WO1995033813A1

WO1995033813A1 - Improved detergent composition

Info

Publication number: WO1995033813A1
Application number: PCT/EP1995/000766
Authority: WO
Inventors: Suk Hyung Cho; Velayudhan Nair Gopa Kumar; Perincheery Aravindakshan; Madukkarai Krishna Nagarajan
Original assignee: Unilever N.V.; Unilever Plc
Priority date: 1994-06-02
Filing date: 1995-03-01
Publication date: 1995-12-14
Also published as: GB9411079D0; AU1947995A; AU2564195A; WO1995033814A1

Abstract

A detergent composition is provided, comprising a detergent active material, a detergency builder and a bleaching system, said system comprising a peroxy bleach and a polysaccharide graft copolymer. It was found that incorporation of said copolymer, particularly cationic starch graft poly-methacrylic acid and starch graft polyvinyl acetate, into the composition improves the bleaching efficiency thereof.

Description

IMPROVED DETERGENT COMPOSITION

Field of the invention

The present invention relates to fabric washing having low temperature bleaching stainremoval -efficiency and more particularly to compositions which include polysaccharide graft copolymer for obtaining this efficiency.

Background of the invention Fabric bleaching is well known and bleach systems commonly used in the detergent industry are perborate bleaches. The perborate bleaches are a category of oxygen bleaches. From the fabric safety point of view the oxygen bleaches are preferred to the chlorine bleaches.

Sodium perborate is widely used as bleaching agent in detergent formulations. The bleaching action of such for¬ mulations where perborate alone is used as the active bleaching agent, is effective only at high temperatures of over about 60°C. Thus, a detergent formulation containing perborate alone as the active bleach ingredient or similar oxygen bleach compounds such as percarbonate does not exhibit desirable or effective bleach properties at temperatures lower than 60°C.

Considerable research efforts are being made to provide detergent formulation with perborates having bleaching efficiency at lower temperatures. The use of activators for perborates have been suggested and efficient bleaching at lower temperatures could be achieved. These activators combine with the perborates to form percompounds which have higher bleaching potency at lower temperatures.

The activators/bleach precursors which are commonly used are N,N,N*N* Tetraacetylethylene diamine (TAED) , sodium nonanoyl oxy benzene sulphonate (SNOBS) , sodium acetoxy benzene sulphonate (SABS) and sodium benzoyl oxy benzene sulphonate (P-15) . The use of transition metal ions (e.g., Mn ions) also was found to improve the low temperature bleaching efficiency of perborate/activator systems.

As an alternative to perborate/activator systems, preformed peracids e.g., phthaloyl a ino percaproic acid (PAP) are also known to perform at lower temperatures. Previous studies revealed that peracid ions can undergo decom- position in detergent solution by self hydrolysis or by interaction with some sensitive ingredients (e.g. stabilizers) present in the formulation.

The inventors have surprisingly found that the incor- poration of a polysaccharide graft copolymer (e.g. cationic starch graft polymethacrylic acid, such as shown in figure 1) into a detergent composition comprising peroxy compound bleach synergistically improve the bleaching efficiency of the detergent composition at low temperatures. More particularly, it has been found that the presence of this copolymer along with the surfactant, bleach and water helps in better stain removal than when the stained cloth is washed with only surfactant, bleach and water.

DEFINITION OF THE INVENTION

Accordingly, the present invention relates to a detergent composition comprising a detergent active material, a detergency builder, and a bleaching system comprising a peroxy bleach and a polysaccharide graft copolymer.

DETERGENT ACTIVE MATERIAL

The detergent active material may be selected from anionic, cationic, ampholytic, zwitterionic or nonionic detergent active materials or mixtures thereof. Particularly preferred are mixtures of anionic and nonionic detergent active materials such as a mixture of an alkali metal salt of an alkyl benzene sulphonate together with an alkoxylated alcohol. The level of detergent active material or materials in the composition is preferably from 2% to 50%, more preferably from 5% to 30% by weight.

