NZ248471A - A "freezer" soap bar comprising mostly na and k soaps of: myristic, palmitic and stearic acids plus oleic and/or lauric acid and/or minor fatty acid soap; water; and optionally a lathering synthetic surfactant and a sugar - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £48471 C. \ Priority Date(s): Complete Specification Filed: Class: Publication Date: ZJ...

P.O. Journal No: .l!r££>..,i N.Z. P"Tr"MT OFFICE 2 3 AUG 1993 r- c;:ived No.: Date: NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION "IMPROVED FREEZER PERSONAL CLEANSING BAR WITH SELECTED FATTY ACID SOAPS FOR IMPROVED MILDNESS AND GOOD LATHER" We, THE PROCTER & GAMBLE COMPANY, a corporation organised under the laws of the State of Ohio, United States of America, located at One Procter & Gamble Plaza, Cincinnati, Ohio 45202, United States of America hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page la) 4402/JH 24 84 7] - la - TECHNICAL FIELD This invention relates to freezer personal cleansing bar 15 soaps.

BACKGROUND OF THE INVENTION This invention relates to personal cleansing bar soaps prepared from soap using a "freezer" bar process of the general type disclosed in U.S. Pat. No. 3,835,058, White, issued Sept. 10, 20 1974, incorporated herein by reference. These bars are called "freezer bars," and White teaches a freezer bar soap process.

Japanese Pat. J5 7030-798, July 30, 1980, discloses transparent solid "framed" or "molded" soap in which fatty acids constituting the soap component are myristic, palmitic, and 25 stearic acids. A transparent soap is described in which at least 90 wt.% of the fatty acids which constitute the soap component are myristic acid, palmitic acid, and stearic acid. The product is reported as a transparent, solid soap having good frothing and solidifying properties, good storage stability, and a low irritant 30 effect on human skin. The process and transparent composition exemplified in Jap. J5 7030-798 are distinguished from nontrans-parent freezer bars. A freezer bar process is also distinguished from a transparent framed bar process.

SUMMARY OF THE INVENTION 35 The present invention relates to an improved freezer bar soap comprising selected saturated Ci4-C1Q fatty acid soaps and 24847 lathering soap selected from 1 auric, oleic, and other minor selected more soluble soaps. The bars of this invention have improved mildness while maintaining acceptable lathering/sudsing characteristics. Freezer bar soaps can be made using a process 5 generally disclosed in U.S. Pat. No. 3,835,058, White, supra.

OBJECT OF THE INVENTION It is an object of the present invention to provide a mild, good lathering freezer bar soap. Another object is to provide a freezer bar soap that is milder than the current standard good 10 lathering freezer bar soap which is identified below in the Examples as the Comparative Bar.

Yet another object of the present invention is to provide a good lathering freezer bar without impairing mildness.

Still another object is to provide a freezer bar composition 15 which is processable.

Other objects of the present invention will be apparent in the light of the following disclosure.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved freezer bar soap 20 comprising selected saturated C14-C13 fatty acid soaps and lathering soap selected from lauric, oleic, and Cs, C10, and Cjs;2 soaps. The bars of this invention have improved mildness while maintaining acceptable sudsing characteristics, Freezer bar soaps can be made using a process generally disclosed in U.S. Pat. No. 25 3,835,058, White, supra. Such bars are highly desirable from the standpoint of skin mildness and processability while maintaining other acceptable bar qualities including good sudsing and/or good smear characteristics.

The present invention is broadly defined as: A mild, lathering personal cleansing freezer soap bar comprising: I. saturated fatty acid soaps selected from the group consisting of: myristic, palmitic, anci stearic acid soaps and mixtures thereof at a level of from about 50% to about 85% by weight of total fatty acid soap; and II. from about 15% to about 50% by weight of ^afAfktfcy^cid soap, of soap selected from the group consj oleic and lauric acid soaps and minor fatty acid soap selected from the group consisting essentially of: Cs, Cjo» ^18:2 ar|d mixtures thereof; wherein said bar contains from about 8% to about 25% by weight of said selected oleic and lauric soap, and minor (Cg, Ciq, Cig:2^ soaps? wherein said oleic soap level is from 0% to about 25% by weight of the bar; and said lauric soap is from 0% to about 10% by weight of said bar; and wherein said minor (Cq, Cio> Cis:2) soaP level is from 0% to about 5% by weight of said bar; and wherein said selected lauric/oleic soap to said minor soap have a ratio of from about 1:1 to about 1:0; and wherein said Na/K soap mixture level is from about 90% to about 100% by weight of said total soap; and wherein said Na/K soap has a ratio of from about 19:1 (95/5) to about 1.5:1 (60/40); and wherein said freezer soap bar comprises from about 30% to about 70% of total fatty acid soap by weight of said bar; and III. from about 15% to about 30% of water by weight of said bar.

In view of the above definition, a preferred mild, lathering personal cleansing freezer'soap bar comprises: I. said saturated fatty acid soaps selected from the group consisting of: myristic, palmitic, and stearic acid soaps and mixtures thereof are present at a level of from about 65% to about 80% by weight of total fatty acid soap; and n. from about 20% to about 35% by weight of total fatty acid soap of selected oleic and lauric acid soaps and minor (C8, C10, Ci8;2) fatty acid soap; wherein said bar contains from about 8% to about 25% of said selected oleic and lauric soap, and minor (Cs, Cio, Cis:2) soaps; wherein said oleic soap level is from about 5% to about 20% by weight of the bar; and said lauric soap is from about 5% to about 10% by weight of said bar; and 248471 wherein said minor (C8, Cio> Ci8:2) soaP lGVel is ^rom about 1% to about 3% by weight of said bar; and wherein said selected lauric/oleic soap and said minor soap have a ratio of from about 1:1 to about 1:0; and wherein said Na/K soap mixture level is from about 95% to about 100% by weight of said total soap; and wherein said Na/K soap has a ratio of from about 90/10 to about 65/35; and wherein said total soap comprises other soap selected from the group consisting of Mg and TEA soaps at a level of from 0% to about 5% by weight of said total soap; and wherein said freezer soap bar comprises by weight of said bar: A. from about 30% to. about 60% of said total fatty acid soap; B. from 0% to about 30% of nonreducing sugar; C. from 0% to about 35% of hydrophobic/lipophilic soap additive material; and D. from about 20% to about 25% of said water.

Another preferred bar of the present invention comprises said selected saturated fatty acid soaps level is from about 65% to about 80% by weight of said total soap; and wherein the sum of said selected minor, lauric, and oleic acid soap level is from about 10% to about 20% by weight of said bar; and wherein said lauric/oleic soap have a ratio of from about 2:1 to about 1:4; and wherein said Na/K ratio is 90/10 to 65/35; and wherein said lauric/oleic acid soap and said minor (Cs, C10, Ci8:2) soaP have a ratio of about 6:1 to about 4:1.

Yet another preferred freezer bar of this invention comprises: said selected saturated fatty acid soaps level is about 70% to about 75% by weight of said total soap; and wherein the sum level of said lauric and said oleic acid soaps is from about 12% to about 18% by weight of said bar and the ratio of said 1 auric/-olelc acids is from about 1.5:1 to about 1:3 and wherein said Na/K ratio is from 85/15 to 70/30.

Still another preferred freezer bar comprises: said selected saturated fatty acid soaps (myristic, stearic, and palmitic acid 24847 soap) level is from about 20% to about 50% by weight of said bar; and wherein said nonreducing sugar is from about 5% to about 20%; and said hydrophobic/lipophilic material is from about 2% to about 5 25%; and said water is from about 20% to about 25% by weight of said bar; and wherein said bar contains from about 10% to about 20% of said selected lauric/oleic acid soaps by weight of the said bar. 10 A preferred bar of this invention comprises: said freezer soap bar comprises by weight of said bar: from about 30% to about 55% of said total fatty acid soap; and wherein said oleic acid soap is primarily cis.

A particularly preferred bar of this invention comprises by 15 weight of said bar: from about 30% to about 55% of said total fatty acid soap; from about 5% to about 20% of said nonreducing sugar; from about 5% to about 20% of said hydrophobic/lipophilic material; and from about 20% to about 25% of said water; and wherein lauric and oleic soap level is from about 12% to about 18% by weight of the said bar; wherein said oleic soap rjias a cis/trans isomer ratio from about 1:0 to about 20:1.

