United States Patent Office

Transcription

1 United States Patent ffice PAQUE LIQUID DETERGENT CMPSITIN William C. Krumrei, Springdale, and Joseph Blinka, Cin cinnati, hio, assignors to The Procter & Gable CoR pany, Cincinnati, hio, a corporation of Chic No Drawing. Filed Apr. 16, 197, Ser. No. 63,02 12 Claims. (C ) This invention relates to a liquid anionic organic syn thetic detergent composition which gives good perform ance and which has a desirable nacreous appearance without the use of opacifiers that affect stability or act as performance loads. The opacifying agent of this inven tion consists essentially of suspended crystals of an un dissolved portion of an anionic organic synthetic deter gent constituent and thus contributes to, rather than de tracts from, the active detergent of the composition. Translucent and transparent liquid synthetic detergents are common in the industry, but, from a consumer point of view, it has become desirable to develop an efficient opaque product which has the appearance of liquefied white or colored bar soap. pacity in a liquid product increases its sight appeal to the purchaser who associates the opacity with his favorite bar soap, powdered soap, or hand lotion which he has been accustomed to over the years; a transparent or translucent product does not have this particular appeal. Previous attempts to produce opacity in liquid soaps involved the use of inorganic solids or dispersible or ganic solids or liquids which did not contribute to de tergency and which, in most instances, acted as perform ance inhibitors and resulted in products which were un stable against phase separation. Thus there is a demand for a mild, high Sudsing good cleansing, concentrated liquid synthetic detergent composition which is opaque and which has favorable physical characteristics. Common methods of producing opacity in liquids are the use of finely divided insoluble solids. These solids are dispersed in the liquid product and nearly always affect the Sudsing performance. In a product designed for dishwashing, for example, good sudsing and suds which last a long time are important because the house wife has come to associate sudsing with cleansing action and as an indicator of the presence of active detergent. The sudsing action of fatty acid soaps is functional, but the synthetic detergents common today generally do not require Sudsing for adequate cleaning. However, be cause of the association of good sudsing with good clean ing quality, it is desirable to market synthetic detergents which Suds well. An opacifier which would inhibit good Sudsing would be undesirable since it would only add one marketing feature at the expense of another. Common opacifiers, finely divided organic solids such as wax or Stearic acid, and organic liquids such as emulsified fats or oils, adversely affect the sudsing performance of the detergent. Inactive opacifying particles are similar to dirt particles which the detergent is designed to remove from the fabric and thus create a slightly greater deter gency requirement for the product. While some sub stances such as wax may help produce bubbles, the bubbles are short lived and are unsuitable for dishwash ing or laundry sudsing. paque liquids are difficult to prepare from the above mentioned opacifiers because the solids must often be very finely ground or finely ground and introduced into the liquid as a paste. Fine grinding is difficult in the Patented Fei. 7, case of some solids, but often is essential to reduce the tendency toward gravitational separation. Many of the opacifiers comomnly used such as titanium oxide and bentonite have a specific gravity greater than that of the vehicle in which the opacifier is suspended. This factor increases the tendency to settle. An opaque product, to be successful, must have a high degree of stability on standing. In a highly competitive market, such as household dishwashing detergents, appearance is important. Since pearls and mother-of-pearl have been associated with desirability, product excellence, value and high quality, peariness and a satiny sheen is believed to enhance a product's appearance. While opacity and an opales cent sheen give an appealing appearance, the product must meet other standards in that it must be uniform in composition and stable and must not affect the sudsing and detergency performance. An object of this invention is to provide a quality opaque liquid detergent in which the opacifier is also an active component. A further object