IL29064A - Detergent compositions - Google Patents

Description

Detergen compositions SOCIESB BEIGE DB L'AZOTE ST DBS PRODUITS This invention relates to detergent compositions and the like and including solid detergent compositions which can he formed or extruded into chips, flakes, or bars to be used as ordinary toilet bars, and, more particularly, to such compositions comprising only surface-active synthetic compounds and being entirely free of soap.

This invention relates generally to detergent compositions for extrusion or formation into cakes or bars of toilet soap, the term "soap" here meaning the common usage of such a word for such toilet bars. In the past, when such bars or cakes were formed with natural soaps, they were easily extruded or formed and had a soft feel and were shiny and attractive in appearance. However, they did not possess the surface -active qualities necessary for thorough cleaning called for in today's usage. Therefore, synthetic compositions were. : developed to take the place of natural soaps, and these compositions contain both combinations of detergents and j natural soaps, and/or merely detergent compositions alone.

However, such compositions may have a tendency not to pack firmly together so that they can be extruded or formed into bars, but rather crumble and have a flaky, or coarse and grainy feeling and appearance which, of course, is not satisfactory for use as a toilet bar. Further, some of these compositions which can be extruded into cakes of soap have a tendency later on in use to crack or split as they are sequentially wetted and then allowed to be dried. Further, they do not lather well at low temperatures, as for example when used with cold water.

If it is attempted to overcome some of the above difficulties by using sodium . sulphates of fatty alcohols (or sodium sulphates of higher aliphatic alcohols), such compositions may not lend themselves, as soap does, to formations through compression of a mass or bar of soap having the desira-' ble qualities for calendering and extruding. Another drawback of these compositions is that the product shaped therefrom i has a tendency to expand too much when contacting water, to be very sticky when used, and to be used up too rapidly, or to become tough.

If it is attempted to overcome the difficulties described above in the use of sodium alkyl sulphate compositions by adding various agents to the sodium sulphates (such as monoglycerides of fatty acids, fatty alcohols, polyglycolic ethers, etc ..), these agents may improve the plasticity of the compositions and their ability to be extruded, but the bars resulting therefrom may have a tendency to be brittle and have a matted appearance.

If other synthetic detergent compositions are used containing potassium sulphates of fatty alcohol (either alone or mixed with inorganic inert ingredients, anhydrous salts, waxes or paraffin, etc ..), these compositions may successfully overcome the brittleness of the resulting bars and the dull lustreless appearance, but they may be undesirable because e, they are not homogenous to the extent where they are easily shaped into common toilet soap bars by conventional soap-making machinery therefor.

Again, if the various disadvantages . are attempted to be avoided by using such synthetic detergent compositions containing potassium sulphates or sodium sulphates by combining these two substances with alkaline soaps and an ^Lectrolyte , these compositions may successfully overcome the various difficulties in formulation of the compositions into the desired shapes for toilet bars and may have the desired feel and lustre in appearance . =■ However, when these bars are placed in water, because of the hydrolysis of the soap that is -present in the composition, the pH of the composition becomes alkaline. Because of the superior wetting power of the synthetic washing agent contained in the composition, the resulting alkalinity penetrates the skin deeply. This alkalinity damages the epidermis of the skin, therefore making it dry and rough to the touch.

According to this invention, however, there are provided detergent compositions containing potassium alkyl sulphates, alone or in combination with sodium alkyl sulphates, and containing no soap. They have a neutral pH, or are even slightly acid, in aqueous solutions. They have the special touch of traditional toilet cakes composed of soap, and are-hard. They have excellent plasticity which allows them to be easily shaped and extruded, using the usual common at lower temperatures for providing "better, lather or foaming during use. Also, they have a softer touch and feeling or action on the skin and give the skin a better of softer feeling after use.

