SE453100B - WHITE DETERGENT COMPOSITION, ITS USE AND SET FOR ITS PREPARATION - Google Patents

Description

Among which are carboxylic acid anhydrides, such as those described in U.S. Pat. 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 No. 2,419,466; 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 4,005,029 reports that selected aldehydes, ketones and compounds which give aldehydes or ketones in aqueous solution (e.g., 8-hydroxyquinoline) can be used to activate aliphatic peroxyacids, such as disperazelic acid, diperadic acid, and aromatic peroxyacids (and water-soluble salts thereof) such as monoperoxyphthalic acid and diperoxyterephthalic acid. U.S. Pat. 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 Gf 1 position in relation to the carbonyl group. Specifically in column 2 of the patent, beginning with 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 monperoxyphthalic acid in the bleaching agent of this patent.

European Patent 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 IQ aldehyde or ketone peroxyacid activator described in U.S. Pat. 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. However, nothing is said about the beneficial effects that 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. Thus, although the art has been interested in improving the stability of the bleaching peroxy and peroxyacid compounds by means of chelating agents, it has hitherto been neglected to describe or propose the particular combination of peroxyacid compounds and chelating agents of the type which mainly forms water-soluble compounds or complexes with metal cations in the wash water solution, since this type of chelating agent has only been described in combination with peroxy compounds used alone or in combination with activators.

In addition, the beneficial effect resulting from the combination of these chelating agents and in particular monoperoxyphthalic acid and / or a water-soluble salt thereof has been little appreciated in the prior art.

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. Therefore, the chelating agents used herein do not include the inorganic compounds commonly included in detergent compositions in the form of active salts. The chelating agents which are useful 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 numbers fl ë fi ions such as those mentioned above. Suitable chelating agents are thus ethylenediaminetetraacetic acid (EDTA), nitriletriacetic acid (NTA), diethylenetriaminepentaacetic acid, ethylenediaminetetramethylenephosphonic acid (EDITEMPA), aminotrimethylenephosphonic acid (APAicurpetraine); In contrast, chelating agents such as 8-hydroxyquinoline, which in aqueous solution form a precipitated metal complex, are not included in the present invention.

A preferred class of chelating agents are the organic phosphonate compounds, such as those described in U.S. Patent 4,225,452, the formulas of which are set forth in Equations I, II and III, columns 3 and 4, of the patent. Among the materials in this class, especially diethylenetriamine pentamethylene phosphonic acid (herein referred to as "DTPMP") and / or a water-soluble salt thereof as a chelating agent are preferred to achieve the object of the present invention. Among the salts of DTPMP, the sodium, potassium and ammonium salts are generally preferred because of their relatively greater solubility and ease of preparation.

The bleach used in the bleach composition described herein does not contain any peroxy compound but consists only of MPPA and / or water-soluble salts thereof.

In general, such bleach compositions are most effective at the relatively low washing temperatures used in typical household washing machines in the United States.

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

MPPA and / or a water-soluble salt thereof in combination with a chelating agent may be formulated as a separate bleach product, or alternatively included in a detergent-activated .fl -... hu-a- fi .. .. 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, antifoulants, foam stabilizers and the like, all of which may be added. varying quantities depending on the desired properties of the bleach composition and their compatibility therewith. The bleach compositions may also be incorporated into detergent compositions containing one or more surfactants selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants.

When the bleaching compositions are incorporated into a conventional detergent composition and thus constitute a complete bleaching detergent composition according to the invention, the latter composition 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 surfactant material, preferably 5 to 30% by weight, and about 5% and 80% by weight of a detergent active salt, which may also act as a buffer to required pH value should be obtained when the detergent composition is added to water. The aqueous washing solutions should have a pH range of approx. 7-12, preferably approx. 8-10, and preferably approx. 8.5-9. A preferred quantity of detergent salt is between approx. 20 and approx. 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, antifoulants and the like.

In a preferred embodiment of the invention, the components of the bleaching detergent composition are present in the following weight ratios. The total weight of surfactant surfactant, detergent salt and optional filler salts is present in a proportion of approx. 6: 1 to approx. 20: 1, preferably 6.5: 1 to approx. 15: 1, in relation to the sum of bleach and chelating agents.