The preferred detergent compounds which can be used are synthetic anionic and nonionic compounds. The former are usually water soluble alkali metal salts of organic sul¬ phates and sulphonates having alkyl groups containing from about 8 to 22 carbon atoms. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C₈ - C₁₈) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C₉ - C₂₀) benzene sulphonates, particularly from sodium linear secondary alkyl (C₁₀ - C₁₅) benzene sulphonates, sodium alkyl glyceryl ether sulphates especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from pertroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates, sodium and potassium salts of sulphuric acid esters of higher (C₈ - C₁₈) fatty alcohol-alkene oxide, particularly ethylene oxide reaction products; the reaction products of fatty acids such as coconut fatty acid esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reaction of alpha-olefins (C₈ - C₂₀) with sodium bisulphite and those derived from reaction of paraffins with S0₂ and Cl₂ and then hydrolysing with a base to produce a random sul¬ phonate; and olefin sulphonates, which terms is used to describe the material by reacting olefins, particularly (C₁₀ - C₂₀) alpha olefins with S0₃ and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C_1]L - C₁₅) alkyl benzene sulphonates and sodium (C₁₂ - C₁₈) alkyl sulphates. 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 alkyl (C₆ - C₂₂) phenols-ethylene oxide condensates, containing generally 5 to 25 units of ethylene oxide per molecule. Other suitable nonionic com- pounds are the condensation products of aliphatic (C₈ - C₁₈) primary or secondary linear of branched alcohols with ethylene oxide, generally 5 to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.

Mixtures of detergent compounds, for example, mixed anionic or mixed anionic and nonionic compounds may be used in the detergent compositions, particularly, in the latter case to provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds in¬ tolerant automatic washing machines.

Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent com¬ pounds are used, it is generally in small amounts in com¬ positions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds.

Many suitable detergent active compounds are available and fully described in literature, e.g., surface active agents and detergents, vols. I and II by Schwartz, Perry and Berch. DETERGENT BUILDER

The builder may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the suspen¬ sion of the fabric softening clay material. The level of the builder may be from 0.5% to 70% by wt. more preferably from 15% to 50% by wt.

Examples of detergency builders include precipitating builders, such as the alkali metal carbonates with or without high surface area calcite, bicarbonates, pyrophophates, sequestering builders, such as the alkali metal tripoly-phosphates, citrates or nitrilotriacetates, or ion exchange builders such as amorphous alkali metal aluminosilicates or zeolites.

PEROXY BLEACH The peroxy bleaching agent may be a compound which is capable of yielding hydrogen peroxide in aqueous solution.

Hydrogen peroxide sources are well-known in the art. They include the alkali metal peroxides, organic peroxides and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persul- phates. Mixtures of two or more such compounds may also be suitable.

Particularly preferred are sodium perborate tetrahydrate and especially, sodium perborate monohydrate. Sodium per¬ borate monohydrate is preferred because it has excellent storage stability while also dissolving very quickly in aqueous solutions. Sodium percarbonate may also be preferred for environmental reasons. The amount of these inorganic persalts in the composition of the invention will usually be from 5 to 35% by weight, preferably from 5 to 20% byweight.

Organic peroxy acids may also be suitable as the peroxy bleaching agent, such material have a general formula

O II HO-O-C-R-Y wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbons atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl , a COOH group or

0

// C OOH group, or a quaternary ammonium group.

The organic peroxy acids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.

Typical monoperoxy acids useful herein include alkyi peroxy acids and aryl peroxy acids such as: i) peroxybenzoic acid and ring subtstituted peroxybenzoic acids, e.g., peroxy-a-naphthoic acid; ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g., peroxylauric acid, peroxystearic acid, and N,N'phthaloyl-aminoperoxycaproic acid (PAP) .

Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as: iii) 1,12-diperoxydodecanedioic acid (DPDA) ; iv) 1,9-diperoxyazelaic acid; v) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid; vi) 2-decyldiperoxybutane-l,4-dioic acid; vii) 4,4 'sulfonylbisperoxybenzoic acid. Particularly preferred organic acids are peracetic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and diperoxydodecanedioic acid. Under certain circumstances hydrogen peroxide itself may directly be employed as the peroxygen compounds.

If organic peroxyacids are used as the peroxy bleach, the amount thereof will normally be within the range of 2-20% by weight, preferably from 4-8% by weight of the detergent composition.

All these peroxy bleaching agents may be utilised alone or preferably in conjunction with a peroxyacid bleach precur¬ sor, hereinafter also called activator. The bleach precursors of this invention are compounds that react with peroxide anion and form therewith a peracid, percarbonic acid or perimidic acid. Precursors of this invention are water soluble materials, being soluble generally to an extent of at least 1%, preferably at least about 5% by wt. at 25°C.

