DK160265B - BLEACHING INCLUDING BLEACHING LOW TEMPERATURE - Google Patents

Description

DK 160265 B

The present invention relates generally to bleaching and bleaching detergents and their use in laundry. More particularly, the invention relates to bleaching agents and bleaching detergents which provide effective bleaching at low washing temperatures.

5

Bleaches which release active oxygen in washing solutions are widely described in the prior art and are commonly used for laundry. Generally, such bleaches contain peroxygen compounds, such as perborates, percarbonates, perphosphates and the like, which promote bleaching by forming hydrogen peroxide in aqueous solution. A major disadvantage of using such peroxygen compounds is that they are not usually effective at the relatively low washing temperatures used in most household washing machines in the United States, ie. temperatures in the range of 27 - 66 ° C. In comparison, European washing temperatures are generally substantially higher and range from typically 32 to 93 ° C. However, even in Europe and the other countries which generally use laundry temperatures near boiling at present, there is a tendency for laundry at lower temperature.

In an effort to promote bleaching at low washing temperatures, the prior art has used peroxyacid compounds 25 as active bleaches at low temperature. Organic peroxyacid compounds are generally known to be more active bleaches than hydrogen peroxide at lower temperatures, the use of peroxygen bleaches being generally considered unsatisfactory for stain removal at temperatures below about 30 ° C. 60 ° C. Bleaching with peroxyacid compounds is therefore generally carried out in the prior art by either forming the peroxyacid compound in situ, in the washing solution, or alternatively introducing pre-formed peroxyacid compounds into the washing solution. The use of activator materials in combination with peroxygen compounds is extensively described in the patent literature and is the usual way to develop peroxyacid compounds in the wash solution, namely reaction

DK 160265 B

2 of the activator, typically a carboxylic acid derivative, and the peroxygen compound which forms a peroxyacid, typically peracetic acid. Among the compounds that have been proposed as activators for peroxygen bleaches are carboxylic anhydrides, such as those described in U.S. Patents 3,298,775 and 3,338,839; carboxylic acid esters such as those disclosed in U.S. Patent No. 2,995,905; and N-acyl compounds, as disclosed in U.S. Patents 3,912,648 and 3,919,102. Bleaches containing a pre-formed peroxyacid compound 10 are also known and U.S. Patents Nos. 3,170,453 and 4,259,920 illustrate this prior art.

The bleaching effect of agents containing a peroxyacid compound is further enhanced at low temperatures, especially at temperatures of 38 ° C or below, by the addition of bromide ions to the bleaching agents. U.S. Patent No. 4,338,210 discloses e.g. a bleaching system designed to operate at temperatures as low as 40 ° C and below, said bleaching system comprising a peroxide precursor such as diphthaloyl peroxide and sodium bromide. The theory of the patent is that the bromide reacts with the peroxy acid to form a hypobromite compound, the latter being a more effective bleach at low temperature than the peroxy acid compound. European Patent Application No. 00 24,367, published March 25, 1981, discloses a low temperature bleaching system comprising an organic peroxy acid such as diperisophthalic acid or monoperoxyphthalic acid in combination with bomid ion. U.S. Patent Nos. 4,123,376 and 4,300,897 disclose bleaches containing a peroxymonosulfate bleach, an inorganic bromide salt, and an aromatic sulfonamide compound such as an alkali metal toluene sulfonamide. The function of the aromatic sulfonamide compound in this bleach is, according to the patent, to prevent the bleaching of colored materials and, moreover, to regulate and control the bleaching effect provided by the peroxymonosulfate and bromide in an aqueous medium.

DK 160265 B

3

The present invention provides a bleach comprising: (a) monoperoxyphthalic acid (also referred to herein as MPPA) and / or a water-soluble salt thereof; (B) a water-soluble inorganic bromide salt, and (c) an aromatic sulfonamide compound selected from 1. benzenesulfonamide, toluene sulfonamide, ethylbenzene sulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, N-alkali metal salts of these sulfonamides, N-acetyl and N-benzoyl derivatives of these aforementioned sulfonamides and salts, and mixtures thereof.

The weight ratio of MPPA (or its salt) to bromide salt in the agent is from ca. 10: 1 to approx. 1: 5, preferably from ca.

