Personal cleansing freezer bar made with a rigid, interlocking mesh of neutralized carboxylic acid

The invention provides a personal cleansing freezer bar comprising a skeleton structure having a relatively rigid, interlocking, semi-continuous, open, three-dimensional, crystalline mesh of neutralized carboxylic acid soap selected from the group consisting of sodium soap; wherein said bar is made by the following steps: PA1 (1) mixing a molten mixture comprising by weight of said bar: from about 15% to about 85% of said soap and from about 15% to about 40% water; PA1 (2) cooling said mixture to a semi-solid in a scraped wall heat exchanger freezer; PA1 (3) extruding said semi-solid as a soft plug; and PA1 (4) further cooling said soft plug to provide said personal cleansing bar.

TECHNICAL FIELD 
This invention relates to a personal cleansing freezer bar made with a 
rigid, semi-continuous, interlocking mesh of neutralized carboxylic acid. 
BACKGROUND 
The formation of a shaped, solid, three-dimensional skeleton (core) 
structure is described in commonly assigned, copending U.S. patent 
application Ser. No. 07/617,827, Kacher/Taneri/Camden/Vest/Bowles, filed 
Nov. 26, 1990 and now abandoned, whereby incorporated herein by reference. 
Kacher et al. does not specifically teach freezer bars. The present 
invention relates to personal cleansing freezer bars comprising said 
structure. A freezer bar process is disclosed in U.S. Pat. No. 3,835,058, 
White, issued Sep. 10, 1974, incorporated herein by reference. White, 
however, does not specifically teach freezer bars with such structure. 
The formation of rigid, soap curd fibers of sodium laurate is reported by 
L. Marton et al. in a 1940 Journal of American Chemical Society (Vol. 63, 
pp. 1990-1993). However, there is no apparent utility for the curd. 
Products made in the form of shaped solids, cakes and bars are numerous. 
E.g., certain high moisture and low smear personal cleansing bars are 
disclosed in U.S. Pat. No. 4,606,839 Harding, issued Aug. 19, 1986. 
Harding reports that his bars suffer from moisture loss; which loss is 
reduced by wrapping the bars in waterproof wraps. 
It is also difficult to produce firm, nonsticky bars that contain 
relatively high levels (15-40%) of moisture (especially in the presence of 
most synthetic surfactants), hygroscopic surfactants and/or higher levels 
of nonsolids, such as water-soluble polyols and hydrocarbon greases. 
Japanese Pat. J5 7030-798, Jul. 30, 1980, discloses transparent solid 
"framed" or "molded" soap in which fatty acids constituting the soap 
component are myristic, palmitic, and 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 effect 
on human skin. The process and transparent bar soap composition 
exemplified in Jap. J5 7030-798 do not appear to contain synthetic 
surfactant and are not made using the freezer process. 
U.S. Pat. No. 2,988,511, Mills and Korpi, issued Jun. 13, 1961, for a 
nonsmearing "milled" detergent bar with at least 75% by weight of which 
consists essentially of (1) from about 15% to about 55% of normally solid 
detergent salts of anionic organic sulfuric reaction products which do not 
hydrolyze unduly under conditions of alternate wetting and drying, said 
salts being selected from the group consisting of the sodium and potassium 
salts, and said anionic organic sulfuric reaction products containing at 
least 50% alkyl glyceryl ether sulfonates from about 10% to about 30% of 
which alkyl glyceryl ether sulfonates are alkyl diglyceryl ether 
sulfonates, the alkyl radicals containing from about 10 to about 20 carbon 
atoms; (2) from about 5% to about 50% of a water-soluble soap of fatty 
acids having from about 10 to about 18 carbon atoms; and (3) from about 
20% to about 70% of a binder material selected from the group consisting 
of freshly precipitated calcium soaps of fatty acids having from about 10 
to about 18 carbon atoms, freshly precipitated magnesium soap of fatty 
acids having from about 10 to about 18 carbon atoms, starch, normally 
solid waxy materials which will become plastic under conditions 
encountered in the milling of soap and mixtures thereof. Freezer soap bars 
are distinguished from milled soap bars and there is still a need to 
improve bar smear. 
SUMMARY OF THE INVENTION 
The invention provides a personal cleansing freezer bar comprising a 
skeleton structure having a relatively rigid, interlocking, 
semi-continuous, open, three-dimensional, crystalline mesh of neutralized 
carboxylic acid soap selected from the group consisting of sodium and 
lithium soaps, and mixtures thereof, wherein said freezer bar is made by 
the following steps: 
(1) mixing a molten mixture comprising by weight of said bar: from about 
15% to about 85% of said soap and from about 15% to about 40% water; 
(2) cooling said mixture to a semi-solid in a scraped wall heat exchanger 
freezer; 
(3) extruding said semi-solid as a soft plug; and 
(4) further cooling and crystallizing said soft plug until firm to provide 
said personal cleansing freezer bar.

DETAILED DESCRIPTION OF THE INVENTION 
The invention provides a personal cleansing freezer bar comprising a 
skeleton structure having a relatively rigid, interlocking, 
semi-continuous, open, three-dimensional, crystalline mesh of neutralized 
carboxylic acid soap selected from the group consisting of sodium and 
lithium soaps, and mixtures thereof, wherein said freezer bar is made by 
the following steps: 
(1) mixing a molten mixture comprising by weight of said bar: from about 
15% to about 85% of said soap and from about 15% to about 40% water; 
(2) cooling said mixture to a semi-solid in a scraped wall heat exchanger 
freezer or an equivalent freezer device; 
(3) extruding said semi-solid as a soft plug; and 
(4) further cooling and crystallizing said soft plug until firm to provide 
said personal cleansing freezer bar. 
