EP0037184B1 - Flüssige Reinigungsmittelzusammensetzungen, deren Herstellung und deren Verwendung in Waschverfahren - Google Patents

Flüssige Reinigungsmittelzusammensetzungen, deren Herstellung und deren Verwendung in Waschverfahren Download PDF

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Publication number
EP0037184B1
EP0037184B1 EP19810300964 EP81300964A EP0037184B1 EP 0037184 B1 EP0037184 B1 EP 0037184B1 EP 19810300964 EP19810300964 EP 19810300964 EP 81300964 A EP81300964 A EP 81300964A EP 0037184 B1 EP0037184 B1 EP 0037184B1
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EP
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Prior art keywords
composition according
weight
surfactant
alkali metal
phosphonate
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EP19810300964
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English (en)
French (fr)
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EP0037184A3 (en
EP0037184A2 (de
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Eileen Smith
Doreen Ann Timperley
Dorothy Margaret Titchener
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Solvay Interox Ltd
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Interox Chemicals Ltd
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Priority to AT81300964T priority Critical patent/ATE11427T1/de
Publication of EP0037184A2 publication Critical patent/EP0037184A2/de
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to liquid detergent compositions and more particularly to built liquid detergents compositions containing an active oxygen-containing compound.
  • the rate of loss of activity of the solid active oxygen-containing compound can be significantly reduced to acceptable levels by contacting the compound with various peroxygen compound stabilisers, of which a particularly appropriate sort comprises alkali or alkaline earth metal silicates, as described for example in GB-A-1553505 to Interox Chemicals Ltd., and alternatively or additionally coating the solid particles of the compound with a suitable organic or inorganic barrier to prevent the compound coming into contact with the other components of the washing composition.
  • suitable organic or inorganic barrier to prevent the compound coming into contact with the other components of the washing composition.
  • compositions stabilised by coating are described in US-A-3847830 assigned to Laporte Industries Limited and US-A-3992317 and US-A-41 05827, both assigned to Interox S.A.
  • detergent compositions can include organic complexing agents as builders.
  • organic complexing agents such as about 1 percent by weight were tested at 32°C for long-term storage compatibility with hydrogen peroxide under mildly alkaline conditions, the result was, in general, an unacceptable loss of peroxidic activity.
  • an aqueous hydrogen peroxide solution containing 1 percent of ethylenediamine tetraacetic acid, tetra sodium salt lost a remarkable 96 percent within two weeks and that containing 1 percent of nitrilotriacetic acid, trisodium salt lost an enormous 79 percent in one week.
  • a stabilised aqueous built liquid detergent composition comprising a surfactant, builder, water, hydrotrope and if desired one or more detergent adjuvants characterised in that contains
  • the anionic surfactant is an alkyl aryl sulphonate and in order to assist its biodegradability is preferably a linear alkyl aryl sulphonate.
  • the alkyl group preferably contains from 9 to 18 carbon atoms, particularly the decyl, dodecyl or tetradecyl groups. Although other aryl groups can be used, the aryl group is normally benzene. Examples of suitable commercially available alkali metal alkyl aryl sulphonates are available under the trade names Warcodet K54 from Warwick Chemicals, England, Nansa SS60 from Albright and Wilson, England and especially Hetsulf 60S from Heterene Chemicals Co., New Jersey.
  • Suitable anionic sulphate surfactants include primary alcohol sulphates and primary alcohol ether sulphates, the alkyl group in the alcohol moiety of such compounds normally containing from 9 to 18 and frequently from 12 to 15 carbon atoms.
  • Commerically available examples of such compounds include Perlankrol D.S.A., E.S.D and E.A.D.
  • sulphonate surfactants include n-alkane and olefin sulphonates, the aliphatic moiety normally containing at least 12 and often from 13 to 18 carbon atoms. Examples of such compounds are available under the trade name Hostapur S.A.S. and O.S. from Hoechst (UK). Mixtures of any two or more of the foregoing anionic surfactants can be employed. Generally the concentrate contains at least 3% of the anionic sulphate and/or sulphonate surfactant and usually not more than 15%.
  • the non-ionic surfactant component of the composition is selected from primary alcohol ethoxylates and linear secondary alcohol ethoxylates.
  • the alcohol component in each of these compounds preferably has a carbon chain length of R in the general formula RO(C Z H 4 0) " H of at least 9 and frequently not more than 18 carbon atoms, extending away from the ethoxylate moiety.
  • the linear carbon chain of R is in the range of from 11 to 16 carbon atoms and in many cases the surfactant is derived from a mixture of alcohols.
  • the degree of ethoxylation n is generally in the range of from 5 to 20 and in many very desirable ethoxylates, n is from 7 to 12.
  • the proportion is desirably at least 50%, normally not more than 85% and preferably at least 60% up to 80%.
  • a most desirable range of surfactants contains from 60 to 80%, preferably 65 to 75% by weight of the ethoxylate moiety and the alcohol moiety is a linear C, 2 , C, 3 , C 14 , C, 5 or C, 6 or a mixture of linear alcohols having an average carbon chain length within the range of 12 to 16. It will be recognised that in many preferred alcohol ethoxylates, the ratio of the number of carbon atoms in R to the degree of ethoxylation n in the ethoxylate moiety is generally in the range of from 3:2 to 2:1.
