FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
IMPROVEMENTS TO LAUNDRY COMPOSITIONS
HINDUSTAN UNILEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Unilever Limited, Unilever House, B.D.Sawant Marg, Chakala, Andheri (East) Mumbai-400 099, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed

IMPROVEMENTS TO LAUNDRY COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to improvement to laundry compositions. More particularly, the invention is directed to a polymer, an emulsion comprising the polymer and to a laundry composition comprising the emulsion.
BACKGROUND OF THE INVENTION
Silicone oils are known to be useful for softening fabrics, and are included in many laundry compositions. There is a problem with these materials, as they are expensive components, but the deposition onto fabrics is inefficient.
One way to increase the deposition of silicones is to formulate them in the form of an emulsion, using for example nonionic surfactants as an emulsifier.
However, the problem remains that the deposition is still inefficient.
There is thus a need to increase the efficiency of deposition of silicones onto fabric.
SUMMARY OF THE INVENTION
In a first aspect, the invention relates to a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer.
In a second aspect, this invention is directed to an emulsion comprising:-

(a) a particle comprising (i) the polymer of the first aspect, and (ii) a silicone liquid; and,
(b) an aqueous continuous phase.
A third aspect of the invention relates to a process to make the emulsion of the second aspect. The process comprises mixing together a silicone liquid, a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer, and water.
The fourth aspect of the invention relates to a laundry composition comprising:-
a) from 5 to 65 wt.% of a surfactant; and,
b) from 0.05 to 10 wt.% of a polymer according to the first aspect or from 0.5 to 30 wt.% an emulsion according to the second aspect.
Another aspect of the invention relates to the use of a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer to increase the level of deposition of a silicone onto fabric. The copolymer is ideally used in the form of an emulsion either alone, or as part of a laundry composition.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the term "comprising" means including, made up of, composed of, consisting and/or consisting essentially of.
All percentages quoted are wt.% unless otherwise stated.

Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about".
As used herein, a formula shall be considered physically "stable" when after 1 week at 21 degrees Celsius it exhibits no signs of phase separation.
The copolymer of polyethylene terephthalate and polyoxyethylene terephthalate is modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer.
The copolymer of polyethylene terephthalate and polyoxyethylene terephthalate prior to modification preferably has a molecular weight of from 1000 to 50,000 Daltons.
The emulsion comprises:-
(a) a particle comprising (i) copolymer of polyethylene terephthalate and polyoxyethylene terephthalate, which is modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer, and (ii) a silicone liquid; and,
(b) an aqueous continuous phase.
The particle present in the emulsion is preferably in the form of a liquid droplet. Preferably the size of the liquid droplet is from 0.5 to 20um.
The silicone liquid present in the particle of the emulsion preferably has a viscosity of from 5,000 to 100,000 cP.

A particle is considered as a discrete entity which is stable in its surrounding medium. For example, the medium can be air for an isolated solid particle, or water (an example of an aqueous continuous phase) for a liquid particle in an emulsion.
Process to make the Polymer
The modified copolymer of polyethylene terephthalate and polyoxyethylene terephthalate can be easily prepared. An example process is to mix together a silicone oil with the commercially available copolymer under vacuum (for example at 1 mbar (1 OOPa)) at a high temperature (for example 165°C) for three hours.
Process to Make the Emulsion
The process to make the emulsion comprises mixing together a silicone liquid, a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate (PET-POET) modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer, and water.
Preferably the modified copolymer is first dissolved in water prior to addition to the silicone oil. More preferably the copolymer is dissolved in water to a concentration of 1% by weight to provide an emulsifier solution.
Suitable mixing methods for the process include mixing the ingredients together using a high shear stirrer. A suitable time period is 90 seconds.
The emulsion typically comprises from 30 to 99.9 wt.%, preferably from 40 to 99 wt.% of the aqueous continuous phase. The aqueous continuous phase may be solely water, or a water based mixture comprising water as a majority component.

