EP0499434B1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0499434B1
EP0499434B1 EP92301101A EP92301101A EP0499434B1 EP 0499434 B1 EP0499434 B1 EP 0499434B1 EP 92301101 A EP92301101 A EP 92301101A EP 92301101 A EP92301101 A EP 92301101A EP 0499434 B1 EP0499434 B1 EP 0499434B1
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EP
European Patent Office
Prior art keywords
composition according
detergent composition
formula
surfactant
glycolipid
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EP92301101A
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German (de)
English (en)
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EP0499434A1 (fr
Inventor
Peter John Unilever Research & Engineering Hall
Johan Unilever Research & Engineering Haverkamp
Cornelis Gerhard Unilever Research Van Kralingen
Michael Unilever Research & Engineering Schmidt
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB919102945A external-priority patent/GB9102945D0/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters

Definitions

  • the present invention relates to detergent compositions, particularly to compositions used for washing fabrics, dishes and household surfaces.
  • the compositions of the invention which are especially but not exclusively suitable for fabric washing, contain one or more glycolipid biosurfactants.
  • Detergent compositions traditionally contain one or more detergent active material in addition to various other ingredients such as detergency builders, bleaches, fluorescers, perfumes etc. Notable applications of detergent compositions are to clean fabrics, usually by washing portable fabric items in a bowl or in a washing machine, to clean crockery and cooking utensils, again by washing in a bowl (hand dishwashing), and to clean hard surfaces such as glass, glazed surfaces, plastics, metals and enamels.
  • surfactant materials A number of classes of surfactant materials have been used, some for many years, as detergent active materials, including anionic and nonionic materials.
  • WO 90 09451A Novo Nordisk discloses fatty acid esters of methyl glycosides useful as surfactants.
  • WO 91 00331A Unilever
  • EP 423 968A Unilever
  • O-alkanoyl derivatives of reducing hexose sugars for example, O-alkanoyl glucoside, and their use as detergent surfactants.
  • the present invention is concerned with glycolipid biosurfactants, and specifically with rhamnolipids, sophorose lipids, glucose lipids, cellobiose lipids and trehalose lipids.
  • glycolipid biosurfactants are derived from biological fermentation processes (either bacterial or yeast fermentation). This is inherently advantageous in that products of fermentation can generally be derived from renewable raw materials and are likely to be biodegradable after use.
  • glycolipid biosurfactants can give a synergistic enhancement of oily/fatty soil detergency when used in certain combinations with each other, or jointly with other surfactant(s). Enhanced detergency has been observed even with glycolipids that exhibit poor detergency when used alone.
  • JP 63 077 535A discloses an emulsion composition containing alpha-decenoic bonded rhamnolipid or its salt as emulsifying agent.
  • the emulsion is said to be useful for cosmetics, health-care products, medicines, toiletries, detergents and foods.
  • compositions containing sophorose lipid lactone are of particular use for combating dandruff and as a bacteriostatic agent in, for example, deodorants.
  • the compositions disclosed include a shampoo, a foam bath and a shower gel containing high levels (30-40 wt%) of high-foaming anionic surfactants (alkyl ether sulphate and acyl glutamate), and also containing low levels (2-3 wt%) of sophorose lipid lactone to provide antibacterial and skin care benefits.
  • Us 4 216 311 discloses the production of a glycolipid methyl ester from sophorose lipid. These glycolipid methyl esters are waxy hydrophilic surface-active materials useful, for example, as emulsifying agents, wetting agents, and oil and fat improvers. JP 63 063 389A (Kao) relates to a biological production of a similar disaccharide glycolipid intended for similar uses.
  • JP 62 091 236A (Nippon Oils and Fats) describes a succinic trehalose lipid consisting of a succinic acid moiety linked to a fatty acid moiety.
  • the lipid is used as an emulsion stabiliser.
  • the present invention provides a detergent composition comprising from 1 to 60 wt% in total of:
  • the invention also provides a method of washing which comprises contacting fabrics, or an inanimate surface to be cleaned, with a composition according to the previous paragraph, or a wash liquor obtainable by adding the composition to water, notably in an amount ranging from 0.5 to 50 grams of compositions per litre of water.
  • the detergent composition of the invention contains at least two different surfactants having different characteristics, at least one of which must be a glycolipid biosurfactant.
  • micellar phase and lamellar phase surfactants relate to the phase in which the surfactants are likely to be present under typical wash conditions.
  • the two types of surfactant may be distinguished by the behaviour of a 1 % by weight aqueous solution in demineralised water at pH 7.0 and 25°C.
  • a surfactant solution containing dispersed lamellar phases exhibits birefringent textures when viewed under a polarising optical microscope, while a micellar solution does not.
  • micellar phase surfactant will provide a clear solution when present at a concentration of 1% by weight in demineralised water at pH 7.0 and 25°C, although the presence of small amounts of impurities may reduce the clarity.
  • a lamellar phase surfactant will always provide a cloudy solution when present at a concentration of 1% by weight in demineralised water at pH 7.0 and 25°C.
