DK161841B - Bleach and Detergent Free from Water Soluble Silicates and Bleaching Procedures - Google Patents

Description

in

DK 161841 B

The present invention relates generally to bleaching detergents containing, as a bleaching agent, an inorganic peroxygen compound in combination with an organic activator therefor, and the use of such agents for washing processes. More particularly, the present invention relates to granular bleaching detergents which provide improved bleaching performance while substantially improving the stability of the peroxyacid bending types in the wash solution.

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Bleaches that release active oxygen into the wash solution are extensively described in the art and commonly used in washing processes. In general, such bleaches contain per-oxygen compounds, such as perborates, percarbonates, perphosphates, and the like, which promote bleaching activity by forming hydrogen peroxide in aqueous solution. A major disadvantage of using such peroxygen compounds is that they are not optimally effective at the relatively low washing temperatures used in most household washing machines 20 in the U.S. temperatures in the range of 27-54 ° C.

In comparison, European washing temperatures are generally substantially higher, typically extending over a range of 32 - 93 ° C. However, even in Europe and the other countries that usually use washing temperatures near the boiling point, 25 there is a tendency towards washing at lower temperatures.

In an attempt to improve the bleaching activity of peroxygen bleaches, the prior art has used materials called activators in combination with the peroxygen compound. It is generally believed that the interplay of the peroxygen compound and activator results in the formation of a peroxyacid which is a more active bleaching type than hydrogen peroxide at lower temperatures.

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Several compounds have been proposed in the art as activators for peroxygen bleaches, including carboxylic acid anhydrides such as those described in U.S.A. U.S. Patent Nos. 3,298,775, 3,338,839, and 3,532,634, 3 carboxylic acid esters such as those disclosed in U.S.A. No. 2,995,905, N-acyl compounds such as those described in U.S.A. U.S. Patent Nos. 3,912,648 and 3,919,102, cyanoamines as disclosed in U.S.A. U.S. Patent No. 4,199,466, and acylsulfoamides as disclosed in U.S.A. patent specification no.

3 3,245,913.

The formation and stability of the peroxyacid bleach types in bleach systems containing a peroxygen compound and an organic activator is recognized as a problem in the prior art. U.S.A. Patent No. 4,255,452 is specifically directed to the problem of avoiding the reaction of peroxyacid with peroxygen compound to form what is described in the patent as "useless products, namely, the corresponding, carboxylic acid, molecular oxygen and water". Patent 3 states that such side reactions are "doubly harmful as per acid and per-compound are degraded simultaneously". The patent then describes certain polyphosphonic acid compounds as chelating agents which are said to inhibit the above-described peroxyacid consuming side reaction and provide an enhanced bleaching effect. Contrary to the use of these chelating agents, the patent states that other more commonly known chelating agents such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) are substantially ineffective and do not provide enhanced bleaching effects. A disadvantage of the bleaching agents of the aforementioned patent application is therefore that they necessarily preclude the use of conventional sequestering agents, many of which are less costly and more readily available than the polyphosphonic acid compounds described.

The effect of silicates on the degradation of peroxyacid in 5 3

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washing and / or bleaching solution has so far been unnoticed in the art. IN USA. U.S. Patent Nos. 3,860,391 and 4,292,575 disclose that silicates are commonly used as additives for peroxide-containing bleaching solutions for the purpose of stabilizing peroxide compounds therein. However, the patents note that the use of silicates in such bleaching solutions can cause other problems in the bleaching process, such as the formation of silicate precipitates which deposit on the bleached articles.

Accordingly, the patents are directed to methods of bleaching cellulose fibers with silicate-free bleach solution, in which peroxide stability is enhanced by compounds other than silicates.

European Patent Specification No. 0.028,432 discloses a granular detergent containing, among other things, a water-soluble silicate and an organic activator compound for a peroxygen bleach. The pH properties of such a detergent are said to be critical, in particular the pH in a 2% aqueous dispersion is from 2-9 and preferably from 4-7. On page 7 of the specification 20, certain polyphosphonic acid compounds are described as highly preferred components of the agent, the specification in this regard stating that the polyphosphonates "have been found to be uniquely effective in stabilizing organic peroxyacids with the generally detrimental effect of water-insoluble silicates. , especially those belonging to the zeolite and kaolin classes ". The nature of such "adverse effect" is not specified.

On page 38 of the specification, granular detergents are described in Examples VIII-X which do not contain sodium silicate, all such agents being found to contain "Dequest" 2041 (ethylene-diamine tetramethylene phosphonic acid). The agents of the aforementioned examples also contain a peroxygen compound activator incorporated into agglomerate particles constituted by said activator, a water-insoluble silicate compound and a nonionic surfactant.

According to the present invention there is provided a granular bleaching detergent comprising: (a) a bleaching agent comprising:

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they comprise an inorganic peroxygen compound in combination with an activator therefor, and (b) at least one surfactant selected from the group of anionic, cationic, nonionic, ampholytic and zwitterionic detergents, the detergent being characterized in that substantially are free of (i) water-soluble silicate compounds, and (ii> agglomerate particles substantially comprising said activator, a water-insoluble silicate compound and a nonionic surfactant.