When the bar contains 95/5 Na/K soap, it should contain some sucrose and/or TEA soap to ensure good lather. Some preferred bars can have a substantial amount of a soap structure disclosed 1n New Zealand Patent Specification No. 240709, for a "Shaped Solid Made with a Rigid, Interlocking Mesh of Neutralized Carboxylic Acid," said specification being incorporated herein by reference. Such bars can have very little smear formed on standing in a wet soap dish. Such bars comprise a structure which is a continuous or semi-continuous, relatively 35 rigid, interlocking, open, three-dimensional crystalline mesh of neutralized carboxylic acid, i.e., the selected fatty acid soaps defined herein, particularly sodium soap of saturated fatty acids. n1 - 6 I.e., these bars contain a substantial amount (e.g., at least about 5% to about 75% by volume) of the continuous or semi-continuous, rigid, interlocked mesh of neutralized fatty carboxylic acid, preferably sodium soap of saturated fatty acids.

Bars containing substantial amounts of said mesh structure tend to be harder, with improved smear. Bars with said mesh structure are not typically translucent. Other advantages of this type of mesh structure and guidance for obtaining said mesh structure are found generally in said nz specification no. 240709. When a freezer 10 process is used rather than a frame process, additional soap may be required to achieve sufficient viscosity to form a soft plug on exiting the freezer and subsequently still form the same level of structure. Agitation, which tends to destroy the structure, is minimized at the time said mesh structure is forming. Higher 15 levels of individual saturated chain length(s) tend to form the said mesh structure better.

The levels, parts, percentages and ratios herein are by weight unless otherwise specified. Note that the levels of the soaps expressed herein are in terms of weight percent (wt.%) of 20 the total soap and also in terms of wt.% of the bar. All numerical limits, ranges, ratios, etc., are approximations unless otherwise specified.

Within the scope of the invention, there are several different preferred embodiments.

All parts, levels, percentages and ratios herein are by weight unless otherwise specified. Note that the levels of the soap are expressed herein as weight percent (wt.%) of the total soap and as wt.% of the bar. The numerical limits, ranges, temperatures, ratios, etc., are approximations unless otherwise 30 specified.

The term "insoluble" soap as used herein means soap less soluble than sodium myristate (C14).

Soap The fatty acid soap component (A) suitable for use in the compositions and processes of the present Invention includes \ alkali metal, especially sodium and potassium, ion soaps of higher fatty acids and mixtures thereof, as defined above. Mixtures of \i^ 1 24 O u sodium and potassium soaps are required for lather. Other cations with similar properties can be used, at least in small amounts, like triethanolammonium (TEA), lithium, and magnesium cations. Such other cations, when used, are used at a level of from 0% to 5 10%, preferably from about 2% to about 5%, by weight of the total soap.

TABLE 1 Solubility of Soaps. Molar. 25°C Na K Mq C12 0.11 Freely Insoluble Ci8:l 0.49 Freely N/A C14 0.004 Freely Insoluble Ci6 Insoluble N/A Insoluble Ci8 Insoluble N/A Insoluble The term "insoluble" soap as used herein means soap less soluble than sodium myristate.

The term "coconut" as used herein in connection with soap or fatty acid mixtures refers to materials having an approximate 20 carbon chain length distribution of: 8% Cq; 7% Cjo; 48% C12; 17% C14; 9% Ci6; 2% Ci8; 7% Ci8:1 oleic and 2% linoleic (the first six fatty acids being saturated).

The term "palm oil stearin" as used herein refers to materials having an approximate carbon chain length distribution of 25 about: 1% C14, 58% Cj6» 5% Cis, 29% oleic, and 7% linoleic (the first three fatty acids being saturated).

The term "tallow" as used herein refers to a mixture of soaps having an approximate chain length distribution of: 2.5% C14; 29% Ci6; 23% Cig; 2% palmitoleic; 41.5% oleic and 3% linoleic. 30 The term "triple pressed stearic" as used herein refers to fatty acids having an approximate chain length distribution of 55% palmitic, Ci6, 45% stearic, Cis.

The term-"relatively more soluble soap" as used herein means a soap of which the fatty chain length or level of unsaturation is 35 such that it is more soluble than sodium myristate, or a soap that has the solubility on the order of sodium laurate or oleate soaps, excluding potassium soaps. 24 D li ' 8 - The fatty acid soap can be made using pure chain fatty acids, or by using the proper levels and ratios of common fatty acid mixtures such as coconut, palm oil stearin, tallow, and triple pressed stearic.

The preferred levels and ratios can vary with the levels of cation mixtures.

The levels of potassium soap preferably should not exceed about one-third or four-tenths that of the total soap and the level of TEA or magnesium soap should not exceed about one-tenth 10 of the level of total soap, and is preferably less than about one-twentieth that of the total soap. E.g., the sodium soap is preferably at least about 60% of the total soap present in the bar. Na/K ratio range is from 95/5 to 60/40, preferably about 80/20 to 70/30.

TABLE 2 Total Fatty Acid Soap Full Preferred More Preferred FA Chain C12+I8:1 15-50% 20-35% 25-30% FA Chain C14-18 50-85% 65-80% 70-75% Preferably the FA soap C12/C18:1 ratio is from about 2:1 to about 1:4, more preferably from about 1.5:1 to about 1:3.

Table 3 shows some preferred levels of FA's used in compositions of the present invention. Some preferred compo-25 sitions contain little or no short chain FA's of ten carbon atoms or less. The terms "soap" and "fatty acid (FA) salts" as used herein are sometimes interchangeable. "Soap" is normally used since it is easier to relate to and and have a generic connotation. The term "soap" as used herein can mean a single 30 fatty acid soap or a mixture of fatty acid soaps. Examples of "minor, more water-soluble soaps" are Cs, Cio» Cjs:2 and the like which are present at a level of from 0% to about 5%, preferably from about 1% to about 3%, by weight of the bar. Such minor soaps help lather. 2 4 6 , TABLE 3 Percent Ci?. Unsaturated and/or Minor Chain Soaps in Total Bar Broad Preferred More Preferred C12 + Ci8:l + Minors 8-25% 10-20% 12-18% Better lather is achieved by using more Ciq;i cis and potassium cation soaps and, optionally, sugar within the levels and ranges defined herein. It is somewhat surprising that the use 10 of the Ci8:l cis vs. the Ci8:1 trans, K vs. Na soaps, and sugar, all of which increase soap solubility, are not adverse to mildness.

It is important to selectively balance the amount of more water-soluble lauric and oleic soaps and minor, more water-soluble 15 soaps to from 8-25% by weight of the bar to achieve good lather and mildness. More lather is realized at the higher end of the level (25%) and better mildness is realized at the lower (8%) end of the level.

On the other hand, Cis:1 cis isomer (which is more soluble 20 than the Ci8:l trans isomer) is preferred for lather and is surprisingly just as mild as the trans Cis: 1 isomer. In bars which contain oleic acid soap, the lather of such bars is increased with increasing Ci8:1 cis isomer. Conversely, the lather is reduced with more trans and is dramatically reduced when the 25 trans oleic acid isomer is present at a substantial level by weight of the total soap or at a level of about 5-8% or more by weight of the bar. The ratio of oleic cis/trans isomers is from 1:0 to 1:1, preferably 1:0 to 3:1, and more preferably 1:0 to 19:1. The preferred Ci8:1 isomer levels are set out in Table 4.

TABLE 4 Wt.% of Oleic C^fl-i Isomers Broad Preferred More Preferred Ci8:i trans 0-50% 0-25% 0-5% C18:1 cis 50-100% 75-100% 95-100% 24 t - 10 -Water The level of water in the bar can range from about 15% to about about 30%, preferably from about 15% to about 25%, more preferably from about 20% to about 25%. Higher levels of water within these preferred ranges are preferred for mildness and cost reduction. Excess amounts of water can be used in a process for making the bars of this invention; but, when sucrose is used the excess water should be removed prior to the addition of any sucrose to avoid burning (degrading) the sucrose in the 300°F (149"C) drying step. In a preferred aerated freezer bar process, the amount of water used does not require a drying step.

It should be noted that in frame bar processes higher levels of water or solvent can be used because the bars are not required to stand up (hold their shape) upon extrusion as in a freezer bar process.

Nonreducing Sugar The nonreducing sugar, e.g., sucrose, is optional, but preferred. The nonreducing sugar (when used) is used at a level of from about 5% to about 30% and replaces at least a comparable amount of soap. The net effect of less soap in this case is a corresponding mildness benefit, as well as an unexpected processing benefit and a lather benefit.