  • micellar phase surfactant must be chosen from a specific class of surfactant the glycolipid biosurfactants; while the lamellar phase surfactant may or may not also be a glycolipid biosurfactant. Thus some glycolipids are micellar phase surfactants and others are lamellar phase surfactants.
  • Glycolipid surfactants with which the present invention are concerned are rhamnolipids, glucoselipids, sophoroselipids, trehaloselipids, cellobioselipids and mixtures thereof. Within any one class of glycolipids, some materials may be micellar and others lamellar.
  • Micellar phase glycolipid biosurfactants may suitably be selected from rhamnolipids, glucoselipids, sophoroselipids, cellobioselipids and mixtures thereof.
  • Lamellar phase glycolipid biosurfactants may suitably be selected from rhamnolipids, glucoselipids, trehaloselipids and mixtures thereof.
  • the surfactants (i) and (ii) may both be glycolipids.
  • the micellar phase glycolipid is then most preferably a rhamnolipid, a sophoroselipid or a cellobiose lipid, while the lamellar phase glycolipid is most preferably a trehaloselipid, a glucoselipid or a rhamnolipid.
  • the lamellar phase surfactant (ii) may be a non-glycolipid surfactant, preferably an anionic or nonionic surfactant.
  • Zwitterionic and cationic surfactants are not preferred, and if present it is desirable that they are at low levels, such as not more than 10% by weight of all surfactant present.
  • the weight ratio of the first surfactant (i) to the second surfactant (ii) is preferably in the range from 20:1 to 1:20, and may lie in a narrower range, for example from 10:1 to 1:10, more preferably 4:1 to 1:4.
  • biosurfactants include rhamnolipids, glucoselipids, sophoroselipids, trehaloselipids, cellobioselipids and mixtures thereof. Each will now be described in more detail below:
  • biosurfactants have the formula (I): where a is 1 or 2; b is 1 or 2, n is 4 to 10. preferably 6; R1 is H or a cation, preferably H, or a monovalent solubilising cation, R2 is H or the group preferably H; m is 4 to 10; and the values of m and n need not be the same at each occurrence.
  • Rhamnolipids can be produced by bacterial fermentation. This is inherently advantageous in that products of bacterial fermentation can generally be derived from renewable raw materials and are likely to be biodegradable after use. Another advantage of the surfactants of formula (I) is that they can be produced as a by-product of enzyme manufacture.
  • Rhamnolipids can be produced by bacteria of the genus Pseudomonas .
  • the bacterial fermentation typically utilises as substrates a sugar or glycerol or an alkane or mixtures thereof.
  • any sample of rhamnolipid will generally contain a variety of individual compounds within the general formula (I).
  • the proportions of individual compounds is governed by the microorganism species, and the particular strain employed for fermentation, the substrate materials supplied to the fermentation, and other fermentation conditions.
  • the bacterial fermentation generally produces compounds in which R1 is hydrogen or a solubilising cation. Such compounds can undergo conversion between the salt and the acid forms in aqueous solution, according to the pH of the solution. Common solubilising cations are alkali metal, ammonium and alkanolamine.
  • a second class of glycolipid biosurfactant in accordance with the present invention comprises glucoselipids of the formula (II). where R1 is H or a cation; p is 1 to 4; and q is 4 to 10, preferably 6.
  • Glucoselipids can be produced by the bacterium Alcaligenes Sp.MMl . Appropriate fermentation methods are reviewed by M. Schmidt in his PhD thesis (1990), Technical University of Braunschweig, and by Schulz et al (1991) Z. Naturforsch 46C 197-203. The glucoselipids are recovered from the fermentation broth via solvent extraction using ethyl ether or a mixture of either dichloromethane:methanol or chloroform:methanol.
  • a third class of glycolipid biosurfactant in accordance with the present invention comprises sophoroselipids of the formula (III) where R3 and R4 are individually H or an acetyl group; R5 is a saturated or unsaturated, hydroxylated or non-hydroxylated hydrocarbon group having 1 to 9 carbon atoms, preferably being a methyl group; R6 is a saturated or unsaturated hydroxylated or non-hydroxylated hydrocarbon group having 1 to 19 carbon atoms; with the proviso that the total number of carbon atoms in the groups R5 and R6 does not exceed 20 and is preferably from 14 to 18.
  • the sophoroselipid may be incorporated into detergent compositions of the present invention as either the open chain free acid form, where R7 is H and R8 is OH, or in its lactone form, where a lactone ring is formed between R7 and R8 as shown by formula (IV).
  • R3, R4 and R6 are as defined above; with the proviso that at least one of R3 and R4 is an acetyl group.
  • Sophoroselipids can be produced by yeast cells, for example Torulopsis apicola and Torulopsis bombicola .
  • the fermentation process typically utilises sugars and alkanes as substrates.
  • Appropriate fermentation methods are reviewed in A P Tulloch, J F T Spencer and P A J Gorin, Can. J Chem (1962) 40 1326 and U Gobbert, S Lang and F Wagner, Biotechnology Letters (1984) 6 (4), 225.
