SE455792B - WHITE DETERGENT COMPOSITION CONTAINING MONOPEROXIFTAL ACID, A CHELATING SUBSTANCE, A PEROXY COMPOUND AND AN ACTIVATOR FOR THE PEROXIFICATION SUBSTANCE AND USING THE COMPOSITION IN THE WASHING PROCEDURE - Google Patents

Description

455,792 hydrides, such as those described in U.S. Patent Nos. 3,928,775, 3,338,839 and 3,352,634; carboxylic acid esters such as those described in U.S. Patent No. 2,995,905; N-acyl compounds such as those described in U.S. Patent Nos. 3,912,648 and 3,919,102; cyanomines such as those described in U.S. Patent 4,199,466; and acylsulfoamides such as those described in U.S. Pat. No. 3,245,913.

Peroxy acids already prepared have also been used to effect the bleaching in washing solutions. U.S. Pat. Nos. 3,770,816, 4,170,453 and 4,259,201 illustrate prior art bleach compositions containing a peroxyacid compound.

It is generally accepted in the art that metal ions have the ability to act as decomposing catalysts for inorganic peroxy compounds and organic peroxyacids. In an attempt to stabilize the bleaching agents in the washing solution, chelating agents have been incorporated into bleaching detergent compositions. For example, U.S. Patent 3,243,378 to Stoltz discloses a bleaching composition composition containing a bleaching peroxy compound and a chelating agent for sequestering metal cations. In general, the chelating agents used for this purpose belong to one of two categories: (a) materials such as heterocyclic compounds and ketones, in particular 8-hydroxyquinoline, which bind the metal ions in the wash liquor by precipitating them from solution; and (b) materials such as aminopolycarboxylate and aminopolyphosphonate compounds which form water-soluble metal complexes with the cations present in the wash solution. Thus, U.S. Patent No. 4,005,029 reports that selected aldehydes, ketones and compounds which give aldehydes or ketones in aqueous solution 455 792 (eg 8-hydroxyquinoline) dipic acid, and aromatic peroxyacids (and water-soluble salts thereof) such as monoperoxyphthalic acid and diperoxyterephthalic acid. U.S. Patent No. 4,170,453 discloses a mixture of 8-hydroxyquinoline, phosphoric acid and sodium pyrophosphate as a preferred chelating system for stabilizing the active oxygen generated in washing solutions containing diperoxydodecanedioic acid. U.S. Patent 4,225,452 to Leigh discloses combinations of special classes of chelating agents (among which phosphonate compounds are present) and inorganic peroxy compounds as well as an organic activator intended to inhibit the decomposition of the peroxy compound in the bleaching composition.

More specifically, the chelating agent is said to inhibit the undesired side reaction between the peroxy compound and the peroxyacid formed in the primary reaction between the peroxy compound and the activator, the side reaction effect being that the bleaching peroxyacid substances are consumed in the solution. However, the Leigh patent advises against using these chelating agents in solutions where the peroxyacid has a double bond between the carbon atoms in the α, β1 position relative to the carbonyl group. In particular, in column 2 of the patent, beginning on line 63, the patentee excludes phthalic anhydride as an activator for the bleach compositions in question due to instability. Since the peroxyacid formed in the reaction between phthalic anhydride and an inorganic peroxy compound is monoperoxyphthalic acid, the Leigh patent obviously discourages the use of monoperoxyphthalic acid in the bleaches of this patent.

European Patent Specification No. 0 027 693, published April 29, 1981, discloses the use of magnesium monoperoxyphthalate as an effective bleaching agent. It also describes the optimal combination of a bleaching agent and an "aldehyde or ketone peroxyacid activator" described in U.S. Patent No. 4,005,029, such as 8-hydroxyquinoline, which is a known peroxy stabilizer ". This publication also describes organic phosphonate compounds, together with a large number of other compounds, as useful detergent activating salts which may optionally be included in the detergent compositions described, but nothing is said about the beneficial effects which accompany the use of a small amount of organic phosphonate compounds. , used as chelating agents in bleach compositions and especially in compositions containing magnesium monoperoxyphthalate.