Sucrose will not reduce Fehling's solution and therefore is classified as a "nonreducing" disaccharide. Sucrose, commonly known as table sugar, is by far the most abundant carbohydrate found in the sap of land plants. It is one of the few nonreducing sugars available in a state of unexcelled purity, in highly crystalline form, on a very large scale, and at low cost. It has been produced since 2000 B.C. from the juice of the sugar cane and since the early 1800's from the sugar beet. Sucrose is a sweet, crystalline (monoclinic) solid which melts at 160-186*C, depending on the solvent of crystallization.

Unless otherwise specified, the term "sucrose" as used herein includes sucrose, its derivatives, and similar nonreducing sugars and similar polyols which are substantially stable at a soap processing temperature of up to about 210"F (994C), e.g., trialose, raffinose, and stachyose; and sorbitol, lactitol and 24 maltitol.

In contrast, starch, a complex sugar, is a reducing sugar and turns brown or "burns" at the typical soap processing pH and/or temperature. It is important for the preferred execution of the 5 present invention to have a pumpable, stable soap mix which turns pure white upon aeration to provide a white soap bar that floats. Starch increases the viscosity of the soap mix.

The sucrose has an unexpectedly dramatic thinning effect on the soap mix which eliminates the need to add excess water or 10 solvent for homogeneous mixing. Sucrose reduces the viscosity profile of the soap mix that goes into the freezer at comparable shear rates by about 20% up t; about 99%. Preferably, the amount of sucrose used to replace a comparable amount of soap would decrease the viscosity of an otherwise comparably dried soap bar 15 mix by at least 50%, and more preferably by at least 75%.

When the soap/sucrose mix is homogeneous, it is then cooled in a freezer to a temperature of from at least about 49*C to about 66*C. Again, the soap/sucrose mix is still pumpable and has a viscosity which does not require extraordinary equipment or excess 20 water or excess solvent. The use of excess water/solvent requires an additional step for drying. Preferably, no moisture reduction (drying) step is required. The soap/sucrose mixes are preferably formulated without excess water, but so that they are mixable and pumpable. The mixing temperature is typically from about 82#C to 25 about 10CC. The sucrose/soap composition crutcher mix, upon cooling, is used to make firm, stamped bars which stand up on a freezer process belt.

Alternatively, the sucrose can be added to a dried soap mix and still reduce its viscosity and provide a mildness benefit for 30 the final bar. A "dried soap mix" is a mix wherein the water level has been reduced from about 30% to about 20-25%.

Hydrophobic/Lipophilic (Hydrophobic) Material A preferred bar of the present invention can contain from 0% to about 35%, preferably from about 2% to about 25%, more prefer-35 ably from about 5% to about 20%, of hydrophobic/lipophilic (hydrophobic) soap bar additive material; preferably hydrophobic/lipophilic material selected from the group consisting of: (1) wax; (2) other hydrophobic material, including free fatty acids; mono-, di-, and triglycerides; and fatty alcohols containing from about 8 to about 18 carbon atoms in each acyl or alkyl group; and (3) mixtures thereof, and wherein the maximum of said wax is about 25%; and wherein the maximum of said other hydrophobic material is about 10% by weight of the bar.

The hydrophobic material optional component when used in this invention is selected from: waxes; mono-, di-, and triglycerides; fatty acids; fatty alcohols; other similar materials; and mixtures thereof. Preferably the bars contain at least 3% wax and the wax to other hydrophobic material have a ratio of from about 25:1 to about 1:3, more preferably from about 1:1 to about 10:1. The use of a hydrophobic component is highly preferred, but soap bars of the present invention can be made with little, or no, hydrophobic material as shown below in Example 7.

A preferred aerated bar soap composition comprises: (1) from about 30 wt.% to about 70 wt.% of selected fatty acid soap, as defined hereinabove; (2) from 10% to about 30% of a nonreducing sugar; (3) from 3 wt.% to about 30 wt.% of hydrophobic material as defined hereinabove; and (4) from about 15% to about 30% water.

The hydrophobic material can be present in preferred bars of this invention at a level up to about 30%, but is preferably used at a level of from about 5% to about 20%. The levels of some hydrophobic materials, e.g., fatty acids, can be increased in the bar soap composition as the amount of sucrose is increased. The higher the amount of sucrose present, the more of such hydrophobic material can be present. Soap bars with or without sucrose can benefit from hydrophobic material, particularly the waxes. Triglycerides (Cs-Cia alkyl chain) can be used up to about 10% without adversely affecting lather performance. The preferred and exemplified bars of the present invention have good lathering properties equal to the Industry standard aerated freezer bar soap IVORY®.

The preferred hydrophobic material is a wax having a melting point (M.P.) of from about 120°F to about 185*F (49°-85°C), 24 8 4 7 preferably from about 125'F to about 175*F (52'-79'C). Another preferred hydrophobic material is petrolatum.

Waxes include petroleum based waxes (paraffin, microcrystal-line, and petrolatum), vegetable based waxes (carnauba, palm wax, candelilla, sugarcane wax, and vegetable derived triglycerides) animal waxes (beeswax, spemaceti, wool wax, shellac wax, and animal derived triglycerides), mineral waxes (montar, ozokerite, and ceresin) and synthetic waxes (Fischer-Tropsch).

A preferred paraffin wax is a fully refined petroleum wax having a melting point ranging from about 120'F to about 160°F (49°-71°C). This wax is odorless and tasteless and meets FDA requirements for use as coatings for food and food packages. Such paraffins are readily available commercially. A very suitable paraffin can be obtained, for example, from The Standard Oil Company of Ohio under the trade name Factowax R-133.

Other suitable waxes are sold by the National Wax Co. under the trade names of 9182, 6971, and 6975, respectively having melting points of 131*F, 130*F (~55'C), and 155°F (-68*C).

The paraffin preferably is present in the bar in an amount ranging from about 5% to about 20% by weight. The paraffin ingredient is used in the product to impart skin mildness, plasticity, firmness, and processability. It also provides a glossy look and smooth feel to the bar.

The paraffin ingredient is optionally supplemented by a microcrystalline wax. A suitable microcrystalline wax has a melting point ranging, for example, from about 140°F (60#C) to about I'85#F (85*C), preferably from about 145"F (62°C) to about 175*F (79'C). The wax preferably should meet the FDA requirements for food grade microcrystalline waxes. A very suitable micro-crystalline wax is obtained from Witco Chemical Company under the trade name Multiwax X-145A. The microcrystalline wax preferably is present in the bar in an amount ranging from about 0.5% to about 5% by weight. The microcrystalline wax ingredient imparts pliability to the bar at room temperatures.

Fatty acids are preferably used in the process of the invention. Preferred are those having from 8 to 18 carbon atoms. Normally a mixture of free fatty acids derived from natural 2 4 o - ' •' sources is employed. Preferred mixtures of fatty acids are the saturated C14-C18 fatty acid mixtures hereinbefore described.

The free fatty acids improve the quantity and quality of the lathering characteristics of bars prepared in accordance with the process of the present invention. The advantage of free fatty acids in tending to provide a lather of desirable stability and having small air bubbles so as to provide a rich or creamy lather has been known in the art. Fatty acids also provide an emollient effect which tends to soften the skin or otherwise improve feel-on-skin characteristics and scavenge any excess alkalinity.

The amount of free fatty acid incorporated into the preferred finished bars of the invention ranges from about 0.5% to about 8%. A preferred amount of fatty acid ranges from about 2% to about 7%.

The free fatty acid can be incorporated into bars of the present invention in a number of suitable ways. The free fatty acid component is desirably incorporated into the soap mixture either prior to, or simultaneously with, the high-shear mixing step used to form the bar composition. Uniform distribution of the free fatty acid throughout the finishad bar composition is facilitated by the high-shearing action. The free fatty acid component can be added subsequent to the high-shear mixing step if other subsequent mixing means are employed so as to substantially uniformly distribute the free fatty acid throughout the soap mixture or resulting bar composition.

The free fatty acid component is preferably introduced into the soap mixtures of the present invention by addition of the free fatty acid to the soap mixture in the initial crutching stage. Alternatively, the free fatty acid component can be introduced prior to or during the aeration stage where perfume and other additives, if desired, are incorporated into the soap mixture. The free fatty acid component can also be introduced as a prepared mixture of soap and free fatty acid, such as an acid-reacting mixture of soap and free fatty acid prepared by under-neutrali-zation in the soap making process.

