EP0037184A2 - 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
EP0037184A2
EP0037184A2 EP81300964A EP81300964A EP0037184A2 EP 0037184 A2 EP0037184 A2 EP 0037184A2 EP 81300964 A EP81300964 A EP 81300964A EP 81300964 A EP81300964 A EP 81300964A EP 0037184 A2 EP0037184 A2 EP 0037184A2
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EP
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Prior art keywords
composition according
weight
surfactant
phosphonate
alkali metal
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EP81300964A
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English (en)
French (fr)
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EP0037184B1 (de
EP0037184A3 (en
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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
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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 GBPS 1,553,505 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.
  • detergent compositions can include organic complexing agents as builders.
  • organic complexing agents such as about 1 per cent 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 per cent of ethylenediamine tetraacetic acid,tetra sodium salt lost a remarkable 96 per cent within two weeks and that containing 1 per cent of nitrilotriacetic acid, trisodium salt lost an enormous 79 per cent in one week.
  • a stabilised aqueous built liquid detergent composition comprising at least 4 % of an anionic sulphate or sulphonate surfactant and/or of a non-ionic ethoxylate surfactant, at least 5 % of a builder selected from alkali metal polyphosphates, and carboxylic acid complexing builders, at least 2 % hydrogen peroxide, sufficient alkali metal aryl sulphonate hydrotrope to maintain the composition in a single phase, either by itself or in conjunction with other components, and a stabilising amount of a combination comprising a low molecular weight mono-hydroxy aliphatic alcohol, and/or a polyhydroxy aliphatic carboxylate and an aminomethylene phosphonate or hydroxy alkyl diphosphonate. Percentages for any component herein are by weight, based on the composition, unless specifically stated to the contrary.
  • 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.
  • anionic surfactants that demonstrate compatability with hydrogen peroxide include alkyl sulphosuccinamate, the alkyl group preferably containing from 12 to 18 carbon atoms.
  • alkyl sulphosuccinamate the alkyl group preferably containing from 12 to 18 carbon atoms.
  • ALCOPOL FA from Allied Colloids, England.
  • 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.
  • Commercially 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 2 H 4 0) n 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. However,it is desirable also to take into account the relative proportions of the two moieties in the non-ionic surfactant involved, and this is often expressed in terms of the weight proportion of the ethoxylate moiety in the molecule.
  • 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 12 , C 13 , C 14 , C 15 or C 16 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 13 and C 15 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 ll-15 linear secondary alcohol ethoxylates, having degrees of ethoxylation of respectively 9 and 12, L U B ROL 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 and RENEX 20 being a polyoxyethylene mixed fatty acid ester available from Honeywell Atlas.
  • 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 non ionic 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.
  • polyphosphates it is especially suitable to employ pyrophosphates, and more particularly the tetra potassium or tetra sodium 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, eg 30-60 % of the 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.
  • 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 amd 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 8 to C 12
  • 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 hydroxy alkyl 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 are generally 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 polyhydroxy aliphatic 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 potasium. 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 in many cases 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 performance 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 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) OT 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.
  • any two or more of the aforementioned amino-methylene phosphonates and/or diphosphonates can be employed, as desired.
  • Such a compound or compounds are preferably employed in an amount of at least 0.075 % by weight of the composition and generally an amount of 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, eg 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.
  • 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 %.
  • a total proportion eg 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.
  • the totaled proportions of components other than water and hydrogen peroxide in the built compositions is at least 35 % and frequently not more that 45 %.
  • the prefered 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. eg. 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.
  • 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
  • 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
  • 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 3 to 8 % is non-ionic ethoxylated surfactant, from 9 to 15 % alkali metal preferably, potassium tetra pyrophosphate; 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 7 aliphatic carboxylate, preferably an alkali metal gluconate and an alkali metal methylene phosphonate complexing agent, preferably ethylene diaminetetra methylene phosphonate or
  • 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 built 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 o 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 process has been described in a batch manner it will be readily apparent to a skilled engineer how to carry out the process on a continuous basis.
  • the composition when throroughly 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 o C and, depending on local washing customs, frequently at a temperature of at least 60 o 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 herein before 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',-tetraacetylethylene-diamine of N-acylated alkyleneamines, benzoic or phthalic anhydride, tetra acetyl glycoluril,N-alkyl-N-sulphonyl-carbonamides, N-acyl hydantoins, 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 0 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 0 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 0 C in order to accelerate proceedings.
  • the washing trials were carried out in the following manner:-Prestained swatches of cotton were washed in a laboratory scale washing machine, sold under the name TERGOTOMETER (US Testing Corporation) which simulates the action of a vertical agitator type of domestic washing machine.
  • the machine trials were carried out under standard conditions of two stained swatches, each of 5g, being washed at a temperature maintained at 60 0 C with one litre of an aqueous washing solution containing 4 grams of the selected detergent composition.
  • the first washed swatches were removed from the wash water after 10 minutes washing, rinsed with cold water and dried, and the second removed after 20 or 30 minutes washing and similarly rinsed and dried.
  • the extent of stain removal from each swatch was determined by measuring the reflectance of the swatches before and after washing, using a Zeiss ELREPHO Reflectance Photometer having a Xenon lamp light source equipped with a y-tristimulus filter. Each swatch was measured four times with a backing of three thicknesses of material.
  • % stain removal (abbreviated to % SR ) was obtained using the following formula: where R u represents reflectance of the unstained cloth, Ri reflectance of the cloth after staining, and R f reflectance of the the stained cloth after bleaching.
  • R u represents reflectance of the unstained cloth
  • Ri reflectance of the cloth after staining
  • R f reflectance of the the stained cloth after bleaching.
  • 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 under the name 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 WISK
  • C42 was an approximately 50/50 W/W mixture of WISK with an active-oxygen containing bleach additive CLOROX 2.
  • Analysis of the products C41 and C42 showed that at the levels of detergent composition employed, 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 0 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 150ppm 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 WISK and 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 a bleach additive CLOROX 2.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
EP19810300964 1980-04-01 1981-03-09 Flüssige Reinigungsmittelzusammensetzungen, deren Herstellung und deren Verwendung in Waschverfahren Expired EP0037184B1 (de)