is to develop an opacifier in a liquid detergent composition which will act compatibly with the rest of the components to form a stable product. A further object is to produce a liquid detergent with a desirable opalescent sheen. The present invention is based on the discovery that Suspended crystals of alkyl glyceryl ether sulfonates im part to concentrated liquid synthetic detergent solutions a desirable opaque appearance. Thus, in accordance with the present invention, the aqueous solution of syn thetic detergent contains in suspension an alkali metal Salt, such as a sodium or potassium salt, of an alkyl glyceryl ether sulfonate having from about 16 to about 18 carbon atoms in the alkyl radical. Electrolyte salts which usually accompany anionic organic sulfuric re action products together with common water soluble organic Solvents, can also be present in the detergent Solution as more fully hereinafter defined. The opacifier is normally suspended in the detergent Solution by first dissolving a suitable alkyl glyceryl ether sulfonate Salt in the detergent solution at a temperature at which the said salt is substantially completely soluble and then cooling the solution to a temperature, preferably room temperature, at which the alkyl glyceryl ether sul fonate salt is substantially insoluble. As the solution is cooled, the alkyl glyceryl ether sulfonate salt precipi tates in the form of fine crystals which remain Suspended in the detergent solution and which cause the product to have an over-all pearly white opacity. An orientation of the precipitated crystals and a slight crystal growth often causes an opalescent sheen which enhances the Paque appearance. A suitable composition can also be made by reducing the alkyl glyceryl ether sulfonate salt to very small particle form in a colloidal mill and then appropriately suspending such particles in the detergent Solution at room temperature, for example. The Specific gravity of the alkyl glyceryl ether sulfo nate Salts used as opacifiers in accordance with this in Vention is about 1.2, which is only slightly higher than the Specific gravity of the detergent solutions (about l.02 to 1.). Thus, there is but little tendency toward the gravitational separation that is normally encountered in the use of conventional opacifying agents which pre Sent a greater specific gravity differential. Although the opacifier is substantially insoluble in the concentrated detergent solution at room temperatures, it becomes dissolved when the detergent solution is diluted to the concentrations normally used in forming a Washing solution. Thus, the opacifiers employed in the instant invention have the additional advantage of ultimately becoming available as cleansing agents to

2 3 contribute to the overall detergency characteristics of the product. It will be readily understood that while the liquid detergent compositions of this invention contain from about 2% to about 8% water, they are diluted 0 or more fold when added to water to form the conven tional washing solution. This dilution is sufficient to effect substantially complete solution of the suspended opacifier of the detergent composition when the tempera ture of the wash water is within the temperature range normally employed, i.e., from about 90 F. to about 1 F. Thus, during use, the opacifier dissolves to become a part of the active detergent ingredient. Although com plete solution of the alkyl glyceryl ether sulfonate opaci fier is desirable for achieving maximum detergency bene fit, it has been observed that any undissolved opacifier does not remain completely inert but rather enhances Sudising performance during the washing operation. The substantially insoluble alkyl glyceryl ether sul fonates are those with alkyl chain lengths of about C to about C18. Alkyl glyceryl ether sulfonates with alkyl chain lengths of C14 or less are too soluble to be used as opacifiers but are, of course, used extensively as the Substantially complete dissolved primary detergent in the present compositions. In order to obtain the opalescent sheen in the opaqe composition of this invention it has been found that at least 2% by weight of alkyl glyceryl ether sulfonate having alkyl chains of C4 or less must be present. This portion of the more soluble alkyl glyceryl ether sul fonate is necessary to cause a slight crystal growth and an orientation of the suspended, precipitated, opacifying crystals. Single alkyl glyceryl ether sulfonates with an alkyl radical of 16 or 18 carbon