  • the resultant product is a mixture of various open-chain sophoroselipids and sophoroselipid lactones, which may be utilised as a mixtures, or the required form can be isolated.
  • the glycolipid biosurfactant comprises sophoroselipids
  • the weight ratio of sophoroselipids to additional surfactant is preferably in the range 4:1 to 3:2 and is more preferably 4:1.
  • a fourth class of glycolipid biosurfactant in accordance with the present invention comprises trehaloselipids of the general formula (V). where R9, R10 and R11 are individually a saturated or unsaturated, hydroxylated or non-hydroxylated hydrocarbon of 5 to 13 carbon atoms.
  • Trehaloselipids can be produced by bacteria fermentation using the marine bacterium Arthrobacter sp. Ek 1 or the fresh water bacterium Rhodococcus erythropolis . Appropriate fermentation methods are provided by Ishigami et al (1987) J. Jpn Oil Chem Soc 36 847-851, Schultz et al (1991), Z. Naturforsch 46C 197-203; and Passeri et al (1991) Z Naturforsch 46C 204-209.
  • a fifth class of glycolipid biosurfactant in accordance with the present invention comprises cellobioselipids of the general formula (VI).
  • R1 is H or a cation
  • R12 is a saturated or non-saturated, hydroxylated or non-hydroxylated hydrocarbon having 9 to 15 carbon atoms, preferably 13 carbon atoms
  • R13 is H or an acetyl group
  • R14 is a saturated or non-saturated, hydroxylated or non-hydroxylated hydrocarbon having 4 to 16 carbon atoms.
  • Cellobioselipids can be produced by fungi cells from the genus ustilago . Appropriate fermentation methods are provided by Frautz, Lang and Wagner (1986) Biotech Letts 8 757-762.
  • the weight ratio of cellobioselipids to additional surfactant is preferably in the range 4:1 to 2:3.
  • the detergent composition of the invention may optionally contains at least one non-glycolipid surfactant in addition to the glycolipid biosurfactant(s) described above, provided that at least one micellar phase glycolipid surfactant is present.
  • the non-glycolipid surfactant can be chosen from anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants; but if zwitterionic or cationic surfactants are present, it is desirable that they are incorporated at low levels, such as not more than 10% by weight of all surfactant present.
  • anionic surfactants examples include alkyl benzene sulphonates, alkyl ether sulphates, olefin sulphonates, alkyl sulphonates, secondary alkyl sulphonates, fatty acid ester sulphonates, dialkyl sulphosuccinates, alkyl orthoxylene sulphonates and other disclosed in the literature, especially 'Surface Active Agents' Vol. 1, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.
  • alkyl benzene sulphonates include alkali metal, ammonium or alkanolamine salts of alkylbenzene sulphonates having from 10 to 18 carbon atoms in the alkyl group.
  • Suitable alkyl and alkylether sulphates include those having from 10 to 24 carbon atoms in the alkyl group, the alkylether sulphates have from 1 to 5 ethylene oxide groups.
  • Suitable olefin sulphonates are those prepared by sulphonation of C10-C24 alpha-olefins and subsequent neutralisation and hydrolysis of the sulphonation reaction product.
  • alkyl sulphates or sulphated fatty alcohol salts
  • alkyl sulphates include those of mixed alkyl chain length, in which the ratio of C12 alkyl chains to C18 alkyl chains is in the range of from 9:4 to 1:6.
  • a suitable material can be obtained from a mixture of synthetic lauryl and oleyl alcohols in appropriate properties.
  • fatty acid ester sulphonates include those of the general formula wherein R1 is derived from tallow, palm or coconut oil and R2 is a short chain alkyl group such as butyl.
  • dialkyl sulphosuccinates include those in which both alkyl substituent contains at least 4 carbon atoms, and together contain 12 to 20 carbon atoms in total, such as di-C8 alkyl sulphosuccinate.
  • alkyl orthoxylene sulphonates include those in which the alkyl group contains from 12 to 24 carbon atoms.
  • anionic surfactants which may be used include alkali metal soaps of a fatty acid, preferably one containing 12 to 18 carbon atoms.
  • Typical such acids are oleic acid, ricinoleic acid and fatty acids derived from caster oil, rapeseed oil, groundnut oil, coconut oil, palmkernal oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • soaps can act as detergency builders or fabric conditioners.
  • Dialkyl sulphosuccinates are of especial interest as lamellar phase anionic surfactants for use in the present invention.
  • Nonionic detergent compounds which may be used are alkyl (C6 ⁇ 22) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C8 ⁇ 20 primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long-chain tertiary amine oxides; alkyl sulphoxides C10-C14 alkyl pyrollidones and tertiary phosphine oxides.
  • Suitable lamellar phase nonionic surfactants include those with an HLB value below 10.5, preferably below 10 and more preferably in a range of from 8.5 to 9.5.
  • HLB value is defined as one fifth of the mole per cent of ethylene oxide in the molecule.
  • Suitable nonionic surfactants may be ethoxylated materials, especially ethoxylated aliphatic alcohols, with a relatively low proportion of ethoxylation so as to give an HLB value below 10.5.
