Note: Descriptions are shown in the official language in which they were submitted.
: \
11 7332ll JBP 184
',
~ DETERGENT COMPOSITIONS
:
Background of the Invention
Detergent and cleansing compositions intended for use as
personal cleansing products not only must exhibit good
cleansing and foam characteristics but they must also be
non-irritating or have low irritation potential to the
skin and the eyes.
' ` 1 0
: Synthetic detergents which are useful in such detergent
. .
and cleansing compositions are well known in the art and
include anionic, cationic, amphoteric and nonionic
detergents or surfactants, as they are usually referred
to. The surfactants generally exhibiting the mo~e
: superior properties in terms of foamingi cleaning and end
result attributes are the anionic detergents. Thus, most
~t"'~' detergent and cleansing formulations intended for personal
~; use contain anionic surfactants as one of the active
- ~ 20 ingredients. These surfactan~s, however, have a tendency
f to be very irritating to the skin and the eyes in the
levels normally utilized, i.e., above 10% by weight of the
total composition. For this reason, detergent composi-
tions intended for personal use containing anionic
surfactants are modified by substituting a significant
`~ amount of nonionic surfactants which are generally mild
although of less effective foaming and cleansing ability.
; Certain amphoteric surfactants have also been reported to
~` have a low eye irritation potential. Although numerous
:! 30 detergent and cleansing compositions are available
commercially, there is still a need for compositions in
which irritancy can be substantially eliminated without
~; sacrificing other desired properties such as cleansing and
foaming attributes.
: .
'~ .
:;
.. ~
7332A~
--2--
Several U.S. patents describe compositions in which both
amphoteric and nonionic surfactants are incorporated in
detergent compositions containing anionic surfactants.
Thus, in U.S. Patents Nos. 2,999~069 an 3,055,836 there
are described shampoo compositions comprising certain
mixtures of ethoxylated anionic, amphoteric and
polyethoxylated nonionic surfactants. Further, in
U.S. Patqn~ No. 3,928,251 there are described shampoo
compositions comprising certain mixtures of anionic,
nonionic and zwitterionic surfactants. Similarly, in
U.S. Patent No. 3,950,417 shampoo compositions are
described for which low ocular irritancy is claimed. In
; these compositions, nonionic and amphoteric surfactants
have been added to modify anionic surfactants. A11 of
these compositions include a nonionic surfactant as an
essential component as well as an anionic surfactant and
as mentioned above, these surfactants have various
negatives~
;, ~
;; ~ 20 It is, therefore, an object of this invention to provide
improved detergent and cleansing compositions.
;~". "
It is a further objec~ of this invention to provide
~- improved detergent and cleansing compositions which
~ .; .
~ 1 25 exhibi~ low irritation potential to the eyes and skin.
,.. .
:' ~
It is a further object of this invention to provide
improved detergent and cleansing compositions which
exhibit good foaming properties including excellent foam
stability.
Other objects of this invention will be set forth in or be
apparent from the following detailed description of the
invention.
;'. '
. ~ .
~ ~ ~33~4
--3--
Summary of the Inven~ion
:`
The foregoing objects and other features and advantages of
the present invention are achieved by detergent and
S cleansing compositions comprising a synergistic mixture of
~ surfactants which exhibit low eye and skin irritancy and
-i~ good foam properties. More specifically, the present
invention relates to detergent and cleansing compositions
comprising a synergistic mixture of a specific amphoteric-
fatty acid complex and specific anionic surfactants
~i containing at least one carboxylic acid moiety.
r ~
Detailed ~escriotion of the Invention
In general, this invention comprises a synergistic mixture
of a specific amphoteric-fatty acid complex and a specific
~` anionic surfactant in a ratio of from about 1:4 to 4:1.
' The ~erm "synergis~ic mixture" as used herein refers to a
mixture of two discrete compounds which display a degree
of initial foam height and quality which is greater than
the sum of the initial foam heights of the compounds taken
individually.
The specific amphoteric-fatty acid complexes which have
been found useful in ~he present invention are
;~ non-zwitterionic in nature and are of the formula
.:~
[ R ]
~ ~ wherein Rl is alkyl or substituted alkyl containing
j 35 from about 6 to 18 carbon atoms and mixtures thereof.
i'''
.
. .
,
'
i ' , '
~ l73324
-4-
R2 is alkyl containing from about 8 to 18 carbon atoms
and mixtures thereof or alkyl amido of the formula
~ ~Z -I .
t R -C-N-Y~
:~ wherein R3 is aIkyl containing from about 8 to 18
carbon atoms, Z is H or lower alkyl containing from
... 1 to 4 carbon atoms, and Y is lower alkylene contain-
ing from 1 to 4 carbon atoms;
.~ Al and A2 are the same or different and are selected
~: from the group of anionic salt moieties consisting
, 10 of the following:
~,",;, ~cH2cH2-coox !n l
;,,.. ,, ~ H2-cOox]n
~CH2CHOH-CH2S03x]n l
~CH2 CHOH-CH2-OPo3x]n
:
wherein X is a water soluble cation such as ~a , K+,
Ca++, Mg+~ and the like and ~ is an integer of 1 or
2 with the proviso that if only one of Al and A2 are
. selected from the anionic salt moieties above the
other can be lower alkyl or lower hydroxyalkyl
containing from 1 to 4 carbon atoms.
.. - ~he amphoteric-fatty acid complexes which are useful
in the present invention are novel compounds described
and claimed in Applicant's copending Canadian patent
application Serial ~o. 397,740, filed March 5, 1982,
and can be prepared in accordance with the processes
~' dsscribed therein.
. .
Representative amphoteric-fatty acid complexes useful
in the present invention in~lude the following:
. ~ ~
. ~ . .
