CA1227717A - Bleaching and laundering composition free of water- soluble silicates - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
An improved particulate bleaching detergent composition is provided comprising (a) a bleaching agent comprising a peroxyacid compound and/or a water-soluble salt thereof; and (b) at least one surface active agent selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents; said bleaching detergent composi-tion being substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles which essentially comprise said activator, a water-insoluble silicate compound and a nonionic surfactant.

Description

- Jo 122'7717 This application is related to cop ending Canadian application Serial No. Jo I filed on even date herewith, which describes a par-ticulate bleaching detergent composition which is substantially free of water-soluble silicate compounds and agglomerate particles of the type described above, said composition comprising an inorganic per oxygen come pound with an activator therefore and at least one surface active detergent compound.

I

~2277~7 The present invention relates, in general, to bleaching detergent compositions containing as a bleaching agent a per oxygen compound in combination with an organic activator therefore and the application of such compositions to laundering operations. More particularly, the present invention relates to granular bleaching detergent compositions which provide enhanced bleaching performance concomitant with a significant improvement in the stability of the peroxyacid bleaching species in the wash solution.
Bleaching compositions which release active oxygen in the wash solution are extensively described in the prior art and commonly used in laundering operations. In general, such bleaching compositions contain per oxygen compounds, such as, perorates, per carbonates, per phosphates and the like which promote the bleaching activity by forming hydrogen peroxide in aqueous solution. A major drawback attendant to the use of such per-oxygen compounds is that they are not optimally effective at the relatively low washing temperatures employed in most household washing machines in the United States, i.e., temperatures in the range of 80 to 130F. By way of comparison, European wash temperatures are generally substantially higher extending over a range, typically, from 90 to 200F. Ilowever, even in Europe and those other countries which generally presently employ near boiling washing temperatures, there is a trend towards lower temperature laundering.
In an effort to enhance the bleaching activity of per oxygen bleaches, the prior art has employed materials called activators in come bination with the per oxygen compound. It is generally believed that the interaction of the per oxygen compound and the activator results in the formation of a peroxyacid which is a more active bleaching species than hydrogen peroxide at lower temperatures.

Numerous compounds have been proposed in the art as activators for per oxygen bleaches among which are included carboxylic acid androids such as those disclosed in US. Patent ooze. 3,298,775; 3,338,839; and 3,532,634; carboxylic esters such as those disclosed in US. Patent No. 2,995,905; Nuzzle compounds such as those described in US. Patent Nos. 3,912,648 and 3,919,102; cyan-amine such as described in US. Patent No. 4,199,466; and azalea sulfonamides such as disclosed in US. Patent No. 3,245,913.
The formation and stability of the peroxyacid bleaching species in bleach systems containing a per oxygen compound and an o~gaDic activator has been fee-ogDized as a problem in the prior art. US. Patent No. 4,255,452 to Leigh, for example, specifically addresses itself to the problem of avoiding the no-action ox peroxyacid with per oxygen compound to form what the patent kirk-torsos as "useless products, viz. the corresponding carboxylic acid, molecular oxygen and water". The patent states that such side-reaction is "doubly de-lotteries since pursued and per compound. . . are destroyed simultaneously."
The patentee thereafter describes certain polyphosphonic acid compounds as chelating agents which are said to inhibit the above-described peroxyacid-consuming side reaction and provide an improved bleaching effect. on contrast with the use of these chelating agents, the patentee states that other more commonly known chelating agents, such as, ethylene Damon tetraacetic acid (ETA) and nitrilotriacetic acid (NOAH) are substantially ineffective and do not provide improved bleaching effects. Accordingly, a disadvantage of the bleaching compositions of the Leigh patent is that they necessarily preclude the use of conventional sequestrants, many of which are less expensive and more readily available than the disclosed polyphosphonic acid compounds.
The influence of silicates on the decomposition of peroxyacid in the wash and/or blenching solution has heretofore gone unrecognized in the art. US.
Patent Nos. 3,860,391 and 4,292,575 disclose that silicates are conventionally employed as additives to peroxide-containing bleaching solutions for the purpose of stabilizing peroxide compounds therein. however, the patentees note the fact that the use of silicates in such bleaching solutions may create other problems in the bleaching operations, such as, the formation of silicate precipitates which deposit on the bleached goods. Consequently, the patents are directed to processes for bleaching cellulose fiber with silicate-free bleaching soul-lions in which peroxide stability is enhanced with compounds other than sift-gates.
European Patent Publication No. 0,02B,432, published May 13, 1981, discloses a granular laundry composition containing, among other things, a water-insoluble silicate and an organic activator compound for a per oxygen bleach. The pi char-acteristics of such laundry composition are said to be critical; specifically, the pi in a 2% aqueous dispersion being from 2 to 9, and preferably from 4 to 7.
At page 7 of the Publication there are described certain polyphosphonic acid compounds as being highly preferred components of the composition, the public-lion stating in this regard that the polyphosphonates "have been found to be uniquely effective in stabilizing organic peroxyacids against the generally deleterious effect of water-insoluble silicates, especially those belonging to the zealot and kaolin classes". The nature of such "deleterious effect" is not specified. At page 38 of the Publication granular laundry compositions are disclosed in Examples VIII to X which do not contain sodium silicate, all of such compositions being shown to contain Request 2041 (ethylenediamine twitter-.~, ethylene phosphoric acid). The compositions of the aforementioned Examples also contain a per oxygen compound activator which is incorporated into agglomer-ate particles consisting of said activator, a water-insoluble silicate compound and a non ionic surfactant.
Accordingly, the art has heretofore failed to appreciate or suggest the imp proved bleaching performance which-can be achieved with particulate bleaching detergent compositions containing a peroxyacid compound when such compositions are characterized my the absence of water-soluble silicate compounds.