  • Suitable commercially available alcohol ethoxylates are available under the tradenames Synperonic A.7, A.9, and A.11, all from I.C.I., England, in which R is a mixture of C, 3 and C '5 and the degree of ethoxylation are respectively 7, 9 and 11, Tergitol 15-S-9 and 15-S-12, from Union Carbide, U.S.A., being C 11-15 linear secondary alcohol ethoxylates, having degrees of ethoxylation of respectively 9 and 12, Lubrol 12 A.9 and 17 A.10 from I.C.I., England, the average chain lengths of R being respectively 12 and 17 and the degrees of ethoxylation 9.5 and 10, Ethylan CD9112 and D259, both from Diamond Shamrock, and Brij 35, 78 and 98, being respectively the lauryl, stearyl and oleyl ethers of polyoxyethylenes from I.C.I., and Renex 20 being a polyoxyethylene mixed fatty acid ester
  • a further polyethylene oxide condensate that can be employed is available under the trade name Mykon 100 from Warwick Chemicals. Mixtures of two or more ethoxylated surfactants can be used. The amount of nonionic surfactant used is normally at least 3% and frequently not more than 15%.
  • a third essential component of the built liquid detergent composition of the present invention is a builder selected from polyphosphate and carboxylic acid complexing builders.
  • the polyphosphates it is especially suitable to employ pyrophosphates, and more particularly the tetrapotassium or tetrasodium salts or mixtures thereof.
  • the tetra-potassium pyrophosphate salt is selected, by virtue of its solubility being superior to that of the corresponding sodium salt in concentrated liquid detergent compositions.
  • a di-alkali metal di-hydrogen pyrophosphate as a proportion of the polyphosphate builder, its incorporation e.g.
  • polyphosphate builder mix tends to produce a lower pH in the washing solution obtained simply by dissolution of the liquid detergent composition, providing a wash and stain removal detectably inferior to that obtained when the tetra alkali metal salt is employed instead, in otherwise identical compositions.
  • the polyphosphate can be introduced into the detergent composition either as a solid which is dissolved, or in the form of an aqueous solution, but the percentages given herein are of a dry weight basis.
  • the organic complexing builders contemplated herein tend to fall into three classes, hydroxycarboxylic acid, aminocarboxylic acid and oxacarboxylic acid.
  • hydroxycarboxylic acid builders a particularly suitable one is citric acid, usually introduced as the tri-alkali metal salt, and on cost grounds, as the trisodium salt.
  • Mixtures of the hydroxycarboxylic acid builders and polyphosphates, for example citric acid and tetrapyrophosphate both in salt form, can also be used, often in a weight ratio of 2:1 to 1:2.
  • an alkaline adjuster, sodium metaborate is very suitable. It is desirable to use not more than about 20% of pyrophosphates and where tripolyphosphate is used not more than about 10 to 15%.
  • nitrilo triacetic acid normally alkali metal salt thereof, (NTA) is most prominent.
  • NTA alkali metal salt thereof
  • use of the salt tends to produce a somewhat higher pH than of a corresponding weight of hydroxycarboxylic acid complexing builder and probably as a result thereof the resultant built detergent composition tends to show slightly inferior hydrogen peroxide stability.
  • it is preferable to downwardly adjust the pH of the mix by introducing it in part acid form. In practice, often not more than 10% NTA is employed.
  • carboxymethyloxysuccinate deserves mentioned. For practical reasons it is preferable to employ from 5 to 8% of this builder. Where higher than 8% builder is desired, the balance above 8% is more advantageously provided by one of the other aforementioned builders.
  • the sulphonate hydrotropes are suitably the alkali metal salts of benzene or methyl-substituted benzene sulphonates, most commonly xylene sulphonate and toluene sulphonate.
  • the sodium or potassium salt is employed.
  • a proportion of the hydrotrope can be provided by incorporation of one or more ethoxylated phosphate esters. Such esters chemically can be regarded as phosphate ester derivatives of the aforementioned non-ionic ethoxylate surfactants described hereinbefore. In many embodiments, the product used is a mixture of the two.
  • the degree of ethoxylation in the ethoxylated moiety is generally the range from 2 to 12 and often in the range of 2 to 6, and the carbon chain length of the hydrophobic alkyl group R is normally from 9 to 18.
  • the alkyl group is often from C ⁇ to C, 21 their use for such purposes is being increasingly viewed with hostility by water authorities because suitable methods have not yet been found to degrade them biologically.
  • the phosphate esters often are available in the acid form and they can be employed as such in the liquid detergent compositions of the present invention, but their use in that way does tend to lower the pH of the composition and of the subsequent washing solution and if desired, the phosphate ester can be partially or completely neutralised with alkali metal hydroxide, especially sodium or potassium hydroxide or ammonium hydroxide.
  • the total proportion of sulphonate hydrotrope plus ethoxylated phosphate ester is normally selected within the range of from 3% to 12%, of which the sulphonate hydrotrope is frequently from 3 to 9% and the ethoxylated phosphate ester the balance.
  • a small proportion of ethoxylated phosphate ester, for example from 1 to 3% can be advantageous in improving the washing ability of the composition for certain commonly encountered stains like cocoa, for example where the ratio of the anionic to non-ionic surfactant is relatively high, such as at approximately 1:1 or higher.
  • the stabiliser system for hydrogen peroxide in the composition comprises an amino methylene phosphonate or hydroxyalkyl diphosphonate and either or both of a low molecular weight aliphatic alcohol, and a polyhydroxy aliphatic carboxylate.
  • the low molecular weight aliphatic alcohol is most preferably ethanol, particularly in the view of its combination of properties in that, not only does it effectively and surprisingly improve the storage stability of hydrogen peroxide in the composition, in combination with the other components despite the fact that its presence tends to increase the alkalinity of the solution, as measured by a standard pH electrode, but it also cooperates with the aforementioned hydrotropes in retaining a one phase system and consequently provides higher flexibility in formulating compositions.
  • the low molecular weight aliphatic alcohol is employed, preferably in an amount of at least 5% of the composition and is not more than 15%. In many embodiments it is employed within the range of from 7 to 12%.
  • the higher weight aliphatic alcohols such as propanol and butanol are considerably less desirable by virtue, it is believed, of their poorer water solubility so that the compounds can be employed to only a much smaller proportion of the composition than can ethanol.
