WO2019219531A1 - Composition de nettoyage - Google Patents

Composition de nettoyage Download PDF

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Publication number
WO2019219531A1
WO2019219531A1 PCT/EP2019/062050 EP2019062050W WO2019219531A1 WO 2019219531 A1 WO2019219531 A1 WO 2019219531A1 EP 2019062050 W EP2019062050 W EP 2019062050W WO 2019219531 A1 WO2019219531 A1 WO 2019219531A1
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WO
WIPO (PCT)
Prior art keywords
surfactant
rhamnolipid
cleaning composition
fluid cleaning
composition according
Prior art date
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PCT/EP2019/062050
Other languages
English (en)
Inventor
Clare Ann JONES
Paul Simon Stevenson
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to BR112020023083-9A priority Critical patent/BR112020023083A2/pt
Priority to EP19722150.0A priority patent/EP3775127B1/fr
Priority to CN201980032774.3A priority patent/CN112119147B/zh
Publication of WO2019219531A1 publication Critical patent/WO2019219531A1/fr

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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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to a fluid cleaning composition.
  • the invention relates to fluid cleaning compositions in the form of liquid laundry detergent compositions.
  • fluid cleaning compositions in particular laundry liquid detergent compositions desirably contain cleaning polymers.
  • cleaning polymers in particular alkoxylated polyamines and polyester-based soil release polymers are desirable to include because they provide weight efficient cleaning to the formulation.
  • alkoxylated polyamines and polyester-based soil release polymers are desirable to include because they provide weight efficient cleaning to the formulation.
  • there is a problem with the inclusion of these polymers because they reduce the viscosity of the composition.
  • the rheology of many fluid cleaning compositions could be improved in the eyes of the consumer. Consumers dislike fluid cleaning compositions that have a too low viscosity, there can be a perception that these compositions are not thick enough to provide adequate cleaning.
  • One way of improving the viscosity is to include a further polymer, a thickening polymer such as a so-called HASE polymer (hydrophobically modified alkali soluble emulsion polymer).
  • a thickening polymer such as a so-called HASE polymer (hydrophobically modified alkali soluble emulsion polymer).
  • HASE polymer hydrophobically modified alkali soluble emulsion polymer
  • US 2018/0044614 discloses in the claims and examples various formulations in the examples that include (a) a surfactant combination (rhamnolipid and other surfactant); (b) one or more viscosity modifiers; (c) EPEI; and (d) perfume.
  • the viscosity modifiers are essential to the compositions of US 2018/0044614, which are most preferentially pH greater than 7 to 13.
  • the invention provides a fluid cleaning composition comprising:
  • a surfactant system comprising:
  • a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.%, preferably from 1 to 50 wt.%, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.% of the total surfactant in said surfactant system;
  • composition has a pH of from 3 to 6.
  • the invention provides the use of a surfactant combination comprising a rhamnolipid biosurfactant and a zwitterionic surfactant to increase the viscosity of a fluid cleaning composition at a pH of 3 to 6, preferably from 3.5 to 6, more preferably from 4 to 6, even more preferably from 4 to 5.75, most preferably from 4.5 to 5.5.
  • the rhamnolipid biosurfactant comprises at least 70 wt.% di-rhamnolipid, preferably at least 80 wt.% di-rhamnolipid, preferably of formula: Rha2C8-i2C8-i2, where the alkyl chains may be saturated or unsaturated.
  • the fluid cleaning composition comprises from 5 to 70 wt.% of a surfactant system.
  • the fluid cleaning composition comprises from 5 to 60 wt.%, more preferably from 5 to 50 wt.%, even more preferably from 7.5 to 30 wt.%, most preferably from 7.5 to 25 wt.%, for example from 8 to 25 wt.%, or even from 8 to 20 wt.% of a surfactant system.
  • the surfactant system comprises at least one anionic or nonionic surfactant and a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.% of the total surfactant in said surfactant system.