8: 1 to approx. 1: 2, and most conveniently from approx. 6: 1 to approx.

1: 1. The weight ratio of aromatic sulfonamide compound to bromide salt in the agent is from ca. 5: 1 to 1: 7, preferably 20 from ca. 2: 1 to 1: 4.

The bleaching detergent of the invention comprises the above-defined bleaching agent in combination with one or more of the cleansing surfactants and a builder salt. In the process of the invention, bleaching of discolored and / or soiled materials is effected by contacting these materials with an aqueous solution of the above-defined agents.

The present invention is based on the finding that the low temperature bleaching activity of agents containing MPPA and bromide can be significantly increased by the addition of an aromatic sulfonamide compound to these bleaches. In contrast to the agents disclosed in U.S. Patents Nos. 4,123,376 and 4,300,897, wherein the aromatic sulfonamide compounds serve to inhibit the activity of bromo-activated peroxymonosulfate bleaches for the purpose of

DK 160265 B

4 to provide greater certainty for colors and clearances in the wash solution, the addition of aromatic sulfonamide compounds in the present compositions has the unexpected beneficial effect of providing a bleach with markedly increased activity.

5

Monoperoxyphthalic acid and / or one or more of its water-soluble salts are the primary bleaching agents in the bleaching agents and the bleaching cleaners of the invention. Although MPPA provides acceptable bleaching activity, it has the disadvantage of relatively poor stability when stored in admixture with other components usually found in household detergents. Therefore, for reasons of stability, the magnesium salt of MPPA is preferably used in the compositions of the invention, namely, magnesium monoperoxyphthalate. The magnesium monoperoxyphthalate is preferably provided in the form of an agent containing about 65% of the magnesium MPPA salt as the active ingredient and with an active oxygen content of approx. 5 to 6%. The alkali metal salts, calcium salts or barium salts 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 preferred from a stability point of view than the aforementioned magnesium salt.

The preparation of MPPA is generally carried out by reaction of hydrogen peroxide and 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 of the preparation of MPPA and its magnesium salt can be found on pages 7 -30 10 of European Patent Publication No. 0.027,693, published April 29, 1981, the MPPA bleach (or a salt thereof) may optionally be combined. in the present bleaches with a conventional peroxygen bleaching compound and an activator therefor. Examples of suitable peroxygen compounds include alkali metal perborates,

DK 160265B

5 percarbonates, perphosphates and the like, with sodium perborate being particularly preferred because of its industrial availability. Conventional activators such as those described e.g. in column 4 of U.S. Patent No. 4,259,200 are suitable for use with such peroxygen compounds.

The polyacylated amines are generally of particular interest, and TAED is especially a preferred activator. Other suitable activators include anhydride compounds such as anhydrides of benzoic acid, maleic acid, succinic acid and phthalic acid; and acyl compounds such as N-acetyl and N-benzoylimidazoles. In general, the mole ratio of peroxygen compound to activator may vary greatly depending on the particular choice of peroxygen compound and activator. Mole ratio from approx. 0.5: 1 to approx. However, 25: 1 is generally suitable to provide satisfactory whitening effect.

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

The aromatic sulfonamides used in the present compositions include the aforementioned sulfonamides, N-acetyl and N-benzoyl derivatives thereof, such as N-acetyl-paratoluenesulfonamide, N-acetylbenzenesulfonamide and N-benzoylbenzenesulfonamide, and the N-alkali metal salts of above mentioned. Preferred compounds include sodium and potassium para-toluenesulfonamide, ortho-toluenesulfonamide, benzenesulfonamide, and the corresponding alkali metal salts of the above. The alkali metal toluene sulfonamides are particularly preferred for the present invention.

The amount of bleach added to the wash solution is generally selected so as to provide an amount of peroxyacid compound within a range of about 3 - 100 parts of active oxygen per million parts of wash solution, with a concentration of approx. 5 to 40 ppm is generally preferred.

DK 160265 B

6

The present bleaches containing MPPA and / or its water-soluble salt, an inorganic bromide salt and an aromatic sulfonamide may be formulated as a separate bleaching product, or alternatively may be used in a builder-containing detergent.

