EP2670788B1 - Alkaline liquid detergent compositions - Google Patents

Alkaline liquid detergent compositions Download PDF

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Publication number
EP2670788B1
EP2670788B1 EP20120700850 EP12700850A EP2670788B1 EP 2670788 B1 EP2670788 B1 EP 2670788B1 EP 20120700850 EP20120700850 EP 20120700850 EP 12700850 A EP12700850 A EP 12700850A EP 2670788 B1 EP2670788 B1 EP 2670788B1
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Prior art keywords
preferably
polymer
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wt
eo
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German (de)
French (fr)
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EP2670788A1 (en
Inventor
Robert John Carswell
Martin Charles Crossman
Adam Peter Jarvis
Alyn James Parry
Susan Henning ROGERS
John Francis Wells
Jeremy Nicholas Winter
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP20120700850 priority patent/EP2670788B1/en
Priority to PCT/EP2012/050945 priority patent/WO2012104159A1/en
Publication of EP2670788A1 publication Critical patent/EP2670788A1/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines, polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715Polyesters; Polycarbonates

Description

    TECHNICAL FIELD
  • This invention relates to alkaline liquid detergent compositions comprising soil release polymer (SRP) substantive to polyester fabrics, the soil release polymers assist with cleaning of oily soils from fabrics comprising polyester during a laundry wash process.
  • BACKGROUND
  • There is spanning many years and in many documents disclosure of polymeric or oligomeric soil release agents designed to assist with the removal of soils from fabrics comprising polyester fibres. In this specification, unless indicated to the contrary, no distinction is made between polymer and oligomer. Both are termed polymers.
  • Many SRPs intended to promote improved soil removal from polyester fabrics are themselves polyesters. We have found that these prior art polyesters are unsuitable for use in alkaline laundry liquids. The patent specifications, or other documents, disclosing the SRPs may be unclear in that regard as examples are possibly given of use of the polymer in such a liquid. The fact is that the resistance of most prior art polyester SRPs to hydrolytic attack is insufficient to allow them to be incorporated into alkaline liquid detergent compositions with sufficient stability that their performance is not compromised due to hydrolytic breakdown on storage of the composition.
    This hydrolysis is made even worse when triethanoloamine (TEA) is used in the composition. TEA is commonly used as a neutralising agent and buffer in detergent liquids and has now been found to catalyse the decomposition of many polyester SRPs, especially if they comprise ethylene oxide or unsubstituted ethylene next to an ester bond. Most soil release polymers designed to be substantive to polyester do comprise such ethylene oxide or ethylene moieties, or both. Many such polymers have these moieties (or a polyethylene glycol group) in the polymer mid block. Such moieties in the polymer mid block, especially those adjacent to ester moieties, have now been found to be a major factor in SRP decomposition via hydrolysis.
  • Many proposals have been made for SRPs to have a permanent charge, including balanced positive and negative charges on different moieties in the SRP. We have now found that such charged polymers are unsuitable for use in liquid compositions that comprise other charged species, especially anionic surfactants.
  • There have been proposals for polyester SRPs of the type E-M-E. M is the fabric substantive mid block and each E is a generally hydrophilic end block, preferably comprising a block of ethylene oxide repeat units such as mPEG (methyl endcapped polyethylene glycol) that acts to modify the normally hydrophobic polyester fabric surface once the fabric substantive mid block has caused the SRP to deposit on the surface. It is this type of E-M-E SRP that we wish to stabilise in alkaline detergent liquid compositions, especially compositions comprising anionic surfactant and TEA.
  • WO2009/153184 proposes to dose a main wash surfactant at low levels so that the in wash surfactant level is lower than normal. What would be the consequential unsatisfactory wash performance resulting from the low in wash surfactant levels, is boosted by inclusion of unusually high levels of specific polymers and enzymes in the liquid. One of the key polymers that is preferably included at high levels in the composition is a SRP substantive to polyester. The one used in the examples of WO2009/153184 , and also one of the three preferred on page 39, is of polyester chemistry (terephthalic acid/propandiol condensation polymer with methoxy PEG 750 end cap). It is sold under the trade name Texcare® SRN170 by Clariant. It is now thought that this material is substantially linear.
  • We have found that the storage stability of the SRP included in the examples of WO2009/153184 is not sufficient for a commercial product that may be subjected to high temperatures and needs to give performance that is not compromised by storage for long periods of time. Thus it is desirable to replace this SRP with a modified SRP that is sufficiently resistant to hydrolysis in alkaline detergent compositions, especially those comprising anionic surfactant and most preferably further comprising TEA, and yet retains the excellent soil release performance, that is the case for Texcare ®SRN 170 when freshly formulated into such an alkaline liquid composition.
  • In practice, despite the vast array of options that present themselves from the literature it seems that not many SRPs are soluble in alkaline detergent liquids. If solubility is not achieved the liquid turns hazy and the product performance may be compromised, especially if the lack of solubility leads to uneven distribution of the SRP through the composition. Solubility of an SRP in a composition is defined as its ability to remain isotropic within the composition and not produce the unwanted hazing effect. Thus solubility may simply be determined for any given SRP in a given composition.
  • EP 1 661 933 (Sasol) describe amphiphilic non-ionic oligoesters that have soil release properties after storage in alkaline detergent liquid.
  • In the exemplary formulae a PO block of up to 10, but preferably 2 to 4 may be adjacent to the mid block. The tested material has 4 PO. The mid block is essentially 1,4 - phenylene and 1,2 propylidene. TEA is not used with these polymers.
  • We have now found several modified SRPs that have the required alkaline stability, formulation compatibility and polyester soil release performance. These SRPs and other SRPs that can be conceived by the skilled worker without the need for further inventive effort once the information concerning the SRPs we have produced is known, when formulated into alkaline liquid detergents, provide a novel group of stable compositions that may be linked together and generalised to form a single inventive concept that is broader than the compositions comprising the individual SRPs. The resulting invention therefore encompasses further groups of polymers that the skilled person, aware of the teaching in this patent specification, would expect to have the same or similar properties in the alkaline liquids of the type claimed.
  • SUMMARY OF THE INVENTION
  • According to the present invention there is provided an aqueous alkaline isotropic concentrated detergent liquid composition with an undiluted pH of at least 7.8 and at most 9 comprising:
  1. a) 10 to 60 wt% non-soap surfactant,
  2. b) 0 to 20 wt% hydrotrope.
  3. c) 0 to 4 wt% soap,
  4. d) 0 to 10 wt% nonionic EPEI,
  5. e) at least 1 wt% triethanolamine (TEA),
    characterised in that dissolved in the alkaline isotropic liquid there is:
  6. f) at least 1 wt%, preferably at least 1.5 wt% of a polyester substantive nonionic soll release polymer of the type E-M-L-E, where the midblock M is connected to a generally hydrophilic end block E and blocks E each comprise capped oligomers of polyethylene glycol remote from the midblock, with at least 10 EO repeat units, the end blocks being free from ester bonds, either directly or via linking moiety L which comprises the motif: B-Ar-B where B is selected from ester moieties and Ar Is 1,4 phenylene, and midblock M comprises the motif:
    Figure imgb0001
    wherein R1 and R2 may be the same or different selected from C1-C4 alkyl, C1-C4 alkoxy and Hydrogen, provided that R1 and R2 may not both be hydrogen, n is at least 2, preferably more than 6, the ester bonds may by formed the other way around (not shown), if they are so reversed then all of them will be so reversed,
    wherein the composition comprising the polymer provides soll release less than a ΔE of 6 with DMO on woven polyester after storage of the polymer In the detergent composition at 60°C for 8 days at a pH >7.5.
  • Preferably each E comprises C1-C4 capped chains of polyethylene glycol remote from the midblock, with at least 10 EO repeat units, the end blocks being free from ester bonds, because the substituted ethylene moiety In the mid blocK motif cannot link directly to an end block E the mid block is connected to that and block E via a linking moiety L, wherein the polymer has a molecular weight Mw of at least 4000 and is provided with sufficient hindering of its ester bonds to provide soil release greater than a ΔE of 5 with DMO on woven polyester after storage of the polymer at 37°C for 8 weeks, or at 60°C for 8 days, at a pH >7.5 in a composition In the presence of 1% or more TEA.
  • By a soll release value ΔE of 5 or less we intend to cover removal of the DMO from an initial stain reflectance of 42 down to at most 5. In fact the likely removal is more than that.
  • Preferably each E in polymer (f) oomprises alkyl capped oligomers of polyethylene glycol, and the polymer has a molecular weight Mw of at least 4000. More preferably each E comprises C1-C4 capped oligomers of polyethylene glycol.
  • It is important to keep the esters in the midblock intact as fabric substantivity and thus soil release properties are otherwise lost and the improved resistance to hydrolysis Is of no practical significance.
  • The alkaline liquid detergent compositions may comprise the polymer (f) in amounts of from 1 to 15 wt%, preferably from 1 to 10 wt%, most preferably from 1.5 to 7 wt%.
  • Preferably the alkaline isotropic concentrated detergent liquid composition comprises at. least 5 wt% anionic surfactant. Suitably the liquid may comprise LAS, SLES, Nonionic and optionally betaine, the LAS being neutralised from LAS acid, at least in part, with TEA,
  • To maximise the benefit of the other cleaning technologies that are essentially or optionally included in the liquid, especially anionic surfactant, the liquid has an undiluted pH of at least 7.8. The alkaline detergent liquid has an undiluted pH of at most 9, preferably at most 8.4, even at most 8.2.
  • Desirably R1 and R2 in the mid block motif are selected from H and Me.
  • Prior art unstable polymers comprise mPEG as E and use esters throughout M and L. The more stable of this type of polymer disclosed in the prior art, for example Texcare 240 use ethylene substituted by one Me and one H in the midblock M and the Linking group L. This single methyl side group of the otherwise linear motive does not provide sufficient hindering of the adjacent esters. A number of strategies can be used to increase the degree of hindering of the ester bonds and thereby to improve the polymer's resistance to alkaline hydrolysis.
  • A first strategy is to insert a polypropylene oxide block as part of the endblock E situated between the ester bonds at the end of the mid block M and the polyethylene oxide hydrophilic block forming the part of endblock E furthest from the midblock M. Such PO insertions have been mentioned in the prior art but their significance for improved alkaline stability has not been recognised.
  • A second strategy is to introduce into the midblock M ethylene that is substituted by 2 methyl groups. That is both R1 and R2 are methyl. Not all of the substituted ethylene groups should be replaced in this way. A convenient way to achieve this is to use a mixture of a minor part of 2,3 butandiol with a major part of the conventionally used 1,2 propandiol to form the mid block M.
  • In a third strategy the endblock E may comprise at least 40, preferably at least 45 EQ groups and the ratio of the number of EO groups in each of the end blocks E to the number of repeat units in the midblock n is from 4 to 8.
  • Each of these strategies may be employed on its own, or even more preferred combinations of 2 or even all three of the strategies may be used.
  • Compositions in WO09153184 had high levels of soap for antifoam effect when the compositions are used In front loading automatic washing machines, We have noW found that this may require too much hydrotrope to stabilise the composition. Thus it is preferred for the amount of fatty acid added to the composition (soap precursor before neutralisation) to be kept to a maximum of 1.5wt% to facilitate the hydrotrope levels claimed, especially at the lower levels of hydrotrope. Keeping the soap level low means that the compositions may be formulated with low levels of hydrotrope (less than 15 wt%, even less than 12 wt%. This low hydrotrope level means that only certain SRPs and especially the ones according to the invention can be incorporated in isotropic form (dissolve in the composition). Many known polymers, especially those using groups other then esters as B and those having very high molecular weight mid blocks M will cause undesirable hazing of the composition.
  • We have found that formulation flexibility is best with the SRPs having end esters in the midblock motif and B protected by blocks of PO, slightly less preferred are SRPs with large EO groups and large mid blocks and least preferred, but still acceptable are the SRPs made using 2,3 butandiol as a diol to form the mid block M.
  • The polyester soil release polymers (f) are selected from those having the general formula (I):

