SE460054B - Bleaching detergent composition free from water-soluble silicates and its use in bleaching - Google Patents

Description

46Û 054 activator leads to the formation of a peroxyacid which at lower temperatures is a more effective bleaching agent than hydrogen peroxide. A variety of compounds have been proposed as activators for peroxy bleaches including carboxylic acid anhydrides such as those described in U.S. Patents 3,298,775, 3,338,839 and 3,532,634; carboxyl esters such as those described in U.S. Patent 2,995,905; N-acyl compounds such as those described in U.S. Patents 3,912,648 and 3,199,102; cyanoamines as described in U.S. Patent 4,199,466; and acylsulfonamides described in U.S. Patent 3,245,913.

The formation and stability of the peroxyacid bleach in bleach systems containing a peroxy compound and an organic activator is a problem recognized in the art. For example, U.S. Patent 4,255,452 to Leigh addresses the problem of avoiding the reaction between peroxyacid and peroxy compound which yields what are characterized in the patent as useless products, namely the corresponding carboxylic acid, molecular oxygen and water. The patent states that these side reactions are doubly harmful because peracid and per compound are destroyed at the same time. The patentee then describes certain polyphosphonic acid compounds as chelating agents which are said to inhibit the peroxyacid-consuming side reaction described above and provide improved bleaching effect.

In contrast to these chelating agents, the patentee states that other more commonly known chelating agents, such as ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), are virtually ineffective and do not provide any enhanced bleaching effects. Thus, a disadvantage of the bleaching compositions described in the Leigh patent is that they do not allow the use of conventional sequestrants, many of which are cheaper and more readily available than the polyphosphonic acid compounds described.

The effect of silicates on the decomposition of peroxyacid in detergent and / or bleach solutions has not been previously noted in the art. U.S. Pat. Nos. 3,860,391 and 4,292,575 disclose that silicates are conventionally employed as additives in peroxide-containing bleaching solutions for the purpose of stabilizing the constituent peroxide compounds. However, patent holders note that the use of silicates in these bleach solutions can present other problems in the bleaching processes, e.g. emergence of silicate precipitates deposited on the bleached goods. Accordingly, the patents are directed to processes for bleaching cellulosic fibers with silicate-free bleach solutions in which the stability of the peroxide is enhanced with compounds other than silicates.

European Patent Publication 0 028 432, published 13 May 1981, describes a granular detergent composition which contains, inter alia, a water-insoluble silicate and an organic compound as activator of a peroxy bleach. The pH characteristics of this detergent composition are stated to be critical; The pH of a 2% aqueous slurry is specifically between 2 and 9, and preferably from 4 to 7. On page 7 of the patent publication, certain polyphosphonic acid compounds are described as being highly preferred ingredients in the composition, and the publication states in this connection that Polyphosphonates have been shown to be uniquely active in stabilizing organic peroxyacids against the generally harmful effects of water-insoluble silicates, especially those belonging to the zeolite and kaolin class. The nature of these adverse effects is not specified. Page 38 of the publication describes granular detergent compositions of Examples 8-10 which do not contain sodium silicate, 460,054 and all of these compositions contain Dequest 2041 (ethylenediaminetetramethylenephosphonic acid). The compositions of these examples also contain a compound which is a peroxy activator which is incorporated into agglomerated particles consisting of this activator, a water-insoluble silicate compound and a nonionic surfactant.

Summary of the Invention The present invention provides a particulate bleaching detergent composition comprising: (a) a bleaching agent comprising a peroxy compound in combination with an activator therefor; and (b) at least one surfactant selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents; wherein said bleaching detergent composition is substantially free of (i) water-soluble silicate compounds and (ii) agglomerated particles which mainly comprise said activator, a water-insoluble silicate compound and a nonionic surfactant.

In accordance with the process of the invention, bleaching of stained and / or soiled materials is carried out by contacting these materials with an aqueous solution of the above bleaching detergent composition.

The present invention is based on the discovery that the undesired loss of peroxyacid in the aqueous wash solution by reacting peroxyacid with a peroxy compound (or more specifically, hydrogen peroxide formed from this peroxy compound) to form molecular oxygen is markedly reduced in bleach systems which are substantially free of water-soluble silicate compounds 460 054. Although the applicant does not wish to be bound by any particular theory as to the mode of action, it is believed that the presence of water-soluble silicates in the peroxy compound / activator bleach system catalyzes the aforementioned reaction between peroxyacid and hydrogen peroxide which leads to loss of active oxygen from the wash solution. available for bleaching. It is known in the art that metal ions, such as iron ions and copper ions, catalyze the decomposition of hydrogen peroxide as well as the reaction between peroxyacid and hydrogen peroxide. However, with respect to this metal ion catalysis, the applicant has surprisingly discovered that conventional sequestrants, such as EDTA and NTA, which are considered in the art to be ineffective in inhibiting the aforementioned peroxyacid-consuming reaction (see, for example, the statement in column 4 of U.S. Patent 4,225 452), can be incorporated into the compositions of the present invention and stabilize the peroxyacid in solution.

