SE459973B - Bleach and detergent composition and its use in the washing process - Google Patents

Description

459,975 stain removal results at temperatures below about 50 ° C. Thus, bleaching with peroxyacid compounds is generally practiced in the art by either preparing the peroxyacid compounds in situ in the wash solution or by introducing preformed peroxyacid compounds into the wash solution. The use of activating agents in conjunction with peroxy compounds is extensively described in the patent literature and is the usual method of preparing peroxyacid compounds in the washing solution, the activator, usually a carboxylic acid derivative, reacting with the peroxy compound to form a peroxyacid, typically peracetic acid. Among the compounds proposed as activators of peroxy bleaches are carboxylic acid anhydrides, such as those described in U.S. Pat. Nos. 3,298,775 and 3,338,839; carboxylic acid esters, e.g. those described in U.S. Patent No. 2,995,905; and N-acyl compounds, e.g. those described in U.S. Pat. Nos. 3,912,648 and 3,919,002. Bleach compositions containing a preformed peroxyacid compound are also common, and U.S. Patent Nos. 4,170,453 and 4,259,920 are mentioned as examples.

The bleaching ability at low temperatures, especially at temperatures below 380 ° C, of compositions containing a peroxyacid compound can be further enhanced by the addition of bromide ions to the bleach compositions. Thus, for example, U.S. Patent 4,338,210 discloses a bleach system intended to operate at temperatures as low as 40 ° C and below, which bleach system comprises a peroxy precursor, such as diphthaloyl peroxide, and sodium bromide. The patent hypothesizes that the bromide reacts with the peroxyacid to form a hypobromite compound, the latter being a more effective bleaching agent than the peroxyacid compound, at low temperatures. European Patent Application No. 00 24 367, published March 4, 1981, discloses a low temperature bleach system which comprises an organic peroxyacid, such as diperisophthalic acid or monoperoxyphthalic acid, in combination with bromide ions. U.S. Patent Nos. 4,123,376 and 4,300,897 disclose bleach compositions containing a peroximonosulfate bleach, an inorganic bromide salt, and an aromatic sulfonamide compound, such as an alkali metal toluene sulfonamide. The aromatic sulfonamide compound in this bleaching composition, as the patent applicant states, aims to prevent excessive bleaching of colored materials and to otherwise regulate and control the bleaching action produced by peroxy monosulfate and bromide in an aqueous medium. .

Summary of the Invention The present invention provides a bleach composition comprising: (a) monoperoxyphthalic acid (for the sake of brevity also referred to herein as MPPA) and / or a water-soluble salt thereof; (b) a water-soluble inorganic bromide salt; and (c) an aromatic sulfonamide compound selected from benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylenesulfonamide, N-alkali metal salts of said sulfonamides, N-acetyl and N-benzoyl derivatives of the aforementioned and said sulfonamides, thereof. The weight ratio between MPPA (or its salts) and bromide salt in the preparation is from if? about 10: 1 to about 1: 5, preferably from about 8: 1 to about 1: 2, and most preferably from about 6: 1 to 459,973 about 1: 1. The weight ratio of aromatic sulfonamide compound to bromide salt in the compound is from about 5: 1 to 1: 7, preferably from about 2: 1 to 1: 4.

The invented bleaching composition as well as embodiments thereof are set forth in claims 1 to 6. An invented bleaching detergent composition as well as embodiment thereof comprising the invented bleaching composition is set forth in claims 7 to 12.

The process according to the invention as well as embodiments thereof are stated in claims 13 to 19. The process according to the invention provides bleaching of stained and / or soiled materials by contacting these materials with an aqueous solution of a composition according to the invention.

The present invention is based on the discovery that the bleaching ability at low temperatures of compositions containing MPPA and bromide can be considerably enhanced by adding an aromatic sulfonamide compound to said bleaching composition.

In contrast to the compositions described in U.S. Patent Nos. 4,123,376 and 4,300,897, in which the aromatic sulfonamide compounds aim to counteract the activity of chromium-activated peroximonosulfate bleaches in order to provide better safety for dyes and bleaches in the wash solution, the incorporation provides of aromatic sulfonamide compounds in the present compositions the unexpected advantage of obtaining a bleaching composition with markedly improved activity.

