US3749673A - Bleach-fabric softener compositions - Google Patents

Abstract

CONCENTRATED, DRY BLEACH AND FABRIC-SOFTENING COMPOSITIONS CONTAINING A PEROXYGEN BLEACHING AGENT, A QUATERNARY AMMONIUM COMPOUND, A BUFFERING AGENT AND IONIZABLE CHLORINE. SUCH COMPOSITIONS WHEN DISSOLVED IN WATER PROVIDE FAST-ACTING CATALYZED BLEACHING AND SOFTENING OF TEXTILES AT ALL PRATICAL SOLUTION TEMPERATURES WITHOUT THE COLOR AND FABRIC DAMAGE USUALLY ASSOCIATED WITH HARSH HYPOCHLORITE BLEACHES.

Description

2:11UE5-0l on July 31, 1973 J. P. JONES ETAL 3,749,673

BLEACH-FABRIC SOF'IENER COMPOSITIONS Filed Feb. 22. 1971 EFFECT OF TIME AND TEMPERATURE ON BLEACHING 9 I20 OFHHO) 80F. (#II) II b I20 F(#l3) 80F. (#13) 3 l l I l l Time (min.)

INVENTORS John Paul Jones Charles H. Nicol MW A TURNEY Int. Cl. Clld 7/54 U.S. Cl. 252-95 8 Claims ABSTRACT OF THE DISCLOSURE Concentrated, dry bleach and fabric-softening compositions containing a peroxygen bleaching agent, a quaternary ammonium compound, a buffering agent and ionizable chlorine. Such compositions when dissolved in water provide fast-acting catalyzed bleaching and softening of textiles at all practical solution temperatures without the color and fabric damage usually associated with harsh hypochlorite bleaches.

BACKGRQQND @F INVEN IQN Field o th nven ion Thi inven ion re ates is d y hs ash conincsitiens liarii b "s fishin an on solarilaiiiess hlsashiiig sha a is 'ish s when shin l in aqueous sols sh resinous may lso he used fornd for r stor n natura lo, a ti i ial hair c lqr na As ii. ed, these A it c in the m Bi 2 ca flied PWdUQi Wlllll aii he added to Weir-i o actua l, at both high and low bleaching t mp atu es Th in en ion employs ii combination o a Peron/gen achin compound; quaternary ammonium salt a micelle catalyst and fabric softenerf a buffering COIIPDI l'ld to maintain the bleaching solution at a proper p p izable chlorine to provide a type of halogen bleach referred m od me s emp y n a kal m t l or al s earth met l hloride salt to provide t e a p r on e the ionlzable chlorine. Additional preferred embodiments mp oy a 'll l whi h w ll provide t ansi ion metal n h s ca aly i in mind While a ing micelle catalyst for the inc-aching 11?. action, the qua erna ry ammonium retain their fabric softening capabilitie" and can also provide a. source of: necessary chloride ion 1 h non quai rnm'y chl r de QlIl pounds leg. alkali metal or alkaline earth metal f lllon ides) on t be employed in the pr '11? compositions to provide chloride ions if the quad nonium com: pound does not movide these ion in s 7 nt concentrav iion. Inclusion :l the ll an" dry compos ons of a source of transition metal ions is not. tial to the invention but enhanced bleacl'ling performance is obtained it such source cornponruj is; employed,

pounds are effective stain-removing b r ilil lfifi when 1 4 hi I vely high conccntratio chl 1 Q1 a in chlorine bicacl'ies o ruse rather severe damage to fabric colors and can in addition damage textile fibr ls with repeated use. Liquid bleachesof this type also pre- 3,749,673 Patented July 31, 1973 sent handling and packaging problems. While color and fabric damage may be minimized by employing milder oxygen bleaches such as potassium monopersulfate, soil and stain removal characteristics of these oxygen bleaches are much less desirable than those of the halogen bleachlng agents.

Likewise, several types of fabric softeners are presently available for home use, but all must be added separately to the fabric rinse solution since they are chemically incompatible with many laundering products.

Many of the above-described shortcomings of prior art compos tions are overcome by a chlorine-free bleaching composition described in the concurrently filed application of John Paul Jones and Charles H. Nicol entitled Bleach Compositions, Ser. No. 117,814, filed Feb. 22, 197 l. It is an object of the present invention to provide an improved concentrated chlorine-containing bleaching composition which can be safely applied to colored as Well White fabrics= It is a further shiest of this inven: h m is provide eornsatihle hlseshiah'ric softener co hinatios which is m d in the form oi s ls shit i ls i it is further onset of the i mvenon is provide 2 catalyzed hlashiah q when which has he 'l sd at low so he was alien and wh' h is eiieciive a law tsiiies hires and. after short is M Whi e b each and fab. taiiiing cs sin o the abm :1. mm. s v been disclosed in the prior art it h .i now bee ihiithy combining ssriaintypssofca .l hated bleaching agents, a so ed aching a taboo softening p oduct can be created whish accomp ishes he above oh silvers and which i uneiipestedly SUP TlQTiQ that attainable using the scmpositions of the prior art SUMMAR OF HE VEN IQN D S Q l fi fil d, h aqh fabric Softener compositions and me hods for u ing said compo tion ar provide e compo iti ns c nsi s n ially of:

(a) about 8% to 60% by eight of a. peroxy bleaching agent selec ed from th group onsis fi o sodium r potassium monopei' ulfate; organ p nny a ids in wa el s luh e s ts th eof) of the e eral f rm l QIJQHT- 10% to 60% of a qu ifimnry ammonium com pound of th g neral form la wherein R is an alkyl group containing from about 12 to 20 carbon atoms, R is selected from the group consistingof alkyl groups containing about 1 to 14 carbon atoms, cycloalltyl groups containing about to 8 carbon atoms, carboxymethyl groups, aryl groups 5 containing from 6 to 8 carbon atoms, alkaryl groups containing from 7 to carbon atoms, pyridyl and groups of the general formula -(C H O),,(C H,O) H wherein a and b are integers and a+b is 1 to 50; R R and R are each selected from the group consisting of alkyl groups containing about 1 to 3 carbon atoms, cycloalkyl groups containing about 5 to 8 carbon atoms, carboxymethyl groups, aryl groups containing from 6 to 8 carbon atoms, alkaryl groups containing from about 7 to 10 carbon atoms, pyridyl, and groups of the general formula (C H O) (C H O) H wherein a and b are integers and a+b is 1 to 50; R is a group within the definition of the R R and R groups or H; R; is an alkylene group containing from 1 to 3 carbon atoms, an arylene group containing from 5 to 8 carbon atoms or a group having the formula said compositions containing from about 5 to about 100 grams of ionizable chlorine per kilogram of the total composition. The compositions can contain from about 1% to 15% by weight of an alkali metal or alkaline earth metal chloride to provide all or part of the ionizable chlorine. Alternatively, all of the ionizable chlorine can be provided by the quaternary ammonium compound as hereinafter detailed. A preferred embodiment of the invention contains, in addition to the above components, from about 0.08% to about 8% by weight of a watersoluble salt of a transition metal element.

The compositions are dissolved in water to provide fabric softening and catalyzed bleaching of both colored and white fabrics. Such aqueous solutions may also be used as hard surface or denture cleaners and as agents for restoring natural color to artificially colored hair.

BRIEF DESCRIPTION OF THE DRAWING The drawing provides a graphical representation of the elfect of time and temperature upon the bleaching activity of the compositions of the instant invention relative to the prior art. The horizontal axis represents time in minutes. The vertical axis represents AW, a measure of stain removal performancedescribed in column 9, lines 73-75, hereof. Each curve represents a particular bleaching composition of Table I (col. 9) identified by number and utilized at the indicated temperature.

DETAILED DESCRIPTION OF THE INVENTION At this juncture the theoretical nature ofthe present catalyzed bleaching system and the individual components of the compositions will be described in detail.

(A) Catalysis of bleaching reactions Although the scope of the present invention is not limited by any particular theory, the monopersulfate bleaches of this invention are believed to ionize in the bleaching solution according to the equation KHSO =K++HSO The HSO further dissociates in solution as follows:

'HSO 1 *H++SO It has been discovered that the etfectivenessho f-rthe per-- sulfate-bleaching is dependent on the formatio insolm tion of a bi-anionic transition state complex having the formula Such a complex is formed from the SO and H80 anions present in the bleaching solution.

The organic monoand diperoxyacid bleaches of the instant compositions, representative compounds having the general formulas,

wherein R is an alkylene or arylene group, likewise form bianionic dimers during the bleaching process. As with the monopersulfates, such complexes are formed from the combination of (l) the above compounds which have lost one proton upon dissolution and/or (2) the above compounds which have lost both protons. Thus, these bianionic complexes, for example, can have the general formulas,

or if the above two representative compounds are mixed,

O 0 O O a. [-o-o-dR- ioo Ho oii-R Ji0-] wherein R is again an alkylene or arylene group.

It has been discovered that formation of these various complexes from two negatively charged ions can be facilitated by the addition to the solution of positively charged micelles and/ or transition metal ions.

A micelle' is a highly charged colloidal aggregate. It is believed that such positively charged aggregates, as well as positive transition metal ions, serve as rallying points for the S0 and HSO anions and their organic peroxyacid counterparts, thereby facilitating formation of the indispensible transition complex of the bleaching reaction. Quaternary ammonium salts are employed in order to form the necessary miceslles in solution. In addition, bleaching catalysis may be enhanced by addition of a transition metal salt such as copper sulfate, to provide more complex-creating cations in solution.

