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EP0095904B1 - Detergens-Flüssigkeiten und Zusammensetzungen für ihre Verwendung - Google Patents

Detergens-Flüssigkeiten und Zusammensetzungen für ihre Verwendung Download PDF

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Publication number
EP0095904B1
EP0095904B1 EP83303058A EP83303058A EP0095904B1 EP 0095904 B1 EP0095904 B1 EP 0095904B1 EP 83303058 A EP83303058 A EP 83303058A EP 83303058 A EP83303058 A EP 83303058A EP 0095904 B1 EP0095904 B1 EP 0095904B1
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EP
European Patent Office
Prior art keywords
acetylated
aldohexopyranose
pyranoside
perhydrate
wash liquor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP83303058A
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English (en)
French (fr)
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EP0095904A1 (de
Inventor
Frederick Edward Hardy
Michael Crombie Addison
John George Bell
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
Procter and Gamble Co
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Priority to AT83303058T priority Critical patent/ATE21930T1/de
Publication of EP0095904A1 publication Critical patent/EP0095904A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C11D3/3912—Oxygen-containing compounds derived from saccharides

Definitions

  • This invention relates to laundry wash liquors and detergent compositions for use therein, capable of removing oxidisable stains from fabrics washed therein at temperatures at or below 60°C. More particularly the invention relates to wash liquors containing mixtures of inorganic peroxygen bleaches of the perhydrate type and certain acetylated sugars and their derivatives serving as organic peroxy bleach precursors, which mixtures can be made to deliver improved bleaching performance under defined conditions.
  • peroxy bleach precursors together with peroxygen bleaches of the perhydrate type (i.e. alkali metal perborates, percarbonates, persilicates, perpyrophosphates and the like) for removing oxidisable stains at low temperatures (i.e. : 5 60'C) is well known in the detergent art.
  • acetylated polyols including acetylated mono- and di-saccharides as peroxy bleach precursors is also disclosed in the prior art, notably in British Patent No. 836,988 where fructose penta acetate, glucose penta acetate, glucose tetra acetate and sucrose octa acetate are taught for this purpose.
  • British Patent 836,988 discloses that the release of one mole of peracetic acid would be expected from glucose tetra acetate and two moles would be expected from glucose penta acetate. No predictions are given for other disclosed polyol esters but it is assumed that they would behave similarly and release one or two moles of peracetic acid under the conditions employed in British Patent 836 988.
  • saccharide esters are derived from materials available in bulk which are not petroleum based, and which therefore constitute a potentially high volume source of organic peroxy acid bleaching agent, which is less subject to the cost inflation associated with chemicals derived wholly from petroleum sources.
  • a laundry wash liquor adapted for the removal of oxidisable stains, particularly at temperatures of less than 60°C, said liquor containing 0.1% to 2.0% by weight of a detergent composition comprising an organic surfactant present in an amount to give from 10 to 5000 ppm in solution, an inorganic peroxygen bleach of the perhydrate type, and a peracetic acid precursor comprising an acetylated aldohexopyranose or acetylated aidohexopyranoside containing acetyl groups on at least three adjacent carbon atoms, present in an amount to give from 10 to 1000 ppm in solution, said wash liquor having a starting pH of at least 9.5, said starting pH being defined as the pH of a 0.5 wt% solution of said composition measured at 20°C after all of the soluble components have dissolved and prior to the addition of any soiled fabrics wherein the inorganic peroxygen bleach is present in an amount of at least 8.5 millimoles/dm 3
  • the precursor is a fully acetylated aldohexopyranose or aldohexopyranoside.
  • the molar ratio of perhydrate to sugar alcohol is .15:1 and the starting pH of the wash liquor is at least 10.0.
  • a highly preferred acetylated aldohexopyranose is penta acetyl glucose (in either alpha- or beta-form, or mixtures thereof), and preferred aldohexopyranosides include octa acetyl lactose and octa acetyl sucrose.
  • the present invention in its broadest aspect requires the formation of a laundry wash liquor incorporating an organic surfactant, an inorganic peroxygen bleach of the perhydrate type and an acetylated aldohexopyranose or pyranoside containing acetyl groups on at least three adjacent carbon atoms, the liquor pH being at least 9.5 under the conditions defined above.
  • a wide range of organic surfactants are believed to e suitable i.e. anionic, nonionic, ampholytic, zwitterionic or cationic surfactants may be employed either alone or in admixture.
  • detergents having an overall anionic or nonionic character are usually employed, such detergents being totally anionic, or mixtures of anionic and nonionic types or mixtures of anionic, nonionic and ampholytic types of mixtures of anionic, nonionic and cationic types.
  • the anionic surfactant may be any one or more of the materials used conventionally in laundry detergents.
  • Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulpho-carboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates 2-acyloxy alkane-1-sulphonate, and beta-alkyloxy alkane sulphonate.
  • a particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts or organic sulphuric reaction products having in their molecular structure an alkyl or alkaryl group containing from 8 to 22, especially from 10 to 20 carbon atoms and a sulphonic acid or sulphuric acid ester group. (included in the term "alkyl” is the alkyl portion of acyl groups).
  • Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C B - 18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulphonates, in which the alkyl group contains from 9 to 15, especially 11 to 13, carbon atoms, in straight chain or branched chain configuration, e.g.
