EP2473590B2

EP2473590B2 - Process for treatment of a fabric

Info

Publication number: EP2473590B2
Application number: EP10742151.3A
Authority: EP
Inventors: Aravindakshan Perincheery; Sameer Keshav Barne; Abhishek Rastogi; Archana Sinha
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2009-09-02
Filing date: 2010-08-12
Publication date: 2018-01-17
Anticipated expiration: 2030-08-12
Also published as: EP2473590A1; CL2012000538A1; EA201200401A1; CA2770869A1; ES2531418T5; CN102575197A; ES2531418T3; AU2010291392B2; EP2473590B1; BR112012003018A2; EA022063B1; AU2010291392A1; MX2012002748A; AR078146A1; ZA201200792B; WO2011026718A1; CN102575197B

Description

Technical Field

The present invention relates to a process for treatment of a fabric. It further relates to a composition and a kit for treatment of a fabric. The invention will be described hereinafter with reference to this application. However, it will be appreciated that the invention is not limited to this particular field of use.

Background and Prior Art

Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.
Better cleaning of fabric articles during washing has been the primary focus of laundry detergent research for decades. However, since the present day consumer has ever higher demands for the effectiveness of washing detergents, substantial improvements remain to be desired.
US2006046950A (Penninger and Bastigkeit, 2006 ) teaches a detergent composition for cleaning textile materials comprising a combination of a soil release-capable alkyl or hydroxyalkyl cellulose derivative and a hygroscopic polymer selected from the class consisting of polypeptides, hydrogels, polyvinyl alcohol, the polyalkylene glycols, the homopolymers of acrylic acid, methacrylic acid, and maleic acid, copolymers of acrylic acid, methacrylic acid, and maleic acid and mixtures of the homo and copolymers. The use of the hygroscopic polymers in combination with the cellulose derivatives is said to result in improved cleaning performance.
EP0256696 (Unilever, 1988 ) teaches that improvement in soil suspension is achieved by adding mixture of vinyl pyrrolidone polymer and a nonionic cellulose ether to a detergent composition. GB994353 (Domestos, 1965 ) teaches that mixtures of certain polymeric materials, when incorporated into unbuilt detergent compositions based on synthetic surface active agents, provide enhanced anti-redeposition as compared to activity of individual polymers alone when added alone to same detergent compositions.
US3771951 (Berni et al, 1973 ) and GB133803 (Gaf Corp, 1973 ) teach that detergent composition comprising a water soluble detergent and a mixture of water soluble polyvinyl alcohol and a water soluble poly vinyl pyrollidone exhibits enhanced degree of soil suspension
The above methods are reported to provide improved antiredeposition of soils and better cleaning of fabrics. However, reduction in subsequent post-wash soiling of fabrics is not reported. Further, the cleaning compositions essentially comprise of a surfactant and the pH of wash liquor is alkaline or neutral.
US4007305 (Kakar et al, 1977 ) addresses the problem of providing satisfactory nondurable finishes to textiles which impart optimum soil release and soil repellent properties. According to D5, the textiles must be treated with an alkaline aqueous medium having pH value of 7.5-11 and containing water soluble hydrophilic soil release polymer having carboxylic acid groups and a dispersed hydrophobic soil repellent fluorochemical.
On the other hand, various industrial treatments for fabric modification are known to render the fabric less prone to soiling. The fabric modification of this type is normally carried out during textile manufacture. The treatments, besides being substrate-specific, are relatively difficult to practice in household.
In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a process for reducing soiling of fabrics that can be easily used in the household.
Another object of the present invention is to provide a process of treatment of a fabric for reducing soiling of fabrics.
Yet another object of the present invention is to provide a process for treatment of a fabric that improves efficacy of subsequent cleaning.
Yet another object of the present invention is to provide a process for reducing soiling of fabrics that allows enhanced deposition of benefit agents, such as perfume and fluorescer.
Yet another object of the present invention is to provide a process for treatment of a fabric which is effective on various types of fabrics such as cotton, polyester and polycotton.
Yet another object of the present invention is to provide a process for treatment of a fabric which is relatively easy to practice in household.
It is yet another object of the present invention to provide such a composition either solid or liquid and process for easier cleaning in the form of a single product having good storage stability.
Surprisingly it is found that a mixture of two or more complex forming polymers, wherein one of the polymers is shielded from the other by using a stabilizer solves the problem of stability due to complex formation during storage, while providing the desired cleaning benefit.
The present inventors have found that a composition comprising a carboxylic acid polymer that has been neutralised at least partially to the salt form and a second polymer, capable of forming hydrogen bonds with the first polymer in the present of an acid, provides both a secondary cleaning benefit and good storage stability, without forming polymer-polymer complex when it is in the solid formulation and give a complex when dispersed in water.
The present inventors also have been found that a liquid composition of two polymers dispersed in a solvent in presence of a stabilizer provides a stable preformed complex at high concentration with very good storage stability and it provides a secondary cleaning benefit.