  • many of the compositions described herein containing comparatively high amounts of surfactant and builder can remain in a single-storage stable phase when they contain 10% of ethanol, but when the same amount of butanol or propanol is employed instead, phase separation occurs.
  • the polyhydroxyaliphatic carboxylate generally contains at least 5 carbon atoms and normally up to 10 carbon atoms. Although the carbon chain in the molecule can be branched, in many effective examples the compound is linear, terminating at one end in a carboxylate group, and preferably having a chain length of 5, 6 or 7 carbon atoms. Desirably all, or at least the majority of the remaining carbon atoms are substituted by an hydroxyl group.
  • the compound can be in acid form, but preferably is neutralised with an alkali metal, preferably sodium or potassium. Preferred compounds of this class include the acid or neutralised forms of gluconic acid and glycero-ido heptonate.
  • the polyhydroxy compound is employed in an amount of at least 0.08% of the composition and not more than 1%.
  • the phosphonate component of the stabilised system can be introduced in the acid form, but it will be recognised that, if the acid form is employed initially, to a certain extent the resultant solution will have a lower pH and impairment of overall washing perfoimance can thereby ensue.
  • the phosphonate component is therefore introduced preferably in an at least partial alkali metal salt form.
  • amino methylene phosphonates is meant any compound containing an amino group substituted by a methylene phosphonic acid group or a salt thereof.
  • Many suitable phosphonates can be represented by the general formula, in acid form:- in which p is normally from 2 to 6 and q is normally from 0 to 2.
  • ethylene diamino tetra (methylene phosphonic acid) hexa potassium salt and diethylene triamino penta (methylene phosphonic acid) or hexa potassium salt.
  • Further suitable examples include hexamethylene diamino tetra (methylene phosphonic acid), penta sodium salt and amino tri(methylene phosphonic acid) penta sodium salt.
  • one or more of the methylene groups linking the amino groups can be substituted at the carbon atom by a lower alkyl group or at one carbon only by an hydroxyl group or the substituents of two such suitably spaced, preferably adjacent carbon atoms can combine to form cycloaliphatic ring preferably containing 5 or 6 carbon atoms.
  • the aliphatic diphosphonates can conveniently be represented in acid form by the formula YZC(P0 3 H 2 ) 2 in which Y represents an hydroxyl or amino group, the amino group itself optionally being substituted by a lower alkyl, a lower alkylamino or a lower hydroxyalkyl group, lower indicating from 1 to 4 carbon atoms, and Z represents a lower alkyl, preferably methyl group.
  • Y represents an hydroxyl or amino group
  • the amino group itself optionally being substituted by a lower alkyl, a lower alkylamino or a lower hydroxyalkyl group, lower indicating from 1 to 4 carbon atoms
  • Z represents a lower alkyl, preferably methyl group.
  • Examples of such diphosphonates include 1-amino ethane-1,1-diphosphonic acid and 1-hydroxyethane-1,1- diphosphonic acid, and preferably the alkali metal salts thereof.
  • Mixtures of any two or more of the aforementioned amino-methylene phosphates and/or diphosphonates can be employed, as desired.
  • Such a compound or compounds are employed in an amount of at least 0.075% by weight of the composition and not more than 1% and often the amount is selected from the range of 0.1% to 0.4%.
  • Use of larger amounts than 1 % do not in general repay the additional cost of their incorporation, and for each phosphonate an amount is reached beyond which increasing the amount leads to impaired stabilisation.
  • the weight ratio of the polyhydroxy compound to the phosphonate is within the range of 3 to 1 to 1 to 3 and often within the range of 2 to 1 to 1 to 1, and their combined % is preferably from 0.2 to 1.0%.
  • the lower molecular weight aliphatic alcohol is selected within a weight ratio to the phosphonate of from 50:1 to 2.5:1, and preferably from 50 to 1 to 20 to 1, when the stabiliser system consists of the phosphonate and the alcohol, preferably employing a comparatively high amount of the phosphonate, namely at least 0.15% generally up to 0.4%.
  • the weight ratio is varied inversely to variation in the phosphonate concentrate.
  • the product of the weight ratio of alcohol to phosphonate and the concentration of the phosphonate expressed as a percentage in the two component stabiliser system is preferably at least 8 and often from 9 to 12. It is specially desirable to employ all three stabiliser components together in the detergent composition especially in a combined amount of at least 0.2% for the polyhydroxy compound and the phosphonate, and at least 5% of the aliphatic alcohol. In many embodiments, it is convenient and advantageous to select the components within the ranges of 0.1 to 0.4% for each of the polyhydroxy and phosphonate components and from 5 to 12 and particularly from 8 to 12% for the aliphatic alcohol, especially ethanol.
  • the hydrogen peroxide can conveniently be incorporated in the form of the appropriate amount of concentrated hydrogen peroxide, e.g. 35 to 85% W/W hydrogen peroxide commercially available, which often contains from 10 ppm pyrophosphate. It is often incorporated in the solution in the range of from 3 to 10%, frequently from 5 to 8% and for industrial uses often from 10 to 20% (expressed as 100%). Lower concentration of hydrogen peroxide could be employed, but in general these would not enable a desirable amount of active oxygen to be provided in the washing solution unless the concentration of the other components in the detergent composition were correspondingly reduced also.
  • concentrated hydrogen peroxide e.g. 35 to 85% W/W hydrogen peroxide commercially available, which often contains from 10 ppm pyrophosphate. It is often incorporated in the solution in the range of from 3 to 10%, frequently from 5 to 8% and for industrial uses often from 10 to 20% (expressed as 100%). Lower concentration of hydrogen peroxide could be employed, but in general these would not enable a desirable amount of active oxygen to be provided
  • the concentration of hydrogen peroxide in the range 5 to 8% in the detergent composition when diluted to form a washing solution by a factor selected within the range of 100:1 to 1000:1 and often preferably from 200:1 to 500:1 can readily provide active oxygen concentrations commensurate with those provided by normal concentrations of many heavy duty solid detergent compositions or by the addition of an active oxygen bleach at recommended levels to commercially obtainable active oxygen-free liquid detergents.