Among the anionic substances useful in the present invention are the surfactants or surfactants which contain an organic hydrophobic group having generally about 8-26 carbon atoms and preferably 10-18 carbon atoms in the molecular structure and at least one water-solubilizing group selected from the groups sulfonate, sulfate, carboxylate, phosphonate and phosphate, so that a water-soluble detergent is obtained.

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 approx. 8 and 20 carbon atoms and preferably 10-18 carbon atoms. Suitable fatty acids may 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 sulphated and sulphonated surfactants with an alkyl radical containing between approx. 8 and 26 and preferably between approx. 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 alkyl group of straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkylbenzenesulfonates, 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 R 1 represents an alkyl group having between approx. 1 and 17 carbon atoms or hydrogen, to obtain a mixture of sultones and alkenesulfonic acids which are then treated to convert the sultones to sulfonates.

Other examples of sulphate or sulphonate surfactants are paraffin sulphonates containing between approx. 10 and 20 carbon atoms, preferably between approx. 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. Other useful sulfate and sulfonate surfactants are sodium and potassium sulphate of higher alcohols containing between approx. 8 and 18 carbon atoms, such as sodium lauryl sulphate and sodium tallow alcohol sulphate, sodium and potassium salts of alpha-sulpho fatty acid esters containing approx. 10-20 carbon atoms in the acyl group, for example methyl alpha-sulfomyristate and methyl alpha-sulfotalgoate, ammonium sulphate of mono- or di-glycerides of higher (C10-C18) fatty acids, for example stearic acid monoglyceride monosulphate; 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 with approx. 1-6 oxyethylene groups per molecule and in which the alkyl radicals contain approx. 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 metal (such as calcium and magnesium). salts of higher alkylbenzene sulfonates, olefin sulfonates and higher alkyl sulfates.

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 or 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 approx. 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 substances are the condensation product of coconut fatty alcohol together with approx. 6 moles of ethylene oxide per mole of coconut fat alcohol, the condensation product of tallow fatty alcohol with approx. 11 moles of ethylene oxide per mole of tallow fatty alcohol, the condensation product of a secondary fatty alcohol containing approx. 11-15 carbon atoms with approx. 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: R 2 \ R-N-R 4 -x = o g I R / J 1 -o in which R represents an alkyl group having between about 8 and 18 2 and R 3 each represent an alkylene or hydroxyalkylene group having approx. 1-4 carbon atoms, R 4 represents a carbon atom, R is an alkylene or hydroxyalkylene group having 1-4 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 S = O, the surfactant is denoted by a sulfo-beta or sultain.

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

Examples of suitable synthetic cationic surfactants are: common primary amines of the formula RNH2, in which R represents an alkyl group having approx. 12-15 carbon atoms; diamines of the formula RNHC2H4NH2, having between 12 and 22 carbon atoms, such as N-2-aminoethyl-stearyl- in which R represents an alkyl group amine and N-2-aminoethyl-myristylamine; amide-linked amines such as those of the formula R 1 CONHC 2 H 4 NH 2, in which R 1 represents an acyl group having approx. 8-20 carbon atoms, such as N-2-aminoethyl-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 approx. 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 with inert substituents, such as phenyl groups, an anion such as halogen, acetate, methyl sulfate, etc. being present. The alkyl groups may contain intermediate bonds such as amide, which do not significantly affect the hydrophobic character of the group, for example quaternary stearylamidopropylammonium 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 propyl ammonium dimethyl chloride corresponding methyl sulphates and acetates. Ampholytic surfactants are also useful according to 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. 2. Examples of suitable amphoteric surfactants are 4COMM) 2; alkyl-beta-COOM; and long chain imidazole alkyl beta-iminodipropionates, RN (C2H aminopropionates, RH (H) C2H4 derivatives of the general formula CH2 / \ E * 'fHz RC - N-CHZCHZOCHZCOOM ÖH CHZCOOM wherein in each of the above-mentioned formulas R an acyclic hydrophobic group having between about 8 and 18 carbon atoms, and M is a cation which neutralizes the charge of the anion Particularly suitable amphoteric surfactants are the disodium salt of undecylcycloimidine ethoxythione acid-2-ethionic acid, dodecyl beta- alanine and the inner salt of 2-trimethyl-amino-lauric acid.

