Note: Descriptions are shown in the official language in which they were submitted.
Express Mail No.: MB106539521
Attorne s Docket No.: I.R. 4748
201~3~ 0
LIQUID DISHWASHING DETERGENT COMPOSITION
This invention relates to liquid dishwashing
detergent compositions. More particularly, it relates to
such compositions which are suitable for hand washing of
dishes, and which lea~e the skin of the hands non-greasy and
noticeably smoother than it is after washing dishes with
ordinary or conventional liquid dishwashing detergent composi-
tions. Additionally, the invention also relates to processes
for washing dishes with such detergent compositions and to
processes for manufacturing such compositions.
Light duty liquid dishwashing detergent compositions
have been and are presently being commercially marketed for
use in diluted form in hand washing of dishes or in dishpan
dishwashing. Highly alkaline granular dishwashing compositions
are often employed for washing dishes in automatic dishwashing
machines and recently liquid dishwashing compositions intended
for use in automatic dishwashers have also been marketed.
Despite the increasing popularity of automatic dishwashers
there is still a significant portion of the dishwashing
detergent composition market that is held by compositions
intended for hand dishwashing applications. Unlike automatic
. .
dishwasher detergent compositions which are never in contact
with human skin, ~hose intended for hand dishwashing applications
201~3~0
should be mild to the skin, and yet must still be effective
cleaning agents. This can be difficult to accomplish because
immersion of the hands in dishwater removes natural oils
from the skin and tends to make it lose its suppleness, so
that the hands often may feel dry and hard to the touch.
Merely adding emollients to the dishwashing composition has
not been found to be a successful solution to this problem
because their effects are usually insufficient. Now, however,
applicants ha~e discovered that certain types of dishwashing
detergent compositions, which are of s~tisfactory foaming
capability, can effectively wash dishes and at the same
tlme leave the hands feeling smooth and non-greasy, which
represents a significant advance in the hand dishwashing
detergent composition art.
In accordance with the present in~ention a liquid
dishwashing detergent composition for hand washing of dishes,
which is mild to human hands and leaves the skin thereof notice-
ably smoother than a control dishwashing composition, comprises
5 to 40% of synthetic organic detergent selected from the group
cons~sting o~ synthetic organic anionic detergents and synthetic
organic nonionic detergents, and mixtures thereof, and 0.1 to
10% of a skin smoothening compound (SSC) which is a hydro-
carbon, an organic acid, a~ ester, an amide, an amine, a quaternary
ammonium compound, such as a salt, e.g., a chloride, or an al-
cohol, each of which includes in its formula a hydrocarbyl chainof at least 25 carbon atoms, or any mixture thereof, in
.
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2~1~3~0
an aqueous medium. The invention also includes processes
for using the invented compositions and for manufacturing
them.
A search of prior art patents in Class 252 r subclasses
108~ 114~ 115~ 157~ 162~ 169~ 173~ 550~ 551 and 558r and in
Digests 1, 5 and 14 did not result in the finding of any
references which teach the present invention. Among the
patents noted in the search were the following:
1 r 703 ~ 602; 4 r 056 r 481; 4 r 247 r 424;
3r708~435; 4~192~761; 4~446~042;
3~798~182; 4~228~044; 4~673~525; and
4~035~514; 4~708~813~
Some of the mentioned patents refer to incorporating emollients
in detergent compositions to make such compositions milder
15 to the human skin,with which it comes into contact during
use. Among various adjuvants mentioned in the references
are beeswax, paraffin wax, petrolatum, petroleum jelly and
microcrystalline wax. Some of the patents describe the
employment of petrolatum and beeswax as additives to deter-
20 gent compositions for diminishing foaming characteristics ofsuch compositions, and one mentions the use of moisturizers,
such as petrolatum and beeswax, in mild skin cleansing
compositions.
Although the art indicates that materials which
25 contain compounds that include straight chain alkane groups
of 25 carbon atoms or more have been suggested for inclusion
in various products, including detergent compositions,
nowhere is the importance of the C25 normal alkyl moiety mentioned.
20~3~
The! art does not disclose nor does it suggest applicants'
invention of dishwashing detergent compositions containing
such compounds, which compositions are satisfactorily foaming,
non-greasy and especially mild to the hands. Furthermore, the
art does not describe or suggest applicants'use of such
compositions and their process for the manufacture thereof,
which results in the composition produced being especially
effective in smoothening the skin of one who uses it for hand
washing of dishes.