These new compositions utilize the advantages of using potassium alkyl sulphates in combination with a. solubi- . liser or binding or softening substance in an. amount up. o about 70 Wi't . tho forogoing Jand additional obioot in view,, . by way. of example , T/Ehis invention will now be described in more detail,/and other objects and advantages thereof will be apparent from the following description. and the appended claims.

As will, be understood, and especially with the manufacture and sale of toilet soaps, the evolution of compositions and manufacturing techniques to accomplish the desired results may be a highly complex technical problem, whereas the complete and crucial evaluation thereof commercially is most frequently a purely subjective whim of the user. Thus, it can be appreciated that, this is a situation where two incompatible desires are involved in attempting to produce new .compositions to achieve such results as. providing solid detergent compositions which can be easily formed or extruded. into toilet bars or. cakes, while,at the. same .time having the resulting bars possess the desired characteristics of bars made with natural soap in that they have a substantially translucent and shiny appearance and are soft to the feel, and which lather well in any temperature water without turning alkaline therein, while at the same time having the desired surfactant qualities of synthetic detergents in producing a superior degree of wetting power. Purther, they must be such as to produce a softening effect to the skin when used. It must be remembered that the user is not even aware of the problem or of the need for detergent compositions which are easily formed or extruded into cakes, and pays little or not attentio in deciding whether the composition is satisfactory for such highly technical factoss , to such an extent that, in providing new compositions which give completely unexpected and hitherto unknown physiological results, it is preferred that such new compositions also continue to exhibit most if not all of the physical and mechanical characteristics of conventional natural soap bars, even if such characteristics are completely inimical to the new results desired, so that the new toilet bars will not be initial-■ ly rejected without trial by the user as being something completely foreign in handling or initial appearance to what he or she is used to.

These solid detergent compositions may use as synthetic washing agents potassium sulphates of fatty alcohols alone. However, it is preferred to use a mixture of potassium sulphates with sodium sulphates of fatty alcohols.

This mixture is then plasticized by one or more substances having a fatty character and a molecular weight higher than about 200, a melting point of at least about 50°C. , and preferably higher than about 55°C, while being substantially non-soluble in water. These plasticizing substances possess one or several solubilizing groups in the molecule, such as, for example, the hydroxy-OH group which gives the substances a hydrophilic character for emulsifying into the composition even though they are non-soluble in water.

The potassium and sodium sulphates used herein are, preferably, those obtained from higher aliphatic alcohols containing about 10 to 18 carbon atoms, with alcohols. having about 12 to 14 carbon atoms being especially . preferred. ■-■<■■ .

In practising this invention, when a- mixture of both potassium and sodium alkyl sulphates is used, it has been · found that particular proportions thereof bring about the best results. For example, it has been found that a final composition having excellent plasticity and having no splitting between 80/20 and 65/35? with the ratio e-f- about 70/30 and 75/25 being preferred.

A series of systematic tests were made of final compositions having different ratios of potassium alkyl sulphates to sodiaunmdailknylt,hseulapchcaotmepsa,nyainndg tahreawiesngul s are shown in the table, below. That table shows, among other things, that the variations in splitting of the final detergent compositions is a function of the respective quantities of the two sulphates. (The splitting is an indication of the tendency of toilet cakes made from these final compositions to become tough and to form soft pastes in the presence of water).

Referring to Table I, the splitting tendency or characteristic was determined by using. a standard toilet bar having the dimensions of 4-5 mm x 40 xmm x 10 mm, which was e dipped into water and maintained at a temperature of 25°C. for six hours. After the six-hour interval, the softened part of the cake was careffully scraped av/ay by means of an edgeless .tool and weighed again. The weiglrb of the split part was obtained through, differentiation and expressed in grams per cent. This indicates that the degree of splitting varies dramatically depending upon the ratio of potassium to sodium alkyl sulphates, with the least amount of splitting taking place with the above noted preferred ratios.

