WO1995033814A1

WO1995033814A1 - Improved detergent composition

Info

Publication number: WO1995033814A1
Application number: PCT/EP1995/001823
Authority: WO
Inventors: Suk Hyung Cho; Velayudhan Nair Gopa Kumar; Perincherry Aravindakshan; Iyer Varadarajan Nagarajan
Original assignee: Unilever N.V.; Unilever Plc
Priority date: 1994-06-02
Filing date: 1995-05-15
Publication date: 1995-12-14
Also published as: GB9411079D0; WO1995033813A1; AU1947995A; AU2564195A

Abstract

A detergent composition is provided, comprising a detergent active material, optionally 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 polymethacrylic 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 compositions having low temperature bleaching efficiency and more particularly to compositions which include polysaccharide graft copolymers 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 and colour 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 formulations where perborate alone is used as the active bleaching agent is effective only at high temperatures of about 60°C and above. 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 formulations with perborates having bleaching efficiency at lower temperatures. The use of activators for perborates has been suggested and efficient bleaching at lower temperatures could be achieved. These activators combine with the perborates to form perco pounds which have higher bleaching potency at lower temperatures. The activators which are commonly used are N,N,N',N' tetraacetylethylene diamine (TAED) , sodium nonanoyloxybenzene sulphonate (SNOBS) , sodium acetoxybenzene sulphonate (SABS) , sodium benzoyloxybenzene sulphonate (P-15) . The use of transition metal ions (e.g. Mn ions) was found to improve further the low temperature bleaching efficiency of perborate/activator systems.

Alternative to perborate/activator systems, preformed peracids, e.g., phthaloyl-a ido-percaproic acid (PAP), are also known to perform at lower temperatures. Previous studies revealed that peracid ions can undergo decomposition 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 incorporation of a polysaccharide graft copolymer (e.g., starch graft polymethacrylic acid) into a detergent composition comprising peroxy compound bleach synergistically improves the bleaching efficiency of the detergent composition at low temperatures.

More particularly, it has been found that the presence of polysaccharide graft copolymer along with a surfactant, peroxy 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 provides a detergent composition comprising: i) a detergent active material; ii) a bleaching system comprising a peroxy bleach, a polysaccharide graft copolymer and, optionally, a bleach activator; and iii) optionally, a detergency builder;

Detailed description of the invention

Detergent active material

The detergent active material may be selected from anionic, cationic, amphoteric, zwitterionic or nonionic detergent active materials or mixtures thereof. 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 sulphates 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 - C_w) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C₉ - C^o) benzene sulphonates, particularly from sodium linear secondary alkyl (Cι₀ - C-₅) benzene sulphonates, sodium alkyl glyceryl ether sulphates especially the ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates, sodium and potassium salts of sulphuric acid esters of higher (C₈ - Cι_g) 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 onosulphonates such as those derived by reaction alpha-olefins (C_g - C_JQ) with sodium bisulphite and those derived from reaction of paraffins with S0₂ and Cl₂ followed by hydrolysis with a base to produce a random sulphonate; olefin sulphonates, which term is used to describe the material obtained by reacting olefins, particularly (Cι₀ - C₂₀) alpha olefins with S0₃ and then neutralizing and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C_u - Cι₅) alkyl benzene sulphonates and sodium (C_n - 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 poly condensates, containing generally 5 to 25 units of ethylewne oxide (EO) per molecule. Other suitable nonionic compounds are the poly condensation products of aliphatic (C₈ - C₁₈) primary or secondary linear or 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. Other so called nonionic detergent compounds include long chain tertiary a ine oxides and dialkyl sulphoxides.

Mixtures of detergent compounds, for example, mixed anionic or mixed anionic and nonionic compounds may be used in the detergent compositions. The latter in particular provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds intolerant 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 compounds are used, it is generally in small amounts in compositions 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 the literature, e.g: Surface active agents and detergents, vols. I and II, by Schwartz, Perry and Berch.

Bleaching system

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 persulphates. Mixtures of two or more such compounds may also be suitable.

Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because it has excellent storage stability while also dissolving very quickly in aqueous solutions. Sodium percarbonate may also be preferred as peroxide ion source, 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% by weight.

