US3265624A - Detergent composition - Google Patents

Description

Aug. 9, 1966 J. T. INAMORATO DETERGENT COMPOSITION Filed Oct. l, 1963 INVENTOR. JAcK THoMAs INAMoRATo 3,265,624 DETERGENT COMPGSE'HON Ilack Themas lnamorato, Flushing, NSY., assigner to Colgate-Pairnoiive Company, New York, NX., a corporation of Delaware Fiied st. 1, i963, Ser. No. 312,968 i@ Claims. (Cl. 252-9?) This invention relates to detergent compositions, and more particularly to anionic detergent compositions containing a chlorine bleach, such -compositions being characterized -by controlled foam levels and particularly effective heavy duty cleansing power at use concentrations as hereinafter described.

The development of a universally acceptable heawy duty laundry composition satisfactory `for use in any washing machine has been complicated by the housewifes acceptance of laundering machines having different mechanical characteristics.V At present, mechanical characteristics determine to a large extent the nature of a detergent product that may satisfactorily be used in a particular machine. For example, highly eiective heavy duty detergent products containing anionic detergents may be satisfactorily used in top-'loading machines in which agitation of the Wash solution is provided by a reciprocating agitator or a pulsating agitator mounted in a vertical position. Such products produce. a high stable `foam which persists throughout the laundering cycle. However, this same high stable foam tends to interfere with use of such products at concentration levels consistent with satisfactory detergency in front-loading washing machines in which agitation is provided by a horizontally mounted rotating drum having internal ridges thereon. It has been found that high foam levels in the latter type machines adversely affect detergency action by impeding agitation of the soiled laundry such that the laundered articles still eibit high residual soil levels. This foam also increases mechanical wear which, in turn, leads to higher maintenance costs, Further, eX- cessive foam levels often cause a front-loading machine to foam over, resulting in puddles of detergent solution in the oor area around the machine which must be mopped up by the housewife or laundry operator. Thus, this type of machine has created a need for controlled sudsing detergents.

In attempting to solve the problem of excessive foam levels, detergent compositions containing nonionic synthetic detergents have been developed. Such compositions are based on alkylene oxide condensation products and these condensates generally possess cleansing ability with a minimum of suds. However, indications are that in the laundering of normally soiled clothes such co-mpositions are not equal in cleansing action to the high sudsing anionic detergents and possess the added disadvantage of being incompatible with chlorine bleaches which are desirable constituents of modern-day, heavyduty detergent compositions.

Therefore, a further need exists for controlled sudsing detergent compositions containing particularly effective anionic detergent materia-ls in combination with chlorine bleaches. Such desired compositions wlould provide superior detergency and would truly be universally acceptable for use in all laundering machines, e.g., agitator-type and tumbler-type washing machines.

It is also known in the art that certain cationic agents are useful in detergent compositions, particularly to rende-r textiles soft. However, such cationic agents generally react with anionic detergents to form precipitates which are deposited upon articles being washed, thereby giving the washed articles an undesirable appearance. This reaction or interaction has eifectively depleted the 3,265,624 Patented August 9, 1966 concentration of an anionic detergent in a washing bath to the detriment of detergency action and, therefore,

should be avoided.

It is an object of the present invention, therefore, to provide a detergent composition of controlled sudsing capability. Another object is to provide a controlled sudsing composition containing an effective anionic detergent and a chlorine bleach compatible therewith. A further object is to provide an association of a cationic agent and a chlorine bleach, such association effectively controlling sudsing capabalities of an anionic detergent composition without materially decreasing the cleansing action of the composition. Another object is to provide a suds depressing additive composition. Still another object is to provide a controlled sudsing, heavy-duty detergent composition. A further object is to provide a composition of the last-mentioned character suitable for use in laundering machines of diverse types. Other objects o-f the invention will become apparent from the following description.

Broadly stated, according to the present invention the foregoing objects are realized with compositions comprising:

(a) a quaternary ammonium salt having one higher alkyl group and preferably a quaternary ammonium salt represented by the general formula wherein R1 is a higher alkyl group containing fromv and (b) an organic chlorine-containing bleach such as a heterocyclic N-ch'lor imide or alkali metal salt thereof.

Another embodiment of the invention comprises cornpositions (a) and (b), each identified above, and a water-soluble, builder salt.

Another embodiment of the invention serving to meet the foregoing objects comprises compositions comprising:

(a) and (b), each identified above,

(c) a Iwater-soluble Ianionic organic detergent, and

(d) a water-soluble, builder salt.

In general, compositions of the invention are eminently satisfactory for use in any of the present day automatic washing machines because they are characterized by particularly effective detergency, effective bleaching action at normal washing temperatures and a moderate sudsing level in tumbler-type Washing machines operating on normally soiled laundry.

