WO2023006382A1

WO2023006382A1 - Laundry detergent product

Info

Publication number: WO2023006382A1
Application number: PCT/EP2022/069035
Authority: WO
Inventors: Stephen Norman Batchelor; Neil Stephen Burnham
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2021-07-26
Filing date: 2022-07-08
Publication date: 2023-02-02
Also published as: EP4377428A1

Abstract

A liquid laundry detergent comprising from 5 to 70 wt. % of surfactant; and from 0.0001 to 0.1 wt. % of a copper-complex of chlorophyllin.

Description

LAUNDRY DETERGENT PRODUCT

Field of the invention

The present invention relates to liquid laundry detergents comprising surfactant and a copper-complex of chlorophyllin.

Background of the invention

Liquid laundry detergents are widely used by consumers to wash their laundry in domestic situations. Liquid laundry detergents come in a variety of product forms. Examples are in the form of a liquid laundry bottle, which contains a plurality of doses, or in the form of discrete unit-dose laundry detergent water-soluble capsules. Such unit-dose capsules usually contain at least one compartment with liquid laundry detergent. Liquid laundry products are dispensed into a washing machine where they are diluted with additional water to form a wash liquor. The wash liquor is used to wash clothes in the laundry machine.

Many laundry detergent cleaning actives themselves, such as most surfactants and polymers, builders and-so-on tend to be pale yellow or brown in colour. Hence for aesthetic appeal synthetic organic dyes are added to liquid laundry detergents to provide a bright colour, such as blue or pink. This is not trivial as consumers are loath to wash their textiles with a detergent liquid which has a pale-yellow to brown colour. Synthetic organic dyes are derived from the petrochemical industry. Another problem with synthetic organic dyes is that these tend to be poorly biodegradable. Natural dyes however tend to be unstable in domestic liquid laundry detergents and rapidly degrade from the original bright colour into undesired (e.g. brown/black) off- colours or otherwise tend to undesirably shift colour in the laundry detergent environment. Furthermore, it was found that natural dyes are prone to precipitation during storage. This presents a serious problem when creating liquid laundry detergents with natural colorants. Another problem when using natural dyes to colour the liquid laundry product is that these can undesirably stain the textiles when the liquid is applied neat and/or during the laundry wash itself. Neat application of liquid detergent is done by consumers to pre-treat visibly stained areas. It is an object of the present invention to provide a liquid laundry detergent with a stable natural colorant, which also shows reduced staining on fabrics.

Summary of the invention The above objective is achieved by a liquid laundry detergent comprising:

• from 5 to 70 wt. % of surfactant, preferably comprising surfactant derived from a renewable source; and

• from 0.0001 to 0.1 wt. % of a copper-complex of chlorophyllin. The liquid laundry detergent is preferably an aqueous liquid laundry detergent, more preferably comprising from 20 to 90 wt. % water, even more preferably comprising from 35 to 80 wt. % water and still even more preferably comprising from 50 to 70 wt. % water. It was surprisingly found that the presence of the copper-complex of chlorophyllin provides a liquid laundry detergent with a stable natural green color, despite being in an (aqueous) liquid laundry environment comprising surfactants. The natural green color of the liquid (aqueous) laundry detergent was found to be less sensitive to color- change and precipitation when compared to other colorants derived from plant- sources. Furthermore, it was found that the copper-complex of chlorophyllin provides reduced textile staining when applied neat onto fabrics and/or during the laundry wash itself. Also, importantly Cu-Chlorophyllin was found to provide a natural green color, reminiscent of the green color of plants, which can authentically communicate the reduced environmental impact of a liquid laundry detergent to the consumer. Furthermore, as opposed to current synthetic colorants suitable for liquid laundry detergents, the copper-complex of chlorophyllin is itself made from renewable sources (notably chlorophyll) and is also biodegradable, thus further reducing the overall environmental impact of the liquid laundry detergent. In a further aspect the inventio relates to the use of a copper-complex of chlorophyllin to provide a green liquid laundry detergent, preferably wherein the liquid laundry detergent is aqueous, and more preferably to provide a liquid laundry detergent with reduced environmental impact. Detailed description of the invention

Definitions

Weight percentage (wt. %) is based on the total weight of the liquid laundry detergent 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 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.

Copper-complex of chlorophyllin

Cu-chlorophyllins are described in EFSA ANS Panel (EFSA Panel on Food Additives and Nutrient Sources Added to Food), 2015. Scientific Opinion on re-evaluation of copper complexes of chlorophylls (E 141 (i)) and chlorophyllins (E 141 (ii)) as food additives. EFSA Journal 2015; 13(6):4151 , 60 pp. doi:10.2903/j.efsa.2015.4151. Cu- chlorophyllins can be obtained by addition of copper to the product obtained by saponification of a solvent extraction of strains of (edible) plants material. Examples of such plant materials are grass, lucerna and nettle. Alfaalfa ( Medicago sativa) and pasture grasses are preferred sources.

