Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 2019~6~
PERSONAL CLEANSING PRODUCT WITH ODOR C0MPATrBLE
BULKY AMINE CATIONIC POLYMER
~:
.
FIELD OF T~E INVENTION
This invention pertains to personal cleansing compositions
for personal washing, which compositions comprise quaternary amine
polymers.
BA~KGROUND OF THE INVENTION
Liquid and solid bar compositions based on soap and/or
synthetic surfactants are commonly used for cleansing the human
body. A wide variety of additives have been suggested for inclu-
sion in said compositions. Some enhance the physical properties,
e.g., bar hardness, wear rate, resistance to water. Others
enhance the in-use properties such~ as lather characteristics and
some impact on the impression the composition has on the skin both
during washing ~bar feel) and afterwards.
It has been discovered that the addition of certain polymeric
materials to such liquids and bars can have a beneficial skin
mildness effect for the user without deleteriously affecting other
product properties. In general, the useful polymers should be
soluble or dispersible in water to a level of at least 1% by
weight, preferably at least 5% by weight at 25-C. Suitable
polymers are high molecular weight materials (mass-average molecu-
lar weight determined, for instance, by light scattering, being
generally from about 20,000 to about 5,000,000, preferably from
about 50,000 to about 4,000,000, and more preferably from about
500,000 to about 3,000,000) and preferably have a thickening
ability such that a 1% dispersion of the polymer in water at 20-C
exceeds about 1 PaS(10 poise) at a shear rate of 10-2 sec-l.
Useful polymers are the cationic, nonionic, amphoteric, and
anionic polymers useful in the cosmetic field. Preferred are
cationic and nonionic resins and mixtures thereof. Highly pre-
- ferred are the cationic res;ns.
To date the preferred cationic polymers include cationic guar
gums such as hydroxyproxyltrimethylammonium guar gum.
~ - 2 - 2 0 19264
However, it has been discovered that there is an odor problem
with using such "cationic trimethylamine quaternized polymers" in
compositions having a pH of 7.5 or above. They break down and
release odoriferous labile amines.
Odoriferous labile amines are detectable at levels as low as
2 ppb. Personal cleansing products containing odoriferous quat-
ernary amine polymers are disclosed in one or more of the follow-
ing patents:
Pat. No. Date Inventor~s~
US 3,761,4189/1973 Parran, Jr.;
US 4,234,46411/1980 Morshauser;
US 4,061,60212/1977 Oberstar et a1.;
US 4,472~2979/1984 Bolich et al.;
US 4,491,5391/1985 Hoskins et al.;
US 4,540,5079/1985 Groll;er;
US 4,673,5256/1987 Small et al.;
US 4,704,22411/1987 Saud; and
Jap. J571056/30/82 Pola.
SU M M A R Y O F T H E IN V EN TIO N
The present invention relates to a personal cle~nsing composition
comprising from about 5% to about 90~o by weight of surfactant selected from
the group consisting of synthetic surfactant, alkali metal soap, and mixtures
thereof; and from about 0.?.% to about 5% by weight bulky amine cationic
polymer, said bulky amine cationic polymer being essent;ally free of potential
labile odoriferous amine groups; wherein said bulky amine cationic polymer
is: Guar (POL~IER)-CRlHCR~R3-CH2NR~R5R~ wherein Rl-R3 is a -H or
-OH: substituent, and wherein at least one of R4, R~ and R6 are selected from
the group consisting of alkyl having a chainlength of from about 2 to about 24
carbon atoms, and alkoxy allyl containing from about 7 to about 1? carbon
atoms, and mixtures thereof; and wherein said personal cleansing composition
has an alkaline pH of at least about 7.5 in a 1% aqueous solution.
DETAIL~ DESCRIPTION OF THE INVE~TION
The present invention comprises basic personal cleansing compo-
sitions comprising from about 0.7~ to about 5% by weight selected
- cationic polymer wherein each cationic group is derived from a "bulky"
amine. Compared to personal cleansing compositions
.. ~ ...
=~
2~19264
- 3 -
~ which are prepared with cationic polymers which comprise a poten-
tial labile amine moiety, e.g., trimethylamine-based cationic
polymers, the compositions of this invention consistently exhibit
superior odor stability due to the selected "bulky amine" cationic
polymers. The term "basic personal cleansing compositions" as
used herein means that the composition has a pH of at least about
7.5, preferably at least about 8.5.
