-02-20 1991-11-12 Colgate Palmolive Co Compositions detergentes et assouplissantes solides sans phosphate pour le lavage du linge contenant un compose diammonique.
US4919845A (en) * 1987-05-21 1990-04-24 Henkel Kommanditgesellschaft Auf Aktien Phosphate-free detergent having a reduced tendency towards incrustation
WO1989009204A1 (en) * 1988-04-02 1989-10-05 Henkel Kommanditgesellschaft Auf Aktien Quaternary ammonium compounds
EP0336267A3 (de) * 1988-04-02 1989-10-25 Henkel Kommanditgesellschaft auf Aktien Quartäre Ammoniumverbindungen
EP0336267A2 (de) * 1988-04-02 1989-10-11 Henkel Kommanditgesellschaft auf Aktien Quartäre Ammoniumverbindungen
US5149455A (en) * 1988-04-15 1992-09-22 Henkel Kommanditgesellschaft Auf Aktien Process for increasing the density of spray dried, phosphate-reduced detergents
US5354493A (en) * 1988-10-21 1994-10-11 Henkel Kommanditgesellschaft Auf Aktien Process for the production of surfactant-containing granulates
EP0364881A2 (de) 1988-10-21 1990-04-25 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung von tensidhaltigen Granulaten
US5501810A (en) * 1992-04-08 1996-03-26 Henkel Kommanditgesellschaft Auf Aktien Process for increasing the apparent density of spray-dried detergents
US5480578A (en) * 1993-03-03 1996-01-02 Sud-Chemie Ag Detergent additive for detergents containing a fabric softener
DE4306665A1 (de) * 1993-03-03 1994-09-08 Sued Chemie Ag Waschmittelzusatz für gewebeweichmachende Waschmittel
US5883066A (en) * 1993-06-28 1999-03-16 The Procter & Gamble Company Liquid detergent compositions containing cellulase and amine
US5767057A (en) * 1993-09-04 1998-06-16 Henkel-Ecolab Gmbh & Co. Ohg Spray-dried granules of high apparent density
WO1995029217A1 (en) * 1994-04-25 1995-11-02 The Procter & Gamble Company Stable, aqueous laundry detergent composition having improved softening properties
WO1995029218A1 (en) * 1994-04-25 1995-11-02 The Procter & Gamble Company Stable, aqueous laundry detergent composition having improved softening properties
US5622925A (en) * 1994-04-25 1997-04-22 The Procter & Gamble Company Stable, aqueous laundry detergent composition having improved softening properties
US5880083A (en) * 1994-08-16 1999-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquid bleach-containing formulation for washing or cleaning
US6413929B1 (en) 1996-03-26 2002-07-02 Basf Aktiengesellschaft Bleaching efficiency boosters for bleach and textile detergent compositions
US6136769A (en) * 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
WO1997044432A1 (en) * 1996-05-17 1997-11-27 The Procter & Gamble Company Detergent composition
WO1997044431A1 (en) * 1996-05-17 1997-11-27 The Procter & Gamble Company Detergent composition
JPH11510554A (ja) * 1996-05-17 1999-09-14 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物
JPH11511795A (ja) * 1996-05-17 1999-10-12 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物
JPH11511799A (ja) * 1996-05-17 1999-10-12 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物
JP2000504061A (ja) * 1996-05-17 2000-04-04 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物
WO1997043390A1 (en) * 1996-05-17 1997-11-20 The Procter & Gamble Company Detergent composition
WO1997043389A1 (en) * 1996-05-17 1997-11-20 The Procter & Gamble Company Detergent composition
US6562769B1 (en) 1997-10-23 2003-05-13 Henkel Kommanditgesellschaft Auf Aktien Method for producing aromatic beads
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
US6780829B1 (en) 1998-12-19 2004-08-24 Cognis Deutschland Gmbh & Co. Kg Tenside granulates comprising fatty alcohol sulfate and olefin sulfonates
US6494920B1 (en) 1999-02-04 2002-12-17 Cognis Deutschland Gmbh & Co. Kg Detergent mixtures
US6521578B1 (en) 1999-04-22 2003-02-18 Cognis Deutschland Gmbh Cleaning agents for hard surfaces
US6664429B1 (en) 1999-08-20 2003-12-16 Cognis Deutschland Gmbh & Co. Kg Production of branched, largely unsaturated fatty alcohol polyglycolethers