The bars of this invention can show a mildness improvement without free fatty acids as the result of the presence of the 24 8 <■' specific fatty acid soaps, either alone or in combination with the sucrose and/or hydrophobic material.

Synthetic Detergent Surfactant An alternative bar can contain from 0% to about 30%, pref-5 erably from about 4% to about 15%, synthetic detergent surfactant, preferably a mild lathering synthetic detergent surfactant; however, the bars of this invention are preferably soap bars with little or no synthetic surfactant.

The optional synthetic detergent surfactant is typically 10 selected from the group consisting of: anionic, nonionic, amphoteric and zwitterionic synthetic detergents. Both low and high lathering and high and low water-soluble surfactants can be used in the bar compositions of the present invention. Suds boosting synthetic detergent surfactants and/or synthetic detergent, sur-15 factants that are known as good dispersants for soap curds that are formed in hard water, are particularly desirable.

Examples of suitable synthetic detergents for use herein are those described in U.S. Pat. No. 3,351,558, Zimmerer, issued Nov. 7, 1967, at column 6, line 70 to column 7, line 74, incor-20 porated herein by reference.

Examples include the water-soluble salts of organic, sulfonic acids and of aliphatic sulfuric acid esters, that is, water-soluble salts of organic sulfuric reaction products having in the molecular structure an alkyl radical of from 10 to 22 carbon atoms 25 and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.

Synthetic sulfate detergents of special interest are the normally solid alkali metal salts of sulfuric acid esters of normal primary aliphatic alcohols having from 10 to 22 carbon 30 atoms. Thus, the sodium and potassium salts of alkyl sulfuric acids obtained from the mixed higher alcohols derived by the reduction of tallow or by the reduction of coconut oil, palm oil, palm kernel oil, palm oil stearin, babassu kernel oil or other oils of the coconut group can be used herein.

Other aliphatic sulfuric acid esters which can be suitably employed include the water-soluble salts of sulfuric acid esters of polyhydric alcohols incompletely esterified with high molecular V* * f'V. C' V weight soap-forming carboxylic acids. Such synthetic detergents include the water-soluble alkali metal salts of sulfuric acid esters of higher molecular weight fatty acid monoglycerides such as the sodium and potassium salts of the coconut oil fatty acid monoester of l,2-hydroxypropane-3-sulfuric acid ester, sodium and potassium monomyristoyl ethylene glycol sulfate, and sodium and potassium monolauroyl diglycerol sulfate.

The synthetic surfactants and other optional materials useful in conventional cleaning products are also useful in the present invention. In fact, some ingredients such as certain hygroscopic synthetic surfactants which are normally used in liquids and which are very difficult to incorporate into normal cleansing bars are very compatible in the bars of the present invention. Thus, essentially all of the known synthetic surfactants which are useful in cleansing products are useful in the compositions of the present invention. The cleansing product patent literature Is full of synthetic surfactant disclosures. Some preferred surfactants, as well as other cleansing product ingredients, are disclosed in the following references: u.s.Pat. No.

Issue Date Inventorfsl 4,061,602 12/1977 Oberstar et al. 4,234,464 11/1980 Morshauser 4,472,297 9/1984 Bolich et al. 4,491,539 1/1985 Hosklns et al. 4,540,507 9/1985 Grollier 4,565,647 1/1986 Llenado 4,673,525 6/1987 Small et al. 4,704,224 11/1987 Saud 4,788,006 11/1988 Bolich, Jr., et al 4,812,253 3/1989 Small et al. 4,820,447 4/1989 Medcalf et al. 4,906,459 3/1990 Cobb et al. 4,923,635 /1990 Simlon et al. 4,954,282 9/1990 Rys et al.

All of said patents are incorporated herein by reference. Some preferred synthetic surfactants are shown in the Examples herein. Preferred synthetic surfactant systems are selectively designed / . ? & p / ^ ■- S ^ ./ * / i for bar appearance, stability, lather, cleansing and mildness.

It is noted that surfactant mildness can be measured by a skin barrier destruction test which is used to assess the irritancy potential of surfactants. In this test the milder the surfactant, the less the skin barrier is destroyed. Skin barrier destruction is measured by the relative amount of radio-labeled water (3H-H20) which passes from the test solution through the skin epidermis into the physiological buffer contained in the diffusate chamber. This test is described by T.J. Franz in the J. Invest. Dermatol.. 1975, 64, pp. 190-195; and in U.S. Pat. No. 4,673,525, Small et al., issued June 16, 1987, incorporated herein by reference. These references disclose a mild alkyl glyceryl ether sulfonate (AGS) surfactant based synbar comprising a "standard" alkyl glyceryl ether sulfonate mixture and define the criteria for a "mild surfactant." Barrier destruction testing is used to select mild surfactants. Some preferred mild synthetic surfactants are disclosed in the above Small et al. and Rys et al. patents. Some specific examples of preferred surfactants are used in the Examples herein.

Some examples of good mild, lather-enhancing, synthetic detergent surfactants are, e.g., sodium lauroyl sarcosinate, alkyl glyceryl ether sulfonate, sulfonated fatty esters, and sulfonated fatty acids.

Numerous examples of other surfactants are disclosed in the patents incorporated herein by reference. They include other alkyl sulfates, anionic acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideceth sulfates, protein condensates, mixtures of ethoxylated alkyl sulfates and alkyl amine oxides, betaines, sultaines, and mixtures thereof. Included in the surfactants are the alkyl ether sulfates with 1 to 12 ethoxy groups, especially ammonium and sodium lauryl ether sulfates.

Alkyl chains for these other surfactants are Cs-C22» preferably C10-C18- Alkyl glycosides and methyl glucose esters are preferred mild nonionics which can be mixed with other mild anionic or amphoteric surfactants in the compositions of this 248471 invention. Alkyl polyglycoside detergents are useful lather enhancers. The alkyl group can vary from about 8 to about 22 and the glycoside units per molecule can vary from about 1.1 to about 5 to provide an appropriate balance between the hydrophilic and hydrophobic portions of the molecule. Combinations of Cs-Cis, preferably C12-C16, alkyl polyglycosides with average degrees of glycosidation ranging from about 1.1 to about 2.7, preferably from about 1.2 to about 2.5, are preferred.

Sulfonated esters of fatty esters are preferred wherein the chain length of the carboxylic acid is Cs~C22» preferably C12-C18; the chain length of the ester alcohol is C1-C6. These include sodium methyl alpha-sulfo laurate, sodium methyl alpha-sulfo cocoate, and sodium methyl alpha-sulfo tallowate.

Amine oxide detergents are good lather enhancers. Some preferred amine oxides are Cs-Cis, preferably C10-C16, alkyl dimethyl amine oxides and C8-C18, preferably C12-C16, fatty acyl amidopropyl dimethyl amine oxides and mixtures thereof.

Fatty acid alkanolamides are good lather enhancers. Some preferred alkanolamides are Cs-Cis, preferably C12-C16, mono-ethanolamides, diethanolamides, and monoisopropanolamides and mixtures thereof.

Other detergent surfactants are alkyl ethoxy carboxylates having the general formula R0(CH2CH2O)kCH2C0O-M+ wherein R is a Cs-22 alkyl group, k is an integer ranging from 0 to 10, and M is a cation; and polyhydroxy fatty acid amides having the general formula 0 Rl R2 - C - N - Z wherein Rl is H, a Cj-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof.

Betaines are good lather enhancers. Betaines such as Cs-Cis, preferably C12-C16, alkyl betaines, e.g., coco betaines or C8-C18, - 19 24 84 7 1 preferably C12-C16, acyl amido betaines, e.g., cocoamidopropyl betaine, and mixtures thereof, are preferred.

Examples of specific surfactants follow.