            X-[(EQ)q1-block-(PO)p]-[(A-G1-A-G2)n]-B-G1-B-[(PO)p-block-(EO)q2]-X     (I)

    • where EO is ethylene oxide (CH2CH2O);
    • where PO is at least 80 wt% propylene oxide (CH2CH(CH3)O), and preferably 100% PO units;
    • where p Is a number from 0 to 60, and when p is not zero is preferably from 2 to 50, more preferably from 5 to 45, even more preferably from 6 to 40, yet more preferably from 7 to 40 and most preferably from 8 to 40, even from 11 to 35;
    • where q1 and q2 is a number from 6 to 120, preferably 18 to 80, most preferably 40 to 70, provided that q2 is greater than p and preferably q2 is at least 1.5 times as large as p;
    • where X is a capping molety, preferably selected from C1-4 alkyl, branched and unbranched;
    • where n Is a number from 2 to 26; preferably 5 to 15;
    • A and B are ester moieties;
    • when the moleties A and B adjacent to the PO blocks are esters then it is preferred that p is not zero,
    • alternatively, it is preferred that the ratio of (q1+q2)n is from 4 to 10 and that q2 Is from 40 to 120;
    • G1 comprises 1,4 phenylene;
    • G2 is ethylene, which is substituted;
  • It is preferred that moieties G2 are all ethylene of formula (II)
    Figure imgb0002
    wherein G3 and G4 are selected from Hydrogen, C1-4 alkyl and C1-4 alkoxy, provided that at least one of G3 and G4 is not hydrogen and that at least 10% of the groups G2 have neither G3 nor G4 as hydrogen. Preferably when G3 and G4 are not hydrogen then they are methyl moieties. Preferably the non H substituents, more preferably the methyl moieties, are arranged in syn configuration on the ethylene backbone -CH-CH- of moieties G2.
  • In formula (I) the groups correspond to the general formula E-M-L-E as follows:
    • E is X-[(EO)q1-block-(PO)p]- and -[(PO)p-block-(EO)q2]-X
    • M is -[(A-G1-A-G2)n]-; and
    • L is -[B-G1-B]-
  • Because it is an average, n is not necessarily a whole number for the polymer in bulk. The same holds true, to a lesser extent, for p, q1 and q2. Since p and q1 and q2 are made by anionic polymerisation routes (resulting in polymer blocks with very discreet block lengths) as against the midblock made by polycondensation routes (resulting in polymer blocks with more polydisperse block lengths).
  • In formula (I) the moiety [(A-G1-A-G2)n]-B-G1-B]- forms the polymer mid block or backbone and is described in more detail below. For the advantages of the invention to be achieved, by hindering of the hydrolytic attack on ester bonds, the moieties A and B nearest to any PO blocks are esters. Without wishing to be bound by theory it Is believed that the defined PO blocks adjacent to those end easter moieties hinder the hydrolysis of those ester moieties. The protection of those ester moieties has been found to provide a significant benefit in terms of overall polymer stability. This is thought to be due to the hydrolysis starting from the end of the midblock which immediately cleaves the functional EO end block from the mid block, fabric substantive, part of the polymer, If it occurs. This separation of the hydrophilic PEO end blocks (EO)q from the fabric substantive (e.g. phenylene/alkylene containing) mid block reduces the soil release properties of the polymer,
  • When p is zero it is preferred for q2, and q1, if present, to be at least 40. Furthermore we have determined that for such polymers it is desirable that they are provided with a large mid block where n is at least 5 and preferably at least 8 as this seems to confer advantages for sustained soil release after prolonged storage under alkaline conditions.
  • Preferably the moieties G1 are 1,4 phenylene for maximum fabric substantivity of the mid block motif.
  • If the mid block is formed by the condensation of an ester of terephthalic acid with a diol a preferred diol to form the desired group G2 may be selected from the group of diols of formula (III):

            syn n+1,n+2 alkylene diol     (III)

    n being an integer from 1 to c-3, where c is the number of carbons in the alkylene chain. The most preferred diols are syn 2,3 butane diol and 1,2 propane diol.
    when q1 is 0, or from 40 to 120, and q2 is from 40 to 120, n is preferably a number from 5 to 26 and the ratio of (q1 +q2):n is from 4 to at most 10, preferably from 5 to 8;
  • Formula (IV) shows a suitable polymer where the mid block is formed entirely from oxypropylene moieties and terephthaloyl moieties (1,4-dicarboxy-phenylene and 1,2 propylene), linked via ester groups to one or more capped polyethylene glycol end blocks, one of which is depicted as having p units of ethylene oxide (q2). The polyester substantive motif in the mid block is repeated n times.
    Figure imgb0003
  • DETAILED DESCRIPTION OF THE INVENTION
  • The invention is a combination of a selected group of polyester soil release polymers with high performance and stability and a liquid detergent base that holds the polymer stably in solution or dissolution and yet does not cause unwanted destruction of the polymer structure and performance via hydrolysis as we have found to be the case with prior art preferred polymers when incorporated into such isotropic alkaline detergent liquids.
  • All percentages are weight percent except where indicated otherwise or where the context makes it obvious that something else is intended.
  • The hydrolytically stable Soil release polymer (with hindered bonds)
  • The Invention requires the selection of a stable high performance soil release polymer and Its incorporation into an alkaline ooncentrated detergent liquid, comprising surfactant and triethanolamine that is known to catalyse the polymer hydrolysis.
  • The SRPs have the formula (I);

            X-[(EO)q1-block-(PO)p]-[(A-G1-A-G2)n-B-G1-B-[(PO)p-block-(EO)q2] -X     (I)

    X-[(EO)q1-block-(PO)p]- and -[(PO)p-block-(EO)q2] -X are generally connected at the ends of the polymer backbone or mid block. The mid block is responsible for making the polymer fabric substantive, particularly towards polyester fabrics. The endcaps of large blocks of EO groups are highly hydrophilic and can be considered to swing away from the fabric to provide the surface modification that promotes soil release. Thus it is an essential feature of the polymers of the present invention to have capped EO end block(s).
  • Mid block or backbone
  • The mid block [(A-G1-A-G2)r]-B-G1-B (-M-L-) is responsible for making the polymer fabric substantive, particularly towards polyester fabrics.
  • The linking moieties A are esters. Moieties B in linking group L are also esters. In the polymer structure such an ester may be formed either way around and it may thus take the form of the molety:
    Figure imgb0004
  • The A moieties consist entirely of such ester moieties.
  • The G1 moieties comprise 1,4-phenylene moieties.
  • It is possible, as taught by the prior art, to partially substitute some of these 1, 4 phenylene moieties with other arylene or alkarylene moieties, for example 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2'-biphenylene, 4,4'-biphenylene and mixtures thereof. However, such substitution is undesirable as it adversely affects the ability of the mid block to deposit onto polyester fabric. A minor amount, less than 10 mol%, of such substitution is permissible, but not preferred.
  • The G2 moieties are substituted ethylene moieties having C1-A alkyl or alkoxy substituents, The G2 moieties consist entirely of substituted ethylene moieties. A preferred substituted ethylene moiety Is 1,2 propylene which is derived from the condensation of 1,2 propane diol. It is preferred to fully avoid the use of unsubstituted ethylene.
  • For the G2 moieties, suitable substituted ethylene moieties are the monomethyl substituted G2 formed from 1,2-propylene diol, and the dimethyl substituted G2 formed from 2,3 butylene diol. Without wishing to be bound by theory It is thought that the 1,2 di methyl substituted ethylene shows superior protection of adjacent ester bonds due to that fact that it Is always going to be the case that there is a methyl group on the carbon atom adjacent to the ester. The contrasts with the situation for the monomethyl material formed from 1,2 propane diol. In that case the methyl group may arrange Itself adjacent to the ester or it may alternatively arrange Itself to be on the carbon of the ethylene that is more remote from the ester.
  • 2,3 butylene is a meso stereo isomeric compound. It is thought that once reacted into the polymer chain the different forms behave in similar ways so far as the hindering of hydrolysis Is concerned. The optically active RR or SS diastereoisomers are preferred over the RS (meso) diastereoisomer. Thus, the preferred form of the 2,3 butylene glycol used is the RR or SS optically active forms either isolated, or as a racemic mixture. In practice a mixture of the meso and racemic forms has been found to give satisfactory results.
  • Generally, the degree of partial replacement of G1 which can be tolerated will depend upon the number of repeat units n In the mid block, i.e. longer mid blocks can have greater partial replacement. So for a polymer where n Is at least 5 the degree of replacement of the preferred G1 in the fabric substantive motif may be as high as 20 mol%. However, it is desirable to minimize such partial replacement, for best soil release activity it is preferably absent.
  • G2 comprises 100 mol% substituted ethylene moieties which give a carbon chain length of 2 in the backbone. Such moieties include 2,3 butane diol derivatives, i.e. an ethylene moiety with a methyl group substituted on each carbon in the backbone.
  • The skilled person will appreciate that although linear polymer backbones are preferred some degree of branching can be introduced by using triols or 1,3,5 phenylene moieties and these too may be used as substituent G1 groups provided that at least 80 mol% of those groups are the preferred moieties described above.
  • The polymer should preferably be nonionic as ionic polymers are generally not phase stable in concentrated alkaline detergent liquids.
  • It has been found that the value of n needs to be at least 2 in order for the stable polymers used in the invention to have sufficient polyester substantivity. The maximum value for n can range up to 26. By comparison, polyesters used in fibre making typically have a much higher molecular weight with n from 50 to 250. Typically, n ranges from 2 to 16, preferably 4 to 9. Generally, the larger the n value, the less soluble Is the polymer.
  • Preferred G2 moieties are essentially substituted ethylene moieties, selected from substituted ethylene of formula (II)
    Figure imgb0005
    wherein G3 and G4 are selected from Hydrogen, C1-4 alkyl and C1-C4 alkoxy provided that at least one of G3 and G4 is not hydrogen and that at least 10 mol%, preferably at least 20 mol% of the groups G2 have neither G3 nor G4 as hydrogen. Preferably when G3 and G4 are not hydrogen then they are methyl moieties. Preferably the non Hydrogen substituents, more preferably the methyl moieties, are arranged In syn configuration on the ethylene backbone.
  • If the mid block is formed by the condensation of an ester of terephthalic acid with a diol the preferred diol to form the desired group is selected from the group of diols of formula (III):

