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Title:
WATER-SOLUBLE UNIT DOSE ARTICLE COMPRISING AN AMPHIPHILIC GRAFT POLYMER AND A POLYESTER TEREPHTHALATE
Document Type and Number:
WIPO Patent Application WO/2019/032257
Kind Code:
A1
Abstract:
A water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition, said composition comprising; a. between 0.1% and 10% by weight of the liquid laundry detergent composition of a first polymer, wherein the first polymer is an amphiphilic graft polymer; and b. between 0.1% and 10% by weight of the liquid laundry detergent composition of a second polymer, wherein the second polymer is a polyester terephthalate. c. up to 50% by weight of the liquid laundry detergent composition of a non-soap anionic surfactant. Use of a combination of an an amphiphilic graft polymer and a polyester terephthalate to reduce residual surfactant remaining on fabrics following a wash operation..

Inventors:
VAN ELSEN, Katrien, Andrea Lieven (Procter & Gamble, Temselaan 100, 1853 Strombeek-Bever, Strombeek-Bever, BE)
DEPOOT, Karel, Jozef Maria (Procter & Gamble, Temselaan 100, 1853 Strombeek-Bever, Strombeek-Bever, BE)
KEULEERS, Robby, Renilde Francois (Procter & Gamble, Temselaan 100, 1853 Strombeek-Bever, Strombeek-Bever, BE)
Application Number:
US2018/042784
Publication Date:
February 14, 2019
Filing Date:
July 19, 2018
Export Citation:
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Assignee:
THE PROCTER & GAMBLE COMPANY (One Procter & Gamble Plaza, Cincinnati, Ohio, 45202, US)
International Classes:
C08G63/183; C08G81/02; C08L1/28; C08L51/00; C08L51/08; C11D1/02; C11D3/37; C11D11/00; C11D17/04
Domestic Patent References:
WO2016048969A12016-03-31
Foreign References:
EP3101106A12016-12-07
US20140296124A12014-10-02
US20160340611A12016-11-24
EP3312266A12018-04-25
Other References:
None
Attorney, Agent or Firm:
KREBS, Jay A. (Global IP ServicesOne Procter & Gamble Plaza, C, Cincinnati Ohio, 45202, US)
Download PDF:
Claims:
CLAIMS

What is claimed is:

1. A water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition, wherein the liquid laundry detergent composition comprises; a. between 0.1% and 10%, preferably between 0.5% and 5% even more preferably between 0.75% and 4%, most preferably between 1 % and 3% by weight of the liquid laundry detergent composition of a first polymer, wherein the first polymer is an amphiphilic graft polymer; and

b. between 0.1% and 10%, preferably between 0.15% and 5% even more preferably between 0.2% and 4%, most preferably between 0.25 % and 3% by weight of the liquid laundry detergent composition of a second polymer, wherein the second polymer is a polyester terephthalate.

c. up to 50%, preferably between 5% and 50%, more preferably between 7.5% and 45%, even more preferably between 10% and 40%, or even more preferably between 12% and 37%, most preferably between 15% and 30% by weight of the liquid laundry detergent composition of a non-soap anionic surfactant.

2. The water-soluble unit dose article according to claim 1, wherein the liquid laundry detergent composition comprises between 0.1% and 10%, preferably between 0.2% and 7%, more preferably between 0.3% and 5% by weight of the liquid laundry detergent composition of a combination of the first polymer and the second polymer.

3. The water-soluble unit dose article according to any preceding claims, wherein the first polymer is based on polyalkylene oxides and vinyl esters, preferably based on water- soluble polyalkylene oxides (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), said polymer having an average of < 1 graft site per 50 alkylene oxide units, more preferably wherein the molar ratio of grafted to ungrafted alkylene oxide units is from 0.002 to 0.05, preferably from 0.002 to 0.035, more preferably from 0.003 to 0.025, most preferably from 0.004 to 0.02, and preferably wherein the polyalkylene oxide graft base (A) is a polyethylene glycol.

4. The water-soluble unit dose article according to any preceding claims, wherein the first polymer has a mean molecular mass Mw of from 3000 to 100 000, or a polydispersity Mw Mn of less than 3, or a mixture thereof and wherein Mn is the mean molar mass.

