CA1208852A - Low temperature bleaching composition - Google Patents

Abstract

LOW TEMPERATURE BLEACHING COMPOSITION
ABSTRACT OF THE DISCLOSURE

An improved bleaching composition is provided comprising: (a) mono-peroxyphthalic acid and/or a water-soluble salt thereof; (b) a water-soluble inorganic bromide salt; and (c) an aromatic sulfonamide compound selected from the group consisting of benzene sulfonamide, toluene sulfonamide, ethylbenzene sulfonamide, dodecylbenzene sulfonamide, xylene sulfonamide, N-alkali metal salts of said sulfonamides, N-acetyl and N-benzoyl derivatives of the aforesaid sulfonamides and salts, and mixtures thereof.

Description

~201~1~152 BACKGROUND OF THE INVENTION
The present invention relates, in general, to bleaching and laundering compositions and their application to laundering operations. More specifically, -the present invention relates -to bleaching and laundering compositions which provide effective bleaching a-t low wash -temperatures.
Bleaching compositions which release active oxygen in laundry solutions are extensively described in -the prior art and commonly used in laundering operations. In general, such bleaching compositions contain peroxygen compounds, such as, perborates, percarbonates, perphosphates and -the like which prornote -the bleaching activity by forming hydro~
gen peroxide in aqueous solution~ A major drawback at-tendan-t to the use of such peroxygen compounds is that they are not optimally effective at the relatively low washing temperatures employed in mos-t household washing machines in the United States, i.e., tempera-tures in the range of 80 to 150F.
By way of comparison, European wash temperatures are generally substan-tially higher extending over a range typically from 90 to 200F. However~ even in Europe and those other coun-tries which generally presently employ near boiling washing temperatures there is a trend towards lower temperature laundering.
In an effor-t to enhance bleaching a-t low wash water temperatures, the prior ar-t has employed peroxyacid compounds as active low temperature bleaching agents. OrgcLnic peroxy-acid compounds are generally recognized -to be more active bleaching agents than hydrogen peroxide at lower -temperatures, the use o~ peroxygen bleaches being generally considered ~lr~

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unsatisfac-tory for s-tain removal a-t -temperatures below about 140F. Accordingly, bleaching with peroxyacid compounds is generally effected in the ar-t buy either forming the peroxy-acid compounds, in situ, in -the wash solution, or alterna-tively, by in-troducing preformed peroxyacid compounds into the wash solution. The use of activator materials in com-bination with peroxygen compounds is extensively described in the patent literature and is the conventional approach to generating peroxyacid compounds in the wash solu-tion;
-the reaction of the activator, usually a carboxylic acid deriva-tive, and the peroxygen compound forming a peroxyacid, typically, perace-tic acid. Among the compounds which have been proposed as activators for peroxygen bleaches are carboxylic acid anydrides such as those disclosed in U.S.
Patent Nos. 3,298,775 and 3,338,839; carboxylic esters, such as disclosed in U.S. Patent No. 2,995,905; and N-acyl com-pounds such as described in U.S~ Pa-tent Nos. 3,912,648 and 3,919,102. Bleaching compositions containing a pre-formed peroxyacid compound are also conven-tional, U.S. Patent Nos.
4,170,453 and 4,259,920 being illus-trative of such prior art.
The bleaching action of composi-tions containing a peroxyacid compound has been further enhanced at low temperatures, particularly at temperatures of 100F or below, by the addition of bromide ions to the bleach com-positions. Thus, for example~ U.S. Paten-t 4,338,210 dis-closes a bleach svstem intended to operate a-t -temperatures as low as 40C and below, such bleach system comprising a peroxide precursor such as diphthaloyl peroxide, and sodium bromide. It is theorized in the paten-t tha-t the bromide reacts with the peroxyacid to form a hypobromi-te compound, the latter being a more effective low--temperature bleach than the peroxyacid compound. European Pa-tent Applica-tion Publication No. 00 24 367, publ:ished March 4, 1981, des-cribes a low temperature bleach system comprising an organic peroxyacid such as dipexisophthalic acid or mono-peroxyph-thalic acid in combination with bromide ion. U.S.
Patent Nos. 4,123,376 and 4,300,897 disclose bleaching composi-tions containing a peroxymonosulfate bleach, an inorganic bromide salt, and an aromatic sulfonamide com-pound, such as an alkali metal toluene-sulfonamide. The function of -the aroma-tic sulfonamide compound in such bleach composition, as sta-ted by the patentee, is to prevent overbleaching of dyed materials and otherwise regulate and con-trol the bleaching activity provided by peroxymonosulfate and bromide in an aqueous medium.
SU~ARY OF'THE INVENTION
The present invention provides a bleaching compos-ition comprising: (a) monoperoxyphthalic acid ~also referred to herein as MPPA for convenience) and/or a water-soluble sal-t -thereof; (b) a water-soluble inorganic bromide salt; and (c) an aromatic sulfonamide compound selected from the group consisting of benzene sulfonamide, toluene sulfonamide, ethylbenzene sulfonamide, dodecylbenzene sulfonamide, xylene sulfonamide, N-alkali metal salts of said sulfonamides, N-ace-tyl and N-benzoyl deriva-tives of the aforesaid sulfonamides and sal-ts, and mixtures thereof. The weight ratio of MPPA (or its salt) -to bromide sal-t in the composi-tion is from about 10:1 to about 1:5, preferably from "
, ,,;

