NL8400161A - WASHING PREPARATION AT LOW TEMPERATURE. - Google Patents

Description

* '............ ^ VO 6020

Washing composition bleaching at low temperature.

The invention relates to bleaching and washing compositions and their use in washing. More specifically, the invention relates to bleaching and washing compositions which have been found to be effective even at low washing temperatures,

Bleaching compositions that release active oxygen in wash solutions have been extensively described and are widely used in washing. Generally, such bleaching compositions contain peroxygen compounds, such as perborates, percarbonates, perfosphates, and the like, which aid the bleaching process by forming hydrogen peroxide in aqueous solution. A major drawback of these types of peroxygen compounds is that they are not optimally effective at the relatively low washing temperatures used in most household washing machines, i.e. at temperatures between 26 and 76 ° C. This is especially true for the United States, as Europe tends to wash at higher temperatures, although there too the trend is toward 15 lower wash temperatures.

Peroxyacid compounds have been used to improve the bleaching effect at low washing temperatures. Organic peroxyacids are usually considered to be more active bleaching agents than hydrogen peroxide at lower temperatures, but the use of peroxygen bleaching is usually considered unsatisfactory for removing stains at temperatures below about 60 ° C. Therefore, bleaching with peroxyacids is usually done by forming the peroxyacid in situ in the wash solution or adding pre-formed peroxyacid compounds to the wash solution. The use of activator materials in combination with peroxygen compounds has been extensively described in the patent literature and is the common approach for forming peroxyacid compounds in the wash solution, involving the reaction of the activator, usually a carboxylic acid derivative, with a peroxygen compound and peroxyacid, usually peracetic acid. Of the compounds which have been proposed as activators for peroxygen bleaching, also carboxylic anhydride are 8400161 * * V? 2 - As disclosed in U.S. Pat. Nos. 3,298,775 and 3,338,839, carboxylic acid esters as disclosed in U.S. Patent 2,995,905 and N-acyl compounds disclosed in U.S. Pat. Nos. 3,912,648 and 3,919,102. Bleaching compositions containing a preformed peroxyacid compound are also common, examples of which may be cited are U.S. Pat. Nos. 4,170,453 and 4,259,920.

The bleaching effect of compositions containing a peroxyacid compound can be further enhanced at low temperatures, especially at temperatures of 40 ° C or less, by adding bromide ions to the bleaching compositions. For example, e.g. U.S. Pat. No. 4,338,210 again a bleaching system intended for temperatures of 40 ° C and below, the bleaching system containing a peroxide precursor such as dipthaloyl peroxide, and sodium bromide. The bromide 15 was believed to react with the peroxyacid to form a hypobromite compound, the latter being more effective in low temperature bleaching than the peroxyacid compound. European patent application 24 367 published on March 4, 1981 describes a low temperature bleaching system with an organic peroxyacid, such as diperisophthalic acid or monoperoxyphthalic acid in combination with bromide ions. U.S. Pat. Nos. 4,123,376 and 4,300,897 disclose bleaching compositions containing a peroxymonosulfate bleach, an inorganic bromide salt, and an aromatic sulfonamide, such as an al potassium metal toluenesulfonamide. The function of this aromatic sulfonamide in this type of bleaching composition is, according to the authors, to avoid the over-bleaching of dyed materials and further the control and control of the bleaching activity. of the combination of peroxymonosulfate and bromide in an aqueous medium.

The invention now relates to bleaching compositions comprising: (a) monoperoxyphthalic acid (hereinafter referred to as MPPA) and / or a water-soluble salt thereof; (b) a water-soluble inorganic bromide salt; and (c) an aromatic sulfonamide compound in the form of benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, N-alkali metal salts of these sulfonamides, N-acetyl and N-benzoyl derivatives of these sulfonamides and salts mixtures thereof. The weight ratio, from MPPA (or its salt) 8400161-3 / * to the bromide salt in the composition is between about 10: 1 and about

1: 5, preferably between 8: 1 and 1: 2, most preferably between 6: 1 and about t: 1. The weight ratio of aromatic sulfonamide compound to bromide salt in the composition is between about 5: 1 and 1: 7, most preferably 5 between 2: 1 and 1: 4.

The bleaching detergent composition of the invention contains the bleaching material shown above in combination with one or more surfactants and a conventional builder salt. According to the invention, stained and / or dirty materials are bleached by contacting this material and contacting it with an aqueous solution of the above compositions.

The invention is based on the discovery that the low temperature bleaching activity of preparations containing MPPA and bromide can be markedly improved by adding an aromatic sulfone-amide compound to such preparations. Unlike the compositions of U.S. Pat. Nos. 4,123,376 and 4,300,897, in which the aromatic sulfonamide compounds are to inhibit the activity of bromide-activated peroxymonosulfates for improved safety of dyes and whiteners in the wash solution, the addition of the aromatic sulfonamide compounds has in the present compositions the beneficial effect is that the bleaching composition is markedly improved in activity.

Monoperoxyphthalic acid and / or one or more of its water-soluble salts are the main bleaching agents in the present compositions and bleaching detergents of the invention. Although MPPA exhibits an acceptable bleaching activity, it has the drawback of relatively poor storage stability mixed with other compounds commonly present in household laundry detergent compositions. Hence, for better stability, the magnesium salt of MPPA is preferred in the present compositions, especially the magnesium monoperoxy phthalate. This magnesium monoperoxyphthalate is preferably used in the form of a composition with about 65¾ of the magnesium MPPA salt as the active ingredient and an active oxygen content of about 5 to 6¾. The alkali metal, calcium, barium and / or ammonium salts of 35 MPPA can also be used in the bleaching and washing compositions herein, 8400161 4% -4, although, due to their stability, these salts are less preferred than the magnesium salt .

The production of. MPPA is usually performed by a reaction of hydrogen peroxide with phthalic anhydride. The MPPA obtained thereby can be used for the production of magnesium monoperoxyphthalate by reaction with a magnesium compound in the presence of an organic solvent. A detailed description of the production of MPPA and its magnesium salt is provided on pages 7-10 of European Patent Publication 27 693, published April 29, 1981.

The MPPA bleach (or its salt) can be optionally combined with a conventional peroxygen bleaching compound and an activator therefor. Examples of suitable peroxygen compounds include potassium metal perborates, percarbonates, perfosphates and the like, with sodium perborate being preferred because of its technical availability. Conventional activators such as e.g. described in column 4 of U.S. Patent 4,259,200 are suitable for use in combination with such a peroxy compound. The polyacylated amines are usually of great interest, with TAED being a preferred activator. Other suitable activators include anhydride compounds, such as benzoic, maleic, succinic and phthalic anhydride, as well as acyl compounds, such as N-acetyl and N-benzoylimidazole. Generally, the molar ratio of peroxygen compound to activator will vary widely depending on the specific choice of peroxy compound and activator. Usually, however, molar ratios between about 0.5: 1 and about 25: 1 are suitable for satisfactory bleaching behavior.

The water-soluble bromide salt to be used is preferably an al-potassium bromide, such as potassium or sodium bromide, the latter being especially preferred because of its good availability and low price.

The aromatic sulfonamides used in the present compositions include the above sulfonamides, N-acetyl and N-benzoyl derivatives thereof, such as N-acetyl-paratoluenesulfonamide, N-acetylbenzenesulfonamide and N-benzoylbenzenesulfonamide as well as the 8400161-5 N-alkali metal salts thereof. Preferred compounds include sodium and potassium p-toluenesulfonamide; o-toluenesulfonamide, benzenesulfonamide and the corresponding al potassium metal salts thereof. The alkali metal toluene sulfonamides are most preferred in the invention.

The amount of bleaching composition added to a wash solution is usually so sized, in terms of the peroxyacid compound, that 3 to 100 parts of active oxygen per million parts of wash solution are obtained, with a concentration between 5 and 40 ppm usually being preferred.

The present bleaching compositions with MPPA and / or a water-soluble salt thereof, an inorganic bromide salt and an aromatic sulfonamide can be used as a separate bleaching product or used in a builder-containing detergent solution. Thus, the present bleaching composition may also contain conventional additives used in washing textiles, such as binders, fillers, builder salts, proteolytic enzymes, optical brighteners, perfumes, dyes, corrosion inhibitors, anti-redeposition agents, foam stabilizers, and the like. can be added in varying amounts depending on the desired properties of the bleaching composition and their compatibility with such a composition. In addition, the bleaching composition of the invention can be incorporated into detergent compositions containing one or more surfactants in the form of anionic, cationic, nonionic, ampholytic and zwitterionic detergents.

When the present bleaching compositions are incorporated in a conventional detergent composition and thus a completely bleaching detergent composition is obtained, the latter compositions will usually contain the following ingredients: about 5 - 50% by weight of the present bleaching composition, about 5 - 50, most preferably 5-30 wt% surfactant mid-30 parts and 5 - 80, most preferably 10 - 60 wt% of a builder salt, which can also act as a buffer to achieve the desired pH in water.

The aqueous wash solutions have a pH between about 7 and 12, preferably between 8 and 10, and most preferably between 8 S 9. A preferred amount of the builder salt is between 20 and 65% by weight of the whole composition. The remainder of the preparation consists mainly of water, fill with medium salts, such as sodium sulfate and various auxiliaries described below.

The present compositions contain one or more surfactants in the form of anionic, nonionic, cationic, ampholytic or zwitterionic detergents. The synthetic organic detergents which can be used in the invention may be among the long range of compounds which e.g. are described in Service Active Agents, Part II, of Schwartz, Perry and Berch, published in 1958 by Interscience Publishers.

TO The detergent compositions herein usually contain as main detergent one or more anionic detergents, which may be supplemented or replaced by nonionic detergents if desired.

Among the anionic detergents which can be used in the invention may be mentioned the surfactants having a hydrophobic group of 8-26, preferably 10-18 carbon atoms and a water solubilizing group in the form of a sulfonate, sulfate, carboxylate, phosphonate or sulfate group. Examples of suitable anionic detergents include the soaps, such as the water-soluble salts (e.g., sodium, potassium, ammonium and alkanolamine salts) of 2 O higher fatty acids and resin salts with 8-20 carbon atoms, most preferably 10-18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, e.g. 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 oil, e.g. sodium coconut soap and potassium tallow soap.

The anionic class of the detergents also includes the water-soluble sulfated and sulfonated detergents having an alkyl group having 8-26, preferably 12-22 carbon atoms (The term "alkyl" here includes the alkyl moiety of the higher acyl groups.) Examples of sulfonated anionic detergents, the higher alkyl mononuclear aromatic sulfonates, such as the higher alkyl benzene sulfonates having 10-16 carbon atoms in the straight or branched chain alkyl group, eg sodium, potassium and ammonium salts of alkyl benzene sulfonates, alkyl toluene sulfonates and alkyl phenol sulfonates.

Other suitable anionic detergents are the olefin sulfonates, including the long chain olefin sulfonates, long chain hydroxyalkane sulfonates or mixtures of olefin sulfonates and hydroxyalkane sulfonates. The olefin sulfonate detergents can be prepared in a conventional manner by reacting SO 2 with a long chain-5 olefin with 8 to 25, preferably 12 to 21, carbon atoms, such as olefins of the formula RCH = CHR. J, wherein R is an alkyl group with 6-23 carbon atoms, and R 1 represents an alkyl group of 1 to 17 carbon atoms or hydrogen, thereby forming a mixture of sulfones and olefin sulfonic acids which is then treated to convert the sulfones into sulfonates. Other examples of sulfate or sulfonate detergents are paraffin sulfonates with 10-20, most preferably 15-20 carbon atoms,

The primary paraffin sulfonates are prepared by reacting long chain C-olefins with bisulfites. Paraffin sulfonates with sulfonate groups along the paraffin chain are shown in U.S. Patent Nos. 2,503,280, 2,507,088, 3,260,741, and 3,372,188, as well as German Patent 735,096.

Other suitable anionic detergents are sulfated ethoxylated higher fatty alcohols of the formula R0 ^ H ^ O ^ SO ^ M, where R is a fatty alkyl group having 10-18 carbon atoms, m 2-6 (most preferably ca.

1/5 to 1/2 of the number of carbon atoms in R) and M represent a solubilizing salt-forming cation, such as an alkali metal, ammonium, alkylamino or alkanolamino, or an alkyl benzene sulfonate having an alkyl group of 10-15 carbon atoms. The amount of ethylene oxide in the polyethoxylated higher alkanol sulfate is preferably 2-5 moles of ethylene oxide groups per mole of anionic detergent, most preferably 3 moles, especially when the higher alkanol has 11-15 carbon atoms.

In order to maintain the desired hydrophilic-lipophilic balance, when the number of carbon atoms in the alkyl chain is at the lower limit of 10-18, the ethylene oxide content of the detergent must then be reduced to about 2 moles per mole, while at higher alkanols with 16-18 carbon atoms the number of ethylene oxide groups can be increased to 4 or 5 and in some cases even to 8 or 9. Also, the salt-forming cation can be modified to obtain the best solubility.

This cation can be any suitable solubilizing metal or group, but usually an alkali metal is used, e.g. sodium or ammonium. In- 8400161

* V

When lower alkyl amine or alkanolamine groups are used, the alkyl and alkano groups usually have 1 to 4 carbon atoms and the amines or alkanolamines are mono-, di- or tri-substituted, such as monoethanolamine, di-sopropanolamine and trimethyl amine .

A preferred polyethoxylated alcohol sulfate detergent is sold by Shell Chemical Company under the name of Neodol 25-3S.

The most preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, di- and triethanolamine), alkali metal (such as sodium 10 and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkyl benzene sulfonates, olefin sulfonates and higher alkyl sulfates. Of these anionics, the most preferred are sodium linear alkyl benzene sulfonates (LABS), especially those having a straight alkyl group having 12-13 carbon atoms.

The nonionic synthetic organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and are usually produced by condensation of a hydrophobic aliphatic or alkyl aromatic compound with ethylene oxide (hydrophilic). In practice, any hydrophobic compound with a carboxyl, hydroxyl, amido, or amino group with a free hydrogen atom on the nitrogen can be condensed with ethylene oxide or with a polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be precisely controlled to achieve the desired balance between hydrophobic and hydrophilic groups.

The most preferred nonionic detergents are polyalkoxylated higher alkanols, with the al canoe Has 10-18 carbon atoms and the number of alkylene oxide units (2 or 3 carbon atoms) is 3-12. Of these materials are preferred, with the higher already canoe! is a higher fatty alcohol with 11-15 carbon atoms containing 5-9 alkoxy groups per mole. Preferably, the alkoxy group is the ethoxy group, but in some cases it may be desirable to mix it with the propoxy group, in which case the latter is usually in the minority. Examples of this kind of compounds are those in which the alkanol has 12-15 carbon atoms 8400161 * * - 9 - and contains 7 ethylene oxide groups per mole, e.g. Neodol 25-7 or Neodol 23-6.5, which products are manufactured by Shell Chemical Company.

The first is a condensation product of a mixture of higher fatty alcohols with an average of 12-15 carbon atoms, and with about 7 moles of ethylene-5 oxide, and the latter a corresponding mixture where the number of carbon atoms in the fatty alcohol is 12-13 and the number of ethyleneoxy groups per mole averages 6.5. The higher alcohols are primary alkanols. Other examples of these detergents include Teritol 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol-10 ethoxylates from Union Carbide Corporation. The former is a mixed ethoxylation product of a linear secondary alkanol with 11-15 carbon atoms and 7 moles of ethylene oxide and the latter a corresponding product with 9 moles of ethylene oxide.

The higher molecular nonionics are also useful in the invention, such as Neodol 45-11, a corresponding ethylene oxide condensation product of a higher fatty alcohol, wherein the fatty alcohol has 14-15 carbon atoms and the number of ethylene oxide groups per mole is about 11. These types of products are manufactured by Shell Chemical Company.

Zwitterion detergents, such as the betaines and sulfobetas, correspond to the formula 1 of the formula sheet, and are also useful. In this formula, R is an alkyl group with 8-18 carbon atoms,

Rg and Rl are alkyl one or hydroxyalkylene groups with 1 to 4 carbon atoms, Rg is an alkylene or hydroxyalkylene group with 1 to 4 carbon atoms and X is C or S: 0. The alkyl group may contain one or more intermediates such as amido, ether or polyether groups or non-functional substituents, such as hydroxyl or halogen, which do not significantly affect the hydrophobic character of the group. When X = C ,. if the detergent is a betaTne, if X = S: 0, then the detergent is a sulfobetane 30 or sultane.

Cationic surfactants can also be used. These include surfactants with a hydrophobic organic group as part of the cation when the compound is dissolved in water, along with an anion group. Characteristic cationic surfactants are amine and quater 8400161

. V

- 10 - / Na ammonium compounds.

Examples of suitable synthetic cationic detergents include: normal primary amines of the formula RNl · ^, where R is an alkyl group with 12-15 carbon atoms, diamines of the formula RNHCgH ^ Nl · ^, where R is an alkyl group with 12- Carbon atoms, such as N-2-aminoethyl-stearylamine and N-2-aminoethyl-myristylamine, are amide-bonded amines, such as those of the formula R 1 CONF 1 H 1 N 1 2, where R 1 1 is an alkyl group with 8-20 carbon atoms such as N-2-aminoethyl stearylamide and N-aminoethyl myristylamide; further quaternary ammonium-10 compounds, wherein one of the groups bonded to the nitrogen atom is an alkyl group of 8-22 carbon atoms, and three of the groups bonded to the nitrogen atom are alkyl groups of 1 to 3 carbon atoms including alkyl groups with inert substituents grafts, such as phenyl groups, and in addition an anion in the form of a halogen, acetate or methosulfate anion. The alkyl group may contain intermediate groups, such as amide groups, which do not significantly affect the hydrophobic character of the group, e.g. stearylamidopropyl quaternary ammonium chloride. Typical quaternary ammonium detergents are ethyl dimethyl stearyl ammonium chloride, benzyl dimethyl stearyl -20 ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl cetyl ammonium bromide, dimethyl ethyl lauryl ammonium chloride, dimethyl propyl myristyl ammonium chloride and the corresponding methosulfates and acetates.

Ampholytic detergents are also useful in the invention. Ampholytic detergents are well known and described by Schwartz, Perry and Birch in "Surface Active Agents and Detergents", Interscience Publishers, New York, 1958, part 2. Examples of suitable amphoteric detergents include: alkylbetaquinodipropionates, RN ^ H ^ COOM ^ ; alkyl beta aminopropionates, RNiH 2 H 2 COOM; and long-chain-shaped imidazole derivatives of the formula II of the formula sheet, wherein each of the groups R represents an acyclic hydrophobic group having 8-18 carbon atoms and M a cation to neutralize the anion. Specifically suitable amphoteric detergents include the disodium salt of undecylcycloimidium ethoxyethionic acid 2-ethionic acid, dodecyl beta-35 alanine, and the inner salt of 2-trimethylamino lauric acid.

8400161 4Γ '' ..- 11 -

The present bleaching compositions further contain a detergent builder of the type commonly used in detergent compositions. Suitable builders include any of the conventional inorganic water-soluble builder salts, such as the water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates and the like. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylates, succinates and the like.

Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphate, pyrophosphate and hexametaphosphate. The organic polyphosphonates especially include, e.g. the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of these and other phosphorus builder compounds are shown in U.S. Patent Nos. 3,213,030, 3,422,021, 3,422,137, and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are the preferred water-soluble inorganic builders.

Specific examples of non-phosphorus inorganic builders include the water-soluble inorganic carbonates, bicarbonates and silicate salts. Hetalkali metal, e.g. sodium and potassium carbonates, bicarbonates and silicates are the most practical in this case.

Water-soluble organic builders are also applicable.

E.g. the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are particularly useful builders for the compositions and method of the invention. Specific examples of polyacetate and polycarboxylate builders include the sodium, potassium, lithium, and ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, benzene polycarbonate (tw penta and tetra) acids, carboxy methoxy succinic acid, and citric acid .

Water-insoluble builders can also be used, especially the complex silicates and more particularly the complex sodium aluminosilicates, such as zeolites, e.g. zeolite 4A, a type of zeolite molecule, in which the univalent cation is sodium and the pore size is approx. 4 8. The preparation of this type of zeolite is described in 84 00 1 6 1 - 12 -

U.S. Patent No. 3,114,603. These zeolites can be amorphous or crystalline and contain water of hydration, as is otherwise known.

The use of an inert water-soluble filler salt is desirable in the washing compositions of the invention. A preferred filler salt is an al potassium metal sulfate, such as potassium or sodium sulfate, the latter being especially preferred.

Various adjuvants can also be incorporated into the present bleaching wash compositions. Generally, these excipients include perfumes, dyes such as pigments and soluble dyes, anti-redeposition agents such as al potassium salts of carboxymethyl cellulose; optical brighteners, such as anionic, cationic or nonionic brighteners; foam stabilizers, such as al-canamides and the like, all of which are otherwise well known in laundry detergent compositions. The flow promoters, commonly referred to as flow aids, may also be added to give the present bleaching detergents the form of free-flowing granules or powders. Starch derivatives and special clays are commonly used as additives that improve the flow properties of otherwise tacky or pasty particulate preparations, two of these clay additives are commercially available under the names "Satintone" and "Microsil".

The detergent bleaches herein are particulate preparations which can be prepared by spray drying as well as by dry mixing or agglomerating the individual components. These compositions are preferably prepared by spray drying an aqueous suspension of the non-heat sensitive components including the bromide salt to obtain spray dried particles, followed by admixture of the heat sensitive components such as the MPPA bleach and the aromatic sulfonamide compound, if it is not sufficiently stable (usually if the decomposition loss is more than 20%), and auxiliary agents such as the perfume and enzymes. Mixing usually takes place in an equipment such as a rotary drum. If desired, the MPPA bleach and / or the bromide salt can be capsules or otherwise stabilized against premature reactions. Suitable coating materials include compounds, such as magnesium sulfate, polyvinyl alcohol and lauric acid or its salts, such as magnesium sulfate, 8400161-13.

A particularly favorable bleaching detergent composition according to the invention comprises: (a) 5 - 50% by weight of a bleaching composition consisting of mainly (1) monoperoxyphthalic acid and / or a water-soluble salt thereof; (2) a water-soluble inorganic bromide salt; and (3) an aromatic sulfonamide compound in the form of benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, the N-alkali metal salts or mixtures thereof, the weight ratio of 1 to 2 being between 8: 1 and 1: 2 and the weight ratio of 3 to 2 is between 2: 1 and 1: 4; (b) 5-30 wt. 56 of a detergent surfactant in the form of an anionic or nonionic detergent or mixtures thereof; (c) 10-60 wt. 56 of a detergent builder salt and (d) the residue: 15 water and optionally a filler salt.

Example 1 Investigation procedure.

Bleaching tests were performed on standard stained sample patches (described below) using the various bleaching and washing compositions described in Table A of this example in a Tergoto meter holder of the U.S. Testing Company. This tergotometer was kept constant at a temperature of 49 ° C while operating at 100 rpm.

Each of the test preparations according to Table A was added to 1 dm3 tap water at 49 ° C with a water hardness of about 100 ppm, calculated as calcium carbonate. The test preparations were stirred for about 1 minute and then a mixed fabric, consisting of two patches of 76 x 102 mm each, of the soiled fabrics described below was added to each wash container. After washing at 49 ° C for 15 minutes, the 30 samples were washed with 37 ° C tap water and then dried.

The degree of stain removal was measured by measuring the refraction reading for each soiled sample patch vddr and after washing with a Gardner Color Difference Meter and calculating the percentage stain removal (56 SR) as follows: 8400161 - 14 -% SR = after washing ) - (Rd before washing) χ 1Qq (Rd before soiling) - (Rd before washing) where "Rd before washing" represents the Rd value after soiling.

5 The value for the percentage of stain removal calculated for all five rags was averaged for each test wash composition. A difference greater than 2% in the average for the five stained patches is considered significant.

After each wash, the active oxygen content of the wash solution was determined by acidification with dilute sulfuric acid followed by treatment of the wash solution with potassium iodide and a minor amount of ammonium molybdate, followed by titration with standardized sodium thiosulfate using starch as an indicator.

15 The respective spots and test patches were the following:

Stain Textile type 1. grapes - 65 dacron - 35J cotton 2. blueberry - cotton 3. sulfo dye - EMPA 115 (cotton) 20 4. red wine - EMPA 114 (cotton) 5. coffee / tea - cotton

Stained samples 1 and 2 were obtained by passing rolls of soiled fabric through an impregnation and drying equipment from Benz of Zurich with grape or blueberry solutions at 32 ° C. After drying at 120 ° C, the fabric was cut into 76 x 102 mm patches. 80 of these patches, impregnated with the same kind of stains, were rinsed in 65 dm3 of water from 30 ° Cinene automatic household washing machine. They were then dried by passing through a Besel er Print Dryer at a machine temperature setting of 6 and a speed of 10.

The stained fabrics 3 and 4 were obtained from Test Fabrics

Incorporated, Middlesex, New Jersey, and cut into 76 χ 102 mm pieces.

Stained fabric 5 was obtained by stirring and impregnating impure cotton strip material (45 x 90 cm) in a washing machine filled with a coffee / tea solution (8: 1 weight ratio) at 66 ° C. The machine was then rinsed and centrifuged to remove the coffee / 8400161-15 tea solution. The stained fabric was then machine washed twice with a hot pyrophosphate surfactant solution followed by two complete water washes at 60 ° C. Then, the strips were dried by two passes through an Ironrite machine adjusted to 10 and then cut into 76 x 102 mm rags.

A granular detergent formulation (hereinafter further referred to as HDD) was prepared by a conventional spray drying and had the following approximate composition: 10 Composition wt% sodium tri decyl benzene sulfonate 15 ethoxylated primary alcohol with 7 moles EO / mole alcohol) 1 sodium tri polyphosphate 33 15 sodium carbonate 5 sodium silicate 7 sodium carboxymethyl cellulose 0.5 optical brightener 0.2 perfume 0.2 20 water 11 sodium sulfate residue

Detergent formulations A - 6 with HDD were formulated as described in Table A below. The pH of the formulations in aqueous solution ranged from 9.2 to 9.7.

25 Table A

Component Composition _____ A B C D E F G_ detergent, HDD 4.50g 4.50g 4.50g 4.50g 4.50g 4.50g 4.50g

Mg salt of MPPA1} 0.49 0.49 0.49 - 0.40 0.40 0.40 30 NaBr - 0.07 0.07 - 0.07 0.07 0.07 TSA2 ^ - - 0, 03 - - 0.02 0.03 ^ A bleaching composition with as active ingredient about 65% by weight of magnesium monoperoxyphthalate and an active oxygen content of 5.1%.

2) para-toluenesulfonamide.

8400161 w N- - 16 -

Compositions A - 6 were tested according to the procedure described above and the results of these bleaching tests listed in Table B showing stain removal. achieved with formulations A through G for each of the five stains.

5 Table B

Comparative bleaching behavior (% S.R.)

Stain Composition

_ _A_ _B__ _C_ JD_ E F G

grapes 63% 65% 75% 37% 62% 67% 68% 10 blueberries 63 64 68 41 62 65 67 sulfo dye 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 average (%) 42 44 53 24 41 47 48 15 The results of Table B show the marked improvement

behavior achieved with preparations containing MPPA as a bleaching agent in combination with sodium bromide and TSA, compared with preparations containing MPPA alone (in the absence of bromide and TSA) or MPPA and sodium bromide. Thus, the compositions C, F and G according to the invention show a marked improvement in the average percentage of S.R. from 6 to 9% (depending on the specific composition) compared to the corresponding preparations B and E, both of which contain MPPA and sodium bromide, but no TSA. A comparison of preparation 0 according to the invention with preparation A containing only MPPA (in the absence of bromide and TSA in '25) shows an improvement in the average percentage of S.R. of 11% (53% compared to 42%) in bleaching achieved with a prior art formulation. Example II

The bleaching tests described in Example I were carried out with the preparations H - K shown in Table C. The stained fabric patches used were the same as described in Example I.

The detergent preparations H - K had the composition according to Table C, the composition of detergent HDD is described in Example 1. The pH of the preparations in an aqueous solution ranged from 8.2 to 8.6.

5 8400161 «, <

- 17 - Table C

Components Composition

____ Η I J K

detergent, HDD 1.50g 1.50g 1.50g 1.50g 5 Mg salt of MPPA1 ^ 0.26 0.26 0.26 0.26

Na Br - - 0.10 0.10 TSA2 5 - 0.08 - 0.08 1 ^ A bleaching composition with as active ingredient about 65% by weight of magnesium monoperoxyphthalate and with an active oxygen content of 5.1%.

2) Para-toluenesulfonami.

Preparations H-K were tested according to Example I and the results of the bleaching tests are shown in Table D in which the percent stain removal achieved with the compositions H-K is listed for each of the five stains.

Table D

Stain Comparative bleaching behavior (% S.R.)

HE K

grapes 75% 76% 82% 85% 20 blueberries 70 67 75 80 sulfo dye 43 9 8 red wine 37 36 35 46 coffee / tea _78 _74 _86 87 average (%) 53 51 57 61 25 The figures in Table D show the synergy achieved with formulation K, a formulation according to the invention, compared to formulations Η, I and J to, which contain only MPPA alone or in combination with either NaBr or TSA. For example, the average percentage of S.R. achieved with preparations H and I was almost the same (53 and 51%), the presence of TSA having even a slightly negative effect on the bleaching activity of MPPA. Preparation J with MPPA in combination with bromide provided the expected improvement in bleaching activity, an average S.R. of 57%. The addition of TSA to a combination of MPPA and bromide (formulation K) produced a marked synergistic effect, since a marked improvement in bleaching activity was achieved, ie an average S.R. of 61%.

8400161

Claims (18)

Preparation according to Claim 1, characterized in that the aromatic sulfonamide compound is a toluenesulfonamide or an N-alkali metal salt thereof, and the bromide salt is an al-potassium bromide. Preparation according to claim 1, characterized in that the aromatic sulfonamide compound is the p-toluenesulfonamide. Preparation according to claim 1, characterized in that it contains magnesium monoperoxyphthalate. Preparation according to claim 1, characterized in that the weight ratio of (a) to (b) is between about 10: 1 and about 1: 5 and the weight ratio of (c) to (b) is between approx. 5: 1 20 and approx. 1: 7, Preparation according to claim 1, characterized in that it additionally contains one or more surfactant detergents in the form of anionic, nonionic, cationic, ampholytic and / or zwitterionic detergents. Bleaching and washing composition containing: (a) 5-50% by weight of a bleaching agent comprising: (1) monoperoxyphthalic acid and / or a water-soluble salt thereof; (2) a water-soluble inorganic bromide salt; and 30 (3) an aromatic sulfonamide compound in the form of benzenesulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, 8400161J. N-alkali metal salts of these sulfonamides, N-acetyl and N-benzoyl derivatives of said sulfonamides and salts, and mixtures thereof; (b) 5-50% by weight of a surfactant detergent in the form of an anionic, cationic, nonionic, ampholytic and / or black ion detergent; (c) 5 - 80% by weight of a detergent builder salt and (d) the remainder of water and optionally a filler salt. Preparation according to claim 7, characterized in that the weight ratio of (1) to (2) is about 10: 1 to about 1: 5 and the weight ratio of (3) to (2) is about 10: 1. 5: 1 to 1: 7. 9. A composition according to claim 7, characterized in that the bleaching agent contains magnesium monoperoxyphthalate, the aromatic sulfonamide compound is the toluene sulfonamide or an N-alkali metal salt thereof and the bromide salt is an al potassium metal bromide. Composition according to claim 7, characterized in that the detergent is an anionic or non-ionic detergent or a mixture thereof. 11. A composition according to claim 7, characterized in that the aromatic sulfonamide compound is the p-toluenesulfonamide. Preparation according to claim 7, characterized in that it contains 5-30% by weight of a surfactant detergent and 10-60% by weight of a builder salt. 13. A bleaching process characterized in that a stained and / or soiled material 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; (C) an aromatics sulfonamide compound in the form of benzene sulfonamide, toluenesulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, N-alkali metal salts of these sulfonamides, N-acetyl and N-benzoyl derivatives of these and sulfonamides thereof and salts thereof the weight ratio of (a) to 35 (b) is about 10: 1 to 1: 5 and the weight ratio of (c) to (b) is about 8400161 - 20 - -t · * ϊ ~ 5: 1 to about 1 : 7, 14. Process according to claim 13, characterized in that the preparation additionally contains one or more surfactant detergents in the form of anionic, nonionic, cationic, ampholytic and / or zwitterionic detergents. The method according to claim 14, characterized in that the composition comprises about 5-50% by weight of the components (a), (b) and (c) together, about 5-50% by weight of a detergent surfactant and contains about 5-80 wt% of a builder salt, the remainder consisting of water and optionally a filler salt. Process according to claim 13, characterized in that the aromatic sulfonamide is the toluene sulfonamide or an N-alkali metal salt thereof. 17. Process according to claim 13, characterized in that the preparation used contains magnesium monoperoxyphthalate. Process according to claim 13, characterized in that the bromide salt is an alkali metal bromide. Method according to claim 13, characterized in that the weight ratio of (a) to (b) is between about 8: 1 and about 20 1: 2 and the weight ratio of (c) to (b) is between about 2: 1 and about 1: 4. 8400161 -f Sr * r2. R ——- R / —X = fl u I r -o 2 CB? / N XH2 R-C-N —CHo CH0 OCHoCQOM Z \ 2 2 2 OH CHROME COLGATA-PALMOLIVS COMPANY f400161