One component, (a), of the compositions of this invention is a cationic material, namely, a quaternary arnmonium compound having the general formula:

wherein R1 is a higher alkyl group containing from about l0 to about 20 carbon atoms, R2 and R3 are lower alkyl groups each having from 1 to 3 carbon atoms, and R4 is selected from the group consisting of lower alkyl groups having from l to 3 carbon atoms and aralkyl groups, and X is a halogen. Such compounds are characterized by some solubility in water. A wide variety of suitable cationic sulface active agents can be employed herein, typical of which are:

Stearyl dimethyl benzyl ammonium chloride,

Cetyl trimethyl ammonium bromide,

Lauryl trimethyl ammonium chloride,

Lauryl dimethyl benzyl ammonium chloride,

Myristyl diethyl benzyl ammonium bromide,

Decyl trimethyl ammonium bromide,

Arachidyl diethyl benzyl ammonium chloride,

Oleyl triethyl ammonium chloride,

n-Alkyl dimethyl ethyl benzyl ammonium chloride wherein the n-alkyl comprises a mixture of normal C12 to C18 groups.

It is to be understood that mixtures of two or more cationic agents can be employed if desired.

Suitable qu-aternary ammonium compounds are available as 95 percent active powders, 57 percent active aqueous pastes and in 25-50 percent aqueous alcholic solutions. It is preferred to use the 95 percent active powder material, but choice of physical form is dependent upon storage and production facilities.

Component (b) of the compositions of this invention is a water-soluble, organic chlorine-containing dry bleach, particularly a heterocyclic N-chloro imide or alkali metal salt thereof. Such cyclic imides have from 4 to about 6 members in the ring, and are characterized by the following structure:

o o1 o ll I Il -C-N-C- in which the electron donating nitrogen is doubly activated to a highly acidic state by virtue of its proximity to two electro-positive carbonyl groups. Such N-chloro imides are known to the pri-or art, usually being prepared by passing chlorine gas into an alkaline aqueous solution of the parent imide. Compounds suitable for use in the present compositions include the N-chloro derivatives of cyanuric acid (eg. mono, diand tri-chloro-cyanuric acid) and hydantoin as well as N-chloro succinimide, N-chloro malonimide, N-chloro phthalimide and N-chloro napthalimide. In general it is preferred to employ those imides containing a plurarity of chlorine-containing nitrogen atoms, e.g. trichlorocyanuric acid, dichlorocyanuric acid, sodium and potassium dichloroisocy-anurates, etc. Suitable N-chloro hydant-oins include: 1,3-dichloro- 5,5-dimethyl hydantoin; N-monochloro-C,Cdimethy1 hydantoin; methylene-bis-(N-chloro-C,Cdimethy1 hydantoin); l,3,-dichloro-S-methyl-S-isobutyl hydantoin; 1,3- dichloro-S-methyl-S-ethyl hydantoin; 1,3-dichloro-5,5di isobutyl hydantoin; 1,3-dichloro-S-methyl-S-n-amyl hydantoin, and the like.

Such bleaches are compatible with anionic-detergentcontaining compositions contemplated herein. They are effective at normal Washing temperatures. Normally, the bleaching agents are employed in a proportion in the mixture such that about 2O to about 200 parts per million (ppm.) of available chlorine will be present in a washing bath. However, other proportions of the bleach can be used if desired.

- One bleach or a mixture of the same identified as component (b), can be used herein. Additional dry bleaching -agents can also be present in the new compositions. Typical of the additional bleaching agents are sodium hypochlorite (NaOCl-5H2O), sodium and potassium perborates, potassium monopersulfate, etc.

As indicated above, one component of compositions contemplated herein is a water-soluble, anionic, organic detergent (c) above. Such a detergent is stable in the presence of the bleaching agent (b). It is to be understood that one or several of such detergents can be used in compositions of this invention. The said detergents may be designated as water-soluble salts of organic reaction products having in their molecular structure an anionic solubilizing group such as SO4H, SO3H, COOH and PO4H and an alkyl or aralkyl radical having about 8 to 22 carbon atoms in the alkyl group. Suitable detergents are anionic detergent salts having alkyl substituents of 8 to 22 carbon atoms, such as: Water-soluble higher fatty acid alkali metal soaps, e.g., sodium myristate and sodium palmitate; water-soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal detergent salts containing a hydrophobic higher alkyl moiety, such as salts of higher alkyl monoor poly-nuclear aryl sulfonates having from about 8 to 18 carbon atoms in the alkyl group which may have a straight or branched srtucture, e.g., sodium dodecylbenzene sulfonate, magnesium tridecylbenzene sulfonate, lithium or potassium pentapropylene benzene sulfonate; -alkali metal salts of sulfated condensation products of ethylene oxide (e.g. 3 to 20 and preferably 3-10 mols of ethylene oxide per mol of other compound) with aliphatic alcohols containing 8 to 18 carbon atoms, or with alkyl phenols having alkyl groups containing 6 to 18 carbon atoms, eg., sodium nonyl phenol pentaethoxamer sulfate and sodium lauryl alcohol triethoxamer sulfate; alkali metal salts of sulfated alcohols containing from about 8 to 18 carbon atoms, e.g., sodium lauryl sulfate and sodium stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol ysulfonic acid, eg., fatty acid esters of the sodium salt of isethionic acid; fatty ethanolamide sulfates; fatty acid amides of amino alkyl sulfonic acids, eg., lauric acid amide of taurine; alkali metal salts of hydroxy alkane sulfonic acids having 8 to 18 carbon atoms in the alkyl group, e.g., hexadecyl alpha-hydroxy sodium sulfonate. In general these organic surface active agents are employed in the form of their alkali metal salts or alkaline earth metal salts because such salts possess the requisite stability, water solubility, and low cost essential to practical utility.