Priority Applications (1)

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AT81300964T ATE11427T1 (de) 1980-04-01 1981-03-09 Fluessige reinigungsmittelzusammensetzungen, deren herstellung und deren verwendung in waschverfahren.

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Application Number Priority Date Filing Date Title
GB8010885 1980-04-01
GB8010885 1980-04-01
GB8010887 1980-04-01
GB8010887 1980-04-01

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EP0037184A2 true EP0037184A2 (de) 1981-10-07
EP0037184A3 EP0037184A3 (en) 1982-03-17
EP0037184B1 EP0037184B1 (de) 1985-01-23

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Country Link
EP (1) EP0037184B1 (de)
AU (1) AU544887B2 (de)
BR (1) BR8101906A (de)
CA (1) CA1174550A (de)
DE (1) DE3168426D1 (de)
ES (1) ES8405839A1 (de)
PT (1) PT72722B (de)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076166A2 (de) * 1981-09-30 1983-04-06 Interox Chemicals Limited Bleichmittelzusammensetzungen
US4470919A (en) * 1982-02-03 1984-09-11 The Procter & Gamble Company Oxygen-bleach-containing liquid detergent compositions
GB2158453A (en) * 1984-04-06 1985-11-13 Colgate Palmolive Co Liquid laundry detergent composition containing polyphosphate
EP0376704A1 (de) * 1988-12-28 1990-07-04 Unilever Plc Bleichmittelzusammensetzung
EP0385522A2 (de) * 1989-02-27 1990-09-05 Unilever N.V. Flüssiges Reinigungsmittel
EP0468103A1 (de) * 1989-02-22 1992-01-29 The Procter & Gamble Company Stabilisierte, Bleichmittel enthaltende, flüssige Reinigungsmittel
WO1992002607A1 (de) * 1990-07-27 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Bleichendes flüssigwaschmittel
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
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
US5275753A (en) * 1989-01-10 1994-01-04 The Procter & Gamble Company Stabilized alkaline liquid detergent compositions containing enzyme and peroxygen bleach
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
WO1996001309A1 (en) * 1994-07-01 1996-01-18 Warwick International Group Limited Bleaching compositions
WO1996030483A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
WO1996030485A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
WO1996030486A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
WO1996030484A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
EP0892040A2 (de) * 1997-07-16 1999-01-20 Nippon Shokubai Co., Ltd. Chelatbildende Zusammensetzungen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2402725B1 (es) * 2011-10-28 2014-03-11 Betelgeux, S.L. Detergente líquido para eliminación de biofilms en superficies.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2175922A1 (de) * 1972-03-10 1973-10-26 Benckiser Knapsack Gmbh
FR2321302A1 (fr) * 1975-08-16 1977-03-18 Henkel & Cie Gmbh Concentres d'agents microbicides a base de peracides organiques et d'eau oxygenee