5. The water-soluble unit dose article according to any preceding claims wherein the first polymer has from 20% to 70%, preferably from 25% to 60% by weight of the first polymer of the polyalkylene oxide (A), preferably the water-soluble polyalkylene oxide (A) as a graft base and preferably, wherein the first polymer comprises from 30% to 80% by weight of the vinyl ester component (B), preferably wherein the vinyl ester component (B) comprises a vinyl acetate, vinyl propionate or a mixture thereof (Bl) , and optionally an Cl-CS-alkyl acrylate (B2) more preferably from 70%; to 100% by weight of vinyl acetate (Bl) and from 0% to 30% by weight of a Cl -C8-alkyl acrylate (B2),

6. The water-soluble unit dose article according to any preceding claims wherein the first polymer comprises less than 10% by weight of the amphiphilic graft polymer of polyvinyl ester (B) in ungrafted form.

7. The water-soluble unit dose article according to any of the preceding claims wherein the second polymer is a polyester terephthalate backbone grafted with one or more anionic groups.

8. The water-soluble unit dose article according to any preceding claims wherein the second polymer is a polyester terephthalate comprising the structural units (I) to (III):

(II) -[(OCHR3-CHR4)b-0-OC-sAr-CO-]e

(III) -[(OCHR5-CHR6)c-OR7]f wherein:

a, b and c are from 1 to 200;

d, e and f are from 1 to 50;

Ar is a 1,4-substituted phenylene;

sAr is 1,3-substituted phenylene substituted in position 5 with SCbMe; Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are (C1-C22) alkyl or (C2-C10) hydroxyalkyl, or mixtures thereof;

R1, R2, R3, R4, R5 and R6 are independently selected from H or (Ci-Cis) n- or iso- alkyl preferably methyl; and R7 is a linear or branched (Ci-Cis) alkyl, or a linear or branched (C2-C30) alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, a (C6- C30) aryl group or a (C6-C50) arylalkyl group preferably phenyl or benzyl.

9. The water-soluble unit dose article according to claim 11 wherein the anionic polyester comprises the structural units (I) to (III), wherein :

R1 to R6 independently are H or methyl,

R7 is methyl,

a, b and c are a number from 1 to 20, preferably a and b are 1 and c is a number from 2 to 10,

d is a number between 1 and 25, preferably between 1 and 10, more preferably between 1 and 5,

e is a number between 1 and 30, preferably between 2 and 15, more preferably between 3 and 10, and

f is a number between 0.05 and 15, preferably between 0.1 and 10, more preferably between 0.25 and 3.

10. The water-soluble unit dose article according to any preceding claims wherein the second polymer is an anionic polyester of propylene terephtalate. 11. The water-soluble unit dose article according to any preceding claims wherein the non-soap anionic surfactant comprises linear alkylbenzene sulphonate, alkoxylated alkyl sulphate or a mixture thereof, more preferably a mixture thereof wherein the ratio of linear alkylbenzene sulphonate to alkoxylated alkyl sulphate preferably the ratio of linear alkylbenzene sulphonate to ethoxylated alkyl sulphate is from 1:2 to 20: 1, preferably from 1.1: 1 to 15: 1, more preferably from 1.2: 1 to 10: 1, even more preferably from 1.3: 1 to 5: 1, most preferably from 1.4: 1 to 3: 1.

12. The water-soluble unit dose article according to any preceding claims wherein the liquid laundry detergent composition comprises between 0% and 10%, preferably between 0.01% and 8%, more preferably between 0.1% and 6%, most preferably between 0.15% and 4% by weight of the liquid laundry detergent composition of the non-ionic surfactant, preferably wherein the non-ionic surfactant is selected from alcohol alkoxylate, an oxo- synthesised alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates or a mixture thereof.

13. The water-soluble unit dose article according to any preceding claims wherein the liquid laundry detergent composition comprises between 1.5% and 20%, more preferably between 2% and 15%, even more preferably between 3% and 10%, most preferably between 4% and 8% by weight of the liquid detergent composition of soap, preferably a fatty acid salt, more preferably an amine neutralized fatty acid salt, wherein preferably the amine is an alkanolamine more preferably selected from monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, more preferably monoethanolamine.

14. The water-soluble unit dose article according to any preceding claims wherein the liquid laundry detergent composition comprises; a. a cationic polysaccharide, preferably selected from cationically modified hydroxyethyl cellulose, cationically modified hydroxypropyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxypropyl cellulose, or a mixture thereof, more preferably cationically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, or a mixture thereof; b. an alkoxylated polyethyleneimine, preferably an ethoxylated polyethyleneimine; c. carboxymethylcellulose or a derivative thereof, preferably selected from carboxymethyl cellulose, a hydrophobically modified carboxymethyl cellulose or a mixture thereof, more preferably a hydrophobically modified carboxymethylcellulose ;

d. a mixture thereof.