  • anionic detergent compounds herein include the sodium C 10 - 1S alkyl glyceryl ether sulphonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphonates and sulphates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulphate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
  • Other useful anionic detergent compounds herein include the water-soluble salts or esters of alpha-sulphonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulphonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulphates containing from 10 to 18, especially 12 to 16, carbon atoms in the alkyl group and from 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates containing from 12to 24, preferably 14to 16, carbon atoms, especially those made by reaction with sulphur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulphonates; water-soluble salts of paraffin sulphon
  • alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred. Suitable fatty acid soaps can be selected from the ordinary alkali metal sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from 8 to 24, preferably from 10 to 22 and especially from 16 to 22 carbon atoms in the alkyl chain.
  • Suitable fatty acids can be obtained from natural sources such as, for instance, from oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard and mixtures thereof.
  • the fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process).
  • Resin acids are suitable such as rosin and those resin acids in tall oil.
  • Naphthenic acids are also suitable.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from tallow and hydrogenated fish oil.
  • Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:5, preferably from 5:1 to 1:1, more preferably from 5: 1 to 1.5: 1.
  • an alkyl benzene sulphonate having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical the cation being an alkali metal preferably sodium; and either an alkyl sulphate having from 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical or an ethoxy sulphate having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6, having an alkali metal cation, preferably sodium.
  • the nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic surfactants include:
  • Especially preferred nonionic surfactants for use herein are the C 9 -C, 5 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 12 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.
  • Suitable amine oxides have the general formula I wherein R is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, each R 1 is independently selected from C 1-4 alkyl and ⁇ (C n H 2n O) m H where i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of C n H 2n O groups in a molecule being no more than 7.
  • R has from 10 to 14 carbon atoms and each R 1 is independently selected from methyl and ⁇ (C n H 2n O) m H wherein m is from 1 to 3 and the sum total of C n H 2n O groups in a molecule is no more than 5, preferably no more than 3.
  • j is 0 and each R 1 is methyl, and R is C 12 -C 14 alkyl.
  • Another suitable class of amine oxide species is represented by bis-amine oxides having the following substituents.
  • Ampholytic detergents include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Examples of compounds falling within this definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino) propane-1-suiphonate, sodium 2-(dodecylamino)ethyl sulphate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyl-dodecylamino)propane-1-sulphonate, disodium octadecyl-iminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
  • Sodium 3-(dodecylamino)-propane-1-sulphonate is preferred.
  • Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
  • Cationic surfactants useful in the present invention can be broadly defined as quaternary ammonium compounds having the general formula: wherein R 2 is a linear or branched alkyl, alkenyl or alkaryl group having 8 to 16 carbon atoms and each R 3 is independently selected from C 1-4 alkyl, C 1-4 alkaryl and-(C n H 2n O) m wherein i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3 and m is from 1 to 7, the sum total of C n H 2n O groups in a molecule being no more than 7, and wherein Z represents a counteranion in number to give electrical neutrality.
  • R has from 10 to 14 carbon atoms and each R 3 is independently selected from methyl and (C n H 2n O) m H wherein m is from 1 to 3 and the sum total of C n H 2n O groups in a molecule is no more than 5, preferably no more than 3.
  • j is 0, R 3 is selected from methyl, hydroxyethyl and hydroxypropyl and R 2 is C 12 -C 14 alkyl.
  • Particularly preferred surfactants of this class include C 12 alkyl trimethylammonium salts, C 14 alkyltrimethylammonium salts, coconutalkyltrimethyl- ammonium salts, coconutalkyldimethyl-hydroxyethylammonium salts, coconutalkyldimethyl- hydroxy-propylammonium salts, and C 12 alkyldihydroxyethylmethyl ammonium salts.
  • Another group of useful cationic compounds are the diammonium salts of formula II in which j is 1, R is C 12 -C, 4 alkyl, each R 3 is methyl, hydroxyethyl or hydroxypropyl and i is 2 or 3.
  • R is coconut alkyl, R 3 is methyl and i is 3.
  • Preferred anionic surfactants are linear alkyl benzene sulphonates in which the alkyl group has from 11 to 15 carbon atoms, two highly preferred examples having an average of 11.8 carbon atoms and 13 carbon atoms respectively in the alkyl group.
  • Other preferred anionic surfactants are the alkyl sulphates particularly those having between 14 and 18 carbon atoms in the alkyl chain. Mixtures of alkyl benzene sulphonates and alkyl sulphates are also highly preferred.
  • Nonionic surfactants preferred for use in the invention are the C 12 -C 15 primary alcohols condensed with an average of from 5 to 7 moles of ethylene oxide per mole of alcohol.
  • the alkyl groups may be unbranched as in groups derived from natural fats and oils, or may be branched to different degrees as in synthetically derived materials.
  • anionic-nonionic surfactant mixture An example of a suitable anionic-nonionic surfactant mixture is disclosed in European Patent Application No. 81301983.3 (Publication No. 0040038).
  • Exemplary anionic-nonionic-cationic mixtures are disclosed in European Patent Application No. 78200050.2 (Publication No. 0000225).
  • the surfactant system contains anionic and cationic surfactants in an equivalent ratio of at least 1:1, the weight ratio of anionic:cationic surfactants is ⁇ 5:1 and the weight ratio of nonionic to cationic surfactants is in the range from 100:1 to 2:3.