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In accordance with the process of the invention, bleaching of stained and / or soiled materials is accomplished by contacting such materials with an aqueous solution of the bleaching detergent defined above.

The present invention is based on the discovery that the undesirable loss of peroxyacid in the aqueous wash solution by reacting peroxyacid with a peroxygen compound (or 2q more particularly hydrogen peroxide formed from such peroxy recombination) to produce molecular oxygen is noticeably reduced in bleaching systems which are essentially free of water-soluble silicate compounds. Although applicants do not wish to be bound to any particular process theory, it is believed that the presence of water-soluble silicates in peroxygen compound / activator bleach systems catalyzes the aforementioned reaction of peroxyacid with hydrogen peroxide, resulting in the loss of active oxygen from the wash solution, which otherwise would be available for bleaching. It is recognized in the art that metal ions such as e.g. Iron and copper ions serve to catalyze the degradation of hydrogen peroxide and also the peroxyacid reaction with hydrogen peroxide. Regarding such a metal ion catalysis, however, it has surprisingly been found that conventional sequestering agents, such as EDTA 35 or NTA, which in the art were judged to be ineffective in inhibiting the aforementioned peroxyacid-consuming reaction (see, for example, the disclosure in column U.S. Patent No. 4,225,452) may be incorporated into the agents of the present invention.

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The present invention for stabilizing the peroxyacid in solution.

The term "water-soluble silicate compounds" refers to compounds such as sodium silicate which are substantially soluble in aqueous wash solutions and generally present in conventional bleaching detergents, but are substantially removed in the compositions of the present invention. However, the present invention contemplates incorporating substantially water-insoluble silicates, especially aluminum silicate materials such as clays and zeolites into the bleaching detergents described herein, water-soluble silicate compounds being considered far more detrimental to the peroxyacid stability than water-insoluble materials such as water-insoluble materials.

In a preferred embodiment of the invention, the bleaching agents described herein further contain a sequestering agent to enhance the stability of the peroxyacid bleaching compound in solution by inhibiting its reaction with hydrogen peroxide in the presence of metal ions. The term "sequestering agent" 20, as used herein, refers to organic compounds capable of forming a complex with Cu ions such that the stability constant (pK) of the complex formation is equal to or greater than 6 in water at 25 ° C with an ionic strength of 0.1 mol / liter, pK being usually defined by the formula: pK = -log K, where K represents the equilibrium constant. Thus, the pK values for the complexation of copper ion with NTA and EDTA are under the indicated conditions, e.g. 12.7 and 18.8, respectively. The term "sequestering agent" is therefore used herein in a sufficiently restrictive sense to exclude inorganic compounds commonly used in detergent formulations as builder salts. Particularly useful sequestrants include EDTA, diethylenetriamine penta-acetic acid (DEPTA), and the various phosphonate sequestrants marketed by Monsanto Company under the trademark "Dequest", e.g. "Dequest" 2000, 2006, 2041, 2051 and 2060.

In accordance with another embodiment of the invention

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the described bleaching agents are further distinguished from certain water-soluble silicate-free agents described in the art by limiting the use of sequestering agents in the present bleaching agents to those having a stability constant no greater than about 5 20 for Cu + + complex formation in water at 25 ° C

and at an ionic strength of 0.1 mol / liter. This restriction necessarily precludes the presence of polyphosphonic acid compounds such as "Dequest" 2041 (ethylenediaminetetramethylene-phosphonic acid) and "Dequest" 2060 (diethylenetriamine pentamethylene-phosphonic acid) in the bleaching agents of the invention, the aforementioned sequestering agents having about stability constants. 20. Accordingly, suitable sequestrants for this embodiment of the invention include the sodium salts of nitrilotriacetic acid (ΝΤΆ), ethylenediamine tetraacetic acid (EDTA), ethylenediamine, tetramine, i.e.

N- (CH2 ~ c2 -NH2 ^ 3 'bis (aminoethyl) glycol ether-NNN'N'-tetraacetic acid (EGTA) and KKCH2 -PO ^ I ^ Jg marketed under the trademark "Dequest" 2000. EDTA and the The above-mentioned "Dequest" 2000 is particularly preferred for use in this embodiment 20 of the invention.

The bleaching detergents of the invention are comprised of two essential components: (a) a bleaching agent; and. (b) a surfactant detergent.

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The bleach useful in such agents comprises a per-oxygen compound in combination with an organic activator therefor.

The peroxygen compounds useful in the present agents 7 include compounds which release hydrogen peroxide in aqueous media such as alkali metal perborates, e.g. sodium perborate and potassium perborate, alkali metal perphosphates and alkali metal percarbonates. The alkali metal perborates are usually preferred because of their commercial availability and relatively low price.