The term "water-soluble silicate compounds" refers to compounds such as sodium silicate which are substantially soluble in aqueous washing solutions and which are often included in conventional bleaching detergent compositions, but which are substantially eliminated in the compositions of the present invention. However, the present invention seeks to incorporate substantially water-insoluble silicates, especially aluminosilicates such as clays and zeolites, into the bleaching detergent composition described herein, and water-soluble silicate compounds are considered to be much more harmful to peroxyacid stability than water-insoluble substances such as aluminum solids. silicates. In a preferred embodiment of the invention, the bleaching compositions described herein further contain a sequestering agent to improve in solution the stability of the bleaching peroxyacid compound by inhibiting its reaction with hydrogen peroxide in the presence of metal ions. The term "sequestering agent" as used herein refers to organic compounds capable of forming a complex with Cu 2+ ions so that the stability constant (pK) of complex formation is equal to or greater than 6 in water of 25 ° C and with an ionic strength of 0.1 mol / - liter, where pK is defined in the usual way by the formula pK = - log K where K represents the equilibrium constant. Thus, for example, the pK values for the complex formation between copper ions and NTA or EDTA are 12.7 and 18.8, respectively, at the specified conditions. The term "sequestering agent" is therefore used herein in a sufficiently limited sense to exclude inorganic compounds commonly used as detergent salts in detergent compositions. Particularly useful sequestrants include EDTA, diethylenetriaminepentaacetic acid (DEPTA) and various phosphonate sequestrants marketed by Monsanto Company under the trademark Dequest, e.g. Dequest 2000, 2006, 2041, 2051 and 2060.

In addition, in accordance with another embodiment of the invention, the bleach compositions described are distinguished from certain water-soluble silicate-free compositions described in the art by using in the present bleach compositions only sequestrants having a stability constant not greater than to form Cu 2+ complexes. water of 250 C and at an ionic strength of 0.1 mol / liter. This limitation precludes the presence of polyphosphonic acid compounds such as Dequest 2041 (ethylenediaminetetramethylenephosphonic acid) and 460,054 Deguest 2060 (diethylenetriaminepentamethylenephosphonic acid) in the bleach compositions of the invention, as these sequestering agents have higher sequencing constituents. nitrilotriacetic acid (NTA); ethylenediaminetetraacetic acid (EDTA); ethylenediamine; tetramine, i.e. N- (CH2-CH2-NH2) 3; bis (aminoethyl) glycol ether-NNN'N'-tetraacetic acid (EGTA): and N (CH2-PO3H2) 3 Dequest 2000. EDTA and the aforementioned Dequest 2000 are specifically marketed under the trademark separately preferred for use in this embodiment of the invention.

Detailed Description of the Invention The bleaching detergent compositions of the invention consist of two main ingredients: (a) a bleaching agent; and (b) a cleaning surfactant.

The bleach useful in these compositions comprises a peroxy compound in combination with an organic activator therefor.

The peroxy compounds useful in the present compositions 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.

Alkali metal perborates are generally preferred due to their commercial availability and relatively low cost.

Conventional activators such as those described in, for example, U.S. Patent No. 4,259,200, column 460 Q54 4, are suitable for use with the aforementioned peroxy compounds, and this disclosure is incorporated herein by reference. The polyacylated amines are generally of particular interest, and especially tetraacetylethylenediamine (TAED) is a highly preferred activator. TAEDs are preferably included in the compositions of the invention in the form of "coated" granules containing TAEDs and a suitable carrier material such as a mixture of sodium and potassium triphosphate. These coated TAED granules are conveniently prepared by mixing finely divided particles of sodium triphosphate and TAED and then spraying on this mixture an aqueous solution of potassium triphosphate and using suitable granulating equipment such as a rotary drum type granulator. A typical method of making this type of coated TAED is described in U.S. Patent 4,283,302 to Foret et al. The TAED granules have a preferred particle size distribution as follows: 0 - 20% greater than 150 microns 10 - 100% greater than 100 microns but less than 150 microns; O - 50% less than 75 21; and 0% less than 50 μl. Another particularly preferred particle size distribution is obtained when the median particle size of TAED is 160 21, i.e. 50% of the particles are larger than 160 in. The aforementioned size distribution refers to the TAED that is included in the coated granules and not the coated granules themselves. The molar ratio between peroxy compound and activator can vary within a wide range depending on the choice of peroxy compound and activator. However, molar ratios of from about 0.5: 1 to about 25: 1 are generally suitable for imparting satisfactory bleaching properties.

The bleach may optionally also contain a peroxyacid compound in combination with the peroxy compound and the activator.

Useful peroxyacid compounds include water-soluble 460,054 peroxyacids and their water-soluble salts. The peroxyacids can be characterized by the following general formula O n H00 - C - R - Z wherein R is an alkylene group containing from 1 to about 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 about 1 to about 4, preferably 1 or 2, peroxy groups and may be aliphatic or aromatic.

The preferred aliphatic peroxyacids include diperoxyazelanoic acid, diperoxydodecanedioic acid and monoperoxy succinic acid. Among the aromatic peroxyacid compounds useful herein, monoperoxyphthalic acid (MPPA), especially its magnesium salt, and diperoxyterephthalic acid are especially preferred. A detailed description of the preparation of MPPA and its magnesium salt is given on p. 7 - 10 of European Patent Publication 0 027 693, published April 29, 1981, and the aforementioned pages 7 - 10 are incorporated herein by reference.

The bleaching detergent composition of the invention is characterized in that it is substantially free of (i) water-soluble silicate compounds and (ii) agglomerated particles consisting essentially of a mixture of three components: the organic activator of the peroxy compound; a water-insoluble silicate compound such as clay or zeolite; and a nonionic surfactant, which mixture constitutes at least 80% by weight of the agglomerated particles. The agglomerated particles excluded from use herein are of the type prepared 460,054 in equipment such as a "pan granulator" and serve to incorporate the bleach activator into a matrix of material as described in European Patent Publication 0 028 432 In a particular embodiment of the invention, the bleaching compositions are further characterized in that they are substantially free of sequestering agents having a stability constant greater than about for Cu 2+ complex formation in water of 25 ° C and at an ionic strength of 0.1 mol / liter.