  • the rhamnolipid is present at a level in the range of from 1 to 50 wt.% of the total surfactant in said surfactant system, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.%, for example from 7.5 to 25 wt.% of the total surfactant in said surfactant system.
  • the fluid cleaning compositions comprise water.
  • Water is usually the balancing agent in the formulation, and may make up all or the bulk of the non-surfactant wt.% in the composition.
  • Typical water inclusion levels may be from 50 to 90 wt.%, preferably from 60 to 90 wt.%, more preferably from 65 to 88 wt.%.
  • the composition comprises a rhamnolipid biosurfactant.
  • Mono-rhamnolipids have a single rhamnose sugar ring.
  • Di-rhamnolipids have two rhamnose sugar rings.
  • R1 is mono-rhamnolipid and R2 is di-rhamnolipid.
  • the mono-rhamnolipid may be L-rhamnosyl-3-hydroxydecanoyl-3-hydroxydecanoate (RhaCioCiowith a formula of C26H48O9) produced by P. aeruginosa .
  • a typical di-rhamnolipid is L-rhamnosyl-L-rhamnosyl-3-hydroxydecanoyl-3- hydroxydecanoate (Rha2CioCiowith a formula of C32H58O13).
  • Rha2CioCio with a formula of C32H58O13.
  • the ratio of mono-rhamnolipid and di-rhamnolipid may be controlled by the production method.
  • rhamnolipids are sources of mono- and di- rhamnolipids encompassed within the invention (C12:1 , C14:1 indicates fatty acyl chains with double bonds):
  • Rha-Ce-C-io Rha-C-io-Ce, Rha-Cio-Cio, Rha-Cio-Ci2, Rha-Cio-Ci2:i, Rha-Ci2-Cio, Rha- Cl2:1"Cl O
  • Rha-C-io-Ce Rha-Cio-Cio, Rha-Ci2-Cio, Rha-Ci2:i-Cio, Rha-Ci2-Ci2, Rha-Ci2:i-Ci2, Rha-Ci4-Cio, Rha-Ci4:i-Cio.
  • Mono-rhamnolipids may also be produced from P.putida by introduction of genes rhIA and rhIB from Psuedomonas aeruginosa [Cha et al. in Bioresour Technol. 2008. 99(7):2192-9 ]
  • the rhamnolipid comprises at least 50 wt.% di-rhamnolipid, more preferably at least 60 wt.% di-rhamnolipid, even more preferably 70 wt.% di-rhamnolipid, most preferably at least 80 wt.% di-rhamnolipid.
  • the rhamnolipid is a di-rhamnolipid of formula: Rha2C 8 -i 2 Cs-i 2 .
  • the preferred alkyl chain length is from Cs to C12, the alkyl chain may be saturated or unsaturated.
  • the fluid cleaning composition comprises at least one anionic and/or non-ionic surfactant.
  • the composition may comprises a single anionic surfactant, or a mixture of anionic surfactants, or a single nonionic surfactant, or a mixture of nonionic surfactant, or a mixture of one or more anionic surfactants with one or more nonionic surfactants.
  • Suitable nonionic and anionic surfactants may be chosen from the surfactants described "Surface Active Agents” Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, Alkyl ether carboxylic acids; sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; alkyl ether carboxylates, and mixtures thereof.
  • More preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof.
  • the alkyl ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units.
  • Sodium lauryl ether sulphate is particularly preferred (SLES).
  • the linear alkyl benzene sulphonate is a sodium Cn to C15 alkyl benzene sulphonates.
  • the alkyl sulphates is a linear or branched sodium C12 to C18 alkyl sulphates.
  • Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
  • the anionic surfactant comprises linear alkyl benzene sulphonates and/or alkyl ether sulphates.
  • two or more anionic surfactants are present, for example linear alkyl benzene sulphonate together with an alkyl ether sulphate.
  • composition may comprise anionic and/or non-ionic surfactants.