Summary of the invention

According to a first aspect, the present invention provides a liquid fabric treatment composition comprising base composition comprising a mixture of polymer A and a stabilizer wherein the polymer A is selected from the group of homopolymers and copolymers of carboxylic acid wherein the polymer A is atleast partially neutralised;, a polymer B selected from the group of homopolymers and copolymers of alkylene oxides having a molecular 10 mass greater than 2x104 D, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; and a pH adjustment agent selected from organic acids, selected from citric acid, formic acid, oxalic acid, phtalic acid ascorbic acid, glutamic acid, salicylic acid, tartaric acid, pyroglutamic acid, malic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, propane 1,2,3 tricarboxylic acid, butane 1,2,3,4 tetra arboxylic acid and their anhydides, inorganic acids and/or buffers,
wherein the combination of polymer A and polymer B is selected from one of the following combinations:

polyacrylic acid and poly vinyl pyrrolidone
polyacrylic acid and polyethylene oxide
polyacrylic acid and polyethylene glycol
polyacrylic acid and poly vinyl alcohol
Sodium carboxymethyl cellulose and polyethylene oxide
polyacrylic acid and hydroxyethyl cellulose
starch-graft-polymethacrylic acid and polyethylene oxide
starch-graft-polymethacryrlic acid and polyvinyl pyrrolidone
Pluronic-g-polyacrylic acid and polyethylene oxide
Pluronic-g-polyacrylic acid and polyvinyl pyrrolidone
Sodium carboxymethyl cellulose and hydroxyethyl cellulose
Sodium carboxymethyl cellulose and polyvinyl alcohol; and wherein the complex of polymer A and polymer B is preformed; and wherein the pH of a 1 % aqueous solution of the composition is less than 6; and further comprising a solvent selected from water or a mixture of water and lower alcohol

According to a second aspect, the present invention provides a wash or rinse liquor 20 comprising between 0.02 and 40 g/l of the composition according to the invention, having a pH < 6
According to a third aspect, the present invention provides a process for washing fabric comprising the steps in sequence of contacting the fabric with a wash or rinse liquor 25 comprising between 0.02 and 40 g/l of the composition according to the invention; leaving the fabric to dry; leaving the fabric for soil and/or dirt to deposit onto the fabric; washing the fabric with a conventional washing detergent in a conventional way.
According to a forth aspect, the present invention provides a process for preparing the liquid composition according to the invention comprising the steps of: (a) preparing solution of polymer A and polymer B separately with or without the stabilizer (b) adding the stabilizer if it is not added while preparing the solution of polymer A and polymer B and then (c) Mixing the both solution and stirring it with the pH adjustment agent.
By mentioning the term storage stability here we mean, that such a formulation in powder form exhibit no complex formation between the interacting polymers and it readily forms the complex when dispersed in water and in liquid form the complex will be well dispersed and not precipitated in the composition. By secondary cleaning benefit is meant that a fabric treated with the composition exhibits benefits such as reduction in soiling, ease of subsequent cleaning and/or enhanced deposition of benefit agents.
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of." In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.

