Note: Descriptions are shown in the official language in which they were submitted.
3 5
SHAPED SOLID MADE WITH A RIGID
INTERLOCKING MESH OF NEUTRALIZED CARBOXYLIC ACID
TECHNICAL FIELD
This invention relates to neutralized carboxylic acid shaped solid
compositions, particularly cleansing bars, cakes, soap bars, synbars and the
like.
5BACKGROUND
Products made in the form of shaped solids, cakes and bars are
numerous. Cleansing bars are well known in the art.
Cleansing bars with reduced bar smear are reported in the art. E.g.,
U.S. Pat. No. 2,988,511, Mills, issued June 13, 1961, discloses a low smearing
bar.
Bar smear, also referred to as bar sloth, is the soft solid or mush
that forms at the surface of a bar when submerged in water and is regarded by
consumers as messy, unattractive, and uneconomical. 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 uses coconut and/or palm kernel oil soap.
One only has to examine a used personal cleansing bars in their
bathroom to see that there is still a need for improved cleansing bars with
little or no smear.
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). The report does not teach a
B
- 2 ~ 3 ~ ~
utility for the soap curd. Shaped solids, as defined herein, are not
disclosed by Marton et al.
Japanese Pat. J5 7030-798, July 30, 1980, discloses transparent solid
framed or molded soap bar 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.
It is also difficult to produce firm, non-sticky 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
non-solids and soft solids, such as water-soluble polyols and hydrocarbon
greases.
SUMMARY OF THE INVENTION
In accordance with one aspect of the invention there is provided A
personal cleansing bar composition comprising a rigid, crystalline
interlocking mesh of elongated sodium soap crystals; said soap bar comprising:
from about 15% to about 50% sodium fatty acid soap composed of at least about
50% 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;
from about 15% to about 60% water; and from about 2% to about 60% by weight
of a hygroscopic synthetic surfactant wherein said hygroscopic synthetic
surfactant is selected from surfactants which absorb at least about 20% of
their dry weight in water at 26~C and 80% Relative Humidity in three days.
BRIEF DESCRIPTION OF THE FIGURES
Figures 1-8 show magnified views of bar samples of the present
invention. Figures 9 and 10 show magnified views of two different
conventional soap bars.
DETAILED DESCRIPTION OF FIGURES
The Scanning Electron Microscope (SEM) sample preparation involves
fracturing a shaped solid with simple pressure to obtain a fresh
surface for examination. The fractured sample is reduced
B
W O 92/09679 3 2 0 9 5 3 51 P~/US91/08733
in size (razor blade) to approximately a 10 mm x 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.
FIGS. 1 and 2 are copies of photographs of a highly enlarged
skeleton core structure comprising a rigid, interlocking mesh of
elongated neutralized carboxylic acid crystalline fibers. More
specifically FIGS. 1 and 2 are elongated C12 sodium soap fibers,
enlarged respectively at 5000X and 2500X magnifications. The
structure of FIGS. 1 and 2 are made with 5% soap; 94% water; and
1% sodium chloride. See Example 10 in Table 7 herein. Note that
larger fibers in the interlocking mesh can be composed of smaller
fibers. Also, note the "void" spaces. See FIG. 2.
FIGS. 3, 4 and 5 are copies of photographs of a skeleton
structure made with 25% sodium C12 soap; 74% water; and 1% sodium
chloride. The crystalline fiber-like structure is shown respec-
tively at 3000X, 5000X and 1000X magnifications.
FIG. 6 is a copy of a photograph of a skeleton structure made
with 20% disodium salt of 1,12-dodecanedioic acid. The crystal-
line fiber-like structure is shown at 2000X magnification. See
Example 26.
FIG. 7 is a copy of a photograph of a skeleton (core) struc-
ture comprising crystalline lithium neutralized C14 carboxylic
acid mesh, shown at 1500X magnification. See Example 27.
FIG. 8 is a copy of a photograph of a cleansing bar (Exam-
ple I hereinbelow) comprising: coated C14 16 sodium soap fibers.
The fibers are coated and/or commingled with the other bar compo-
nents. The magnification is 1500X.
FIG. 9 shows a sample of a market IVORY~ freezer bar made
with sodium/potassium coconut/tallow soap at 1000X on the scale.
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The air in the IVORY bar soap makes it float.
FIG. 10 shows a sample of a market NEUTROGENA~ transparent
bar at 1500X.
In FIGS. 1 and 2, the samples are first melted on a hot plate
and recooled on a glass slide. The other samples, FIGS. 3-10, are
samples of original shaped solid structures or the conventional
bar prepared as set out herein.
DETAILED DESCRIPTION OF THE INVENTION
The invention provides a shaped solid comprising two or more
phases. One phase is a crystalline skeleton structure comprising
a rigid interlocking, open, three-dimensional mesh of neutralized
carboxylic acid elongated crystals. The other essential phase
is an aqueous phase which is soft or flowable at 25-C.
More specifically, the skeleton structure is a relatively
rigid, interlocking, open, three-dimensional mesh of neutralized
mono- and/or di-carboxylic acid elongated crystals.
The terms: skeleton structure, skeletal structure, core, and
skeleton frame are often used interchangeably herein.
The term "shaped solid" as used herein includes forms such as
bars, cakes and the like. The term "bar" as used herein includes
the same unless otherwise specified.
The term "mesh" as used herein means an interlocking crystal-
line skeleton network with voids or openings when viewed under
magnification by scanning electron microscopy.
In another respect, the present invention provides an
improved cleansing bar which is comprised of said skeleton struc-
ture. Some shaped solids are in the form of cleansing bars which
contain surprisingly high levels of said aqueous phase comprising
water, other liquids and soft materials. Notwithstanding the
presence of relatively large levels of an aqueous phase. the
preferred bars of the present invention maintain their rigidity
and excellent smear properties, even when allowed to soak over-
night in water. While not being bound to any theory, the shapea
solid comprising these phases is similar to a relatively rigid we~
sponge.
The crystalline phase comprises crystals in the form of
either interlocking platelets and~or fibers, preferably fibers.
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Preferably said fibers are composed of sodium soap. The inter-
locking mesh of said fibers and/or platelets imparts strength to
the three-dimensional structure, even in the presence of rela-
tively high levels of water or other soft materials; even when
allowed to soak overnight in water.
The strength of the skeleton structure can be measured
indirectly by the hardness of the shaped solid, as determined by
the resistance to penetration of the solid using a Standard
Weighted Penetrometer Probe. See Bar Harness Test below for more
details. The skeleton structure is of sufficient rigidity that a
20 mm thick or greater cleansing bar sample has a penetration of
from about zero mm to about 12 mm, preferably from about l mm to
about 10 mm, more preferably from about 3 mm to about 8 mm.
The present bars are distinguished from conventional trans-
parent bars based on crystal size, as well as other character-
istics. The crystals or crystal bundles that make-up the inter-
locking mesh structure of the present invention preferably are of
a size that diffracts light and consequently are greater than 400
nm in either diameter or length. On the other hand, conventional
transparent bars gain their transparency by having crystal
diameters or length less than the wavelength of white light, which
is greater than about 400 nm and consequently do not diffract
light.
Once formed, a bar (shaped solid) comprising the rigid
skeletal structure of the present invention loses its rigidity
when subjected to fracturing mechanical forces, e.g., those used
in a conventional plodded bar making process as disclosed in U.S.