  • the total proportion of components other than water and hydrogen peroxide normally is selected to be not greater than 52%. Use of a higher proportion, particularly where the composition contains relatively high proportions of builder and anionic surfactants tends to become more sensitive to phase separation. Although a total proportion, e.g. below 20% of such components could be employed in compositions, whether built or not, it is more desirable to provide such components to a total proportion of at least 20% and more preferably at least 30% of the liquid composition, not only from the point of view of reducing the volume of unnecessary water to be transported but also because the user often associates dilute products with inferior products. In many embodiments, the totaled proportions of components other than water and hydrogen peroxide in the built compositions is at least 35% and frequently not more than 45%.
  • the preferred concentration of polyphosphate or citrate in the detergent compositions is from 9 to 16%.
  • the proportion of anionic sulphate or sulphonate surfactant plus ethoxylated non-ionic surfactant in the concentrate is preferably within the range of from 6 to 15%, the weight ratio of anionic to non- ionic surfactants normally being selected within the range of 5:2 to 2:5, in order to produce a balanced surfactant mix for the treatment of the general mix of household stains.
  • anionic to non-ionic surfactant weight ratios outside the aforementioned range can be readily contemplated. Hence, e.g.
  • a lower anionic to non-ionic ratio can be more desirable, for example in the range of 1 to 2.5 to 1 to 5.
  • the anionic surfactants are present preferably in an amount from 3 to 8%, and often at least 4%, and the builder is preferably polyphosphate or citrate, frequently at from 9 to 16%, and the non-ionic surfactant content is normally at least 3% and again often at least 4%, with the result that the anionic sulphonate or sulphate surfactant and nonionic ethoxylated surfactant are present in such compositions in total amount advantageously of at least 8%.
  • the total amount of adjuvants generally up to 8% and in many cases, being from 1 to 5%.
  • adjuvants include soil anti-redeposition agents, for example polyvinylpyrrolidone, and sodium carboxymethylcellulose, often in an amount of from 0.1 to 0.3% and an optical brightener or a range of brighteners to allow for the various sorts of fibres from which household laundry articles are made, to a total amount often in the range of 0.5 to 2% of the composition. It is generally desirable to select as brightener those of the stilbene type which have demonstratable storage compatibility with hydrogen peroxide in solution.
  • the composition will also contain a very small proportion of alkali metal sulphate formed during the neutralisation of the anionic surfactant during its preparation.
  • the compositions can also include a small amount of mono-or di or tri ethanolamine, or alkali metal borates as pH adjusters, but alkali metal silicates and carbonates are excluded, or of amphoteric surfactants such as imidazoline based fatty acid carboxysulphates, e.g. from 0.5 to 2%.
  • the adjuvants can also include a small amount of foam regulators, for example ethylene oxide/propylene oxide copolymers such as are available from Ugine Kuhlmann, France under the Tradename Pluronic, grades L42 and F.108, and soaps i.e. alkali metal salts of aliphatic carboxylic acids, having a chain length of at least 8 carbon atoms and normally from 10 to 20 carbon atoms, examples of which include stearate, and soaps derived from natural sources, particularly tallow and coconut oils, again often up to 2% by weight.
  • Other adjuvants can comprise compatible tarnish inhibitors, cationic softeners, dyes, perfumes and thickeners, such as xanthan gum for citrate-built formulations. The amounts of the adjuvants can be varied by the skilled worker within or outside the exemplified ranges.
  • compositions according to the present invention comprise from 8 to 12% in total of anionic sulphate or sulphonate surfactant and nonionic ethoxylated surfactants of which preferably from 3 to 8% is anionic sulphate or sulphonate surfactant and preferably from 2 to 8% is non-ionic ethoxylated surfactant, from 9 to 15% alkali metal preferably, potassium tetrapyrophosphate; from 3 to 6% alkali metal aryl sulphonate hydrotrope; from 5 to 12%, preferably 8 to 12% ethanol; from 5 to 10%, preferably 5 to 8% hydrogen peroxide; from 0.2 to 1% in total of a polyhydroxy linear C 6 or C, aliphatic carboxylate, preferably an alkali metal gluconate and an alkali metal methylene phosphonate complexing agent, preferably ethylene diaminetetra methylene phosphonate or hexamethylene diamine tetra methylene
  • unbuilt detergent compositions according to the present invention contain at least 5% nonionic surfactant and in total at least 10% surfactants.
  • the presence of the extra surfactants means that the balance of anionic to nonionic generally favours the nonionic to a much greater extent than in built compositions according to the present invention.
  • the anionic surfactant is normally selected in the range of 3 to 15%, but the nonionic is normally selected in the range of 5 to 35%.
  • the weight ratio of anionic surfactant to nonionic surfactant is preferably selected in the range of 1:1 to 1:6, and in practice is often likely to be in the range of 1:3 to 1:6.
  • the anionic surfactant often represents from 3 to 10% of the unbuilt composition and the nonionic surfactant at least 15% and frequently from 20 to 35%.
  • the surfactants concentration is not more than 40% and particularly is from 25 to 40%, of which the anionic comprises from 3 to 8% and the nonionic from 22 to 35%.
  • the unbuilt compositions can, in practice, be slightly more concentrated than the bulit compositions. Thus, the total proportion of components other than water and hydrogen peroxide is generally up to 65% and frequently from 40 to 60%.
  • compositions either built or unbuilt, be free from alkali metal carbonates or silicates.