Therefore, the bleaching agent of the invention may contain usual laundry additives such as binders, fillers, builder salts, proteolytic enzymes, optical cleaners, perfumes, dyes, corrosion inhibitors, dirt repellant preventing agents, foam stabilizers, and the like, are added in varying amounts depending on the desired properties of the bleach and their compatibility in such agent. In addition, the bleaching agents of the invention can be incorporated into laundry detergents containing one or more surfactants selected by the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents.

When the present bleaching agents are incorporated into a conventional laundry detergent and thus supplied as a fully composed bleaching cleanser, the latter will comprise the following: 5 to 50% by weight of the present bleach, from approx. 5 to 50% by weight, preferably from 5 to 30%, of a cleansing surfactant, and from approx. 5 to 80% by weight, preferably from about 10 to 60% by weight, of a builder salt, which can also act as a buffer, to provide the required pH range when the laundry detergent is added to water. The aqueous wash solutions will have a pH range of approx. 7 to 12, preferably from ca. 8 to 10, and most conveniently from approx. 8 to 9. A preferred amount of the builder salt is from ca. 20 to 30 approx. 65% by weight of the agent. The remainder of the composition will predominantly comprise water, filler salts such as sodium sulfate, and various additives described below.

The agents of the present invention contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents. The synthetic organic detergents,

DK 160265 B

7 used in the practice of the invention may be any of many different such compounds well known and described in the text Surface Active Agents, Volume II by Schwartz, Perry and Berch, published 1958 by Interscience Pub = 5 lishers.

The detergents according to the invention usually contain as the primary surfactant one or more anionic purifying compounds which, if desired, can be supplemented or replaced entirely by a nonionic detergent.

Among the anionic surfactants useful in the present invention are the surfactants which contain an organic hydrophobic group containing from ca. 8 to 26 carbon atoms, and preferably from 10 to 18 carbon atoms in their molecular structure, and at least one water-solubilizing group selected from the group of sulfonate, sulfate, ca = boxylate, 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 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. sebum, lard, coconut oil and mixtures thereof. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and sebum, e.g. sodium coconut soap and potassium tallow soap.

The anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents, which have an alkyl radical containing from ca. 8 to 26 and preferably from ca. 12 to 22 carbon atoms. (The term "alkyl" includes the alkyl portion of the higher acyl radicals). Examples of the 8

DK 160265 B

sulfonated anionic detergents are the higher alkylene-core aromatic sulfonates such as higher alkylbenzene sulfonates containing from ca. 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as e.g. sodium, potassium and the ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluenesulfonates and higher alkylphenol sulfonates.

Other suitable anionic detergents are the olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkanesulfonates or mixtures of alkenesulfonates and hydroxyalkanesulfonates. The olefin sulfonate detergents can be prepared in the usual manner by reaction of SO 2 with long-chain defines containing from ca. 8 to 25 and preferably from ca. 12 to 21 carbon atoms which have the formula 15 RCH = CHR1 where R is a higher alkyl group having from about Is from 6 to 23 carbon atoms and R 1 is an alkyl group containing from ca. 1 to 20 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 sulfonate or sulfate detergents are paraffin sulfonates containing from ca. 10 to 20 carbon atoms, and preferably from ca. 15 to 20 carbon atoms. The primary paraffin sulfonates are prepared by reaction of long chain α-olefins and bisulfites. Paraffin sulfonates having the sulfonate group distributed along the paraffin chain are disclosed in U.S. Patents Nos. 2,503,280, 2,507,088, 3,260,741, 3,372,188, and German Patent No. 735,096.

30

Other suitable anionic detergents are sulfated ethoxylated higher fatty alcohols of the formula R0 (C2H40) mSO3M 'where R is a fatty alkyl having from 10 to 18 carbon atoms, m is from 2 to 6 (preferably having a value of about 1/5 to one half). of the number of carbon atoms in R) and M is a solvent