The detergent composition of the invention may optionally contain a detergent salt of the type 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, 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-1,1,2-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 active 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, benzenepoly (i.e. penta- and tetra-) -carboxylic acid methoxy acids.

Water-insoluble detergent active compounds can also be used, in particular complex silicates and especially the 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 the pore size is approx. 4 Å. The production of this type of zeolite is described in the American; U.S. Patent No. 3,114,603. The zeolites may be amorphous or crystalline and contain hydrated water in a manner known in the art.

An inert water-soluble salt in the form of a filler is preferably included in the detergent compositions of the invention. A preferred filler is an alkali metal sulfate, such as potassium or sodium sulfate, the latter being especially preferred.

Various additives may be included in the bleaching detergent compositions of the invention. Thus, for example, colorants, such as pigments and dyes, are antifoulants such as carboxymethylcellulose, optical brighteners such as anionic, cationic or nonionic whitening agents; foam stabilizers such as alkanolamides, proteolytic enzymes and the like well known in the art, as useful in fabric detergent compositions.

In the use according to the invention, the 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 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, MPPA and / or a salt thereof and the selected chelating agent may either be directly mixed with the surfactant compound, the detergent salt and the like, or MPPA and / or a salt thereof is coated with a coating material to prevent premature activation of the bleach. The transfer takes place 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.

(N 10 15 20 25 30 453 100 15 Example 1 A preferred low temperature bleach has the following composition: Component Weight% Linear sodium C 10 -C 13 alkylbenzenesulfonate Etoxylated C11-C18 alcohol (11 ethoxy moles per mole of alcohol) Soap (sodium salt of C12-C22 carboxylic acids) Sodium silicate (1 Na2O: 2 S102) Pentasodium tripolyphosphate (TPP) Sodium salt of diethylenetriamine-pentamethylene-0.5phosphonic acid (DTPMP) Enzyme (a) 7 0.4 Optical white matter 0.2 mg salt of MPPA (b) 7.0 Perfume 0.18 Sodium sulphate 22 Water qs (a) Proteolytic enzyme in the form of Alcalase 2M (2 anson units / gram) or Maxatase P. (b) Bleaching composition containing as active ingredient about 65% by weight of magnesium monoperoxyphthalate and with an active oxygen content of 5.1%.

The product as above was prepared by spray drying an aqueous slurry containing 60% by weight of a mixture of all the above components, with the exception of enzyme, perfume and H-48 bleach composition. The resulting spray-dried product had a particle size in the range of 8-150 mesh (American screen series) and a moisture content of about 14%. 92.5 parts by weight of the spray-dried product were mixed with 7 parts by weight of H-48 of the same mesh size, 0.3 parts by weight of enzyme and 0.18 parts by weight of perfume in a rotating drum to give a comminuted product. with the above composition and a moisture content of approx. 13% by weight.

The product described above was used in washing soiled fabrics in a washing machine, and good washing and bleaching results were obtained.

Example 2 Bleaching experiments were performed with standard specimen samples 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 experimental compositions described in Table 1 was added to 1 liter of tap water at 49 ° C with a water hardness of approx. 100 ppm, as calcium carbonate. The test compositions were stirred for approx. 1 minute, after which different fabrics each consisting of two sample patches (76.2 x 101.6 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 stain removal was measured by determining the reflectance factor for each stained cloth patch before and after washing using a Gardner Color Difference Meter, and the percentage stain removal (% SR) was calculated as follows: (Rd after washing) - (Rd before washing)% SR = X 100 (Rd before staining) ° (Rd before washing) where "Rd before washing" refers to the Rd value after staining. 10 15 20 25 30 453 100 17 Based on the percentage values obtained for the stain removal, 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 thiosulphate solution using starch.

