DK158954B - WHITE DETERGENTS CONTAINING MONOPEROXYPHTHALIC ACID, A CHELATING COMPOUND AND AN ACTIVATOR FOR THE PEROXYGEN COMPOUND AND THE USE OF TOUCH WASH - Google Patents

Description

in

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The present invention relates generally to bleaching and washing agents as well as their use for washing clothes. More particularly, the invention relates to bleaching and detergents comprising mono-peroxyphthalic acid and / or a water-soluble salt thereof / a chelating agent capable of forming a water-soluble metal complex in aqueous solution, a peroxygen compound and an organic activator for the peroxygen compound comprising phthalic anhydride.

Bleaches that release active oxygen into the wash solution 10 are extensively described as known in the art and are commonly used for washing clothes. In general, such bleaches contain peroxygen compounds, such as perborates, percarbonates, perphosphates and the like, which promote the bleaching effect of hydrogen peroxide formation in aqueous solution. A major disadvantage associated with the use of such peroxygen compounds is that they are not optimally effective at the relatively low washing temperatures used in most household washing machines, i.e. temperatures in the range of approx. 21 ° C to approx. 54 ° C. In comparison, 20 European washing temperatures are generally significantly higher and extend over a range that typically ranges from approx. 32 ° C to approx. 93 ° C. However, in Europe and the other countries, which generally use washing temperatures near the boiling point, there is also a movement towards laundry at lower temperatures.

In an attempt to increase the bleaching effect of peroxygen bleaches, the materials used in the prior art have required activators in combination with the oxygen compounds. It is generally believed that the reaction between the peroxygen compound 30 and the activator results in the formation of a peroxyacid which is the active bleaching compound. Numerous compounds have heretofore been proposed as activators for peroxygen bleaches to which carboxylic acid anhydrides, such as the 2

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U.S. Patent Nos. 3,928,775, 3,338,839, and 3,352,634 to carboxylic acid esters, such as those disclosed in U.S. Patent No. 2,995,905, N-acyl compounds such as U.S. Patent Nos. 3,916,648 and 3,919. 102, 5 cyanoamines, such as U.S. Patent Nos. 3,916,648 and 3,919,102, and acylsulfoamides, such as U.S. Patent No. 3,245,913.

Pre-prepared peroxyacids have also been used to produce bleaching in laundry solutions for laundry.

U.S. Patent Nos. 3,770,816, 4,170,453, and 4,259,201 illustrate prior art bleaching agents comprising a peroxyacid compound.

It is generally recognized in the prior art that metal ions are capable of acting as decomposition catalysts for inorganic peroxygen compounds and organic peroxyacids.

In an attempt to stabilize such bleaching compounds in the wash solution has chelating. agents have been incorporated into bleaching detergents. U.S. Patent No. 3,243,378, for example, discloses a bleach containing a bleaching peroxygen compound as well as a chelating agent for sequestering metal cations. Generally, the chelating agents used for this purpose fall into one or two categories: (a) materials such as heterocyclic compounds and ketones, especially 8-hydroxyquinoline, which binds metal cations 25 in the wash liquid by precipitation of them from the solution, and ( b) materials such as aminopolycarboxylates and aminopolyphosphonate compounds which form water-soluble metal complexes with the cations present in the wash solution. Accordingly, U.S. Patent No. 4,005,029 states that selected aldehydes, 30 ketones, as well as compounds that form aldehydes or ketones in aqueous solution (e.g., 8-hydroxyquinoline) can be used to activate aliphatic peroxyacids such as diperazelaic acid, diperadipic acid and aromatic peroxyacids (and water-soluble salts thereof) including monoperoxyphthalic acid and 3