TABLE I Composition K/lTa Ea';::.o # Splitting These mixtures of potassium and sodium alkyl sulphates may be prepared by separate preparation of the salts in he dry state, followed by the addition of the sodium 'alfcyl sulphates to the corresponding potassium alkyl sulphates "being careful to keep within the desired ratios. The sulphates may be obtained by treating the fatty alcohols thereof with chloro-sulfonic acid. This is followed by neutralization of the resulting solution with potash, or caustic soda, and finally concentrating the resulting solution either by vacuum-evaporation, atomization, or salting-out.. 7/ith the salting-out process^n the neutralization, it is preferred to have about 6 to 12-1/2$ by weight of sodium chloride in the caustic potash solution so that the resulting mixture of alkyl sulphates may be easily separated. In this manner, a product is obtained containing about-70-75 $ of the active materials and having the potassium/sodium ratio precisely within the limits desired for the final composition.

As was stated above, the plasticity of these detergent compositions is achieved by adding to the potassium alkyl salts alone or to a mixture of potassium and sodium alkyl sul a oo substantially water-insoluble substances having a fatty character while still being hydrophilic by having a hyarophilic group in the molecule. Some of the plasticizing substances which have been effectively utilized are fatty alcohols or higher aliphatic alcohols containing at least about 16 carbon atoms, partial polyol esters such as glycerine mono- and distearate^ propylene glycol or ethelyne glycol monostearate , or esters of fatty hydroxylated acids such as hydrogenated castor oil, or mixtures thereof.

However, it has been found preferable to utilize fatty alcohols mixed wi h another plasticizer. The reason for this is that fatty alcohols with 16—18 carbon atoms per molecule have a tendency to give final detergent compositions which become soft at a temperature slightly higher than room temperature, which often occurs during storage of the resulting products. Stearylic alcohol, on the other hand, has a tendency to migrate to the surface of the resulting detergent cake, thus/modifying its properties in use by decreasing the ability of the cake to foam quicklv. ' Therefore, another plasticizing agent- is used with the preferred fatty alcohols, with hydrogenated castor oil being preferred, and. with the ratios varying between one to five parts of the fatty alcohol for one part (by weight) of the hydrogenated casto^r oil.

The amount. of plasticizer or mixture thereof to be added to the potassium alkyl sulphate, or the mixture of potassium and sodium sulphates of fatty alcohols, may vary within large limits, but lies generally within the range of about 10 io to 50 > by weight of the sulphates cycled. Lower amounts of plasticizer produce poor plasticity in the resulting cakes, while higher proportions reduce the foam formation.

Because of the good plasticity characteristics of these compositions, a softening or binding agent may be incorporated or utilized in the final composition without reducing the superior compacting or extruding qualities thereof Therefore, these detergent compositions preferably contain one or more of these binding or softening agents, such as amylaceous substances or proteinous substances obtained from the milk industry and consisting mainly of proteins and carbohydrates. These binding or softening agents e particularly useful for providing stability of the cakes made therefrom at different temperature levels. In addition, they provide the solubility varying less ΐ-^θίΕΪοκ^ temperature ΐβ-βΗβ§ Ι_?. Also, with these binding and softening agents, the final detergent composition can have a higher water content without decreasing the quality of the final product-.. In this connection, compositions without these binding or softening agents satisfactorily contain no more than about five or six per cent water content, while with such binders they may reach about eight to ten per cent water content. Furthermore, conven tional soap-making apparatus may be utilized without any special provision for formulating toilet cakes herein when the final Solid detergent compositions contain these binders, and the final cakes feel softer and have a softer touch or action on the skin.

Some of the softening or binding substances which have been successfully utilized herein are such amylaceous substances as starch obtained from maize, corn, or wheat, and which have a solubility which may vary within i rge limits, from insolubility to complete solubility when cold. Those substances may be utilized which have a solubility that lies between that of a true solution and that of a colloidal solution. Prom the economical point of view, non-soluble starch may be utilized, and those proteinous substances derived from the milk industry, such" as milk powders. However, starch designed under various commercial designations, such as gelatinized starch, degraded starch, solubilized starch, and oxythylated starch are particularly preferred herein.