Wh;le not being bound to any theory, illustrations A and B
show the theoretical degradati~on of labile amine containing
0 cationic polymers in a basic environment. Generic degradation:
(A) Polymer-CHR-CH2-N+(CH3)3 ----> polymer-CR=CH2 + N(CH3)3
where R can be meant to represent any group (e.g., H~ OH, alkyl
chain); e.g.,
(B) Guar-CH2-O-CH2-CH(OH)-CH2-N+(CH3)3 ----> Guar-CH2-O-CH2-
C(OH)=CH2 + N(CH3)3
The extent of this degradation and the effect of it on
product odor were not appreciated heretofore. The level of
hydration required to cause a problem is very low and therefore it
is extremely difficult to detect and identify the offending
~o material.
The BulkY Amine Cationic PolYmers
Bulky amine polymers are defined herein as POLYMERS with the
following non-labile cationic functional group:
(I~ (PoLYMER)-CRlH-CR2R3-NR4R5R6 wherein Rl-R3 is H or any
other substituent and R4, R5 and R6 combine with N to form an
amine with less odor impact than trimethylamine, preferably at
least one of R4, R5 and R6 js alkyl having a chain length of from
about 2 to about 24 carbon atoms, or an alkoxy alkyl group con-
taining from about 2 to about 12 carbon atoms.
30Some examples of preferred bulky amine polymers are cationic
guar gums having the following structures:
(II) Cl2H25
I
Guar-CH2-0-CH2-CH(OH) -CH2-N+CH3
CH3
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( I I I ) CH2CH20H
Guar-CH2-0-CH2-CH(OH)-CH2-N+CH3
I
CH3
An example of a bulky amine hydroxyethyl cellulose (HEC)
polymer is:
(IY) C12H25
I
HEC-CH2-0-CH2-CH(OH~-CH2-N+CH3
I
CH3
These "bulky amine" groups add additional complexity to the
preparation of the polymer and the finished compositions. They
would not be used7 except for the existence of the odor problem
with the trimethylamine derived polymer. They may. also have
improved skin conditioning benefits.
The composition of this invention preferably comprises from
about 0.2% to about 5%, preferably from about 0.5~O to about 2%, of
the cationic polymer. The average molecular wei~ht of the pre-
ferred cationic ~uar gum is from about 50,000 to about 1,000,000,
preferably from about 100,000 to about 500,0~0, and more prefer-
ably from about 250,000 to about 400,000 and the degree of sub-
stitution is from about 0.5 to about 4, preferably from about 1 to
about 2.5. Some preferred cationic ~uars (galactomannans) are
disclosed in U.S. Pat. No. 4,758,282, Stober et al., issued
July 19, 1988. The cationic guar gum polymers disclosed in commonly
assigned C~n~ n Pat. Application Ser. No. 7,001,314-1, J.R. Knochel and
P.E. Vest, filed Oct. 24, 1990, would be suitable when the cationic groups are
substituted with bully amine groups.
Other bully amine cationic polymeric skin conditioning agents useful
in the present invention have molecular weights of from 1,000 to 3,000,000.
Useful polymers are selected from the group consisting of:
(I) cationic polysaccharides;
(II) cationic copolymers of saccharides and synthetic cationic
monomers, and
~ 5 ~ 20i~26~
(III) synthetic polymers selected from the group consisting
of any other synthetic polymer containing pendant
quaternary amine groups, e.g., quaternized silicones and
quaternized methacrylates.
s Specific examples of members of the bulky amine cationic
polysaccharide class include the cationic hydroxyethyl cellulose,
e.g., LM-200 made by Union Carbide Corporation.
The cationic copolymers of saccharides and synthetic cationic
monomers useful in the present invention encompass those con-
taining the following saccharides: glucose, galactose, mannose,
arabinose, xylose, fucose, fructose, glucosamine, galactosamine,
glucuronic acid, galacturonic acid, and 5 or 6 membered ring
polyalcohols. Also included are hydroxymethyl, hydroxyethyl and
hydroxypropyl derivatives of the above sugars.
The boiling points of some exemplary substituted amines are
set out in Table 1.
TABLE 1
Eliminated Amine Boilinq Point/-C
Labile Amine
Trimethylamine 3
BulkY Amine
Dimethylethylamine 36
Methyldiethylamine 63
Triethylamine 89
2s Dimethyloctylamine 195
Dimethylcyclohexylamine158
Dimethylbenzylamine 183
Dimethylethanolamine 133
Diethylethanolamne 161
For a homologous series of compounds ~e.g., tri-substituted
amines), volatility decreases with increasing molecular weight.