Pat. No. 4,812,253, Small et al., or U.S. Pat. No. 4,820,447,
Medcalf et al. This is because the fracturing mechanical forces
shear and break up the rigid, skeletal structure into smaller
pieces. Thus, when a bar of the present invention is sheared in a
plodder, a much softer bar results.
On the other hand, when a finished conventional bar is
plodded or replodded, the replodded conventional bar is still very
hard. See Example 28 and Table 12 for more details on this point.
W O 92/09679 2 0 9 5 3 S 1 - 6 - P~/US91/08733
The skeletal structure contains substantial "void" areas
which are filled by soft and/or liquid aqueous phases. It is a
surprising aspect of this invention that the physical properties
of the bar, such as bar hardness and little smear, are mostly
dependent on the crystalline interlocking mesh structure, even
when the other phases make up a majority of the materials present.
In conventional bars, many components can impact the overall bar
physical properties because the components either modify the phase
and structure of the soap or synthetic surfactant components that
primarily determine the bar's physical properties. The combina-
tion of two or more phases (e.g., soap and aqueous solution)
drastically changes the colloidal structure, and consequently, the
physical properties of a conventional bar.
Thus, conventional bars are more limited in the type, levels
and composition of soft phase materials that can be incorporated
into the bar than the present invention. Such phases include most
materials that are either flowable liquids or materials that are
softer than the minimum hardness of an acceptable bar. These
phases include aqueous solutions, liquid crystalline phases
composed of water and surfactant, polymers; particularly sur-
factant-containing crystalline phases, and especially hygroscopic
surfactants, which tend to become soft and sticky when mixed with
water or other liquid phases including water-soluble organics
(e.g., propylene glycol and glycerine), hydrophobic materials
(e.g., mineral oil, liquid triglycerides), or soft hydrophobic
materials, e.g., petrolatum, low melting paraffin, and low melting
triglycerides.
In physical terms, all these phases can be characterized as
being flowable liquids or so soft that a Standard Weighted Pene-
trometer Probe, as defined herein, will penetrate all the waythrough a 12 mm thick sample. These phases can be selectively
included in the structure of the present invention without loss of
the interlocking mesh structure and certain desirable physical
properties.
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WO 92/09679 PCI/US91/08733
DESCRIPTION OF PREFERRED EMBODIMENTS
The invention is a shaped solid comprising a skeleton struc-
ture that is a relatively rigid interlocking, open three-dimen-
sional mesh of neutralized mono- and/or di-carboxylic acid elon-
gated crystals.
The preferred embodiment is a cleansing bar comprising at
least two phases: (1) an aqueous phase having a penetration value
of about 12 mm for a 12 mm deep sample; said aqueous phase being
soft or flowable; (2) a rigid crystalline phase comprising a rigid
crystalline phase skeleton structure comprising an interlocking,
open three-dimensional mesh of neutralized mono- and/or di-car-
boxylic acid elongated crystals; wherein said cleansing bar
comprising said rigid crystalline phase skeleton structure and
said aqueous phase has a penetration value of of from zero to
about 12 mm for a 25 mm deep sample; and wherein said penetration
values are measured as 25-C using a 247 gram Standard Weighted
Penetrometer Probe having a conical needle attach to a 9 inch
(22.9 cm) shaft weighing 47 grams, with 200 grams on top of said
shaft for a total of said 247 grams, said conical needle having a
19/32 inch (1.51 cm) top and a 1/32 inch (0.08 cm) point.
The above cleansing bar is preferred when said neutralized
carboxylic acid is selected from the group consisting of: lithium
and/or sodium neutralized: monocarboxylic acid (soap) and/or
dicarboxylic acid; and mixtures thereof; wherein said monocar-
boxylic acid has a fatty alkyl(ene) chain of from about 12 to
about 24 carbon atoms; wherein said dicarboxylic acid has a fatty
alkyl(ene) chain of from about 12 to about 18 carbon atoms; and
wherein at least about 80% of said carboxylic acid has saturated
alkyl(ene) chains; and wherein said rigid crystalline phase
skeleton structure occupies from about above 3% to about 75% of
said cleansing bar by volume; and wherein said neutralized car-
boxylic acid comprises from about above 5% to about 75%; and
wherein said cleansing bar contains from about 15% to about less
than 94% water by weight of said cleansing bar.
The above cleansing bar is preferred when at least 80%.
preferably 90%, of the carboxylic acid has the following general
formula:
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W O 92/09679 PC~r/US91/08733
- 8 -
H - (CH2Ja - CH - (CH2)b - C~2 - M+
I
X
wherein:
a + b = 8 to 20
- each a, b = O to 20
o
X = H, OR, O-C-R, R, or mixtures thereof
R = C1-C3 alkyl, H, or mixtures thereof
M = Na, Li, or mixtures thereof.
The above cleansing bar is more preferred when said a + b =
10-16; each of said a, b = 0-16; said X = H, OR; R = H; and M =
Na.
The above cleansing bar is highly preferred when said elon-
gated crystals are composed of fiber-like sodium fatty acid soap
of which at least about 25% of said saturated fatty alkyl chains
is of a single chain length; and wherein said bar contains: from
about 15% to about 75% of said sodium soap; wherein the ratio of
said unneutralized (free) carboxylic acid to soap is from about
1:2 to about 0. In other words, the free fatty acid is no more
than 50% by weight of the soap in the formulation.
The above cleansing bar is preferred when said bar contains
said sodium soap and water; and from about 2% to about 60% of a
synthetic surfactant selected from the group consisting of: alkyl
sulfates, paraffin sulfonates, alkylglycerylether sulfonates, acyl
sarcosinates, methylacyl taurates, linear alkyl benzene sulfo-
nates, N-acyl glutamates, alkyl glucosides, alpha sulfo fatty acid
esters, acyl isethionates, alkyl sulfosuccinates, alkyl ether
carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate
esters, methyl glucose esters, protein condensates, alkyl amine
oxides, alkyl betaines, alkyl sultaines, the alkyl ether sulfates
with 1 to 12 ethoxy groups, and mixtures thereof, wherein said
surfactants contain Cg-C22 alkyl chains.
The above cleansing bar is preferred when said synthetic sur-
factant is hygroscopic; said hygroscopic surfactant being defined
as a surfactant which absorbs at least 20% of its dry weight in
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WO 92/09679 PCI'/US91/08733
g
water at 26-C and 80% Relative Humidity in three days and wherein
said bar is relatively non-swelling.
The above cleansing bar is preferred when said hygroscopic
surfactant is selected from the group consisting of alpha sulfo
5 fatty acid esters; alkyl sulfates; alkyl ether carboxylates; alkyl
betaines; alkyl sultaines; alkyl amine oxides; alkyl ether sul-
fates; and mixtures thereof.
The above cleansing bar is preferred when the ratio of said
water to said soap is from about 1:1 to about 5:1; said water is
present at a level of from about 25% to about 60%; wherein said
fatty alkyl chains are C14 to C22 and said soap level in said bar
is from about 15% to about 35%; wherein at least about 85% of said
alkyl chains are saturated; wherein the weight ratio of said
unneutralized (free) carboxylic acid to said soap is from about
1:4 to 0; and wherein said synthetic surfactant level is from
about 4% to about 25% by weight of the bar and said surfactant is
selected from the group consisting of: sodium acyl isethionates,
sodium acyl sarcosinates, sodium alpha sulfo fatty acid esters,
sodium paraffin sulfonates, sodium alkyl ether sulfates, sodium
alkyl sulfates, sodium linear alkyl benzene sulfonates, alkyl
betaines, alkyl sultaines, and trialkyl amine oxides.
