Field of the invention

The present invention relates to a plastic transparent container comprising an aqueous liquid laundry detergent, wherein the aqueous liquid laundry detergent comprises an alkoxylated active.

Background of the invention

Plastics, especially synthetic plastics, are ubiquitous in daily life due to their relatively low production cost and good balance of material properties. Synthetic virgin plastics are used widely to make containers, such as bottles for liquid laundry detergent products. The overwhelming majority of synthetic plastics are produced from increasingly scarce fossil sources, such as petroleum and natural gas. Additionally, the manufacturing of synthetic plastics from fossil sources produces CO2 as a by-product. Plastics recycling has emerged as one solution to mitigate the issues associated with the wide-spread usage of virgin plastics. Reclaiming plastics and re-using reclaimed plastics diverts waste from landfills and reduces the demand for virgin plastics made from fossil-based resources, which consequently reduces greenhouse gas emissions and other environmental problems.

The recycling process of reclaimed plastic typically consists of sorting the reclaimed plastics into predominately uniform streams of plastic types (e.g. PET, PVC etc...), washing with aqueous and/or caustic solutions and reprocessing into a plastic pellet, which can be used as plastic feed to form new plastic products. On general problem with using plastic feeds derived from recycled plastic is that these often are contaminated with unwanted impurities, such as spoiled food residue, residual perfume and colorants. In particular, reclaimed opaque plastics provide high levels of colorant impurities in the plastic feeds derived from recycled plastic (e.g. dyes and pigments). One way of reducing the level of impurities in the plastic feeds derived from recycled plastic is to decrease the amount of opaque plastics in the reclaimed plastic. Concomitantly there is a need to reduce the amount of opaque plastics in consumer products in favor of transparent (or translucent) plastics, which include plastic transparent containers for storing/transporting/dosing of liquid laundry compositions. Furthermore, transparent containers (e.g. bottles) for liquid laundry products are also desired as these allow the consumer to inspect the color of the product, its consistency and any suspended particles if present.

However, transparent plastic containers, present problems when used to store aqueous liquid laundry detergent compositions comprising amylase (i.e. an enzyme that catalyzes the hydrolysis of starch into sugars) and/or protease (i.e. an enzyme that catalyzes the hydrolysis of bonds within peptides and proteins). It was observed that upon exposure to sunlight of such products, the enzyme activity of the amylase and/or protease is reduced over time.

WO2021/15136A1 discloses a transparent plastic container comprising an aqueous liquid laundry detergent composition wherein the liquid detergent composition comprises:

• from 5 to 60 wt. % of surfactant; and

• from of 0.0005 to 0.01 wt.% of an amylase or from 0.0005 to 0.01 wt.% of a protease or a combination thereof; and

• from 0.00005 to 0.02 wt. % of a dye comprising an anthraquinone chromophore which contains an amine group or an acid amide group in the 1-position of the anthraquinone ring; and wherein the container has an internal volume of from 0.1 to 10 L.

WO2021/15136A1 teaches that use of from 0.00005 to 0.02 wt. % of a dye comprising an anthraquinone chromophore which contains an amine group or an acid amide group in the 1-position of the anthraquinone ring significantly reduces the loss of amylase and protease activity upon exposure to sunlight.

We have found that when using such products, the level of alkoxylated actives can change during storage. More specifically we found that when using containers with post-consumer recycled plastic (PCR), the level of alkoxylated actives during storage can change when compared to using virgin-based plastic containers. This was observed in particular for plastic containers comprising low density polyethylene (LDPE) plastic, high density polyethylene (HDPE) plastic or a combination thereof. This represents problems when providing consistent detergent product quality, as the PCR and/or virgin content of the plastic container may not be fully controlled by the detergent manufacturer and can vary. The PCR/virgin content may depend on the region where the plastic containers are produced and can also depend on the availability of PCR and virgin plastic. To provide consistent detergent product quality it is therefore desirable to maintain the level of alkoxylated actives irrespective of the level of PCR/virgin plastic of the container.

It is an object of the present invention to improve the invention disclosed in WO2021/15136A1 , by not just reducing the loss of amylase and protease activity upon exposure to sunlight but to also reduce changes in the level of alkoxylated actives during storage between containers having different levels of PCR or virgin plastic.

Summary of the invention

One or more objects of the above objects are achieved in a first aspect of the invention by a transparent plastic container comprising an aqueous liquid laundry detergent composition wherein the liquid detergent composition comprises:

• from 0.01 to 40 wt. % of alkoxylated active; and

• from of 0.0005 to 0.01 wt.% of an amylase or from 0.0005 to 0.01 wt.% of a protease or a combination thereof; and

• from 0.00005 to 1 wt. % of a dye comprising an anthraquinone chromophore which contains an amine group or an acid amide group in the 1-position of the anthraquinone ring; and wherein the container has an internal volume of from 0.1 to 10 L; and wherein the plastic of the container comprises high density polyethylene (HDPE), low density polyethylene (LDPE) or a combination thereof; and wherein the anthraquinone dye is alkoxylated

It was surprisingly observed that use of an alkoxylated anthraquinone dye of the invention reduced observed changes in the level of alkoxylated active in the liquid when exposed to wither PCR HDPE plastic or virgin plastic HDPE. This effect is beneficial in addition to the effect of the composition significantly reducing the loss of amylase and protease activity upon exposure to sunlight.

This effect is highly beneficial for detergent manufacturers as it enables them to deliver more stable and more consistent product quality even though the level of virgin or PCR plastic in HDPE/LDPE comprising containers can vary. In a second aspect the invention relates to a process for the manufacture of a detergent product according to the first aspect of the invention, wherein the process comprises the steps of: a) providing a transparent plastic container having an internal volume of 0.1 to 10 L, wherein the plastic of the container comprises low-density polyethylene, high- density polyethylene or a combination thereof; b) providing an aqueous liquid laundry detergent composition according to the first aspect of the invention; c) filling the container provided at step a) with the aqueous liquid laundry detergent composition provided at step b) to provide the detergent product.

In a third aspect the invention relates to the use of an alkoxylated anthraquinone dye of the invention to improve product consistency of an aqueous liquid laundry detergent in a transparent plastic container, preferably wherein the container comprises LDPE, HDPE or a combination thereof, even more preferably while also reducing loss of proteases and/or amylase activity during storage.