Detailed description of the invention

The present invention thus aims for a composition in form of a liquid and process for the application of a sacrificial layer of polymeric material onto a fabric surface, before dirt and/or soil is deposited onto the fabric. Upon the subsequent (conventional) washing of the fabric the dirt and/or soil are removed by dissolution of the sacrificial layer of the polymeric material from the fabric surface. This is also referred to in the art as a secondary cleaning benefit or next-time-cleaning-benefit. Without wishing to be bound by a theory, it is thought that the polymers in the compositions of the invention form a complex when in contact with aqueous solvent under acid conditions by the formation of hydrogen bonds. The complex disperses into an aqueous solvent and does not dissolve, like the individual polymers. The dispersed complex in turn is thought to bind or precipitate onto a fabric surface, thus forming a layer. The complex is thought to disintegrate when in alkaline conditions, such as the conditions in a laundry main wash, thereby removing the layer and soil or stains deposited onto the layer from the fabric.

Fabric

The fabric that can be treated includes synthetic as well as natural textiles. Fabrics may be made of cotton and other cellulosic materials, polycotton, polyester, silk or nylon. It is envisaged that the method of the present invention can be used to treat garments and other clothing and apparel materials that form typical wash load in household laundry. The household materials that can be treated according to the process of the present invention include, but are not limited to, bedspreads, blankets, carpets, curtains and upholstery. Although the process of the present invention is described primarily for treatment of a fabric, it is envisaged that the process of the present invention can be advantageously used to treat other materials such as jute, leather, denim and canvass. It is envisaged that the process of the present invention can be used to treat articles such as shoes, rain-wear and jackets.

Polymers

The composition according to the invention comprises a polymer A and a polymer B. Polymers A and B are selected such that they form a complex due to the formation of hydrogen bonds.
The polymers may be homo polymers or co polymers. Wherein by copolymer of monomer X is meant any polymer that contains the monomer X and at least one further monomer.

Polymer A

Polymer A has a plurality of carboxyl groups. The polymer A has a molecular mass preferably from 300 to 10⁹ D. Polymer A has a molecular mass of preferably from 2x10³ to 10⁷ D more preferably from 5x10⁴ to 10⁶ D and most preferably from 9x10⁴ to 5x10⁵ D.
The particle size is preferably less than 200µm, preferably less than 100 µm, more preferably 30 less than 50µm still more preferably less than 10µm, or even less than 5µm.
Polymer A is at least partially neutralised in the Sodium (Na⁺) form, preferably at least 10%w of polymer A is neutralised, more preferably at least 20%, still more preferably at least 50%.
Polymer A is preferably water soluble or water dispersible, most preferably polymer A is water soluble.
Polymer A is preferably a polyacrylic acid.
The concentration of polymer A in a fabric cleaning or fabric rinse composition is preferably between 0.01 and 25% by weight, more preferably at least 0.1%, or even at least 1%, but preferably not more than 20%, more preferably less than 15%.
The amount of polymer A relative to the fabric surface area is preferably from 0.5 to 200 µg/cm² of fabric surface area, more preferably from 1 to 100 µg/cm², and most preferably from 2 to 50 µg/cm² of fabric surface area. The term "fabric surface area" as used herein refers to surface area of one side of the fabric.