atoms, for example, can be employed in this invention; but it is ordinarily more convenient and less expensive to use a mixture of such compounds in which the alkyl radicals are derived from readily available fatty alcohol mixtures. The higher alcohols derived from the reduction of tallow is a pre ferred source for the production of the opacifier used in the composition of this invention because they contain predominantly 16 and 18 carbon atoms. Another source is the higher molecular weight fraction from a fatty alcohol mixture derived from coconut oil or palm kernel oil. Such mixtures are commonly fractionated in the 4. sodium sulfite and bisulfite to produce the sodium alkyl glyceryl ether sulfonate. To produce the potassium alkyl glyceryl ether sulfonate the corresponding potassium salts are used in the processes. Many of the various synthetic sulfate and sulfonate detergents well known in the art are useful as the basic 2 3 active cleaning agent in the practice of this invention. The following examples of suitable water soluble anionic synthetic detergents are given only for the purpose of illustrating the wide variety of types of detergent com pounds useful in the practice of the invention and it will be appreciated that the scope of the invention is not thereby limited. The basic anionic synthetic detergents referred to in this invention are the substantially completely water soluble (at room temperature) alkali metal (to be in terpreted as including ammonium) salts of organic sul furic recation products having in their molecular struc ture alkyl radicals having from about 8 to about 18 carbon atoms and radicals selected from the group con sisting of sulfonic acid and sulfuric. acid ester radicals. The alkali metal salts of the sulfuric reaction products which find greatest utility are those which have from 10 to 14 carbon atoms and predominantly 12 carbon atoms in the alkyl radical, but since other constituents of the detergent molecule can be varied to increase the degree of solubility, the number of carbon atoms in the alkyl radical can also be adjusted upwardly in such instances to as high as 18, for example. Important examples of the synthetics which may be used in the composition of the present invention are the sodium or potassium lauryl glyceryl ether sulfonates made by the processes described above; sodium or potassium alkyl benzene sulfonates especially those of the types described in U.S. Patents 2,2,099 and 2,477,383 in which the alkyl groups contain from about 9 to about 1 carbon atoms; sodium, potassium or ammonium alkyl sulfates, especially those derived by sulfation of higher alcohols produced by reduction of glycerides of coconut oil; so dium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium, potassium and ammonium salts of Sulfuric acid esters of the reaction product of one mole of coconut oil fatty alcohol and about 3 moles of ethylene oxide or of one mole of tallow fatty alcohol and about 4 10 moles of ethylene oxide; alkali metal salts of alkyl ethylene oxide ether sulfate which have an average of one industry to produce a fraction consisting predominantly unit of ethylene oxide per molecule; the reaction product of C12 and C14 alcohols which have outstanding utility of fatty acids esterified with isethionic acid and neu in the preparation of the more soluble synthetic de tralized with sodium hydroxide where, for example, the tergents. A by-product of such fractionation is mix 0 fatty acids are derived from coconut oil; alkali metal ture of alcohols commonly referred to as Stenol, a fatty salts of fatty acid amide of a methyl taurine in which alcohol mixture consisting predominantly of C16 and the fatty acids, for example, are derived from coconut C18. These latter mixtures can also be employed as a oil; and others known in the art, a number being spe Source of alkyl radicals in the preparation of the opacifier cifically set forth in U.S. Patents 2,396,278, Lind; 2,486,- of this composition. 