The above cleansing bar is preferred when the ratio of said
water to soap ratio is from about 1.5:1 to about 2:1; the ratio of
said unneutralized (free) carboxylic acid to said soap is from
about 1:6 to 0; said water level is from about 30% to about 45%;
said fatty alkyl chain is from about C14 to about Clg; wherein at
least about 95% of said alkyl chains are saturated; said soap
level is from about 15% to about 30%; and said synthetic sur-
factant level is from about 8% to about 16%.
The above cleansing bar is preferred when said bar contains
from about 0.1% to about 40% of a hydrophobic material selected
from the group consisting of: microcrystalline wax, petrolatum,
carnauba wax, palm wax, candelilla wax, sugarcane wax, vegetable
derived triglycerides, beeswax, spemaceti, lanolin, wood wax~
shellac wax, animal derived triglycerides, montar, ozokerite,
ceresin, and Fischer-Tropsch wax.
WO 92/09679 PCI/US91/08733
20y53Sl - 10-
The above cleansing bar is preferred when said bar contains
from about 2% to about 35% of said hydrophobic material selected
from the group consisting of petrolatum and wax, said petrolatum
and wax, and mixtures thereof melting melting about 49-C (120-F)
to about 85-C (185-F).
The above cleansing bar is preferred when said bar comprises
from about 5% to about 25% by weight of the bar of paraffin wax.
The above cleansing bar is preferred when said bar contains
from about 1% to about 50% of a non-volatile, water-soluble,
nonionic organic material having a solubility of at least 5 parts
in 10 parts of water; and wherein said water-soluble nonionic
organic material is selected from the group consisting of a polyol
of the structure:
Rl - O(CH2 - CHO)nH
R2
where Rl = H, Cl-C4; R2 = H, CH3; and n = 1-200;
C2~C10 alkane diols; sorbitol; glycerine; sugars; sugar deriva-
tives; urea; and
ethanol amines of the general structure (HOCH2CH2)XNHy where x =
1-3; y = 0-2; and x+y = 3, and mixtures thereof.
The above cleansing bar is preferred when said bar contains
from about 2% to about 40% of said non-volatile, water-soluble.
nonionic organic material.
The above cleansing bar is preferred when said non-volatile.
water-soluble, nonionic organic material comprises from about 5~~O
to about 20~o by weight of the bar; and wherein said organic
material is selected from the group consisting of: propylene
glycol, glycerine, sucrose, and urea, and mixtures thereof.
The above cleansing bar is preferred when said bar contains
said sodium soap, said water, and said synthetic surfactant, and
from about 0.1% to about 70% of other ingredients selected from
the group consisting of:
from about 1% to about 10% said potassium soap;
from about 1% to about 35% said magnesium soap;
from about 1% to about 35% said calcium soap;
from about 1% to about 15% triethanolammonium soap;
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from about 1% to about 60% of impalpable water-insoluble
materials selected from the group consisting of calcium
carbonate and talc;
from about 0.1% to about 20% of a polymeric skin feel aid;
wherein said polymeric skin feel aid is selected from
the group consisting of cationic polysaccharides,
preferably cationic guar gum with molecular weights of
1,000 to 3,000,000; cationic polyalkylene imines,
ethoxypolyalkylene imines, and poly[N-[-3-(dimethyl-
ammonio)propyl]-N'-[3-ethyleneoxyethylene dimethylammo-
nio)propyl]urea dichloride]; silicone gum; and silicone
fluids; JR polymers; Celquat0;
from about 0.5% to about 25% of aluminosilicate clay and/or
other clays; wherein said aluminosilicates and clays are
selected from the group consisting of zeolites; kaolin,
kaolinite, montmorillonite, attapulgite, illite, benton-
ite, halloysite, and calcined clays;
from about 1% to about 50% of salt and salt hydrates; and
mixtures thereof; and wherein said salt and salt hydrate
have a cation selected from the group consisting of:
sodium, potassium, magnesium, calcium, aluminum, lithi-
um, ammonium, monoethanol ammonium, diethanolammonium,
and triethanolammonium; and wherein said salt and salt
hydrate have an anion selected from the group consisting
of: chloride, bromide, sulfate, metasilicate, ortho-
phosphate, pyrophosphate, polyphosphate, metaborate
tetraborate, carbonate, bicarbonate, hydrogen phosphate,
methyl sulfate, and mono- and polycarboxylate of 6
carbon atoms or less.
The above cleansing bar is preferred when said elongated
crystals contain platelets and wherein said soap consists of
lithium neutralized monocarboxylic acid.
The above cleansing bar is preferred when said elongated
crystals are fiber-like and wherein said neutralized dicarboxylic
acid is the disodium salt 1,12-dodecanedioic acid and wherein said
neutralized dicarboxylic acid comprises from about 20% to about
70% by weight of said bar.
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A Preferred Process for Makinq the Bar
A process of making the above preferred cleansing bar of the
present invention comprises the steps of:
I. forming an aqueous molten liquid comprising about 15% to
5about 94% water and from about 6% to about 75% by weight
said neutralized carboxylic acid;
II. pouring said molten liquid into a bar shaped mold; and
III. crystallizing said molded molten liquid by cooling to
provide said cleansing bar.
10The above process is preferred when the aqueous molten liquid
is made by neutralizing an aqueous mixture of said carboxylic acid
with sodium hydroxide or lithium hydroxide with stirring at a
temperature of from about 50-C (120-F) to about 95-C (205-F).
The above process is preferred when from about 2% to about
1515% by weight of said bar is a "crystallization enhancing salt"
selected from the group consisting of: sodium or lithium salt of
sulfate, chloride, acetate and citrate, and mixtures thereof.
The above process is preferred when said aqueous molten
liquid aqueous phase contains from about 2% to about 40% of a
20solubilizing aid selected from the group consisting of:
(a) non-volatile, water-soluble nonionic organic solvents
selected from the group consisting of: a polyol of the
structure:
Rl - O(CH2 - CHO)nH
R2
where Rl = H, C1-C4; R2 = H, CH3; and n = 1-200;
C2-C1o alkane diols; sorbitol; glycerine; sugars; sugar
derivatives; urea; and
ethanol amines of the general structure (HOCH2CH2)XNHy
where x = 1-3; y = 0-2; and x+y = 3;
(b) alcohols of from 1 to 5 carbon atoms;
(c) synthetic surfactant selected from the group consisting
of: alkyl sulfates, paraffin sulfonates, alkyl glyceryl
ether sulfonates, anionic acyl sarcosinates, methyl acyl
taurates, linear alkyl benzene sulfonates, N-acyl
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glutamates, alkyl glucosides, alpha sulfo fatty acid
esters, acyl isethionates, alkyl sulfosuccinates, alkyl
ether carboxylates, alkyl phosphate esters, ethoxylated
alkyl phosphate esters, methyl glucose esters, protein
condensates, alkyl amine oxides, alkyl betaines, alkyl
sultaines, the alkyl ether sulfates with 1 to 12 ethoxy
groups, and mixtures thereof, wherein said surfactants
contain Cg-C22 alkylene chains; and
mixtures thereof; and
wherein said solubilizing aid is added to increase the level
of said neutralized carboxylic acid dissolved in said con-
tinuous molten aqueous phase in step I.