Detailed description of the invention

Definitions

Unless otherwise stated or is made clear from the context, with ‘the composition’ or ‘the detergent’ is meant the aqueous liquid laundry detergent composition as such, not including the container; with ‘the container’ is meant the plastic transparent container as such, not including the aqueous liquid laundry detergent composition; with ‘the product’ is meant the plastic transparent container + the aqueous liquid laundry detergent composition contained therein. Weight percentage (wt. %) is based on the total weight of the aqueous liquid laundry detergent composition, the container, or the product as indicated or as made clear from the context. It will be appreciated that the total weight amount of ingredients will not exceed 100 wt. %.

Amounts of wt. % enzymes in the aqueous liquid laundry composition refer to wt. % of active protein levels, unless otherwise indicated.

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 non-limiting 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 plastic container of the invention is transparent. 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 (i.e. x100) can be converted to a Transmittance ranging from 0% (no incoming light having passed through) to 100% (i.e. all incoming light having passed through). As used herein transparent refers to a Transmittance of at least 30% within the wavelength range of 400 to 700 nm, preferably of at least 40 %, 50 % and more preferably at least 60 %. The Transmittance refers to at least one wavelength of light within the visible spectrum, preferably to at least 40 %, more preferably at least 60%, even more preferably at least 80 % of the wavelengths within the visible spectrum, still even more preferably refers to the whole of the wavelength within the visible spectrum. Preferably at least 30 %, 50 %, 70 % and even more preferably at least 85 % of the total outer container surface area of the plastic container is transparent. Transmittance of the plastic container material can be suitably measured by using a UV-VIS Spectrometer, preferably as based on a light path-length through the plastic of 1 mm. Suitable UV-VIS spectrometers are available from a variety of suppliers, including Thermo Scientific, Perkin Elmer and Shimadzu.

With plastic containers are meant containers which are suitable for storing multiple doses of detergent and are preferably shape-stable when empty. With the term “plastic container” are meant containers which predominantly consist of plastic although they may comprise non-plastic additional materials. Preferably the plastic container comprises at least 60 wt.%, more preferably at least 80 wt.%, even more preferably at least 90 wt.% and still even more preferably at least 95 wt. % of plastic.

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, known as gels or pastes. 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 sec ¹ . 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.

The liquid detergent of the invention is aqueous, meaning it has an aqueous continuous phase. By “aqueous continuous phase” is meant a continuous phase which has water as its basis. 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 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. Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid color care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.

Plastic container

The plastic container of the invention has a preferred internal volume of from 0.2 to 5 L, even more preferably from 0.5 to 5 L and still even more preferably of from 0.5 to 2 L.

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. Preferably the container has a minimum width at it base, of 3 cm, more preferably 4 cm. The width is measured parallel to the flat surface on which the container stands in an upright position. On initial sale the container preferably is filled to greater than 95% of the container capacity by weight.

The plastic of the container may be coloured although it is at least in part transparent. This can be easily achieved by reducing the amount of colorant in the plastic as needed and/or by modifying the container wall thickness. Advantageously the plastic of the container contains essentially no added colorant (e.g. dyes or pigments) and has no perceivable colour (i.e. non-white, non-grey) to the untrained human eye. Plastics having little or no added colorants are preferred to improve the recyclability of the container.

The plastic of the container comprises low density polyethylene (LDPE), high density polyethylene (HDPE) or a combination thereof. The plastic may comprise further types of plastic. The plastic of the plastic container preferably comprises at least 20 wt.%, more preferably at least 50 wt.%, even more preferably at least 70 wt. % and still even more preferably at least 90 wt. % of LDPE, HDPE or a combination thereof, as based on the total weight of plastic in the plastic container. HDPE is the more preferred plastic-type to be comprised by the plastic container.

Preferably the plastic of the container comprises at least 30 wt. %, more preferably at least 50 wt. %, even more preferably at least 70 wt.%, still even more preferably at least 80 wt. % and still even more preferably at least 90 wt. % of recycled plastic, based on the total weight of the plastic of the container. These amounts advantageously refer to the amount of HDPE/LDPE recycled plastic content, based on the total HDPE/LDPE weight of the plastic container. 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 plastic container. The UV absorbers are present as additive in the plastic. Advantageous UV absorbers are one or more of benzophenones, salicylates, benzotriazoles, hindered amines and alkoxy (e.g. methoxy) cinnamates). More preferred UV absorbers are benzotriazole-based absorbers. Benzotriazole-based UV absorbers are described in Cantwell et. al. “Benzotriazoles: History, Environmental Distribution, and Potential Ecological Effects”, Chapter 16, Comprehensive Analytical Chemistry, Vol. 67, 2015, pages 513-545; and in Pospisil et. al. “Oxidation Inhibition in Organic Materials”, CRC Press, 1990. Benzotriazole-based UV absorbers are commercially available from e.g. BASF and Clariant.

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 and/or paper. 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 %.

Advantageously the transparent plastic container is marked by one or more symbols, letters and/or numbers identifying the amount of recycled plastic comprised by the transparent plastic container. Moreover, preferably the transparent plastic container is marked by one or more symbols, letters and/or numbers identifying the plastic container is recyclable.

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.

Alkoxylated anthraquinone dye

Alkoxylated anthraquinone dyes are dyes which contain at least one [alkoxy] _n containing group covalently bound to the chromophore, where n is the mole average value and is greater than or equal to 1.9, preferably greater than or equal to 2. The [alkoxy] _n 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 [alkoxy] _n containing group may include a linker moiety and have the following structure:

-linker-[alkoxy] _n R

The alkoxy-monomers preferably have 2 to 4 carbon atoms and may form a mixed [alkoxy] _n containing group, such as a [alkoxy] _n groups containing mixtures of ethoxylate, propoxylate and butoxylate monomers. Dyes which have alkoxy monomers of the same type are preferred. [alkoxy] _n containing group(s) with ethoxy monomers are preferred. R is an organic group and preferably selected from alkyl, H, SO3H, CH2COOH, and quaternary amines, more preferably CH3, C2H5, and H, most preferably H.

As indicated, the at least one [alkoxy] _n containing group can suitably have a linker moiety between the [alkoxy] _n moiety and the remainder of the dye-structure. The linker is preferably an alkyl-group, which can be branched or linear, but preferably is linear. In general, overall linear structures for the poly-alkoxy containing groups are preferred. Also preferred are those which are end-capped with -OH (i.e. an hydroxy end-capping structure).