DK 160265 B

9, salt-forming cation such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkylbenzenesulfonate wherein the higher alkyl has 10 to 15 carbon atoms. The amount of ethylene oxide in the polyethoxylated higher alkanol sulfate is preferably 2-5 moles of ethylene oxide groups per liter. moles of anionic detergent, with three moles being most preferred, especially when the higher alkanol has 11-15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic balance when the carbon atom content of the alkyl chain is in the lower part of the range of 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to approx. two moles per moles, whereas when the higher alkanol has 16 to 18 carbon atoms in the higher range, the number of ethylene oxide groups can be increased to 4 or 5 and in some cases to as much as 8 or 15 9. Similarly, the salt-forming cation can be changed thus that the best solubility is obtained. It may be any suitable solubilizing metal or radical, but will most often be alkali metal, e.g. sodium or ammonium. If lower alkylamine or alkanolamine groups are used, the alkyls and alkanols will usually contain from 1 to 4 carbon atoms and the amines and alkanolamines may be mono-, di- and trisubstituted, as in monoethanolamine, diisopropanolamine and trimethylamine. A preferred polyethoxylated alcohol sulfate as a detergent can be obtained from Shell Chemical Company and sold as Neodol 25-3S.

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

The nonionic synthetic organic detergents are characterized by

DK 160265 B

10 is present in the presence of an organic hydrophobic group and an organic hydrophilic group and is typically prepared by condensing 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 bonded to the nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be readily adjusted to achieve the desired balance between hydrophobic and hydrophilic groups.

The nonionic detergent used is preferably a poly lower alkoxylated higher alkanol wherein the alkanol has 10 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (with 2 or 3 carbon atoms) is from 3 to 12. Among these materials, it is preferred. to use those wherein the higher alkanol is a higher fatty alcohol having 11 to 15 carbon atoms 20 and containing from 5 to 9 lower alkoxy groups per moth.

Preferably, it is lower alkoxy ethoxy, but in some cases it may conveniently be mixed with propoxy, the latter, if present, usually constituting a minor component (less than 50%). Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and contains approx. 7 ethylene oxide group per moles, e.g. Neodol ® 25-7 and Neodol 23-6.5, which are manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of approx. 12-30 carbon atoms, with approx. 7 moles of ethylene oxide and the latter is a similar mixture in which the carbon atom content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups per mole mol on average of approx. 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol® 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The former is a mixed ethoxylation agent.

DK 160265 B

11 product of a linear secondary alkanol having 11-15 carbon atoms with 7 moles of ethylene oxide and the latter being a similar product but with 9 moles of ethylene oxide.

Also useful in the present compositions are the more high molecular weight non-ionic substances, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, wherein the higher fatty alcohol has 14 to 15 carbon atoms and the number of ethylene oxide groups per mole is approx. 11. Such products are also manufactured by Shell Chemical Company.

Zwitterionic detergents such as the betaines and sulfobetaines having the following formula are also useful:

R - N ------- R4-X = O

wherein R is an alkyl group containing from ca. 8 to 18 carbon atoms, R 5 and R 2 each are an alkylene or hydroxyalkylene group containing about 1-4 carbon atoms, R 1 is an alkylene or hydroxyalkylene group containing 1-4 carbon atoms, and X is C or S: 0. The alkyl group may contain one or more intermediate bonds such as amido, ether or polyether bonds, or nonfunctional substituents such as hydroxyl or halogen which do 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 sulfate.

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 amine compounds and quaternary ammonium compounds.

12 DK 160265 B

Examples of suitable synthetic cationic detergents include: normal primary amines of the formula RNH2 wherein R is an alkyl group containing from ca. 12 to 15 carbon atoms, diamines of the formula RNHC ^ H ^ NH, wherein R is an alkyl group containing from ca. 12 to 22 carbon atoms, such as N-2-aminoethyl = 5 stearylamine and N-2-aminoethylmyristylamine, amide bonded amines such as those having the formula R 1 CONHC 2 H 2 NH 2 wherein R 1 is an alkyl group containing about 8-20 carbon atoms, such as N-2-amino = ethyl stearyl amide and N-aminoethyl myristyl amide, quaternary ammonium compounds, wherein typically one of the groups attached to the nitrogen atom is an alkyl group containing ca. 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 bearing inert substituents such as phenyl groups and in which there is an anion such as halogen, acetate, methosulfate, etc .. The alkyl group may contain intermediate bonds, such as amide, which do not significantly affect the hydrophobic nature of the group, e.g. stearylamidopropyl quaternary ammonium chloride. Typical quaternary ammonium detergents are ethyl dimethyl stearyl ammonium chloride, benzyldimethyl = 20 stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl cetylammonium bromide, dimethyl ethyl lauryl ammonium chloride, dimethylpropylmyristyl ammonium chloride, and