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diperoxyterephthalsyre. 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 formed in wash solutions 5 containing diperoxydodecandic acid. U.S. Patent No. 4.22! 452 discloses the combination of specified classes of chelating agents (including phosphonate compounds) with inorganic peroxygen compounds and an organic activator for suppressing the decomposition of peroxygen compound 10 in the bleach. In particular, the chelating agent is said to inhibit the undesirable side reaction of the peroxygen compound with the peroxyacid formed by the primary reaction of the peroxygen compound and activator, the effect of side reactions being: removing the bleaching peroxyacid compounds from the solution. However, United States Patent No. 4,225,452 dispenses with the use of such chelating agents in solutions wherein the peroxy acid has a double bond between the carbon atoms ία, α1 position relative to the carbonyl group. Especially in the second column of the patent beginning at line 63, 20 phthalic anhydride is excluded as activator of the present bleach due to instability. In so far as the peroxyacid formed in the reaction between phthalic anhydride and an inorganic peroxygen compound is monoperoxyphthalic acid, United States Patent No. 5,225,452 is clearly disregarding the use of 25 monoperoxyphthalic acid in the bleaches disclosed in the patent.

European Patent Publication No. 27,693 discloses the use of magnesium monoperoxyphthalate as effective bleach. The disclosure also discloses the optional combination of a bleach with an "aldehyde or ketone peroxyacid activator as disclosed in U.S. Patent No. 4,005,029, e.g.

8-hydroxyquinoline is a known peroxygen stabilizer. "The publication also discloses organic phosphonate compounds as well as a variety of other compounds as useful detergent builders which may be included.

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4 is incorporated in the described detergents. However, there is no mention of the beneficial effects accompanying the use of a small amount of organic phosphonate compounds for use as dhelating agents in bleaching agents and in particular in magnesium monoperoxyphthalate containing agents.

The above-mentioned European publication also discloses that peroxygen compounds can optionally be incorporated into detergents containing the described peroxyacid bleaches to obtain bleaching at higher washing temperatures. However, there is no indication therein of the use of an organic activator in combination with such peroxygen compounds, and in particular, of the desirability of using a peroxygen compound in combination with phthalic anhydride as activator in a bleaching system containing mono-peroxyphthalic acid and / or a salt thereof and a chelating agent of the type described herein.

The bleaching detergent of the invention is peculiar in that it contains: (a) from ca. 5 to approx. 50% by weight of an agent comprising monoperoxyphthalic acid and / or a water-soluble salt thereof, a chelating agent consisting essentially of a diethylene-triamine-pentamethylene phosphonic acid and / or a water-soluble salt thereof, a non-monoperoxyphthalic acid peroxygen compound, and an activator for said peroxygen compound 25 consisting essentially of phthalic anhydride; 5 to approx. 50% by weight of one or more surfactants selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants, (c) from ca. 5 to approx. 80% by weight of a detergent builder salt and (d) the residue comprising water and optionally a filler salt.

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Embodiments of the detergent of the invention are set forth in the dependent claims directed to the detergent. In the process of the invention, bleaching of the stained and / or contaminated material occurs by contacting the material with an aqueous solution of the present detergent.

With the agent and method according to the invention, an increased bleaching effect is obtained.

The term "chelating agent" as used herein refers to organic compounds capable of binding, in small amounts, to transition metal cations (e.g., iron, nickel and cobalt) which are known to adversely affect the stability of peroxygen compounds and / or peroxyacids in aqueous bleaching solutions. Therefore, the chelating agents used herein do not include inorganic compounds usually used as builder salts in detergents. The chelating agents useful for the purposes of the present invention are of the type capable of forming a substantially water-soluble rather than a precipitated metal complex in aqueous metal ion solutions, especially transition metal cations such as those listed above. Suitable chelating agents include the di-ethylamine pentamethylene phosphonic acid (herein referred to as "DTPMP") and / or a water-soluble salt thereof. Among the salts of the DTPMT, the sodium, potassium and ammonium salts are generally preferred due to their relatively greater solubility and ease of preparation.