  • Combinations of anionic, ethoxylated nonionic, semipolar amine oxide and cationic surfactants are disclosed in European Patent Application No. 83200064.0 filed 14th January, 1983 (pub. 10.08.83; No. 85448).
  • the laundry liquors of the present invention contain from 10-5000 parts per million, more preferably from 100 to 1500 parts per million of surfactant.
  • the level of surfactant in the composition lies in the range from 1 to 25%, preferably from 5 to 15% by weight, such compositions being employed at levels of from 0.1% to 2.0% by weight of the liquor.
  • the second components of the laundry liquor is an inorganic peroxygen bleach of the perhydrate type which is present at a level of at least 8.5 millimoles/dm 3 corresponding, e.g., to 1300 ppm sodium perborate tetrahydrate.
  • the wash liquor can contain up to 7000 ppm of perhydrate product expressed on the foregoing basis, but formulation and cost constraints normally limit the maximum level to a value less than this. If the perhydrate is added as part of a detergent composition of the type commercially available in Europe, or as part of an additive product intended for use under conventional European wash conditions, the level generally lies in the range from 1300 ppm to 3200 ppm, more usually in the range from 1500 ppm to 2000 ppm.
  • perhydrate type bleaches are defined as those having hydrogen peroxide associated with the molecule such as alkali metal perborates, percarbonates, persilicates and perpyrophosphates.
  • the inorganic peroxygen bleach is present at a level of from 15% to 35% by weight, preferably from 15% to 25% by weight of the composition.
  • Preferred perhydrates are sodium perborate mono- and tetrahydrate and sodium percarbonate.
  • ester-type peroxy bleach precursors of the present invention can be broadly defined as acetylated aldohexopyranoses or aldohexopyranosides containing at least three acetyl groups on adjacent carbon atoms.
  • the aldohexopyranoses or aldopyranosides are fully acetylated.
  • Suitable acetylated aldohexopyranoses include penta acetyl glucose, penta acetyl galactose and penta acetyl mannose.
  • aldohexopyranosides include galactopyranoside derivatives such as octa acetyl lactose and glucopyranosides such as octa acetyl sucrose and tetra acetyl alpha-C 1 -C 12 alkyl glucosides such as alpha-methyl, alpha-butyl and alpha-lauryl glucoside.
  • all of the available hydroxyl groups are acetylated as this is convenient from a manufacturing standpoint and facilitates the most efficient use of the molecule, but the invention does not preclude the use of less than fully acetylated molecules.
  • this general class of materials is known as a source of acetyl groups for the production of peracetic acid when mixed with inorganic perhydrate salts.
  • the literature appears to have considered peracetic acid formation from acetylated sugar-perhydrate salt mixtures largely, if not exclusively, in terms of the reactivities of individual acetate groups.
  • this can give rise to misleading predictions, as the reactivity of an acetate group is less important than its selectivity i.e. its ability to perhydrolyse rather than hydrolyse.
  • the ratio between hydrolysis and perhydrolysis can range from 10 4 :1 to 1:3x10 2 .
  • acetylated aldohexopyranoses can be utilised more effectively, i.e. can be induced to provide more peracetic acid per mole than hitherto considered possible, if the molecules satisfy certain structural criteria which enhance the acidity of the substituent acetyl groups.
  • An example of a preferred acetylated aldohexopyranose to which this correlation applies is penta acetyl glucose.
  • British Patent No. 836 988 identifies a mole of this material as being capable of producing two moles of peracetic acid and provides an illustrative detergent composition in which it is used at an unspecified alkaline pH and a molar ratio of sodium perborate to glucose ester of 2:1.
  • the conversion of acetyl groups to peracetic acid can be expressed as a conversion efficiency i.e. as a percentage of the acetyl groups present in the molecule.
  • a conversion efficiency i.e. as a percentage of the acetyl groups present in the molecule.
  • Conversion efficiencies both estimated and achieved, for other preferred materials are shown in the table below.
  • conversion efficiency in general, although an appreciable increase in conversion efficiency can be achieved for most acetylated aldohexopyranoses and pyranosides, those having conversion efficiencies of less than about 50% are of less interest as they have to be used in amounts that are too large to be economically attractive.
  • the materials of the present invention have estimated conversion efficiencies in excess of 50%, and preferably in excess of 60%.
  • Most preferred materials are penta acetyl glucose and octa acetyl lactose.
  • Levels of incorporation of the acetylated aldohexopyranoses in the detergent liquors of the invention lie in the range 10-1000 ppm, preferably from 150-500 ppm.
  • the level of acetylated aldohexopyranoses in the composition lie in the range from 0.5 to 10%, preferably from 1% to 5% by weight of the product, more preferably from 2% to 4%.
  • the invention also requires that the wash liquor have a starting pH of at least 9.5.
  • the starting or initial wash liquor pH is at least 10.0 and most preferably at least 10.2.
  • the wash liquor product concentration can lie within the range 0.1-1.0% by weight but for the purposes of determining the starting wash liquor pH, measurement is made of a 0.5% wt solution at 20°C and references to the wash liquor pH shall be construed accordingly.