Bleaching activity is enhanced even further by virtu-re of chloride ions in bleaching solutions. Consequently, dry compositions of the present invention must contain enough of a water-soluble chloride compound or mixtures thereof to provide from about 5 to about grams of ionizable chlorine per kilogram of dry composition. Ionizable chloride is that portion of any compound of the present invention which when dissolved contributes chloride ions to the aqueous solutions. Ionizable chlorine is, of course, provided by chloridesalts. The necessary ionizable chlorine content of the instant composition can be provided in the form of the quaternary ammonium chloride, an added alkali metal or alkaline earth metal chloride and/or by the transition metal chlorides. It is known that these chloride salts in solution with certain oxygen bleaches do not yield chloride ions but rather, in combination with such oxygen bleaches, provide enhanced bleaching of a hypochlorite type. It has been discovered, however, that addition of chloride ions to a micelle-catalyze'd oxygen bleaching system yields an active chlorine species in solution to provide mixed oxygenchlorine bleaching even more effective than the known hypdchloriteforming peroxygen/chloride salt combination..-, Furthermore,-= this etfective bleaching is acco solution than, prior art hypochlorite-forming combinations.

It is believed that the effective micelle catalysis of the bleaching reaction is responsible for the very favorable color damage characteristics of the instant compositions. Although some hypochlorite is formed in solution from the compositions of the instant invention, it is formed over an extended period of time and at a lower concentration than the directly added hypochlorite of the prior art. Performance loss due to this indirect method of hypochlorite bleaching is more than adequately compensated for by the effectiveness of the rnicelle-cattalyzed oxygen bleaching. Overall bleaching performance thus compares favorably with harsh concentrated hypochlorite with little hypochlorite-type color damage occurring.

It should be noted that the compositions of the instant invention should contain no more bromide than would be present if the optional transition metal salt is a bromide. This is so since large amounts of bromide ions in solution with some peroxygen bleaches can cause severe color damage to fabrics. Consequently, the quaternary ammonium compound (which can be present in a relatively high concentration in the composition) cannot be a bromide salt, i.e. bromide is an interfering anion.

(B) Individual components (1) Bleaching agents.The principal bleaching active-s in the instant compositions are sodium or potassium monopersulfate (NaHSO and KHSO and the organic monoand diperoxyacids (or water-soluble salts thereof) having respectively the following formulas:

O MONOPEROXY ACID HO C-RYH and O O DIPEROXY ACID wherein R can be alkylene or arylene and Y can be any group which yields an anionic moiety in solution such as Potassium monopersulfate is available commercially from E; I. du Pont de Nemours and Company under the trade name Oxone. It contains aproximately 42.8% by weight KHSO the balance being KHSO and K 80 in about equal proportions.

The organic peroxyacids or salts thereof of the invention, as noted above, can contain either one or two peroxy groups and can be either aliphatic or aromatic. When the organic peroxyacid is aliphatic, the unsubstituted acid has the general formula where Y, for example, can be and n can be an integer from 1 to 12 with perazelaic acids (n=7) being the prefer-red compounds. The alkylene linkage between the anionic groups can contain halogen or othe non-interfering groups.

When the organic peroxyacid is aromatic, the unsubstituted acid has the general formula Where Y is for example. The

and YH groupings can be in any relative position around the aromatic ring. The ring can contain any noninterfering substituent such as halogen groups. Examples of suitable aromatic peroxy acids include monoperoxyphthalic acid, dip-eroxyterephthalic acid, 4-chlorodiperoxyphthalic acid and the monosodium salt of diperoxyterephthalic acid. The preferred aromatic peroxyacids are the monoand diperoxyisophthalic acids.

The bleaching compositions can contain from about 8% to about 60% by weight of the bleaching agent. The preferred monopersulfate weight range is from about 25% to about 30% by weight. A preferred organic peroxyacid weight range is from about 16% to about 35% by weight. Mixtures of the monpersulfate compounds and the peroxyacids can be employed in the instant invention. These bleaching compositions are, of course, dissolved in aqueous solutions for actual use on fabrics, sinks, dentures or hair. Dependin upon the bleaching strength desired and the intended use, the bleaching composition is added in quantities suflicient to yield from about 5 to ppm. available oxygen in solution from either the persulfate or organic peroxyacid bleach actives. The above bleaching actives when employed in the catalyzed compositions of the present invention provide effective bleaching at all practical bleaching solution temperatures and bleach effectively after a. very short contact time with the material to be bleached. As noted, color and fabric damage is minimal.