2® Ampholytic detergents are also suitable for the invention. Ampho-lytic detergents are well known and many useful detergents of this class are described by AM Schwartz, J. W. Perry, and J. Birch in "Surface Active Agents and Detergents", Inter-science Publishers, New York, 1958, Volume 2. Examples of oak Lower amphoteric detergents include: alkyl beta-aminodipropionates, RN (C 2 H 4 COOM) 2, alkyl-β-aminopropionates, RN (H) C 2 H 2 COCM, and long-chain imidazole derivatives of the general formula: CH-35 / \ N CH

II

R-C-N-CH and CHOCOL COOM

^ z z z

OH CH2C00M

13

DK 16026SB

wherein R in each of the above formulas is an acyclic hydrophobic group containing from ca. 8 to 18 carbon atoms, and M is a cation to neutralize the charge of the anion. Particular useful amphoteric detergents include the disodium salt 5 of undecylcycloimidinium-ethoxyethionic acid-2-ethionic acid, dodecyl-β-alanine, and the inner salt of 2-trimethylaminolauric acid.

The bleaching cleaners of the invention optionally contain a builder of the type commonly used in cleansing agents. Useful builders include any of the usual inorganic water-soluble builder salts, such as e.g. water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates and the like. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxy sulfonates, polyacetates, carboxylates, polycarboxylates, succinates and the like.

Specific examples of inorganic phosphate builders are sodium 20 and potassium tripolyphosphates, pyrophosphate and hexametaphosphate.

The organic polyphosphonates include, e.g. the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of these and other phosphorus-containing builder compounds are described in U.S. Patents Nos. 3,213,030, .422,021, 3,422,137, and 3,400,176. Pentane sodium tripolyphosphate and tetra-sodium pyrophosphate are particularly preferred as water-soluble inorganic builders.

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

35 Water-soluble organic builders are also useful. Eg.

For example, alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates are useful builders for the agents and process of the invention.

DK 160265B

14

Concrete examples of polyacetate and polycarboxylate builders are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acid (i.e. penta- and tetra-), carboxymethoxyacetic acid and citric acid.

Water-insoluble builders can also be used, especially the complex silicates and more specifically the complex sodium aluminum silicates, such as the zeolites, e.g. zeolite 4A, a type 10 zeolite molecule in which the monovalent cation is sodium and the pore size is approx. 4 Å. Preparation of such a type of zeolite is disclosed in U.S. Patent No. 3,114,603. The zeolites may be amorphous or crystalline and have hydration water in known manner.

15

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

20

Various additives may be included in the bleaching cleaners of the invention. Generally, these perfumes include coloring agents, e.g. pigments and dyes, dirt repellents, such as alkali metal salts of carboxymethyl cellulose, optical cleaners, such as anionic, cationic or non-ionic cleaners, foam stabilizers such as alkanol blacks, and the like, all well known for laundry cleansers. Flow enhancers, commonly referred to as flow aids, can also be used to maintain the particulate bleaching cleaners as free flowing beads or powders. Starch derivatives and special clays are industrially available as additives that promote the flowability of otherwise sticky or paste-like particulate agents, and two of these clay additives are currently on the market under the trade names "Satintone" and "Microsil".

DK 160265B

15

The bleaching cleaners of the invention are particulate agents which can be prepared by spray drying methods and by methods comprising dry mixing or agglomeration of the individual components. The agents are preferably prepared by spray drying an aqueous slurry of the non-heat-sensitive components, including the bromide salt, to form spray-dried particles, followed by mixing such particles with the heat-sensitive components such as the MPPA bleach, and the aromatic sulfonamide compound. if the 10 is not sufficiently stable (usually if there is more than 20% decomposition loss), and additives such as perfume and enzymes. Mixing is conveniently carried out in an apparatus such as a rotary drum. If desired, the MPPA bleach and / or bromide salt can be encapsulated or otherwise stabilized to prevent premature reactions. Suitable coating materials include compounds such as magnesium sulfate, polyvinyl alcohol and lauric acid or its salts.

