US2438169A - Manufacture of detergents - Google Patents

Description

Patented Mars 23,

orrlc 2,438,169 MANUFACTURE OF EETERGEN'ES Lester Francis Hoyt,

to Allied Chemical York, N.Y.,

No Drawing.

East Aurora,

8: Dye Corporation, acorporat N. 2., assignor New ion of New York Application duly 12, 1945,

Serial No. 604,731

1! Claims. (01- 252-=-=121)' This invention relates to improvements in the manufacture of detergents, more particularly milled soaps and especially milled soapsO! the type employed for toilet purposes. It relates to improvements in milled soap compositions containing a hard soap and a synthetic detergent of the higher petryl sultan-ate type and especially of the higher petryl aromatic sulionate type, and to improvements inthe processes of manufacturing milled soaps containing a hard soap and a synthetic detergent of the higher petryl sulionate type and especially of the higher petryl aromatic sulfonate type.

As employed throughout this specification and claims, the term soap denotes and includes the water-soluble ganic amine salts or" higher fatty 10 to 20 carbon atoms; the term "hard soap" denotes and includes those "soaps which Iorm solid masses under normal atmospheric conditions; and the terms higher petryl sulionate" and higher petryl aromatic sulionate denote and include mixtures of organic sulionates and substituted aromatic sulionates, respectively, in which an organic radical which is part of the organic sulfonate, or which is a substituent in the aromatic nucleus oi the aromatic sulionate, is derived irom a polycomponent hydrocarbon mixture of the type of a petroleum distillate (a petroleum distillate or a synthetic mixture whose composition is similar to a petroleum distillate) boiling for the most part Within the range 100 to 300 C. at atmospheric pressure. such soaps are the sodium, potassium, ammonb um, and triethanolamine salts of saturated and unsaturated higher fatty acids derived from coconut oil, palm oil, olive oil, tallow, cottonseed oil, and the like, and. mixtures thereof, well known to those skilled in the soap-making art. Detergents of the higher petryl aromatic sulfonate type are disclosed, for example, in United States Patents 2,196,985; 2,218,472; 2,220,099; 2,223,364; 2,233,- 408; 2,267,725; 2,364,782; and British Patent e16,- 379. Other examples of detergents of the higher petryl sulfonate type are petroleum sulfonates obtained in the refining of lubricating oils, and sulionated products obtained by treating mineral oil fractions by the process of United States Reissue Patent No. 20,968 and United States Patents Nos. 2,197,800; 2,202,791; 2,239,974; and 2,276,090.

It is known to produce soap compositions containing a hard soap and a higher petryl sulionate for use as effective detergents and washing agents in water of varying degrees hardness, and in acids contai Examples of sea water.

alkali metal, ammonium, and orv Such com ositions have been prepared, for example, by mixing a higher petryl aromatic sulionate with molten kettle soap in a crutcher, allowing the resulting mixture to cool and solidify in frames, and cutting the resulting solid soap composition into bars or cakes.

A. milled soap cannot be prepared from the result framed soap compositions because the high content of water present in said composititans (30% or more) renders them .soft and mushy, so that plodding cannot be satisfactorily effected. Preparation of a milled soap product by mixing a hard soap in a form usually employed for milling (e. g. in the form of ribbons, beads, particles, flakes, grains, or the like, containing 5% to 15% .oi'moisture) with a higher petryl sulionate in a substantial amount le. g. 15% of the weight of the soap) presents difilcultles; the mixture becomes sticky and tough so that it opposes milling and plodding in the usual commercial soap-making equipmen. If it is attempted to improve the plasticity of such mixture by the addition of water, the mixture merely becomes more tacky and its working properties are not materially improved. In View of these difllculties, heretofore the manufacture of soap bars and cakes containing mixtures oisoap and higher petryl sulionates has been largely restricted to framed soap products.

