EP4688586A1

EP4688586A1 - Laundry detergent bottle

Info

Publication number: EP4688586A1
Application number: EP24809664.6A
Authority: EP
Inventors: Stephen Norman Batchelor; Liam Martin BREEN; Jamie Mark King; Natasha Louise Olenka GUNN
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Priority date: 2024-01-12
Filing date: 2024-11-21
Publication date: 2026-02-11
Also published as: WO2025149345A1; WO2025149208A1; WO2025149371A1; PL4688586T1; DE24809664T1; ES3061917T1

Abstract

A transparent laundry bottle which is suitable to hold 0.2 to 5 L of liquid laundry detergent, and which comprises a liquid laundry detergent, wherein the bottle comprises a bottle body formed of transparent plastic material and one or more labels, wherein the plastic material of the bottle comprises at least 70 wt.%, based on the total weight of the plastic of polyethylene terephthalate (PET); and wherein the liquid laundry detergent comprises surfactant and a dye; and wherein the bottle body comprises: a bottom wall providing a base structure for supporting the bottle in an upright position; and a top orifice suitable to be closed by a cap; and one or more side walls extending from the bottom wall to the top-orifice, and wherein the bottle, when positioned upright on a horizontal flat surface provides a front-view wall, a rear-view wall and two side-view walls, wherein one or more grooves and/or ridges circumference a continuous smooth plane on the front-view wall of the bottle, wherein the surface area of said smooth front plane is at least 50 % of the total front-view wall surface area of the bottle; and wherein the continuous smooth plane comprises a label; and wherein, at least 70 % of the front-view wall area is covered by the one or more grooves and/or ridges and the label on the continuous smooth front-plane.

Description

LAUNDRY DETERGENT BOTTLE

Field of the Invention

The present invention relates to a transparent laundry detergent bottle comprising a liquid laundry detergent.

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.

Colored laundry liquid detergents are often packed in transparent containers (unit-dose or multidose bottles). The combination offers the advantage that the consumer can easily visually inspect the liquid level during use, as well as improved distinction. 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). These problems were observed in particular for bottles based on polyethylene terephthalate (PET) plastic.

It is an object of the present invention to provide a liquid laundry detergent bottle based on PET plastic comprising a liquid laundry detergent with a dye which provides 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 transparent laundry bottle which is suitable to hold 0.2 to 5 L of liquid laundry detergent, and which comprises a liquid laundry detergent, wherein the bottle comprises a bottle body formed of transparent plastic material and one or more labels,

• wherein the plastic material of the bottle comprises at least 70 wt.%, based on the total weight of the plastic of polyethylene terephthalate (PET); and • wherein the liquid laundry detergent comprises surfactant and a dye; and

• wherein the bottle body comprises: o a bottom wall (Fig. 6, 3) providing a base structure for supporting the bottle in an upright position; and o a top orifice (Fig. 5, 4) suitable to be closed by a cap; and o one or more side walls extending from the bottom wall to the top-orifice, and o wherein the bottle, when positioned upright on a horizontal flat surface provides a front-view wall (Fig. 1), a rear-view wall (Fig. 2) and two side-view walls (Fig. 3 and Fig. 4),

• wherein one or more grooves and/or ridges (1) circumference a continuous smooth plane (2) on the front-view wall of the bottle, wherein the surface area of said smooth front plane (2) is at least 50 % of the total front-view wall surface area of the bottle; and

• wherein the continuous smooth plane (2) comprises a label (8); and

• wherein, at least 70 % of the front-view wall area is covered by the one or more grooves and/or ridges (1) and the label (8) on the continuous smooth front-plane (2).

It was surprisingly found that use of a bottle according to the invention with a particular arrangement of labels, smooth planes and surface grooves and/or ridges improves the color stability of the liquid detergent upon exposure to sunlight when the bottle is PET-based and especially when the bottle contains recycled PET.

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 laundry bottle of the invention is transparent by virtue of having a bottle body formed from a transparent plastic material. 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 surface area of the bottle body is transparent, wherein these numbers exclude the area covered by the label, but preferably include the area covered by the label. Transmittance of the plastic 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.