Class: Nonionic Sulfonates Na Cs Glyceryl Ether Sulfonate Na C12-14 Glyceryl Ether Sulfonate Na Ci6 Glyceryl Ether Sulfonate Sodium Cocomonoglyceride Sulfonate 10 Sodium Salt of C8-16 Alkyl Glyceryl Ether Sulfonates Alpha Sulfo Esters and Acids Na Alpha Sulfo Methyl Laurate/Myristate Na Alpha Sulfo Methyl Myristate Na Alpha Sulfo Hexyl Laurate 15 Na Alpha Sulfo Methyl/Hexyl Laurate and Myristate Na Alpha Sulfo Methyl Palmitate Na Alpha Sulfo Methyl Stearate Na 2-Sulfo Lauric Acid Na 2-Sulfo Palmitic Acid 20 Na 2-Sulfo Stearic Acid Rl-C(S03-Na+)-C02R2 Rl = C3-14; R2 =■ Ci-8 Sodium Alkvl Isethionates Sodium Lauryl Isethionate Sodium Cocoyl Isethionate 25 Sarcosinates Sodium Lauryl Sarcosinate Sodium Stearyl Sarcosinate Sodium Cocoyl Sarcosinate Alkvl Sulfates 30 Sodium Lauryl Sulfate Sodium Laureth-1 Sulfate Sodium Oleyl Sulfate Sodium Cetearyl Sulfate Sodium Cetyl Sulfate 35 Ri(0CH2CH2)n0S°3-X R1 = c8-14» c16-20 with at least one double bond, X » 0-18 Acvl Glutamates Sodium Cocoyl Glutamate Sodium Lauryl Glutamate Sodium Myristyl Glutamate Sodium Stearyl Glutamate Alkvl Ether Carboxvlates Sodium Laureth-5 Carboxylate Sodium Palmityl-20 Carboxylate Rl-(O-CH2CH2)nc02* R1 a c8-18> n = 1-30 Sulfosuccinates Disodium Laureth Sulfosuccinate Phosphates Sodium Monoalkyl (70% Ci2/30% C14) Phosphate Class: Amphoterics Betaines Coco Betaine Cocoamidopropyl Betaine Palmitylamidopropyl Betaine Isostearamidopropyl Betaine . Sultaines Cocoamidopropylhydroxy Sultaine Amine Oxides Palmityl Dimethyl Amine Oxide Myristyl Dimethyl Amine Oxide Cocoamidopropyl Amine Oxide Prfftein Derived Na/TEA C12 Hydrolyzed Keratin The bar compositions of the present invention can optionally contain from about 1% to about 30% organic nonsoap synthetic detergent, preferably at a level of from about 4% to about 25%, more preferably from about 5% to about 20%, by weight of the bar. Normally the soap/synthetic bars are prepared to contain a ratio of soap to synthetic detergent of from about 3:1 to about 25:1. The choice of suitable ratios will depend upon the particular ,0 f. *7 . H «.',a / synthetic detergent, the desired performance and physical characteristics of the finished bar, temperature, moisture and like processing considerations. A preferred ratio is from about 4:1 to about 7:1.

The bars of this invention do not require the optional ingredients, thus zero is the lowest level for each optional ingredient. Some preferred bars contain from about 1% to about 65% of selected optional ingredients.

The levels set out in Other Ingredients Table are particularly illustrative for bars containing other optional ingredients.

OTHER INGREDIENTS TABLE Practical Wt.% of Other Ingredients More Most Preferred Preferred Preferred Filler Salts and Salt Hydrates 0.5-50% 0.75-25% 1-15% Water-Soluble Organics 1.0-50% 2-40% 5-20% Polymeric Mildness Enhancers 0.25%-20% 0.5%-10% 1-5% Other Impalpable Water-insolubles 1-60% 2-30% 4-25% Aluminosilicates/Clay 0.5-25% 1-10% 3-8% The bar soap compositions of the present invention can contain other additives commonly included in toilet bars such as perfumes, other fillers, sanitizing or antimicrobial agents, dyes, and the like.

Polymeric skin mildness aids are disclosed in the Small et al. and Medcalf et al. patents. The cationic synthetic polymers useful in the present invention are cationic polyalkylene imines, ethoxypolyalklene imines, and poly[N-[-3-(dimethylammonio)propyl]-N'-[3-(ethyleneoxyethylene dimethylammonio)propyl]urea dichloride] the latter of which is available from Miranol Chemical Company, Inc. under the trademark of Miranol A-15, CAS Reg. No. 68555-36-2.

Preferred cationic polymeric skin conditioning agents of the present invention are those cationic polysaccharides of the 24 8 4/ cationic guar gum class with molecular weights of 1,000 to 3,000,000. More preferred molecular weights are from 2,500 to 350,000. These polymers have a polysaccharide backbone comprised of galactomannan units and a degree of cationic substitution ranging from about 0.04 per anhydroglucose unit to about 0.80 per anhydroglucose unit with the substituent cationic group being the adduct of 2,3-epoxypropyltrimethyl ammonium chloride to the natural polysaccharide backbone. Examples are JAGUAR C-14-S, C-15 and C-17 sold by Celanese Corporation. In order to achieve the benefits described in this invention, the polymer must have characteristics, either structural or physical which allow it to be suitably and fully hydrated and subsequently well incorporated into the soap matrix.

A mild skin cleansing bar of the present invention can contain from about 0.5% to about 20% of a mixture of a silicone gum and a silicone fluid wherein the gum:fluid ratio is from about 10:1 to about 1:10, preferably from about 4:1 to about 1:4, most preferably from about 3:2 to about 2:3.

Silicone gum and fluid blends have been disclosed for use in shampoos and/or conditioners in U.S. Pat. Nos.: 4,906,459, Cobb et al., issued March 6, 1990; 4,788,006, Bolich, Jr. et al., issued Nov. 29, 1988; 4,741,855, Grote et al., issued May 3, 1988; 4,728,457, Fieler et al., issued March 1, 1988; 4,704,272, Oh et al., issued Nov. 3, 1987; and 2,826,551, Geen, issued March 11, 1958, all of said patents being incorporated herein by reference.

The silicone component can be present in the bar at a level which is effective to deliver a skin mildness benefit, for example, from about 0.5% to about 20%, preferably from about 1.5% to about 16%, and most preferably from about 3% to about 12% of the composition. Silicone fluid, as used herein, denotes a silicone with viscosities ranging from about 5 to about 600,000 centistokes, most preferably from about 350 to about 100,000 centistokes, at 25*C. Silicone gum, as used herein, denotes a silicone with a mass molecular weight of from about 200,000 to about 1,000,000 and with a viscosity of greater than about 600,000 centistokes. The molecular weight and viscosity of the particular selected siloxanes will determine whether it is a gum or a fluid. 24 8 a y The silicone gum and fluid are mixed together and incorporated into the compositions of the present invention.

Other ingredients of the present invention are selected for the various applications. E.g., perfumes can be used in formulating the skin cleansing products, generally at a level of from about 0.1% to about 2.0% of the composition. Alcohols, hydro-tropes, colorants, and fillers such as talc, clay, water-insoluble, impalpable calcium carbonate, starch, and dextrin can also be used. The preferred bar of this invention contains from about 3% to about 5% impalpables, preferably, calcium carbonate. These additives make the finished bar compositions either more attractive or effective without detracting from the desirable attributes of the bar. Cetearyl alcohol is a mixture of cetyl and stearyl alcohols. Preservatives, e.g., sodium ethylened'aminetetraacetate (EDTA), generally at a level of less than 1% of the composition, can be incorporated in the cleansing products to prevent color and odor degradation. Antibacterials can also be incorporated, usually at levels up to 1.5%. The above patents disclose or refer to such ingredients and formulations which can be used in the bars of this invention, and are incorporated herein by reference.

Some bars of this invention contain at least about 1% of another bar ingredient selected from: other soaps, moisturizers, colorants, solvents, fillers, synthetic detergent surfactants, polymeric skin feel and mildness aids, perfumes, preservatives, and mixtures thereof.

Compatible salt and salt hydrates can be used as fillers. Some preferred salts are sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate.

Generally, compatible salts and salt hydrates include the sodium, potassium, magnesium, calcium, aluminum, lithium, and ammonium salts of inorganic acids and small (6 carbons or less) carboxylic or other organic acids, corresponding hydrates, and mixtures thereof, are applicable. The inorganic salts include chloride, bromide, sulfate, metasilicate, orthophosphate, pyrophosphate, polyphosphate, metaborate, tetraborate, and carbonate. The organic salts include acetate, formate, methyl sulfate, and citrate.

Water-soluble organics can also be used to stabilize the appearance of the bar soaps of the present invention. Some preferred water-soluble organics are propylene glycol, glycerine, ethylene glycol, sucrose, and urea, and other compatible polyols.