Generally, the chelating agents used in the bleaching agents of the invention are present in a weight ratio to MPPA and / or its salts from ca. 1: 5 to approx. 1:50 and more preferably from ca. 1: 7 to approx. 1:20. In the builder-containing bleaching detergents of the invention, the concentration of 35 is 6

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the chelating agent is generally below about 5% by weight, preferably below about 2% by weight and most preferably less than approx. 1% by weight of such detergents.

Monoperoxyphthalic acid and / or one or more of the water-soluble salts thereof in combination with a peroxygen compound are the bleaching agents of the compositions of the invention. Although MPPA provides acceptable bleaching effect, it has the disadvantage of having relatively poor stability when stored in blend 10 with other components usually found in household detergents. For reasons of stability, therefore, the magnesium salt of MPPA is preferably used in the compositions of the invention, namely magnesium monoperoxyphthalate. The alkali metal salt, calcium or barium alkaline earth metal salts and / or the ammonium salt of 15 MPPA can also be used in the bleaching and detergent compositions described herein, although such salts are generally less preferred than the above-mentioned magnesium salt from a stability point of view.

The preparation of MPPA is generally carried out by reacting hydrogen peroxide with phthalic anhydride. The resulting MPPA can then be used to prepare magnesium monoperoxyphthalate by reaction with a magnesium compound in the presence of an organic solvent. A detailed description 25 of the preparation of MPPA and its magnesium salt is set forth on pages 7 to 10 of European Patent Publication No. 27,693, the pages of pages 7 to 10 of which are incorporated herein by reference.

The peroxygen compounds useful in the invention include compounds which release hydrogen peroxide in aqueous media such as alkali metal perborates, percarbonates, perphosphates and the like. Sodium perborate is particularly preferred as 7

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due to its commercial availability.

In the bleaching agent, the peroxygen compound is generally present in relation to the phthalic anhydride active ingredient. in a molar ratio of peroxygen compound to phthalic anhydride from ca. 1: 1C 5 to approx. 10: 1, with the preferred ratio being from approx. 1: 2 to approx. 3: 1. It will be appreciated that the concentration of phthalic anhydride will depend on the concentration of peroxygen compounds which in turn is controlled by the desired degree of bleaching. The peroxygen compound is typically present in the bleach in an amount of about 10 to about 1% by weight to approx. 50 wt., Preferably from 3 to 25 wt.% And most preferably from 5 to 20 wt.% Of the bleach.

The amount of bleach added to the wash solution is generally selected to obtain an amount of peroxygen compound and peroxyacid compound in the range of about 3 to 15 10 parts of active oxygen per million parts of the wash solution.

MPPA and / or a water-soluble salt thereof in combination with the selected gelling agent, peroxygen compound and phthalic anhydride may be formulated as a separate bleaching product or alternatively may be used in a composite detergent. Accordingly, the bleaching agent of the invention may include conventional additives used in the textile washing field such as binders, fillers, builder salts, proteolytic enzymes, optical cleaners, perfumes, dyes, corrosion inhibitors, antigen deposition agents, foam stabilizers, and the like. in varying amounts depending on the desired properties of the bleach and their compatibility with such bleach. Furthermore, the bleaching agents of the invention can be incorporated into laundry detergents containing surfactants such as anionic, cationic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof.

When the bleaches in question are incorporated into a conventional 8

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detergent and therefore available as a fully composed bleaching detergent, the latter detergents will comprise the following: 5 to 50% by weight of the subject bleach, from approx. 5 to approx. 50% by weight of a detergent surfactant, preferably from ca. 5 to approx. 30% by weight, and from approx. 5 to approx.

80% by weight of a detergent builder salt which can also act as Buffer to achieve the required pH range when the detergent is added to water. The aqueous wash solutions will have a pH range of approx. 7 to approx. 12, preferably from ca. 8 10 to approx. 10 and most preferably from ca. 8.5 to approx. 9. A preferred amount of the builder salt is from ca. 20 to 65% by weight of the agent. The remainder of the agent will mainly comprise water, filler salts / such as sodium sulfate, and optionally minor additives, such as optical brighteners, perfumes, dyes, antigen deposits, and the like.