(2) Quaternary ammonium compounds-Quaternary ammonium compounds useful herein have the general formulas and Ilia lla Rr-III-Ih-III-Rg R: R5

[ -his wherein R is an alkyl group containing from about 12 to 20 carbon atoms, R is an alkyl group of about 1 to 14 carbon atoms, a cycloalkyl group of about 5 to 8 carbon atoms, a carboxymethyl group, a 6 to 8 carbon aryl group, an alkaryl group of 7 to 10 carbon atoms, a pyridyl group, or a group of the general formula either a 1 to 3 carbon atom alkylene group, a 5 to 8 carbon arylene group or a group of the formula X is any non-interfering anion such as chloride, nitrate, fluoride, sulfate, methylsulfate, carbonate, hydrogen phosphate, dihydrogen phosphate, chlorate or hydroxide; and n is 1 when X is monovalent and n is 2 when X is divalent. Examples of quaternary ammonium compounds employable in the compositions include tetradecyltrimethylammonium chloride; tetradecyltrimethylammonium methylsulfate; tetradecyltrimethylammonium nitrate; cetyltrimethylammonium hydrogen phosphate;

[C16H35N 3 a 1 2 4;

cetyltrirnethylammonium nitrate; octadecyltrimethylammonium chloride; octadecyltrimethylammonium chlorate; octadecyltrimethylammonium nitrate; eicosyltrimethylammonium chloride; eicosyltrimethylammonium hydroxide; eicosyltrimethylammonium nitrate;

[C20H39N(CH3)3[2HP04, the ethylbenzyl ammonium chlorides of Petrocci et al., US. Pat. 3,525,793, Aug. 25, 1970; Armour Industrial Chemical Companys Ethoquad and Propoquad and singly or doubly quaternized compounds derived from Wyandotte Chemical Corporations Tetronic compounds. Preferred quaternary ammonium compounds are the C C and C alkyltrimethylammonium chlorides. Depending upon the particular quaternary ammonium compound employed, the compositions contain from about 10% to about 60% by weight of the quaternary ammonium component.

The quaternary ammonium constituent serves two purposes in the instant compositions. These surface active compounds form the micelles for catalysis of the peroxygen bleaching, and in addition they impart fabric softening characteristics to the bleaching solutions. In solutions prepared from the compositions of this invention the quaternary ammonium salt concentration should range from about 100 p.p.m. to about 500 p.p.m.

It is well-known that quaternary ammonium compounds of the type herein employed function as fabric softeners. They have heretofore been utilized alone in laundry rinse water since they are incompatible with anionic detergents. It has been discovered, however, that these compounds are compatible with the bianionic, complex-forming bleach agents of the present invention and, in fact, act as micelle catalysts while retaining their fabric softening properties.

It has been found that the shorter chain quaternary ammonium salts (C provide slightly better micelle catalysis while the longer chain salts C1840 are better fabric softeners. Conseqeuntly, a mixture of long and short chain quaternary ammonium compounds is preferred for use in the instant compositions. Thus a preferred embodiment of the invention is a dry composition which contains about 2% to about 30% by weight of a carbon chain quaternary ammonium salt and about 8% to 30% by weight of 14, 16 or 18 carbon chain quaternary ammonium salts. In aqueous solution prepared from this preferred composition there should be from about 20 p.p.m. to about 80 p.p.m. of the C1840 quaternary ammonium salt to provide softening capability. As discussed more fully below, the quaternary ammonium compound, if a chloride salt, can contribute to the total required ionizable chlorine content of the composition.

(3) Buffering agent.-It has been discovered that micelle catalysis and formation of the bianionic complexes discussed above are greatly facilitated by maintenance of the bleaching solution at a carefully controlled pH. The pH of the solution at which the concentration of the SO and HSO]- anions are equal (the pK/,) occurs at apH of 9.2 The pK/ ofth'eorganic peroxyacid'systemf from'a' pH of 7 to Consequentlythe best bleaching performance occurs when the pH of the bleaching solution is maintained between about 7 and about 10. Outside this pH range, bleaching performance diminishes markedly.

To maintain this controlled pH in solution, any noninterfering compound which can alter and maintain pH such as any standard buffering agent or combination is employed. For example, phosphates, carbonates or bicarbonates which buffer within the 7-10 pH range are useful. Examples of suitable buffering agents include sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate and sodium dihydrogen phosphate. Sodium carbonate is the preferred buffering agent for monopersulfate systems. Disodium hydrogen phosphate and sodium dihydrogen phosphate are preferred for peroxy acid systems. Other buffering compositions for any desired pH can be obtained by the skilled artisan from any standard chemistry handbook or textbook. Buffering agents comprise from about 10% to about 75% by weight of the compositions.

(4) Alkali metal or alkaline earth metal chl0ride. Addition of a compound of this type to the concentrated bleaching composition of this invention is optional if the quaternary ammonium compound is a chloride and is present in the dry compositions in sufiicient amount to provide the necessary 5 to grams of ionizable chlorine per kilogram of the total composition. If, however, the quaternary ammonium compound is not a chloride or is not present in an amount sufiicient to provide the proper ionizable chlorine content, this alkali metal or alkaline earth metal chloride is a necessary component. Suitable chlorides include, for example, NaCl, KCl, C-aCl and Mgclg.