15. Use of a combination of a first polymer and a second polymer to reduce residual surfactant remaining on fabrics following a wash operation, wherein the first and second polymers are formulated into a water-soluble unit dose article and wherein the first polymer is an amphiphilic graft polymer and the second polymer is a polyester terephthalate.

Description:
WATER-SOLUBLE UNIT DOSE ARTICLE COMPRISING AN AMPHIPHILIC GRAFT POLYMER AND A POLYESTER TEREPHTHALATE

FIELD OF THE INVENTION

The present invention relates to water-soluble unit dose articles containing amphiphilic graft polymer and polyester terephthalate and processes of washing fabrics using said water- soluble unit dose articles.

BACKGROUND OF THE INVENTION

Water-soluble unit dose articles are liked by consumers as they are convenient and efficient to use. Such water-soluble unit dose articles often comprise laundry detergent compositions.

During the laundry operation, various detergent actives are deposited on fabrics. The rinse step of the wash operation is designed to remove any residual material before the end of the of the wash. However, occasionally some residual material may remain. In fact, residual material, especially surfactant material can remain on fabrics from previous wash operations as well as from the wash operation currently being performed.

Consumers do not like the residual material remaining on fabrics following the wash and so there is a desire to further reduce instances of material remaining on fabrics following the wash.

Due to the compact nature of unit dose articles, there is finite space available for formulating actives into the composition. Therefore, there is a desire to reduce instances of material remaining on fabrics without further addition of chemistry actives specific to achieve this benefit.

It was surprisingly found that when formulating a mixture of two polymers (amphiphilic graft polymer and polyester terephthalate), improved removal of residual surfactant from the fabrics was achieved across both natural and synthetic fibers. Furthermore, both polymers provide cleaning benefits as soil release polymers, meaning there is no need for addition of single purpose chemistries for removal of the residual surfactant.

SUMMARY OF THE INVENTION A first aspect of the present invention is a water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition, wherein the liquid laundry detergent composition comprises;

a. between 0.1% and 10%, preferably between 0.5% and 5% even more preferably between 0.75% and 4%, most preferably between 1 % and 3% by weight of the liquid laundry detergent composition of a first polymer, wherein the first polymer is an amphiphilic graft polymer; and

b. between 0.1% and 10%, preferably between 0.15% and 5% even more preferably between 0.2% and 4%, most preferably between 0.25 % and 3% by weight of the liquid laundry detergent composition of a second polymer, wherein the second polymer is a polyester terephthalate.

c. up to 50%, preferably between 5% and 50%, more preferably between 7.5% and 45%, even more preferably between 10% and 40%, or even more preferably between 12% and 37%, most preferably between 15% and 30% by weight of the liquid laundry detergent composition of a non-soap anionic surfactant.

A second aspect of the present invention is a process for washing fabrics comprising the steps of;

a. Combining a water-soluble unit dose article according to the present invention with sufficient water to dissolve the water-soluble film and dilute the laundry detergent composition by a factor of between 300 and 3000 fold to form a wash liquor; b. Combining the wash liquor with at least one fabric to be washed,

optionally wherein the at least one fabric comprises residual surfactant, preferably non- soap anionic surfactant deposited thereon.

A third aspect of the present invention is the use of a combination of a first polymer and a second polymer to reduce residual surfactant remaining on fabrics following a wash operation, wherein the first and second polymers are formulated into a water-soluble unit dose article and wherein the first polymer is an amphiphilic graft polymer and the second polymer is a polyester terephthalate.

BRIEF DESCRIPTION OF THE DRAWINGS FIG.1 is a water-soluble unit dose article according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION Water-soluble unit dose article

The present invention discloses a water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition. The water-soluble film and the liquid detergent composition are described in more detail below.

The water-soluble unit dose article comprises the water-soluble film shaped such that the unit-dose article comprises at least one internal compartment surrounded by the water-soluble film.

The unit dose article may comprise a first water-soluble film and a second water-soluble film sealed to one another such to define the internal compartment. The water-soluble unit dose article is constructed such that the detergent composition does not leak out of the compartment during storage. However, upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.

The compartment should be understood as meaning a closed internal space within the unit dose article, which holds the detergent composition. During manufacture, a first water-soluble film may be shaped to comprise an open compartment into which the detergent composition is added. A second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment. The first and second films are then sealed together along a seal region.