Polymer B

According to the present invention, polymer B has a monomeric unit comprising a group that can form hydrogen bonds with the carboxyl groups of polymer A.
Poly-vinyl alcohol and, hydroxyethyl cellulose, are generally not water soluble. In order to obtain the benefit of this group of polymers the particle size is set such that the particles are easily dispersible in water or and aqueous solution (i.e. a wash or rinse liquor). The particle size is preferably less than 200µm, more preferably less than 100µm, even more preferably less than 50µm still more preferably less than 10µm, or even less than 5µm.
Without wishing to be limited by theory, it is believed that the two polymers A and B, when dissolved in water, form a complex with a solubility lower than each of the polymers A and B, which helps in enhanced deposition and other benefits.
Polymer B has a molecular mass preferably from 10³ to 10⁹ D.
Homopolymers of vinyl pyrrolidone or vinyl alcohol preferably have a molecular mass of between 10³ and 10⁷ D, more preferably from 10⁴ to 10⁶ D and most preferably from 30,000 to 500,000 D. Commercially available polyvinyl pyrrolidone can be used, one example of which is LUVISKOL® (BASF).
Polyethylene oxide preferably has a molecular mass greater than 2x10⁴ D. The molecular mass is preferably from 2x10⁴ to 10⁶ D, more preferably from 3x10⁴ to 5x10⁵ D and most preferably from 5x10⁴ to 2x10⁵ D.
According to a preferred aspect, the polymer B is water soluble.
It is particularly preferred that the polymer B is selected from a class consisting of homopolymers of vinyl pyrrolidone or alkylene oxide.
The concentration of polymer B in a fabric cleaning or fabric rinse composition is preferably between 0.01 and 20% by weight, more preferably at least 0.1%, or even at least 1%, but preferably not more than 15%, more preferably less than 10%.
The amount of polymer B relative to the fabric surface area is preferably from 0.5 to 200 µg/cm² of fabric surface area, more preferably from 1 to 100 µg/cm², and most preferably from 2 to 50 µg/cm² of fabric surface area. The term "fabric surface area" as used herein refers to surface area of one side of the fabric.
The most preferred combinations of the polymer A and polymer B are PAA-PVP, PAA-PEO, PEG-PAA, Starch-graft-polymethacrylic acid-Polyethylene Oxide.

Stabilizers

According to another preferred embodiment the present invention provides a liquid fabric treatment composition. In the liquid treatment composition the stabilizers are preferably selected from polyvinyl alcohol, silicone, Carboxymethyl cellulose, ethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose. Alternatively the stabiliser may be selected from surfactants such as anionic, cationic, non-ionic especially ethoxylated fatty alcohols. However these surfactant stabilizers are typically less preferred.
If one of the polymers A is polyvinyl alcohol (PVA) then there is no need to add the stabilizer separately. PVA will act both as the polymer A and also as a stabilizer.

pH adjustment agent

The polymers of the invention are best applied to the fabric at acidic pH and removed at alkaline pH. A normal washing process is done at alkaline pH, generally pH between 8 and 11. When an article is washed under such conditions there will be carry over of some of the high pH (alkaline) washing liquor from the main wash to the rinse step. This carry over is typically in the order of 1:10 and cause the rinse liquor to be alkaline.
Therefore the composition of the invention further comprises a pH adjustment agent or a buffer.
Suitable pH adjustment agents are, organic and inorganic acids. Such acids are preferably in solid form and have a high water solubility, most preferably they are fully soluble in water.
Suitable inorganic acids are boric acid, sodium dihydrogen phosphate, aluminium chloride, aluminium sulphate, cupric sulphate etc.
Suitable organic acids in the context of the present invention are citric acid, formic acid, oxalic acid, phtalic acid ascorbic acid, glutamic acid, salicylic acid, tartaric acid, pyroglutamic acid, malic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, propane 1,2,3 tricarboxylic acid, butane 1,2,3,4 tetra carboxylic acid. The anhydrides of all the abovementioned acids may also be used for this purpose.
The wash liquor or rinse liquor wherein the composition of the invention is dissolved, preferably has a pH of less than 6, preferably less than 5 and more preferably less than 4. Aqueous medium has pH preferably greater than 2 and more preferably greater than 3.
The polymers may be also chosen in such a way that when the polymers are added to the aqueous medium, pH of the aqueous medium is less than 6. Preferably, an acidic ingredient is added to aqueous medium to ensure that the pH of the aqueous medium is less than 6. Acidic ingredients that reduce pH of resulting aqueous medium to less than 6 are well known to a person skilled in the art and any suitable acidic ingredient may be chosen.

