Peroxyacid bleaching and laundering composition

(42) Date of commencement of the patent: 15. 9.1991 (45) Date of issue: 25. 3.1992 (30) Priority:

29.10.1981 US 316173 claims. 20. 5. 1982 US 379824 claims.

(56) Documents:

EP-A-127693 EP-A-137146 GB-PS 1355855 (54) BLEACHING GRAINED DETERGENT COMPOSITION (57) Bleaching granular detergent compositions having improved bleaching action, which are characterized by a content of monoperoxyphthalic acid and / or a water-soluble salt thereof, dietylenetriaminepentamethylenephosphonic acid and / or a water-soluble salt thereof as chelating agents, washing-active surfactants, builder salts, the remainder water and optionally a filling salt. Furthermore, the invention also relates to a process for the preparation of the detergent composition.

MH <3078012 (51) Int. Cl.⁵ : C11D 3/39 C11D 3/395 (73)

COLGATE-PALMOLIVE COMPANY 10022 NEW YORK (US).

AT394 386B

The present invention relates to a bleaching granular detergent composition and a process for its preparation.

Bleaching compositions that release active oxygen in the wash solution have been previously described in detail and are commonly used in laundry processes

Bleaching Compositions Peroxy compounds, for example perborates, percarbonates, perphosphates and the like. Like., Promoting the bleaching effect by the formation of hydrogen peroxide in aqueous solution. A significant disadvantage associated with the use of such peroxy compounds is that these peroxy compounds are not effective at the relatively low wash temperatures in the range of 26.7 to 54.4 ° C used in most household washing machines used in the US are optimally effective. in the

At the same time, in European washing machines, generally much higher washing temperatures are used, namely in the range of 32 to 94 ° C. But even in Europe, as well as in other countries, where washing temperatures near the boiling point of water are generally used, there is a trend towards washing at lower temperatures.

So-called activators in combination with the peroxy compounds have hitherto been used to increase the bleaching effect of peroxy bleaching. It is generally believed that the interaction between the peroxy compound and the activator results in the formation of a peroxy acid which is the actually active compound for bleaching Numerous activators for peroxy bleaching have already been proposed, including carboxylic acid anhydrides, e.g. B. those described in U.S. Patents 3,928,775, 3,338,839, and 3,352,634; furthermore carboxylic esters, as described, for. B. in US Pat. No. 2,995,905, N-acyl compounds, for example those known from US Pat. Nos. 3,912,648 and 3,919,102; also the cyanamines described in US Pat. No. 4,199,466 and acylsulfoamides, as described, for example, in US Pat. No. 3,245,913.

Prefabricated peroxyacids have also been used to effect bleaching in wash solutions, see, for example, U.S. Patent Nos. 3,770,816,417,053 and 4,259,201.

It is well known that metal ions are capable of acting as catalysts for the decomposition of inorganic peroxy compounds and organic peroxyacids. To stabilize such bleaching compounds in the washing solution, chelating agents have already been incorporated into bleaching detergent compositions. For example, US Pat. No. 3,243,378 (Stoltz) discloses a bleaching composition containing a bleaching peroxy compound and a chelating agent for masking metal cations. In general, the chelating agents used hitherto for this purpose belong to one of two categories:

a) substances such as heterocyclic compounds and ketones, in particular 8-hydroxyquinoline, which bind metal cations during laundry washing by precipitation from the solution; and

b) Substances, such as aminopolycarboxylates and aminopolyphosphonates, which form water-soluble metal complexes with cations present in the wash solution.

Thus, it is known from US-PS 4 005 029 that certain aldehydes, ketones and compounds which form aldehydes or ketones in aqueous solution (eg 8-hydroxyquinoline), for the activation of aliphatic peroxyacids, such as diperazelaic acid and diperadipic acid, and aromatic peroxyacids and their water-soluble salts, including monoperoxyphthalic acid and diperoxyterephthalic acid. Out

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 produced in wash solutions containing diperoxydodecanedicarboxylic acid.