            syn n+1,n+2 alkylene diol     (III)

    n being an integer from 1 to c-3, where c is the number of carbons in the alkylene chain.
  • The most preferred diols are syn 2, 3 butane diol and 1,2 propane diol.
  • Especially preferred are mixtures of up to 80 mol% 1,2 propylene with the condensation product of SS or RR 2,3 butylene; each X is C1-4 alkyl, preferably methyl or n-butyl; each q is from 12 to 80; each p is from 0 to 50; n is from 3 to 10;
  • In a preferred embodiment, the polymeric soil release agents according to the present invention have the formula (V):

            X-[(EO)q(PO)p]-[(OC(O)-G1-C(O)O-G2)n]-OC(O)-G1-C(O)O-[(PO)p(EO)q]-X     (V)

    wherein :
    • each of the G1 moieties is a 1,4-phenylene moiety;
    • the G2 moieties are each selected from the group consisting of monomethyl ethylene and dimethyl ethylene, provided that the dimethyl ethylene has the two methyl groups on separate carbons and that this moiety forms at least 20 mol% of the moieties G2
    • each X is C1-C4 alkyl; each q is from 40 to 70; n is from 3 to 10.
    Preferably, in the formula (V), G2 moieties comprise a mixture of from 40 to 90 mol% monomethyl substituted ethylene moieties, and from 10 to 60 mol% 1,2 dimethyl ethylene moieties.
  • In most preferred embodiments of the present invention, the polymeric soil release agents have the formula (VI) or (VII):
    Figure imgb0006
    Figure imgb0007
    Where in formula VII a+b=1 and "a" lies in the range 0 to 0.8 and In both formulae,
    n has the value from 2 to 20,
  • End block
  • The soil release polymer comprise two end blocks E.
  • The end blocks X-[EOq1] and [EOq2]-X may be the conventional capped PEG groups of various molecular weight or alternatively, in the case where p is not zero, they may be blocked mPEG/PPG groups i.e. X-[(EO)q-block-(PO)p]- and -[(PO)p-block-(EO)q]-X. The end blocks are connected to the polymer mid block M or linking block L by ester moieties, A and B.
  • To obtain the combination of hydrolytic stability and soil release properties when stored in, and delivered from, an alkaline liquid optional end block PO groups may be arranged in blocks adjacent the end ester moieties of the mid block M and the linking part L and the end block EO groups are similarly arranged in blocks more remote from the mid block. Pure, i.e. 100%, EO and PO blocks are preferred. Thus a preferred EO block is made using a capped PEG such as methyl capped PEG, or mPEG. The molecular weight Mw of the mPEG may be in the range 700 to 3000 Da.
  • When present the PO block should comprise at least 80% by number PO units. We have determined that a stat block PO/EO block confers some improvement of resistance to hydrolysis of the end ester moieties A and B. However, to avoid this hydrophobic block becoming unnecessary large it is preferred that it comprises as much as possible of the ester bond hindering PO units. Preferably it consists of at least 90% and most preferably 100%, by number, PO units. The number, p, of units in the PO block is from 2 to 50, more preferably from 5 to 45, even more preferably from 6 to 40, yet more preferably from 7 to 40 and most preferably from 8 to 40, even from 11 to 35;
  • Preferred polymers have an EO block that has more units than the PO block, when present, preferably the EO block has at least 1.5 times the number of moles or units (q2) as the PO block (p).
  • The terminal end cap X on the EO block is preferably as small as possible, for example C1-C4 alkyl. X is preferably methyl, ethyl, or n-butyl and most preferably methyl or n-butyl.
  • When p is not zero, q is at least 6, and is preferably at least 10. The value for q usually ranges from 18 to 80. Typically, the value for q is in the range of from 30 to 70, preferably 40 to 70.
  • As the value for q increases, the value for n should be increased so that the polymer will deposit well on the fabric during laundering.
  • Preferred compounds of formula (I) are polymers having formula (VIII):

            X-[(OCH2CH2)q-]-block-[(OCH2CH(CH3))p]-[(OC(O)-G1-C(O)O-G2)n]-OC(O)-G1-C(O)O-[((CH3)CHCH2O)p-]-block-[(CH2CH2O)q]-X     (VIII)

    wherein the G1 moieties are all 1,4-phenylene moieties; the G2 moieties are all substituted ethylene moieties, each X is C1-4 alkyl, preferably methyl or n-butyl; each q is from 12 to 120; each p is from 2 to 50, preferably 6 to 40; and n is from 2 to 10.
  • The block polyesters of formula VIII are linear block polyesters. For these preferred linear block polyesters, n preferably ranges from 3 to 9, especially for those made from dimethyl terephthalate, and 1,2-propylene glycol. The most preferred of these linear block polyesters are those where n is from 3 to 5.
  • Most preferably, in the formula (VIII), in the polymer according to the present invention p is from 11 to 50 and q is from 18 to 60.
  • A particularly preferred embodiment of this type of soil release polymer of formula (I) has the formula (IX), where n is at most 15, preferably at most 12 and more preferably at most 9 and n is at least 2, preferably at least 3 and more preferably at least 4, for example n is from 2 to 15, preferably 3 to 12 more preferably 4 to 9.
    Figure imgb0008
  • As the value for q increases, the value for n should be increased so that the compound will deposit better on the fabric during laundering.
  • q1 is either zero, or is at least 40, preferably about 45 and q2 is at least 40, preferably about 45. We have found that the ratio of the end block to mid block is important for the soil release and stability. The prior art polymer Texcare® SRN 240 appears to have almost the same end block (a methyl capped PEG of a molecular weight of approximately 2000), yet it proved to be unsuitable for use in alkaline liquid compositions, particularly those comprising triethanolamine (TEA).
  • As the value for q1+q2 increases, the value for n should be increased to keep the ratio within the defined limits and to ensure that the compound will deposit well on the fabric during laundering.
  • Preferred compounds of the present invention are polyesters having the formula (X):
    Figure imgb0009
    where n is at least 7.
  • Molecular weight
  • Preferred polymers for use in liquid detergent compositions have molecular weights Mw within the range of from 1000 to 20 000, preferably from 1500 to 10 000.
  • The polydispersity of the polymers is preferred to be less than 3.
  • Preparation of the polymer
  • The soil release polymers of the present invention can be prepared by methods known to the person skilled in the art. US 4,702, 857 and US 4,711,730 describe a method of synthesis that may be adapted to produce the block polyesters of the present invention.
  • In a preferred process the end blocks are made in a separate process and then added to the mid block. A suitable process to manufacture the block copolymers used for the end blocks is described below.
  • End block manufacture
  • The mPEG for variants of the polymer without PO blocks in the end blocks (p=0) may be prepared by methods known to the person skilled in the art.
  • In a preferred process the optional PO/EO end blocks are preformed by anionic polymerisation of propylene oxide using a preformed mono-functional PEG as the initiator. Such a process is, for example, described in M. I. Malik, B. Trathnigg, C.O. Kappe, Macromol. Chem. Phys., 2007, 208, 2510-2524.
  • The reaction scheme is set forth below:
    Figure imgb0010
  • Reaction A: Sodium hydride reacts with PEG to yield activated chain ends. Reaction B: The addition of PO proceeds at the ends of the PEG chains to form a block of PO.
  • An alternative, but less controllable and therefore less preferred, process to construct the end blocks would be to take the mid block and react it with PO and mPEG.
  • Mid block manufacture
  • It is preferred to manufacture the mid block by condensation of methyl esters of terephthalic acid with the appropriate aliphatic diol, preferably using an excess of one of them as set forth in more detail in the following examples. If the dicarboxylic acid is used in alkyl ester form, the reaction is suitably carried out in the presence of a base catalyst, at an elevated temperature, for example, 120 to 180 °C, and, if desired, under reduced pressure. The lower alcohol, normally methanol, generated during the reaction is distilled off.
  • Suitable catalysts include alkyl and alkaline earth metals, for example, lithium, sodium, calcium and magnesium, as well as transition and Group IIB metals, for example, antimony, manganese, cobalt and zinc. The catalysts are usually used as oxides, carbonates or acetates. A preferred catalyst comprises antimony trioxide and calcium acetate.
  • The esters and oligomers produced in the condensation (ester interchange) reaction may then be polymerised to the desired molecular weight, by raising the temperature further, typically to 180 to 250 °C.
  • The degree of polymerisation may be monitored by gel permeation chromatography, NMR, and end-group titrations.
  • However, it is also possible to obtain a very similar polyester recognition motif with the ester moieties reversed if the starting materials are aliphatic biscarboxylic acids and aromatic bisalcohol. For example, hydroquinone may be used as the aromatic alcohol and derivatives of succinic acid may be used as the carboxylic acid (in this case, R' and R" = H).
    Figure imgb0011
  • The isotropic liquids
  • The amount of detersive surfactant makes up at least 10 wt% of the total liquid composition, preferably it makes up from 12 to 60 wt%. The compositions according to the invention most preferably have total active detersive surfactant levels of at least 15 wt%.
  • The compositions may be concentrated compositions designed to be added to a 10 litre wash in small doses that require them to be diluted in at least 500 times their own volume of water to form a main wash liquor comprising at most 0.5 g/l surfactant. They may also be concentrated compositions designed for hand wash or top loading automatic washing machines. In hand wash less water may be used and in top loading automatic washing machines a higher amount of water would normally be used. The dose of detergent liquid is adjusted accordingly to give similar wash liquor concentrations.
  • Surfactants
  • Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor. Anionic or blends of anionic and nonionic surfactants are a preferred feature of the present invention. The amount of anionic surfactant is preferably at least 5 wt%.
  • Preferably, the anionic surfactant forms the majority of the non soap surfactant (a).
  • Anionic
  • Preferred alkyl sulphonates are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-C15. The counter ion for anionic surfactants is generally an alkali metal, typically sodium, although other counter-ions such as MEA, TEA or ammonium can be used.
  • Preferred linear alkyl benzene sulphonate surfactants are Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14.
  • It is further desirable that the composition comprises an alkyl polyethoxylate sulphate anionic surfactant of the formula (I):