abou-t 8:1 to about 1:2, and mos-t preferably from about 6:1 -to about 1:1. The weight ratio of aromatic sulfonamide compound to bromide salt in the composi-tion is from about 5Ol to 1:7, preferably from about 2:1 to 1:4.
The bleaching detergent composition of the inven-tion comprises the above-defined bleaching composi-tion in combination with one or more detergent surEace ac-tive agents and a detergent builder salt. In accordance wi-th the process of the invention, bleaching of stained and/or soiled materials is effected hy con-tacting such materials with an a~ueous solution of the above-defined compositions.
The present invention is predica-ted on the discov-ery that -the low-temperature bleaching activity of compos-itions containing r~PPA and bromide can be significantly enhanced by the addition of an aroma-tic sulfonamide compound to such bleach composi-tions. Unlike -the composi-tions des-cribed in U.S. Paten-t Nos. 4,123,376 and 4,300,897 wherein the aromatic sulfonamide compounds serve to inhibit the activity of bromide-activa-ted peroxymonosulfate bleaches for the purpose of providing grea-ter safety to colors and brighteners in the wash solu-tion, the inclusion of aromatic sulfonamide compounds in the present compositions has the unexpec-ted beneficial effect of providing a bleaching composition of markedly increased ac-tivity.
DETAILED DESCRIPTION OF THE INVENTION
Monoperoxyphthalic acid and/or one or more of its water-soluble salts are -the primary bleaching agents in the bleaching compositions and bleaching detergen-t compos-itions of the invention. Al-though MPPA provides acceptable --S~
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bleaching activity, it has the disadvantage of relatively poor stability when stored in admix-ture with other compon-ents ordinarily present in household laundry detergent compositions. Hence, for purposes of stability, the mag-nesium salt of MPPA is preferably employed in the compos-itions of the invention, namely, magnesium monoperoxyphthalate The magnesium monoperoxyphthalateispreferably provided in -the form of a composition containing about 65% of the magnesium MPPA sa].-t as the active ingredient and having an ac-tive oxygen content of from about 5 -to 6%. The alkali metal, calcium or barium alkaline earth and/or ammonium salts of L~PPA may also be employed in the bleaching and laundering compositions of the invention, al-though such salts are generally less preferred from the s-tandpoint of stabili-ty than -the aforementioned magnesium salt.
The production of MPPA is generally ef:Eec-ted by the reaction of hydrogen peroxide and phthalic anhydride. The resultant MPPA can then be used to produce magnesium monoperoxyphthalate by reac-tion with a magnesium compound in the presence of an organic solvent. A detailed description of the production of MPPA and its magnesium salt is set forth on pages 7 to 10, inclusive, of European Patent Pub-lication No. 0,027,693, published April 29, 1981.
The MPPA bleaching agent (or a salt thereof) may op-tionally be combined in the present bleaching compositions with a conventional peroxygen bleach compound and an activator therefor. Examples of suitable peroxygen compounds include alkali metal perborates, percarbonates, perphospha-tes and the like, sodium perborate being particularly p.~eferred ~2~