To -i227717 2301-1267 The present invention provides a particulate bleach-in detergent composition comprising: (a) a bleaching agent comprising a peroxyacid compound and/or a water-soluble salt thereof; and (b) at least one surface active agent selected from the group of anionic, cat ionic, non ionic, ampholytic and zwitterionic detergents; said bleaching detergent compost-lion being substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles which essentially comprise an activator, a water-insoluble silicate compound and an non ionic surfactant.
In accordance with the process of the invention, bleaching of stained and/or soiled materials is effected by contacting such materials with an aqueous solution of the above-defined bleaching detergent composition.
The present invention is predicted on the discovery that the undesired loss of peroxyacid in the aqueous wash solution by reaction of peroxyacid with a per oxygen compound (or more specifically, hydrogen peroxide formed from such per oxygen compound) to form molecular oxygen is markedly reduced in bleaching systems which are substantially free of water-soluble silicate compounds. Although the applicants do not wish to be bound to any particular theory of operation it is believed that the presence of water-soluble silicates in bleaching systems containing a peroxyacid compound catalyzes the aforementioned reaction of peroxyacid with hydrogen peroxide which results in the loss of active oxygen from the wash soul-lion which would otherwise be available for bleaching. It has been recognized in the art that metal ions, such as, for example, ions of iron and copper serve to catalyze the decomposition of hydrogen peroxide and also the peroxyacid lZ277~ 7 reaction with hydrogen peroxide. However, with regard to such metal ion catalysis, the applicants have surprisingly discovered that conventional sequestrants, such as, ETA or NAT, which the prior art has deemed to be ineffective for inhibiting the aforement-toned peroxyacid-consuming reaction see, for example, the statement in column 4 of United States Patent 4,225,452) can be incorporated into the compositions of the present invention to stabilize the peroxyacid in solution.
The term "water-soluble silicate compounds" refers to compounds such as sodium silicate which are substantially soluble in aqueous laundering solutions and commonly present in conventional bleaching detergent compositions, but are - I -~227717 .

substantially eliminated in the compositions of the present invention. The present invention contemplates, however, incorporating substantially water-insoluble silicates, most notably, alumino-silicate materials such as clays and zealots into the bleaching detergent compositions described herein, water-soluble silicate compounds being considered far more detrimental to peroxyacid stability than water-insoluble materials such as alumino-silicates.
In a preferred embodiment of the invention, the bleaching compositions described herein additionally 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 "so-questering agent" as used herein refers to organic compounds which are able to form a complex with Cut+ ions such that the stability constant (pi) of the come plexation is equal to or greater than 6 in water at 25C at an ionic strength of 0.1 mole/liter, pi being conventionally defined by the formula: pi = - log K wherein K represents the equilibrium constant. Thus, for example, the pi values for complexation of copper tan with NAT and ETA at the stated condo-lions are 12.7 and 18.8, respectively. The term "sequestering agent" is there-fore used herein in a sufficiently restrictive sense to exclude inorganic come pounds commonly used in detergent formulations as builder salts. Especially useful sequestering agents include ETA, diethylene thiamine pentaacetic acid (DEPTH) and the various phosphonate sequestrants marketed by Monsanto Company under the trademark Request, e.g., Request 2000, 2006, 2041, 2051 and 2060 In accordance with another embodiment of the invention, the described bleaching compositions are further distinguished from certain water-soluble silicate free compositions disclosed in the art by restricting the use of so-questering agents in the present bleaching compositions to those having a stay ability constant no greater than about 20 for Cut + complex formation in water at 25C and at an ionic strength of 0.1 mole/liter. This limitation necessary fly precludes the presence of pol~phosphonic acid compounds such as Request 2041 ~Z27717 (ethylene Damon tetramethylene phosphoric acid) and Request 2060 (depth-tone thiamine pentamethylene phosphoric acid) in the bleaching compositions of the invention, the aforementioned sequestrants having stability constants above about 20. Accordingly, suitable sequestering agents for this embodiment of the invention include the sodium salts of nitrilotriacetic acid (NAT); elk-ylene Damon tetraacetic acid (ETA); ethylene Damon; tetramine, i.e., N-(CH2-CH2-NH2)3; bis(aminoethyl) glycolether-NNN'N'-tetraacetic acid (ETA);
and N(CH2-P03H2)3,which is marketed under the.:~radename Request 2000. ETA
and the aforementioned Request 2000 are especially preferred for use in this embodiment of the invention.