Volatility is dependent, among other things on the boiling point
of the neat component. Odor impact also has a strong dependence
on the amount of volatilized material that reaches the nose.
Table 1 demonstrates the significant effect which adding "bulky"
groups has on volatility and, hence, odor impact of amines. For
pure hydrocarbon substitution, the larger the alkyl chains (or the
2~192~4
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- larger the degree of long chain substitution) the lower the odor
impact. Thus, bulky amines have boiling points of greater than
ambient temperature, and preferably at least about 30C, more
preferably more than about 80-C.
The Surfactant ~om~onent
The surfactant component of the present compositions com-
prises alkali metal soap or synthetic surfactant or mixtures
thereof.
Alkali metal soaps can be made by direct saponification of
the fats and oils or by the neutralization of the free fatty acids
which are prepared in a separate manufacturing process. Par-
ticularly useful are the sodium and potassium salts of the mix-
tures of fatty acids derived from coconut oil and tallow, i.e.,
sodium and potassium tallow and coconut soaps.
The term "tallow" is used herein in connection with fatty
acid mixtures which typically have an approximate carbon chain
length distribution of 2.5X C14, 29% C16, 23% C18~ 2% palmitoleic,
41.5Yo oleic and 3% linoleic. (The first three fatty acids listed
are saturated.) Other mixtures with similar distribution, such as
the fatty acids derived from various animal tallows. The tallow
can also be hardened (i.e., hydrogenated) to convert part or all
of the unsaturated fatty acid moieties to saturated fatty acid
moieties.
When the terms "coconut oil" and "coconut fatty acid" (CNFA)
are used herein, they refer to fatty acid mixtures which typically
have an approximate carbon chain length distribution of about 8%
C7~ 7% C10~ 48% C12, 17% C14~ 9% C16, 2X C18, 7r. oleic, and 2Yo
linoleic. (The first six fatty acids listed are saturated.)
Other sources having similar carbon chain length distribution such
as palm kernel oil and babassu kernel oil are included with the
terms coconut oil and coconut fatty acid.
A preferred soap bar of this inYention comprises soap as its
primary or sole surfactant It also contains as an essential
ingredient a skin conditioning amount of a hydrated, cationic guar
gum provided by a cationic guar gum polymer. This polymer is
uniformly distributed in the soap bar matrix without affecting the
smooth feel of the dry or wet bar.
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Another preferred toilet bar is based on mild synthetic
surfactants as disclosed in commonly assigned U.S. Pat. No.
4,673,525, Small et al., issued June 16, 1987.
Synthetic detergents can also be present in compositions
herein. Preferred types of synthetic detergents are of the
anionic or nonionic type. Examples of anionic synthetic deter-
gents are the salts of organic sulfuric reaction products such as
alkyl sulfates having the formula R24OSO3M;
alkyl sulfonates having the formula R24SO3M;
alkyl ether sulfates having the formula R24(0C2H4)XOSO3M;
alkyl mono glyceride sulfonates having the formula
CH
I
R240 - CH0 H
I
H - C - H
I
X _ y
and alkyl benzene sulfonates having the formula
R24 ~ - SO3M
In the above formulae, R24 is a straight or branched chain
alkyl of from about 8 to about 24 carbon atoms; M is an alkali
metal or ammonium ion; x is a number of from 1 to about 10; y is a
number of from 1 to 4; and X is selected from the group consisting
of chlorine, hydroxyl, and -SO3M, at least one X in each molecule
being -SO3M. Examples of nonionic synthetic detergents are
ethoxylated fatty alcohols (e.g , the reaction product of one mole
of coconut fatty alcohol with from about 3 to about 30 moles of
ethylene oxide) and fatty acid amides such as coconut fatty acid
monoethanolamide and stearic acid diethanolamide. Although it may
be desirable in some instances to incorporate synthetic detergents
into the compositions of the present invention, the compositions
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herein can be free of synthetic detergents. Preferred are the
mild synthetic surfactants disclosed in U.S. Pat. No. 4,673,525,
Small et al., issued June 16, 1987.