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2175922A1 (de) * 1972-03-10 1973-10-26 Benckiser Knapsack Gmbh
FR2321302A1 (fr) * 1975-08-16 1977-03-18 Henkel & Cie Gmbh Concentres d'agents microbicides a base de peracides organiques et d'eau oxygenee
US4051058A (en) * 1975-08-16 1977-09-27 Henkel & Cie Gmbh Stable peroxy-containing microbicides

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076166A3 (en) * 1981-09-30 1984-10-17 Interox Chemicals Limited Bleach composition
EP0076166A2 (de) * 1981-09-30 1983-04-06 Interox Chemicals Limited Bleichmittelzusammensetzungen
US4470919A (en) * 1982-02-03 1984-09-11 The Procter & Gamble Company Oxygen-bleach-containing liquid detergent compositions
GB2158453A (en) * 1984-04-06 1985-11-13 Colgate Palmolive Co Liquid laundry detergent composition containing polyphosphate
FR2568886A1 (fr) * 1984-04-06 1986-02-14 Colgate Palmolive Co Composition detergente liquide de blanchissage contenant du 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
EP0376704A1 (de) * 1988-12-28 1990-07-04 Unilever Plc Bleichmittelzusammensetzung
US5275753A (en) * 1989-01-10 1994-01-04 The Procter & Gamble Company Stabilized alkaline liquid detergent compositions containing enzyme and peroxygen bleach
EP0468103A1 (de) * 1989-02-22 1992-01-29 The Procter & Gamble Company Stabilisierte, Bleichmittel enthaltende, flüssige Reinigungsmittel
US5264143A (en) * 1989-02-22 1993-11-23 The Procter & Gamble Company Stabilized, bleach containing, liquid detergent compositions
TR25960A (tr) * 1989-02-22 1993-11-01 Procter & Gamble Kararli hale getirilmis agartici ihtiva eden, sivi deterjan terkipleri.
EP0385522A2 (de) * 1989-02-27 1990-09-05 Unilever N.V. 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
EP0385522A3 (de) * 1989-02-27 1991-01-09 Unilever N.V. Flüssiges Reinigungsmittel
WO1992002607A1 (de) * 1990-07-27 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Bleichendes flüssigwaschmittel
US5271860A (en) * 1990-07-27 1993-12-21 Henkel Kommanditgesellschaft Auf Aktien Bleaching liquid detergent
WO1996001309A1 (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
WO1996001311A1 (en) * 1994-07-01 1996-01-18 Warwick International Group Limited Bleaching compositions
US5801138A (en) * 1994-07-01 1998-09-01 Warwick International Group Limited Bleaching compositions
US5914304A (en) * 1994-07-01 1999-06-22 Warwick International Group, Ltd. Bleaching compositions
WO1996030483A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
WO1996030485A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
WO1996030486A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
WO1996030484A1 (en) * 1995-03-24 1996-10-03 Warwick International Group Limited Alkaline isotropic liquid detergent with peroxide
EP0892040A2 (de) * 1997-07-16 1999-01-20 Nippon Shokubai Co., Ltd. Chelatbildende Zusammensetzungen
EP0892040A3 (de) * 1997-07-16 2001-01-03 Nippon Shokubai Co., Ltd. Chelatbildende Zusammensetzungen

Also Published As

Publication number Publication date
ES500915A0 (es) 1984-06-16
DE3168426D1 (en) 1985-03-07
EP0037184B1 (de) 1985-01-23
EP0037184A3 (en) 1982-03-17
BR8101906A (pt) 1981-10-06
CA1174550A (en) 1984-09-18
ES8405839A1 (es) 1984-06-16
AU6881281A (en) 1981-10-08
PT72722B (en) 1982-03-24
PT72722A (en) 1981-04-01
AU544887B2 (en) 1985-06-20

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