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 UV-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 %. It is preferred that at least part of the light in the range of 400 to 700 nm is able to pass through the laundry bottle when filled (i.e., bottle body + detergent) in one or more light-paths.

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. 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 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 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.

In case of doubt, when reference is made to the front-, rear- or one of the side-view walls, reference is made to the bottle-wall area visible from the relevant front-, rear- or side-view perspective, with the bottle positioned upright on a horizontal and flat surface. The front-, rear- and both side-walls may form one continuous wall extending up from the bottle-base wall to bottle top opening, but which as such nevertheless still provide wall areas which are a front-, rear and side-wall exterior facing. In other words, with ‘the front wall’ is meant the wall-portion of the bottle visible from a front-view perspective. Would there remain any further doubt, with a view perspective beneficially is meant an orthographic projection. To further simply, the laundry bottle may be placed on its base in upright position on a horizonal flat surface, where the horizontal flat-surface represents a x, y plane and the bottle-top lies in the positive Z direction of a Cartesian 3-dimensional coordinate system (x, y, z). The bottle is than positioned such that the front and rear wall face (in opposite directions) along the x-axis; and each side-wall face (in opposite directions) face along the y-axis. In this case the front- and rear-view walls are the wall areas visible from an orthographic projection along the x-coordinate axis (looking-direction either in the +x or -x direction). In this case the side walls are the wall areas visible from an orthographic projection along the y-coordinate axis (looking-direction either in the +y or -y direction). The wall areas visible from these viewing angles may partially overlap, whereby part of the bottle wall may be part of both the front-wall view area and a side-view wall area. Brief Description of Drawings

Fig. 1 is a front view of the laundry bottle showing the front-view wall according to an embodiment of the invention. The dashed line representing the preferred size and shape of a label.

Fig. 2 is a rear view of the laundry bottle showing the rear-view wall according to an embodiment of the invention. The dashed line representing the preferred size and shape of a label.

Fig. 3 is a side view of the laundry bottle showing one of the side-view walls according to an embodiment of the invention.

Fig. 4 is the other side-view of the laundry bottle showing the other side-view wall according to an embodiment of the invention.

Fig. 5 is the top view of the laundry bottle according to an embodiment of the invention.

Fig. 6 is the bottom view of the laundry bottle according to an embodiment of the invention.

The laundry bottle

The bottle body is made from transparent plastic material and comprises at least 70 wt.% based on the total weight of the plastic of polyethylene terephthalate (PET), preferably at least 80 wt.%, more preferably at least 90 wt.% and even more preferably essentially consist of PET plastic as based on the total amount of plastic. These levels relate to the plastic of the bottle body per se and do not include any plastic which may be present in labels placed on the exterior of the bottle body.

The plastic of the bottle body 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 PET plastic. Here as well, these levels relate to the plastic of the bottle body per se and do not include any plastic which may be present in labels placed on the exterior of the bottle body.

It is considered that the invention is advantageously applied to liquid detergents which are contained in transparent plastic-based bottles, wherein the plastic comprises recycled PET and especially recycled PET. It is considered that recycled plastic, especially recycled PET can increase the negative effects sunlight exposure on the color stability of the liquid detergent contained. 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. The UV absorber are present as additive in the plastic. Advantageous UV absorbers are one or more of benzophenones, salicyclates, benzotriazoles, hindered amines and alkoxy (e.g. methoxy) cinnamates). Cyanoacrylate UV absorbers are particularly preferred, preferably at level 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, (Uvinul), Deltachem(QingDao) (Ominstab), MPI Chemie, (UV), Shipro Kasei Kaisha (Seesorb).

It is considered that cyanoacrylate UV blockers are particularly effective for bottles of the invention which comprise PET and specially recycled PET.

The laundry bottle is suitably rigid to be shape stable when placed in upright position on a flat surface. The bottle comprises a preferred internal volume of from 300 to 3500 ml, more preferably of from 500 to 3000ml, even more preferably of from 600 to 2800 ml and still even more preferably of from 650 to 2600 ml.