Detailed Description of the Invention Monoperoxyphthalic acid and / or one or more of its water-soluble salts constitute the primary bleaches in the bleach compositions and the bleaching detergent compositions of the invention. Although MPPA provides an acceptable bleaching effect, it has the disadvantage of having rather low stability during storage together with other components that are normally included in household detergent compositions. For stability reasons, therefore, the magnesium salt of MPPA is preferably used in the compositions of the invention, i.e. magnesium monoperoxyphthalate. The magnesium monoperoxy phthalate is preferably provided in the form of a composition containing about 65% magnesium MPPA salt as active ingredient and containing from about 5 to 6% active oxygen. Alkali metal, calcium or barium alkaline earth metal and / or ammonium salts of MPPA can also be used in the bleach and detergent compositions of the invention, although these salts are generally less preferred, in terms of stability, than the aforementioned: agnesium salt .

The production of MPPA is generally carried out by reaction between hydrogen peroxide and phthalic anhydride. The obtained MPPA can then be used to prepare magnesium monoperoxyphthalate by reaction with a magnesium compound in the presence of an organic solvent.

A detailed description of the preparation of MPPA and its magnesium salt can be found on p. 7 - 10 of European Patent Publication 0 027 693, published April 29, l981, and the mentioned pages 7 - 10 are incorporated by reference into the present description.

The MPPA bleach (or a salt thereof) can be combined in the present bleaching composition if desired with a conventional bleaching peroxy compound and an activator therefor. Examples of suitable peroxy compounds include perborates, percarbonates, perphosphates and the like of alkali metals, with sodium perborate being particularly preferred because it is commercially available. Conventional activators, e.g. those described in column 4 of U.S. Patent 4,259,200 are suitable for use with these peroxy compounds. The polyacylated amines are generally of particular interest, with TAED in particular being a preferred activator. Other suitable activators include anhydride compounds such as benzoic acid, maleic acid, succinic acid and phthalic anhydride; and acyl compounds such as N-acetyl and N-benzoylimidazoles. The molar ratio between peroxy compound and activator can generally vary within wide limits depending on the choice of peroxy compound and activator. However, molar ratios from about 0.5: 1 to about 1: 1 are generally suitable for achieving satisfactory bleaching properties.

The water-soluble bromide salt used is preferably an alkali metal bromide, such as potassium bromide or sodium bromide, the latter being especially preferred because it is readily available and comparatively inexpensive.

The aromatic sulfonamides used in the present compositions include the aforementioned sulfonamides, N-acetyl and N-benzoyl derivatives thereof, such as N-acetyl-paratoluenesulfonamide, N-acetyl-benzenesulfonamide and N-benzoyl-benzenesulfonamide , and N-alkali metal salts thereof. Preferred compounds include sodium and potassium para-toluenesulfonamide; ortho-toluenesulfonamide; benzenesulfonamide; and corresponding alkali metal salts thereof. The alkali metal toluenesulfonamides are particularly preferred in the present invention. The amount of bleach composition added to the wash solution is generally selected so as to obtain an amount of peroxyacid compound in the range corresponding to about 3 to 100 parts of active oxygen per million parts of wash solution, with a content of from about S to 40 ppm being generally preferred.

The present bleach composition containing MPPA and / or a water-soluble salt thereof, an inorganic bromide salt and an aromatic sulfonamide may be prepared in the form of a separate bleach product, or alternatively used in a laundry assisted detergent composition. Thus, the bleach composition of the invention may include conventional additives used in the laundry process, such as binders, fillers, detergent salts, proteolytic enzymes, optical brighteners, perfumes, dyes, corrosion inhibitors, antifoulants, foam stabilizers and the like. amounts depending on the desired properties of the bleach composition and their compatibility with this composition. In addition, the bleach compositions of the invention may be incorporated into household detergent compositions which contain one or more surfactants selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents.

When the present bleach composition is incorporated into a conventional detergent composition and thus provided as a ready-made bleaching detergent composition, the latter composition comprises the following; from about 5 to 50% by weight of the present bleach composition; from about to 50% by weight, preferably from about S to 459,975 15%, surfactant detergent compound; and from about 5 to 80% by weight, preferably from about 10 to 60% by weight, of detergent salt which may also act as a buffer to provide the required pH range when the detergent composition is added to water. The aqueous washing solutions should have a pH range of from about 7 to 12, preferably from about 8 to 10, and most preferably from about 8 to 9. A preferred amount of detergent salt is from about 20% to about 65% by weight of the composition. The remainder of the composition mainly comprises water, filler salt, such as sodium sulfate, and various adjuvants described below.