`\
~227717 The bleaching detergent compositions of the invention are sub Stan-tidally free of water-soluble silicate compounds and are comprised of two essential components: (a) a bleaching agent; and (b) a detergent surface active agent.
The bleaching agent useful in such compositions comprises a water-soluble peroxyacid compound and/or a water-soluble salt thereof. Proxy-acid compounds are characterized by the following general formula:
o wherein R is an alkaline group containing from 1 to about 20 carbon atoms, or a phenylene group, and Z is one or more groups selected from among hydrogen, halogen, alkyd, aureole and anionic groups.
The organic peroxyacids and the salts thereof can contain from about 1 to about 4, preferably 1 or 2, proxy groups and can be aliphatic or aromatic. The preferred aliphatic peroxyacids include diperoxyazelaic acid, diperoxydodecanedioic acid and monoperoxysuccinic acid. Among the aromatic peroxyacid compounds useful herein, monoperoxyphthalic acid (MPPA), particularly the magnesium salt thereof, and diperoxyterephthalic acid are especially preferred. A detailed description of the production of MPPA and its magnesium salt is set forth on pages 7-10, inclusive, of European Patent Publication 0,027,693, published April 29, 1981.
The bleaching agent may optionally also include a per oxygen come pound in addition to the peroxyacid compound. The useful per oxygen compounds include compounds that release hydrogen peroxide in aqueous media, such as, alkali metal perorates, e.g., sodium perorate and potassium perorate alkali metal per phosphates and alkali metal per carbonates. The alkali metal perorates are usually preferred because of their commercial availability and relatively low cost. If desired, an organic activator may be used in conjunction with such per oxygen compo~md.

~22~7~7 Conventional activators such as those disclosed, for example, at column 4 of United States Patent 4,259,200 are suitable for use in conjunct lion with the aforementioned per oxygen compounds. The polyacylated amine are generally of special interest, tetraacetyl ethylene Damon (TOED) in particular being a highly preferred activator. The TOED is preferably pro-sent in the compositions of the invention in the form of "coated" granules which contain the TOED and a suitable carrier material such as a mixture of sodium and potassium triphosphate. Such coated TOED granules are convenient-lye prepared by mixing finely divided particles of sodium triphosphate and TOED and then spraying onto such mixture an aqueous solution of potassium triphosphate using suitable granulation equipment such as a rotating pan granulator. A typical method of preparation for this type of coated TOED is described in United States Patent 4,283,302 to Fret, et at. The granules of TOED have a preferred particle size distribution as follows: 0-20%
greater than 150 micrometers; 10-100% greater than 100 em but less than 150 em; 0-50% less than 75 em; and C-20% less than 50 em. Another part-ocularly preferred particle size distribution is where the median particle size of TOED is 160 microns, i.e., 50% of the particles have a size greater than 160 microns. The aforementioned size distributions refer to the TOED
present in the coated granules, and not to the coated granules themselves.
The molar ratio of per oxygen compound to activator can vary widely depending upon the particular choice of per oxygen compound and activator. Louvre, molar ratios of from about 0.5:1 to about 25:1 are generally suitable for providing satisfactory bleaching performance.
The bleaching detergent compositions of the invention are character-iced by being substantially free of I) water-soluble silicate compounds and (ii) agglomerate particles which are essentially comprised of a mixture of three components: the organic activator for the per oxygen compound; a water-insoluble silicate compound, such as clay or zealot; and a nonio~ic surfactant, such mixture being at least 80%, by weight of the agglon;era~e particles. The agglomerate particles which are precluded for use herein are of the type formed in equipment such as a pan granulator and serve to incorporate the bleach activator in a matrix of materials as described in European Patent Publication No. 0,028,432. In one particular embodiment of the invention, the bleaching compositions are further characterized by being substantially free of sequestering agents having a stability constant for Cut + complex formation above about 20 in water at 25C and at an ionic strength of 0.1 mole/liter.
The water-insoluble silicate materials which may be advantageously em-plowed in the present bleaching compositions are preferably aluminosilicates such as zealots and smectite-type clays. The crystalline types of zealot which may be employed include those described in "Zealot Molecular Series"
by Donald W. Brook, published in 1974 by John Wiley & Sons, typical commercially available zealots being listed in Table 9.6 at pages 747-749 of the text, such Table being incorporated herein by reference. Zealot structures of type A are especially desirable and are extensively described in the art; see, for example, page 133 of the aforementioned Brook Text as well as US. Patent No. 2,882,243.
The zealots are particularly useful as builder salts in heavy duty detergent compositions.
The aforementioned smectite-type clays are three-layer clays characterized by the ability of the layered structure to increase its volume several-fold by swelling or expanding when in the presence of water to form a thixotropic gel-attunes substance. There are two classes of smectite-type clays: in the first class, aluminum oxide is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice. Atom sub-stitution by iron, magnesium, sodium, potassium, calcium and the like can occur within the crystal lattice of the smectite clays. it is customary to distinguish between clays on the basis of their predominant cation. For example, a sodium clay is one in which toe cation is predominantly sodium. With regard to the I

