C4512/C
FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)


LAUNDRY COMPOSITION
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India

The following specification particularly describes the invention and the manner in which it is to be performed


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LAUNDRY COMPOSITION
FIELD OF INVENTION 5 This invention relates to the use of agricultural waste in laundry products.
BACKGROUND OF INVENTION
United States Patent 6677290, to Procter and Gamble,
10 discloses a composition having a plasma-induced, graft polymerized, water-soluble coating for controlling solubility, chemical stability and physical properties is disclosed. A process for making such a composition is also disclosed which involves subjecting a particulate material
15 to plasma after which a water-soluble organic monomer is
graft polymerized onto at least a portion of the particulate material. Examples of the particulate material used as cosmetic components include corn cob powder, peach pit powder, pecan shell powder, walnut shell powder, and wheat
20 bran.
W09732966, to Colgate Palmolive Co, discloses liquid crystal detergent compositions that contain wood particles which are abrasive particles designed to improve the scouring power of
25 the instant liquid crystal detergent composition. The surfactant in the composition is also absorbed on the surface of the wood particles. The wood particles have a particle diameter of 200 millimicrons to 600 millimicrons. The concentration of the wood particles in the liquid
30 crystal detergent composition is from 0.1 to 10 wt%.

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CN 1205358 discloses a natural plant washing powder prepared from edible plants containing rice husks, broken rice, corn, maize cob, egg shell, balsam pear, and Chinese prickly ash.
5 EP 0 004 111 discloses the use of base treated pre-
gelatinized starch. Starch is a complex carbohydrate found chiefly in seeds, fruits, tubers, roots and stem pith of plants, notably in corn, potatoes, wheat, and rice; an important foodstuff and used otherwise especially in 10 adhesives and as fillers and stiffeners for paper and
textiles. Starch is not an agricultural waste product but an agricultural end product. Starch is the most import carbohydrate source in human nutrition.
15 US 4,056,400 discloses the treatment of cellulose,
hemicellulose and lignin with hypochlorite under base conditions. US 4,056,400 discloses a treatment that results in an aqueous solution that is filtered to remove insoluble material after which the aqueous solution is treated with a
20 water miscible organic solvent (methanol) to precipitate a material that may used as a builder. There is no use ascribed to the insoluble material.
US 5,830,445 discloses the use of bleached plant by-products 25 in cosmetics as abrasive materials for scrubbing skin.
There is an ongoing search to find better performing ingredients that provide better cleaning, a cheaper product, and ingredients that come from sustainable resources. 30

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SUMMARY OF INVENTION
Agricultural waste by-products (APB) suffer from low detergency activity. The performance of the agricultural waste product may be greatly increased by pre-treating the 5 material with a strongly basic solution.
The APBs are subjected to a minimum of processing before being incorporated into a granular laundry detergent composition but have been pre-treated with a strongly 10 alkaline solution, optionally rinsed and/or bleached, and dried.
In one aspect the present invention provides a granular laundry detergent composition comprising from 2 and 70 wt %
15 of a surfactant, 2 to 40 wt % of sodium carbonate, and from 5 to 80 wt % of an insoluble agricultural plant by-product, the insoluble agricultural plant by-product is in the form of a particulate having a particle size of 1 mm or below, wherein the insoluble agricultural plant by-product has been
20 treated with an aqueous solution, the aqueous solution
having a pH of at least 12, and subjected to a drying step.
The aforementioned laundry detergent composition is also applicable to other formats including a liquid detergent 25 composition.
In another aspect the present invention a method of treating a textile comprising the following steps:
(i) treating a textile with the composition as defined in 30 any preceding claim in an aqueous medium, wherein the aqueous medium comprises from 0.2 g/L to 5 g/L of a

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surfactant, the aqueous medium having a pH in the range 4 to 11; and,
(ii) rinsing the textile with water; and, (iii) drying the textile. 5
DETAILED DESCRIPTION OF THE INVENTION
Agricultural plant by-products (APB) in the context of the current invention are defined as waste parts of plants grown as animal food and waste products from natural materials
10 used to make consumer goods. The APB is the organic
insoluble remnants of plant material and does not include vegetable oils that may be present on or in the material. The APB is insoluble in water in the pH range 3 to 11; in contrast, carboxymethylcellulose is soluble in some
15 solvents. The APB is also insoluble in organic solvents such as alcohols and hydrocarbons. The APB may have been subjected for example, to a drying step, solvent extraction to remove oils, a bleaching step or milling and sieving step. If the step of removing oils is omitted, the oils
20 present may form soaps in situ with the overall basically of the composition.
It will be evident to one skilled in the art that the agricultural plant by-products (APB) as described are the 25 fibrous remnants of the plant after removal of the higher value components. APB do not include starch per se. APB's are preferably the pith, chaff, stones, stems, husks, cobs and seed remnants of plants.
30 The APB is not solubilised and reclaimed by precipitation before use in a detergent product. The APB remains as a solid during base treatment and any optional oxidation step.