The compositions of the present invention contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents. The synthetic organic detergents used in the practice of the invention may be any of a wide variety of such compounds which are well known and described in detail in the publication Surface Active Agents, Vol. II, by Schwartz, Perry, and Berch, published in 1958 by Inter-Science Publishers, the relevant parts of which are incorporated herein by reference.

The detergent compositions of the invention comprise, as the primary surfactant, usually one or more anionic detergent compounds which may be supplemented or, if desired, completely replaced with a nonionic detergent.

Among the anionic surfactants useful in the present invention are those surfactants which contain an organic hydrophobic group having generally about 8-26 carbon atoms and preferably 10 to 18 carbon atoms in the molecular structure and at least one water solubility. group selected from the groups sulfonate, sulphate, carboxylate, phosphonate and phosphate, to obtain a water-soluble detergent.

Examples of suitable anionic detergents are soaps such as water-soluble salts (eg the sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids, or resin salts containing between about 8 and 20 carbon atoms and preferably 10-18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example tallow, fat, coconut oil and mixtures thereof. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, for example sodium coconut soap and potassium tallow soap.

The class of anionic detergents also includes water-soluble sulfated and sulfonated detergents having an alkyl radical containing between about 8 and 26 and preferably between about 12 and 22 carbon atoms. (The term "alkyl" includes the alkyl moiety of higher acyl radicals.) Examples of sulfonated anionic detergents are higher alkyl monocyclic aromatic sulfonates such as the higher alkylbenzene sulfonates containing between about 10 and 16 carbon atoms in the higher straight or branched chain alkyl group, such as sodium. , the potassium and ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluenesulfonates and higher alkylphenolsulfonates.

Other suitable anionic detergents are olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfonate detergents can be prepared in a conventional manner by reacting SO 3 with long chain olefins containing between about 8 and 25 and preferably between 12 and Z1 carbon atoms, such as olefins of the formula RCH = CHR 1, in which R represents a higher alkyl group having 6 - 23 carbon atoms and R1 represents an alkyl group having between about 1 and 17 carbon atoms or hydrogen, to obtain a mixture of sultones and alkene sulfonic acids which are then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergents are paraffin sulfonates containing between about 10 and 20 carbon atoms, preferably between about 15 and carbon atoms. The primary paraffin sulfonates are prepared by reacting long-chain alpha-olefins with bisulfites. Paraffin sulfonates having the sulfonate groups distributed along the paraffin chain are described in U.S. Pat. Nos. 2,503,280, 2,507,088, 3,260,741 and 3,372,188 and German Pat. No. 735,096.

Other suitable anionic detergents are sulphated ethoxylated higher fatty alcohols of the formula R0 (C2H4O) m $ O3M, in which R is fatty alkyl having from 10 to 18 carbon atoms, m is from 2 to 6 (preferably has a value of from about 1/5 to 1/2 of the number of carbon atoms in R) and M is a solubilizing salt-forming cation, such as alkali metal, ammonium, lower alkylamino or a higher alkylbenzenesulfonate in which the higher alkyl has 10 to 15 carbon atoms. The proportion of ethylene oxide in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 ml of ethylene oxide groups per mole of anionic detergent, with 3 moles being particularly preferred, especially when the higher alkanol has 11 to 15 carbon atoms.

To maintain the desired balance between hydrophilic and lipophilic groups, when the carbon atom content of the alkyl chain is in the lower part of the range of 10 to 18 carbon atoms, the detergent content of ethylene oxide can be reduced to about 2 moles per mole, whereas the number of ethylene oxide groups can be increased to 4 or 5 and in some cases even to 8 or 9, when the higher alkanol has 16 to 18 carbon atoms in the upper part of the range. In the same way, the salt-forming cation can be changed to give the best solubility. It can consist of any suitable solubilizing metal or radical but usually becomes alkali metal, e.g. sodium, or ammonium. If lower alkylamine or alkanolamine groups are used, the alkyls and alkanols will usually contain from 1 to 4 carbon atoms and the amines and alkanolamines may be mono-, di- or trisubstituted as in monoethanolamine, diisopropanolamine and trimethylamine. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and is marketed as Neodol -3S.