When the alkali metal or alkaline earth metal chloride is employed, it should comprise from about 1% to 15% by weight of the total composition. In general, preferred embodiments of the present invention employ enough chloride compound of any type so that in solution the chloride ion, (although as noted above, the chloride ion as such probably does not exist in the bleaching solution) is present from whatever source in a theoretical p.p.m. amount equal to the p.p.m. of available oxygen (av. 0 from the oxygen bleaching actives. A more specific preferred embodiment of the present invention would employ a quaternary ammonium chloride of the type defined above in an amount of from about 15 to about 25% by weight with an alkali metal or alkaline earth metal chloride compound being present in a concentration of from about 2% to about 10% by weight.

(5) Transistion metal salt.Improved bleaching can also be obtained by the optional addition to the compositions of a source of transition metal ions. Any soluble salts which yield such ions in bleaching solution are useful in this invention. Such ions are believed to further catalyze the formation of the active peroxy compound and chlorine species to provide synergistic bleaching enhancement.

Transition metal salts which can be used in the instant compositions include copper sulfate, copper chloride, cobalt chloride, manganese bromide, nickel nitrate, copper nitrate, chromium chloride, manganese nitrate and chromium bromide. It should be noted that if chloride transition metal salts are employed, they also can contribute to the necessaary ionizable chlorine content of the compositions.

Such transition metal salts can be employed in the present compositions in a concentration range of from about 0.08% to about 8% by weight. The salts are preferably present in an amount efifective to provide a transition metal ion concentration in bleaching solution of from about 5 10- M to about 3 10 M.

(6) Other additives.0ther optional additives such as builders, perfumes, coloring agents, fillers, etc., .can be added to the dry bleaching and softening compositions.

These additional components, however, must not interfere with the essential chemical or physical functioning of the compositions as catalyzed bleaches and fabric softeners.

The above-described components of the bleaching compositions of this invention are all available in dry form.

10 (grass, tea, wine, gravy and Empa-Sulfur Black). A AW difference of 2 is readily apparent to the human eye.

PREPARATION OF STAINED SWATCHES Formulation, therefore, of dry compositions s Simply The swatches used in the development of these tests accompllshed y thoroughly {mxmg the gr anu1ar or are obtained from several sources. The respective swatches powdered components together in the appropriate weight and their Sources (commercial or method of prepara percentage concentrations. It would be possible to tion) are outlinedin the following Summary provide a bleaching solution containing the components of this present invention by adding such components to the Grass stain bleaching solution in liquid form. Besides creating handling and packaging problems, however, concentrated liquid gg gfi j g i i wlth i g ofdthis type ariirelatively unstable and tend until a uniforri slirr y i s pi' t lii il iiiis slu3 5 i: s iiz i ri d to rapi y egra e upon stan ing.

of cata ze ox en-c orine a ents erein, textl e er damayge is cogiarable to pergborate washing agents In suctilessve times. The cloth is aged three days and stored addition, the bleaching solution resulting from the commt e positions of the present invention do not cause running Tea of textile colors or undesirable color transfer. The fastacting low temperature bleaching activity of the dissolved gli gi zi g xgg s igigg fg zfi gg g g f compositions makes the present invention especially suited The solution is filtered through cotton cloth and H for use in fabric rinse water after normal textile laundering. made up to 11/2 gallon with hot Water Two S are ds The following tests serve to illustrate the bleaching, of cotton are immersed into the tea socllutionyThe Softening and other performance Properties of the temperature is raised to boil and maintained for two positions of the instant invention. Table I provides 16 hours The cloth is lifted out of the liquor and trans concentrated bleaching compositions by component weight f d to about 3 gallons of 5 grjgal. water (pH=9.5) percentages composlilons 12 at 100 F. to rinse. Wringing is done using the Atlas and 15 are representative examples of compositions of the Electric Padder The cloth is ironed to fix the stain and instant invention. Composition No. 8 contains dihydroanowedtoalgefrthreedaysat120,, F genated tallow ammonium monoperoxysulfate. Composition No. 11 is a hypochlorite formulation. Composition Gravy No. 16 is a potassium dichloroisocyanurate composition. The others are compositions with one or more of the essenoneounce Package of Durkees brown Y miX is tial components of the instant invention omitted. These Wlth 1 P of Water and brought t0 a boil With compositions are employed in the following Bleaching stirring. Tllfl mixture is removed Il'Om the heat and stirred Performance Test. Color Damage Test, Bleaching Time With a high-Shear homogenilef for 5 inutes- The warm and Temperature Test, and Fabric Softening Test. gravy solution is then placed in a container and the cloth TABLE I Y Concentrated composition number 1 2 3 4 5 6 7 8 9 10 ll 12 13 14 15 16 Component, weight percent:

Potassium monopersulfate 27 29 25 27 31 18 25 Diperazelaic acid Monoperoxyphthalic acid- Dlperoxyisophthalic acid Dihydrogenated tallow ammonium monoperoxysnlfatp Sodium hypochlorite Potassium dichloroisocyanurete Elcosyltrimethylammonium chloride. Octadecyltlimethylammonium chloride Cetyltrimethylammonium choride Ethoquad 18/12 1 Cetyltrimethylammonium nitrate 14 38 Sodium choride 10 Chloride ion content (g. Cl-lkg. composition) 16.8 35 2 0 15 5 63 19 5 15 5 Copper sulfate- Butler". 22 21 12 20 20 22 2a 15 26 20 22 26 15 20 Inerts 37 36 29 30 15 38 40 13 33.82 94. 75 36.8 43 25 33.8 85 See the following formulawherein R is stea yl and the compound contains 2 moles combined and the color differences, AW, so obtained were taken as a measure of stain removal performance. The average AW values for five stains are reported in the example ethylene oxide and has a molecular weight of 422. See Armour Industrial Chemical Company Technical Bulletin F-4.

For Compositions 1, 2, 4 6, 7, 8, 10, 12, 13, 14 and 15 the buffering agent s sodium carbonate. For Compositions 2, 5 and 9 the bufien'ng agent is a mixture of dlsodium hydrogen phosphate and sodium dihydrogen phosphate in a NazHPO; to N8H2PO4 ratio of approximately 5:1.

is run through the solution and padded. The stained cloth is then dried in an oven. Two applications are given.

Empa-sulfur black and red wine These cloth samples are obtained commercially from Test Fabrics Inc., 55 Vandam St., New York 13, N.Y., manufactured by E.M.P.A., Unterstasse II, 9001 St. Gall, Switzerland.

BLEACHING PERFORMANCE TEST Bleaching activity of Compositions of Table I is compared. Table II provides the concentration in bleaching solution of components of the various compositions. Table II also summarizes the AW value of each composition, thereby indicating their relativ bleaching performance.

'tained.

When the cetyltrimethylammonium nitrate of Com--..-

TABLE II Concentrated composition number 3* Component-solution concentration:

Potassium monopersuliete (p.p.m. av. 09-.-"--- Diperazelaic acid (ppm. av.

Sodium chllfoit-idzibgpdn ii) 100 Copper a e Initial Solution pH 9. 3 10.0 12. 3

AW Color damage index 1 See Table I, footnote 1.

These compositions were used after or as the cloths were washed'in Tide" at 125 F. with 7 grain/gallon hardness water.

It can be seen from Table II that the compositionsof the instant invention provide stain removal superior to the other prior art compositions at comparable strength in solution and superior to compositions not containing all of the essential components of the instant invention. Preferred Composition No. performs at a very low strength about as well as a highly concentrated NaOCl bleaching solution (No. 11).- Substantially similar AW results are obtained with the compositions of the present invention not appearing in Table 11 (Nos. 5 and 9).

When the potassium monopersulfate of Compositions 2, 4, 6, 10, 12 and is replaced with sodium monopersulfate and when the diperazelaic acid of Composition 3 is replaced with monoperazelaic acid, substantially similar performance results are obtained.

When the diperoxyisophthalic acid of Composition 9 is replaced with diperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid, the monosodium salt of diperoxymonium fluoride, sulfate, methylsulfate, hydrogen phosphate, dihydrogen phosphate, chlorate, carbonate or hydroxide substantially similar performance of the compositions is obtained.

COLOR DAMAGE TEST Color damage characteristics of the compositions of the instant invention are compared to each other and to the other compositions of Table I. Color damage is ascertained and evaluated by the following procedures. Thirtytwo difierent articles of clothing having characteristics summarized in Table III are first washed in Tide, a representative commercially available laundering detergent, with water of 7 grain hardnessat 125 F. Compositions 11 and 16 were employed in the wash water itself. The other compositions were utilized in 7 grain hardness rinse water at 100 F. All compositions were employed at the concentrations of Table II.

TABLE III.CLOTHING USED FOR COLOR DAMAGE TEST Fiber content Color Item Brand Cnttnn Yellow Girl's dress Bonnie Press.

Do Blue Sheet Wamsutta Lustercale.

Do Turquo Towel Stevens Utica.

Do Green Girl's dress. Bonnie Press.

Do B1uck Man's Slacks Wrangler.

% polyester/50% cotton- Turquoise Child's shirt- True Merit.

D0 do Womans skirt Donnkenny. Polyester Yellow Woman's shelL- Sweetree.

1) Women's dress John Meyer.

Do. Womans slacks S.S. Kresge.

Do. o Do.

Acetate- Woman's shell. W.T. Grant C0.

D0. Woman's dress Berkshire B-Tween.

Do Woman's shell W.T. Grant Co. camel/15% nylon Womans dress Jule-Wyn.