The required synthetic organic detergent component
of the present compositions is a synthetic organic anionic
detergent or synthetic organic nonionic detergent or a mixture
thereof (and of course, mixtures of anionic detergents and
mixtures of nonionic detergents may also be employed~.
Optionally, amphoteric, ampholytic, zwitterionic and even
cationic detergents and surface active agents (surfactants~
may be preRent in the invented compositions. Various suitable
anionic and nonionic detergents that may be employed are
li.sted in McCutcheon's Detergents and Emulsifiers, North
American Edition, 1984, which is incorporated by reference
herein. Of those compounds the preferred anionic detergents
are of the sulfated and/or sulfonated types, which may be
designated as "sulf(on~ated". Such detergents are water
soluble salts of a lipophile sulfuric or sulfonic acid. The
lipophilic moiety of such acid will normally be of 8 to 30
carbon atoms and will desirably include an alkyl group,
201~ 0
preferably a chain, of 8 or 10 to 18 carbon atoms, more
preferably 12 to 14 or 16 carbon atoms, e.g., about 12
carbon atoms. Among such anionic detergents there may be
mentioned, as exemplary thereof, the higher alkyl sulfates,
the linear higher alkylbenzene sulfonates, the paraffin
sulfonates, olefin sulfonates, monoglyceride sulfates and
higher fatty alcohol lower alkoxy sulfates. Such higher
fatty alcohol or higher alkyl lower alkoxy sulfates are prefer-
ably of 10 to 14 or 16 carbon atoms in the higher fatty
alcohol or alkyl moiety thereof and of up to 20 moles of
lower alkoxy per mole, such as 2 to 20, more preferably 2 to
4 or 6, (with the lower alkoxy normally being ethoxy but
sometimes also including up to 30% propoxy). ~ particularly
preferred higher fatty alcohol poly-lower alkoxy sulfate is
that wherein the higher fatty alcohol is lauryl alcohol, which
is triethoxylated. The anionic detergents are normally
employed as watex soluble salts of alkali metal, ammonia or
alkanolamine, such as triethanolamine~ For the most prefer-
red anionic detergents, which are desirably utilized together
in applicants' invented anionic compositions, such salts
will be sodium salts and the compounds will be sodium linear
dodecylbenzene sulfonate and sodium lauryl alcohol triethoxy
sulfate.
When the invented detergent compositions are to be
nonionic or primarily nonionic, the major detergent component
'~01~0
will be a lower alkoxylated alcohol or phenol (the phenol
may be substituted with an alkyl group, often a chain of 8
to 10 carbon atoms). The lower alkoxy is normally ethoxy
but may also be at least partially propoxy (up to 3~% of the
alkoxy). Preferably the nonionic detergent will be a condensation
product of a higher fatty alcohol of 8 to 15 carbon atoms
with 5 to 12 moles of lower alkylene oxide, more preferably
with the higher fatty alcohol being of 8 to 12 ca~bon atoms
and condensed with 6 to 10 moles of lower alkylene oxide, and
most preferably with the higher fa~ty alcohol being be of 2
to 11 carbon atoms and condensed with 7 to 9 moles of ethylene
oxide, e.g., with 8 moles of ethylene oxide. Similarly, when
the ethylene oxide is condensed with alkyl phenol, the moles
of ethylene oxide employed will be in similar ranges, per mole
of phenol, as per mole of alcohol.
Although dishwa~hing detergent compositions can be
made which utilize only nonionic detergent as the surfactant
it is often preferable to incorporate some anionic detergent
in such compositions because nonionic detergents are generally
low foaming and it is usually desirable to have the liquid
dishwashing detergent composition capable of producing foam
in the dishwater. While any of the anionic detergents
previously mentioned in this specification may be employed
in supplementation of the nonionic detergent, it has been
found preferable to utilize one which is of a sulfated or
sulfonated type and more preferably such is a fatty
20~3~ 0
alkyl sulfate of 8 to 18 or of 10 to 16 carbon atoms, such as
ammonium lauryl sulfate.
