EP2880143B1 - Konzentrierte flüssige reinigungsmittelzusammensetzungen - Google Patents

Konzentrierte flüssige reinigungsmittelzusammensetzungen Download PDF

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EP2880143B1
EP2880143B1 EP13733305.0A EP13733305A EP2880143B1 EP 2880143 B1 EP2880143 B1 EP 2880143B1 EP 13733305 A EP13733305 A EP 13733305A EP 2880143 B1 EP2880143 B1 EP 2880143B1
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EP
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Prior art keywords
composition according
surfactant
soil release
moieties
alkyl
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English (en)
French (fr)
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EP2880143A1 (de
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Julie Bennett
Alyn James Parry
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—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 concentrated aqueous alkaline liquid detergent compositions with low intrinsic foaming and in particular to liquids comprising soil release polymer (SRP) substantive to polyester fabrics.
  • SRP soil release polymer
  • polyester based SRPs in detergent compositions, especially in laundry detergent compositions to promote improved soil removal from polyester fabrics.
  • Such polymers may have a polyester midblock with one or two end blocks of capped polyethylene glycol attached to the midblock via ester linkages, see e.g. WO 2012/104159 , EP 0523956 and GB 1 466 639 .
  • US 4759876 proposes an aqueous liquid concentrate comprising such a SRP.
  • the preferred liquids have around 80 wt% of the surfactant system as nonionic which gives these compositions low in wash foaming and furthermore is expected to provide the concentrated compositions with low intrinsic foaming.
  • the compositions are formulated to be acidic and triethanolamine free to protect the SRP.
  • the SRP used is a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate of molecular weight 22 000 wherein the polyoxyethylene is of molecular weight 3 400, the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate units is about 3:1 and the proportion of ethylene oxide to phthalic moiety in the polymer is about 22:1.
  • WO2009/153184 (Unilever) 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.
  • the one used in the examples of WO2009/153184 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.
  • the examples of this document suggest using a higher ratio of non-soap anionic surfactant to nonionic than is found in the examples of US 4759876 .
  • Concentrated detergent liquids following the principles set out in WO2009/153184 may suffer from high levels of intrinsic foaming.
  • intrinsic foaming is meant that the concentrated composition itself forms a foam layer when subjected to aeration. This is a problem for handling of the compositions in the factory, particularly the bottle filling operation. It is, however, a considerable problem when the consumer will dose the composition using a volume measure, as is frequently the case for detergent compositions used for laundry. If the composition foams as it is dispensed through a nozzle or some similar dispensing device the mass dose will be too low for the measured volume dose and the consumer will not obtain the expected performance from her product. Compositions with increased levels of solvent hungry ingredients, in particular sequestrants, may exhibit even higher intrinsic foaming. High levels of perfume, the incorporation of ethoxylated polyethyleneimine and the use of amino based counter ions also tend to make intrinsic foaming more significant.
  • EP 1 661 933 (Sasol) describes 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 added between the midblock esters and the PEG endblock.
  • the tested material has 4 such PO repeat units added.
  • the mid block is essentially 1,4 - phenylene and 1,2 propylidene. Neither TEA nor alkoxylated polyethyleneimine is used with these polymers. The examples show that the soil release performance of this polymer after storage is superior to a polymer not having a PO block.
  • a concentrated alkaline liquid detergent composition comprising:
  • compositions are especially useful as laundry detergent compositions.
  • compositions comprise at least 0.5 wt% of the soil release polymer.
  • compositions comprise at least 0.5 wt% triethanolamine, more preferably they comprise at least 1 wt% triethanolamine.
  • compositions comprise at least 0.5 wt% of the soil release polymer and at least 1 wt% triethanolamine.
  • the ratio of non-soap anionic surfactant to soil release polymer should preferably be at most 25:1, more preferably 15:1 and most preferably at most 9:1.
  • the polyesters soil release polymers of formula (I) have surprisingly been found to confer significant intrinsic antifoaming benefits to the concentrated detergent liquids.
  • the composition further includes at least 2 wt% nonionic alkoxylated polyethyleneimine with at least 3 moles of alkoxylation per nitrogen.