According to the present invention, the production oi milled soaps containing a hard soap and a higher petryl sulfonate can be efiectively carried out in the ordinary soap-making equipment and with the use of commercially available higher petryl sulfonate detergents, by incorporating a substantial amount soluble form, into a mixture of the higher petryl sulionate and hard soap containing moisture. In accordance with the present invention, it has been found that the presence of starch in the insoluble form serves to overcome the stickiness and toughness of the composition, with the result that the mixtures flow readily through the plodder without requiring greater pressure than is normally employed in the manufacture of the usual milled toilet soaps, and the resulting bars issuing from the plodder are smooth and light colored. Further, the presence of the starch in the resulting soap products imparts a satiny feel to the products.

Corn starch is ordinarily employed, because of its low cost and general availability, but any other water-insoluble starch may be used; such as, wheat starch, tapioca starch, potato starch, etc. The starch is present in the novel compositions of starch, in the ordinary inand milled bars or cakes essentially in the form 01' unruptured, insoluble particles.

and other inorganic salts present in the mixture, and the use to which the product is to be put. In general, the amount of starch should be at least suiiicient to provide compositions which may be milled and plodded without dificulty in the usual of the bars or find that soap-higher petrylbenzene sulionate-starch mixtures of the type of the present invention containing as high as 40% by weight of starch will yield milled bars possessing a feel and mixtures is as low as 25%.

As employed herein, the expression "total weight of basic components refers to the sum hydrous, inorganic-sait-free basis), (3) starch (on an anhydrous basis), and (4). if present, sodium sulfate and/or other inorganic salts.

In preparing the milled soaps in accordance with the present invention, the hard soap, in the form of ribbons, flakes, beads, or other form commonly employed for making milled soaps, is mixed with a higher petryl sulfonate and starch in suitable mixing apparatus, such as a soap mill, and the resulting mixture is introduced into a stamped or otherwise converted into the desired form. As in usual in the mixtures contain water, which is ordinarily introduced in the form of moisture present in the soap. The amount of water preferably should not exceed of the above total weight of basic components. Greater amounts 01 moisture render the composition too soft for satisfactory working, Preferably, the mixtures contain an amount of water equal to at least 6% of the total weight of basic components," to provide desirable working properties. In general, amounts of water equal to 10% to 12% of the total weight of basic components" upon the uses to which the resulting products are to be put. In general, an amount of higher petryl the making of milled soaps;

4 sulionate (on an anhydrous, basis) equal to at least 6%, preferably at least of the total weight of :basic components" For use in water inorganic-salt-free with the use of the products in sea water, such a minimum ount of soap is desirable to pro= vide the products with advantageous washing ability in sea water.

Within these limits, the proportio example, in tallow soap, or other toilet employed in making milled and about 20% (mainly sodium sulfate), the proportions of ingredients (in terms to about 40% of inorganic salts of 100 parts of the total weight of the three com ponents on an anhydrous basis) may be as follows:

I Component: Parts sodium higher petryi benzene sulfo nate composition 20 to to ap 15 to 55, preferably 25 to Starch" 5 to 40, preferably 20 to 30 Another commercially available higher petryl benzene sulfonate composition, containing about 95% to about of a sodium higher petryl benzene sulfonate derived from a kerosene frac- 5% to about 15% of Component:

Sodium higher petryl nate composition- Parts 10 to 40 30 to 80, preferably 40 to 70 Starch 5 to 40, preferably 20 to 30 Other forms of commercially available higher petryl sulfonates may be employed, a number of which are disclosed in the patents above referred to, Of these, the higher petryl aromatic sulfonates are preferred.

The higher petryl aromatic sulfonates are mixbenzene sulfotures of substituted derivatives of aromatic sulreferred to as wherein A represents is hydrogen or droxy-alkyl ammonium,

petroleum distillate. and preferably of mineral origin, of which at least 80% boils (distills) between 150" and 250 C. (Ranges herein stated include the limits. The term a poly-component non-aromatic hydrocarbon mixture" as employed herein, means a hydrocarbo petroleum or a petroleum distillate or otherwise refined petroleum fraction, or other mixture of similar composition, containing straight and/or branched chain alkanes and which may also contain cycloalkanes and aryl hydrocarbons but does not contain more than 20% of aryl hydrocarbons. For convenience, stituted derivatives of aromatic sulfonates are mixtures of alkyl aromatic sulfonates," the term "alky being used in its broad sense to include straight or branched, open-chain aliphatic hydrocarbon radicals, as well as radicals derived from cyclophatic and aromatic-aliphatic hydrocarbons which may be present in the polycomponent hydrocarbon mixture).