US Pat. No. 4,225,452 (Leigh) describes the combination of certain classes of chelating agents (among them phosphonate compounds) with inorganic peroxy compounds and an inorganic activator for

Suppression of the decomposition of the peroxy compound in the bleaching composition. In particular, it is believed that the chelating agent inhibits the undesired side reaction of the peroxy compound with the peroxy acid formed by the primary reaction of the peroxy compound with the activator, since the by-reaction can deplete the peroxyacid bleaches from the solution to exhaustion. However, one skilled in the art will be prevented from using such chelating agents in solutions containing peroxyacids having a double bond between the carbon atoms in the α, α'-position to the carbonyl group. In particular, in the cited US Pat. No. 4,225,452, column 2, lines 63 et seq., The use of phthalic anhydride as activator is precluded because of its instability for the bleaching composition described therein. In this case, the reaction of phthalic anhydride with an inorganic peroxy compound is formed as peroxyacid monoperoxyphthalic acid, follows from US-PS 4,225,452 casual that of ³³ The use of monoperoxyphthalic acid in the bleaching compositions described there is obviously discouraged.

In European Patent Application No. 27693, published April 29, 1981, the use of

-2AT394 386B

Magnesium monoperoxyphthalate is described as an effective bleaching agent. Further, this document discloses the optional combination of a bleaching agent with an aldehyde or ketone peroxyacid activator such as described in US Pat. No. 4,005,029, for example, 8-hydroxyquinoline, which is known as a peroxy stabilizer. In this document, in addition to a large number of other compounds, organic phosphonate compounds are mentioned as suitable detergent builders which may be can be incorporated into the detergent compositions described. However, there is no suggestion that very favorable effects can be achieved when using a small amount of organic phosphonate compounds as chelating agents in bleaching compositions, especially in compositions containing magnesium monoperoxyphthalate.

Thus, while the prior art has been concerned with improving the stability of bleaching agents containing peroxy and peroxyacid compounds using chelating agents, there has been no suggestion or suggestion to the specific combination of peroxyacid compounds with chelating agents of the type specified in the present invention, namely those containing metal cations in aqueous wash solutions form substantially water-soluble compounds or complexes. The use of such chelating agents is hitherto known only in combination with peroxy compounds alone or together with activators. In particular, it has not been foreseen on the basis of the known prior art that the special combination of such specific chelating agents with monoperoxyphthalic acid and / or a water-soluble salt thereof in detergents has such remarkably favorable effects

The invention is therefore an object of the invention to provide a bleaching granular detergent composition, which is characterized by an excellent bleaching and washing effect and above-average stability in aqueous washing solutions

This object is achieved according to the invention by a detergent composition, which is characterized in that they contain (a) from 5 to 50% by weight of a bleaching agent of monoperoxyphthalic acid and / or a water-soluble salt thereof, wherein the bleaching agent is free of inorganic peroxy compounds, (b) diethylenetriaminepentamethylenephosphonic acid and / or a water-soluble salt thereof as a chelating agent, with which a substantially water-soluble metal complex can be formed in aqueous solution, (c) 5 to 50% by weight of one or more washing-active substances from the group of anionic, cationic, nonionic, ampholytic and zwitterionic surfactants, (d) 5 to 80% by weight of a builder salt, and (e) the balance is water and optionally a filler salt.

According to the invention, with this bleaching detergent composition a bleaching process can be carried out in which the material to be bleached, stained and / or soiled is brought into contact with an aqueous solution of a detergent composition according to the invention as indicated above.

As a rule, in the compositions according to the invention, the weight ratio of chelating agent to monoperoxyphthalic acid (MPPA) and / or their salts is 1: 4 to 1:15, preferably 1:12 to 1:15. In the detergent compositions according to the invention, the concentration of the chelating agent is generally below 5% by weight, preferably below 2% by weight and very particularly preferably below 1% by weight.

Monoperoxyphthalic acid (MPPA) and / or one or more of its water-soluble salts is used as a bleaching agent in the detergent compositions of the invention. Although the MPPA has acceptable bleaching activity, it has the disadvantage of aa^- relatively low stability when stored in admixture with other ingredients commonly present in household detergents. Therefore, for reasons of stability, it is preferable to use the magnesium salt of MPPA of the invention's compositions. The alkali metal, calcium, barium and / or ammonium salts of MPPA can also be used in detergent compositions according to the invention, although these salts are generally less preferred than the magnesium salt for stability reasons.

