EP0026529B1 - Reinigungsmittelzusammensetzungen - Google Patents

Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0026529B1
EP0026529B1 EP19800200878 EP80200878A EP0026529B1 EP 0026529 B1 EP0026529 B1 EP 0026529B1 EP 19800200878 EP19800200878 EP 19800200878 EP 80200878 A EP80200878 A EP 80200878A EP 0026529 B1 EP0026529 B1 EP 0026529B1
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EP
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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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EP0026529B2 (de
EP0026529A1 (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

    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary 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 3,644,203.
  • 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.
  • European Patent Applications Publication Nos. 0011340 and 0023367 also disclose cleaning and softening compositions comprising a tertiary amine, containing at least one and preferably two C 10 ⁇ C 26 alkyl groups and being of nonionic character under alkaline conditions, in combination with a smectite-type clay in an alkaline anionic surfactant-based detergent.
  • a tertiary amine containing at least one and preferably two C 10 ⁇ C 26 alkyl groups and being of nonionic character under alkaline conditions
  • a smectite-type clay in an alkaline anionic surfactant-based detergent is taught in British Patent Specification No. 1,400,898.
  • This type of softening agent does not affect the cleaning performance of the detergent composition but, if used on its own, requires a high level of incorporation for effective softening performance possibly because the deposition of the clay on fabrics is not very efficient in the presence of anionic surfactants.
  • 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 comprising component (d).
  • the invention comprises three components, namely the anionic surfactant component (a), 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-sulfo- carboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acyloxy-alkane-1-sulfonates, and beta-alkyloxy alkane sulfonates. Soaps are also suitable anionic surfactants.
  • Especially preferred alkyl benzene sulfonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, more especially 11 to 13 carbon atoms.
  • Suitable alkyl sulfates have 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms.
  • Suitable alkyl polyethoxy ether sulfates have 10 to 18 carbon atoms in the alkyl chain and have an average of 1 to 12 ⁇ CH 2 CH 2 O ⁇ representativess per molecule, especially 10 to 16 carbon atoms in the alkyl chain and an average of 1 to 6 -CH 2 CH 2 0- groups per molecule.
  • Suitable paraffin sulfonates are essentially linear and contain from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms.
  • Suitable alphaolefin sulfonates have 10 to 24 carbon atoms, more especially 14 to 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 alphasulfocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alphasulfonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms.
  • Suitable alkyl glyceryl ether sulfates are ethers of alcohols having 10 to 18 carbon atoms, more especially those derived from coconut oil and tallow.
  • Suitable alkyl phenol polyethoxy ether sulfates have 8 to 12 carbon atoms in the alkyl chain and an average of 1 to 6 ⁇ CH 2 CH 2 O ⁇ groups per molecule.
  • Suitable 2-acryloxy-alkane-1-sulfonates contain from 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane moiety.
  • Suitable beta-alkyloxy alkane sulfonates contain 1 to 3 carbon atoms in the alkyl group and 8 to 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 8 to 18 carbon atoms, more especially 12 to 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 anionic detergent, preferably from 4 to 15% of anionic detergent, more preferably 5-10% of anionic surfactant.
  • the second 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;
  • 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, methosulphate, acetate and phosphate ions.
  • 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 15% 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 50 microns (um); the clays used herein normally have a particle size range of from 5 microns (um) to 50 microns ( ⁇ m).
  • the clay minerals can be descrined 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 4.0 and y has a value of from 0 to 2.0.
  • montmorillonites having exchange capacities greater than 50 meq/100 g. are suitable for the present invention and provide fabric softening benefits.
  • 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 (M 6-x Li x )O 20 , saponite (OH) 4 Si 8-y Al y (Zn 6-x 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 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.
  • Smectite clay (Na) + smectite clay (NH 4 )+NaOH. Since in the foregoing equilibrium reaction one equivalent weight of ammonium ion replaces an equivalent weight of sodium, it is customary to measure cation exchange capacity (sometimes termed "base exchange capacity") in terms of milli- equivalents per 100 g. of clay (meq/100 g).
  • base exchange capacity cation exchange capacity
  • the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971).
  • 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 2 meq/100 g. for kaolinites to 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 AI and Mgatoms.
  • smectite clays useful herein can be characterised as montmorillonite, hectorites, and saponite clay minerals having an ion exchange capacity of at least 50 meq/100 g. and preferably at least 60 meq/100 g.
  • Most of the smectitie clays useful in the compositions herein are commercially available under various trade names, for example, Thixogel No. 1 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 When used in compositions according to the invention, is present in an amount of from 1.5% to 45% by weight of the composition, preferably from 2% to 15%, especially from 5% to 12%.
  • the detergent compositions of the present invention may of course include, as optional ingredients, components that are usually found in laundry detergents, these components being present in an amount of up to 95% by weight of the composition.
  • 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 ⁇ 18 (EO) 11 .
  • Suitable zwitterionic surfactants include the C, 2 -C, 6 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, tri-polyphosphates, 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 Si0 2 :Na z 0) from 1:1 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.
  • 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 0.5:1 and x is an integer from 15 to 264.
  • a preferred material is Na,2(SiOAI02),227H20. If present, incorporation of 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-ethanolamides 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 1% to 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 disclosed 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. Down 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 Publication No. 0000216 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 0.1 to 10%, such as water soluble salts of carboxymethyl cellulose, carboxyhydroxymethyl cellulose, polyethylene glycols of molecular weight from 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 optional 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, 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 which may be admixed the heat sensitive components such as persalts, enzymes, perfumes.
  • 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 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 70 g 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 softeness 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
  • compositions 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, 4 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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Claims (8)