They are mixtures of water-sigluble products represented by the general formul son! an aromatic nucleus preferably containing not more than two benzene nuclei which may be condensed or not (for example, a benzene nucleus. a naphthalene nucleus, a diphenyl nucleus, or a diphenyl oxide nucleus); R represents an alky group which is directly attached to a carbon atom of the nucleus represented by A and which is derived from the hydrocarbon mixture and corresponds with a component thereof; X represents a replaceable hydrogen of the aromatic nucleus represented b A or a substituent such as an allryl group containing 1 to 8 carbon atoms, a hydroxyl group, an alkoxy or aralkoxy group containing 1 to 8 carbon atoms, or halogen; n represents the numbers 1, 2 or 3; and SOaY represents a sulfonate group which is attached to a carbon atom of the aromatic nucleus represented by A andin which Y its stoichiometric equivalent of a salt-forming metal or radical; such as sodium, potassium, ammonoum, alkyl ammonium, hy-

and the like. Thus the mixtures of higher petryl aromatic sulfonates may be derived from benzene, toluene, xylene, phenol, cresol, anisole, phenetole. chlorbenzene, diphen l, hydroxydiphenyl, diphenyl oxide, naphthalene, alpha-naphthol, beta-naphthol, etc. Those derived from mononuclear aromatic compounds, and especially benzene, are preferred. Ordinarily the sodium salts are prefei'red b reason of their lower cost.

Preferably, they are mixtures obtained by a process comprising chlorinating the polycomponent hydrocarbon mixture to form mixed alkyl chlorides, condensing resulting mixed alkyl chlorides with a mononuclear aromatic hydrocarbon or a derivative thereof to produce a mixture of alkyl derivatives of said aromatic hydrocarbon or derivative, and sulfonating a mixture of said alkyi derivatives.

The following example illustrates the preparation of such a higher petryl benzene sulfonate by such a process. The parts are-by weight:

Exsmta A A Pennsylvania kerosene boiling from 180 C. to 280 C., 80% of which boiled between 190 and 255 0., was chlorinated between 70 and 75 until the n mixture, such as the mixture of subspecific gravity of the latter had increased from 0.788 at 24 C. to 0.918 at 24 C. 10 parts of the resulting chlorinated kerosene were introduced during 75 minutes into a mixture of 20 parts of benzene and 0.5 part of aluminum chloride, while gradually raising the temperature to 45 C., after which the mixture was agitated at 45 C. for 15 minutes and then allowed to stratify. The upper layer of oil was removed from the tarry lower layer and distilled, and the fraction which boiled between and 240 C. at 3 to "1 mm. of mercury absolute pressure was collected separately. The collected fraction was refined by agitating it with 18.4% of its weight of sulfuric acid at about 40 C. for 30 to 40 minutes, allowing the mass to settle 30 minutes, and discarding the lower acid layer. The refined 011 was mixed with 1.35 times its weight of 100% sulfuric acid at 30 0., the mixture was warmed to 55 to 60 C., agitated at that temperature for 1 hour and allowed to stratify for 4hours, and the lower layer was drawn oil. The remainder containing higher petryl benzene sulfonic acid was rendered neutral to Nitrazine Yellow paper by stirring it into about one and one-half times its. weight of water simultaneously with 50% aqueous caustic soda. To the neutralized mass, which contained about 35% of inorganic salt (mostly sodium sulfate) and about 65% of sodium higher petryl benzene sulfonate on a dry basis, sufficient sodium sulfate was added to give a dry composition containing 60% of sodium keryl benzene sulfonate. and the resulting mixture was drum dried.