Insoluble Alkaline Earth Metal SoaDs
Insoluble alkaline earth metal soaps such as calcium stearate
and magnesiu~ stearate can also be incorporated into compositions
of the present invention at levels up to about 30%. These materi-
als are particularly useful in toilet bars in which synthetic
detergents are present in that they tend to reduce the relatively
high solubility which such bars normally have. These alkaline
earth metal soaps are not include~ within the term "soap" as
otherwise used in this specification. The term "soap" as used
herein refers to the alkali metal soaps.
Ootional ComDonents
The compositions of the present invention can contain
optional components such as those conventionally fou~d in personal
cleansing products. Conventional antibacterial agents can be
included in the present compositions at levels of from about 0.5%
to about 4%. Typical antibacterial agents which are suitable for
use herein are 3,4-di and 3,4',5-tribromosalicyla-anildes; 4,4'-
dichloro-3-(trifluoromethyl)carbanilide; 3,4,4'-trichlorocarbanil-
ide and mixtures of these materials. Conventional nonionic
emollients can be included as additional skin conditioning agents
in the compositions of the present invention at levels up to about
40%, preferably at levels of from about 1% to about 25%. Such
materials i~clude, for example, mineral oils, paraffin wax having
a melting point of from about 100F., fatty sorbitan esters (see
U.S. Pat. No. 3,9~8,~55, Seiden, issued Oct. 26, 1976, lanolin and lanolin
derivatives, esters such as isopropyl myristate and triglycerides such as coconut
oil or hydrogenated tallow.
Free fatty acid such as coconut fatty acid can be added to the
compositions herein to improve the volume and quality (creaminess) of the
lather produced by the compositions herein.
Conventional perfumes, dyes and pigments can also be incorporated
- into compositions of the invention at levels up to about
. . .
.' 3._
2Q~9~
g
= 5%. Perfumes are preferably used at levels of from about 0.5% to
3% and dyes and pigments are preferably used at levels of from
about 0.001% to about 0.5%.
Bar PreParation
- Toilet bars of the present invent;on can be prepared in any
conventional manner. E.g., the bulky amine cationic polymer can
be added to noodles of the base soap mixture containing from about
10% to about 22% moisture in an amalgamator. Any optional ingre-
dients such as perfumes, dyes, etc., are also added to the amal-
gamator. The mixture is processed in the amalgamator and milled
in the conventional manner under conventional conditions. It is
then extruded (plodded~ into logs for cutting and stamping into
toilet bars.
In a method of making the bar of the present invention, the
bulky amine cationic polymer is added to soap noodle and ~ixed in
the soap mixing steps of the soap bar making process.
The soap bars of this invention preferably contain up to 20%
of a synthetic surfactant. If a synthetic surfactant is included,
a mild one is preferred. A mild synthetic surfactant is defined
herein as one which does relatively little damage to the barrier
function of the stratum corneum. The mild surfactant is prefer-
ably used at a level of 0-20%~ preferably about 2-15%. The fatty
acid soap and mild surfactant mixture preferably has a ratio of
Z.5:1 to 37:1, preferably from 2.5:1 to 14:1, and most preferably
from 6.5:1 to 14:1, soap:synthetic.
A preferred soap bar of this invention also contains from
about 270 to about 17Y. moisturizer, preferably one selected from
glycerin and free fatty acid or mixtures thereof. The more
preferred bar of this invention contains at least 4Y. moisturizer.
Some preferred mild synthetic surfactants useful in this
invention include alkyl glyceryl ether sulfonate (AGS), anionic
acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, alkyl
glucosides, acyl isethionates, alkyl sulfosuccinate, alkyl phos-
phate esters, ethoxylated alkyl phosphate esters~ alkyl ether
sulfates, methyl glucose esters, protein condensates, mixtures of
alkyl ether sulfates and alkyl amine oxides, betaines, sultaines,
and mixtures thereof. Included in the surfactants are the alkyl
,
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ether sulfates with 1 to 12 ethoxy groups, especially ammonium and
sodium lauryl ether sulfates. Alkyl chain lengths for these
surfactants are Cg-C22, preferably C10-cl8~ The most preferred
mild surfactant is sodium CN AGS.
The following examples are presented by way of illustration
only.
EXAMPLES 1 AN~ 2
Toilet bars made using the ingredients set out in Table 2.