The most preferred water-soluble anionic detergent compounds are salts of higher alkyl benzene sulfonates, olefin sulfonates and higher alkyl sulfates with ammonium and substituted ammonium (such as mono-, di- and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium). and magnesium). Among the anionic agents listed above, sodium linear alkyl benzene sulfonates (LABS) are the most preferred, and especially those in which the alkyl group is a straight chain alkyl radical having 12 or 13 carbon atoms.

The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically prepared by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic to nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen bonded to the nitrogen can be condensed with ethylene oxide or with the polyhydrated product thereof, i.e. polyethylene glycol, to form a nonionic detergent. of the hydrophilic chain or of the polyoxyethylene chain can be easily adjusted to give the desired balance between hydrophobic and hydrophilic groups.

The nonionic detergent used is preferably a poly-lower-alkoxylated-higher alkanol in which the alkanol has 10 to 18 carbon atoms and in which the molar number of lower alkylene oxide (having 2 or 3 carbon atoms) is from 3 to 12. Among these substances, it is preferred to use those in which the higher alkanol is a higher fatty alcohol having 11 to 15 carbon atoms and which contains from 5 to 9 lower alkoxy groups per mole. The lower alkoxy group is preferably ethoxy, but in some cases it can be advantageously mixed with propoxy, the latter, in the case being included, usually constituting a smaller part (less than 50%). Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. Neodol 25-7 and Neodol 23-6.5, which products are manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of about 12 to 1S carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups is on average 6.5 per mole. The higher alcohols are primary alkanols. Other examples of these detergents include Tergitolc 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The former is a mixed ethoxylated product of a linear secondary alkanol having 11 to 15 carbon atoms and 7 moles of ethylene oxide and the latter is a similar product but reacted with 9 moles of ethylene oxide. Higher molecular weight nonionic substances can also be used in the present compositions, such as Neodol 45-111, which are similar condensation products between ethylene oxide and higher fatty alcohols, the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups being about ll per mole.

These products are also manufactured by Shell Chemical Company.

Zwitterionic detergents, such as betaines and sulphobetaines, of the following formula are also useful: R 2 \ R-N-R 4 -> | <= o Ry! O in which R represents an alkyl group having between about 8 and 18 carbon atoms, R 2 and R 3 each represent an alkylene or hydroxyalkylene group having about 1 to 4 carbon atoms, R 4 represents an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms , and X is C or S = 0. The alkyl group may contain one or more intermediate bonds, such as amido, ether or polyether bonds or non-functional substituents, such as hydroxyl or halogen, which do not appreciably affect the hydrophobic character of the group. When X is C, the detergent is denoted a betaine, and when X is S = 0, the detergent is denoted a sulfobetaine or sultain.

Cationic substances can also be used. These consist of surfactant detergent compounds containing an organic hydrophobic group which forms part of a cation when the compound is dissolved in water, and an anionic group. Typical cationic substances are amine and quaternary ammonium compounds.

Examples of suitable synthetic cationic detergents are: common primary amines of the formula RNH 2, in which R represents an alkyl group having about 12 to 15 carbon atoms; diamines of the formula RNHC2H4NH2, in which R represents an alkyl group having between 12 and 22 carbon atoms, such as N-2-aminoethyl-stearylamine and N-2-aminoethyl-myristylamine; - amide-linked amines such as those of the formula R1CONHC2H4NH2 R 1 represents an alkyl group having about 8 to 20 carbon atoms, such as N-2-amino-ethyl-stearylamide and N-amino-ethylmyristylamide; quaternary ammonium compounds in which typically one of the groups attached to the nitrogen atom is an alkyl group having about 8 to 22 carbon atoms and three of the groups attached to the nitrogen atom are alkyl groups containing 1 to 3 carbon atoms, including alkyl groups having inert substituents such as phenyl groups, in which there is an anion such as halogen, acetate, methyl sulphate, etc. The alkyl groups may contain intermediate bonds such as amide, which do not substantially affect the hydrophobic character of the group, for example quaternary stearylamidopropylammonium chloride. Typical quaternary ammonium detergents are ethyl dimethyl-stearyl-ammonium chloride, benzyl-dimethyl-stearyl-ammonium chloride, trimethyl-stearyl-ammonium chloride, trimethyl-ethyl-ammonium bromide, dimethyl-ethyl-lauryl-ammonium chloride, di-15 -propyl-myristyl-ammonium chloride and the corresponding methosulfates and acetates.

