EP2670788B1 - Alkalische flüssigreinigungszusammensetzungen - Google Patents

Alkalische flüssigreinigungszusammensetzungen Download PDF

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Publication number
EP2670788B1
EP2670788B1 EP12700850.6A EP12700850A EP2670788B1 EP 2670788 B1 EP2670788 B1 EP 2670788B1 EP 12700850 A EP12700850 A EP 12700850A EP 2670788 B1 EP2670788 B1 EP 2670788B1
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European Patent Office
Prior art keywords
polymer
moieties
composition according
hydrogen
block
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EP12700850.6A
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English (en)
French (fr)
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EP2670788A1 (de
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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Priority to EP12700850.6A priority Critical patent/EP2670788B1/de
Priority to PL12700850T priority patent/PL2670788T3/pl
Publication of EP2670788A1 publication Critical patent/EP2670788A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • 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.
  • SRP soil release polymer
  • 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.
  • 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.
  • polyester SRPs of the type E-M-E are 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.
  • mPEG methyl endcapped polyethylene glycol
  • 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.
  • 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.
  • 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.
  • an aqueous alkaline isotropic concentrated detergent liquid composition with an undiluted pH of at least 7.8 and at most 9 comprising:
  • 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 ⁇ E 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.
  • 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.
  • 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%.
  • the alkaline isotropic concentrated detergent liquid composition comprises at. least 5 wt% anionic surfactant.
  • the liquid may comprise LAS, SLES, Nonionic and optionally betaine, the LAS being neutralised from LAS acid, at least in part, with TEA,
  • 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.
  • 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.
  • 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.
  • 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.
  • the amount of fatty acid added to the composition to be kept to a maximum of 1.5wt% to facilitate the hydrotrope levels claimed, especially at the lower levels of hydrotrope.
  • 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.
  • polyester soil release polymers (f) are selected from those having the general formula (I): X-[(EQ) q1 -block-(PO) p ]-[(A-G 1 -A-G 2 ) n ]-B-G 1 -B-[(PO) p -block-(EO) q2 ]-X (I)
  • moieties G 2 are all ethylene of formula (II) wherein G 3 and G 4 are selected from Hydrogen, C 1-4 alkyl and C 1-4 alkoxy, provided that at least one of G 3 and G 4 is not hydrogen and that at least 10% of the groups G 2 have neither G 3 nor G 4 as hydrogen.
  • G 3 and G 4 are not hydrogen then they are methyl moieties.
  • the non H substituents, more preferably the methyl moieties are arranged in syn configuration on the ethylene backbone -CH-CH- of moieties G 2 .
  • n is not necessarily a whole number for the polymer in bulk. The same holds true, to a lesser extent, for p, q 1 and q 2 . Since p and q 1 and q 2 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).
  • the moiety [(A-G 1 -A-G 2 ) n ]-B-G 1 -B]- forms the polymer mid block or backbone and is described in more detail below.
  • the moieties A and B nearest to any PO blocks are esters.
  • 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.
  • q 2 , and q 1 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.
  • the moieties G 1 are 1,4 phenylene for maximum fabric substantivity of the mid block motif.
  • a preferred diol to form the desired group G 2 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.
  • 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.
  • 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-G 1 -A-G 2 ) n -B-G 1 -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).
  • the mid block [(A-G 1 -A-G 2 ) r ]-B-G 1 -B (-M-L-) is responsible for making the polymer fabric substantive, particularly towards polyester fabrics.
  • 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:
  • the A moieties consist entirely of such ester moieties.
  • the G 1 moieties comprise 1,4-phenylene moieties.
  • 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.
  • 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 G 2 moieties are substituted ethylene moieties having C 1-A alkyl or alkoxy substituents, The G 2 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.
  • suitable substituted ethylene moieties are the monomethyl substituted G 2 formed from 1,2-propylene diol, and the dimethyl substituted G 2 formed from 2,3 butylene diol.
  • 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.
  • 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.
  • 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.
  • the degree of partial replacement of G 1 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 G 1 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.
  • G 2 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.
  • 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 G 1 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.
  • 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.
  • polyesters used in fibre making typically have a much higher molecular weight with n from 50 to 250.
  • n ranges from 2 to 16, preferably 4 to 9.
  • the larger the n value the less soluble Is the polymer.
  • G 2 moieties are essentially substituted ethylene moieties, selected from substituted ethylene of formula (II) wherein G 3 and G 4 are selected from Hydrogen, C1-4 alkyl and C1-C4 alkoxy provided that at least one of G 3 and G 4 is not hydrogen and that at least 10 mol%, preferably at least 20 mol% of the groups G 2 have neither G 3 nor G 4 as hydrogen.
  • G 3 and G 4 are not hydrogen then they are methyl moieties.
  • the non Hydrogen substituents, more preferably the methyl moieties are arranged In syn configuration on the ethylene backbone.
  • 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.
  • each X is C 1-4 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;