  • the weight fraction of non-ionic surfactant to anionic surfactant is from 0 to 0.3. This means that non-ionic surfactant can be present (or it may be absent if the weight fraction is 0), but if non-ionic surfactant is present, then the weight fraction of the non-ionic surfactant is preferably at most 30% of the total weight of anionic surfactant + non-ionic surfactant.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are the condensation products of aliphatic Cs to C18 primary or secondary linear or branched alcohols with ethylene oxide.
  • the non-ionic surfactant is an alcohol ethoxylate, more preferably a C10-C18 alcohol ethoxylate having an average of 3-10 moles of ethylene oxide, most preferably a C12-C15 alcohol ethoxylate having an average of 5-9 moles of ethylene oxide.
  • surfactants used are saturated.
  • the surfactant system comprises from 0.5 to 10 wt.% of a zwitterionic surfactant.
  • the composition comprises from 0.5 to 10 wt.%, preferably from 0.75 to 5 wt.%, most preferably from 1 to 4 wt.% of the zwitterionic surfactant, said surfactant being counted as part of the surfactant system.
  • the zwitterionic surfactant is preferably a betaine surfactant.
  • the composition comprises from 0.5 to 10 wt.%, preferably from 0.75 to 5 wt.%, most preferably from 1 to 4 wt.% of a betaine surfactant, said surfactant being counted as part of the surfactant system.
  • a preferred betaine surfactant is cocoamidopropyl betaine.
  • a preferred fluid cleaning composition is a liquid laundry detergent composition.
  • a preferred laundry detergent composition comprises:
  • a surfactant system comprising:
  • a rhamnolipid biosurfactant which is present at a level in the range of from 1 to 95 wt.%, preferably from 1 to 50 wt.%, more preferably from 2.5 to 50 wt.%, most preferably from 5 to 25 wt.% of the total surfactant in said surfactant system;
  • composition has a pH of from 3 to 6, preferably from 4 to 5.5;
  • the rhamnolipid biosurfactant comprises at least 70 wt.% di-rhamnolipid, preferably at least 80 wt.% di-rhamnolipid, preferably of formula: Rha2C8-i2Cs-i2, where the alkyl chains may be saturated or unsaturated.
  • the fluid cleaning compositions have a pH of from 3 to 6, preferably from 3.5 to 6, more preferably from 4 to 6, even more preferably from 4 to 5.75, most preferably from 4.5 to 5.5.
  • composition comprises from 0.1 to 15 wt.%, preferably from 0.1 to 10 wt.% of a polymer selected from the group consisting of: an alkoxylated polyamine, a polyester soil release polymer and mixtures thereof.
  • the composition may comprise from 0.05 to 6 wt.%, preferably from 0.1 to 5 wt.% of one or more polyester soil release polymer(s). Suitable polyester based soil release polymers are described in WO 2014/029479 and WO 2016/005338.
  • polyester based soil release polymer is a polyester according to the following formula (I)
  • R 1 and R 2 independently of one another are X-(OC2H4) n -(OC3H6) m wherein X is Ci -4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C 3 H 6 ), and preferably are independently of one another X- (OC 2 H4)n-(OC 3 H6)m,
  • n is based on a molar average number of from 12 to 120 and preferably of from 40 to 50,
  • m is based on a molar average number of from 1 to 10 and preferably of from 1 to 7, and
  • a is based on a molar average number of from 4 to 9.
  • polyester provided as an active blend comprising:
  • R 1 and R 2 independently of one another are X-(OC2H4) n -(OC3H6) m wherein X is Ci -4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C 3 H 6 ), and preferably are independently of one another X- (OC 2 H4)n-(OC 3 H6)m,
  • n is based on a molar average number of from 12 to 120 and preferably of from 40 to 50,
  • m is based on a molar average number of from 1 to 10 and preferably of from 1 to 7, and
  • a is based on a molar average number of from 4 to 9 and
  • active blend is meant that it is preformed and added to the remainder of the fluid cleaning composition, or to components which ultimately form the fluid cleaning composition.
  • the composition may and preferably does comprise of an alkoxylated polyamine.