  • the block polyesters of formula (I) are linear block polyesters. n preferably ranges from 3 to 9, especially for polymers made from dimethyl terephthalate, and 1,2-propylene glycol.
  • the most preferred linear block polyesters are those where n is from 6 to 8.
  • p is 2 and q is from 18 to 60.
  • At least 10% of the groups G 2 are dimethylene substituted. This optional modification helps to keeps 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. This midblock modification appears to make no difference to the anti foam properties of the polymer.
  • end blocks - [((CH 3 )CHCH 2 O) p -]-block-[(CH 2 CH 2 O) q ]-X may both be present, alternatively only one of the two possible end blocks needs to be present, throughout this specification and claims references to end blocks include the situation where one or other end block is missing unless the context requires otherwise.
  • the polymer has two end blocks. If one of the end blocks is missing then capping group X will similarly be missing from that end.
  • the alkaline liquid detergent compositions may comprise the polymer (d) in amounts of up to 15 wt%, preferably from 1 to 10 wt%, most preferably from 1.5 to 7 wt%.
  • the alkaline concentrated detergent liquid composition is isotropic.
  • the composition may comprise at least 5 wt% non-soap anionic surfactant.
  • the liquid may comprise linear alkyl benzene sulphonate (LAS), Alkyl ether sulphate (AES), Nonionic and optionally an amine oxide or betaine, the LAS being formed from LAS acid, neutralized at least in part, with TEA. Amines may also be used as the counter ion for the AES. It is preferred for stability reasons to keep the total level of alkali metal ions less than 1 wt% of the composition.
  • the liquid is alkaline. It is preferred that the maximum concentrated composition pH is 8.4, more preferably at most 8.2.
  • the invention is a combination of a selected group of polyester soil release polymers with surprising antifoaming properties and a liquid detergent base that has high intrinsic foaming.
  • polyester soil release polymer (with antifoam properties)
  • the invention requires the selection of a soil release polymer with a polyester mid block and its incorporation into an alkaline concentrated detergent liquid, comprising surfactant and triethanolamine.
  • the SRPs with suitable antifoam effect have the formula (I): 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 (I) X-[(OCH 2 CH 2 ) q ]-block-[(OCH 2 CH(CH 3 )) p ]- and - [((CH 3 )CHCH 2 O) p -]-block-[(CH 2 CH 2 O) q ]-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.
  • the polymer will be nonionic. Ionic polymers are generally not phase stable in concentrated alkaline detergent liquids.
  • the mid block ]-[(OC(O)-G 1 -C(O)O-G 2 ) n ]-OC(O)-G 1 -C(O)O- is responsible for making the polymer fabric substantive, particularly towards polyester fabrics. It has little effect on the antifoam properties of the polymer.
  • the esters in the midblock may in practice be formed either way around.
  • the G 1 moieties comprise 1,4-phenylene moieties.
  • the G 2 moieties are substituted ethylene moieties having C 1-4 alkyl substituents.
  • a preferred mono substituted ethylene moiety is 1,2 propylene which is derived from the condensation of 1,2 propane diol.
  • 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 as 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.
  • a preferred diol to form the desired group G 2 may be selected from the group of diols of formula (II): syn n+1,n+2 alkylene diol (II) 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.
  • G 2 may comprise up to 20 mol% moieties derived from 2,3 butane diol derivatives, i.e. an ethylene moiety with a methyl group substituted on each carbon in the backbone.
  • n needs to be at least 2 in order for the antifoam 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 most preferably 6 to 8.
  • the larger the n value the less soluble is the polymer. Because it is an average, n is not necessarily a whole number for the polymer in bulk.
  • the following examples suggest that it is the propoxylation of the end blocks that gives the antifoam benefit.
  • the degree of propoxylation should be from 1 to 10 propylene oxide units on average per end block. It is in a block. 2 to 5 PO is preferred due to having the right balance of antifoam properties.
  • the antifoam benefit does not seem to increase linearly with the amount of propoxylation.