The water-insoluble silicate materials which can be advantageously used in the present bleach compositions are preferably aluminosilicates such as zeolites and smectite clays. The crystalline types of zeolites that can be used include those described in the "Zeolite Molecular Series" by Donald W. Breck, published in 1974 by John Wiley & Sons, and representative available zeolites are listed in Table 9.6 on p. 747 - 749 in the text, which table is incorporated herein by reference. Type A zeolite structures are particularly desirable and are extensively described in the art; see for example p. 133 in the aforementioned text by Breck and also U.S. Pat. No. 2,882,243. The zeolites are particularly useful as detergent salts in high performance detergent compositions.

The aforementioned smectite-type clays are three-layer clays which are characterized by the ability of the layer structure to increase its volume many times by swelling or expansion in the presence of water and give thixotropic gelatinous substances. There are two classes of smectite clays: in the first class, alumina is included in the silicate crystal lattice; in the second class, magnesium oxide is included in the silicate crystal lattice. Atomic substitution by iron, magnesium, sodium, potassium, calcium and the like may occur within the crystal lattice of smectite clays.

It is common to distinguish the clays on the basis of their dominant cation. For example, a sodium clay is one in which the cation is predominantly sodium. In the case of the present bleaching detergent compositions, aluminosilicates in which sodium is the predominant cation, such as bentonite clays, are preferred.

Among the bentonite clays, those from Wyoming (commonly referred to as western or Wyoming bentonite) are especially preferred. Calcium and magnesium clays are also useful but are less preferred in this invention.

Preferred swelling bentonites of this type are sold under the trade names Mineral Colloid, as industrial bentonites, by Benton Clay Company which is a subsidiary of Georgia Kaolin Co. These substances are the same as those previously sold under the THIXO-JEL brand and are selectively broken and enriched bentonites, and those considered most useful are available as Mineral Colloid No. 101, etc., which correspond to THIXO-JBL No. 1, 2, 3 and 4. Such substances have pH values (6% concentration in water) in the range of 8 to 9.4, maximum free moisture content of about 8%, and specific weights of about 2.6, and of the powdered varieties of these substances, at least about 85% (and preferably 100%) pass through a 200 mesh screen (American screen series). The bentonite is more preferably one in which substantially all of the particles (i.e. at least 90% of these, and preferably more than 95%) pass through a 325 mesh screen, and most preferably all of the particles should pass through such a screen. The swelling capacity of the bentonite in water is usually in the range of 3 to 15 ml / g, and its viscosity, at 6% concentration in water, is usually from about 8 to 30 centipoise. In a particularly preferred embodiment of the invention, the carrier particles comprise agglomerates of finely divided bentonite, with particle sizes of less than 200 mesh, agglomerated into particles having sizes substantially in the range of 10 - 100 mesh, having a bulk density in the range of 0 mesh. 7 to 0.9 g / ml and a moisture content of 8 to 13%. These agglomerates contain about 1 to 5% of a binder or agglomerating agent which helps to maintain the agglomerate in an undisturbed state until it is added to water. in which they are intended to decompose and slurry.

A detailed description of the method of making these agglomerates is given in U.S. Patent Application 366,587, filed April 8, 1982, which is incorporated herein by reference.

Instead of using THIXO-JEL or Mineral Colloid bentonites, one can also use equivalent competing products, such as the one sold by the American Colloid Company, Industrial Division as General Purpose Bentonite Powder, 325 mesh, of which at least 95% is finer than 325 mesh or 44 ju and at least 96% is finer than 200 mesh or 74/1 in diameter (dry particle size). Such an aqueous aluminosilicate consists in principle of montmorillonite in diameter (wet particle size) (at least 90%), with minor proportions of feldspar, biotite and selenite. A representative composition, on an "anhydrous" basis, is 63.0% silica, 21.5% alumina, 3.3% ferric iron (as Fe2O3), 0.4% ferrous iron (as Fe0), 2.7% magnesium (as MgO), 2.6% sodium and potassium (as Na 2 O), 0.7% calcium (as CaOY, 5.6% crystal water (as H 2 O) and 0.7% trace elements. bentonites are preferred, it is also possible to use synthetic bentonites, such as those which can be manufactured by treating Italian or similar bentonites, which contain comparatively small proportions of exchangeable monovalent metals (sodium and potassium), with alkaline substances such as sodium carbonate, to increase It is considered that the Na 2 O content of the bentonite should be at least 0.5%, preferably at least 1% and most preferably at least 2% so that the clay can swell to the desired extent, and provide good emollient and Dispersing properties in aqueous suspension Preferred swelling bentonites of the described synthetic type are sold under the trade names Laviosa and Winkelmann, e.g.

Laviosa AGB and Winkelmann G-13.

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

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

Examples of suitable anionic detergents are soaps such as water-soluble salts (eg the sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids, or resin salts containing between about 8 and 20 carbon atoms and preferably 10-18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example tallow, fat, coconut oil and mixtures thereof. The sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, for example sodium coconut soap and potassium tallow soap, are particularly useful.