Ampholytic detergents are also useful according to the invention. Ampholytic detergents are well known in the art and many useful detergents of this class are described by A. M. Schwartz, J. W. Perry and J. Birch in "Surface Active Agents and Detergents", Interscience Publishers, New York, 1958, vol. Examples of suitable amphoteric detergents are alkyl beta-iminodipropionates, RN (C 2 H 4 COOM) 2; alkyl beta-aminopropionates, RN (H) C 2 H 4 COOM; and long chain imidazole derivatives of the general formula / CH 2 N 2 CH 2] in 2 R c N-c fi zcnzoc fi zcomom on CH 2 CoOM wherein in each of the above formulas R represents an acyclic hydrophobic group having between about 8 and 18 carbon atoms, and M is a cation that neutralizes the charge of the anion. Particularly suitable amphoteric detergents are the disodium salt of undecylcycloimidinium ethoxyethionic acid 2-ethionic acid, dodecyl beta-alanine and the inner salt of 2-trimethylamino-lauric acid.

The bleaching detergent composition of the invention may optionally contain a detergent salt of the type generally used in detergent compositions. Useful detergent compounds are the conventional inorganic water-soluble detergent salts, such as, for example, water-soluble salts of phosphates. pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates and the like. Organic laxatives are water-soluble phosphonates, polyphosphonates, polyhydroxyisulfonates, polyacetates, carboxylates, polycarboxylates, succinates and the like.

Particular examples of inorganic detergent phosphates are sodium and potassium tripolyphosphate, pyrophosphate and hexametaphosphate. The organic polyphosphonates especially include, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,2,2-triphosphonic acid. Examples of these and other phosphorus-containing detergent compounds are given in U.S. Pat. Nos. 3,213,030, 3,422,021, 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are especially preferred water-soluble inorganic detergent salts.

Particular examples of non-phosphorus inorganic detergent compounds are water-soluble inorganic carbonate, bicarbonate and silicate salts. Alkali metals, such as sodium and potassium, carbonates, bicarbonates and silicates are particularly suitable here.

Water-soluble organic detergent compounds are also useful. Thus, for example, alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are suitable detergent compositions for the compositions and process of the invention. Particular examples of detergent polyacetate and polycarboxylate compounds are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, 459,975 l of nitrilotriacetic acid. benzene poly (i.e. penta- and tetra-) carboxylic acids, carboxymethoxy succinic acid and citric acid. Also water-insoluble detergent compounds can be used, especially complex silicates and in particular complex sodium aluminum silicates such as zeolites, e.g. zeolite 4A, which is a type of zeolite molecule in which the monovalent cation is sodium and in which the pore size is about 4 Angstroms¿ The preparation of this type of zeolite is described in U.S. Pat. No. 3,114,603. The zeolites may be amorphous or crystalline and contain hydrating water in a manner known in the art.

The detergent compositions of the invention may advantageously contain an inert, water-soluble filler salt. A preferred filler salt is alkali metal sulfate, such as potassium or sodium sulfate, the latter being particularly preferred.

Various adjuvants may be included in the bleaching detergent compositions of the invention. These generally include perfumes; dyes, e.g. pigments and dyes; anti-precipitating agents, such as alkali metal salts of carboxymethylcellulose; optical brighteners, such as anionic, cationic or nonionic brighteners; foam stabilizers, such as alkanolamides, and the like, all of which are well known for use in laundry detergent compositions.

Flow enhancers, commonly referred to as "flow aids", may also be used to maintain the particulate bleaching detergent composition in the form of free-flowing granules or powders.The starch derivatives and special clays are commercially available as additives which improve the flowability of pairs. tick-like compositions which are otherwise sticky or doughy, and two such clay additives are currently sold under the trade names "Satintone" and "Microsil".

The bleaching detergent compositions according to the invention are particulate compositions which can be prepared by methods involving spray drying as well as by dry mixing or agglomeration of the individual constituents. The compositions are preferably prepared by spray drying an aqueous slurry of the non-heat sensitive components including the bromide salt, and forming spray dried particles, after which these particles are mixed with heat sensitive components such as the MPPA bleach and the aromatic sulfonamide compound if it is not sufficiently stable. (usually if the loss due to decomposition is greater than 20%), and with adjuvants such as perfume and enzymes. The mixing is suitably carried out in a device of the rotating drum type. If desired, the MPPA bleach and / or bromide salt can be encapsulated or otherwise stabilized to prevent premature reaction. Suitable coating materials include compounds such as magnesium sulfate, polyvinyl alcohol and lauric acid and its salts.