The above process is preferred when said aqueous phase
contains from about 20~h to about 100% water by weight of said
aqueous phase.
The above process is preferred when said rigid crystalline
phase contains from about 75% to about 100% of said neutralized
carboxylic acid by weight of said crystalline phase.
The above process is preferred when said bar has a pene-
tration value of from about 3 mm to about 9 mm for said 25 mm bar
sample.
The above process is preferred when said bar has miscel-
laneous non-carboxylic acid phases comprising droplets or crystals
selected from waxes, petrolatum, clays, and the like.
A highly preferred embodiment of the present invention is: a
personal cleansing bar composition comprising a rigid, crystalline
interlocking mesh of elongated sodium soap crystals; said soap bar
comprising: from about 15% to about 50% sodium fatty acid soap
composed of at least about 50% saturated fatty alkylene chains
having 12-24 carbon atoms of which at least about 25% of said
saturated fatty alkyl chains is of a single chain length; from
about 15% to about 60% water; and from about 2% to about 60% by
weight of a hygroscopic synthetic surfactant wherein said hygro-
scopic synthetic surfactant is selected from surfactants which
absorb at least about 20% of their dry weight in water at 26-C and
80% Relative Humidity in three days.
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The above highly preferred personal cleansing bar is more
preferred when said hygroscopic synthetic surfactant is selected
from the group consisting of alpha sulfo fatty acid esters; alkyl
sulfates; alkyl ether carboxylates; alkyl betaines; alkyl sul-
taines; alkyl amine oxides; alkyl ether sulfates; and mixturesthereof.
This highly preferred personal cleansing bar is more pre-
ferred when said bar contains from about 0.5% to about 40% of
salts and/or salt hydrates selected from the group consisting of:
sodium chloride, sodium sulfate, disodium hydrogen phosphate,
sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium
citrate, and other compatible salts of inorganic acids and short
chain organic acids.
A highly preferred cleansing bar comprises: various combi-
nations of the core structure of sodium soap fibers, water, mildsynthetic surfactants, bar appearance stabilizers, skin mildness
aides and other cleansing bar adjuvants. Such preferred bar can
be formulated to have essentially no bar smear.
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 50% saturated fatty alkyl chains having 12 to 24 carbon
atoms. Preferably at least about 25% of said saturated alkyl
chains are of a single chain length.
Some compositions of this invention comprise the above-
defined rigid mesh with water and without water. These compo-
sitions must be formed with water or another suitable solvent
system. The compositions can be made with large amounts of water
and the water level in the final composition can be reduced to as
low as about 1% or 2%.
However, it is a special advantage of some structures de-
scribed herein that they can be dehydrated without loss of the
integrity of the mesh. Some preferred shaped solids can be
dehydrated without appreciable change in their outer dimensions.
Other bars shrink while maintaining their three-dimensional form.
Some bars herein have the unique characteristic that they are not
destroyed by dehydration.
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More complex bars of the present invention comprise a skele-
tal structure comprising other salts of fatty acids selected from
potassium, magnesiumt triethanolammonium 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 aids and other cleansing bar adjuvants;
yet are mild and have very good low smear.
Tables 1-3 set out some preferred 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 l
15Preferred Bars~ Chain Lenqths and Levels
More Most
Preferred Preferred Preferred
Water Level 15-94% 25-60% 30-45%
Water:Soap Ratio 0.7:1 1:1-5:1 1.5:1-2:1
FA Chain Length Cl2-24 Cl4-22 Cl4-l8
FA Soap Level in
Total Formulation 6-50% 15-35% 15-30%
All highs and lows are not necessarily shown in Table 1. For
example, some selected sodium soap can be used at a level up to
about 75%. Thus, the range is from about 5% to about 75%. The
preferred levels and ratios can vary from cation to cation, etc.,
and from mono- to polycarboxylic acids.
The bars shown in Table 1 are made with the level of water
indicated, but the water level of the final bars can be reduced to
provide bars which contain reduced levels of water or even little
or no water. A preferred level of water is from about 20% to
about 80% by weight of the bar.
Table 2 below shows some preferred levels of soaps of a
single FA chain length. Table 3 shows some preferred levels of
unsaturation in the FA's used in the compositions of the present
WO 92/09679 2 o 9 5 3 5 1 - ! ~ PCI/US91/08733
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invention. Some preferred compositions contain little or no 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 % SoaD of Single Chain Lenqth
(of Total Fibrous SoaD Content)
More Most
Preferred Preferred Preferred
Cl2-24 25-100% 50-100% 75-100%
TABLE 3
The Total % Unsaturated or Low (C1o or less) Chain Lenqth SoaDs
More
Broad Preferred Preferred
Cl2 0-15% 0-5% 0-1%
C14-24 0-50% 0-10% 0-1%
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 ingredients 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 0.1% 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 more than
5% to about 75% selected sodium soap and other ingredients.
It should be understood that solid shapes can be made with
just lithium soap or just neutralized polycarboxylic acid, but
would be expected to be somewhat different from the levels and
ratios given for sodium soaps.
WO 92/096792 ~ 9 5 3 5 1 ~ ! ~ PCI'/US91 /08733
- 17 -
TABLE 4
Hiqhs and Lows Wt.% of Other Inqredients for
More ComDlex Sodium Soa~ Bars
More Most
5Preferred Preferred Preferred
Neutralized Dicar-
boxylic Acid 1-40% 2-30% 5-25%
Lithium "Soap" 1-40% 2-30% 5-25%
Potassium Soap 1-10% 2-10% 5-8%
Magnesium or Calcium Soap 1-35% 1-12% 3-8%
Triethanolammonium Soap 1-15% 2-15% 5-10%
Synthetic Surfactant 1-60% 4-25% 8-16%
Other Salts and
Salt Hydrates 0.5-50% 1-25% 2-15%
Non-Volatile, Water-Soluble
Nonionic Organics 1.0-50% 2-40% 5-20%
Polymeric Mildness
Enhancers 0.1-20% 0.25-10% 1-5%
Waxes 0.1-40% 2-35% 3-10%
Other Impalpable
Water-insolubles 1-60% 4-25% 8-16%
Aluminosilicates/Clay 0.5-25% 1-10% 3-8%
The soaps useful in the present invention can be of the same
alkyl chain lengths, i.e., which are selected from the 12 to 24
carbon atoms as set out in Table 2. The same chain lengths apply
for the other non-sodium soaps used in the bars of the present
invention.
The sodium soap is preferably at least about 50% of the soap
present in the bar.
The levels of potassium soap and/or triethanolammonium soap
should not exceed one-half, preferably one-third, more preferably
less than one-fourth, that of the sodium soap and the level of
-magnesium soap should not exceed about one-third of the level of
sodium soap, and is preferably less than about one-fourth that of
the sodium soap.
-
- 18 ~ 3 ~ ~
The total of other soaps, save lithium soap, should preferably not
exceed one-half, preferably one-third, 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.