A particularly suitable water-soluble organic is propylene glycol. Other compatible organics include polyols, such as ethylene glycol or 1,7-heptane-diol, respectively the mono- and polyethylene and propylene glycols of up to about 8,000 molecular weight, any mono-Ci-4 alkyl ethers thereof, sorbitol, glycerol, glycose, diglycerol, sucrose, lactose, dextrose, 2-pentanol, 1-butanol, mono- di- and triethanolamine, 2-amino-l-butanol, and the like, especially the polyhydric alcohols.

Water-soluble amine salts can also be used. Monoethanol-amine, diethanolamine, and triethanolamine (TEA) chloride salts are preferred.

Aluminosilicates and other clays are useful in the present invention. Some preferred clays are disclosed in U.S. Pat. Nos. 4,605,509 and 4,274,975, incorporated herein by reference.

Other types of clays include zeolite, kaolinite, montmoril-lonite, attapulgite, illite, bentonite, and halloysite. Another preferred clay is kaolin.

Preferred Bar Processing The following process is used to make the exemplified freezer bars of the present invention. The process comprises the following steps: I. Mixing a soap composition comprising: (A) from about 30% to about 70% of the above defined selected fatty acid soap; (B) from 0% to about 20% synthetic detergent surfactant, preferably mild synthetic detergent surfactant, as defined above; (C) from 0% to about 30%; preferably from about 5% to about 30%, more preferably from about 5% to about 20%, of nonreducing sugar, preferably sucrose (Note: The addition of sucrose to an aerated or a freezer soap bar process results in a more pro-cessable soap mix which does not require as much drying or moisture reduction.); (D) from 0% to about 30%, preferably from about 2% to about 25%, more preferably from about 5% to about 20%, of hydrophobic/lipophilic soap bar additive material as defined hereinabove; and (E) from about 15% to about 30%, preferably from about 20% to about 25%, water; wherein said fatty acids, sugar, wax, and other ingredients are mixed at a temperature of from about 65°C to about 74°C (from about 150°F to about 1650F); soap is made in situ by blending the selected fatty acids into dilute NaOH and K0H at an initial temperature of from about 52°C to about 57"C (125-135°F) and a final temperature of from about 85°C to about 99°C (185-210'F); the other ingredients are added; and wherein, if and when said mix is dried to reduce the amount of said water, preferably said sugar/sucrose is added after said drying or in place of drying; II. Aerate (optional) said mix and add perfume with positive displacement pump or other in line mixer; III. Cool the mix using a scraped wall heat exchanger (freezer) to crystallize the components from an initial temperature of from about 79'C to about 99*C (from about 175*F to about 210*F) to a final temperature of from about 46'C to about 66#C (115-155'F), preferably from about 49*C to about 60*C (120-140'F); and IV. Cooled mix of Step III. is extruded out onto a moving belt as a soft plug which is then cooled and fully crystallized and then stamped and packaged.

A process for making a nonaerated soap bar from the composition comprises the steps of: 1. Mixing said (A)-(E) as above; 2. Cooling said mix of Step I. to a temperature as above; and 3. Forming said nonaerated bars (plugs) from said cooled mix as above. - 26 The optimum mixing temperatures of the above steps can vary depending on the particular formulation. Preferably, the formed soap bars (plugs) of Step IV. are formed from a mix which is cooled sufficiently to provide free standing bars (plugs). The preferred process does not require a moisture reduction step. The plugs are preferably formed via an extrusion operation, as shown in U.S. Pat, No. 3,835,058, supra.

Nonaerated freezer bar soap compositions preferably contain less than about 5% of organic solvents, e.g., alcohols, etc. Preferably they contain less than 3% of such organic solvents and, more preferably, from 0% to less than about 1% of such organic solvents is added. A preferred process does not have a drying step.

In a continuous freezer bar process the formed bars (plugs) stand up on a belt. Many cast bar compositions which use higher levels of water and/or organic solvent, e.g., 40-50% water, will not hold their forms or stand up on a freezer bar belt. Similarly, many bars which depend on the formation of large detergent, or soap, crystals to set up will not stand up on the belt.

Frequently, some of the composition crystallizes in the freezer in order to provide sufficient viscosity to stand up on the belt, while further crystallization occurs after exiting the freezer, resulting in hardening of the bar. For some preferred bars, the later crystallization results in substantial structure of the type disclosed in NZ Patent Specification No. 240709, SUpra, incorporated herein by reference.

The formed freezer bars (plugs) containing sucrose typically hold their forms better and stand up on the belt. In the freezer step, lowering the temperature of the composition by a delta of from about 10*C to about 60*C, preferably by a delta of from about 15"C to about 50*C, is sufficient to create a dimensionally stable plug that does not slump while being processed. Needless to say, the elimination of a costly and time consuming moisture or solvent reducing (drying) step in a freezer bar process or a cast bar process is an advantage. See the Figure of U.S. Pat. No. 3,835,058, supra, for a schematic drawing of a prior art 2<>347i continuous freezer soap bar making process with a moisture reducing step. volume measurements for the lather performance of skin cleansing bars. The test measures both the ultimate lather volume generated and the volume which is generated after a very short lathering period (to reflect lathering ease). The lather volumes are generated under soil-loaded conditions.

Synthetic soil is used for the soil-loaded lather volume test reported herein. Its formula and procedure for making it are set out below.

Bar Soap Handwash Lather Volume Test The handwash lather test is used to provide in-use lather Synthetic Soil Ingredients Hyfac 430* Lauric Acid^ Neo-fat 14c Neo-fat 16d Neo-fat 186 Neo-fat 90-04^ Industrene 2269 Paraffin Wax Squalane^ Lanolin Anhydrous Coconut Oil Tallow Wt. % 1.87 1.42 5.68 11.16 5.40 9.81 1.26 7.30 3.70 19.40 3.30 29.70 100.00% a Emery Industries, Inc., Cincinnati, Ohio b Emery Industries, Inc., Cincinnati, Ohio c Armour Industrial Chemical Co., Chicago, Illinois d Armour Industrial Chemical Co., Chicago, Illinois e Armour Industrial Chemical Co., Chicago, Illinois f Armour Industrial Chemical Co., Chicago, Illinois 9 Humko Products, Memphis, Tennessee h Robeco Chemicals, Inc., New York, New York 2 4 & /■ Procedure 1. Heat above materials together stirring continuously between 160-175'F. .2. Mix 25 parts of above formula with 25 parts of a 5% to 80% 5 tallow/20% coconut soap solution and 50 parts of distilled water at 150°F. 3. Cool mixture to room temperature while stirring constantly. 4. Store in covered glass container.

Equipment The following equipment is used: 1. Water source and sink with temperature control. The water source should be medium hardness (6-9 grain/gallon) for most testing, although water of lower and higher hardness can be used for special purposes. 2. Synthetic soil (see Table 1). 3. Paper towels. 4. Test bars.

. Control bars.

Procedure The following procedure is used: 1. Set temperature at 95-100°F. 2. Rub 0.22 cc of soil on hands. 3. Wet hands. 4. Rotate bar 3 times in both hands-. 5. Add a little water, rub both hands 5 times. 6. Rotate hands 3 times (without soap), grade for flash volume. 7. Rotate 7 more times, grade for ultimate volume. 8. Collect lather and deposit on sink top. 9. Compare volume with standard bar target volume and assign 30 grade.

Grading Scale Soil Loaded 7 - Exceptional 35 6 - Very much higher than target - Higher than target 4 - Target volume 3 - Slightly lower than target 2 - Lower than target EXAMPLES The following Examples illustrate the practice of this invention and are not intended to be limiting. All percentages, parts and ratios herein are by weight unless otherwise specified. The free fatty acids used in the examples are used at about the same ratio as the fatty acid soaps. The soaps are made in situ, unless otherwise specified. The levels of soaps are given as a total soap weight percent (wt.%), as well as a bar weight percent (wt.%).

The soap bar compositions of the Examples are mixed at a temperature of about 190*F (88#C) and pumped into a scraped wall heat exchanger where the temperature of the mix is cooled to about 130*F {SS'C) and where the mix is aerated. The aerated and cooled soap mix is then extruded and bar plugs are cut and conditioned. The final bars are then stamped.