The respective stains and test fabric samples were as follows: Elägk Test Fabric 1. Grape 65 dakron - 35 cotton 2. Blueberry Cotton 3. Sulfo color EMPA 115 (cotton) 4. Red wine EMPA 114 (cotton) 5. Coffee / tea Cotton The stained test fabrics 1 and 2 was obtained by passing rolls of unstained cloth 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 121 ° C, the fabric was cut into pieces measuring 76.2 x 101.6 mm. Eighty such cloth patches, impregnated with the same stain type, 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 through a Beseler Print Dryer at a machine temperature setting of 6 and a speed of 10.

The stained test fabrics 3 and 4 were obtained from Testfabrics Incorporated of Middlesex, New Jersey, and were cut into 76.2 x 101.6 mm pieces. 10 15 20 25 455 1ÜÛ 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 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 wash cycles 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 carbonylate Sodium carbonylate Optical brighteners 0.2 Perfume 0.2 Water 11 Sodium sulphate residual Detergent compositions AE containing HDD had the composition shown in Table 1. Table 15 Component Composition .ê ES 2 å Detergent, HDD 4.50g 4, 50g 4,509 4,50g 4,509 Mg salt of MPPAÜ) ----- 0,49 0,49 0,49 0,49 DTPMP (2) '' - '“'“ - _ ”Ü, Û9 -“ * ““ ~ - - - EDTÅ (3) NTAM) (1) A bleaching composition containing approx. 65% by weight of monoperoxyphthalic acid (as magnesium salt) and with 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. (4) Nitrile triacetic acid, trisodium salt.

Compositions AE 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 "remaining", respectively). grams ") and the stain removal obtained for each of the five stain types. 10 15 20 453 100 20 Table 2 Relative bleaching capacity Grams from the beginning (A.0. X 103) Remaining grams (A.0. X 103) Consumed, grams (AO x 103) Stain removal: Grape Blueberry Sulpho dye (EMPA 115) Red wine ( EMPA 114) Coffee / tea Mean value (%) Composition è å 9 2 E ----- 25.0 25.0 25.0 25.0 ----- 15.9 16.6 18.5 15.6 ----- 9.1 6.4 6.5 9.4 å å å å å 47 69 72 74 12 44 65 68 66 67 3 3 3 3 4 36 49 51 44 45 17 43 39 38 41 30 46 47 The results in Table 2 show that compositions C and D (containing the chelating agents DTPMP and EDTA, respectively) consume less active oxygen, but they still provide approximately the same degree of color removal as Composition E containing NTA or Composition B containing no chelating agent. <1 10 15 20 25 453 100 21 Example gel 3 Bleaching experiments were performed using a detergent composition "A" having the following composition: Component yiktâ Linear sodium alkylbenzenesulfonate (LAS) 5 Soap (sodium salt of high molecular weight fatty acid) 5 Etoxylated alcohol (11 moles of E0 O alcohol) 3 Sodium silicate 3 Sodium tripolyphosphate (TPP) 40 Optical white matter 0.2 Sodium sulphate 23.5 Enzyme 0.3 Perfume 0.2 Mg salt of MPPA (1) 9 Water residues (1) A bleaching composition described in note (b) after the table in Example 1.

The tests were performed in an Ahiba washing machine under the following test conditions: Ahiba wash cycle = warm-up period + wash period Bath initial temperature = 30 ° C Cycle Owl warm-up period Washing period 4000 5 minutes 15 minutes 60oC 15 minutes 15 minutes 95 ° C 30 minutes 15 minutes Detergent concentration: 10 grams / The hardness of the tap water: 350 ppm 453 100 22 Six 10 x 10 cm wine-stained test pieces per container in 600 ml detergent solution.

The reflection factors were determined before and after washing using a Gardner reflectometer XL-20, and all results are given as 5.

ARd Detergent compositions B-F were obtained by adding the sequestrants to composition A described below.

