WO2014019792A1 - Concentrated liquid detergent compositions - Google Patents

Concentrated liquid detergent compositions Download PDF

Info

Publication number
WO2014019792A1
WO2014019792A1 PCT/EP2013/063967 EP2013063967W WO2014019792A1 WO 2014019792 A1 WO2014019792 A1 WO 2014019792A1 EP 2013063967 W EP2013063967 W EP 2013063967W WO 2014019792 A1 WO2014019792 A1 WO 2014019792A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
surfactant
moieties
soil release
alkyl
Prior art date
Application number
PCT/EP2013/063967
Other languages
English (en)
French (fr)
Inventor
Julie Bennett
Alyn James Parry
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to BR112015001487-9A priority Critical patent/BR112015001487B1/pt
Priority to CN201380040587.2A priority patent/CN104508104B/zh
Priority to MX2015000894A priority patent/MX2015000894A/es
Priority to AU2013298898A priority patent/AU2013298898B2/en
Priority to EP13733305.0A priority patent/EP2880143B1/en
Priority to ES13733305.0T priority patent/ES2569375T3/es
Priority to IN104MUN2015 priority patent/IN2015MN00104A/en
Publication of WO2014019792A1 publication Critical patent/WO2014019792A1/en
Priority to ZA2015/00456A priority patent/ZA201500456B/en
Priority to PH12015500129A priority patent/PH12015500129A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715Polyesters 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.
  • 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:
  • surfactant comprising anionic surfactant and optionally nonionic surfactant and optionally amphoteric surfactant and optionally soap of which at least 35% of the total surfactant is anionic non-soap surfactant
  • the soil release polymer has the formula (I), and X-[(OCH 2 CH 2 ) q -]-block- [(OCH 2 CH(CH 3 )) p ]-[(OC(0)-G 1 -C(0)0-G 2 ) n ]-OC(0)-G 1 -C(0)0- [((CH 3 )CHCH 2 0) p -]-block- [(CH 2 CH 2 0) q ]-X (I) wherein the G 1 moieties are all 1 ,4-phenylene moieties; the G 2 moieties are all C -4 alkyl 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 1 to 10, preferably 2 to 5; and n is from 2 to 10.
  • block is used here as is known to the polymer chemist to mean that the parts of the backbone either side of this notional division
  • 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. Because the non-soap anionic surfactant is believed to be the main source of the intrinsic foaming 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. Most preferably, in the formula (I), 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
  • the end blocks - [((CH 3 )CHCH 2 0)p-]-block-[(CH 2 CH 2 0) 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 ]- and - [((CH 3 )CHCH 2 0) p -]-block-[(CH 2 CH 2 0) 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.
  • Mid block or backbone The mid block ]-[(OC(0)-G 1 -C(0)0-G 2 ) n ]-OC(0)-G 1 -C(0)0- 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.
  • the use of 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. End block
  • 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 4,71 1 ,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. End block manufacture
  • 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, CO. Kappe, Macromol. Chem. Phys., 2007, 208, 2510-2524.
  • 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 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 MB 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%.
  • compositions according to the invention most preferably have total active detersive surfactant levels of at least 15 wt%.
  • the 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.
  • alkyl sulphonates are alkylbenzene sulphonates, particularly linear
  • alkylbenzene sulphonates having an alkyl chain length of C 8 -Ci 5 .
  • 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.
  • MEA monoethanolamine
  • TEA triethanolamine
  • 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 (I I): RO(C 2 H 4 0) x S0 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 2 o 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,
  • a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside
  • alkyldimethylamineoxide ethoxylated fatty acid monoethanolamide
  • fatty acid ethoxylated fatty acid monoethanolamide
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 2 o 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.
  • Amine Oxide especially the C 8 -C 2 o 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 (I II): R 1 N(0)(CH 2 R 2 ) 2 (I I I)
  • R 1 is a long chain moiety
  • 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 -Ci 8 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:
  • 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 Other surfactants than the preferred LAS, AES, and nonionic may be added to the mixture of detersive surfactants. However, cationic surfactants are preferably
  • 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.
  • the EPEI comprises a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight; and the polyalkoxylation comprises
  • 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.
  • 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%.
  • Sequestrants There is not room to include high levels of builders in the concentrated compositions.
  • sequestrants are preferably included. Such materials tend to have low solubility in the concentrated liquids so the multifunctionality of the antifoam soil release polymer assists in stably incorporating these materials into the compositions.
  • 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
  • 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,
  • 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.
  • MPG is mono propylene glycol.
  • TEA is triethanolamine
  • ME A is Monoethanolamine.
  • Nl 7EO is C12-15 alcohol ethoxylate 7EO nonionic
  • Neodol® 25-7 (ex Shell Chemicals).
  • LAS acid is C12-14 linear alkylbenzene sulphonic acid.
  • Prifac® 5908 is saturated lauric fatty acid ex Croda.
  • SLES 3EO is sodium lauryl ether sulphate with 3 moles EO.
  • EPEI Sokalan HP20 - ethoxylated polyethylene imine
  • Perfume is free oil perfume.
  • Dequest® 2010 is HEDP (1 -Hydroxyethylidene -1 ,1 ,-diphosphonic acid).
  • TexCare SRN-170 is soil release polymer ex Clariant.
  • SRP 1 is an antifoam soil release polymer with propoxylation and having:
  • SRP 2 is an antifoam soil release polymer with propoxylation and having
  • SRP 3 is an antifoam soil release polymer with propoxylation and having
  • Preservative is Proxel GLX antimicrobial preservative, a 20% solution of 1 ,2 benzisothiazolin-3-one in dipropylene glycol and water ex Arch Biocides.
  • Colorant is a mixture of equal part patent blue and acid yellow 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:
  • a 30 ml sample of the concentrated detergent composition was added to a 100 ml measuring cylinder.
  • the cylinder was sealed and shaken 20 times to generate foam.
  • the cylinder was left to stand for 1 minute and the foam height measured.
  • the protocol was repeated up to 6 times for each sample and the average taken. The results are given in Table 2.
  • 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
  • MPG 100 20.00 20.00 20.00 20.00 20.00 20.00 20.00
PCT/EP2013/063967 2012-07-31 2013-07-02 Concentrated liquid detergent compositions WO2014019792A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BR112015001487-9A BR112015001487B1 (pt) 2012-07-31 2013-07-02 composição detergente líquida alcalina concentrada
CN201380040587.2A CN104508104B (zh) 2012-07-31 2013-07-02 浓缩液体洗涤剂组合物
MX2015000894A MX2015000894A (es) 2012-07-31 2013-07-02 Composiciones detergentes liquidas concentradas.
AU2013298898A AU2013298898B2 (en) 2012-07-31 2013-07-02 Concentrated liquid detergent compositions
EP13733305.0A EP2880143B1 (en) 2012-07-31 2013-07-02 Concentrated liquid detergent compositions
ES13733305.0T ES2569375T3 (es) 2012-07-31 2013-07-02 Composiciones detergentes líquidas concentradas
IN104MUN2015 IN2015MN00104A (ru) 2012-07-31 2013-07-02
ZA2015/00456A ZA201500456B (en) 2012-07-31 2015-01-22 Concentrated liquid detergent compositions
PH12015500129A PH12015500129A1 (en) 2012-07-31 2015-01-22 Concentrated liquid detergent compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12178620.6A EP2692842B1 (en) 2012-07-31 2012-07-31 Concentrated liquid detergent compositions
EP12178620.6 2012-07-31