It is preferred to use a combination of detergents, specifically one or more water-soluble, anionic, non-soap organic detergents with one or more water-soluble, higher fatty acid salt detergents. The two detergents and the quatemary compound cooperate to provide an accelerated rate of collapse of static foam without adversely affecting either dynamic foam balance or the detersive efciency of a composition.

Another component of compositions of this invention is a water-soluble, builder salt, component (d). The salt can be inorganic or organic, illustrative of which are:

Trisodium phosphate,

Tetrasodium pyrophosphate,

Sodium acid pyrophosphate,

Sodium tripolyphosphate,

Sodium monobasic phosphate,

Sodium dibasic phosphate,

Sodium hexametaphosphate,

Sodium metasilicate,

Sodium silicates, Na2O/SiO2 of 1.6/1 to 3.2/1, Sodium carbonate,

Sodium sulfate,

Borax,

Nitriloacetic acid trisodium salt,

Ethylene diamine tetraacetic acid tetrasodium salt, etc.

Mixtures of two or more inorganic or organic salts can be used, as can mixtures of inorganic organic salts.

Particularly preferred herein are water-soluble, alkali metal polyphosphate builder salts. These salts form water-soluble complexes with calcium and magnesium ions found in hard water and thereby prevent the formation of insoluble salts which tend to deposit upon textiles during a Washing cycle. Further, such phosphates enhance the detersive efficiency of anionic detergents, aid in controlling sudsing power and aid in keeping soil suspended in the washing bath after its removal from the soiled textiles.

Proportions of the various components of the new compositions should be properly related in order to achieve the desired objects. The weight ratio of a quaternary ammonium salt to a chlorine-containing bleach, (a)/(b), should range from about 0.01/1 to about 2/1, preferably from 0.1/l to 1/1. As a general guiding principle, proportions of components (a) and (b) of this foam depressing combination generally vary inversely with each other. Thus, a minor proportion of cationic agent (a) is sufficient when the proportion of chlorine bleach (b) is high, and a larger proportion of cationic agent (a) is required when a lesser amount of chlorine bleach (b) is used generally. In addition, the nature of the cationic agent (a) used and the proportions of the anionic detergent (c) and builder (d) affect the proportion of cationic agent to be used. r[herefore, the cationic agent (a) is to be suitably proportioned in each composition such that ardesired suds level can be attained.

Advantageous additive compositions for depressing foam are those comprising from about l to about 67 percent by weight of one or more of the quaternary ammonium salts having one higher alkyl group and from about 33 to about 99 percent by weight of one or more of the bleaches. Such compositions generally comprise amounts of from about 2 to about 30 percent by weight of heavy-duty detergent compositions.

As indicated, a quantity of the bleach employed should be such that about to about 200 p.p.m. of available bleach is present in a washing bath having a total detergent concentration greater than about 0.075 percent by weight, and preferably from about 0.1 to about 0.4 percent by weight. With respect to an anionic organic detergent (c), from about 5 to about 50 percent by weight of a detergent composition should comprise this component. Preferably, the quantity will be of the order of about 7.5 to 40 percent by weight. In general, for laundering compositions, the balance of a formulation is primarily a water-soluble, builder salt or salts. The latter is generally used in an amount ranging from about 5 to about 90 percent by weight, particularly the polyphosphate, and preferably from about percent to `about 60 percent. In such laundering compositions, the amounts of quaternary compound and bleach will be variable as indicated above. Generally, the quaternary compound will be present in amounts from about 0.01 to about 4, and preferably from about 0.3 to about 3, percent by weight. The bleach will be present in an amount ranging from about 2 to about 30, and preferably from about 5 to about 20, percent by weight.

In addition to the foregoing components, the compositions contemplated herein can beneficially include various other substances generally employed in the art in such detergent compositions, provided that the use of any such materials does not substantially adversely affect the desired properties of the compositions. Examples of suitable materials are hydrotropic solubilizing agents such as sodium xylene and toluene sulfonates; sodium carboxymethylcellulose and polyvinyl alcohol anti-redeposition agents; optical or uorescent brightener materials of the triazole or benzidine sulfone type which are partieularly effective in the presence of a chlorine-containing bleach; germicides; coloring agents; perfumes; and the like.

Preferred compositions advantageously contain a hydrophobic cellulosic soil-suspending agent which is soluble or dispersible in water also. The joint use of the combination of the cellulosic compound and polyvinyl alcohol is particularly effective for soil-suspending properties during the washing of a variety of fabrics, including both cotton and synthetic fibers such as nylon, dacron and resin-treated cottons. The mixture is used preferably in a total amount of 0.1 to 2 percent by weight of the solids. Preferred cellulosic compounds are the alkali metal salts of a carboxy lower alkyl cellulose having carbons in the alkyl group, such as the sodium Suitable salts are sodium carboxyethylcellulose, the cellulose sulfates and lower alkyl and hydroxyalkylcellulose ethers such as methylethyland hydroxyethyl-celluose.