  • any ethylene oxide content of the nonionic surfactant be ⁇ 5% by weight of the surfactant system, or zero, and various non-ethoxylated nonionic surfactants are also suitable for use in the present invention.
  • alkyl polyglycosides of general formula R15O(R16O) t (G) y or in which R15 is an organic hydrophobic residue containing 10 to 20 carbon atoms, R16 contains 2 to 4 carbon atoms, G is a saccharide residue containing 5 to 6 carbon atoms, t is in the range 0 to 25 and y is in the range from 1 to 10.
  • the hydrophobic group R15 is preferably alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl. However, it may include an aryl group for example alkyl-aryl, alkenyl-aryl and hydroxyalkyl-aryl. Particularly preferred is that R is alkyl or alkenyl of 10 to 16 carbon atoms, more particularly 12 to 14 carbon atoms.
  • t in the general formula above is preferably zero, so that the -(R16O) t - unit of the general formula is absent.
  • R16O is an ethylene oxide residue.
  • Other likely possibilities are propylene oxide and glycerol residues.
  • the value of t (which may be an average value) will preferably lie in the range from 0.5 to 10.
  • the group G is typically derived from fructose glucose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and/or ribose.
  • the G is provided substantially exclusively by glucose units.
  • Intersaccharide bonds may be from a 1-position to a 2, 3, 4 or 6-position of the adjoining saccharide.
  • Hydroxyl groups on sugar residues may be submitted, e.g. etherified with short alkyl chains of 1 to 4 carbon atoms.
  • y which is an average, desirably lies between 1 and 4, especially 1 and 2.
  • Alkyl polyglycosides of formula R15O(G) y i.e. a formula as given above in which t is zero, are available from Horizon Chemical Co.
  • O-alkanoyl glucosides are described in International Patent Application WO 88/10147 (Novo Industri A/S).
  • the surfactants described therein are glucose esters with the acyl group attached in the 3- or 6-position such as 3-0-acyl-D-glucose or 6-0-acyl-D-glucose.
  • a 6-0-alkanoyl glucoside especially compounds having the formula: wherein R17 is an alkyl or alkenyl group having from 7 to 19 preferably 11 to 19 carbon atoms, and R18 is hydrogen or an alkyl group having from 1 to 4 carbon atoms.
  • R18 is an alkyl group, such as ethyl or isopropyl.
  • Alkylation in the l- position enables such compounds to be prepared by regiospecific enzymatic synthesis as described by Bjorkling et al. (J.Chem. Soc., Chem. Common. 1989 p934) the disclosure of which is incorporated herein by reference.
  • esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reduced sugars, such as galactose and mannose are also suitable.
  • R19 is preferably a saturated or unsaturated aliphatic residue.
  • R19 may be linear or branched alkyl or alkenyl. More preferably, R19 is a substantially linear alkyl or alkenyl moiety having from 9 to 16 carbon atoms, notably a C8-C12 alkyl moiety. Most preferably, R19 is decyl, undecyl or dodecyl.
  • the monoglyceryl ethers of alkanols are known materials and can be prepared, for example by the condensation of a higher alkanol and glycidol.
  • Glycerol monoesters are of course well know and available from various suppliers including Alkyril Chemicals Inc.
  • Nonionic surfactants of interest for use in the present invention is comprised by 1,2- diols of the general formula where R is a saturated or unsaturated hydrocarbon group containing from 8 to 16 carbon atoms.
  • compositions of this invention will generally contain a surfactant mixture comprising micellar phase surfactant (i) and lamellar phase surfactant(s) (ii) in an amount which is from 1 to 60% by weight of the composition; preferably from 2 to 45%; more preferably from 5 to 40%; most preferably from 5 to 35%.
  • a surfactant mixture comprising micellar phase surfactant (i) and lamellar phase surfactant(s) (ii) in an amount which is from 1 to 60% by weight of the composition; preferably from 2 to 45%; more preferably from 5 to 40%; most preferably from 5 to 35%.
  • the amount of glycolipid biosurfactant present is more than 5% by weight of the overall composition.
  • the weight ratio range which gives enhanced detergency will vary depending on the specific surfactants used and can be determined by experiment. In general the proportion of glycolipid biosurfactant should be low when its alkyl chains are shorter, but higher if its alkyl chains are longer.
  • micellar phase surfactant to lamellar phase surfactant will generally lie within a range of 20:1 to 1:20 and may lie in a narrower range, e.g. from 10:1 to 1:10, more preferably from 4:1 to 1:4.
  • the proportions of the surfactants are desirably such as to give better oily soil detergency than given by the (or either) glycolipid biosurfactant alone, the total amount of surfactant being the same.
  • the proportions are desirably such as to give better oily soil detergency that that given by the non-glycolipid surfactant alone, the total amount of surfactant being the same.
  • composition of the invention is intended for fabric washing, it will generally contain one or more detergency builders, suitably in an amount of from 5 to 80% by weight, preferably from 7 to 70% by weight, more preferably from 20 to 80% by weight. If it is in solid form, the composition is likely to contain at least 10 or 15% of builder. This may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the compositions with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.
