WO2025149371A1

WO2025149371A1 - Detergent composition

Info

Publication number: WO2025149371A1
Application number: PCT/EP2024/088289
Authority: WO
Inventors: Jessica Mary ANDREWS; Stephen Norman Batchelor; Neil Stephen Burnham; Ami Swapnil Wagle
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Priority date: 2024-01-12
Filing date: 2024-12-23
Publication date: 2025-07-17
Anticipated expiration: 2026-07-12
Also published as: WO2025149345A1; WO2025149208A1

Abstract

A liquid detergent composition comprising: from 1 to 70 wt.% surfactant; and from 0.1 to 25 wt.% of a combined amount of methylglycinediacetic acid (MGDA) and ethylglycinemonoacetic acid (MGMA), wherein the molar fraction of MGDA/MGMA is at least 3.6.

Description

DETERGENT COMPOSITION

Field of the Invention

The present invention relates to a liquid detergent composition comprising MGDA.

Background of the Invention

Liquid detergents generally contain a variety of actives. One of the most prevalent cleaning actives are surfactants. Surfactants are important for lowering water-tension to ensure the wash-liquor (a suitable dilution of the neat liquid detergent with water) gets into more effective contact with the surface to be cleaned. Surfactants also play a role in suspending/dissolving soils more easily from the surface into the wash liquor. To reduce the negative effects of calcium and magnesium ions on surfactants so called 'builders' (complexing agents) are used in detergent compositions. Complexing agents also serve the function to complex transition metal ions in the wash, thereby aiding stain removal.

Phosphorous based builders have set the benchmark for effective builders and complexing agents. A well know example is sodium tripolyphosphate (STPP). Their use is largely curtailed being a cause of environmental eutrophication. There has been a continuous desire for effective environmentally friendly alternative builders and complexing agents to replace phosphorous based chemistry. One example thereof is methylglycinediacetic acid (MGDA). The use of MGDA however also presents its own unique challenges especially in liquid detergents.

Liquid detergents may be packed in transparent containers (unit-dose or multi-dose bottles). Such transparent containers offer the advantage that the consumer can visually inspect the liquid. This allows not only for providing distinct-looking liquid detergent products (e.g., through coloring and/or by suspending bodies in the liquid) but also allows monitoring the amount of liquid detergent remaining during use. A problem is that exposure of the detergent liquid in a transparent container to sunlight can cause formulation instability over time (off-smell and/or discoloration). Part of the current invention is that the cause of these problems can be attributed to the MGDA the liquid detergent.

It is an object of the present invention to provide a liquid detergent which comprises MGDA, but which provides a reduced off-smell and/or an improved color stability upon exposure to sunlight. Summary of the Invention

One or more of the above objectives are achieved in a first aspect of the invention by a liquid detergent composition comprising:

• from 1 to 70 wt.% surfactant; and

• from 0.1 to 25 wt.% of a combined amount of methylglycinediacetic acid (MGDA) and methylglycinemonoacetic acid (MGMA), wherein the molar fraction of MGDA/MGMA is at least 3.6; and

• preferably a dye.

It was surprisingly found that MGDA materials can comprise significant amounts of methylglycinemonoacetic acid (MGMA). MGMA has the following chemical structure: wherein X is H or a counterion such as Na or an amine.

It was however found that if the MGDA:MGMA ratio is kept within certain bounds, the negative effects of using MGDA material could be controlled. Allowing an acceptable level of MGMA is relevant to reduce processing complexity and maintain acceptable cost of the MGDA material.

A further aspect of the invention is the use of MGDA material having a mole ratio of MGDA:MGMA of at least 3.6 to improve liquid detergent stability during storage.

Detailed Description of the Invention

Definitions

Weight percentage (wt.%) is based on the total weight of the detergent composition unless otherwise indicated or as made clear from the context. It will be appreciated that the total weight amount of ingredients will not exceed 100 wt. %. Whenever an amount or concentration of a component is quantified herein, unless indicated otherwise, the quantified amount or quantified concentration relates to said component per se, even though it may be common practice to add such a component in the form of a solution or of a blend with one or more other ingredients. It is furthermore to be understood that the verb "to comprise" and its conjugations is used in its nonlimiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. Finally, reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements. The indefinite article "a" or "an" thus usually means "at least one". Unless otherwise specified all measurements are taken at standard conditions. Whenever a parameter, such as a concentration or a ratio, is said to be less than a certain upper limit it should be understood that in the absence of a specified lower limit the lower limit for said parameter is 0.

The wt.% of MGDA actives and any MGMA actives is based on the equivalent weight of their protonated form (assuming all carboxylate groups as -COOH). Unless otherwise made clear from the context ‘MGDA’ or ‘MGDA material’ refers to MGDA material including any byproducts, such as MGMA. ‘MGDA active’ is used as required to refer to the MGDA as specific chemical in the MGDA (material) unless this is already clear from the context. For example, the MGDA (material) can comprise at least 70 wt.% of MGDA active as based on total solids. The amount of MGDA actives based on total solids is especially relevant in the context of MGDA material supplied in dissolved form in which case the MGDA material used can contain further solvent. MGDA can be supplied in both solid and dissolved forms as component to make liquid detergents compositions. When talking about molar fractions of MGDA:MGMA the context clearly refers to molar fractions of the MGDA active: MGMA active. When talking about combined amounts of MGDA and MGMA the context clearly refers to levels of actives.

The liquid detergent of the invention is preferably in a transparent container. The term ‘transparent’ as used herein refers to the ability of light within the visible spectrum (400 to 700 nm) to pass through the container wall. The transparency can be quantified as the ratio between the light intensity measured after the light has passed through a material sample and the light intensity measured when the material sample has been removed. The ratio can be converted to a percentage Transmittance (multiply the ratio x 100) ranging from 0% (no incoming light having passed through the material sample) to 100% (i.e. no difference in light having passed through with and without material sample). As used herein the term ‘transparent’ refers to a Transmittance of at least 10% within the wavelength range of 400 to 700 nm, preferably of at least 20 %, 30 %, 40 %, 50 %, 60%, 70%, 80%, in increasing order of preference, and still even more preferably of at least 90 %.

Preferably at least 30 %, 50 %, 70 % and even more preferably at least 85 % of the total outer container surface area of the container is transparent. This is preferably determined while taking into account externally applied labels and/or stickers. Transmittance of the container material can be suitably measured by using a LIV-VIS Spectrometer, preferably as based on a light path- length through the plastic of 1 mm. Suitable LIV-VIS spectrometers are available from a variety of suppliers, including Thermo Scientific, Perkin Elmer and Shimadzu.