Among the anionic surfactants useful in the present invention are the surfactants: compounds or detergent compounds which contain an organic hydrophobic group containing generally from ca. 8 to approx. 20 26 carbon atoms and preferably from 10 to 18 carbon atoms in their molecular structure and at least one water solubilizing group selected from sulfonate, sulfate, carboxylate, phosphonate and phosphate to form a water-soluble detergent.

Examples of suitable anionic detergents include soaps, such as the water-soluble salts (e.g., sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from ca. 8 to approx. 20 carbon atoms and preferably 10 to 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 suitable are the sodium and potassium salts of fatty acid mixtures extracted from coconut oil and sebum, e.g. coconut sodium soap and sebum potassium soap.

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The anionic detergent class also includes the water-soluble sulfated and sulfonated detergents having an alkyl group containing from ca. 8 to 26 and preferably from ca. 12 to approx. 22 carbon atoms. Examples of the sulfonated anionic detergents are the higher alkyl mono-nuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing from ca. 10 to approx. 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkylbenzenesulfonates, 10 higher alkyltoluenesulfonates and alkylphenol sulfonates.

Other suitable anionic detergents are the olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkanesulfonates or mixtures of alkene sulfonates and hydroxyalkanesulfonates. The olefin sulfonate detergents can be prepared in a conventional manner by reacting SO 2 with long-chain defines containing from ca. 8 to approx. 25 and preferably from ca.

12 to approx. 21 carbons, such olefins having the formula RCH = CHR 2, wherein R is a higher alkyl group having 6 to 23 carbon atoms and R 1 is an alkyl group containing from ca. 1 to 20 approx. 17 carbon atoms or hydrogen, to form a mixture of sultones and alkenesulfonic acids, which are then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergent paraffin fin sulfonates containing from ca. 10 to approx. About 20 carbon atoms and preferably 25 from ca. 15 to approx. 20 carbon atoms. The most important paraffin sulfonates are produced by reaction of long chain α-olefins and bisulfites -Paraffin sulfonates with the sulfonate group distributed along the paraffin chain are shown in United States Patent Specification No. 2,503. 280, 2,507,088, Nos. 3,260,741 and Nos. 3,372,188, and in German 30 Patent No. 735,096. Other useful sulfate and sulfonate detergents include sodium and potassium sulfonates of higher alcohols containing from ca. 8 to approx. 18 carbon atoms, such as, for example, sodium lauryl sulfate and sodium tallow alcohol sulfate, sodium and potassium salts of α-sulfo fatty acid esters containing from ca. 10 to approx. 20 carbon atoms in 10

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the asylum group, e.g. methyl α-sulfomyristate and methyl α-sulfo talloate, ammonium sulphates of higher mono- or di-glycerides of (cig "c18 fatty acids, for example, stearin monoglyceride monosulfate, sodium and alkylolammonium salts of alkyl polyethene oxyether sulfates prepared by condensation of 1 to 5 moles of ethylene oxide with 1 mole of higher (Cg "Cig) alcohol, sodium higher alkyl (C1-C6g) glyceryl ether sulfonates, and sodium or potassium alkylphenol polyethene oxyether sulfates having about 1 to 6 oxyethylene groups per molecule, and wherein the alkyl groups 10 contain from about 8 to about 12 carbon atoms.

The most preferred water-soluble anionic detergent compounds are the ammonium salts and the substituted ammonium salts (such as mono-, di- and triethanolamine salts), alkali metal salts (such as sodium and potassium salts) and alkaline earth metal salts (such as calcium and magnesium sulfate), and the higher alkyl salts, higher alkyl sulfates. Among the anionic detergent compounds listed above are the most preferred sodium linear linear alkylbenzene sulfonates (LABS).