Publications (1)

Publication Number Publication Date
WO2014019792A1 true WO2014019792A1 (en) 2014-02-06

Family

ID=48745955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/063967 WO2014019792A1 (en) 2012-07-31 2013-07-02 Concentrated liquid detergent compositions

Country Status (13)

Country Link
EP (2) EP2692842B1 (ru)
CN (1) CN104508104B (ru)
AR (1) AR091933A1 (ru)
AU (1) AU2013298898B2 (ru)
BR (1) BR112015001487B1 (ru)
CL (1) CL2015000213A1 (ru)
ES (1) ES2569375T3 (ru)
IN (1) IN2015MN00104A (ru)
MX (1) MX2015000894A (ru)
PH (1) PH12015500129A1 (ru)
PL (1) PL2880143T3 (ru)
WO (1) WO2014019792A1 (ru)
ZA (1) ZA201500456B (ru)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
EP2987848A1 (en) 2014-08-19 2016-02-24 The Procter & Gamble Company Method of laundering a fabric
WO2016044200A1 (en) 2014-09-15 2016-03-24 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
US9365806B2 (en) 2012-07-31 2016-06-14 Conopco Inc. Alkaline liquid laundry detergent compositions comprising polyesters
JP2016124978A (ja) * 2014-12-26 2016-07-11 ライオン株式会社 繊維製品用の液体洗浄剤
JP2016124984A (ja) * 2014-12-29 2016-07-11 ライオン株式会社 繊維製品用の液体洗浄剤
US9732308B2 (en) 2012-07-31 2017-08-15 Clariant International Ltd. Polyesters