To obtain a reasonable low temperature bleaching effect a bleach precursor, hereinafter also called activator, may be used. The bleach precursors of this invention are compounds that react with peroxide anion, and form therewith a peracid, percarbonic acid or perimidic acid. These bleach precursors are water soluble materials, being soluble generally to an extent of at least 1%, preferably at least about 5% by weight, at 25°C.

Activators which may be effectively utilized in detergent compositions 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'-tetra acetyl 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 and 1,3-dipropionyl 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- mesylbenzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide;

(c) N-acylated cyclic hydrazides acylated triazones or urazoles for example onoacetylmaleic acid hydrazide; (d) 0,N,N-trisubstituted hydroxylamines such as O-benzoyl-N-N-succinyl hydroxylamine,O-acety1-N-N- succinylhydroxylamine, O-p-methoxy benzoy1-N-N-succinylhydroxylamine, O-p-methoxy benzoyl-N-N-succinylhydroxylamine,O-p-nitrobenzoyl-N, N-succinyl hydroxylamine and 0,N,N,-triacetyl and 0,N,N,-triacetyl hydroxylamine;

(e) N,N'diacyl-sulphurylamides, for example, N,N'dimethyl-N,N'-diacetyl - sulphuryla ide and N,N'-diethy1-N,N'dipropiony1 sulphurylamide;

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

(g) Carboxylic acid anhydrides such as benzoic anhydride, m-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 l,4-diacetyl-2,5 diketopirazine, 4-dipropionyl -2,5-diketopiperazine and 1, 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,l)-nonane-tetraacetyl - or the tetrapropionylpropylenediurea or their dimethyl derivatives;

( ) Carbonic acid esters, for example, the sodium salts of p-(ethoxycarbonyloxy)-benzoic acid and p-(propoxycarbonyloxy)-benzenesulphonic 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 2-12% by weight.

Organic peroxy acids may also be suitable as the peroxy bleaching agent. Such materials have a general formula HOOO-C-R-Y

wherein R is an alkylene or substituted alkylene group containing from 1 to about 22 carbons atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, COOH or COOOH .

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 alkyl peroxy acids and aryl peroxy acids such as: i) peroxybenzoic acid and ring substituted peroxybenzoic acids, peroxy-α-naphthoic acid; ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g., peroxylauric acid, peroxystearic acid, and N,N^#-phthaloylamino-peroxycaproic acid (PAP) .

Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as: iii) 1,12-diperoxy-dodecanedioic acid; 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 peroxy acids are peracetic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and diperoxydodecanedioic acid. Under certain circumstances hydrogen peroxide itself may directly be employed as the peroxy compound. If organic peroxyacids are used as the peroxy bleaching compound, the amount thereof will normally be within the range of 2-20% by weight, preferably from 4-8% by weight, of the detergent composition.

POLYSACCHARIDE COPOLYMER

The polysaccharide graft copolymers used in this invention may be prepared according to methods known in the art, particularly as described in Indian patent no. 172039. The process essentially consists of preparing graft copolymer of a polysaccharide and an unsaturated monomer by

i. treating the polysaccharide with a free radical initiator system, particularly the reducing agent portion (preferably in the presence of hydrotrope in aqueous medium) ,

ii. reacting the pre-treated polysaccharide with the monomer in the presence of an oxidising agent, and

iii. recovering the graft copolymer. The polysaccharide graft copolymers used in this invention may be further modified by making them cationic e.g. by reacting with quaternary amine.

A representative structure of the cationic starch graft polymethacrylic acid which is a preferred material for the purpose of the present invention, is shown in fig. l of the accompanying drawings. It is however possible to use other cationic polysaccharide graft copolymers prepared from natural polymers of carbohydrates such as glucose, xylose, mannose, galactose and thereby have five me bered or six membered pentose or hexose rings joined together by glycosidic linkages. In some cases, like guar gum, tamarind polysaccharide, and starch, the polymers are branched and in other cases, like cellulose the polymers are completely linear. Fig. 2 gives the representative structure of starch graft polyvinyl acetate, another preferred polysaccharide copolymer.

In the polysaccharide graft copolymer as shown in Figure 1, the polymethacrylic acid and the cationic ingredient are both present at a level ranging between 0.1-40% of the polysaccharide graft copolymer.

The content of polyvinyl acetate is at a level ranging between 0.1-20% of the starch graft polyvinyl acetate.