In addition to the essential components above referred to, other substances usually incorpo rated in milled soaps may be included in the compositions of the present invention. Thus, perfumes, pigments, coloring agents, antiseptics, and the like may be incorporated into the compositions. In general, it is preferred not to have considerable amounts of such substances in the compositions.

Inorganic salts, chiefly sodium sulfate, which are frequently present in commercial forms of higher petryl sulfonates, may be included in the compositions of invention; but the amount of inorganic and preferably should not exceed 20%. total weight of basic components.

Further, substances imparting supplementary surface activity to the above essential components of higher petryl sulfonate is relatively small; for example, lower alkyl aromatic sulfonates, and particularly sodium isopropyl naphthalene suifonate. sodium di-isopropyl naphthalene sulfonate, sodium butyl naphthalene sulfonate.

The ingredients may be mixed and converted into bar form in any suitable equipment. Thus, the mixture may be milled, plodded and stamped in apparatus commonly used for manufacturing high-grade toilet soaps. Where highly comminuted compositions are employed, relatively little milling may achieve the desired degree of homogeneity, and such compositions may be formed directly into bars by passage through a plodder, which itself provides some milling action.

To promote easy working, it is helpful to warm 90 to F. Such temperatures may be developed in part or completely by the friction of the milling and plodding action. The shaping die of the plodder may be heated, say to about F., to facilitate the ex- 40% of inorganic salts and about going manner, showed better ataamo trusion of the composition in the form of a smooth bar. The resulting bars may be cut and stamped to suitable size and shape.

The following examples illustrate the invention. The parts are by weight. The corn starch used was "Argo edible corn starch and contained about of moisture.

Example 1 A mixture of 420 parts of powdered corn starch, 515 parts of "S soap (a pure soap of 39 titre sold by John Powell and Company, Inc., New York city), adjusted to contain 110 parts of moisture, and 675 parts of the product of Example A (a sodium higher petryl benzene sulfonate detergent containing about 40% of sodium sulfate and about 60% of asodium higher petryl benzene sulfonate derived from a, kerosene fracor doughinessfi' was of a Houchin soap plodder. The mixture flowed into the plodder desired form in a stamping machine, did not sweat on exposure to the atmosphere, or frost," disintegrate or become soft in use, and lathered and washed well in water of positions employing starch.

The following examples illustrate additional soaphigher petryl sulfonate-starch mixtures which, in accordance with this invention, when milled and plodded into bar form in the forepossessed good firmness and appearance, and did sweat, frost, disintegrate, or become soft in use.

Example 2 Parts "818 soap chips (a pure tallow soap of 41 titre sold by Armour & Company) adjusted to contain about 7 parts of moisture Sodium higher petryl benzene sulfonate detergent employed in Example 1 p 45 Corn starch 28 Example 3 Parts "#818" soap chips adjusted to contain about a 7 parts of moisture 34 Detergent composition containing approximately 8 parts of inorganic salts (mostly sodium sulfate) and 292 parts of a mixture consisting of a sodium higher petryl m benzene sulfonate derived from a kerosene fraction of Pennsylvania petroleum (11.7 parts) and sodium di-lsopropylnaphthalene sulfonate (17.5 parts) 45 Cornstarch 28 15 Example 4 Pa #818 soap chips adjusted to contain about 9 parts of moisture go Sodium higher petryl benzene sulfonate detergent employed in Example 1 40 Corn starch Example 5 25 Parts #818 soap chips adjusted to contain about.