The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically prepared by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen atom attached to the nitrogen atom can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic chain or polyoxyethylene chain can be readily adjusted to achieve 30 ° of the desired balance between the hydrophobic and hydrophilic groups.

The nonionic detergents include the polyethylene oxide condensate of 1 mole of alkylphenol containing from ca. 6 to approx.

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12 in a straight or branched chain configuration with approx. 5 to approx. 30 moles of ethylene oxide, e.g. 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 with 5 to 30 moles of ethylene oxide are also suitable.

Of non-ionic surfactants of the types described above, those of the ethoxylating alcohol type are preferred. Particularly preferred nonionic surfactants include the condensation product of coconut fatty alcohol by about 6 moles of ethylene oxide per mole of coconut fat alcohol, the condensation product of sebum fat alcohol by approx. 11 moles of ethylene oxide per mole of sebum fat alcohol, the condensation product of a secondary fat alcohol containing approx. 11-15 carbon atoms with approx. 9 15 moles of ethylene oxide per moles of fatty alcohol and condensation products of more or less pre-branched primary alcohols, the branching being predominantly 2-methyl, with from approx. 4 to approx.

12 moles of ethylene oxide.

Zwitterionic detergents, such as the betaines and sulfobetainers, of the following formula are also applicable: R2 R-N-R.-X == 0

II 4 I

Wherein R is an alkyl group having from about 8 to approx. 18 carbon atoms, R 3 and R 2 each are an alkylene or hydroxyalkylene group containing from about 1 to approx. 4 carbon atoms, R4 is an alkylene or hydroxyalkylene group containing 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 polyethyl bond, or non-functional substituents such as

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droxyl all halogen which does not significantly affect the hydrophobic nature of the group. When X is C, the detergent is called a betaine and when X is S = 0, the detergent is called a sulfobetaine or sultain.

Cationic surfactants may also be used. They include surfactant detergent compounds containing an organic hydrophobic group which forms part of a cation when the compound is dissolved in water, and an anionic group. Typical cationic surfactants are amino compounds 10 and quaternary ammonium compounds.

Examples of suitable synthetic cationic detergents include normal primary amines of the formula RN ^ wherein R is an alkyl group containing from ca. 12 to approx. 15 carbons, diamines of the formula RNIK ^ H ^ Ni ^ r wherein R is an alkyl group 15 containing from ca. 12 to approx. 22 carbons, such as N-2-aminoethyl-stearylamine and N-2-aminoethyl-myristylamine, amide-linked amines, such as those of the formula R 1 -CONITC 2 H 2 Ni 2, wherein R 2 is an alkyl group containing from 8 to approx. 20 carbon atoms, such as N-2-aminoethylstearylamine and N-aminoethylmyrimethyl-20-amide, quaternary ammonium compounds, wherein typically one of the nitrogen-linked groups is an alkyl group containing from ca. 8 to approx. 22 carbon atoms and three of the nitrogen atom linked groups are alkyl groups containing 1 to 3 carbon atoms, including alkyl groups bearing inert substituents such as phenyl groups and containing an anion such as halogen, acetate, methosulfate etc. The alkyl group may contain intermediates bonds such as amide bonds that do not significantly affect the hydrophobic nature of the group, e.g. stearylamidopropyl quaternary ammonium chloride. Typical quaternary ammonium detergents are ethyl dimethylstearyl ammonium chloride, benzyldimethylstearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethylcetylammonium bromide, dimethylethyl-laurylammonium chloride, dimethylpropylmyristylammonium chloride

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and the corresponding methosulfates and acetates.

Ampholytic. detergents are also suitable for the purposes of the invention. Ampholytic detergents are well known and many useful detergents belonging to this class are disclosed by A.M.

5 Schwartz, J. W. Perry and J. birch in "Surface Active Agents and

Detergents ", Interscience Publishers, New York, 1958, Volume 2. Examples of suitable amphoteric detergents include: alkyl β-iminodipropionates, RN (C2H4COOM) 2r alkyl-β-aminopropionates, RN (H) C2H4COOM, and long chain imidazole derivatives 10 the general formula: / ¾

N I

12

R-C-N-CH 0CH and 0CH oC00M

Z Z z

OH CH2COOM

wherein R in each of the above formulas is an acyclic hydrophobic group containing from ca. 8 to approx. 18 carbon atoms, and M is a cation for neutralizing the anion charge. Specific useful amphoteric detergents include the disodium salt of undecylcycloimidinium ethoxyethionic acid-2-ethionic acid, dodecyl-3-alanine and the inner salt of 2-trimethylaminolauric acid.

The detergent of the invention may optionally contain a detergent builder of the type commonly used in detergents. Suitable builders include any of the conventional inorganic water-soluble builder salts, such as, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates and the like. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxy sulfonates, polyacetates, carboxylates, polycarbozylates, succinates and the like.

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Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. In particular, the organic polyphosphonates include, for example, the sodium and potassium salts of ethane-1-5 hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,2-triphosphonic acid. Examples of these and other phos-phorbuilder compounds are disclosed in United States Patent Nos.

3,213,030, Nos. 3,422,021, Nos. 3,422,137 and 3,400,176. Penta-sodium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred water-soluble inorganic builders.

Specific examples of non-phosphorus-containing inorganic builders include water-soluble inorganic carbonate, bicarbonate, and silicate salts. Alkali metal, e.g. sodium and potassium, the carbonates, bicarbonates and silicates are particularly useful.

Water-soluble organic builders can also be used. Eg. alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates are useful builders for the agents and methods of the invention. Specific examples of polyacetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acid (i.e., penta and tertracarboxylic acids)

The bleaching agents of the invention are prepared by mixing the ingredients as illustrated below. In the preparation of detergents containing the bleach in combination with a surfactant detergent compound and / or builder salts, the components of the bleach can be mixed directly with the detergent compound, builder and the like. Alternatively, the peroxy gene activator, MPPA, and peroxygen compound may be coated with one-coat material to improve stability and /

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or prevent premature activation of the bleach. The coating process is performed in accordance with procedures well known in the art. Suitable coating materials include such compounds as magnesium phosphate, polyvinyl alcohol, lauric acid or salts thereof and the like.

EXAMPLE 1

Afprøvninqsprocedure

Bleaching experiments were performed with standard dyed sample fabrics (described below) using the various bleach and detergents described in Table 1 of this example in a tergotometer container manufactured by the US Testing Company. The tergotometer was kept at a constant temperature of 49 ° C and operated at 100 rpm. mine.

Each of the test materials listed in Table 1 was added to 15 L of tap water at 49 ° C with a water hardness of approx. 100 ppm, calculated as calcium carbonate. The test materials were stirred for approx. 1 min, and then a mixed textile filling. , consisting of two pieces of textile, each of them (7.5 cm x 10 cm) consisting of the spotted textiles described below, 20 set for each wash container. After a wash of 15 minutes at 49 ° C, the test fabrics were rinsed in tap water at 38 ° C and then dried. The percent stain removal was measured by taking a reflectance reading for each colored test fabric before and after washing using a Gardner Color Difference Meter, and the percent stain removal (% SR) was calculated as follows: (Rd after washing) - (Rd before washing)% SR = -1- x 100 (Rd before pollution) - (Rd before washing) where "Rd before washing" denotes the Rd value after staining.

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The percentage of stain removal calculated for all five textile pieces was used to calculate an average for each test detergent. A difference of more than 2% in the average of five tested 5 spotted textile pieces is considered to be significant.