  • Preferred builders include alkali metal (preferably sodium) aluminosilicates, which may suitably be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, and may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na20.Al203.0.8-6 SiO2
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble).
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
  • Also of interest is the novel zeolite P described and claimed in EP 384070 (Unilever).
  • Phosphate-built detergent compositions are also within the scope of the invention.
  • phosphorus-containing inorganic detergency builders include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, ortho phosphates and hexametaphosphates.
  • preferred detergent compositions of the invention preferably do not contain more than 5% by weight of inorganic phosphate builders, and are desirably substantially free of phosphate builders.
  • Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates; and organic precipitant builders such as alkyl- and alkenylmalonates and succinates, and sulphonated fatty acid salts.
  • alkali metal generally sodium
  • organic builders include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinate
  • Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15% by weight, especially from 1 to 10% by weight; and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 20% by weight, more preferably from 5 to 15% by weight.
  • fabric washing compositions according to the invention be approximately neutral or at least slightly alkaline, that is when the composition is dissolved in an amount to give surfactant concentration of 1 g/l in distilled water at 25°C the pH should desirably be at least 7.5.
  • the pH will usually be greater, such as at least 9.
  • the compositions may include a water-soluble alkaline salt. This salt may be a detergency builder (as described above) or a non-building alkaline material.
  • compositions of the invention may contain an electrolyte, for instance present in such an amount to give a concentration of at least 0.01 molar, when the composition is added to water at a concentration of 1 g/litre.
  • Electrolyte concentration may possibly be higher such as at least 0.05 or 0.1 molar especially if the composition is of solid form: liquid compositions generally limit electrolyte for the sake of stability. 1 g/litre is approximately the lowest level at which detergent compositions for fabric washing are used in usual practice. More usual is usage at a level of 4 to 50 g/litre.
  • the amount of electrolyte may be such as to achieve an electrolyte concentration of 0.01 molar, most preferably at least 0.1 molar, when the composition is added to water at a concentration of 4 g/litre.
  • ingredients which can optionally be employed in the detergent composition of the invention include polymers containing carboxylic or sulphonic acid groups in acid form or wholly or partially neutralised to sodium or potassium salts, the sodium salts being preferred.
  • Preferred polymers are homopolymers and copolymers of acrylic acid and/or maleic acid or maleic anhydride.
  • polyacrylates polyalphahydroxy acrylates, acrylic/maleic acid copolymers, and acrylic phosphinates.
  • Other polymers which are especially preferred for use in liquid detergent compositions are deflocculating polymers such as for example disclosed in EP 346995.
  • the molecular weights of homopolymers and copolymers are generally 1000 to 150 000, preferably 1500 to 100 000.
  • the amount of any polymer may lie in the range from 0.5 to 5% by weight of the composition.
  • Other suitable polymeric materials are cellulose ethers such as carboxy methyl cellulose, methyl cellulose, hydroxy alkyl celluloses, and mixed ethers, such as methyl hydroxy ethyl cellulose, methyl hydroxy propyl cellulose, and methyl carboxy methyl cellulose. Mixtures of different cellulose ethers, particularly mixtures of carboxy methyl cellulose and methyl cellulose, are suitable.
  • Polyethylene glycol of molecular weight from 400 to 50 000, preferably from 1000 to 10 000, and copolymers of polyethylene oxide with polypropylene oxide are suitable as also are copolymers of polyacrylate with polyethylene glycol.
  • Polyvinyl pyrrolidone of molecular weight of 10 000 to 60 000, preferably of 30 000 to 50 000 and copolymers of polyvinyl pyrrolidone with other poly pyrrolidones are suitable.
  • Polyacrylic phosphinates and related copolymers of molecular weight 1000 to 100 000, in particular 3000 to 30 000, are also suitable.
  • an amount of an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
  • alkali metal silicates at levels, for example, of 0.1 to 10% by weight, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits.
  • ingredients which may be present in the composition include fabric softening agents such as fatty amines, fabric softening clay materials, lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids; lather depressants; oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate; peracid bleach precursors; chlorine-releasing bleaching agents such as trichloroisocyanuric acid; heavy metal sequestrants such as EDTA; fluorescent agents; perfumes including deodorant pefumes; enzymes such as cellulases, proteases, lipases and amylases; germicides; pigments, colourants or coloured speckles; and inorganic salts such as sodium and magnesium sulphate.
  • Sodium sulphate may if desired be present as a filler material in amounts up to 40% by weight of the composition; however, as little as 10% or less by weight of the composition of sodium sulphate, or even none at all,
  • the detergent compositions according to the invention may be in any suitable form including powders, bars, liquids and pastes.
  • suitable liquid compositions may be non-aqueous or aqueous, the latter being either isotropic or lamellar structured.
  • the compositions may be prepared by a number of different methods according to their physical form. In the case of granular products they may be prepared by dry-mixing, coagglomeration, spray-drying from an aqueous slurry or any combination of these methods.