An especially preferred bleaching detergent composition of the invention comprises: (a) from about 5 to 50% by weight of bleaching composition consisting essentially of (i) monoperoxyphthalic acid and / or a water-soluble salt thereof; (ii) a water-soluble inorganic bromide salt; and (iii) an aromatic sulfonamide compound selected from benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, N-alkali metal salts of these sulfonamides and mixtures thereof, wherein the weight ratio of (i) is from (8) to (8) : 1 to about 1: 2, and the ratio of (iii) to (ii) is from about 2: 1 to about 1: 4: (b) from about 5 to about 30% by weight of a cleaning surfactant selected among anionic and nonionic detergents and mixtures thereof; (C) from about 10% to about 60% by weight of a laxative salt; and (d) the balance water and, if desired, a filler salt.

Example 1 Test Method Bleaching experiments were performed with a standard sample patch: for stain testing (described below), using the various bleach and detergent compositions described in Table 1 of this example in a Tergotometer vessel made by U.S. Pat. Testing Company. The tergotometer was maintained at a constant temperature of 49 ° C and operated at a speed of 100 rpm.

Each of the test compositions described in Table 1 was added to 1 liter of tap water at 49 DEG C. with a water hardness of about 100 ppm, as calcium carbonate. The test compositions were stirred for about 1 minute, after which different fabrics each consisting of two test pieces (76.2 x 101.6 mm) of the stained fabrics, described below, were added to each wash container. After washing for 15 minutes at 49 ° C, the fabric samples were rinsed in tap water at a temperature of 380 ° C, after which they were dried. The percentage stain removal was measured by determining the reflectance factor for each stained cloth patch before and after washing using a Gardner 459 UT 975 Color Difference Meter, and the percentage stain removal (% SR) was calculated as follows: (Rd after washing) - (Rd before washing)% SR = _ X l00 (Rd before staining) - (Rd before washing) 'where "Rd before washing" refers to the Rd value after staining.

Based on the percentage values obtained for the stain removal for all five test fabrics, the average value for each detergent composition tested was calculated. A difference greater than 2% of the mean value of the five stained test fabrics was considered significant.

At the end of each wash procedure, the active oxygen content of the wash solution was determined by acidifying it with dilute sulfuric acid, after which the wash solution was treated with potassium iodide and a small amount of ammonium molybdate and then titrated with a standard sodium thiosulfate solution using starch.

The respective stains and test fabric samples were as follows: Stain Test l. Grape 65 dakron - 35 cotton 2. blueberry cotton EMPA ll5 (cotton) iEMPA 114 (cotton) cotton 3. sulfo color 4. red wine. coffee / tea The stained test fabrics 1 and 2 were obtained by passing rolls of non-stained fabric through a surface-dyeing and drying device (manufactured by Benz of 459 973 21 Zurich, Switzerland) containing either grape or blueberry solutions at a temperature of 329 C. After drying at 21 ° C, the fabric was cut into pieces measuring 76.2 x 101.6 mm. Eighty such cloth patches, impregnated with the same type of stain, were rinsed in 64.3 liters of water at a temperature of 290 C in an automatic household washing machine. These were then dried by passing them through a Beseler Print Dryer at a setting of the machine temperature of 6 and the speed of 10.

The stained test fabrics 3 and 4 were obtained from Test Fabrics Incorporated of Middlesex, New Jersey, and were cut into 76.2 x 101.6 mm pieces.

The stained test cloth 5 was obtained by soaking non-soiled cotton strips (457.2 x 914.4 mm) while stirring in a washing machine filled with a solution of coffee / tea (a folding raw material) at s5, s ° c.

This was followed by rinsing and centrifugal drying in the machine to remove the coffee / tea solution. The stained fabric was then machine washed twice with hot surfactant pyrophosphate solution followed by two complete wash cycles in water at 600 DEG C. Then the strips were dried by passing twice through an Ironrite machine set at 10, and cut into test pieces. with a size of 76.2 x 101.6 mm.

