USOO54.

82643A
United States Patent (19) 11 Patent Number: 5,482,643
Chambers et al. (45) Date of Patent: Jan. 9, 1996
54) SOAP BARS MADE WITH TERNARY 3,376,229 4/1968 Haass .................................. 252/121 X
SYSTEM OF FATTY SETHIONATE ESTER, 4,234,464. 11/1980 Morshauser ...
FATTY ACID, AND WATER 4,536,338 8/1985 Urban et al. ...
4,707,288 11/1987 Irlam et al. ............................. 252/121
75 Inventors: John G. Chambers; Geoffrey Trlam, 5,030,376 7/1991 Lee et al. ............... . . 252/121 X
both of Merseyside, Great Britain 5,284,598 2/1994 Subramanyam et al. ............... 252/121
FOREIGN PATENT DOCUMENTS
73) Assignee: Lever Brothers Company, DIvision of
Conopco, Inc., New York, N.Y. 249474 12/1987 European Pat. Off..
434460 671991 European Pat. Off..
0472.320 2f1992 European Pat. Off..
21 Appl. No.: 246,047 537964 4/1993 European Pat. Off. .
22 Filed: May 18, 1994 2285.452 4f1976 France.
1294.754 1/1972 United Kingdom.
30 Foreign Application Priority Data 1381773 1/1975 United Kingdom.
90/13283 1/1990 WIPO.
May 19, 1993 GB) United Kingdom ................... 931.0323 93,06205 4/993 WIPO.
(51 Int. Cl. ............................. C11D 1/755; C11D 3/20; Primary Examiner-Douglas J. McGinty
C11D 3/34; C11D 1/04 Attorney, Agent, or Firm-Ronald A. Koatz
52 U.S. Cl. .......................... 252/121; 252/108; 252/132;
252/134; 252/DIG. 4; 252/DIG. 14; 252/ DIG. 16;
252/173 57 ABSTRACT
58) Field of Search ............................ 252/DIG. 16, 108, Formation of soap bars comprising fatty isethionate esters
252/121, DIG. 4, 132, 134, DIG. 14, 173 and fatty acid can be achieved without an energetic mixing
step by forming an isotropic solution of the fatty isethionate
56) References Cited ester, fatty acid and water.
U.S. PATENT DOCUMENTS
2,894,912 7/1959 Geitz ....................................... 252A12 3 Claims, 3 Drawing Sheets
U.S. Patent 5,482,643
U.S. Patent 5,482,643

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 5,482,643
1. 2
SOAP BARS MADE WITH TERNARY one-pass mixing. These alternatives to the use of conven
SYSTEM OF FATTY ISETHIONATE ESTER, tional batch mixers have proved expensive to install and
FATTY ACID, AND WATER operate.
We have now determined how the required intimate
The present invention relates to improved soap bars and mixture may be formed without use of energetic mixing. We
in particular to soap bars comprising synthetic surfactant have determined that by formation of an isotropic solution of
components in addition to fatty acid soaps. a fatty isethionate ester, fatty acid and a relatively small
Soap bars are known from antiquity. Fatty acid soaps are amount of water, the energetic mixing step can be avoided
however relatively harsh surfactants and much effort has while the process temperature need not exceed 130° C.
been expended in formulating mild soap bars by replace 10 According to a first aspect of the present invention there
ment of a portion of the soap with other surfactant compo is provided a liquid isotropic mixture comprising:
lents. a) a first surfactant component having a T in excess of
Mild soap bars are generally manufactured from a feed 15° C.
stock comprising neat soap and one or more synthetic b) fatty acid in an amount such that the ratio of first
co-active components. These are combined together in an 15 surfactant component to fatty acid is not more than 2:1,
intimate mixture and formed into bars. and,
Soap plants typically comprise a plurality of mixing, c) 2-15% water.
working, heating and cooling apparatus for the treatment of The T is the minimum temperature above which the first
the feedstock. The heating apparatus conventionally com surfactant component forms a liquid crystalline phase: i.e.
prises steam jacket and steam injection apparatus. By use of 20 the T of a material indicates the lowest temperature at
super-heated steam it is practical to raise the temperature of which significant quantities of the material will dissolve in
Water.
components to, at most, 150° C. To reach temperatures in Under factory and transport conditions components hav
excess of 150° C., specialised apparatus must be employed. ing a T below 15° C. will generally be treated as liquids,
Consequently, for reasons of economy, the hot portions of whereas components having a Tabove 15°C. will generally
soap plants normally operate at maximum temperatures in 25
exhibit the properties of, and be handled as, solids.
the range 100°-130° C., and have normal operating tem Generally, the first surfactant component will be a fatty
peratures in the range 85-95°C. isethionate ester.