  • One preferred physical form is a granule incorporating a detergency builder salt. This may be prepared by conventional granulation techniques or spray-drying.
  • micellar phase surfactant (i) a rhamnolipid produced as a by-product during fermentation using Pseudomonas glumae with glucose and glycerol as substrates. Partial characterisation of the dried material obtained from the fermentation showed that it contained one or more compounds of formula I above, in which the value of n was 10.
  • the lamellar phase surfactant (ii) was an ethoxylated aliphatic alcohol.
  • Aqueous wash liquors were prepared containing the following materials in deionised water:
  • the wash liquor had pH about 10.7 resulting from the presence of the metaborate.
  • Wash liquors were prepared with various ratios of the two surfactants and used to wash polyester test cloths soiled with radiolabelled triolein. Washing was carried out at 40°C for 20 minutes in a Tergotometer.
  • triolein The removal of triolein was determined using radiotracer techniques and the results are set out in Table 1. Clearly all the mixtures of the rhamnolipid and the ethoxylate nonionic surfactant gave better detergency than either surfactant alone.
  • Example 1 was repeated, replacing the ethoxylate nonionic surfactant with an anionic surfactant, di-C8 alkyl sulphosuccinate, as the lamellar surfactant (ii).
  • the results are set out in Table 2.
  • micellar surfactant i
  • BioEm-LKP trade mark
  • Results are set out in Table 3, which shows a very considerable synergistic effect.
  • Aqueous wash liquors were prepared containing the following materials in deionised water:
  • the wash liquor had a pH of about 10 resulting from the presence of metaborate.
  • the tests were performed in 100 ml polyethylene bottles with 30 ml/bottle wash liquor, 1 piece of 6 x 6 cm text cloth and 1 piece of 6 x 6 cm white (clean) cotton as a redeposition cloth.
  • the cloth:liquor ratio/bottle was 1:30.
  • a maximum of 50 of these bottles were agitated for 30 minutes in a Miele TMT washing machine at 40°C. Afterwards, the washed test fabrics were rinsed 3 times with cold water before drying.
  • - BioEm-LKP trade mark (trade mark) (Petrogen Inc, Illinois) is a mixture of rhamnolipids from Pseudomonas as described in Example 2. Results are shown in Table 5.
  • sophoroselipids SOL-TUBS (micellar phase) was tested in combination with several lamellar phase surfactants in the described wash liquor. Cosurfactants tested were Synperonic A3, C12-1,2-diol and C10-mono-glycerolether. Results are shown in Table 6.
  • the sophoroselipid SOL-CH (micellar phase) was tested as described in Example 5. Results are shown in Table 7.
  • SOL-CH is a sophoroselipid produced by the yeast strain Torulopsis bombicola . It consists of a mixture of at least 8 sophoroselipids of formula (III) and (IV).
  • the sophoroselipid (SOL-COO ⁇ ) (micellar phase) was tested as described in Example 5. Results are shown in Table 8.
  • SOL-COO ⁇ is a sophoroselipid produced by the yeast strain Torulopsis bombicola and is partially hydrolysed, ie has the structure (III) where R3 and R4 are H; R5 is 1; R6 is 15; R7 is H and R8 is OH.
  • CELL-TUBS Cellobioselipids
  • Ustilago maydis were tested in combination with several lamellar phase surfactants in the described wash liquor.
  • Cosurfactants tested were Synperonic A3, C12-1,2-dio and C10-mono-glycerolether. Results are shown in Table 9.
  • CBL-TUBS consists of approximately 4 cellobioselipids of formula (IV).
  • R1 is H;
  • R12 is 15;
  • R13 is acetyl;
  • R14 is 4.
  • Trehaloselipid (THL-4) (lamellar phase) was tested in combination with rhamnolipid BioEm-LKP as described in Example 2 (micellar phase).
  • the trehaloselipid THL-4 was produced by the bacterium Arthrobacter sp.Ek1 and consists of trehaloselipid of formula (V) in which R9, R10, R11 have an average of 7-9 carbon atoms.
  • test system The test system
  • Aqueous wash liquors were prepared containing the following materials in deionised water: glycolipid biosurfactant(s) (as dried material from the fermentation) any non-glycolipid surfactant detergent base powder as shown in Table 12.
  • Total surfactant concentration was 0.5 g/litre.
  • the detergent base powder was incorporated at 2.5 g/litre. Test conditions and monitoring methods were as described for Examples 4 to 10.
  • the cellobioselipid CBL-TUBS as described in Example 8 was tested in combination with Synperonic A3 (lamellar phase). Results are shown in Table 14.