The unit dose article may comprise more than one compartment, even at least two compartments, or even at least three compartments. The compartments may be arranged in superposed orientation, i.e. one positioned on top of the other. In such an orientation the unit dose article will comprise three films, top, middle and bottom. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e. one orientated next to the other. The compartments may even be orientated in a 'tyre and rim' arrangement, i.e. a first compartment is positioned next to a second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment. Alternatively one compartment may be completely enclosed within another compartment.

Wherein the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment. Wherein the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are superposed on the larger compartment. The superposed compartments preferably are orientated side-by-side.

In a multi-compartment orientation, the detergent composition according to the present invention may be comprised in at least one of the compartments. It may for example be comprised in just one compartment, or may be comprised in two compartments, or even in three compartments.

Each compartment may comprise the same or different compositions. The different compositions could all be in the same form, or they may be in different forms.

The water-soluble unit dose article may comprise at least two internal compartments, wherein the liquid laundry detergent composition is comprised in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments, wherein the detergent composition is comprised in at least one of the compartments.

FIG.l discloses a water-soluble unit dose article (1) according to the present invention. The water-soluble unit dose article (1) comprises a first water-soluble film (2) and a second water- soluble film (3) which are sealed together at a seal region (4). The liquid laundry detergent composition (5) is comprised within the water-soluble soluble unit dose article (1).

Water-soluble film

The film of the present invention is soluble or dispersible in water. The water-soluble film preferably has a thickness of from 20 to 150 micron, preferably 35 to 125 micron, even more preferably 50 to 110 micron, most preferably about 76 micron.

Preferably, the film has a water- solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:

5 grams ± 0.1 gram of film material is added in a pre-weighed 3L beaker and 2L ± 5ml of distilled water is added. This is stirred vigorously on a magnetic stirrer, Labline model No. 1250 or equivalent and 5 cm magnetic stirrer, set at 600 rpm, for 30 minutes at 30°C. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max. 20 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). Then, the percentage solubility or dispersability can be calculated.

Preferred film materials are preferably polymeric materials. The film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.

Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, poly acrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof. Preferably, the level of polymer in the pouch material, for example a PVA polymer, is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to

1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.

Preferably, the water-soluble film comprises polyvinyl alcohol polymer or copolymer, preferably a blend of polyvinylalcohol polymers and/or polyvinylalcohol copolymers, preferably selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers, most preferably a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer.

Preferred films exhibit good dissolution in cold water, meaning unheated distilled water. Preferably such films exhibit good dissolution at temperatures of 24°C, even more preferably at 10°C. By good dissolution it is meant that the film exhibits water- solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above.

Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310.

The film may be opaque, transparent or translucent. The film may comprise a printed area.

The area of print may be achieved using standard techniques, such as flexographic printing or inkjet printing.

The film may comprise an aversive agent, for example a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine

hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable level of aversive agent may be used in the film. Suitable levels include, but are not limited to, 1 to 5000ppm, or even

100 to 2500ppm, or even 250 to 2000rpm.

Liquid laundry detergent composition The water-soluble unit dose article comprises a liquid laundry detergent composition. The term 'liquid laundry detergent composition' refers to any laundry detergent composition comprising a liquid capable of wetting and treating a fabric, and includes, but is not limited to, liquids, gels, pastes, dispersions and the like. The liquid composition can include solids or gases in suitably subdivided form, but the liquid composition excludes forms which are non-fluid overall, such as tablets or granules.

Without wishing to be bound by theory, preferably the polymers are formulated into a liquid laundry detergent as this enables faster release into the wash liquor. This is especially beneficially in quick and cold wash cycles in which the risk of the being stuck in undissolved powder pasty phase is minimised.

The liquid detergent composition can be used in a fabric hand wash operation or may be used in an automatic machine fabric wash operation.

The liquid laundry detergent composition comprises between 0.1% and 10%, preferably between 0.25% and 5% even more preferably between 0.5% and 4%, most preferably between 0.75 % and 3% by weight of the liquid laundry detergent composition of a first polymer, wherein the first polymer is an amphiphilic graft polymer. The first polymer may be fully dissolved in the liquid laundry detergent composition, may be partially dissolved or maybe a dispersed particulate, or a mixture thereof. The first polymer is described in more detail below.

The liquid laundry detergent composition comprises between 0.1% and 10%, preferably between 0.15% and 5% even more preferably between 0.2% and 4%, most preferably between 0.25% and 3% by weight of the liquid laundry detergent composition of a second polymer, wherein the second polymer is a polyester terephthalate. The second polymer may be fully dissolved in the liquid laundry detergent composition, may be partially dissolved or maybe a dispersed particulate, or a mixture thereof. The second polymer is described in more detail below.