The following Examples are illustrative and are not intended to limit the scope of the invention. All levels and ranges, temperatures, results etc., used herein are approximations unless otherwise specified. *4 0 & *5^ /l <> 1 COMPARATIVE BAR VS. EXAMPLE 1 ADDroximate Chain Lenqth Distribution (Wt.%) (The percent by weight of total soap is given parenthetically) ComDarative Bar (CB) Examde 1 Na/K Ratio 80/20 75:25 In Bar In Soap In Bar In Soap Inaredient Wt.% Wt.% Wt.% Wt.% C8 1.30 (1.73) 0.91 (1.79) Cio 1.10 (1.47) 0.78 (1.53) Cl2 9.40 (12.53) 6.72 (13.20) Cl4 6.00 (8.00) 2.81 (5.53) C]6 16.80 (22.40) 21.66 (42.58) Cl8 13.60 (18.13) 9.67 (19.02) Cl8:l 24.90 (33.20) 6.91 (13.59) Cl8:2 1.90 (2.53) 1.40 (2.75) Total Soap 75.69 50.86 Water 23.76 23.00 Sucrose - 7.50 Paraffin (M.P. 52-79'C) - 7.50 Ca Carbonate - 4.00 FFA (same as soap) - 6.00 Free Caustic 0.05 - Minors (Perfumes, Preservatives) 0.50 1.14 Totals 100.00 100.00 Example 1 i s significantly milder than the Comparative Bar (CB), in a forearm wash test, and is about as mild as a very mild, commercially available combo bar, Neutrogena® Dry Skin Formula: Approximate Neutrogena® Formula Ingredient Na 80T/20Cn Soap TEA 80T/20Cn Soap Free TEA Glycerine Nonionic Surfactant Water Minors Wt.% Total 30 15 10 8.4 .5 1.1 100.0 The forearm wash test is a modified Lukacovic, Dunlap, Michaels, Visscher, and Watson: "Forearm wash test to evaluate the clinical mildness of cleansing products," J. Soc. Cosmet. Chem., 39, 355-366 (November/December 1988). One week of testing is used instead of two weeks.

Advantages of.Example 1 versus the Comparative Bar and other mild bars are: 1. Example 1 is much milder than the Comparative Bar (CB). 2. The lather volumes are about the same (usually milder bars lather much less). 3. Example 1 has a creamier lather than the Comparative Bar. 4. Example 1 is made by using a simpler process.

. Example 1 does not wear away as fast as other bars in its mildness class (e.g., Neutrogena®). 6. Example 1 is less expensive than other bars in its mildness The Ci8:l in Example 1 is substantially all cis isomer. The trans/cis content of the Cis:1 in "CB" is 60/40.

The major differences between CB and Example 1 are: (1) CB has C12 soap at 9.4% in bar, and Example 1 has 'Cj2 at 6.7% (delta is 2.7% by wt.% of bar); (2) CB has Ci8:1 at 24.9% by wt.% of bar, and Example 1 has Cis: 1 at about 6.9% by wt.% of bar (delta is 18%).

The Comparative Bar (CB) contains a total of about 75% soap by weight of the bar and the Z\i and Cis:i content by weight of class. 2 4 3 4 7 total soap is 45.7% (12.5% and 33.5%); the bar wt.% of C12 and Cis: 1 for CB is 34.3% or 9.3% over the maximum level of 25% for the bar of the present invention.

SYNTHETIC EXAMPLES 2 and 3 Approximate Chain Length Distribution (Wt.%) (The percent by weight of total soap is given parenthetically) Example 2 Example 3 Na/K Ratio 75:25 67:33 In Bar In Soap In Bar In Soap Inaredient Wt.% Wt.% Wt.% Wt.% C8 0.91 (1.79) 0.76 (1.75) C10 0.78 (1.53) 0.65 (1.50) Cl2 6.69 (13.20) .70 (13.07) C14 2.80 (5.53) 2.43 (5.58) Ci6 21.56 (42.58) 19.28 (44.20) Cl8 9.63 (19.02) .09 (11.66) Cl8:l 6.88 (13.59) 8.06 (18.48) Cl8:2 1.39 (2.75) 1.64 (3.76) Total Soap 50.64 43.63 Water 23.00 28.15 Sucrose 6.00 .58 Paraffin (M.P. 52-79* C) . 6.00 6.86 Ca Carbonate - 3.43 Sodium Coconut Alkyl Glyceryl Ether Sulfo nate (AGS) 8.00 7.51 FFA (same as soap) 4.00 3.43 Minors 1.86 1.41 Totals 100.00 100.00 Examples 2 and 3 are similar to Example 1 in mildness and lather. 24 8 4 7 1 ALL SOAP EXAMPLES 4 and 5 Approximate Chain Length Distribution (Wt.%) (The percent by weight of total soap is given parenthetically) Example 4 Example 5 Na/K RaLio 85:15 85:15 In Bar In Soap In Bar In Soap Ingredient Wt.% Wt.% Wt.% Wt.% C8 - (-) - (-) ClO - (-) - (-) C12 .00 (23.26) 7.60 (17.67) C14 .00 (11.63) 4.20 (9.77) Ci6 8.50 (19.77) 9.30 (21.63) ci8 7.30 (16.98 8.30 (19.30) Cl8:l 11.80 (27.44) 13.20 (30.70) Cl8:2 0.40 (0.93) 0.40 (0.93) Total Soap 43.00 43.00 Water 23.00 23.00 Sucrose .00 .00 Paraffin (M.P. 52-79*C) .00 .00 Ca Carbonate 4.00 4.00 FFA (same as soap) 4.00 4.00 Minors 1.00 1.00 Totals 100.00 100.00 Examples 4 and 5 have varying levels of C12 and Cis:1• The cis/trans Ci8:1 ratio in Examples 4 and 5 is about 1:1. Their lathers are acceptable, but comparable bars with all cis isomer lather better than Examples 4 and 5. 4 tj / °=~» o 4 / EXAMPLE 6 Approximate Chain Length Distribution (Wt.%) (The percent by weight of total soap is given parenthetically) Example 6 Na/K Ratio 70:30 In Bar In Soap Ingredient Wt.% Vlt.% Cs " (") Cio " (") C12 8.00 (18.60) C14 3.40 (7.91) Cis 18.40 (42.79) Ci8 1-80 (4.19) Ci8;l 9.50 (22.09) Ci8:2 1-90 (4.42) Total Soap 43.00 Water 23.00 Sucrose 12.00 20 Paraffin (M.P. 52-79'C) 13.00 Ca Carbonate 4.00 FFA (same as soap) 4.00 Minors 1.00 Total 100.00 The Ci8:i in Examples 6 and 7 is substantially all cis. 24 8 ^ 7 EXAMPLE 7 Approximate Chain Length Distribution (Wt.%) (The percent by weight of total soap is given parenthetically) Example 7 Na/K Ratio Ingredient Cl2 C14 Ci6 Cl8 Cl8:l Cl8:2 70:30 In Bar Wt.% 4.6 2.0 17.9 1.6 9.1 1.8 In Soap Wt.% (12.4) (5.4) (48.4) (4.3) (24.6) (4.9) Total Soap 37.0 Water 30.0 Starch (common corn) 20.0 FFA (same as soap) 3.0 Minors 1.00 Propylene Glycol 5 Polyethylene Glycol (PEG) 4 Total 100.00 Example 7 has no sugar, wax, or synthetic. This Example has good lather and is milder than CB.

EXAMPLE 8 Example 8 is the same as Example 5, except that Example 8 has a Ci8:l cis/trans isomer ratio of about 0.8:1. Example 8 is mild, but does not lather as well as Example 5. Example 5 has a lower level of trans oleic acid soap and has better lather.

EXAMPLE 9 Approximate Chain Length Distribution (Wt.%) (The percent by weight of total soap is given parenthetically) Example 9 Na/K Ratio 80:20 In Bar In Soap Ingredient Wt.% Wt.% Cl2 10 (20) C14 40 (80) Total Soap 50.0 Water 25.0 Sucrose 24.0 FFA (same as soap) 1.0 Total 100.0 Example 9 contains a semi-continuous, relatively rigid interlocking, open, three-dimensional mesh structure. The composition is mixed at a temperature of 170*F (200'C) and pumped into a scraped wall heat exchanger where the temperature of the mix is cooled to 120"F (160'C). The mix is then extruded and bar plugs are cut and then conditioned. The final bars are then stamped.

The bars of Examples 1-9 are milder than the Comparative Bar (CB), which is representative of the prior art. The Comparative Bar is the standard froezer bar for lather. Example 4 is slightly less mild than Examples 1-3 and Examples 5-6; but is significantly milder than the CB.