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Conventional activators such as those described, e.g. in column 4 of U.S.A. Patent No. 4,259,200, are suitable for use in connection with the aforementioned peroxygen compounds, such a description being incorporated herein by reference "pert." usually of particular interest, with tetraacetylethylenediamine (TAED> being a highly preferred activator. TAED is preferably present in the agents, 0 according to the invention in the form of "coated" grains containing TAED and a suitable carrier material such as a mixture of sodium and Such coated TAED grains are conveniently prepared by mixing finely divided particles in sodium triphosphate and TAED and then spraying such an aqueous solution of potassium triphosphate using suitable granulating equipment such as a rotary pan granulator. A typical process for making this type coated TAED is disclosed in U.S. Patent No. 4,283,302. The TAED grains have a preferred particle size distribution as follows: greater than 150 microns, 10-100% greater than 100 μπι, but less than 150 μιη, 0-50% less than 75 μπι and 0-20% less than 50 μπι. Another particularly preferred particle size distribution is where the average particle size of TAED is 160 microns, ie. 50% of the particles have a size greater than 160 microns. The aforementioned size distributions refer to TAED present in the coated grains and not to the coated grains themselves. The mole ratio of peroxygen compound to activator may vary widely depending on the particular choice of peroxygen compound and activator. Mole ratio 30 from approx. 0.5: 1 to approx. However, 25: 1 is generally suitable to provide satisfactory bleaching effect.

The bleach may optionally also contain a peroxyacid compound in combination with the peroxygen compound and activator. Useful 3g peroxyacid compounds include water-soluble peroxyacids and their water-soluble salts. The peroxyacids can be characterized by the following general formula: i 8

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- 0 -HOO --- C - R-Z

5 wherein R is an alkylene tip containing from 1 to ca. 20 carbon atoms, or a phenylene group, and Z is one or more groups selected from hydrogen, halogen, alkyl, aryl and anionic groups.

The organic peroxyacids and their salts may contain from ca. 1 to approx. 4, preferably 1 or 2, peroxy groups which may be aliphatic or aromatic. The preferred aliphatic peroxyacids include diperoxyazelaic acid, diperoxydodecanedioic acid and monoperoxyacetic acid. Of the aromatic peroxyacid compounds useful herein, mono-peroxyphthalic acid (MPPA), especially the magnesium salt thereof, is particularly preferred, and diperoxy-terephthalic acid is particularly preferred. A detailed description of the preparation of MPPA and its magnesium salt is given on pages 7-10, inclusive, in European Patent Specification No. 0.027,693.

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The bleaching detergents of the invention are characterized by being substantially free of (i) water-soluble silicate compounds, and (ii) agglomerate particles consisting essentially of a mixture of three components: the organic 2® activator for the peroxygen compound, a water-insoluble silicate compound, such as clay or zeolite, and a nonionic surfactant, such a mixture being at least 80% by weight of the agglomerate particles. The agglomerate particles excluded for use herein are of the type formed in equipment. such as a brow granulator, and serves to incorporate pale agent activator one into a matrix of materials as disclosed in European Patent Specification No. 0.028432. In a particular embodiment of the invention, the bleaching agents are further characterized by being essentially free of sequestrants. 2 '2 "f" with a stability constant for Cu complex formation over ca.

20 in water at 25 ° C and at an ionic strength of 0.1 mol / liter.

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The water-insoluble silicate materials which can be advantageously used in the present bleaching agents are preferably aluminum silicates such as zeolites and smectite-type clays. The crystalline types of zeolites that can be used include those described in "Zeolite Molecular Series" by Donald W. Breck, published in 1974 by John Wiley & Sons, wherein typically commercially available zeolites are listed in Table 9.6 on pages 747-749 of the text, this table being incorporated herein by reference. Type A zeolite structures are particularly desirable and are widely described in the art, see e.g. page 133 of the previously mentioned Breck text, as well as in U.S.A. U.S. Patent No. 2,882,243. The zeolites are particularly useful as builder salts in powerful detergents.

The aforementioned smectite-type clays are three-layered clays characterized by the ability of the layered structure to increase its volume several times by swelling or expansion in the presence of water to form a thixotropic gelatinous substance. There are two classes of clays of the smectite type: 20 In the first class, alumina is present in the silicate crystal lattice, in the second class magnesium oxide is present in the silicate crystal lattice. Atomic substitution by iron, magnesium, sodium, potassium, calcium, and the like can occur in the crystal lattices of the smectite clays. It is usual to distinguish between 25 clays on the basis of their dominant cation. Eg. is a sodium clay one in which the cation is essentially sodium. With respect to the present bleaching detergents, aluminum silicates are preferred, wherein sodium is the dominant cation, such as e.g. bentonite clays. Among the bentonite species, they are particularly preferred from Wyoming (usually referred to as western or Wyoming bentonite). Calcium and magnesium clays are also useful, though less preferred, for the purposes of the present invention.

35 Preferred asphyxiating bentonites are sold under the trademark "Mineral Colloid" as industrial bentonites by Benton Clay

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Company, a subsidiary of Georgia Kaolin Co. These materials, which are the same as those previously sold under the trademark "THIXO-JEL", are selectively broken and reprocessed bone-5 tonites and those considered to be most useful are available as "Mineral Colloid" No. 101, etc. corresponding to "THIXO-JEL" Nos. 1, 2, 3 and 4. Such materials have pH values (6% concentration in water) in the range of 8 to 9.4, maximum moisture content ^ of free moisture of approx. 8% and densities of approx. 2.6, and for the pulverized grade, at least approx. 85% (and preferably 100%) through a 200 mesh U.S. term series. More preferably, the bentonite is one in which substantially all of the particles (i.e. at least 90% thereof, preferably above 95%) pass through a No. 325 sieve and most preferably all the particles pass through such a sieve. The swelling capacity of the bentonites in water is usually in the range of 3 to 15 ml / g, and its viscosity at a 6% concentration in water is usually from ca. 8-30 centipoise.