The liquid laundry detergent composition comprises up to 50%, preferably between 5% and 50%, more preferably between 7.5% and 45%, even more preferably between 10% and 40%, or even more preferably between 12% and 37%, most preferably between 15% and 30% by weight of the liquid laundry detergent composition of a non-soap anionic surfactant. The non-soap anionic surfactant is described in more detail below.

Preferably, the liquid laundry detergent composition comprises between 0.1% and 10%, preferably between 0.2% and 7%, more preferably between 0.3% and 5% by weight of the liquid laundry detergent composition of a combination of the first polymer and the second polymer. In other words, the total concentration of the two polymers may be between 0.1% and 10%, preferably between 0.2% and 7%, more preferably between 0.3% and 5% by weight of the liquid laundry detergent composition.

The liquid laundry detergent composition preferably comprises between 0% and 10%, preferably between 0.01% and 8%, more preferably between 0.1% and 6%, most preferably between 0.15% and 4% by weight of the liquid laundry detergent composition of a non-ionic surfactant. Preferably, the non-ionic surfactant is selected from alcohol alkoxylate, an oxo- synthesised alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl phenol alcohol alkoxylates or a mixture thereof.

Preferably, the liquid laundry detergent composition comprises between 1.5% and 20%, more preferably between 2% and 15%, even more preferably between 3% and 10%, most preferably between 4% and 8% by weight of the liquid detergent composition of soap, preferably a fatty acid salt, more preferably an amine neutralized fatty acid salt, wherein preferably the amine is an alkanolamine more preferably selected from monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, more preferably monoethanolamine.

The liquid laundry detergent composition preferably comprises a cationic polysaccharide, preferably selected from cationically modified hydroxyethyl cellulose, cationically modified hydroxypropyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxypropyl cellulose, or a mixture thereof, more preferably cationically modified hydroxyethyl cellulose, cationically and hydrophobically modified hydroxyethyl cellulose, or a mixture thereof. The cationic polysaccharide preferably is present between 0.05% and 3%, preferably between 0.1% and 2%, more preferably between 0.2% and 1%, most preferably between 0.25% and 0.75% by weight of the liquid laundry detergent composition.

Preferably, the liquid laundry detergent composition comprises an alkoxylated polyethyleneimine, preferably an ethoxylated polyethyleneimine. Preferably, the liquid laundry detergent composition comprises between 0.1% and 10%, preferably between 0.5% and 7%, more preferably between 1% and 5% by weight of the liquid laundry detergent composition of the ethoxylated polyethyleneimine.

Preferably, the liquid detergent composition further comprises a carboxymethylcellulose or a derivative thereof, preferably selected from carboxymethyl cellulose, a hydrophobically modified carboxymethyl cellulose or a mixture thereof, more preferably a hydrophobically modified carboxymethylcellulose. The carboxymethylcellulose preferably is present between 0.1% and 10%, preferably between 0.25% and 5% even more preferably between 0.5% and 4%, most preferably between 0.75 % and 3% by weight of the liquid laundry detergent composition. As used herein, the term "celluloses" includes natural celluloses and synthetic celluloses. Celluloses can be extracted from plants or produced by microorganisms.

Methods of producing carboxymethyl cellulose are well described in the art.

Various methods of producing hydrophobically modified carboxymethyl cellulose are disclosed in the art.

Carboxymethylcellulose polymers include Finnfix GDA (sold by CP Kelco), a hydrophobically modified carboxymethylcellulose, e.g. the alkyl ketene dimer derivative of carboxymethylcellulose sold under the tradename Finnfix SHI (CP Kelco), or the blocky carboxymethylcellulose sold under the tradename Finnfix V (sold by CP Kelco).

The water-soluble unit dose article preferably comprises 15% or less by weight of the unit dose article of water, preferably comprising between 0.1% and 15%, more preferably between 1% and 12.5% by weight of the unit dose article of water.

Preferably, the water-soluble unit dose article comprises between 10% and 60%, preferably between 12% and 50%, most preferably between 15% and 40% by weight of the liquid laundry detergent composition of a non-aqueous solvent, preferably wherein the non-aqueous solvent is selected from 1,2-Propanediol, glycerol, sorbitol, dipropylene glycol, tripropyleneglycol, or a mixture thereof.

The liquid laundry detergent composition may further comprise an adjunct ingredient selected from further polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti- redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments and mixtures thereof.

Preferably, the liquid laundry detergent composition has a pH between 6 and 10, more preferably between 6.5 and 8.9, most preferably between 7 and 8. The pH of the liquid laundry detergent composition may be measured as a 10% dilution in demineralized water at 20°C.