Optional ingredients

The aqueous medium may comprise an electrolyte. The electrolyte is preferably present in a concentration from 0.001 to 5%, more preferably from 0.01 to 1%, and most preferably from 0.04 to 0.2% by weight of the aqueous medium.
Without wishing to be limited by theory, it is believed that the addition of electrolyte allows the process of the invention to be carried out with relatively low amounts of polymers A and B.
Electrolytes that can be used according to the present invention include water soluble ionic salts. The cation of the salt includes an alkali metal, alkaline earth metal or trivalent metal cation. The anion of the salt includes chloride, sulphate, nitrate and phosphate. Some examples of electrolytes include chlorides, sulphates or nitrates of sodium, potassium, magnesium or calcium. Calcium salts are particularly preferred.
The invention may further comprise natural or synthetic clays, preferably kaolin (kaolinite), bentonite or attapulgate.
According to a preferred aspect, the aqueous medium comprises no more than 200 ppm anionic surfactant. The aqueous medium comprises no more than 100 ppm, more preferably 5 less than 50 ppm anionic surfactant. It is particularly preferred that the aqueous medium is substantially free of anionic surfactant.
The aqueous medium may further comprise at least one benefit agent. The benefit agent that can be included in the aqueous medium includes, but not limited to ingredients such as perfume, fluorescer, deodorant, antibacterial agent, shading dye and bluing agent. One of the advantages of the present invention is that the deposition of benefit agent is enhanced.

Process

The composition according to the invention may be applied to a fabric in different ways. One way of applying the composition is by adding the composition to the rinse water of a manual or automatic washing process. The fabric may be added to the rinse water either before or after addition of the composition.
Alternatively, the composition may be applied by use of a trigger spray dispenser. In another aspect the invention provides a process for washing fabric comprising the steps in sequence of: contacting the fabric with a wash or rinse liquor comprising between 0.02 and 40 g/l of the liquid composition according to the invention; leaving the fabric to dry; leaving the fabric for soil and/or dirt to deposit onto the fabric; washing the fabric with a conventional washing detergent in a conventional way.
The wash liquor preferably comprises at least 0.1 g/l of the total liquid composition, more preferably at least 0.25 g/l, still more preferably more than 19 g/l, but typically less than 20 g/l, more preferably less than 10 g/l, and even less than 5 g/l. The conventional washing process may be any washing process, such as machine wash in an automatic or semi-automatic vertical axis or horizontal axis washing machine or a hand wash process.
The detergent may be any conventional washing detergent composition, typically comprising surfactant and builder and optionally perfume, optical brighteners, building aids, etc.

Composition

The composition comprises preferably 5-95%, more preferably 10-90% and most preferably 20-80% by weight polymer A. The composition comprises preferably 5-95%, more preferably 10-90% and most preferably 20-80% by weight polymer B.
The liquid composition of the present invention is preferably prepared by first preparing the solution of polymer A and polymer B separately with or without the stabilizer. After that the stabilizer has been added if it is not added while preparing the solution of polymer A and 15 polymer B. Then followed by mixing both solution and stirring it with the pH adjustment agent. For the liquid composition the solvent is selected from water or a mixture of water and lower alcohol. The preferable lower alcohol is selected from methanol, ethanol, iso-propanol etc. The preferred ratio of water to lower alcohol is 6:4 more preferably 9:1 and most preferably 10:0.
The polymers may be chosen in such a way that pH of 1 % aqueous solution of the composition is less than 6.
Preferably, an acidic ingredient is present in the composition at 0.1-10% by weight of the composition to ensure that the pH of 1 % aqueous solution of the composition is less than 6. Acidic ingredients that reduce pH of resulting aqueous medium to less than 6 are well known to a person skilled in the art and any suitable acidic ingredient may be chosen.