The freezer bars of the present invention can be formulated to have 
essentially no, or extremely low, bar smear. Some cleansing freezer bars 
of the present invention can comprise surprisingly large amounts of water, 
other liquids, greases and nonsolids. They can also contain larger amounts 
of hygroscopic materials including surfactants, while maintaining their 
rigidity. 
The term "shaped, three-dimensional structure" as used herein includes 
forms such as bars, cakes and similarly shaped solids. The term "bar" as 
used herein includes the same unless otherwise specified. 
The term "mesh" as used herein means an interlocking crystalline skeleton 
frame with voids or openings when viewed under high magnification. 
The terms "core" and "skeleton frame" are often used interchangeably 
herein. 
The term "semi-continuous" as used herein means that the entire shaped 
skeleton is composed of an overall mesh comprising one or more large 
interlocking meshes fused together. 
U.S. patent application Ser. No. 07/617,827, Kacher et al., supra, does not 
specifically teach the required selected composition ingredients, i.e., 
the levels of soap and water, to successfully make a freezer bar 
comprising the rigid, semi-continuous, interlocking mesh. 
In the preferred freezer process of the present invention, (1) mixtures of 
fatty acids, triglycerides, sodium hydroxide, other caustics (e.g., 
Mg(OH).sub.2, KOH, Ca(OH), LiOH), synthetic surfactants, waxes, greases, 
water, preservatives, and other desired ingredients are combined and 
reacted; (2) this mixture is pumped into a scraped wall heat exchanger 
"freezer" which cools and partially crystallizes the said mixture, 
subsequently extruding it onto a moving belt as a very soft paste while 
maintaining its shape; (3) the soft extruded plugs are cut into 
appropriate sizes and placed into a cooling and conditioning house until 
firm; and (4) the plugs are then stamped and packaged. Optionally, this 
mixture can be dried and/or aerated before Step 2. 
The freezer process is significantly different than either the frame or 
milled processes. In the frame process, plugs are formed by simply pouring 
the liquid final composition into a mold. The mold is cooled and 
conditioned, until solid and the plugs are cut and stamped if need be. The 
frame process is not continuous. The milled bar process is even more 
different. In the milled process, the mixture is dried to moistures 
between 5% and 15% at which time the mixture is fully crystallized and is 
extruded as noodles. The noodles are combined with other ingredients, 
milled to obtain uniform mixing, and compacted into plugs with a plodder. 
These plugs are then cut, stamped and packaged. 
The milled process is continuous but requires more unit operations and 
higher moisture level bars are difficult to make. Most bars made in the 
U.S. are made using the milled or a similar process. 
DETAILED DESCRIPTION OF THE FIGURES 
All figures are photomicrographs of bars which demonstrate the presence of 
the relatively rigid, semi-continuous, interlocking mesh structure. All 
figures show elongated crystalline fibers. 
FIGS. 1 and 2, respectively, show photomicrographs at 2000.times. and 
3000.times.magnifications of a fractured section of the freezer bar of the 
composition of Example 1. 
FIG. 3 is a photomicrograph at 3000.times.magnification of a fractured 
section of the freezer bar of the composition of Example 3. Example 3 
contains other preferred ingredients (11.7% sodium lauroyl sarcosinate; 
9.3% cocobetaine; and 5.8% propylene glycol) in addition to saturated 
sodium soap and water. 
FIGS. 4 and 5, respectively, show photomicrographs at 2000.times. and 
3000.times.magnifications of a fractured section of the freezer bar of the 
composition of Example 4, which includes potassium soap. 
FIGS. 6 and 7, respectively, show photomicrographs at 1500.times. and 
3000.times.magnifications of a fractured section of the freezer bar of the 
composition of Example 5, which has a lower level of sodium soap. 
FIG. 8 is a photomicrograph at 2000.times.magnification of a fractured 
section of the freezer bar of the composition of Example 9. Example 9 has 
a high level of magnesium soap which is a viscosity-enhancing agent. 
Example 9 also has a relatively low level of sodium soap. 
Characterization of Structure Via Scanning Electron Microscopy (SEM) Photos 
All photographed samples, FIGS. 1-8, are prepared as follows. 
The SEM samples preparation involves first drying the samples a minimum of 
two days at low humidity conditions (e.g., 27.degree. C. and 15% relative 
humidity). The sample is then fractured with simple pressure to obtain a 
fresh surface for examination. The fractured sample is reduced in size 
(razor blade) to approximately a 10 mm.times.15 mm rectangle with a 
thickness of about 5 mm. The sample is mounted on an aluminum SEM stub 
using silver paint adhesive. The mounted sample is coated with 
approximately 300 angstroms of gold/palladium in a Pelco sputter coater. 
Prior to coating, the sample is subjected to vacuum for a period of time 
which is sufficient to allow sufficient loss of bar moisture assuring 
acceptable coating quality. After coating, the sample is transferred to 
the SEM chamber and examined under standard SEM operating conditions with 
an Hitachi Model S570 Scanning Electron Microscope in order to see the 
skeletal (core) frame. 
DESCRIPTION OF PREFERRED EMBODIMENTS 
The improved personal cleansing freezer bar of the present invention is 
comprised of a special core structure, i.e., a rigid, semi-continuous, 
interlocking mesh of neutralized fatty carboxylic acid soap selected from 
sodium and/or lithium soaps. The mesh occupies from about 5% to about 75%, 
preferably from about 15% to about 40%, by volume of the bar. 
Tables 1-3 set out some preferred freezer bars which are made with the 
sodium salts of the fatty carboxylic acid, (FA) soap. 