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

Detergency 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 suspension of the fabric softening clay material. The level of the builder may be from 0.5% to 70% by weight, more preferably from 15% to 50% by weight. In the case of detergent formulations based on nonionic surfactants, it is possible to avoid use of detergent builders.

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

Other ingredients

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

Process

The detergent composition of the invention is prepared by mixing the various components at desired levels, using the methods known in the art such as spray drying or dry mixing, followed by post dosing of sensitive ingredients.

The invention will now be illustrated by the following non-limiting Examples, in which parts and pecentages are by weight unless indicated otherwise.

EXAMPLES

The following starch graft copolymers were prepared

STARCH GRAFT POLYMETHACRYLIC ACID COPOLYMER NO. 1

Tapioca starch (1000 g 13% moisture) was slurried in urea solution (30 g urea in 1 liter water) maintained at ambient temperature (30°C) in a 5 liter three necked round bottomed flask fitted with a mechanical stirrer. The slurry was stirred for 1 hr and ferrous ammonium sulphate (1.0 g in 10 ml water) and 10 minutes later ascorbic acid solution (5 g in 25 ml water) was added to it under stirring. 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 volumes of water (1 liter) and dried initially in air at room temperature for 18 hours and finally in an 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 cationic starch graft polymethacrylic acid.

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

COPOLYMER NO.3

Copolymer no. 2 was slurried in 1500ml of distilled water and reacted with 100 gms of 3-chloro, 2-hydroxypropyl trimethyl ammonium chloride at 50°C for 16 hours at a pH of 11.5-11.8 maintained by the addition of 3% sodium hydroxide solution. The product was neutralised to pH 6.5-7 using 10% HC1, filtered, washed (three times with 1L of water each time) , air dried and finally dried in an oven.

STARCH-GRAFT POLYVINYL ACETATE (COPOLYMER NO 4) COPOLYMER NO.4

This is starch graft polyvinyl acetate synthesised by reacting lOOOg of starch with lOOg vinyl acetate using redox initiator. The % polyvinyl acetate add-on is 8.4

WASHING OF TEST FABRICS

Various test formulations were prepared using the following components:

Detergent Product - The detergent product used for the studies contained about 30% by weight each of detergent active (linear alkyl benzene sulphonate, sodium salt) and phosphate builder (STPP) . It also contained usual components like soda ash (10%) , ARD agent(sodium carboxy methyl cellulose, 1%), fillers (20%), perfume(0.25%) , other minor ingredients (colour, structurant) and water (to 100%) . Bleaching Agent - Sodium perborate or PAP. Activators (for - TAED, SNOBS or P-15 perborates) Polymer - Copolymer no.l to copolymer no. 4. The required amounts of the detergent product (2.5 g/liter for low product concentration and 10 g/liter for high product concentration) along with the required amounts of bleach activators (when perborate is used) and polymer were added and stirred for 5 minutes.

For the low product concentration, the amounts of the bleach/activators were chosen to give 10 ppm available oxygen in solution. Thus, for low product 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 was used. 0.075 g cooked polymer (dissolved by heating in lml of water at 90°C for 20min) as solution in water was also added to the solutions.

For high product concentration 0.30 g PAP or 1.0 g of sodium perborate along with, as activators, 0.3 g of TAED/SNOBS/P-15 was 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 of fabric were added to the solutions in a 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 conditioned to equilibrium moisture content.

The reflectance values of the original stained fabric and the reflectance of the fabric after the bleaching experiment were measured using an Elrepho reflectance spectrophotometer fitted with UV filter and 250 W Xenon lamp. The difference in the reflectance of the original fabric and the washed fabric at 460 n.m. is ΔR 460. The test fabrics used were (10cm x 10cm, 3 numbers) standard tea stained BC-l (weight of fabric 4.5g) and wine stained EMPA-114 (weight of fabric 6.0g) fabrics.

The effect of polymer 3 in improving bleach efficiency of perborate/activator system was studied at 30 and 45°C using TAED, SNOBS and P-15 as activators at low and high detergent concentrations. The ΔR 460 values indicated in the table are average values of three replicates. The results (tables I-V) indicate significant improvement in bleaching induced by the polymer at low temperature (30°C) and at low detergent concentration.

The effect of polymer 3 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 detergent concentration.

Experiments were designed to verify the effect of the polymer on detergency by measuring the ΔR 460 after washing with individual components (alone and with polymer no. 3, TAED and Sodium perborate) separately. Combination of these individual additives were also tested for comparison purposes. The results are given in Tables I and II.