  • the starting or initial wash liquor pH is defined as the pH of the detergent liquor measured after all of the soluble components have dissolved and before any soiled fabrics have been added.
  • Achievement of a wash liquor pH above the minimum recited value is preferably secured by control of the component levels during manufacture of the detergent composition but can be achieved by direct addition of alkaline ingredients such as alkalis or alkali metal silicates, carbonates or phosphates to the wash liquor following dissolution of the detergent composition.
  • alkaline ingredients such as alkalis or alkali metal silicates, carbonates or phosphates
  • the detergent liquors of the invention and compositions for their production can contain any of the optional ingredients customarily used in fabric washing processes. As these ingredients are not essential to the practice of the invention, their usage therein is described for convenience with reference to their level in the detergent composition aspect of the invention.
  • Organic and inorganic salts are contained in the detergent compositions of the invention in an amount of from 30 to 83.5% by weight.
  • a principal optional component of the invention particularly in its granular form is at least one detergent organic or inorganic builder salt which can be any one of the water soluble or water insoluble salts conventionally used for this purpose.
  • Suitable inorganic builder salts include orthophosphates, pyrophosphates, tripolyphosphates and the higher polymeric glassy phosphates, silicates, carbonates, and the water insoluble crystalline aluminosilicates such as hydrated Zeolite A, X or P.
  • Organic builder salts include the aminocarboxylates such as the salts of nitrilotriacetic acid (NTA), ethylene diaminetetra acetic acid (EDTA) and diethylenetriaminepenta acetic acid (DETPA) and the methylene phosphonate analogues of these materials NTMP, EDTMP and DETPMP, as well as the salts of polycarboxylic acids such as lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patents 821,368, 821,369 and 821,370; succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citraconic acid, carboxymethyloxysuccinic acid, lactoxysuccinic acid, and 2-oxy-1,1,3-propane tri-carboxylic acid; oxydisuccinic acid, 1,
  • the builder salts preferably comprise from 5% to 70% by weight of the composition, preferably from 10% to 50% by weight for granular detergents, and may comprise mixtures of any of the above-mentioned.
  • compositions of the present invention can be supplemented by all manner of detergent components.
  • Soil suspending agents at 0.1% to 10% by weight e.g. methyl cellulose and its derivatives such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethyl cellulose and polyethylene glycols having a molecular weight of 400 to 10,000 are common components of the present invention.
  • Anti caking agents such as sodium sulphosuccinate or sodium benzoate, dyes, pigments, optical bleaches such as tri- and tetra-sulphonated zinc phthalo cyanine, and perfumes can be included in varying amounts as desired.
  • Enzymes in minor amounts are conventional ingredients of the compositions, those suitable for use including the materials discussed in U.S. patents 3,519,570 and 3,533,139 to McCarty and McCarty et al.
  • Anionic fluorescent brightening agents are well-known ingredients, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene:2:2'-disulphonate, disodium 4',4-bis-(2,4-dianilino- s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,4'-bi-(2-anilino-4-(N-methyl N-2-hydroxy- ethylamino)-S-triazin-6-ylamino)stilbene-2,2'-disulphonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2
  • alkali metal, or alkaline earth metal, silicate can also be present.
  • the alkali metal silicate preferably is used in an amount from 0.5% to 10% more preferably from 3% to 8%.
  • Suitable silicate solids have a molar ratio of Si0 2 /alkali metal 2 0 in the range from 0.5 to 4.0, but much more preferably from 1.0 to 1.8, especially about 1.6.
  • the alkali metal silicates suitable herein can be commercial preparations of the combination of silicon dioxide and alkali metal oxide, fused together in varying proportions.
  • the present compositions also preferably contain suds regulating components in an amount of from 0.05% to 3%.
  • Preferred are microcrystalline waxes having a melting point in the range from 35°C-115°C and saponification value of less than 100.
  • the microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
  • Suitable examples of the above waxes include microcrystalline and oxidized micro-crystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax, candelilla; and carnauba wax.
  • U.S. Patent 3,933,672 issued January 20 1976, to Bartollota et al. discloses silicone suds controlling agents suitable herein.
  • the silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
  • the silicone material can be described as siloxane having the formula: wherein x is from 20 to 2,000 and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
  • the polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from 200 to 2,000,000, and higher, are all useful as suds controlling agents.
  • Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties.
  • the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenyl-, methylpolysiloxanes and the like.
  • Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from 10 nm to 20 nm and a specific surface area above 50 m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from 500 to 200,000 at a weight ratio of silicone to silanated silica of from 1:1 to 1:10.
  • the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
  • Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in DE-A-2,646,126 published April 28, 1977.
  • An example of such a compound is DB-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • a highly preferred ingredient of the detergent liquors and of compositions for their production is a polyphosphonic acid or salt thereof in an amount from 0.01 to 4%, especially from 0.1 to 1.0% by weight. At this level of incorporation, which is below the range of levels normally employed for detergent builders, the polyphosphonic acid or salt thereof is found to provide bleachable stain detergency benefits.
  • Especially preferred polyphosphonates have the formula:- wherein each R is CH 2 P0 3 H 2 or a water-soluble salt thereof and n is from 0 to 2.
  • Examples of compounds within this class are aminotri-(methylenephosphonic acid), ethylene diamine tetra(methylenephosphonic acid) and diethylene triamine penta(methylene phosphonic acid). Of these, ethylenediamine tetra-(methylene phosphonic acid) is particularly preferred.