Examples

The invention will now be illustrated by means of the following, non-limiting examples.

Example 1: Dispersibility of the formulations;

Dispersion of polymers by in-situ Gas generation

In this example the compositions according to the invention (1 and 2) are compared with comparative compositions outside the scope of the invention, with respect to the required dissolution or dispersion time and the uniformity of the solution or dispersion.

For each of the compositions (1, 2 and A-D) 100 ml deionized water was taken in a 250 ml glass beaker and stirred over a magnetic stirrer at controlled speed. The formulation was added to water with continuous stirring and the required time to form a dissolution/dispersion was noted as well as the nature of the dispersion (especially uniformity and/or for lumps remaining).

Table 2: dissolution results

Comp.		Amount	Time	Remarks
		(mg / 100ml dispersion)	(for full dissolution/dispersion)
A	PAA ¹⁾	180	>40 min	Few lumps remaining
B	PAA	180	15 min	lumps
	Soda ²⁾	30
C	PAA	180	>40	lumps
	Citric Acid	70
D	PAA ¹⁾	180	9 min	Clear solution
	Citric Acid	70
	Soda ²⁾	30
1	PAA ¹⁾	180	>9 min	Uniform dispersion
	Citric Acid	70
	Soda ²⁾	30
	PEO ³⁾	113
2	PAA ¹⁾	180	10 min	Uniform dispersion
	Citric Acid	70
	Soda ²⁾	30
	PEO ³⁾	113
	NaCl	500

1) PAA is polyacrylic acid
2) Soda is Na₂CO₃
3) PEO is poly ethylene oxide.

The table above shows that the compositions according to the invention show fast dissolution and a uniform dispersion of the polymer complex, whilst the comparative compositions A-D show either long dissolution times, or do not show a uniform dispersion.

Example 2: Best mode formulations

Table 3: best mode solid formulations

Example composition 3	(g/l)	%
PAA	0.15	7.3
PEO	0.10	4.9
Soda	0.15	7.3
NaCl	0.75	37
Citric acid	0.65	32
Kaolin	0.25	12
Total	2.05	100

This formulation (example composition 3) gives good dispersion and turbidity in 30 seconds.
For polymer coating treatment the cotton, poly cotton and polyester fabric swatches (commercially available from WFK, Germany) were soaked in this dispersion for 30 minutes, and dried in air overnight. The swatches were 10x10 cm.
A composite soil was prepared by sonicating a mixture containing 100 ml triolein, 4 mg carbon soot and 4 mg iron oxide for 1 hour. A homogeneous soil dispersion was obtained.
The fabric swatches were soiled with composite soil and aged for a day at room temperature (ca 24°C). The swatches were then washed in surf XL (ex Unilever) by hand wash procedure.
The swatches treated with the composition of Table 2 were completely cleaned by this procedure. Table 4: best mode liquid formulations