  • the polymers have an EO block that has more alkoxy units than the PO block, preferably the EO block has at least 1.5 times the number of moles or units (q) as the PO block (p), more preferably at least 5 times as many, even 10 times as many, or more.
  • 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.
  • the terminal end cap X on the EO blocks is preferably as small as possible.
  • X is preferably methyl, ethyl, or n-butyl and most preferably methyl or n-butyl.
  • the value for n in the midblock should be increased so that the polymer will deposit well on the fabric during laundering.
  • 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. Preferably the molecular weight is greater than 4 000.
  • 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.
  • 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.
  • the PO/EO end blocks may be preformed by anionic polymerisation of propylene oxide using a preformed mono-functional PEG as the initiator.
  • 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 .
  • An alternative process forms the mid block and reacts it with PO and mPEG.
  • the mid block may be formed 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.
  • 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.
  • the preferred liquids have high amounts of soil release polymer, EPEI, enzymes, and sequestrant relative to the total detersive surfactants level.
  • EPEI soil release polymer
  • enzymes enzymes
  • sequestrant relative to the total detersive surfactants level.
  • the amount of surfactant makes up at least 5 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 laundry detergent 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 ratio of nonionic surfactant to total surfactant is at most 3:2. Compositions with higher levels of nonionic do not suffer from intrinsic foaming to such an extent.
  • Preferred alkyl sulphonates are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 .
  • the preferred counter ion for concentrated alkaline liquids is one or more ethanolamines, for example monoethanolamine (MEA) and triethanolamine (TEA). This introduces TEA into the composition.
  • the linear alkyl benzene sulphonate surfactants may be 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 (II): RO(C 2 H 4 O) x SO 3 - M + (II) 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 ammonium or substituted ammonium cation, or less preferably an alkali metal, and x averages from 1 to 15.
  • 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 ammonium or substituted ammonium cation, or less preferably an alkali metal, and x averages from 1 to 15.
  • R is an alkyl chain having from 12 to 16 carbon atoms, x averages from 1 to 3, preferably x is 3;
  • M may be an ethanolamine, or other material chosen from the list of buffers, to avoid ion exchange of sodium with the counter ion of the LAS.
  • the counter ion can be sodium if low levels of this surfactant are used.
  • the anionic surfactant sodium lauryl ether sulphate (SLES) may be used provided total alkali metal salts in the composition remain low. An average of 3 moles of ethylene oxide per mole is preferred.
  • 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 (III): R 1 N(O)(CH 2 R 2 ) 2 (III)
  • 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 Huntsman 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 (IV) 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 carbobetaine, is present.
  • a preferred zwitterionic material is a betaine available from Huntsman under the name Empigen® BB. Betaine improves particulate soil detergency in the compositions of the invention.
  • surfactants than the preferred LAS, AES, and nonionic 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. Soap may be used. Levels of soap are preferably lower than 5 wt%; more preferably lower than 3 wt% most preferably lower than 1 wt%.
  • a second polymer with the soil release polymers of the present invention is a polyalkoxylated polyethyleneimine.
  • 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.
  • the EPEI comprises a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight; and the polyalkoxylation comprises polyethoxylation.
  • the polymer is nonionic and has no permanent quaternisation of the polyamine nitrogens; although they may be protonated depending on the pH.
  • a preferred 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 3 to 40 ethoxy moieties per polyalkoxyl chain, preferably it is in the range of 16 to 26, most preferably 18 to 22. A minority of the ethoxy units may be replaced by propoxy units.
  • the alkoxylated polyethyleneimine polymer is present in the composition at a level of between 0.01 and 25 wt%, and 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.
  • the composition may comprise other polymeric materials, for example: dye transfer inhibition polymers, anti redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials.
  • the composition may further comprise a polymer of polyethylene glycol and vinyl acetate, for example the lightly grafted copolymers described in WO2007/138054 .
  • amphiphilic graft polymers based on water soluble polyalkylene oxides as graft base and side chains formed by polymerisation of a vinyl ester component have the ability to enable reduction of surfactant levels whilst maintaining high levels of oily soil removal.
  • a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components, especially polymer and sequestrant, in the 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. MPG and glycerol are preferred hydrotropes.