The emulsion may further contain an emulsifying agent, for example a surfactant such as nonionic, anionic, cationic, zwitterionic and amphoteric surfactants. The emulsifier can be mixed together with the other emulsion ingredients as hereinbefore described.
If an emulsifying agent is used, preferably it is a nonionic surfactant. Preferably the modified PET-POET copolymer can act itself as an emulsifier, without the requirement for an additional emulsifier to be employed.
Suitable nonionic surfactants as emulsifiers include the (poly)-alkoxylated analogues of saturated or unsaturated fatty alcohols, for example, having from 8 to 22, preferably from 9 to 18, more preferably from 10 to 15 carbon atoms on average in the hydrocarbon chain thereof and preferably on average from 3 to 11, more preferably from 4 to 9 alkyleneoxy groups. Most preferably, the alkyleneoxy groups are independently selected from ethyleneoxy, propyleneoxy and butylenoxy, especially ethyleneoxy and propylenoxy, or solely ethyleneoxy groups and alkyl polyglucosides as disclosed in EP 0 495 176.
Form of the Invention
The modified PET-POET polymer or emulsion comprising the modified polymer can be included in laundry products taking a number of forms. The laundry product can take the form of a laundry treatment agent for fabric, in which case it can be a laundry composition comprising:-
a) from 5 to 65 wt.% of a surfactant; and,
b) from 0.05 to 10 wt.% of a polymer according to the first aspect or from 0.5 to 30 wt.% an emulsion according to the second aspect.

In one embodiment, the laundry composition may comprise:-
a) from 5 to 65 wt.% of a surfactant; and,
b) from 0.05 to 10 wt.% of a polymer material which is a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer.
In one embodiment, the laundry composition may comprise:-
a) from 5 to 65 wt.% of a surfactant; and,
b) from 0.5 to 30 wt.% of an emulsion comprising (a1) a particle which comprises (i) a polymer material which is a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer, and (ii) a silicone liquid; and, (a2) an aqueous continuous phase.
Preferably the polymer is present in the laundry composition at a level of from 0.1 to 10 wt.%, more preferably from 0.5 to 5 wt.% based on the total composition.
Preferably the emulsion is present in the laundry composition at a level of from 0.1 to 20 wt.%, more preferably from 1 to 10 wt.% based on the total composition. ■
The laundry composition may be a main wash composition, a rinse composition, or a pre- or after-wash treatment composition, all of which may be dilutable or non-dilutable. Main wash compositions are preferred.
The compositions of the invention may be in any physical form e.g. a solid such as a powder or granules, a tablet, a solid bar, a paste, gel or liquid, especially, an

aqueous based liquid. In particular the compositions may be used in laundry compositions, especially in liquid, gel, powder or tablet laundry composition.
If the laundry composition is a main wash composition, then the pH range of the composition is from pH 7-12, preferably from pH 8.0 to 10.5. It is desirable to buffer the formulation at whatever the target pH of the composition is.
Another aspect of the invention relates to the use of a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer to increase the level of deposition of a silicone onto fabric.
The modified PET-POET copolymer is ideally used in the form of an emulsion either alone, or as an emulsion included as part of a laundry composition.
Thus the invention also may relate to the use an emulsion comprising a particle comprising a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer to increase the level of deposition of a silicone onto fabric. Preferably the emulsion is incorporated as part of a laundry product as described herein.
COMPONENTS
Surfactants
The laundry composition comprises a surfactant, preferably a detersive surfactant. Suitable surfactants comprise nonionic surfactants and anionic surfactants.

They may be chosen from the surfactants described in "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated.
Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6 to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C8 to C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates 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 detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C8 to C18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium C11 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulphates. Further anionic surfactants include fatty acid-based soaps containing

between C8-C26 carbon atoms. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alky! polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.
The total amount of surfactant present in the laundry composition is from 5 to 65 wt.%. Preferably the total amount of surfactant is from 10 to 65 wt.%, preferably from 15 to 50 wt.%.
Other surfactants such as amphoteric, zwitterionic and cationic surfactants may also be present in addition to the aforementioned nonionic and anionic surfactants.
Optional Ingredients
The laundry composition may additionally comprise one or more of the following optional ingredients.
BUILDERS OR COMPLEXING AGENTS
The laundry composition optionally comprises from 1 to 50 wt.% of a builder. Preferably the builder is present at a level of from 1 to 40 wt.%.
Builder materials may be selected from 1) calcium sequestrant materials, 2)
precipitating materials,
3) calcium ion-exchange materials and 4) mixtures thereof.
It is preferred that when an insoluble inorganic builder, e.g., zeolite is used, the size is in the range 0.1 to 10 microns (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex Malvern™).