The proportion of these binding and softening substances in the final product may vary within large limits ranging up to about 40 fo of the weight of the final composition , . or from zero to 70 fo of the weight of the potassium alkyl sulphates or a mixture, of the potassium and sodium sulphates of the fatty alcohol cycled. Higher proportions reduce the foaming power of the detergent composition, or reduce the soft feel of the final toilet cake. Preferably, the amount of binder is between about 15 io and 30 fc of the total weight of the final de+nrgent composition, or between about 30 fo and 70 fo of the weight of the sulphates of the fatty alcohols contained therein.

The final solid detergent compositions described herein may contain all of the above mentioned wetting, plasticizing, and binding agents. They are entirely free from soap and have a neutral pH in aqueous solution, or are even slightly acid. They may also contain the usual other inert additives employed in the soap-making practice, such as cellulosic materials urea, lanolin, lecithine, as well as coloring matters and perfumes. The total amount of these additional additiges is generally within the range of about 2 f> to 25 f° of the weight of the sulphates of fatty alcohols contained therein, or from about 2 o to 20 fo of the weight of the final composition.

When preparing these compositions, it has been found advantageous to mix the sulphates of fatty alcohols and the plasticizers first while warm, and thereafter to mix in the binder and continuing the mixing until an homogenous paste is obtained. The water content of the pasteis thereafter reduced, r 9. either by deselectio in a mixer, preferably under vacuum, or upon a heating cylinder, or similar appropriate, procedure, until the water content of the composition is within the range of about 5 i to 6 $ of those compositions having no "binder and about 8 io to 10 io of those compositions containing binding substances. The' final solid detergent compositions obtained are completely free from soap and preferably contain about 35 to 75 parts of potassium and sodium sulphates of fatty alcohols with the amountof potassium sulphates in relationship to that of the sodium sulphates being between about 80/20 and 65/35, and preferably between about 70/30 and 75/25· In addition, the compositions preferably contain. about 15 to 25 parts of plasticizer up to about 25 parts of binding and softening agents, 1 to 10 parts of neutral agents, such as urea, coloring substances, perfumes, and inorganic salts, and about 5 to 10 parts of- water.

As wiil11 be understood from the foregoing, conventional knowledge and teaching as to the proper proportioning of particular wetting and plasticizing and binding components to achieve, in the final solidified toilet cakes in accordance herewith, the desired characteristics of being soft to the touch, and easily lathered at varying degrees of temperature,^ and of neutral alkalinity in water, without splitting or becoming pasty during use are readily applicable to the detailed formulation of compositions in accordance herewith without experime tation by men skilled in this art. Nevertheless, and merely as illustrative of various different specific formulations with which satisfactory results are achieved in accordance herewith, the following examples may be noted : Example 1 : . Treating with chloro sulfonic acid a mixture of fatty alcohols comprising : 63 parts of alcohols (aliphatic alcohols containing ■ · 12 carbon atoms) · ' ~ -·■·- · . 27 psirts of C14 alcohols parts of C16 alcohols.