The production of MPPA is generally carried out by reacting hydrogen peroxide with phthalic anhydride. The resulting MPPA can be reacted with a suitable magnesium compound in the presence of an organic solvent to produce magnesium monoperoxyphthalate. A detailed description of the preparation of MPPA and its magnesium salt is described in European Patent Application No. 27693, pages 7-10.

The amount of the detergent added to the washing solution is generally selected so that the amount of the peroxyacid compound added is in a range of from 3 to 100 parts of active oxygen per

Corresponds to one million parts of the washing solution

-3AT394 386B

The detergent composition of the invention may also contain conventional additives such as those used in the textile washing industry, for example binders, fillers, proteolytic enzymes, optical brighteners, perfumes, dyes, corrosion inhibitors, anti-aging agents, foam stabilizers, and the like. Like., All of these additives can be added in different amounts, depending on the desired properties of the detergent composition and its compatibility with the components of such a composition.

The aqueous washing solutions generally have a pH range of from 7 to 12, preferably from 8 to 10, and more preferably from 8.5 to 9. The preferred amounts of builder salts are from 20 to 65% by weight, based on the total composition , The rest of the composition consists mainly of water, filling salts, such as. For example, sodium sulfate, and optionally minor additives, such as optical brighteners, perfumes, dyes, anti-aging agents u. like.

In a preferred embodiment of the invention, the constituents in the bleaching detergent composition are present in particularly advantageous weight ratios, namely the total amount of detergent surfactants, builder salts and optionally filler salts to the total amount of bleach and chelating agent in the weight ratio of 6: 1 to 20: 1, preferably from 6.5: 1 to 15: 1, before.

Anionic detergents, which can be used advantageously in the bleaching detergent composition according to the invention, include such surfactants, which is an organic hydrophobic group having generally about 8 to 26 C atoms, preferably 10 to 18 carbon atoms, contain in their molecular structure and at least one water-solubilizing group, selected from the group of sulfonates, sulfates, carboxylates, Phosphonates and phosphates, so that they form a water-soluble surfactant.

Examples of suitable anionic surfactants are soaps, for example the water-soluble salts (e.g. B. the sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts having about 8 to 20 C atoms, preferably 10 to 18 C atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, e.g. B. from tallow, fat, coconut oil and their mixtures. Particularly preferred are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, z. B. Sodium coke soap and potassium tallow soap.

The anionic class of surfactants also includes the water-soluble sulfated and sulfonated surfactants having an alkyl group of about 8 to 26 carbon atoms, preferably of about 12 to 22 carbon atoms. Examples of the sulfonated anionic surfactants are the higher mononuclear alkyl aromatic sulfonates, for example the higher alkyl benzene sulfonates having from about 10 to 16 carbon atoms in the alkyl group, which may be straight chain or branched chain, e.g. B. the sodium, potassium and ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluene sulfonates and higher alkylphenol sulfonates.

Other suitable anionic surfactants are the olefin sulfonates including the long chain alkene sulfonates, the long chain hydroxyalkanesulfonates, or mixtures of alkene sulfonates and hydroxyalkanesulfonates. The olefin sulfonate surfactants can be prepared in a conventional manner by reacting SOA with long chain olefins of about 8 to 25 carbon atoms, preferably about 12 to 21 carbon atoms, such olefins having the formula RCH = CHR | in which R is an alkyl group having 6 to 23 C atoms and Rj is an alkyl group having 1 to 17 C atoms or hydrogen. In this reaction, a mixture of sultones and alkene sulfonic acids is obtained, which is then treated to convert the sultones to sulfonates.