US6723867B1 (en) 1999-08-20 2004-04-20 Cognis Deutschland Gmbh & Co. Kg Branched, substantially unsaturated fatty alcohol sulfates
US6951838B1 (en) 1999-09-15 2005-10-04 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
DE19948670A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmittel
US6610752B1 (en) 1999-10-09 2003-08-26 Cognis Deutschland Gmbh Defoamer granules and processes for producing the same
US6686327B1 (en) 1999-10-09 2004-02-03 Cognis Deutschland Gmbh & Co. Kg Shaped bodies with improved solubility in water
US7145001B1 (en) 1999-10-27 2006-12-05 Cognis Deutschland Gmbh & Co. Kg Method for producing solid sugar surfactants
US7199096B1 (en) 1999-11-09 2007-04-03 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
US7049279B1 (en) 1999-11-25 2006-05-23 Cognis Deutschland Gmbh & Co. Kg Process for preparing detergent granules with an improved dissolution rate
US6977239B1 (en) 1999-11-25 2005-12-20 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
WO2001046088A2 (de) 1999-12-22 2001-06-28 Cognis Deutchland Gmbh & Co. Kg Mehrkomponentige wertstoffgemische in fester form zur anregung und förderung des wachstums von pflanzen
US7087570B2 (en) 1999-12-24 2006-08-08 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
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US6881359B2 (en) 2000-01-26 2005-04-19 Cognis Deutschland Gmbh & Co. Kg Processes for the preparation of low dust, limited particle size distribution, surfactant granules
US7098178B2 (en) 2000-03-16 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Silicic acid ester mixtures
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US6756351B2 (en) 2000-04-18 2004-06-29 Cognis Deutschland Gmbh & Co. Kg Detergents and cleaning agents
US6479452B2 (en) 2000-06-29 2002-11-12 Cognis Deutschland Gmbh & Co. Kg Surfactant granules with an improved dissolving rate comprising alky and alkenyl sulfates
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DE102013226098A1 (de) 2013-12-16 2015-06-18 Henkel Kgaa Silylenolether von Riechstoffketonen oder -aldehyden
DE102013226216A1 (de) 2013-12-17 2015-06-18 Henkel Ag & Co. Kgaa Michael-Systeme für die Duftstoff-Stabilisierung
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DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit
DE102016201295A1 (de) 2016-01-28 2017-08-03 Henkel Ag & Co. Kgaa C8-10-Alkylamidoalkylbetain als Antiknitterwirkstoff
DE102017206013A1 (de) 2017-04-07 2018-10-11 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit verbessertem Schaumverhalten
WO2019068505A1 (de) 2017-10-06 2019-04-11 Henkel Ag & Co. Kgaa Hydrolyselabile silylenolether von riechstoffketonen oder -aldehyden
DE102017123282A1 (de) 2017-10-06 2019-04-11 Henkel Ag & Co. Kgaa Hydrolyselabile Silylenolether von Riechstoffketonen oder -aldehyden
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DE102017124611A1 (de) 2017-10-20 2019-04-25 Henkel Ag & Co. Kgaa Thermolabile Duftspeicherstoffe von Riechstoffketonen
WO2019076589A1 (de) 2017-10-20 2019-04-25 Henkel Ag & Co. Kgaa Hydrolyselabile dienolsilylether von riechstoffketonen oder -aldehyden
WO2019076588A1 (de) 2017-10-20 2019-04-25 Henkel Ag & Co. Kgaa Thermolabile duftspeicherstoffe von riechstoffketonen
DE102017127776A1 (de) 2017-11-24 2019-05-29 Henkel Ag & Co. Kgaa Hydrolyselabile Heterocyclen von Riechstoffketonen oder -aldehyden
WO2019101444A1 (de) 2017-11-24 2019-05-31 Henkel Ag & Co. Kgaa Hydrolyselabile heterocyclen von riechstoffketonen oder -aldehyden
EP3578629A1 (de) 2018-06-07 2019-12-11 Henkel AG & Co. KGaA Verfahren zur herstellung eines flüssigen wasch- oder reinigungsmittels mit einer konservierungsmittelfreien farbstofflösung
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Also Published As

Publication number Publication date
EP0026529B1 (de) 1984-12-05
EP0026529B2 (de) 1992-08-19
DE3069768D1 (en) 1985-01-17

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