The acid sulphate obtained was introduced into an aqueous solution of caustic potash containing, about $ ..sodium... chloride and 12.5 $> potassium hydroxide for neutralization thereof. The alcohol sulphates were salted out. The mixture was allowed to stand' for a number of hours at 60°G. for decaja.ta.ti.on... The lower aqueous layer was separated, with the latter being entirely free from sulphates of fatty~alcoh.ols,...wi"th 'the upper layer being in the form of a grainy paste, and having approximately the following composition bgr--weight : Potassium and sodium sulphates of fatty alcohols- - ■ 70-$' Potassium sulphates of fatty alcohols 53 i° Sodium sulphates of fatty alcohols 17 # Sodium chloride ··■ 2 Potassium sulphate 1 # Patty alcohols plus inert ingredients 3 i° Water - 24 # Therefore, in the composition obtained, the weight ratio of potassium sulphates to sodium sulphates is approximately 76/24. parts of a mixture containing equal parts of stearylic and cetylic alcohols and substantially 5 parts of hydrogenated castor oil were mixed together while warmed in a mixer until the iodine index was lower than four. The resulting mixture was mixed while still warm in a mixer together with 100 parts by weight of the above noted sulphate mixture. The resulting mixture was evaporated until the amount of water therein was reduced to approximately 5 ° to 6 , with the evaporation being effected either in the mixer itself or upon a heating cylinder. The resulting mass was transformed into vermicelli or chips, and finally into bars and cakes. At the output of the extruding machine the vermicelli and bars presented a good plasticity, a smooth and homogenous appearance, was not brittle, and had splitting characteristics ranging in the neighborhood of about 30 The cakes obtained in Example I wore compared with soap and v/ith commercial products based upon mixtures of synthetic washing agents and soaps with the results noted in Table II below.

TABLE II PH(in aqueous) Split¬ Appearance solution of 1$) ting Product following Example I smooth 6.5 30 brilliant Soap (sodium salts of fatty smooth, 10.3 42.5 acids) brilliant Products based on mixtures rdatted 5.8 50 of synthetic washing 'matted 10 58.5 agents and soaps '■ .3 Products, based on synthetic matted 7.0 55 washing agents matted 8.5 55 matted 0.4. 54 . matted 8.0 42.5 Example II Operations were carried out in this example in the same manner as in Example I, except that ishe plasticizer was Replaced by one of the following compositions t 20 parts of a mixture comprising glyceryl mono- and distearates having a melting point of 60°G. The vermicelli and bars obtained demonstrated a lower plasticity, and were substantially less translucent than those prepared according to Example I. They were, nevertheless, transformed into homogenous cakes having a good appearance, with the splitting characteristics being very favorable, and in the neighborhood of 27.5 Example III j Operations were carried out i a manner similar to that of Example I, but with a different plasticizer substituted therein comprising the following materials : 20 parts of a mixture containing equal amounts of glyceryl mono- and distearates having a melting point of 60°C. and the rest consisting of fatty alcohols having 16 to 18 carbon atoms per molecule and having a melting point of 48°C. The cakes obtained in this example exhibited a superior plasticity and were more translucent than those obtained in Example II. Their hardness and softening point, however, were somewhat lower. They exhibited smooth and brilliant appearance, and had a splitting index of between 30 § Example IV In order to make- an effective comparison, operations in this example were carried out in the manner of Example I, but replacing the plasticizing agent with paraffin (that is, by a substance not having a hydroxylic group). The melting point of the paraf fin was between 40° and 42°C. The mixture obtained exhibited very poor binding qualities. After lowering the water content down to approximately 5 f> to 6 f, and cooling the mixture, , it was very difficult to shape the composition into bars, as the bars obtained exhibited very little plasticity, and their splitting index was very high and in the neighborhood of Example V. 22 parts of maize starch finely granulated, and 10 parts of urea were mixed while cold in a mixer for about 15 minutes, together with 57 parts' by weight of a mixture of C12-C14-C16 alcoylsulphates containing 70 fo of the sulphates, and in which the potassium to sodium ratio was 74/26 as in Example I.

The resulting paste, was heated to about 70°C. by means of steam, circulation through a double jacket surrounding the mixer. While the mixing was carried on, a plasticizer was added comprising 20 parts by weight of a previously melted mixture comprising 15 parts of e¾ual amounts of stearylic and cetylic alcohols, and 5 parts hydrogenated castor oil. After this addition, the water excess was eliminated through evaporation in the mixer, until the water content of the final mixture was within 8 f to IO0 The resulting paste was allowed to cool down to approximately 40°G and the coloring agent and perfume were added. Thereafter, the e, paste was cooled and presented a very homogenous appearance. It was easily removed from the walls of the mixer, and from the vanes of the stirrer. The paste was then fct/ansforme'd~i¾'xo""'verniicellx , and thereafter into bars in a conventional extruding machine. The bars were then cut and formed into cakes which had an excellent appearance, and presented all of the desirable characteristics for a good toilet cake. The plasticity of the cakes was good and their splitting index was in the range of about 30 f>.