% cruel/5% nylon. do Hargro.

Do--- Mens shirt Mc Gregor Miracle. Orlon acry Womans sweater... Talbott Taralau. Acrylic.- Boys shirt Garan.

Antron ny Womans slip. Vassarette.

Do do Do. Nylon do S.S. Kresge.

0-- Woman's shell. Cobble Knits. Wool Man's vest Me Gregor Scotch dz Water.

0 Alan Paine. Croslan acrylic Aileen. 75% cotton/25% nylon Do. Cott Do. Do. Do.

- Warner terephthalic acid or a monoperoxy compound of the general formula positions 4 and 9 is replaced with cetyltrimethylam- After only two cycles (many fewer than the number of times an article of clothing would be bleached in the home over a period of time) each article was graded on a scale from 0 to 3. 0 corresponded to no color change; 1 to slight change; 2 to noticeable change and 3 to damage leaving the article unwearable. The value grades from all 32 articles were then added to provide a composite color damage indication for each composition tested.

Each composition tested for color damage was also tested for bleaching performance in a manner similar to that used in the Bleaching Performance Test. AW values after one cycle were ascertained as. in the Bleaching Performance Test. It should be noted that the AW values BLEACHING TIME AND TEMPERATURE TEST Composition Nos. 10, 11 and 13 of Table I are placed in bleaching solutions in the component concentrations described in Table IV.

TABLE IV Concentrated composition number 10 11 13 Component-solution concentration, p.p.m.:

Potassium monopersuliate (ppm. av. 02).-. 53 45 Sodium hypochlorite (p.p.m. av. C12) 200 Cetyltrimethylammonium chloride (pipini. i

Eicosyltrimethylammonium chloride (p.p.m.) Sodium chloride (p.p.m.) Copper sulfate (M X1O- Initial solution pH- Bleaching of these solutions was then tested at various solution temperatures and performance recorded over periods of bleaching time. Results are summarized graphically in the drawing. The composition of the in vention (No. performs significantly better than monopersulfate alone (No. 13) and compares favorably with highly concentrated NaOCl (No. 11).

FABRIC SOFT ENING TEST Softening was tested under standard U.S. conditions of 125 F. wash (7 gr./gal. hardness) followed by 100 F. rinse with 7 gr./gal. hardness. Loads were washed in the automatic mini washer using 0.9 cup Tide, 1 /2 gallons of water and a 5 /2 pound load equivalent. The standard load contained 4 terry wash cloths. Compositions were tested for two cycles, and the terry cloths were graded by a panel of 5 expert judges using the method of round robin paired comparisons.

The softness of the fabrics treated with Composition N0. 10 (Table II concentration) was judged to be signifi cantly greater than the Tide control, Substantially similar results are obtained with Compositions Nos. 3 and 9.

What is claimed is:

1. A dry bleach and fabric-softening composition consisting essentially of:

(A) from about 8% to about 60% by weight of a bleaching agent selected from the group consisting of (1) sodium monopersulfate, (2) potassium monopersulfate, (3) an organic peroxyacid or water-soluble salt thereof, said peroxyacid having the general formula wherein R is selected from the group consisting of alkylene groups containing from 1 to about 16 carbon atoms and arylene groups containing from 6 to about 8 carbon atoms and Y is a group providing an anionic moiety in aqueous solution, and (4) mixtures thereof; (B) from about 10% to about 60% by weight of a quaternary ammonium compound selected from the group consisting of i Br fillband of alkyl groups containing from about 1 to 3 carbon atoms, aryl groups containing from about 6 to 8 carbon atoms, cycloalkyl groups containing from about 5 to 8 carbon atoms, carboxymethyl groups, alkaryl groups containing from about 7 to 10 carbon atoms, pyridyl, and groups of the general formula wherein a and b are integers and a+b is.-1 to 50; R has the definition of the R R and R groups or is H; R-, is selected from the group consisting of alkylene groups containing 1 to 3 carbon atoms, arylene groups containing 5 to 8 carbon atoms and groups of the formula wherein X is selected from the group consisting of chloride, fluoride, nitrate, sulfate, methylsulfate, carbonate, chlorate, hydrogen phosphate, dihydrogen phosphate and hydroxide; and wherein n is 1 when X is monovalent and n is 2 when X is divalent;

(C) from about 10% to about by weight of a buffering agent effective to maintain a solution pH of from about 7 to about 10 when said composition is dissolved in water for bleaching;

said composition containing sufiicient chloride sa to provide from about 5 to about grams of ioniza le chlorine per kilogram of the total composition.

2. The composition of claim 1 wherein the bleaching agent is potassium monopersulfate.

3. A composition in accordance with claim 1 wherein the bleaching agent is selected from the group consisting of monoperazelaic acid and diperazelaic acid.

4. A composition in accordance with claim 1 which contains in addition from about 0.08% to about 8% by weight of a water-soluble salt of a transition metal element.