Polymer no.3 alone along with detergent product had shown marginal improvement in ΔR 460. A combination of sodium perborate and TAED along with polymer no.3 gave synergistic benefits.

The results given in Tables VI shows the synergistic effect of polymer no. 4 on bleaching efficacy on the fabric BC-l at 30°C. Table - I

Effect of individual components on bleaching for the system

•

Detergent product/TAED/sodium perborate/polymer no. 3 at 30°C and 45°C.

A. Detergent product concentration 2.5 g/liter,Sodium perborate 0.25 g,TAED 0.0725 g and polymer 0.075 g. Total volume : 1 liter

ΔR 460^* Test fabric BC-l EMPA-114 BC-l EMPA-

114

Temperature 30°C 5°C

1. DETERGENT PRODUCT -0.5 4.6 0.7 6.1

2. DETERGENT PRODUCT + 0.1 5.3 0.7 6.7 POLYMER NO.3

3. DETERGENT PRODUCT + -0.1 5.8 1.7 7.6 SODIUM PERBORATE

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

POLYMER NO.3

5. DETERGENT PRODUCT + TAED 0.2 4.6 0.9 6.4 POLYMER NO.3

6. DETERGENT PRODUCT + TAED 1.7 7.2 5.5 11.2 SODIUM PERBORATE +

POLYMER NO.3

Test conditions: Terg-o-tometer 100 cpm, 30 mins stirring Table - II

Effect of individual components on bleaching for the system: Detergent product/TAED/sodium perborate/polymer no.3 at 30°C and 45°C

Detergent product concentration 10 g/litre, Sodium perborate lg, TAED 0.3 g and polymer 0.3 g Total volume : 1 litre

ΔR 460^*

Temperature 30°C 45°C

Test fabric BC-l EMPA-114 BC-l EMPA-

114

7. DETERGENT PRODUCT 0.7 6. 6 1.8 7.1

8. DETERGENT PRODUCT + 1.0 5.7 3.3 7.4

POLYMER NO. 3

9. DETERGENT PRODUCT + 2.5 7.4 5.0 12.1

SODIUM PERBORATE

10. DETERGENT PRODUCT 3.3 7.9 7.4 13.7

+ SODIUM PERBORATE + POLYMER NO. 3

11. DETERGENT PRODUCT + TAED 1.1 5.6 3.4 8.5

POLYMER NO.3

12. DETERGENT PRODUCT + TAED 5.7 12.0 12.0 12.9

SODIUM PERBORATE + POLYMER NO.3

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

Table III

Effect of Polymer no. 3 on bleaching with P-15/ Sodium perborate at 30°C and 45°C.

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

_{ΔR 46cr}

Test fabric BC-l EMPA-114 Temperature 30°C 45°C 30°C 45°C

13. DETERGENT PRODUCT + P-15 -0.2 0.2 4.5 6.1

14. DETERGENT PRODUCT + P-15 3.6 7.4 8.9 12.5 + SODIUM PERBORATE

15. DETERGENT PRODUCT + P-15 4.8 8.1 10.0 14.5 SODIUM PERBORATE + POLYMER NO. 3

B. Detergent product concentration 10 g/liter sodium perborate 1.0 g,P-15, 0.3 g and polymer 0.3 g Total volume: 1 liter

ΔR 460^*

Test fabric BC-l EMPA-114

Temperature 30°C 45°C 30°C 45°C

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

17. DETERGENT PRODUCT + p-15 + SODIUM PERBORATE 4.8 10.9 10.2 19.7

18. DETERGENT PRODUCT + P-15 SODIUM PERBORATE + POLYMER NO.3 7.1 12.7 12.1 21.2

Test conditions: Terg-o-tometer 100 cpm 30 mins stirring Table IV

Effect of Polymer no.3 on bleaching with SNOBS/sodium perborate at 30°C and 45°C and at two (low and high) detergent product concentrations

A. Detergent product concentration 2.5 g/liter, Sodium perborate 0.25 g, SNOBS 0.210 g and polymer 0.075 g Total volume : 1 liter

ΔR 460'