The transparency of the liquid detergent is suitably measured in the same way but using a light path-length of 1 cm to standardize the measurement. Transparency of liquid is typically determined by use of a cuvette, wherein the transmittance of the liquid is based on the ratio between a cuvette with the liquid detergent versus an empty cuvette (x100). The suitable cuvette to use is usually indicated in the Supplier instructions of the LIV-VIS spectrometer. The liquid detergent preferably has an average transmittance in the wavelength range of from 400 to 700 nm, based on a path-length of 1cm, of at least 20 %. More preferably the transmittance is at least 30%, even more preferably at least 50 % and still even more preferably at least 70%. Obviously as the liquid is colored, the average transmittance across the visible wavelengths will be below 100% and preferably is at most 90 % and even more preferably at most 80 %.

The term “liquid” in the context of this invention denotes that a continuous phase or predominant part of the detergent is liquid and that the composition is flowable at 15 degrees Celsius or higher. Accordingly, the term “liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, such as gels. The viscosity of the detergent is preferably from 200 to about 10,000 mPa.s at 25 degrees Celsius at a shear rate of 21 sec¹. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. Pourable liquid detergents preferably have a viscosity of from 200 to 1 ,500 mPa.s, preferably from 200 to 700 mPa.s.

Preferably the liquid detergent of the invention is aqueous, meaning it contains at least 10 wt.% water. Preferably, the composition comprises at least 40 wt.%, more preferably 50 wt.%, even more preferably 60 wt.% water and still more preferably at least 70 wt.% water.

The detergent of the invention is preferably a liquid laundry detergent or a liquid machine dishwash detergent and more preferably is a laundry detergent. The term “laundry detergent” in the context of this invention denotes detergents intended for and capable of wetting and cleaning domestic laundry such as clothing, linens and other household textiles, preferably also when diluted in washing machine to form a wash liquor. A label carrying product information may be applied onto the outside of the transparent container surface. The label is advantageously in part non-transparent to improve readability of any information thereon. Application of such labels is to communicate information about the product to the consumer, some of which information is necessitated by law or regulation. The label can be applied as a heat-shrinkable sleeve, a suitable sticker, or in any other suitable manner. It is advantageous that the label, if present, is thin, meaning it has a thickness of from 0.01 to 2 mm and is itself made from a recyclable plastic. More preferably the label does not reduce the transparent surface area of the plastic transparent container by more than 50 %, preferably by no more than 30 % and even more preferably by no more than 20 %.

Surfactant

The liquid detergent of the invention preferably comprises from 2 to 60 wt. % of surfactant, more preferably from 3 to 50 wt. % and even more preferably from 4 to 30 wt.%. Preferably greater than 95 wt.% of the total weight of the surfactant is selected from anionic and nonionic surfactant and mixtures thereof.

In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated.

Anionic surfactants are discussed in the Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series published by CRC press. Preferred anionic surfactants are sulfonate and sulfate surfactants, preferably alkylbenzene sulphonates, alkyl sulfates and alkyl ether sulfates. Preferred alkyl groups for alkyl sulfates and alkyl ether sulfates are selected from linear of branched C12-C18 saturate alkyl chains and monounsaturated C18 chains. C12-C14 alkyl ether sulfates having a straight or branched chain alkyl group having 12 to 14 carbon atoms (C12-14) and containing an average of 1 to 3EO units per molecule are preferred. 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. LAS (linear alkyl benzene sulphonate) is a preferred anionic surfactant at from 1 to 20 wt.%, more preferably from 2 to 15 wt.% of the composition, most preferably 8 to 12 wt.%. The anionic surfactant is preferably added to the detergent composition in the form of a salt. Preferred cations are alkali metal ions, such as sodium and potassium. However, the salt form of the anionic surfactant may be formed in situ by neutralization of the acid form of the surfactant with alkali such as sodium hydroxide or an amine, such as mono-, di-, or triethanolamine. Weight ratios are calculated for the protonated form of the surfactant.

Ethoxy units may be partially replaced by propoxy units in anionic and non-ionic surfactants.

Further examples of suitable anionic surfactants are rhamnolipids, alpha-olefin sulfonates, olefin sulfonates, alkene sulfonates, alkane-2,3-diylbis(sulfates), hydroxyalkanesulfonates and disulfonates, fatty alcohol sulfates (FAS), paraffin sulfonates, ester sulfonates, sulfonated fatty acid glycerol esters, methyl ester sulfonate alkyl- or alkenylsuccinic acid, dodecenyl/tetradecenyl succinic acid (DTSA), fatty acid derivatives of amino acids, DATEM’s, CITREM’s and diesters and monoesters of sulfo-succinic acid.

Preferably, especially for liquid laundry detergents, the weight fraction of non-ionic surfactant/total anionic surfactant is from 0.1 to 9, more preferably 0.15 to 2, most preferably 0.2 to 1. By total anionic surfactant means the total content of any of the classes of anionic surfactant

Nonionic surfactant are discussed in Non-ionic Surfactants: Organic Chemistry edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series published by CRC press. Preferred non-ionic surfactants are alkoxylate, preferably ethoxylated, Preferred non-ionic surfactant are alcohol ethoxylates and methyl ester ethoxylates, with C10-C18 alkyl chains. Commonly used in laundry liquid compositions are C12-C18 satuarated and monounsaturated alcohol ethoxylates having a straight or branched chain alkyl group and containing an average of 5 to 12EO units per molecule. Preferred examples are selected from saturated linear C12, C14 or C16 chains and branched or linear saturated C15 alcohol ethoxylates with a mole average of 7 to 9 ethoxylate units. A preferred methyl ester ethoxylate comprised C16, C18 and C18:1 and a mol average of 8 to 12 ethoxylate groups. More preferably the the methyl ester comprises 20 to 50wt% C16 MEE and 20 to 50wt% C18:1 MEE. C18:1 is preferably an oleic moiety and C16 and C18 are saturated.