8 parts of moisture 23 Sodium higher petryl benzene sulfonate de-. tergent employed in Example 1 60 a0 Corn starch 25 Example'ti Parts #818 soap chips adjusted to contain about 10 parts of moisture 55 Sodium higher petryl benzene sulfonate detergent employed in Example 1 45 Corn starch 10 40 Example 7 Parts "Harris soap chips (10% coconut oil soap and 90% tallow soap) containing about 10 parts of moisture 60 Sodium higher petryl benzene sulfonate detergent containing about 10% of inorganic salts (mostly sodium sulfate) and about 90% of a sodium higher petryl benzene sulfonate derived from a kerosene fraction of Pennsylvania petroleum 25.5 Corn starch 22.5

Example 8 Parts Lux" soap flakes adjusted to contain about 9 parts of moisture 45 Detergent composition containing approximately 9.1 parts of inorganic salts (mostly sodium sulfate), and 27.4 parts of a mix-' ture consisting of a sodium higher petryl benzene sulfonate derived from a kerosene fraction of Pennsylvania petroleum (11 5 parts) and sodium di-isopropylnaphtha-r lene sulfonate (1,6.4 parts) 36.5 Corn starch 26 Example 9 P #818 soap chips adjusted to contain about 10 parts of moisture 1 52 Sodium higher petryl benzene sulfonate detergent employed in Example 7 32 Corn starch 25 Toilet soap stock adjusted to contain about Example 11 Parts Toilet soap stock adjusted to contain about '7 parts of moisture Sodium higher petryl benzene sulionate detergent employedin Example 'l Corn starch 11 Titanox (titanium oxide Example 12 Parts 8 parts of moisture tergent employed in Example 1 29 Corn starch 30 Example 13 Parts Toilet soap stock adjusted to contain about parts of moisture Sodium higher petryl benzene sulionate detergent employed in Example 1..-; 29 Corn starch 26 Example 14 Parts Toilet soap stock adjusted to contain about 10 parts of moistur 52 Sodium higher petryl benzene sulionate detergent employed in Example 1 25 Corn stare 25 Example 15 Parts Toilet soap stock adjusted to contain about 10 parts of moisture Sodium higher petryl benzene sulionate detergent employed in Example 1 35 Corn starch Example 16 Parts Toilet soap stock adjusted to contain about 9 parts of moisture Sodium higher petryl benzene sulionate detergent employed in Example 1 40 Corn starch 2'7 It will be realized by those'skilled in the art that the invention is not limited specific examples and that changes may be made in the compositions and processes of preparing them, within the scope or the appended patent claims.

Thus, instead or the specific components employed in the above examples, others oi the substances referred to above may be substituted in equal amounts. I tional substances may be incorporated into the compositions besides the essential components: a. hard soap, a higher petryl sulfonate, and starch.

As above noted, the alt employed amount of s relative to the amount of. higher petry-l sultonate to the above Y will depend upon several factors, one oi which is sodium other inorganic salts present in the higher petryl sultonate or otherwise sition subjected to milling. In 8 amount or soap is reduced to compensate for the amount or sodium sulfate and/or other inorganic salts present in the composition.

Thus, in accordance with the present invention, the compositions subjected to milling may contain the following components: (1) a hard soap, (2) a higher petryl suiionate, and 3) starch, together with (4) inorganic salt in an amount ranging from 0% to 25% of the wei htv oi the admixture, in the following proportions by weight ofsaid componen (l), (2), and (3). on the basis of a total weight of 100 parts 02 said four components:

In this case, the minimum amount of soap is 15 parts by weight,

and the maximum amount is 5 parts by weight less the weight of inorganic salt. i

Or, in the case 01 preferred compositions containing the following components: (1) a hard soap,

(2) a higher petryl aromatic sulfonate. and (3) starch, together with (4) sodium sulfate in an amount ranging from to 20% of the weight of the admixture, the proportions by weight of said components (1) (2) and (3) on the basis of a total weight or 100 parts or said tour components, may be within the following ranges:

Parts sulfonate...... at least 10 30 to 80, less the weight of sodium sulfate amount of soap may vary by weight, minus the weight of the by Weight, minus the In this instance, the from '30 parts sodium sulfate, to parts weight of sodium sulfate.