Composition Added sequestering agent B 0.5% by weight of diethylenetriamine-pentamethylenephosphonic acid (1) C 0.1% by weight of diethylenetriamine-pentaacetic acid - Mg salt D 1% by weight of nitrile triacetic acid (NTA) 1% by weight of EDTA 0.5% by weight ethylenediamine tetra- tFJ 15 F methylene phosphonic acid (2) (1) Sold as Dequest 2060 by Monsanto Company, Inc. St. Louis, Missouri (2) Sold as Dequest 2041 by Monsanto Company, Inc. The results of the bleaching experiments are summarized in Table 1 below, where the ¿ÄRd values were obtained as an average value for the particular composition at the indicated temperature. 1 ,, 10 23 Table 1 ¿1Rd values (average) Temperature § 1o ° c 36 eo ° c 41 9s ° c 47 As can be seen from Table 1, all compositions containing sequestrants showed improved bleaching properties. E 34.5 39 45 B 34.5 39 44 E. 33 38.5 43 453 E 33 38.5 43 100 è 32 38 43 creates compared to composition A which did not contain any sequestering agent. Composition B, containing Dequest 2060, presented. the most bleaching ability of all the compositions tested.

Claims (16)

10 15 20 25 1. 453 100 24 P a t e n t k r a v Bleaching detergent composition, k n n e t e c k - n a d in that it contains: (a) (b) (c) (d) (e) 2. between approx. 5 and 50% by weight of a bleaching agent consisting of monoperoxyphthalic acid and / or a water-soluble salt thereof, which bleaching agent does not comprise any inorganic peroxy compound; a chelating agent capable of forming a substantially water-soluble metal complex in aqueous solution; between approx. 5 and 50% by weight of one or more surfactants selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants; between approx. 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 total weight proportion of surfactant surfactant, detergent-assisting salt, and any filler in the form of a salt is between approx. 6: 1 and approx. 20: 1 in relation to the sum of the bleach and the chelating agent. 3. n e t e c k n a d in that the total weight proportion of Bleaching Detergent Composition according to claim 1, k - surfactant surfactant, detergent salt and optionally E filler in the form of a salt is between approx. 6.5: 1 and approx. l5: 1 in relation to the sum of the bleach and the chelating agent. was characterized in that the bleaching agent comprises magnesium Bleaching detergent composition according to claim 1, n e t e c k n a d monoperoxyphthalate. Composition according to Claim 1, characterized in that the chelating agent is diethylenetriamine-pentamethylenephosphonic acid and / or a water-soluble salt thereof. Composition according to Claim 1, characterized in that the chelating agent is ethylenediaminetetraacetic acid and / or a water-soluble salt thereof. Composition according to Claim 1, characterized in that the weight ratio between the chelating agent and the monoperoxyphthalic acid and / or the salt thereof is between approx. 1: 4 and approx. 1:15. Bleaching detergent composition according to claim 1, characterized in that the content of the chelating agent is lower than approx. 5% by weight. Bleaching detergent composition according to claim 1, characterized in that the content of the chelating agent is lower than approx. 2% by weight. A method of preparing the composition according to claim 1, characterized in that: (a) providing a water slurry containing the surfactant (s) and the detergent salt; (b) spray drying the water slurry to obtain granulated particles thereof; and (c) to the granular particles obtained in step (b), the composition contains a monoperoxyfthalic acid and / or a water-soluble salt thereof and a chelating agent capable of forming a substantially water-soluble metal complex in aqueous solution, for to provide the bleaching detergent composition. 11. ll. Use of an aqueous solution of a composition containing monoperoxyphthalic acid and / or a water-soluble salt thereof and a chelating agent capable of forming a substantially water-soluble complex in aqueous solution, which composition does not comprise any inorganic peroxy compound for the staining of and / or soiled materials, these materials being brought into contact with the aqueous solution. Use according to claim 11, characterized in that the composition contains magnesium monoperoxyphthalate. Use according to claim 11, characterized in that the chelating agent is diethylenetriamine-pentamethylenephosphonic acid and / or a water-soluble salt thereof. Use according to claim 11, characterized in that the chelating agent is present in a weight proportion relative to monoperoxyphthalic acid and / or the salt thereof of between approx. 1: 4 and approx. 1:15. Use according to claim ll, characterized in that the weight proportion is between approx. 1:15 and approx. 1:12. Use according to claim ll, characterized in that the composition further contains one or more surfactants selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants. 'HRS