The compositions of this invention are stable during storage. These compositions can be prepared by dry blending the powder or granular materials in any suitable blender. Preferably all the ingredients, except the bleaching agent, are prepared in particulate form by heat drying an aqueous slurry, such as by spray drying or drum drying at temperatures about 212 F., and the dry bleach is then blended with the heat dried composition.

In the manufacture of an additive composition comprising a cationic agent and a bleach, the two materials can be intimately admixed in desired proportions in a ribbon blender -or similar mixing apparatus. Manufacture of the low-sudsing, heavy duty detergents can be accomplished by following various procedures used for compounding detergent compositions. However, a preferred procedure involves addition of Water to a soap crutcher, followed by an aqueous solution of an anionic detergent (e.g., a sulfonate) and then by a builder or builders (eg, sodium tripolyphosphate). Thereafter, a cationic agent is added. The temperature of the slurry formed in the crutcher is maintained at about i60-189 F. for a period of time ranging from about 10 minutes to one hour. A smooth, pumpable mixture having a total solids content of about 55-60 percent by weight, is formed. The mixture is then pumped into a spray tower where it is spray-dried with air heated to about 600 F., whereupon a product in the form of beads is obtained. A bleach is then admixed with the product in bead lor in any other suitable form in a suitable mixer such as a twin-shell blender, ribbon blender, etc.

A particularly advantageous process herein involves forming a fluid aqueous slurry comprising water and an anionic organic detergent with a fatty acid salt. The slurry flows or is pumped into a conventional soap crutcher or any other suitable mixinfy apparatus such as a ribbon blender. The anionic detergent should desirably be added to the crutcher prior to addition of the quaternary compound in order to avoid formation of any significant amount of insoluble, anionic-cationic complex. The other ingredients are then added in any suitable order and form. The cationic quaternary ammonium compound is added, usually as a fine white powder, with stirring. The resulting slurry should be sufficiently fluid at the elevated temperatures to insure adequate mixing and formation of a uniform product, and is subjected to a heat treatment at an elevated temperature such as within the range of about to about 200 F., and usually from about to 155 F. The slurry is heated by external means or even by the exothermic heat of reaction of certain ingredients. For example, the addition of hydratable inorganic salts such as the anhydrous forms of sodium tripolyphosphate and sodium pyrophosphate results in exothermic reactions as hydration occurs. It is desirable generally to add the polyphosphate and/or other builder salt or salts in the final stages of the crutching operation. A fatty acid salt can be added at `any suitable stage of the crutching operation, preferably before addition of polyphosphate. Thus, all of the components, except the bleach and miscellaneous characterizing agents, can be added to thecrutcher without any need to shield one component from another. Mixing time is suicient to insure adequate mixing and will usually be at least a few minutes, e.g. 5 minutes. The aqueous mixture prior to drying can be aged at the elevated temperature for a time sufficient to insure adequate solubilization or hydration of certain ingredients. Such aging period can be a number of hours, such as up to about 8 hours. In general, it is preferred to employ time intervals of less than three hours and preferably less than one hour. It is understood that excessively high temperatures or unduly long aging periods are to be avoided to prevent any possible decomposition and insure efcient processing.

The solids content of the aqueous slurry is usually within the range of from about 20 percent to 90 percent of total solids. In the manufacture of heat-dried products involving vaporization of the water, the solids content is usually within the range of about 40 to 65 percent by weight, the remainder being substantially free Water content. The slurry is usually maintained at a ternperature from about 160 to 180 F. This slurry is subjected to known spray-drying operations utilizing temperatures above about 212 F. to produce the detergent composition in particulate form, generally in the form of hollow, thin-walled spherical particles. The `detergent composition can be transformed into beads, granules, flakes, chips, powders or the like as desired by use of the conventional techniques.

In spray-drying the aqueous slurry, it is atomized or forced through spray nozzles into towers, with small liquid particles discharged from the nozzles becoming solidified and drying as they contact or fall through a stream or vortex of heated air or other inert gas which is at about 600 F. The composition is produced thereby in the form of hollow thin-walled spheres or beads having a small residual moisture content usually of about 3 to l5 percent by weight.

The present invention is more fully described and exempliiied in the following examples. It is to be understood, however, that the invention is not to be limited to any specific form of materials or conditions set forth in the examples, but is limited solely by the description in the specification and the appended claims. All quantities are expressed in parts by weight unless otherwise indicated.

Example 1 In this illustration, a comparison is made of several related compositions one of which is typical of the new compositions contemplated herein. All parts are by weight unless otherwise specified. The compositions cornpared are:

(A) Comprising essentially 12 percent of sodium tridecylbenzene sulfonate (anionic detergent), 3 percent sodium tallow soap (anionic detergent), 50 percent sodium tripolyphosphate (builder), 24 percent sodium sulfate (builder), and 11 percent water;

(B) Composition A in which l percent of the Water is replaced with 1 percent stearyl dimethyl benzyl ammonium chloride (cationic agent);

(C) Composition A in which percent of the water is replaced with 10 percent of potassium dichloroisocyanurate (bleach); and

(D) Composition A in which 11 percent of the waterall of the water-is replaced by 1 percent of stearyl dimethyl benzyl ammonium chloride and by 10 percent of potassium dichloroisocyanurate (identied herein as Product 1).