Other examples of sulfate or sulfonate surfactants are paraffin sulfonates of about 10 to 20 carbon atoms, preferably about 15 to 20 carbon atoms. The primary paraffin sulfonates are prepared by reacting long chain α-olefins with bisulfites. Paraffin sulfonates in which the sulfonate groups are distributed along the paraffin chain are described in U.S. Patents Nos. 2,503,280, 2,507,088, 3,260,741, 3,372,188, and German Patent No. 735,096. Also suitable sulfate and sulfonate surfactants include sodium and potassium sulfates of higher alcohols containing about 8 to 18 carbon atoms, such as sodium lauryl sulfate and sodium tallow alcohol sulfate, sodium and potassium salts of α-sulfofatty acid esters, about 10 to 20 C atoms in the acyl group include, for example, methyl-a-sulfomyristate and methyl-a-sulfo-salt, ammonium sulfates of the mono- or diglycerides of higher fatty acids (having 10 to 18 carbon atoms), e.g. B. S tearinmonoglyceridmonosulfat, sodium and alkylolammonium salts of Alkylpolyethenoxyethersulfaten, which are prepared by condensation of 1 to 5 moles of ethylene oxide with 1 mole of a higher alcohol (having 8 to 18 carbon atoms), and the sodium salts of higher alkyl glyceryl ether sulfonates having 10 to 18 carbon atoms in the alkyl group and sodium or Kaliumalkylphenolpolyethenoxyethersulfate having about 1 to 6 oxyethylene groups per molecule and about 8 to 12 CAtomen in the alkyl radicals.

Very particularly preferred as water-soluble anionic surfactants are the ammonium and substituted

Ammonium salts (such as those of mono-, di- and triethanolamine), alkali metal salts (for example, those of the

Sodium and potassium) and alkaline earth metal salts (for example, those of calcium and magnesium) of higher

Alkylbenzenesulfonates, Olefinsulfonaten and higher alkyl sulfates. Among the above anionic

-4AT394 386B

Surfactants, the sodium salts of linear, ie straight-chain alkylbenzenesulfonates (LABS) are very particularly preferred.

The nonionic synthetic organic surfactants are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group. They are usually prepared by condensation of organic aliphatic or alkyl aromatic hydrophobic compounds with ethylene oxide (which is hydrophilic by nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen atom on the nitrogen can be prepared with ethylene oxide or with the corresponding polyhydrated product, namely polyethylene glycol, to form a nonionic surfactant. The length of the hydrophilic chain or polyoxyethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.

Suitable nonionic surfactants include the polyethylene oxide condensation products of 1 mole of alkylphenol having 6 to 12 carbon atoms in the straight chain or branched alkyl radical and about 5 to 30 moles of ethylene oxide, for example nonylphenol condensed with 9 moles of ethylene oxide, dodecylphenol condensed with 15 moles Ethylene oxide and dinonylphenol condensed with 15 moles of ethylene oxide. The condensation products of the corresponding alkylthiophenols with 5 to 30 moles of ethylene oxide are suitable nonionic surfactants.

Of these nonionic surfactants mentioned above, those of the ethoxylated alcohol type are preferred. Particularly preferred nonionic surfactants are the condensation products of one mole of coconut fatty alcohol and about 6 moles of ethylene oxide, 1 mole of tallow fatty alcohol and about 11 moles of ethylene oxide, 1 mole of a secondary fatty alcohol of about 11 to 15 carbon atoms, and about 9 moles of ethylene oxide and more or less branched primary alcohols in which the branching is mainly in a 2-methyl group and about 4 to 12 moles of ethylene oxide.

Zwitterionic surfactants, such as betaines and sulfobetaines of the formula

<img file="AT394386B_D0001.tif" />

in the R, an alkyl group having about 8 to 18 carbon atoms, Rβ and Rβ each represents an alkylene or hydroxyalkyl group having about 1 to 4 carbon atoms, R₄ An alkylene or hydroxyalkylene group having 1 to 4 carbon atoms and X = C or S = O, are also suitable for the purpose of the invention. The alkyl group may contain one or more intermediate members, such as. B. Amido, ether or polyether linkages, or non-functional substituents, such as hydroxyl or halogen groups, which do not substantially affect the hydrophobic nature of the group. When X = C, then the surfactant is called betaine; when X = S = O, then the surfactant is referred to as a sulfobetaine or sultaine.

In the bleaching detergent composition of the present invention, cationic surfactants may also be used. These consist of detergent-active compounds with an organic hydrophobic group that forms part of a cation upon dissolution of the compound in water, and with an anionic group. Typical cationic surfactants are amine and quaternary ammonium compounds.