  • the detergent composition preferably contains a water-soluble copolymeric carboxylic acid or salt thereof in an amount of from 0.1% to 5% by weight of the composition as a soil antiredeposition agent.
  • the copolymeric polycarboxylic acid which comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms and which has an average molecular weight in the range from 500 to 2,000,000, more preferably from 12,000 to 1,500,000 comprises:
  • carboxylates are 1:1 styrene/maleic acid copolymer, di-isobutylene/ maleic acid copolymers, methyl vinyl ether/maleic acid copolymers and maleic acid/acrylic acid copolymers having a molar ratio between 1:1 and 1:4.
  • Other suitable polycarboxylates are poly-alpha- hydroxy acrylates and lactones thereof as described in Belgian Patent 817,678 and B.P. 1,425,307.
  • Another suitable component of detergent compositions in accordance with the invention is a water-soluble magnesium salt which is added at levels in the range from 0.015% to 0.2%, preferably from 0.03% to 0.15% and more preferably from 0.05% to 0.12% by weight of the compositions (based on weight of magnesium).
  • Suitable magnesium salts include magnesium sulphate, magnesium sulphate heptahydrate, magnesium chloride, magnesium chloride hexahydrate, magnesium fluoride and magnesium acetate.
  • the various components can be added independently and directly to the water to form the wash liquor, the only requirement being that the acetylated aldohexopyranose or -pyranoside should not be added before the inorganic peroxy bleach.
  • Simultaneous addition of all of the ingredients is a convenient method of operation, and a preferred mode comprises the use of a preformed detergent composition to form the detergent liquor.
  • the surfactant typically together with builder and filler salts is formed into an aqueous slurry and converted into a granule, preferably by spray drying.
  • the aqueous slurry is mixed at a temperature in the range 70-90°C and the water-content of the slurry adjusted to a range of 25% to 45%, preferably 30%-38% by weight.
  • Spray drying is undertaken with drying gas inlet temperature of from 250-350°C, preferably 275-330°C, providing a final moisture content in the range of from 8% to 14% by weight.
  • Nonionic surfactant, where present, can then be sprayed in fluid form onto the spray dried detergent granules.
  • the inorganic peroxy bleach and the acetylated aldohexopyranose or -pyranoside are then dry-mixed independently with the spray dried granules to form the detergent composition.
  • a preferred form of the acetylated aldohexopyranose or -pyranoside for incorporation into a detergent composition is as an extrudate formed by the process described in European Patent Application Publication No. 0062523 filed October 23, 1981 (pub. 13.10.82).
  • the acetylated aldohexopyranose or -pyranoside is first formed into a particulate having a particle size distribution such that at least 50%, preferably at least 80% passes a 250 pm screen. in preferred embodiments of the invention at least 50% and most preferably at least 80% of the acetylated compounds pass through a 100 pm screen.
  • This particulate material is then mixed with an ethoxylated nonionic surfactant melting in the range from 20°C to 60°C to give a homogeneous friable mass comprising from 75% to 95%, preferably from 84% to 90% of solid and from 5% to 25%, preferably from 10% to 16% of ethoxylated alcohol.
  • Suitable nonionic surfactants are primary or secondary C 9 -C 18 alcohols haying an average degree of ethoxylation of from 3 to 30, more preferably 5 to 14, an example being tallow alcohol condensed with an average of 11 ethylene oxide groups per mole of alcohol.
  • the incorporation into the extrusion mixture of a low level of an acidic material prevents or minimises the discolouration of the extrudates when they are subsequently incorporated into, and stored in contact with, alkaline detergent compositions.
  • This discolouration arises as a result of alkali attack on aldehyde-sugars which leads to the formation of complex coloured compounds.
  • acetylated aldohexopyranosides such as alpha-methyl tetraacetyl glucose do not suffer this discolouration as they lack the hemiacetyl linkages which are prone to alkaline attack.
  • octaacetyl lactose which does contain such a linkage does not display discolouration when incorporated into an extrudate with a nonionic as described above and subjected to storage.
  • the tetra acetyl C l -C 12 alkyl glucosides and octa acetyl lactose are the preferred ester type peroxy bleach precursors for incorporation into particulate alkaline detergent compositions.
  • the detergent composition aspect of the invention can take a variety of particulate forms other than spray dried granules such as agglomerates made in rotary drums, pans or fluidised beds, noodles or ribbons made by extrusion techniques, as well as compressed particulate forms such as tablets or pellets.
  • the acetylated aldohexopyranose or -pyranoside can be processed with the other components provided that, as discussed above, it is not formed into intimate mixtures with those components which are alkaline in nature, or processed under hot aqueous alkaline conditions, which promote hydrolysis of the acyl groups and thus reduce the potential for peroxy acid production.
  • Typical detergent compositions contain 5-15% of the surfactant system, 15-25% of an inorganic perhydrate such as sodium perborate or percarbonate, 1-5% of acetylated aldohexopyranose or -pyranoside and 55-69% of organic or inorganic salts, miscellaneous additives and water.
  • a preferred surfactant system is a water soluble anionic-cationic-nonionic mixture in which the anionic is present in an amount greater than the stoichiometric equivalent of the cationic surfactant and the ratio of anionic:nonionic surfactants is >1:1 by weight.