921, Byerly; and 2,486,922, Strain. The alkyl glyceryl ether sulfonates which are suitable The synthetic detergents preferred for use as the basic for the opacifier of the composition of this invention and active cleaning agent in the compositions of this inven the more soluble alkyl glyceryl ether sulfonates which tion include the water soluble alkali metal salts, such as can be used as an active synthetic detergent of the com the Sodium, potassium, or ammonium alkyl ethylene oxide position are produced in the same manner. The first ether sulfates which have an average of three ethylene Step consists of reacting fatty alcohols with epichloro oxide units per molecule, alkyl sulfates, alkyl glyceryl hydrin to produce alkyl chloroglyceryl ethers. To pro ether sulfonates and alkyl benzene sulfonates and mix duce the opacifier, fatty alcohols with alkyl radicals of tures thereof. The basic synthetic detergents can be predominantly 16 or 18 carbon atoms are used; fatty present in the liquid composition of this invention in alcohols with alkyl radicals chiefly of 12 or 14 carbon 6 percentages of about % to 4% by weight although atoms are used in the preparation of the more readily the preferred range is about 1% to %. Water Soluble anionic synthetic detergents. The alkyl Sufficient alkyl glyceryl ether sulfonate opacifying chloroglyceryl ethers of step one are then sulfonated to agent is dissolved in a heated detergent mixture so that produce the final alkyl glyceryl ether sulfonates. Two from 0.% to about 10% by weight is insoluble at room Sulfonation methods are commonly used. ne method temperature. 0.% of opacifier is about the minimum consists of reacting the alkyl chloroglyceryl ethers with amount permissible for a satisfactory opaque product; Sodium sulfite. The other method involves treating the heating to about 9 F. dissolves the opacifier at such alkyl chloroglyceryl ethers with a strong caustic soda concentrations. The presence of about 3% of the in Solution which forms alkyl glycidyl ethers which in turn Soluble opacifier at room temperature is preferred to re are separated from the salt solution and treated with 7 tain a proper opacity up to about 110 F. Above this

3 -6 temperature this amount of opacifier completely dissolves. used in the preparation of the detergent compositions of The top limit of opacifier content is not critical and up this invention, but which are not necessary, are the mono to about 10% or more of the opacifier can be utilized and diethanolamides of coconut fatty acids. - in the practice of this invention although heating the liq The following examples are given to illustrate the uid detergent composition to about 180 F. and above manner in which this invention may be practiced. Its is required to dissolve such amounts of opacifier. While scope is not limited to the ingredients named in the ex other ingredients of the compositions of this invention amples since it is apparent that some may be interchanged often exert a slight solubilizing effect on the opacifier, it with each other or equivalents substituted. Likewise, is merely necessary to add enough of the substantially its scope is not limited to the proportions shown in these insoluble alkyl glyceryl ether sulfonate so that at least examples since the proportions may be varied to modify about 0.% exists as undissolved suspended crystals at the viscosity or active detergent concentration and to room temperature, generally averaging about 80 F. adjust for variations in properties of substituted equiv When the amounts of opacifier and active synthetic alent ingredients. The main feature of the invention is detergents used in the practice of this invention result the obtaining of a stable, pleasing appearing opacity in a in a product that is thick or viscous when combined only with water, it is often desirable to thin the mixture with a suitable water soluble organic solvent. Ethanol, pro panol, isopropanol, ethylene glycol and propylene glycol are useful in this respect and the amounts used are from about 0% to about 2% (ordinarily about 3%-%) by weight of the composition. Up to about % sodium or potassium toluene or benzene sulfonate can also be used as a hydrotrope in conjunction with the above men tioned solvents. The use of water soluble organic solvents also increases the solubility of the active synthetic detergents in water, the solubility increasing in substantially direct propor tion to the amount of solvent used. For example, the practical limit of the solubility of common active syn thetic detergent salts in water alone is about 2%. How ever, up to about 4% of these detergent salts can be used in the liquid compositions of this invention when about 2% of any of the above-mentioned water soluble organic solvents are added. Satisfactory viscosities for the liquid compositions of this invention are in the range of about 10 to about 00 centipoises at room temperature. Preferred viscos ities are in the range of about 0 to 800 centipoises at room temperature. The suspended crystals of