The class of anionic detergents also includes water-soluble sulfated and sulfonated detergents having an alkyl radical containing between about 8 and 26 and preferably between about 12 and 22 carbon atoms. (The term "alkyl" includes the alkyl moiety of higher acyl radicals.) Examples of sulfonated anionic detergents are higher alkyl monocyclic aromatic sulfonates such as the higher alkylbenzene sulfonates containing between about 10 and 16 carbon atoms in the higher straight or branched chain alkyl group, such as sodium. , the potassium and ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluenesulfonates and higher alkylphenolsulfonates.

Other suitable anionic detergents are olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfonate detergents can be prepared in a conventional manner by reacting SO 3 with long chain olefins containing between about 8 and 25 and preferably between 12 and 21 carbon atoms, such as olefins of the formula RCH = CHR 1, in which R represents a higher alkyl group having 6 to 23 carbon atoms and R 1 represents an alkyl group having between about 1 and 17 carbon atoms or hydrogen, to give a mixture of sultones and alkene sulfonic acids which are then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergents are paraffin sulfonates containing between about 10 and 20 carbon atoms, preferably between about 15 and 20 carbon atoms. The primary paraffin sulfonates are prepared by reacting long-chain alpha-olefins with bisulfites. Paraffin sulfonates having the sulfonate groups distributed along the paraffin chain are described in U.S. Pat. Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188 and German Patent 735,096.

Other suitable anionic detergents are sulphated ethoxylated higher fatty alcohols of the formula RO (C 2 H 4 O) mSO 3 M, in which R is fatty alkyl having from 10 to 18 carbon atoms, m is from 2 to 6 (preferably has a value of from about 1/5 to 1/2). of the number of carbon atoms in R) and M is a solubilizing salt-forming cation, such as alkali metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkylbenzene sulfonate in which the higher alkyl has 10 to 15 carbon atoms. The proportion of ethylene oxide in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, with 3 moles being particularly preferred, especially when the higher alkanol has 11 to 15 carbon atoms. To maintain the desired balance between hydrophilic and lipophilic groups, when the carbon atom content of the alkyl chain is in the lower part of the range 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about 2 moles per mole, while the number of ethylene oxide groups can be increased to 4 or 5 and in some cases all the way to 8 or 9, when the higher alkanol has 16 to 18 carbon atoms within the upper part of the range. In the same way, the salt-forming cation can be changed to give the best solubility. It can consist of any suitable solubilizing metal or radical but usually becomes alkali metal, e.g. sodium, or 460 054 16 ler 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 detergent is available from Shell Chemical Company and is marketed as Neodol 25-3S.

The most preferred water-soluble anionic detergent compounds are salts of higher alkyl benzene sulfonates, olefin sulfonates and higher alkyl sulfates with 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). Among the anionic agents listed above, sodium linear alkyl benzene sulfonates (LABS) are the most preferred, and especially those in which the alkyl group is a straight chain alkyl radical 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 alkylaromatic hydrophobic compound with ethylene oxide (hydrophilic to nature). Virtually 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 the polyhydrated product thereof, i.e. polyethylene glycol, and form a nonionic detergent. The length of the hydrophilic chain or of the polyoxyethylene chain can be easily adjusted to give the desired balance between hydrophobic and hydrophilic groups. The nonionic detergent used is preferably a poly-lower alkoxylated-higher alkanol in which the alkanol has 10 to 18 carbon atoms and in which the molar number of lower alkylene oxide (having 2 or 3 carbon atoms) is from 3 to 12.

Among these substances, it is preferable to use those in which the higher alkanol is a higher fatty alcohol having 11 to 15 carbon atoms and which contains from 5 to 9 lower alkoxy groups per mole. The lower alkoxy group is preferably ethoxy, but in some cases it may be advantageously mixed with propoxy, the latter, if included, usually being a minor part (less than 50%). Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. Neodol® 925-7 and Neodol 23-6.5, which products are manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols having an average of about 12 to 15 carbon atoms, with about 7 moles ethylene oxide and the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups is on average 6.5 per mole. The higher alcohols are primary alkanols. Other examples of these detergents include Tergitol 15-S-7 and Tergitol -S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The former is a mixed ethoxylated product of a linear secondary alkanol having 11 to 15 carbon atoms and 7 moles of ethylene oxide and the latter is a similar product but reacted with 9 moles of ethylene oxide. Higher molecular weight nonionic substances can also be used in the present compositions, such as Neodol 45-1, which are similar condensation products between ethylene oxide and higher fatty alcohols, the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups. is about ll per mole. These products are also manufactured by Shell Chemical Company.

Zwitterionic detergents, such as betaines and sulphobetaines, of the following formula are also useful: R 2 \ RN-R 11 -x 1/1 å 3 in which R represents an alkyl group having between about 8 and 18 carbon atoms, R 2 and R 3 represent each an alkyl or hydroxyalkyl group having about 1 to 4 carbon atoms, R 4 represents an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms, and X is C or S = O. The alkyl group may contain one or more intermediate bonds, such as amido, ether or polyether bonds, or non-functional substituents, such as hydroxyl or halogen, which do not appreciably affect the hydrophobic character of the group. When X is C, the detergent is denoted a betaine, and when X is S = O, the detergent is denoted a sulfobetaine or sultain.

Cationic substances can also be used. These consist of 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 substances are amine and quaternary ammonium compounds.