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL3167033T3 (pl) * 2014-07-09 2020-11-02 Unilever Nv Sposób wytwarzania ciekłej kompozycji piorącej
BR112017015580A2 (pt) * 2015-01-21 2018-03-13 Basf Se composição de limpeza para lavagem de louça, e, método para formar uma composição de limpeza para lavagem de louça
EP3371292B1 (en) 2015-11-02 2021-04-14 Colgate-Palmolive Company Hard surface cleaning compositions
WO2017162378A1 (en) 2016-03-21 2017-09-28 Unilever Plc Laundry detergent composition
CN108779416B (zh) 2016-04-08 2021-01-05 荷兰联合利华有限公司 洗衣洗涤剂组合物
BR112019011999B1 (pt) 2016-12-15 2022-11-08 Unilever Ip Holdings B.V Composição de detergente líquida aquosa para lavagem de roupas e método doméstico de tratamento de um tecido
BR112019023383A2 (pt) 2017-05-10 2020-06-16 Unilever N.V. Composição de detergente líquida aquosa para lavagem de tecidos e método doméstico de tratamento de um tecido
WO2018206197A1 (en) 2017-05-10 2018-11-15 Unilever Plc Laundry detergent composition
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
CN108949394B (zh) * 2018-08-14 2020-09-11 广州立白企业集团有限公司 一种基本不含增溶剂的浓缩型液体洗涤剂组合物
WO2020109227A1 (en) 2018-11-28 2020-06-04 Unilever N.V. Large particles
MX2022000913A (es) * 2019-07-24 2022-02-16 Basf Se Composicion colectora.
WO2021180546A1 (en) 2020-03-11 2021-09-16 Unilever Ip Holdings B.V. Low foaming solid cleaning composition
BR112023002786A2 (pt) 2020-08-26 2023-03-14 Unilever Ip Holdings B V Composição detergente sólida para lavagem de roupas, método de lavagem de uma superfície têxtil com a composição detergente e uso

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182306A (en) 1935-05-10 1939-12-05 Ig Farbenindustrie Ag Polymerization of ethylene imines
US2208095A (en) 1937-01-05 1940-07-16 Ig Farbenindustrie Ag Process of producing insoluble condensation products containing sulphur and nitrogen
US2553696A (en) 1944-01-12 1951-05-22 Union Carbide & Carbon Corp Method for making water-soluble polymers of lower alkylene imines
US2806839A (en) 1953-02-24 1957-09-17 Arnold Hoffman & Co Inc Preparation of polyimines from 2-oxazolidone
US3033746A (en) 1958-06-19 1962-05-08 Dow Chemical Co Polyalkyleneimine, phenol germicides
GB1466639A (en) * 1974-06-25 1977-03-09 Procter & Gamble Liquid detergent compositions having soil release properties
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4759876A (en) 1985-03-19 1988-07-26 Colgate-Palmolive Company Stable soil release promoting enzymatic liquid detergent composition
EP0523956A2 (en) * 1991-07-17 1993-01-20 Unilever Plc Fabric care composition comprising water soluble or water dispersible copolymer containing UV-absorbing monomer
EP1661933A1 (de) 2004-11-24 2006-05-31 SASOL Germany GmbH Fließfähige, amphiphile und nichtionische Oligoester
WO2007138054A1 (en) 2006-05-31 2007-12-06 The Procter & Gamble Company Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
WO2009153184A1 (en) 2008-06-16 2009-12-23 Unilever Plc Improvements relating to fabric cleaning
WO2012104159A1 (en) * 2011-01-31 2012-08-09 Unilever Plc Alkaline liquid detergent compositions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE502998T1 (de) * 2006-07-07 2011-04-15 Procter & Gamble Waschmittelzusammensetzungen

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182306A (en) 1935-05-10 1939-12-05 Ig Farbenindustrie Ag Polymerization of ethylene imines
US2208095A (en) 1937-01-05 1940-07-16 Ig Farbenindustrie Ag Process of producing insoluble condensation products containing sulphur and nitrogen
US2553696A (en) 1944-01-12 1951-05-22 Union Carbide & Carbon Corp Method for making water-soluble polymers of lower alkylene imines
US2806839A (en) 1953-02-24 1957-09-17 Arnold Hoffman & Co Inc Preparation of polyimines from 2-oxazolidone
US3033746A (en) 1958-06-19 1962-05-08 Dow Chemical Co Polyalkyleneimine, phenol germicides
GB1466639A (en) * 1974-06-25 1977-03-09 Procter & Gamble Liquid detergent compositions having soil release properties
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
US4759876A (en) 1985-03-19 1988-07-26 Colgate-Palmolive Company Stable soil release promoting enzymatic liquid detergent composition
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
EP0523956A2 (en) * 1991-07-17 1993-01-20 Unilever Plc Fabric care composition comprising water soluble or water dispersible copolymer containing UV-absorbing monomer
EP1661933A1 (de) 2004-11-24 2006-05-31 SASOL Germany GmbH Fließfähige, amphiphile und nichtionische Oligoester
WO2007138054A1 (en) 2006-05-31 2007-12-06 The Procter & Gamble Company Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
WO2009153184A1 (en) 2008-06-16 2009-12-23 Unilever Plc Improvements relating to fabric cleaning
WO2012104159A1 (en) * 2011-01-31 2012-08-09 Unilever Plc Alkaline liquid detergent compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. I. MALIK; B. TRATHNIGG; C.O. KAPPE, MACROMOL. CHEM. PHYS., vol. 208, 2007, pages 2510 - 2524

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9365806B2 (en) 2012-07-31 2016-06-14 Conopco Inc. Alkaline liquid laundry detergent compositions comprising polyesters
US9732308B2 (en) 2012-07-31 2017-08-15 Clariant International Ltd. Polyesters
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
EP2987848A1 (en) 2014-08-19 2016-02-24 The Procter & Gamble Company Method of laundering a fabric
WO2016044200A1 (en) 2014-09-15 2016-03-24 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
JP2016124978A (ja) * 2014-12-26 2016-07-11 ライオン株式会社 繊維製品用の液体洗浄剤
JP2016124984A (ja) * 2014-12-29 2016-07-11 ライオン株式会社 繊維製品用の液体洗浄剤

Also Published As

Publication number Publication date
AU2013298898A1 (en) 2015-02-05
CN104508104A (zh) 2015-04-08
BR112015001487A2 (pt) 2017-07-04
PH12015500129A1 (en) 2015-03-02
EP2692842A1 (en) 2014-02-05
IN2015MN00104A (ru) 2015-10-16
PL2880143T3 (pl) 2016-09-30
CN104508104B (zh) 2017-09-22
ZA201500456B (en) 2016-09-28
EP2880143B1 (en) 2016-03-23
AR091933A1 (es) 2015-03-11
ES2569375T3 (es) 2016-05-10
AU2013298898B2 (en) 2015-05-14
BR112015001487B1 (pt) 2021-05-04
EP2880143A1 (en) 2015-06-10
CL2015000213A1 (es) 2015-06-12
MX2015000894A (es) 2015-04-17
EP2692842B1 (en) 2014-07-30

Similar Documents

Publication Publication Date Title
EP2880143B1 (en) Concentrated liquid detergent compositions
EP2880074B1 (en) Alkaline liquid laundry detergent compositions comprising polyesters
ES2788101T3 (es) Detergentes para la ropa que contienen polímeros que facilitan el desprendimiento de la suciedad
US10351802B2 (en) Laundry detergents containing soil release polymers
AU2021280970B2 (en) A liquid laundry composition
WO2019105939A1 (en) Detergent compositions containing renewably sourced soil release polyesters
CN111433340B (zh) 去污聚合物及含有其的洗衣洗涤剂组合物
WO2017174258A1 (en) Laundry liquid composition
WO2021118774A1 (en) Fabric care composition
AU2013298728B9 (en) Alkaline liquid laundry detergent compositions comprising polyesters

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13733305

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2013733305

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: MX/A/2015/000894

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 12015500129

Country of ref document: PH

WWE Wipo information: entry into national phase

Ref document number: IDP00201500506

Country of ref document: ID

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2013298898

Country of ref document: AU

Date of ref document: 20130702

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112015001487

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112015001487

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20150122