A particularly preferred bleaching detergent according to the invention comprises: (a) from ca. 5 to 50% by weight of a bleaching agent consisting essentially of (i) monoperoxyphthalic acid and / or a water-soluble salt thereof, (ii) a water-soluble inorganic bromide salt, and (iii) an aromatic sulfonamide compound selected from benzenesulfonamide, toluene sulfonamide, ethylbenzenesulfonamide , dodecylbenzenesulfonamide, xylenesulfonamide, N-alkali metal salts of these sulfonamides and mixtures thereof, wherein the weight ratio of (i) to (ii) is from ca. 8: 1 30 to 1: 2, and the ratio of (iii) to (ii) is from approx. 2: 1 to approx. 1: 4; (b) from ca. 5 to approx. 30% by weight of a cleansing surfactant selected from anionic and non-ionic detergents and mixtures thereof; 10 to approx. 60% by weight of a builder salt; and

DK 160265B

(D) the remainder water and optionally a filler salt.

Example 1, 5 Test Method.

Bleaching tests were performed on standard discolored test pieces (described below) using various bleaching and washing agents described in Table 1 of this example in a tergotometer container manufactured by U.S. Pat. Testing Company.

The tergotometer was kept at a constant temperature of 49 ° C and operated at 100 rpm. minute.

Each of the sample materials described in Table 1 below 15 was added to 1 liter of tap water at 49 ° C with a hardness of approx. 100 ppm, as calcium carbonate. The test materials were stirred for approx. 1 minute and then to each wash container was added a mixed portion of two pieces (7.5 x 10 cm) of each of the stained or discolored fabrics described below. After 15 minutes of washing at 49 ° C, the test substances were rinsed in 38 ° C in tap water and then dried.

The percent removal of discoloration was measured by taking a reflectance reading for each discolored piece of fabric before and after washing using a Gardner color-25 difference meter, and the percent stain removal (% SR) was calculated as follows: (Rd after washing) - ( Rd before washing)% SR = - x 100 30 (Rd before discoloration) - (Rd before washing) where "Rd before washing" represents the Rd value after discoloration.

33 The value of percent removal of discoloration calculated for all five pieces of fabric was averaged for each sample detergent. A difference greater than 2% on average for those

DK 160265 B

Seventeen five discolored pieces of fabric that were examined are considered significant.

After each wash, the active oxygen content of the wash solution 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, and then titration with standardized sodium thiosulfate using starch as indicator.

10

The respective discolorations and specimens were as follows: Discolouration Test substance 15 1. Grape - 65 Dacron - 35 cotton 2. Blueberry - Cotton 3. Sulfur dye - EMPA 115 (cotton) 4. Red wine - EMPA 114 (cotton) 5. Coffee / The - Cotton 20

The discolored samples 1 and 2 are prepared by passing non-soiled rolls through a foulard and dryer (manufactured by Benz in Zurich, Switzerland) containing either grape or blueberry solution at 32 ° C. After drying at 121 ° C, the fabric is cut into 7.5 x 10 cm pieces. 80 of these pieces, impregnated with the same discoloration, are rinsed in 64 1 69 ° C water in an automatic home washing machine. They are then dried by passing through a Beseler Print Dryer at a machine temperature setting of 6 and a speed of 10.

30

The discolored pieces 3 and 4 are purchased by Testfabrics Incorporated, Middlesex, New Jersey, and cut into 7.5 x 10 cm pieces.

The discolored piece of fabric 5 is prepared by stirring and soaking clean cotton strips (45 x 90 cm) in a washer filled with a coffee / tea solution (weight ratio 8: 1) at 66 ° C. The machine is allowed to spin dry to remove the coffee / tea solution. The discolored fabric is then machine washed twice

DK 160265 B

18 hot solution of pyrophosphate and surfactant followed by two complete washing periods at 60 ° C. The strips are then dried by two passes through an Ironrite machine set to 10 and then cut to 7.5 x 10 cm pieces.

5

A granular detergent (herein referred to as "HDD") was prepared by conventional spray drying and had the following approximate composition: 10 Composition Weight%

Sodium tridecylbenzenesulfonate 15

Ethoxylated ^ 2 ^ 15 1 Primary Alcohol (7 moles EO / mole Alcohol) Sodium Tripolyphosphate 33

Sodium carbonate 5

Sodium silicate 7

Sodium carboxymethyl cellulose 0.5

Optical Clarifiers 0.2 20 Perfume 0.2

Water 11

Sodium sulfate residue

The cleaning agents A-G containing HDD were compiled as listed in Table 1. The pH of the agents in aqueous solution ranged from 9.2 to 9.7.