Examples of suitable synthetic cationic detergents are: common primary amines of the formula RNH 2, in which R represents an alkyl group having about 12 to 15 carbon atoms; diamines of the formula RNHC2H4NH2, in which R represents an alkyl group having between 12 and 22 carbon atoms, such as N-2-460 054 19 aminoethyl-stearylamine and N-2-aminoethyl-myristylamine; amide-bonded amines such as those of the formula R 1 CONHC 2 H 4 NH 2, in which R 1 represents an alkyl group having about 8 to 20 carbon atoms, such as N-2-amino-ethyl-stearylamide and N-amino-ethylmyristylamide; quaternary ammonium compounds in which typically one of the groups attached to the nitrogen atom is an alkyl group having about 8 to 22 carbon atoms and three of the groups attached to the nitrogen atom are alkyl groups containing 1 to 3 carbon atoms, including alkyl groups having inert substituents , such as phenyl groups, in which there is an anion such as halogen, acetate, methyl sulphate, etc. The alkyl group may contain intermediate bonds such as amide, which do not significantly affect the hydrophobic character of the group, for example quaternary stearylamidopropylammonium chloride. Typical quaternary ammonium detergents are ethyl dimethyl stethyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl cetyl ammonium bromide, dimethyl ethyl lauryl ammonium chloride, dimethyl propyl myristyl ammonium chloride and the like methyl sulfates acetates.

Ampholytic detergents are also useful according to the invention. Ampholytic detergents are well known in the art and many useful detergents of this class are described by Schwartz, Perry and Berch in the aforementioned "Surface Active Agents and Detergents". Examples of suitable amphoteric detergents are alkyl beta-iminodipropionates, RN (C2H4COOM) 2; alkyl-beta-aminopropionates, RN (H) C2H4COOM; and long-chain imidazole derivatives of the general formula 460 054 RC - N-CH2CH20CH COOM 2 OH CHZCOOM wherein in each of the above formulas R an acyclic hydrophobic group having between about 8 and 18 carbon atoms, and M is a cation which neutralizes the charge of the anion Particularly suitable amphoteric detergents are the disodium salt of undecylcycloimidine ethoxythionic acid 2-ethionic acid, dodecyl-beta-alanine and the inner salt of 2-trimethyl -amino-lauric acid.

The bleaching detergent composition of the invention may optionally contain a detergent salt of the type generally used in detergent compositions. Useful detergent compositions are the conventional inorganic water-soluble detergent salts, such as, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, carbonates and the like. Organic detergent compounds are water-soluble phosphonates, polyphosphonates, polyhydroxyisulfonates, polyacetates, carboxylates, polycarboxylates, succinates and the like.

Specific examples of inorganic detergent phosphates are sodium and potassium tripolyphosphate, pyrophosphate and hexametaphosphate. The organic polyphosphonates include in particular, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,2,1-triphosphonic acid. Examples of these and other phosphorus-containing detergent compounds are given in U.S. Patent Nos. 3,213,030, 460,054,213,422,021; 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are especially preferred water-soluble inorganic detergent salts.

Particular examples of non-phosphorus inorganic detergent active compounds are water-soluble inorganic carbonate and bicarbonate salts. Alkali metal, for example sodium and potassium, carbonates and bicarbonates are especially suitable here.

Water-soluble organic detergent compounds are also useful. Thus, for example, alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates are suitable detergent active compounds for the compositions and methods of the invention. Particular examples of detergent polyacetate and polycarboxylate compounds are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzenepoly- (ie penta- and tetra-) carboxymethoxycarboxylic acid and citric acid. Also water-insoluble detergent active compounds can be used, especially complex silicates and in particular complex sodium aluminum silicates such as zeolites, e.g. zeolite 4A, which is a type of zeolite molecule in which the monovalent cation is sodium and in which the pore size is around 4 Ångström. The preparation of this type of zeolite is described in U.S. Pat. No. 3,114,603.

The zeolites can be amorphous or crystalline and contain hydrating water in a manner known in the art.

The detergent compositions of the invention may advantageously contain an inert, water-soluble filler salt. A preferred filler salt is alkali metal sulfate, such as potassium or sodium sulfate, the latter being particularly preferred.

Various adjuvants may be included in the bleaching detergent compositions of the invention. These generally include perfumes; dyes, e.g. pigments and dyes; bleaching agents such as sodium perborate; anti-precipitating agents, such as alkali metal salts of carboxymethylcellulose; optical brighteners, such as anionic, cationic or nonionic bleaches; foam stabilizers, such as alkanolamides, and the like, all of which are well known for use in laundry detergent compositions. Flow promoters, commonly referred to as "flow aids", can also be used to maintain the particulate bleaching detergent composition in the form of free-flowing granules or powder. Starch derivatives and special clays are commercially available as additives which improve the flowability of particulate compositions which are otherwise sticky or degenerate, and two such clay additives are currently sold under the trade names "Satintone" and "Microsil".

A preferred bleaching detergent composition according to the invention typically comprises (a) from about 2 to 50% by weight of bleach consisting of a peroxy compound in combination with an activator therefor; (b) from about 5% to 50% by weight of a detergent surfactant: (c) from about 1% to about 60% by weight of a detergent salt; and (d) from about 0.1 to about% by weight of a sequestering agent; which composition is characterized in that it is substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles consisting essentially of said activator, a water-soluble silicate compound and a nonionic surfactant. The rest of the composition consists mainly of water, filler salts such as sodium sulphate, and minor additives selected from the various adjuvants described above.