Cu-Chlorophyllins are found to be generally soluble/dispersible in liquid laundry detergent with surfactants. In contrast, chlorophylls were not found to be soluble/dispersible in liquid laundry detergents. The copper-complex of chlorophyllin of the invention are water-soluble and/or water-dispersible when dosed at 0.1 wt. % in water at 293K. Copper-complexes of chlorophyllins are well-known and have been commercially produced since the 1920s. Methods to produce copper-complexes of chlorophyllins are disclosed in A.M. Humphrey ‘Chlorophyll’, Food Chem. 1980.

Copper-complexes of chlorophyll general are mixtures of different copper-complex species of which the major types are:

The preferred amount of the copper-complex of chlorophyllin is from 0.0005 to 0.05 wt. %, more preferably from 0.001 to 0.02 wt. % and even more preferably from 0.005 to

0.01 wt. %. Such ranges provide increasing optimization between providing natural color to the liquid laundry detergent and reducing unwanted staining.

These amounts of the copper-complex of chlorophyllin were found to provide a clearly visible natural green color to the liquid laundry detergent in the presence of 5 to 70 wt. % surfactant, whilst causing little or no staining and/or coloring of the textile after a wash even when applied neat onto the textile and followed by a handwash-rinse. Moreover, the Copper-complex of chlorophyllin was found to be stable, in terms of color and precipitation, more so than other tested natural colorants.

In view of the current invention, it will be clear that the liquid laundry detergent composition of the invention comprises from 0.0001 to 0.1 wt. % of a copper-complex of chlorophyllin, which need not be encapsulated. Encapsulation is also not preferred as it can reduce the transparency of the liquid laundry detergent. The liquid laundry detergent may however contain further colorants as desired (encapsulated or not). Preferably however the liquid laundry detergent does not contain any encapsulates colorants. Encapsulation of ingredients, in particular of perfumes, is described for example in EP3390601B1 in the context of fabric conditioning compositions. Surfactant

The liquid laundry detergent composition of the invention comprises preferably from 5 to 60 wt. % of a surfactant and more preferably from 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 or monounsatu rated.

Suitable nonionic surfactants may include, in particular, 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. Specific nonionic surfactants are the condensation products of aliphatic Cs to Cie primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 20 EO, preferably C12 to C15 alcohols with 7EO to 9EO or C16 to C18 alcohols with 6 to 10 EO. C12 to C18 Methyl ester ethoxylate are preferred with 6 to 12 EO groups. 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 Cie alcohols and alcohol ethoxylates, produced for example from tallow or palm oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C13 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 C10 to C13 alkyl benzene sulphonates and sodium C12 to Cis alcohol ether sulfates with 2 to 6EO groups. 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-328177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.

Numerical values give for the number of EO groups are mole averages unless otherwise stated. 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-346995 (Unilever). Especially preferred is surfactant system that is a mixture of anionic and non-ionic surfactants. Zwitterionic surfactants may be present at levels of 0.1 to 4wt% to build viscosity.

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 anionic surfactants selected from linear alkyl benzene sulfonates and alcohol ether sulfate, based on the total weight of surfactants. Beneficially, the weight ratio of anionic:nonionic surfactant is greater than 2 (i.e. more than twice the weight amount of anionic compared to the amount of nonionic). Qb

Preferably the liquid laundry detergent has a pH from 5 to 10, preferably from 6 to 9 and more preferably from 7-8, as measured at 293K and otherwise standard conditions. Shading dyes

Preferably the liquid laundry detergent according to the invention further comprises shading dye. 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 DE value, such that DE = (DI_²+ Aa²+ Ab²)⁰⁵ where DI_ = L(control)-L(dye); a = a(control)-a(dye); Ab = b(control)-b(dye)

The actual color of the cloth was calculated as the hue angle, which for the current range of colors is given by: Hue angle = 270+180/p x atan(-Aa/Ab)

A hue angle of 360/0 is red, 270 is blue and 180 is green.

A shading dye according to the invention is a shading dye which means it 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 DE value.

The shading dye preferably contains a chromophore selected from the following chromophore classes: anthraquinone, azo, oxazine, azine, triphenodioxazine, triphenyl methane, xanthene and phthalocyanin, more preferably azo and anthraquinone most preferably mono-azo or bis-azo. Preferably the shading dye chromophore is a mono- azo or bis-azo dye, ethoxylated mono azo thiophene dye, solvent violet 13, disperse violet 28, direct violet 9, direct violet 99, direct violet 35, acid violet 50 or combinations thereof.