A granular detergent composition (herein referred to as "HDD") was prepared by conventional spray drying, which had the following approximate composition: 459 973 22 Composition sodium tridecylbenzenesulfonate ethoxylated.Cl 2 -C 15 primary alcohol (7 mol EO / mol alcohol) sodium tripolyphosphate sodium carbonate sodium watercarbonate sodium carbonate % by weight 33 II OCDOQLH NNLVI In the remaining detergent compositions A - G containing HDD had the composition shown in Table 1. The pH values of aqueous solutions of the compositions varied between 9.2 and 9.7. 459 975 23 uw flfi wzmcc fl Hwww fl cmßwøs> fl uxm Eom cwxH fl> mo ~ O No ~ o I I> o_ ° ~ o «o> o.o | o «~ oo« _o Q «. @ 1 mQm.« mom_ <m @ m. «m @ m_« M mm _m co fl u fl momëøx mo \ o> oQ m «.o mom.q U> ø.om« .o mom . «Ma Hawßm fifl wšmzow fifl mcmø fl oulmumm Awv wuæm u> fl» xm w ~ .m Hw fifl m fl w fififl S00 um ~: J @ ~ xOuwm0COEE5HmwnmmE æ | #M fl> mm mc fl hxñü co fl v am mom m. Hwm | mz Dam ~ ucmmHwuwU MCÜQONEOM 459 973 24 Compositions A - G were tested according to the procedure described above, and the results of the bleaching experiments are summarized in Table 2, which shows the stain removal obtained with compositions A - G for each of the five spot types.

Table 2 Relative bleaching ability (% SR) stain fabric composition ê ä EQEE å grape 63% 65% 75% 37% 62% 67% 68% blueberries 63 64 68 41 62 65 67 sulfo color 4 5 7 3 3 5 6 red wine 47 46 56 33 44 48 48 coffee / tea 32 41 61 5 32 51 52 mean value {%) 42 44 53 24 41 47 48 The results in table 2 show that you get a markedly improved bleaching ability with compositions containing MPPA bleach in combination with sodium bromide and TSA compared to compositions containing only MPPA bleach (in the absence of bromide and TSA) or MPPA and sodium bromide. Compositions C, F and G according to the invention gave an improvement in the average stain removal of from 6 to 9% (depending on the particular composition) compared to the corresponding compositions B and E, both of which contain MPPA bleach in combination with sodium bromide, but no TSA. A comparison between composition C according to the invention and composition A which contains only MPPA (in the absence of bromide and TSA) shows an improvement of the average stain removal 459 973 of 11% (53% and 42%, respectively) compared to the bleaching obtained with a known composition.

Example 2 The bleaching experiments described in Example 1 were carried out with the detergent compositions described in Table 3 below. The stained test fabrics used were essentially the same as in Example 1.

The detergent compositions H - K were formulated as shown in Table 3 below, and the composition of the detergent (HDD) is described in Example 1. The aqueous solutions of the compositions had pH values varying between 8.2 and 8.6.

Table 3 Component Composition E 1 J. to Detergent, HDD 1.50g 1.50g 1.50g 1.50g Mg Site of MPPAU) 0.26 0.26 0.26 0.26 NaBr - - 0.10 0, TsA (2) - 0.08 - o, os (1) Bleach composition which as active ingredient contains about 65% by weight of magnesium monoperoxyphthalate and contains 5.1% of active oxygen (2) Para-toluenesulfonamide Compositions H - K were tested in In accordance with the procedure described in Example 1, the results of the bleaching experiments are summarized in Table 4, which sets forth the percentage of stain removal obtained with compositions H - K for each of the five stain types.

Table 4 Relative bleaching ability (% SR) stain type E 2 Q § grape 75% g 76% 82% 85% blueberries \ 70 '67 75 80 sulfo color 4 3 9 8 red wine 37 36 35 46 coffee / tea 78 74 86 87 average value (%) 53 51 57 61 Data from Table 4 show the synergy obtained with composition K, which is a composition according to the invention, compared to compositions H, I and J which individually contain MPPA alone or in combination with either NaBr or TSA. The mean percentage of stain removal achieved with compositions H and I was thus largely equal (53 and 51%), and the presence of TSA was shown to have a slightly negative effect on the bleaching ability of MPPA. Composition J containing MPPA in combination with bromide gave an unexpectedly improved bleaching ability, and gave an average stain removal of 57%. Addition of TSA to a composition containing MPPA and bromide (Composition K) produced a clear synergistic effect in the sense that it gave a markedly increased bleaching ability, and gave an average stain removal of 61%.