In a particularly preferred embodiment of the invention, the carrier particles comprise finely divided bentonite agglomerates having particle sizes smaller than # 200 sieve, agglomerated to particles having sizes substantially in the 10-1000 sieve range, with a space weight in the range of 0.7 -0.9 g / ml 25 and a moisture content of 8-13%. Such agglomerates include ca. 1-5% of a binder or agglomerating agent to aid in the preservation of the innocence of the agglomerates until they are added to water in which they are intended to decompose and disperse.

Instead of using "THIXO-JEL" or "Mineral Colloid" bentonites, equivalent competing products such as that sold by the American Colloid Company, 35 Industrial Division, such as General Purpose Bentonite Powder, 11 may also be used.

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having a minimum of 95% thereof finer than 325 mesh or 44 microns in diameter (wet particle size) and a minimum of 96% finer than 200 mesh or 74 microns in diameter (dry particle size). Such aqueous aluminum silicate is composed mainly of montmorillonite (90% minimum), with smaller amounts of feldspar, biotite and selenite. A typical analysis on an "anhydrous" basis is 63.0% silica, 21.5% alumina, 3.3% ferric iron (as Fe2 ° 3), 0.4% ferro-iron (as FeO), 2.7% magnesium (as MgO), 2.6% sodium and potassium (as Na 2 O), 0.7% calcium (as CaO), 5.6% crystal water (as E 2 O), and 0.7% trace elements.

Although western bentonites are preferred, it is also possible to use synthetic bentonites such as those which can be prepared by treating Italian or similar bentonites containing relatively small amounts of exchangeable monovalent metals (sodium and potassium) with alkaline materials such as sodium carbonate, to increase the cation exchange capacities of such products. It is believed that the Na 2 O content of the bentonite 20 should be at least approx. 0.5%, preferably at least 1% and more preferably at least 2%, so that the clay will swell satisfactorily, with good softening and dispersing properties in aqueous suspension. Preferred swelling bentonites of the synthetic types described are sold under the trademarks "Laviosa" and "Win-25 kelmann", e.g. "Laviosa" AGB and "Winkelmann" G-13.

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

Among the anionic surfactants useful in the present invention are the surfactants containing an organic hydrophobic group containing from 8 to 26 carbon atoms and preferably from ca. 10 to 18 carbon atoms in their molecular structure and at least one

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12 solubilizing group selected from the group of 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, am (monium and alkanolammonium salts)) of higher fatty acids or resin salts containing from about 8-20 carbon atoms and preferably 10- Suitable fatty acids can be obtained from 10 oils and waxes of animal or vegetable origin, such as sebum, fat, 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.

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The anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an alkyl group containing from about 8-26, and preferably from ca. 12-22 carbon atoms. (The term "alkyl" includes the alkyl portion of the higher acyl groups). Examples of the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing from ca. 10-1.6 carbon atoms in the higher alkyl group of a straight or branched chain, such as e.g. the sodium, potassium and 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 alkene sulfonates and hydroxyalkanesulfonates. The olefin sulfonate detergents can be prepared in a conventional manner by reacting SO 2 with long chain olefins containing from ca. 8-25 and preferably from 12-21 carbon atoms, such olefins having the formula RCH = CHR 2 wherein 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. 1-17 carbon atoms, or hydrogen 13

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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 detergents are paraffin sulfonates containing from ca. 10-20 carbon atoms, and preferably from ca. 15-20 carbon atoms. The primary paraffin sulfonates are prepared by reacting long chain α-olefins and bi-sulfites. Paraffin sulfonates with the sulfonate group distributed along the paraffin chain are disclosed in U.S. Patent Nos. 2,503,280, 2,507,088, 3,260,741 and 3,372,188, and in German Patent No. 10,355,096.

Other suitable anionic detergents are sulfated ethoxylated higher fatty alcohols of the formula R0 (CoH.0) SOm, wherein R is a fatty alkyl having from 10 to 18 carbon atoms, m is from 2-6 (preferably having a value of about 1 / 5 to 1/2 of the number of carbon atoms in R) and M is a solubilizing salt-forming cation such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkylbenzene sulfonate wherein the higher alkyl has 10-15 carbon atoms. The proportion of ethylene oxide 20 in the polyethoxylated higher alkanol sulfate is preferably 2-5 moles of ethylene oxide groups per moles of anionic detergent, with three moles being most preferred, especially when the higher alkanol has 11-15 carbon atoms. To maintain the desired hydrophilic-lipophilic balance when the carbon atom content of the alkyl chain is 25 in the lower portion of the 10-18 carbon atom range, the ethylene oxide content of the detergent can be reduced to approx. two moles per mols, while when the higher alkanol has 16-18 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 30 8 or 9. Similarly, the salt-forming cation can be changed to obtain the best solubility. It may be any suitable solubilizing metal or group, 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 1-4 carbon atoms and the amines and alkanolamines may be mono-, di- and tri-substituted, as in monoethanolamine, diisopropanolamine.