The percentages, ratios, and parts herein are on a total composition weight 
basis, unless otherwise specified. All levels and ranges herein are 
approximations unless otherwise specified. 
TABLE 1A 
______________________________________ 
Preferred Freezer Bar Ingredient Levels and Chain Lengths 
More Most 
Preferred 
Preferred 
Preferred 
______________________________________ 
Water Level 15-40% 20-35% 20-30% 
Water: Soap Ratio 
0.25:1-4:1 
0.5:1-3:1 
0.7:1-1.5:1 
FA Chain Length C.sub.12-24 
C.sub.14-22 
C.sub.14-18 
FA Soap Level in Total 
15-85% 20-50% 30-40% 
Formulation 
Viscosity-Enhancing Agents 
0-70% 1-35% 5-30% 
Soap + Viscosity-Enhancing 
30-85% 35-65% 40-50% 
Agents 
______________________________________ 
TABLE 1B 
______________________________________ 
Preferred Viscosity-Enhancing Agents 
More Most 
Preferred 
Preferred 
Preferred 
______________________________________ 
Magnesium or Calcium Soap 
1-35% 5-30% 5-20% 
Waxes, Greases, and Jellies 
1-40% 2-35% 5-25% 
Aluminosilicates/Clay 
0.5-25% 1-10% 3-8% 
______________________________________ 
All highs and lows are not necessarily shown in Table 1. The preferred 
levels and ratios can vary from cation to cation, etc. 
The freezer bar ingredient levels shown in Table 1A are made with the level 
of water indicated, but the water level of the final bars can be reduced 
to provide bars (core structures) which contain lower levels of water or 
even little or no water. 
Table 1B shows preferred types and levels of viscosity-enhancing agents. 
Table 2 shows some preferred levels of selected single FA chain length by 
weight of soap. 
Table 3A shows some preferred levels of unsaturation in the FA's by weight 
of the soap of the present invention. Table 3B shows some preferred levels 
of saturated C.sub.12 -C.sub.24 chain soap by weight of soap. 
Some preferred compositions contain little or no unsaturated fatty acids 
and short chain FA's of ten carbon atoms or less. The terms "soap", "fatty 
acid (FA) salts" and "monocarboxylic acid salts" as used herein are 
sometimes interchangeable. "Soap" is used since it is easier to relate to 
and is the preferred embodiment. 
TABLE 2 
______________________________________ 
The % Saturated C.sub.12 -C.sub.24 Sodium/Lithium Soap of Single 
Chain Length by Weight of Soap 
Preferred 25-100% 
More Preferred 50-100% 
Most Preferred 75-100% 
______________________________________ 
TABLE 3A 
______________________________________ 
The Total % Unsaturated and Low (C.sub.10 or less) 
Chain Soaps by Weight of Soap 
Preferred 0-20% 
More Preferred 0-10% 
Most Preferred 0-1% 
______________________________________ 
TABLE 3B 
______________________________________ 
The Total % Saturated C.sub.12 -C.sub.24 Chain Soap by Weight of Soap 
Preferred 75-100% 
More Preferred 85-100% 
Most Preferred 95-100% 
______________________________________ 
The highs and lows of some key preferred optional ingredients for complex 
soap bar compositions of this invention are set out in Table 4. None of 
these optional ingredients or viscosity-enhancing agents is essential for 
the basic, preferred bar core structure. Zero is the lowest level for each 
optional ingredient. Some preferred bars can contain a total of from about 
1% up to about 70% of such ingredients. The idea here is that the core 
bars can contain large amounts of other ingredients besides soap and 
water. The levels set out in Table 4 are particularly illustrative for 
bars containing from about 15% to about 85% selected sodium soap and other 
ingredients. 
It should be understood that bar cores (skeletons) can be made with lithium 
soap, but would be expected to be somewhat different from the levels and 
ratios given for sodium soaps. 
TABLE 4 
______________________________________ 
Highs and Lows Wt. % of Other Ingredients for 
More Complex Sodium Soap Bars 
More Most 
Preferred 
Preferred Preferred 
______________________________________ 
Neutralized Dicar- 
1-40% 2-30% 5-25% 
boxylic Acid 
Potassium Soap 1-15% 2-12% 5-10% 
Magnesium Soap 1-35% 5-30% 5-20% 
Calcium Soap 1-35% 5-30% 5-20% 
Triethanolamine Soap 
1-15% 2-12% 5-10% 
Synthetic Surfactant 
1-60% 4-25% 8-16% 
Other Salts and 
0.5-50% 1-25% 2-15% 
Salt Hydrates 
Water-Soluble Organics 
1.0-50% 2-40% 5-20% 
Polymeric Mildness 
0.25%-20% 0.5%-10% 1-15% 
Enhancers 
Waxes, Greases, and 
1-40% 2-35% 5-25% 
Jellies 
Other Impalpable 
1-60% 4-25% 8-16% 
Water-insolubles 
Aluminosilicates/Clay 
0.5-25% 1-10% 3-8% 
______________________________________ 
The soaps useful in the present invention are of the same alkyl chain 
lengths, i.e., selected from the 12 to 24 carbon atoms, as set out in 
Table 2. The same chains apply for the other soaps used in the bars of the 
present invention. 
A highly preferred cleansing freezer bar comprises: various combinations of 
the core structure of sodium soap fibers, water, mild synthetic 
surfactants, viscosity-enhancing agents, bar appearance stabilizers, skin 
mildness aides and other cleansing bar adjuvants. Such preferred freezer 
bar can be formulated to have essentially no bar smear. 
Viscosity-enhancing agents, mild surfactants are defined herein. 