Precursors which may be effectively utilized for the pur¬ pose of the present invention include:

(a) N-diacylated and N'N'-polyacylated amines, such as, N,N,N* ,N'-tetra acetyl methylene diamine and N,N,N*N*- ^' tetraacetyl ethylene diamine, N,N,-diacetylaniline, N,N- diacetyl-p-toluidine; 1,3-diacylated hydantoins, such as, for example l,3-diacetyl-5, 5-dimethyl hydantoin; acetoxy- (N,N,N')~ polyacylmalonamide, for example, acetoxy-(N,N)- diacetylmalonamide;

(b) N-alkyl-N-sulphonyl carbonamides, for example, the compounds N-methyl-N-mesyl-acetamide, N-methyl-N- mesyl- benzamide, and N-methyl-N-mesyl-p-nitrobenzamide; (c) N-acylated cyclic hydrazides acylated triazones or urazoles for example monoacetylmaleic acid hydrazide;

(d) 0,N,N-trisubstituted hydroxylamines such as O-benzoyl- N-N-succinyl hydroxylamine,

O-acetyl-N-N-succinylhydroxylamine, O-p-methoxyben- zoyl-N-N-succinylhydroxylamine, O-p-methoxy- benzoyl-N-N- succinylhydroxylamine, and 0-p-nitrobenzoyl-N,N- succinyl hydroxylamine;

(e) N,N'diacyl-sulphurylamides, for example, N,N'dimethyl- N,N'diacetyl-sulphurylamide and N,N'-diethyl- N,N'dipropionyl sulphurylamide;

(f) Triacyanurates for example, triacetyl cyanurate and tribenzoyl cyanurate;

(g) Carboxylic acid anhydrides such as benzoic anhydride, -chloro-benzoic anhydride, phthalic anhydride, 4-chloro phthalic anhydride;

(h) Esters, for example, glucose pentaacetate, xylose tetraacetate, sodium acetyloxybenzene sulfonate, sodium nanoyloxybenzene sulfonate and sodium benzoyloxybenzene- ' sulfonate;

(i) l,3-diacyl-4-5-diacyloxy-imidazolidine, for example, 1,3-diformyl-4,5-diacetoxy-imidazoline, 1,3-diacetyl-4, 5-imidazoline,

(j) Tetraacetylglycoluril and tetrapropionyl glycoluril;

(k) Diacylated 2,5-diketopiperazine such as 1,4-diacetyl- 2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine and l,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine; (1) Acylation products of propylenediurea or 2,2-dimethyl propylenediurea (2,4,6,8-tetraaza-bicyclo (3,3,1)-nonane- tetraacetyl- or the tetrapropionylpropylenediurea or their dimethyl derivatives;

( ) Carbonic acid esters, for example, the sodium salts of p-(ethoxycarbonyloxy)-benzoic acid;

(n) Acyloxy-(N,N' )polyacyl malonamides such as alpha- acetoxy (N,N') diacetyl malonamide; and

(o) Quaternary ammonium substituted peroxycarbonic or carboxylic acid esters, such as 2-(N,N,N-trimethyl ammonium ethyl sodium 4-sulphophenyl carbonate.

The precursors mentioned under (a) , (h) and (j) are of special interest, particularly, N,N,N' ,N'-tetraacetyl ethylene diamine (TAED) , tetraacetyl-glycoluril (TAGU) , glucose pentaacetate, xylose tetraacetate, sodium acetyloxybenzene sulfonate (SABS) and sodium nonanoyloxybenzene sulfonate (SNOBS) .

When present in the detergent composition, the level of the precursor may be up to 12% by weight, preferably from 2-10% by weight.

POLYSACCHARIDE COPOLYMER

A representrative structure of cationic starch graft polymethacrylic acid which is a preferred polysaccharide graft copolymer for the purpose of the present invention is shown in figure 1. It is however possible to use other cationic polysaccharides graft copolymers, as described in our copending application no.308/BOM/91. Figure 2 gives the representative structure of starch graft polyvinyl acetate, another preferred polysaccharide copolymer. Not being bound by theory, it is believed that the polysac¬ charide copolymer of the invention interacts with the stain thereby modifying its surface characteristics and enhancing removal of the stain.