1. Wasch- und Reinigungsmittel enthaltend
(a) 3 bis 40% eines anionischen oberflächenaktiven Stoffes,
(b) 0,5 bis 15% einer stickstoffhaltigen organischen Verbindung, die in kationischer Form in einer 0,1 %igen wäßrigen Lösung bei einem pH-Wert von 10 existieren kann und ausgewählt ist aus
(i) quaternären Ammoniumverbindungen der Formel
Figure imgb0011
worin R7 C8―C16-Alkyl, R8, R9 und R10 jeweils unabhängig voneinander C1―C4-Alkyl oder -Hydroxyalkyl, Benzyl oder ―(C2H4O)xH, worin x einen Wert von 2 bis 5 aufweist und worin nicht mehr als eines von R8, R9 oder R10 Benzyl ist und X-ein Anion bedeuten,
(ii) Aminen der allgemeinen Formel
Figure imgb0012
worin R11 C8―C18-Alkyl, R12 und R13 unabhängig voneinander Wasserstoff, C1―C4-Alkyl oder - Hydroxyalkyl, Benzyl oder ―(C2H4O)xH bedeuten, worin x einen Wert von 2 bis 5 aufweist und deren wasserlösliche Salze;
(c) 1,5 bis 45 Gew.-% des Mittels eines sehr feinen nicht tastbaren Smectittons mit einer lonenaustauschkapazität von mindestens 50 mÄq. je 100 g, vorausgesetzt, daß das Molverhältnis von Komponente (b) zu Komponente (a) weniger als 1:1 ist und
(d) 0 bis 95% Waschmittelkomponenten unterschiedlich von denjenigen von a), b) und c), wobei die Mengen von a), b), c) und falls vorhanden d) eine Gesamtmenge von 100 Gew.-% ausmachen.
2. Wasch- und Reinigungsmittel nach Anspruch 1, worin das Molverhältnis von (b) zu (a) weniger als 1:2 beträgt.
3. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 und 2, worin die wasserlösliche kationische Verbindung (b) ausgewählt ist aus quaternären Ammoniumsalzen, worin R7 C12―C14-Alkyl und R8, R9 und R10 ausgewählt sind aus Methyl- und Hydroxyethylgruppen.
4. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 bis 3, worin der Smectitton ein Natrium- oder Calciummontmorillonitton ist.
5. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 bis 4, enthaltend 4 bis 15% der Komponente (a), 1 bis 5% der Komponente (b) und 2 bis 15% der Komponente (c).
6. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 bis 5, worin Komponente (d) 10 bis 80 Gew.-%, bezogen auf das Mittel, eines Detergensgerüststoffsalzes enthält.
7. Granulares Wasch- und Reinigungsmittel nach Anspruch 6, worin Komponente (b) vorgeformten Granulaten zugesetzt ist, enthaltend Komponenten (a), (c) und (d).
8. Granulares Wasch- und Reinigungsmittel nach Anspruch 7, wirin die vorgeformten Granulate sprühgetrocknet sind.
EP19800200878 1979-09-29 1980-09-18 Reinigungsmittelzusammensetzungen Expired EP0026529B2 (de)

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EP0173398B1 (de) * 1984-08-29 1991-10-16 Unilever N.V. Detergenszusammensetzung

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