  • At least one or more enzymes selected from protease, mannanase, pectate lyase, cutinase, esterase, lipase, amylase, and cellulase may be present in the compositions. Less preferred additional enzymes may be selected from peroxidase and oxidase.
  • the enzymes are preferably present with corresponding enzyme stabilizers.
  • the total enzyme content is preferably at least 2 wt%, even as high as at least 4 wt%.
  • Preferred sequestrants include organic phosphonates, alkanehydroxy phosphonates and carboxylates available under the DEQUEST trade mark from Thermphos.
  • the preferred sequestrant level is less than 10 wt% and preferably less than 5 wt% of the composition.
  • a particularly 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 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.
  • Other suitable buffer materials may be selected from the group consisting of amino alcohol compounds having a molecular weight above 61 g/mol, which includes MEA.
  • Suitable materials also include, in addition to the already mentioned materials: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoamino hexanol, 2-[(2-methoxyethyl) methylamino]-ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanolamine, isobutanolamine, monopentanolamine, 1-amino-3-(2-methoxyethoxy)- 2-propanol, 2-methyl-4-(methylamino)-2-butanol and mixtures thereof.
  • compositions may contain viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
  • the compositions may further comprise, pearlisers and/or opacifiers or other visual cues and shading dye.
  • the liquids may be packaged as unit doses in polymeric film soluble in the wash water.
  • the liquids may be supplied in multidose plastics packs with a top or bottom closure.
  • a dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
  • Example 1 concentrated liquid compositions with SRP
  • compositions designed to be dosed at 35 ml per wash was formulated with no SRP, with prior art SRPs and with propoxylated SRPs.
  • the compositions used are given in Table 1. They were subjected to a foam evaluation using the following protocol:
  • TexCare® SRN240 a polymer of similar molecular weight and construction to that of the propoxylated SRPs (but without any propoxylation), causes the composition to foam and is very similar to that of the base alone and TexCare® SRN170. All three propoxylated SRPs cause a significant reduction in foaming.
  • Table 1 - Liquid detergent compositions Compositions Wt % as 100% Ingredient %AD 1 2 3 4 5 6 Demin water and MEA to adjust pH 100 balance balance balance balance balance balance MPG 100 20.00 20.00 20.00 20.00 20.00 TEA 100 2.00 2.00 2.00 2.00 2.00 2.00 NI 7EO 100 7.28 7.28 7.28 7.28 7.28 LAS Acid 97.1 4.85 4.85 4.85 4.85 4.85 4.85 4.85 Prifac 5908 100 0.69 0.69 0.69 0.69 0.69 SLES 3EO 70 2.42 2.42 2.42 2.42 2.42 2.42 2.42 2.42 2.42 Empigen OB 30 0.86 0.86 0.86 0.86 0.86 0.86 EPEI 80 3.14 3.14 3.14 3.14 3.14 3.14 3.14 Dequest 2010 60 1.50 1.50 1.50 1.50 1.50 1.50 TexCare SRN-170 70 0.00 2.14 0.00 0.00 0.00 0.00 SRP 1 100 0.00 0.00 2.14 0.00 0.00 0.00 SRP 2 100 0.00 0.00 0.00 2.14 0.00 0.00 S

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Claims (19)

  1. Konzentrierte alkalische flüssige Reinigungsmittelzusammensetzung, umfassend:
    a) 5 bis 60 Gew.-% Tensid, umfassend anionisches Tensid und gegebenenfalls nichtionisches Tensid und gegebenenfalls amphoteres Tensid und gegebenenfalls Seife, wovon mindestens 35% des gesamten Tensids ein anionisches Nicht-Seifentensid darstellt,
    b) mindestens 30 Gew.-% Wasser,
    c) mindestens 0,25 Gew.-% Soil-Release-Polymer,
    dadurch gekennzeichnet, dass
    (i) das Soil-Release-Polymer die Formel (I) und

            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     (I)

    hat,
    worin die G1-Anteile sämtlich 1,4-Phenylen-Anteile sind,
    die G2-Anteile sämtlich C1-4-Alkyl-substituierte Ethylenanteile sind,
    jedes X ist C1-4-Alkyl, vorzugsweise Methyl oder n-Butyl,
    jedes q von 12 bis 120 ist, jedes p von 1 bis 10 ist, vorzugsweise 2 bis 5, und n von 2 bis 10 ist.