            RO(C2H4O)xSO3 -M+     (I)

    where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
  • Preferably R is an alkyl chain having from 12 to 16 carbon atoms, M is Sodium and x averages from 1 to 3, preferably x is 3; This is the anionic surfactant sodium lauryl ether sulphate (SLES). It is the sodium salt of lauryl ether sulphonic acid in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.
  • Nonionic
  • Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used. When included therein the composition contains from 0.2 wt% to 40 wt%, preferably 1 wt% to 20 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Amine Oxide
  • The composition may comprise up to 10 wt% of an amine oxide of the formula (2):

            R1N(O)(CH2R2)2     (2)

  • In which R1 is a long chain moiety each CH2R2 are short chain moieties. R2 is preferably selected from hydrogen, methyl and -CH2OH. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R1 is a primary alkyl moiety. R1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
  • Preferred amine oxides have R1 is C8-C18 alkyl, and R2 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
  • A preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Hunstman under the trade name Empigen® OB.
  • Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • Whereas in certain of the preferred embodiments R2 is H, it is possible to have R2 slightly larger than H. Specifically, R2 may be CH2OH, such as: hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide.
  • Preferred amine oxides have the formula:

            O--N+(Me)2R1     (3)

    where R1 is C12-16 alkyl, preferably C12-14 alkyl; Me is a methyl group.
  • Zwitterionic
  • Nonionic-free systems with up to 95 %wt LAS can be used provided that some zwitterionic surfactant, such as sulphobetaine, is present. A preferred zwitterionic material is a betaine available from Huntsman under the name Empigen® BB. Betaines, improve particulate soil detergency in the compositions of the invention.
  • Additional surfactants
  • Other surfactants than the preferred LAS, SLES, nonionic and zwitterionic (betaine) may be added to the mixture of detersive surfactants. However cationic surfactants are preferably substantially absent.
  • Although less preferred, some alkyl sulphate surfactant (PAS) may be used, especially the non-ethoxylated C12-15 primary and secondary alkyl sulphates. A particularly preferred material, commercially available from Cognis, is Sulphopon 1214G.
  • Other Polymer EPEI
  • A particularly preferred class of polymer for use in combination with the soil release polymers of the present invention is polyethylene imine, preferably modified polyethylene imine. Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939 ; U.S. Pat. No. 3,033,746, Mayle et al., issued May 8, 1962 ; U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16, 1940 ; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957 ; and U.S. Pat. No. 2,553,696, Wilson, issued May 21, 1951 .
  • Preferably, the EPEI comprises a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight; wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without quaternisation. Such nonionic EPEI may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone. The ethoxylation may range from 9 to 40 ethoxy moieties per modification, preferably it is in the range of 16 to 26, most preferably 18 to 22.
  • The polyethyleneimine polymer is present in the composition preferably at a level of between 0.01 and 25 wt%, but more preferably at a level of at least 2 wt% and/or less than 9.5 wt%, most preferably from 3 to 9 wt% and with a ratio of non-soap surfactant to EPEI of from 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5:1.
  • Other polymer types
  • In addition to a soil release polymer there may be used dye transfer inhibition polymers, anti redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials.
  • Hydrotrope
  • In the context of this invention a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components in the aqueous liquid to render it isotropic. Among suitable hydrotropes there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene glycol, diethers and urea.
  • Enzymes
  • It is preferable that at least one or more enzymes may be present in the compositions.
  • Lipase
  • Lipase is a particularly preferred enzyme. The composition preferably contains from about 5 to about 20000 LU/g of a lipase. Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola, more preferably ones which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginose, most preferably strain DSM 4109. The amount in the composition is higher than typically found in liquid detergents. This can be seen by the ratio of non-soap surfactant to lipase enzyme, in particular. A particularly preferred lipase enzyme is available under the trademark Lipocean from Novozymes.
  • As noted above, 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 WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1, 372, 034 ), P. fluorescens, Pseudomonas sp. strain SD 705 ( WO 95/06720 and WO 96/27002 ), P. wisconsinensis ( WO 96/12012 ), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus ( JP 64/744992 ) or B. pumilus ( WO 91/16422 ). As noted above the preferred ones have a high degree of homology with the wild-type lipase derived from Humicola lanuginose.
  • Other examples are lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 .
  • Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean (Novozymes A/S).
  • In addition to or as an alternative to lipase one or more other enzymes may be present. However lipase is particularly preferred.
  • Advantageously, the presence of relatively high levels of calcium in the poorly built or unbuilt compositions of the invention has a beneficial effect on the turnover of certain enzymes, particularly lipase enzymes and preferably lipases from Humicola.
  • The preferred lipases include first wash lipases which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109 and compared to said wild-type lipase, comprises a substitution of an electrically neutral or negatively charged amino acid within 15 A of E1 or Q249 with a positively charged amino acid; and may further comprise:
    1. (I) a peptide addition at the C-terminal;
    2. (II) a peptide addition at the N-terminal;
    3. (III) meets the following limitations:
      1. i. comprises a negatively charged amino acid in position E210 of said wild-type lipase;
      2. ii. comprises a negatively charged amino acid in the region corresponding to positions 90-101 of said wild-type lipase; and
      3. iii. comprises a neutral or negatively charged amino acid at a position corresponding to N94 of said wild-type lipase; and/or
      4. iv. has a negative charge or neutral charge in the region corresponding to positions 90-101 of said wild-type lipase; and
      5. v. mixture thereof.
  • These are available under the Lipex brand from Novozymes. A similar enzyme from Novozymes but believed to fall outside of the above definition is sold by Novozymes under the name Lipoclean and this is also preferred.
  • Phospholipase:
  • 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. As used herein, the term 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. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
  • Protease:
  • Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™, (Novozymes A/S), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™, Purafect OxP™ , FN2™, and FN3™ (Genencor International Inc.).
  • Cutinase:
  • The method of the invention may be carried out in the presence of 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.
  • Amylase:
  • Suitable amylases (alpha and/or beta) 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 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 Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (from Genencor International Inc.).
  • Cellulase:
  • 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 Celluzyme™, Carezyme™, Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation).
  • Peroxidases/oxidases:
  • 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 Guardzyme™ and Novozym™ 51004 (Novozymes A/S).
  • Pectate Lyases:
  • Pectate lyases (also called polygalacturonate lyases): Examples of pectate lyases include pectate lyases that have been cloned from different bacterial genera such as Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from Bacillus subtilis (Nasser et al. (1993) FEBS Letts. 335:319-326) and Bacillus sp. YA-14 (Kim et al. (1994) Biosci. Biotech. Biochem. 58:947-949). Purification of pectate lyases with maximum activity in the pH range of 8-10 produced by Bacillus pumilus (Dave and Vaughn (1971) J. Bacteriol. 108:166-174), B. polymyxa (Nagel and Vaughn (1961) Arch. Biochem. Biophys. 93:344-352), B. stearothermophilus (Karbassi and Vaughn (1980) Can. J. Microbiol. 26:377-384), Bacillus sp. (Hasegawa and Nagel (1966) J. Food Sci. 31:838-845) and Bacillus sp. RK9 (Kelly and Fogarty (1978) Can. J. Microbiol. 24:1164-1172) have also been described. Any of the above, as well as divalent cation-independent and/or thermostable pectate lyases, may be used in practicing the invention. In preferred embodiments, the pectate lyase comprises the pectate lyase disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact. 8: 331-334 and Henrissat et al., (1995) Plant Physiol. 107: 963-976. Specifically contemplated pectatel lyases are disclosed in WO 99/27083 and WO 99/27084 . Other specifically contemplated pectate lyases (derived from Bacillus licheniformis) are disclosed in US patent no. 6,284,524 (which document is hereby incorporated by reference). Specifically contemplated pectate lyase variants are disclosed in WO 02/006442 , especially the variants disclosed in the Examples in WO 02/006442 (which document is hereby incorporated by reference).
  • Examples of commercially available alkaline pectate lyases include BIOPREPT™ and SCOURZYME™ L from Novozymes A/S Denmark.
  • Mannanases:
  • Mannanase: Examples of mannanases (EC 3.2.1.78) include mannanases of bacterial and fungal origin. In a specific embodiment the mannanase is derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus ( WO 94/25576 ). WO 93/24622 discloses a mannanase isolated from Trichoderma reseei. Mannanases have also been isolated from several bacteria, including Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994) describes a beta-mannanase derived from Bacillus subtilis. JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp.
  • JP-A-63056289 describes the production of an alkaline, thermostable beta-mannanase. JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase. JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001. A purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/11164 . WO 91/18974 describes a hemicellulase such as a glucanase, xylanase or mannanase active. Contemplated are the alkaline family 5 and 26 mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO 99/64619 . Especially contemplated are the Bacillus sp. mannanases concerned in the Examples in WO 99/64619 .
  • Examples of commercially available mannanases include Mannaway™ available from Novozymes A/S Denmark.
  • The enzyme and any perfume/fragrance or pro-fragrance present may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme and pro-fragrance and/or other segregation within the product.
  • Enzyme Stabilizers:
  • 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 .
  • Fluorescent Agents:
  • It may be advantageous to include fluorescer in the compositions. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt %.
  • 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.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-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' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
  • Bleach Catalyst:
  • Detergent compositions according to the invention may comprise a weight efficient bleach system. Such systems typically do not utilise the conventional percarbonate and bleach activator approach.
  • The present invention may be used in a formulation that is used to bleach via air, or an air bleach catalyst system. Suitable complexes and organic molecule (ligand) precursors for forming complexes are available to the skilled worker, for example, from: WO 98/39098 ; WO 98/39406 , WO 97/48787 , WO 00/29537 ; WO 00/52124 , and WO00/60045 , incorporated by reference. An example of a preferred catalyst is a transition metal complex of MeN4Py ligand (N,N-bis(pyridin-2-yl-methyl)-1-,1-bis(pyridin-2-yl)-1-aminoethane). Suitable bispidon catalyst materials and their action are described in WO02/48301 .
  • Photobleaches may also be employed. In the context of the present invention a "photobleach" is any chemical species that forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction. Preferred photo-bleaches include singlet oxygen photo-bleaches and radical photo-bleaches. Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably the phthalocyanin has 1-4 SO3X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba).
  • When present, the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10wt%, preferably about 0.001 to about 5wt%.
  • Perfume
  • Given that the composition of the present invention is designed to be used at very low levels of product dosage, it is advantageous to ensure that perfume is employed efficiently.
  • A particularly preferred way of ensuring that perfume is employed efficiently is to use an encapsulated perfume. Use of a perfume that is encapsulated reduces the amount of perfume vapour that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.
  • It is even more preferable that the perfume is not only encapsulated but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics. The deposition aid is preferably attached to the encapsulate by means of a covalent bond, entanglement or strong adsorption, preferably by a covalent bond or entanglement.
  • Further Optional Ingredients:
  • The compositions of the invention may contain one or more other ingredients. Such ingredients include viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anticorrosion agents, drape imparting agents, anti-static agents and ironing aids. The compositions may further comprise, colorants, pearlisers and/or opacifiers, and shading dye.
  • Shading dyes
  • Shading dye can be used to improve the performance of the compositions used in the method of the present invention. The deposition of shading dye onto fabric is improved when they are used in compositions of the invention and according to the process of the invention. Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
  • Suitable and preferred classes of dyes are discussed below.
  • Direct Dyes:
  • Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have an affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
  • Preferably bis-azo or tris-azo dyes are used.
  • Most preferably, the direct dye is a direct violet of the following structures:
    Figure imgb0012
    or
    Figure imgb0013
    wherein:
    • ring D and E may be independently naphthyl or phenyl as shown;
    • R1 is selected from: hydrogen and C1-C4-alkyl, preferably hydrogen;
    • R2 is selected from: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
    • R3 and R4 are independently selected from: hydrogen and C1-C4-alkyl, preferably hydrogen or methyl;
    • X and Y are independently selected from: hydrogen, C1-C4-alkyl and C1-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
  • Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99. Bis-azo copper containing dyes such as direct violet 66 may be used. The benzidene based dyes are less preferred. Preferably the direct dye is present at 0.000001 to 1 wt% more preferably 0.00001 wt% to 0.0010 wt% of the composition.