Examples of suitable synthetic cationic surfactants are normal primary amines of the formula RNHβ in which R is an alkyl group containing from about 12 to 15 carbon atoms, diamines of the formula RNHCβH ^ NH3 wherein R is an alkyl group of about 12 to 22 carbon atoms such as N-2-aminoethylstearylamine and N-2Aminoethyl-myristylamine; further amide-linked amines, for example those of the formula RjCONHCβH₄NH 3 wherein R 1 represents an alkyl group having 8 to 20 carbon atoms, such as N-2-aminoethylstearylamide and N-aminoethylmyristylamide; further quaternary ammonium compounds in which typically one of the groups attached to the nitrogen atom is an alkyl group of about 8 to 22 carbon atoms and three of the groups attached to the nitrogen atom are alkyl groups of 1 to 3 carbon atoms, including those alkyl groups which are inert substituents wear, such. B. Phenyl groups, where as anions halogens, acetates, methosulfates, etc. available. The alkyl group may have intermediates, such as amide groups, which do not significantly affect the hydrophobic character of the group, e.g. B. Stearylamidopropylammoniumchlorid. Examples of suitable quaternary ammonium compounds are ethyl-dimethylstearylammonium chloride, benzyl-dimethylstearylammonium chloride, trimethylstearylammonium chloride, trimethylcetylammonium bromide, dimethylethyllaurylammonium chloride, dimethylpropylmyristylammonium chloride, and the like

-5AT394 386 B

Methosulfates and acetates.

Ampholytic surfactants are also suitable for the purpose of the invention. They are also well-known surfactants, many of which are von. M. Schwartz, JW Perry and J. Birch in "Surface Active Agents and Detergents", Interscience Publishers, New York, 1958, Vol. 2. Examples of suitable ampholytic surfactants are alkyl-β-iminodipropionate RN ^ fyCOOM) ^ alkyl-β-aminopropionateRNHC ^ COOM and long-chain imidazole derivatives of the general formula

CIL

RC

CH "

I ²

CH₂CH₂OCH₂COOM

<img file="AT394386B_D0002.tif" />

OH CH₂C00M wherein in each of the above formulas R is an acyclic hydrophobic group of about 8 to 18 carbon atoms and M is a cation which neutralizes the charge of the anion. Particularly suitable amphoteric surfactants are the disodium salt of undecyl-cycloimidinium-ethoxy-2-ethionic acid, furthermore dodecyl-alanine and the inner salt of 2-trimethylaminolauric acid.

Suitable builders for the detergent composition according to the invention are the conventional inorganic water-soluble builder salts, such as. As water-soluble phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates and. Like. As organic builders are water-soluble phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylates, succinates u. Like. In question.

Specific examples of inorganic phosphate builder salts are sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. Suitable organic polyphosphonates are, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-l, 1,2-triphosphonic acid. Examples of these and other phosphorus-containing builders are described in US Pat. Nos. 3,213,030, 3,422,021.3, 422137 and 3,400,176. Very particular preference is given as water-soluble inorganic builder salts to pentasodium tripolyphosphate and tetrasodium pyrophosphaL

Specific examples of non-phosphorus inorganic builder salts are water-soluble carbonates, bicarbonates and silicates, the alkali metal salts, especially the sodium and potassium salts, the carbonates, bicarbonates and silicates being considered particularly suitable.

Water-soluble organic builders are suitable for the purpose of the invention, such. B. the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Specific examples of polyacetates and polycarboxylates as builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acids, d. H. the penta- and tretracarboxylic acids, the carboxymethoxysuccinic acid and the citric acid.

Furthermore, it is also possible to use water-insoluble builders, in particular complex silicates and very particularly complex sodium aluminosilicates, for example zeolites, eg. Zeolite 4A in which the monovalent cation is sodium and which has a pore size of about 0.4 nm. The preparation of such zeolites is described in U.S. Patent 3,114,603. The zeolites may be amorphous or crystalline and hydrated, as known in the art.

It is further desirable that the detergent compositions of the invention also contain an inert, water-soluble filling salt. As such, an alkali metal sulfate is preferred, for example, potassium or sodium sulfaL, the latter being particularly preferred.

Finally, various adjuvants may also be included in the bleaching detergent compositions of the present invention, for example, colorants, e.g. As pigments and dyes, Antivergiauungsmittel such. As carboxymethylcellulose, optical brighteners, eg anionic, cationic or nonionic brighteners, foam stabilizers, eg. Alkonolamides, proteolytic enzymes, etc., ie, additives well known for use in detergent compositions.