Typically, ethoxylation reactions to form alcohol ethoyxlates are base catalysed using NaOH, KOH, or NaOCH3. The reaction produces a distribution of ethoxy chain lengths in the alcohol ethoxylate. Narrow range ethoxylation provides a narrower distribution of ethoxy chain lengths than NaOH, KOH, or NaOCH3. Narrow range ethoxylation is achieved using narrow range ethoxylation catalysts Narrow range ethoxylation catalyst are described in EP3289790 (Procter & Gamble), EP1747183(Hacros); Santacesatia et al Ind. Eng. Chem. Res. 1992, 31 , 2419- 2421; US4239917(Conoco); Li et al ACS Omega. 2021 Nov 9; 6(44): 29774-29780; Hreczuch et al J. Am. Oil Chem. Soc. 1996, 73, 73-78 and WO2022/ 129374 (Unilever). Ethoxylation reactions are described in Non-lonic Surfactant Organic Chemistry (N. M. van Os ed), Surfactant Science Series Volume 72, CRC Press.

For machine dishwash detergents, the composition of the invention advantageously comprises from 0.5 to 20 wt. % of a non-ionic surfactant or a mixture of two or more non-ionic surfactants. A more preferred amount of total non-ionic surfactant is from 1 to 15 wt. %, even more preferably from 2 to 10 wt. % and still even more preferably from 3 to 6 wt.%. Such levels are considered optimal. The non-ionic surfactant is preferably present in amounts of 25 to 90 wt. % based on the total weight of the surfactant system. Preferably, if present, the amount of anionic surfactant is at most 5 wt. %, more preferably at most 3 wt. %, even more preferably at most 2 wt. % and even more preferably at most 1 wt. %, still even more preferably essentially no anionic surfactant is present. Highly advantageous for machine dishwash surfactant systems is that they provide a little or no foaming during operation of the dishwasher (i.e. are low-foaming surfactant systems).

Especially for liquid laundry detergents these 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 wt.%. 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 preferably selected from 012:0, 014:0, 016:0 ,018:0 and C18: 1 , 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 wt.%. Mixtures of any of the above-described materials may also be used.

Preferred surfactant systems for liquid detergents of the invention are however selected from the list consisting of non-ionic surfactants, anionic surfactants and combinations thereof.

The liquid detergent preferably comprises from 1 to 5 wt.% ethanol.

MGDA

MGDA has the following structure (I):

[CH₃-CH(COO)-N(CH2-COO)2]M3-XHX (I) wherein M is selected from alkali metal cations or quaternary amines, the cations can be the same or different. Preferred are cations of lithium, sodium, potassium, protonated triethanolamine, protonated monoethanolamide or combinations thereof. More preferred are alkali metal cations, and even more preferred are sodium and potassium and combinations of sodium and potassium, x in formula (I) is in the range of from 0 to 1.0, preferred is a range of 0 to 0.5. In a particularly preferred embodiment, x is zero. MGDA can be partially or preferably fully neutralized with the respective alkali. In a preferred embodiment, an average of from 2.7 to three COOH groups of MGDA is neutralized with alkali metal, preferably with sodium. In a particularly preferred embodiment, the MGDA is a trisodium salt of MGDA of the form:

MGDA and its respective alkali metal salts are selected from the racemic mixtures, the D- isomers and the L-isomers, and from mixtures of the D- and L-isomers other than the racemic mixtures. Preferably, the MGDA is selected from the racemic mixture and from mixtures containing in the range of from 55 to 95 mole % of the L-isomer, the balance being D-isomer. Particularly preferred are mixtures containing in the range of from 60 to 80 mole % of the L- isomer, the balance being D-isomer. Other particularly preferred embodiments are racemic mixtures. The level of MGMA can be controlled by (partial) purification of the MGDA product and/or by driving the MGDA synthesis reaction to greater completion, with the latter being preferred. For example MGDA may be synthesized by reacting ammonia, methanal and hydrogen cyanide at pH 6 to form iminodiacetonitrile, then placing in a strongly acidic medium (pH 1.5) and reacting with ethanal to produce trinitrile methylglycinonitrile-A/, /V-diacetonitrile. Alkaline hydrolysis then yields trisodium MGDA. An alternative is to produce alaninotrile by a Stecker synthesis with HCN, NH3 and CH3CHO, the alaninotrile is convert to methylglycinonitrile-A/, /V-diacetonitrile by double cyanomethylation with methanal and hydrogen cyanide, then hydrolyzed with NaOH to yield MGDA. Increasing the level of methanal can drive the reaction more to completion, i.e. convert more MGMA to MGDA in the final product. In doing so additional glycolic acid may be formed in the end-product, which was surprisingly found to have little or no negative stability effects. Preferably the mole fraction of glycolic acid I (MGDA + MGMA) is at least 0.010, more preferably is at least 0.011 to 0.1 and even more preferably is from 0.011 to 0.045.

The Mole fraction (ratio) of MGDA to MGMA may be determined by 1 H NMR spectroscopy. The sample is dried, preferably by freeze-drying then fully dissolved in a deuterated solvent. The deuterated solvent preferably is D₂O or a deuterated alcohol, more preferably deuterated D₂O. The integral of the N-CH2- protons are taken from the spectra, in D₂O these are at ~3.2ppm for MGDA and ~3.3ppm for MGMA. Peak splitting may occur due to the presence of stereo and optical isomers. The mole fraction is given by the equation:

Mole fraction = IMGDA/(2*IMGMA) wherein IMGDA is the integral for N-CH2- protons for MGDA and IMGMA is the integral for N-CH2- protons for MGMA. IMGMA is multiplied by 2, to account for the fact MGMA has 2 N-CH2- protons compared to 4 for MGDA.

Preferably the combined amount of MGDA and MGMA is from 0.1 to 20 wt.% more preferably from 0.2 to 15 wt.% even more preferably from 0.4 to 4 wt.% and still even more preferably is from 0.5 to 2.5 wt.%.

An advantageous molar fraction of MGDA/MGMA is at least 3.7 (i.e., 3.7 time more moles of MGDA than moles of MGMA), preferably 3.8, more preferably 3.9 and even more preferably is at least 4.0. MGDA is commercially available from several companies including Shijiazhuang Jackchem Co., ltd, BASF (Trilon product range) and Nouryon (Dissolvine product range). These commercial sources may have some level of MGMA. Allowing some level of MGMA in the composition is important to reduce manufacturing complexity while still providing good formulation stability.

Hence it is beneficial that the molar fraction of MGDA/MGMA is at most 100, more preferably at most 50, even more preferably at most 25, still even more preferably is at most 20, still even more preferably is at most 15, still even more preferably at most 6, still even more preferably is at most 5 and still even more preferably is at most 4.5.