Table 1.

Component Medium

A B C D E F G

Detergent, HDD 4.50g 4.50g 4.50g 4.50g 4? 50g 4.50g 4.50g

Mg salt of MPPA ^ 0.49 0.49 0.49 0.40 0.40 0.40 35

NaBr ----- 0.07 0.07 0.07 0.07 0.07 TSA ^ ----- ----- 0.03 ----- ----- 0.02 0.03

DK 160265 B

19 (1) A bleach containing as active ingredient approx. 65% by weight of magnesium monoperoxyphthalate and with an active oxygen content of 5.1%.

(2) Para-toluenesulfonamide.

Agents A - G were tested according to the procedure described above and the results of the bleaching tests are shown in Table 2, which indicates the removal of discoloration obtained with Agents A - G for each of the 5 discolorations.

Table 2.

Compared Bleaching Capacity (% S.R.) 15

Discoloration Medium

A B C D E F G

Grape 63% 65% 75% 37 / o 62 / »67 <& 68 / o 20 Blueberries 63 64 68 41 62 65 67

Sulfo dye 4 5 7 3 3 5 6 Red wine 47 46 56 33 44 48 48

Coffee / The _4] _ _61 ^ _ _5_ _32_ _51_ 52 25

Average (%) 42 44 53 24 41 47 48

The results in Table 2 demonstrate the markedly improved bleaching effect obtained with the agents containing the MPPA bleach in combination with sodium bromide and TSA compared to the agents containing the MPPA bleach alone (in the absence of bromide and TSA) or MPPA and sodium bromide. Thus, agents C, F and G of the invention gave an improvement in the average SR from 6 to 9% (depending on the agent in question) over the corresponding agents B and E, both containing MPPA bleach and sodium bromide in combination, but no TSA. Comparison of agent C according to DK 160265 B: 20j invention and agent A containing MPPA alone (in the absence of bromide and TSA) shows an improvement in the average percent SR of 11% (53% versus 42%) in relative to the bleaching obtained by a known agent.

5

Example 2.

The bleaching tests described in Example 1 were performed with the detergents' H-K described in Table 3 below. The discolored pieces of fabric used were substantially similar to those described in Example 1.

The detergents H-K were formulated as listed below in Table 3, and the composition of the detergent (HDD) is described in Example 1. The pH of the aqueous solutions varied from 8.2 to 8.6.

Table 3.

20 Component Medium

Η I J K

Detergent, HDD 1.50 g 1.50 g 1.50 g 1.50 g

Mg salt of MPPA 1 0.26 0.26 0.26 0.26 25 NaBr - - 0.10 0.10 TSA 2 - 0.08 -. 0.08

A bleach containing as active ingredient approx. 65% by weight of magnesium monoperoxyphthalate and containing a content of 30. o c, 0 tive oxygen of 5.1%.

2

Para-toluene sulfonamide.

Agents H to K were tested by the procedure of Example 35 1 and the results of the bleaching samples are summarized in Table 4, which indicates the percent removal of discoloration obtained with Agents H-K for each of the 5 discolorations.

Claims (19)