The detergent compositions of the invention are prepared by mixing together the ingredients, as set forth below. In the preparation of detergent compositions containing the

Bleach composition in combination with a detergent compound and / or builder salts, MPPA and / or a salt thereof and the selected chelating agent may be directly coupled with the surfactant compound, the builder, etc. but also the MPPA and / or a salt thereof may be coated with a coating material to prevent premature activation of the bleaching agent. The coating process is carried out in a manner known per se. Suitable coating materials are compounds such as magnesium sulfate, polyvinyl alcohol, lauric acid or their salts, and the like. like.

The invention will be further illustrated by the following examples.

example 1

A bleaching agent preferably having a low temperature was prepared having the following composition:

<td>component</td><td>Wt.%</td>

<td>Straight-chain sodium CjQ-alkyl alkylbenzenesulfonate</td><td>5</td>

<td>ethoxylated Cj jC ^ g alcohol (11 moles EO per mole of alcohol)</td><td>3</td>

<td>Soap (sodium salt of C |₂-C₂₂Carboxylic acid)</td><td>5</td>

<td>Sodium silicate (1 Na₂O: 2 SiO₂)</td><td>3</td>

<td>Pentasodium tripolyphosphate (TPP)</td><td>40</td>

<td>Sodium salt of diethylenetriaminepentamethylenephosphonic acid (DTPMP)</td><td>0.5</td>

<td>enzymes ^</td><td>0.4</td>

<td>Optical brighteners</td><td>03</td>

<td>Mg ^ SalzderMPPA</td><td>7.0</td>

<td>Perfume</td><td>0.18</td>

<td>sodium sulphate</td><td>22</td>

<td>water</td><td>rest</td>

(a) Proteolytic enzymes, commercially available as Alcalase 2M (Anson units / g) or as Maxatase P.

(b) bleaching composition containing about 65% by weight of magnesium monoperoxyphthalate as an active ingredient and having an active oxygen content of 5.1%.

This product was prepared by first treating an aqueous slurry containing 60% by weight of a mixture of all of the above ingredients, except for the enzyme, perfume and bleach composition containing about 65% by weight of MPPA MG salt as described in b) was spray-dried. The spray-dried product had a particle size ranging from 2.38 mm to 0.099 mm and a moisture content of about 14%. 92.5% by weight of this spray dried product was mixed with 7 parts by weight of the bleach composition of footnote (b) of similar grain size, 0.3 parts by weight of enzyme and 0.18 parts by weight of perfume in a rotating drum, the particulate product having the above composition and obtained with a moisture content of about 13 wt.%

Became -7AT394 386B.

This product was used to wash soiled fabrics in a washing machine while maintaining good washing performance and bleaching performance.

Example 2: Test Method

Bleaching tests were performed on standardized contaminated test fabric samples using the various bleaching and detergent compositions listed in Table 1 in a Tergotometer container (manufacturer: US Testing Company). The tergotometer was maintained at a constant temperature of 49 ° C and operated at 100 rpm.

Each of the test compositions described in Table 1 was stirred in the water to 11 tap water of 49 ° C and with a water hardness (as calcium carbonate) of about 100 ppm for one minute, followed by a mixed textile fabric load. each of two fabric samples (7.62 cm x 10.16 cm) of soiled fabric, as described below, duration, added to the respective wash tank After washing for 15 minutes at 49 ° C, the Teststoffprobai were rinsed in tap water of 38 ° C and then dried. The percentage of soil removed was measured by reflectance measurements on each soiled test fabric sample before and after washing using a Gardner Color Difference Meter. The percentage of dirt removal (% SR) was calculated as follows:

(Rd after washing) - (RD before washing)% SR = -x 100 (Rd before soiling) - (RD before washing) where "Rd before washing" represents the Rd value after soiling

Thus, the percentage of soil removal percentages were calculated for all five fabric samples and the values ​​obtained were averaged for each of the detergent compositions tested. A difference of more than 2% on average of the five soiled test fabric samples is considered significant.