Examples include the water-soluble salts of organic, sulfonic a~k~
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-hydroxy-propane-3-sulfuric acid ester, sodium and potassium
monomyristoyl ethylene glycol sulfate, and sodium and potassium monolauroyl
diglycerol sulfate.
B
-
- 19 -
5 1
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
5 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:
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 Ll enado
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.
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
30 destruction test which is used to assess the irritancy potential ofsurfactants. 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 (3H-H2o) which passes from the test solution
through the skin epidermis into the physiological buffer contained in the
B
- 20 -
3 ~ ~1
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, 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,
sulfonated fatty esters, paraffin sulfonates, and sulfonated fatty acids.
Numerous examples of other surfactants are disclosed in the above
patents. 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 C8-C22, preferably C10-Cl8.
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 C8-Cl8, preferably Cl2-Cl6, alkyl polyglycosides withaverage degrees of glycosidation ranging from about 1.1 to about 2.7,
preferably from about 1.2 to about 2.5, are preferred.
W O 92/09679 2 0 9 5 3 S 1 - PC~r/US91/08733
- 21 -
Sulfonated esters of fatty esters are preferred wherein the
chain length of the carboxylic acid is C8-c227 preferably C12-C18;
the chain length of the ester alcohol is Cl-C6. These include
sodium alpha sulfomethyl laurate, sodium alpha sulfomethyl coco-
ate, and sodium alpha sulfomethyl tallowate.
Amine oxide detergents are good lather enhancers. Some
preferred amine oxides are Cg-Clg, preferably Clo-C16, alkyl
dimethyl amine oxides and Cg-Clg, preferably C12-C16, fatty acyl
amidopropyl dimethyl amine oxides and mixtures thereof.
Fatty acid alkanolamides are good lather enhancers. Some
preferred alkanolamides are Cg-C1g, preferably C12-C16, mono-
ethanolamides, diethanolamides, and monoisopropanolamides and
mixtures thereof.
Other detergent surfactants are alkyl ethoxy carboxylates
having the general formula
RO(CH2CH20JkCH2COO-M+
wherein R is a Cg 22 alkyl group, k is an integer ranging from O
to 10, and M is a cation; and polyhydroxy fatty acid amides having
the general formula
o R1
ll I
R2 - C - N - Z
wherein Rl is H, a C1 4 alkyl group, 2-hydroxy ethyl, 2-hydroxy
propyl, or mixtures thereof, R2 is a Cs 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 Cg-C1g,
preferably C12-C16, alkyl betaines, e.g., coco betaines or Cg-Clg,
preferably C12-C16, 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~C and 80% relative humidity in three days. Hygroscopic sur-
factants help to improve bar lather. Some preferred hygroscopicsynthetic surfactants are listed below. Note that all are not
hygroscopic.
~ . ! .
W O 92/09679 2 0 9 ~3 51 22 - P~/US91/08733
HYqroscoDicity of Some Surfactants
The hygroscopic surfactants are defined herein as having a
minimum of 20% total moisture gain after 3 days at 26-C and 80%
Relative Humidity.
C1ass: Nonionic
Sulfonates Total % Moisture Pick-Up*
Sodium C8 Glyceryl Ether Sulfonate 39.8
Sodium C12 14 Glyceryl Ether Sulfonate 22.9
Sodium C16 Glyceryl Ether Sulfonate 71.4
Sodium Cocomonoglyceride Sulfonate 3.5
Sodium Salt of Cg 16 Alkyl Glyceryl Ether Sulfonates
AlDha Sulfo Esters and Acids Total % Moisture Pick-UD*
Sodium Alpha Sulfo Methyl Laurate/Myristate 39.3
Sodium Alpha Sulfo Methyl Myristate44.5
Sodium Alpha Sulfo Hexyl Laurate 23.2
Sodium Alpha Sulfo Methyl/Hexyl Laurate
and Myristate 26.3
Sodium Alpha Sulfo Methyl Palmitate 3.7
Sodium Alpha Sulfo Methyl Stearate 4.2
Sodium 2-Sulfo Lauric Acid 0.2
Sodium 2-Sulfo Palmitic Acid 3.8
Sodium 2-Sulfo Stearic Acid 0.0
Na+Rl-C(s03-)-co2R2 Rl = C8-14 alkyl; R2 = Cl 8 alkyl
Sodium Alkvl IsethionatesTotal % Moisture Pick-UP*
Sodium Lauryl Isethionate 31.7
Sodium Cocoyl Isethionate 11.0
Sarcosinates Total % Moisture Pick-UD*
Sodium Lauryl Sarcosinate 8.8
Sodium Stearyl Sarcosinate 13.3
Sodium Cocoyl Sarcosinate 18.7
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- 23 -
AlkYl Sulfates Total ~O Moisture Pick-UP*
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
Na+R1(OCH2CH2)nOS03~ R1 = C8 14 alkyl, C16 20 alkyl(ene)
with at least one double bond, n = 0-18
ACY1 Glutamates Total % Moisture Pick-UP*
Sodium Cocoyl Glutamate 26.7
Sodium Lauryl Glutamate 17.8
Sodium Myristyl Glutamate 18.1
Sodium Stearyl Glutamate 12.0
AlkYl Ether CarboxYlates Total % Moisture Pick-UP*
Sodium Laureth-5 Carboxylate 32.2
Sodium Palmityl-20 Carboxylate 50.2
Na+R1-(0-CH2CH2)nc02- R1 = Cg 18 alkyl, n = 1-30
Sulfosuccinates Total % Moisture Pick-UP*
Disodium Laureth Sulfosuccinate33.6
PhosDhates Total % Moisture Pick-UP*
Sodium Monoalkyl (70% C12/30% C14)
Phosphate 21.1
Class: AmDhoterics
Betaines Total ~/O Moisture Pick-UP*
Coco Betaine 70.0
Cocoamidopropyl Betaine 48.2
Palmitylamidopropyl Betaine 46.5
Isostearamidopropyl Betaine 44.3
r ~ P
3 ~
- 24 -
Sultaines Total % Moisture Pick-Up*
Cocoamidopropylhydroxy Sultaine 59.5
Amine Oxides Total % Moisture Pick-Up*
Palmityl Dimethyl Amine Oxide 34.0
Myristyl Dimethyl Amine Oxide 46.0
Cocoamidopropyl Amine Oxide 43.3
Protein Derived Total % Moisture Pick-Up*
Na/TEA C12 Hydrolyzed Keratin 34.7
*3 days, 26~C/80% Relative Humidity
Polymeric skin mildness aids are disclosed in the Small et al. and
Medcalf et al. patents. Both cationic polysaccharides and cationic
synthetic polymers are disclosed. 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] thelatter 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~ 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 suitable and fully hydrated
and subsequently well incorporated into the soap matrix.
- 25 - 2 ~ ~ 5 3 ~ ~
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.
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. 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 ethylene-diaminetetraacetate (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
B
2o9l53,sl ~
WO 92/09679 I ~ P~/US91/08733
- 26 -
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 from about more than 5%
5 to about 75% said sodium fatty acid soap fibers; from about 10% to
about less than 94% water; and 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.
Some bars of this invention comprise: more than 5% to 50%
fibrous sodium fatty acid soap composed of at least about 50%
saturated fatty alkyl chains having 12-24 carbon atoms of which at
least about 25% of said saturated fatty alkyl chains is of a
15 S i ngle chain length.
Some bars of this invention comprise said fibers which occupy
from about 3% to about 75%, preferably from about 15% to about
40%, of the volume of the bar structure.