The level of the polysaccharide copolymer in the detergent composition of the invention is preferably from 0.1-10% by weight.

OTHER INGREDIENTS

Apart from the components already mentioned, a detergent composition of the invention can contain any of the conven- tional additives in amounts in which such additives are normally employed in fabric washing detergent compositions. Examples of these additives include lather boosters, such as alkanolamides, particularly monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen releasing bleaching agents, such as trichloroisocyanuric acid, inorganic salts, such as sodium sulphate, other fillers, such as kaolin, and usually present in very minor amounts, fluorescent agents, per¬ fumes, enzymes such as proteases, lipases, cellulases and amylases, germicides and colourants.

PROCESS

The detergent composition of the invention is prepared by mixing the various components at desired levels.

The invention will now be illustrated by the following non-limiting Examples.

EXAMPLES For the purpose of the experiments, the following starch graft copolymers were prepared.

CATIONIC STARCH GRAFT POLYMETHACRYLIC ACID COPOLYMER NO. 1 Tapioca starch (1000 g 13% moisture) was slurried in urea solution (30 g urea in 1 litre water) maintained at ambient temperature (30°C) and added into 5 litre capacity three necked RB flask fitted having a mechanical stirrer. The slurry was stirred for 1 hr and ferrous ammonium sulphate (1.0 g in 10 ml water) and ascorbic acid solutions (5 g in 25 ml water) were added to it under stirring with 10 minutes interval between additions. To this mixture, methacrylic acid (50 g) was added. After 10 minutes, hydrogen peroxide solution (10 ml, 30% solution) was added and the reaction mixture was stirred for 2 hrs. The product was filtered, washed 3 times with equal volume of water (1 litre water) and dried initially in air at room temperature for 18 hours and finally in an air oven at 55°C till the moisture content was less than 13%.

COPOLYMER NO. 2

This copolymer was prepared according to the same procedure as for Copolymer no. 1, the only difference being that the amount of methacrylic acid employed in this case was 100 g instead of 50 g. After stirring for 2 hours, the product slurry was directly used for preparing the different grades of cationic starch graft polymethacrylic acid.

For the preparation Copolymers 3-6 the entire quantity of Copolymer no.2 obtained as per the procedure described above was used.

COPOLYMER NO. 3

Copolymer no. 2 was reacted with 25 gms of 3-chloro,

2-hydroxypropyl trimethyl ammonium chloride.

COPOLYMER NO. 4

Copolymer no. 2 was reacted with 50 gms of 3-chloro,

2-hydroxypropyl trimethyl ammonium chloride. COPOLYMER NO. 5

Copolymer no. 2 was reacted with 100 gms of 3-chloro,

2-hydroxy-propyl trimethyl ammonium chloride.

COPOLYMER NO. 6

Copolymer no. 2 was reacted with 200 gms of 3-chloro, 2-hydroxy-propyl trimethyl ammonium chloride.

In the case of copolymer no. 3-6, the desired amount of 3-chloro, 2-hydroxypropyl trimethyl ammonium chloride was added to copolymer no. 2 and the pH was maintained between 11.5 to 11.8 for 16 hrs with constant stirring at 40°C. After 16 hours, the pH was adjusted to 5.8 and the product was filtered, washed 3 times, with equal volume of water and dried in air overnight and at 55°C in an air oven till the moisture content was less than 13%.

STARCH-GRAFT POLYVINYL ACETATE COPOLYMER NO. 7 This is starch graft polyvinyl acetate synthesised by reacting starch with 8.4% by weight vinyl acetate using redox initiator.

WASHING OF TEST FABRICS Various test formulations were prepared using the following components: Detergent Product - The detegent product used for the studies contained about 30% each of detergent active and phosphate builders. It also contained usual components like soda ash, ARD agent, colour, structurants and perfume. BLeaching Agent - Sodium perborate or PAP. Activators (for - TAED, SNOBS or P-15 perborates)

Polymer - Copolymer no. 1 to copolymer no. 7 The required amounts of the detergent product (2.5 g/litre for low detergent concentration and 10 g/litre for high detergent concentration) along with the required amounts of bleaching agent activators (when perborate is added) and preformed polymer were added and stirred for 5 minutes. For the low detergent concentration, the amounts of the bleach/activators were chosen to give 10 ppm available oxygen in solution. Thus, for low detergent concentration 0.22 g PAP alone or 0.25 g of sodium perborate along with, as activators, 0.0725 g TAED/0.210 g SNOBS/0.187g P-15 were used. 0.075 g cooked polymer as solution in water was also added to the solutions.