The particulate bleaching detergent composition of the invention is prepared by mixing the bleaching agent and any sequestering agent with the spray-dried detergent composition, the latter being formulated in such a manner that it does not use water-soluble silicate compounds, and especially not sodium silicate. Presence of very small amounts of water-soluble silicate compounds in the final composition, i.e. less than about 0.5% by weight, preferably less than about 0.2% by weight, and most preferably not more than about 0.1% by weight, which may occur when using silicate-containing pigments or dyes, or upon contact between the aqueous slurry base mixture and residues of sodium silicate in the spray tower, is included in the present invention.

The spray-drying of a silicate-free detergent composition can give a rather dusty granular product due to the fact that no silicate is included as a binder for the spray-dried grains. However, alternative organic binders may be used, such as, for example, starch, carboxymethylcellulose and similar substances. The strength of the spray-dried granules can also be increased by maximizing the content of solids in the silicate-free slurry in the mixer and / or by keeping the inlet temperature of the hot air stream to the spray tower as low as possible. The bleach can either be mixed directly with the spray-dried powder or the bleach and any sequestering agent can be coated individually or together with cover material to prevent premature activation of the bleach. The coating process is carried out in accordance with methods known in the art.

Suitable cover materials include compounds such as magnesium sulfate, polyvinyl alcohol, lauric acid and its salts and the like. The bleaching detergent composition of the invention is added to the wash solution in an amount sufficient to provide from about 3 to about 100 parts of active oxygen per million parts of solution, and a content of from about 5 to about 40 ppm is generally preferred.

The particulate bleaching detergent compositions described above can be made by methods such as spray drying, dry blending, or agglomerating the individual ingredients.

Example 1 A preferred silicate-free bleaching detergent composition consists of the following: 460,054 Component Weight percent sodium linear C10-C13 alkylbenzene sulfonate ethoxylated C11-C18 primary alcohol (11 moles EO per mole alcohol) soap (sodium salt of C12-C22-4 carboxylic acid ) pentasodium tripolyphosphate (TPP) 32.0 EDTA 0.5 TAED 2, 2.3 carboxymethylcellulose 0.5 sodium perborate tetrahydrate 13.2 optical brighteners, pigments and perfume 0.4 proteolytic enzymes 0.5 sodium salt and water residue The above product is prepared by spray drying of a water slurry containing 60% by weight of a mixture containing all of the above components except 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 (US screen series). The spray dried product is then mixed in a rotating drum, with appropriate amounts of sodium perborate of similar particle size, TAED, enzyme and perfume to give a particulate product having a moisture content of approximately 18% by weight.

The product described above is used for washing soiled textiles by hand washing or by washing in an automatic washing machine, whereby good washing and bleaching results are obtained with both washing methods.

Other satisfactory products can be obtained by varying the contents of the following main components of the above composition as follows: Component Weight percentage of alkyl benzene sulfonate 4-12 ethoxylated alcohol 1-6 soap 1-10 TPP 15-50 enzymes 0.1-1 EDTA 0 , 1-2 TAED '1 ~ 10 sodium perborate 5-20 For highly concentrated high performance detergent powders, the alkylbenzenesulfonate, TPP, and soap components of the composition described above may be omitted, and the content of ethoxylated alcohol may be increased to an upper limit of 20%.

Example 2 Bleaching tests are performed according to the following description in which the bleaching ability of water-soluble silicate-free bleaching detergent compositions according to the invention is compared with the corresponding silicate-containing compositions, the latter compositions being comparable to the aforementioned in almost all respects. .

The silicate-free composition is particularly characterized by the presence of sodium metaborate; the silicate-containing composition contains sodium silicate. The compositions are prepared by subsequently adding to a spray-dried particulate detergent composition granules of sodium perborate tetrahydrate and tetraacetylethylenediamine (TAED) to obtain the bleaching detergent composition shown in Table 1 below. The numerical values given in the table refer to the percentage, in weight percent, of each component in the preparation.

Table 1 Component Composition is sodium-linear C10-C13-alkylbenzene sulphonate '8% 8% 8% 8% 8% ethoxylated C11-C18 primary alcohol Ill mol E0 per mole of alcohol) 3 3 3 3 3 soap (sodium salt of C12-C22 -carboxylic acid) 3 3 3 3 3 sodium silicate (1Na2O: 2SiO2) _ - - 4 4 sodium metaborate 5 5 - - pentasodium tripolyphosphate P11 1 (TPP) 35 35 35 35 35 optical brightener (stilbene) 0.2 0.2 0.2 0.2 0.2 sodium perborate tetrahydrate 6 6 6 TAED 5 5 5 5 5 EDTA - 1 - - 1 EDITEMPA (1) - - 1 - - sodium sulfate 21 20 20 21 20 water ------ - residue --- ---- - (1) Sold as Dequest 2041 by Monsanto Company, St. Louis, Missouri 460 054 28 Test Method Bleaching experiments are performed in an Ahiba apparatus at maximum temperatures of 600 ° C and 900 ° C, respectively, in the manner described below. 600 ml of tap water with a hardness of about 320 ppm, as calcium carbonate, is introduced into each of the six vessels in the Ahiba apparatus. Six cloth patches (8 cm x 12 cm) of cotton soiled with "immedial black" are inserted into each vessel, and the initial reflectance of each patch was measured with a Gardner XL 20 reflectometer.

Six grams of each composition A - F described in Table 1 are introduced separately into the six vessels of the Ahiba apparatus, and with different compositions into the respective vessels. The bleaching detergent compositions are thoroughly mixed in each vessel with a mixer, after which the washing process begins. The bath temperature, which is initially 30 ° C, is allowed to rise about one degree per minute until the maximum test temperature (60 ° or 900 ° C) is reached, and this maximum temperature is then maintained for about minutes. The vessels are then removed and each patch is washed twice with cold water and dried.