because of i-ts commercial availability. Conventional activators such as those disclosed, for example, at column 4 o the U.S.
Patent 4,259,200 are suitable for use in conjunction with such peroxygen compound. The polyacylated amines are generally of special in-terest, TAED in par-ticular being a preferred activator. Other suitable activa-tors include anhy~ride com-pounds, such as, benzoic, maleic, succinic and phthalic; and acyl compounds such as ~-ace-tyl and N-benzoylimidazoles. In general, the molar ratios of peroxygen compound to ac-tivator can vary widely depending upon the par-ticular choice of peroxygen compound and activator. However, molar ratios of from about 0.5:1 -to about 25:1 are generally sui-table for providing satisfactory bleaching performance.
The water-soluble bromide salt employed is prefer-ably an alkali metal bromide, such as po-tassium or sodium bromide, the latter being especially preferred because i-t is readily available and comparatively inexpensive.
The aromat:ic sulfonamides utilized in the present compositions include the aforementioned sulfonamides, N-acetyl and N-benzoyl deriva-tives thereof such as, N-acetyl-paratoluenesulonamide, N-ace-tyl-benzenesulfonamide and N-benzoyl-benzenesulfonamide, and the N-alkali metal salts of the above. Preferred compounds include sodium and potassium para-toluenesulfonamide; orthotoluenesulfonamide; benzene-sulfonamide; ancl-the corresponding alkali metal salts of the above. The alkali me-tal toluenesulfonamides are par-ticularly preferred for the presen-t invention.
The amount of bleaching composition added -to -the wash solution is generally selec-ted -to provide an amoun-t of ,,, ~z~sz peroxyacid compound within -the range corresponding -to about 3 to 100 parts of active oxygerl per million parts of the wash solution, a concentration of from about 5 to 40 ppm being generally preferred.
The present bleaching composi-tions containing MPPA
and/or its water-soluble salt, and inorganic bromide salt and and aromatic sulfonamide may be formulated as a separate bleach product, or alternatively may be employed in a buil-t detergent composition. Accordingly, -the bleaching compos-i-tion of the invention may include conventional additives used in -the fabric washing art, such as, binders, fillers, builder salts, pro-teolytic enzymes, optical brighteners, perfumes, dyes, corrosion inhibitors, anti-redeposition agents, foam stabilizers and the like, all of which may be added in varying ~uantities depending on the desired prop-erties of the bleaching composition and their compatability wi-th such composi-tion. Additionally, -the bleaching composi-tions of the invention may be incorporated into launderingdetergen-t compositions containing one or more surface ac-tive agents selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic detergents.
When the instant bleaching compositions are incor-porated in-to a conventional laundering composition and are thus provided as a fully formula-ted bleaching detergent com-position, the latter compositions will comprise -the following:
from about 5 to 50%, by weight, of -the instant bleaching composition; from about 5 to 50%, by weight, preferably from about 5 to 30%, of a detergent surface active agen-t; and from abou-t 5 to 806, by weight, preferably from abou-t 10 to 60%, -~3-~2e~

by weight, of a detergent builder salt which can also function as a buffer to provide the requisi-te p~ range when the laun-dering composi-tion is added to water. The aqueous wash solu-tions will have a pH range of from about 7 to 12, preferably from abou-t 8 to 10, and mos-t preferably from abou-t 8 to 9.
A preferred amount of the builder salt is from abou-t 20% to about 65%, by weight of the composition. I'he balance of the composition will predominantly comprise water, filler salts, such as, sodium sulfate, and various adjuvants which are hereinafter described.
The compositions of the presen-t invention contain one or more surface active agents selected from the group of anionic, nonionic, cationic, ampholytic and zwitterionic detergents. The synthe-tic organic detergents employed in the practice of the invention may be any of a wide varie-ty of such compounds which are well known and are described at length in the text Surface Active Agents, ~ol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers.
The detergent compositions of the invention usually include as the primary surfactant one of more anionic deter-gen-t compounds which can be supplemented, or if desired, replaced entirely with a nonionic detergent.
Among -the anionic surface active agen-ts 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 a-toms in their molecular structure and at least one water solubilizing group selected from the group of sulfonate, ~L2~

sulfate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.
Examples of suitable anionic detergen-ts include soaps, such as, the water-soluble sal-ts te-g-, the sodium, potassium ammonium and alkanolammonium salts) of higher fa-tty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms. Suit-able fatty acids can be obtained from oils and waxes of animal or vege-table orlgin, for example, -tallow, grease, coconut oil andmix-tures-thereof. Particularly useful are the sodium and potassium salts of -the fatty acid mix-tures derived from coconut oil and tallow, for example, sodium coconu-t soap and potassium tallow soap.
The anionic class of detergents also includes the water-soluble sulfated and sulonated detergents having an alkyl radical containing from about 8 -to 26, and preferably from about 12 to 22 carbon atoms. (The -term "alkyl" includes the alkyl portion of -the higher acyl radicals). Examples of the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates and higher alkyl phenol sulfonates.
Other suitableanionic detergents are the olefin sulfonates.
including long chain alkene sulfonates, long chain hydroxy-alkane sulfonates or mixtures of alkene sulfona-tes and hydroxy alkane sulfonates. The oleEin sulfonate detergen-ts may be -~rLO-~

prepared in a conventional manner by the reaction of SO3 with long chain olefins con-taining from about 8 to 25, and preferably from about 12 to 21 carbon a-toms, such olefins having -the formula RCH=CHRl wherein R is a higher alkyl group of :Erom about 6 to 23 carbons and Rl is an alkyl group containing from abou-t 1 to 17 carbon a-toms, or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones -to sulfonates.
Other examples of sulate or sulfonate detergents are para-ffin sulfonates containing from abou-t 10 to 20 carbon a-toms, and preferably rom about 15 to 20 carbon a-toms. The primary paraffin sulfonates are made by reacting long chain alpha olefins and bisulfites. Paraffin sulfonates having the sul-fonate group distributed along the paraffin chain are shown in U.S. Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188 and German Paten-t No. 735,096.
Other suitable anionic detergents are sulfated e-thoxyla-ted higher fatty alcohols of the formula RO(C2H4O)mSO3M, wherein R is a fa-tty alkyl 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 ca-tion, such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkyl benzene sulfonate wherein the higher alkyl is of 10 to 15 carbon atoms. The proportion of ethylene oxide in the polye-thoxy-la-ted higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergen-t, with three moles being mos-t preferred, especially when the higher alkanol is of 11 to 15 carbon a-toms. To main-tain the desired '.,/!