Examples VI to XIV Operations were carried out substr J ally as in Example .V, "but with different ratios of potassium and sodium alkyl sulphates, with the different ratios being obtained "by va^rying the amount of sodium chloride contained in the neutralizing solution of the caustic potash, or by obtaining separate mixtures of the desired ratios by evaporation of aqueous solutions of the potassium and sodium alkyl sulphates having the desired ratios. The final toilet calces obtained in these nine examples exhibited varying degrees of plasticity, and varying splitting values, depending upon the potassium and sodium alkyl sulphate ratios. The results obtained are compared in the following Table III.

TABLE III Ratio Splitting SAK: SANa Value Plasticity Ex. VI 100:0 80 No e Ex. VII 85: 15 45 Low' Ex. VIII 80:20 33 Good . IX 73:5;26.5 31 Very go d Ex. XI 60:40 36 Rathe good Ex. XII 40:60 52 Poor Ex. XIII 20:80 65 Poor Ex. XIV 0: 100 78 Poor As will be apparent from the foregoing, they arc provided 'in accordance herewith a variety of detergent compositions having physical and handling qualities and characteristic so similar to those of conventional toilet cakes containing soap that the conventional use and handling thereof by the ultimate consumer does not require change, yet which produces advantages and enhanced results in use by providing substantially increased wetting qualities for increased effective cleansing action, while eliminating or minimizing the usual "splitting" or pasty characteristics usually associated with toilet cakes made from detergent compositions,

Claims (14)

and, inaddition, eliminating the irritating qualities to the skin usually associated with the prior detergent compositions. The physiological advantages with compositions in accordance herewith additionally produce greater satisfaction to the user, although he may not realize why, "because of the more soft feel of the resulting cake and its superior lathering ualities. Similarly, these compositions exhibit superior plasties zing and extruding qualities which make them especially useful because conventional soap-making equipment can be used for making toilet cakes therefrom and in the absence of substantially increased cost factors over those normally encountered in the production of conventional toilet soap. While the compositions herein described form preferred embodiments of this invention, this invention is not limited to these precise compositions, and modifications may be made therein without departing from the scope of this invention which is defined in the appended claims. WHat is claimed is : HAVING NOW particularly described and ascertained the nature of our said invention and in what manner the same is „to be, performed, we declare that ,what„w.e claim is:

1. A -aoap-iree aetergenv composition capable of being- formed and extruded into solid toilet cakes and bars, and having a substantially -neutral ρΗ in aqueous solution which comprises in combination a substantial proportion of a wetting agent component consisting essentially of sulphates of higher aliphatic alcohols and selected from the group consisting of potassium sulphates of higher aliphatic alcohols, sodium sulphates of higher aliphatic alcohols, and mixtures thereof, combined with a substantially water-insoluble plasticizing component within the range of about 10 o to 50 by weight of said wetting agent component and having a fatty character and a hydroxy group and which has a molecular weight above about 200 and a melting point above- about 50°C. and selected from the group consisting of high, aliphatic alcohols containing 1 6 to 18 carbon atoms, partial esters of higher aliphatic acids and polyols, hydrogenated castor oil, and mixtures thereof. ' 'l "■

2. A soap-free detergent composition as recited in claim 1 in which the wetting agent component is a mixture of potassium and sodium sulphates of high aliphatic alcohols containing 10 to 18 carbon atoms per molecule and in which the weight ratio of potassium sulphates to sodium sulphates is

3. A soap-free detergent composition as recited in claim 1 in which the wetting agent component is substantially within the range of about 35 $> to 7 by w&igjat of said composition and is a mixture of potassium and sodium sulphates of high aliphatic alcohols containing 12 to 16 carbon atoms pe£ molecule and in v/hich the weight ratio of potassium to sodium sulphates is within the range of about 80 to 20 and 65 to 35, in which the plasticizing component is substantially within the range of about 15 $ to 25 by weight of said composition, and which also includes up to about 25 by weight of said composition of softening and binding substances selected from the group consisting of gelatinized starch, degraded starch, solubili ed starch, ox thylated starch, milk powders, non-soluble starch, and mixtures thereof.