The "skin smoothening compound" (SSC) of the present
compositions, which is so designated for simplicity in view
of the unexpectedly beneficial property found by applicants for
such group of compollnds, is a hydrocarbon, an organic acid, an
ester, an amide, an amine, a quaternary ammonium salt or an
alcohol, or any mixture thereof, but it is required that such
compound employed in the present compositions, to be effective as
a non-greasy skin smoothening agent, must include in its formula
a hydrocarbyl chain, preferably an alkyl chain, of at least 25
carbon atoms. Preferably, such chain is a normal alkyl or alkylene
chain, and is of 25 to 50 carbon atoms in length. It is applicants'
discovery that when such a chain is present and is of a length of
at least 25 carbon atoms, more preferably 27 to 39 carbon atoms
for the n-alkyl or n-alkane thereof, the dishwater, which is made
by dilution of the invented composition with water, is capable of
smoothening hands that are immersed in it during dishwashing, and
accomplishes that without imparting objectionable greasiness
to the hands, such as is often associated with uses of other
lipophilic compound~. Despite the fact that the dishwater is
very dilute with respect to the SSC, in these compositions and in
these applications the SSC does deposit on the skin in sufficient
quantities to have noticeable and desirable smoothening
effects. Such results are surpri$ing in view ~f the fact that the
function of the dishwashing detergent composition is to remove
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2~1~3~ 0
lipophilic materials from surfaces, not to deposit them. Also,
it would be expected that the lipophilic SSC would tend to
dissolve in the lipophilic phase of any resulting emulsion of
oily material from the dishes in the washwater. Contrarily
but fortunately, such are not the cases, and although some of
the SSC may remain in the wash water, at least a significant
proportion thereof deposits on the skin of the hands and
smoothens it without making the hands feel greasy. Among the
various C25+ alkyl-containing compounds that are useful as SSC's
in practicing the present invention are pentacosane, heptacosane,
nonacosane, melene, cerotic acid, melissic acid, psyllic acid,
C26_36 alcohols, myricyl palmitate, lacceryl palmitate,
myricyl cerotate, myricyl hypogaetel ceryl-2-hydroxypalmitate,
C31 n-alkane, C39 n-alkane, mono- and diamines of the mentioned
hydrocarbons, alcohols of the mentioned hydrocarbons and amides
of the mentioned acids. As will be seen, the various mentioned
SSC's all include at least one normal alkyl or alkylene group
of from 25 to 39 carbon atoms, which may be considered as a
more preferred range. However, the mentioned compounds are
listed as representative and not exclusive. Also, while
saturated compounds are preferred, usually in part at least,
for stability reasons, unsa~urated materials are also useful.
The various SSC's may be employed as pure compounds
or in mixtures. They may be synthetic or may be obtained
-- 8 --
2~1~3~0
from natural materials. Some have been synthesized and may
be employed as the sole SSC in the present compositions or
they may be mixed with other such synthesized compounds.
Alternatively, such compounds may be obtained from natural
materials and products of chemical refineries, such as oil
refineries. Such materials and products may be processed
to produce higher concentrations of the more desirable SSC's
or they may be employed directly. Among some sources of
SSC's which are components of the compositions of the
present invention are petrolatums, paraffin waxes, beeswax,
various waxes from the group of candelilla, Japan, bayberry
and montan, and other natural waxes which include the requisite
amounts of C25 and C25+ normal alkyl or normal alkylene-
containing compounds. Experimentation has shown that carnauba
wax does not produce the desired results. However, micro-
crystalline waxes, which include secondary branched chains
and primary alicyclic chains, in addition to normal alkanes,
have been found to be useful, which apparently indicates
that minor branching in a alkyl chain does not seriously
interfere with the skin softening function of the C25 and
C~5+ alkyl- and alkylene-containing compounds.
The only other re~uired component of the present
composition is an aqueous medium, in which the synthetic
_ g _
20~3~0
organic detergent is dissolved and in which the skin smoothening
connpound is emulsified. Such emulsion, to be effective for
the intended purpose, should be made by a certain procedure,
which will be described subsequently. The aqueous medium
may be water or an aqueous alcoholic medium that may also contain
various normal adjuvants, such as are employed in liquid
dishwashing detergent compositions. The water utilized is
preferably deionized water but tap waters are also satisfactory.
The alcohol employed will normally be denatured alcohol,
such as SD-40, and when it is present in the liquid dishwashing
detergent composition it will usually constitute about 5 to
20% thereof (on the basis of the water and ethanol only~,
which may be equivalent to about 3 to 15% o~ ethanol in the
final composition. It has been found that it is normally
more desirable to employ ethanol in the all-anionic detergent
compositions and it has been found that it is sometimes
preferable to omit it from the detergent compositions which
are primarily based on nonionic detergent.
Among the adjuvants that may be utilized together
with the three required components of the invented compositions,
in addition to ethanol or other co-solvent, when present, there
may be mentioned hydrotropes, detergency improving agents,
other surfactants, foaming agents, thic~eners, opacifying
agents, pearlescing agents, colorants, and perfumes. For
example, lauric~myristic monoethanolamide may be employed as
a foaming agent (and thickener~, sodium cumene sulfonate and
-- 10 --
2~3~0
sodium xylene sulfonate may be utilized as hydrotropes, and
magnesium sulfate may be present to improve detergency (at
least for use in areas where the water contains little
magnesium ion). Polymeric materials such as hydroxyethyl
cellulose, may be employed as thickeners, together with
various gums, including carrageenan. Supplemental surfactants,
such as cocoamidopropyl betaine may also be employed. Of
course, if other properties are desirable in the product the
appropriate adjuvants may be included in the formula.
The various proportions of components in the
present compositions are important for the obtaining of
satisfactory results. Thus, the proportion of synthetic
organic detergent will normally be in the range of 5 to 40%,
preferably being 5 to 35% and more preferably 15 to 35%.
For all-anionic detergent compositions the most preferred
range is 25 to 35% of anionic detergent and for compositions
which are primarily based on nonionic detergent such more
preferred and most preferred ranges are 5 to 30% and 10 to
25%. For the anionic compositions which contain sodium
linear dodecylbenzene sulfonate and sodium laur~l alcohol
triethoxy sulfate or equivalent detergents the proportion of
such sulfonate to such sulfa'te will usually be within the
range of 1:1 to 3:2, and in a most preferred formula there
will be present about 17% of sodium linear dodecylbenzene
sulfonate and about 13% of sodium lauryl alcohol triethoxy
-- 11 --
20~93~0
sulfate. For the primarily nonionic detergent compositions
the proportion of anionic detergent will preferably be with-
in the range of 2 to 10% and that of the nonionic detergent
will be within the range of 8 to 15~, with the proportion of
anionic detergent to nonionic detergent being in the range of
2:1 to 8:1. For example, when the nonionic detergent is a
condensation product of a higher fatty alcohol of 9 to 11
carbon atoms with 7 to 9 moles of ethylene oxide and the
synthetic organic anionic detergent is ammonium fatty alcohol
sulfate of 10 to 16 carbon atoms the proportion of the
nonionic detergent to the anionic detergent will preferably
be within the range of 2:1 to 5:1, as it is in those composi-
tions which contain about 16% of a condensation product of
higher fatty alcohol of 9 to 11 carbon atoms with about 8
moles of ethylene oxide, and about 4% of ammonium lauryl
sulfate.
The percentage of SSC will normally be within the
range of 0.1 to 10% of the composition and preferably will
be 0.2 to 5% thereof. More preferably, the normal alkane
content of such compound will be 0.2 to 3% of the composition
and most preferably it will be 0.5 to 2%. Within the group
of SSC's mentioned a sub-group which includes the hydro-
carbons, organic aci~s, alcohols and esters is preferred
and within that sub-group it is preferred to employ the
hydrocarbons. Such may be obtained from petrolatum, paraffin,
- 12 -
2~3~ ~
beeswax or various other natural materials, refinery products or
products of syntheses, providing that such contain the required
25 carbon straight alkyl chain structure. The preferred SSC's,
the normal alkanes of 25 to 50 carbon atoms, are readily avail-
able from petrolatum and/or beeswax. Petrolatum includes about 60 or70% of such compounds and beeswax includes about 15~ thereof,
together with other SSC's. In some formulas, including the
preferred formulas of this invention, a preferred proportion
of the SSC (preferably n-alkane) is in the range of 0.5 to 1.5%,
more preferably 0.5 to 1.0%, e.g., about 0.8% or 0.9%. Such a
0.85% content of the hydrocarbon can be obtained by inclusion
of about 1% of the specified type of petrolatum (desirably one
which is of a normal distribution curve for carbon chain length,
with a peak at: about 27 to 33 carbon atoms) and about 1% of
beeswax in the formula, but such proportions may desirably vary
from 0.1 to 2% of one such component and 0.1 to 2% of the other.
The proportion of aqueous medium will normally be in
the range of 45 to 85%, preferably 50 to 80%, for both the
anionic and nonionic based compositions. For the anionic compo-
sitions a more preferred range is 50 to 70% and still more prefer-
red is 50 to 65%, e.g., about 60% (excluding an~ ethanol present)
and, for the nonionic detergent based compositions the aqueous
medium, usually water, will normally be in the range of 60 to
80%, such as about 71%.
The adjuvant contents of the invented detergent
composition, excluding ethanol or other solvent, will normally
- 13 -
be in the range of 1 to 15% and usually will be in the range
of 2 to 10%, such as about 7 or 8%.
Use of the invented composition in dishwashing is a
simple matter. All that is required is to fill a sink or dishpan
with water, preferably warm or hot water, pour in the desired
amount of liquid dishwashing detergent composition, mix it in
and add the dirty dishes (preferably after initially scraping
and/or rinsing them). The dishes are then rubbed with a cloth,
sponge or dishmop to remove remaining food from them, and are
rinsed and dried. The amount of dishwashing composition added
to the water may be whatever is desired by the user and is
considered to be most effective under the circumstances. Usually
such proportion will be in the range of 0.1 to 2% of the total
dishwater and preferably will be in the range of 0.2 to 1.5~,
for example, 0.5 to 1%, but lower proportions can also be effective,
especially when only a few dishes are being washed and the soil
thereof is relatively light. The temperature of the dishwater
is desirably in the range of 30 to 55C., preferably 35 to 50C.,
and the time of immersion of the washer's hands in the dishwater
will normally be from 1 or 2 to 5 or 10 minutes. After completion
of the washing of the dishes the hands will be rinsed and dried
and at that time, after drying, it will be noticed that they are
appreciably smoother than after comparahle dishwashing operations
utilizing control compositions that do not contain the SSC('s~
of the invention.
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20193S0
In the process for manufacturing the invented composi-
tions it is important to follow a particular procedure to
produce the best and most effective product. Such procedure
involves melting the SSC and mixing it with a heated aqueous
solution of the synthetic organic detergent, both of which
are at about the same elevated temperature, at which the skin
sm~ot~ng compound and the solution are both in liquid state,
such as 75 to 85C., e.g., about 8QC. In mixing together
these components in such manner there results a stable emulsion
or microemulsion, which is especially stable in the presence
of suitable hydrotrope(s), and which is more effective in
smoothening the hands when it is dispersed in the dishwater
than are control compositions made by merely mixing together
or homogenizing the various components at room temperature,
even when the skin smoothening compound is in very finely
divided state. While it might be argued that it would be
expected that a superior emulsion could be formed by following
the invented method, it is surprising that after dispersion
in the dishwater there would be an appreciable difference in
skin smoothening between the compositions made by the invented
process and those that were merely mixed together (or
homogenized).
The elevated temperature at which the aqueous
detergent solution and melted skin smoothening compound are
mixed, in accordance with the invention, will normally be in
the range of 70 to 100C., preferably 75 to 85C. and
after making of the emulsion it will be stirred and cooled
2~133~
to room temperature. It has been found that other lipophilic
components of the dishwashing composition may be melted
together with the skin softening compound or with a mixture
of such compounds, and other water soluble components and
adjuvants may be dissolved with the detergent component(s)
in the aqueous phase, and the desired results are still
obtained. The described mixing may be effected by normal
mixing equipment, including Lightni ~ mixers, homogenizers,
static mixers, in-line mixers, and even conventional stirrers,
and the desired emulsions will result. The remaining adjuyants,
including any that are temperature sensitive, plus any solvents
or other volatiles, such as the ethanol, are gradually added to the
cooled emulsion, with stirring, with care being taken so as not
to break the emulsion during such additions. Some ~djuvants,
such as the perfume, may be dissolved in the solvent before
such admixing. The products made are stable on storage at
room temperature and at elevated temperature, and they satisfac-
torily smoothen the hands during dishwashing, without making
them feel greasy afterward.
The following examples illustrate but do not limit
the invention. Unless otherwise indicated, all parts are
by weight and all temperatures are in C.
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20193~0
EXAMPLE 1
Component Percent (by weight)
Sodium linear dodecylbenzene sulfonate 17.0
Sodium lauryl alcohol triethoxy sulfate 13.0
5 Lauric/myristic monoethanolamide 4.0
* Hydrotrope mixture 3.0
Magnesium sulfate (anhydrous) l.0
Beeswax (yellow) l.0
** Petrolatum 1.0
lO Perfume 0 8
Ethyl alcohol (95%) 5.0
Deionized water 54.5
100.O
* Two parts of sodium cumene sulfonate and one part of sodium
xylene sulfonate
** Higher molecular weight, with peak distribution for alkyl
chain at C27, obtainable from Petroleum Industries, Inc.
The liquid dishwashing detergent composition of
this formula is made by fir~t dissol~ing the anionic deter-
gents, hydrotropes and magnesium sulfate in the deionized
water, melting the beeswax, petrolatum and lauric/myristic
monoethanolamide together by heating to a temperature of
about 80C., heating the aqueous solution to about 80C.,
and mixing the solution and melt together with ~igorous mixing
- 17 -
20~3~
(using a Lightnin mixer or equivalent) to form a stable emulsion.
The emulsion is then cooled to room temperature, which is about
25C., with stirring, and the perfume, colorant and ethyl alcohol
are then admixed with the balance of the formula to produce the
final product, which is a stable emulsion.
The liquid dishwashing detergent made is employed
in normal manner to hand wash dishes, in both practical use
tests and in control tests wherein red dyed beef fat is
washed off test plates. In such tests the dishwater is of a
mixed calcium and magne~ium hardness equivalent to about 150
p.p.m. of CaCO3, its temperature is 41C. and the concentration
of the liquid dishwashing detergent in the dishwater is 1%.
The experimental or invented dishwashing detergent was tested
against a popular commercial product and also against a
control liquid dishwashing composition of the same formula
except that the SSC's were omitted and 2% of deionized water
was substituted. The invented composition ~as found to clean
the dishes as well as the commercial product and the control,
and produced shiny clean dishes, which were not objectionably
coated with any greasy or waxy films. Moreover, it was found
by the persons running the tests that their hands felt
smoother after being Lmmersed in the dishwater during the
washings.
To verify the skin smoothening properties of the
invented dishwashing composition a panel of six evaluators
... . ..
- 18 -
201~350
tested the invented formula and the control for skin smooth-
ening properties. In such test each panelist separately
immersed his or her hands in 41C. dishwaters (before addi-
tion of any dishes to them, to avoid any effects of fatty
materials from the dishes) for sixty seconds, after which the
hands were rinsed under running tap water for sixty seconds
and were dried with towels. The observers examined their hands
as they dried them, and evaluated the smoothnesses thereof.
All six observers found that their hands were smoother after
being immersed in the dishwater made from the invented dish-
washing composition than when they were immersed in dishwater
of the same dilution (1%) made from the control composition.
When the above experiment is repeated, utilizing
0.5% and 1.5% of the dishwashing liquids (invented and control)
in the wash water the same superiority in skin smoothening is
observed in favor of the invented composition. In further
tests, when a twenty-member panel evaluated the same composi-
tions by soaking the hands for ten minutes in 0.1~ solutions
thereof the invented liquid dishwashing compositions were
found to be significantly more effective than the controls in
softening the skin of the hands. Because smoothening effects
on the skin are very important advantages for hand dishwashing
compositions the present results are significant and the
advance made in the art by this invention is note~orthy.
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201~3~0
EXAMPLE 2
-
Cornponent Percent (by weight)
+ Neodol~ 91-8 16.0
Ammonium lauryl sulfate 4.0
5 Cocoamidopropyl betaine 3.0
Lauric/myristic monoethanolamide 4.0
Beeswax (yellow) 1.0
++ Petrolatum 1.0
Perfume 0.3
10 Colorant 0.2
Deionized water 70.5
100.O
+ Condensation product of one mole of fatty alcohol of 9-11
carbon atoms and eight moles of ethylene oxide
++ Higher molecular weight, with peak distribution for alkyl chain
at C27
The primarily nonionic dishwashing detergent composi-
tion of this example is made in substantially the same manner
and is tested in the same way as the composition of Example 1,
with the only changes being those necessitated by the different
materials being employed. Thus, an aqueous solution of the
nonionic detergent and ammonium lauryl sulfate is made and a
lipophilic melt is made of petrolatum, beeswax, lauric/myristic
monoethanolamide and cocoamidopropyl betaine. The lipophiles
are heated to 80C. and subsequently are mixed with the aqueous
phase at 80C., followed by cooling and addition of the colorant
- 20 -
2 ~ 3 ~ 0
liquid dishwashing detergent composition and against a control
from which the skin smoothening compounds were omitted (replaced
by deionized water) are effected in the same manner as described
in Example 1 and the same good comparative dishwashing action
and improved skin smoothening effects result, as were described
in Example 1. Thus, it is seen that the desirable effects of the
presences of smoothening SSC's are obtainable with liquid
dishwashing detergent compositions of both nonionic and anionic
types.