Some bars comprise a rigid, low smearing structure of: more
20 than 5% to 75% sodium fatty acid soap composed of at least about
50% 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; from about 10% to about 94% water; and
about 0% to a total of about 70% of other selected soap bar
25 ingredients selected from the group set out above in Table 4.
Some personal cleansing soap bar compositions comprise a
rigid interlocked mesh of sodium soap fibers; wherein the sodium
fatty acid soap is composed of at least about 50% 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 synthet-
ic surfactant wherein said hygroscopic synthetic surfactant is
selected from surfactants which absorb at least about 20% of its
dry weight in water at 26~C and 80% Relative Humidity in three
'5 days.
W O 92/09679 2 0 9 S 3 5 1 PC~r/US91/08733
- 27 -
Bar ADDearance Aids
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 above in Table 4.
Water-soluble organics are also used to stabilize the appear-
ance 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-Cl 4 alkyl ethers thereof, sorbitol, glycerol,
glycose, diglycerol, sucrose, lactose, dextrose, 2-pentanol,
l-butanol, mono- di- and triethanolammonium, 2-amino-1-butanol,
and the like, especially the polyhydric alcohols.
The term "polyol" as used herein includes non-reducing sugar,
e.g., sucrose. Sucrose will not reduce Fehling's solution and
therefore is classified as a "non-reducing" disaccharide. Unless
otherwise specified, the term "sucrose" as used herein includes
sucrose, its derivatives, and similar non-reducing sugars and
similar polyols which are substantially stable at a soap pro-
cessing temperature of up to about 210-F (98-C), e.g., trialose,
raffinose, and stachyose; and sorbitol, lactitol and maltitol.
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, pyro-
- 28 -
phosphate, 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 triethanolammonium (TEA) chloride salts are preferred.
5Aluminosilicates 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.
Other types of clays include zeolite, kaolinite, montmorillonite,
attapulgite, illite, bentonite, and halloysite. Another preferred clay is
kaolin.
10Waxes 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, and animal derived triglycerides). mineral waxes
(montar, ozokerite, and ceresin) and synthetic waxes (Fischer-Tropsch).
15A preferred wax is used in the Examples herein. A useful wax has a
melting point (M.P.) of from about 120~F to about 185~F (49-85~C), preferably
from about 125~F to about 175~F (52~-79~C). A preferred paraffin wax is a
fully refined petroleum wax having a melting point ranging from about 130~F
to about 140~F (49~-60~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 mark
Factowax R-133.
Other suitable waxes are sold by the National Wax Co. under the trade
25names of 9182 and 6971, respectively, having melting points of 131~F and 130~F(-55~C).
The paraffin preferably is present in the bar in an amount ranging from
about 5X 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
- 29
microcrystalline wax. A suitable microcrystalline wax has a
melting point ranging, for example, from about 140-F (60-C) to
about 185-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 mark Multiwax X-145A. The microcrystalline wax preferabiy
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.
EXAMPLES
The following examples are illustrative and are not intended
to limit the scope of the invention. Unneutralized or "free"
fatty acids, as used in the examples, are of the same chain
lengths as those used to make the soaps, unless otherwise speci-
fied. All levels and ranges, temperatures, results, etc., used
herein, are approximations unless otherwise specified.
A Frame Process for Makinq the Bars of the Present Invention
The cleansing bars in the Examples are made by the following
procedure unless otherwise specified:
1. Fatty acid precursor, propylene glycol, sodium chloride,
and water (excluding water coming in with other raw
materials) are mixed and heated to 71'C.
2. Caustic solution (50% sodium hydroxide) is added and the
mixture is stirred until smooth forming an aqueous
molten liquid comprising from 15% to 94% water and from
5.5% to 75% soap (neutralized carboxylic acid). The
temperature during neutralization of the molten liquid
increases to -95-C.
3. Other ingredients are added preferably in the following
order and the temperature is maintained at -88-C: coco
betaine; sodium lauroyl sarcosinate; or sodium alpha-
sulfo methyl cocoate; kaolin clay; or hydrated zeolite
(synthetic sodium aluminosilicate); and paraffin.
Perfume is added last.
4. The molten liquid mixture is poured into shaped molds.
W O 92/09679 2 0 9 ~3 51 - 30 - P~/US91/08733
5. The molten liquid crystallizes (solidifies) on cooling
to room temperature and the resultant bars are removed
from the molds.
The bars of the examples are made using the above general
procedure, unless otherwise specified.
It is important to note that, when the formulations which are
used in the Examples of the present invention are subjected to a
conventional plodding or freezer process very soft or no bars are
formed. Example II is a very highly preferred overall bar.
TABLE 5
Preferred Bars
Ex. I Ex. IIEx. III Ex. IV
Ingredient (Wt.%) (Wt.%)(Wt.%) (Wt.~,')
Na C14 Soap 20 20 - -
Na C16 Soap - - 20 16
K C16 Soap - - - 4
Free Fatty Acid
Sodium Lauroyl
Sarcosinate 7 7 12
Sodium Alpha Sulfo
Methyl Cocoate - - - 7
Coco Betaine 5 5 7 5
Sodium Chloride 3.0 3.0 3.0 3.0
Propylene Glycol 14.5 14.5 14.5 15.0
Hydrated Zeolite A
(Aluminosilicate) 4.0 4.0
Kaolin Clay 4.0 - 4.0
Paraffin (M.P.=55-C) 6.5 6.5 4.5
Perfume
Water 37.25 37.25 31.95 36.25
Hardness (mm~ 5.5 6.4 4.2 5.1
Smear 9.5 9.0 8.5 8.5
~escription of Testinq for ExamPles
35Bar Hardness Test
1. The hardness of a bar is determined by measuring at 25~C
the depth of penetration (in mm) into the bar of a 247 gram
, ~ ~
; .
W O 92/09679 2 0 9 5 3 5 1 PCT/US91/08733
- 31 -
Standard Weighted Penetrometer Probe having a conically shaped
needle attached to a 22.9 cm (9 inch) shaft weighing 47 grams with
200 grams on top of said shaft. A hardness measurement of 5 mm or
less indicates a very hard bar; 5-10 mm indicates a moderately
hard bar; 10-12 mm indicates a somewhat soft bar of marginal
acceptance; and greater than 12 mm indicates a very soft bar that
is unacceptable for most uses. This defines "hardness" as used
herein unless otherwise specified.
Bar Smear Test
2. The smear grade is determined by a (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 over-
night (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, 8.0-9.5 equals
low smear amount, 5.0-7.5 equals moderate smears similar to most
marketed bars, and 4.5 or less equals very poor smear.
Commercial soap bars, e.g., SAFEGUARD~, ZEST~, IVORY~, and
LAVA~, have smears of about 5, 6, 6, and 6, respectively. See
Table 12 for more data.
Bar Shrinkaqe Test
3. Shrinkage is measured by placing a freshly made un-
wrapped bar in a room that is held at 26~C and 15% relative
humidity for one week. The amount of shrinkage from the original
bar shape is determined on a qualitative scale where O indicates
no shrinkage, + indicates slight shrinkage, ++ indicates moderate
shrinkage, and +++ indicates great shrinkage.