Certain types of mild soap bar include synthetic co-active Commercially available fatty isethionate esters typically
components which require high temperatures, typically in have T values above 30°C. These values are high compared
excess of 100° C., to enter a molten state. Amongst these 30 with surfactants such as sodium lauryl ether sulphates
high melting components are the so-called 'fatty isethionate (SLES), a polyoxyethylated surfactant with an average of
esters', which become pumpable only above 100-150° C. three ethoxy units per molecule: which has a T of less than
One advantage of using these high melting components is 0° C. and Disodium lauryl monethoxy-sulphosuccinate
that they give structure to the eventual bar. Other, low (DMLS) again having a T value less than 0° C.: i.e. both
melting, liquid or highly soluble synthetic components, such 35 SLES and DLMS can be handled as liquids.
as sodium lauryl ether sulphate and alkyl glyceryl ether Typically, the fatty isethionate ester (component a) is an
sulphate are known, but do not provide structure in the ester of fatty acids having Co-Cs average chain length
eventual product: these products require additional structur with isethionates. Mixed esters of fats obtained from the
ing agents such as polymers, long chain fatty acids, and saponification of coconut and other vegetable oils and fats,
electrolytes the presence of which can interfere with the 40 and fractions thereof are particularly preferred.
lather performance of the soap bar and add to the cost of the Cocoyl isethionate, comprising fatty acid residues con
product. taining a high proportion of lauric acid residues is the most
Fatty isethionate esters are typically used in soap bar preferred isethionate for use in the embodiments of the
products at levels of around 25 to 70% wt. At very low levels present invention. This material ms available from many
sources, including Mazer (as the Jordapon Series' (TM)),
of fatty isethionate, i.e. well below 30% on product, mild 45
GAF (as Fenopon (TM) ACT8 and AM78), AKZO (as Elfan
ness benefits, somewhat reduced, are still obtained. At (TMAT84 and 84G), Hoechst (as Hostapon (TM) KA and
higher levels of fatty isethionate, i.e. above 70%, products Hoe S 3390-2), ICI (as Arlatone TM SCI and Tensianol
become unprocessable due to the physical properties of the TM 399 series) and Finerex (as Tauranol series surfac
fatty isethionate, leading to a product which is too hard to tants).
process. 50 Generally, the fatty acid (component b) comprises one or
As the aforementioned melting points of 100-150° C. more fatty acids obtained from vegetable or animal oils and
are at or above the upper limits of the operating temperature fats. Mixtures of fatty acids having an average chain length
of the plant, energetic mixing at a temperature of around 70 of C-C are preferred. In particular, fatty acids with chain
C. is used in order to form an intimate mixture of these lengths of Co-C as these are simple to process due to their
components with the balance of the components of the bar 55 relatively low melting point. Fatty acids with C-C1s
so as to avoid the formation of a gritty product. Moreover, chains are more difficult to process but have a better bar
significant hydrolysis of the isethionates begins to occur at structuring effect due to their higher melting points. Most
temperatures above 110° C. preferable are saturated fatty acids as these are chemically
One problem with the energetic mixing step is that it more stable than the corresponding unsaturates.
must generally be conducted as a batch operation or, where 60 Typical sources of suitable fatty acids are tallow, palm,
semi-continuous operation is desired, a plurality of mixers lard, tallow stearines and palm stearines, soya bean oil,
may be employed in a phased, parallel, batch process. sunflower oil, linseed oil, rice bran oil and lauric oils, such
Alternatives to batch operation have included re-cycling of as coconut, palm kernel, babassu and other palm nut oils rich
a large portion of the product such that it passes through the in laurics.
mixer more than once. Other alternatives have included the 65 Permissible ratios of components (a), (b) and (c) are
use of highly specialised mixers of the cavity transfer type defined by reference to a phase diagram as elaborated upon
which, while being sufficiently energetic, are also capable of hereafter. If the ratio of first surfactant component to fatty
 5,482,643
3 4.
acid exceeds 2:1, products are formed which are non In order that the present invention may be further under
homogeneous and difficult to process due to phase separa stood, it will be illustrated hereafter by way of example and
tion. with reference to the accompanying figures which shows
According to a second aspect of the present invention phase diagrams for mixtures of fatty acid, fatty isethionate
there is provided a process for the manufacture of soap bars ester and water, indicating the region wherein isotropic
which includes the step of forming a liquid isotropic mixture systems are formed.
comprising: The enclosed FIGS. 1, 2 and 3 are phase' diagrams for
a) a fatty isethionate ester, mixtures of fatty acid, fatty isethionate esters and water
b) fatty acid in an amount such that the ratio of fatty indicating the region (I) wherein isotropic systems are
isethionate ester to fatty acid is not more than 2:1, and, 10 formed. Region (P) is that of a multiphase system.
c) 2-15% water, EXAMPLES
said mixture being at a temperature of 40°-110° C.