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14 and trimethylamine. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and is labeled as "Neodol" 25-3S.

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The most preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono- / di- and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts. the higher alkylbenzene sulfonates, olefin sulfonates and higher alkyl sulfates. Among the above anionic agents, the most preferred are the linear sodium alkyl benzene sulfonates (LABS), and especially those wherein the alkyl group is a straight chain alkyl group having 12 or 13 carbon atoms.

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 character). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached 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 the hydrophobic and hydrophilic groups.

The nonionic detergent used is preferably a poly lower alkoxylated higher alkanol wherein the alkanol has from 10 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials, it is preferred to use those wherein the higher alkanol is a higher fatty alcohol having 11-15 carbon atoms and containing from 5-9 lower alkoxy groups per liter. moth. The lower alkoxy is preferably ethoxy, but in some cases it may, if desired, be mixed with propoxy, the latter, if present, usually constituting a less significant

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15 (less than 50%) component. Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and contains approx. 7 ethylene oxide groups 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.

12-15 carbon atoms, with approx. 7 moles of ethylene oxide, and the latter is a similar mixture, wherein the carbon atom content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups 10 per mole on average is approx. 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergdjtol® 15-S-7 and Tergitol® 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The first is a mixed ethoxylation product 15 of an 11-15 carbon-containing linear secondary alkanol with seven moles of ethylene oxide, and the latter is a similar product, but reacting 9 moles of ethylene oxide.

Also useful in the present agents are higher molecular weight nonionic agents 20, such as "Neodol" 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol having 14-15 carbon atoms, and the number of ethylene oxide groups per liter. mole is approx. 11. Such products are also manufactured by Shell Chemical Company.

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Zwitterionic detergents such as the betaines and sulfobetaines of the following formula are also useful: R - - - N - R4-X = O R

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wherein R is an alkyl group containing from ca. 8-18 carbon atoms, R5 and R4 are each an alkyl or hydroxyalkyl group containing about 1-4 carbon atoms, R 1 is an alkylene or hydroxyalkylene group containing 1-4 carbon atoms and X is 16

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C or S: 0. The alkyl group may contain one or more intermediates such as amido, ether or polyether linkers or non-functional substituents such as hydroxyl or halogen which do not significantly affect the hydrophobic nature of the group. When X 5 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 comprise 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 and quaternary ammonium compounds.

Examples of suitable synthetic cationic detergents include: Normal primary amines of the formula RNE ^ wherein R is an alkyl group containing from ca. 12-15 atoms; diamines of the formula RNIK ^ H ^ N ^ wherein R is an alkyl group containing from ca. 12-22 carbon atoms such as N-2-aminoethylstearylamine 20 and N-2-aminoethylmyristylamine; amide-linked amines such as those of formula R 1 CONBK 2 H 3 N 1, wherein R 2 is an alkyl group containing from 8 to 20 carbon atoms such as N-2-aminoethylstearyl amide and N-aminoethylmyristyl amide; quaternary ammonium compounds, wherein typically one of the groups bonded 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 there is an anion such as halogen, acetate, methosulfate, etc. .

30 present. The alkyl group may contain intermediates such as amide which do not substantially affect the hydrophobic nature of the group, e.g. stearylamidopropyl quaternary ammonium chloride. Typical quaternary ammonium detergents are ethyl-dimethyl-stearyl-ammonium chloride, benzyl-dimethyl-stearylammonium chloride, trimethyl-stearyl-ammonium chloride, trimethyl-cetylammonium bromide, dimethyl-ethyl-lauryl-ammonium chloride, and dimethyl-propylmethyl

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Ampholytic detergents are also suitable according to the invention. Ampholytic detergents are well known in the art, and many effective detergents of this class are described by Schwartz, Perry and Berch in the previously mentioned "Surface Active Agents 5 and Detergents". Examples of suitable amphoteric detergents include: alkyl beta-iminodipropionates, RN (C 2 H 4 COOM) 2; alkyl beta-aminopropionates, RN (H) C 2 H 4 COOM and long chain imidazole derivatives of the general formula: 10 CHO / \ N CHO II

R-C - N-CH2CH2OCH2COOM

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

The bleaching detergents of the invention optionally contain a detergent builder of the type commonly used in detergent formulations. Useful builders include any of the conventional inorganic water-soluble builder salts, such as e.g. water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, 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 include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates include 18

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especially 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 builder compounds are described in U.S.A. U.S. Patent Nos. 3,213,030, 5,422,021, 3,422,137, and 3,400,176. Pentanium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred water-soluble inorganic builders.

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

Water-soluble organic builders are also useful. Eg. 15 alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates are useful builders for the compositions and methods of the invention. Specific examples of polyacetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acid (i.e. penta and tetraacetic acid, carboxylic acid and carboxylic acid

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

Desirably, an inert water-soluble filler salt is included 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.