For high detergent concentration 0.30 g PAP or 1.0 g of sodium perborate along with, as activators, 0.3 g of

TAED/SNOBS/P-15 were employed. 0.3 g of cooked polymer as solution in water (wt. on dry basis) was also added to the solutions.

The stained standard test pieces were added to the solutions in Terg-o-tometer and stirred for 30 minutes. The washed fabrics were rinsed three times in 24°FH water and air dried. The test fabrics were equilibrated to atmospheric moisture content.

The reflectance values of the original stained fabric and of the fabric after the bleaching experiment were measured using Elrepho reflectance spectrophotometer fitted with UV filter and 250 W Xenon lamp. Delta(Δ) R 460 is the dif- ference in the reflectance of the original fabric and the washed fabric at 460 n.m. The test fabrics used were standard tea stained BC-1 and wine stained EMPA fabrics.

Tables la and lb summarises the results for three copolymers (polymer 1, 5 and 7) . The results indicate that Polymer no. 5 showed improved performance over formulations containing no polymer (Tables la and lb) whereas Polymer no 7 showed improved performance in case of BC-1 test fabric where P15 was the activator (Table lb) .

To some extent, improvement in bleaching performance was observed for all the bleach precursors (TAED, SNOBS and P-15) .

The effect of polymer 5 in improving the bleach effieciency of the perborate/activator system was further studied at 30 and 45°C using TAED, SNOBS and P-15 as activators at low and high detergent concentrations. The results in terms of the ΔR values obtained (see tables II-IV) indicate sig¬ nificant improvement in bleaching induced by the polymer.

The effect of polymer 5 in improving bleach efficiency of PAP was studied at 30 and 45°C at low and high detergent concentrations. The results (table V) indicate improvement in bleaching induced by the polymer at low and high deter¬ gent concentration.

Experiments were designed to verify the effect of the polymer on detergency by measuring the Δ R after washing with detergent product containing the individual components separately (i.e. with only polymer no. 5, TAED and Sodium perborate) and with detergent not containing any of these ingredients. A combination of these individual additives was also tested for comparison purposes.

The results are given in Tables VI and VII. Incorporation of a combination of sodium perborate, TAED and polymer no. 5 into the detergent product was found to provide synergis- tic benefits.

The results given in table VIII and IX, show a comparative evaluation of the effect of polymers 3-6 on bleaching. Table la Initial screening of polymers for Bleach Delivery Reflectance change ( Δ R460) due to washing)

Reflectance change Δ R 460* Test fabric EMPA Activator TAED

1. DETERGENT 4.2

PRODUCT + ACTIVATOR

2. DETERGENT PRODUCT 6.4 ACTIVATOR +

SODIUM PERBORATE

DETERGENT PRODUCT + 6.3 ACTIVATOR + SODIUM PERBORATE + POLYMER NO. 1

DETERGENT PRODUCT + 6.5 ACTIVATOR + SODIUM PERBORATE + POLYMER NO. 7

5. DETERGENT PRODUCT 7.1 + ACTIVATOR + SODIUM PERBORATE + POLYMER NO. 5

Test condtions: - Terg-o-tometer wash with 100 rpm Wash temp. : 30°C ' - Duration of washing: 30 minutes - Product concentration

Detergent product 2.5 gms

Polymer 0.075 gms

Sod.perborate 0.25 gms

Activator

TAED 0.0725 gms

P-15 0.187 gms

SNOBS 0.21 gms

Total volume 1 litre Table lb Initial screening of polymers for Bleach Delivery Reflectance change ( R460) due to washing)