At the end of each wash, the active oxygen wash solution content was determined by dilution with dilute sulfuric acid, followed by treatment of the wash solution with potassium iodide and a small amount of ammonium molybdate, then titrated with standard sodium thiosulfate using starch as indicator.

The respective stains and test fabrics were as follows:

Braid with: Test fabrics 1. Grape - 65 dacron - 35 cotton 15 2. Blueberries - cotton 3. Sulfur dye - EMPA 115 (cotton) 4. Red wine - EMPA 114 (cotton) 5. Coffee / tea - cotton 20 Spotted experimental fabrics 1 and 2 were prepared by passing rolls of unpainted textile through a foulard and dryer (manufactured by Benz in Zurich, Switzerland) containing either grape or blueberry solutions at 32 ° C. After drying at 121 ° C, the fabric is cut into 7.5 cm x 25 io cm textile pieces. Eighty of these textile pieces impregnated with the same stain type are rinsed in 65 liters at 29 ° C in an automatic household washing machine. They are then dried by passage through a Beseler pressure dryer at a machine temperature setting of 6 and a speed of 10.

30 Spotted fabrics 3 and 4 are purchased from Testfabrics Incorporated 17

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in Middlesex, New Jersey, and cut into 7.5 cm x 10 cm textile pieces.

The spotted textile 5 was prepared by stirring and soaking uncontaminated cotton strips (46 cm x 91 cm) in a washing machine filled with a coffee / tea solution (weight ratio 8: 1) at 66 ° C. The machine is allowed to rinse rotation dryer to remove the coffee / tea solution. The dyed textile is then machine-washed twice with warm solution of pyrophosphate surfactant followed by two complete wash cycles of 10 water at 60 ° C. The strips are then dried by means of two passages through an "Ironrite" machine set to 10 and then cut into 7.5 cm x 10 cm textile pieces.

A granular detergent (herein referred to as "HDD") was prepared by conventional spray drying and had the following approximate composition:

Composition Weight% Sodium Tridecylbenzenesulfonate 15 Ethoxylated (^ C C Primary Alcohol (7 mol EO / mol Alcohol) 1 20 Sodium Tripolyphosphate 33 Sodium Carbonate 5 Sodium Silicate 7 Sodium Carboxymethyl Cellulose 0.5 Optical Clarifiers 0.2 25 Perfume 0.2 Water 11 Sodium Sulphate

Detergents A-D containing HDD were composed as listed in Table 1.

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Table 1

Component Composition

A B C D

Detergent, HDD 4.50 g 4.50 g 4.50 g 4.50 g 5 H-48 (1) ---- 0.25 0.25 0.25 DTPMP ---- ---- 0, 02 0.09

Sodium perborate 0.32 0.16 0.16 0.16

Phthalic anhydride ---- 0.125 0.125 0.125 (1) A bleach containing monoperoxyphthalic acid (as magnesium salt) obtained from Interox Chemicals Houston, Texas and containing an active oxygen content of 5.1% (2) Sodium diethylenetriamine pentamethylene phosphonate obtained from P.A. Hunt Chemical Corporation, Lincoln, Rhode Island.

Agents A to D were tested in accordance with the procedure described above, and the results of the bleaching tests are listed in Table 2, which indicates the initial and final values of active oxygen (AO) in the wash solution (expressed as "grams to begin with", respectively). and "residual gram") and the pollution removal achieved for each of the five 20 contaminants or stains.

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Table 2

COMPARATIVE WHITE EFFECT

composition

Grams to begin with - - - - 5 (A.O. x 103) 32.8 28.7 28.7 28, '7

Remaining grams (A.O. x 103) 30.4 12.4 19.5 19.9

Gram Consumed (A.O. x 103) 2.4 16.4 9.2 8.8 10 Color or Pollution Removal:%%%%

Grapes 61 63 67 67

Blueberries 56 65 67 68

Sulfur Dye (EMPA 115) 3444 15 Red Wine (EMPA 114) 41 46 49 53

Coffee / tea 26 30 39 40

Average (%) 37 42 45 46

The results in Table 2 show that agents C and D consume significantly less active oxygen to achieve enhanced color or contaminant removal over agent B, which is an agent similar to agents C and D except that it does not contain the chelating agent. DTPMP.