In other comparative experiments, instead of the
SSC's of the previous working examples, other lipophilic
materials are employed, such as mineral oils and carnauba wax. Such
are not effective for softening the hands of one washing dishes
in a dishwater containing such dishwashing compositions. It
appears that the reasons for this are that mineral oil contains
a relatively large percentage of branched chain hydrocarbons and
in carnauba wax the major components (esters) include a substan-
tial proportion of aromatic compounds.
- 21 -
2~93~
EXAMPLE 3
Component Percent (by weight)
Sodium Cl2_l4 alkyl ether ethylenoxy 16.0
(6 EtO) sulfate
5 Ammonium lauryl sulfate 6.0
Cocoamidopropyl dimethyl betaine 4.0
Lauric/myristic monoethanolamide 3.0
Sodium xylene sulfonate 1.8
Hydroxyethyl ethylene diamine 0.2
10 Beeswax (yellow) 0 5
++ Petrolatum 0.5
Ethyl alcohol (95%) 4.0
Colorant (0.5% aqueous dye solution) Q.2
Perfume 0 5
15 Deionized water 63.3
100.O
++ Higher molecular weight, with peak distribution for alkyl
chain at C27
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2~3~0
EXAMPLE 4
Component Percent (by weiqht)
Sodium C12 14 alkyl ether ethylenoxy 12.0
(12 EtO) sulfate
5 Ammonium lauryl sulfate 6.0
Lauryl dimethylamine oxide 4.0
Lauric/myristic monoethanolamide 3.0
Sodium xylene sulfonate 1.8
Hydroxyethyl ethylene diamine 0.2
10 l-Tricontanol 1.0
Ethanol (95%) 4.0
Color (1% aqueous dye solution) 0.4
Perfume 5
Deionized water 67.1
' 100.0
EXAMPLE 5
Component Percent (by weight)
Sodium linear dodecylbenzene sulfonate 17.0
Higher alkyl polyglucoside (APG-625~17.0
20 Lauric/myristic monoethanolamide 2.0
Sodium xylene sulfonate 3.0
Beeswax, yellow 1.0
++ Petrolatum 1.O
Perfume Q 3
25 Colorant (1% aqueous dye solution~ 0.2
Deionized water 58.5
100.O
2 ~ ~ 3 3 ~ O
++ Higher molecular weight, with peak distribution for alkyl
chain at C27
When the liquid dishwashing detergent compositions
of Examples 3-5 are made in the manner described in Example
1, with the mPlted lipophilic phase being admixed with the
aqueous phase at elevated temperature (about 80C.) and then
cooled to room temperature with stirring, followed by addition
of any heat sensitive components, such as perfume and ethanol,
the products resulting are excellent liquid, hand dishwashing
detergents which foam satisfactorily, remove greasy soil
from dishes without more than light sponging of the dish
surfaces, rinse easily from the dishes and leave them shiny
clean and with no objectionable cloudy film. Like the
products of Examples 1 and 2 the dishwashing detergent
compositions of Examples 3-5 also leave the hands of the
dish washer feeling smooth, which is attributable to the
presence of the SSC('s) therein. Similar results are obtain-
able when the SSC's of these examples are replaced by long
chain length paraffins, such as those averaging in the range
of 25 to 39 carbon atoms in straight chain alkanes, by
montan wax, candelilla wax, the purified components of
beeswax, such as nonacosane, melissic acid, myricyl cerotate, and
n-hentriacontanyl trimethyl ammonium chloride, nonacosyl
amine and melissamide r which may be considered as derivatives of
such purified components.
- 24 -
'20~ 5~
Although the embodiments of the present invention
primarily described in this specification are liquid dish-
washing detergent compositions, in which the surprisingly
beneficial skin smoothening effect of the described long
chain alkyl containing compounds is very beneficial, in a
broader aspect the invention is of skin smoothening detergent
compositions which contain such a long chain compound and a
synthetic detergent or soap, and which smoothen the skin.
~xamples 6 and 7 illustrate other such compositions.
EXAMPLE 6
Component Percent (by weight)
A B
Sodium laureth sulfate (2 EtO) 17.0 17.0
Coco fatty acids diethanolamide 6.0 6.0
C12_14 fatty alcohol 1.0 0.5
Propylene glycol 0.5 0.5
Sodium chloride 0.5 0.5
Citric acid 1.0 1~0
Preservative (Germaben II) 0.5 0.5
20 Beeswax, yellow - 1.0
++ Petrolatum 1.0 1.0
Deionized water 73.4 71.9
100.O 100.O
++ Higher molecular weight, with peak distribution for alkyl
.chain at C27
- 25
~0~3~
The above formula is of a gel type product which
is intended for use in the bath or shower to clean both the
skin and the hair. In tests similar to those described in
Example 1 the experimental formula, 6B, was found by expert
evaluators to be significantly better than the formula of
Example 6A in smoothening skin and was also found to condition
hair better. Such results were confirmed by actual use
testing of the products.