The final reflectance of the patches was measured and the differences (A.Rd) between the final and original values of the reflectance were determined. An average value of ARd for the six pieces in each vessel was calculated. The results from the bleaching experiments are shown in Table 2 below, in which the values of .ARd are given as the mean value for the specified special composition and the experiment. 460 054 29 w.> H w. «H w.wH o ~ ßH m_ß ~ o.mH U com m.>>. @ @ .W ww Hm H. @ u oow På .E ESE 2: fl mzm fi uom fi øøwä wønmuwu dmzmaanm Hmnwä wwcmumu w fl dust wa | uww> xwm ømuø w fi NANM æ f | UMW> XMM cwvø uwno fl u fi womñox mwcma fi mnmcn fi UMX flfifl m umso fi uwmomäox m f uuumx flfifi m .añwu nwxwmuww .w © Hm> Hw fi MeV Umnw N HHMQMB 460 054 As table 2 gives the silicate compositions nerna (A, B and C) an improved bleaching effect compared to the silicate-containing compositions at both test temperatures. Among the silicate-containing compositions, the one containing 1% EDITEMPA (F) gives an improved bleaching effect compared to composition D which contains no sequestering agent, but only at the higher test temperature 900 ° C. At both test temperatures, however, the silicate-free composition A , which does not contain any sequestering agent, best bleaching effect of all tested compositions.

Example 3 The content of active oxygen in solution is determined as a function of time for washing solutions containing each of the compositions A - F described in Table 1. The test method is described below: One liter of tap water is introduced into a two-liter beaker and then heated to a constant temperature of 600 C in a water bath. Ten grams of the composition to be tested is added to the beaker (time = 0) with thorough stirring and gives a uniform washing solution. After given time intervals (5, 15, 30, 45 and 60 minutes) a 50 ml sample is taken from the washing solution and the total active oxygen content is determined by the procedure given below.

Determination of the total active content 02 The above 50 ml sample is poured into a 300 ml Erlenmeyer flask equipped with a ground stopper and containing 15 ml of a sulfuric acid / molybdate mixture, the latter mixture being prepared on a larger scale by dissolving 0 18 g of ammonium molybdate in 750 ml of deionized water, after which 320 ml of H 2 SO 4 (about 36 N) were added with stirring. The solution in the Erlenmeyer flask is stirred thoroughly, after which 5 ml of a 10% CI solution in deionized water are added thereto. The Erlenmeyer flask is closed with a stopper, shaken and then allowed to stand in a dark room for seven minutes. The solution in the flask is then titrated with a solution of 0.1 N sodium thiosulphate in deionized water. The required volume of thiosulphate, in milliliters, is equal to the total active oxygen content, in millimoles / liter, in the washing solution. The experimental results for the six tested compositions are given in Table 3 below. 460 054 32 H ~ m mo Nmo oN ß.N v ~ a om må m6 <6 mä må må 2 ° _ ~ m. ° m. ° mm om mm om må .im ... H .im mm .om mm mm im ñm mm mm m_m. m Am. .m. An. Auv .mv .4. ÉNENBHDW .HÜÜÜE ÜUCNHUH ÅmÉm-UEHQW HÜUÜE ÜÜCGHÜH wa Mwm Cmß fl wa 480m wa lum0> x0m Cmu fl Hwno fl u fi momëox m fl nma fi mnmcn fl umx. Ux. Mx. CwmG fl: w @ Huvm> uw mnwm u> fi # xm uamuoà m H fl wnmä 460 054 33 As shown in Table 3, the silicate-free compositions A, B and C are considerably more stable and are characterized by a much slower loss of active oxygen from solution than the corresponding silicate-containing D, E and F.

Among the silicate-containing compositions, the one containing 1% EDITEMPA (F) provides maximum stability, but this composition is less stable than all the silicate-free compositions, including composition A which does not contain any sequestering agent. In the silicate-free compositions, the presence of a sequestering agent in compositions B and C provides improved oxygen stability compared to composition A.

Example 4 Bleaching experiments are performed in an AHIBA apparatus in the manner indicated below comparing the bleaching ability of a bleaching detergent composition free of water-soluble silicates in accordance with the invention (A) and a composition (B) containing water-soluble silicates.

As shown below, the two compositions are comparable in almost all respects except the presence of sodium silicate in composition A. A crystalline zeolite material is included in both compositions. The compositions are prepared by subsequently adding to a particulate detergent composition, prepared from an aqueous slurry which has been dried on a steam dryer (spray equivalent procedure), subsequently adding particles of sodium perborate tetrahydrate and tetraacetylethylenediamine (TAED 4) as shown in Table 4 below. bleaching detergent composition. The numerical values given in the table refer to weight percentages of each component in the composition. 460 054 34 Table 4 Component composition AB (silicate (silicate-free) sodium-linear C10-C13-alkylbenzenesulfonate 6 6 ethoxylated C11-C18 primary alcohol (11 moles EO per mole alcohol) 3 3 soaps ( sodium salt of C12-C22 carboxylic acid) 4 4 sodium silicate (1Na2O: 2SiO2) 4-pentasodium tripolyphosphate (TPP) 19 19 optical brightener (stilbene) 0.2 0.2 zeolite 19 19 sodium perborate tetrahydrate 13.3 13.3 TAED. 2.3 2.3 water 5 5 sodium sulfate residual residue Bleaching experiments are carried out according to the test procedure shown in Example 2, and the results of these experiments are shown in Table 5 below. The values of. ARd refers to a mean value for the specified experiments. 460 054 Table 5 §Rd (mean) experimental composition containing composition free temp. water-soluble silicate from water-soluble silicate A B so ° c 5.0 6.1 9s ° c 13.2 14.9 As can be seen from Table 5, the water-soluble silicate-free composition B gives a considerably improved bleaching compared to the silicate-containing composition A.