Reflectance change Δ R 460*

Test fabric BC-1

Activator P-15 SNOBS

1. DETERGENT -0.2 1.0

PRODUCT + ACTIVATOR

2. DETERGENT PRODUCT + 0.5 3.3 ACTIVATOR +

SODIUM PERBORATE

3. DETERGENT PRODUCT + -1.1 3.1 ACTIVATOR + SODIUM PERBORATE + POLYMER NO. 1

4. DETERGENT PRODUCT + 1.4 3.0 ACTIVATOR + SODIUM PERBORATE + POLYMER NO. 7

5. DETERGENT PRODUCT 2.8 4.2 + ACTIVATOR + SODIUM PERBORATE + POLYMER NO. 5

Test condtions - Terg-o-tometer wash with 100 rpm Wash temp. : 30°C - Duration of washing: 30 minutes Product concentration Detergent product 2.5 gms

Polymer 0.075 gms Sod.perborate 0.25 gms Activator TAED 0.0725 gms P-15 0.187 gms

SNOBS 0.21 gms

Total volume : 1 litre Table II

Effect of Polymer no. 5 on bleaching with TAED/Sodium perborate at 30°C and 45°C and at two (low and high) deter- gent product concentrations.

A. Low detergent product concentration 2.5 /litre; Sodium perborate: 0.25 g; TAED: 0.0725 g; and polymer 0.075 g Total volume: 1 litre R 460

Test fabric BC- -1 EMPA

Temperature 30^υC 45°C 30°C 45^υC

6. DETERGENT PRODUCT + TAED 0.8 0.8 4.3 6.4 7. DETERGENT PRODUCT + TAED 0.9 5.2 6.1 11.5 + SODIUM PERBORATE

DETERGENT PRODUCT + TAED 2.1 5.8 7.4 12.9 SODIUM PERBORATE + POLYMERNO. 5

B. High detergent product concentration: 10 g/litre;

Sodium perborate 1.0 g TAED 0.3 g and polymer 0.3 g Total volume 1 litre Δ R 460*

Test fabric BC-1 EMPA

Temperature 30^UC 45^υC 30^ϋC 45^υC

9. DETERGENT PRODUCT + TAED 0.1 2.7 5.0 7.2

10. DETERGENT PRODUCT + TAED 3.8 10.9 11.0 10.9 + SODIUM PERBORATE

11. DETERGENT PRODUCT + TAED 5.4 11.7 12.4 11.7 SODIUM PERBORATE +

POLYMER NO. 5 Test conditions: Terg-o-tometer, 100 rpm, 30 mins stirring Table III

Effect of Polymer no. 5 on bleaching with P-15/Sodium perborate at 30°C and 45°C.

A. Low Detergent product concentration: 2.5 g/litre; Sodium perborate: 0.25 g; P15: 0.187g; and polymer 0.075 g. Total volume: 1 litre

Δ R 460*

Test fabric BC-1 EMPA

Temperature 30^υC ϊfT-'C 3CFC 45^UC 12. DETERGENT PRODUCT + P-15 -0.2 θ72 4^~5 U7Ϊ

13. DETERGENT PRODUCT + P-15 3.6 7.4 8.9 12.5 + SODIUM PERGBORATE 14. DETERGENT PRODUCT + P-15 4.8 8.1 10.0 14.5 SODIUM PERBORATE + POLYMERNO. 5

Test conditions: Terg-o-tometer, 100 rpm, 30 mins stirring

B. High detergent product concentration 10 g/litre; sodium perborate 1.0 g; P-15: 0.3 g; and polymer: 0.3 g Total volume: 1 litre Δ R 460*

Test fabric BC-1 EMPA

Temperature 30°C 45°C 30°C 45°C

15. DETERGENT PRODUCT + P-15 0.0 1.5 4.9 7.2

16. DETERGENT PRODUCT + p-15

+ SODIUM PERBORATE 4.8 10.9 10.2 19.7

17. DETERGENT PRODUCT + P-15 SODIUM PERBORATE +

POLYMER NO. 5 7.1 12.7 12.1 21.2 Test conditions: Terg-o-tometer, 100 rpm, 30 mins stirring Table IV

Effect of Polymer no. 5 on bleaching with SNOBS/sodium perborate at 30°C and 45°C and at two (low and high) detergent product concentrations.