Laundry bottles of the invention, especially those having a fill volume of more than 1.5L preferably have one or more additional grooves and/or ridges inside (and preferably fully encircled by) the smooth plane (1) and/or (5) to improve handling the bottle.

Advantageous bottles, have 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. 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.

Beneficially a horizontal cross-section of the bottle half-way of the height, in upright position, is elliptical in shape, whereby the maximum distance between the rear and front wall is smaller than the maximum distance between the side walls. Preferably the ratio between the maximum distance between the front and rear wall : the maximum distance between the side walls is from 0.2 to 0.9, more preferably is from 0.3 to 0.8, even more preferably is from 0.4 to 0.7. The frontview wall area is preferably larger than either one of the side-view wall areas. The rear-view wall area is preferably larger than either one of the side-view wall areas.

The bottle body advantageously comprises side-walls which have a curved shape, running from top to bottom. This can be observed for example in Fig. 1, which is the front-view perspective of the bottle, where the sides are indeed curved. In this case when aligning bottles side-by-side the contact area between bottles can be rather small. In this case the bottle side-walls comprise smooth reinforced patches (Fig. 3, 6; Fig. 4, 7) located at the position where two bottles, when placed in a upright on a horizontal flat surface may touch. These smooth areas have a sideview wall surface area% of from 1 to 15 % of the total side-on view surface area. These help in stabilizing the upright positions and reduce bottle-to- bottle shear damage during transport and packaging. The reinforced patches are preferably patches which provide larger bottle-to-bottle contact areas and/or patches with a greater wall thickness. Analogous smooth areas may also be present on the front- and rear wall.

Advantageously the surface area of the horizontal cross section of the bottle when in upright position is smaller at the bottom-end and the top-end and has a maximum at 20 to 80 % of the vertical distance from bottom to top of the bottle.

The surface area covered by the one or more labels (8, 9), as based on the total outer surface area of the front-, rear- and both side walls of the bottle, is at most 70 %, preferably at most 65%, even more preferably at most 60 %, still even more preferably at most 55%. Grooves and/or ridges

The bottle comprises one or more grooves and/or ridges (1) defining one or more smooth planes (2, 5) on the front-view wall and rear-view wall of the bottle by virtue of being arranged around said one or more smooth planes. This is what is meant by the smooth planes being ‘encircled’ or ’ circumferenced’ by one or more grooves and/or ridges. The encirclement need not be continuous, but sufficient for the smooth plane(s) to have a generally defined continuous shape. For example, a continuous line can define a circle, but so can a dashed line. The continuous smooth plane(s) are preferably generally elliptical or generally tear-drop like in shape (2, 5).

The one or more grooves and/or ridges (1) circumference a continuous smooth plane on at least the front-view wall (2), wherein the surface area of said smooth front plane (2) is at least 50% of the total front-view surface wall area of the bottle. Importantly said smooth area (2) is covered by one or more labels, preferably one label. Of the total smooth plane surface area on the front-view wall (2), as circumferenced by one or more grooves and/or ridges (1), at least 70% is covered by a label. This coverage is preferably at least 75%, more preferably at least 80 %, even more preferably at least 90% and still even more preferably at least 95%. Higher values of label coverage of the smooth plane on the front wall provide improved color stability.

The invention in part is that the sunlight induced instability is greatly reduced by providing one or more grooves and/or ridges (1) on those parts not covered by a label present on the at least smooth planes (2, 5). In other words, that the label on the front-view wall, positioned on the smooth plane (2), provides greater protection against the effects of sunlight than would be expected based on the area covered by the label.

Advantageously, at least 75 % of the front-view wall area is covered by the one or more grooves and/or ridges (1) and the label (8) on the continuous smooth front-plane (2), this amount is preferably at least 80%, more preferably at least 85%, even more preferably at least 90% and still even more preferably at least 95%.

The smooth plane (2) preferably covers from 55% to 80% of the total front-view wall area, more preferably covers from 57% to 75%, and even more preferably covers from 60% to 70%. The smooth plane (2) comprises a label (8), wherein the label preferably covers at least 55%, more preferably (in increasing order of preference) at least 65%, at least 70%, at least 75%, at least 80%, at least 85% at least 95% of the total front-view wall smooth-pane area.