Some preferred freezer bar compositions of the present invention which 
comprise lower levels of sodium soap, e.g., less than 30-35% by weight of 
bar, include viscosity-enhancing agents so that in the process for making 
the freezer bar it will maintain its shape and stand up upon extrusion 
from the freezer. 
In yet another respect, this invention provides an improved cleansing 
freezer bar which is comprised of compositions that can have improved bar 
smear and/or be able to incorporate components that cannot normally be 
used in appreciable quantities in bars, such as moisture (especially in 
the presence of most synthetic surfactants), hygroscopic materials 
including surfactants, and other liquids and nonsolids such as polyols and 
hydrocarbon greases that improve performance properties such as lather, 
mildness, bar appearance, and bathtub ring, while maintaining firm, 
nonsticky bars. 
It should be understood that some viscosity-enhancing agents" and some 
"other bar ingredients" used in the freezer bars of the present invention 
can serve more than one function and/or provide more than one benefit as 
indicated herein. Therefore, some of them appear under more than one 
category as specified herein. 
Some preferred bars of the present invention comprise: a rigid, 
interlocking mesh of neutralized carboxylic acid fiber-like core 
consisting essentially of sodium fatty acid soap composed of at least 75% 
saturated fatty alkyl chains having 12 to 24 carbon atoms. Preferably at 
least about 25% of said saturated alkyl chains is of a single chain 
length. 
Some compositions of this invention comprise the above-defined rigid mesh 
with water and without water. These compositions must be formed with water 
or another suitable solvent system. The freezer bar compositions can be 
made with large amounts of water and the water level in the final freezer 
bar composition can be reduced to as low as about 1% to 10%. 
However, it is a special advantage of the freezer bars described herein 
that they can be dehydrated without loss of the integrity of the mesh. 
Some bars can be dehydrated without appreciable change in the outer 
dimensions. Other structures shrink while maintaining their 
three-dimensional form. The freezer bars herein have the unique 
characteristic that they are not destroyed by dehydration. 
More complex freezer bars of the present invention comprise other salts of 
fatty acids selected from potassium, magnesium, triethanolamine and/or 
calcium soaps used in combination with the selected levels of sodium 
and/or lithium soaps. More complex cleansing bars can contain surprisingly 
large amounts of water, mild synthetic surfactants, bar appearance 
stabilizers, skin mildness aides and other cleansing bar adjuvants; yet 
are mild and can have very good low smear. 
Some preferred viscosity-enhancing agents are Mg and Ca soaps, 
aluminosilicates and clays, waxes and greases such as paraffin and 
petrolatum, respectively. 
These agents will increase viscosity by either forming an emulsion or 
crystallizing in the crutcher or freezer, but preferably in the freezer. 
In the absence of a viscosity-enhancing agent, a larger amount of sodium 
soap is required to crystallize in the freezer to provide the necessary 
viscosity for the bar composition to stand up upon extrusion onto the 
freezer belt. The remainder of the sodium soap will crystallize and form 
the interlocking mesh structure after exiting the freezer. With a 
viscosity-enhancing agent, less sodium soap is required to obtain the same 
level of the interlocking mesh structure. 
The presence of a viscosity-enhancing agent lowers the total level of harsh 
sodium soap required to form the interlocking mesh structure. 
An especially preferred viscosity-enhancing agent is petrolatum, since 
petrolatum typically results in higher freezer outlet temperature (FOT). 
It is preferred that the FOT is as high as possible while still having the 
bar stand up on the belt and maintain its shape. This is because more 
crystallization will occur after the freezer, and consequently more of the 
interlocking mesh structure can form, with higher FOT. Typically, the 
addition of petrolatum will raise the FOT from about 10.degree. C. to 30 
C. to about 60 C. to 80.degree. C. 
The sodium soap is preferably at least about 50% of the total soap present 
in the bar or is at least 15% of the total bar composition. 
The levels of potassium and/or triethanolamine soap should not exceed 
one-third, preferably one-quarter, that of the sodium soap. 
The synthetic detergent constituent of the bar compositions of the 
invention can be designated as being a detergent from the class 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. 
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, incorporated 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 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 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, stearine, palm kernel oil, 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 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 1,2-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. Additionally, it is difficult to 
incorporate in normal cleansing bars even nonhygroscopic surfactants with 
high levels of water (greater than 20% water), while this is easily 
accomplished in 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: 
______________________________________ 
Pat. No. Issue Date Inventor(s) 
______________________________________ 
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 Hoskins 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 5/1990 Simion 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 the Examples herein. Preferred synthetic 
surfactant systems are selectively designed 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 lesser the skin 
barrier is destroyed. Skin barrier destruction is measured by the relative 
amount of radio-labeled water (.sup.3 H-H.sub.2 O) 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 Jun. 16, 1987, incorporated herein by 
reference, and which disclose a mild alkyl glyceryl ether sulfonate (AGS) 
surfactant based synbar comprising a "standard" alkyl glyceryl ether 
sulfonate mixture. Barrier destruction testing is used to select mild 
surfactants. Some preferred mild synthetic surfactants are disclosed in 
the above Small et al. patents and Rys et al. Some specific examples of 
preferred surfactants are used in the Examples herein. 