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

In the following compilation it is indicated, with which the spots on the test substance samples were caused and from which material the respective test substance sample consisted.

spot

1. grape

Second bilberry

Third Sulfo dye 4. red wine

5th Coffee, tea

test samples

Daaon - 35 cotton cotton

EMPA 115 (cotton) EMPA 114 (cotton) cotton

Spotted test fabric samples 1 and 2 were prepared by passing non-abrasive cloth rolls through a padding and drying apparatus (manufacturer: Benz, Zurich, Switzerland), this apparatus serving 32 ° C warm solutions of, for example, grapes or Contained blueberries. After drying at 121 ° C, the fabric was cut into fabric samples measuring 7.62 cm x 10.16 cm. 80 these fabric samples, which had been impregnated with the same spots, were rinsed with 64.351 of 29.4 ° C water in an automatic household washing machine. They were then dried by passing them through a Beseler pressure dryer.

The soiled test fabric samples 3 and 4 were from fabrics available from Testfabrics Incorporated of

Middlesex, New Jersey, USA, and cut into 7.62 cm x 10.16 cm test fabric samples.

The soiled test fabric sample 5 was prepared by stirring and soaking unimpregnated cotton strips (dimensions 45.72 cm x 91.44 cm) at 65.6 ° C in a washing machine with a coffee and tea solution

-8AT394 386B

Weight ratio 8: 1 produced. Thereafter, the strips were rinsed in the machine and tumbled dry with the coffee / tea solution removed from the machine. The spotted fabric was then washed twice in the machine with hot pyrophosphate wash, followed by two complete washes at 60 ° C with water. The strips were then dried by passing them through an Ironrite drying machine twice, whereupon the strips were cut into fabric samples of the dimensions indicated above.

A granular detergent composition (HDD) was prepared by conventional spray drying. It had the following approximate composition:

Composition% by weight

Sodium tridecylbenzenesulfonate 15 ethoxylated primary C j₂ C 1 Alcohol 1 (7 moles EO / mole alcohol)

Sodium tripolyphosphate 33

Sodium carbonate 5

Sodium silicate 7

Sodium carboxymethylcellulose 0.5

Optical brighteners 02

Perfume 0.2

Water 11

Sodium sulphate remainder

Detergent compositions A to E were also prepared containing the detergent mixture HDD and also the ingredients listed in Table 1:

Table 1

<td rowspan="2">component</td><td colspan="5">Composition (in g)</td>

<td>A</td><td>_B</td><td>Ω</td><td>D</td><td>e</td>

<td>Detergent, HDD</td><td>4.50</td><td>4.50</td><td>4.50</td><td>4.50</td><td>4.50</td>

<td>Mg salt of MPPA ^</td><td></td><td>0.49</td><td>0.49</td><td>0.49</td><td>0.49</td>

<td>DTPMP^{1 2})</td><td></td><td></td><td>0.09</td><td></td><td></td>

<td>EDTA³)</td><td></td><td></td><td></td><td>0.09</td><td></td>

<td>NTA⁴)</td><td></td><td>-</td><td>-</td><td>-</td><td>0.18</td>

1) Bleaching composition comprising about 65% by weight monoperoxyphthalic acid (as magnesium salt) and having 5.1% active oxygen content.

2) Sodium diethylene triamine pentamethylene phosphate from PA Hunt Chemical Corp., Lincoln, Rhode Island.

3) disodium salt of ethylenediaminetetraacetic acid.

4) Trisodium salt of nitrilotriacetic acid.

The detergent compositions A to E were tested by the method described above. The

Results of the bleaching tests are summarized in Table 2, in which also starting and final weights for the active

Oxygen (AO) in the wash solution (expressed as "initial amount in g" and "final amount in g") and the stain removal values ​​were recorded for each of the five different types of stains.

-9AT394 386B

Table 2

Comparison of bleaching power

composition

<td></td><td>A</td><td>B</td><td>£</td><td>D</td><td>e</td>

<td>Initial quantity (g)</td><td>___</td><td>25.0</td><td>25.0</td><td>25.0</td><td>25.0</td>

<td>(AO x 10³)</td><td></td><td></td><td></td><td></td><td></td>

<td>Final amount (g)</td><td>-</td><td>15.9</td><td>18.6</td><td>18.5</td><td>15.6</td>

(AO x 10³)

<td>consumed (g)</td><td>...</td><td>9.1</td><td>6.4</td><td>6.5</td><td>9.4</td>