Bleach, including bleaching detergent, characterized in that it contains: (a) monoperoxyphthalic acid and / or a water-soluble salt thereof, (b) a water-soluble inorganic bromide salt, and (c) an aromatic sulfonamide compound selected from benzenesulfonamide, toluene sulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, N-alkali metal salts of the sulfonamides, N-acetyl and N-benzoyl derivatives of the aforementioned sulfonamides and salts, and mixtures thereof. An agent according to claim 1, characterized in that the aromatic sulfonamide compound is toluene sulfonamide or an N-alkali metal salt thereof and the bromide salt is an alkali metal bromide. An agent according to claim 1, characterized in that the aromatic sulfonamide compound is para-toluenesulfonamide. An agent according to claim 1, characterized in that it contains magnesium monoperoxyphthalate. . 25 A composition according to claim 1, characterized in that the weight ratio of (a) to (b) is from about. 10: 1 to approx. 1: 5 and the weight ratio of (c) to (b) is from approx. 5: 1 to approx. 1: 7th 30 5 Discoloration Η I J K Grape 75% 76% 82% 85% Blueberry 70 67 75 80 Sulfo dye 4 398 Red wine 37 36 35 46 An agent according to claim 1, characterized in that it further contains one or more scavenging surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents. DK DK 26265 B Bleaching detergent according to claim 1, characterized in that it contains: 5 (a) from ca. 5 to 50% by weight of a bleach comprising: (i) monoperoxyphthalic acid and / or a water-soluble salt thereof; (ii) a water-soluble inorganic bromide salt; N-alkali metal salts of these sulfonamides, N-acetyl and N-benzoyl derivatives of said sulfonamides and salts, and mixtures thereof, (b) from ca. 5 to 50% by weight of a cleansing surfactant selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents; 5 to 80% by weight of a builder salt, and 2 * (d) the remainder comprising water and optionally a filler salt. A composition according to claim 7, characterized in that the weight ratio of (i) to (ii) is from approx. 10: 1 to approx. 1: 5 and the weight ratio of (iii) to (ii) is from ca. 5: 1 to approx. 30 1: 7. An agent according to claim 7, characterized in that the bleach contains magnesium monoperoxyphthalate, the aromatic sulfonamide compound is toluene sulfonamide or a N-alkali metal salt thereof, and the bromide salt is an alkali metal bromide. DK 160265B Agent according to claim 7, characterized in that the detergent surfactant is selected from anionic and nonionic detergents and mixtures thereof. 5 10 Coffee / The 78 74 86 87 Average (%) 53 51 57 61 The data in Table 4 demonstrates the synergy obtained with Agent K, an agent of the invention, relative to agents H, 15 I and J, each containing MPPA alone or in combination with either NaBr or TSA. The average percent S.R. thus obtained with agents H and I were essentially the same (53 and 51%), and the presence of TSA is shown to have a slightly negative effect on the effect of MPPA. Agent J containing MPPA in combination with bromide produced an expected improvement in bleaching effect, an average S.R. of 57%. The addition of TSA to an agent containing MPPA and bromide (agent K) produced an apparent synergistic effect in that it produced a pronounced increase in bleaching effect, namely an average S.R. of 61%. Claims. 30 An agent according to claim 7, characterized in that the aromatic sulfonamide compound is para-toluenesulfone amide. A composition according to claim 7, characterized in that it comprises from ca. 5 to 30% by weight of the cleansing surfactant, and from approx. 10 to 60% by weight of the builder salt. A method of bleaching textiles, characterized in that the discolored and / or soiled material to be bleached is contacted with an aqueous solution of an agent comprising: (a) monoperoxyphthalic acid and / or a water-soluble salt thereof; (b) a water-soluble inorganic bromide salt, and (c) an aromatic sulfonamide compound selected from benzenesulfonamide, toluene sulfonamide, ethylbenzenesulfonamide, dodecylbenzenesulfonamide, xylene sulfonamide, N-alkali metal salts of these sulfonamides, N-acetyl derivatives and N salts, and mixtures thereof, the weight ratio of (a) to (b) being from ca. 10: 1 to 1: 5, and the weight ratio of (c) to (b) is from approx. 5: 1 to approx. in 1: 7. Process according to claim 13, characterized in that the agent further contains one or more scavenging surfactants selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents. A method according to claim 14, characterized in that the agent comprises from ca. 5 to 50% by weight of the components (a), (b) and (c) together, from ca. 5 to 50% by weight of the cleansing surfactant, the composition further comprising a builder salt in an amount of about 5 to 80% by weight, with the remainder of the agent being water and optionally a rich substance salt. Process according to claim 13, characterized in that the aromatic sulfonamide compound is toluene sulfonamide or an N-alkali metal salt thereof. 15 Process according to claim 13, characterized in that the agent contains magnesium monoperoxyphthalate. Process according to claim 13, characterized in that the bromide salt is an alkali metal bromide. 20 The method according to claim 13, characterized in that the weight ratio of (a) to (b) is from approx. 8: 1 to approx. 1: 2 and the weight ratio of (c) to (b) is from approx. 2: 1 to approx. 1: 4. 30 35