  • the polymeric soil release agents according to the present invention have the formula (V): X-[(EO) q (PO) p ]-[(OC(O)-G 1 -C(O)O-G 2 ) n ]-OC(O)-G 1 -C(O)O-[(PO) p (EO) q ]-X (V) wherein :
  • 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.
  • 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.
  • 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.
  • the PO block should comprise at least 80% by number PO units.
  • a stat block PO/EO block confers some improvement of resistance to hydrolysis of the end ester moieties A and B.
  • it comprises as much as possible of the ester bond hindering PO units.
  • 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 C 1 -C 4 alkyl.
  • X is preferably methyl, ethyl, or n-butyl and most preferably methyl or n-butyl.
  • q is at least 6, and is preferably at least 10.
  • the value for q usually ranges from 18 to 80.
  • the value for q is in the range of from 30 to 70, preferably 40 to 70.
  • 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-[(OCH 2 CH 2 ) q -]-block-[(OCH 2 CH(CH 3 )) p ]-[(OC(O)-G 1 -C(O)O-G 2 ) n ]-OC(O)-G 1 -C(O)O-[((CH 3 )CHCH 2 O) p -]-block-[(CH 2 CH 2 O) q ]-X (VIII) wherein the G 1 moieties are all 1,4-phenylene moieties; the G 2 moieties are all substituted ethylene moieties, each X is C 1-4 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.
  • 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.
  • 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.
  • 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.
  • q2 is at least 40, preferably about 45.
  • 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).
  • 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): where n is at least 7.
  • 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.
  • 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.
  • 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.
  • the optional PO/EO end blocks are preformed by anionic polymerisation of propylene oxide using a preformed mono-functional PEG as the initiator.
  • a preformed mono-functional PEG as the initiator.
  • 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.
  • 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.
  • 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.
  • 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.
  • polyester recognition motif with the ester moieties reversed if the starting materials are aliphatic biscarboxylic acids and aromatic bisalcohol.
  • 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%.
  • 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 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%.
  • the anionic surfactant forms the majority of the non soap surfactant (a).
  • alkyl sulphonates are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 .
  • 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.
  • composition comprises an alkyl polyethoxylate sulphate anionic surfactant of the formula (I): RO(C 2 H 4 O) x SO 3 - 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.
  • formula (I): RO(C 2 H 4 O) x SO 3 - 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.
  • 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;
  • SLES sodium lauryl ether sulphate
  • 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 surfactants include primary and secondary alcohol ethoxylates, especially C 8 -C 20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 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.
  • 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").
  • 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 C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • composition may comprise up to 10 wt% of an amine oxide of the formula (2): R 1 N(O)(CH 2 R 2 ) 2 (2)
  • R 1 is a long chain moiety each CH 2 R 2 are short chain moieties.
  • R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
  • R 1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
  • Preferred amine oxides have R 1 is C 8 -C 18 alkyl, and R 2 is H. These amine oxides are illustrated by C 12-14 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.
  • R 2 is H
  • R 2 may be CH 2 OH, 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) 2 R 1 (3) where R 1 is C 12-16 alkyl, preferably C 12-14 alkyl; Me is a methyl group.
  • 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.
  • surfactants than the preferred LAS, SLES, nonionic and zwitterionic (betaine) may be added to the mixture of detersive surfactants.
  • cationic surfactants are preferably substantially absent.
  • alkyl sulphate surfactant may be used, especially the non-ethoxylated C 12-15 primary and secondary alkyl sulphates.
  • 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.
  • 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.
  • dye transfer inhibition polymers 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.
  • 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.
  • 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.
  • At least one or more enzymes may be present in the compositions.
  • 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.
  • 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 TM from Novozymes.
  • 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 .
  • 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 LipolaseTM and Lipolase UltraTM, LipexTM and Lipoclean TM (Novozymes A/S).
  • lipase In addition to or as an alternative to lipase one or more other enzymes may be present. However lipase is particularly preferred.
  • 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:
  • phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
  • phospholipase is an enzyme which has activity towards phospholipids.
  • Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
  • Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
  • phospholipases A 1 and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
  • lysophospholipase or phospholipase B
  • Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
  • proteases 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 AlcalaseTM, SavinaseTM, PrimaseTM, DuralaseTM, DyrazymTM, EsperaseTM, EverlaseTM, PolarzymeTM, and KannaseTM, (Novozymes A/S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM, PurafectTM, Purafect OxPTM , FN2TM, and FN3TM (Genencor International Inc.).
  • 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.
  • Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of 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 .
  • amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 .
  • cellulases include CelluzymeTM, CarezymeTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation).
  • Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C . cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
  • Pectate lyases also called polygalacturonate lyases
  • 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 ).
  • 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 .
  • pectatel lyases are disclosed in WO 99/27083 and WO 99/27084 .
  • pectate lyases derived from Bacillus licheniformis
  • US patent no. 6,284,524 which document is hereby incorporated by reference
  • 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).
  • alkaline pectate lyases examples include BIOPREPTTM and SCOURZYMETM L from Novozymes A/S Denmark.
  • Mannanase examples include mannanases of bacterial and fungal origin.
  • 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.
  • 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.
  • mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO 99/64619 .
  • Bacillus sp. mannanases concerned in the Examples in WO 99/64619 .
  • mannanases examples include MannawayTM 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.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
  • fluorescer in the compositions.
  • 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.
  • Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-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.
  • 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).
  • 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 WO02/48
  • Photobleaches may also be employed.
  • 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.
  • the phthalocyanin has 1-4 SO 3 X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba).
  • the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10wt%, preferably about 0.001 to about 5wt%.
  • 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.
  • 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.
  • 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 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.
  • Direct 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.
  • bis-azo or tris-azo dyes are used.
  • the direct dye is a direct violet of the following structures: or wherein:
  • 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.
  • the direct dye is present at 0.000001 to 1 wt% more preferably 0.00001 wt% to 0.0010 wt% of the composition.
  • the direct dye may be covalently linked to the photobleach, for example as described in WO2006/024612 .
  • Cotton substantive acid dyes give benefits to cotton containing garments.
  • Preferred dyes and mixes of dyes are blue or violet.
  • Preferred acid dyes are:
  • Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
  • non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
  • the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
  • 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.
  • the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
  • 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 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.
  • 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 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.
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • 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.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Thermphos and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • 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 TM .
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • DMO 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.
  • 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.
  • Composition A 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.
  • DMO dirty motor oil
  • ⁇ E 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.
  • composition B 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 1 H NMR. Time to failure is defined as significant loss of polymer peaks as determined by examination of 1 H-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.
  • 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.
  • TEA TEA to pH 8.
  • the amount of polymer in 3 x (composition B) is 2.14% and in 5 x (composition A) is 3.75% wt.
  • Texcare SRN®240 the only SRP with marginal acceptability is Texcare SRN®240.
  • 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%.
  • 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 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.
  • Example 3 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 1 H-NMR (D 2 O) as the polymer stability tracking tool).
  • Example 4 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 1 H-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
  • the polymer of example 6 was shown to be hydrolytically stable in concentrated Laundry liquid composition B buffered with TEA to pH 8 (using 1 H-NMR as the polymer stability tracking tool).
  • Example 1 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 ⁇ E in Table 3. Table'3 Example ⁇ E Example 1a using Polymer of example 1 0.62 Comparative example C 4.7
  • 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 -D 2 O-as the polymer stability tracking tool).
  • Example 1 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.
  • Comparative example D was repeated using Texcare®SRN300 in place of Texcare® SRN170.
  • the performance after storage under acidic conditions gave an excellent ⁇ E of 0.5. However, after storage at pH 8.5 this dropped to 32.8. A ⁇ E 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
  • the Texcare SRN170 polymer performance drops significantly.
  • 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.
  • a washed stain without SRP in the prewash has a ⁇ E value of 42.
  • Complete removal of the stain gives a ⁇ E of zero.
  • the Texcare® SRN170 polymer performance drops significantly.
  • 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.
  • 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 ⁇ E.
  • Table 7 Composition and polymer Storage ⁇ E 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
  • 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.
  • 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.
  • Examples 7 to 17 are alkaline isotropic detergent liquid compositions comprising the stable soil release polymers described above.