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Claims (20)

  1. Composition détergente comprenant au total 1 % à 60 % en poids de :
    (i) un premier agent tensio-actif qui est un agent tensio-actif en phase micellaire dont une solution acqueuse à 1 % en poids dans de l'eau déminéralisée au pH 7,0 et à 25° C ne présente pas de texture biréfringente lorsqu'elle est examinée au microscope optique polarisant, l'agent tensio-actif en phase micellaire étant un bio-agent tensio-actif de glycolipides sélectionné parmi des lipides sophoroses, des rhamonolipides, des lipides de glucose, des lipides de cellobiose et des mélanges de ceux-ci, et
    (ii) un second agent tensio-actif qui est un agent tensio-actif en phase lamellaire dont une solution acqueuse à 1 % dans de l'eau déminéralisée au pH 7,0 et à 25° C présente des textures biréfringentes lorsqu'elle est examinée au microscope optique polarisant, l'agent tensio-actif en phase lamellaire étant un bio-agent tensio-actif de glycolipide sélectionné parmi des rhamnolipides, des lipides de glucose, des lipides de tréhalose et des mélanges de ceux-ci, ou d'un agent tensio-actif non-glycolipidique,
       et, facultativement 5 % à 80 % d'un adjuvant de pouvoir détergent,
       la composition contenant plus de 5 % en poids d'un bio-agent tensio-actif de glycolipides.
  2. Composition détergente selon la revendication 1, qui comprend comme bio-agent tensio-actif de glycolipides un rhamnolipide de la formule (I) :
    Figure imgb0045
     dans laquelle a est égal à 1 ou à 2 ; b est égal à 1 ou 2, n est égal à 4 jusqu'à 10 ; R¹ est H ou un cation, R² est H ou le groupe
    Figure imgb0046
     m est égal à 4 jusqu'à 10 ; et les valeurs de m et de n n'ont pas besoin d'être les mêmes à chaque fois.
  3. Composition détergente selon la revendication 2, qui comprend comme bio-agent tensio-actif un rhamnolipide de la formule (I) dans laquelle n est égal à 6.
  4. Composition détergente selon la revendication 3, qui comprend comme bio-agent tensio-actif un rhamnolipide de la formule (I) dans laquelle R² est H.
  5. Composition détergente selon la revendication 1, qui comprend comme bio-agent tensio-actif de glycolipides un glucoselipide de la formule (II)
    Figure imgb0047
        dans laquelle R¹ est H ou un cation ; p est égal à 1 jusqu'à 4 ; et q est égal à 4 jusqu'à 10.
  6. Composition détergente selon la revendication 5, qui comprend comme bio-agent tensio-actif de glycolipides un glucoselipide de la formule (II) dans laquelle q est égal à 6.
  7. Composition détergente selon la revendication 1, qui comprend comme bio-agent tensio-actif, un sophoroselipide de formule la (III)
    Figure imgb0048
     dans laquelle R³ et R⁴ sont chacun H ou un groupe acétyle ; R⁵ est un groupe de carbure d'hydrogène saturé ou insaturé, hydroxylé ou non hydroxylé ayant 1 à 9 atomes de carbones, et R⁶ est un groupe de carbure d'hydrogène saturé ou insaturé, hydroxylé ou non hydroxylé ayant 1 à 19 atomes de carbones, à la condition que le nombre total d'atomes de carbone dans les groupes R⁵ et R⁶ ne soit pas supérieur à 20 ; R⁷ est H ou un composé cyclique de lactone formé avec R⁸ ; R⁸ est OH ou un composé cyclique de lactone formé avec R⁷.
  8. Composition détergente selon la revendication 7, dans laquelle le sophoroselipide a la formule (IV)
    Figure imgb0049
     dans laquelle R³, R⁴, R⁵ et R⁶ sont comme défini dans la revendication 7, à la condition qu'au moins un des groupes R³ et R⁴ soit un groupe acétyle.
  9. Composition détergente selon la revendication 7 ou la revendication 8, qui comprend comme bio-agent tensio-actif de glycolipides, un sophorolipide de la formule (III) ou de la formule (IV) dans laquelle R⁵ est un groupe méthyle.
  10. Composition détergente selon l'une quelconque des revendications 7 à 9, qui comprend comme bio-agent tensio-actif de glycolipides,7 un sophoroselipide de la formule (III) ou de la formule (IV) dans laquelle le nombre total d'atomes de carbone dans les groupes R⁵ et R⁶ est compris entre 14 et 18.
  11. Composition détergente selon la revendication 1, qui comprend comme bio-agent tensio-actif de glycolipides, un tréhaloselipide de la formule (V)
    Figure imgb0050
     dans laquelle R⁹, R¹⁰ et R¹¹ sont chacun un groupe de carbures d'hydrogène saturé ou insaturé, hydroxylé ou non hydroxylé de 5 à 13 atomes de carbone.
  12. Composition détergente selon la revendication 1, qui comprend comme bio-agent tensio-actif de glycolipides, un cellobioselipide de la formule (VI)
    Figure imgb0051
     dans laquelle R¹ est H ou un cation ; R¹² est un groupe de carbures d'hydrogène saturé ou inaturé, hydroxylé ou non hydroxylé ayant 9 à 15 atomes de carbone ; R¹³ est H ou un groupe acétyle ; R¹⁴ est un carbure d'hydrogène saturé ou insaturé, hydroxylé ou non hydroxylé ayant 4 à 16 atomes de carbone.