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The APB is treated with a basic aqueous solution. The basic aqueous solution should have a pH of at least 12, preferably at least 13, most preferably at least 14. The alkaline pH may be provided by many common strong bases, but caustic 5 soda (NaOH) is preferred.
The APB is preferably left in contact with the alkaline solution for at least 20 minutes, preferably for at least 2 hours, most preferably for at least 6 hours. Preferably the 10 APB is treated for a maximum of 15 hours.
The treatment with the alkaline solution may take place at wide variety of temperatures, for example from 0 to 100 °C, but preferably in the range 15 to 40°C. The treatment is 15 preferably conducted with agitation.
The treatment may be carried out with bubbling of air through the alkaline solution.
20 For white products, the APB has preferably been subjected to a bleaching, hueing agent or a fluorescent agent. For coloured products, the APB is subject to colouring with a dye or pigment, preferably a pigment and most preferably a blue or violet pigment. The hueing agent or a fluorescent
25 agent is preferably applied to the ABP in the form of solution in the form of a spray. Hueing agents and fluorescent agent are discussed below with respect to the composition per se but these are equally applicable to the APB per se. These adjuncts are added to the APB after base
30 and if applicable bleaching treatment.

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The most preferred APB are not strongly coloured. The colour of the raw, i.e., before any bleaching, hueing or fluorescer step, milled material is measured using a reflectometer and expressed as the CIE LAB values is preferably L* at least 5 60, preferably at least 70. The b* value from 0 to 35 preferably 0 to 25 and the a* value from -10 and +10.
To lighten the colour of the APB a further bleaching step may be included in the treatment of the materials. Preferred
10 bleaches are hydrogen peroxide; hydrogen peroxide activated by a transition metal catalyst, preferably the manganese catalyst of 1,4,7-trimethyl-l,4,7-triazacyclononane (EP 458397); hydrogen peroxide activated by an organic precursor to give a peracid, particularly peracetic acid. Chlorine
15 dioxide may also be used for bleaching but is not preferred and is preferably avoided. The APB is preferably not subjected to a hypohalite (e.g. hypochlorite) bleaching step to avoid the formation of high levels undesirable organo-chlorine compounds. If a chlorine bleach is used it is
20 preferably used at a level of less than 10 wt % of the APB being treated, most preferably less than 1 wt %.
The APB is preferably uncoated per se by an encapsulating coat. The ABP may however be coated with a fine particulate 25 matter that makes up the granule per se. In particular, the APB has not been subjected to a plasma coating per USP 6,677,290 which encapsulates the particle.
The size of the APB is measured using graded sieves and is 30 that the is retained or passes through such sieves.

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The APB is sized preferably from 100 to 1000 microns, most preferably from 200 to 800 microns.
Preferably the agricultural waste products are dried and 5 milled such that particles are produced which are smaller than 1mm, preferably 0.2 to 0.8 mm.
The following are examples of APBs:
1. The stones and seeds of fruits, preferably olive, peaches,
10 avocado's, plums, most preferably olives.
2. The shells of nuts, preferably peanut, walnuts, hazelnuts, almonds, coconut most preferably coconuts and peanuts.
3. The stems, cobs and husks from cereal production, preferably wheat, corn, sorghum, barley and rye, most
15 preferably wheat and corn cobs.
4. The stems and husks from rice production
5. The remnants of the plant and seeds from edible oil production, preferably sunflower, soybean, rapeseed, cottonseed, canola, most preferably sunflower and
20 soybeans.
6. The plant remnants from sugarbeet and sugarcane.
7. The skin and pith of fruits and vegetables, preferably the pith of citrus fruit, preferably the pith of oranges.
25 With respect to the above nut allergies must be considered. In this regard, nut APBs are least preferred.
The pith and chaff portions have a low bulk density which means that for a given volume of product, the weight is 30 relatively low. In general, high volume and low weight
translates to high freight costs for finished products. For some products, we increase the bulk density, by compressing

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the pith and chaff into pellets. The pellets are then reprocessed into various particle sizes.
SURFACTANT 5 The composition comprises between 2 to 70 wt % of a
surfactant, most preferably 10 to 30 wt %. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol.
10 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.
15
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
20 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
25 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 30 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.