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
The composition may also contain 1-50 wt.% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrtlotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred builders.
The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt.%. Aluminosilicates are materials having the general formula:


where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to aluminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate.
SHADING AGENT
The laundry composition preferably comprises a blue or violet shading agent in the range from 0.0001 to 0.01 wt.%. The shading agents reduce the perception of damage to many coloured garments and increase whiteness of white garments.
The shading agents are preferably selected from blue and violet dyes of the solvent, disperse, basic, direct and acid type listed in the Colour Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002).

Preferably a direct violet or direct blue dyes is present. Preferably the dyes are bis-azo, tris-azo dyes or triphendioxazine dye. The carcinogenic benzidene based dyes are not preferred.
FLUORESCENT AGENT
The laundry composition preferably comprises a fluorescent agent (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 composition 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]trazole, 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-sulfos!yryl)biphenyl.
PERFUME
Preferably the laundry composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
In perfume mixtures preferably 15 to 25 wt.% are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
Perfume and top note may be used to cue the fabric care benefit of the invention.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
POLYMERS
The laundry composition may comprise one or more polymers. Examples are carboxymethylcellulose, poly(ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers, lauryl methacrylate/acrylic acid copolymers, and cationic polysaccharide-based polymers.
HYDROTROBE
A liquid detergent composition may optionally include a hydrotrope, which can prevent liquid crystal formation. The addition of the hydrotrope thus aids the clarity/ transparency of the composition. Suitable hydrotropes include but are not limited to propylene glycol, ethanol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate. Suitable salts include but

are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine. Preferably, the hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance. The amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%.
Examples
Example 1 Preparation of aminosilicone with polyethylene terephthalate-co-polyoxyethylene terephthalate (PET-POET) functionality
HANSA ASR 7020 (aminosilicone oil ex. CHT) and TexCare SRN300 (polyethylene terephthalate-co-polyoxyethylene terephthalate Mn= 4900 ex. Clariant) were added to a single-neck round bottomed flask with a magnetic stirring bar at a ratio of 1/0.025 by weight respectively. The reaction was carried out at 165°C under high vacuum level (~1mbar(100Pa))for 180 minutes. The resulting product was a viscous oil.
Example 2 Improved deposition due to PET-POET modification of aminosilicone
Emulsification of PET-POET modified aminosilicone
The PET-POET modified aminosilicone, prepared as described in example 1, was emulsified in water using a blend of non-ionic surfactants (85:15 ratio of Neodol 25-7 (primary alcohol ethoxylate ex. Shell Chemicals) to Synperonic A20 (POE primary alcohol ex. Croda) by weight respectively). Modified aminosilicone oil (0.1g) was added to a 14ml capacity squat form glass vial along with 9.9g of emulsifier solution (1 % solution of non-ionic surfactant blend in deionized water)

and mixed using a high shear stirrer (VWR VDI12 microhomogenizer with S12N-12S tool on setting '5') for 90 seconds.
Comparative example A
A comparative (control) sample was prepared using a procedure identical to the above, with Hansa ASR 7020 aminosilicone oil ex.CHT being used instead of PET-POET modified aminosilicone oil.
Model wash evaluation
a) Preparation of wash liquor:
The wash liquor was prepared by diluting Persil® Small and Mighty (concentrated liquid detergent) with local medium/soft water (typically 6-18°FH (french water hardness)) to achieve a 2.5g/l concentration. 50ml of wash liquor was added to each 500ml Linitest pot.
b) Simulated Wash (Linitest)
0.313g of 1 % PET-POET modified aminosilicone emulsion or unmodified aminosilicone emulsion (comparative example A) was added to the linitest pots containing wash liquor and agitated slightly to ensure mixing.
A sample of knitted polyester measuring 21cm by 21cm was placed into each linitest pot containing the wash liquor and aminosilicone emulsions, and the pots were sealed.
Washes were done in quadruplicate for each sample and results averaged.