Claims (30)

460 054 10 15 20 25 36 P a t e n t k r a v 1. A particulate bleaching detergent composition, characterized in that it comprises: (a) a bleaching agent consisting of a peroxy compound together with an activator therefor: and (b) at least one surfactant selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents; which bleaching detergent composition is substantially free of (i) water-soluble silicate compounds and (ii) agglomerated particles which consist essentially of a mixture of said activator, a water-insoluble silicate compound and a nonionic surfactant. Composition according to Claim 1, characterized in that it also contains a sequestering agent. 3. A composition according to claim 2, characterized in that the sequestering agent consists of ethylenediaminetetraacetic acid and / or a water-soluble salt thereof. k n n e t e c k - n a d that the sequestering agent consists of di- A composition according to claim 2, ethylenetriaminepentamethylenephosphonic acid and / or a water-soluble salt thereof. A composition according to claim 1, characterized in that it is substantially free of sequestering agents having a stability constant greater than about 20 for Cu 2+ complex formation in water of 250 ° C and at an ionic strength of 0.1 mol / liter. Composition according to Claim 1, characterized in that the bleaching agent comprises an alkali metal perborate in combination with tetraacetylethylenediamine (TAED). 7. A composition according to claim 6, characterized in that said TAED is enclosed in granules together with a mixture of sodium and potassium triphosphate. Composition according to claim 6, characterized in that said TAED has the following particle size distribution: 0 - 20% greater than 150 μl (micrometers); 10 - 100% greater than 100) 1 but less than 150 fn 0 - 50% less than 75/1; and 0 - 20% less than 50 / L 9. A composition according to claim 6, characterized in that about 50% of the TAED particles have a size greater than 160 .mu.m. 10. A composition according to claim 1, characterized in that at least 80% by weight of said agglomerated particles constitute said mixture 11. ll. Composition according to Claim 1, characterized in that it also contains a washing-assisting salt. 12. A composition according to claim 11, characterized in that said detergent salt is a zeolite. 460 054 38 13. l3. Composition according to Claim 1, characterized in that the surfactant is an anionic detergent. 14. A composition according to claim 13, characterized in that the anionic detergent is a linear alkyl benzene sulfonate. A composition according to claim 1, wherein it also contains a bentonite clay. Bleaching detergent composition, characterized in that it comprises: (a) from about 1% to about 50% by weight of a bleaching composition consisting of a peroxy compound together with an activator thereof; (b) from about 5% to about 50% by weight of a detergent surfactant selected from anionic, cationic, nonionic, ampholytic and zwitterionic detergents; (c) from about 1% to about 60% by weight of a detergent. (d) from about 0.1 to about 10% by weight of a sequestering agent; and (e) the remainder water and optionally a filler salt, which bleaching detergent composition is substantially free of (i) water-soluble silicate compounds and (ii) agglomerated particles which consist essentially of a mixture of said activator, a water-insoluble silicate compound and a nonionic surfactant. Composition according to Claim 16, characterized in that the bleaching agent consists of an alkali metal perborate in combination with tetraacetylethylenediamine. 18. A composition according to claim 16, characterized in that at least 80% by weight of said agglomerated particles are constituted by said mixture. 19. A composition according to claim 16, characterized in that the sequestering agent is ethylenediaminetetraacetic acid and / or a water-soluble salt thereof. A composition according to claim 16, characterized in that it is substantially free of sequestering agents having a stability constant greater than about 20 for Cu 2+ complex formation in water of 25 ° C and at an ionic strength of 0, 1 mol / liter. Bleaching process, characterized in that the stained and / or soiled materials to be bleached are contacted with an aqueous solution of a particulate bleaching detergent composition comprising: (a) a bleaching agent consisting of a peroxy compound together with an activator for this; and (b) at least one surfactant selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents, which bleaching detergent composition is substantially from (i) water-soluble silicate compounds and (ii) agglomerated particles which consist essentially of a mixture of said activator, a water-insoluble silicate compound and a nonionic surfactant. 22. A process according to claim 21, characterized in that the bleaching agent comprises an alkali metal perborate together with tetraacetylethylenediamine. 23. A process according to claim 21, characterized in that the bleaching agent also contains a peroxyacid compound. ß A method according to claim 22, characterized in that said TAED has the following particle size distribution: 0 - 20% greater than 150/1 (micrometers); 10 - 100% greater than 100 li but less than 150) n 0 - 50% less than 75} 1; and 0 - 20% less than 50 fn 25. A method according to claim 21, characterized in that said composition also contains a sequestering agent. 26. A process according to claim 25, characterized in that the sequestering agent is ethylenediaminetetraacetic acid and / or a water-soluble salt thereof. 27. A method according to claim 21, characterized in that the composition also contains a washing-assisting salt. 28. A process according to claim 27, characterized in that the detergent salt is pentasodium tripolyphosphate. 460 054 41 29. A process according to claim 27, characterized in that the detergent salt is a zeolite. 30. A method according to claim 21, characterized in that the bleaching detergent composition also contains a bentonite clay.