Composition A was formed by mixing an aqueous solution of the sulfonate with an aqueous solution of the soap. Dry builders were added to and were mixed with the resulting aqueous solution. The concentration of the entire detergent system (sulfonate, soap and builders) was approximately 0.15 percent by weight. Composition B was formed in much the same manner, except that an aqueous solution of the cationic agent was mixed with the aqueous solutions containing sulfonate and soap prior to addition of the builders. Composition C was formed by adding the dry bleach to a composition formed in accordance with the procedure for preparing Composition B. `Composition D was prepared by: mixing together aqueous solutions containing, respectively: sulfonate, -soap and cationic agent; adding dry builders to the resulting solution; and then adding the dry bleach to the solution formed following addition of the builders.

Compositions A through D were subjected to an evaluation test, referred to as a Dynamic Foam Test, which has been found to correlate with conditions normally encountered with use of detergent compositions. Foam behavior of the compositions is determined in the presence of soil by employing soiled cotton fabrics in a standard laboratory Tergotometer apparatus. The soil employed was a synthetic sebum comprising:

Percent wt. Palmitic acid 10 Stearic acid 5 Oleic acid 15 Coconut oil 20 Olive oil 20 Squalene 5 Parafnn (M. Pt., 48 C.) 10 Spermaceti 15 The test procedure used follows:

(1) 50 grams of the sebum mixture was dissolved in a 1:1 isopropanol-benzene mixture, and was made up to 250 milliliters in a volumetric flask (1 ml.=200 milligrams of sebum);

(2) 0.2 ml. of the solution formed in 1 was added to each of a number of terry cloth swatches measuring 1 inch by 1 inch;

(3) 0.45 gram of the composition to be tested, and 300 milliliters of water at 125 F., were added to a beaker and were thoroughly mixed;

(4) The mixture formed in 3 was tested in the Tergotometer for a period of 3 minutes, and the height of the foam which formed was recorded as soon as the Tergotometer stopped;

(5 One soiled terry cloth swatch was added to the beaker and step 4 was repeated;

(6) 1 soiled swatch was added at 3 minute intervals until foam had completely collapsed.

Results of the test so conducted are provided in the figure appended hereto wherein a series of curves are shown. Foam height, in inches, is plotted as the ordinate, and the cumulative amount of sebum soil added is plotted as the abscissa, Curves identified by A, B, C, and D are obtained by testing Compositions A through D, respectively. The curve labelled E represents the calculated or expected foam behavior of Composition D, based upon the properties of the individual components.

A number of features are shown by the curves set out in the figure, namely:

1) Composition A exhibits excellent foam stability in the presence of soil, but would be unacceptable for use in tumbler-type automatic washers unless unrealistically heavy soil levels were encountered;

.(2) Composition B indicates that the addition of `a minor amount (1%) of a cationic agent to Composition A depresses the dynamic foam in the presence of soil;

(3) Composition C exhibits such foam stability in the presence of soil as to be undesirable for use in tumblertype automatic washers despite the fact that addition of the bleaching agent to Composition A reduces the dynamic foam stability in the presence of soil, though not enough to eliminate a foaming problem at normal soil levels corresponding to -150 mgs. of sebum soil in tumbler-type automatic washers;

(4) Composition D contains both the 1% cationic quaternary ammonium compound of Composition B and the bleaching agent of Composition C and exhibits the absence of foam in the 100-150 mgs. soil range which is equivalent to soil range expected for normal loads of soiled fabrics in tumbler-type washing machines; this curve illustrates that by suitably adjusting the proportions of the two components-cationic compound and bleacha product having a predetermined foam level in tumblertype washing machines can be formulated; and

(5) Comparison of the curve for Composition D with curve E, representing the calculated or expected foam behavior for Composition D, reveals a substantial synergistic foam depressant relationship.

Example 2 Components: Parts Sodium tridecyl benzene sulfonate 25 Potassium dichloroisocyanurate (equivalent to 100 p.p.m./17 gallons of water) 10 Stearyl dimethyl benzyl ammonium chloride 3 Sodium tripolyphosphate 25 Sodium sulfate 29 The composition of Example Z-identied herein as product 2-was prepared in the same manner as was Composition D of Example 1. It was tested at 0.15% concentration in the Dynamic Foam Test, wherein the foam level fell from 11/2 inches without any soil to 1/2 inch after the addition of 80 mgs. of soil and to a trace level after 160 mgs. of sebum soil. For comparison, in the absence of the chlorine bleach-cationic agent foam depressant combination, the foam level Vremained at 11/2 inches until 500 mgs. of sebum soil had been added. Approximately one inch of foam was formed in a tumble-r 4washer when laundering a normally soiled eight pound load of soiled textiles with product 2.