Claims (19)

10 15 20 25 459 975 27 P a t e n t k r a v A bleach composition for household detergents, characterized in that it comprises: (a) monoperoxyphthalic acid and / or a water-soluble salt thereof; (b) a water-soluble inorganic bromide salt; and (c) an aromatic sulfonamide compound selected from benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylenesulfonamide, N-alkali metal salts of these sulfonamides, N-acetyl and N-benzoyl derivatives of the aforementioned sulfonamides and salts, salts and salts. 2. A composition according to claim 1, characterized in that the aromatic sulfonamide compound is toluenesulfonamide or an N-alkali metal salt thereof and the bromide salt is an alkali metal bromide. 3. A composition according to claim 1, characterized in that the aromatic sulfonamide compound is para-toluenesulfonamide 4. A composition according to claim 1, characterized in that it contains magnesium monoperoxyphthalate. Composition according to claim 1, characterized in that the weight ratio between (a) and (b) is from about 10: 1 to about 1: 5, and that the weight ratio between (c) and (b) is from about 5: 1 to about 1: 7. 10 15 20 25 459 973 28 Composition according to Claim 1, characterized in that it further contains one or more cleaning surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents. Bleaching detergent composition, characterized in that it comprises: (a) from about 5 to 50% by weight of a bleaching agent containing: (i) monoperoxyphthalic acid and / or a water-soluble salt thereof; (ii) a water-soluble corganic bromide salt; and (iii) an aromatic sulfonamide compound selected from benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylenesulfonamide, N-alkali metal salts of said sulfonamides, N-acetyl and N-benzoyl derivatives of sulphonides and precursors i thereof; (b) from about 5% to 50% by weight of a cleansing surfactant selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents; (c) from about 5 to 80% by weight of detergent salt; and (d) the balance water and, if desired, a filler salt. B. Composition according to claim 7, characterized in that the weight ratio between (i) and (ii) is from about 10: 1 to about 1: 9, and the weight ratio between (iii) and (ii) is from about 5: 1 to about 1: 7. 10 15 20 25 459 975 29 9. A composition according to claim 7, characterized in that the bleaching agent contains magnesium monoperoxyphthalate, that the aromatic sulfonamide compound is toluenesulfonamide or an N-alkali metal salt thereof, and that the bromide salt is an alkali metal bromide. 10. A composition according to claim 7, characterized in that the cleaning detergent is selected from anionic and nonionic detergents and mixtures thereof. 11. ll. Composition according to Claim 7, characterized in that the aromatic sulfonamide compound is para-toluenesulfonamide. 12. l2. A composition according to claim 7, characterized in that it comprises from about 5 to 30% by weight of said cleaning surfactant and from about 10 to 60% by weight of said detergent salt. A bleaching process, characterized in that the colored and / or soiled material to be bleached is contacted with an aqueous solution of a composition comprising: (a monoperoxyphthalic acid and / or a water-soluble salt thereof; (b) a water-soluble inorganic bromide salt, and '(c) an aromatic sulfonamide compound selected from benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylenesulfonamide, N-alkali metal salts of said sulfonamides, N-acetyl and N-benzoyls. sulfonamides and salts, and mixtures thereof, the weight ratio of (a) to (b) being from about 10: 1 to about 1: 5, and the weight ratio of (c) to (b) being from about 5: 1 to about 1: 7. A method according to claim 13, characterized in that said composition further contains one or more cleaning surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents. A method according to claim 14, characterized in that said composition together comprises from about 5 to 50% by weight of the components (a), (b) and (c); from about 5 to 50% by weight of said cleaning surfactant, and said composition further contains a detergent salt in an amount of from about 5 to 80% by weight, and the remainder of the composition is water and, if so. desired, a filler salt. 16. l6. A process according to claim 13, characterized in that said aromatic sulfonamide compound is toluenesulfonamide or an N-alkali metal salt thereof. 17. l7. A process according to claim 13, characterized in that said composition contains magnesium monoperoxyphthalate. 18. A process according to claim 13, characterized in that said bromide salt is an alkali metal bromide. 459 975 31 The method of claim 13, characterized in that the weight ratio of (a) to (b) is from about 8: 1 to about 1: 2, and the weight ratio of (c) to (b) is from about 2: 1 to about 1: 4.