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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 5 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
10 preferred anionic detergent compounds are sodium C11 to C15 alkyl benzene sulphonates and sodium C12 to C16 alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants
15 described in EP-A-070 074, and alkyl monoglycosides.
Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants 20 pointed out in EP-A-346 995 (Unilever). Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C16 to C18 primary alcohol sulphate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate.
25 The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system.
30
Soaps and non-ionic detergents derived from plant/renewable sources may be used.

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BALANCE CARRIERS AND ADJUNCT INGREDIENTS
The composition in addition to above comprises the balance carriers and adjunct ingredients to 100 wt % of the 5 composition.
These may be, for example, other surfactants, builders, foam agents, anti-foam agents, solvents, fluorescers, enzymes and bleaching agents e.g., peroxides. The use and amounts of
10 these components are such that the composition performs
depending upon economics, environmental factors and use of the composition. Preferably the composition comprises a builder, in particular sodium carbonate in the range from 2 to 40 wt %.
15
BUILDER
The composition of the present invention preferably comprises one or more detergency builders. The total amount of detergency builder in the compositions will preferably
20 range from 2 to 80 wt%, more preferably from 10 to 60 wt%.
Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950
25 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 fProcter s Gamble); and layered
30 silicates as disclosed in EP 164 514B (Hoechst). Inorganic phosphate builders, for example, sodium orthophosphate,

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pyrophosphate and tripolyphosphate are also suitable for use with this invention.
The compositions of the invention preferably contain an 5 alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
10 The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na2O. A12O3. 0.8-6 SiO2.
These materials contain some bound water and are required to 15 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). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply 20 described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and 25 mixtures thereof.
The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite 30 builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever). Zeolite MAP is defined as



We Claim:
1. A granular laundry detergent composition comprising
from 2 and 70 wt % of a surfactant, 2 to 40 wt % of
5 sodium carbonate, and from 5 to 80 wt % of an insoluble agricultural plant by-product, the insoluble agricultural plant by-product is in the form of a particulate having a. particle size of 1 mm or below, wherein the insoluble agricultural plant by-product has
10 been treated with an aqueous solution, the aqueous
solution having a pH of at least 12, and subjected to a drying step, wherein the insoluble agricultural plant by-product is selected from: pith; chaff; stones; stems; husks; cobs; and, seed remnants of plants.
15
2. A granular laundry detergent composition according to
claim 1, wherein the composition comprises from 20 to
40 wt % of an insoluble agricultural plant by-product.
20 3. A granular laundry detergent composition according to claim 1 or 2, wherein the by-product has only been subjected to one or more steps selected from bleaching, the application of a hueing agent, and a fluorescent agent.
25
4. «. granular laundry detergent composition according to
claim 1, wherein the plant products has been bleached.
5. A granular laundry detergent composition according to
30 any preceding claim, wherein the plant by-product
comprises from Q.005 to 2 wt % of a fluorescent agent.
1 AMENDED SHEET 2£/10/2007

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6. A granular laundry detergent composition according to any preceding claim, wherein the plant by-product comprises from 0.00005 to 0.01 wt % of a hueing dye.
5 7. A granular laundry detergent composition according to any preceding claim, wherein the raw plant by-product has an L* value of at least 60, a b* value from 0 to 35 and an a* value from -10 to +10.
10 8. A granular laundry detergent composition according to
any preceding claim, wherein the by-product is selected from: remnants of stems, cobs and husks from cereal production.
15 9. A granular laundry detergent composition according to claim 9, wherein the by-product is selected from: remnants of wheat, corn, sorghum, barley and rye.
10. A granular laundry detergent composition according to
20 any one of claims 1 to 8, wherein the by-product is
selected from: remnants of stems and husks from rice production.
11. A granular laundry detergent composition according to
25 any one of claims 1 to 8, wherein the by-product is
selected from: remnants of plant and seeds from edible oil production.
12. A granular laundry detergent composition according to
30 claim 12, preferably sunflower, soybean, rapeseed,
cottonseed, canola, most preferably sunflower and soybeans.

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13. A method of treating a textile comprising the following steps:
(i) treating a textile with the composition as 5 defined in any preceding claim in an aqueous medium,
wherein the aqueous medium comprises from 0.2 g/L to 5 g/L of a surfactant, the aqueous medium having a pH in the range 4 to 11; and,
fii) rinsing the textile with water; and, 10 (iii) drying the textile.
Dated this 17th day of October 2008
HINDUSTAN UNILEVER LIMITED
(S. Venkatramani) Senior Patents Manager