The compositions shown in Examples 3 through 18, below, were prepared by following the procedure of Example 1, Composition D.

Examples 3 and 4 Parts Components Sodium tridccyl benzene sulionatc 9 9 Potassium dichloroisocyanurate 2 5 Stearyl dimethyl benzyl ammonium chloride.. 0.8 0.5 Sodium tripolyphosphate 30 30 Sodium sulfate 51 48 The compositions of Examples 3 and 4 were tested at 0.15 concentration in the Dynamic Foam Test and the foam level fell from l inch in the absence of soil to a trace level after 40 mgs. were added. Both compositions are satisfactory for laundering soiled textiles in tumblertype washing machines.

Examples 5 and 6 Parts Components High titer soda talloW soap 12 l2 Potassium dichloroisocyanm-ate 2 Stearyl dimethyl benzyl ammonium chloride 0.3 Sodium tripolyphosphate 50 50 Sodium sulfate 30 27 The product 5 of Example 5 was evaluated in the Dynamic Foam Test at 0.15 concentration and exhibited the following foam behavior: mg. soil-1% inches; 40 mgs. soil- 1% inches; 80 mgs. soil-1% inches; 120 mgs. soil-7A; inch; 160 mgs. soil-V2 inch. The effect of incorporating the foam control combination of the invention is characterized by the product 6 of Example 6 which exhibits an initial foam height of /fs inch and a trace foam level in the presence of 80 mgs. of sebum soil. The compositions also demonstrate the foam suppressing ellect of the additive mixture of this invention.

v Examples 7, 8 and 9 Parts Components Sodium tridecyl benzene sulfonate 12 12 12 High titer soda tallow soap 3 3 3 Potassium dicliloroisocyanurate 10 10 Dodecyltrimethyl ammonium chloride 0.8 1. 5 3.0 Sodium tripolyphosphate 50 50 50 Sodium sulfate 16 l5 14 Examples 10 and 11 The following compositions showed excellent heavy duty performance with low sudsing characteristics and served as excellent detergents for use in tumblentype washers.

Parts Components Sodium tridecyl benzene sulfonatc 6. 0 Sodium lauryl alcohol suliato G. 0 12. 0 High titer soda tallow soap 3.0 3. 0 Sodium tripolyphosphate 50.0 50.0 Mixed 0124315 alkyl dimethyl benzyl ammonium chloride 0.8 0. 8 Sodium carboxy-methyl cellnlose 0.5 0.5 Potassium dichloroisocyanurate... 10.0 10.0 Water 8. 5 8. 5 Sodium sulfate 15.2 15. 2

Example 12 The following composition was prepared: Components: Parts Sodium tridecyl benzene sulfonate 12.0 High titer soda tallow soap 3.0 Sodium tripolyphosphate 50.0 Stearyl dimethyl benzyl ammonium chloride 0.8 Trichloro cyanuric acid 10.0 Water 1.5 Sodium sulfate 22.7 This composition gave the same general results as Example 2 and proved satisfactory for use in horizontal, front-loading washers.

Examples 73, 14 and 15 Parts Components Sodium alpha-hydroxy liexadecyl sulfonate l2 Sodium lauryl alcohol sulfate 12 Sodium sulfate of tctraethoxylated nonyl phenol l5 co (/15) soap 3. 2 2 3.5 Stearyl dimethyl benzyl ammonium ohloride 1. 2 0.8 1 Sodium silicate solids 3 3 3 Sodium tripolypliosph 40 45 40 Sodium sulfate. 25.6 22. 2 22.5 Potassium dichlorc ate 10 10 10 Water 5 5 5 The -term coco refers to fatty acid groups found in coconut 4oil fatty acids. Such acids contain from about 8 to about 18 carbon atoms per molecule, predominating lIl C12-C14 aCldS.

Examples 16, 17 and J8 Parts Components Sodium tridecyl benzene sulfonate 12 l2 12 Sodium tallow soap 3 3 3 Nitriloacetic acid, trisodium salt 50 5 Ethylene diamine tetraacetic acid, tetr sodium salt 5 Sodium sulfate 30 30 Sodium tripolyphosphate 35 35 Sodium silicate 3 3 3 Stearyl dimethyl benzyl ammonium chor 0.8 1 1 Potassium dichloroisocyanurate 10 10 10 Water q.s. q.s. q.s.

1 1 Example 19 Components: Parts Sodium tridecyl benzene sulfonate 12 High titer soda tallow soap 3.2 Stearyl dimethyl benzyl ammonium chloride 0.8 Sodium tripolyphosphate 50 Sodium silicate solids 3 Sodium sulfate 16.9 Sodium carboxymethyl cellulose 0.5 Polyvinyl alcohol 0.2 Brighteners, perfume, etc. 0.4 Potassium dichloroisocyanurate Water 3 The product 19 of this example has been found to exhibit highly superior properties as a heavy-duty detergent composition. Product 19 was formed in accordance with the spray drying techniques described above.

The foregoing compositions performed satisfactorily when used in tumbler-type Washing machines.