present bleaching detergent compositions, a æ ales wherein sodium is the predominant cation are preferred, such as, for example, bentonite clays. Among the bentonite clays, those from Wyoming (generally referred to as western or Wyoming bentonite) are especially preferred. Calcium and magnesium clays are also useful albeit less preferred for purposes of this invention.
Preferred swelling bentonites are sold under the trademark Mineral Killed, as industrial bentonites, by Kenton Clay Company, an affiliate of Georgia Kaolin Co. These materials which are the same as those formerly sold under the trademark THIXO-JEL, are selectively mined and beneficiated bentonites, and those considered to be most useful are available as Mineral Killed No's. 101, etc. corresponding to THIXO-JELs No's. 1, 2, 3 and 4.
Such materials have oh's (6% concentration in water) in the range of 8 to 9.4, maximum free moisture contents of about 8% and specific gravities of about 2.6, and for the pulverized grade at least about 85% (and preferably 100%) passes through a 200 mesh So Sieve Series sieve. More preferable, the bentonite is one wherein essentially all the particles (i.e., at least 90% thereof, preferably over 95%) pass through a No. 325 sieve and most preferably all the particles pass through such a sieve. The swelling gape-city of the bentonites in water is usually in the range of 3 to 15 ml/gram,and its viscosity, at a 6% concentration in water, is usually from about 8 to 30 centipoises.
In a particular preferred embodiment of the invention, the carrier particles comprise agglomerates of finely divided bentonite, of particle sizes less than No. 200 sieve, agglomerated to particles of sizes essential-lye in the No's. 10-100 sieve range, of a bulk density in the range of 0.7 to 0.9 gel and a moisture content of 8 to 13%. Such agglomerates include about 1 to 5% of a binder or agglomerating agent to assist in maintaining the integrity of the agglomerates until they are added to water, in which it is intended that they disintegrate and disperse.

. I 1--~22~717 Instead of utilizing the THIXO-JEL or Mineral Killed bentonites one may also employ equivalent competitive products, such as that sold by American Killed Company, Industrial Division, as General Purpose Bentonite Powder, 325 mesh, which has a minimum of 95% thereof finer than 325 mesh or 44 mix crows in diameter (wet particle size) and a minimum of go% finer than 200 mesh or 74 microns diameter (dry particle size). Such a hydrous aluminum silicate is comprised principally of montmorillonite (907~ minimum), with smaller proportions of feldspar, biotite and silent. A typical analysis, on an "an hydrous" basis, is 63.0% silica, 21.5% alumina, 3.3% of ferris iron (as Foe), 0.4% of ferrous iron (as Foe), 2.7% of magnesium (as Moo), 2.6% of sodium and potassium (as Noah), 0.7% of calcium (as Coo), 5.6% of crystal water (as ~2) and 0.7% of trace elements.
Although the western bentonites are preferred it is also possible to utilize synthetic bentonites, such as those which may be made by treating Italian or similar bentonites containing relatively small proportions 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 considered that the Noah content of the bentonite should be at least about 0.5%, preferably at least 1% and more preferably at least 2%
so that the clay will be satisfactorily swelling, with good softening and dispersing properties in aqueous suspension. Preferred swelling bentonites of the synthetic types described are sold under the trade names Levis and Winkelmann, e.g., Levis AGO and Winkelmann G-13.
The compositions of the present invention contain one or more surface active agents selected from the group of anionic, non ionic, cat ionic, amp ho-lyric and zwitterionic detergents.