EXAMPLE 7
10 Component Percent (by weight)
A B
Sodium alpha C12_14 olefin sulfonate16.0 16.0
Coco fatty acids amidopropyl betaine0.8 0.8
Coco fatty acids diethanolamide 5.0 5.0
15 Styrene maleic anhydride copolymer 0.8 0.8
(opacifier)
Glycerine 1.0 1.0
Preservative (Germaben II) 0.5 0.5
Sodium chloride 0.8 0.8
20 Citric acid 0.2 0.2
Perfume 0-4 0 4
++ Petrolatum - 1.0
Beeswax - 1.0
Deionized water 74.5 72.5
100.0 100.0
++ Higher molecular weight, with peak distribution for alkyl chain
at C27
- 26 -
201~3~0
The "liquid soaps" formulations (which are really
synthetic organic detergent formulations) of this example are
tested in the manner described for the products of Example 6
with essentially the same results. Both the laboratory
testing and actual use tests of the formulas of this example
prove that Formula 7B, containing the long chain alkyl
containing compounds, as such are present in the petrolatum
and beeswax, smoothen the hands and condition the hair
better than the control compositions o~ Example 7A.
For the skin smoothening detergent compositions,
the broadest proportions of components recited for the
liquid dishwashing detergent compositions also apply, 5 to
40% of synthetic organic detergent which is anionic and/or
nonionic detergent, and 0.1 to 10% of SSC, in an aqueous
medium. For the shower-bath gel formulations and the liquid
soap preparations such ranges will normally be 10 to 25%,
0.2 to 3% and 50 to 80%, respectively, more preferably being
10 to 20%, 0.5 to 2% and 65 to 80%, respectiYely.
EXAM2LE 8
When the inYented compositions of the preYious
examples are modified by substituting for the petrolatum and
beeswax components the same total proportion of microcrystalline
wax (which is of a molecular weight of about 500~ the desired
good cleaning effects and skin softening properties are also
obtainable, especially if the microcrystalline wax is employed
2019350
in combination with an equal or greater proportion of the
petrolatum and/or beeswax, or active component(s) of such
material(s). Similarly, paraffin and paraffin wax may be
substituted for the combination of skin softening compounds
5 of the previous examples, providing that alkyl chain lengths
thereof are in the required range (C25 and higher). In all
such cases good cleaning and skin smoothening are obtained
and the skin smoothemng actions are significantly better than
for controls, from the formulas of which such skin smoothen-
ing compounds are omitted. Similarly good washing and skinsmoothening actions are obtained when other such high molecular
weight linear alkyl containing hydrocarbons, esters, "quats", fatty
acids, amides, amines and alcohols are substituted for the
skin smoothening compounds in the described formulas and in
such modifications of such formulas in which other synthetic
organic detergents, such as C12_14 olefin sulfonates, C14_16
paraffin sulfonates, coco monoglyceride sulfates and C8_10
alkyl phenol polyethoxylates, are employed. For illustrations,
when pentacosane, heptacosane, nonacosane, cerotic acid,
~0 melissic acid, psyllic acid, myricyl palmitate, lacceryl
palmitate, myricyl cerotate, C31 n-alkane, C39 n-alkane, C26 36 n-
alcohols, C26 n-alkyl trimethyl ammonium chloride, n-hen-
triacosyl trimethyl ammonium chloride, amides of the mentioned
acids and alcohols and amines of the mentioned hydrocarbons
are employed, either singly or in mixture, in replacement of the
- 28 -
2~33~
skin- smoothening compounds of the examples, improved skin
smoothenings and good cleanings result.
Additionally, the proportions of the detergents,
SSC's, adjuvants and aqueous medium may be varied ~10%, +20~
and i30%, while maintaining them within the ranges heretofore
described in this specification, and effective dishwashing
detergent compositions,which are significantly better in skin
smoothening activity than control compositions which do not
contain the skin softening compound(s), are obtained.
The invention has been described with respect to
working examples, illustrations and embodiments thereof but
is not to be limited to these because it is evident that
one of skill in the art, with the present specification
before him, will be able to utilize substitutes and
equivalents without departing from the invention.
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