  • In another embodiment the direct dye may be covalently linked to the photobleach, for example as described in WO2006/024612 .
  • Acid dyes:
  • Cotton substantive acid dyes give benefits to cotton containing garments.
    Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:
    1. (i) azine dyes, wherein the dye is of the following core structure:
      Figure imgb0014
      • wherein Ra, Rb, Rc and Rd are selected from: H, a branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl;
      • the dye is substituted with at least one SO3 - or -COO- group; the B ring does not carry a negatively charged group or salt thereof;
      • and the A ring may further substituted to form a naphthyl;
      • the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2.
  • Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
  • Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
  • Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
  • Hydrophobic dyes:
  • The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
  • Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
  • Preferably the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
  • Basic dyes:
  • Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
    Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
  • Reactive dyes:
  • Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
  • Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
  • Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
  • Dye conjugates:
  • Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces. Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787 .
  • Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
  • Shading dye can be used in the absence of fluorescer, but it is especially preferred to use a shading dye in combination with a fluorescer, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescer.
  • Builders and sequestrants
  • The detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material. Examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Thermphos and alkanehydroxy phosphonates.
  • Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN.
  • If utilized, the organic builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition. The preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition. A preferred sequestrant is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid), for example sold as Dequest 2010. Also suitable but less preferred as it gives inferior cleaning results is Dequest® 2066 (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
  • Buffers
  • In addition to the 1% TEA the presence of buffer is preferred for pH control; preferred buffers are MEA, and TEA. They are preferably used in the composition at levels of from 5 to 15 wt%, including the 1% TEA.
  • External Structurants
  • The compositions may have their rheology modified by use of a material or materials that form a structuring network within the composition. Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants such as citrus pulp fibre. Citrus pulp fibre is particularly preferred especially if lipase enzyme is included in the composition.
  • Visual Cues
  • The compositions may, and preferably do, comprise visual cues of solid material that is not dissolved in the composition. Preferably they are used in combination with an external structurant to ensure that they remain in suspension. Preferred visual cues are lamellar cues formed from polymer film and possibly comprising functional ingredients that may not be as stable if exposed to the alkaline liquid. Enzymes and bleach catalysts are examples of such ingredients. Also perfume, particularly microencapsulated perfume.
  • Packaging and dosing
  • The liquids may be packaged as unit doses in polymeric film adapted to be insoluble until added to the wash water. More preferred the liquids are supplied in multiuse plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a past of the cap or as an integrated system.
  • Method of use
  • Following the teaching in WO2009/153184 the liquids according to the invention are intended to be formulated to allow them to be dosed to a typical front loading automatic washing machine at a dosage level of 20ml. The low in wash surfactant level being compensated by the presence of enzymes, the stable soil release polymer and optional additional high efficacy cleaning ingredients, such as EPEI. However, the invention is also suitable for the more conventional dosage levels of about 35 ml. the obtain suitable liquids of this type all that is necessary is to add further water and possibly perfume to the 20ml type of liquid. The soil release polymers claimed are also stable in these more dilute compositions.
  • The invention will now be further described with reference to the following non-limiting examples.
  • EXAMPLES Soil Release (DMO) evaluation:
  • DMO is dirty motor oil. Soil release polymer was dissolved or dispersed in concentrated alkaline liquid detergent bases to make the concentrated alkaline liquid detergent compositions given in Table 1.
  • MPG
    is mono propylene glycol.
    TEA
    is triethanolamine.
    NI 7EO
    is C12-15 alcohol ethoxylate 7EO nonionic Neodol® 25-7 (ex Shell Chemicals).
    LAS acid
    is C12-14 linear alkylbenzene sulphonic acid.
    Prifac® 5908
    is saturated lauric fatty acid ex Croda.
    SLES 3EO
    is sodium lauryl ether sulphate with 3 moles EO.
    Empigen® BB
    is an alkyl betaine ex Huntsman (Coco dimethyl carbobetaine).
    EPEI
    is Sokalan HP20 - ethoxylated polyethylene imine cleaning polymer: PEI(600) 20EO ex BASF.
    Perfume
    is free oil perfume.
    SRP
    is soil release polymer.
    PCF
    is Herbacel AQ plus citrus fibre, a powdered citrus peel fruit material ex Herba foods.
    SLES 1 EO
    is Sodium Lauryl Ether Sulphate with average of 1 EO.
    Prifac® 5908
    is saturated lauric fatty acid ex Croda.
    MEA
    is Monoethanolamine.
    NaOH
    is 47% sodium hydroxide solution.
    Dequest® 2066
    is Diethylenetriamine penta(methylene phosphonic acid (or Heptasodium DTPMP).
    Dequest® 2010
    is HEDP (1-Hydroxyethylidene -1,1 ,-diphosphonic acid).
    Lipex®
    is Lipex 100L ex Novozymes.
    Carezyme®
    is a cellulase ex Novozymes.
    Stainzyme 12L
    is an amylase formulated for liquids ex Novozymes.
    Mannaway
    is a mannanase ex Novozymes.
    Table 1 - Liquid detergent compositions
    Composition A (5x) Composition B (3x)
    Component Ingredient (as 100% active) %
    Demin water (initial - more added when pH is adjusted) 27.85 45.91
    MPG 20.00 20.00
    TEA 2.00 1.14
    NI 7EO 12.74 7.28
    LAS acid 8.49 4.85
    Prifac® 5908 1.50 0.86
    SLES 3EO 4.24 2.42
    Empigen® BB 1.50 0.86
    EPEI 5.50 3.14
    SRP 3.75 2.14
    Perfume 2.43 1.39
    pH adjustment hole* 10.00 10.00
    TOTAL 100.00 100.00
    * comprising NaOH to required pH, and demineralised water balance. Essentially the 3x Composition B is a dilution of the 5x Composition A (i.e. the 5x ingredient percentage concentration x 20/35. A 5x composition is one designed to have a recommended dose per wash of 20ml; A 3x composition is one that has a recommended dose per wash of about 35ml. The exceptions to the scaling between Compositions A and B are the water level and the MPG hydrotrope level which was kept at 20% for both compositions.
  • The compositions, comprising the polymer, were stored to allow the polymer to be exposed to conditions where it may undergo hydrolysis, with consequent reduction of the soil release performance.
  • Thus whilst the theoretical level of polymer dosed to the wash is stated to be 50ppm the actual level used after storage would have been lower due to polymer degradation during storage.
  • Wash Method
  • All washes and pre-washes were carried out in a Tergotometer containing 1 litre of wash liquor at 25°C. Wash liquors were prepared using 26°FH water. The Tergotometer speed was set at 100 oscillations/minute for all pre-washes and washes.
  • 1.3 g/l of Composition A or 2.3 g/l of Composition B was added to water to make a wash liquor.
  • Two 30 minute pre-washes of knitted polyester test pieces were carried out with polyester and cotton ballast such that the total fabric weight was 40g and the ratio of cotton : polyester was 1:1. After each pre-wash the fabric was rinsed twice (for 20 seconds) in 26°FH water and dried. Fresh ballast was used for each pre-wash (and subsequent wash). After the polyester test pieces had dried, following the second pre-wash, they were stained using one drop of dirty motor oil (DMO) added from a disposable glass pipette. The stains were quickly stretched by hand in order to assist wicking and ensure a uniform stain, and left overnight before washing. Three replicate stained polyester test pieces were included in each wash; three repeat washes were carried out.
  • ΔE of the dried residual stain was measured (relative to clean unstained substrate, i.e. knitted polyester) using a Hunterlab Ultrascan XE reflectance spectrophotometer equipped with a UV filter at 420nm. Specular reflectance was included.
  • Polymer stability screening
  • To test for the resistance of a polymer to hydrolysis the sample was included in composition B and then stored at 60°C in sealed glass containers for up to 8 days. Periodically the sample was subjected to 1H NMR. Time to failure is defined as significant loss of polymer peaks as determined by examination of 1H-NMR aromatic signals in the region of 7.9 - 8.1 ppm, corresponding to the aromatic proton signals. We use the term 'significant' when the appearing (new, as they are the breakdown product) signals due to the small molecule aromatic signals are greater than the remaining (original polymer aromatic proton signals), which, we have defined as the failure point for a polymer. The compositions contained an amount of polymer sufficient to deliver to the wash when freshly prepared 50 ppm polymer and were buffered with TEA to pH 8. We have shown - see example 1 b and 1c - that the actual storage stability of a SRP is in line with that predicted by the accelerated test. The amount of polymer in 3 x (composition B) is 2.14% and in 5 x (composition A) is 3.75% wt.
  • Comparative Examples
  • To illustrate the problem we first tested some prior art and known through public use polymers. These included the polymer Texcare®SRN 170 as disclosed in WO2009/153184 . The results are given in Table 2. Table 2
    Polymer name Supplier active ingred (wt%) Probable building blocks Mn Time to failure (hrs)
    Texcare® SRN170 Clariant 70 PEG-(TA-PG) 1,702 24
    Texcare® SRN240 Clariant 40 PEG-(TA-PG) 7,220 72
    Texcare® SRN300 Clariant 100 PEG-(TA-PG)(TA-PEG) 11,512 24
    Marloquest® L235M Sasol 70 PEG-PG-(TA-PG) 2,815 24
    Marloquest® HSCB Sasol 70 PEG-(TA-EG) 3,311 24
    Repelotex® Crystal Rhodia 70 PEG-(TA-PG) 1,868 24
  • Of these, the only SRP with marginal acceptability is Texcare SRN®240. However, this polymer does not dissolve easily in alkaline detergent compositions comprising up to 40% surfactant and EPEI so it is difficult to form an isotropic liquid using it as levels in excess of 1%.
  • The following are preparative methods and screening test results for six polymers suitable for use in the invention:
  • Example 1 - Synthesis of PO block EO end-capped terephthalate/propane diol polyester using 2-stage reaction process
  • Figure imgb0015
  • Using a 3-necked 100 ml round bottom flask fitted with a digital thermometer, argon inlet and bubbler connected to an air condenser, dimethylterephthalate (3.88 g, 0.02 mol) and 1,2 propane diol (3.35 g, 0.04 mol) were weighed into the flask, which also contained a magnetic stirrer bar. Also added were the condensation catalyst titanium tetraisopropylate (0.004g, 1.4x10-5 mol) and sodium acetate (0.0074g, 9x10-5 mol).The contents of the flask were heated to 240°C to 260°C under a constant stream of argon and constant stirring. When the temperature of the molten mixture in the flask reached 160 °C, methanol was distilled off, indicating that polycondensation was occurring. Heating continued until the temperature of the mixture reached 240 °C, which was held for 3 hours. The contents of the flask was then allowed to cool to about 140 °C, at which point Antarox B500 (supplied by Rhodia) (6g, 0.003 mol) was added to the flask. Antarox B500 is a block copolymer with an n-butyl capped block of 50 ethylene oxide units polymerised with a block of 30 propylene oxide units. The propylene oxide end of the polymer is hydrophobic. The mixture was then reheated to 240 °C and held at this temperature for 1 hour. The product was purified by sublimation to remove any residual dimethylterephthalate. Final yield = 6.6g
    1H-NMR (CDCl3) - indicates n = 7.7
    TD-SEC (THF) - av Mn = 1,616; av Mw = 2,904; av PD = 1.8
    PD = polydispersity = Mw/Mn
  • Example 2 Synthesis of PO block EO end-capped terephthalate/2,3 butandiol polyester SRP using a 2-stage reaction process
  • Figure imgb0016
  • The 2,3-butandiol used was a mixture of the racemic and meso forms from Aldrich: B84904, 2,3-Butanediol, 98%, CAS no. 513-89-5.
  • Using a 3-necked 100 ml round bottom flask fitted with a digital thermometer, argon inlet and bubbler connected to an air condenser, dimethylterephthalate (11.64g, 59.94 mmol) and 2,3 butandiol (10.80g, 119.89 mmol) were weighed into the flask, which also contained a magnetic stirrer bar. Also added were the condensation catalyst titanium tetraisopropylate (3 drops) and sodium acetate (2 small spatulas). The contents of the flask were heated under a constant stream of argon and constant stirring. When the temperature of the molten mixture in the flask reached 160°C, methanol was distilled off, indicating that polycondensation was occurring. Heating continued until the temperature of the mixture reached 240°C, which was held for 2.75 hours. The contents of the flask was then allowed to cool to about 140°C, at which point Antarox B500 (supplied by Rhodia) (11.99g, 5.99 mmol) was added to the flask and a further 3 drops of titanium tetraisopropylate. The mixture was reheated to 250°C and held at this temperature for 2.5 hours. The product was purified by sublimation to remove any residual dimethylterephthalate. Final yield = 18.9g.
    1H-NMR (D2O) - Accelerated data in concentrated Laundry liquid Composition B buffered with TEA to pH 8 and held at 60°C for 8 days (using 1H-NMR as the polymer stability tracking tool) has shown the polymer of example 1 to be hydrolytically stable.
    TD-SEC (THF) - av Mn = 4,800; av Mw = 14,150; av PD = 2.95
  • Example 3 - Synthesis of Poly(ethylene glycol) methyl ether 2000 end-capped terephthalate/2,3 butandiol polyester using a 2-stage reaction process
  • Using a 3-necked 100ml round bottom flask fitted with a digital thermometer, argon inlet and bubbler connected to an air condenser, dimethylterephthalate (11.64g, 59.94 mmol) and 2,3 butandiol (10.80g, 119.89 mmol) were weighed into the flask, which also contained a magnetic stirrer bar. Also added were the condensation catalyst titanium tetraisopropylate (3 drops) and sodium acetate (2 small spatulas). The contents of the flask were heated under a constant stream of Argon and constant stirring. When the temperature of the molten mixture in the flask reached 160°C, methanol was distilled off, indicating that polycondensation was occurring. Heating continued until the temperature of the mixture reached 220°C, which was held for 3 hours. The contents of the flask was then allowed to cool to about 140°C, at which point Poly(ethylene glycol) methyl ether 2000 (11.99g, 5.99 mmol) was added to the flask and a further 2 drops of titanium tetraisopropylate. The mixture was then heated to 250°C and held at this temperature for 3 hours. The product was purified by sublimation to remove any residual dimethylterephthalate. Final yield = 20.0g
    Figure imgb0017
  • Characterisation of polymer of Example 3:
    • TD-SEC (THF) - av Mn = 3,400; av Mw = 4,230; av PD = 1.23
  • The polymer of Example 3 was shown to be hydrolytically stable in concentrated Laundry liquid Composition B buffered with TEA to pH 8 at 60°C for 8 days (using 1H-NMR (D2O) as the polymer stability tracking tool).
  • Example 4 - Synthesis of Poly(ethylene glycol) methyl ether 2000 end-capped terephthalate/1,2 propandiol (80 mol.%) / 2,3-butandiol (20 mol.%) polyester using a 2-stage reaction process
  • Using a 3-necked 100ml round bottom flask fitted with a digital thermometer, argon inlet and bubbler connected to an air condenser, dimethylterephthalate (10.0g, 51.50 mmol) and 1,2 propandiol (6.27g, 82.40 mmol) and 2,3-butandiol (1.86g, 20.60 mmol) were weighed into the flask, which also contained a magnetic stirrer bar. Also added were the condensation catalyst titanium tetraisopropylate (3 drops) and sodium acetate (1 small spatula). The contents of the flask were heated under a constant stream of argon and constant stirring. When the temperature of the molten mixture in the flask reached 160°C, methanol was distilled off, indicating that polycondensation was occurring. Heating continued until the temperature of the mixture reached 220°C, which was held for 3 hours. The contents of the flask was then allowed to cool to about 140°C, at which point Poly(ethylene glycol) methyl ether 2000 (10.30g, 5.15 mmol) was added to the flask and a further 3 drops of titanium tetraisopropylate. The mixture was then heated to 250°C and held at this temperature for 2 hours. The product was purified by sublimation to remove any residual dimethylterephthalate. Final yield = 14.5g
    Figure imgb0018
  • Characterisation of Polymer of Example 4:
    • 1H-NMR (d6-acetone) - Composition PO:BO = 85.9:14.1
    • Note that the theoretical ratio of 80:20 is found to be 86:14 by this NMR study.
    • TD-SEC (THF) - av Mn = 2,130; av Mw = 6,890; av PD = 3.24
    Figure imgb0019
  • The polymer of Example 4 was shown to be hydrolytically stable in concentrated Laundry liquid Composition B buffered with TEA to pH 8 at held at 60°C for 8 days (using 1H-NMR as the polymer stability tracking tool).
  • Example 5 - Synthesis of Poly(ethylene glycol) methyl ether 2000 end-capped terephthalate/1,2 propandiol (60 mol.%) / 2,3-butandiol (40 mol.%) polyester using a 2-stage reaction process
  • Using a 3-necked 100ml round bottom flask fitted with a digital thermometer, argon inlet and bubbler connected to an air condenser, dimethylterephthalate (10.0g, 51.50 mmol) and 1,2 propandiol (4.70g, 61.80 mmol) and 2,3-butandiol (3.71 g, 41.20 mmol) were weighed into the flask, which also contained a magnetic stirrer bar. Also added were the condensation catalyst titanium tetraisopropylate (3 drops) and sodium acetate (1 small spatula). The contents of the flask were heated under a constant stream of Argon and constant stirring. When the temperature of the molten mixture in the flask reached 160 °C, methanol was distilled off, indicating that polycondensation was occurring. Heating continued until the temperature of the mixture reached 200 °C, which was held for 2 hours. The contents of the flask was then allowed to cool to about 140 °C, at which point Poly(ethylene glycol) methyl ether 2000 (10.30g, 5.15 mmol) was added to the flask and a further 3 drops of titanium tetraisopropylate. The mixture was then heated to 250°C and held at this temperature for 2 hours. The product was purified by sublimation to remove any residual dimethylterephthalate.
    Final yield = 13.6g.
    Figure imgb0020
    1H-NMR (D2O) - The polymer of example 5 was shown to be hydrolytically stable in concentrated Laundry liquid Composition B buffered with TEA to pH 8 and held at 60°C for 8 days (using 1H-NMR as the polymer stability tracking tool).
  • Characterisation:
    • 1H-NMR (d6-acetone) - Composition PO:BO = 70.3:29.7
    • Note that the theoretical ratio of 60:40 is found to be 70:30 by this NMR study.
    • TD-SEC (THF) - av Mn = 2,910; av Mw = 10,530 av PD = 3.61
    Figure imgb0021
    Example 6 - Synthesis of Poly(ethylene glycol) methyl ether 2000 end-capped terephthalate/1,2 propandiol polyester using a 2-stage reaction process
  • Using a 3-necked 100ml round bottom flask fitted with a digital thermometer, argon inlet and bubbler connected to an air condenser, dimethylterephthalate (10.0g, 51.50 mmol) and 1,2 propandiol (7.84g, 103.00 mmol) were weighed into the flask, which also contained a magnetic stirrer bar. Also added was the condensation catalyst titanium tetraisopropylate (3 drops). The contents of the flask were heated under a constant stream of argon and constant stirring. When the temperature of the molten mixture in the flask reached 160°C, methanol was distilled off, indicating that polycondensation was occurring. Heating continued until the temperature of the mixture reached 220°C, which was held for 2 hours. A further amount of 1,2 propandiol (2.0g, 26.28 mmol) was added due to the loss by evaporation. The polymerisation was heated for a further 1 hour. The contents of the flask was then allowed to cool to about 140°C, at which point Poly(ethylene glycol) methyl ether 2000 (10.30g, 5.15 mmol) was added to the flask and a further 3 drops of titanium tetraisopropylate and 1,2 propandiol (1.0g, 13.15 mmol. The mixture was then heated to 240°C and held at this temperature for 2 hours. The product was purified by sublimation to remove any residual dimethylterephthalate. Final yield = 13.3g
    Figure imgb0022
    TD-SEC (THF) - av Mn = 2,700; av Mw = 7,650; av PD = 2.83
  • The polymer of example 6 was shown to be hydrolytically stable in concentrated Laundry liquid composition B buffered with TEA to pH 8 (using 1H-NMR as the polymer stability tracking tool).
  • Example 1 a
  • Freshly prepared polymer of Example 1 was included in detergent composition A such that the wash liquor concentration of soil release polymer was 100ppm. Comparative example C used half that level of Texcare® SRN170. The effectiveness of the SRP is indicated by a low ΔE in Table 3. Table'3
    Example ΔE
    Example 1a using Polymer of example 1 0.62
    Comparative example C 4.7
  • Thus it appears that the Example 1 polymer with polydispersity less than 3 has excellent soil release properties.
  • This polymer has been shown to be hydrolytically stable in concentrated Laundry liquid composition B buffered with TEA to pH 8 (using 1 H-NMR -D2O-as the polymer stability tracking tool).
  • Examples 1b and 1c and comparative examples D and E
  • The polymer of Example 1 was tested for soil release properties after storage in (8 days at 60°C) and delivery from detergent compositions A (Example 1 b) and B (Example 1c) over a range of pH. Control compositions using Texcare SRN®170 were made up as comparative examples D and E. Samples were stored in closed screw-top glass jars in oven at either 60°C for 8 days, or 37°C for 8 weeks.
    • Polymer levels (based on level before storage) = 50 ppm
    • Data values given in Tables 4 and 5 are ΔE (ΔE = 0 = complete DMO removal; ΔE = 42 for washed stain with no SRP in pre-wash formulation).
    Table 4 (60°C)
    pH Comparative Example D (Texcare SRN 170 in comp A) Example 1 b (Example 1 polymer in comp A) Comparative Example E (Texcare SRN 170 in comp B) Example 1c (Example 1 polymer in comp B)
    6.5 6.7 2 6.8 2.3
    7.5 22.4 2.1 18.2 2.4
    8.5 35.1 16 36.1 15.4
  • Comparative example D was repeated using Texcare®SRN300 in place of Texcare® SRN170. The performance after storage under acidic conditions gave an excellent ΔE of 0.5. However, after storage at pH 8.5 this dropped to 32.8. A ΔE value greater than 5 is unacceptable. Table 5 (37°C)
    pH Comparative Example D (Texcare SRN 170 In A) Example 1b (Example 1 polymer in comp A) Comparative Example E (Texcare SRN 170 in comp B) Example 1c (Example 1 polymer in comp B)
    6.5 2.3 1.1 3.0 1.5
    7.5 16.2 1.4 11.1 1.6
    8.5 37.7 29.0 38.9 23.8
  • At alkaline pH the Texcare SRN170 polymer performance drops significantly. In contrast the polymer according to the invention maintains excellent performance under alkaline conditions, particularly at a pH below 8.5, even after storage under those alkaline conditions in the presence of TEA.
  • Example 4a - Soil Release (DMO) evaluation:
  • The polymer of Example 4 was pre-dissolved/dispersed in Composition A (5x base). Two pre-washes were carried out prior to staining with DMO and subsequent washing for 30 mins in a tergotometer at 25°C. The experimental polymer was included such that wash liquor conc. was 100ppm. ΔE = 3.15 ± 0.65
    Figure imgb0023
  • The same composition with Texcare SRN170 @ 50 ppm: ΔE = 4.7 zero means complete stain removal , no removal is 42 .
    Figure imgb0024
  • Examples 4a, 5a and Comparative Example F showing Soil release performance after accelerated aging
  • Polymers from examples 4 and 5 and a comparative polymer, Texcare ®SRN170, were stored in concentrated detergent liquid composition A containing 1% TEA in closed screw-top glass jars in an oven at 60°C for 8 days. Then they were tested for soil release performance in tergotometers using an in wash polymer concentration of 50 ppm. The ΔE results are given in Table 6 below.
  • All polymers show excellent performance at pH 6.5; performance was also very good at pH 7.5 provided that the butandiol proportion was less than 40% of the total diol.
  • It was noted that after storage the compositions comprising the butane diol polymers showed better clarity of the liquid. Table 6
    pH E.g. 4a E.g. 5a E.g. F Texcare ®SRN170
    6.5 4.7 5.7 6.7
    7.5 6.3 19.2 22.4
    8.5 34.9 35.0 35.1
  • For comparison, a washed stain without SRP in the prewash has a ΔE value of 42. Complete removal of the stain gives a ΔE of zero.
  • At alkaline pH the Texcare® SRN170 polymer performance drops significantly. In contrast the polymers according to the invention maintain good performance under alkaline conditions, particularly at a pH below 8.5, even after storage under those alkaline conditions in the presence of TEA. The tested variation in the concentration of TEA does not appear to affect the result significantly.
  • Example 6a - Soil Release (DMO) evaluation:
  • The polymer of example 6 was included in composition A such that the wash liquor concentration of soil release polymer was 100ppm.
  • The DMO removal effectiveness of the SRP is indicated in Table 7 by a low ΔE. We have found that there is a good correlation between the 8 day at 60°C accelerated test and the 8 week at 37°C data for polymer stored in compositions A and B. Table 7
    Composition and polymer Storage ΔE
    Comp A with Texcare®SRN 240 Fresh 1.2
    Comp A with Polymer Example 6 Fresh 1.5
    Comp A with Texcare®SRN 240 after 8 wks @ 37 °C / TEA pH 8 35
    Comp A with Polymer Example 6 8 days @ 60 °C / TEA pH 7.5 2.3
    Texcare® SRN170 @ 50 ppm Fresh 4.7
  • From nmr spectra we have concluded that the Example 6 polymer using PEG 2K as the endcap looks to be very similar to Texcare® SRN 240 apart from the ratio of the end block(s) to the polymer mid block. Evidence suggests that the Polymer of example 1 has a longer mid block. The nmr analysed difference in mid blocks between Texcare®SRN240 and the polymer of Example 1 is that the ratio of the end block units to the mid block repeat n for Texcare®SRN 240 is 15 to 22, whereas the ratio for the polymer of example 6 is about half this at 7 to 9. The value of n may be calculated assuming one or two end blocks per polymer chain. If there are two end blocks each with say 45 EO units then the size of the mid blocks and consequently the value of n is doubles compared to a polymer with only one end block of 45 EO units.
  • Texcare® SRN 240, does not appear to have any EO in the polymer mid block, but we do see higher intensity signals due to PEO end block(s), which, when, when ratioed with the methoxy end cap, come to about 42 repeat units, which appears to indicate that the manufacturer (Clariant) used a MeO-PEG 2K as the end cap.
  • Texcare® SRN170 has been identified as mPEG750 end blocks and PO in mid block.
  • Texcare® SRN 300 contains EO and PO in the polymer mid block. Also see higher intensity signals for PEO, which could be from a long PEO incorporated in the mid block and/or from the end block.
  • Texcare® SRN 240 shows slightly better hydrolytic stability than Texcare® SRN 300 with TEA at pH 7 in Composition B, but both fail dramatically at pH 8. The same is true for Texcare® SRN170.
  • This contrasts with the improved stability at pH 8 using TEA that we have seen with the Example 6 polymer.
  • Example 6b
  • Example 6b is a composition, comprising polymer 6 in base composition A and comparative composition F is a composition comprising the Texcare SRN®170 polymer used in WO2009/153184 also in base composition A. These compositions were stored for 8 days in sealed glass containers in an oven at 60°C to allow the polymer to be exposed to accelerated conditions where it may undergo hydrolysis, with consequent reduction of the soil release performance. Then the potentially decomposed compositions were wash tested. The results are given in table 8. The method used was the same as for Example 6a except that the polymer concentration was reduced to 50ppm in the wash.
  • Whilst the theoretical level of polymer dosed to the wash is stated to be 50ppm the actual level used after storage would have been lower due to polymer degradation during storage. Table 8
    pH Example 6b (Polymer of Example 6 in Composition A) Comparative example F (Texcare®SRN170 in Composition A)
    6.5 4.1 6.7
    7.5 2.3 22.4
    8.5 34.9 35.1
  • Examples 7 to 17 are alkaline isotropic detergent liquid compositions comprising the stable soil release polymers described above. Table 9
    Formulation E.g. 7 E.g. 8 E.g. 9 E.g. 10 E.g. 11
    Material % as 100% % as 100% % as 100% % as 100% % as 100%
    LAS Acid 4.85 8.49 8.49 7.26 6.97
    SLES 3EO 2.42 4.24 4.24 3.59 3.44
    NI 7EO 7.28 12.74 12.74 10.85 10.41
    Prifac® 5908 0.85 1.50 1.50 2.56 2.46
    Empigen® BB 0.86 1.50 1.50 1.50 1.50
    EPEI 3.10 5.50 5.50 5.50 5.50
    SRP1 3.75
    SRP2 2.10
    SRP3 3.75
    SRP4 3.68
    SRP5 3.68
    NaOH 0.07 0.07 0.07
    TEA 2.00 3.50 3.50
    MPG 15.00 20.00 20.00 15.38 14.76
    Glycerine 4.27 4.10
    Dequest® 2010 2.62 2.00
    Fluorescer 0.10 0.10
    Protease 1.75 1.75
    Stainzyme® 12L 0.700 0.700
    Carezyme® 1000L
    Lipex® or Lipoclean® 100L 2.00 3.00 3.00 3.00* 3.00*
    Mannaway® 0.70 0.70
    PCF 0.25 0.25 0.25 0.21 0.20
    Preservative 0.16 0.01 0.01
    Perfume 1.39 2.43 2.43
    Water and impurities 57.67 29.77 27.15 balance balance
    TOTAL 100 100 100 100 100
    *A 3% hole was left in the base to accommodate lipase enzyme.
  • In examples 7 to 17:
    • SRP1 is the polymer of Example 1
    • SRP2 is the polymer of Example 2
    • SRP3 is the polymer of Example 3
    • SRP4 is the polymer of Example 4
    • SRP5 is the polymer of Example 5
    • SRP6 is the polymer of Example 6
    Table 10
    Formulation 12 13 14 15 16 17
    Material % as 100% % as 100% % as 100% % as 100% % as 100% % as 100%
    LAS Acid 7.22 4.81 4.81 3.21 3.21 14.17
    SLES 1 EO 9.02 6.01 6.01 4.01 4.01 8.97
    NI 7EO 1.81 1.20 1.20 0.80 0.80
    Empigen® BB 0.86 0.86 0.57 0.86 0.38 0.86
    EPEI 3.10 3.10 2.07 3.10 1.38 3.10
    SRP1 2.10 2.10
    SRP2 1.40 2.10
    SRP6 0.93 2.10
    NaOH 0.93 0.62 0.62 0.27 0.27 1.40
    TEA 4.00
    Citric Acid Solution 1.25 1.25 1.25 1.25 1.25 1.00
    MPG 4.91 3.27 3.27 2.18 2.18 5.00
    Fluorescer 0.20 0.20 0.20 0.20 0.20 0.20
    Savinase® Ultra 16L Ex 2.00 2.00 2.00 2.00 2.00 2.00
    Colorant 0.003 0.003 0.00 0.00 0.003 0.003
    Perfume 0.98 0.98 0.98 0.98 0.98 0.98
    Water and minors balance balance balance balance balance balance
    Total 100.00 100.00 100.00 100.00 100.00