~2277~7 Among the anionic surface active agents useful in the present invention are those surface active compounds which contain an organic hydrophobic group containing from about 8 to 26 carbon atoms and preferably from about 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulk fate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.
Examples of suitable anionic detergents include soaps, such as, the water-soluble salts (e.g., the sodium, potassium, ammonium and alkanol-ammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example, tallow, grease, coconut oil and mixtures thereof. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, for example, sodium coconut soap and potassium tallow soap.
The anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an alkyd radical containing from about 8 to 26, and preferably from about 12 to 22 carbon atoms. (The term "alkyd" includes the alkyd portion of the higher azalea radicals). Examples of the cellophane-axed anionic detergents are the higher alkyd mononuclear art-matte sulfonates such as the higher alkyd Bunsen sulfonates containing from about 10 to 16 carbon atoms in the higher alkyd group in a straight or a branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyd Bunsen sulfonates, higher alkyd Tulane sulfonates and higher alkyd phenol sulfonates.
Other suitable anionic detergents are the olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfonate detergents may be prepared in a conventional manner by the reaction of SO with long chain olefins containing from about 8 to 25, and preferably from about 12 to 21 -aye-~22~7~717 carbon atoms, such olefins having the formula COUCH wherein it a higher alkyd group of from about 6 to 23 carbons and R1 is an alkyd group containing from about 1 to 17 carbon atoms, or hydrogen to form a mixture of sultans and alkene sulfonic acids which is then treated to convert the sultans to sulfonates. Other examples of sulfate or sulfonate detergents are paraffin sulfonates containing from about 10 to 20 carbon atoms, and preferably from about 15 to 20 carbon atoms. The primary paraffin sulfa-notes are made by reacting long chain alpha olefins and bisulfites. Pane-fin sulfonates having the sulfonate group distributed along the paraffin chain are shown in US. Nos. 2,503,280; 2,507,0S8; 3,260,741; 3,372,188 and German Patent No. 735,096.
Other suitable anionic detergents are sulfated ethoxylated higher fatty alcohols of the formula RO(C2H40)mS03M, wherein R is a fatty alkyd of from 10 to 18 carbon atoms, m is from 2 to 6 preferably having a value from about 1/5 to 1/2 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 alkyd Bunsen sulfonate wherein the higher alkyd is of 10 to 15 carbon atoms. The proportion of ethylene oxide in the polyethoxylated hither alkanol sulfate is preferably 2 to 5 moles of ethyl tone oxide groups per mole of anionic detergent, with three moles being most preferred, especially when the higher alkanol is of 11 to 15 carbon atoms.
To maintain the desired hydrophile-lipophile balance, when the carbon atom content of the alkyd chain is in the lower portion of the 10 to I carbon atom range, the ethylene oxide content of the detergent may be reduced to about two moles per mole whereas when the higher al~anol is of 16 to I car-bun atoms in the higher part of the range, the number of ethylene oxide groups may be increased to 4 or 5 and in some cases to as high as S or 9. Similarly, the salt-forming cation may be altered to obtain the best volubility. It may be any suitably solubilizing metal or radical but will most froquoncly be alkali metal, e.g., sodium, or ammonium. If lower alkylamine or alkanol-amine groups are utilized the alkyds and alkanols will usually contain from 1 to 4 carbon atoms and the amine and alkanolamines may be moo-, dip and tri-substituted, as in monoethanolamine, diisopropanolamine and trim ethyl-amine. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and is marketed as Nudely 25-3S.
The most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as moo, do and tri-ethanol-amine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such as, calcium and magnesium) salts of the higher alkyd Bunsen sulfonates, olefin sulfonates and higher alkyd sulfates. Among the above-listed avionics, the most preferred are the sodium linear alkyd Bunsen sulk donates (LABS), and especially those wherein the alkyd group is a straight chain alkyd radical of 12 or 13 carbon atoms.
The non ionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyd aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a car boxy, hydroxy, amino or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyp ethylene glycol, to form a non ionic 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 non ionic detergent employed is preferably a poly-lower alkoxy-fated higher alkanol wherein the alkanol is of 10 to 18 carbon atoms and wherein the number of moles of lower alkaline oxide of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 11 to 15 carbon *Trade mark 1227717 ~301-1267 atoms and which contain from 5 to 9 lower alkoxy groups per mole.
Preferably, the lower alkoxy is ethics but in some instances it may be desirably mixed with propoxy, the latter, if present, usually being a minor (less than 50%) constituent. Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g., Nudely 25-7 and Nudely 23-6.5, which products are made by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole averages about 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corporation. The former is a mixed ethoxylation product of an 11 to 15 carbon atom linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted. Also useful in the present compositions are the higher molecular weight nonionics, such as Nudely 45-11, which are Sims liar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also made by Shell Chemical Company.
Zwitterionic detergents such as the buttons and sulfobetaines having the following formula are also useful:

2 \
R N R O

so Jo i2277~7 2301-1267 wherein R is an alkyd group containing from about 8 to 18 carbon atoms, R2 and R3 are each an alkyd or hydroxyalkyl group con-twining about 1 to 4 carbon atoms, R4 is an alkaline or hydroxyalkylene group containing 1 to 4 carbon atoms, and x is C or SO. The alkyd group can contain one or more intermediate linkages such as amino, ether, or polyether linkages or non-functional substituents such as hydroxyl or halogen which do not substantially affect the hydrophobic character of the group.
When X is C, the detergent is called a button; and when X is SO, the detergent is called a sulfobetaine or sultan.
Cat ionic surface active agents may also be employed.
They comprise surface active detergent compounds which contain an organic hydrophobic group which forms part of a cation when the compound is dissolved in water, and an anionic group. Typic eel cat ionic surface active agents are amine and qua ternary ammonium compounds.
Examples of suitable synthetic cat ionic detergents include: normal primary amine of the formula RNH2 wherein R is an alkyd group containing from about 12 to 15 atoms;
dominoes having the formula RNHC2H4NH2 wherein R is an alkyd group containing from about 12 to 22 carbon atoms, such as N-2-aminoethyl-stearyl amine and N-2-aminoethyl myristyl amine;
amide-linked amine such as those having the formula RlCONHC2H4NH2 wherein Al is an alkyd group containing about 8 to 20 carbon atoms, such as N-2-amino ethylstearyl aside and N-amino ethylmyristyl aside; qua ternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyd group containing about 8 to 22 carbon atoms and three of the groups linked to the nitrogen atom are alkyd groups which contain 1 to 3 carbon atoms, including alkyd groups bearing inert substituents, such as phenol groups, and there is present an anion such as halogen, acetate, methosulfate, etc. The i227717 alkyd group may contain intermediate linkages such as aside which do not substantially affect the hydrophobic character of the group, for example, stroll amino propel qua ternary ammonium chloride. Typical qua ternary ammonium detergents are ethyl-dimethyl-stearyl-ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl-stearyl ammonium chloride, trim ethyl-Seattle ammonium bromide, dimethyl-ethyl-lauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the correspond-in methosulfates and acetates.
Ampholytic detergents are also suitable for the invention. Ampholytic detergents are well known in the art and many operable detergents of this class are disclosed by Schwartz, Perry and Bench in the aforementioned "Surface Active Agents and Detergents." Examples of suitable amphoteric detergents include:
alkyd betaiminodipropionates, RN(C2H4COOM)2; alkyd beta-amino preappoints, RN(H)C2H4COOM; and long chain imidazole derivatives having the general formula:
OH
Jo N OH