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EXAMPLE 2

Detergents E-J were formulated to contain 0.15% detergent concentration as shown below in Table 3.

Table 3 5 Components Composition

E F G Η I J

Detergent, HDD 1.50 g 1.50 g 1.50 g 1.50 g 1.50 g 1.50 g H-48 (1) 0.20 0.20 0.20 0.07 0.07 0. 07 DTPMP1 ---- 0.02 ---- ---- 0.02 ---- 10 EDTA2 ---- ---- 0.02 ---- ---- 0.02

Sodium perborate (10.1% A.O.) ---- ---- ---- 0.15 0.15 0.15

Phthalic anhydride ---- ---- ----- 0.06 0.06 0.06 (1) A bleach containing monoperoxyphthalic acid (such as magnesium salt) obtained from Interox Chemicals, Houston,

Texas, and with an active oxygen content of 5.1%.

Sodium diethylenetriamine pentamethylene phosphonate obtained from P.A. Hunt Chemical Corporation, Lincoln, Rhode Island.

2

Ethylenediaminetetraacetic acid, disodium salt.

The agents E to J were tested in accordance with the procedures described in Example 1, and the results of the bleaching experiments are listed in Table 4. The initial and final values of active oxygen in the wash solution as well as the stain or contaminant removal obtained for the 5 stains shown are expressed as 25. in Table 2 of Example 1.

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Table 4

COMPARATIVE WHITE EFFECT

E F G Η I J

Grams to begin with 5 (A.O. x 1 (T) 10.2 10.2 10.2 18.6 18.6 18.6

Remaining grams (A.O. x 10J) 3.6 5.5 3.6 9.4 13.8 10.0

Gram Consumed (A.O. x 10) 6.6 4.7 6.6 9.2 4.8 8.6 10 Color Iron: 111111

Grapes 65 64 64 62 63 61

Blueberries 46 47 44 43 47 44

Sulfur dye (EMPA 115) 344455 Red wine (EMPA 114) 37 35 35 33 34 33 15 Coffee / tea 70 72 70 11 82 86

Average (%) 44 44 43 45 46 46

The results in Table 4 show that the bleaching effect obtained by the agent G is improved by using the means I and J according to the invention, which contain a reduced amount 20 of the MPPA bleach component compared to agents with F and G,

but which additionally contains perborate and phthalic anhydride activator. Furthermore, a comparison between the effect of agents I and J shows that agent I provides a bleaching efficiency equivalent to agent J but less consumption of significantly less active oxygen, the agents I

and J are identical except for the presence of DTPMP in the former and EDTA in the latter.

Claims (9)

Bleaching detergent according to claim 1, characterized in that component (a) in said agent contains magnesium monoperoxyphthalate. 25 Agent 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. 30 Bleaching detergent according to claim 1, characterized in that the concentration of the chelating agent is less than approx. 5% by weight. Bleaching detergent according to Claim 1, characterized in that the concentration of the chelating agent t is less than about 10%. 2% by weight. DK 158954 B An agent according to claim 1, characterized in that the peroxygen compound is an alkali metal perborate. Process for bleaching, characterized in that the stained and / or contaminated material to be bleached is contacted with an aqueous solution of a bleaching detergent according to claim 1. Process according to claim 7, characterized in that the agent contains magnesium monoperoxyphthalate. Process according to claim 7, characterized in that the chelating agent is in a weight ratio in relation to the amount of monoperoxyphthalic acid and / or the salt thereof from ca. 1: 5 to approx. 1:50. A method according to claim 7, characterized in that the weight ratio is from approx. 1: 7 to approx. 1:20. 20 25 30 35