First polymer

The first polymer is an amphiphilic graft polymer. Preferably, the first polymer is based on polyalkylene oxides and vinyl esters, preferably based on water-soluble polyalkylene oxides (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), said polymer having an average of < 1 graft site per 50 alkylene oxide units, more preferably wherein the molar ratio of grafted to ungrafted alkylene oxide units is from 0.002 to 0.05, preferably from 0.002 to 0.035, more preferably from 0.003 to 0.025, most prefereably from 0.004 to 0.02. The first polymer preferably has a mean molecular mass Mw of from 3000 to 100 000. Preferably, the first polymer has a polydispersity Mw/Mii of less than 3, wherein Mn is the mean molar mass.

The first polymer may have from 20% to 70%, preferably from 25% to 60% by weight of the first polymer of the polyalkylene oxide (A), preferably the water-soluble polyalkylene oxide (A) as a graft base. Preferably, the polyalkylene oxide graft base (A) is a polyethylene glycol.

Preferably, the first polymer comprises from 30% to 80% by weight of the vinyl ester component (B), preferably wherein the vinyl ester component (B) comprises a vinyl acetate, vinyl propionate or a mixture thereof (B l), and optionally an Cl-C8-alkyl acrylate (B2) more preferably from 70% to 100% by weight of vinyl acetate (Bl ) and from 0% to 30% by weight of a CI -C8- alkyl acrylate (B2).

Preferably, the first polymer comprises less than 10% by weight of the amphiphilic graft polymer of poly inyl ester (B) in ungrafted form.

Preferably, the first polymer is a polyethylene glycol graft base and vinyl acetate side chains, as accordin to the following structure; wherein, preferably the ethylene oxide / vinyl acetate content is from 30%/70% to 50%/50%, and wherein preferably the amphiphilic graft polymer has a mean molar mass (Mn) value of from lOOOOg/mol to 20000g/mol, more preferably from lOOOOg/mol to 15000g/mol, and wherein preferably the amphiphilic graft polymer has a mean molecular mass (Mw ) value of from

20000g/mo1 to 30000g/mo1, preferably from 25000g/mo1 to 30000g/mol, more preferably, yielding a polydispersity Mw/Mn of from 1 to 3, preferably 1.5 to 2.5, wherein preferably the amphiphilic graft polymer has an average degree of grafted units per polyethyleneglycol polymer graft base preferably is less than 2.7, preferably between 0.5 and 2.5, more preferably between 1 and 2, wherein preferably the amphiphilic graft polymer has an average n value of between 30 and 70, more preferably between 40 and 60, most preferably between 50 and 55.

Second polymer

The second polymer is a polyester terephthalate. Preferably, the second polymer is a polyester terephthalate backbone grafted with one or more anionic groups, more preferably, the second polymer is an anionic polyester of propylene terephtalate. Suitable anionic polyesters are those that are derived from terephtalic acid, 5- sulfoisophtalic acid or the salt of 5-sulfoisophtalic acid, from ethylene glycol or polyethylene glycol, propylene glycol or polypropylene glycol and polyalkyleneglycol monoalkyl ether, and optionally from further monomers having 3 to 6 functions capable of polycondensation, in particular acid, alcohol or ester functions. In particular, suitable polyesters comprise structural units (I) to (III) : (II) -[(OCHR 3 -CHR 4 ) b -0-OC-sAr-CO-]e

(III) -[(OCHR 5 -CHR 6 ) c -OR 7 ] f wherein:

a, b and c are from 1 to 200;

d, e and f are from 1 to 50;

Ar is a 1,4-substituted phenylene;

sAr is 1,3-substituted phenylene substituted in position 5 with SCbMe;

Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are (C1-C22) alkyl or (C2-C10) hydroxyalkyl, or mixtures thereof;

R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H or (Ci-Cis) n- or iso-alkyl preferably methyl; and

R 7 is a linear or branched (Ci-Cis) alkyl, or a linear or branched (C2-C30) alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, a (C6-C30) aryl group or a (C6-C50) arylalkyl group preferably phenyl or benzyl.

Preferred are anionic polyesters as defined above, where R 1 to R 6 independently are H or methyl, R 7 is methyl, a, b and c are a number from 1 to 200, preferably 1 to 20, more preferably a and b are 1 and c can be a number from 2 to 10. Herein d is a number between 1 and 25, preferably between 1 and 10, more preferably between 1 and 5, e is a number between 1 and 30, preferably between 2 and 15, more preferably between 3 and 10, and f is a number between 0.05 and 15, preferably between 0.1 and 10, more preferably between 0.25 and 3.