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19

Various adjuvants may be included in the laundry detergents of the invention. Usually these include perfumes, dyes, e.g. pigments and dyes, antigen deposits, such as alkali metal salts of carboxymethyl cellulose, optical brighteners such as anionic, cationic or nonionic brighteners, foam stabilizers such as alkanolamides, and the like, all of which are known in the laundry detergent field for use in detergents. Current enhancers, usually referred to as power assistants, can also be used to preserve the particulate forms as free flowing beads or powders. Starch derivatives and special clays are commercially available as additives that enhance the flowability of otherwise sticky and paste-like particulate agents, two such clay resins. - Additives are currently marketed under the trade names "Satinlo ton" and "Microsil".

A preferred bleaching detergent according to the invention typically comprises (a) from ca. 2-50% by weight of a bleach comprising 2Q a peroxygen compound in combination with an activator therefor; 5-50% by weight of a surfactant detergent; 1 to approx. 60% by weight of a detergent builder salt, and (d) from ca. 0.1 to approx. 10% by weight of a sequestering agent, such agent being characterized by being substantially free of (i) water-soluble silicate compounds, and (ii) agglomerate particles substantially comprising said activator, a water-insoluble silicate compound, and a nonionic surfactant. The remainder of the agent will substantially comprise water, filler salts such as sodium sulfate, and less significant additives selected from the various excipients described above.

The particulate bleaching detergents of the invention are prepared by mixing the bleaching agent and any sequestering agent with the spray-dried detergent, the latter being formulated so that the use of water-soluble silicate preparations is used.

DK 161841 B

20 binders, especially sodium silicate, are avoided. The presence of very small amounts of water-soluble silicate compounds in the finished agents, viz. below approx. 0.5%, preferably below ca. 0.2%, and most preferably no greater than ca. 0.1 wt%, as may be found in the use of silicate pigments or dyes, or in contact with the aqueous mixture slurry with residual sodium silicate in the spray tower, is contemplated by the present invention.

Spray drying of silicate-free detergent formulation may result in a relatively dusty grained product due to the absence of silicate as a binder for the spray-dried beads. However, alternative organic bonding materials may be used, such as e.g. starch, carboxymethyl cellulose and materials comparable therewith. The strength of the spray-dried beads can also be increased by maximizing the solids content of the silicate-free slurry in the mixer and / or by keeping the supply air temperature of the hot air stream in the spray tower as low as possible.

20

The bleach can be blended either directly with the spray-dried powder, or the bleach and any sequestering agent can be coated separately or combined with the coating material to prevent premature activation of the bleach. The coating process is carried out in accordance with known methods. Suitable coating materials include compounds such as magnesium sulfate, polyvinyl alcohol, lauric acid and its salts and the like.

The bleaching detergents of the invention are added to the wash solution in a sufficient amount to give from 3 to approx. 100 parts of active oxygen per million parts of solution, with a concentration of approx. 5 to approx. 40 ppm is generally preferred.

The particulate bleaching detergents described above may be prepared by such methods as spray drying, drying,

DK 161841B

mixing or agglomerating the individual components.

Example 1 A preferred silicate-free bleaching detergent is the following:

Component Weight%

Linear Sodium C ^ q-C ^, alkylbenzenesulfonate 6 10 Ethoxylated C - ^ - C gg Primary alcohol (11 moles EO per mole of alcohol) 3 Soap (sodium salt of i2 ~ ^ 22 cark ° xylic acid) 4

Pentanium Tripolypho-Spat (TPP) 32.0 EDTA 0.5 TAED 2.3

Carboxymethyl cellulose 0.5

Sodium perborate tetrahydrate 13.2

Optical brighteners, pigments and perfumes 0.4

Proteolytic enzymes 0.5 20 Sodium sulfate and water residue

The above product is prepared by spray drying an aqueous slurry containing 60% by weight of a mixture containing all of the above components except for the enzyme, perfume, TAED and sodium perborate. The resulting particulate spray-dried product has a particle size in the range of 14 mesh to 270 mesh (U.S. sieve series).

The spray-dried product is then mixed in a rotary drum with the appropriate amounts of sodium mesh of similar mesh size, TAED, enzyme and perfume to obtain a particulate product having a moisture content of about 30%. 18% by weight.

The product described above is used to wash dirty fabrics by hand washing, as well as in an automatic washing machine, with good washing and bleaching effect being achieved by both washing methods.

22

DK 161841B

Other satisfactory products can be obtained by altering the concentration of the following principal components in the foregoing! described agent as follows: 5 Component Vasqt%

Alkylbenzenesulfonate 4-12

Ethoxylated Alcohol 1-6 Soap 1-10 TPP 15-50 10 Enzymes 0.1-1 EDTA 0.1-2 TAED 1-10

Sodium Perborate .5-20 15 For highly concentrated powerful washing powders, the alkyl benzene sulfonate, TPP and soap components of the above-described agent may be omitted and the content of ethoxylated alcohol may be increased to an upper limit of 20%.

Example 2.

Bleaching tests are carried out as described below, comparing the bleaching effect of water-soluble silicate-free bleaching detergents of the invention to similar silicate-containing agents, the latter being comparable to the former mentioned in almost all respects except for the presence of a water-soluble silicate compound. In particular, the silicate-free agents are characterized by the presence of sodium metaborate; the silicate-containing agents contain sodium silica.