Bluish violet and Violet shading dyes are preferred as in combination with the Cu Chlorophyllins in order to provide attractive blue shades. Fluorescent Agent

The liquid laundry detergent 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 liquid laundry detergent of the invention comprises a fluorescer. When the liquid laundry detergent 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 liquid laundry detergent 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 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 liquid laundry detergent of the invention does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid. Polymers

The liquid laundry detergent of the invention may comprise one or more further polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. Polymers present to prevent dye deposition, for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from the formulation.

Detergency Builder

One or more detergency builders are preferably present in the liquid detergent of the invention. The term ‘builder’ as used herein includes sequestrants. Examples of suitable organic detergency builders include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates, citrate, carboxymethyloxysuccinates, carboxymethyloxymalonates, ethylene diamine-N,N-disuccinic acid salts, polyepoxysuccinates, oxydiacetates, triethylene tetramine hexa-acetic acid salts, N-alkyl imino diacetates or dipropionates, alpha sulpho-fatty acid salts, dipicolinic acid salts, oxidised polysaccharides, polyhydroxysulphonates and mixtures thereof. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamino- tetraacetic acid, nitrilo-triacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid, tartrate mono succinate and tartrate di succinate.

Preferred builders comprise one or more of catechols, hydroxymates, aminocarboxylates, 4-Pyridinones, aminopolycarboxylates and alkyl- or alkenylsuccinic acid. 4-Pyridinone based builder’ are discussed in W02007042140 and W015028395. 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 following builders are especially preferred as may reduce colour fading of the Cu- chlorophyllin of the invention overtime, especially upon (prolonged) exposure to sunlight: 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), iminodisuccinic acid (IDA), 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 (TUDA) and N'-(2-hydroxyethyl)ethylenediamine-N,N,N'-triacetic acid (HEDTA), diethanolglycine (DEG). Although these builder’ 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 builder’ are preferred. These builders are preferably present in an amount of from 0.01 to 4wt. %, more preferably from 0.2 to 1 wt. %, %. These amounts are considered to strike an optimal balance between stability of the copper-complex of chlorophyllin in the liquid laundry detergent according to the invention and minimizing staining.

Enzymes

Preferably one or more enzymes may be present in the liquid laundry detergent 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 proteases, amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof. Any enzyme present in the detergent may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.

Form of the liquid laundry detergent

The liquid laundry detergent may be contained in any suitable form. Examples are in the form of a liquid laundry bottle containing multiple doses and water-soluble film- wrapped unit-doses, having at least one compartment with the laundry liquid of the invention.

The liquid laundry detergent is advantageously contained in a form where the aqueous detergent is visible from the outside. For example, when contained in a multiple-dose container, such as a bottle, the container should beneficially be at least in part transparent. For example, when contained as a film-wrapped unit-dose, the film is at least in part transparent. The preferred form of a multi-dose container is that of a plastic bottle having a preferred internal volume of from 0.2 to 5 L, more preferably of from 0.5 to 2 L. Highly advantageous are transparent plastic containers, wherein at least 10 %, more preferably 20%, 30%, 40%, 50%, 60% and even more preferably at least 70 % of the outer surface area is transparent.

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, of 4 cm, more preferably 8 cm. The width is measured parallel to the flat surface on which the container stands in an upright position. This width reduces the light fading of the copper-complex of chlorophyllin. The plastic of the container should as indicated beneficially remain 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 and has no perceivable colouring to the untrained human eye. The container-plastic preferably comprises polyethylene terephthalate (PET), high density polyethylene (HDPE) or a combination thereof and more preferably PET. It is advantageous that the plastic of the container comprises at least 80 wt. %, more preferably at least 95 wt. % of PET and/or HDPE, preferably PET.

Preferably the transparent plastic of the container comprises from 50 to 100 wt. %, preferably from 80 to 100 wt. % and more preferably from 90 to 100 wt. % of recycled plastic, based on the total weight of the plastic of the 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 container-plastic. The UV absorber 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.

The liquid laundry detergent according to the invention can be made by using conventional techniques known in the art of liquid detergent manufacture. Preferably, before addition to the remainder of the ingredients, a concentrated liquid pre-mix is made of the copper-complex of chlorophyllin of the invention to ease dosing.