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hydrophile-lipophile balance, when the carbon a-tom content of the alkyl chain is in the lower portion of -the 10 to 18 carbon a-tom range, the e-thylene oxide content of -the deter-gen-t may be reduced -to about two moles per mole whereas when the higher alkanol is of 16 to 13 carbon atoms in the higher part of the range, the number of ethylene oxide groups may be increased to ~ or 5 and in some cases -to as high as 8 or 9. Similarly, the sal-t-forming ca-tion may be altered to obtain the bes-t solubility. :[-t may be any suitably solu-bilizing me-tal or radical but will most frequently be alkali me-tal, e.g., sodium, or ammonium. If lower alkylamine or alkanolamine groups are u-tilized -the alkyls and alkanols will usually contain from 1 to 4 carbon atoms and the amines and alkanolamines may be mono- di- and tri-substituted, as in monoethanolamine, diisopropanolamine and -trimethylarnine.
A preferred polyethoxyla-ted alcohol sulfate detergent is available from Shell Chemical Company and is marketed as Neodol*25-3S.
The most highly preferred water-soluble anionic detergent compounds are the ammonium and subs-titu-ted ammonium (such as mono, di and tri-ethanolamine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such as, calcium and magnesi~m) salts of the higher alkyl benzene sulfonates, olefin sulfonates and higher alkyl sulfates.
Among the above-listed anionics, the most preferred are the sodium linear alkyl benzene sulfonates (LABS), and especially those wherein the alkyl group is a s-traight chain alkyl radical of 12 or 13 carbon atoms.
The nonionic synthetic organic detergents are *l'rade Mark /

sz 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 alkyl aromatic hydrophobic compound with ethylene cxide (hydrophillc in nature). Practically any hydrophobic com-pound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with -the polyhydration product there-of, polyethylene glycol, -to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.
The nonionic detergent employed is preferably a po]y-lower alkoxyla-ted higher alkanol wherein the alkanol is of 10 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 -to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 11 to 15 carbon a-toms and which contain from 5 to 9 lower alkoxy groups per mole. Preferably, -the lower alkoxy is ethoxy but in some instances it may be desireably mixed with propoxy,the latter, if present, usually being a minor (less than 50%) constituen-t. Exemplary of such compounds are those wherein the alkanol is of 12 -to 15 carbon atoms and which contain about 7 e-thylene oxide groups per mole, e.g., Neodol~ 25-7 and ~eodol 23-6~5, which produc-ts are made by Shell Chemical Company, Inc. The former is a con-densation product of a mixture of higher fa-tty alcohols averaging about 12 to 15 carbon atoms, with abou-t 7 moles ~Z~35;~

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 abou-t 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 ethoxyla-tes made by Union Carbide Corporation. The former is a mixed ethoxyla-tion product of an 11 to 15 carbon atom linear secondary alkanol with seven moles of ethylene oxide and -the latter is a similar produc-t but wi-th nine moles of ethylene oxide being reacted.
Also useful in -the present compositions are the higher molecular weigh-t nonionics, such as Neodol 45-11, which are similar 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 be-taines and sulfobetaines having the following formula are also useful:

R2 N .R4 X- O

wherein R is an alkyl group containiny from about 8 to 18 carbon atoms, R2 and R3 are each an alkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms, R4 is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms, and X is C or S:O. The alkyl group can contain one or more -13a-8~3S~