  • compositions described herein can be made conveniently by mixing the components in the desired proportions in a mixing tank, and to avoid and minimise loss of hydrogen peroxide by decomposition it is preferable to add it as the last step, or at least after the two stabiliser components have been introduced.
  • the surfactants are preferably mixed at a moderately elevated temperature, often from 35 to 60°C, and then combined with the other components which brings the mixture to near ambient for the introduction of the hydrogen peroxide.
  • the polyphosphate is introduced in aqueous solution, either supplied as such by the manufacturer or prepared on site by dissolution.
  • the minor components, detergent adjuvants and sulphonate hydrotrope can be mixed in with the surfactant mix.
  • the various solutions and water can be introduced consecutively or concurrently into the mixing tank except as mentioned hereinbefore that the hydrogen peroxide solution is preferably introduced last or starting last.
  • the composition when thoroughly mixed, can then be poured into containers or dispensers.
  • the containers or dispensers for such embodiments need not be of the specially vented and thus expensive types, but instead containers having a slightly loose fitting closure means, such as cap or stopper can be used.
  • washing processes, or laundering, according to the present invention can be carried out by diluting the liquid concentrate of the present invention with water to a desired extent, and contacting the aqueous washing solution with the articles to be washed at any temperature from ambient to the boiling point of the solution.
  • the process is carried out at hand hot temperature or hotter, often a temperature of at least 45°C and, depending on local washing customs, frequently at a temperature of at least 60°C.
  • a one shot liquid detergent composition containing not only hydrogen peroxide, but also a high concentration of anionic and non- ionic surfactants of the order needed to form a washing solution without the addition of any further components.
  • the detergent composition described hereinbefore can be employed in conjunction with one or more bleach activators, i.e. compounds which react in aqueous solution with hydrogen peroxide to generate peroxy acids, preferably added separately to the washing solution to prevent premature interaction.
  • bleach activators i.e. compounds which react in aqueous solution with hydrogen peroxide to generate peroxy acids, preferably added separately to the washing solution to prevent premature interaction.
  • Such compounds are normally N-acyl or 0-acyl compounds.
  • each activator which each represents, includes N,N,N',N'-tetraacetyl- ethylene-diamine of N-acylated alkyleneamines, benzoic or phthalic anhydride, tetra acetyl glycoluril, N-alkyl-N-sulphonyl-carbonamide, N-acylhydantoins, carbonic acid esters, triacetyl cyanurate, O,N,N'-tri substituted hydroxylamines and diacyl peroxides such as benzoyl glutaryl peroxide and diphthaloyl peroxide.
  • the concentrates of the present invention are diluted to produce washing solutions containing from 0.1 to 1.5 gpl surfactant.
  • concentration of surfactants is within the range of 0.2 to 0.6 gpl and such concentrations can be obtained from many of the preferred detergent compositions of the present invention such as those containing at least 8% surfactants at a dilution of greater than 100 to 1, and often at a dilution of from 200 to 1 to 300 to 1.
  • the washing period can range from as low as a minute or a few minutes e.g. 5 minutes at washing temperature at or near the boiling point of the washing solution, e.g. from 90 to 100°C up to a period of several hours at cooler wash temperatures, such as overnight steeping at ambient temperature.
  • the washing period can be varied at the discretion of the user. Typical washing times at a temperature of 40 to 70°C are of the order from 5 to 40 minutes.
  • compositions can be used neat or after dilution to cleanse hard surfaces, such as those of enamel, paint, metal, plastic, wood, glass or ceramics.
  • Liquid detergent compositions according to the present invention were prepared by the following general route, employing the weight proportions summarised in Tables 1, 2 and 3 below.
  • compositions to one or more of the exemplified compositions were obtained by substituting alternative nonionic surfactants such as poly oxyethylene alkyl ethers or poly oxyethylene alkyl ethers for the specified ethoxylates, and/or substituting ammonium primary alcohol ether sulphate for the specified sulphate surfactant, and/or by substituting ethoxylated phosphate mono ester of higher degree of ethoxylation for the specified di-ester, and or by substituting other polyphosphate builders for those specified.
  • alternative nonionic surfactants such as poly oxyethylene alkyl ethers or poly oxyethylene alkyl ethers for the specified ethoxylates, and/or substituting ammonium primary alcohol ether sulphate for the specified sulphate surfactant, and/or by substituting ethoxylated phosphate mono ester of higher degree of ethoxylation for the specified di-ester, and or by substituting other polyphosphate builders for those specified.
  • the storage stability trial for Tables 1 and 2 was effected by transferring a small sample of the given composition into a clean plastic bottle housed in a constant temperature enclosure at 32°C.
  • the available oxygen concentration (Avox) in the composition was determined by the standard acidified potassium permanganate titration method on a small portion extracted from the sample and the result obtained after storage for a given period compared with the original content.
  • the result given in Tables 1 and 2 is the percentage of Avox lost from the hydrogen peroxide after 3 weeks storage, except in Examples 43 to 52 in which it is after 4 weeks storage.
  • the storage stability trials for Table 3 were carried out in the same manner as that for Tables 1 and 2 except that the temperature of the enclosure was 50°C in order to accelerate proceedings. The result is given after 24 hours, approximately.
  • the gluconate and phosphonate were introduced separately, except in Examples 1 to 30 and 43 to 58 where they were provided in the form of a premix of SG and SP available under the gradename Polyron 1020.
  • the washing solution water had a hardness of 150 ppm as calcium carbonate in a Ca:Mg ratio of 2:1 and in those summarised in Table 6, a hardness of 250 ppm as calcium carbonate in a Ca:Mg ratio of 3:1.
  • the detergent composition of the present invention additionally contained 0.5% by weight of a bleach stable stilbene optical brightener obtainable from Ciba Geigy under the tradename Uvitex BHT. Washing trials using compositions C41, and C42 are present by way of comparison only.