Typically, the process further comprises the step of com In FIG. 1, points 1-9 indicate embodiments of the inven
bining the isotropic mixture of the above mentioned com 15 tion as set out as examples 1-9 in table 1 below. These form
ponents (a), (b) and (c) with neat soap and processing the an isotropic system at temperatures of 85°C. Points 10-23
resulting product into soap bars. are comparative examples which do not form an isotropic
Preferably, said combination of the isotropic mixture and mixture, but form a higher viscosity, phase-separated system
neat soap is performed by injection of one of said combined at 85° C.
components into the other of said combined components. 20 Table 1 below gives both embodiments of the present
More preferably, the isotropic mixture is injected into the invention and comparative examples. Composition data in
neat soap. Simple mixing means can be employed as an the table is such that the wt % DEFI, wt % FFA and wt %
alternative to injection apparatus. water are given with respect to the isotropic mixture formed
It should be noted that while the isotropic mixture is from them. DEFI is around 70% directly esterified cocoyl
generally stable at temperatures above 40° C. the preferred 25 fatty isethionate as obtained from the Lever Brothers Com
temperature for performance of the method is 70°-110° C. pany, the bulk of the remainder of the material being fatty
In this temperature range the process stream is pumpable acids and free isethionate.
and the potential for hydrolyis is minimised. Taking example 5 as representative, the isotropic mixture
Overall, the soap making process of the present invention was formed by combination of the three components (coco
can be seen as:
A) forming a liquid isotropic mixture comprising: 30 nut fatty acid/DEFI flake slurry plus water) in a electrically
heated, thermostatted vessel at a temperature of 80 C., with
a) a fatty isethionate ester, mechanical stirring. The mixture was injected into a neat
b) fatty acid in an amount such that the ratio of fatty soap stream emerging from the heat-exchangers of a con
isethionate ester to fatty acid is not more than 2:1, and, ventional vacuum soap drier. At the exit of the heat-ex
c) 2-15% water, 35 changers commonly used in the soap making process, the
said mixture being at a temperature of 40°-110° C., neat soap streamis generally at a temperature of around 130
B) preparing a neat soap at a temperature of 80°-95 C., C. As is commonplace in soap making plant, a fatty acid
and, injection port is provided at this location for the production
C) combining (A) and (B) in a ratio such that the final of so called 'super-fatted' soaps. This port was used for the
product comprises: 40 injection of the fatty acid/DEFI mixture.
a) 5-30% fatty isethionate ester, The injected stream was mixed in-line with the neat-soap
b) at least 2.5% fatty acid, and the combined process stream sprayed into a vacuum
drier and dried to a final water content of 12%. Thereafter,
c) 8-18% water, and, the process stream was milled, plodded and stamped into
d) 40-80% soap, and, 45 soap bars.
D) forming the product of step (C) into bars.
According to a third aspect of the present invention there TABLE 1
are provided soap bars produced by the above-mentioned wt % wt % wt %
method. DEF FFA Water DEFIFFA
In typical embodiments of the invention, the overall fatty 50
isethionate ester content of finished soap bars does not Example
exceed 30% wton bar. If this figure is exceeded, the related 1 6 34 5 1.79
level of fatty acid in the finished product is such that high 2 43 52 5 0.83
wear rates and poor lather result. In practice, there is no 3 52 43 5 1.21
critical, minimum level for the fatty isethionate ester 55 4. 41 49 10 0.84
although reduction of the level of this component leads to 5 49 4. 10 120
6 40 50 10 0.80
progressively less mild bars. In embodiments of the inven 7 35 60 5 0.58
tion, the fatty isethionate ester level in the finished bars will 8 25 70 5 0.36
generally lie between 5-30wt.% on bar, preferably between 9 5 90 5 0.06
7-15 wt % on bar, and most preferably around 10wt % (i.e. 60 Comparatives
8-12wt %) on bar. 10 57 33 10 173
Preferred ratios of fatty isethionate ester to fatty acid fall 11 39 46 15 0.85
in the range 1:1 to 2:1. Excess of fatty acid leads to high 12 47 38 15 24
levels of fatty acid in the final product. This can be disad 13 54 31 15 14
14 65 30 5 2.20
vantageous where the fatty acid is required to provide 65 15 64 36 O 70
structure. An isotropic melt cannot be formed when the fatty 16 55 45 O 120
acid level is too low.