It is clear to the expert that these values are always statistical average values with a natural distribution that varies from system to system. Besides linear polyesters which result from the structural units (I) to (III) above, crosslinked or branched polyester structures are also possible for the purpose of the invention, the polymer as such further comprising a cross-linking polyfunctional structural unit with at least 3 to at most 6 functional groups capable of the esterification reaction. Functional groups may be for example acid, alcohol, ester, anhydride or epoxy groups. The weight fraction of the cross-linking monomers, based on total mass of the polyesters, is preferably 0 to 10%, more preferably 0 to 5%, most preferably 0 to 3%. Preferably the anionic polyester is a linear anionic polyester with no cross- linking.

The polyesters according to the invention generally have a number average molecular weight in the range of 700 to 50000 g/mol, preferably 800 to 25000 g/mol, more preferably 1000 to 15000 g/mol, most preferably 1200 to 12000 g/mol.

Suitable soil release polymers are sold by Clariant under the TexCare® series of polymers, e.g. TexCare® SRN240 and especially TexCare® SRA300. Other suitable soil release polymers are sold by Solvay under the Repel-o-Tex® series of polymers, e.g. Repel-o-Tex® SF2 and Repel-o-Tex® Crystal.

Non-soap anionic surfactant

Preferably, the non-soap anionic surfactant comprises linear alkylbenzene sulphonate, alkoxylated alkyl sulphate or a mixture thereof. More preferably, the non-soap anionic surfactant is a mixture of linear alkylbenzene sulphonate and alkoxylated alkyl sulphate, more preferably a mixture of linear alkylbenzene sulphonate and ethoxylated alkyl sulphate.

Preferably, the weight ratio of linear alkylbenzene sulphonate to alkoxylated alkyl sulphate, more preferably linear alkylbenzene sulphonate to ethoxylated alkyl sulphate is from 1:2 to 20:1, preferably from 1.1:1 to 15:1, more preferably from 1.2:1 to 10: 1, even more preferably from 1.3:1 to 5 : 1 , most preferably from 1.4 : 1 to 3 : 1.

The weight ratio of linear alkylbenzene sulphonate to ethoxylated alkyl sulphate may be from 1:10 to 20:1, preferably from 1:7 to 3:1, more preferably from 1:5 to 1.5:1.

Preferably, the weight ratio of total anionic surfactant (i.e. all anionic surfactant present in the liquid composition) : non- ionic surfactant in the liquid composition is between 5:1 and 23:1. Preferably, the non-soap anionic surfactant is neutralised with an amine, preferably selected from monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, more preferably monoethanolamine.

Process of making Those skilled in the art will know how to make the water-soluble unit dose article and liquid laundry detergent composition of the present invention using commonly known manufacturing techniques.

Process for washing

A further aspect of the present invention is a process for washing fabrics comprising the steps of; a. Combining a water-soluble unit dose article according to the present invention with sufficient water to dissolve the water-soluble film and dilute the laundry detergent composition by a factor of between 300 and 3000 fold, preferably from 300 to 800 fold to form a wash liquor;

b. Combining the wash liquor with at least one fabric to be washed,

optionally wherein the at least one fabric comprises residual surfactant, preferably non-soap anionic surfactant deposited thereon. The non-soap anionic surfactant is as described above.

Use

Another aspect of the present invention is the use of a combination of a first polymer and a second polymer to reduce residual surfactant remaining on fabrics following a wash operation, wherein the first and second polymers are formulated into a water-soluble unit dose article and wherein the first polymer is an amphiphilic graft polymer and the second polymer is a polyester terephthalate.

The first polymer and the second polymer are as described above. Preferably the residual surfactant is non-soap anionic surfactant as described above.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

EXAMPLES

The impact of formulating a dual polymer system according to the invention, comprising an amphiphilic graft polymer and a polyester based soil release polymer, in a soluble unit dose laundry composition, on amount of remaining anionic surfactant on fabrics at the end of a wash cycle has been assessed for both cotton and polyester fabrics through running a full scale washing test, extracting the remaining anionic surfactant from said fabrics and quantifying the amount of said anionic surfactant through analytical titration.

Formula compositions :

The following base formula composition was prepared through mixing of the individual components.

*ethoxylated polyethyleneimine having an average degree of ethoxylation of 20 per EO chain and a polyethyleneimine backbone with MW of about 600

Pre-dissolved polymer solutions in demineralized water have been prepared separately by mixing the polymer starting material in demineralized water.