the alkyl glyceryl ether sul fonate in the composition of this invention have a high degree of stability against gravitational separation. Tend encies for the crystals to settle can be decreased, for ex ample, by increasing the specific gravity of the solution or by dispersion of the opacifier in very fine crystalline form. The specific gravity of the solution can be increased by the inclusion of sodium salts such as sodium chloride, sodium sulfate, sodium acetate or other compatible salts in the formulation. Thus, the difference between the specific gravity of the solution and that of the suspend ed crystals can be decreased. The salts may be added in amounts up to the limit of their solubility in the deter gent composition. Some salts are present in the compo sition as by-products from the synthetic detergent manu facture. Additional salts can be added. Sodium sulfate is one of the least soluble of the salts (approximately 6% at room temperature) although mixtures of it and other more soluble salts allow an electrolyte content in the compositions of about 2 to 1% by weight. Correspond ing potassium salts can be used with potassium salts of the opacifier and synthetic detergent with similar results. The presence of electrolyte in the warmed clear deter gent solution increases the tendency of the opacifier to form fine substantially insoluble crystals upon cooling. A rapid rate of cooling also tends to produce finer crystals of the suspended alkyl glyceryl ether sulfonate. In the preparation of the mixture it should be heated to a temperature only high enough to dissolve all the opacifier, 1 F. to 1 F. is ordinarily sufficient. Cooling by allowing the mixture to stand at room tem perature is sufficient to produce a satisfactory opaque product although finer crystals result when the mixture is cooled in a heat exchanger, especially one provided with a mechanical agitator, such as a "Votator." Examples of suds stabilizer additives which can be liquid detergent with good cleaning and sudsing perform ance and controlable physical properties. All parts are shown by weight. Example I-Three moles of ethylene oxide were re acted with one mole of a middle cut coconut fatty alco hol which contained about 6% dodecanol, the balance being essentially fatty alcohols with 14 to 16 carbons. The reaction product was sulfated with chlorosulfonic acid and then neutralized with caustic soda. The re Sulting alkyl ethylene oxide ether sulfate had an average of three units of ethylene oxide per molecule. The same middle cut coconut alcohol was reacted with 1% excess epichlorohydrin. The chloroglyceryl ether thus formed was sulfonated with sodium sulfite, form ing an alkyl glyceryl ether sodium sulfonate. A sodium tallow alkyl glyceryl ether sulfonate was made by the process described above, using a fatty al cohol mixture derived by the reduction of tallow and containing about 6% Cia alcohol, about 33% C, al cohol and about 2% Calcohol. A liquid detergent was made by dissolving the follow ing amounts of ingredients in the water shown at about 1 F. parts alkyl ethylene oxide ether sodium sulfate derived from the middle cut coconut alcohol 4 parts alkyl glyceryl ether sodium sulfonate derived from the middle cut coconut alcohol parts alkyl glycery ether sodium sulfonate derived from tallow fatty alcohol 3 parts monoethanolamide of coconut fatty acids 1. parts sodium chloride 6 parts sodium sulfate 6 parts water to make 100 parts After complete solution of all the materials the formula was rapidly cooled to about 3 F. by passing it through a Wotator. It is not necessary to cool as low as 3 F. Passing the detergent solution through a heat ex changer, so that the temperature is brought down to room temperature, about 80 F. rapidly, also produces good appearance and stability. This preparation performed very well in dishpan and fine fabric sudsing and detergency and had the desired pearly opacity and opalescent sheen. When the alkyl glyceryl ether sulfonate is derived solely from C8 fatty alcohol or C16 fatty alcohol instead of tallow fatty alcohol mixture in the above example, sub stantially equal results are obtained. Example II.-The following materials were prepared in the same manner as those in Example I and were dis solved in the water shown below at about 1 F. The sodium alkyl glyceryl ether sulfonates shown below were prepared by the method described in Example I parts alkyl ethylene oxide ether sodium sulfate de rived from the middle cut coconut alcohol described in - Example I. 2.9 parts monoethanolamide of coconut fatty acids 3.09 parts alkyl glyceryl ether sodium sulfonate derived from a fractionated mixture of coconut fatty alcohols