  • Suitable inclusion levels for the polymer are from 0.25 to 8 wt.%, preferably from 0.5 to 6 wt.% of an alkoxylated polyamine. Another preferred level is from 1 to 4 wt.%.
  • a preferred alkoxylated polyamine comprises an alkoxylated polyethylenimine, and/or alkoxylated polypropylenimine.
  • the polyamine may be linear or branched. It may be branched to the extent that it is a dendrimer.
  • the alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25.
  • a preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30 preferably from 15 to 25, where a nitrogen atom is ethoxylated. Salt
  • the composition comprises a sodium chloride or magnesium sulfate salt.
  • the composition preferably comprises a perfume.
  • the perfume is preferably present in the range from 0.001 to 3 wt.%, more preferably 0.05 to 0.5 wt.%, even more preferably from 0.1 to 2 wt.%, most preferably 0.1 to 1 wt.%.
  • the perfume can be provided as a free oil, or may in encapsulated form.
  • the composition comprises an ionic salt.
  • the salt preferably comprises any organic or inorganic cation, including without limitation cations of alkali metals Cs, Na, K, Ca, Mg etc., with anions including halide anions, more preferably Cl.
  • Other preferred salts compise organic cations e.g. amides (- + NH-R ) or ammonium cations or substituted forms thereof e.g. triethylammonium.
  • Anions for organic cations may comprise any akyl, aryl, arylalkyl moiety which may be short, medium, long, branched, cyclic or linear.
  • the composition comprises from 0.01 - 5wt.% by weight of the salt.
  • the level is in the range 0.5 - 2 wt.%
  • Fluid cleaning compositions may, depending on their end use further comprise any of the following as a single ingredient, or a mixture thereof: polymers, sequestrants, hydrotropes (such as glycerol or monoproylene glycol), opacifiers, preservatives, colorants (e.g.
  • enzymes for example proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof
  • further surfactants such as cationic surfactants, fatty acids, softeners, polymers for anti redeposition of soil, bleach, bleach activators and bleach catalysts, antioxidants, pH adjusting agents (such as citric acid and NaOH), pH control agents and buffers.
  • pH adjusting agents such as citric acid and NaOH
  • pH control agents and buffers can suitably be used with the preferred fluid cleaning composition, namely a laundry liquid detergent composition.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially.
  • these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
  • Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulphophenyl)-2H-napthol[1 ,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5-triazin-2- yl)]amino ⁇ stilbene-2-2' disulophonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1 ,3,5- triazin-2-yl)]amino ⁇ stilbene-2-2' disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.
  • the total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt.%, more preferably 0.005 to 2 wt.%, most preferably 0.05 to 0.25 wt.%.
  • the aqueous solution used in the method preferably has a fluorescer present.
  • the fluorescer is preferably present in the aqueous solution used in the method in the range from 0.0001 g/l to 0.1 g/l, more preferably 0.001 to 0.02 g/l.
  • One or more enzymes are preferably present in the laundry composition of the invention and when practicing a method of the invention.
  • the level of each enzyme in the laundry composition of the invention is from 0.0001 wt.% to 0.1 wt.%.
  • Levels of enzyme present in the composition preferably relate to the level of enzyme as pure protein.
  • Contemplated enzymes include proteases, alpha-amylases, cellulases, lipases,
  • peroxidases/oxidases peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
  • the enzyme is selected from: proteases, alpha-amylases; cellulases and lipases.
  • Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa ( T . lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in Humicola (synonym Thermomyces), e.g. from H. lanuginosa ( T . lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in
  • WO 96/13580 a Pseudomonas lipase, e.g. from P. alcaligenes or
  • lipase variants such as those described in WO 92/05249,
  • Preferred commercially available lipase enzymes include LipolaseTM and Lipolase UltraTM, LipexTM and LipocleanTM(Novozymes A/S).
  • the method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
  • phospholipase is an enzyme which has activity towards phospholipids.
  • Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1 ) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
  • Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
  • phospholipases Ai and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
  • lysophospholipase or phospholipase B
  • Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
  • proteases hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases;
  • proteases aspargine peptide lyase; serine proteases and threonine proteases.
  • protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk).
  • Serine proteases are preferred.
  • Subtilase type serine proteases are more preferred.
  • the term "subtilases” refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991 ) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523.
  • Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
  • the subtilases may be divided into 6 sub- divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
  • subtilases are those derived from Bacillus such as Bacillus lentus, B.
  • trypsin-like proteases examples include trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270, WO 94/25583 and WO 05/040372, and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146.
  • protease is a subtilisins (EC 3.4.21.62).
  • subtilases are those derived from Bacillus such as Bacillus lentus, B.
  • subtilis alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and W009/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140).
  • the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B.
  • subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
  • Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase®, Esperase® and
  • the invention may be use cutinase, classified in EC 3.1.1.74.
  • the cutinase used according to the invention may be of any origin.
  • Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
  • Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha- amylases obtained from Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of Bacillus, e.g. a special strain of
  • B. licheniformis described in more detail in GB 1 ,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060.
  • Commercially available amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora
  • thermophila and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691 ,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307.
  • Commercially available cellulases include CelluzymeTM, CarezymeTM, CellucleanTM, EndolaseTM,
  • RenozymeTM Novozymes A/S
  • ClazinaseTM and Puradax HATM
  • KAC-500(B)TM Kao Corporation
  • CellucleanTM is preferred.
  • Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
  • the aqueous solution used in the method preferably has an enzyme present.
  • the enzyme is preferably present in the aqueous solution used in the method at a concentration in the range from 0.01 to 10ppm, preferably 0.05 to 1 ppm.
  • Suitable enzymes may be included as a blend or 2 or more enzymes.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
  • the composition comprises from 0.1 to 5 wt.%, preferably from 0.25 wt.% to 4 wt.%, more preferably from 0.5 to 2.5 wt.% of a sequestrant.
  • Preferred sequestrants include phosphonic acids or salts thereof.
  • the phosphonic acid (or salt thereof) sequestrant is preferably selected from the group consisting of: 1-Hydroxyethylidene-1 ,1-diphosphonic acid (HEDP);
  • DTPMP Diethylenetriaminepenta(methylenephosphonic acid)
  • HDTMP Hexamethylenediaminetetra(methylenephosphonic acid)
  • AMP Aminotris(methylenephosphonic acid)
  • ETMP Ethylenediaminetetra(methylenephosphonic acid)
  • TTMP Tetramethylenediaminetetra(methylenephosphonic acid)
  • PBTC Phosphonobutanetricarboxylic acid
  • the sequestrant is preferably in acid form. This means that it is a phosphonic acid.
  • the preferred phosphonic acid sequestrant is 1 -Hydroxyethylidene-1 ,1 -diphosphonic acid (HEDP).
  • the composition may preferably comprise one or more polymers.
  • Example polymers are carboxymethylcellulose, polyethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Polymers present to prevent dye deposition may be present, for example
  • Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).
  • Shading Dyes for use in laundry compositions preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than
  • the dyes are blue or violet in colour.
  • the composition comprises a shading dye.
  • the shading dye is present at from 0.0001 to 0.1 wt.% of the composition.
  • Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane.
  • Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged.
  • Azine preferably carry a net anionic or cationic charge.
  • Blue or violet shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric.
  • the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280.
  • the white cloth used in this test is bleached non-mercerised woven cotton sheeting. Shading dyes are discussed in WO 2005/003274, WO 2006/032327(Unilever),
  • Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
  • Bis-azo dyes are preferably sulphonated bis-azo dyes.
  • Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , Direct Violet 66, direct violet 99 and alkoxylated versions thereof. Alkoxylated bis-azo dyes are discussed in WO2012/054058 and W02010/151906.
  • alkoxylated bis-azo dye is :
  • Thiophene dyes are available from Milliken under the tradenames of Liquitint Violet DD and Liquitint Violet ION.
  • Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59, and the phenazine dye selected from:
  • X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5;
  • X 4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;
  • Y 2 is selected from: -OH; -OCH 2 CH 2 OH; -CH(OH)CH 2 OH; -OC(0)CH 3 ; and, C(0)OCH 3.
  • the shading dye is present is present in the composition in range from 0.0001 to
  • the shading dye is a blue or violet shading dye.
  • a mixture of shading dyes may be used.
  • the shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine.
  • the alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation.
  • the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
  • An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
  • composition may comprise from 0.001 to 3 wt.% of a perfume, preferably from 0.1 to 2 wt.% perfume. This suitably may be present as a free perfume oil or as an encapsulated perfume. Misc
  • alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains.
  • the alkyl groups are preferably linear or branched, most preferably linear.
  • the indefinite article“a” or“an” and its corresponding definite article“the” as used herein means at least one, or one or more, unless specified otherwise.
  • This example shows the detrimental effect of the addition of the alkoxylated polyamine and polyester based soil release polymer to a fluid cleaning composition (laundry liquid), and the need to include a HASE polymer to overcome the detrimental effect on viscosity.
  • Formulation A has neither the polyester soil release polymer (Texcare UL50), nor the alkoxylated polyamine (HP20); formulations B and C have one or the other; formulation D has both polymers.
  • the viscosity was measured using the Anton Paar ASC rheometer - using a Bob set-up and reporting the viscosity measured at a shear rate of 23s 1 based upon HASE thickening polymer inclusion levels (Acusol WR) of from 0.55 to 0.85.
  • This example shows the improved viscosity build using rhamnolipid at low pH
  • Formulation E has neither the polyester soil release polymer (Texcare UL50), nor the alkoxylated polyamine (HP20), nor the rhamnolipid; formulation 1 has both polymers and rhamnolipid (R2 rhamnolipid at inclusion level of 10% of total surfactant.
  • the viscosity was measured using the Anton Paar ASC rheometer - using a Bob set-up and reporting the viscosity measured at a shear rate of 23s 1 at different pH from pH -3 to ⁇ 6 by addition of citric acid

Abstract

La présente invention concerne une composition fluide de nettoyage comprenant a) 5 à 70% en poids d'un système tensioactif comprenant : (i) au moins un tensioactif anionique ou non ionique ; (ii) un tensioactif biologique à base de rhamnolipide qui est présent à un niveau dans la plage de 1 à 95 % en poids du tensioactif total dans ledit système tensioactif ; (iii) 0,5 à 10 % en poids d'un tensioactif zwittérionique ; et (b) de l'eau ; et (c) 0,1 à 15 % en poids d'un polymère choisi dans le groupe constitué par : une polyamine alcoxylée, un polymère antisalissure à base de polyester et des mélanges correspondants ; la composition présentant un pH de 3 à 6. L'invention concerne en outre l'utilisation d'une combinaison tensioactive comprenant un tensioactif biologique à base de rhamnolipide et un tensioactif zwittérionique pour augmenter la viscosité d'une composition fluide de nettoyage à un pH de 3 à 6.
PCT/EP2019/062050 2018-05-17 2019-05-10 Composition de nettoyage WO2019219531A1 (fr)

Priority Applications (3)

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BR112020023083-9A BR112020023083A2 (pt) 2018-05-17 2019-05-10 composição de limpeza fluida, composição detergente líquida para lavanderia e uso de uma combinação de tensoativos
EP19722150.0A EP3775127B1 (fr) 2018-05-17 2019-05-10 Composition de nettoyage
CN201980032774.3A CN112119147B (zh) 2018-05-17 2019-05-10 清洁组合物

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EP18172880 2018-05-17
EP18172880.9 2018-05-17

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AR (1) AR117430A1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022128786A1 (fr) * 2020-12-17 2022-06-23 Unilever Ip Holdings B.V. Utilisation et composition de nettoyage

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