  • the composition C41 was a commercially available built liquid detergent composition from Lever Bros. under the tradename Wisk, and C42 was an approximately 50/50 W/W mixture of Wisk with an active-oxygen containg bleach additive from Clorox under the tradename Colorox 2.
  • the washing solution contained total surfactants in the range of 0.3 to 0.4 gpl and an initial builder plus pH adjuster concentration of about 0.4 gpl. These concentrations are very comparable with the concentrations of surfactants and builders present under standard conditions of use of the invention compositions (4 gpl) and in broad terms double those when the invention compositions are used at only 2 gpl.
  • compositions of the instant invention combine the advantages of good storage stability with good washing performance.
  • washing trials were repeated employing washing compositions that omitted the phosphonate and gluconate stabilisers, but were otherwise identical, the washing results were also identical, being within 1% stain removal, i.e. within the limits of reproducibility of the washing tests, indicating that the presence of the phosphonate and gluconate stabiliser had not impaired the washing performance even though they had considerably improved the storage stability of the composition.
  • compositions were prepared by the method for Examples 1 to 64 except that the step relating to incorporating builder was omitted.
  • the Avox of the compositions was required after 4 weeks storage at 32°C and the washing trials were carried out in exactly the same manner as those whose results are summarised in Tables 4 to 6, in hard water having a hardness of 150 ppm as calcium carbonate in a Ca:Mg ratio of 2:1.
  • the effectiveness of the soil removal can be judged by comparison with commercially available detergent compositions in the USA, viz the aforementioned "Wisk” and a product available from Colgate-Palmolive under the trade “Dynamo", each at 2 gpl, on further examples of the stains under the same conditions of wash temperature, water hardness and wash duration, either alone or in 50:50 weight mix with the aforementioned bleach additive "Clorox 2".

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Claims (36)

1. Stabilisierte wässerigegerüstoffhaltige flüssige Waschmittelzusammensetzung aus einem Tensid, Waschmittelverstärker (Builder), Wasser, Hydrotrop und gegebenenfalls einem oder mehreren Waschmittelhilfsstoffen, dadurch gekennzeichnet, daß sie
(i) mindestens 3% Tenside, ausgewählt aus anionischen Sulfat- oder Sulfonat-Tensiden und nicht-ionischen Äthoxylat-Tensiden;
(ii) mindestens 5% eines Builders, ausgewählt aus Alkalimetallpolyphosphaten und Karbonsäure-Builders;
(iii) mindestens 2% Wasserstoffperoxid;
(iv) ausreichend Alkalimetallarylsulfonat als Hydrotrop, um entweder als solches oder in Verbindung mit anderen Bestandteilen die Zusammensetzung in einer einzigen Phase zu halten; und
(v) eine stabilisierende Menge einer Kombination aus
(a) 0,075 bis 1% eines Aminomethylenphosphonates oder Hydroxyalkyldiphosphonates, zusammen mit
(b) 0,08 bis 1% eines aliphatischen Polyhydroxycarboxylates in einem Gewichtsverhältnis zu (a) von 3:1 bis 1:3 und/oder bis zu 15% eines niedermolekularen aliphatischen einwertigen Alkohols in einem Gewichtsverhältnis zu (a) von mindestens 2,5:1 wobei % auf das Gewicht der Zusammensetzung bezogen sind,

enthält.
2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil des anionischen Sulfat- oder Sulfonat-Tensides im Bereich von 3 bis 15 Gew.% liegt.
3. Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Anteil des nicht- ionischen Alkohol-äthoxylats im Bereich von 3 bis 15 Gew.% liegt.
4. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Gewichtsanteil des Äthoxylates in dem nicht-ionischen Alkohol-äthoxylat 60 bis 80% des Moleküls beträgt.
5. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Gesamtanteil an anionischem Sulfat oder Sulfonat- und nicht-ionischen Alkohol-äthoxylat-Tensiden 6 bis 15% beträgt.
6. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Gewichtsverhältnis von anionischem Sulfat- oder Sulfonat-Tensid zu nicht-ionischem Alkohol-äthoxylat-Tensid 5:2 bis 2:5 beträgt.
7. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Builder ein Polyphosphat oder ein Hydroxycarbonsäure-Builder ist.
8. Zusammensetzung nach Anspruch 7, dadurch gekennzeichnet, daß der Anteil an Builder im Bereich von 9 bis 16 Gew.% liegt.
9. Zusammensetzung nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß das Polyphosphat Kaliumtetrapyrophosphat ist.
10. Zusammensetzung nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß der Builder ein Alkalimetallcitrat ist.
11. Zusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Builder bis zu 10% Nitriloessigsäure als Alkalimetallsalz oder bis zu 8% Carboxymethylsuccinat als Alkalimetallsalz umfaßt.
12. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Gesamtanteil aller Bestandteile mit Ausnahme von Wasser und Wasserstoffperoxid 30 bis 45 Gew.% ausmacht.
13. Stabilisierte wässerige flüssige Waschmittelzusammensetzung aus einem Tensid, Hydrotrop, Wasser und gegebenenfalls einem oder mehreren Waschmittelhilfsstoffen, dadurch gekennzeichnet, daß sie
(i) mindestens 10% Tensid, ausgewählt aus anionischen Tensiden und nicht-ionischen Athoxylat-Tensiden, wobei mindestens 5% ein nicht-ionisches Tensid ist,
(ii) mindestens 2% Wasserstoffperoxid,
(iii) ausreichend Alkalimetallarylsulfonat als Hydrotrop, um als solches oder in Verbindung mit anderen Bestandteilen die Zusammensetzung in einer einzigen Phase zu halten, und
(iv) eine stabilisierende Menge einer Kombination aus
(a) 0,075 bis 1% eines Aminomethylenphosphonates oder Hydroxyalkyldiphosphonates zusammen mit
(b) 0,08 bis 1 % eines aliphatischen Polyhydroxycarboxylates in einem Gewichtsverhältnis zu (a) von 3:1 bis 1:3 und/oder bis zu 15% eines niedermolekularen aliphatischen einwertigen Alkohols in einem Gewichtsverhältnis zu (a) von mindestens 2,5:1, wobei % auf das Gewich der Zusammensetzung bezogen sind,

anthält.