4 7 containing about 6% C12, % C4 and 1% Cie alcor hols 4.92 parts propylene glycol 4.92 parts ethanol 2.9 parts sodium alkyl glyceryl ether sulfonate derived from a mixture of alcohols consisting essentially of C16 and C18 alcohols and derived as the high boiling cut in the fractionation of a mixture of coconut oil alco hols 10 parts of a mixture of sodium chloride and sodium sul fate 1.47 parts water to make 100 parts This preparation was cooled in a Votator to room temperature, about 80 F. and had good detergent and sudsing properties as well as the desired opaque opalescent sheen. Example III.-The following materials were dissolved the water shown below at about 1 F. Sodium alkyl glyceryl ether sulfonate derived from tallow fatty alcohol was prepared as shown in Example I. 37 parts ammonium salt of the sulfated middle cut coco nut alcohol containing 6% dodecanol, the remainder consisting essentially of alcohols of 14 and 16 carbon atoms 12 parts monoethanolamide of coconut fatty acids 18 parts ethanol 6 parts sodium alkyl glyceryl ether sulfonate derived from tallow fatty alcohol as described in Example I 2 parts of a mixture of sodium chloride and sodium sul fate occurring in the synthetic detergents employed 2 parts water to make 100 parts This preparation had excellent detergent and sudsing properties and the desired white opacity. If propanol is substituted for the ethanol, substantially equal results are obtained. Example IV.- The following materials were dissolved in the water shown below at about 1 F. The sodium alkyl glyceryl ether sulfonate was prepared using fatty alcohols derived by the reduction of tallow and contain ing about 6% C18, 33% C16 and 2% C14 alcohols. 18 parts sodium polypropylene benzene sulfonate, the polypropylene averaging about 12 carbons 13 parts diethanolamide of coconut fatty acids 19 parts ethanol 2. parts sodium tallow alkyl glyceryl ether sulfonate prepared as described in Example I 2.0 parts of a mixture of sodium chloride and Sodium sulfate occurring in the synthetic detergents employed 4. parts water to make 100 parts After being cooled by passage through a heat ex changer, this preparation was an excellent detergent for dishwashing and had a pleasing opaque appearance with a viscosity of about 0 centipoises. If isopropanol is substituted for the ethanol, substantially equal results are obtained. Example V-The following ingredients were added to the water shown below at about 1 F. and then cooled to form a white opaque rather viscous liquid which was pourable, performed excellently as a detergent and foam ing agent. The alkyl glyceryl ether sulfonate was pre pared from a mixture of fatty alcohols derived from the reduction of coconut oil and containing about 6% C, 2% C14, and 10% C16 alcohols. 1 parts potassium alkyl glyceryl ether sulfonate 10 parts ethylene glycol. 73 parts water 2 parts potassium chloride occurring in the synthetic de tergents employed If two parts of potassium acetate or potassium sulfate are added to the composition in the above example, sub stantially equivalent results are obtained. Example VI-A composition of the following ingredi ents was prepared by first effecting substantially complete solution of the solid constituents in the liquid constituents at slightly elevated temperature about 12 F. and then cooling to room temperature, about 80 F. in a heat ex changer. An opaque product having an opalescent sheen and excellent detergency and sudsing properties resulted. parts sodium alkyl ethylene oxide ether sulfate pro duced by reacting 3 moles of ethylene oxide with 1 mole of fatty alcohol containing about 6% C1, % C14 and 1% C16 alkyl radicals then sulfating and neu tralizing the reaction product. 