Considering the [alkoxy] _n moiety, n is advantageously from 2 to 20, more preferably from 2 to 15 and even more preferably from 2 to 8. In case more than one poly-alkoxy containing group is present, it is preferred that each has a mole average from 2 to 20, more preferably 2 to 15 and even more preferably 2 to 8 alkoxy units.

In the [alkoxy] _n moiety, ‘n’ generally refers to the mole average number of alkoxymonomers, in which ‘n’ thus can represent the average of a distribution. In this case beneficial are [alkoxy] _n moiety distributions in which the most prevalent molecular species has an alkoxy 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, a molar distribution of 25% n=2, 50% n=4 and 25% n=6 is more preferred than a molar 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 [alkoxy] _n containing group.

The molar % of the molecular species with an ‘n’ closest to the average of the [alkoxy] _n distribution is preferably at least 2 molar %, more preferably at least 5 molar %, even more preferably at least 10 molar % and still even more preferably at least 15 molar % higher than the molar % of the molecular species with an ‘n’ second-closest to the average of the [alkoxy] _n distribution. For example, where the average of the [alkoxy] _n is 4, the molecular species with [alkoxy^ is the species with ‘n’ closest to the average. Would the distribution contain also [alkoxy^, [alkoxy^ and [alkoxy]s, both the [alkoxy^ and [alkoxy]s are molecular species with a second closest value of ‘n’. In this case it is than preferred that the species [alkoxy^ is at least 2 molar % higher than the highest molar amount of [alkoxy^ or [alkoxy]s (i.e. whichever one of these is present in the distribution with the higher molar %).

In case where the dye is a mixture of molecular species of different alkoxy chain length it is preferred if the mole fraction of molecular species with only a single alkoxy group in the chain is less than 5 mol%, preferably less than 2 mol%, more preferably less than 0.5 mol%, most preferably less than 0.1 mol%. An example of a single alkoxy group in a chain is N-CH2CH2OH.

The distribution of chain lengths is preferably measured using accurate mass spectroscopy in conjunction with chromatography, preferably with detection of the radical cations.

The alkoxylated dyes of the invention preferably have a maximum extinction coefficient of greater than 5000 L/mol/com in the range of 400 to 700 nm. Preferably the dyes are green, blue or violet in colour.

Preferably the alkoxylated dye of the invention is added to the aqueous liquid detergent in amount to provide an optical density of from 0.05 to 2 and preferably of from 0.1 to 0.5, as measured at the absorption maximum of the dye and using a path-length of 1 cm. The absorption maximum of dye should be within the range of from 400-700nm. Preferably the amount of alkoxylated dye in the detergent of the invention is from 0.0001 to 0.4 wt. %, more preferably from 0.0005 to 0.1 wt. %, even more preferably from 0.001 to 0.05 wt. %, still even more preferably from 0.002 to 0.02 wt.% and still even more preferably from 0.005 to 0.01 wt.%

The alkoxylated dye of the invention may be a leuco dye, although non-leuco dyes are the more preferred. More preferably the alkoxylated dye of the invention comprises or essentially is an alkoxylated anthraquinone dye of the following structure: wherein the anthraquinone chromophore contains an amine group or an acid amide group at least in the 1 -position, preferably also in the 4-position; and wherein the chromophore 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.

Preferably the number of alkoxy monomers in an anthraquinone dye as a whole is from 2 to 40, preferably from 3 to 30 and more preferably from 4 to 20. 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.

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 -[CFkCFWjnRi 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 -

Preferred examples of dyes 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.

(Further) beneficial alkoxylated anthraquinone dyes are the following: It is preferred that an anthraquinone dye does not contain sulphate or sulphonate groups and more preferably contains no charged groups. In case of doubt the presence of charged groups is determined in water at a pH of 7.0 in otherwise standard conditions.

Further dyes

Besides the presence of alkoxylated anthraquinone dye of the invention one or more further dyes may be present in the aqueous liquid detergent. Dyes are described in Industrial Dyes edited by K. Hunger 2003 Wiley-VCH ISBN 3-527 -30426-6. Further dyes are preferably selected from cationic, anionic and non-ionic dyes and more 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.

Further dye may be any color, preferable the dye is blue, violet, green or red. Most preferably the dye is blue or violet. Preferably the further dye is selected from acid dyes and disperse dyes. Most preferably the dye is a non-ionic dye. Preferably the dye is selected from those having: anthraquinone; mono-azo; bis-azo; xanthene; phthalocyanine; and, phenazine chromophores. More preferably the dye is selected from those having: phenazine, anthraquinone and, mono-azo chromophores.

Preferably the dye is selected from: acid blue 80, acid blue 62, acid violet 43, acid green 25, direct blue 86, acid blue 59, acid blue 98, direct violet 9, direct violet 99, direct violet 35, direct violet 51 , acid violet 50, acid yellow 3, acid red 94, acid red 51 , acid red 95, acid red 92, acid red 98, acid red 87, acid yellow 73, acid red 50, 5 acid violet 9, acid red 52, food black 1 , food black 2, acid red 163, acid black 1 , acid orange 24, acid yellow 23, acid yellow 40, acid yellow 11 , acid red 180, acid red 155, acid red 1 , acid red 33, acid red 41, acid red 19, acid orange 10, acid red 27, acid red 26, acid orange 20, acid orange 6, sulphonated Al and Zn phthalocyanines, solvent violet 13, disperse violet 26, disperse violet 28, solvent 10 green 3, solvent blue 63, disperse blue 56, disperse violet 27, solvent yellow 33, disperse blue 79:1.

The alkoxylated anthraquinone dye of the invention may be a shading dye. If further dye besides the alkoxylated dye of the invention is present preferably the further dye shading dye. Leuco based shading dyes as described in W02020/023812, most preferably a triphenyl methane leuco colourant are contemplated as well. Such leuco dyes are included by the term shading dyes, although preferably the shading dyes according to the invention are non-leuco shading dyes.