Amphiphilic graft polymer** solution: 7% active in water

Texcare SRA300 solution : 1.5% active in water **poly ethylene glycol graft polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, comprising 40% by weight of the polymer system of a polyethylene glycol backbone polymer and 60% by weight of the polymer system of the grafted vinyl acetate side chains

Test legs :

Pre-dissolved polymer solutions were mixed with 22.7g of base formulation such that below tabulated active polymer levels were obtained. To calculate the active polymer in the respective test legs the add-on water from the pre-dissolved polymer solutions was not considered, e.g. 0.34g of 100% active polymer has been added on top of 22.7g base formulation to obtain a 1.5% active polymer formula composition, such that all base leg active components were kept constant across all test legs. Test leg B describes a formula composition according to the invention, comprising a dual amphiphilic graft polymer polyester based soil release polymer system, contrary to nil polymer test leg A which is a comparative example outside the scope of the invention.

Test method :

Wash cycle :

The nil polymer base and mixed polymer-base compositions were added together with 10 terry cotton fabric tracers (Type : Calderon RN37004-LL-B2 fabrics, 59g per tracer - sourced from Calderon Textiles LLC, Indianapolis) or with 10 100% polyester white fabric tracers (30cm * 30cm - 1 lg per tracer - sourced from Maison Doree, Brussels) in a Miele W1714 automatic washing machine. A 30 minutes express cycle was selected with 15 gpg water at 30°C. This washing step has been repeated 3 more times. After 4 cycles the cotton terry towel and polyester fabric tracers were line dried and submitted for analytical quantification of remaining anionic surfactant content.

Analytical quantification of remaining anionic surfactant content The anionic surfactant (LAS) remaining on the fabric tracers has been extracted from the fabric tracers and analytically quantified following the test methods described herein :

Extraction process :

The anionic surfactant has been extracted from the fabric tracers using an Accelerated

Solvent Extractor (ASE) type Dionex ASEIOO. Herefore 22-25g of fabric sample was put within a 66ml ASE sample holder and extracted using an 800ml chloroform / 200ml acetonitrile / 25ml acetic acid extraction solvent mixture.

Extraction conditions were set as follow :

· Temperature : 80°C

• Static time : 5 minutes

• Flush volume : 70%

• Purge time 120s

• Static cycle : 2 The collected extract was then further diluted to 100ml with chloroform using 100 ml volumetric flasks. After mixing 25 ml of the resulting mixture has been submitted for analytical quantification of the extracted anionic surfactant content.

Anionic surfactant titration process :

The amount of extracted anionic surfactant has been analytically quantified through manual titration. The method is based on the dye-complexing property of anionic surfactants. The extraction sample containing the anionic surfactants dissolved in chloroform (25 mL) is mixed with 20 mL of a mixed indicator solution of cationic and anionic-complexing dyes (dimidium bromide and disulfine blue VN150, both available from Sigma) in water. The anionic surfactant cationic dye complex is soluble in the organic layer and gives it a red-pink color. The surfactant is titrated with a 0.004N solution of Hyamine 1622 (available from Sigma), with the Hyamine 1622 preferentially displacing the dye in the dye-surfactant complex that produces the pink color. As the Hyamine 1622 displaces the dye, the color in the organic layer changes from pink to gray at the endpoint. This is where all the red dye has been replaced with Hyamine 1622. If excess Hyamine 1622 is added, it complexes the anionic dye, giving blue color to the organic layer indicating that the endpoint has been overshot. The amount of anionic surfactant present in the extracted solution can consequently be calculated from the amount of titrant used to reach the end point, and back-calculated towards amount of anionic surfactant present on the original fabric tracers trough considering the starting weight of the fabric in the extraction process. Test results :

Remaining anionic surfactant levels on the fabric have been summarized in tables below. The data clearly show that a soluble unit dose laundry composition comprising a dual polymer system according to the invention, comprising both an amphiphilic graft polymer and a polyester based soil release polymer, shows a statistically superior surfactant rinsing profile across both cotton terry towels and synthetic polyester fabrics compared to composition not comprising these polymers hence outside the scope of the invention.

Cotton terry towel :

Test leg : Remaining anionic surfactant content

(mg LAS /g fabric)

A : nil polymer 0.69

B : dual polymer system (according to the 0.63s

invention)

Polyester fabrics :

Test leg : Remaining anionic surfactant content

(mg LAS /g fabric)

A : nil polymer 0.28

B : dual polymer system (according to the 0.21s

invention)