intermediate llnkages sueh as amido, ether, or polyether linkages or nonfunetional substituents sueh as hydroxyl or halogen whieh do not substantially aEfeet the hydrophobie eharaeter of the group. When X is C, -the detergent is ealled a betaine; and when X is S:O, the detergen-t is ealled a sulfobetaine or sultaine.
Cationie surfaee aetive agents may also be employed.
They eomprise surface active detergentcompoundswhichcontain an organic hydrophobic group which forms part of a cation where the compound is dissolved in water, and an anionic group. Typical cationic surface ac~ive agents are amine and quaternary ammonium eompounds.
Examples of suitable synthetic cationic detergents include: normal primary amines of the formula RN~2 wherein R is an alkyl group containing from abou-t 12 to 15 atoms;
diamines having the formula RNHC2H4NH2 wherein R is an alkyl group containing from about 12 to 22 carbon atoms, sueh as N-2-aminoethyl stearyl amine and N-2-aminoethyl myristyl amine; amide-linked amines such as those having the formula P~lCONHC2H4NH2 wherein Rl is an alky group con-tainlng about 8 to 20 carbon a-toms, sueh as N-2-amino ethyl-s-tearyl amide and N-amino ethylmyris-tyl amide; quaternary ammonium eompounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group eontaining about 8 to 22 earbon atoms and three of -the groups linked -to -the nitrogen atom are alkyl groups whieh eontain 1 to 3 carbon atoms, ineluding alkyl groups bearing iner-t substituents, sueh as phenyl groups, and there is present an anion sueh as halo-gen, acetate, methosulfate, ete. The alkyl group may eontain intermediate linkages such as amide which do no-t substantially 1 3 ~r h~
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affect the hydrophobic character of -the group, for example, stearyl amldo propyl qua-ternary ammonium chloride. Typical quaternary ammonium detergen-ts are ethyl-dimethyl-stearyl-ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trime-thyl-s-tearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl-lauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the correspondiny methosulEates and acetates.
Ampholytic detergents are also suitable for -the invention. Ampholy-tic detergents are well known in the art and many operable detergents of this class are disclosed by A. M. Schwartz, J. W. Perry and J. Birch in "Surface Active ~gents and Detergents", Interscience Publishers, New York, 1358, Vol. 2. Examples of suitable amphoteric de-texgents include: alkyl be-taiminodipropiona-tes, RN(C2H4-COOM)2; alkyl beta-amino propiona-tes, R~(H)C2H4COOM; and long chain imidazole derivatives having the general formula:

Il I
R-C JN~CH2CH2OCH2COO

wherein in each of the above formulae R is an acyclic hydro-phobic group containing from about 8 to 18 carbon atoms and M is a cation to neutralize the charge oE the anion. Spec-ific operable amphoteric detergents include the disodium salt of undecylcycloimidinium-ethoxyethionic acid-2-e-thionic acid, dodecyl beta alanine, and the inner salt o~ 2-trimethyl-amino lauric acid~

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8~3S2 lhe ~leaclling detergent composi~ions of the invention optionally contain a detergent builder of the type commonly used in ~etergent 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, silicates, carbonates, and the like. Organic builders include water-soluble phosphonates, poly-phosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycar-boxylates, succinates and the like.
Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates specifically include, for example, the sodium and potassium salts of ethane l-hydroxy-l,l-dlphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic ackl ~ Examp~es of thcsc and other phosphorous builder compounds are disclosed in U.S. Yatent Nos.
3,213,030; 3,422,021; 3,422,137 and 3,400,176. Pentasodium tripolyphos-phate and tetrasodium pyrophosphate are especially preferred water-soluble inorganic builders.
Specific examples of non-phosphorous inorganic builders include water-soluble inorganic carbonate, bicarbonate and silicate salts. The alkali metal, for example, sodium and potassium, carbonates, bicarbonates and silicates are particularly useful herein.
Water-soluble organic builders are also useful. For example, the alkali metal, ammonium and substi~uted ammonium polyacetates, carboxylates, poly-carboxylates and polyhydroxysulfonates are useful builders for the compo-sitions and processes of the invention. Specific examples of polyacetate and polycarboxylate builders include sodium, potassium, llthium, ammonium and substituted ammonium salts of ethylenc diaminetetracctic acid, nitriloLri-acetic acid, benzene polycarboxylic (i.e. penta- and tetra-) acids, carboxy-methoxysuccinic acid and citric acid.

~iLZ~8~2 Water-insoluble builders may also be used, particularly, the complex silicatcs an~ more particularly, the comylcx sodium alumino silicates such as, ~eolites, e.g., zeolite ~A, a type of ~eolite molecule wherein the univalent cation is sodium and the pore si~e is about ~ ~ngstroms.
The ~eparation of such type ~eolite is described in U.S. Patent 3,11~,603 The zeolites may be amorphous or crystalline and have water of hydration as known in the art.
The use of an inert, water-soluble filler salt is desirable in the laundering compositions of the invention. A preferred filler salt is an alkali metal sulfate, such as, potassium or sodium~suIfate,:the latt~r-being especially preferred.
Various adjuvants may be included in the bleaching detergent compo-sitions of the invention. In general, these include perfumes; coloran~s, e.g., pigments and dyes; antiredeposition agents, such as, alkali metal salts of carboxymethylcellulose; optical brighteners, such as, anionic, cationic or nonionic brighteners; foam stabili~ers, such as alkanolamides, and the like, all of which are well-known in the fabric washing art for use in detergent compositionsO Flow promoting a~ents, commonly referred to as flow aids, may also be employed to maintain the particulate bleaching detergent compositions as free-flowing beads or powder. Starch derivatives and special clays are commercially available as additives which enhance the flowability of otherwise tacky or pasty particulate compositions, two of such clay additives being presently marketed under the tradenames "Satinton~"
and "Microsil".
The bleaching detergent compositions of the invention are particulate compositions which may be produced by spray-drying methods of manufacture as well as by methods of dry-blending or agglomeration of the indivi(lual commponents. The compositions are preferably prepared by spray drying an aqueous slurry of the non-heat-sensitive components including the bromide salt to Lorm spray-dried particles, fol:lowed by admixin~ such par~icles ith the heat-lsensitive components, such as th~ MPPA bleaclling agent and -IS-~ZQ~S~