  2. Zusammensetzung gemäß Anspruch 1, des Weiteren umfassend mindestens 0,5 Gew.-% Triethanolamin (TEA).
  3. Zusammensetzung gemäß Anspruch 2, umfassend mindestens 1 Gew.-% Triethanolamin.
  4. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 0,5 Gew.-% des Soil-Release-Polymers (c).
  5. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, worin das Verhältnis des anionischen Nicht-Seifen-Tensids zu dem Soil-Release-Polymer höchstens 9:1 ist.
  6. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, wobei jedes G2 einen oder zwei C1-C4-Alkyl-Substituenten mit höchstens einem an jedem Kohlenstoff aufweist.
  7. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, worin die C1-C4-Alkyl-Anteile Methyl-Anteile darstellen.
  8. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 2 Gew.-% alkoxylierte Polyethylenimine.
  9. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 5 Gew.-% anionisches Tensid.
  10. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend als anionisches Tensid Alkylethersulfat.
  11. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, umfassend lineares Alkylbenzolsulfonat (LAS), wobei das LAS von LAS-Säure, zumindest zum Teil, mit Triethanolamin (TEA) neutralisiert ist.
  12. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 2 Gew.-% des Soil-Release-Polymers (c).
  13. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens drei Enzyme.
  14. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 1 Gew.-% Komplexbildner.
  15. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend mindestens 0,5 Gew.-% Aminoxid.
  16. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend bis zu 25 Gew.-% hydrotropes Mittel.
  17. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend höchstens 1 Gew.-% Alkalimetallionen.
  18. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch mit einer Viskosität, gemessen bei 23 s-1 bei 25°C, von weniger als 0,1 Pa.s.
  19. Zusammensetzung gemäß irgendeinem vorhergehenden Anspruch, umfassend weniger als 5 Gew.-% Seife, vorzugsweise weniger als 3 Gew.-% und höchst bevorzugt weniger als 1 Gew.-%.
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PCT/EP2013/063967 WO2014019792A1 (en) 2012-07-31 2013-07-02 Concentrated liquid detergent compositions

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EP3167033B1 (de) * 2014-07-09 2020-04-29 Unilever Plc. Verfahren zur herstellung einer flüssigen waschmittelzusammensetzung
EP2987848A1 (de) 2014-08-19 2016-02-24 The Procter & Gamble Company Verfahren zum Waschen eines Stoffs
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JP6521507B2 (ja) * 2014-12-29 2019-05-29 ライオン株式会社 繊維製品用の液体洗浄剤
MX2017009569A (es) * 2015-01-21 2017-11-28 Basf Se Composicion de limpieza y metodo para formarla.
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BR112018070468B1 (pt) 2016-04-08 2022-07-12 Unilever Ip Holdings B.V Composição de detergente líquida aquosa para lavagem de roupas e método doméstico de tratamento de um tecido
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JP7155300B2 (ja) 2018-06-26 2022-10-18 ザ プロクター アンド ギャンブル カンパニー 液体洗濯洗剤組成物
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CN104508104A (zh) 2015-04-08
CL2015000213A1 (es) 2015-06-12
EP2692842A1 (de) 2014-02-05
BR112015001487A2 (pt) 2017-07-04
AU2013298898A1 (en) 2015-02-05
WO2014019792A1 (en) 2014-02-06
MX2015000894A (es) 2015-04-17
ZA201500456B (en) 2016-09-28
BR112015001487B1 (pt) 2021-05-04
AU2013298898B2 (en) 2015-05-14
IN2015MN00104A (de) 2015-10-16
ES2569375T3 (es) 2016-05-10
PH12015500129A1 (en) 2015-03-02
CN104508104B (zh) 2017-09-22
AR091933A1 (es) 2015-03-11
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PL2880143T3 (pl) 2016-09-30

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