A. Low detergent product concentration: 2.5 g/litre; Sodium perborate: 0.25 g; SNOBS: 0.210 g and polymer 0.075 g Total volume: 1 litre Δ R 460*

Test fabric BC- -1 EMPA Temperature 30^υC 45^ϋC 30"C 45^υC

18. DETERGENT PRODUCT + SNOBS -0.2 0.3 4.4 5.8 19. DETERGENT PRODUCT + SNOBS 3.4 6.5 8.4 12.3

20. DETERGENT PRODUCT + SNOBS 4.1 7.9 9.0 13.3 SODIUM PERBORATE + POLYMER NO. 5

B. High detergent product concentration: 10 g/litre; Sodium perborate: 1.0 g; SNOBS: 0.3 g and polymer: 0.3g Total volume: 1 litre

ΔR 460

Test fabric BC- -1 EMPA Temperature 30°C 45°C 30°C 45°C

21. DETERGENT PRODUCT + SNOBS 0.0 1.8 5.1 6.7 22. DETERGENT PRODUCT + SNOBS 5.0 10.3 9.3 10.3 + SODIUM PERBORATE

23. DETERGENT PRODUCT + SNOBS + 6 6..55 13.8 11.1 12.3 SODIUM PERBORATE + POLYMER NO. 5

Test conditions: Terg-o-tometer, 100 rpm 30 mins stirring Table V

Effect of Polymer no. 5 on bleaching with PAP at 30°C and 45°C and at two (low and high) detergent product con- centrations.

A. Low detergent product concentration: 2.5 g/litre; PAP: 0.22 g; and polymer: 0.075 g Total volume : l litre

Δ R 460*

Test fabric BC-1 EMPA Temperature 30^υC Pc 3CFC 45^UC

24. DETERGENT PRODUCT -0.6 0.5 3.8 6.1

25. DETERGENT PRODUCT + PAP 4.4 5.5 9.2 11.0

26. DETERGENT PRODUCT + PAP 4.7 6.4 9.7 11.8 POLYMER NO. 5

B. High detergent product concentration: 10 g/litre; PAP: 0.3 g and polymer: 0.3 g Total volume: 1 litre

Δ R 460*

Test fabric BC-1 EMPA

Temperature 30^υC 45^σCΪ 30^ 45^σC

27. DETERGENT PRODUCT ^■0.2 1.8 4.9 6.3

28. DETERGENT PRODUCT + PAP 4.9 6.1 8.8 9.3

29. DETERGENT PRODUCT + PAP 5.8 7.7 9.9 11.4 POLYMER NO. 5

Test conditions: Terg-o-tometer, 100 rpm 30 mins stirring Table VI

Effect of individual components on bleaching for the system : Detergent product/TAED/sodium perborate/polymer no. 5, at 30°C and 45°C.

A. Low detergent product concentration: 2.5 g/litre; Sodium perborate: 0.25 g, TAED: 0.0725 g and polymer: 0.075 g Total volume: 1 litre

Δ R 460*

Test fabric BC-1 EMPA BC-1 EMPA

Temperature 30°C 45^υC

30. DETERGENT PRODUCT -0.5 4.6 0.7 6.1

31. DETERGENT PRODUCT + 0.1 5.3 0.7 6.7

POLYMER NO. 5 32. DETERGENT PRODUCT + -0.1 5.8 1.7 7.6

SODIUM PERBORATE

33. DETERGENT PRODUCT + -0.8 4.3 0.8 6.4 TAED

34. DETERGENT PRODUCT 0.8 5.8 1.7 8.3 + SODIUM PERBORATE +

POLYMER NO. 5 35. DETERGENT PRODUCT + TAED 0.2 4.6 0.9 6.4 POLYMER NO. 5

36. DETERGENT PRODUCT + TAED 1.7 7.2 5.5 11.2 SODIUM PERBORATE + POLYMER NO. 5

Test conditions: Terg-o-tometer 100 rpm, 30 mins stirring Table VII

Effect of individual components on bleaching for the system :Detergent product/TAED/sodium perborate/polymer no. 5, at 30°C and 45°C.