Shading dyes provide a shade to white fabric and preferably provide a blue or violet shade to white fabric. In this regard the shading dye gives a blue or violet color to a white cloth with a hue angle of 240 to 330, more preferably 260 to 320, most preferably 265 to 300. The white cloth used is bleached non-mercerised woven cotton sheeting. Preferably a 10 cm by 10 cm piece of white bleached non-mercerised woven cotton cloth is agitated in an aqueous solution (6° French Hard water, liquor 298K: cloth 30:1) 2g/L of a base detergent (10 wt.% linear alkyl benzene sulfonate, 5 wt.% primary alcohol ethoxylate (C12-15, with 7 moles of ethoxy groups), pH=8) for 30 minutes at room temperature. The cloths are removed, rinsed and tumble dried. The experiment is repeated with and without the addition of shading dye. The color of the cloth is measured using a reflectometer and expressed as the CIE L*a*b* values. The experiment was repeated with the addition of 0.001 wt.% of the dye to the formulation.

The total color added to the cloth was calculated as the AE value, such that AE = (AL ² + Aa ² + Ab ² ) ⁰⁵ where AL = L(control)-L(dye); Aa = a(control)-a(dye); Ab = b(control)-b(dye)

The actual color of the cloth is calculated as the hue angle, which for the current range of colors is given by: Hue angle = 270+180/TT X atan(-Aa/Ab). A hue angle of 360/0 is red, 270 is blue and 180 is green.

A shading dye is able to deposit onto textile during domestic wash conditions in the presence of a wash liquor comprising surfactant. This may be assessed using the above test, where a shading dye will give a non-zero AE value. The preferred total amount of shading dye in the laundry detergent according to the invention preferably is from 0.00001 to 0.1 wt. % more preferably from 0.0001 to 0.05 wt. %.

More preferably further anionic dyes are not present, most preferably further dyes are not present.

Amylase

The amylase, when present, is present in an amount of active protein at a level of 0.0005 to 0.01 wt.%, preferably 0.001 to 0.005 wt. %.

Suitable amylases may be an alpha-amylase or a glucoamylase and may be of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Preferred are alpha-amylases. Amylases include, for example, alphaamylases obtained from Bacillus, e.g., a special strain of Bacillus licheniformis, described in more detail in GB 1 ,296,839 or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060.

Preferred amylases include: a) amylases having SEQ ID NO: 2 in WO 95/10603 or variants having 90% sequence identity to SEQ ID NO: 2 thereof. Beneficial variants are described in WO 94/02597, WO 94/18314, WO 97/43424 and SEQ ID NO: 4 of WO 99/019467, such as variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 178, 179, 181 , 188, 190, 197, 201 , 202, 207, 208, 209, 211 , 243, 264, 304, 305, 391 , 408, and 444. Further beneficial amylases include amylases having SEQ ID NO: 6 in WO 02/010355 or variants thereof having 90% sequence identity to SEQ ID NO: 6. Preferred variants of SEQ ID NO: 6 are those having a deletion in positions 181 and 182 and a substitution in position 193. b) hybrid alpha-amylase comprising residues 1-33 of the alpha-amylase derived from B. amyloliquefaciens shown in SEQ ID NO: 6 of WO 2006/066594 and residues 36-483 of the B. licheniformis alpha-amylase shown in SEQ ID NO: 4 of WO 2006/066594 or variants having 90% sequence identity thereof. Preferred variants of this hybrid alphaamylase are those having a substitution, a deletion or an insertion in one of more of the following positions: G48, T49, G107, H156, A181 , N190, M197, 1201 , A209 and Q264. Most preferred variants of the hybrid alpha-amylase comprising residues 1-33 of the alpha-amylase derived from B. amyloliquefaciens shown in SEQ ID NO: 6 of WO 2006/066594 and residues 36-483 of SEQ ID NO: 4 are those having the substitutions: M197T; H156Y+A181T+N190F+A209V+Q264S; or G48A+T49I+G107A+H156Y+A181T+N190F+I201 F+A209V+Q264S. c) amylases having SEQ ID NO: 6 in WO 99/019467 or variants thereof having 90% sequence identity to SEQ ID NO: 6. Preferred variants of SEQ ID NO: 6 are those having a substitution, a deletion or an insertion in one or more of the following positions: R181 , G182, H183, G184, N195, I206, E212, E216 and K269. Particularly preferred amylases are those having deletion in positions R181 and G182, or positions H183 and G184. Additional advantageous amylases which can be used are those having SEQ ID NO: 1 , SEQ ID NO: 3, SEQ ID NO: 2 or SEQ ID NO: 7 of WO 96/023873 or variants thereof having 90% sequence identity to SEQ ID NO: 1 , SEQ ID NO: 2, SEQ ID NO: 3 or SEQ ID NO: 7. Preferred variants of SEQ ID NO: 1 , SEQ ID NO: 2, SEQ ID NO: 3 or SEQ ID NO: 7 are those having a substitution, a deletion or an insertion in one or more of the following positions: 140, 181 , 182, 183, 184, 195, 206, 212, 243, 260, 269, 304 and 476, using SEQ ID 2 of WO 96/023873 for numbering. More preferred variants are those having a deletion in two positions selected from 181, 182, 183 and 184, such as 181 and 182, 182 and 183, or positions 183 and 184. Most preferred amylase variants of SEQ ID NO: 1 , SEQ ID NO: 2 or SEQ ID NO: 7 are those having a deletion in positions 183 and 184 and a substitution in one or more of positions 140, 195, 206, 243, 260, 304 and 476. d) amylases having SEQ ID NO: 2 of WO 08/153815, SEQ ID NO: 10 in WO 01/66712 or variants thereof having 90% sequence identity to SEQ ID NO: 2 of WO 08/153815 or 90% sequence identity to SEQ ID NO: 10 in WO 01/66712. Preferred variants of SEQ ID NO: 10 in WO 01/66712 are those having a substitution, a deletion or an insertion in one of more of the following positions: 176, 177, 178, 179, 190, 201, 207, 211 and 264. e) amylases having SEQ ID NO: 2 of WO 09/061380 or variants having 90% sequence identity to SEQ ID NO: 2 thereof. Preferred variants of SEQ ID NO: 2 are those having a truncation of the C-terminus and/or a substitution, a deletion or an insertion in one of more of the following positions: Q87, Q98, S125, N128, T131 , T165, K178, R180, S181 , T182, G183, M201 , F202, N225, S243, N272, N282, Y305, R309, D319, Q320, Q359, K444 and G475. More preferred variants of SEQ ID NO: 2 are those having the substitution in one of more of the following positions: Q87E,R, Q98R, S125A, N128C, T131 I, T165I, K178L, T182G, M201 L, F202Y, N225E.R, N272E.R, S243Q,A,E,D, Y305R, R309A, Q320R, Q359E, K444E and G475K and/or deletion in position R180 and/or S181 or of T182 and/or G183. Most preferred amylase variants of SEQ ID NO: 2 are those having the substitutions: N128C+K178L+T182G+Y305R+G475K;