The suitable pH of the liquid detergent depends on the surface to be treated. In case of laundry detergents, preferably the liquid detergent has a pH from 5 to 9.0, preferably from 6.0 to 8.0. In case the liquid detergent is a machine dishwash detergent the preferred pH is from 7.0 to 11.0, preferably 8.0 to 10.0 and more preferably is from 8.5 to 9.5. The pH of the liquid detergent is measured at 20 degrees Celsius in otherwise standard conditions. The desired pH value can be set by using suitable amounts of acid and alkali. Preferred acids are organic acids. In this sense it is noted that the sodium salt of MGDA material is alkaline.

Product form

The liquid detergent product may be in the form of a water-soluble unit-dose or a multi-dose liquid detergent, such as a bottle. The liquid detergent product is preferably in a bottled form.

Unit-dose products comprising multiple compartments are preferred and especially those which have at least one compartment with a liquid phase and at least compartment with a solid phase (e.g., powder). Unit dose products are typically contained in water-soluble transparent film, such as based on PVA.

Suitable multiple-dose containers, such as a rigid bottle, preferably have an internal volume of from 0.1 to 10L, more preferably of from 0.2 to 5L and even more preferably of from 0.5 to 2.2L. Advantageously the container has a pouring neck with a resealable screw top where the maximum dimension of the pouring neck of the container is at least 3 times smaller than the maximum dimension of the container. On initial sale the container preferably is filled to greater than 95% of the container capacity by weight. The plastic container of the invention is most advantageously in the shape of a bottle. Bottle shapes are predominantly devoid of sharp edges and corners, for example as opposed to cuboid boxes. Bottles are further generally characterized by having a height which exceeds the width and depth of the bottle when in upright position on a flat horizontal surface. Highly advantageous are transparent bottles, wherein at least 30 %, more preferably at least 40%, 50%, 60% and even more preferably at least 70 % of the outer surface area is transparent.

When the container is plastic-based, the plastic preferably comprises at least 20 wt.%, more preferably 30 wt.%, even more preferably at least 50 wt.%, still even more preferably at least 70 wt. % and still even more preferably at least 95 wt. % of recycled plastic. The recycled plastic is advantageously recycled HDPE, LDPE and/or PET and more preferably is recycled PET.

When the container is plastic-based, the plastic preferably comprises at least 20 wt.%, more preferably 30 wt.%, even more preferably at least 50 wt.%, still even more preferably at least 70 wt. % and still even more preferably at least 95 wt. % of polyethylene terephthalate (PET).

It is considered that the invention is advantageously applied to liquid detergents which are packaged in transparent plastic-based bottles, wherein the plastic preferably comprises recycled PET. It is considered that recycled plastic, especially recycled PET can increase the negative effects of off-smell formation and/or colour instability during storage and/or exposure to (sun)light.

The wt. % of recycled plastic can be determined by measuring the tensile strength of the plastic. Alternatively, recycled plastics can be distinguished from virgin plastic in various ways as recycled plastic often has polymers of reduced molecular weight and are characterized by the presence of impurities (see Rahimi et. al. “Chemical recycling of waste plastics for new materials production”, Nature Reviews Chemistry”, vol. 1, Art. No. 0046, 2017).

Advantageously the plastic of the container contains from 0.01 to 6 wt. %, more preferably from 0.1 to 5 wt. % and even more preferably from 1 to 4.5 wt. % of a UV absorber, based on the total weight of the container plastic. UV absorber is present as additive in the plastic.

Advantageous UV absorbers are Cyanoacrylate UV absorbers. These are particularly preferred at level from 0.03 to 0.3 wt.%, more preferably from 0.05 to 0.2 wt.%, based on the total weight of the container plastic. Preferred Cyanoacrylate UV absorbers comprise/are diphenylacrylates, more preferably alkyl-2-cyano-3, 3-diphenyl acrylates, where alkyl is a branched or linear saturated alkyl group of molecular weight of less than 120 and even more preferably pentaerythritol tetrakis(2-cyano-3,3-diphenylacrylate), 1 ,3-bis-((2’-cyano-3’, 3’-diphenylacryloyl) oxy)-2, 2-bis-(((2’-cyano-3’, 3’-diphenylacryloyl) oxy) methyl)-propane, ethyl-2-cyano-3, 3- diphenyl acrylate, 2-cyano-3,3-diphenyl-2-propenoicaciethylester, 2-ethylhexyl-2-cyano-3,3- diphenylacrylate or mixtures thereof. Cyanoacrylate UV-Absorbers are available from BASF, (llvinul), Deltachem(QingDao) (Ominstab), MPI Chemie, (UV), Shipro Kasei Kaisha (Seesorb).

Dye

The application of the invention is especially advantageous for providing liquid dye-colored detergents with improved color stability. The dyes of the invention preferably have a maximum extinction coefficient of greater than 5000 L/mol/cm, preferably greater than 10000 L/mol/cm in the range of 400 to 700 nm. Dyes are preferably selected which contain a chromophore selected from azine, anthraquinone, mono-azo or triphenylmethane, most preferably anthraquinone. Dyes are described in Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527 -30426-6. Dyes for use in the current invention are selected from cationic, anionic and non-ionic dyes and preferably are selected from anionic and non-ionic dyes. Anionic dyes are negatively charged in an aqueous medium at pH 7. Examples of anionic dyes are found in the classes of acid and direct dyes in the Color Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists). Anionic dyes preferably contain at least one sulphonate or carboxylate groups. Non-ionic dyes are uncharged in an aqueous medium at pH 7, examples are found in the class of disperse dyes in the Color Index.

The dye may be any color, but preferred dye is blue, violet, green or red. Most preferably the dye is blue or violet. The dyes may be alkoxylated. described below. Examples of polyoxyalkylene chains include ethylene oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

The dye is preferably present in the liquid detergent at a level to give an optical density, as measured with a 1cm path length and at the absorption maximum of the dye, of from 0.05 to 2, most preferably 0.4 to 0.8. This is typically provided by dye levels from 0.001 to 2 wt.%, more preferably from 0.005 to 0.1 wt.% of the liquid detergent.