B High detergent product concentration: 10 g/litre;

Sodium perborate: 1 g, TAED: 0.3 g; and polymer: 0.3 g Total volume: 1 litre

Δ R 460*

Temperature 30°C 45^υC

Test fabric BC-1 EMPA BC-1 EMPA

37. DETERGENT PRODUCT 0.7 6.6 1.8 7.1

38. DETERGENT PRODUCT + 1.0 5.7 3.3 7.4 POLYMER NO. 5

39. DETERGENT PRODUCT + 2.5 7.4 5.0 12.1 SODIUM PERBORATE

40. DETERGENT PRODUCT + 0.1 5.0 2.7 7.2 TAED

41. DETERGENT PRODUCT 3.3 7.9 7.4 13.7

+ SODIUM PERBORATE + POLYMER NO. 5

42. DETERGENT PRODUCT + TAED 1.1 5.6 3.4 8.5 POLYMER NO. 5

43. DETERGENT PRODUCT + TAED 5.7 12.0 12.0 12.9 SODIUM PERBORATE + POLYMER NO. 5

Test conditions: Terg-o-tometer 100 rpm, 30 mins stirring Table VIII

Effect of polymer no. 3 and polymer no. 4 and polymer no. 5 and polymer no. 6 on bleaching efficiency; Test fabric 5 BC-1, temperature 30°C.

Δ R 460*

10 Polymer Number 3 4 5 6

15 44. DETERGENT PRODUCT 0.7 0.7 -0.03 -0.9

45. DETERGENT PRODUCT + 1.3 0.9 1.5 1.7

SODIUM PERBORATE + TAED

20 46. DETERGENT PRODUCT + 2.2 1.7 1.6 2.5 SODIUM PERBORATE + SNOBS

47. DETERGENT PRODUCT -0.2 0.8 1.03 -0.2

25 + POLYMER

48. DETERGENT PRODUCT + 1.3 2.7 2.7 2.2 SODIUM PERBORATE + TAED + POLYMER

30

49. DETERGENT PRODUCT + 1.9 3.2 3.8 4.1 SODIUM PERBORATE SNOBS + POLYMER

35 Test conditions: Terg-o-tometer at 100 rpm, 30 mins stir- ring Detergent product : 2.5 gms in one litre Polymer : 0.075 gms Perborate : 0.25 gms 0

Activator :

TAED : 0.0725 g

SNOBS : 0.21 gms Total volume : 1 litre Table IX

Effect of polymer no.3 and polymer no.4 and polymer no.5 and polymer no. 6 on bleaching efficiency; Test fabric: EMPA; temperature: 30°C

Δ R 460*

Polymer Number 3 4 5 6

50. DETERGENT PRODUCT 3.9 5.2 4.2 3.7

51. DETERGENT PRODUCT + 6.4 7.0 6.9 5.3 SODIUM PERBORATE + TAED

52. DETERGENT PRODUCT + 5.7 7.6 5.9 5.2 SODIUM PERBORATE

+ SNOBS

53. DETERGENT PRODUCT 6.5 7.8 7.3 7.8

+ SODIUM PERBORATE + TAED + POLYMER 54. DETERGENT PRODUCT + 5.8 8.3 7.9 8.6 SODIUM PERBORATE + SNOBS + POLYMER

Test conditions: Terg-o-tometer 100 rpm, 30 mins stirring

Detergent product : 2.5 gms in one litre Polymer : 0.075 gms Perborate : 0.25 gms

Activator :

TAED : 0.0725 g

SNOBS : 0.21 gms

Total volume : 1 litre

Claims

1. Detergent composition comprising a detergent active material, a detergency builder, and a bleaching system, said system comprising a peroxy bleach and a polysaccharide graft copolymer (as herein defined) .

2. Composition according to claim 1, wherein the polysac¬ charide copolymer is selected from the group consisting of cationic starch graft polymethacrylic acid and starch graft polyvinyl acetate.

3. Composition according to claim 1 or 2, wherein the polysaccharide copolymer is present at a level of from 0.1 to 10% by weight of the composition.

4. Composition according to any of claims 1-3, wherein the peroxy bleach is selected from the group of sodium per¬ borate monohydrate, sodium perborate tetrahydrate, and sodium percarbonate.

5. Composition according to any of claims 1-4, wherein the bleach system further comprises a bleach precursor, in an amount of up to 12% by weight of the detergent composition.

6. Composition according to claim 5, wherein the bleach precursor is selected from the group consisting of N,N,N' ,N'-tetraacetyl ethylene diamine (TAED), tetraacetyl glycoluril (TAGU) , glucose pentaacetate, xylose tetraacetate, sodium acetyloxybenzene sulphonate (SABS) , and sodium nonanoyloxybenzene sulphonate (SNOBS) .