N 128C+K178L+T182G+F202Y+Y305R+D319T+G475K;

S125A+N 128C+K178L+T182G+Y305R+G475K; or S125A+N128C+T1311+T165I+K178L+T182G+Y305R+G475K wherein the variants are C-terminally truncated and optionally further comprises a substitution at position 243 and/or a deletion at position 180 and/or position 181. f) alpha-amylase having SEQ ID NO: 12 in WQ01/66712 or a variant having at least 90% sequence identity to SEQ ID NO: 12. Preferred amylase variants are those having a substitution, a deletion or an insertion in one of more of the following positions of SEQ ID NO: 12 in WQ01/66712: R28, R118, N174; R181, G182, D183, G184, G186, W189, N195, M202, Y298, N299, K302, S303, N306, R310, N314; R320, H324, E345, Y396, R400, W439, R444, N445, K446, Q449, R458, N471 , N484. Particular preferred amylases include variants having a deletion of D183 and G184 and having the substitutions R1 18K, N195F, R320K and R458K, and a variant additionally having substitutions in one or more position selected from the group: M9, G149, G182, G186, M202, T257, Y295, N299, M323, E345 and A339, most preferred a variant that additionally has substitutions in all these positions.

Other examples are amylase variants such as those described in WO2011/098531 , WO2013/001078 and WO2013/001087. Advantageous amylases are also sold under the tradenames Duramyl™, Termamyl™, Fungamyl™, Stainzyme™, Stainzyme Plus™, Natalase™, Amplify Prime® and BAN™ (from Novozymes A/S), and Rapidase™, Purastar™/Effectenz™, Powerase™, Preferenz S1000™ Preferenz SI 10™ and Preferenz S100™ (from Genencor International Inc./DuPont). The Amplify Prime® amylase is most advantageous of the commercial amylase enzyme. Protease

The protease of the invention, when present, is present at a level of from 0.0005 to 0.01 wt.% preferably of from 0.005 to 0.05 wt. %, more preferably of from 0.01 to 0.03 wt. %.

Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Protease enzymes hydrolyze bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Examples of suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; asparagine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (htp://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred. The term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523.

Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. The subtilases may be divided into 6 sub-divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.

Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and W009/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89/06279 and protease PD138 described in (WO 93/18140). Preferably the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6,312,936 Bl, US 5,679,630, US 4,760,025, US7,262,042 and WO 09/021867. More preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus. Other useful proteases may be those described in WO 92/175177, WO 01/016285, WO 02/026024 and WO 02/016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270, WO 94/25583 and WO 05/040372, and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146.

Further examples of useful proteases are the variants described in: W092/19729, WO96/034946, WO98/201 15, WO98/201 16, WO99/01 1768, WO01/44452, W003/006602, W004/03186, W004/041979, W007/006305, W01 1/036263, W01 1/036264, especially the variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 106, 1 18, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using the BPN' numbering. More preferred the subtilase variants may comprise the mutations: S3T, V41 , S9R, A15T, K27R, *36D, V68A, N76D, N87S, R, *97E,A98S, S99G,D,A, S99AD, S101 G, M, R S103A, V104I.Y, N, S106A, G1 18V, R, H120D, N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V2051, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).

Most preferably the protease is a subtilisin (EC 3.4.21.62).

Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; Duralase™, Durazym™, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A/S).

Those sold under the tradename Maxatase®, Maxacai®, Maxapem®, Purafect®, Purafect Prime®, Preferenz™, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®, Effectenz™, FN2®, FN3®, FN4®, Excellase®, Opticlean® and Optimase® (from Genencor International Inc./ Danisco/DuPont), Axapem™(Gist- Brocases N.V.).

Those available from Henkel/Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + SIOI R + S103A+ V1041+ G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V41+ V199M + V2051 + L217D), BLAP X (BLAP with S3T + V41 + V2051) and BLAP F49 (BLAP with S3T + V41+ A194P + V199M + V2051 + L217D) - all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao.

The invention may use cutinase, classified in EC 3.1.1.74. The cutinase used according to the invention may be of any origin. Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.

Further enzymes

It is particularly preferred that the aqueous liquid laundry composition comprises a combination of amylase and protease.

One or more further enzymes may be present in the aqueous liquid laundry detergent composition of the invention. Preferably the level of each enzyme in the laundry detergent composition of the invention is from 0.0001 wt. % to 0.1 wt. % of active protein. Especially contemplated enzymes include more lipases, cellulases, hemicellulases, peroxidases, hemicellulases, xylanases, xantanase, lipases, phospholipases, esterases, cutinases, pectinases, carrageenases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, p-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, tannases, nucleases (such as deoxyribonuclease and/or ribonuclease), phosphodiesterases, or mixtures thereof..

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

Sequestrant

It was even further surprising to observe that loss of amylase and protease activity upon exposure to sunlight could be further reduced by including 0.001 to 0.1 wt. % of sequestrant, wherein the common logarithm (i.e. log™) of the Fe ³⁺ binding constant of the sequestrant is at least 19.0. Preferably the common logarithm of the Fe ³⁺ binding constant is from 20.0 to 45.0, more preferably is from 21.0 to 40.0, even more preferably is from 22.0 to 36.0 and still even more preferably is from 23.0 to 35.0.

More preferred amount of said sequestrant is from 0.002 to 0.05 wt. %, more preferably of from 0.005 to 0.04 wt. % and even more preferably of from 0.01 to 0.03 wt. %. Sequestrants are chemicals which non-covalently bind to metal ions, preferably transition metal ions, to form a complex according to the following general reaction scheme:

L + M „ ML wherein the sequestrant is denoted as ‘L’, the metal ion is denoted as ‘M’ and the resulting sequestrant-metal complex is denoted as ‘ML’. The sequestrant strength is indicated by the equilibrium constant ‘K’ according to the following formula: where [ML], [M] and [L] are the concentrations of the species in equilibrium in moles per litre. The greater the equilibrium constant K, the stronger is the sequestrant strength of the chelator ‘L’.