Anthraquinone Dyes

Preferably the detergent comprises an anthraquinone dye according to the following structure: wherein the anthraquinone chromophore contains an amine group or an acid amide group in the 1 -position, the 4-position or both in the 1-position and the 4-position; and wherein the chromophore preferably contains at least one group containing an [alkoxy]_n moiety; wherein the at least one group containing an [alkoxy]_n moiety can be covalently bound at any of the numbered positions, directly or via the amine or acid amide group; and wherein n of the at least one group containing an [alkoxy]_n moiety is from 2 to 20. More preferred anthraquinone dyes of the invention have an amine group or acid amine group in both the 1- and 4-position.

The anthraquinone dye may have more than one [alkoxy]_n containing group. The number of [alkoxy]_n containing groups in an anthraquinone dye of the invention can suitably be from 1 to 8, but preferably is from 1 to 4, more preferably is 1 or 2 or 3 and even more preferably is 2. Preferably the total number of alkoxy monomers in an anthraquinone dye is from 2 to 40, preferably from 3 to 30 and more preferably from 4 to 20.

Advantageously, the at least one [alkoxy]_n containing group is covalently attached at any one of the positions 1 to 4 of the anthraquinone dye of the invention, directly or via the N-atom of the amine or acid group. Beneficial are anthraquinone dyes of the following structure: where R2, R3, X and Y are H or an organic group and at least one of the groups R2, R3, X and Y contains a -[CH₂CH2O]_nRi group, where

• n is from 2 to 20; and

• R1 is an organic group or H, preferably R1 is CHs or H and more preferably R1 is H; and • preferably X and Y represent the same group and more preferably are H; and

• preferably R2 and R3 are -CH2CH2CH2O(CH2CH2O)2RI and more preferably R1 is -H.

Alkoxylated dyes are preferred. An alkoxylated dye contains at least one poly-alkoxy containing group covalently bound to the chromophore. The poly-alkoxy containing group may be bound directly to an aromatic ring of the chromophore or more may be bound indirectly, such as via an N-atom of an amine or acid amide group. The polyalkoxy group may contain a linker moiety and have the following structure: -linker-(alkoxy)_n. The alkoxy-monomers preferably have 2 to 4 carbon atoms and may form a mixed poly-alkoxylate, such as a poly-alkoxylate comprising both ethoxylate, propoxylate and butoxylate monomers. Dyes which have alkoxy monomers of the same type are preferred. Dyes with ethoxy monomers are preferred. Alkoxylated dyes are described in W02022056205 (Milliken).

Blue Dyes are preferably selected from: and from equivalent molecules which differ from these structures in their degree of ethoxylation, where preferably each ethoxy chain has a mole average of 2 to 15 ethoxy units.

Further preferred blue dyes are selected from: where R2, R3, X and Y are H or an organic groups and at least one of the groups R2, R3, X and Y contains a -[CFkCFWjnH group. Preferred examples are 1-amino-2-polyethylenoxy-4- phenylamino-anthraquinone, 1-amino-2-methoxy-4-[-4-polyethleneoxy-anilyl]anthraquinone, 1- amino-2-polyethyleneoxy-4-(2,4,6-trimethylphenylamino) anthraquinone and N,N'- dialkyleneoxy-substituted 1 ,4-diaminoanthraquinones. More preferred are N,N'-dialkyleneoxy- substituted 1 ,4-diaminoanthraquinones. Most preferably X=Y=H and R2 and R3 are - CH₂CH2CH2O(CH2CH2O)2RI as described in example 1 and 2 of US7632682. Green dyes are preferably selected from: and from equivalent molecules which differ from these structures in their degrees of ethoxylation, where preferably each ethoxy chain has a mole average of 2 to 15 ethoxy units.

Red dyes are preferably selected from: and from equivalent molecules which differ from these structures in their degrees of ethoxylation, where preferably each ethoxy chain has a mole average of 2 to 15 ethoxy units.

Yellow dyes are preferably selected from: and from equivalent molecules which differ from these structures in their degrees of ethoxylation, where preferably each ethoxy chain has a mole average of 2 to 15 ethoxy units.

Violet dyes are preferably selected from: and from equivalent molecules which differ from these structures in their degrees of ethoxylation, where preferably each ethoxy chain has a mole average of 2 to 15 ethoxy units.

In the -[ethoxy]_n moiety, ‘n’ generally refers to the average number of alkoxy-monomers, in which n thus can represents the average of a distribution. In this case beneficial are -[ethoxy]_n moieties distribution in which the most prevalent molecular species has an ethoxy number which corresponds to that of the distribution average ‘n’. Further preferred are those distributions in which the molecular species with a degree of alkoxylation corresponding to the average number ‘n’ is present in a higher molar %. For example, if ‘n’ is 4, then a distribution of 25% n=2, 50% n=4 and 25% n=6 is more preferred than a distribution of 30% n=2, 40% n=4 and 30% n=6. This beneficially applies to the average number of alkoxy-monomers in the alkoxylated dye as a whole and/or the average number of alkoxy-monomers in an individual poly-alkoxy containing group.

Leuco dyes as described in EP 3 535 369 (Millken) may be used but are less preferred.

Shading dyes

Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300. The white cloth used in this test is bleached non-mercerised woven cotton sheeting.

The shading dye chromophore is preferably selected from mono-azo, bis-azo, anthraquinone, and azine. In an embodiment, a mixture of the shading dyes may be used. One type of shading dye may be used, but preferably, at least two, at least three or at least four shading dyes are used in combination.

Preferably, the shading dye is a mono-azo dye. Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes. The mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH=7. Alkoxylated thiophene dyes are discussed in WO2013/142495 and W02008/087497. More preferred mono-azo thiophene dyes have the following structure (a [2EO], 3[EO] dye): and from equivalent molecules which differ from this structure in the degree of ethoxylation, where preferably each ethoxy chain has a mole average of 2 to 15 ethoxy units. Also advantageous are bis-azo shading dye. Bis azo-dyes are preferably sulphonate bis-azo- dyes. Preferred bis-azo shading dye is of the following structures: wherein: ring D and E may be independently naphthyl or phenyl as shown;

R¹ is selected from: hydrogen and Ci-C4-alkyl, preferably hydrogen;

R² is selected from: hydrogen, Ci-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

R³ and R⁴ are independently selected from: hydrogen and Ci-C4-alkyl, preferably hydrogen or methyl;

X and Y are independently selected from: hydrogen, Ci-C4-alkyl and Ci-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 11 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51, direct violet 66, direct violet 99 and alkoxlyated versions thereof. Alkoxylated bis-azo dyes are discussed in WO2012/054058 and W02010/151906. In yet another preferred embodiment, the shading dye is an azine dye. Azine dyes typically have the following core structure: wherein R_a, Rb, R_c and Rd are selected from: H, an branched or linear Ci to Cy-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SO₃' or -COO' group; the B ring does not carry a negatively charged group or salt thereof; and the A ring may be further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2.