1'. claim:

1. In the manufacture oi a milled soap from a mixture comprising water and at least the following components: ii) a soap which forms solid masses under normal atmospheric conditions and which is selected from the group consisting of the alkali metal, ammonium, and organic amine salts 02 higher fatty acids containing ill to as carbonatoms, and (2) a higher petryl sulionate, the improvement which comprises incorporating (3) starch into a mixture of said type containing an (4) inorganic salt ranging from 0% to mixture, milling and Component:

Soap

' Parts to (-1!) where X equals the weight of inorganic salt Higher petryl sulfonatei. at least Starch -4 5 to 40 and limiting the amount-oi water-in said mixture to 6 to 15 parts per "parts of the total weight of components (1), (2), (3), and (4).

(1), (2), and (3) So that l Component:

Component: Parts Soap to (85X), where X equals the W i ht of sodium sulfate Higher petryl sulfonate at least 10 Starch 10 to and limiting the amount of water in said mixture to 6 to 15 parts per 100 parts of the total weight of components (1), (2), (3), and (4).

3. In the manufacture of a milled soap from a mixture comprising water and at least the following components: (1) a soap which forms solid a higher petryl aromatic sulfonate, milling and plodding the resulting mixture: and controlling the workability of the mix- Parts Soap 15 to (85X), where X equals the weight of sodium sulfate 7 Higher petryl aromatic sulfonate at least6 Starch and limiting the amount of water in Said mixture to 6 to 15 parts per 100 parts of the total weight of components the plodded mixture into bars.

' 4. In the manufacture of a, milled soap from a I the mixture in the milling and plodding operations by proportioning the 12 amounts of components (1) (2), and (3) so that their relative weights, on the basis of a total weight of parts of components (1), (2), (3), and (4), lie within the following ranges:

Component:

Soap 30 to 80, less the Weight of sodium sulfate Higher petryl aromatic su11'onate at least 10 Starch ranges 1 Component:

Soap

- Parts 30 to 80, less the weight of sodium sulfate Higher petryl mononuclear aromatic sulfonate 6 to 40 Starch 10 to 40 and limiting the amount of water in said mixture to 6 to 15 parts per 100 parts of the total weight or the mixture; milling and plodding the resulting mixture: and controlling the workability nents (1), (2), weights, on the basis of a total weight of 100 parts of components (1), (2), (3), and (4), lie within the following ranges:

Component: Parts Soap 30 to 80, less the weight of sodium sulfate Higher petryl benzene sulfonate 10 to 40 Sta 10 to 40 Parts said composition mosaics Component:

Soap Sodium higher petryl benzene sulionate composition 20 to 60 Starch 10 to 40 and limiting the amount of water in said mix:

ture to 6 to 15 parts per 100 parts of the total weight of said components (1), (2) and (3) 8. In the manufacture of a milled soap from a mixture comprising water and at least the following components: (1) a sodium soap for toilet use and (2) a sodium higher petryl benzene sulfonate composition containing 95% its weight of sodium petryl benzene of its weight of inorganic salts, the improvement which comprises incorporating or said type; milling and plodding the resulting mixture; and controlling the workabi ity of the mixture in the milling and plodding operations by proporamounts or components (1), (2),

and (3), so that their relative weights, based on a total weight of 100 parts of said components (1),

(2), and (3), lie within the following ranges:

Parts 15 to 55 Component: Parts Soap 30 to 80 Sodium higher etryl benzene su fonate composition 10 to 40 Starch 5 to 40 and limiting the amount of water in said mixture to 6 to 15 parts per 100 parts of the total weight of said components (1), (2) ,and (3).

9. A milled soap composition comprising as its essential components: (1) a soap which forms solid masses under normal atmospheric conditions and which is selected from the group consisting Of the alkali metal, ammonium, and organic amine salts of higher fatty acids contain- (2) a higher petryl sulionate. V together with (4) inorganic salt in 20% of the total weight of said four components, the proportions by weight of said components (1) (2), and (3), on the basis of a total weight of 100 parts of said four components, lying within the following ranges:

Parts 15 to (85-1!) where X equals the weight of inorganic salt Higher petryl sulfonate at least 6 Starch 5 to 40 containing not more than 15 the total weight Component Soap parts of water per 100 parts of of said four components.