As used herein the term “Fe ³⁺ binding constant” is the equilibrium binding constant K between a sequestrant and Fe ³⁺ , where K is calculated according to equation (2) and as determined in water (pH 7), at 25 degrees Celsius and an ionic strength of 0.1 mol/L. The table below gives the common logarithm log (K) of the equilibrium binding constants of selected sequestrants determined in these conditions. The specific values are taken from the National Institute of Standards and Technology (“NIST”), R.M. Smith, and A.E. Martell, NIST Standard Reference Database 46, NIST Critically Selected Stability Constants of Metal Complexes: Version 8.0, May 2004, U.S. Department of Commerce, Technology Administration, NIST, Standard Reference Data Program, Gaithersburg, MD.

DTPA is diethylenetriaminepentaacetic acid. EDDS is ethylenediamine-N,N'-disuccinic acid. NTA is 2 ,2',2"-nitrilotriacetic acid. MECAMS, 4-LICAMS and 3,4-LICAMS are described by Raymond et. al. in “Inorganic Chemetal-ion sequestrantry in Biology and Medicine”, Chapter 18, ACS Symposium Series, Washington, D.C. 1980. Desferrioxamine B is a commercially available iron chelating drug desferal®.

Methods to determine the equilibrium binding constant of sequestrants are described in Orama et. a. “Complexation of [S,S] and mixed stereoisomers of N,N’- ethylenediaminedisuccinic acid (EDDS) with FE(III), Cu(ll), Zn(ll) and Mn(ll) ions in aqueous solution”, J. Chem. Soc., Dalton Trans., 2002, 4644-4648.

Preferred sequestrants comprise one or more of catechols, hydroxymates, aminocarboxylates, 4-Pyridinones, aminopolycarboxylates and alkyl- or alkenylsuccinic acid. 4-Pyridinone based sequesterants are discussed in W02007042140 and WO1 5028395. Examples of a hydroxymate are acetohydroxamic acid and Desferrioxamine B is a commercially available iron chelating drug, desferal®. Example of a catechol is MECAMS, 4-LICAMS and 3,4-LICAMS are described by Raymond et al. in "Inorganic Chemistry in Biology and Medicine", Chapter 18, ACS Symposium Series, Washington, D.C. (1980).

The sequestrant more preferably comprises one or more of 2,2',2"-nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), iminodisuccinic acid (IDS), ethylenediamine-N,N'-disuccinic acid (EDDS), methylglycine-N,N- diacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), N- (2-hydroxyethyl)iminodiacetic acid (EDG), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP, N- (sulfomethyl)aspartic acid (SMAS), N-(2-sulfoethyl)-aspartic acid (SEAS), N- (sulfomethylglutamic acid (SMGL), N-(2-sulfoethyl)-glutamic acid (SEGL), N- methyliminodiacetic acid (MID A), serine-N,N-diacetic acid (SEDA), isoserine-N,N- diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N- diacetic acid (ANDA), sulfanilic acid-N,N-diacetic acid (SLDA) , taurine-N,N-diacetic acid (TLIDA) and diethanolglycine (DEG). Although these sequestrant species are mentioned using their acid form, it is to be understood that their partial or full salt forms are included in this denomination. The acid forms of the sequestrants are preferred.

Best results were achieved with sequestrant comprising aminopolycarboxylate and particularly advantageous are ethylenediaminetetraacetic acid (EDTA) and ethylenediamine-N,N'-disuccinic acid (EDDS).

Alkoxylated Active

Alkoxylated actives are ingredients which have a beneficial effect in removing soil from textile during a laundry wash and/or preventing soil in the wash-liquor from (re)depositing onto the textile. Such actives can also include alkoxylated actives which affect the stability of the detergent, such as thickeners. Examples of alkoxylated actives include alkoxylated surfactants, alkoxylated soil release polymers, alkoxylated polymeric cleaning boosters and alkoxylated polymeric thickeners.

The preferred amount of total alkoxylated active is from 0.05 to 30 wt. %, more preferably from 0.1 to 20 wt. %, even more preferably from 0.5 to 10 wt. %.

The amount of total alkoxylated active does not include the amount of alkoxylated anthraquinone dye. In view of the current invention alkoxylated active does not include alkoxylated anthraquinone dye.

Preferably the alkoxylated active essentially consists of alkoxylated surfactant alkoxylated soil release polymer, alkoxylated polymeric cleaning booster, alkoxylated polymeric thickener or a combination thereof, wherein the alkoxylated active are actives different from the alkoxylated dye. Alkoxylated surfactans

Preferred alkoxylated surfactants of the invention are alkoxylated non-ionic surfactants. These include, advantageously, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides with alkylene oxides, especially ethylene oxide either alone or with propylene oxide and methyl ester ethoxylates. Example nonionic surfactants are the condensation products of aliphatic Cs to Cis primary or secondary linear or branched alcohols with ethylene oxide>3EO generally 5 to 40 EO, preferably 7EO to 9EO mole average units.

Preferably the non-ionic surfactant comprises C12/14 alcohol ethoxylates with 7EO to 9EO mole average units; C16/18 alcohol ethoxylates with 7 to 13 EO mole average units; C16/18 Methyl ester ethoxylates with 7 to 13 EO mole average units or mixtures thereof and even more preferably essentially consists of such non-ionic surfactants or mixtures thereof.

For the non-ionic with C16/18 alcohol ethoxylates it is preferred that the predominant C18 moiety is 018:1 and more preferably 018:1 (A9). Preferably polyunsaturated chains are present at less than 11wt%.

The preferred amount of alkoxylated non-ionic surfactant of the invention is from 0.1 to 20 wt. %, more preferably from 1 to 12 wt. %, even more preferably from 3 to 8 wt.% and still even more preferably is from 4 to 6 wt.%.

Surfactant

In general, the aqueous liquid laundry detergent composition of the invention preferably comprises from 5 to 60 wt. % of a surfactant, most preferably 10 to 30 wt. %. 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. Suitable anionic surfactants which may be used are usually water-soluble alkali metal salts of organic sulfates and sulphonates 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 suitable synthetic anionic surfactants are sodium and potassium alkyl sulfates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulfates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic surfactants are sodium C11 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulfates. Highly preferred are anionic alkyl benzene sulfonates, which more advantageously are linear alkyl benzene sulphonates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.