Composition 9 (Liquid) % wt

PAA (100k) 5

PVA(125k) 5

PEG (20k) 2.5

Citric Acid 10

Perfume 1

Water to 100

Example 3: Effect of each of the ingredients on cleaning performance

In this example a number of compositions according to the invention are compared to comparative compositions.
Polymer formulations (as specified in the table below) were prepared according to the method of example 1. The dispersion was checked for lump formation and uniformity.
Desized cotton, polycotton and polyester fabric swatches of 10 x 10 cm (cotton, polycotton and polyester, ex WFK, Germany) were pretreated by soaking into the polymer composition (dispersion) at a liquid to cloth ratio of 5:1 and soaked for 20 minutes. The fabrics used, had a mass of 1.5 g each (i.e. for 100 cm²), resulting in a total of 18.75 µg of total polymer per cm² of fabric (one side), in the examples where polymer was present.
Fabrics were taken out, squeezed out the excess liquor and dried in air.
Fabrics were soiled with 0.3 ml of composite soil dispersion (see example 2) applied to about 20 cm² area and kept for ageing for 16 hours.
The fabric swatches were than washed by hand wash, in 1.5 g/l Surf XL wash liquor, at a wash liquor to cloth ratio of 5:1. The fabric swatches were soaked in the liquor for 30 minutes. The soaked fabrics were washed by a handwash protocol by brushing 5 times on both side of the fabrics. After brushing the fabrics were rinsed three times with clean water and dried in air. The reflectance of the soil region was measured before and after washing using a reflectometer; the cleaning performance is indicated as the difference ("Delta R") between the reflectance (at 460 nm) before and after washing, as is a commonly known procedure in the art.

Control (compositions E and F)

Two control examples were included wherein untreated fabric was soiled and washed with

Composition E: 3 g/l Surf XL (ex Unilever); and

Composition F: 1.5 g/l Surf XL (ex Unilever).
3 g/l detergent product is representative for normal hand wash and horizontal axis machine wash. 1.5 g/l is included because the fabrics that are pre-treated with the compositions of the invention are washed with only half of the standard main wash dosage.

Comparative compositions (compositions G - M)

In comparative examples G-M one or more of the features of the inventions are omitted.

Example compositions (4 - 8)

Examples 4-8 show compositions according to the invention.
Unless otherwise indicated the concentrations in which the ingredients were used were:

PAA (poly acrylic acid; Mw 450,000 D, ex Sigma-Aldrich): 0.15 g/l, PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich): 0.10 g/l, NaCl: 0.75 g/l, Perfume: 0.045, Kaolin: 0.25 g/l, Citric acid: 0.2 g/l, Adipic acid: 0.4 g/l, Phthalic anhydride: 0.4 g/l, Soda 0.15 g/l in the pre-treating wash liquor.

Table 5: Comparative test results for solid composition

	Rinse Formulation	Remarks	Cotton Delta R	Polycotton Delta R	Polyester Delta R
E	3 g/l Surf Excel		14	6	4
F	1.5 g/l Surf Excel		13	5	3
G	PAA 0.25 g/l	Lumps	14	7	6
		Non uniform dispersion
		No turbidity
H	PEO 0.25 g/l	Lumps	15	4	5
		Non uniform dispersion
		No turbidity
I	PAA+PEO	Lumps	16	5	6
		Non uniform dispersion
		Slight turbidity
J	PAA+PEO+NaCl	Lumps remaining	18	6	8
		Non uniform dispersion
		Low turbidity
K	PAA+PEO+Citric acid	Lumps remaining	15	5	6
		Non uniform dispersion
		No turbidity
L	PAA+PEO+ Citric acid + NaCl	Lumps remaining	18	5	7
	PAA+PEO+ Citric acid + NaCl	Non uniform dispersion
M	PAA+PEO+Soda+Kaolin	Few very small lumps	15	12	7
	PAA+PEO+Soda+Kaolin	Good turbidity
4	PAA+PEO+	Few very small lumps	19	15	9
	Citric acid+Soda	Good turbidity
5	PAA+PEO+ Citric acid+ NaCl+ Soda	No lumps	20	17	11
		Uniform dispersion
		Good turbidity
7	PAA+PEO+ Soda+Kaolin+ citric acid	No lumps	22	19	14
		Uniform dispersion
		Good turbidity
8	PAA+PEO+ Soda+Kaolin+ citric acid+NaCl	No lumps	24	21	15
		Uniform dispersion
		Good turbidity

NB PAA is polyacrylic acid; Soda is Na₂CO₃; PEO is poly ethylene oxide; NaCl is sodium chloride

The results in the table above shows that the compositions according to the invention provide substantially better cleaning than the comparative example compositions. Table 6: Comparative test results for liquid composition

Rinse Formulation Cotton Delta R Polycotton Delta R Polyester Delta R

N Without the polymer of the composition 20 10 8

9 Composition 9 22 20 17
The dose of the composition in case to liquid formulation is 2g/lit of rinse liquor. After the fabric treated with the composition of the invention, it is then soiled by composite soil and then usual detergency test was done on the fabric.