14. Zusammensetzung nach Anspruch 13, dadurch gekennzeichnet, daß der Anteil an anionischem Sulfat- oder Sulfonat-Tensid im Bereich von 3 bis 15 Gew.% liegt.
15. Zusammensetzung nach Anspruch 13 oder 14, dadurch gekennzeichnet, daß der Anteil an nicht-ionischem Alkohol-äthoxylat im Bereich von 5 bis 35 Gew.% liegt.
16. Zusammensetzung nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, daß der Gewichtsanteil des Äthoxylates im nichtionischen Alkohol-äthoxylat 60 bis 80% des Moleküls ausmacht.
17. Zusammensetzung nach einem der Ansprüche 13 bis 16, dadurch gekennzeichnet, daß der Gesamtanteil an anionischem Sulfat- oder Sulfonat- und nicht-ionischem Alkohol-äthoxylat-Tensiden 25 bis 40% ausmacht.
18. Zusammensetzung nach einem der Ansprüche 13 bis 17, dadurch gekennzeichnet, daß das Gewichtsverhältnis von anionischem Sulfat- oder Sulfonat-Tensid zu nicht-ionischem Alkohol-äthoxylat-Tensid 1:3 bis 1:6 beträgt.
19. Zusammensetzung nach einem der Ansprüche 13 bis 18, dadurch gekennzeichnet, daß der Gesamtanteil aller Bestandteile mit Ausnahme von Wasser und Wasserstoffperoxid 40 bis 65 Gew.% beträgt.
20. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Anteil an Wasserstoffperoxid im Bereich von 3 bis 20 Gew.% liegt.
21. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Anteil an Sulfonat als Hydrotrop im Bereich von 3 bis 9 Gew.% liegt.
22. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie 1 bis 3 Gew.% eines äthoxylierten Phosphatesters enthält.
23. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Anteil an niedermolekularem aliphatischem Alkohol im Bereich von 5 bis 15 Gew.% liegt.
24. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der niedermolekulare aliphatische Alkohol Äthanol ist.
25. Zusammensetzung nach Anspruch 24, dadurch gekennzeichnet, daß der Äthanol in Form von Brennspiritus vorliegt.
26. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Anteil an Polyhydroxycarboxylat 0,1 bis 0,4 Gew.% beträgt.
27. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Polyhydroxycarboxylat ein Alkalimetallgluconat ist.
28. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Phophonat eine Äthylendiamintetra (methylenphosphonsäure) oder Hexamethylendiamintetra (methylenphosphonsäure) oder Diäthylentriaminpenta (methylenphosphonsäure) oder ein Alkalimetallsalz davon ist.
29. Zusammensetzung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß sie in einer Menge von 5 bis 12 Gew.% Äthanol, ein Polyhydroxycarboxylat und ein Phosphonat enthält.
30. Zusammensetzung nach Anspruch 1, 13 oder 29, dadurch gekennzeichnet, daß das Gewichtsverhältnis des Polyhydroxycarboxylates zum Phosphonat 2:1 bis 1:1 ist, wobei der Gesamtanteil der zwei Bestandteile 0,2 bis 1 Gew.% ausmacht.
31. Gerüststoffhaltige flüssige Waschmittelzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß sie aus insgesamt 8 bis 12% an anionischem Sulfat- oder Sulfonat-Tensid und nichtionischem äthoxyliertem Tensid; 9 bis 15% Builder, ausgewählt aus Alkalimetalltetrapyrophosphat oder Alkalimetallcitrat; 3 bis 9% Alkalimetallarylsulfonat als Hydrotrop; 5 bis 12% Äthanol; 5 bis 10% Wasserstoffperoxid; insgesamt 0,2 bis 1 % eines aliphatischen linearen Cs- oder C,-Polyhydroxycarboxylates und eines Alkalimetallmethylenphosphonat- Komplexbildners, bis zu 5% Waschmittelhilfstoff oder-hilfsstoffen und Rest Wasser besteht, wobei % Gew.% sind.
32. Zusammensetzung nach Anspruch 31, gekennzeichnet durch die folgenden Merkmale (i) bis (v) in Kombination:
(i) die Zusammensetzung enthält 3 bis 8% anionisches Tensid und 2 bis 8% nicht-ionisches Tensid; und
(ii) der Builder ist ausgewählt aus Kaliumtetrapyrophosphat und Natriumcitrat; und
(iii) das aliphatische Carboxylat ist ein Alkalimetallgluconat; und
(iv) der Phosphonat-Komplexbildner ist ein Äthylendiamintetramethylenphosphonat, Hexamethylendiamintetramethylenphosphonat oder Diäthylentriaminpentamethylenphosphonat; und
(v) das aliphatische Carboxylat und der Phophonat-Komplexbildner stehen in einem Gewichtsverhältnis von 2:1 bis 1:1.
33. Gerüststoffloses flüssiges Waschmittel nach Anspruch 13, dadurch gekennzeichnet, daß es insgesamt aus 25 bis 40% anionischem Sulfat- oder Sulfonat-Tensid und nicht-ionischem äthoxyliertem Tensid; 3 bis 9% Alkalimetallarylsulfonat als Hydrotrop; 5 bis 12% Äthanol; 5 bis 10% Wasserstoffperoxid; insgesamt 0,2 bis 1% eines aliphatischen linearen Cfi oder C7-Polyhydroxycarboxylates und eines Alkalimetallmethylenphosphonat-Komplexbildners, bis zu 5% Waschmittelhilfsstoff oder -hilfsstoffen und Rest Wasser besteht, wobei % Gew.% sind.