In summary, compositions of the present invention provide detergent compositions acceptable for use in both agitator-type and tumbler-type washing machines. Further, these compositions exhibit eiective detergency action of anionic detergent phosphate mixtures, bleaching action of a chlorine bleach and desired foam control in the presence of soil. Foam control is achieved by a novel combination of a cationic agent and the chlorine bleaching agent.

Performance of the compositions of this invention is excellent. Advantages realized therewith include: soft, uffy towels, diapers, etc.; smooth, silky sheets, pillow cases, etc.; easy-to-iron shirts, sheets, etc.; reduced cling on nylon and other synthetics; long garment life, less wrinkling.

The new compositions can be used to launder a variety of fabrics, which can be made from natural animal bers, natural vegetable fibers, mineral fibers and synthetic bers. These include wool, silk, cotton, linen, glass, acetate, rayon, nylon, Orlon, Dacron, and others. The fabrics can be those classied as outer garments, under garments, diapers, etc.

It is to be understood, in keeping with the illustrations given above, that the additive compositions, etc. of this invention can be in solid form in the character of freeilowing powders, granules, tablets, etc. By the term solids used herein, it is intended to include sizes and shapes of material having at least one dimension of relatvely low order, such as grains, chips, ilakes and other forms having proportionally large surface areas, and in any other suitable form The new compositions can be packaged in paper, plastic or any other suitable packaging medium. For example, an additive combination of a cationic `agent and a bleach can be packaged in a Water-soluble plastic material such as polyvinyl alcohol, for use either in a wash or a rinse cycle, or in both cycles, or in loose particulate from such as powders and granules. If desired, the bleach can also be contained in a Water-soluble polyvinyl alcohol packet or the like and the other ingredients can be combined in the container which also includes the bleach packet. Anther technique for insuring long shelf life involves coating of the bleach with a coating agent such as a suitable fatty alcohol, e.g. stearyl alcohol; the coated bleaching agent can then be mixed with all other ingredients without necessity for separated compartments in a container.

Although the present invention has been described and illustrated with a reference to specic examples, it is understood that modifications and variations of composition and procedure may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims.

I claim:

1. A controlled sudsing, heavy-duty detergent composition consisting essentially of:

(a) from about 5 to about 50 percent by weight of -a water-soluble, anionic organic detergent having an alkyl group of about 8 to 22 lcarbon atoms in its molecular structure,

(b) from about 5 to about 90 percent by weight of a builder salt selected from the group consisting of sodium inorganic phosphates, silicates, carbonates, sulf-ates, borates and mixtures thereof,

(c) from about 0.01 to about 4 percent by weight of a quaternary ammonium salt having |the formula wherein R1 is an alkyl group of about 10 to 2Q carbon atoms, R2 and R3 are alkyl g-r-oups of 1 to 3 carbon atoms each, R4 is selected from the group consisting of alkyl groups 'of l to 3 carbon atoms and benzyl groups, and X is a halogen selected from the group consisting of chlorine and bromine, and (d) from about 2 Ito about 30 percent by 4weight of a heterocyclic N-chloro imide bleach containing a plurality of chlorine-containing nitrogen atoms, the total quantity of (c) and (d) being sufficient to depress foam normally developed in the absence of said (c) and (d) to a pre-determined level at use concentrations of said composition under laundering conditions.

2. A controlled sud'sing, heavy-duty detergent composition consisting essentially of:

(a) from about 5 to about 50 percent by Weight of a water-soluble, alkali metal anionic organic detergent having an alkyl group of about 8 to 22 carbon atoms in its molecular structure, (b) from about 5 to about 90 percent by weight of a builder salt selected from the group consisting of sodium inorganic phosphates, silicates, carbonates, sulfates, borates and mixtures thereof, (c) from about 0.01 to about 4 percent by weight of a quarternary ammonium salt having the formula wherein R1 is an alkyl group of about l0' to 20 carbon atoms, R2 and R3 are alkyl groups of l to 3 carbon atoms each, R4 is selected from the group consisting of `alkyl groups of l to 3 carbon atoms and benzyl groups, land X isa halogen selected lfrom the group consisting of chlorine and bromine, and

(d) from about 2 to about 30 percent by weight of a bleach selected from the group consisting of t-richlorocyanuric acid, dischlorocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocyanurate.

3. A composition dened by claim 2 wherein the total quantity of (c)|(d) is sufcient to provide from about 20 to about 200 parts pe-r lmillion of available chlorine in a washing bath at total detergent composition concentrations in excess of 0.075 percent by weight in said bath.

4. A composition defined by claim 2 wherein the total quantity of (c)-|(d) lis sucient to provide from about 20 to about 200 parts per million of available chlorine in a Washing bath at total detergent composition concentrations from about 0.1 to about 0.4 percent by weight in said bath.