In Tables 6 and 7, soap bars 1-10 are set out to show bar
hardness, smear and shrinkage for C1o, Cl2~ C14, C16~ and C18
alkyl chain soaps as shown. The preferred alkyl chain soaps of
the present invention are set out above in Tables l and 2.
The term "X." means that the example is a comparative
example.
WO 92/09679 2 0 9 S3~1 32 PCI/US91/08733
TABLE 6
Sinqle Saturated Chain Lenqth Sodium Soap/Water StudY
Ex.1 Ex.2 Ex.3 Ex.4 Ex.5
Ingredient Wt.% Wt.% Wt.% Wt.% Wt.%
Sodium Soap
C10 33 - -
C12 - - 33
C14 - - 33
C16 - - - 33
C18 - - - - 33
Free Fatty Acid 1.0 1.0 1.0 1.0 2.0
Excess Sodium
Hydroxide
Sodium Chloride 2.0 1.0 1.0 1.0 1.0
Water 64 65 65 65 64
Hardness (mm) 8.9 2.3 2.2 5.4 4.2
Smear 3 10 10 9.5 10.0
Shrinkage +++ +++ + 0
Note that Ex. 1 has a very poor smear, notwithstanding a
hardness of 8.9 as the smear methodology dissolves away the
soluble C1o soap.
TABLE 7
Single Chain Lenqth Sodium SoaD/Water StudY
X.6 Ex.7 Ex.8 Ex.9 Ex.10
Ingredient Wt.% Wt.% Wt.% Wt.% Wt.~o
Sodium Soap
C12 - - - 15 5
C16 10
C18 - - 10
C18:1 33
Free Fatty Acid 1.0 - 2.0 1.0
Excess Sodium
Hydroxide - 0.07
Sodium Chloride 1.0 1.0 1.0 1.0 1.0
Water 65 87 82.8 83 94
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_ - 33 -
Hardness (mm) ** 11.8 11.9 14.0
Smear 10.0 10.0 9.0
Shrinkage 0 +++ ++++ ++++
** Solid bar not formed due to too much unsaturated soap.
Example 10 has the rigid structure, but is not preferred as a
cleaning bar because its hardness is 14.
TABLE 8
BinarY Chain Lenqth Sodium SoaD/Water Study
X.11 Ex.12 Ex.13
InqredientWt.% Wt.% Wt.%
Sodium Soap
C10 - - 16.5
Cl2 16.5 - -
C14 - 16.5 16.5
C1g:1 16.5 16.5
Free Fatty Acid 1.0 1.0 1.0
Excess Sodium
Hydroxide
Sodium Chloride 1.0 1.0 1.0
Water 65 65 65
Hardness (mm) ** 9.0 9.0
Smear 9.0 8.0
**Solid Bar not formed due to too much
unsaturation combined with C12 soap.
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TABLE 9
Binarv Saturated Chain Lenqth Sodium SoaD/Water Studv
Ex.14 Ex.15 Ex.16
Inqredient Wt.% Wt.% Wt.%
Sodium Soap
Cl2 16.5
C14 16.5
C16 - 16.5 10
C18 - 16.5 10
Free Fatty Acid 1.0 1.0 1.0
Sodium Chloride 1.0 1.0 1.0
Water 65 65 78
Hardness (mm) 2.8 4.5 7.3
Smear 9.5 10.0 10.0
Shrinkage 0 ++
Examples 12-16 are excellent bars of the present invention.
TABLE 10
20ComDlex Chain Lenqth Sodium SoaD/Water Studv
Ex.17 Ex.18 Ex.19
Inqredient Wt.% Wt.% Wt.%
Sodium Soap*
Emersol 132 - (33) (15)
C8 0.56
C1o 0.64
Cl2 10.14 0.12 8.1 (8.0)
C14 4.54 0.79 10.4 (10.0)
C16 8.51 15.6 7.10
C17 0.76 0.76 0.35
Cl8 19.85 15.3 7.0
C20 - 0.26 0.12
Free Fatty Acid - 1.0
Sodium Chloride 1.1 1.0 1.0
Water 53.9 65 66
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Hardness (mm) 7.6 4.7 5.8
Smear 9.5 10 9.5
Shrinkage + ++
*Composition by Chain Length, () indicate
actual level of materials.
Examples 17-19 are made with more complex mixtures of soaps than
the prior examples. They form very good bars of the present
invention. They have little or no smear. Compare their hardness
and smears with those made with conventional tallow and coconut
soap shown in Table 11 .
TABLE 11
ComPlex Chain Lenqth Sodium SoaD/Water StudY
X.20 X.21 X.22
Inqredient Wt.% Wt.% Wt.%
Sodium Soap*
Tallow (33) - (26.4)
Coconut - (33) (6.6)
C8 - 2.31 0.46
C10 - 2.0 0.40
C12 ~ 16.5 3.3
C14 1.0 5.94 4.95
Cl6 7.92 2.81 6.90
C18 0-5 - 0.40
C20 6.6 1.0 5.48
C14:1 0.33 - 0.26
C16:1 0.83 - 0.66
C1g:1 14.2 2.0 11.76
C1g:2 0.75 0.5 0-7
Free Fatty Acid 1.0 1.0 1.0
Sodium Chloride 1.0 1.0 1.0
Water 65 65 65
Hardness (mm) Soft 15.8 12.5
~5 Smear Poor 3.0 5.0
*Composition by Chain Length, () indicate
actual level of materials.
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These comparative examples, X.20, X.21, and X.22, do not form the
rigid structure of the present invention. Note that they are made
with the typical commercial soaps. They are soft soaps with
terrible smears. Compare with Example 15 of the present invention
; which is made with 65% water and C16 and C1g saturated soap and
forms a hard bar with no smear.
Example 23 is a bar of the present invention which contains
more synthetic surfactant than soap. It has low smear and good
lather. Example 24 is a bar of the present invention which
contains polymer and other bar soap ingredients.
EXAMPLE 23
SYndet Bar ExamPle
Inqredient Wt.%
Sodium Palmitate 20
Sodium Lauroyl Sarcosinate 9*
Sodium Laureth-3 Sulfate 7*
Sodium Cetearyl Sulfate 5*
Free Fatty Acid (Palmitic)
Sodium Chloride 3
Propylene Glycol 14
Hydrated Zeolite A 3
Perfume
Water 37
*Total 21% Synthetic Surfactant
20953~1
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EXAMPLE 24
PolYmer-Containinq ExamDle
Ingredient Wt.%
Sodium Palmitate 20
Sodium Alpha-Sulfo Methyl Cocoate 8. 7
Coco Betaine 4.65
Jaguar C376 1.5
Propylene Glycol 15
Kaolin Clay 5
Paraffin, (M.P.=55-C) 4.5
Sodium Chloride 3
Perfume
Water 35.5
Examples 23 and 24 are similar to Example IV of Table 5.
Example 24 is a mild bar formulation with polymeric skin
mildness aid.
EXAMPLES 25 - 27
Ex. 25 Ex. 26 Ex.27
Inqredient Wt.% Wt.% Wt.%
Lithium Myristate 33
Lithium Chloride 5 - -
Disodium Salt of
Dodecanedioic Acid - 20 20
Sodium Lauroyl Sarcosinate - - 5
Water 62 80 75
Penetration Values N/A N/A N/A
N/A = Not available
For Example 25, the formulation is prepared by heating the
fatty acid precursor to 71-C, separately adding lithium hydroxide
to water, and then adding the fatty acid and lithium hydroxide
solution together, mixing together for 30 minutes maintaining the
35 heat at least at 71-C, adding lithium chloride salt and stirring
for an additional 5 minutes, then pouring into a mold and letting
...