Preferred surfactant systems are mixtures of anionic and nonionic surfactants, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever). Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C16 to C18 primary alcohol sulfate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate. More preferably the surfactant systems are mixtures of anionic and nonionic surfactants exclusively.

The nonionic surfactant is preferably present in amounts of less than 50 wt. %, most preferably of less than 20 wt. % based on the total weight of the surfactant system. Anionic surfactants can be present for example in amounts in the range from 50 to 100 wt. % based on the total weight of the surfactant system. Thus, a highly advantageous surfactant comprises 50 to 100 wt. % of linear alkyl benzene sulfonates, based on the total weight of surfactants. Beneficially, the weight ratio of anionicmonionic surfactant is greater than 2 (i.e. more than twice the weight amount of anionic compared to the amount of nonionic).

A detergent 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 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 C12:0, C14:0, C16:0 ,C18:0 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.

(Alkoxylated) polymeric cleaning boosters

Anti-redeposition polymers stabilize the soil in the wash solution thus preventing redeposition of the soil. Suitable soil release polymers for use in the invention include alkoxylated polyamine, preferably 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. 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.

A composition of the invention will preferably comprise from 0.025 to 8% wt. of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines which are described above. More 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 quaternizsed, 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 hydrolyzed, at least one, preferably all of the hydrolyzed 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. Acid amide and ester groups may be included using lactones or sodium chloroacetate respectively (Modified Williamson synthesis), addition to an OH or NH group, then subsequent ethoxylation.

An example reaction scheme for inclusion of an ester group is

Addition of lactones is discussed in WO2021/165468.

(alkoxylated) 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 starshaped. 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, 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 detergent in concentrations ranging from 0.01 to 10 wt.%, more preferably from 0.1 to 5 wt.%.

(alkoxylated) polymeric thickeners

A detergent 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. When included, a detergent of the invention will preferably comprise from 0.01 to 5 wt. % but depending on the amount intended for use in the final diluted product and which is desirable, from 0.1 to 3 wt. % based on the total weight of the diluted composition. PH

Preferably the aqueous liquid laundry detergent has a pH from 5 to 9, preferably from 6 to 8, as measured at 293K.

Fluorescent Agent

The aqueous liquid laundry detergent composition of the invention preferably comprises a fluorescent agent (also known as optical brightener). Fluorescent agents are well-known, and many such fluorescent agents are available commercially.

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 laundry detergent composition of the invention is generally from 0.005 to 2 wt. %, more preferably 0.01 to 0.1 wt. %. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di- sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. 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-sulfostyryl)biphenyl.

It is preferred that the aqueous liquid laundry detergent composition according to the invention comprises a fluorescer. When the aqueous liquid laundry detergent composition of the invention is used to make a diluted wash liquor in a domestic method of treating a textile, the fluorescer is preferably present in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l in the diluted wash liquor.

Perfume

Preferably the aqueous liquid laundry detergent composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt. %, most preferably 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. It is commonplace for a plurality of perfume components to be present in a laundry formulation. In the laundry detergent compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components. 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. Perfume and top note are advantageously used to cue the whiteness benefit provided by the laundry detergent composition of the invention.

It is preferred that the aqueous liquid laundry detergent composition of the invention does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.

Preservative

Food preservatives are discussed In Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th edition Springer. Isothiazolone based preservative may also be used. The detergent preferably contains a preservative or a mixture of preservatives, selected from benzoic acid and salts thereof, alkylesters of p-hydroxybenzoic acid and salts thereof, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and salts thereof, most preferably sodium benzoate. The preservative is preferably present at 0.1 to 3 wt.%, preferably 0.3 wt.% to 1.5 wt.%, where the weight is calculated for the protonated form of the preservative.

External Structurants

Detergents of the invention may have their rheology further modified by use of one or more external structurants which form a structuring network within the detergent. Examples of such materials include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre. The presence of an external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid.

Further optional ingredients

The detergent of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include foam boosting agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti- corrosion agents, drape imparting agents, anti-static agents, ironing aids, further colorants such as pigments, pearlisers and/or opacifiers. 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.

The aqueous liquid laundry composition according to the invention preferably does not comprise tocopherols in an amount of from 0.001 to 2 wt. % and more preferably does not comprise 0.001 to 2 wt. % of anti-oxidant as defined in claim 1 (f) of

US2005/0130859 A1. It was found that such anti-oxidants are not necessary to include in the aqueous liquid laundry detergent composition of the invention, while still reducing enzyme loss upon exposure to sunlight. Omitting these anti-oxidants from the composition reduces the ingredient listing and simplifies manufacturing.

For the same reason the aqueous liquid laundry composition according to the invention preferably also does not comprise pearlescent agent as disclosed in US2008/0234169. These pearlescent agents are crystalline or glassy solids capable of reflecting and refracting light to produce a pearlescent effect. Such pearlescent agents are not needed and since their inclusion complicates manufacturing.

Even though not preferred, such tocopherols and pearlescent agents may however be present in the aqueous liquid laundry composition according to the invention.

It is preferred that the aqueous liquid laundry detergent composition of the invention does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.

Process

The process according to the invention relates to the manufacture of a detergent product according to the first aspect of the invention, wherein the process comprises the steps of: a) providing a plastic transparent container having an internal volume of from 0.1 to 10 L, wherein • the plastic comprises low density polyethylene, high density polyethylene or a combination thereof; and

• wherein the plastic preferably comprises recycled plastic; b) providing an aqueous liquid laundry detergent composition according to the invention; c) filling the container provided at step a) with the aqueous liquid laundry 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.

A particular benefit of the invention is that the detergent of the invention shows improved stability against change induced by the type of plastic present in the container. In particular the presence of the alkoxylated dye maintains the level of the alkoxylated active during storage. Hence advantageously the process of the invention includes a further step d) which is to store the detergent product for at least two weeks, preferably at least 4 weeks and more preferably for at least 6 weeks before first opening/use by the consumer. This storage time includes factory storage time as well as the in-store shelf-time of the product. The storage conditions may be any convenient conditions but preferably is at ambient temperature (i.e. between 15 and 25 degrees Celsius, preferably 20 degrees Celsius).