Preferably, the azine dyes have the following general structure: wherein:

X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5;

X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;

Y₂ is selected from: -OH; -OCH2CH2OH; -CH(OH)CH₂OH; -OC(O)CH₃; and, C(O)OCH₃.

Azine dyes are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-NO 72749-80-5, acid blue 59. Also preferred are azine shading dyes of the following structure:

An additional preference for shading dye are reactive blue anthraquinone dye. An example of an anthraquinone dye has the following structure:

In a preferred embodiment, the shading dye is a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. The alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation. Preferably 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation. Preferably the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800. An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is the following structure:

Perfume

The detergent of invention preferably comprises one or more perfumes. Perfume may be present in the range from 0.1 to 1 wt. %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. In perfume mixtures preferably 15 to 25 wt. % are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

Preferably the perfume contains a substituted benzaldehyde where the substitution is preferably at the at the 3,4 or 5 position, more preferably the subsituent is an alkoxy group. Preferably the benzaldehyde is selected from 4-Methoxybenzaldehyde, 5- Methoxybenzaldehyde, 3- Methoxybenzaldehyde. Preferablythe benzaldhyde is present at from 0.5 to 5wt% of the perfume.

Particularly preferred perfume components are selected from verdyl acetate; verdyl propionate; or tert butyl cyclohexyl acetate; tetrahydro linalool; bornyl acetate; bornyl propionate; dihydromyrcenol; hexyl salicylate, Tetramethyl acetyloctahydronaphthalenes; eucalyptol; 2- methyl undecanal; citronellol; geraniol; benzyl acetate; (E)-4-methyldec-3-en-5-ol.

Preferably the perfume contains at least 6 of these components, more preferably each at a level of at least 0.01wt% in the detergent product. Tricyclodecenyl based perfumes are verdyl acetate; verdyl propionate; bornyl acetate and bornyl propionate. The sum of the weights of verdyl acetate; verdyl propionate; bornyl acetate and bornyl propionate, will be called Tricyclodecenyl sum. Tert butyl cyclohexyl acetate is preferably ortho tert butyl cyclohexyl acetate or para tert butyl cyclohexyl acetate.

Preferably the perfume contains at least 4, more preferably at least 5 components selected from a tricyclodecenyl perfume; tert butyl cyclohexyl acetate; dihydromyrcenol; Tetramethyl acetyloctahydronaphthalenes; hexyl salicylate; tetrahydrolinalool.

Preferably the weight ratio of Tricyclodecenyl sum: tert butyl cyclohexyl acetate: dihydromyrcenol is selected from 30 to 40 : 20 to 30: 10 to 20 for long lasting perfumes and 5 to 15 : 20 to 30 : 35 to 50 for freshness perfumes.

Preferably the weight ratio of Tetramethyl acetyloctahydronaphthalenes : hexyl salicylate is from 5 to 15 : 10 to 16. Preferably the weight fraction of dihydromyrcenol/ hexyl salicylate is from 0.5 to 6.0, more preferably from 1.0 to 3.0.

The composition comprises an alkoxylated polyamine polymer. Preferably, the polyamine is an alkoxylated cationic or zwitterionic di or polyamine polymer, wherein the positive charge is provided by quaternisation of the nitrogen atoms of the amines, and the anionic groups (where present) by sulphation or sulphonation of the alkoxylated group.

Preferably the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

Preferably greater than or equal to 50 mol% of nitrogen amines are quaternised, preferably with a methyl group. Preferably the polymer contains 2 to 10, more preferably 2 to 6, most preferably 3 to 5 quanternised nitrogen amines. Preferably the alkoxylate groups are selected from ethoxy and propoxy groups, most preferably ethoxy.

Preferably the polymer contains ester (COO) or acid amide (CONH) groups within the structure, preferably these groups are placed, so that when all the ester or acid amide groups are hydrolysed, at least one, preferably all of the hydrolysed fragments has a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.

Preferably the polymer is of the form:

Where Ri is a C3 to C8 alkyl group, X is an a (C2H4O)nY group where n is from 15 to 30, where m is from 2 to 10, preferably 2, 3, 4 or 5 and where Y is selected from OH and SOs" and preferably the number of SOa" groups is greater than the number of OH groups. Preferably there are from 0, 1 or 2 OH groups. X and Ri may contain ester groups within them. X may contain a carbonyl group, preferably an ester group. There is preferably 1 C2H4O unit separating the ester group from the N, such that the structural unit N- C2H4O-ester- (C2H4O)_n-iY is preferred.

Such polymers are described in WO2021239547 (Unilever), An example polymer is sulphated ethoxylated hexamethylene diamine and examples P1 , P2, P3, P4, P5 and P6 of WO2021239547. Ester groups may be included using lactones or sodium chloroacetate (Modified Williamson synthesis), addition to an OH or NH group, then subsequent ethoxylation.

Polyamine polymer is preferably present at from 0.1 to 3 wt.% of the composition.

Soil release polymers

Soil release polymers (SRP) help to improve the detachment of soils from the surface to be cleaned, such as a fabric or hard surface, by modifying the surface during washing. 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.

Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, C1-C4 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.

The overall level of SRP in the detergent preferably is from 0.1 to 10 wt.%, more preferably is from 0.3 to 7 wt.% and even more preferably is from 0.5 to 5%.

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.

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. The detergent preferably comprises from 0.01 to 5 wt.% of polymeric thickener and more preferably from 0.1 to 3 wt.%.

HEPP

Especially advantageous for machine dishwash detergents the detergent according to the invention beneficially comprises from 0.1 to 5 wt. % of hydroxy-ethylene 1,1- diphosphonate (HEDP), more preferably from 0.5 to 4 wt. %, even more preferably from 1.0 to 3.0 wt. % and still more advantageously from 1.5 to 2.5 wt. %.

Enzymes

The detergent composition of the invention may comprise enzyme. Suitable enzymes include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others. Enzymes may be added in liquid or in encapsulated form. In a preferred embodiment of this invention the enzymes are present in encapsulated form. Suitable levels of each enzyme are from 0.01 to 10 mg, more preferably from 0.2 to 5 mg and even more preferably from 0.3 to 2 mg active enzyme per gram of the composition. Combinations of at least one protease and at least one amylase are especially advantageous.