4 parts sodium alkyl glyceryl ether sulfonate prepared using a mixture of fatty alcohols derived by the re duction of coconut oil and containing about 90% Cia, % C4 and % C6 alkyl radicals 3 parts sodium alkyl glyceryl ether sulfonate prepared as described in Example I using the fatty alcohol de rived by the reduction of tallow parts monoethanolamide of coconut fatty acids 2 parts sodium toluene sulfonate 6 parts sodium acetate 6 parts sodium chloride 47 parts water In this example the following amounts of ingredients in separate compositions can be substituted for equal amounts of the alkyl ethylene oxide ether sulfate with substantially the same results: and 10 parts sodium polypropylene benzene sulfonate described in Example IV and 10 parts sodium alkyl phenol ethylene oxide ether sulfate in which there was an average of four ethylene oxide units per molecule and in which the alkyl radical contained about 9 carbon atoms 10 and parts potassium alkyl ethylene oxide ether sul fate produced by reacting one mole of ethylene oxide with one mole of the fatty alcohol mixture as described in this Example VI - and 10 parts coconut fatty acid ester of sodium isethion ate produced commercially under the trade name "Igepon AC-78" parts ammonium salt of the alkyl ethylene oxide ether sulfate prepared as described in this Example VI Example VII-A liquid detergent composition was pre pared by dissolving the following ingredients in water: parts sodium alkyl ethylene oxide ether sulfate de sribed in Example I 3 parts monoethanolamide of coconut fatty acids 1. parts of a mixture of sodium chloride and sodium Sulfate occurring in the synthetic detergents employed 62 parts water 4 parts of sodium alkyl glyceryl ether sulfonate pre pared from coconut oil fatty alcohol as described in Ex ample VI and 2. parts of sodium alkyl glyceryl ether sulfonate prepared from tallow fatty alcohol as described in Example I was dispersed in the above composition in a colloidal mill at F. An excellent opaque liquid dish washing detergent resulted. Example VIII.-An opaque, fairly viscous, liquid de tergent composition was prepared by dissolving the foll lowing ingredients in the water shown at about 10 F. and cooling the composition to room temperature. 10 parts sodium alkyl ethylene oxide ether sulfate de scribed in Example I 10 parts Sodium, polypropylene benzene sulfonate de scribed in Example IV parts sodium alkyl glyceryl ether sulfonate describe in Example I using tallow fatty alcohol 2 parts of a mixture of sodium chloride and sodium sul fate occurring in the synthetic detergents employed 73 parts water to make 100 parts Small amounts of perfumes and fluorescent brightening

5 agents known in the art can be added to improve product appeal and performance. Since the nacreous opacity is the basic feature of the invention, dyes can be added to produce pastel shades which can greatly enhance the customer attraction to the product. If desired, sudsing depressing agents can be employed to yield products especially designed for uses where excessive foaming properties would interfere with the use of the product. This invention results in a stable, efficient, light duty detergent with a highly desirable appearance. It is in tended mainly for dishwashing and the washing of fine fabrics but can also be used as a hair shampoo and as a detergent for laundry and other general household re quirements. What is claimed is: 1. As an opaque liquid detergent composition an aque ous vehicle containing in solution about % to about 2% by weight of a water soluble anionic non-soap syn thetic detergent salt and suspended therein about 0.% to 10% by weight of a crystaline opacifying agent se lected from the group consisting of sodium and potassium salts of an alkyl glyceryl ether sulfonate with alkyl radi cals ranging in chain length from Cs to Cia and which is Substantially insoluble in the composition at room tem perature. 2. As an opaque liquid detergent composition an aque ous vehicle containing in solution about % to 2% by Weight of a water-soluble anionic synthetic detergent salt selected from the group consisting of anionic sulfate and Sulfonate synthetic detergents and mixtures thereof, and suspended therein at least about 0.% to 10% by weight of a crystalline opacifying agent selected from the group consisting of sodium and potassium salts of an alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from Cs to Cls and which is substantially insoluble in the composition at room temperature. 3. An opaque liquid detergent composition comprising essentially about % to 4% by weight of a water-solu ble anionic synthetic detergent salt selected from the group consisting of anionic sufate and sulfonate synthetic de tergents and mixtures thereof, about 0.