As indicated preferably the container contains at least some recycled plastic. The amount of recycled plastic comprised by the plastic container provided at step a) can be determined by the wt.% of recycled plastic feed material used to make the plastic container (i.e. as based on the total plastic used to make the container). Plastic containers comprising (or made essentially from) recycled plastic are nowadays also commercially available and the methods of their manufacture are well 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 containers 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 containers. Such shaping techniques include thermoforming, blow molding, injection-molding or injection stretch blow molding. A general description thereof can be found e.g. in Hans-Georg Elias “An introduction to plastics”, 1993. The UV absorber, if present, is preferably added to the plastic feed material while it is molten and mixed therewith prior to forming the container.

Preferably the plastic container obtainable by a process wherein based on the total amount of plastic feedstock, at least 30 wt.%, preferably at least 50 wt.%, more preferably 70 wt.% and even more preferably at least 90 wt.% of the feedstock is recycled plastic, preferably post-consumer recycled plastic, where the remainder may be virgin plastic.

The provision of the aqueous liquid detergent at step b) can be done using conventional methods know in the art. Generally, the methods comprise the step of adding ingredients in any suitable order and mixing to obtain a desired homogeneity of the final aqueous liquid detergent. It was surprisingly found that the aqueous liquid laundry detergent could be manufactured with water containing 0.1 to 10 ppm transition metal ions, without negatively affecting the colour stability of the aqueous laundry detergent composition. 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.

Preferably the product of the invention is obtainable by the process of the invention.

It will be appreciated that the aqueous liquid detergent can be advantageously enclosed in the container in such a way as to be at least in part in direct contact with the plastic of the container. An added benefit of the invention is that the container of the invention reduces the need for any inner liner material which prevents or reduces contact of the detergent with the plastic of the container.

Preferably the ratio of the plastic surface area in direct contact with the liquid detergent is from 400 to 6000 cm ² /L, more preferably from 1000 to 5000 cm ² /L and even more preferably from 2000 to 4500 cm ² /L.

Unless otherwise indicated, preferred aspects in the context of one aspect of the invention (e.g. the transparent plastic container comprising an aqueous liquid laundry detergent composition) are also applicable as preferred aspects in the context of one of the other aspects, (e.g. the process to manufacture the transparent plastic container comprising an aqueous liquid laundry detergent composition) mutatis mutandis.

It will be appreciated that the aqueous liquid detergent can be advantageously enclosed in the container in such a way as to be at least in part in direct contact with the plastic of the container. Conversely an added benefit of the invention is that the container of the invention does not require any inner liner material which prevents or reduces contact of the detergent with the plastic of the container.

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

Examples

Example 1

An ethoxylated blue anthraquinone dye was synthesized according to example 1 of US7632682. The blue dye had the following structure:

The dye contains 2 chains, each with 3 repeating CH2CH2O alkoxylate units as shown in the structure by the bold bonds, giving a total of 6 alkoxy units in the dye.

Analysis of the dye by accurate mass spectroscopy in conjunction with supercritical CO2 based chromatography (Waters LIPC2, BEH column, SM - Methanol + 10mM Ammonium Acetate BSM - MethanokIPA 80:20 + 10mM Ammonium Acetate), showed it to contain a minor amount of dye with the same chromophore but a lower number of CH2CH2O alkoxylate units. The results are shown in the table below:

An aqueous liquid laundry detergent was formulated to contain 5 wt.% linear alkyl benzene sulfonate and 5 wt.% C12-14 alcohol ethoxylate with an average of 7 moles of ethoxylation at a pH=7. A sulfonate acid dye (Acid Violet 50, comparative) or the ethoxylated anthraquinone of the structure as indicated directly above (of the invention) were each separately dissolved in the detergent formulation to give an optical density of approx. 1 (1cm max visible absorption). The formulations were divided in portions of 2 g. To each aliquot was added 1 g of PCR HDPE or virgin HDPE pellets and the aliquots were stored for 1 month.

The relative concentration of the alcohol ethoxylate with exactly 7, 8, 9 and 10 ethoxylate units was measured by chromatography in combination with accurate mass spectrometry detection (UPC ² Agilent, BEH Hillic column, positive ion). The results in Table 1 show the % difference in the amount of the non-ionic in a liquid sample of the detergent stored in the presence of virgin plastic pellets versus when stored in the presence of recylced plastic pellets (virgin/PCR). This when using either the ethoxylated anthraquinone dye (inventive) or the acid dye (comparison). The experiments were conducted twice.

Table 1 : % difference of the non-ionic in the liquid when using recycled or virgin plastic pellets.

The results show that use of alkoxylated anthraquinone dye according to the invention maintains the level of alkoxylated non-ionic surfactant when exposed to recycled and virgin plastic pellets whereas use of the acid dye does not. Example 2

An aqueous liquid laundry detergent was formulated to contain 5 wt.% linear alkyl benzene sulfonate and 5 wt.% C12-14 alcohol ethoxylate with an average of 7 moles of ethoxylation. A sulfonate anthraquinone acid dye (Acid Green 25, comparative) or the ethoxylated anthraquinone of the structure as used in Example 1 (of the invention) were each separately dissolved in the detergent formulation to give an optical density of approx. 1 (1cm max visible absorption). The formulations were divided in portions of 2 g. To each aliquot was added 1 g of PGR HDPE or 1g of virgin HDPE pellets or 1g of virgin PET (Polyethylene terephthalate) pellets and the aliquots were stored for 18 days.

The relative concentration of the alcohol ethoxylate with exactly 5, 6, 7, 8, 9 and 10 ethoxylate units was measured by chromatography in combination with accurate mass spectrometry detection (UPC ² Agilent, 2-pic, positive ion). The results in Table 2 show the % difference in the amount of the non-ionic in a liquid sample of the detergent stored in the presence of the HDPE plastics in comparison to PET when using either the ethoxylated anthraquinone dye (inventive) or the acid dye (comparison). The values are calculated using the equation (HDPE/PET -1)*100, where HDPE is the integral for the HDPE and PET for the PET. The experiments were conducted twice with 2 chromatographic runs per repeat.

Table 2: % difference of the non-ionic in the liquid when using recycled or virgin plastic HDPE pellets in comparison to PET. The results show that use of alkoxylated anthraquinone dye according to the invention maintains a more consistent level of alkoxylated non-ionic surfactant across when exposed to PET, recycled and virgin plastic HDPE pellets whereas use of the acid green 25 dye does not. In PCR HDPE a significant change in the alkoxylated non-ionic surfactant is seen when using Acid Green 25.