  13. Composition détergente selon la revendication 11, qui comprend comme bio-agent tensio-actif de glycolipides, un cellobioselipide de formule (VI) dans laquelle R¹² est un carbure d'hydrogène ayant 13 à 15 atomes de carbone.
  14. Composition détergente selon la revendication 1, dans laquelle l'agent tensio-actif en phase lamellaire (ii) est sélectionné parmi des agents tensio-actifs anioniques et non ioniques non-glycolipidiques, et des combinaisons de ceux-ci.
  15. Composition détergente selon la revendication 14, dans laquelle l'agent tensio-actif en phase lamellaire (ii) est un sulfosuccinate dialkyle, un alcool éthoxylé, un diol alcane, ou un éther monoglycéryle.
  16. Composition détergente selon la revendication 1, dans laquelle l'agent tensio-actif en phase micellaire (i) et l'agent tensio-actif en phase lamellaire (ii) sont tous les deux des agents tensio-actifs de glycolipides.
  17. Composition détergente selon la revendication 1, dans laquelle la proportion en poids de l'agent tensio-actif en phase micellaire (i) par rapport à l'agent tensio-actif en phase lamellaire (ii) est comprise dans l'intervalle de 20:1 à 1:20.
  18. Composition détergente selon la revendication 17, dans laquelle la proportion en poids de l'agent tensio-actif en phase micellaire (i) par rapport à l'agent tensio-actif en phase lamellaire (ii) est comprise dans l'intervalle de 10:1 à 1:10.
  19. Composition détergente selon la revendication 1, dans laquelle la proportion en poids de l'agent tensio-actif en phase micellaire (i) par rapport à l'agent tensio-actif en phase lamellaire (ii) est comprise dans l'intervalle de 4:1 à 1:4.
  20. Procédé de nettoyage qui comprend le contact des tissus ou d'autres surfaces inertes à nettoyer avec une composition selon la revendication 1, ou un bain de lessive comprenant de l'eau et une composition selon la revendication 1, ajoutée à de l'eau dans une quantité se situant entre 0,5 à 50 grammes par litre d'eau.
EP92301101A 1991-02-12 1992-02-10 Compositions détergentes Expired - Lifetime EP0499434B1 (fr)

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DE102022210850A1 (de) 2022-10-14 2024-04-25 Henkel Ag & Co. Kgaa Reinigungsmittelzusammensetzung umfassend Sophorolipid-Tensid und eine antimikrobielle Verbindung
DE102022210849A1 (de) 2022-10-14 2024-04-25 Henkel Ag & Co. Kgaa Sophorolipid-Tenside mit oberflächenaktiven Gegenkationen
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WO2024115213A1 (fr) 2022-11-30 2024-06-06 Evonik Operations Gmbh Capsule à détergent comprenant des biotensioactifs
EP4382090A1 (fr) 2022-12-08 2024-06-12 Evonik Operations GmbH Compositions cosmétiques et pharmaceutiques contenant des souches de bacillus ou des bouillons de fermentation de celles-ci

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US20140113818A1 (en) * 2011-06-06 2014-04-24 Ecover Co-Ordination Center N.V. Sophorolactone compositions and uses thereof
WO2013182759A1 (fr) 2012-06-06 2013-12-12 Soliance Biosolubilisant
DE102014225789A1 (de) 2014-12-15 2016-06-16 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel
WO2016096478A1 (fr) 2014-12-15 2016-06-23 Henkel Ag & Co. Kgaa Agent de lavage et de nettoyage
US10718060B2 (en) 2015-06-25 2020-07-21 Basf Se Additive for alkaline zinc plating
WO2019034490A1 (fr) 2017-08-16 2019-02-21 Henkel Ag & Co. Kgaa Détergent et nettoyant à base de rhamnolipides
DE102017214265A1 (de) 2017-08-16 2019-02-21 Henkel Ag & Co. Kgaa Rhamnolipidhaltige Wasch- und Reinigungsmittel
EP3663386A1 (fr) 2018-12-05 2020-06-10 LANXESS Deutschland GmbH Tensioactif contenant du glycolipide
EP4198112A1 (fr) 2021-12-20 2023-06-21 Henkel AG & Co. KGaA Combinaison tensioactive et produits de lavage et de nettoyage contenant cette combinaison
DE102021214680A1 (de) 2021-12-20 2023-06-22 Henkel Ag & Co. Kgaa Neue Tensidkombination und Wasch- und Reinigungsmittel, welche diese enthalten
EP4353806A1 (fr) 2022-10-14 2024-04-17 Henkel AG & Co. KGaA Mélanges de tensioactifs
DE102022210879A1 (de) 2022-10-14 2024-04-25 Henkel Ag & Co. Kgaa Tensidmischungen

Also Published As

Publication number Publication date
DE69203473T2 (de) 1996-01-11
JPH0559394A (ja) 1993-03-09
EP0499434A1 (fr) 1992-08-19
DE69203473D1 (de) 1995-08-24
CA2060698A1 (fr) 1992-08-13
ES2075608T3 (es) 1995-10-01
CA2060698C (fr) 1997-09-30

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