The one or more grooves and/or ridges preferably (1) cover at least in order of increasing preference at least 40%, 50%, 60%, 70%, 80% and even more preferably at least 90% of the front-view wall area, which is not covered by the smooth plane (2).

It is preferred that the grooves and/or ridges (1) are continuous and therefore preferably the number of non-continuous grooves and/or ridges running across the whole of the outer surface area of the front- rear-, and side-view walls of the bottle (Fig. 1-4) is preferably at most 20, more preferably at most 15, even more preferably at most 10, still even more preferably at most 5, 4, 3, 2, 1. In the case of for example one continuous groove the groove may continuously run across along the front wall, across one of the side walls, the rear wall, onto the remaining side wall without interruption. Configurations of the bottle with fewer non-continuous grooves and/or ridges is preferred to simply the manufacturing process and to reduce to number of potential stress points in the bottle which can cause the bottle integrity during storage and transport to be compromised.

Beneficially the one or more grooves and/or ridges (1) are also present on one or both of the side-view wall areas. There these beneficially further reduce negative effects of sunlight falling on the side walls of the bottle. Furthermore, these one or more side-wall grooves and/or ridges (1) advantageously run predominantly along the vertical direction (as shown in Fig. 3 and Fig. 4) where they can also act as reinforcements ridges to better withstand vertical forces. Such vertical forces can be significant when stacking boxes of laundry detergent bottles. The grooves and/or ridges (1) on the side wall which predominantly are vertically directed can therefore save plastic usage required to make the laundry bottle.

Beneficially at least one of the grooves and/or ridges runs from front wall, across one of the side-view walls onto the rear wall and is sufficiently wide to provide a gripping portion (10). This gripping portion is advantageously located at the neck portion of the bottle preferably at least at 70%, more preferably at least 75% and even more preferably at least 85% of the height of the total bottle, as seen from the one side wall (Fig. 3)) to aid a secure handgrip around the neck when opening / closing the bottle. To further benefit ergonomics, this groove / ridge tappers downward as seen when starting from the side-view wall when continuing along the front-view wall and the rear-view wall.

The width of the one or more grooves and/or ridges (1) is advantageously such that along at least 75% of the total length of the one or more grooves and/or ridges, the width is from 2 mm to 4 cm, more preferably from 3 mm to 3 cm, even more preferably from 4 mm to 2.5 cm.

The depth of the one or more grooves and/or ridges (1) is advantageously such that along at least 75% of the total length of the one or more grooves and/or ridges, the depth is from 0.1 mm to 10 mm, more preferably from 0.5 mm to 7 mm, even more preferably from 1 mm to 5 mm.

The length of at least one groove and/or ridge is advantageously at least 20 % of the total height of the bottle, when in upright position on a flat horizonal surface, more preferably (in increasing order of preference, at least 50%, 80%, 120%, 160%, 200%, 220%, 240%, 260%, 280%, 300% and still even more preferably at least 400%. This length preference applies advantageously to at least 30%, more preferably at least 50%, more preferably at least 70%, even more preferably at least 80 %, still even more preferably at least 90% of the grooves and/or ridges.

As to the total length of the one or more grooves and/or ridges this preferably, in increasing order of preference, is at least 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 times the total height of the bottle.

The bottle comprises on or more grooves and/or ridges (1), but grooves are preferred. Therefore, of the grooves and/or ridges preferably at least 60%, more preferably at least 75%, even more preferably at least 85% and still even more preferably at least 90% and still even more preferably essentially all are grooves. Grooves protrude toward the interior of the bottle and ridges protrude toward the exterior of the bottle. Preferably the grooves and/or ridges are smooth grooves and or ridges.