  • the invention also embraces the use of additive products together with conventional laundry detergents to form the detergent liquors.
  • the additive products may be in either liquid or solid form, and if solid may be particulate or non-particulate in nature.
  • a particularly preferred non-particulate additive product is disclosed in British Patent Specification No. 1,586,769 and European Application No. 78200051.7 Publication No. 0000226.
  • these disclosures relate to additive products comprising organic peroxy acid bleach precursor in water-releasable combination with a non-particulate flexible substrate, preferably in sheet form, in which the precursor to substrate ratio lies in the range from 1:10 to 30:1, more preferably from 1:2 to 8:1.
  • European Application No. 78200051.7 discloses the combination of this precursor-substrate system with a nonionic-cationic surfactant mixture in which the ratio of nonionic to cationic lies in the range from 20:1 to 1:2, preferably from 5:1 to 3:2.
  • Suitable particulate additive products are disclosed in European Patent Application No. 79200303.0 Publication No. 0006655 and the previously mentioned European Patent Application Publication No. 0062523, both of which relate to the use of normally solid, water soluble or water dispersible organic materials as a component of the additive product.
  • Preferred materials are solid at temperatures below 25°C and more preferably do not soften appreciably below 30°C, such as ethoxylated alcohols having an alkyl chain length greater than 16 carbon atoms and containing at least eleven moles of ethylene oxide per mole of alcohol.
  • a laundry liquor was made up by adding the following ingredients simultaneously to the drum of a Miele Automatic washing machine containing 12 litres water of 10°H (Calcium/Magnesium ratio 5:1) and temperature 18°C.
  • the pH was adjusted to 9.5 with 12 g citric acid and the machine was started using a 40°C low agitation cycle. 25 ml samples of wash liquor were extracted at 2 minute intervals and analysed for peracetic acid using the following technique.
  • This example illustrates the benefit of increased perhydrate:polyol acetate ratio on the yield of peracetic acid per mole of penta acetyl glucose.
  • Example 1 The procedure of Example 1 was repeated using 135 g of commercially available granular detergent containing
  • the molar ratio of H 2 0 2 to PAG was 15:1.
  • the pH 10 and the machine was started using a 40°C low agitation cycle.
  • 25 ml samples of wash liquor were extracted at 2 minute intervals and analysed for peracetic acid. After 14 minutes the maximum level of peracetic acid release was recorded corresponding to 2.8 moles of peracetic acid per mole of PAG (conversion efficiency 56%).
  • a detergent formulation was spray dried to provide the following composition in parts by weight.

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Claims (16)

1. Eine Wäschewaschflüssigkeit, die zur Entfernung oxidierbarer Flecken, insbesondere bei Temperaturen von weniger als 60°C, geeignet ist, wobei die genannte Flüssigkeit 0,1 Gew.-% bis 2,0 Gew.-% einer Detergenszusammensetzung, umfassend ein in einer zur Lieferung von 10 bis 5000 TpM in Lösung entsprechenden Menge vorliegendes organisches oberflächenaktives Mittel, ein anorganisches Persauerstoffbleichmittel vom Perhydrattypus und einen Peressigsäureprecursor, umfassend eine Acetylgruppen an wenigstens drei benachbarten Kohlenstoffatomen enthaltende, acetylierte Aldohexopyranose oder ein solche Acetylgruppen enthaltendes, acetyliertes Aldohexopyranosid, die bzw. das in einer zur Lieferung von 10 bis 1000 TpM in Lösung entsprechenden Menge vorliegt, enthält, wobei die genannte Wäschewaschflüssigkeit einen Ausgangs-pH von wenigstens 9,5 aufweist, welcher Ausgangs-pH als der pH einer 0,5 gew.-%igen Lösung der genannten Zusammensetzung, gemessen bei 20°C, nachdem alle löslichen Komponenten aufgelöst sind, und vor dem Zusatz irgendwelcher verschmutzter Textilien, definiert ist, dadurch gekennzeichnet, daß das anorganische Persauerstoffbleichmittel in einer Menge von wenigstens 8,5 Millimol/dm' vorliegt, und daß das Verhältnis der Anzahl von Mol an in dem Perhydrat verfügbarem Persauerstoff zu der Anzahl von Mol an acetylierter Aldohexopyranose oder acetyliertem Aldohexopyranosid ≥12:1 beträgt, wobei der Prozentsatz der in der acetylierten Aldohexopyranose oder in dem acetylierten Aldohexopyranosid vorliegenden Acetylgruppen, die in Peressigsäure umgewandelt werden, größer als 50% ist.
2. Eine Wäschewaschflüssigkeit nach Anspruch 1, dadurch gekennzeichnet, daß das Molverhältnis von verfügbarem Persauerstoff zu acetylierter Aldohexopyranose oder acetyliertem Aldohexopyranosid ≥15:1 beträgt.
3. Eine Wäschewaschflüssigkeit nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß der Ausgangs-pH der Waschflüssigkeit 10,0 beträgt.
4. Eine Wäschewaschflüssigkeit nach einem der Ansprüche 1 bis 3, wobei das anorganische Perhydrat, ausgedrückt als Natriumperborattetrahydrat, in einer Menge von 1300 bis 7000 TpM vorliegt.