wherein in each of the above formulae R is an cyclic hydrophobic group containing from about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion. Specific operable amp ho-tonic detergents include the disodium salt of undecylcycloimidin-ium-ethoxyethionic acid-2-ethionic acid, dodecyl beta ala nine, and the inner salt of 2-trimethylamino Laurie acid.
The bleaching detergent compositions 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, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, carbonates, and the like.
Organic builders include water-soluble phosphonates, poly-phos-founts, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylates, succinates and the like.
Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates specific gaily include, for example, the sodium and potassium salts of ethanes l-hydroxy-l,l-diphosphonic acid and the sodium and poles-slum salts of ethane-1,1,2-triphosphonic acid. Examples of these and other phosphorous builder compounds are disclosed in US. Patent Nos. 3,213,030; 3,422,021; 3,422,137 and 3,400,176.
Pentasodium tripolyphosphate and tetrasodium pyrophosphate are especially preferred water-soluble inorganic builders.
Specific examples of non-phosphorous inorganic builders include water-soluble inorganic carbonate and bicarbonate salts.
The alkali metal, for example, sodium and potassium, carbonates and bicarbonates are particularly useful herein.
Water-soluble organic builders are also useful. For example, the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy-sulfonates are useful builders for the compositions and processes of the invention. Specific examples of polyacetate and polyp carboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diaminetetracetic acid, nitrilotriacetic acid, Bunsen polycarboxylic (i.e. pent- and twitter-) acids, carboxymethoxysuccinic acid and citric acid.
Water-insoluble builders may also be used, particularly, the complex silicates and more particularly, the complex sodium alumina silicates such as, zealots, eye., zealot PA, a type of zealot molecule wherein the univalent cation is sodium and the Jo 1227717 pore size is about 4 Angstroms. The preparation of such type zealot is described in US. Patent 3,114,603. The zealots may be amorphous or crystalline and have water of hydration as known in the art.

-aye-;,.~,, 1227~1.7 An inert, water-soluble filler salt is desirably included in the laundering compositions of the invention. A preferred ~illcr salt is an alkali metal sulfate, such as, potassium or sodium sulfate, the fatter being especially preferred.
Various adjutants may be included in the laundry detergent compositions of the invention. In general, these include perfumes; colorants, eye., pi-mints and dyes; bleaches, such as, sodium perorate, antircdcposition aquanauts, such as, alkali metal salts of carboxymethylcellulose; optical brighteners, such as, anionic, cat ionic or non ionic brighteners; foam stabilizers, such as alkanolamides, and the like, all of which are well-~nown in the fabric washing art for use in detergent compositions. Flow promoting agents, commonly referred to as flow aids, may also be employed to maintain the particulate compositions as free-flowing beads or powder. Starch derivatives and special clays are commercially available as additives which enhance the flowabiliLy of otherwise tacky or pasty particulate compositions, two of such clay additives being presently marketed under the trade names "Sat intone" and "Microsil", A preferred bleaching detergent composition in accordance with the in-mention typically comprises (a) from about 1 to 50%, by weight, of a bleaching agent comprising a peroxyacid compound and/or a water-soluble salt thereof;
tub) from about 5 to 50%, by weight, of a detergent surface active agent;
(c) from about 1 to about 60%, by weight, of a detergent builder salt; and (d) from about 0.1 to about 10%, by weight, of a sequestering agent; such come position being characterized by being substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles which essentially comprise said activator, a water-insoluble silicate compound and a non ionic surfactant.
The balance of the composition will predominantly comprise water, filler salts, such as, sodium sulfate, and minor additives selected from among the various adjutants described above.
The particulate bleaching deterrent compositions of the invention are pro-pared by admixing the bleaching agent and optional sequestering agent with the . 122771~7 spray-dried detergent composition, the latter being formulated so as to avoid the use of water-soluble silicate compounds, most notably, sodium silicate.
The presence of very minor amounts of water-soluble silicate compounds in the final compositions, i.e., below about 0.5%, preferably below about 0.2%, and most preferably no greater than about 0.1%, by weight, such as may occur with the use of silicate-containing pigments or dyes, or upon contact of the aqueous crutches slurry with residual amounts of sodium silicate in the spray tower, is contemplated by the present invention.
The spray drying of a silicate-free detergent formulation may result in a relatively dusty granular product due to the absence of silicate as a binder for the spray dried beads. However, alternative organic binder materials may be employed, such as, for example, starch, carboxymethyl-cellulose and Metro-awls comparable thereto. The strength of the spray dried beads may also be en-hanged by maximizing the solids content of the silicate-free slurry in the crutches and/or by maintaining the inlet temperature of the hot air stream in the spray tower as low as possible.
The bleaching agent can be mixed either directly with the spray dried powder or the bleaching agent and optional sequestering agent can be separately or collectively coated with coating material to prevent premature activation of the bleaching agent. The coating process is conducted in accordance with pro-seeders well known in the art. Suitable coating materials include compounds such as magnesium sulfate, polyvinyl alcohol, Laurie acid and its salts and the like.
The bleaching detergent compositions of the invention are 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, a concentration of from about 5 to about 40 Pam being generally preferred.
The particulate bleaching detergent compositions described above may be produced by such methods as spray-drying, dry-blending, or agglomeration of the individual components.