Any enzyme present in the detergent may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.

Builders

Although the detergent composition comprises MGDA as builder, the composition may comprise further builders. A beneficial amount of total builder in view of the detergent according to the invention is from 2 to 60 wt. %, more preferably from 5 to 50 wt. %, even more preferably from 8 to 40 wt. % and still even more preferably from 10 to 30 wt. %. Examples of further builders include especially Zeolite and alkali carbonate (carbonate (including bicarbonate and sesquicarbonate), whereof carbonate is the more preferred.

Further ingredients

Particularly beneficial is the inclusion of from 1 to 6 wt. % hydrotrope, more preferably of from 2 to 5 wt.%. An advantageous hydrotrope is sodium xylene sulfonate. A further amine-based organic solvent is also preferably included in the detergent liquid of the invention. The preferred level thereof is from 0.1 to 8 wt.%, more preferably is from 0.5 to 6 wt.%, even more preferably is from 1 to 5 wt.% and still even more preferred is from 1.5 to 4 wt.%. The preferred amine-based organic solvent is ethanolamine and even more preferably triethanolamine. The liquid detergent preferably amine-based organic solvent, which comprises at least 50 wt.%, more preferably at least 75 wt.% and even more preferably at least 85 wt.% and still even more preferably at least 95 wt.% of triethanolamine, as based on the total amount of amine-based organic solvent.

It is considered that the application of the invention is especially beneficial for those detergent liquids which contain amine-based organic solvent, which are believed to be especially susceptible to negative effects of MGDA by-products.

Particularly advantageously the composition of the invention also includes an effective amount of preservative, more preferably from 0.001 to 0.1 wt. %, even more preferably from 0.01 to 0.05 wt.%. Preferred preservative at this level is 1-2-benzisothiazolin-3-one (BIT), although methylisothiazolinone (MIT) may equally well be used, or combinations thereof.

Exemplary formulations

An exemplary dishwash detergent composition of the invention has the following formulation: from 1 to 30 wt.% of linear alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant; and from 0.1 to 15 wt.% of a combined amount of methylglycinediacetic acid (MGDA) and methylglycinemonoacetic acid (MGMA), wherein the molar ratio of MGDA: MGMA is at least 3.6; and from 1 to 15 wt.% organic acid, preferably citric acid; and amylase and protease; and a bleach system; and perfume and colorants; and from 10 to 80 wt.% water; and a pH of a 1 wt.% solution of the detergent aid in water at 25 degrees Celsius and in otherwise standard conditions of from 9.0 to 11.0, preferably from 9.5 to 10.5; and packaged in a multicompartmental water-soluble unit-dose with a liquid phase and a solid phase.

An exemplary laundry detergent composition of the invention has the following formulation: from 1 to 30 wt.% of a surfactant mixture comprising anionic surfactant and nonionic surfactant; and from 0.1 to 15 wt.% of a combined amount of methylglycinediacetic acid (MGDA) and methylglycinemonoacetic acid (MGMA), wherein the molar ratio of MGDA: MGMA is at least 3.6; and An ethoxylated anthraquinone dye, and ethoxylated thiophene mono-azo dye or a combination thereof in a total amount of from 0.00001 to 0.1 wt.%; and Hydrophobically modified Alkali Soluble acrylic polymer Emulsion (HASE); and from 0.025 to 8 wt.% of alkoxylated polyethyleneimines; and Perfume; and water to balance; and neat pH at 25 degrees Celsius of from 5 to 9; and packaged in a transparent plastic bottle having a volume of 0.2 to 5L.

Preferably the detergent composition is phosphate-free, meaning it contains less than 1 wt.% of phosphate, more preferably less than 0.5 wt.% of phosphate and even more preferably less than 0.1 wt.% of phosphate and still even more preferably essentially contains no phosphate.

Preferably the detergent composition is phosphonate-free, meaning it contains less than 1 wt.% of phosphonate, more preferably less than 0.5 wt.% of phosphonate and even more preferably less than 0.1 wt.% of phosphonate and still even more preferably essentially contains no phosphonate.

Process

The liquid detergent product of the invention is preferably made in a process comprising the steps of: a) providing a container according to the invention; and b) providing a liquid detergent composition according to the invention; and c) filling the container provided at step a) with the liquid detergent composition provided at step b) to provide the detergent product.

It will be appreciated that steps a) and b) can be done in any order.

Preferably the container is a bottle, more preferably a plastic bottle and even more preferably a plastic transparent bottle.

The amount of recycled plastic comprised by the container provided at step a) can be determined by determining the wt.% of recycled plastic feed material used, based on the total plastic feed material from which the container is made. Plastic containers comprising (or made essentially from) recycled plastic are commercially available and the methods of their manufacture are known in the art. Information of recycled plastics as well as their use to make detergent bottles is discussed in the literature, such as in Methods of Recycling, Properties and Applications of Recycled Thermoplastic Polymers. M.E. Grigore, Recycling 2017, 2, 24. Generally, to convert reclaimed post-use plastic into a useable feedstock to manufacture new plastic products the plastic is washed, dried and suitably pelletized. The pelletized recycled plastic can then be optionally mixed with virgin pelletized plastic and subjected to processes to shape it into new plastic products.

Processes to convert (pelletized) plastic feed material into final formed plastic products (e.g. detergent bottles) are known in the art. A general description thereof can be found e.g. in Hans- Georg Elias “An introduction to plastics”, 1993. Such techniques include thermoforming, blow molding, injection-molding or injection stretch blow molding. The UV absorber, if present, is preferably added to the (pelletized) plastic feed material, when the plastic feed material is molten, and the UV absorber mixed therewith prior to forming the container.

The provision of the liquid detergent composition at step b) can also be done using conventional methods know in the field. The method may comprise combining the ingredients preferably including mixing to provide the liquid detergent composition. It was found that the liquid detergent could be manufactured with water containing 0.1 to 10 ppm transition metal ions, without negatively affecting the colour stability. Preferred transition metals are iron and copper. It is indeed advantageous to tolerate such levels in the final composition of the invention as this reduces the complexity of water-quality monitoring systems and/or water purification systems, simplifying the processing.