34. Zusammensetzung nach Anspruch 33, gekennzeichnet durch die folgenden Merkmale (i) bis (v) in Kombination:
(i) die Zusammensetzung enthält 3 bis 8% anionisches Tensid und 20 bis 35% nicht-ionisches Tensid; und
(ii) das aliphatische Carboxylat ist ein Alkalimetallgluconat; und
(iii) der Phosphonat-Komplexbildner ist ein Äthylendiamintetramethylenphosphonat, Hexamethylendiamintetramethylenphosphonat oder Diäthylentriaminpentamethylenphosphonat; und
(iv) das aliphatische Carboxylat und der Phosphonat-Komplexbildner stehen in einem Gewichtsverhältnis von 2:1 bis 1:1.
35. Verfahren zur Herstellung von stabilisierten Bleichmittel enthaltenden Waschmittelzusammensetzungen, bei welchen die Bestandteile zusammengebracht und bis zum Erhalt einer homogenen Mischung gemisch werden, dadurch gekennzeichnet, daß die Bestandteile die in einem der vorhergehenden Ansprüche beschriebenen sind und die Reihenfolge der Einbringung der Bestandteile so vorgenommen wird, daß das Wasserperoxid mit den Buildern oder Tensiden nur in Gegenwart des Stabilisierungssystems zusammengebracht wird.
36. Verfahren zum Waschen oder Reinigen, das die Stufen der Verdünnung einer Waschmittelzusammensetzung auf ein gewünschtes Ausmaß und des Zusammenbringens des zu waschenden Gegenstandes mit der verdünnten Lösung bei einer Temperatur zwischen Raumtemperatur und dem Siedepunkt der Lösung umfaßt, dadurch gekennzeichnet, daß eine Waschmittelzusammensetzung nach einem der Ansprüche 1 bis 34 verwendet wird.
EP19810300964 1980-04-01 1981-03-09 Flüssige Reinigungsmittelzusammensetzungen, deren Herstellung und deren Verwendung in Waschverfahren Expired EP0037184B1 (de)

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AR241024A1 (es) * 1981-09-30 1991-04-30 Interox Chemicals Ltd Composicion de peroxido de hidrogeno acuoso apropiada para dilucion,para formar composiciones detergentes liquidas o composiciones de blanqueo,que consiste esencialmente en (a) de 20 a 35% en peso, en base a la composicion , de peroxido de hidrogeno,(b)
EP0086511B1 (de) * 1982-02-03 1986-07-02 THE PROCTER & GAMBLE COMPANY Sauerstoff-Bleichmittel enthaltende flüssige Detergenszusammensetzungen
NZ211550A (en) * 1984-04-06 1987-06-30 Colgate Palmolive Co Liquid detergent composition containing acidic phosphorus compound and polyphosphate
US5250212A (en) * 1987-05-27 1993-10-05 The Procter & Gamble Company Liquid detergent containing solid peroxygen bleach and solvent system comprising water and lower aliphatic monoalcohol
GB8830296D0 (en) * 1988-12-28 1989-02-22 Unilever Plc Bleaching composition
US5275753A (en) * 1989-01-10 1994-01-04 The Procter & Gamble Company Stabilized alkaline liquid detergent compositions containing enzyme and peroxygen bleach
GB8904007D0 (en) * 1989-02-22 1989-04-05 Procter & Gamble Stabilized,bleach containing,liquid detergent compositions
DE69033783T2 (de) * 1989-02-27 2002-04-18 Unilever N.V., Rotterdam Flüssiges Reinigungsmittel
US5160655A (en) * 1989-02-27 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds
DE4023893A1 (de) * 1990-07-27 1992-01-30 Henkel Kgaa Bleichendes fluessigwaschmittel
GB9413307D0 (en) * 1994-07-01 1994-08-24 Warwick Int Group Bleaching compositions
WO1996001311A1 (en) * 1994-07-01 1996-01-18 Warwick International Group Limited Bleaching compositions
WO1996001310A1 (en) * 1994-07-01 1996-01-18 Warwick International Group Limited Bleaching compositions
GB9506093D0 (en) * 1995-03-24 1995-05-10 Warwick Int Group Alkaline isotropic liquid detergent with peroxide
AU5115796A (en) * 1995-03-24 1996-10-16 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
GB9506066D0 (en) * 1995-03-24 1995-05-10 Warwick Int Group Alkaline isotropic liquid detergent with peroxide
GB9506065D0 (en) * 1995-03-24 1995-05-10 Warwick Int Group Alkaline isotropic liquid detergent with peroxide
EP0892040B1 (de) * 1997-07-16 2003-03-05 Nippon Shokubai Co., Ltd. Verwendung von Chelat bildenden Zusammensetzungen zum Reinigen
ES2402725B1 (es) * 2011-10-28 2014-03-11 Betelgeux, S.L. Detergente líquido para eliminación de biofilms en superficies.

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BE795085A (fr) * 1972-03-10 1973-05-29 Benckiser Knapsack Gmbh Procede de blanchiment de fibres cellulosiques seules ou en melange avec des fibres synthetiques
NL7608266A (nl) * 1975-08-16 1977-02-18 Henkel & Cie Gmbh Concentraten van microbicide middelen.

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DE3168426D1 (en) 1985-03-07
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BR8101906A (pt) 1981-10-06
CA1174550A (en) 1984-09-18
ES8405839A1 (es) 1984-06-16
AU6881281A (en) 1981-10-08
EP0037184A2 (de) 1981-10-07
PT72722B (en) 1982-03-24
PT72722A (en) 1981-04-01
AU544887B2 (en) 1985-06-20

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