The agents are formulated by addition to a spray-dry straight particulate detergent of granules of sodium perborate trahydrate and tetraacetylethylenediamine (TAED) to form the bleaching detergents shown in Table 1 below. The numbers listed in the table denote the percentage of each component by weight in the mean.

DK 161841 B

23

Table 1.

Component Medium

A B C D E F

5 Linear Sodium Cio “Ci3 Alkyl Benzenesulfonate 8% 8% 8% 8% 8% 8%

Ethoxy clay C 1 -C 2 g primary alcohol (11 moles EO per mole of alcohol) 333333 Soap (sodium salt of C 2 -C 22 carboxylic acid) 333333

Sodium silicate (lNa20: 2SiO2) - - - 4 4 4

Sodium Metabolate 5 5 5

Pentane Sodium Tripolyphosphate 15 (TPP) 35 35 35 35 35 35

Optical clarifier (stilbene) 0.2 0.2 0.2 0.2 0.2 0.2

Sodium perborate tetrahydrate 666666 TAED 5 5 5 5 5 5 20 EDTA 1 - - 1 EDITEMPA (1) 1 - - 1

Sodium sulphate 21 20 20 21 20 20

Water Rest 25 ^ Sold as "Dequest" 2041 by Monsanto Company, St. Louis,

Missouri.

Test procedure.

Bleaching tests are performed in an Ahiba apparatus at maximum temperatures of 60 ° C and 90 ° C, respectively, as described below.

600 ml tap water with a hardness of approx. 320 ppm as calcium carbonate is introduced into each Ahiba's in six bowls. Six cotton fabric samples (8 cm x 12 cm) dirty with immedial black are placed 35 in each bowl, with the commencement reflection coefficient for each 24

DK 161841B

fabric sample is measured with a Gardner XL 20 reflectometer.

Six grams of each of the agents A to F, described in Table 1, are placed separately in the six bowls of Ahiba, with a different agent being placed in each bowl. The bleaching detergents are thoroughly mixed in each bowl with a blender-type appliance, and the washing cycle is then started. The bath temperature, initially at 30 ° C, is allowed to rise approx. 1 ° C per day 10 minutes, until the maximum sample temperature (60 ° or 90 ° C) 10 is reached, such a maximum temperature being then maintained for approx.

15 minutes. The dishes are then removed and each sample is washed twice with cold water and dried.

The final reflection coefficient of the substance samples is measured and the difference (ARd) between the final and the initial reflection coefficient values is determined. An average value of ARd for the six drug samples in each dish is then calculated. The results of the bleaching tests are listed below in Table 2, with the values of ARd being given as an average value for the particular agent and the specimen cited.

25 30

DK 161841 B

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DK 161841B

As listed in Table 2, the silicate-free agents (A, B and C) provide an improved bleaching effect over the silicate-containing agents at both sample temperatures. Among the silicate-containing agents, the agent containing 1% EDITEMPA (F) provides an enhanced bleaching effect over agent D, which does not contain a sequestering agent, but only at the high sample temperature of 90 ° C. However, at both test temperatures, the silicate-free agent A, which does not contain a sequestering agent, provides the best bleaching effect of all tested agents.

10

Example 3

The concentration of active oxygen in solution is determined as a function of the time for washing solutions containing each of the agents A to F described in Table 1. The test procedure is as follows:

One liter of tap water is introduced into a two liter beaker and then heated to a constant temperature of 60 ° C in a water bath.

20 Ten grams of the particular agent to be tested is added to the beaker (time = 0) with thorough stirring to form a uniform washing solution. After given periods of time (5, 15, 30, 45 and 60 minutes), a 50 ml aliquot is taken from the wash solution and the total concentration of active oxygen is determined by the procedure given below.

Determination of total active Op concentration.

The aforementioned 50 ml aliquot is poured into a 300 ml Erlen-30 meyer flask equipped with a ground stopper and containing 15 ml of a sulfur / molybdate mixture, the latter being prepared in large scale by dissolving 0 18 g of ammonium molybdate in 750 ml of deionized water and then add 320 ml of H 2 SO 4 (ca * 36N) with stirring. The solution in the 35 Erlenmeyer flask is thoroughly mixed and 5 ml of a 10% KI solution in deionized water is then added. Erlenmeyer- 27

DK 161841B

The flask is sealed with a stopper, shaken and placed in a dark place for 7 minutes. The solution in the flask is then titrated with a solution of 0.1N sodium thiosulfate in deionized water. The required volume of thiosulphate in ml is equal to the total 5 active oxygen concentration in mmol / liter in the wash solution.

The test results of the six agents tested are shown in Table 3 below.

10 28

DK 161841B

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DK 161841 B

29

As shown in Table 3, the silicate-free agents A, B and C are substantially more stable and are characterized by a much slower loss of active oxygen from the solution than the corresponding silicate-containing agents, D, E and F., respectively, among the silicate-containing agents. agents give that containing 1% EDXTEMPA (F) the maximum stability, but such agent is less stable than all the silicate-free agents including agent A, which does not contain sequestrant. Among the silicate-free agents, the presence of a sequestering agent in agent B and C results in improved oxygen stability over agent A.