5. A composition in accordance with claim 1 which contains from about 2% to about 10% of a water-soluble alkali metal or alkaline earth metal chloride.

6. A composition in accordance with claim 1 wherein the quaternary ammonium compound is a mixture containing from about 2% to about 10% by weight of the total composition of an eicosyltrimethylammonium 'compound and about 8% to about 30% by weight of the total composition of a cetyltrimethylor octadecyltrimethyl-ammonium compound.

7. A concentrated, dry bleach and fabriosoftening composition consisting essentially of:

(A) from about 8% to about 60% by weight of a bleaching agent selected from the group consisting of (1) sodium monopersulfate, Y (2) p m" ln n n rt ai e,--

(B) from about 10% to about 60% by Weight of a quaternary ammonium compound selected from the group consisting of wherein R is an alkyl group containing from 12 to about 20 carbon atoms; R; is selected from the group consisting of alkyl groups containing from about 1 to 14 carbon atoms, cycloalkyl groups containing from about to 8 carbon atoms, carboxymethyl groups, aryl groups containing from about 6 to 8 carbon atoms, alkaryl groups containing from about 7 to carbon atoms, pyridyl and groups of the general formula --(C H O) (C H O) I-l wherein a and b are integers and a+b is 1 to 50; R R and R are each selected from the group consisting of alkyl groups containing from about 1 to 3 carbon atoms, cycloalkyl groups containing from about 5 to 8 carbon atoms, carboxymethyl groups, aryl groups containing from about 6 to 8 carbon atoms, alkaryl groups containing from about 7 to 10 carbon atoms, pyridyl, and groups of the general formula H; R7 is selected from the group consisting of alkylene groups containing 1 to 3 carbon atoms, arylene and 16 groups containing 5 to 8 carbon atoms and groups of the formula wherein X is selected from the group consisting of chloride, fluoride, nitrate, sulfate, methylsulfate, carbonate, chlorate, hydrogen phosphate, dihydrogen phosphate and hydroxide; and wherein n is 1 when X is monovalent and n is 2 when X is divalent;

(C) from about 1% to 15% of a water-soluble alkali metal or alkaline earth chloride;

(D) from about 0.08% to about 8% by weight of a water-soluble salt of a transition metal element; and

(E) from about 10% to about by Weight of a buffering agent effective to maintain a solution pH of from about 7 to about 10 when said composition is dissolved in water for bleaching; said composition containing suflicient chloride salt to provide from about 5 to about 100 grams of ionizable chlorine per kilogram of the total composition.

8. A composition in accordance with claim 7 wherein the bleaching agent is selected from the group consisting of diperazelaic acid, diperoxyisophthalic acid, diperoxyterephthalic acid, 4 chlorodiperoxyphthalic acid, the monosodium salt of diperoxyterephthalic acid and a monoperoxy compound of the general formula wherein R is an alkyl group of from about 8 to about 18 carbon atoms and wherein X and Y are each selected from the group of cations consisting of hydrogen, sodium, potassium, ammonium and substituted ammonium cations.

References Cited UNITED STATES PATENTS 3,360,470 12/1967 WiXon 25299 3,048,546 8/1962 Lake 252- 3,353,902 11/1967 Diamond 252-8.8

MAYER WEINBLATI', Primary Examiner U.S. Cl. X.R.

8-108, lll; 2528.75, 8.8, 99

237 3 UNITED STATES mm OFFICE CERTIFICATE OF CORRECTION 293mm: 7 Dated y 311 197.3

C John Paul Jones and Charles H. Nicol It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 47, delete "miscslles" and insert therefor .1

-- micelles Column 4, line 51, delete "virture" and insert 'therefor virtue Column 4, line 57, delete "chloride! vand insert therefor chlorine Column 5, line 50, delete '"aproximately" and insert therefor approximately Column ,5, line 70, delete "'othe" and insert therefor other Column 7, line 13, delete" "hydrogen" and insert therefor dihydrogen Column 7, line 22, delete "[C N(CH Column 7, line 53, delete "Consqeuntly" and insert therefor Consequently Column 8, line 50, delete "Transistion" and insert therefor Transition Column 8, line 64,, delete "necessaary" and insert therefor necessary Column 9, line 37, after "Test" replace the period with a comma.

Table I, after "Cetyltrimethylammonium" delete "choride" and insert therefor chloride HPO and insert therefo:

mow UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 23m V l Dated! Ju ly 31 19 73 g'f John Paul Jones and Charles H. Nicol Page 2 It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

Table II after Diperazelaic acid" delete "Q and insert therefor 0 Column 15, line 16 delete "R and insert therefor R Signed and se e this 1st dayof January 1974.

(SEAL) Attest 5 EDWARD M. FLETCHER,JR. RENE D. TEGTMEYER Attesting Officer 7 Acting Commissioner of Patents

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