the aromatic sulfonamide compound if not sufficiently stable (usually, if there is a greater than 20% decomposition loss), and adjuvan-ts such as perfume and enzymes, mixiny is conveniently effected in apparatus such as a rotary drum. If desired, the MPPA bleaching agent and/or -the bromide salt can be encapsulated or otherwise stabilized to prevent premature reac-tions. Sui-table coating materials include compounds such as magnesium sulfate, ~olyvinyl alcohol and lauric acid or i-ts salts.
A par-ticularly preferred bleaching detergent composition in accordance with the invention comprises: (a) from about 5 to 50~, by weight, of a bleaching composition consisting essentially of (i) monoperoxyphthalic acid and/or a water-soluble salt thereof; (ii) a wa-ter-soluble inorganic bromide salt; and (iii) an aromatic sulfonamide compound selected from the group consisting of benzene sulfonamide, toluene sulfonamide, ethylbenzene sulfonamide, dodecylbenzene sulfonamide, xylene sulfonamide, N-alkali metal salts of said sulfonamides and mixtures thereof, wherein the weight ratio of (i) to (ii) is from about 8:1 to about 1:2, and the ratio of (iii) to (ii) is from about 2:1 to about 1:~; (b) from about 5 to about 30%, by weight of a detergent surface active agent selected from the group consisting of anionic and nonionic detergen-ts and mixtures -thereof; (c) from about 10 to about 60%, by weigh-t, of a detergent builder salt; and (d) -the balance comprising water, and op-tionally a filler salt.

; ~ -l6 Test ~roccdure Bleaching tests were carried out on standard staincd tcst swatches (described below) using the various bleaching and laundering composition described in table 1 of this Example in a Tergotometer vessel manufactured by the U.S. Testing Company. The tergotometer was maintained at a con-stant temperature of 120F and operated at 100 rpm.
Each of the test compositions described in Table 1 below was added to one Liter of tap water at 120F having a water hardness of about 100 ppm, as calcium carbonate. The test compositions were agitated for about one minute and then a mixed fabric load consisting of two swatches each (3" x ~") of the stained fabrics described below was added to each wash receptacle. After a 15 minute wash at 120F, the test fabrics were rinsed in 100F tap water and then dried. The percent stain removal was measured by taking a reflectance reading for each stained test swatch prior to and after the washing using a Gardner Color Difference Meter, and the percent stain removal (% S.R.) was calculated as follows:

(Rd after washing) - (Rd before washing) % S~Ro ~ x 100 (Rd before staining) - (~d beLore waslling) wherein "Rd before washing" represents the Rd value after staining.
The value of percent stain removal calculEIted for all five cloths were averaged for each test laundering composition. A difference greater than 2% in the average of the five stained cloths tested is considered significant.
At the cnd of cach wash, the activc oxygen contcnt of LhC wash solu~
tion was determined by acidification with dilu~e sulfuric acid followed by treatment of the wash solution with potassium iodide and a minor ammount of ammonium molybdate, and thereafter titration with starl(l3rd:ized sodium thiosuLfate ~nciing starch as the indicator.

-l7 5~' rhe respective stains and test swatches were as follows:

St Test C1~h 1. Grape - 65 Dacron - 35 Cotton

2. Blueberry - Co~ton

3. Sulfo Dye - EMPA 115 (Cotton)

4. Red Wine - EMPA 114 (Cotton)

5. Coffee/Tea - Cotton Stained test cloths 1 and 2 are prepared by passing rolls of unsoiled fabric through a padding and drying apparatus (manu~actured by Ben~ of Zurich, Switzerland) containing either grape or blueberry solutions at 90F. After drying at 250F, the fabric is cut into 3" x 4" swatches.
Eighty of these swatches, impregnated with the same stain, are rinsed in 17 gallons of 85F water in an automatic home washer. They are then dried by a passage through a E3eseler Print Dryer at a machine tèmperature se~ting of 6 and a speed of 10.
Stained Eal)rics 3 and 4 a~e purcllased from Testrabric~q Tncorl)ornLe(l of Middlesex, ~ew Jersey, and cut into 3" x 4" swatches.
Stained fabric 5 is prepared by agitating and .soaking unsoiled cotton strips (18" x 36") in a washing machine filled with a solution of coffee/tea (8~1 weight ratio) at 150F. The machine is allowed to rinse-spin dry to remove the coffee/tea solution. The stained fabric is then machine washed twice with hot pyrophosphate~surfactant solution followed by two complete water wash cycles at 140F. The strips are then dried by two passes through an Ironrite machine set at 10 and then cut into 3" x 4" swatches.
A granular detergent composition (designated herein as "HDD") was prepared by con~entional spray-drying and had the following approximate composition:

~3 Composition Weight Percent Sodi.um tridecylbenzenesulfonate 15 Ethoxylated C12 - C15 primary alcohol (7 moles EO/mole alcohol) Sodium tripolyphosphate 33 Sodium carbonate 5 Sodium silicate 7 Sodium carboxymethylcellulose 0.5 Optical brighteners 0.2 Perfume 0.2 Water 11 Sodium sulfate balance Detergent compositions A-G containing HDD were formulated as set forth below in Table 1. The pH of the compositions in aqueous solution varied from 9.2 to 9.7.

Table l Component Composition A B C D ~ F G
Detergent, E~DD 4.50g 4.50g 4.50g4.50g 4.50g 4.50g 4.50g Mg salt of MPPA( ) 0.49 0.490.49 0.40 0.40 0.40 NaBr - 0.07 0.07 0 07 0 07 0 07 TsA(2) _ 0.03 0.02 0.03 (l) A bleaching composition containing as active ingredient about 65 wt.% magnesium monoperoxyphthalate and having a~ active oxygen content of 5.1%.
(2) Para-toluenesulfonamide.

~2~8~5~2 Compositions A through G were tested in accordance with the procedure described above and the results of the bleaching tests are tabula-ted in Table 2 which sets for-th the stain removal achieved with compositions A -through G
for each of the 5 stains.
Table 2 Compara-tive Bleaching :Performance (%S. R.) Composition Stain A B C D E F G-Grape 63% 65%75% 37% 62% 67% 68%
Blueberry 63 64 68 41 62 65 67 Sulfo Dye 4 5 7 3 3 5 6 Red Wine47 46 56 33 44 48 48 Coffee/Tea 32 41 61 5 32 51 52 Avg. (%)42 44 53 24 41 47 48 The results of Table 2 demonstrate the markedly improved bleachingperformance achieved with composi-tions containing the ~PPA bleach in combination with sodium bromide and TSA relative to compositions containing the MPPA bleach alone (in the absence of bromide and TSA) or MPPA and sodium bromide. Thus, compositions C, F and G
in accordance with the invention provided an improvement in the average percen-t S. R. of from 6 to 9% (depending on the particular composition) relative to corresponding compositions B and E, both of which contain MPPA bleach and sodium bromide in combination, but no TSA. A compari-son of composition C in accordance with -the invention and composition A which contains MPPA alone (in -the absence of bromide and TSA) shows an improvement in the average percent S. R. of 11% (53% vs. 42%) relative to the bleachi:ng achieved w.ith a compos:ition of the prior art.

-20~
f ",1 , ~2~ 3S2 The bleaching tests described in Example 1 were ca~ried out witll dc~cr-gent compositions H-K described in Table 3 below. The stained test cloths employed were substantially similar to those described in l.xample 1.
Detergent compositions H-K were formulated as set forth below in Table 3, the composition of ~he detergent (HDL)) being described in Example 1. The pH of the compasitions in aqueous solution varied from 8.2 to 8.6.

Component ComposiLion H I J
Detergent, HDD 1.50g 1.50g l.SOg 1.50g Mg salt of MPPA(l) 0~26 0.26 0.26 0.26 NaBr -- -- 0.10 0.10 TSA(2) 0.08 -- 0.08 (1) A bleaching c:amposition containing as active ingredient about 65 wt. %
magnesium monoperoxyphthalate and having an activc oxygen contcnl of 5.1~.

(~) Pur;~-Lolllcncsu.lrollalllidc ~2~B~3S2 Composi-tions H through K were -tested in accordance with the procedure of Example 1 and -the results of -the bleaching tes-ts are summarized in Table 4 which sets forth the percent stain removal achieved with compositions H-K
for each of the 5 stains.
Table 4 Comparative Bleaching Performance (% S. R.) Stain H I J K_ Grape 75% 76~ 82% 85%
Blueberry 70 67 75 80 Sulfo Dye 4 3 9 8 Red Wine 37 36 35 46 Coffee/Tea 78 74 86 87 Avg. (%) 53 51 57 61 The data of Table 4 demonstrates the synergy achieved with composition K, a composition of the invention, rela-tive to compositions H, I and J each of which contain MPPA alone or in combination with either NaBr or TSA. Thus, the average percent S. R. achieved with compositions H and I
were substantially similar (53 and 51%), the presence of TSA
being shown to have a slightly negative effect on -the bleach-ing activity oE MPPA. Composition J containing MPPA in combination with bromide provided an expected improvemen-t in bleaching activ:ity, an average S. R. of 57%. The addition of TSA to a composition containing MPPA and bromide (compos~
ikion K) provided an apparent s~nerges-tic effect insofar as it provided a marked increase in the bleaching ac-tivity, namely, an average S. R. of 61%