Example 4

Bleaching tests are performed in an Ahiba apparatus as set forth below, comparing the bleaching effect of a bleaching detergent free of water-soluble silicates of the invention (A) and a water-soluble silicate-containing agent (B). As noted below, the two agents are comparable in almost all respects except for the presence of sodium silicate in Agent A. A crystalline zeolite material is present in both agents. The agents are formulated by post-addition to a particulate detergent formed from an aqueous slurry dried on a steam drum dryer (an operation similar to spray drying) of particles of sodium perborate tetrahydrate and tetraacetylethylenediamine (TAED ) to form the bleaching detergent shown in Table 4 below. The numbers listed in the table denote the percentage of each component by weight in the mean.

30 35

DK 161841 B

30

Table 4.

Component Medium

A B

5 (silicate-free) Silicate-free)

Linear sodium C c-C13 alkylbenzenesulfonate 6 6

Ethoxy clays a C ^-C- ^ primary alcohol (11 moles of EO per mole of 10 alcohol) 3 3 Soap (sodium salt of i₂2 ^ 22 carboxylic acid)

Sodium silicate (Na 2 O: 2 SiO 2) 4

Pentan sodium tripolyphosphate. (TPP) 19 19

Optical clarifier (stilbene) 0.2 0.2

Zeolite 19 19

Sodium perborate tetrahydrate 13.3 13.3 TAED 2.3 2.3 20

Water 5 5

Sodium sulphate residue

The bleaching test is performed in accordance with the test procedure set forth in Example 2 and the results of such test are shown in Table 5 below. The values of ARd are given as an average value for the indicated experiment.

Table 5.

ARd (average) 30 -

Sample temperature Agent containing Agent free of water-soluble water-soluble ______ silicate__ silicate____

A B

60 ° C 5.0 6.1 35 95 ° C 13.2 14.9

Claims (19)

5 Patent claims. A particulate bleaching detergent comprising: (a) a bleach comprising an inorganic peroxygen compound in combination with an activator thereof, and (b) at least one surfactant selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents, characterized by the detergent is substantially free of (i) water-soluble silicate compounds, and (ii) agglomerate particles substantially comprising a mixture of said activator, a water-insoluble silicate compound, and a nonionic over-20 '("iieak *"). '+ r-hid-- · !. An agent according to claim 1, characterized in that it also contains one sequester mg. An agent according to claim 2, characterized in that said sequestering agent comprises diethylenetriamine pentamethylene phosphonic acid and / or a water-soluble salt thereof. Agent according to claim 1, characterized in that said bleach comprises an alkali metal perborate in combination with tetraacetylethylenediamine (TAED). Agent according to claim 4, characterized in that said TAED is contained in grains in combination with a mixture of sodium and potassium triphosphate. in DK 161841 B An agent according to claim 1, characterized in that at least 80% by weight of said agglomerate particles is constituted by said mixture. 5 An agent according to claim 1, characterized in that said surfactant is an anionic detergent. j An agent according to claim 1, characterized in that it also contains a bentonite clay species. Bleaching detergent according to claim 1, characterized in that it comprises: (a) from 1 to 50% by weight of a bleach comprising a peroxygen compound in combination with an activator thereof, (b) from 5 to 50% by weight of a surfactant detergent selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents, (c) from 1 to 60% by weight of a detergent builder salt, (25) from 0.1 to 10% by weight of a sequestering agent, and ( e; the residue crosses the vane and optionally a filler salt / said bleaching detergent being substantially free of (i) water-soluble silicate compounds, and (ii) agglomerate particles substantially comprising a mixture of said activator, a water-insoluble silicate compound. and a non iop.isR over t iad act in * t means .. Agent according to claim 9, characterized in that said bleach comprises an alkali metal perborate in combination with tetraacetylethylenediamine. DK 161841B An agent according to claim 9, characterized in that said sequestering agent comprises ethylenediaminetetraacetic acid and / or a water-soluble salt thereof. 12. A composition according to claim 9, characterized in that it is substantially free of sequestering agents having a 2+ stability constant of about 5%. 20 for Cu complex formation in water at 25 ° C and at one in Wed of 0, in mo> '·· 1 i *. e r 10 6 A method of bleaching, wherein the bleached and / or soiled material to be bleached is contacted with an aqueous solution of a particulate bleaching detergent comprising: (a) a bleach comprising an inorganic peroxygen compound in combination with an activator therefor, and (b) at least one surfactant selected from anionic, nonionic, cationic, ampholytic, and zwitterionic detergents, characterized in that the detergent is substantially free of (i) water-soluble silicate compounds. and (ii) agglomerate particles substantially comprising a mixture of said activator, a water-insoluble silicate compound and a nonionic surfactant. Process according to claim 13, characterized in that the bleach comprises an alkali metal perborate in combination with tetraacetylethylenediamine. 30 Process according to claim 13, characterized in that the bleaching agent also contains an organic peroxyacid compound. DK 161841B i Method according to claim 13, characterized in that said agent also contains a sequestering agent. Process according to claim 16, characterized in that said sequestering agent comprises ethylenediaminetetraacetic acid and / or a water-soluble salt thereof. Process according to claim 13, characterized in that said agent also contains a detergent builder salt. Process according to claim 13, characterized in that said bleaching detergent also contains a bentonite clay species. 15 20 25 30 35