~227717 A preferred silicate-free bleaching detergent composition is comprised of the following:

Component Weight Percent Sodium linear C10 - C13 -6 alkyd Bunsen sulfonate Ethoxylated Oil - C18 primary alcohol (11 moles HO per mole alcohol) Soap (sodium salt of C12 - C22 4 carboxylic acid) Pentasodium tripolyphosphate (TOP) 32.0 ETA 0.5 M~noperoxyphthalic acid (MPPA), 7 magnesium salt Carboxymethyl cellulose 0.5 Optical brighteners, pigment and 0.4 perfume Proteoly~ic enzymes 0.5 -Sodium sulfate and water balance ~227717 The foregoing product is produced by spray drying an aqueous slurry con-twining 60%, by weight, of a mixture containing all of the above components except the enzyme, perfume and monoperoxyphthalic acid (MPPA). The resultant particulate spray dried product has a particle size in the range of 14 mesh to 270 Messiahs. Sieve Series). The spray dried product is then mixed in a rotary drum with the appropriate amounts of MPPA of similar mesh size, enzyme and perfume to yield a particulate product having a moisture of approx-irately 14%, by weight.
The above-described product is used to wash soiled fabrics by hand-washing as well as in an automatic washing machine, good laundering and bleaching per-pheromones being obtained for both methods of laundering.
Other satisfactory products can be obtained by varying the concentrations of the following principal components in the above-described composition as follows:

Component Weight Percent Alkyd Bunsen sulfonate 4-12 Ethoxylated alcohol 1-6 Soap 1-10 Enzymes 0.1-1 ETA 0.1-2 For highly concentrated heavy duty detergent powder, the alkyd Bunsen sulfonate, TOP and the soap components in the above described composition may be deleted, and the ethoxylated alcohol content may be increased to an upper limit of 20%.

lZ~77~L7 Bleaching tests are carried out as described below comparing the bleach-in performance of a water-soluble silicate-free,bleaching detergent composition in accordance with the invention and a corresponding silicate-containing compost-lion, the latter composition being comparable to the former in nearly all no-specs except for the presence of a water-soluble silicate compound. The bleach-in agent employed is a mixture of monoperoxyphthalic acid salt and sodium per-borate. The compositions are formulated by post-adding to a spray-dried part-curate detergent composition, granules of the H-48 bleaching composition (de-scribed in the footnote of Table 1) to form the bleaching detergent compositions A and B shown in Table 1 below. The numbers indicated in the Table represent the percentage of each component, by weight, in the composition.

Component Composition A B
Silicate free (Silicate--containin~) Sodium linear C10 - C13 6.00% 6.00%
alkyd Bunsen sulfonate Ethoxylated Oil - C18 primary 3.50 3.50 alcohol (11 moles HO per mole alcohol) Soap (Sodium salt of C12 - C22 2.50 2.50 carboxylic acid) Sodium silicate (Nash) ---- 9.00 Pentasodium tripolyphosphate (TOP) 35.00 35.00 Optical brightener (stilbene) 0.22 0.22 Sodium perorate tetrahydrate 3.00 3.00 H_48(1) 9.00 9.00 ETA (Disodium salt) 1.00 1.00 Sodium sulfate 35.00 10.60 Water balance balance (1) A bleaching composition sold by Inter ox Chemicals Limited, London, England,containing about 65 wt. % magnesium monopero~yphthalate, 11 wt. magnesium phthalate, balance H20.

~;~27~7~7 TEST PROCEDURE

The active oxygen concentration in solution is determined as a function of time for separate wash solutions containing compositions A and B, respect-lively, using the following procedure:
- 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. Ten grams of the particular composition being tested (A or B) are added to the beaker (time = O) with thorough mixing to form a uniform wash solution. After given periods of time (3, 7, 13, 20, 30, 40 and 50 minutes), a 50 ml Alcott is withdrawn from the wash solution and the total active oxygen concentration is determined by the procedure set forth below.

Determination of Total Active 2 Concentration The aforementioned 50 ml Alcott is poured into a 300 ml erlenmeyer flask containing 15 ml of a sulfuric/molybdate mixture, the latter mixture having been prepared in large-scale amounts by dissolving 0.18 grams of ammonium molybdate in 750 ml of deionized water and then adding thereto 320 ml of H2S04 (about 36N) with stirring. The solution in the erlenmeyer is thoroughly mixed and 5 ml of a 10% KIT solution in deionized water is then added thereto. The erlenmeyer is sealed with a stopper, agitated and then allowed to stand in a dark place for about seven minutes. The solution in the flask is then titrated with a soul-lion of Own sodium thiosulfate in deionized water. The volume of thiosulfate required in ml, is equal to the total active oxygen concentration, in millimole/
liter, in the wash solution. The tests results for the two compositions tested are shown in Table 2 below.