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Claims (16)

  1. Wässrige, alkalische, isotrope, konzentrierte flüssige
    Waschmittelzusammensetzung mit einem pH-Wert im unverdünnten Zustand von mindestens 7,8 und höchstens 9,
    die Folgendes aufweist:
    a) 10 bis 60 Gew.-% seifenfreies Tensid;
    b) 0 bis 20 Gew.-% Hydrotropikum;
    c) 0 bis 4 Gew.-% Seife;
    d) 0 bis 10 Gew.-% nichtionisches EPEI (ethoxyliertes Polyethylenimin);
    e) mindestens 1 Gew.-% Triethanolamin,
    dadurch gekennzeichnet, dass in der alkalischen isotropen Flüssigkeit Folgendes gelöst vorliegt:
    f) mindestens 1 Gew.-%, vorzugsweise mindestens 1,5 Gew.-% eines für Polyester substantivischen, nichtionischen, schmutzlösenden Polymers vom Typ E-M-L-E, wobei der mittlere Block M an einen im Allgemeinen hydrophilen Endblock E gebunden ist und die Blöcke E vom mittleren Block entfernt jeweils geschützte Oligomere von Polyethylenglycol mit mindestens 10 Struktureinheiten in Form von EO (Ethylenoxid) aufweisen, wobei die Endblöcke frei von Esterbindungen sind,
    entweder direkt oder über eine Brückeneinheit L, die die folgende Struktur hat:
    B-Ar-B, wobei B aus Estereinheiten ausgewählt ist und Ar gleich 1,4-Phenylen ist,
    und der mittlere Block M folgende Struktur hat:
    Figure imgb0029
    worin R1 und R2 gleich oder verschieden sein können und aus C1-C4-Alkyl, C1-C4-Alkoxy und Wasserstoff ausgewählt sind, mit der Maßgabe, dass R1 und R2 nicht beide Wasserstoff sein können, n mindestens 2, vorzugsweise mehr als 5 ist, die Esterbindungen anders herum gebildet sein können (nicht gezeigt), wenn sie so umgekehrt sind, dann sind alle von ihnen so umgekehrt,
    und wobei das Polymer (f) die allgemeine Formel (I) hat:

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

    worin EO Ethylenoxid (CH2CH2O) ist;
    wobei PO mindestens 80 Gew.-% Propylenoxid (CH2CH(CH3)O) ist, und vorzugsweise 100 % PO-Einheiten;
    wobei p eine Zahl von 0 bis 60 ist und wenn p nicht 0 ist, vorzugsweise 2 bis 50, stärker bevorzugt 5 bis 45, noch stärker bevorzugt 6 bis 40, noch stärker bevorzugt 7 bis 40 und besonders bevorzugt 8 bis 40, auch 11 bis 35 ist;
    wobei q1 und q2 eine Zahl von 6 bis 120, vorzugsweise von 18 bis 80, besonders bevorzugt von 40 bis 70 sind, mit der Maßgabe, dass q2 größer als p ist und vorzugsweise q2 mindestens 1,5 mal größer als p ist;
    wobei X eine schützende Einheit ist, die vorzugsweise aus verzweigtem und unverzweigtem C1-4-Alkyl ausgewählt ist;
    wobei n eine Zahl von 2 bis 26, vorzugsweise von 5 bis 15 ist;
    A und B aus Estereinheiten ausgewählt sind;
    wenn die Einheiten A und B, die an die PO-Blöcke angrenzen, Ester sind, dann ist es bevorzugt, dass p nicht 0 ist;
    nach einer anderen Ausführungsform ist es bevorzugt, dass das Verhältnis (q1 + q2):n gleich 4 bis 10 ist und dass q2 gleich 40 bis 120 ist;
    G1 1,4-Phenylen aufweist;
    G2 substituiertes Ethylen ist;
    wobei das Polymer (f) mit mindestens einer der Modifikationen (i) bis (iv) modifiziert ist:
    (i) p ist eine Zahl von 2 bis 50, stärker bevorzugt von 5 bis 45, noch stärker bevorzugt von 6 bis 40, noch stärker bevorzugt von 7 bis 40 und besonders bevorzugt von 8 bis 40, auch von 11 bis 35;
    oder
    (ii) das Verhältnis (q1 + q2):n ist gleich 4 bis 10, und q2 ist gleich 40 bis 120;
    oder
    (iii) die Einheiten G2 sind jeweils substituiertes Ethylen der Formel (II)
    Figure imgb0030
     wobei G3 und G4 aus Wasserstoff, C1-4-Alkyl und C1-4-Alkoxy ausgewählt sind, mit der Maßgabe, dass mindestens einer der Reste G3 und G4 kein Wasserstoff ist und dass mindestens 10 % der Reste G2 weder G3 noch G4 als Wasserstoff aufweisen;
    oder
    (iv) Kombinationen von zwei oder drei Strategien in Form der behindernden Modifikationen (i), (ii) und (iii);
    wobei die Zusammensetzung, die das Polymer aufweist, eine Schmutzlösung von weniger als ΔE gleich 5 mit DMO auf gewebtem Polyester nach einer Aufbewahrung des Polymers für 8 Tage bei 60 °C in der Waschmittelzusammensetzung bei einem pH-Wert > 7,5 bietet.
  2. Zusammensetzung nach Anspruch 1,
    wobei das Polymer (f) ein für Polyester substantivisches, nichtionisches, schmutzlösendes Polymer des Typs E-M-L-E aufweist,
    wobei der mittlere Block M die Struktur hat:
    Figure imgb0031
    worin R1 und R2 gleich oder verschieden sein können und aus C1-C4-Alkyl und Wasserstoff ausgewählt sind, mit der Maßgabe, dass R1 und R2 nicht beide Wasserstoff sein können, n mindestens 2, vorzugsweise mehr als 5 ist, die Esterbindungen anders herum ausgebildet sein können (nicht gezeigt), wenn sie so umgekehrt sind, dann sind alle von ihnen so umgekehrt,
    und die beiden Endblöcke E vom mittleren Block entfernt jeweils mit Alkyl geschützte Oligomere von Polyethylenglycol mit mindestens 10 EO-Struktureinheiten aufweisen, wobei die Endblöcke frei von Esterbindungen sind, und L eine Brückeneinheit B-Ar-B ist, wobei B eine Estereinheit ist und Ar gleich 1,4-Phenylen ist,
    wobei das Polymer ein Molekulargewicht Mw von mindestens 4000 hat.
  3. Zusammensetzung nach Anspruch 1 oder 2,
    wobei R1 und R2 aus H und Me ausgewählt sind.
  4. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die mindestens 5 Gew.-% anionisches Tensid aufweist.
  5. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die SLES (Natriumlaurylethersulfat) aufweist.
  6. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die LAS (lineares Alkylbenzolsulfonat) aufweist, wobei das LAS von LAS-säure zumindest teilweise mit TEA (Triethanolamin) neutralisiert ist.
  7. Zusammensetzung nach einem der vorstehenden Ansprüche,
    wobei die Flüssigkeit einen pH-Wert im unverdünnten Zustand von höchstens 8,4, auch höchstens 8,2 hat.
  8. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die höchstens 1,5 Gew.-% Tensid in Form von Seife aufweist.
  9. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die höchstens 15 Gew.-%, vorzugsweise höchstens 12 Gew.-% Hydrotropikum aufweist.
  10. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die mindestens 1 Gew.-% nichtionisches EPEI (d) und insgesamt mindestens 3 Gew.-% von (d) und dem gehinderten schmutzlösenden Polymer (f) aufweist.
  11. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die mindestens ein Enzym aufweist.
  12. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die mindestens 1 Gew.-% Komplexbildner aufweist.
  13. Zusammensetzung nach einem der vorstehenden Ansprüche,
    wobei, wenn G3 und G4 kein Wasserstoff sind, diese dann Methyleinheiten sind, wobei die Methyleinheiten vorzugsweise in syn-Konfiguration am Ethylengrundgerüst -CH-CH- der Einheiten G2 angeordnet sind.
  14. Zusammensetzung nach Anspruch 1,
    wobei das Polymer (f) ein schmutzlösendes Polymer mit der Formel (Ia) ist:

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

    wobei EO Ethylenoxid (CH2CH2O) ist;
    wobei PO Propylenoxid (CH2CH(CH3)O) ist;
    wobei p eine Zahl von 2 bis 50 ist, stärker bevorzugt von 5 bis 45, noch stärker bevorzugt von 6 bis 40, noch stärker bevorzugt von 7 bis 40 und besonders bevorzugt von 8 bis 40, auch von 11 bis 35 ist;
    wobei q eine Zahl von 6 bis 120, vorzugsweise von 18 bis 80, besonders bevorzugt von 40 bis 70 ist, mit der Maßgabe, dass q größer als p ist.
  15. Zusammensetzung nach Anspruch 1,
    wobei das Polymer (f) die Formel (Ib) hat:

            X-[(EO)q-Block-(PO)p]-[(A-G1-A-G2)n]-A-G1-A-[(PO)p-Block-(EO)q] -X     (Ib)

    wobei EO Ethylenoxid (CH2CH2O) ist;
    wobei PO Propylenoxid (CH2CH(CH3)O) ist;
    wobei n eine Zahl von 2 bis 26 ist;
    wobei p eine Zahl von 0 bis 60, wenn vorhanden vorzugsweise von 2 bis 50, stärker bevorzugt von 5 bis 45, noch stärker bevorzugt von 6 bis 40, noch stärker bevorzugt von 7 bis 40 und besonders bevorzugt von 8 bis 40, auch von 11 bis 35 ist;
    wobei q eine Zahl von 6 bis 120, vorzugsweise von 18 bis 80, besonders bevorzugt von 40 bis 70 ist, mit der Maßgabe, dass q größer als p ist;
    wobei X eine schützende Einheit ist, die vorzugsweise aus verzweigtem und unverzweigtem C1-4-Alkyl ausgewählt ist;
    und die Einheiten G2 jeweils substituiertes Ethylen der Formel (IIb) sind
    Figure imgb0032
     worin G3 und G4 aus Wasserstoff, C1-4-Alkyl und C1-4-Alkoxy ausgewählt sind, mit der Maßgabe, dass mindestens einer der Reste G3 und G4 kein Wasserstoff ist und dass mindestens 10 % der Reste G2 weder G3 noch G4 als Wasserstoff aufweisen; wenn G3 und G4 kein Wasserstoff sind, dann sind sie vorzugsweise Methyleinheiten; vorzugsweise sind die von H verschiedenen Substituenten, stärker bevorzugt die Methyleinheiten, in einer syn-Konfiguration am Ethylengrundgerüst -CH-CH- der Einheiten G2 angeordnet.
  16. Zusammensetzung nach Anspruch 1,
    wobei das Polymer (f) die Formel (Ic) hat:

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

    wobei die Endblöcke aus q1 und q2 Einheiten von Ethylenoxid (EO) oder (CH2CH2O) bestehen;
    wobei q1 gleich 0 oder 40 bis 120 ist und q2 gleich 40 bis 120 ist;
    wobei X eine schützende Einheit ist, die vorzugsweise aus verzweigtem und unverzweigtem C1-4-Alkyl ausgewählt ist;
    wobei n eine Zahl von 5 bis 26 ist;
    wobei die Brückeneinheiten A Ester sind;
    dadurch gekennzeichnet, dass das Verhältnis (q1 + q2):n gleich 4 bis höchstens 10, vorzugsweise 5 bis 8 beträgt.
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CN103347928B (zh) 2016-10-12
BR112013019386A2 (pt) 2020-10-27
CL2013002181A1 (es) 2014-06-27
PL2670788T3 (pl) 2015-08-31
BR112013019386B1 (pt) 2021-04-06
AU2012213597A1 (en) 2013-07-25
MY163351A (en) 2017-09-15
CN103347928A (zh) 2013-10-09
AU2012213597A8 (en) 2014-08-14
ZA201305194B (en) 2014-09-25
WO2012104159A1 (en) 2012-08-09
EP2670788A1 (de) 2013-12-11
AU2012213597B2 (en) 2014-08-28

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