.. ~ . D
",, f '
- 38 -
cool and solidify. A solid bar with excellent smear properties is formed.
For Examples 26 and 27, the diacid is melted (150-180~C) and a hot
(90~C) caustic solution (two equivalents of NaOH) is added. The mixture
is stirred for -5 minutes. For Example 27, the sodium lauroyl sarcosinate
is predissolved in the caustic/water solution. The bar becomes solid on
cooling, with further hardening occurring upon degradation, e.g., to about
35-40% water by weight of the bar.
Example 25 demonstrates the ability to form high moisture, firm and
non-smearing bars without the need for sodium soap. Examples 26 and 27
demonstrate the ability to form a totally soap-free product and still
obtain the relatively rigid intermeshed fiber structure.
FREEZER BAR EXAMPLE 28
Example 28 below is made by a freezer bar process disclosed in
commonly assigned, Canadian Pat. Application Ser. No. 2,113,564, Taneri et
al. This process 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 made by the following steps:
(1) mixing a molten mixture comprising by weight of said bar:
20from 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
25(4) further cooling and crystallizing said soft plug until firm
to provide said personal cleansing freezer bar.
Step 1 - Mixinq
The soap specified in the formulation is made in situ by
mixing the desired fatty acids, consisting essentially of C12-C24
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~F to about 200~F (76~-93~)
209~3~1
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- 3g -
to form the soap. In Example 28, 180-F is used. Sufficient water
is used such that the mixture is stirrable. The other ingredients
are added, maintaining the temperature of from about 180-F to
about 200-F (82--93-C). Example 28 - 180-F. The optimal mixing
temperatures can vary depending on the particular formulation.
SteD 2 Ootionals - Aeration. Minor Addition~
and Flash DrYinq ODtionals
Aerate (optional) said mix and add perfume (only if drying)
and other minors with positive displacement pump or other in-line
mixer. Example 28 is not aerated or dried. 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 tem-
perature is from about 225-F to about 315-F (135~-157-C~ at
pressure of from about 30 to abut 100 psi (115-517 mm Hg).
SteD 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-F to about 200-F (82--93-C) or from about 200~F
to about 22~-F (93--104-C), if dried, to a final temperature
preferably from about 135-F to about 180-F (57--82-C), more
preferably from about 145-F to about 180-F (63--82-C), and most
preferably from about 155-F to about 175~F (68 -79 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). The FOT for Example 28 is 175-F.
SteD 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
3~ extrusion, resulting in hardening of the bar. The final crystal-
lization of the sodium soap forms the interlocking, semi-con-
tinuous, open mesh structure in the freezer bar of the present
20Y~3~1
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- 40 -
invention.
EXAMPLE 28
Inqredient Wt.%
Sodium C14 Soap 27.99
Magnesium C14 Soap 5.00
Sodium Lauroyl Sarcosinate 3.00
Coco Betaine 10.00
Propylene Glycol 3.50
Petrolatum 22. 49
Sodium Chloride 2.58
Free ~atty Acid, C14 0.50
Perfume 0.50
Water 24. 44
The Plodding StamPed Bar Hardness Test
The Plodding Stamped Bar Hardness Test can be used to
differentiate the bars of this invention from other bars. Four
trade bars are selected that represent various soap processes:
SAFEGUARD9, a soap milled bar; ZEST~, a soap/synthetic milled bar;
IVORY0, a freezer bar; and LAVA~, a framed bar. Samples of these
market bars and formed bars of Example 28 and Example II are
plodded using the procedure set out below.
Overall, the market bars after plodding are much harder and
have a better smear versus Example 28 or Example II after plod-
ding. This data is detailed in Table 12. This test clearly is an
excellent method of differentiating bars containing the rigid
skeletal structure versus other bars. Simply stated, the bars of
this invention will become much more soft after replodding than
conventional bars.
The procedure is as follows:
1. Formed bars (about 2.5 Kg or greater) are placed into a
single stage plodder (4 inch/10.16 cm bonnet single stage
plodder) without vacuum and are run through a noodle plate.
The noodle plate contains nineteen 0.37 inch (0.93 cm) holes
in a 3.1 inch (8 cm) plate. The barrel temperature is set at
120-F (49~C) and the nose temperature is set at 110~F
(43.5~C)-
2. Step 1 is repeated with the noodles.
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3. The noodles of Step 2 are placed into the single stage
plodder (4 inch/10.16 cm bonnet single stage plodder) with
vacuum applied and run through a brick-shaped orifice. A
brick-shaped plug with approximate dimensions of 1.88 inches
(4.6 cm) (height) by 1.16 inches (3 cm) (width) by 3 inches
(7.6 cm) (length) is extruded. These plugs should have an
interior temperature of 90'F (32~C) to 105-F (41-C).
4. These plugs are stamped into a brick shape and are allowed to
cool to room temperature (at least 12 hours) before evalua-
tion. TABLE 12
Bar Plodder Data
Bar Hardness (mm~*
1 SAFEGUARD~ Market Bar 3.18
2 SAFEGUARD~ (Plodded/Stamped) 3.13
Delta (The value of Bar 1-Bar 2) 0.05
1 ZEST~ Market Bar 2.25
2 ZEST~ (Plodded/Stamped) 2.33
Delta (0.08)
1 IVORY~ Market Bar 1.g3
2 IVORY~ (Plodded/Stamped) 3.03
Delta (1.10)
1 LAVA~ Market Bar 1.90
2 LAVA~ (Plodded/Stamped) 2.47
Delta (0.57)
1 Example 28 (Formed Bar) 3.35
2 Example 28 (Plodded/Stamped) 10.67
Delta (7.32)
1 Example II (Formed Bar) 6.43
2 Example II (Plodded/Unstamped)18.07
Delta (11.64)
*The "hardness" of the "plodder/stamped" bars is
reported as Bar 2 in Table 12 for each bar tested. The
Bar Hardness Test is set out herein elsewhere.
20g j~,3 jl ~~O 92/09679 PCI/US91/08733 - 42 -
While not being bound to a theory, plodded bars with Delta'sof 4 or greater is a strong indication that there is a skeletal
structure in the original which is fractured or destroyed when
plodded. The hard bars of the present invention will form soft,
messy bars when plodded in a conventional bar process.
The bars of Example 28 bars are first formed using the above
freezer process. The bars of Example II are first formed using
the above-described frame bar process.
About 5-10 Kg of each bar is plodded and stamped.
The market bars are made of tallow and coconut natural soaps.
The hardness of plodded SAFEGUARD9 and ZEST~ bars are about the
same as the original bars. The IVORY~ and LAVA~ plodded bars (2)
are slightly softer than the original bars.
On the other hand, the plodded Bar 2 of Example 28 is much
softer than the original Bar 1 of Example 28. More dramatically,
the plodded Bar 2 of Example II falls apart upon plodding and is
too soft to stamp. Its hardness after plodding is that of a soft
aqueous phase, indicating that the rigidity of the skeletal
structure is essentially destroyed.
WHAT IS CLAIMED IS:
