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EP4196562A1 - Process for making laundry liquid detergent composition - Google Patents

Process for making laundry liquid detergent composition

Info

Publication number
EP4196562A1
EP4196562A1 EP21749520.9A EP21749520A EP4196562A1 EP 4196562 A1 EP4196562 A1 EP 4196562A1 EP 21749520 A EP21749520 A EP 21749520A EP 4196562 A1 EP4196562 A1 EP 4196562A1
Authority
EP
European Patent Office
Prior art keywords
composition
surfactant
concentrated
alkyl
batch
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP21749520.9A
Other languages
German (de)
French (fr)
Inventor
Thatiana Guisolphe CASTRO
Arlene FICHE
Andrew David Green
Alyn James Parry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
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 Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP4196562A1 publication Critical patent/EP4196562A1/en
Pending legal-status Critical Current

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
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/667Neutral esters, e.g. sorbitan esters
    • 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
    • C11D1/90Betaines

Definitions

  • the present invention relates to an improved process for making a concentrated laundry detergent composition.
  • the present invention also relates to a composition obtainable by such process.
  • EP-A-1 367 118 discloses an aqueous liquid laundry detergent composition
  • a detergent surfactant including anionic
  • an emulsifier with an HLB value below about 8.5 an oil
  • an electrolyte in an amount to provide ionic strength indicator of from about 0.55 to about 6.7.
  • the composition separates, upon standing for at most 24 hours at ambient temperature, into at least two layers, one of which is an emulsion with a continuous aqueous phase.
  • the second layer is preferably a transparent composition.
  • WO 2013/043841 discloses liquid cleaning compositions useful in cold water and hard water laundry applications, and methods for making and using such compositions.
  • the compositions of the invention use surfactants or surfactant blends, such as a-sulfofatty acid esters or mixtures thereof (optionally along with one or more additional components), that have increased solubility/stability at cold temperatures, at higher-than-usual concentrations, and/or in hard water, with the composition remaining as a clear liquid.
  • the compositions of the invention may be provided in the form of a unit dose, for example in a water-soluble pack or pouch.
  • compositions of the invention result in an enhanced detergency along with a reduced amount of residue remaining in the machine, on laundered garments or cleaned dishware or hard surfaces, and on the body in personal care settings, and demonstrate a longer shelf-life, particularly when stored or used in colder temperatures.
  • WO 2013/092052 discloses an isotropic liquid detergent composition with an in-bottle pH in the range 6.0 to less than 7, the composition comprising, in addition to water: a) up to 60 wt percent detersive surfactant including at least 5 wt percent anionic sulphonate and /or sulphate surfactant comprising surfactant acid neutralised with one or more materials the pKa of whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition b) at least 0.3 wt percent fatty acid partially neutralised with one or more materials the pKa of whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition c) at least 1.0 wt percent, preferably at least 1.8 wt percent, T riethanolamine (TEA); and d) at least 0.5 wt percent soil release polymer (SRP).
  • detersive surfactant including at least 5 wt
  • WO 2011/120772 discloses a process for the incorporation of microcapsules with anionic charge into a structured aqueous concentrated liquid detergent comprising at least 30 wt percent, preferably at most 65 wt percent, total surfactant of which at least 5 wt percent based on the total composition is anionic surfactant, including soap, and an external structurant, the process comprising the combining of two premixes; Premix A which is the structured aqueous concentrated liquid detergent composition without microcapsules and Premix B which comprises an aqueous dispersion of the microcapsules with anionic charge, characterised in that: Premix B is a slurry of microcapsules with a maximum viscosity at 25 degrees centigrade of 100 mPas and at least 90 wt percent of the microcapsules having a particle size in the range 5 to 30 microns, and that Premix B is added to Premix A and the resulting combined mixture is passed through a static in-line mixer with an energy input
  • WO 2017/075681 discloses a new thickener composition comprising a mixture of one or more alkoxylated polyol esters, one or more ethoxylated sorbitan esters and glycerol, used to increase the viscosity of cosmetic skin and hair cleansing products and of surface and fabric cleaners, as well as to make these products easier to formulate.
  • the thickener composition described is compatible with a great variety of formulations of cosmetic skin and hair cleansing products and of surface and fabric cleaners comprising one or more surfactants, co-surfactants, solvents, fragrances, emulsifiers, preservatives, salts, pigments and/or colouring agents, besides other inert compounds with regard to the end performance, this composition being capable of increasing the viscosity thereof in a stable a measurable manner.
  • WO 96/21721 discloses a sealed container containing a unit dose of a liquid surfactant containing concentrate, which concentrate, on dilution with water, gives a diluted liquid product of similar or increased viscosity.
  • the concentrate may further contain other active ingredients such as bleaching agents, disinfectants and conditioning agents.
  • the concentrate may be adapted for application to hard surfaces such as sinks or floors or to soft surfaces such as fabrics, skin or hair.
  • the dispensing passage has a flow restriction portion and an applicator at the distal end.
  • the container is intended for use with fluids with a viscosity of less than about 500 cP. When so used, and aligned to a dispensing orientation, fluid flows out of the dispensing passage at a rate from about 0 ml/min to about 300 ml/min, unless manual pressure is exerted on the resilient side wall.
  • Concentrated products which can be diluted at home are becoming more and more popular among the more environmentally aware consumers.
  • such products are purchased as concentrated forms of the regular product and they are diluted by the consumer in the domestic environment.
  • the immediate challenge is in the context of viscosity management.
  • the composition after dilution is expected to perform physically as well as functionally as would a regular product.
  • the dilutable composition must have a viscosity which sufficiently matches the viscosity profile of the diluted composition.
  • the viscosity become radically different.
  • the challenge is therefore to make a product which has an appropriate physical profile and performs appropriately on dilution in water.
  • a process for making a concentrated laundry liquid detergent composition comprising the following steps: forming a batch of neutralised LAS acid in water; heating or maintaining the batch temperature at from 40 to 60°C; adding betaine surfactant to the batch; adding non-ionic surfactant to the batch; optionally adding further surfactant, rheology modifier, fragrance, enzymes and preservative where appropriate.
  • the non-ionic surfactant is added after the LAS. It is also preferred that the non-ionic surfactant is added after any secondary surfactant such as any betaine. It is also preferable that the non-ionic surfactant is added before any rheology modifier such as those described herein. This enables the micellar structure to be fully developed prior to any rheology modifier being added. This is important when trying to achieve a viscosity profile for the concentrated composition before dilution and also after dilution by the consumer.
  • the non-ionic mixture comprising neutralised LAS is heated to a temperature at least 7°C above the cloud point of the non-ionic surfactant but always lower than 60C.
  • the neutralised LAS is heated to from 40 to 60°C, preferably from 45 to 55°C before addition of the non-ionic surfactant. This ensures that the non-ionic surfactant is able to achieve the correct physical relationship with the LAS, and optional betaine, as quickly as possible. It is also preferred that this mixture of neutralised LAS and non-ionic surfactant is stirred after addition of the non-ionic surfactant.
  • the non-ionic surfactant and neutralised LAS is stirred for at least five minutes after addition of the non-ionic surfactant to the batch.
  • Fully neutralising the LAS acid and maintaining at a pH of 6.5 to 7.5 helps obtain the correct micellar disposition which is required before further components are added to the mixture. If this is not achieved and instead the LAS is not fully neutralised then the formulator is required to address this later in the process through addition of viscosity modifiers such as salt. In the context of concentrated formulations for which the viscosity profile is so important not just in the concentrated mixture before dilution but also after dilution, this later correction is not possible.
  • the neutralising agent is selected from TEA and sodium hydroxide.
  • the pH is adjusted to from 6.5 to 7.5 by addition of the neutralising agent.
  • the neutralising agent preferably sodium hydroxide
  • the neutralising agent is added to the premix before the LAS acid is added, the LAS acid is then added, and then more neutralising agent is added to adjust the pH of the mixture to from 6.5 to 7.5.
  • the total neutralising agent is added prior to the LAS acid and from 20 to 60% is added after. More preferably, from 50-70% wt. of the total neutralising agent is added before the LAS acid and from 30 to 50% wt. is added after the LAS acid. Most preferably, from 55-65% wt. of the total neutralising agent is added before the LAS acid and from 35 to 45% wt. is added after the LAS acid.
  • the concentrated composition made according to the process of the first aspect comprises detersive surfactant.
  • detersive surfactant in the context of this invention denotes a surfactant which provides a detersive (i.e. cleaning) effect to laundry treated as part of a domestic laundering process.
  • Non-soap anionic surfactants for use in the invention are typically salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof.
  • the alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated.
  • the alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule.
  • the counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed.
  • a preferred class of non-soap anionic surfactant for use in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms.
  • LAS linear alkylbenzene sulfonates
  • Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons.
  • the linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12.
  • Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1 -phenyl isomer.
  • LAS is normally formulated into compositions in acid (i.e. HLAS) form and then fully neutralized in-situ.
  • PES primary alkyl sulfate surfactant
  • the total level of anionic surfactant may preferably range from 20 to 50% by weight based on the total weight of the surfactant. However, it is preferred that the level of anionic surfactant is lower than the level of non-ionic surfactant.
  • the ration between the anionic surfactant and non-ionic surfactant is from 1 : 1 .5 to 1 :20 and more preferably from 1 :3 to 1 :10.
  • alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule.
  • a preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule.
  • SLES sodium lauryl ether sulfate
  • alkyl ether sulphates have a deleterious effect on performance of such compositions for use as premixes as described herein and in such instance it is preferred that the level of any alkyl ether sulphate is from 0 to 10% wt. of the total level of surfactant, more preferably from 0 to 1% wt and most preferably zero.
  • the composition comprises from 20 to 95% wt. non-ionic surfactant based on the total weight of surfactant.
  • Nonionic surfactants for use in the invention are typically polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide.
  • Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate.
  • the polyoxyalkylene compounds can have a variety of block and heteric (random) structures.
  • the blocks can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates.
  • the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides.
  • examples of such materials include Cs to C22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and aliphatic alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
  • a preferred class of nonionic surfactant for use in the invention includes aliphatic Cs to Cis, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.
  • a further class of non-ionic surfactants include the alkyl poly glycosides and rhamnolipids.
  • the selection and amount of surfactant is such that the concentrated laundry detergent formulation and the diluted mixture are isotropic in nature.
  • the composition comprises a rheology modifier.
  • a rheology modifier is a material which adjusts the rheological performance of the composition. The rheology modifier does not necessary thicken or thin and composition it is added to.
  • the rheology modifier comprises ethoxylated sorbitan ester.
  • the ethoxylated sorbitan ester provides improved rheological characteristics in the context of a product which is diluted by the consumer in the domestic environment. It should be noted that this is independent of any rheological behaviour which is affected by pouring or otherwise using the diluted product.
  • the concentrated premix is to be diluted by the user and as such it is necessary for the premix to behave rheologically appropriately.
  • the ethoxylated sorbitan ester comprises from 50 to 1000 ethoxylate units, more preferably from 200 to 700 and most preferably from 300 to 550.
  • the ethoxylated sorbitan ester comprises one to five, more preferably three to five fatty acid esters. More preferably, the ethoxylated sorbitan ester comprises a fatty acid having from 10 to 22 carbons, more preferably from 14 to 20 and most preferably 18 carbons.
  • the fatty acid may be straight chain or branched, saturated or unsaturated.
  • the most preferred fatty acid group is a stearic acid group.
  • the most preferred ethoxylated sorbitan ester is sorbeth-450 tristearate and which is the triester of stearic acid and a polyethylene glycol ether of sorbitol with an average of 450 moles of ethylene oxide.
  • the ethoxylated sorbitan ester is present at from 0.01-8.0% of the final laundry detergent composition.
  • the composition comprises PEG ester fatty acid.
  • PEG fatty acid ester is included top modify the rheological performance of the composition particularly during dilution.
  • Preferred PEG ester fatty acids include PEG 9 cocoate, PEG 32 and PEG 175.
  • the PEG ester fatty acid is present at from 0.01-5.0% of the final laundry detergent composition.
  • the temperature of the neutralised LAS, optional betaine, and non-ionic surfactant is maintained at from 40 to 60°C, preferably from 40 to 55°C, while any rheology modifier is added. This prevents any adverse reaction to the viscosity management before and after dilution caused by the addition of the rheology modifier. It also ensures that the micelles are properly formed before the rheology modifier is added. If the rheology modifier is added before the non-ionic surfactant the resulting micellar formation is disturbed and is irreparable.
  • the rheology modifier is heated to from 35 to 50°C, more preferably from 38 to 43°C, before being added to the neutralised LAS and non-ionic mixture which is preferably being maintained at from 40 to 55°C.
  • the temperature of the mixture is then cooled before adding any further components such as fragrance, preservative and enzymes.
  • the temperature is cooled to below 40°C before such materials are added.
  • the preservative comprises isothiazolinone materials at a level not higher than 500ppm in the concentrate.
  • the temperature is cooled gradually before such materials are added.
  • the rate of cooling is from 0.1 °C per minute to 2°C per minute, more preferably from 0.5 to 1 ,5°C per minute and most preferably from 0.75 to 1 ,25°C per minute.
  • the final pH of the detergent composition is from 7 to 8. In such circumstance it is adjusted after the neutralisation of LA where necessary using and appropriate buffer.
  • a concentrated laundry detergent composition obtainable by a process according to the first aspect.
  • the concentrated product may also comprise an anti-foam.
  • Anti-foam materials are well known in the art and include silicones and fatty acid.
  • the fatty acid anti-foam is present at from 1 .3 to 3.0, more preferably from 1.4 to 2.0% wt. and most preferably from 1.6 to 1.65% wt. of the premix.
  • Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid
  • fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids.
  • Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).
  • the fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • fatty acids and/or their salts are not included in the level of surfactant or in the level of builder.
  • a concentrated composition of the invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers.
  • non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers.
  • Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (M w ) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene,
  • Non-aqueous carriers when included, may be present in an amount ranging from 0.1 to 20%, preferably from 2 to 15%, and more preferably from 10 to 14% (by weight based on the total weight of the concetrate).
  • the level of hydrotrope used is linked to the level of surfactant and it is desirable to use hydrotrope level to manage the viscosity in such concentrated formulations.
  • the preferred hydrotrope is monopropylene glycol.
  • a concentrated composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above.
  • cosurfactants such as amphoteric (zwitterionic) and/or cationic surfactants
  • Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof.
  • Cationic surfactant when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the concentrated composition).
  • amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals.
  • Amphoteric (zwitterionic) surfactant when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
  • the level of betaine is preferably from 0.1 to 4% wt. of the premix.
  • the concentrated composition comprises a builder and more preferably this builder is MGDA.
  • this builder is MGDA.
  • the MGDA provides a wider formulation window for this unusual product format and permits more anti-foam without diminishing the visual appeal, in particular the clarity, of the product before dilution by the consumer. This is particularly the case when the composition also comprises a fatty acid anti-foam.
  • the MGDA is present at from 0.1 to 3% wt. of the premix composition, preferably from 0.1 to 2 and more preferably from 0.2 to 1.0% wt. of the premix composition.
  • the premix composition comprises less than 1 % by weight HEDP sequestrant, more preferably less than 0.1% wt. HEDP sequestrant.
  • the composition of the invention may comprise MGDA, it is preferred that no other builder is present. Accordingly, compositions of the invention may contain from 0 to 1%, more preferably from 0 to 0.1% wt. premix one or more additional builders.
  • a concentrated composition of the invention will preferably contain one or more additional polymeric cleaning boosters such as anti-redeposition polymers.
  • Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil.
  • Suitable soil release polymers for use in the invention include alkoxylated polyethyleneimines.
  • Polyethyleneimines 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.
  • Preferred alkoxylated polyethyleneimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M w ).
  • the polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer.
  • the alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both.
  • a nitrogen atom is alkoxylated
  • a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification.
  • a preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
  • a premix composition of the invention will preferably comprise from 0.025 to 8% wt. premix such materials depending on the parts premix are intended to be mixed with water.
  • Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing.
  • the adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.
  • SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped.
  • the SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity.
  • the weight average molecular weight (M w ) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.
  • SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol).
  • the copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units.
  • oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and folly-anionic-end- capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3, 6- dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.
  • DMT dimethyl terephthalate
  • PG propylene glyco
  • hydroxyether cellulosic polymers such as hydroxyether cellulosic polymers, (X alkylcelluloses and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as
  • Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group.
  • Examples of such materials have a structure corresponding to general formula (I): in which R 1 and R 2 independently of one another are X-(OC2H4) n -(OC3H6)m ; in which X is CM alkyl and preferably methyl; n is a number from 12 to 120, preferably from 40 to 50; m is a number from 1 to 10, preferably from 1 to 7; and a is a number from 4 to 9.
  • n, n and a are not necessarily whole numbers for the polymer in bulk.
  • the overall level of SRP when included, may range from 0.1 to 10%, depending on the level of polymer intended for use in the final diluted composition and which is desirably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the diluted composition).
  • soil release polymers are described in greater detail in II. S. Patent Nos. 5,574,179; 4,956,447; 4,861 ,512; 4,702,857, WO 2007/079850 and W02016/005271. If employed, soil release polymers will typically be incorporated into the liquid laundry detergent premix compositions herein in concentrations ranging from 0.01 percent to 10 percent, more preferably from 0.1 percent to 5 percent, by weight of the premix composition.
  • a composition of the invention may comprise one or more polymeric thickeners.
  • Suitable polymeric thickeners for use in the invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers.
  • HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture including at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer.
  • sociative monomer in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section.
  • a preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section.
  • Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from linear or branched C8-C40 alkyl (preferably linear C12-C22 alkyl) polyethoxylated (meth)acrylates; and (ii) at least one further monomer selected from C1-C4 alkyl (meth) acrylates, polyacidic vinyl monomers (such as maleic acid, maleic anhydride and/or salts thereof) and mixtures thereof.
  • the polyethoxylated portion of the associative monomer (i) generally comprises about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 oxyethylene repeating units.
  • a composition of the invention will preferably comprise from 0.01 to 5% wt. of the premix but depending on the amount intended for use in the final diluted product and which is desirably from 0.1 to 3% wt. by weight based on the total weight of the diluted composition.
  • fluorescer in the concentrated 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 % the premix.
  • 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, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. BlankophorSN.
  • Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. BlankophorSN.
  • 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.
  • Shading dye can be used to improve the performance of the concentrated compositions.
  • 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.
  • Shading dyes are well known in the art of laundry liquid formulation. Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates.
  • 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.
  • Concentrated compositions of the invention may have their rheology further modified by use of one or more external structurants which form a structuring network within the composition.
  • external structurants include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre.
  • the presence of an external structural may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid. Where included it would be preferred that such external structuring agents are added before any rheology modifier such as ethoxylated sorbitan ester.
  • a composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof.
  • the enzymes are preferably present with corresponding enzyme stabilizers.
  • Fragrances are well known in the art and may be incorporated into compositions described herein.
  • microencapsulation may be defined as the process of surrounding or enveloping one substance within another substance on a very small scale, yielding capsules ranging from less than one micron to several hundred microns in size.
  • the material that is encapsulated may be called the core, the active ingredient or agent, fill, payload, nucleus, or internal phase.
  • the material encapsulating the core may be referred to as the coating, membrane, shell, or wall material.
  • Microcapsules typically have at least one generally spherical continuous shell surrounding the core.
  • the shell may contain pores, vacancies or interstitial openings depending on the materials and encapsulation techniques employed.
  • Multiple shells may be made of the same or different encapsulating materials, and may be arranged in strata of varying thicknesses around the core.
  • the microcapsules may be asymmetrically and variably shaped with a quantity of smaller droplets of core material embedded throughout the microcapsule.
  • the shell may have a barrier function protecting the core material from the environment external to the microcapsule, but it may also act as a means of modulating the release of core materials such as fragrance.
  • a shell may be water soluble or water swellable and fragrance release may be actuated in response to exposure of the microcapsules to a moist environment.
  • a microcapsule might release fragrance in response to elevated temperatures.
  • Microcapsules may also release fragrance in response to shear forces applied to the surface of the microcapsules.
  • a preferred type of polymeric microparticle suitable for use in the invention is a polymeric core-shell microcapsule in which at least one generally spherical continuous shell of polymeric material surrounds a core containing the fragrance formulation (f2).
  • the shell will typically comprise at most 20% by weight based on the total weight of the microcapsule.
  • the fragrance formulation (f2) will typically comprise from about 10 to about 60% and preferably from about 20 to about 40% by weight based on the total weight of the microcapsule.
  • the amount of fragrance (f2) may be measured by taking a slurry of the microcapsules, extracting into ethanol and measuring by liquid chromatography.
  • Polymeric core-shell microcapsules for use in the invention may be prepared using methods known to those skilled in the art such as coacervation, interfacial polymerization, and polycondensation.
  • Coacervation typically involves encapsulation of a generally water-insoluble core material by the precipitation of colloidal material(s) onto the surface of droplets of the material.
  • Coacervation may be simple e.g. using one colloid such as gelatin, or complex where two or possibly more colloids of opposite charge, such as gelatin and gum arabic or gelatin and carboxymethyl cellulose, are used under carefully controlled conditions of pH, temperature and concentration.
  • Interfacial polymerisation typically proceeds with the formation of a fine dispersion of oil droplets (the oil droplets containing the core material) in an aqueous continuous phase.
  • the dispersed droplets form the core of the future microcapsule and the dimensions of the dispersed droplets directly determine the size of the subsequent microcapsules.
  • Microcapsule shell-forming materials are contained in both the dispersed phase (oil droplets) and the aqueous continuous phase and they react together at the phase interface to build a polymeric wall around the oil droplets thereby to encapsulate the droplets and form core-shell microcapsules.
  • An example of a core-shell microcapsule produced by this method is a polyurea microcapsule with a shell formed by reaction of diisocyanates or polyisocyanates with diamines or polyamines.
  • Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of precondensate of polymeric materials under appropriate conditions of agitation to produce capsules of a desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, resulting in the condensate separating from solution and surrounding the dispersed core material to produce a coherent film and the desired microcapsules.
  • An example of a core-shell microcapsule produced by this method is an aminoplast microcapsule with a shell formed from the polycondensation product of melamine (2,4,6-triamino-1 ,3,5-triazine) or urea with formaldehyde.
  • Suitable cross-linking agents e.g. toluene diisocyanate, divinyl benzene, butanediol diacrylate
  • secondary wall polymers may also be used as appropriate, e.g. anhydrides and their derivatives, particularly polymers and co-polymers of maleic anhydride.
  • One example of a preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with an aminoplast shell surrounding a core containing the fragrance formulation (f2). More preferably such an aminoplast shell is formed from the polycondensation product of melamine with formaldehyde.
  • Polymeric microparticles suitable for use in the invention will generally have an average particle size between 100 nanometers and 50 microns. Particles larger than this are entering the visible range.
  • particles in the sub-micron range include latexes and mini-emulsions with a typical size range of 100 to 600 nanometers.
  • the preferred particle size range is in the micron range.
  • particles in the micron range include polymeric core-shell microcapsules (such as those further described above) with a typical size range of 1 to 50 microns, preferably 5 to 30 microns.
  • the average particle size can be determined by light scattering using a Malvern Mastersizer with the average particle size being taken as the median particle size D (0.5) value.
  • the particle size distribution can be narrow, broad or multimodal. If necessary, the microcapsules as initially produced may be filtered or screened to produce a product of greater size uniformity.
  • Polymeric microparticles suitable for use in the invention may be provided with a deposition aid at the outer surface of the microparticle.
  • Deposition aids serve to modify the properties of the exterior of the microparticle, for example to make the microparticle more substantive to a desired substrate.
  • Desired substrates include cellulosics (including cotton) and polyesters (including those employed in the manufacture of polyester fabrics).
  • the deposition aid may suitably be provided at the outer surface of the microparticle by means of covalent bonding, entanglement or strong adsorption.
  • Examples include polymeric core-shell microcapsules (such as those further described above) in which a deposition aid is attached to the outside of the shell, preferably by means of covalent bonding. While it is preferred that the deposition aid is attached directly to the outside of the shell, it may also be attached via a linking species.
  • Deposition aids for use in the invention may suitably be selected from polysaccharides having an affinity for cellulose.
  • polysaccharides may be naturally occurring or synthetic and may have an intrinsic affinity for cellulose or may have been derivatised or otherwise modified to have an affinity for cellulose.
  • Suitable polysaccharides have a 1-4 linked p glycan (generalised sugar) backbone structure with at least 4, and preferably at least 10 backbone residues which are pi -4 linked, such as a glucan backbone (consisting of pi -4 linked glucose residues), a mannan backbone (consisting of pi -4 linked mannose residues) or a xylan backbone (consisting of pi -4 linked xylose residues).
  • Examples of such (31-4 linked polysaccharides include xyloglucans, glucomannans, mannans, galactomannans, P(1-3),(1-4) glucan and the xylan family incorporating glucurono-, arabino- and glucuronoarabinoxylans.
  • Preferred pi -4 linked polysaccharides for use in the invention may be selected from xyloglucans of plant origin, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which has a (31-4 linked glucan backbone with side chains of a-D xylopyranose and p-D- galactopyranosyl-(1-2)-a-D-xylo-pyranose, both 1-6 linked to the backbone); and galactomannans of plant origin such as loc ust bean gum (LBG) (which has a mannan backbone of pi -4 linked mannose residues, with single unit galactose side chains linked a1-6 to the backbone).
  • TXG pea xyloglucan and tamarind seed xyloglucan
  • LBG loc ust bean gum
  • polysaccharides which may gain an affinity for cellulose upon hydrolysis, such as cellulose mono-acetate; or modified polysaccharides with an affinity for cellulose such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxypropyl guar, hydroxyethyl ethylcellulose and methylcellulose.
  • Deposition aids for use in the invention may also be selected from phthalate containing polymers having an affinity for polyester.
  • Such phthalate containing polymers may have one or more nonionic hydrophilic segments comprising oxyalkylene groups (such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups), and one or more hydrophobic segments comprising terephthalate groups.
  • the oxyalkylene groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300.
  • a suitable example of a phthalate containing polymer of this type is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate. Mixtures of any of the above described materials may also be suitable.
  • Deposition aids for use in the invention will generally have a weight average molecular weight (M w ) in the range of from about 5 kDa to about 500 kDa, preferably from about 10 kDa to about 500 kDa and more preferably from about 20 kDa to about 300 kDa.
  • M w weight average molecular weight
  • One example of a particularly preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with a shell formed by the polycondensation of melamine with formaldehyde; surrounding a core containing the fragrance formulation (f2); in which a deposition aid is attached to the outside of the shell by means of covalent bonding.
  • the preferred deposition aid is selected from (31-4 linked polysaccharides, and in particular the xyloglucans of plant origin, as are further described above.
  • the present inventors have surprisingly observed that it is possible to reduce the total level of fragrance included in the composition of the invention without sacrificing the overall fragrance experience delivered to the consumer at key stages in the laundry process. A reduction in the total level of fragrance is advantageous for cost and environmental reasons.
  • the total amount of fragrance formulation (f1) and fragrance formulation (f2) in the premix of the invention suitably ranges from 0.5 to 1.4%, preferably from 0.5 to 1 .2%, more preferably from 0.5 to 1 % and most preferably from 0.6 to 0.9% (by weight based on the total weight of the premix).
  • the weight ratio of fragrance formulation (f1) to fragrance formulation (f2) in the composition of the invention preferably ranges from 60:40 to 45:55. Particularly good results have been obtained at a weight ratio of fragrance formulation (f1) to fragrance formulation (f2) of around 50:50.
  • fragrance (f1) and fragrance (f2) are typically incorporated at different stages of formation of the composition of the invention.
  • the discrete polymeric microparticles (e.g. microcapsules) entrapping fragrance formulation (f2) are added in the form of a slurry to a warmed base formulation comprising other components of the composition (such as surfactants and solvents).
  • Fragrance (f1) is typically post-dosed later after the base formulation has cooled.
  • a composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability.
  • additional optional ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye.
  • foam boosting agents e.g. bactericides
  • polyelectrolytes e.g. bactericides
  • anti-shrinking agents e.g. bactericides
  • anti-wrinkle agents antioxidants
  • sunscreens e.g. bactericides
  • anti-corrosion agents e.g. bactericides
  • drape imparting agents e.g. bactericides
  • anti-static agents e.g. bactericides
  • ironing aids e.g. bactericides
  • colorants e.g.
  • ingredients used in embodiments of the invention may be obtained from so called black carbon sources or a more sustainable green source.
  • black carbon sources or a more sustainable green source.
  • the following provides a list of alternative sources for several of these ingredients and how they can be made into raw materials described herein.
  • SLES and other such alkali metal alkyl ether sulphate anionic surfactants are typically obtainable by sulphating alcohol ethoxylates. These alcohol ethoxylates are typically obtainable by ethoxylating linear alcohols.
  • primary alkyl sulphate surfactants (PAS) can be obtained from linear alcohols directly by sulphating the linear alcohol. Accordingly, forming the linear alcohol is a central step in obtaining both PAS and alkali-metal alkyl ether sulphate surfactants.
  • linear alcohols which are suitable as an intermediate step in the manufacture of alcohol ethoxylates and therefore anionic surfactants such as sodium lauryl ether sulphate ca be obtained from many different sustainable sources. These include:
  • Primary sugars are obtained from cane sugar or sugar beet, etc., and may be fermented to form bioethanol.
  • the bioethanol is then dehydrated to form bio-ethylene which then undergoes olefin methathesis to form alkenes.
  • These alkenes are then processed into linear alcohols either by hydroformylation or oxidation.
  • An alternative process also using primary sugars to form linear alcohols can be used and where the primary sugar undergoes microbial conversion by algae to form triglycerides. These triglycerides are then hydrolysed to linear fatty acids and which are then reduced to form the linear alcohols.
  • Biomass for example forestry products, rice husks and straw to name a few may be processed into syngas by gasification. Through a Fischer Tropsch reaction these are processed into alkanes, which in turn are dehydrogenated to form olefins. These olefins may be processed in the same manner as the alkenes described above [primary sugars].
  • Waste plastic is pyrolyzed to form pyrolysed oils. This is then fractioned to form linear alkanes which are dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].
  • the pyrolyzed oils are cracked to form ethylene which is then processed to form the required alkenes by olefin metathesis. These are then processed into linear alcohols as described above [primary sugars].
  • MSWis turned into syngas by gasification. From syngas it may be processed as described above [primary sugars] or it may be turned into ethanol by enzymatic processes before being dehydrogenated into ethylene. The ethylene may then be turned into linear alcohols by the Ziegler Process.
  • the MSW may also be turned into pyrolysis oil by gasification and then fractioned to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.
  • the raw material can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These may be fermented to form bio-ethanol and then processed as described above [Primary Sugars], Waste Oils
  • Waste oils such as used cooking oil can be physically separated into the triglycerides which are split to form linear fatty acids and then linear alcohols as described above.
  • the used cooking oil may be subjected to the Neste Process whereby the oil is catalytically cracked to form bio-ethylene. This is then processed as described above.
  • Methane capture methods capture methane from landfill sites or from fossil fuel production.
  • the methane may be formed into syngas by gasification.
  • the syngas may be processed as described above whereby the syngas is turned into methanol (Fischer Tropsch reaction) and then olefins before being turned into linear alcohols by hydroformylation oxidation.
  • the syngas may be turned into alkanes and then olefins by Fischer Tropsch and then dehydrogenation.
  • Carbon dioxide may be captured by any of a variety of processes which are all well known.
  • the carbon dioxide may be turned into carbon monoxide by a reverse water gas shift reaction and which in turn may be turned into syngas using hydrogen gas in an electrolytic reaction.
  • the syngas is then processed as described above and is either turned into methanol and/or alkanes before being reacted to form olefins.
  • the captured carbon dioxide is mixed with hydrogen gas before being enzymatically processed to form ethanol.
  • This is a process which has been developed by Lanzatech. From here the ethanol is turned into ethylene and then processed into olefins and then linear alcohols as described above.
  • LAS linear alkyl benzene sulphonate
  • alkenes may be produced by any of the methods described above and may be formed from primary sugars, biomass, waste plastic, MSW, carbon capture, methane capture, marine carbon to name a few. Whereas in the processed described above the olefin is processed to form linear alcohols by hydroformylation and oxidation instead, the olefin is reacted with benzene and then sulphonate to form the LAS.
  • a concentrated composition of the invention may be packaged as unit doses in polymeric film soluble in the wash water.
  • a composition of the invention 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.
  • a method of laundering fabric using a composition of the invention will usually involve diluting the dose of detergent composition with water to obtain a wash liquor, and washing fabrics with the wash liquor so formed.
  • a method for forming a concentrated laundry detergent composition by diluting a premix as described above in water.
  • the consumer may add water to the concentrated composition, or alternatively concentrated composition to the water depending on the preferred consumer behaviour in any particular market.
  • the concentrated composition is made available to the consumer in a regular pack conforming with the volume of the concentrated composition purchased.
  • the packaged concentrated composition is available with an appropriately dimensioned dilution container in which water is added from a domestic supply and to which the concentrated composition is added to form the functional liquid detergent composition.
  • said concentrated composition 0.8 to 1 to 10 to 1 in water (water to concentrated composition).
  • the degree of dilution is also dependent on market choice. In some markets a more concentrated product is desired while in others a more dilute product is preferred.
  • the amount of water instructed to be used is thus variable but it is preferred that the dilution is at least 2: 1 and preferably no more than 7 to 1 , water to concentrated composition.
  • a container comprising a concentrated composition as described herein.
  • Containers include bottles, tattles, sealable bags and doy-packs and such like.
  • the container has an orifice which may provide means for adding water from a domestic supply to the container containing a concentrated composition.
  • the container comprises a means for adding water to the container and a separate means for permitting diluted contents to be dispensed.
  • the means for adding water is preferably near the top of the container when in a standing disposition and the means for permitting diluted contents to be dispensed is disposed near the bottom in the same disposition.
  • the container comprises a child resistant closure.
  • the container may comprise recycled materials such as post consumer recycled resin and suchlike.
  • the container may also be of an expansible type wherein the container as purchased by the consumer is to be expanded before dilution with water from a domestic supply.
  • the consumer purchases a container which is folded such that it contains a first volume of concentrated composition and is optionally packaged within a secondary package such that the consumer sees only a regular box or carton.
  • a secondary pack Inside such secondary pack is a bag or other such container and which contains the premix.
  • Water is added from a domestic supply and the concentrate is thus diluted to form the liquid laundry treatment composition which can be used in a regular way by the consumer.
  • it may be added to a shuttle device and placed inside a washing machine drum or it may be dispensed into a washing machine drawer.
  • the water supplied may also be filtered prior to use. This is at the consumer’s discretion but it is expected that the concentrated composition described herein is suitable for a wide variety of water hardnesses.
  • the container displaces a volume appropriate to permit dilution of said premix to form a liquid detergent composition at an appropriate dilution.
  • container may have internal volume (V) and the premix supplied in the container may have volume V/3.
  • the consumer will be directed to add two parts of water to one part of concentrated composition such that the volume of diluted concentrated composition is substantially equal to V.
  • the concentrated composition is marketed in a container of appropriate size to match the volume sold, together with a ‘keeper 1 container which can be sold filled with diluted product or empty as the consumer prefers.
  • the pre-mix container and the keeper container are maintained together by a form of secondary wrapping such as shrinkwrap.
  • the keeper may have a marker assisting the user in achieving the correct dilution levels.

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Abstract

Process for making a concentrated laundry liquid detergent composition comprising the following steps: - forming a batch of neutralised LAS acid in water; - heating or maintaining the batch temperature at from 40 to 60°C; - adding betaine surfactant to the batch; - adding non-ionic surfactant to the batch; - optionally adding further surfactant, rheology modifier, fragrance, enzymes and preservative where appropriate.

Description

PROCESS FOR MAKING LAUNDRY LIQUID DETERGENT COMPOSITION
The present invention relates to an improved process for making a concentrated laundry detergent composition. The present invention also relates to a composition obtainable by such process.
EP-A-1 367 118 (Unilever) discloses an aqueous liquid laundry detergent composition comprising a detergent surfactant (including anionic), an emulsifier with an HLB value below about 8.5; an oil; and an electrolyte in an amount to provide ionic strength indicator of from about 0.55 to about 6.7. The composition separates, upon standing for at most 24 hours at ambient temperature, into at least two layers, one of which is an emulsion with a continuous aqueous phase. The second layer is preferably a transparent composition.
WO 2013/043841 (Sun Products) discloses liquid cleaning compositions useful in cold water and hard water laundry applications, and methods for making and using such compositions. The compositions of the invention use surfactants or surfactant blends, such as a-sulfofatty acid esters or mixtures thereof (optionally along with one or more additional components), that have increased solubility/stability at cold temperatures, at higher-than-usual concentrations, and/or in hard water, with the composition remaining as a clear liquid. In certain embodiments, the compositions of the invention may be provided in the form of a unit dose, for example in a water-soluble pack or pouch. In use, the compositions of the invention result in an enhanced detergency along with a reduced amount of residue remaining in the machine, on laundered garments or cleaned dishware or hard surfaces, and on the body in personal care settings, and demonstrate a longer shelf-life, particularly when stored or used in colder temperatures.
WO 2013/092052 (Unilever) discloses an isotropic liquid detergent composition with an in-bottle pH in the range 6.0 to less than 7, the composition comprising, in addition to water: a) up to 60 wt percent detersive surfactant including at least 5 wt percent anionic sulphonate and /or sulphate surfactant comprising surfactant acid neutralised with one or more materials the pKa of whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition b) at least 0.3 wt percent fatty acid partially neutralised with one or more materials the pKa of whose conjugate acid(s) lies more than 2 units higher than the in-bottle pH of the detergent liquid composition c) at least 1.0 wt percent, preferably at least 1.8 wt percent, T riethanolamine (TEA); and d) at least 0.5 wt percent soil release polymer (SRP). WO 2011/120772 (Unilever) discloses a process for the incorporation of microcapsules with anionic charge into a structured aqueous concentrated liquid detergent comprising at least 30 wt percent, preferably at most 65 wt percent, total surfactant of which at least 5 wt percent based on the total composition is anionic surfactant, including soap, and an external structurant, the process comprising the combining of two premixes; Premix A which is the structured aqueous concentrated liquid detergent composition without microcapsules and Premix B which comprises an aqueous dispersion of the microcapsules with anionic charge, characterised in that: Premix B is a slurry of microcapsules with a maximum viscosity at 25 degrees centigrade of 100 mPas and at least 90 wt percent of the microcapsules having a particle size in the range 5 to 30 microns, and that Premix B is added to Premix A and the resulting combined mixture is passed through a static in-line mixer with an energy input of from 20 to 500 J/kg to form, immediately after the mixer, a structured liquid comprising less than 10 percent, based on the total number of groups of microcapsules, agglomerated groups of microcapsules, an agglomerated group of microcapsules being defined as a group having more than 5 microcapsules grouped together.
WO 2017/075681 (Oxiteno) discloses a new thickener composition comprising a mixture of one or more alkoxylated polyol esters, one or more ethoxylated sorbitan esters and glycerol, used to increase the viscosity of cosmetic skin and hair cleansing products and of surface and fabric cleaners, as well as to make these products easier to formulate. The thickener composition described is compatible with a great variety of formulations of cosmetic skin and hair cleansing products and of surface and fabric cleaners comprising one or more surfactants, co-surfactants, solvents, fragrances, emulsifiers, preservatives, salts, pigments and/or colouring agents, besides other inert compounds with regard to the end performance, this composition being capable of increasing the viscosity thereof in a stable a measurable manner.
WO 96/21721 (Jeyes) discloses a sealed container containing a unit dose of a liquid surfactant containing concentrate, which concentrate, on dilution with water, gives a diluted liquid product of similar or increased viscosity. The concentrate may further contain other active ingredients such as bleaching agents, disinfectants and conditioning agents. The concentrate may be adapted for application to hard surfaces such as sinks or floors or to soft surfaces such as fabrics, skin or hair.
WO 98/16623 (P&G) discloses a hand-held container for pre-dissolving a predetermined amount of detergent with a predetermined amount of solvent comprises a housing, a resilient side wall, and a dispensing passage. The dispensing passage has a flow restriction portion and an applicator at the distal end. The container is intended for use with fluids with a viscosity of less than about 500 cP. When so used, and aligned to a dispensing orientation, fluid flows out of the dispensing passage at a rate from about 0 ml/min to about 300 ml/min, unless manual pressure is exerted on the resilient side wall.
Concentrated products which can be diluted at home are becoming more and more popular among the more environmentally aware consumers. Typically, such products are purchased as concentrated forms of the regular product and they are diluted by the consumer in the domestic environment. The immediate challenge is in the context of viscosity management. The composition after dilution is expected to perform physically as well as functionally as would a regular product. Unexpectedly, the dilutable composition must have a viscosity which sufficiently matches the viscosity profile of the diluted composition. However, when mixing five parts water with one part concentrated product it is usually expected that the viscosity become radically different.
The challenge is therefore to make a product which has an appropriate physical profile and performs appropriately on dilution in water.
To satisfy this challenge the inventors have identified an improved process which makes it more feasible to make a product according to this physical profile.
Accordingly, and in a first a instance, there is provides a process for making a concentrated laundry liquid detergent composition comprising the following steps: forming a batch of neutralised LAS acid in water; heating or maintaining the batch temperature at from 40 to 60°C; adding betaine surfactant to the batch; adding non-ionic surfactant to the batch; optionally adding further surfactant, rheology modifier, fragrance, enzymes and preservative where appropriate.
We have surprisingly found that adding the non-ionic surfactant to the heated batch of neutralised LAS acid results in a more stable micelle formation which is suitable for making concentrated laundry detergent compositions which are dilutable by the consumer in a domestic environment.
The non-ionic surfactant is added after the LAS. It is also preferred that the non-ionic surfactant is added after any secondary surfactant such as any betaine. It is also preferable that the non-ionic surfactant is added before any rheology modifier such as those described herein. This enables the micellar structure to be fully developed prior to any rheology modifier being added. This is important when trying to achieve a viscosity profile for the concentrated composition before dilution and also after dilution by the consumer.
The non-ionic mixture comprising neutralised LAS is heated to a temperature at least 7°C above the cloud point of the non-ionic surfactant but always lower than 60C. Preferably, the neutralised LAS is heated to from 40 to 60°C, preferably from 45 to 55°C before addition of the non-ionic surfactant. This ensures that the non-ionic surfactant is able to achieve the correct physical relationship with the LAS, and optional betaine, as quickly as possible. It is also preferred that this mixture of neutralised LAS and non-ionic surfactant is stirred after addition of the non-ionic surfactant. Again, this helps reduce batch time and does not disturb the micellar structure being generated which assists in maintaining a correct rheology before and after dilution by the consumer. Preferably, the non-ionic surfactant and neutralised LAS is stirred for at least five minutes after addition of the non-ionic surfactant to the batch.
Fully neutralising the LAS acid and maintaining at a pH of 6.5 to 7.5 helps obtain the correct micellar disposition which is required before further components are added to the mixture. If this is not achieved and instead the LAS is not fully neutralised then the formulator is required to address this later in the process through addition of viscosity modifiers such as salt. In the context of concentrated formulations for which the viscosity profile is so important not just in the concentrated mixture before dilution but also after dilution, this later correction is not possible.
By maintaining the pH at this intermediate level of from 6.5 to 7.5, preferably from 6.5 to 7.0, we have found that it is possible to create the right viscosity profile both before and after dilution by the consumer.
Preferably, the neutralising agent is selected from TEA and sodium hydroxide.
In a preferred process the pH is adjusted to from 6.5 to 7.5 by addition of the neutralising agent. By this is meant that the neutralising agent, preferably sodium hydroxide, is added to the premix before the LAS acid is added, the LAS acid is then added, and then more neutralising agent is added to adjust the pH of the mixture to from 6.5 to 7.5.
In such an embodiment preferably from 40 to 80% wt., of the total neutralising agent is added prior to the LAS acid and from 20 to 60% is added after. More preferably, from 50-70% wt. of the total neutralising agent is added before the LAS acid and from 30 to 50% wt. is added after the LAS acid. Most preferably, from 55-65% wt. of the total neutralising agent is added before the LAS acid and from 35 to 45% wt. is added after the LAS acid.
The concentrated composition made according to the process of the first aspect comprises detersive surfactant. The term “detersive surfactant’ in the context of this invention denotes a surfactant which provides a detersive (i.e. cleaning) effect to laundry treated as part of a domestic laundering process.
Non-soap anionic surfactants for use in the invention are typically salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof. The alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule. The counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed.
A preferred class of non-soap anionic surfactant for use in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1 -phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then fully neutralized in-situ.
Some primary alkyl sulfate surfactant (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18.
Mixtures of any of the above described materials may also be used.
In a composition of the invention the total level of anionic surfactant may preferably range from 20 to 50% by weight based on the total weight of the surfactant. However, it is preferred that the level of anionic surfactant is lower than the level of non-ionic surfactant. Preferably, the ration between the anionic surfactant and non-ionic surfactant is from 1 : 1 .5 to 1 :20 and more preferably from 1 :3 to 1 :10.
Also commonly used in laundry liquid compositions are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule. However, we have found that alkyl ether sulphates have a deleterious effect on performance of such compositions for use as premixes as described herein and in such instance it is preferred that the level of any alkyl ether sulphate is from 0 to 10% wt. of the total level of surfactant, more preferably from 0 to 1% wt and most preferably zero.
Preferably, the composition comprises from 20 to 95% wt. non-ionic surfactant based on the total weight of surfactant. Nonionic surfactants for use in the invention are typically polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. The polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides. Examples of such materials include Cs to C22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and aliphatic alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
A preferred class of nonionic surfactant for use in the invention includes aliphatic Cs to Cis, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.
A further class of non-ionic surfactants include the alkyl poly glycosides and rhamnolipids.
Mixtures of any of the above described materials may also be used. Preferably, the selection and amount of surfactant is such that the concentrated laundry detergent formulation and the diluted mixture are isotropic in nature.
Preferably, the composition comprises a rheology modifier. A rheology modifier is a material which adjusts the rheological performance of the composition. The rheology modifier does not necessary thicken or thin and composition it is added to.
Preferably the rheology modifier comprises ethoxylated sorbitan ester. The ethoxylated sorbitan ester provides improved rheological characteristics in the context of a product which is diluted by the consumer in the domestic environment. It should be noted that this is independent of any rheological behaviour which is affected by pouring or otherwise using the diluted product. The concentrated premix is to be diluted by the user and as such it is necessary for the premix to behave rheologically appropriately.
More preferably the ethoxylated sorbitan ester comprises from 50 to 1000 ethoxylate units, more preferably from 200 to 700 and most preferably from 300 to 550.
Preferably, the ethoxylated sorbitan ester comprises one to five, more preferably three to five fatty acid esters. More preferably, the ethoxylated sorbitan ester comprises a fatty acid having from 10 to 22 carbons, more preferably from 14 to 20 and most preferably 18 carbons. The fatty acid may be straight chain or branched, saturated or unsaturated. The most preferred fatty acid group is a stearic acid group.
The most preferred ethoxylated sorbitan ester is sorbeth-450 tristearate and which is the triester of stearic acid and a polyethylene glycol ether of sorbitol with an average of 450 moles of ethylene oxide.
Preferably the ethoxylated sorbitan ester is present at from 0.01-8.0% of the final laundry detergent composition.
Preferably, the composition comprises PEG ester fatty acid. PEG fatty acid ester is included top modify the rheological performance of the composition particularly during dilution. Preferred PEG ester fatty acids include PEG 9 cocoate, PEG 32 and PEG 175.
Preferably, the PEG ester fatty acid is present at from 0.01-5.0% of the final laundry detergent composition. In a preferred process, the temperature of the neutralised LAS, optional betaine, and non-ionic surfactant is maintained at from 40 to 60°C, preferably from 40 to 55°C, while any rheology modifier is added. This prevents any adverse reaction to the viscosity management before and after dilution caused by the addition of the rheology modifier. It also ensures that the micelles are properly formed before the rheology modifier is added. If the rheology modifier is added before the non-ionic surfactant the resulting micellar formation is disturbed and is irreparable.
In a preferred process the rheology modifier is heated to from 35 to 50°C, more preferably from 38 to 43°C, before being added to the neutralised LAS and non-ionic mixture which is preferably being maintained at from 40 to 55°C.
Preferably, the temperature of the mixture is then cooled before adding any further components such as fragrance, preservative and enzymes. Preferably, the temperature is cooled to below 40°C before such materials are added. Preferably the preservative comprises isothiazolinone materials at a level not higher than 500ppm in the concentrate.
More preferably the temperature is cooled gradually before such materials are added. Most preferably, the rate of cooling is from 0.1 °C per minute to 2°C per minute, more preferably from 0.5 to 1 ,5°C per minute and most preferably from 0.75 to 1 ,25°C per minute.
In a preferred embodiment the final pH of the detergent composition is from 7 to 8. In such circumstance it is adjusted after the neutralisation of LA where necessary using and appropriate buffer.
In a second aspect there is provided a concentrated laundry detergent composition obtainable by a process according to the first aspect.
Anti-Foam
The concentrated product may also comprise an anti-foam. Anti-foam materials are well known in the art and include silicones and fatty acid.
Preferably, where present, the fatty acid anti-foam is present at from 1 .3 to 3.0, more preferably from 1.4 to 2.0% wt. and most preferably from 1.6 to 1.65% wt. of the premix.
Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).
The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
Mixtures of any of the above described materials may also be used.
For formula accounting purposes, in the formulation, fatty acids and/or their salts (as defined above) are not included in the level of surfactant or in the level of builder.
Hydrotropes
A concentrated composition of the invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (Mw) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates).
Mixtures of any of the above described materials may also be used.
Non-aqueous carriers, when included, may be present in an amount ranging from 0.1 to 20%, preferably from 2 to 15%, and more preferably from 10 to 14% (by weight based on the total weight of the concetrate). The level of hydrotrope used is linked to the level of surfactant and it is desirable to use hydrotrope level to manage the viscosity in such concentrated formulations. The preferred hydrotrope is monopropylene glycol. Cosurfactants
A concentrated composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above.
Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof. Cationic surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the concentrated composition).
Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
Mixtures of any of the above described materials may also be used.
The level of betaine, more preferably the alkyl amidopropyl betaine, most preferably CAPB, is preferably from 0.1 to 4% wt. of the premix.
Builders
Preferably, the concentrated composition comprises a builder and more preferably this builder is MGDA. We have surprisingly found that the MGDA provides a wider formulation window for this unusual product format and permits more anti-foam without diminishing the visual appeal, in particular the clarity, of the product before dilution by the consumer. This is particularly the case when the composition also comprises a fatty acid anti-foam.
Where present, the MGDA is present at from 0.1 to 3% wt. of the premix composition, preferably from 0.1 to 2 and more preferably from 0.2 to 1.0% wt. of the premix composition. Preferably, the premix composition comprises less than 1 % by weight HEDP sequestrant, more preferably less than 0.1% wt. HEDP sequestrant. While the composition of the invention may comprise MGDA, it is preferred that no other builder is present. Accordingly, compositions of the invention may contain from 0 to 1%, more preferably from 0 to 0.1% wt. premix one or more additional builders.
Polymeric Cleaning Boosters
To further improve the environmental profile of liquid laundry detergents it may be preferred in some cases to reduce the volume of laundry detergent dosed per wash-load and to add various highly weight efficient ingredients to the composition to boost cleaning performance. In addition to the soil release polymers described above, a concentrated composition of the invention will preferably contain one or more additional polymeric cleaning boosters such as anti-redeposition polymers.
Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil. Suitable soil release polymers for use in the invention include alkoxylated polyethyleneimines. Polyethyleneimines 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. Preferred alkoxylated polyethyleneimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (Mw). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
Mixtures of any of the above described materials may also be used.
When included, a premix composition of the invention will preferably comprise from 0.025 to 8% wt. premix such materials depending on the parts premix are intended to be mixed with water. An amount that provides from 0.5 to 6% (by weight based on the total weight of the diluted composition) of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines which are described above.
Soil Release Polymers
Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing. The adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre. SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped. The SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (Mw) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.
SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and folly-anionic-end- capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3, 6- dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.
Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, (X alkylcelluloses and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl ester), for example Ci-Ce vinyl esters (such as poly(vinyl acetate)) grafted onto polyalkylene oxide backbones; poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.
Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (I): in which R1 and R2 independently of one another are X-(OC2H4)n-(OC3H6)m; in which X is CM alkyl and preferably methyl; n is a number from 12 to 120, preferably from 40 to 50; m is a number from 1 to 10, preferably from 1 to 7; and a is a number from 4 to 9.
Because they are averages, m, n and a are not necessarily whole numbers for the polymer in bulk.
Mixtures of any of the above described materials may also be used.
The overall level of SRP, when included, may range from 0.1 to 10%, depending on the level of polymer intended for use in the final diluted composition and which is desirably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the diluted composition).
Suitable soil release polymers are described in greater detail in II. S. Patent Nos. 5,574,179; 4,956,447; 4,861 ,512; 4,702,857, WO 2007/079850 and W02016/005271. If employed, soil release polymers will typically be incorporated into the liquid laundry detergent premix compositions herein in concentrations ranging from 0.01 percent to 10 percent, more preferably from 0.1 percent to 5 percent, by weight of the premix composition.
Polymeric Thickeners
A composition of the invention may comprise one or more polymeric thickeners. Suitable polymeric thickeners for use in the invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture including at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer. The term “associative monomer” in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section. A preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section. Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from linear or branched C8-C40 alkyl (preferably linear C12-C22 alkyl) polyethoxylated (meth)acrylates; and (ii) at least one further monomer selected from C1-C4 alkyl (meth) acrylates, polyacidic vinyl monomers (such as maleic acid, maleic anhydride and/or salts thereof) and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally comprises about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 oxyethylene repeating units.
Mixtures of any of the above described materials may also be used.
If included, a composition of the invention will preferably comprise from 0.01 to 5% wt. of the premix but depending on the amount intended for use in the final diluted product and which is desirably from 0.1 to 3% wt. by weight based on the total weight of the diluted composition.
It may be advantageous to include fluorescer in the concentrated compositions. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt % the premix.
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, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. BlankophorSN.
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.
Shading dye can be used to improve the performance of the concentrated compositions. 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.
Shading dyes are well known in the art of laundry liquid formulation. Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates.
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.
External Structurants
Concentrated compositions of the invention may have their rheology further modified by use of one or more external structurants which form a structuring network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre. The presence of an external structural may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid. Where included it would be preferred that such external structuring agents are added before any rheology modifier such as ethoxylated sorbitan ester.
Enzymes
A composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present with corresponding enzyme stabilizers.
Fragrances
Fragrances are well known in the art and may be incorporated into compositions described herein.
Microcapsules
One type of microparticle suitable for use in the invention is a microcapsule. Microencapsulation may be defined as the process of surrounding or enveloping one substance within another substance on a very small scale, yielding capsules ranging from less than one micron to several hundred microns in size. The material that is encapsulated may be called the core, the active ingredient or agent, fill, payload, nucleus, or internal phase. The material encapsulating the core may be referred to as the coating, membrane, shell, or wall material.
Microcapsules typically have at least one generally spherical continuous shell surrounding the core. The shell may contain pores, vacancies or interstitial openings depending on the materials and encapsulation techniques employed. Multiple shells may be made of the same or different encapsulating materials, and may be arranged in strata of varying thicknesses around the core. Alternatively, the microcapsules may be asymmetrically and variably shaped with a quantity of smaller droplets of core material embedded throughout the microcapsule.
The shell may have a barrier function protecting the core material from the environment external to the microcapsule, but it may also act as a means of modulating the release of core materials such as fragrance. Thus, a shell may be water soluble or water swellable and fragrance release may be actuated in response to exposure of the microcapsules to a moist environment. Similarly, if a shell is temperature sensitive, a microcapsule might release fragrance in response to elevated temperatures. Microcapsules may also release fragrance in response to shear forces applied to the surface of the microcapsules.
A preferred type of polymeric microparticle suitable for use in the invention is a polymeric core-shell microcapsule in which at least one generally spherical continuous shell of polymeric material surrounds a core containing the fragrance formulation (f2). The shell will typically comprise at most 20% by weight based on the total weight of the microcapsule. The fragrance formulation (f2) will typically comprise from about 10 to about 60% and preferably from about 20 to about 40% by weight based on the total weight of the microcapsule. The amount of fragrance (f2) may be measured by taking a slurry of the microcapsules, extracting into ethanol and measuring by liquid chromatography.
Polymeric core-shell microcapsules for use in the invention may be prepared using methods known to those skilled in the art such as coacervation, interfacial polymerization, and polycondensation.
The process of coacervation typically involves encapsulation of a generally water-insoluble core material by the precipitation of colloidal material(s) onto the surface of droplets of the material. Coacervation may be simple e.g. using one colloid such as gelatin, or complex where two or possibly more colloids of opposite charge, such as gelatin and gum arabic or gelatin and carboxymethyl cellulose, are used under carefully controlled conditions of pH, temperature and concentration.
Interfacial polymerisation typically proceeds with the formation of a fine dispersion of oil droplets (the oil droplets containing the core material) in an aqueous continuous phase. The dispersed droplets form the core of the future microcapsule and the dimensions of the dispersed droplets directly determine the size of the subsequent microcapsules. Microcapsule shell-forming materials (monomers or oligomers) are contained in both the dispersed phase (oil droplets) and the aqueous continuous phase and they react together at the phase interface to build a polymeric wall around the oil droplets thereby to encapsulate the droplets and form core-shell microcapsules. An example of a core-shell microcapsule produced by this method is a polyurea microcapsule with a shell formed by reaction of diisocyanates or polyisocyanates with diamines or polyamines.
Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of precondensate of polymeric materials under appropriate conditions of agitation to produce capsules of a desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, resulting in the condensate separating from solution and surrounding the dispersed core material to produce a coherent film and the desired microcapsules. An example of a core-shell microcapsule produced by this method is an aminoplast microcapsule with a shell formed from the polycondensation product of melamine (2,4,6-triamino-1 ,3,5-triazine) or urea with formaldehyde. Suitable cross-linking agents (e.g. toluene diisocyanate, divinyl benzene, butanediol diacrylate) may also be used and secondary wall polymers may also be used as appropriate, e.g. anhydrides and their derivatives, particularly polymers and co-polymers of maleic anhydride.
One example of a preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with an aminoplast shell surrounding a core containing the fragrance formulation (f2). More preferably such an aminoplast shell is formed from the polycondensation product of melamine with formaldehyde.
Polymeric microparticles suitable for use in the invention will generally have an average particle size between 100 nanometers and 50 microns. Particles larger than this are entering the visible range. Examples of particles in the sub-micron range include latexes and mini-emulsions with a typical size range of 100 to 600 nanometers. The preferred particle size range is in the micron range. Examples of particles in the micron range include polymeric core-shell microcapsules (such as those further described above) with a typical size range of 1 to 50 microns, preferably 5 to 30 microns. The average particle size can be determined by light scattering using a Malvern Mastersizer with the average particle size being taken as the median particle size D (0.5) value. The particle size distribution can be narrow, broad or multimodal. If necessary, the microcapsules as initially produced may be filtered or screened to produce a product of greater size uniformity.
Polymeric microparticles suitable for use in the invention may be provided with a deposition aid at the outer surface of the microparticle. Deposition aids serve to modify the properties of the exterior of the microparticle, for example to make the microparticle more substantive to a desired substrate. Desired substrates include cellulosics (including cotton) and polyesters (including those employed in the manufacture of polyester fabrics). The deposition aid may suitably be provided at the outer surface of the microparticle by means of covalent bonding, entanglement or strong adsorption. Examples include polymeric core-shell microcapsules (such as those further described above) in which a deposition aid is attached to the outside of the shell, preferably by means of covalent bonding. While it is preferred that the deposition aid is attached directly to the outside of the shell, it may also be attached via a linking species.
Deposition aids for use in the invention may suitably be selected from polysaccharides having an affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic and may have an intrinsic affinity for cellulose or may have been derivatised or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked p glycan (generalised sugar) backbone structure with at least 4, and preferably at least 10 backbone residues which are pi -4 linked, such as a glucan backbone (consisting of pi -4 linked glucose residues), a mannan backbone (consisting of pi -4 linked mannose residues) or a xylan backbone (consisting of pi -4 linked xylose residues). Examples of such (31-4 linked polysaccharides include xyloglucans, glucomannans, mannans, galactomannans, P(1-3),(1-4) glucan and the xylan family incorporating glucurono-, arabino- and glucuronoarabinoxylans. Preferred pi -4 linked polysaccharides for use in the invention may be selected from xyloglucans of plant origin, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which has a (31-4 linked glucan backbone with side chains of a-D xylopyranose and p-D- galactopyranosyl-(1-2)-a-D-xylo-pyranose, both 1-6 linked to the backbone); and galactomannans of plant origin such as loc ust bean gum (LBG) (which has a mannan backbone of pi -4 linked mannose residues, with single unit galactose side chains linked a1-6 to the backbone).
Also suitable are polysaccharides which may gain an affinity for cellulose upon hydrolysis, such as cellulose mono-acetate; or modified polysaccharides with an affinity for cellulose such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxypropyl guar, hydroxyethyl ethylcellulose and methylcellulose.
Deposition aids for use in the invention may also be selected from phthalate containing polymers having an affinity for polyester. Such phthalate containing polymers may have one or more nonionic hydrophilic segments comprising oxyalkylene groups (such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups), and one or more hydrophobic segments comprising terephthalate groups. Typically, the oxyalkylene groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. A suitable example of a phthalate containing polymer of this type is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate. Mixtures of any of the above described materials may also be suitable.
Deposition aids for use in the invention will generally have a weight average molecular weight (Mw) in the range of from about 5 kDa to about 500 kDa, preferably from about 10 kDa to about 500 kDa and more preferably from about 20 kDa to about 300 kDa.
One example of a particularly preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with a shell formed by the polycondensation of melamine with formaldehyde; surrounding a core containing the fragrance formulation (f2); in which a deposition aid is attached to the outside of the shell by means of covalent bonding. The preferred deposition aid is selected from (31-4 linked polysaccharides, and in particular the xyloglucans of plant origin, as are further described above.
The present inventors have surprisingly observed that it is possible to reduce the total level of fragrance included in the composition of the invention without sacrificing the overall fragrance experience delivered to the consumer at key stages in the laundry process. A reduction in the total level of fragrance is advantageous for cost and environmental reasons.
Accordingly, the total amount of fragrance formulation (f1) and fragrance formulation (f2) in the premix of the invention suitably ranges from 0.5 to 1.4%, preferably from 0.5 to 1 .2%, more preferably from 0.5 to 1 % and most preferably from 0.6 to 0.9% (by weight based on the total weight of the premix).
The weight ratio of fragrance formulation (f1) to fragrance formulation (f2) in the composition of the invention preferably ranges from 60:40 to 45:55. Particularly good results have been obtained at a weight ratio of fragrance formulation (f1) to fragrance formulation (f2) of around 50:50.
The fragrance (f1) and fragrance (f2) are typically incorporated at different stages of formation of the composition of the invention. Typically, the discrete polymeric microparticles (e.g. microcapsules) entrapping fragrance formulation (f2) are added in the form of a slurry to a warmed base formulation comprising other components of the composition (such as surfactants and solvents). Fragrance (f1) is typically post-dosed later after the base formulation has cooled.
Further Optional Ingredients
A composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount of up to 5% (by weight based on the total weight of the diluted composition) and so adjusted depending on the dilution ratio with water.
Many of the ingredients used in embodiments of the invention may be obtained from so called black carbon sources or a more sustainable green source. The following provides a list of alternative sources for several of these ingredients and how they can be made into raw materials described herein.
SLES and PAS
SLES and other such alkali metal alkyl ether sulphate anionic surfactants are typically obtainable by sulphating alcohol ethoxylates. These alcohol ethoxylates are typically obtainable by ethoxylating linear alcohols. Similarly, primary alkyl sulphate surfactants (PAS) can be obtained from linear alcohols directly by sulphating the linear alcohol. Accordingly, forming the linear alcohol is a central step in obtaining both PAS and alkali-metal alkyl ether sulphate surfactants.
The linear alcohols which are suitable as an intermediate step in the manufacture of alcohol ethoxylates and therefore anionic surfactants such as sodium lauryl ether sulphate ca be obtained from many different sustainable sources. These include:
Primary sugars
Primary sugars are obtained from cane sugar or sugar beet, etc., and may be fermented to form bioethanol. The bioethanol is then dehydrated to form bio-ethylene which then undergoes olefin methathesis to form alkenes. These alkenes are then processed into linear alcohols either by hydroformylation or oxidation.
An alternative process also using primary sugars to form linear alcohols can be used and where the primary sugar undergoes microbial conversion by algae to form triglycerides. These triglycerides are then hydrolysed to linear fatty acids and which are then reduced to form the linear alcohols.
Biomass
Biomass, for example forestry products, rice husks and straw to name a few may be processed into syngas by gasification. Through a Fischer Tropsch reaction these are processed into alkanes, which in turn are dehydrogenated to form olefins. These olefins may be processed in the same manner as the alkenes described above [primary sugars].
An alternative process turns the same biomass into polysaccharides by steam explosion which may be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol which in turn is dehydrated to form bio-ethylene. This bio-ethylene is then processed into linear alcohols as described above [primary sugars].
Waste Plastics
Waste plastic is pyrolyzed to form pyrolysed oils. This is then fractioned to form linear alkanes which are dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].
Alternatively, the pyrolyzed oils are cracked to form ethylene which is then processed to form the required alkenes by olefin metathesis. These are then processed into linear alcohols as described above [primary sugars].
Municipal Solid Waste
MSWis turned into syngas by gasification. From syngas it may be processed as described above [primary sugars] or it may be turned into ethanol by enzymatic processes before being dehydrogenated into ethylene. The ethylene may then be turned into linear alcohols by the Ziegler Process.
The MSW may also be turned into pyrolysis oil by gasification and then fractioned to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.
Marine Carbon
There are various carbon sources from marine flora such as seaweed and kelp. From such marine flora the triglycerides can be separated from the source and which is then hydrolysed to form the fatty acids which are reduced to linear alcohols in the usual manner.
Alternatively, the raw material can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These may be fermented to form bio-ethanol and then processed as described above [Primary Sugars], Waste Oils
Waste oils such as used cooking oil can be physically separated into the triglycerides which are split to form linear fatty acids and then linear alcohols as described above.
Alternatively, the used cooking oil may be subjected to the Neste Process whereby the oil is catalytically cracked to form bio-ethylene. This is then processed as described above.
Methane Capture
Methane capture methods capture methane from landfill sites or from fossil fuel production. The methane may be formed into syngas by gasification. The syngas may be processed as described above whereby the syngas is turned into methanol (Fischer Tropsch reaction) and then olefins before being turned into linear alcohols by hydroformylation oxidation.
Alternatively, the syngas may be turned into alkanes and then olefins by Fischer Tropsch and then dehydrogenation.
Carbon Capture
Carbon dioxide may be captured by any of a variety of processes which are all well known. The carbon dioxide may be turned into carbon monoxide by a reverse water gas shift reaction and which in turn may be turned into syngas using hydrogen gas in an electrolytic reaction. The syngas is then processed as described above and is either turned into methanol and/or alkanes before being reacted to form olefins.
Alternatively, the captured carbon dioxide is mixed with hydrogen gas before being enzymatically processed to form ethanol. This is a process which has been developed by Lanzatech. From here the ethanol is turned into ethylene and then processed into olefins and then linear alcohols as described above.
LAS
One of the other main surfactants commonly used in cleaning compositions, in particular laundry compositions is LAS (linear alkyl benzene sulphonate).
The key intermediate compound in the manufacture of LAS is the relevant alkene. These alkenes (olefins) may be produced by any of the methods described above and may be formed from primary sugars, biomass, waste plastic, MSW, carbon capture, methane capture, marine carbon to name a few. Whereas in the processed described above the olefin is processed to form linear alcohols by hydroformylation and oxidation instead, the olefin is reacted with benzene and then sulphonate to form the LAS.
Packaging and Dosing
A concentrated composition of the invention may be packaged as unit doses in polymeric film soluble in the wash water. Alternatively, a composition of the invention 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.
A method of laundering fabric using a composition of the invention will usually involve diluting the dose of detergent composition with water to obtain a wash liquor, and washing fabrics with the wash liquor so formed.
In a third aspect there is provided a method for forming a concentrated laundry detergent composition by diluting a premix as described above in water.
The consumer may add water to the concentrated composition, or alternatively concentrated composition to the water depending on the preferred consumer behaviour in any particular market. Where the concentrated composition is added to water, the concentrated composition is made available to the consumer in a regular pack conforming with the volume of the concentrated composition purchased. In such instances it is preferred that the packaged concentrated composition is available with an appropriately dimensioned dilution container in which water is added from a domestic supply and to which the concentrated composition is added to form the functional liquid detergent composition.
Preferably, by diluting said concentrated composition 0.8 to 1 to 10 to 1 in water (water to concentrated composition). The degree of dilution is also dependent on market choice. In some markets a more concentrated product is desired while in others a more dilute product is preferred. The amount of water instructed to be used is thus variable but it is preferred that the dilution is at least 2: 1 and preferably no more than 7 to 1 , water to concentrated composition.
In a fourth aspect there is provided a container comprising a concentrated composition as described herein. Containers include bottles, tattles, sealable bags and doy-packs and such like. Preferably, the container has an orifice which may provide means for adding water from a domestic supply to the container containing a concentrated composition. It is also preferred that the container comprises a means for adding water to the container and a separate means for permitting diluted contents to be dispensed. In such an embodiment the means for adding water is preferably near the top of the container when in a standing disposition and the means for permitting diluted contents to be dispensed is disposed near the bottom in the same disposition. Preferably, the container comprises a child resistant closure. Preferably, the container may comprise recycled materials such as post consumer recycled resin and suchlike.
The container may also be of an expansible type wherein the container as purchased by the consumer is to be expanded before dilution with water from a domestic supply.
For example, the consumer purchases a container which is folded such that it contains a first volume of concentrated composition and is optionally packaged within a secondary package such that the consumer sees only a regular box or carton. Inside such secondary pack is a bag or other such container and which contains the premix. Water is added from a domestic supply and the concentrate is thus diluted to form the liquid laundry treatment composition which can be used in a regular way by the consumer. For example, it may be added to a shuttle device and placed inside a washing machine drum or it may be dispensed into a washing machine drawer.
The water supplied may also be filtered prior to use. This is at the consumer’s discretion but it is expected that the concentrated composition described herein is suitable for a wide variety of water hardnesses.
Preferably, the container displaces a volume appropriate to permit dilution of said premix to form a liquid detergent composition at an appropriate dilution. For example, container may have internal volume (V) and the premix supplied in the container may have volume V/3. In such an embodiment the consumer will be directed to add two parts of water to one part of concentrated composition such that the volume of diluted concentrated composition is substantially equal to V.
In an alternative embodiment the concentrated composition is marketed in a container of appropriate size to match the volume sold, together with a ‘keeper1 container which can be sold filled with diluted product or empty as the consumer prefers. The pre-mix container and the keeper container are maintained together by a form of secondary wrapping such as shrinkwrap.
The keeper may have a marker assisting the user in achieving the correct dilution levels. EXAMPLE
The following is an embodiment process.
Make a pre-mix of optical brighter, water, dye. Separately, prepare a batch of brine, water, MPG, glycerin, TEA, NaOH (60% of total formula quantity).
Then add LAS acid and allow to react for 5 minutes.
Add the remaining (about 40%) of the NaOH to adjust pH for 6.5 - 7.5 (preferably 6.5 to 7.0).
Add Betaine (55°C) before adding the non-ionic surfactant and maintaining the temperature of the batch at 45°C - 55°C. Mix for 5min. Add pre-heated ethoxylated sorbitan ester and maintain batch temperature at from 45°C - 55°C.
Cool down to 30°C by no more than 1 °C per minute.
At 40°C add preservatives.
Add the premix of optical brighter and dye.
At 30°C add enzymes.

Claims

- 26 - CLAIMS
1 . Process for making a concentrated laundry liquid detergent composition comprising the following steps: forming a batch of neutralised LAS acid in water; heating or maintaining the batch temperature at from 40 to 60°C; adding betaine surfactant to the batch; adding non-ionic surfactant to the batch; optionally adding further surfactant, rheology modifier, fragrance, enzymes and preservative where appropriate.
2. Process according to claim 1 wherein the LAS acid is fully neutralised before the non-ionic surfactant is added.
3. Process according to any preceding claim wherein the LAS acid is neutralised at from 6.5 to 7.5 pH.
4. Process according to any preceding claim wherein the final pH of the detergent composition is from 7 to 8.
5. Process according to any preceding claim wherein the LAS acid is neutralised with a neutralising agent selected from TEA and sodium hydroxide.
6. Process according to any preceding claim wherein a rheology modifier is added after the non-ionic surfactant.
7. Process according to claim 6 wherein the rheology modifier comprises ethoxylated sorbitan ester.
8. A concentrated laundry detergent composition obtainable by a process according to any preceding claim.
9. A laundry detergent composition obtainable by diluting a composition according to claim 8 in water.
10. A composition according to claim 9 wherein the concentrated composition is diluted one part concentrated composition to from 1 to 10 parts, preferably 2 to 7 parts water.
EP21749520.9A 2020-08-12 2021-08-11 Process for making laundry liquid detergent composition Pending EP4196562A1 (en)

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