It will be appreciated that the improved storage stability of the detergent product of the invention allows flexibility in logistics. It may allow energy-efficient central mass-production combined with long-distance international mass distribution which necessitates central accumulation (and prolonged storage times). For example, freighter ships can take 10 to 20 days to cross the Atlantic, which does not include time to load I off-load the ship in port. As such preferably after the manufacturing process of the product of the invention is a mass-production process providing from 10 to 300 kiloton per year, preferably from 15 to 250 kiloton per year and even more preferably from 20 to 200 kiloton per year and still even more preferably from 30 to 150 kiloton per year.

Unless otherwise indicated, preferred aspects in the context of one aspect of the invention (e.g. the detergent formulation) are also applicable as preferred aspects in the context of one of the other aspects, (e.g. process and/or container and/or use) mutatis mutandis.

The invention is now illustrated by the following non-limiting examples. Examples

Example 1

An aqueous laundry detergent formulation of the following composition was made according to

Table 1 :

Table 1 : formulation composition

¹The fragrance contained 4-methoxybenzaldehyde.

A blue dye was added to the formulation so that the Optical Density (1 cm path length) as measured at the absorption maximum of the dye (646nm) was 0.6. The dye used was an ethoxylated 1 ,4-diaminoanthraquinone. The dye structure was:

The formulations were placed in glass bottles, sealed and exposure to simulated outdoor sunlight in a weatherometer for 48 hours @ 43W/m² (300-400). Following exposure, the LIV-VIS spectrum of the detergent was measured (1cm path length) and the absorption measured at 450nm (for the orange/brown) and 646nm (blue) was measured.

The change (A) in absorption at these wavelengths relative to a non-irradiated control was quantified according to the formula:

A ⁼ 100* [1- A|jght)/Acontrol )]

, wherein Aught is the absorption for the light exposed and A_controi the absorption of the control (non-irradiated) sample. The experiment was repeated for 2 different samples which had different MGDA/MGMA mole ratios. The results are shown in table 2 below. The values were estimated to be accurate to +/- 5%.

Table 2: delta (A) values of different MGDA/MGMA samples.

On light exposure the samples become more orange/brown, shown by the increase in the A (450nm) value. The samples become less blue shown by the decrease in the A (646nm) value. Both of these changes become significantly smaller when the MGDA/MGMA molar ratio is 4.1 , compared to 3.5.

Example 2

The formulation of example 1 was remade, but with addition of 1.8wt% triethanol amine rather than 2.3wt%. Fluorescer was added at 0.1 wt% (Tinopal 5BMGX) and neither dye nor fragrance added. The formulations were again irradiated for 48 hours, alongside a control containing no MGDA. Subsequently the odor of the formulations was assessed and ranked by an expert fragrance assessor. The formulations were ranked as follows, were 1 is best and 3 is worst. Surprisingly the formulation with MGDA/MGMA = 4.1 , performs better than MGDA/MGMA = 3.5

Claims

1. A liquid detergent composition comprising:

• from 1 to 70 wt.% surfactant; and

• from 0.1 to 25 wt.% of a combined amount of methylglycinediacetic acid (MGDA) and methylglycinemonoacetic acid (MGMA), wherein the molar fraction of MGDA/MGMA is at least 3.6, and wherein the molar fraction of MGDA/MGMA is determined by 1H NMR spectroscopy.

2. A liquid detergent composition according to claim 1 , wherein the molar fraction of MGDA/MGMA is at least 3.7, preferably 3.8, more preferably 3.9 and even more preferably is at least 4.0.

3. A liquid detergent composition according to claim 1 or claim 2, wherein the molar fraction of MGDA/MGMA is at most 100, preferably at most 50, more preferably at most 25, even more preferably is at most 20 and still even more preferably is at most 15.

4. A liquid detergent composition according to claim 1 , wherein the combined amount of methylglycinediacetic acid (MGDA) and methylglycinemonoacetic acid (MGMA) is from 0.2 to 20 wt.%, preferably from 0.5 to 15 wt.%, more preferably from 1 to 12 wt.% and still even more preferably is from 1.5 to 10 wt.%.

5. A liquid detergent composition according to claim 1 , wherein detergent further comprises ethoxylated dye, preferably wherein the dye is an ethoxylated anthraquinone dye, an ethoxylated mono-azo thiophene dye or a combination thereof and even more preferably is an ethoxylated anthraquinone dye according to any one of the following structures:

6. A liquid detergent composition according to any preceding claim, wherein the detergent further comprises an ethoxylated dye according to the following representative structure: but wherein the average degree of ethoxylation is from 3 to 10 and preferably is from 4 to 8.

7. A liquid detergent composition according to any preceding claim, wherein the liquid is blue or violet.

8. A liquid detergent composition according to any preceding claim, wherein the detergent further comprises from 0.1 to 8 wt.% of amine-based organic solvent, preferably from 0.5 to 6 wt.%, more preferably from 1 to 5 wt.% and even more preferably from 1.5 to 4 wt.%.

9. A liquid detergent composition according to claim 8, wherein the amine-base organic solvent comprises at least 50 wt.%, preferably at least 75 wt.% and more preferably at least 85 wt.% and even more preferably at least 95 wt.% of triethanolamine.

10. A liquid detergent composition according to any preceding claim, wherein the composition is an aqueous laundry detergent or an aqueous machine dishwash detergent, and preferably is an aqueous laundry detergent.

11. A bottle having a volume of 0.2 to 5L, wherein at least 30 %, more preferably at least 40%, 50%, 60% and even more preferably at least 70 % of the outer surface area of the bottle is transparent, while preferably taking into account any exterior applied labels, and wherein the bottle comprises the liquid detergent composition according to any preceding claim.

12. A bottle according to claim 11, wherein the bottle is a plastic-based bottle and wherein the plastic contains at least 20 wt.%, more preferably 30 wt.%, even more preferably at least 50 wt.%, still even more preferably at least 70 wt. % and still even more preferably at least 95 wt. % of recycled (polyethylene terephthalate) PET plastic.

13. An aqueous liquid detergent composition according to any preceding claim, wherein the detergent liquid is transparent.

14. A process to manufacture the detergent product according to any preceding claims comprising the steps of: a. providing a plastic transparent container; and b. providing a liquid detergent composition according to any preceding claim; and c. filling the container provided at step a) with the liquid detergent composition provided at step b) to provide the detergent product; and wherein the process is an industrial production process capable of producing from 10 to 300 kilotons of detergent product per year.

15. Use of MGDA material having MGDA and MGMA, wherein the MGDA material has a ratio of MG DA: MGMA of at least 3.6 to improve liquid detergent stability during storage.