The Linitest™ is a laboratory scale washing machine (Ex. Heraeus). The equipment is designed and built to comply with the requirements for international standard test specifications. It is used for small scale detergency and stain removal testing particularly when low liquor to cloth ratios are required.
There are various models of the Linitest commercially available. The model used in this case has a single rotation speed of 40 rpm. The carrier is capable of accommodating twelve 500ml steel containers and can be operated at temperatures up to 100°C.
The Linitest comprises a 20 litre tank, control system and drive mechanism. Permanent thermostatically controlled tubular heating elements in the base of the tank heat the bath liquor to the required temperature, The stainless steel construction throughout ensures efficient heat transfer to the specimen containers that are mounted on a rotating horizontal carrier driven by a geared motor. The rotating movement of the carrier 'throws' the liquid from one end of the container to the other in a continuous action. This movement simulates the mechanical washing process and additional mechanical action can be obtained by using steel ball bearings or discs.
The Linitest pots were attached to the Linitester cradle and rotated for 45 minutes at 40°C to simulate the main wash.
At the end of the main wash simulation, each linitest pot was emptied of wash liquor. An 85ml aliquot of water was added to each pot and the pots were re-sealed and returned to the Linitester to rotate for a further 10 minutes to simulate rinsing. Rinsing was performed at the same temperature as the mainwash. This was repeated one further time, so that each fabric had experienced two simulated rinses.

After rinsing, the fabrics were squeezed to remove excess liquid and were line
dried at ambient temperature.
Determination of amount of silicone deposited on polyester
The amount of silicone deposited onto polyester fabric as a result of the model wash evaluation was determined by analysis of elemental silicon using X-ray Fluorescence (Phillips PW2400). The mean result from analysis of four fabric samples per treatment is shown in table 1.
The limit of detection for Si using this technique is 10ppm. For the purposes of averaging, where levels were below the limit of detection (<10ppm St), values were considered to be equal to 10ppm.
Table 1: Silicon deposition results:

Fabric treatment Si (ppm)
Liquid detergent only (no silicone emulsion) 10
Comparative example A 19
PETPOET modified aminosilicone 35
The aminosilicone modified with PET-POET functionality showed enhanced silicone deposition compared to unmodified aminosilicone. This result is an improvement in comparison to the known emulsification method using nonionic surfactant.

CLAIMS
1. A polymer material which is a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone group which is covalently bonded either directly or via an optional linker group to the copolymer.
2. A polymer according to claim 1 wherein the copolymer prior to modification has a molecular weight of from 1000 to 50,000 Daltons.
3. An emulsion comprising:-

(a) a particle comprising (i) the modified copolymer of claim 1 or claim 2, and (ii) a silicone liquid; and,
(b) an aqueous continuous phase.

4. An emulsion according to claim 3, wherein the particle is a liquid droplet.
5. An emulsion according to claim 4, wherein the size of the liquid droplet is from 0.5 to 20um.
6. An emulsion according to any one of claims 3 to 5, comprising from 30 to 99.9 wt.%, preferably from 40 to 99 wt.% of the aqueous continuous phase.
7. An emulsion according to any one of claims 3 to 6, wherein the silicone liquid has a viscosity of from 5,000 to 100,000 cP.
8. A process to make the emulsion of any one of claims 3 to 7, comprising mixing together a silicone liquid, a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate modified by attachment of a silicone

group which is covalently bonded either directly or via an optional linker group to the copolymer, and water.
9. A process according to claim 8, wherein the modified copolymer is first dissolved in water prior to addition to the silicone oil.
10. A laundry composition comprising:-

(a) from 5 to 65 wt.% of a surfactant; and,
(b) from 0.05 to 10 wt.% of a polymer according to claim 1 or claim 2 or from 0.5 to 30 of an emulsion according to any one of claims 3 to 7.
11. Use of a copolymer of polyethylene terephthalate and polyoxyethylene
terephthalate modified by attachment of a silicone group which is covalently
bonded either directly or via an optional linker group to the copolymer to
increase the level of deposition of a silicone onto fabric.