% to 10% by weight of a suspension of an opacifying agent selected from the group consisting of sodium and potassium salts of an alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from Cis to Cls and which is sub stantially insoluble in the composition at room tempera ture, about 2% to 8% by weight of water and about 0% to 2% by weight of a water-soluble organic sol vent selected from the group consisting of ethanol, pro panol, isopropanol, ethylene glycol, propylene glycol and mixtures thereof, 4. The detergent composition of claim 3 in which the amount of water-soluble anionic synthetic detergent salts present, includes at least 2% by weight of an alkyl glyc eryl ether sulfonate with an alkyl chain length not greater than C1, whereby an opaque opalescent sheen is ob tained.. The detergent composition in accordance with claim 3 in which the opacifying agent is a sodium alkyl glyceryl ether sulfonate in which the alkyl radicals are derived from a fatty alcohol derived by the reduction of tallow. 6. The detergent composition in accordance with claim 3 in which the water-soluble anionic synthetic detergent salt is selected from the group consisting of alkyl sulfate, alkyl benzene sulfonate, alkyl ethylene oxide ether sul fate, alkyl glyceryl ether sulfonate and mixtures thereof. 7. The detergent composition in accordance with claim 3 in which there is included as an additional ingredient from 2 to 1 percent by weight of a dissolved alkali metal Salt Selected from the group consisting of sodium and potassium chlorides, sulfates and acetates to increase the specific gravity of the liquid phase. 8. An opaque liquid detergent composition comprising essentially, in an aqueous vehicle, about 1% to % by weight of a water-soluble anionic synthetic detergent salt selected from the group consisting of alkyl sulfate, alkyl benzene sulfonate, alkyl ethylene oxide ether sulfate, alkyl glyceryl ether sulfonate and mixtures thereof, about 0.% to 10% by weight, as an opacifying agent, of a sus pension of a sodium salt of an alkyl glyceryl ether sulfo nate in which the alkyl radicals are derived from a fatty alcohol derived by the reduction of tallow, at least 2% by weight of a sodium salt of an alkyl glyceryl ether sul fonate in which the alkyl radicals are derived from a mix ture of coconut oil fatty alcohols, about 3% to % by weight of a water-soluble organic solvent selected from the group consisting of ethanol, propanol, isopropanol, ethyl ene glycol, propylene glycol and mixtures thereof, and about 2% to 1% of a dissolved electrolyte salt selected from the group consisting of sodium chloride, sodium sul fate, sodium acetate and mixtures thereof. 9. The process of preparing opaque liquid detergent compositions which comprises heating a mixture of water, about % to 4% by weight of water-soluble anionic synthetic detergent salts selected from the group consist ing of anionic sulfate and sulfonate synthetic detergents and mixtures thereof, about 0% to 2% by weight of a water-soluble organic solvent selected from the group consisting of ethanol, propano, isopropanol, ethylene gly col, propylene glycol and mixtures thereof, and an opaci fying agent selected from the group consisting of sodium and potassium salts of an alkyl glyceryl ether sulfonate with alkyl radicals ranging in chain length from C to Cs to effect a solution of said mixture and cooling said mix ture to at least room temperature to precipitate from about 0.% to 10% by weight of said opacifying agent in the form of suspended crystals. 10. In the process of claim 9 the step of developing a slight growth and orientation of the suspended crystals of opacifying agent whereby an opalescent sheen is obtained by including as a portion of said detergent salts at least 2% by weight of an alkyl glyceryl ether sulfonate with an alkyl chain length of not greater than C In the process of claim 9 the step of increasing the Specific gravity of said solution by dissolving in said mix ture from about 2% to 1% by weight of an electrolyte Salt selected from the group consisting of sodium chloride, Sodium sulfate, sodium acetate and mixtures thereof. 12. In the process of claim 10 the step of increasing the specific gravity of said solution by dissolving in said mix ture from about 2% to 1% by weight of an electrolyte salt selected from the group consisting of sodium chloride, sodium sulfate, sodium acetate and mixtures thereof. References Cited in the file of this patent UNITED STATES PATENTS 2,094,489 Hueter Sept. 28, ,27,077 Preston ct. 24, 190 2,7,7 Vitale et al Aug. 19, 192 2,674,80 Henkin Apr. 6, 194 2,7,99 Henkin Nov. 13, 196 THER REFERENCES Modern Cosmetics, 1947, 3rd ed., publ. by Drug and Cosmetic Industry, page 36. American Pharmacy, 2nd ed., 1948, publ. by J. B. Lip pincott Co., pages "Soap and Sanitary Chemicals"; January 191, pages 38-41, 11 and 117; article by Lesser.