The above-mentioned European patent also reports that peroxy compounds can optionally be incorporated into the detergent compositions containing the described peroxy bleaches to effect bleaching at higher washing temperatures. However, there is no indication of the use of an organic activator in combination with these peroxy compounds, and in particular no indication of the desirability of using a peroxy compound together with phthalic anhydride as an activator in a bleach system containing monoperoxyphthalic acid and / or a salt thereof and a chelating agent of the type described herein.

Summary of the Invention According to the present invention there is provided a bleaching detergent composition containing (a) between about 5 and 50% by weight of a composition containing monoperoxyphthalic acid and / or a water-soluble salt thereof; a chelating agent consisting essentially of diethylenetriamine-pentamethylenephosphonic acid and / or a water-soluble salt thereof; a peroxy compound other than monoperoxyphthalic acid; and an activator for said peroxy compound consisting essentially of phthalic anhydride; (B) between about 5% and 50% by weight of one or more surfactants selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants; (c) between about 5 and 80% by weight of a detergent salt; and (d) the remainder consisting of water and, if desired, a filler in the form of a salt.

Embodiments of the composition are set forth in the dependent claims.

In the method according to the invention, bleaching of stained and / or dirty materials takes place by bringing the materials into contact with an aqueous solution of the compositions defined above.

The term "chelating agent" as used herein refers to organic compounds which, in small quantities, are capable of binding the transition metal cations (eg iron, nickel and cobalt) which are known to adversely affect the stability of peroxy compounds and / or peroxyacids in bleaching wash water solutions. The chelating agents used herein therefore include non-deorganic compounds which are usually included in detergent compositions in the form of detergent salts. The chelating agents useful in the present invention are of the type capable of forming a substantially water-soluble, rather than a precipitated, metal complex in aqueous solution together with metal ions, and in particular transition metal cations such as those mentioned above. Suitable chelating agents are thus ethylenediaminetetraacetic acid (EDTA), nitrile triacetic acid (NTA), diethylenetriaminepentaacetic acid, ethylenediaminetetramethylenephosphonic acid (EDITEMPA), aminotrimethylenephenphosphonic acid (ATMpertraine);

A preferred class of chelating agents are the organic phosphonate compounds, such as those described in U.S. Patent No. 4,225,452, the formulas of which are set forth in Equations I, II and III, columns 3 and 4, of the patent specification. Among the materials in this class, diethylenetriaminepentamethylenephosphonic acid (hereinafter referred to as "DTPMP") and / or a water-soluble salt thereof is especially preferred as the chelating agent for achieving the object of the present invention. Among the salts of DTPMP, the sodium, potassium and ammonium salts are generally preferred due to their relatively greater solubility and ease of preparation.

The chelating agents contained in the bleaching compositions of the invention are generally present in a weight ratio relative to monoperoxyfthalic acid and / or salts thereof between about 1: 5 and 1: 5 Å, and preferably between about 1: 7 and 1:20.

In bleaching detergent detergent compositions of the invention, the concentration of chelating agent is generally less than about 5% by weight, preferably less than about 2% by weight and most preferably less than about 1% by weight of the detergent compositions. The chelating agent can be used alone or in combination with one or more other chelating agents. Thus, for example, DTPMP can be used in combination with EDTA in the compositions according to the invention.

Detailed Description of the Invention Monoperoxyphthalic acid and / or one or more water-soluble salts thereof are the primary bleaching agent in the compositions of the invention. Although MPPA provides an acceptable bleaching effect, it has the disadvantage that it has relatively poor storage stability together with other components commonly found in household end-use detergent compositions. Therefore, in view of the stability, the magnesium salt of MPPA is preferably used in the compositions according to the invention, i.e. magnesium monoperoxyphthalate. Alkali metal, calcium or barium and / or ammonium salts of MPPA can also be used in the bleaching and detergent compositions of the invention, although these salts are generally less desirable, in terms of stability, than the said magnesium salt. MPPA is generally prepared by reacting hydrogen peroxide with phthalic anhydride. The resulting MPPA can then be used to prepare magnesium monoperoxyphthalate by reacting 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 pages 7-10 of European Patent Specification 0 027 693, published April 29, 1981, and the mentioned pages 7-10 are hereby incorporated by reference.

The peroxy compounds used in the present invention include compounds which release hydrogen peroxide in aqueous media, such as alkali metal perborates, percarbonates, perphosphates and the like. Sodium perborate is especially preferred because of its commercial availability.

The peroxy compound is generally included in a bleaching composition relative to the phthalic anhydride activator, in a molar ratio of about 1:10 to about 10: 1 of peroxy compound to phthalic anhydride, the preferred ratio being from about 1: 2 to about 3: 1. It is understood that the content of phthalic anhydride will depend on the content of peroxy compound, which in turn is determined by the desired degree of bleaching.

The peroxy compound is included in the bleach composition typically in an amount of from about 1% to about 50% by weight, preferably 3 to 25%, and most preferably 5 to 20% by weight.

The amount of bleach composition added to the wash solution is generally selected to give a quantity of peroxy and peroxyacid compound in the range corresponding to about 3-100 parts of active oxygen per million parts of wash solution.

MPPA and / or a water-soluble salt thereof in combination with the selected chelating agent, peroxy compound and phthalic anhydride may be formulated as a separate bleach product, or alternatively included in a detergent activated detergent composition. Thus, the bleach composition may include those conventional additives used in fabric detergents, such as binders, fillers, detergent salts, proteolytic enzymes, optical brighteners, perfumes, dyes, corrosion inhibitors, anti-precipitating agents, foam stabilizers and the like, all of which may be added in varying quantities depending on the desired properties of the bleach composition and their compatibility therewith.

When the bleaching compositions are incorporated into a conventional detergent composition to form a bleaching detergent composition of the invention, it will comprise the following: between about 5 and 50% by weight of the bleaching composition, between about 5 and 50% by weight of a surfactant material, preferably about 5 to 30% by weight, and between about 5 and 80% by weight of a detergent active salt, which may also act as a buffer to obtain the required pH when the detergent composition is added to water. . The aqueous washing solutions should have a pH range of about 7-12, preferably about 8-10, and most preferably about 8.5-9. A preferred quantity of detergent salt is between about 20% and about 65% by weight of the composition. The remaining part of the composition should consist mainly of water, filler salts such as sodium sulphate, and any minor additives such as optical brighteners, perfumes, dyes, anti-redeposition agents and the like. Among the anionic substances useful in the present invention are the surfactants or surfactant compounds which contain an organic hydrophobic group having generally about 8-26 carbon atoms and preferably 10-18 carbon atoms in the present invention. the molecular structure and at least one water-solubilizing group selected from the groups sulfonate, sulfate, carboxylate, phosphonate and phosphate to give a water-soluble detergent. Examples of suitable anionic surfactants 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 surfactants also includes water-soluble sulfated and sulfonated surfactants having an alkyl radical containing between about 8 and 26 and preferably between about 12 and 22 carbon atoms. Examples of sulfonated anionic surfactants 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 the sodium, potassium and ammonium salts of higher alkylbenzene sulfonates, higher alkyltoluenesulfonates and higher alkylphenol sulfonates.

Other suitable anionic surfactants are olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfonate surfactants 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 21 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 surfactants are paraffin sulfonates containing between about 10 and 20 carbon atoms, preferably between about 15 and 20 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. of higher alcohols containing between about 8 and 18 carbon atoms, such as, for example, sodium lauryl sulphate and sodium tallow alcohol sulphate, sodium and potassium salts of alpha-sulpho fatty acid esters containing about 10-20 carbon atoms in the acyl group, for example methyl-alpha-sulphomyristate and methyl-alpha-ammonium sulphotalgoate, of mono- or di-glycerides of higher (C10-C18) fatty acids, for example stearic acid monoglyceride monosulfate; sodium and alkylolammonium salts of alkyl polyethyleneoxyether sulfate prepared by condensation of 1-5 moles of ethylene oxide together with 1 mole of a higher (C8-C18) alcohol; sodium higher alkyl (C 10 -C 18) glyceryl ether sulfonate; and sodium or potassium alkylphenol polyethyleneoxy ether sulfate having about 1-6 oxyethylene groups per molecule and in which the alkyl radicals contain about 8-12 carbon atoms. The most preferred water-soluble anionic surfactant compounds are ammonium and substituted ammonium (such as mono-, di- and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metals. - (such as calcium and magnesium) salts of higher alkylbenzene sulphonates, olefin sulphonates and higher alkyl sulphates.

Among the anionic agents listed above, sodium linear alkyl benzene sulfonates (LABS) are most preferred.

The nonionic synthetic organic surfactants are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and they are typically prepared by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound together with ethylene oxide (hydrophilic to nature). In practice, a hydrophobic compound having a carboxy, hydroxy, amido or amino group and having a free hydrogen atom bonded to the nitrogen can be condensed with ethylene oxide or with the polyhydrated product thereof, polyethylene glycol, to give a nonionic surfactant. The length of the hydrophilic chain and the length of the polyoxyethylene chain can be easily adjusted to obtain the desired balance between hydrophobic and hydrophilic groups.

The nonionic surfactants include the polyethylene oxide condensates of 1 mole of alkylphenol containing between about 6 and 12 carbon atoms in a straight or branched chain configuration together with about 5-30 moles of ethylene oxide, for example nonylphenol condensed with 9 moles of ethylene oxide; dodecylphenol condensed with 15 moles of ethylene oxide; and dinonylphenol condensed with 15 moles of ethylene oxide. Condensation products of the corresponding alkylthiophenols together with 5-30 moles of ethylene oxide are also suitable.

Of the types of nonionic substances described above, those of the ethoxylated alcohol type are preferred. Particularly preferred nonionic agents are the condensation product of coconut fatty alcohol together with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, the condensation product of tallow fat alcohol with about 11 moles of ethylene oxide per mole of tallow fatty alcohol, the condensation fat product of a containing about 11-15 carbon atoms with about 9 moles of ethylene oxide per mole of fatty alcohol, and condensation products of more or less branched primary alcohols, the branches of which consist mainly of 2-methyl, together with 4-12 moles of ethylene oxide.

Zwitterionic surfactants, such as betaines and sulphobetaines, of the following formula are also useful: 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 1-4 carbon atoms, R 4 represents an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms, and X is C or S = O. 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 surfactant is denoted a betaine. When X is S = 0, the surfactant is designated a sulfobetaine or sultain.

Cationic substances can also be used. These consist of surfactant 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 agents are amine- and quaternary ammonium compounds. Examples of suitable synthetic cationic surfactants are: common primary amines of the formula RNH 2, in which R represents an alkyl group having about 12-15 carbon atoms; diamines of the formula RNHC2H4NHz, 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 RICO NHC 2 H 4 NH 2, in which R 1 represents an acyl group having about 8-20 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 8-22 carbon atoms and three of the groups attached to the nitrogen atom are alkyl groups containing 1-3 carbon atoms, including alkyl groups having inert substituents such as phenyl groups, wherein there is an anion such as halogen, acetate, methyl sulfate, 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 stearylamide-propylammonium chloride.

Typical quaternary ammonium surfactants are ethyl dimethyl stearyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl cetyl ammonium bromide, dimethyl ethyl ethyl lauryl ammonium chloride, dimethyl propyl ammonium chloride and the corresponding methyl sulphates and acetates.

Ampholytic surfactants are also useful in the invention.

Ampholytic surfactants are well known in the art and many useful surfactants 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 surfactants 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: 455 792 10 15 20 25 14 / N about HI R- C --- N-CHZCHZOCHZCOOM 2 OH CH2COOM wherein in each of the above formulas R represents an acyclic hydrophobic group with between about 8 and 18 carbon atoms, and M is a cation that neutralizes the charge of the anion. Particularly suitable amphoteric surfactants are the disodium salt of undecylcycloimidine ethoxythionic acid 2-ethionic acid, dodecyl-beta-alanine and the inner salt of 2-trimethylamino-lauric acid. The detergent composition of the invention may optionally contain a detergent-type salt of the detergent. generally used in detergent compositions. Useful detergent salts 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, polyhydroxy sulfonates, polyacetates, carboxylates, polycarboxylates, succinates and the like.

Particular examples of inorganic detergent phosphates are sodium and potassium tripolyphosphate, pyrophosphate and hexa metaphosphate. The organic polyphosphonates specifically 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 non-soluble. detergent salts.

Particular examples of non-phosphorus-containing inorganic detergent compounds are water-soluble inorganic carbonate, bicarbonate and silicate salts. Alkali metals, for example 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 method of the invention. Particular examples of detergent polyacetate and polycarboxylate compounds are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrile triacetic acid, benzene poly (i.e. penta- and tetra-) -carboxylic acid carboxylic acid and carboxylic acid citric acid.

The bleach compositions of the invention are prepared by mixing the components in the manner described below. When preparing detergent compositions containing the bleaching composition in combination with a surfactant compound and / or detergent salts, the components of the bleach composition may be directly mixed with the surfactant compound, detergent compounds, etc. Alternatively, the peroxy activator, MPPA and peroxy compound may be coated with to improve stability and / or to prevent premature activation of the bleach. the coating is carried out in accordance with procedures well known in the art. Suitable coating materials are such compounds as magnesium sulfate, polyvinyl alcohol, lauric acid or a salt thereof, and the like.

Example Gel 1 Test Method Bleaching experiments were performed with standard specimens 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 kept 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 ° 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 sample patches (76.2 x 10 6, 6 mm) of the differently 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 38 ° C, after which they were dried. The percentage of stain removal was measured by determining the reflectance factor for each stained cloth before and after washing using a Gardner Color Difference Meter, and the percentage of stain removal (% SR) was calculated as follows: (Rd after washing) - (Rd before washing) * SJ * - = ma) before staining - (Ra before washing) * (100 where "Rd before washing" refers to the Rd value after staining.

Based on the percentage values for stain removal obtained, the average value of 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 thiosulphate solution using starch.

The respective stains and test fabric samples were as follows: Élëgk Test Fabric 1. Grape 65 dakron - 35 cotton 2. Blueberry Cotton 3. Sulfo color EMPA 115 (cotton) 4. Red wine EMPA ll4 (cotton) 5. Coffee / tea Cotton The stained Experimental fabrics 1 and 2 were obtained by passing rolls of unspotted fabric through a surface dyeing and drying device (manufactured by Benz of Zurich, Switzerland) containing either grape or blueberry solutions at a temperature of 32 ° C.

After drying at 21 ° C, the fabric was cut into pieces measuring 76.2 x 101.6 mm. Eighty such type patches, impregnated with the same type of stain, were rinsed in 64.3 l of water at a temperature of 29 ° C in an automatic household washing machine.

These were then dried by passing them through a Beseler Print Dryer at a setting of machine temperature of 6 and 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. 455 792 10 15 20 25 30 35 18 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 (8 : 1 by weight ratio) at 65.5 ° C.

This was followed by rinsing and centrifugal drying in the machine to remove the coffee / tea solution. The stained fabric was then washed twice with hot pyrophosphate surfactant solution followed by two complete washes in water at 60 ° C. The strips were then dried by passing twice through an Ironrite machine set at 10, and cut into sample pieces measuring 76.2 x 101.6 mm.

A granulated detergent composition (herein referred to as "HDD") was prepared by conventional spray drying, which had the following approximate composition: Composition Weight% Sodium tridecylbenzenesulfonate Etoxylated C12-C15 primary alcohol (7 moles 1 EO / mole alcohol) Sodium tripolyphosphate 33 Sodium cellulose carbonate .5 Optical white matter 0.2 Perfume 0.2 Water ll Sodium sulphate residual Detergent compositions AD containing HDD had the composition shown in Table 1.- 10 l5 20 25 30 19 Table l Component Composition è â E Detergent, HDD 4.509 4.509 4.509 H- 48 (1) - 0.25 0.25 oTPMPm - - 0.02 Sodium perborate 0.32 0.16 0.16 Phthalic anhydride - 0.125 0.125 455 792 U 47509 0.25 0.09 _ 0.16 0.125 (l) En bleach composition containing monoperoxyphthalic acid (as magnesium salt) from Interox Chemicals, Houston, Texas and with an active oxygen content of 5.1%. (2) Sodium diethylenetriamine-pentamethylene phosphate from P A Hunt Chemical Corp., Lincoln, Rhode Island.

The compositions AD were tested according to the procedure described above and the results of the bleaching experiments are summarized in Table 2, which shows the initial and final values for active oxygen (AO) in the washing solution (indicated as "grams from the beginning" and "residual grams", respectively). ) and the stain removal obtained for each of the five stain types. 455 792 10 _15 20 25 30 35 Table 2 Belaši! šlâkâiågâfërllä fl fL Grams from the beginning (A.0.xl03) Remaining grams (AOxlO3) Consumed, grams (A.0.xlO3) Stain removal: Grape Blueberry Sulpho color (EMPA 115) Red wine (EMPA ll4) Coffee / tea Average value .lå ä 9. _12 32.8 28.7 28.7 28.7 30.4 12.4 19.5 19.9 2.4 16.3 9.2 8.8 å; å å å 61 63 67 67 56 65 67_ 68 3 4 4 4 4l 46 49 53 26 30 39 40 37 42 45 46 The results in Table 2 show that compositions C and D consume less active oxygen, but they still provide improved paint removal compared to composition B, which is similar to compositions C and D except that it does not contain the chelating agent DTPMP.

Example Gel 2 Detergent compositions E-J containing a content of 0.15% detergent were prepared according to Table 3 below. 1.1 / 10 15 25 25 455 792 21 Table 3 Component Composition E E ä ä _I. : I Detergent, HDD l, 50g l, 50g l, 50g l, 50g l, 50g l, 50g 11-400) 0.20 0.20 0.20 0.07 0.07 0.07 DTPMPQ) - 0, 02 - - 0.02 - EDTAU) - - 0.02 - - 0.02 Sodium perborate - - - 0.15 0.15 0.15 (10.1% active acid) Phthalic anhydride - - - 0.06 0.06 0.06 (1) A bleach composition containing monoperoxyphthalic acid (as magnesium salt) from Interox Chemicals, Houston, Texas and having an active oxygen content of 5.1%. (2) Sodium diethylenetriamine-pentamethylene phosphate from P.A.