5. A composition defined by claim 2 wherein said builder salt is a Water-soluble, alkali metal inorganic phosphate.

6. A composition -delined by claim 2 wherein the ratio tof (c)/(d) is from about 0.01/1 to about 2/1.

7. A controlled sudsing, heavy-duty detergent composition consisting essentially of:

(a) from about 7.5 to about 40 percent by weight of a water-soluble, anionic organic detergent selected from the group consisting of alkali metal sulfates, sulfonates and carboxylates having in their molecular structure :an alkyl group `of about 8 to 22 carbon atoms,

(b) from about 25 t=o about 60 percent by weight of a water-soluble, alkali metal inorganic phosphate builder salt, and

(c) from about 2 to about 30 percent by weight of a mixture containing from about 1 to about 67 percent by weight of a quaternary ammonium salt having the formula wherein R1 is an alkyl group of about 10 to 20 carbon atoms, R2 and R3 are alkyl groups of 1 to 3 carbon atoms each, R4 is selected from the group consisting of -alkyl groups of 1 to 3 carbon atoms and benzyl groups, and X is a halogen selected from the group consisting of chlorine and bromine, and from about 33 to about 99 percent by weight of a bleach selected from `the group consisting of trichlorocyanuric acid, dichlorocyanuric acid, sodium dichloroisocyanurate and potassium dischloroisocyanurate.

8. A detergent composition consisting essentially of about .01-4% of a quaternary ammonium salt represented by the formula [Ra-IlI-Rd X wherein R1 is an alkyl group of about 10 to 20 carbon atoms, R2 and R3 are alkyl groups of l to 3 carbon atoms each, R4 is selected from the group consisting of alkyl groups of 1 to 3 carbon atoms and benzyl groups, and X is a halogen selected from the group consisting of chlorine and bromine, about 2-30% of a bleach selected from the group consisting of dichlorocyanuric acid, trichlorocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocyanurate, the ratio of said quaternary arnmonium compound to said bleach material being from `about .01/ 1 to about 2/1 by weight, 5-50% of watersoluble, alkali metal, anionic organic detergent having an alkyl group of about 8 to 22 carbon atoms and about to 90% of a water-soluble alkali metal inorganic phosphate, said amounts being by weight thereof.

9. A detergent composition consisting essentially of about 5 to 50% by weight of a water-soluble anionic organic detergent selected from the group consisting of alkali metal sulfates, sulfonates and carboxylates having an alkyl group of about 8 to 22 carbon atoms in their molecular structure, about 5 to 90% by weight of a Water-soluble alkali metal inorganic phosphate builder salt and about 2 to 30% by weight of a mixture of (a) a. quaternary ammonium salt Irepresented by the formula wherein R1 is an alkyl group of about 10 to 2O carbon atoms, R2 and R3 are alkyl -groups of 1 to 3 carbon atoms each, R4 is selected from the group consisting of alkyl groups of l to 3 carbon atoms and benzyl groups, and X is a halogen selected from the group consisting of chlorine and bromine and (b) a bleach selected from the group consisting of -dichlorocyanuric acid, trichlonocyanuric acid, sodium dichloroisocyanurate an potassium dichloroisocyanurate, the Weight ratito of said quaternary ammonium compound to said bleach being from about 0.01/l lto about 2/1.

10. A detergent composition in dry, granular form consisting essentially of about 5 to 50% by weight of an alkali metal higher alkyl benzene sulfonate detergent having about 8 to 18 carbons in the alkyl group, about 5 to 90% by weight of a water-soluble alkali metal inorganic phosphate, about 0.01 to 4% by weight of stearyl dimethyl benzyl ammonium chloride, and about 2 to 30% by weight of an alkali metal salt of dichlonocyanuric :acid selected from the group consisting of sodium and potassium salts.

References Cited by the Examiner UNITED STATES PATENTS 2,834,737 5/1958 Farkas 252-98 2,929,816 3/1960 Chamberlain 252-102 XR 2,987,435 6/1961 Davies et al. 252--187 XR 2,988,471 6/1961 Fuchs et al 252-186 XR 3,044,962 7/ 1962 Brunt et al 252--106 XR FOREIGN PATENTS 525,648 5/1956 Canada.

OTHER REFERENCES Monsanto ACL, Technical Bulletin, 1-177, January 1960, Monsanto Chemical Co., St. Louis, Missouri, pages 3, 10, 11.

ALBERT T. MEYERS, Primary Examiner.

J ULIUS GREENWALD, Examiner.

M. WEINBLATT, Assistant Examiner.

Claims (1)

1. 7. A CONTROLLED SUDSING, HEAVY-DUTY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF: (A) FROM ABOUT 7.5 TO ABOUT 40 PERCENT BY WEIGHT OF A WATER-SOLUBLE, ANIONIC ORGANIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL SULFATES, SULFONATES AND CARBOXYKATES HAVING IN THEIR MOLECULAR STRUCTURE AN ALKYL GROUP OF ABOUT 8 TO 22 CARBON ATOMS, (B) FROM ABOUT 25 TO ABOUT 60 PERCENT BY WEIGHT OF A WATER-SOLUBLE, ALKALI METAL INORGAIC PHOSPHATE BUILDER SALT, AND (C) FROM ABOUT 2 TO ABOUT 30 PERCENT BY WEIGHT OF A MIXTURE CONTAINING FROM ABOUT 1 TO ABOUT 67 PERCENT BY WEIGHT OF A QUATERNARY AMMONIUM SALT HAVING THE FORMULA

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