 5,482,643
5 6
Products were assessed with regard to grit. Grit was
TABLE 1-continued assessed subjectively by a panel of 20 trained operators.
Operators scored the bars on a scale of 1 to 5 with 1
DEF FFA Water DEFIFFA representing Smooth bars; 2: slightly sandy; 3: sandy,
slightly gritty; 4: gritty and 5: very gritty. For commercial
17 45 55 O 0.82 products, an acceptable score on this scale is <2. The mean
18 40 60 O 0.67 score for each bar was calculated. The bars were first
19 35 50 15 0.70 plunged into water at 20° C. and rotated in the hand for 30
20 30 60 10 0.50
2. 30 70 O 0.43 seconds before an assessment was made.
22 10 90 0 0.11 10
23 10 80 10 0.12
24 40 35 25
25 28 46 26 Example No Grit Score
5 1.1
A 3.2
The DEFI and fatty acid content of the final product is 15 B 3.2
determined by the rate of injection of the DEFI/fatty acid C 2.5
mixture into the soap stream. Pilot plant scale samples were Controli 1.6
produced with 9% wt DEFI and 7.5% FFA on product.
Bars according to the present invention were subjected to #Control is a conventional 60/40 tallow/coconut soap base with 7.5% free
fatty acid.
a so-called "flex-wash' test as known in the industry, and 20
were shown to be milder on the skin than conventional soap # Control is a conventional 60/40 tallow/coconut soap
bars. In this in-vivo test, cumulative erythema scores are base with 7.5% free fatty acid.
determined and a minimum difference of 3.33 is required for The results demonstrate the product of example 5 was
a 95% confidence interval. The test gave results as: essentially grit-free', scoring less than 2 on the grit/sand
Conventional toilet soap (80/20): 22.67 25 score. Products made by the high shear routes all had scores
in excess of 2 and, therefore, are unacceptable for commer
Embodiment of example 5: 17.87 cial purposes.
From the above data it can be seen that the bars according We claim:
to the present invention are significantly milder than the 1. A ternary liquid isotropic mixture which is liquid at
control. temperatures of 40°-110°C., said mixture consisting essen
FIG. 2 shows results obtained with Jordapon CIT0 30 tially of:
(55-60% active material) whereas FIG. 3 shows results a) a fatty isethionate ester having a T in excess of 15° C.,
obtained with Jordapon CI-Prilled (circa 80% active, 20% b) fatty acid in an amount such that the ratio of fatty
fatty acids, free isethioninate etc). In FIGS. 2 and 3, stable isethionate ester to fatty acid is not more than 2:1, and,
isotropic formulations are indicated by the index 'I' whereas 35 c) 2-15% wt. water.
unstable, multi-phase formulations are indicated by the 2. A soap bar produced by a process comprising the steps
index "2P. It can be seen that the regions of stability are of:
generally similar in shape allowing for the variation in the A) forming a ternary liquid isotropic mixture consisting
contents of the raw materials. essentially of
For comparison purposes, a series of products with simi a) a fatty isethionate ester,
40
lar levels offatty acid and DEFI (10% wtDEFI and 7.5% on b) fatty acid in an amount such that the ratio of fatty
total product and approximately 12% water) were prepared isethionate ester to fatty acid is not more than 2:1, and,
by a series of routes which involved mixing the dried
materials via high shear mixing. c) 2-15% water,
said mixture being at a temperature of 40°-110° C.,
EXAMPLE A
45 B) preparing a liquid neat soap at a temperature of 80°-95
C., and,
Milling, followed by use of a cavity transfer mixer at 35° C) combining (A) and (B) in a ratio such that the final
C. and finally by vacuum plodding and stamping. product comprises:
a) 5-30% fatty isethionate ester
EXAMPLE B
50 b) at least 2.5% fatty acid,
c) 8-18% water, and,
Zblade mixer used at 58 C. followed by milling, vacuum d) 40-80% soap, and,
plodding and stamping. D) forming the product of step (C) into bars.
55
3. A mixture according to claim 1 wherein the fatty
EXAMPLE C isethionate ester (component a) is an ester of fatty acids
having Co-C1s average chain length with isethionates.
Zblade mixer used at 58° C. followed by milling, vacuum
plodding and stamping. ck k k sk. xk