.Hunt Chemical Corp., Lincoln, Rhode Island. (3) Ethylenediaminetetraacetic acid, disodium salt The compositions were NOT tested according to the procedure described above, and the results of the bleaching experiments are summarized in Table 2, the initial and final values for active oxygen in the washing solution and the stain removal obtained for each and one of the five spot types is given in the same manner as in Table 2 of Example 1. 455 792 10 15 20 25 30 22 Table 4 åelaëi! èlekaia9§färmåaa_ EFGHIJ Grams from the beginning (A.0.xl0) 10.2 10.2 10.2 18.6 18.6 18.6 Remaining grams (Aox1o3) 3.6 5.5 3.6 9.4 13.8 10.0 Consumed, grams Stain removal: å å å å å É Grape 65 64 64 62 63 61 Blueberries A 46 47 44 43 47 44 Sulfo color 3 4 4 4 5 5 (EMPA 115) Red wine 37 35 35 33 34 33 (EMPA 114) Coffee / tea 70 72 70 83 82 86 Mean value (%) 44 44 43 45 46 46 The results in Table 4 show that the bleaching ability of composition G is improved when using compositions I and J according to the invention, which, compared with compositions F and G, contain a reduced amount of MPPA bleach but also contain perborate and phthalic anhydride activator. A comparison of the effectiveness of I and J shows that composition I gives an equivalent bleaching effect in relation to composition J but still consumes considerably less amount of active oxygen. Compositions I and J are identical, except that DTPMP is included in the former and EDTA in the latter.

* II

Claims (13)

10 15 20 1. n a d (a) (C) (d) 2. 455 792 23 P a t e n t k r a v Bleaching detergent composition, characterized in that it contains: between about 5 and 50% by weight of a composition containing monoperoxyphthalic acid and / or a water-soluble salt thereof; a chelating substance consisting essentially of diethylenetriamine-pentamethylenephosphonic acid and / or a water-soluble salt thereof; a peroxy compound other than monoperoxyphthalic acid; and an activator for said peroxy compound consisting essentially of phthalic anhydride; between about 5 and 50% by weight of one or more surfactants selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants; between about 5 and 80% by weight of a detergent salt; and the remainder consisting of water and, if desired, a filler in the form of a salt. Bleaching detergent composition according to claim 1, characterized in that the (a) component in said composition contains magnesium monoperoxyphthalate. Composition according to Claim 1, characterized in that the chelating agent is diethylenetriamine-pentamethylenephosphonic acid and / or a water-soluble salt thereof. 455 792 10 15 20 25 24 4. A composition according to claim 1, characterized in that the chelating agent is ethylenediamine tetraacetic acid and / or a water-soluble salt thereof. Composition according to Claim 1, characterized in that the weight ratio of chelating agent to monoperoxyphthalic acid and / or its salt is from 1: 5 to 1:50, preferably from 1: 7 to 1:20. _ Bleaching detergent composition according to claim 1, characterized in that the content of chelating agent is less than about 5% by weight. Bleaching detergent composition according to claim 1, characterized in that the content of chelating agent is lower than about 2% by weight. 8. A composition according to claim 1, characterized in that said peroxy compound is an alkali metal perborate. 9.; Bleaching process, characterized in that the colored and / or muscled material to be bleached is contacted with an aqueous solution of a bleaching detergent composition containing: (a) between about 5 and 50% by weight of a composition contained in - holds monoperoxide phthalic acid and / or a water-soluble salt thereof; a chelating agent consisting essentially of diethylenetriamine-pentamethylenephosphonic acid and / or a water-soluble salt thereof; a peroxy compound which is not monoperoxyphthalic acid; and an activator for said peroxy compound consisting essentially of phthalic anhydride; (B) between about 5 and 50% by weight of one or more surfactants selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants: (c) between about 5 and 80% by weight. % of a detergent salt; and (d) residues consisting of water and, if desired, a filler in the form of a salt. 10. A process according to claim 9, characterized in that said composition contains magnesium monoperoxyphthalate. 11. ll. Process according to Claim 9, characterized in that the chelating agent is diethylenetriamine-pentamethylenephosphonic acid and / or a water-soluble salt thereof. 12. A process according to claim 9, characterized in that the chelating agent is present in a weight ratio of from about 1: 5 to about 1:50, relative to the amount of nitroxoxyphthalic acid and / or its salt. IN 13. A method according to claim 9, characterized in that said weight ratio is from about 1: 7 to about 1:20.