TABLE 2
Ex. 1 Ex. 2
Ingredient Parts parts
Sodium Tallowate(1~ 32.90 32.90
Sodium Cocoate(1) 32.90 32.90
Water 9.50 9.50
Sodium Cocoglyceryl Ether
Sulfonate (AGS) 8.~30 8.80
Glycerin 4.00 4.00
Coconut Fatty Acid 3.80 3.80
Triclocarban 1.50 1.50
Sodium Chloride 1.20 1.20
Fragrance 1.20 1.20
Polyquaternium-7(2) 1.00 1.00
LM-200(3) 1.00
Guar-HPTC(4) - 1.00
Titanium Dioxide 0.35 0.35
Tetrasodium EDTA 0.06 0.06
BTH(5) 0.02 0.02
Miscellaneous(6) * *
Totals100.00 100.00
(1) The values stated for sodium tallowate and sodium
cocoate include a low level (>0.1%) of unsaponifiable
material.
(2) The trade mark for Polyquaternium-7 is Meraquat 500.
(3) LM-200 is a cationic cellulosic polymer comprising a
- bulky cocoyl amine.
-
.~
~ 11- 2019264
(4) Guar ~PTC i~ guar hyd~ y~lopyltriammonium chlolide for
which the trade mark is Jaguar C-15 (Hi-Tek). Mol~cular
weight is about ~00,000 + 75,000.
(5) BHT is included in the respective perfume formulas to
impart preservative/antioxidant properties both to the
perfume and to the finished bar formula.
(6) "Miscellaneous" includes a low level of sodium sulfate
and unsulfonated alcohol which come in, e.g., as a
by-product of the AGS stream.
o In general, making procedures common to those used for
conventional toilet soap bar making are employed.
Mixinq/Millinq Steps
Polymer Addition SteP
Plodded soap noodles are conveyed to a continuous mixer (CM)
where approximately 1.0 part of cationic polymer is introduced,
mixed, and plodded with the soap noodles. Uniform distribution
during this addition and mixins step is important for acceptable
bar feel performance. The polymer/soap noodles (generic noodles~
are conveyed to milling.
Generic Millinq SteP
Two four-roll soap mills (feed, stationary, middle, and top
rolls) are used in this step. This is a split milling (two set of
mills are used in parallel) process to obtain a homogeneous mix.
Efficient milling is needed in this intimate mixing step.
DrY Mixina Step
The generic noodles are conveyed to a second process system
continuous mixer (CM) for the addition and mixing of other minors.
This mix is plodded and conveyed to the third process CM.
Wet Mixinq Step
The perfume and NaCl/sodium ethylene diamine tetra acetate
(EDTA) solution are added and mixed in this wet mixing (CM) step.
This finished soap formula is then plodded into soap noodles and
conveyed via a transport plodder to a final milling step.
The mixture is milled using a four-roll mill, plodded, and
then stamped into toilet bars of any convenient si~e and shape.
- The resulting bars are tested for odor. The bars have a pH of 9.5
in a 1% aqueous solution.
. ..
7 ~ 2 6 ~
Odor Test Procedure
PolYmer Cleaninq
Stock samples of polymer are cleaned by swelling the polymer
with water followed by extensive aeration. These "cleaned"
polymers are fairly amine odor-free. After long storage times,
some of these polymers exhibited a slight, but recognizable amine
odor. Bulky modified polymers required little, if any, cleansing
prior to testing/evaluating.
Effects Testinq Procedures
The general procedure followed in evaluating the effects of
pH on polymer or final product odor was to place about 200 mg of
the clean polymer (or a finished product) in a screw-top vial (8
dram) and then add the test solution (buffers at pH values o~ 7,
10, or 14~. The vials are capped and the odor allowed to build up
for a short amount of time. Odor is evaluated via olfactory
sensing by a panel of experts.
The pH buffers are commercially available buffers:
pH 7 - KH2P04-NaOH
pH 10 - H3B03-KOH
pH 14 - 1N NaOH.
TABLE 3
Odor Evaluation of PolYmers and Products Under
Induced Alkaline Conditions (PH -10-14)
PQ1 Ymer/Product Odor Evaluation
JR-400 Strong amine odor
Jaguar C-15 Strong amine odor
LM-200 No amine odor
Product of Ex. 1 ~o amine odor
Product of Ex. 2 Strong amine odor
Note: Ex. 1 product produced with LM-200
Ex. 2 product produced with Jaguar
JR-400 made by Union Carbide Corporation and JAGUAR C-15 made
by Hi-Tek Polymers, Inc., are outside the selected polymers of
this invention.