Total Active Oxygen in Wash Solution (milliliter) A B
Time (min.) (Silicate-free) (Silicate-containin~)

3 4.8 2.4 7 4.4 1.2 13 4.2 1.0 3.9 0.8 3.7 0.6 3.4 0.5 3.2 0.4 As shown in Table 2, the silicate-free composition A is significantly more stable and is characterized by a far slower loss of active oxygen from solution than the corresponding silicate-containing composition B.

Claims (33)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A particulate bleaching detergent composition compris-ing:
(a) a bleaching agent comprising a peroxyacid compound and/or a water-soluble salt thereof; and (b) at least one surface active agent selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents; said bleaching detergent composition being substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles which essentially comprise a mixture of an activator, a water-insol-uble silicate compound and a nonionic surfactant.

2. A composition in accordance with claim 1 also contain-ing a sequestering agent.

3. A composition in accordance with claim 2 wherein said sequestering agent comprises ethylene diamine tetraacetic acid and/or a water-soluble salt thereof.

4. A composition in accordance with claim 2 wherein said sequestering agent comprises diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof.

5. A composition in accordance with claim 1 wherein said bleaching agent comprises monoperoxyphthalic acid and/or a water-soluble salt thereof.

6. A composition in accordance with claim 5 wherein said bleaching agent comprises magnesium monoperoxyphthalate.

7. A composition in accordance with claim 1 wherein said bleaching agent also contains a peroxygen compound.

8. A composition in accordance with claim 7 wherein said peroxygen compound is an alkali metal perborate.

9. A composition in accordance with claim 1 also containing a detergent builder salt.

10. A composition in accordance with claim 9 wherein said builder salt is a zeolite.

11. A composition in accordance with claim 1 wherein said surface active agent is an anionic detergent.

12. A composition in accordance with claim 11 wherein said anionic detergent is a linear alkyl benzene sulfonate.

13. A composition in accordance with claim 1 also containing a bentonite clay.

14. A bleaching detergent composition comprising:
(a) from about 1 to about 50%, by weight, of a bleach-ing agent comprising a peroxyacid compound and/or a water-soluble salt thereof;
(b) from about 5 to about 50%, by weight, of a detergent surface active agent selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents;
(c) from about 1 to about 60%, by weight, of a deter-gent builder salt;
(d) from about 0.1 to about 10%, by weight, of a sequestering agent; and (e) the balance comprisina; water and optionally a fil-ler salt; said bleaching detergent composition being substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles which essentially comprise a mixture of an activator, a water-insoluble silicate compound and a nonionic surfactant.

15. A composition in accordance with claim 14 wherein said bleaching agent comprises monoperoxyphthalic acid and/or a water-soluble salt thereof.

16. A composition in accordance with claim 14 wherein said bleaching agent comprises magnesium monoperoxyphthalate.

17. A composition in accordance with claim 14 wherein said bleaching agent also contains a peroxygen compound.

18. A composition in accordance with claim 14 wherein said sequestering agent comprises ethylene diamine tetraacetic acid and/or a water-soluble salt thereof.

19. A composition in accordance with claim 14 wherein said builder salt is a zeolite.

20. A composition in accordance with claim 14 also containing a bentonite clay.

21. A process for bleaching which comprises contacting the stained and/or soiled material to be bleached with an aqueous solution of a granular bleaching detergent composition comprising:

(a) a bleaching agent comprising a peroxyacid compound and/or a water-soluble salt thereof; and (b) at least one surface active agent selected from the group consisting of anionic, nonionic, cat-ionic, ampholytic and zwitterionic detergents, said bleaching detergent composition being substantially free of (i) water-soluble silicate compounds and (ii) agglomerate particles which essentially comprise a mixture of an activator, a water-insoluble silicate compound and a nonionic surfactant.

22. The process of claim 21 wherein the bleaching agent comprises monoperoxyphthalic acid and/or a water-soluble salt thereof.

23. The process of claim 22 wherein said bleaching agent comprises magnesium monoperoxyphthalate.

24. The process of claim 21 wherein the bleaching agent also contains a peroxygen compound.

25. The process of claim 21 wherein said surface active agent is an anionic detergent.

26. The process of claim 25 wherein said anionic detergent is a linear alkyl benzene sulfonate.

27. The process of claim 21 wherein said composition also contains a sequestering agent.

28. The process of claim 27 wherein said sequestering agent comprises ethylene diamine tetraacetic acid and/or a water-soluble salt thereof.

29. The process of claim 27 wherein said sequestering agent comprises diethylene triamine pentamethylene phosphonic acid and/or a water-soluble salt thereof.

-30a-

30. The process of claim 21 wherein said composition also contains a detergent builder salt.

31. The process of claim 30 wherein said builder salt comprises pentasodium tripolyphosphate.

32. The process of claim 30 wherein said builder salt is a zeolite.

33. The process of claim 21 wherein said bleaching detergent composition also contains a smectite-type clay.