    Claims (16)

    1. An aqueous alkaline isotropic concentrated detergent liquid composition with an undiluted pH of at least 7.8 and at most 9 comprising:
      a) 10 to 60 wt% non-soap surfactant,
      b) 0 to 20 wt% hydrotrppe,
      c) 0 to 4 wt% soap.
      d) 0 to 10 wt% nonionic EPEI (ethoxylated polyethylene imine),
      e) at least 1 wt% triethanolamine,
      characterised In that dissolved in the alkaline isotropic liquid there is:
      f) at least 1 wt%, preferably at least 1,6 wt% of a polyester substantive nonionic soil release polymer of the type E-M-L-E, where the midblock M is connected to a general hydrophilic end block E and blocks E each comprise capped oligomers of polyethylene glycol remote from the midblock, with at least 10 EO (ethylene oxide) repeat units, the end blocks being free from ester bonds,
      either directly or via linking moiety L which comprises the motif:
      B-Ar-B where B is selected from ester moieties and Ar Is 1,4 phenylene, and midblock M comprises the motif:
      Figure imgb0025
      wherein R1 and R2 may be the same or different selected from C1-C4 alkyl, C1-C4 alkoxy and Hydrogen, provided that R1 and R2 may not both be hydrogen, n is at least 2, preferably more than 5, the ester bonds may be formed the other way around (not shown), if they are so reversed then all of them will be so reversed,
      and in which the polymer (f) has the general formula (I):
      X-[(EO)q1-block-(PO)p]-[(A-G1-A-G2)n)-B-G1-B-[(PO)p-block-(EO)q2] -X (I) where EO is ethylene oxide (CH2CH2O);
      Where PO is at least 80 wt% propylene oxide (CH2CH(CH3)O), and preferably 100% PO units;
      where p is a number from 0 to 60, and when p is not zero is preferably from 2 to 50, more preferably from 5 to 45, even more preferably from 6 to 40, yet more preferably from 7 to 40 and most preferably from 8 to 40, even from 11 to 35;
      where q1 and q2 is a number from 6 to 120, preferably 18 to 80, most preferably 40 to 70, provided that q2 is greater than p and preferably q2 is at least 1.5 times as large as p;
      where X is a capping moiety, preferably selected from C1-4 alkyl, branched and unbranched;
      where n is a number from 2 to 26; preferably 5 to 15;
      A and B are selected from ester moieties;
      when the moieties A and B adjacent to the PO blocks are esters then it is preferred that p is not zero,
      alternatively, it is preferred that the ratio of (q1+q2):n is from 4 to 10 and that q2 is from 40 to 120;
      G1 comprises 1,4 phenylene;
      G2 is substituted ethylene,
      the polymer (f) being modified by at least one of modifications (I) to (iv):
      (i) p is a number from 2 to 50, more preferably from 5 to 45, even more preferably from 6 to 40, yet more preferably from 7 to 40 and most preferably from 8 to 40, even from 11 to 35;
      or
      (ii) the ratio of (q1+q2):n is from 4 to 10 and that q2 is from 40 to 120;
      or
      (iii) moieties G5 are all subsittuted ethylene of formula (II)
      Figure imgb0026
      wherein G3 and G4 are selected from Hydrogen, C1-4 alkyl and C1-4 alkoxy, provided that at least one of G3 and G4 is not hydrogen and that at least 10% of the groups G2 have neither G3 nor G4 as hydrogen,
      or
      (iv) combinations of two or three of modifications hindering strategies (i), (it) and (iil),
      wherein the composition comprising the polymer provides soil release less than a ΔE of 5 with DMO on woven polyester after storage of the polymer in the detergent composition at 60°C for 8 days at a pH >7.5.
    2. A composition according to claim 1 in which the polymer (f) comprises a polyester substantive nonionic soil release polymer of the type E-M-L-E, where the midblock M comprises the motif:
      Figure imgb0027
      Wherein R1 and R2 may be the same or different selected from C1-C4 alkyl and Hydrogen, provided that R1 and R2 may not both be hydrogen, n is at least 2, preferably more than 5, the ester bonds may by formed the other way around (not shown), if they are so reversed then all of them will be so reversed,
      and the two end blocks E each comprise alkyl capped oligomers of polyethylene glycol remote from the midblock, with at least 10 EO repeat units, the end blocks being free from ester bonds,
      and L is a linking moiety B-Ar-B where B is an ester moiety and Ar is 1,4 phenylene,
      wherein the polymer has a molecular weight Mw of at least 4000.
    3. A composition according to claim 1 or claim 2 where R1 and R2 are selected from H and Me.
    4. A composition according to any preceding claim comprising at least 5 wt% anionic surfactant.
    5. A composition according to any preceding claim comprising SLES (sodium lauryl ether sulphate).
    6. A composition according to any preceding claim comprising LAS (linear alkyl benzene sulphonate), the LAS being neutralised from LAS acid, at least in part, with TEA (triethanolamine).
    7. A composition according to any preceding claim wherein the liquid has an undiluted pH of at most 8.4, even at most 8.2.
    8. A composition according to any preceding claim comprising at most 1.5 wt% soap surfactant.
    9. A composition according to any preceding claim comprising at most 15 wt%, preferably at most 12 wt% hydrotrope.
    10. A composition according to any preceding claim comprising at least 1 wt% of nonionic EPEI (d) and a total of at least 3 wt% of (d) and the hindered soil release polymer (f).
    11. A composition according to any preceding claim comprising at least one enzyme.
    12. A composition according to any preceding claim comprising at least 1 wt% sequestrant.
    13. A composition according to any preceding claim wherein when G3 and G4 are not hydrogen then they are methyl moieties, preferably the methyl moieties are arranged in syn configuration on the ethylene backbone -CH-CH- of moieties G2.
    14. A composition according to claim 1 in which polymer (f) is a soil release polymer with the formula (1a):

              X-[(EO)q-block(-(PO)p]-(A-G1-A-G2)n]-A-G1-A-[(PO)p-block-(EO)q]-X     (Ia)

      where EO is ethylene oxide (CH2CH2O);
      where PO is propylene oxide (CH2CH(CH3)O);
      Where p Is a number from 2 to 50, more preferably from 5 to 45, even more preferably, from 6 to 40, yet more preferably from 7 to 40 and most preferably from 8 to 40, even from 11 to 35;
      Where q is a number from 6 to 120, preferably 18 to 80, most preferably 40 to 70, provided that q is greater than p;
    15. A composition according to claim 1 in which the polymer (f) has the formula (Ib) :

              X-[(EO)q-blook-(PO)p]-[(A-G1-A-G2)n]-A-G1-A-[(PO)p-block-(EO)q] -X     (lb)

      where EO is ethylene oxide (CH2CH2O);
      where PO is propylene oxide (CH2CH(CH3)O);
      where n is a number from 2 to 26
      where p is a number from 0 to 60, when present preferably from 2 to 50, more preferably from 5 to 45, even more preferably from 6 to 40, yet more preferably from 7 to 40 and most preferably from 8 to 40, even from 11 to 35;
      where q is a number from 6 to 120, preferably 18 to 80, most preferably 40 to 70, provided that q is greater than p;
      where X is a capping moiety, preferably selected from C1-4 alkyl, branched and
      unbranched;
      and the moieties G2 are all substituted ethylene of formula (IIb)
      Figure imgb0028
      wherein G3 and G4 are selected from Hydrogen, C1-4 alkyl and C1-4 alkoxy, provided that at least one of G3 and G4 is not hydrogen and that at least 10% of the groups G2 have neither G3 nor G4 as hydrogen. Preferably when G3 and G4 are not hydrogen then they are methyl moieties. Preferably the non H substituents, more preferably the methyl moieties, are arranged in syn configuration on the ethylene backbone -CH-CH- of moieties G2.
    16. A composition according to claim 1 in which the polymer (f) has formula (Ic)

              X-[(EO)q1]-[(A-G1-A-G2)n]-[A-G1-A]-[(EO)q2] -X     (Ic)

      where the end blocks consist of q1 and q2 units of ethylene oxide (EO) or (CH2H2O);
      where q1 is 0, or from 40 to 120, and q2 Is from 40 to 120;
      where X is a capping moiety, preferably selected from C1-4 alkyl, branched and unbranched;
      where n is a number from 5 to 26;
      where the linking moieties A are esters;
      characterised in that the ratio of (q1+q2):n is from 4 to at most 10, preferably from 5 to 8.
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    CN103347928A (en) 2013-10-09
    ZA201305194B (en) 2014-09-25
    EP2670788A1 (en) 2013-12-11
    AU2012213597B2 (en) 2014-08-28
    CL2013002181A1 (en) 2014-06-27
    MY163351A (en) 2017-09-15
    WO2012104159A1 (en) 2012-08-09
    AU2012213597A1 (en) 2013-07-25
    AU2012213597A8 (en) 2014-08-14
    CN103347928B (en) 2016-10-12

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