4. A soap-free detergent composition as recited in claim 3 v/hich also includes inert components substantially within t!ae range of about 7 # to 10 % by weight of said composition, and water substantially, within the range of about 5 -to 10 io by weight of said composition.

5. · A soap-free detergent composition as recited in claim 4 in which said inert components include coloring agents, perfumes, urea and the inorganic salts.

6. A soap-free detergent composition as recited in claim 1 in v/hich the wetting agent component is a mixture of potassium and sodium sulphates of high aliphatic alcohols containing 10 to 18 carbon atoms per molecule and in v/hich the weight ratio of potassium sulphates to sodium sulphates is within the range of about 70 to 30 and 75 to 25.

7. A soap- free detergent composition as recited in claim 6 in which the wetting agent is a mixture of potassium and sodium sulphates of high aliphatic alcohols containing 12 to 16 carbon atoms per molecule.

8. A soap-free detergent composition as recited in claim 7 in which the plasticizing component is substantially about 50 io by weight of the sait wetting agent component and is a mixture of cetylic and stearylic alcohols containing 16 to 18 carbon atoms, and hydrogenated castor oil and in which the weight ratio of alcohols to castor oil is within the range of about 1.5 to 1 and 5 to 1.

9. · A soap-free detergent composition as recited in claim 1 in which the plasticizing component is substantially about 50 o by weight of said wetting agent comp ent in said composition and is a mixture of cetylic and stearylic alcohols containing 1 6 to 18 carbon atoms and hydrogenated castor oil, and in which the weight ratio of alcohols to casto:? oil is within the range of about 1. 5 to 1 and 5 to .

10. A soap-free detergent composition as recited in claim 9 which also includes a binding agent of starch which is substantially about 50 ^ by weight of the said wetting agent.

11. A soap-free detergent composition as recited in claim 1 which also includes a solubilising component and a mixture of binding and softening agents which is present, within the range of up to about 70 i° by weight of the said wetting agent component.

12. 1 2 . A soap-free detergent · compositi on as recited in claim 1 in \v&ich the plasticizing component has a melting point of at leas about 55°C. or more.

13. 1 3 . A §oap-frec detergent composition as recited in claim 1 in which the wetting agent component comprises potassium sulphates of higher aliphatic alcdhols having 1 2 to 1 6 carbon atoms per molecule , and in which the plasticizing component is a mixture of cetylic and stearylic alcohols containing 1 6 to 18 carbon atoms and hydrogenated castoi oil , and in which the v/eight ratio of alcohols to castor oil is w hin the range of about 1. 5 to 1 and 5 to 1, and which also includes a binding agent.

14. . A soap-free detergent composition capable of being formed and extruded into toilet cakes and bars and having a substantially neutral pH in aqueous solution which comprises in combination about 30 by weight of saifi composition potassium sulphates of aliphatic alcohols having 1 2 to 1 6 carbon atoms por molecule, about 10 i by v/eight of said composition sodium sulphates of aliphatic alcohols having 1 2 to 1 6 carbon atoms per molecule, a plasticizing component consisting of about 7. 5 by weight of said composition stearylic alcohol,' 7· 5 ° by weight of said composition cetylic alcohol, and about 5 1° by weight of said composition hydrogenated castor oil, .a component. consisting of about 20 "Jo by weight starch, about 10 > by weight of said composition urea, about 5 ° by weight of said composition inorganic salts, and about 8 by weight of said composition