The grooves and/or ridges (1) circumference a continuous smooth plane on at least the frontview wall (2) (and preferably on the rear-view wall as well (5)). In case of doubt, with circumferencing is meant that the surface edge of the front wall smooth plane for example, is bordered and/or defined largely by surrounding grooves and/or ridges (1). These circumferencing grooves and /or ridges may be continuous or non-continuous, but preferably form at least 70%, more preferably at least 80%, even more preferably at least 90%, still even more preferably at least 95 % and still even more preferably to 100% are continuous on the border of the smooth plane.

The preferred features of the front-view wall apply mutated mutandis to the rear-view wall. Therefore, the front-view wall (Fig. 1) and rear-view wall (Fig. 2) are preferably substantially and more preferably essentially similar (e.g. mirror images).

As such preferably also on the rear-view wall one or more grooves and/or ridges circumference a continuous smooth plane (5). As such the preferred area covered by the one or more grooves and/or ridges, continuous smooth plane (2) and the label (8) indicated for the front-view wall are also preferred for the one or more grooves and/or ridges, continuous smooth plane (5) and the label (9) on the rear-view wall.

Beneficially grooves and/or ridges (1) are present on the front wall, the rear-wall and both side walls, where they predominantly run in a ‘top-to-bottom’ direction. This is considered to controlling pour rate for liquids from the orifice, and especially of those liquids having a viscosity from 200 to 1000cp. In other words, the total vertical distance travelled by the grooves and/or ridges exceeds the total horizontal distance of the grooves and/or ridges, as considered with the bottle in upright position on a flat horizontal surface. More advantageously the vertical distance travelled by the grooves and/or ridges (1) versus the horizontal distance travelled is at least, in increasing order of preferences 1.2, at least 1.4, at least 1.6, at least 1.8, at least 2.0 at least 2.2 at least 2.4, at least 3.0.

Label

The label (8) on the continuous smooth plane (2) of the front-view wall can contain product information. The label is advantageously at least in part non-transparent to visible light to improve readability of any information thereon. The label can be applied as self-adhesive sticker, or in any other suitable manner. It should be borne in mind that labels may themselves contain transparent parts. This can improve the visibility of the liquid in the bottle and provide more complex depictions, while still having an overall simple-shaped label outer edge. Simple overall label outer edges reduce the number of label-placement errors in a factory line, and also improve surface contact with the bottle body when the non-transparent label part is more intricately shaped. Preferably from 5 to 60 % of the total label surface area (8) on the front smooth plane (2) is transparent, more preferably from 10 to 50 %, even more preferably from 15 to 45% and still even more preferably from 20 to 40%.

The superior sunlight protection to color fading when applying a label in part can be due to the label materials themselves, even thought these may in part be transparent. Preferably the label adhesive used is therefore an acrylic based adhesive. Preferably the label is a polypropylene film with a print-receptive coating. The label material preferably has a base weight of from 20 to 200 g I m².

The exceptional protection afforded by the label (8, 9) is considered to be further improved by having the predominant coloring of the label matching more closely the color of the liquid. At least the color of the label (8) applied to the continuous smooth plane (2) of the front-view wall, and preferably also of the label (9) as optionally applied to the preferred continuous smooth plane (5) on the rear-view wall has therefore a label surface area whereof at least 50% is colored with a color which deviates from the color of the liquid detergent by at most 50 degrees, preferably at most 40 degrees, more preferably at most 35 degrees, even more preferably at most 30 degrees and still even more preferably at most 20 degrees from the color of the liquid detergent when the color of the liquid detergent is as portrayed on a color wheel. The color wheel is a usually portrayed with red facing up (Wikipedia, ‘Color Wheel’). The color of the laundry detergent liquid is preferably non-green and more preferably is turquoise, pink, blue or violet in color.

To simplify manufacturing and afford the most benefits of the invention, advantageously at least 70 %, more preferably at least 80 %, even more preferably at least 90 % and still even more preferably essentially all of the outer surface of the bottle covered by the one or more labels (8, 9) is restricted to the one or more smooth continuous planes (2, 5). This applies to the smooth continuous planes on the front-view wall (2) and/or rear-view wall (5) which are encircled by one or more grooves and/or ridges (1).

It is considered that the placement of the label (8) on the continuous smooth plane (2) of the front wall, where both the smooth plane and the label cover the vertical and horizontal center point of the front wall, as based on the front -view perspective of the bottle further helps to improve color stability. The reason being that PET bottle production processes typically involve some degree of blow-molding which tends to provide the thinnest plastic on the front-, rear- and /or side-walls halfway between base and top. This is even more critical for the front- and rear- wall as these are further stretched in the width (being larger in surface area) than the side-walls. Hence placement of the label over the vertical and horizontal center point of the front-view wall provides additional protection versus placement over any other outer-surface wall point of the bottle front wall. The same applies to placing an additional label (9) on the vertical and horizontal center point of the rear-view wall.

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% of the surfactant is selected from anionic and nonionic surfactant and mixtures thereof. Weights of anionic surfactants refer to their protonated form.

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.

In the liquid compositions 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. The key intermediate compound in the manufacture of LAS is the relevant alkene. These alkenes (olefins) may be produced by any of the methods described above and may be formed from primary sugars, biomass, waste plastic, MSW, carbon capture, methane capture, marine carbon to name a few. Whereas in the processed described above the olefin is processed to form linear alcohols by hydroformylation and oxidation instead, the olefin is reacted with benzene and then sulphonate to form the LAS. Linear alkylbenzene sulfonates with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain preferably has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1-phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ. Preferably, linear alkyl benzene sulphonate surfactant is present 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 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 surfactants 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 saturated and monounsaturated alcohol ethoxylates having a straight or branched chain alkyl group 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 comprises C16, C18 and C18:1 and a mol average of 8 to 12 ethoxylate groups. More preferably the methyl ester comprises 20 to 50 wt.% C16 MEE and 20 to 50 wt.% 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 catalyzed 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-ionic Surfactant Organic Chemistry (N. M. van Os ed), Surfactant Science Series Volume 72, CRC Press.

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

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

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 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 -[CH₂CH₂O]_nH 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 most preferably selected from mono-azo, bis-azo, anthraquinone, and azine. In an embodiment, a mixture of the shading dyes may be used. 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:

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 SOa' 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:

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. Aminopolycarboxylate builder

The liquid laundry detergent preferably comprises aminopolycarboxylate which are known in the detergent industry and sometimes referred to as aminocarboxylate chelants. They are generally appreciated as being strong builders. The liquid laundry detergent preferably comprises from 0.1 to 20 wt.% of aminopolycarboxylates, 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.%.

Suitable aminopolycarboxylates include glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA) aspartic acid diethoxysuccinic acid (AES) aspartic acid- N,N-diacetic acid (ASDA) , hydroxyethylene-diaminetetraacetic acid (HEDTA), hydroxyethylethylene-diaminetriacetic acid (HEEDTA) , iminodifumaric (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid (EDDM), ethylenediamineditartaric acid (EDDT), ethylenediaminedimaleic acid and (EDDMAL), dipicolinic acid.

Preferred aminopolycarboxylates are glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM) or a mixture thereof, more preferred are GLDA, MGDA, EDDS or a mixture thereof and even more preferred are GLDA and MGDA or a mixture thereof, still even more preferred is MGDA.

MGDA and GLDA raw material may contain significant amounts of MGMA and GLDA respectively, which was found to negatively impact laundry detergent stability upon exposure to sunlight. 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*I_MGMA) 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. The mole fraction of GLDA to GLMA can be determined in a similar manner.

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. The level of MGMA may also be decreased in the sample by preparative chromatography, such as preparative thin layer chromatography.

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 and GLDA are 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/GLMA 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. This also applies to the molar fraction of GLDA/GLMA. Preferably the liquid detergent has a pH from 5 to 9.0, preferably from 6.0 to 8.0. 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. It is noted the sodium salt forms of aminopolycarboxylate typically are alkaline.

Perfume

The liquid 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 substituent is an alkoxy group. Preferably the benzaldehyde is selected from 4-Methoxybenzaldehyde, 5- Methoxybenzaldehyde, 3- Methoxybenzaldehyde, 4-Ethoxybenzaldehyde, 5- Ethoxybenzaldehyde, 3- Ethoxybenzaldehyde. Preferably the 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 detergent advantageously 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.

A composition of the invention will preferably comprise from 0.025 to 8 wt. % of one or more anti-redeposition polymers. 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. The overall level of SRP, when included, preferably is from 0.1 to 10 wt.%, more preferably from 0.3 to 7 wt.% and even more preferably from 0.5 to 5 wt.%. 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 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 may 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). Other types of SRP for use in the invention include cellulosic derivatives.

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. 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 liquid detergent of the invention preferably comprises polymeric thickeners in an amount of from 0.01 to 5 wt. % and more preferably of from 0.1 to 3 wt. %.

The detergent composition of the invention may comprise enzyme. Preferred are proteases, amylases, cellulases, peroxidases, mannanases, pectate lyases and lipases and combinations thereof. 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.

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. The detergent may beneficially include a bleach system, which advantageously includes from 1 to 25 wt. % of bleach, from 0.1 to 10 wt.% of bleach activator and optionally from 0.0001 to 0.5 wt. % of bleach catalysts.

The liquid detergent preferably comprises an amine-based organic solvent. 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 sunlight exposure.

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

Hence 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 monoazo 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.

Process

Providing bottle bodies according to the invention can be done by conventional techniques known in the art. PET bottles may be made via conventional techniques of Injection Blow Moulding and Injection Strech Blow Moulding. PET bottles are typically made using a 2-Step approach wherein in a first step a pre-form is made via injection moulding of molten PET in a pre-form mould. Subsequently the pre-form is given it final shape in a second mould of the final bottle shape. This shaping preferably involves heating of the pre-form, stretching using a rod and blow-moulding the material to line the interior of the mould of the final bottle shape. A general description 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.

Preferably the plastic material of the bottle body comprises recycled (polyethylene terephthalate) PET plastic. The amount of recycled plastic can be tuned by the wt.% of recycled plastic feed material used, based on the total plastic feed material from which the container is made. PET plastic feed material (both virgin and recycled) are usually supplied in the form of PET pellets. Hence, the amount of recycled PET plastic in the final body of the bottle can be finely determined. 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. The UV absorber, if present, is preferably added to the (pelletized) plastic feed material while it is molten and mixed therewith prior to forming the bottle.

The provision of the liquid detergent composition can be done using conventional methods know in the field. The method may comprise simply combining the ingredients preferably including mixing to provide the liquid detergent composition.

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 laundry bottle 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. product) 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 Aqueous laundry detergent formulations were made having a formulation as set out in Table 1.

Table 1 : formulation composition A blue dye was added to the formulation so that the Optical Density (1cm) at the absorption maximum (646nm) in the visible was 0.6. The dye used was an 1,4, diaminoanthraquinone, which was ethoxylated. The dye structure was:

The formulations were placed in a 1.48 L transparent PET (35% PCR) plastic bottle containing a UV blocker (0.07% UVI) and identical transparent bottle with a label on its front, where the label covered 59% of the liquid. The label was PP CLEAR TC 50 P / RP74 I PET 30. The front of the label was a clear, glossy, biaxially oriented, top-coated polypropylene film. The backing material was a clear polyester backing material. The glue used was an Acrylic, water borne based, Ultra clear permanent adhesive, not requiring a UV cure,

The formulations were exposed to simulated outdoor sunlight in a weatherometer for 48 hours @ 43W/m² (300-400nm). Following exposure, the bottle was shaken, and the UV-VIS spectrum of the detergent was measured (1cm) and compare to an unirradiated control.

The change in absorption of the blue dye was measured by:

ABIue = Z(irradiated)-(control) from 570 to 670nm Browning/Oranging of the formulation was measured. ABrown = Z(irradiated)-(control) from 450 to 500nm. Yellowness of the formulation was measured:

AYellow = Z(irradiated)-(control) from 400 to 420nm.

For all these values a negative value indicates a decrease in the color and positive value an increase. The results are shown in table 2.

Table 2:

The ABIue and the AYellow decrease with and without the label by similar amounts. The

ABrown increases and surprisingly is 9 times smaller with the label. An increase in browning represents a color-deterioration of the detergent. This reduction in browning cannot be due to only a shielding effect of the label, as it only 59% of the liquid was covered, which would give an expected value for ABrown 0.59*0.9 =0.53 for the browning, compared to the measured 0.1. The reduction in browning can therefore be attributed to the presence of the grooves which surround the flat front-plane. No/small effects are seen for ABIue and the AYellow.

Claims

1. A transparent laundry bottle which is suitable to hold 0.2 to 5 L of liquid laundry detergent, and which comprises a liquid laundry detergent, wherein the bottle comprises a bottle body formed of transparent plastic material and one or more labels,

• wherein the plastic material of the bottle comprises at least 70 wt.%, based on the total weight of the plastic of polyethylene terephthalate (PET); and

• wherein the liquid laundry detergent comprises surfactant and a dye; and

• wherein the bottle body comprises: o a bottom wall (3) providing a base structure for supporting the bottle in an upright position; and o a top orifice (4) suitable to be closed by a cap; and o one or more side walls extending from the bottom wall to the top-orifice, and o wherein the bottle, when positioned upright on a horizontal flat surface provides a front-view wall (Fig. 1), a rear-view wall (Fig. 2) and two side-view walls (Fig. 3 and Fig. 4),

• wherein the continuous smooth plane (2) comprises a label (8); and

2. A transparent laundry bottle comprising a liquid laundry detergent according to claim 1, wherein the number of grooves and/or ridges (1) is at most 4, preferably at most 3, more preferably at most 2 and even more preferably is 1 to be essentially a continuous groove and/or ridge visible on each front-, rear- and side-view wall area (Fig. 1-4).

3. A transparent laundry bottle comprising a liquid laundry detergent according to claim 1 or claim 2, wherein rear-view wall (Fig. 2) of the bottle also has one or more grooves and/or ridges (1) which circumference a continuous smooth plane (5) on the rear-view wall of the bottle, wherein the surface area of said continuous smooth rear plane (5) is at least 50 % of the total rear-view wall surface area of the bottle and wherein said continuous smooth rear plane also comprises a label (9).

4. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the front-view wall surface area (Fig. 1), and advantageously also the rear-view wall surface area (Fig. 2), is at least 85 % covered by the one or more grooves and/or ridges (1) and label (8, 9), preferably at least 90% and even more preferably at least 95 %.

5. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the front-view wall label (8) surface area is at least 50% coloured with a dye which deviates from the color of the liquid detergent by at most 50 degrees, preferably at most 40 degrees, more preferably at most 35 degrees, even more preferably at most 30 degrees and still even more preferably at most 20 degrees as based on the liquid detergent color wheel as portrayed on a color wheel.

6. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the bottle comprises an internal volume of from 300 to 3500 ml, preferably from 500 to 3000ml, more preferably from 600 to 2800 ml and even more preferably from 650 to 2600 ml.

7. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the plastic of the body 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.

8. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the bottle body does not comprise a perforation in the front-, rear- and side-view wall areas, and more preferably does not comprise a perforated portion to form a handle.

9. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the bottle is essentially symmetrical in at least one vertical cross-section, with the exception of any threads on the top to accommodate a screw-on cap or other such minor embossments.

10. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the dye comprises 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: wherein the structures, especially the indicated degrees of ethoxylation represent average degrees of ethoxylation.

11. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the dye comprises an ethoxylated dye according to the following but wherein the average degree of ethoxylation is from 3 to 10 and preferably is from 4 to

8.

12. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the liquid is turquoise, pink, blue or violet in color.

13. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the detergent further comprises from 1 to 70 wt. % surfactant, and preferably further comprises from 0.1 to 25 wt.% methylglycinediacetic acid (MGDA).

14. A transparent laundry bottle comprising a liquid laundry detergent according to any preceding claim, wherein the detergent comprises from 0.00005 to 0.02 wt.% of dye, preferably from 0.0001 to 0.01 wt.% and more preferably from 0.001 to 0.005 wt.%.

15. A transparent laundry bottle comprising a liquid laundry detergent 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.%.