Some examples of good lather enhancing detergent surfactants, mild ones, 
are e.g., sodium lauroyl sarcosinate, alkyl glyceryl ether sulfonate, 
sodium dodecyl benzene sulfonate, sulfonated fatty esters, sodium cocoyl 
isethionate, 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, linear alkyl benzene sulfonate, 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 C.sub.8 -C.sub.22, preferably 
C.sub.10 -C.sub.18. Alkyl glycosides and methyl glucose esters are 
preferred mild nonionics which may be mixed with other mild anionic or 
amphoteric surfactants in the compositions of this 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 
C.sub.8 -C.sub.18, preferably C.sub.12 -C.sub.16, 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 C.sub.8 -C.sub.22, preferably C.sub.12 -C.sub.18 ; 
the chain length of the ester alcohol is C.sub.1 -C.sub.6. These include 
sodium alpha-sulfomethyl laurate, sodium alpha-sulfomethyl cocoate, and 
sodium alpha-sulfomethyl tallowate. 
Amine oxide detergents are good lather enhancers. Some preferred amine 
oxides are C.sub.8 -C.sub.18, preferably C.sub.10 -C.sub.16, alkyl 
dimethyl amine oxides and C.sub.8 -C.sub.18, preferably C.sub.12 
-C.sub.16, fatty acyl amidopropyl dimethyl amine oxides and mixtures 
thereof. 
Fatty acid alkanolamides are good lather enhancers. Some preferred 
alkanolamides are C.sub.8 -C.sub.18, preferably C.sub.12 -C.sub.16, 
monoethanolamides, diethanolamides, and monoisopropanolamides and mixtures 
thereof. 
Other detergent surfactants are alkyl ethoxy carboxylates having the 
general formula: 
EQU RO(CH.sub.2 CH.sub.2 O).sub.k CH.sub.2 COO.sup.- M.sup.+ 
wherein R is a C.sub.8-22 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 
##STR1## 
wherein R.sup.1 is H, a C.sub.1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy 
propyl, or mixtures thereof, R.sup.2 is a C.sub.5-31 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 C.sub.8 -C.sub.18, 
preferably C.sub.12 -C.sub.16, alkyl betaines, e.g., coco betaines or 
C.sub.8 -C.sub.18, preferably C.sub.12 -C.sub.6, acyl amido betaines, 
e.g., cocoamidopropyl betaine, and mixtures thereof, are preferred. 
Some of the preferred surfactants are hygroscopic synthetic surfactants 
which absorb at least about 20% of their dry weight at 26.degree. C. and 
80% relative humidity in three days. Hygroscopic surfactants help to 
improve bar lather. Some preferred hygroscopic synthetic surfactants are 
listed below. Note that all are not hygroscopic. 
Hygroscopicity of Some Surfactants 
The hygroscopic surfactants have a minimum of 20% total moisture gain. 
______________________________________ 
Total % Moisture Pick-Up* 
______________________________________ 
Class: Nonionic 
Sulfonates 
Na C.sub.8 Glyceryl Ether Sulfonate 
39.8 
Na C.sub.12-14 Glyceryl Ether Sulfonate 
22.9 
Na C.sub.16 Glyceryl Ether Sulfonate 
71.4 
Sodium Cocomonoglyceride 
3.5 
Sulfonate 
Sodium Salt of C.sub.8-16 Alkyl Glyceryl Ether Sulfonates 
Alpha Sulfo Esters and Acids 
Na Alpha Sulfo Methyl Laurate/ 
39.3 
Myristate 
Na Alpha Sulfo Methyl Myristate 
44.5 
Na Alpha Sulfo Hexyl Laurate 
23.2 
Na Alpha Sulfo Methyl/Hexyl 
26.3 
Laurate and Myristate 
Na Alpha Sulfo Methyl Palmitate 
3.7 
Na Alpha Sulfo Methyl Stearate 
4.2 
Na 2-Sulfo Lauric Acid 
0.2 
Na 2-Sulfo Palmitic Acid 
3.8 
Na 2-Sulfo Stearic Acid 
0.0 
R.sub.1 --C(SO.sub.3 --Na.sup.+)--CO.sub.2 R.sub.2 R.sub.1 = C.sub.8-14 
; R.sub.2 = C.sub.1-8 
Sodium Alkyl Isethionates 
Sodium Lauryl Isethionate 
31.7 
Sodium Cocoyl Isethionate 
11.0 
Sarcosinates 
Sodium Lauryl Sarcosinate 
8.8 
Sodium Stearyl Sarcosinate 
13.3 
Sodium Cocoyl Sarcosinate 
18.7 
Alkyl Sulfates 
Sodium Lauryl Sulfate 
28.2 
Sodium Laureth-1 Sulfate 
37.6 
Sodium Oleyl Sulfate 
20.3 
Sodium Cetearyl Sulfate 
4.7 
Sodium Cetyl Sulfate 
2.25 
R.sub.1 (OCH.sub.2 CH.sub.2).sub.n OSO.sub.3 --X R.sub.1 = C.sub.8-14, 
C.sub.16-20 with at least 
one double bond, X = 0-18 
Acyl Glutamates 
Sodium Cocoyl Glutamate 
26.7 
Sodium Lauryl Glutamate 
17.8 
Sodium Myristyl Glutamate 
18.1 
Sodium Stearyl Glutamate 
12.0 
Alkyl Ether Carboxylates 
Sodium Laureth-5 Carboxylate 
32.2 
Sodium Palmityl-20 Carboxylate 
50.2 
R.sub.1 --(O--CH.sub.2 CH.sub.2).sub.n CO.sub.2 -- R.sub.1 = C.sub.8-18, 
n = 1-30 
Sulfosuccinates 
Disodium Laureth Sulfosuccinate 
33.6 
Phosphates 
Sodium Monoalkyl (70% C.sub.12 / 
30% C.sub.14) Phosphate 
21.1 
Class: Amphoterics 
Betaines 
Coco Betaine 70.0 
Cocoamidopropyl Betaine 
48.2 
Palmitylamidopropyl Betaine 
46.5 
Isostearamidopropyl Betaine 
44.3 
Sultaines 
Cocoamidopropylhydroxy Sultaine 
59.5 
Amine Oxides 
Palmityl Dimethyl Amine Oxide 
34.0 
Myristyl Dimethyl Amine Oxide 
46.0 
Cocoamidopropyl Amine Oxide 
43.3 
Protein Derived 
Na/TEA C.sub.12 Hydrolyzed Keratin 
34.7 
______________________________________ 
*3 days, 26.degree. C./80% Relative Humidity 
The total moisture pick-up is calculated as percent content (after material 
is dried down) plus percent weight gain. 
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 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.RTM. C-14-S, C-15, 
C-17, and C-376FA, 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 Mar. 
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 Mar. 1, 
1988; 4,704,272, Oh et al., issued Nov. 3, 1987; and 2,826,551, Geen, 
issued Mar. 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 sensory skin 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.degree. 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. 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, hydrotropes, colorants, and fillers such as talc, 
clay, water-insoluble, impalpable calcium carbonate and dextrin can also 
be used. Cetearyl alcohol is a mixture of cetyl and stearyl alcohols. 
Preservatives, e.g., sodium ethylenediaminetetraacetate (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 freezer bars of this invention contain from about 15% to about 85% 
said sodium fatty acid soap fibers; from about 15% to about 60% water; and 
at least about 1% of another bar ingredient selected from: other soaps, 
viscosity-enhancing agents, moisturizers, colorants, solvents, 
water-soluble organics, salt and salt hydrates, other impalpable 
water-insolubles, fillers, synthetic detergent surfactants, polymeric skin 
feel and mildness aids, perfumes, preservatives, and mixtures thereof. 
Some freezer bars of this invention comprise: 20%-50% fibrous sodium fatty 
acid soap composed of at least about 75% saturated fatty alkyl chains 
having 12-24 carbon atoms of which at least about 25% of said saturated 
fatty alkyl chains is of a single chain length. See Table 1A for more 
preferred levels. 
Some personal cleansing soap freezer bar compositions comprise a rigid, 
interlocking mesh of sodium soap fibers; wherein the sodium fatty acid 
soap is composed of at least about 75% saturated fatty alkyl chains having 
12-24 carbon atoms of which at least about 25% of said saturated fatty 
alkyl chains is of a single chain length; and from about 2% to about 40% 
by weight of a hygroscopic synthetic surfactant wherein said hygroscopic 
synthetic surfactant is selected from surfactants which absorb at least 
about 20% of its dry weight in water at 26.degree. C. and 80% Relative 
Humidity in three days. 
Also some preferred freezer bars can have the combination of 20-35% water 
and up to 40% of the synthetic detergent herein described. Some bars also 
contain high levels (15-60%) of very mild ingredients, which replace 
harsher sodium soap and result in very mild bars. Some freezer bars can 
contain up to 40% petrolatum which can improve the mildness and processing 
of the bars. The mild ingredients also include water-soluble organics, 
waxes and greases with preferred levels as specified in Table 4. 
Some of the ingredients improve bar appearance. Bar appearance 
(water-retaining and/or shrinkage prevention) aids are preferably selected 
from the group consisting of: 
compatible salt and salt hydrates; 
water-soluble organics such as polyols, urea; 
aluminumosilicates and clays; and 
mixtures thereof, as set out in Table 4. 
Water-soluble organics are also 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-C.sub.1-4 alkyl 
ethers thereof, sorbitol, glycerol, glycose, diglycerol, sucrose, lactose, 
dextrose, 2-pentanol, 1-butanol, mono- di- and triethanolamine, 
2-amino-1-butanol, and the like, especially the polyhydric alcohols. 
The term "polyol" as used herein includes nonreducing sugar, e.g., sucrose. 
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.degree. F. (98.degree. C.), e.g., trialose, raffinose, and 
stachyose; and sorbitol, lactitol and maltitol. 
Sucrose will not reduce Fehling's solution and therefore is classified as a 
"nonreducing" disaccharide. 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.degree.-186.degree. C., depending on the solvent of crystallization. 
Compatible salt and salt hydrates are used to stabilize the bar soap 
appearance via the retention of water. 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 amine salts can also be used. Monoethanolamine, 
diethanolamine, and triethanolamine (TEA) chloride salts are preferred. 
Viscosity-Enhancing Agents 
Aluminosilicates and other clays are useful in the present invention as 
viscosity-enhancing agents. 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, montmorillonite, 
attapulgite, illite, bentonite, and halloysite. Other preferred clays are 
kaolin and cal-cined clays. 
Waxes, jellies, and greases can be effective viscosity-enhancing agents. 
Additionally, they can also be mildness-enhancement aids. Waxes, jellies, 
and greases include petroleum based waxes (paraffin, microcrystalline, and 
petrolatum), vegetable based waxes (carnauba, palm wax, candelilla, 
sugarcane wax, and vegetable derived triglycerides) animal waxes (beeswax, 
spemaceti, wool wax, shellac wax, lanolin, and animal derived 
triglycerides), mineral waxes (montar, ozokerite, and ceresin) and 
synthetic waxes (Fischer-Tropsch). Waxes are fully solid at room 
temperature, (e.g., 15.degree.-30.degree. C.), while jellies and greases 
are semi-solid at room temperature. 
A preferred hydrocarbon grease is petrolatum, such as Snow White Petrolatum 
USP from Penreco Co., with a melting point range of from about 122.degree. 
F. to about 135.degree. F. (50.degree.-57.degree. C.). 
A preferred wax is used in the Examples herein. A useful wax has a melting 
point (M.P.) of from about 120.degree. F. to about 185.degree. F. 
(49.degree.-85.degree. C.), preferably from about 125.degree. F. to about 
175.degree. F. (52.degree.-79.degree. C.). A preferred paraffin wax is a 
fully refined petroleum wax having a melting point ranging from about 
130.degree. F. to about 140.degree. F. (49.degree.-60.degree. 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 and 6971, respectively, having melting points of 131.degree. F. 
and 130.degree. F. (.about.55.degree. C.). 
The paraffin preferably is present in the bar in an amount ranging from 
about 3% 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.degree. F. (60.degree. C.) to about 185.degree. F. 
(85.degree. C.), preferably from about 145.degree. F. (62.degree. C.) to 
about 175.degree. F. (79.degree. C.). The wax preferably should meet the 
FDA requirements for food grade microcrystalline waxes. A very suitable 
microcrystalline 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. 
The magnesium and calcium salts of the saturated fatty acids of chain 
length C.sub.12 -C.sub.24 can also be used as viscosity-enhancing agents. 
These are milder than the corresponding sodium salt of the carboxylic 
acids and can also impart less draggy rinse feel. 
Preferred Bar Processing 
The following process is used to make the exemplified freezer bars of the 
present invention. The process comprises the following steps: 
Step 1--Mixing 
The soap specified in the formulation is made in situ by mixing the desired 
fatty acids, consisting essentially of C.sub.12 -C.sub.24 chain lengths, 
with the appropriate base or mixture of bases, consisting essentially of 
sodium, lithium, magnesium, calcium, and potassium hydroxide and 
triethanolamine. The fatty acid, base, and water are mixed at from about 
170.degree. F. to about 200.degree. F. (76.degree.-93.degree. C.) to form 
the soap. Sufficient water is used such that the mixture is stirrable. The 
other ingredients are added, maintaining the temperature of from about 
180.degree. F. to about 200.degree. F. (82.degree.-93.degree. C.). The 
optimal mixing temperatures can vary depending on the particular 
formulation. 
Step 2 Optionals--Aeration, Minor Addition, and Flash Drying Optionals 
Aerate (optional) said mix and add perfume (only if drying) and other 
minors with positive displacement pump or other in-line mixer. The mixture 
of Step (1) is optionally dried to reduce the amount of said water to the 
desired level, preferably 20-40% water. The flash drying temperature is 
from about 225.degree. F. to about 315.degree. F. (135.degree.-157.degree. 
C.) at pressure of from about 30 to abut 100 psi (115-517 mm Hg). 
Step 3---Freezer 
Cool the mix using a scraped wall heat exchanger (freezer) to partially 
crystallize the components from an initial temperature of from about 
180.degree. F. to about 200.degree. F. (82.degree.-93.degree. C.) or from 
about 200.degree. F. to about 220.degree. F. (93.degree.-104.degree. C.), 
if dried, to a final temperature preferably from about 135.degree. F. to 
about 180.degree. F. (57.degree.-82.degree. C.), more preferably from 
about 145.degree. F. to about 180.degree. F. (63.degree.-82.degree. C.), 
and most preferably from about 155.degree. F. to about 175.degree. F. 
(68.degree.-79.degree. C.). This final temperature, also referred to 
herein as the Freezer Outlet Temperature (FOT), is typically the maximum 
temperature that will form a smooth plug that holds its shape once 
extruded onto a moving belt (Step 4). 
Step 4--Extrusion 
The cooled mix of Step 3 is extruded out onto a moving belt as a soft plug 
which is then cooled and fully crystallized and then stamped and packaged. 
The plugs are preferably formed via an extrusion operation, as shown in 
U.S. Pat. No. 3,835,059, supra. Some of the composition crystallizes in 
the freezer (Step 3) in order to provide a semi-solid having a sufficient 
viscosity to stand up on the belt, while further crystallization occurs 
after extrusion, resulting in hardening of the bar. The final 
crystallization of the sodium soap forms the interlocking, 
semi-continuous, open mesh structure in the freezer bar of the present 
invention. 
EXAMPLES 
The following examples are illustrative and are not intended to limit the 
scope of the invention. All bar compositions are made using the freezer 
process as specified herein. All levels and ranges, temperatures, results 
etc., used herein are approximations unless otherwise specified. 
Description of Testing for Examples 
1. The hardness of a bar is determined by measuring the depth penetration 
(in mm) of a conically shaped, weighted probe into the bar. A hardness 
measurement of 5 mm or less indicates a very hard bar; 5-10 mm indicates a 
moderately hard bar; and greater than 10 mm indicates a soft bar. 
2. The smear grade is determined by: (1) placing a soap bar on a perch in a 
1400 mm diameter circular dish; (2) adding 200 ml of room temperature 
water to the dish such that the bottom 3 mm of the bar is submerged in 
water; (3) letting the bar soak overnight (15 hours); (4) turn the bar 
over and grade qualitatively for the combined amount of smear, and 
characteristics of smear, depth of smear on a scale where 10 equals no 
smear, 9.0-9.5 equals extremely low smear, 7.0-8.5 equals good smear 
superior to currently marketed bars, 4.5-6.5 equals smear essentially 
equivalent to the best of currently marketed bars, and 4.0 or less equals 
very poor smear. 
______________________________________ 
Fatty Acid Chain Length Distribution 
(% of Total Fatty Acid) 
Ex. 1 Ex. 2 Ex. 3 Ex. 4 
Ingredient Wt. % Wt. % Wt. % Wt. % 
______________________________________ 
C.sub.12 12.5 12.5 
C.sub.14 12.5 12.5 
C.sub.16 37.5 37.5 50.0 50.0 
C.sub.18 37.5 37.5 50.0 50.0 
Composition (% of Total Bar): 
Sodium Soap 77.18 44.4 44.4 34.1 
Potassium Soap 8.5 
Free Fatty Acid -- 0.13 1.17 1.12 
Magnesium Soap -- -- -- -- 
Paraffin (M.P. 55.degree. C.) 
-- 3.5 -- -- 
Sodium Lauroyl -- 5.84 11.67 11.21 
Sarcosinate 
CocoBetaine -- 11.65 9.34 8.97 
Propylene Glycol -- 5.84 5.84 5.61 
Sodium Chloride 0.57 3.6 3.11 2.99 
Water 22.2 24.7 24.0 27.0 
Freezer Outlet 66.degree. C./ 
59.degree. C./ 
59.degree. C./ 
63.degree. C./ 
152.degree. F. 
139.degree. F. 
139.degree. F. 
145.degree. F. 
Temperature 
Hardness (mm 2.9 5.5 7.3 6.3 
Penetration) 
Smear 10 7.5 7.0 7.5 
______________________________________ 
Example 1 comprises sodium soap and water. The interlocking mesh structure 
is shown in FIGS. 1 and 2. There is no smear for Example 1, but lather is 
low. 
Examples 2-4 demonstrate the ability to incorporate other actives in a 
freezer bar having the interlocking mesh. FIGS. 3-5 show interlocking mesh 
structure. Examples 2-4 comprise synthetic surfactants, potassium soap, 
and/or propylene glycol. Examples 2-4 are firm bars with good smear and 
good lather. 
______________________________________ 
Composition Ex. 5 Ex. 6 Ex. 7 Ex. 8 
(% of Total Bar) 
Wt. % Wt. % Wt. % Wt. % 
______________________________________ 
Sodium Myristate 
28.52 29.94 33.1 24.86 
Soap (100%) 
Free Fatty Acid 
0.95 1.00 1.10 0.99 
Petrolatum, White USP 
-- 19.96 22.07 9.95 
Paraffin (M.P. 55.degree. C.) 
6.18 -- -- 5.97 
Cal-cined Clay 3.80 2.99 3.31 3.98 
Sodium Lauroyl 6.65 6.99 7.72 6.96 
Sarcosinate 
CocoBetaine 4.75 4.99 5.52 4.97 
Propylene Glycol 
10.46 -- -- 9.95 
Sodium Chloride 
3.84 1.04 1.15 2.03 
Perfume -- 0.20 0.22 -- 
Water 34.53 32.6 25.5 30.01 
Freezer Outlet 49.degree. C./ 
61.degree. C./ 
62.degree. C./ 
48.degree. C./ 
Temperature 120.degree. F. 
142.degree. F. 
143.degree. F. 
118.degree. F. 
Hardness (mm 7.6 4.90 5.0 6.5 
Penetration) 
Smear 8.5 9.5 9.0 9.0 
______________________________________ 
The comparison of Examples 5 and 6 demonstrates the effect of petrolatum on 
processing the freezer bar and smear. Example 5 has good smear of 8.5, but 
Example 6 has a better smear of 9.5. The structure of Example 5 is shown 
in FIGS. 6 and 7. Example 6 also has a better (higher) freezer outlet 
temperature (FOT) than Example 5. Examples 6 and 7 are similar, except 
that the product of Example 7 was partially dried before entering the 
freezer. No loss on key performance parameters is seen. 
The freezer bar of Example 8 comprises a combination of paraffin, 
petrolatum, clay and a lower level of sodium soap. Examples 5-8 all have 
very low smear and good lather. 
______________________________________ 
Composition 
Ex. 9 Ex. 10 Ex. 11 
(% of Total Bar) 
Wt. % Wt. % Wt. % 
______________________________________ 
Sodium Myri- 
18.12 36.09 28.0 
state Soap (100%) 
Free Fatty Acid 
0.10 0.57 0.50 
Magnesium Soap 
27.16 11.29 5.0 
Petrolatum, 
-- -- 22.50 
White USP 
Sodium Lauroyl 
9.56 10.18 3.0 
Sarcosinate 
CocoBetaine 
7.51 5.66 10.0 
Propylene 
10.87 9.05 3.5 
Glycol 
Sodium 2.65 1.64 2.58 
Chloride 
Perfume -- 0.50 0.50 
Water 23.70 25.0 24.08 
Water/Soap 
1.3:1 0.7:1 0.9:1 
Ratio 
Freezer 48.degree. C./119.degree. F. 
56.degree. C./132.degree. F. 
79.degree. C./175.degree. F. 
Outlet 
Temperature 
Hardness 7.3 5.9 3.8 
(mm 
Penetration) 
Smear 5.3 7.25 9.5 
______________________________________ 
Example 9 demonstrates the ability to make a firm freezer bar with average 
smear with 34% liquids (water +propylene glycol), 17% synthetic 
surfactants, and 27% magnesium soap viscosity-enhancing agent, and a lower 
level, 19%, of sodium soap. The structure for Example 9 is shown in FIG. 
8. The hardness and smear of Example 9 are about equal to the averages of 
the current soap bars on the market today. 
Example 10 demonstrates the ability to make firm, good smearing freezer 
bars with about twice the level of sodium soap vs. Example 9 and about 
half the magnesium soap level vs. Example 9. Example 10 has the best 
lather of the Examples. 
Example 11 demonstrates a freezer bar comprising 5% magnesium soap and 
22.5% petrolatum. Example 11 is a firm freezer bar with excellent smear 
and good lather. 
The crystalline meshes of the freezer bars of Examples 9, 10, and 11 are 
estimated to occupy, respectively, about 15%, 15-35%, and 5-25%, by volume 
of the bars.