Test fabric BC-l EMPA-114

Temperature 30^CC 45°C 30°C 45°C

IETERGENT PRODUCT + SNOBS -0.2 0.3 4.4 5.8

20. DETERGENT PRODUCT + SNOBS 3.4 6.5 8.4 12.3

+ SODIUM PERBORATE

21. DETERGENT PRODUCT + SNOBS 4.1 7.9 9.0 13.3

SODIUM PERBORATE +

POLYMER NO.3

Detergent product concentration 10 g/liter

Sodium perborate 1.0 g SNOBS 0.3 g and polymer 0.3 g

Total volume 1 liter

ΔR 460^*

Test fabric BC-l EMPA-114

Temperature 30°C 45°C 30°C 45°C

22. DETERGENT PRODUCT + SNOBS 0.0 1.8 5.1 6.7

23. DETERGENT PRODUCT + SNOBS 5.0 10.3 9.3 10.3 + SODIUM PERBORATE

24. DETERGENT PRODUCT + SNOBS + 6.5 13.8 11.1 12.3 SODIUM PERBORATE +

POLYMER NO.3

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

Effect of Polymer no. 3 on bleaching with PAP at 30°C and 45°C and at two (low and high) detergent product concentrations

A. Detergent product concentration 2.5 g/liter. PAP 0.22 g polymer 0.075 g Total volume : 1 liter

ΔR 460^*

Test fabric BC-l EMPA-114

Temperature 30°C 45°C 30°C 45°C

25. DETERGENT PRODUCT -0.6 0.5 3.8 6.1

26. DETERGENT PRODUCT + PAP 4.4 5.5 9.2 11.0

27. DETERGENT PRODUCT + PAP 4.7 6.4 9.7 11.8 POLYMER NO. 3

B. Detergent product concentration 10 g/liter PAP 0.3 g and polymer 0.3 g Total volume 1 liter

ΔR 460^*

Test fabric BC-l EMPA-114

Temperature 30°C 5°C 30°C 45°C

28. DETERGENT PRODUCT -0.2 1.8 4.9 6.3

29. DETERGENT PRODUCT + PAP 4.9 6.1 8.8 9.3

30. DETERGENT PRODUCT + PAP 5.8 7.7 9.9 11.4 POLYMER NO.3

Test conditions: Terg-o-tometer, 100 cpm 30 tains stirring Table VI

Effect of polymer no. 4 on bleaching efficiency; Test fabric BC-l, temperature 30°C.

ΔR 460^* Polymer 4

31. DETERGENT PRODUCT + P-15 -0.2

32. DETERGENT PRODUCT + 0.5 SODIUM PERBORATE + P-15

33. DETERGENT PRODUCT +P-15 1.4 SODIUM PERBORATE +

+ Polymer no.4

Test conditions: Terg-o-tometer at 100 cpm, 30 mins stirring Detergent product : 2.5 gms Polymer : 0.075 gms Perborate : 0.25 gms

Activator(P-15):0.187 gms

Total volume : 1 litre

Claims

claims

1. Detergent composition comprising:

i) a detergent active material; ii) a bleaching system comprising a peroxy bleach, a polysaccharide graft copolymer and, optionally, a bleach activator; and iii) optionally, a detergency builder.

2. Detergent composition as claimed in claim 1, wherein the polysaccharide graft copolymer is selected from the group consisting of cationic starch graft polymethacrylic acid and starch graft polyvinyl acetate.

3. Detergent composition as claimed in claim 1 or 2, wherein the polysaccharide graft copolymer is present at a level ranging from 0.1 to 10% by weight of the composition.

4. Detergent composition as claimed in any of claims 1-3, wherein the peroxy bleach is selected from the group consisting of inorganic persalts and organic peracids.

5. Detergent composition as claimed in any of claims 1-4, wherein the peroxy bleach is an inorganic persalt and the bleaching system further comprises the bleach activator, in an amount of from 2 to 12% by weight of the detergent composition.

6. Detergent composition as claimed in claim 5, wherein the bleach activator is selected from the group consisting of N,N,N',N'-tetraacetyl-ethylene-diamine (TAED) , tetraacetyl- glycoluril (TAGU) , glucose pentaacetate, xylose tetraacetate, sodium acetyloxybenzene sulfonate (SABS) and sodium nonanoyloxybenzene sulfonate (SNOBS) .

Detergent composition as claimed in any of claims 1-6, wherein the detergency builder is present at a level of 0.5% to 70% by weight of the composition.