5. Eine Wäschewaschflüssigkeit nach Anspruch 4, wobei das anorganische Perhydrat in einer Menge von 1300-3200 TpM vorliegt.
6. Eine Wäschewaschflüssigkeit nach einem der Ansprüche 1 bis 5, wobei der Prozentsatz der in der acetylierten Aldohexopyranose oder in dem acetylierten Aldohexopyranosid vorliegenden Acetylgruppen, die in Peressigsäure umgewandelt werden, größer als 60% ist.
7. Eine Wäschewaschflüssigkeit nach einem der Ansprüche 1 bis 6, wobei die acetylierte Aldohexopyranose oder das acetylierte Aldohexopyranosid eine vollständig acetylierte Glucopyranose oder ein vollständig acetyliertes Glucopyranosid ist.
8. Eine Detergenszusammensetzung zur Verwendung bei der Bildung der Wäschewaschflüssigkeit nach einem der Ansprüche 1 bis 7, welche, bezogen auf das Gewicht der Zusammensetzung, enthält:
1% bis 25% eines anionischen, nichtionischen, ampholytischen, zwitterionischen oder kationischen, organischen oberflächenaktiven Mittels oder eines Gemisches davon; und
30 bis 83,5% eines oder mehrerer organischer oder anorganischer Salze;

wobei die Zusammensetzung in einer 0,5 %igen wässerigen Lösung bei 20°C einen pH von wenigstens 9,5 aufweist, dadurch gekennzeichnet, daß sie
15% bis 35% eines anorganischen Persauerstoffbleichmittels vom Perhydrattypus; und
0,5% bis 10% einer vollständig acetylierten Aldohexopyranose oder eines vollständig acetylierten Aldohexopyranosids enthält;

und daß das Verhältnis der Mole an verfügbarem Persauerstoff in dem Perhydrat zu den Molen von acetylierter Aldohexopyranose oder acetyliertem Aldohexopyranosid ,12:1 beträgt.
9. Eine Detergenszusammensetzung nach Anspruch 8, enthaltend
5-15% eines Gemisches von wasserlöslichen, anionischen, kationischen und nichtionischen oberflächenaktiven Mitteln, in welchem das anionische oberflächenaktive Mittel in einer, bezogen auf das kationische oberflächenaktive Mittel, größeren als der stöchiometrischen Menge vorliegt, und das Gewichtsverhältnis von anionischen:nichtionischen oberflächenaktiven Mitteln >1:1 ist;
5-25% eines anorganischen Perhydrats, ausgewählt aus Natriumperborat und Natriumpercarbonat;
1-5% acetylierte Glucopyranose oder acetyliertes Glucopyranosid; und
55-69% eines oder mehrerer organischer oder anorganischer Salze.
10. Eine Detergenszusammensetzung nach einem der Ansprüche 8 und 9, wobei die organischen oder anorganischen Salze ein oder mehrere Gerüststoffsalze umfassen.
11. Eine Detergenszusammensetzung nach einem der Ansprüche 8 bis 10, enthaltend außerdem 0,1-5 Gew.-% einer wasserlöslichen, copolymeren Polycarbonsäure oder eines Salzes davon, mit wenigstens zwei Carboxylresten, die voneinander durch nicht mehr als 2 Kohlenstoffatome getrennt sind, und mit einem mittleren Molekulargewicht im Bereich von 500 bis 2,000.000, wobei das genannte Copolymer
(a) Polycarbonsäureeinheiten der allgemeinen Formel
Figure imgb0028
worin X, Y und Z jeweils aus der Gruppe ausgewählt sind, die aus Wasserstoff, Methyl, Aryl, Alkaryl, Carboxyl, Hydroxy und Carboxymethyl besteht; wenigstens einer der Reste X, Y und Z aus der Gruppe ausgewählt ist, die aus Carboxyl und Carboxymethyl besteht, mit der Maßgabe, daß X und Y nur dann Carboxymethyl sein können, falls Z aus Carboxyl und Carboxymethyl ausgewählt ist, und wobei nur einer der Reste X, Y und Z Methyl Aryl, Hydroxyl und Alkaryl sein kann, und
(b) Monomereinheiten enthält, die ausgewählt sind aus
Figure imgb0029
worin R1 eine C1-C12-Alkylgruppe oder eine C1-C12-Acylgruppe ist, und R, gegebenenfalls hydroxysubstituiert, ist,
Figure imgb0030
worin R2 H oder CH3 ist, und R3 H oder eine C1-C10-Alkylgruppe ist, wobei R2 und R3 gegebenenfalls hydroxysubstituiert sind,
Figure imgb0031
worin jeder der Reste R4 bis R7 H oder eine Alkylgruppe derart ist, daß R4 bis R7 zusammengenommen 1 bis 20 Kohlenstoffatome haben, wobei R4 bis R7 jeweils gegebenenfalls hydroxysubstituiert ist, und
Figure imgb0032
worin Ra Benzyl oder Pyrrolidon ist.