In a preferred embodiment the liquid composition is isotropic. Preferably the liquid laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e. , contains less than 1 wt.% of phosphate. Further ingredients

It is preferred that the liquid laundry detergent of the invention comprises no dye mordant. Example 1

Product manufacture

A liquid laundry detergent was created of the following composition 9 wt.% linear alkyl benzene sulfonate and 9 wt.% C14-15 alkyl 7-ethoxylate non-ionic surfactant in water. The final pH of the composition was pH 7. Natural colorants were added to give a clear visible color by eye at 2cm and the color observed. The Carotenoid (b-carotene) and Chlorophyl were initial included in the study but excluded as too insoluble (provides no color to the liquid). Anthocyanidin (from Blackberries) was also investigated, when added to formulation the pH of the liquid dropped due to the acidic components present in the extract. When the pH was maintained in the neutral/alkaline region the color changed to a dirty brown/black.

The results are given in the Table below for the 2 successful natural based colors.

When cotton fabrics were washed in 2g/l of the surfactant solution at 30:1 Liquor to

Cloth ratio with the detergents, the curcumin containing detergent gave a visible yellow hue to the fabric. No hueing was observed when using the copper chlorophyllin. The copper chlorophyllin provides a stable color to the detergent that does not stain garments during the wash. In comparison, other natural colorants tested did not dissolve appreciably, showed a color change in the laundry detergent environment or did provide staining problems when applied neat to textile.

Claims

1. A liquid laundry detergent comprising:

• from 5 to 70 wt. % of surfactant; and

• from 0.0001 to 0.1 wt. % of a copper-complex of chlorophyllin.

2. A liquid laundry detergent according to claim 1 , wherein the liquid laundry detergent is an aqueous liquid laundry detergent, preferably comprising from 20 to 90 wt. % water, more preferably comprising from 35 to 80 wt. % water and even more preferably comprising from 50 to 70 wt. % water.

3. A liquid laundry detergent according to claim 1 or claim 2, wherein the chlorophyllin with a central copper anion is obtained from Alfalfa ( Medicago sativa) or pasture grasses.

4. A liquid laundry detergent according to any preceding claim, wherein the amount of the chlorophyllin with a central copper anion is from 0.0005 to 0.05 wt. %, preferably from 0.001 to 0.02 wt. % and more preferably from 0.005 to 0.01 wt. %.

5. A liquid laundry detergent according to any preceding claim, wherein the surfactant comprises a mixture of non-ionic and anionic surfactant.

6. A liquid laundry detergent according to any preceding claim, wherein the amount of surfactant is from 5 to 60 wt. % and preferably 10 to 30 wt. %.

7. A liquid laundry detergent according to any preceding claim, wherein the liquid laundry detergent has a pH from 5 to 9, preferably from 6 to 8 as measured at 293K.

8. A liquid laundry detergent according to any preceding claim, wherein the liquid detergent further comprises a fluorescent agent, preferably in an amount of from 0.005 to 2 wt. %, more preferably from 0.01 to 0.1 wt. %.

9. A liquid laundry detergent according to any preceding claim, wherein the liquid detergent further comprises one or more of the following builders: 2, 2', 2"- nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), iminodisuccinic acid (IDS), ethylenediamine-N,N'-disuccinic acid (EDDS), methylglycine-N,N- diaceticacid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), N-(2-hydroxyethyl)i inodiacetic acid (EDG), aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDA), 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 (TUDA) and N'-(2-hydroxyethyl)ethylenediamine-N,N,N'-triacetic acid (HEDTA), diethanolglycine (DEG).

10. A liquid laundry detergent according to claim 10, wherein the amount of builder is from 0.001 to 0.1 wt. %, preferably 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. %.

11. A plastic bottle which is at least in part transparent and having an internal volume of from 0.2 to 5 L comprising the liquid detergent according to any preceding claim, preferably wherein the plastic bottle is filled to greater than 95 wt. % of the maximum container capacity by weight as based on pure water.

12. A plastic bottle according to claim 12, wherein the plastic of the container comprises from 50 to 100 wt. %, preferably from 80 to 100 wt. % and more preferably from 90 to 100 wt. % of recycled plastic, as based on the total weight of the plastic of the container.

13. A plastic bottle according to any one of claim 12 or claim 13, wherein the plastic contains from 0.01 to 6 wt. %, preferably from 0.1 to 5 wt. % and more preferably from 1 to 4.5 wt. % of a UV absorber, based on the total weight of the plastic.

14. Use of a copper-complex of chlorophyllin to provide a green liquid laundry detergent, preferably wherein the liquid laundry detergent is aqueous, and more preferably to provide a liquid laundry detergent with reduced environmental impact, wherein the copper-complex of chlorophyllin is used in an amount of from 0.0001 to 0.1 wt.%, based on the total weight of the liquid laundry detergent.