Example 1 is significantly milder than the Comparative Bar (CB), in a forearm wash test, and is about as mild as a very mild, commercially available combo bar, Neutrogena® Dry Skin Formula. 248471

Claims (15)

WHAT WE CLAIM IS: 1. A mild, lathering personal cleansing freezer soap bar comprising:
1. I. saturated fatty acid soaps selected from the group consisting of: myristic, palmitic, and stearic acid soaps and mixtures thereof at a level of from about 50% to about 85% by weight of total fatty. acid soap; and \ II. from about 15% to about 50% by weight of total fatty acid soap, of soap selected from the group consisting of: oleic and lauric acid soaps and minor fatty acid soap selected from the group consisting essentially of: C8, C10, C18:2 and mixtures thereof; wherein said bar contains from about 8% to about 25% by weight of said selected oleic and lauric soap, and minor.soaps; wherein said oleic soap level is from 0% to about 25% by weight of the bar; and. said lauric soap is from 0% to about 10% by weight of said bar; and wherein said minor (08, Cio, Cis:2) soap level is from 0% to about 5% by weight of said bar; and wherein said selected lauric/oleic soap to said minor (Cs, Cio, c18:2) soap have a ratio of from about 1:1 to about 1:0; and wherein said soap 1s a mixture of sodium and potassium soap (Na/K); and wherein said Na/K soap mixture level is from about 90% to about 100% by weight of said total soap; and wherein said Na/K soap has a ratio of from about 19:1 (95/5) to about 1.5:1 (60/40); and' wherein said freezer soap bar comprises from about 30% to about 70% of total fatty acid soap by weight of said bar; and III. from about 15% to about 30% of water by weight of said bar.
2. 2. The mlId, lathering personal cleansing freezer soap bar of Claim 1 wherein: I. said saturated fatty acid soaps selected from the group consisting of: myristic, palmitic, and stearic acid soaps and mixtures thereof are present at a level of from about 65% to about 80% by weight of total fatty acid soap; and 248471 -38- II. from about 20% to about 35% by weight o'f total fatty acid soap of selected oleic and lauric acid soaps and minor fatty acid,soap; wherein-said bar contains from about 8% to about 25% of said selected oleic and lauric soap, and minor (Cs, Cio, c18:2) soaps; wherein said oleic soap level 1s from about 5% to about 20% by weight of the bar; and - said lauric soap 1s from about 5% to about 10% by weight of said bar; and wherein said minor (Cs* Cio. Ci8:2) soap Is from about 1% to about 3% by weight of said bar; and wherein said selected lauric/oleic soap and said minor soap have a ratio of from about 1:1 to about 1:0; and wherein said Na/K soap mixture level 1s from about 95% to about 100% by weight of said total soap; and wherein said Na/K soap has a ratio of from about 90/10 to about 65/35; and wherein said total soap comprises other soap selected from the group consisting of Mg and TEA soaps at a level of from 0% to about 5% by weight of said total soap; and wherein said freezer soap bar comprises by weight of said bar: A. from about 30% to about 60% of said total fatty acid soap; B. from 0% to about 30% of nonreducing sugar; C. from 0% to about 35% of hydrophobic/lipophilic soap additive material; and' 0. from about 20% to about 25% of said water.
3. 3. The mild, lathering freezer soap bar of Claim 1 wherein said selected saturated fatty acid soaps level Is from about 65% to about 80% by weight of said total soap; and wherein the sum of said selected minor, lauric, and oleic acid soap level 1s from about 10% to about 20% by weight of said bar; and wherein said lauric/oleic soap have a ratio of from about 2:1 to about 1:4; and wherein said Na/K ratio is 90/10 to 65/35; and 2 4 8'4 7 1; -39- wherein said lauric/oleic acid soap and said minor soap have a ratio of from about 6:1 to about 4:1.
4. 4. The mild, lathering freezer soap bar of Claim 2 wherein said selected saturated fatty acid soaps level is about 70% to about 75% by weight of said total soap; and wherein the sum level of said lauric and said oleic acid soaps is from about 12% to about 18% by weight of said bar and the ratio of said lauric/oleic acids is from about 1.5:1 to about 1:3 and wherein said Na/K ratio is from 85/15 to 70/30.
5. 5. The mild, lathering freezer soap bar of Claim 2 wherein said selected . saturated fatty acid soaps (myristic, stearic, and palmitic acid soap) level is from about 20% to about 50% by weight of said bar; and wherein said nonreducing sugar is from about 5% to about 20%; and said hydrophobic/lipophilic material is from about 2% to about 25%; and said water is from about 20% to about 25% by weight of said bar; and wherein said bar contains from about 10% to about 20% of said selected lauric/oleic acid soaps by weight of the said bar.
6. 6. The mild, lathering freezer'soap bar of Claim 5 wherein said bar contains from about 4% to about 30% of a mild lathering synthetic surfactant.
7. 7. The mild, lathering freezer soap bar of Claim 1 wherein said freezer soap bar comprises by weight of said bar: from about 30% to about 55% of said total fatty acid soap; and wherein said oleic acid soap is primarily cis.
8. 8. The mild, lathering freezer soap bar of Claim 2 wherein said freezer soap bar comprises by weight of said bar: from about 30% to about 55% of said total fatty acid soap; from about 5% to about 20% of said nonreducing sugar; from about 5% to about 20% of said hydrophobic/lipophilic material; and 248 471 -40- from about 20% to about 25% of said water; and wherein lauric and oleic soap levei 1s from about 12% to about 18% by t weight of the said bar.
9. 9. The freezer mild, lathering freezer soap bar of Claim 2 wherein said soap bar comprises by weight of said bar: from about 30% to about 55% of said total fatty acid soap; from about 5% to about 20% of said nonreducing sugar; from about 5% to about 20% of said hydrophobic/lipophilic material; and from about 20% to about 25% of said water; and wherein said oleic soap has a cis/trans isomer ratio from about 1:0 to about 20:1.
10. 10. A process for making a freezer bar comprising the following steps: I. Mixing a soap composition comprising: A. saturated fatty acid soaps selected from the group consisting of: myristic, palmitic, and stearic acid soaps and mixtures thereof at a level of from about 65% to about 85% by weight of total fatty acid soap; and B. from about 15% to about 35% of soap selected from the group consisting of: oleic and lauric acid soaps and minor (Cs, c10» c18:2) fatty acid soap selected from the group consisting essentially of: C8, Cio, Ci8:2 and mixtures thereof; ' wherein said bar contains from about 8% to about 25% of said selected oleic and lauric soap, and minor (Cs, Cio, Ci8:2) soaps; wherein said oleic soap level 1s from 0% to about 25% by weight of the bar; and wherein said lauric soap is from 0% to about 10% by weight of said bar; and wherein said minor (Cs, Cio, Ci8:2) soaP level is from 0% to about 5% by weight of said bar; and 2*8471 - 41 - wherein said selected lauric/oleic soap to said-minor (Cs, ClO» Ci8:2) soaP have a ratio of from about 1:1 to about 1:0; and wherein said soap 1s a mixture of sodium and potassium soap (Na/K); and wherein said Na/K soap mixture level Is from about 90% to about 100% by weight of said total soap; and wherein said Na/K soap has a ratio of from about 19:1 (95/5) to about 1.5:1 (60/40); and wherein said freazer soap bar comprises from about 30% to about 70% of total fatty acid soap by weight of said bar; and C. from about 15% to about 30% of water by weight of said bar; wherein said fatty acid soap and other soap Ingredients are mixed at a temperature of from about 65*C to about 74 *C (from about 150'F to about 165*F); wherein said soap 1s made 1n situ at an Initial temperature of from about 52*C to about 57*C (125-135'F) and a final temperature of from about 85'C to about 99'C (185-210'F); said other soap Ingredients are added;
11. II. Cooling the mix of Step 1. to crystallize said mix from a temperature of from about 85'C to about 99'C (from about 175*F to about 210*F) to a final temperature of from about 46*C to about 66*C (115-155'F); and III. Extruding the cooled mix of Step II. onto a cooling belt to finish crystallization and form bars (plugs). 11< The process of Claim 10 wherein from about 5% to about 30% of sucrose Is added In Step. I.
12. 12. The process of Claim 10 wherein said mix of Step I. is aerated before cooling.
13. 13. A process according to elaim io andf.substantially as herein described with reference to the examples.
14. 14'. A freezer bar whenever produced by the process of any o - 42 - 248471
15. 15. A mild lathering personal cleansing freezer soap bar according to Claim 1 and substantially as herein described with reference to the examples. oy tne authorised agents A. J Park & Son Per,