10. A milled soap composition comprising as its essential components: (1) a soap which forms solid masses under normal atmospheric conditions and which is selected from the group consisting of the alkali metal, ammonium, and organic amine salts of higher fatty acids contain ing 10 to 20 carbon atoms, (2) a higher petryl sulfonate, and (3) starch, together with (4) sodiadapted um sulfate in an amount ranging 1mm 0% to 20% or the total weight or said four components, weight of said components (1), (2) and (3). on the basis or a total weight of 100 parts oi said iour components, lying within the following ranges:

Parts soap 15 to (-1!) where X equals the weight 01 sodium sulfate Higher petryl sulionate at least 10 Starch 10 to 40 said composition containing not more than 15 partsoi water per parts or the total weight of said four components.

11. A milled soap composition comprising as its essential components: (1) a soap which forms solid masses under normal atmospheric conditions and which is selected rrom the group conthe alkali metal, ammonium, and organic amine salts of higher fatty acids containpetryl (3) starch, together sulfate in an amount ranging or the total weight of said four the proportions by weight oi! said (1), (2), and (3), on the basis or a Component:

aromatic sulionate, and with (4) sodium from 0% to 20% components. components total weight of 100 parts of said four components,

lying within Component:

Soap

the following ranges:

Parts 15 to (85-21), where X equals the weight of sodium sulfate Higher petryl aromatic sulionate at least 6 Starch 5 to 40 said composition containing not parts of water per 100 parts of the said four components.

12. A milled soap compositon comprising as its essential components: (1) asodium soap, (2) a higher petryl mononuclear aromatic sulfonate, and (3) starch, together with (4) sodium sulfate in an amount ranging from 0% to 20% of the total weight of said four components, the proportions by weight of said components (1) (2) and (3), on the basis of a total weight of 100 parts of said iourcomponents, lying within the following ranges:

more than 15 total weight of Component: Parts Soap 30 to 80, less the weight of sodium sulfate Higher petryl mononuclear aromatic sniionate 10 to 40 Starch: it to (it) said composition containing not more than 15 parts of water per 100 parts of the total weight of said tour components.

13. A milled soap composition comprising as its essential components: (1) a sodium soap adapted for toilet use, (2) a higher petryl aromatic sulfonate, (3) starch, and (4) an amount of sodium sulfate ranging from 25% to 67% of the weight of the higher petryl aromatic sulfonate, the proportions by weight of said components (1), (2), and (3), on the basis or a total weight of 100 parts of said four components, lying within the following ranges:

Component: Parts Soap 15 to 55 Higher petryl aromatic sulionate 20 to 60 Starch 10 to 40 said composition containin not more than 15 15 parts or water per 100 parts of the total weight of said four components.

14. A milled soap compositon comprising as its essential components (1) a sodium soap. (2) a nents: Component: Parts Soap 15 to 45 Sodium higher petryl' benzene sulfonate detergent 40to 60 Starch 10 to 40 per 100 said three components.

15. A milled soap composition comprising'as its essential components (1) a sodium soap, (2) a said components (1) (2) and (3) on the a total weight of 100 parts of said three components lying within the following ranges: Component: Parts Soap 5 to 45 Sodium higher petryl benzene sulfonate detergent-.- 20 to 60 Starch to 40 ,said composition containing not more than parts of water per said three components.

16, A milled soap composition comprising as its essential said three components lying ranges:

Component: P Soap 40 to Higher petryl aromatic sulionate detergent 10 to 40 Starch 5 to 40 said composition containing not more than 15 parts of water per parts or the total weight of said three components.

lled soap composition comprising as its essential components: (1)

the proportions by weight of said components (1) (2), and (3) on the basis of a total weight of 100 parts of said three components lying within the following ranges: Component: Parts Soap 0 to 80 Sodium higher petryl benzene suitonate detergent 19 to 40 Starch 5 to 40 parts of water per 100 parts of the total of said three components.

LESTER FRANCIS HOYT. REFERENCES CITED The following references are of record in the file of this patent:

NITED STATES PATENTS OTHER REFERENCES Thomssen and Kemp (1937) Pages 141-146 of Modern Soap Making, by