Claims

A liquid fabric treatment composition comprising a base composition comprising
a. a mixture of polymer A and a stabilizer wherein the polymer A is selected from the group of homopolymers and copolymers of carboxylic acid wherein the polymer A is at least partially neutralised,

b. a polymer B selected from
i. the group of homopolymers and copolymers of alkylene oxides having a molecular mass greater than 2x10<4>D, vinyl pyrrolidone; and/or

ii. the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; and

c. 0.1-10% by weight of a pH adjustment agent selected from organic acids, selected from citric acid, formic acid, oxalic acid, phtalic acid ascorbic acid, glutamic acid, salicylic acid, tartaric acid, pyroglutamic acid, malic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, propane 1,2,3 tricarboxylic acid, butane 1,2,3,4 tetra carboxylic acid and their anhydrides, inorganic acids and/or buffers.
wherein the combination of polymer A and polymer B is selected from one of the following combinations:
• polyacrylic acid and poly vinyl pyrrolidone

• polyacrylic acid and polyethylene oxide

• polyacrylic acid and polyethylene glycol

• polyacrylic acid and poly vinyl alcohol

• Sodium carboxymethyl cellulose and polyethylene oxide

• polyacrylic acid and hydroxyethyl cellulose

• starch-graft-polymethacrylic acid and polyethylene oxide

• starch-graft-polymethacrylic acid and polyvinyl pyrrolidone

• Pluronic-g-polyacrylic acid and polyethylene oxide

• Pluronic-g-polyacrylic acid and polyvinyl pyrrolidone

• Sodium carboxymethyl cellulose and hydroxyethyl cellulose

• Sodium carboxymethyl cellulose and polyvinyl alcohol;
and wherein the complex of polymer A and polymer B is preformed; and wherein the pH of a 1 % aqueous solution of the composition is less than 6; and further comprising a solvent selected from water or a mixture of water and lower alcohol.
A liquid fabric treatment composition according to claim 1 wherein the pH adjustment agent in the base composition is an organic acid.
A liquid fabric treatment composition according to claim 1 or 2 wherein the base composition further comprises an electrolyte salt or clay or both.
A liquid fabric treatment composition comprising the base composition as claimed in any one of the preceding claims wherein the stabilizer is selected from polyvinyl Alcohol, silicone, carboxymethyl cellulose, ethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose and surfactants.
A liquid fabric treatment composition according to as claimed in any one of the preceding claims wherein Polymer A is present in a concentration of between 0.01 and 25% by weight on the total composition.
A liquid fabric treatment composition according to as claimed in any one of the preceding claims wherein Polymer B is present in a concentration of between 0.01 and 20% by weight on the total composition.
A wash or rinse liquor comprising between 0.02 and 40 g/l of the composition according to any one of claims 1 to 5, having a pH of < 6.
A process for washing fabric comprising the steps in sequence of:
a. contacting the fabric with a wash or rinse liquor comprising between 0.02 and 40 g/l of the composition according to any one of claims 2 to 6;

b. leaving the fabric to dry;

c. leaving the fabric for soil and/or dirt to deposit onto the fabric;

d. washing the fabric with a conventional washing detergent in a conventional way.
A process for preparing the liquid fabric treatment composition according to the invention comprising the steps of:
a. preparing solution of polymer A and polymer B separately with or without the stabilizer.

b. adding the stabilizer if it is not added while preparing the solution of polymer A and polymer B. mixing both solutions and stirring them together with the pH adjustment agent.