<td>(AO x 10³)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fleckentfemung:</td><td>%.</td><td>&amp;</td><td>%.</td><td></td><td></td>

<td>grape</td><td>47</td><td>69</td><td>72</td><td>74</td><td>72</td>

<td>bilberry</td><td>44</td><td>65</td><td>68</td><td>66</td><td>67</td>

<td>Sulfo-dye</td><td></td><td></td><td></td><td></td><td></td>

<td>(EMPA 115)</td><td>3</td><td>3</td><td>3</td><td>3</td><td>4</td>

<td>Red wine (EMPA 114)</td><td>38</td><td>49</td><td>51</td><td>44</td><td>45</td>

<td>Coffee, tea</td><td>17</td><td>43</td><td>39</td><td>38</td><td>41</td>

<td></td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td>

<td>Average (%)</td><td>30</td><td>46</td><td>47</td><td>45</td><td>46</td>

The results of Table 2 show that compositions C and D containing the chelators DTPMP and EDTA, respectively, had lower active oxygen consumption compared to composition E containing NTA and composition B which did not contain a chelating agent. although they achieved about the same degree of stain removal.

Example 3

Bleach tests were performed using a detergent formulation A having the following composition:

<td>KomDonente</td><td>Wt. &lt;J</td>

<td colspan="2">Straight-chain sodium alkyl</td>

<td>Benzenesulfonate (LAS)</td><td>5</td>

<td>Soap (sodium salt of</td><td></td>

<td>high molecular weight fatty acids)</td><td>5</td>

<td>ethoxylated alcohol (11 mol</td><td></td>

<td>EO per mole of alcohol)</td><td>3</td>

<td>sodium silicate</td><td>3</td>

<td>Sodium tripolyphosphate (TPP)</td><td>40</td>

<td>Optical brighteners</td><td>03</td>

<td>sodium sulphate</td><td>23.5</td>

<td>enzyme</td><td>0.3</td>

<td>Perfume</td><td>03</td>

<td>Mg salt of MPPA ^</td><td>9</td>

<td>water</td><td>rest</td>

1)

Bleaching composition as described in Example 1, footnote (b).

-10AT394 386B

The tests were carried out in an Ahiba washing machine under the following test conditions: Ahiba wash = heating-up period + washing period; initial bath temperature: 30 ° C.

Washing temperature Heating time Washing time ° C 5 min 15 min ° C 15 min 15 min ° C 30 min 15 min

Detergent concentration: 10 g / liter

Hardness of tap water: 350 ppm

Six sampled fabrics (10 cm x 10 cm) per washing machine holder in 600 ml detergent solution. The reflectance measurements were made before and after washing with a Gardner XL-20 reflectometer and the results expressed as ΔRj.

The detergent compositions B to F differed from the detergent composition A by the addition of the complexing agents indicated below for the individual compositions:

composition

Added complexing agent

0.5% by weight of diethylenetriaminepentamethylenephosphonic acid ^

0.1% by weight of diethylenetriaminepentaacetic acid as Mg salt

Wt% nitrilotriacetic acid (NTA)

Weight% EDTA

0.5% by weight of ethylenediamine-tetramethylenephosphonic acid²)

1) Commercially available as Dequest 2060 from Monsanto Company, Inc., St. Louis, Missouri.

2) Commercially available as Dequest 2041 from Monsanto Company, Inc.

The results of the bleach tests are summarized in the following Table 3, wherein the values ​​of ΔRj represent averages for each of the specific compositions at the indicated temperatures.

Table 3

Δ R j values ​​(average)

<td>Temp.</td><td>B</td><td>£</td><td>D</td><td>e</td><td>F</td><td>A</td>

<td>10 ° C</td><td>36</td><td>34.5</td><td>34.5</td><td>33</td><td>33</td><td>32</td>

<td>60 ° C</td><td>41</td><td>39</td><td>39</td><td>38.5</td><td>38.5</td><td>38</td>

<td>95 ° C</td><td>47</td><td>45</td><td>44</td><td>43</td><td>43</td><td>43</td>

11AT 394 386 B

It is apparent from Table 3 that all of the compositions containing a complexing agent exhibit an improved bleaching performance as compared to Composition A which did not contain complexing agents. The composition B showed the greatest improvement in the bleaching effect of all tested compositions.