12. Ein Verfahren zur Bildung einer Waschflüssigkeit nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es
a) die Bildung einer 0,1 gew.-%igen bis 2 gew.-%igen wässerigen Lösung oder Dispersion einer Grundzusammensetzung, enthaltend ein organisches oberflächenaktives Mittel, ein anorganisches Peroxysauerstoffbleichmittel vom Perhydrattypus und ein oder mehrere organische oder anorganische Salze derart, daß der pH der wässerigen Lösung oder Dispersion (mit einem Gehalt von 0,5 Gew.-% der genannten Zusammensetzung, gemessen bei 20°C, nachdem alle löslichen Komponenten aufgelöst sind, und vor der Zugabe irgendwelcher verschmutzter Textilien) ≥9,5 beträgt, und daß die wässerige Lösung oder Dispersion <10 bis 5000 TpM des oberflächenaktiven Mittels und wenigstens 8,5 mMol/dm3 des Perhydrats enthält; und
b) das Zugeben einer Zusatzzusammensetzung dazu, welche die acetylierte Aldohexopyranose oder das acetylierte Aldohexopyranosid und einen Träger hiefür in einer solchen Menge enthält, daß 10 bis 1000 TpM in Lösung abgegeben werden und ein Molverhältnis von verfügbarem Persauerstoff in dem Perhydrat zu der acetylierten Aldohexopyranose oder zu dem acetylierten Aldohexopyranosid von ≥12:1 erhalten wird, umfaßt.
13. Ein Verfahren nach Anspruch 12, wobei die Zusatzzusammensetzung teilchenförmig ist und ein Agglomerat enthält, welches aus der acetylierten Aldohexopyranose oder dem acetyllierten Aldohexopyranosid und einem wasserlöslichen oder wasserdispergierbaren, organischen Material, welches bei Temperaturen unter 25°C fest ist, gebildet ist.
14. Ein Verfahren nach Anspruch 13, wobei der organische Feststoff ein ethoxylierter Alkohol ist.
15. Ein Verfahren nach Anspruch 12, wobei die Zusatzzusammensetzung nicht-teilchenförmig ist und die acetylierte Aldohexopyranose oder das acetylierte Aldohexopyranosid in einer in Wasser freisetzbaren Kombination mit einem flexiblen, flächenförmigen Substrat enthält.
16. Ein Verfahren nach Anspruch 15, wobei die Zusatzzusammensetzung nach 0,1-5 Gew.-% einer wasserlöslichen, copolymeren Polycarbonsäure oder eines Salzes davon, mit wenigstens zwei Carboxylresten, die voneinander durch nicht mehr als zwei Kohlenstoffatome getrennt sind, und mit einem mittleren Molekulargewicht im Bereich von 500 bis 2,000.000, umfaßt, wobei das genannte Copolymer
(a) Polycarbonsäureeinheiten der allgemeinen Formel I
Figure imgb0033
worin X, Y und Z jeweils aus der Gruppe ausgewählt sind, die aus Wasserstoff, Methyl, Aryl, Alkaryl, Carboxyl, Hydroxy und Carboxymethyl besteht; wenigstens einer der Reste X, Y und Z aus der Gruppe ausgewählt ist, die aus Carboxyl und Carboxymethyl besteht, mit der Maßgabe, daß X und Y nur dann Carboxymethyl sein können, falls Z aus Carboxyl und Carboxymethyl ausgewählt ist, und wobei nur einer der Reste X, Y und Z Methyl, Aryl, Hydroxyl und Alkaryl sein kann, und
(b) Monomereinheiten enthält, die ausgewählt sind aus
Figure imgb0034
worin R, eine C1-C12-Alkylgruppe oder eine C1-C12-Acylgruppe ist, und R1 gegebenenfalls hydroxysubstituiert, ist,
Figure imgb0035
worin R2 H oder CH3 ist, und R3 H oder eine Cl-Clo-Alkylgruppe ist, wobei R2 und R3 gegebenenfalls hydroxysubstituiert sind,
Figure imgb0036
worin jeder der Reste R4 bis R7 H oder eine Alkylgruppe derart ist, daß R4 bis R7 zusammengenommen 1 bis 20 Kohlenstoffatome haben, wobei R4 bis R7 jeweils gegebenenfalls hydroxysubstituiert ist, und
Figure imgb0037
worin R8 Benzyl oder Pyrrolidon ist.
EP83303058A 1982-06-01 1983-05-27 Detergens-Flüssigkeiten und Zusammensetzungen für ihre Verwendung Expired EP0095904B1 (de)

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ZA851897B (en) * 1984-04-02 1986-10-29 Colgate Palmolive Co Non-caking bleaching detergent composition containing a lower hydrate of sodium perborate
US4889651A (en) * 1988-01-21 1989-12-26 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
DK27789D0 (da) * 1989-01-23 1989-01-23 Novo Industri As Detergent - sammensaetning
DE4014978A1 (de) * 1990-05-10 1991-11-14 Basf Ag Verfahren zur herstellung einer koernigen bleichaktivatorzusammensetzung
GB9116939D0 (en) * 1991-08-06 1991-09-18 Unilever Plc Bleach precursors and bleaching compositions
NL1012482C2 (nl) * 1999-06-30 2001-01-03 Co Peratie Cosun U A Bleekactivator op basis van inuline.
JP4779229B2 (ja) * 2001-05-09 2011-09-28 大日本印刷株式会社 液体充填装置

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JPS5851999B2 (ja) * 1978-08-30 1983-11-19 花王株式会社 漂白剤組成物
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