/
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Claims (19)

WHAT IS CLAIMED IS:

1. A bleaching and laundering composition comprising:
(a) monoperoxyphthalic acid and/or a water-soluble salt thereof;
(b) a water-soluble inorganic bromide salt; and (c) an aromatic sulfonamide compound selected from the group consisting of benzene sulfonamide, toluene sulfonamide, ethylbenzene sulfon-amide, dodecylbenzene sulfonamide, xylene sulfonamide, N-alkali metal salts of said sulfonamides, N-acetyl and N-benzoyl derivatives of the aforesaid sulfonamides and salts, and mixtures thereof.

2. A composition in accordance with claim 1 wherein the aromatic sulfonamide compound is toluenesulfonamide or an N-alkali metal salt thereof and the bromide salt is an alkali metal bromide.

3. A composition in accordance with claim 1 wherein the aromatic sulfonamide compound is para-toluenesulfonamide.

4. A composition in accordance with claim 1 which contains magnesium mono-peroxyphthalate.

5. A composition in accordance with claim 1 wherein the weight ratio of (a) to (b) is from about 10:1 to about 1:5, and the weight ratio of (c) to (b) is from about 5:1 to about 1:7.

6. A composition in accordance with claim 1 which additionally contains one or more detergent surface active agents selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.

7. A bleaching detergent composition comprising:
(a) from about 5 to 50%, by weight, of a bleaching agent comprising:
(i) monoperoxyphthalic acid and/or a water-soluble salt thereof;

(ii) a water-soluble inorganic bromide salt; and (iii) an aromatic sulfonamide compound selected from the group consisting of benzene sulfonamide, toluene sulfonamide, ethylbenzene sulfonamide, dodecyl-benzene sulfonamide, xylene sulfonamide, N-alkali metal salts of said sulfonamides, N-acetyl and N-benzoyl derivatives of the aforesaid sulfonamides and salts, and mixtures thereof;
(b) from about 5 to 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 5 to 80%, by weight, of a detergent builder salt; and (d) the balance comprising water and optionally a filler salt.

8. A composition in accordance with claim 7 wherein the weight ratio of (i) to (ii) is from about 10:1 to about 1:5, and the weight ratio of (iii) to (ii) is from about 5:1 to about 1:7.

9. A composition in accordance with claim 7 wherein the bleaching agent contains magnesium monoperoxyphthalate, the aromatic sulfonamide compound is toluenesulfonamide or an N-alkali metal salt thereof and the bromide salt is an alkali metal bromide.

10. A composition in accordance with claim 7 wherein the detergent surfactant is selected from the group consisting of anionic and nonionic detergents and mixtures thereof.

11. A composition in accordance with claim 7 wherein the aromatic sulfonamide compound is para-toluenesulfonamide.

12. A composition in accordance with claim 7 which comprises from about 5 to 30%, by weight, of said detergent surface active agent and from about 10 to 60%, by weight, of said builder salt.

13. A process for bleaching which comprises contacting the stained and/or soiled material to be bleached with an aqueous solution of a composition comprising:
(a) monoperoxyphthalic acid and/or a water-soluble salt thereof;
(b) a water-soluble inorganic bromide salt; and (c) an aromatic sulfonamide compound selected from the group consisting of benzene sulfonamide, toluene sulfonamide, ethylbenzene sulfonamide, dodecylbenzene sulfonamide, xylenesulfonamide, N-alkali metal salts of said sulfonamides, N-acetyl and N-benzoyl derivatives of the aforesaid sulfonamides and salts, and mixtures thereof, the weight ratio of (a) to (b) being from about 10:1 to about 1:5, and the weight ratio of (c) to (b) being from about 5:1 to about 1:7.

14. A process in accordance with claim 13 wherein said composition additionally contains one or more deter-gent surface active agents selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic detergents.

15. A process in accordance with claim 14 wherein said composition comprises from about 5 to 50%, by weight, of components (a), (b) and (c), collectively; from about 5 to 50%, by weight, of said detergent surface active agent, and said composition additionally contains a builder salt in an amount of from about 5 to 80%, by weight, the balance of the composition comprising water and optionally a filler salt.

16. A process in accordance with claim 13 wherein said aromatic sulfonamide compound is toluenesulfonamide or an N-alkali metal salt thereof.

17. A process in accordance with claim 13 wherein said compositions contains magnesium monoperoxyphthalate.

18. A process in accordance with claim 13 wherein said bromide salt is an alkali metal bromide.

19. A process in accordance with claim 13 wherein the weight ratio of (a) to (b) is from about 8:1 to about 1:2, and the weight ratio of (c) to (b) is from about 2:1 to about 1:4.