3 3 2 ~1
, `:,. 1
1 ~ t /C2~4oa 1~
. 5 ~A~ l-C~ H23 G ~dtC~2)~
.:
` wherein Rl is a CllH~3 - S1~37 mixture.
$~ 10
11 1 r ~CH2c~2cNa 1
(B ) P~l-C-O ~14H29~N~
:~ 15 . ~ 2CH2~QoNa
wherein Rl i5 ar 80%/20% tallow COCOFI t fatty acid mixture.
."~.:
~.:
20r ~ 3 / 2CHOHCH2SO ~K
( C ) ¦ Rl-C-O R2 C-N- ( C~12 ) 2 N~
~` L I CH2C~HCH20PO3Na2
. wherein Rl is tallow fatty acid and R~ is a
CllH23-~17~25 mixtl~re.
~"
r 1l 1 r cH2cHOHC~2so3
.: 30(D~ RlC-O ~ 18H37-N Mg
_ _ 1~ CH~CHOHCH2So3--
wherein Rl is a ~0%/30~ mixture of lauric and
~, myristic acids.
(E) [RlC ~ [C12H25 I CH2CH2COONa ]
wherein Rl is tallow fatty acid.
,j .,.~
.
i'
.
.~.' .; `' ' ' :
~ .
r,
~:: '':
i ` '
~ 17332~
.: -6-
r u 1 ~ H2COO~a l ~3
(Fl LC12H25~ ~ C14H~9-
:. ~ CB2CH2COONa~
:~ 1 0 r J 1 r ~ C~2CH2COGNa
~,. tG) RlC-O C12H25-N`
_ _ I `CH2CH2COONa
wherein Rl is a C6H13 - ClgN37 mi:cture.
- ~he amphoteric-fatty acid complex~s u eful in ~he composi-
tions of this invention are presen~ in an amo~nt of from
about 1 to 50% by weight of the total composition, prefer-
ably about 5 to 15% by weight o~ the total compo ition.
-~ . The specific anionic surfac~an~s which have been found
`~ ~seful in the present invention are those containing at
,. : least one carboxylic acid moiety and are selected from the
.~ group consisting o~ sulfosuccinates, alkyl carboxylates,
~'. 25 ~ -sulfo ~atty acid and ester carboxylates, alkyl succi-
nates, alkyl sarcosinates and fatty acid protein
condensates. All of these compounds are well known in the
art and can be prepared according to well-recognized
processes.
: 30
. The sulfosuccinates are of the general formula
'." O
11
~-O-C-fHCH2COOX
OSO3Na
.
~,
~ '.
,. ~
117332'L
--7
. . .
. c~,;
, ~ .
and can be prepared by reacting maleic acid with a
- suitable fatty alcohol followed by the addition of
NaHSO3 to ~he d~uble bond.
..~ .
:` S The ~-sulfo fatty acid and ester carboxylates are of the
following general formuli respectively
. '
., 11
10R-fH-C-OX' and
: SO3X
:,:- O
15R-CH-C-OR'
. I
,., S03X
'' ~:.;
and can be prepared by sulfonation of the suitable fatty
. acids and esters.
- ,' ,:~
: The alkyl carboxylates are of the following general
: formula
R-O[(CH2)2O]a-CH2COOX
~- wherein a is 1-4; and these compounds can be prepared by
;-~ the Williamson ether synthesis which involves react~ an~
alkoxide with chloroace~ic acid.
The alkyl succinates are of the general formula
.. O
11
R-O-C-CH2CH2COOX
., .
:. .
', ''
:.
,.......... - - ~: .
`' ~ ' '
.,
,-.. :, ,
; .
17332~
.. .
'. and are the reaction product of a suitable fatty alcohol
,~ with succinic acid or succinic anhydride.
~""
'~` The alkyl sarcosinates are of the general formula
S
~, O X
.:. R-C-N-CH2COOX
` 10 and are the reaction product of a suitable fatty acid with
. a lower substituted amine such as glycine or N-methyl
.. .~ .
glycine.
~; '
`~ The fatty acid protein condensates are of the general
formula
O R' O R"
~, 11 1 11 1
~ R-C-(NH-C-H-C-NH-CH)n COOX
'`; 20
.~ and are the reaction products of a suitabLe fatty acid
: with an amino hydrolysate.
~, ......... .
Specific examples of suita~le anionic surfactants include,
~ 25
:- O O
': ` 11 11
(AA) CllH23-0-C-fHCH2-C-O-Na
; 30 OSO3Na
" O
(BB) C12~2s-fH-C--Na
S03Na
,:
;............ 40 O
: 11
(CC) CloH~l-fH-C-OCH3
. SO3N
:.,; ' ~'.
''''
, .
,
, ~ .
' , ' .
`:
3 3 ~
g
. ~ I o
(DD) R-0-C-CH2-CH2-C-OK
wherein R is 50/50 mixture of C12E25 - C14H29
..
(E~) Cl3H27-o-[(cH2)2o]4 - CH2cooNa
- O C~3O CH3
",~,~ 1 11 1
~ (FF) CllH23-C-(NH-CH-C r~H-C~)soCOONa
:`'`; 15
.:~ o C~3
Il I
(GG) CllH23-C-N-CH2COONa
:~ 20
The anionic surfactants useful in the compositions o~ this
invention are present in an amount of from about 2 to 50~
by weight of the total composition, preferably about 5 to
: 90% by weight of the total composition.
Further, to achieve the desired results of the present
invention, the amphoteric-fatty acid complex and the
:~ specific anionic surfactant should be in a ratio o~ from
about 4:1 to 1:4, preferably ~rom about 2:1 to 1:2.
In preparing various formulations and compositions, if
~ desired and if compatible, various other surfactants can
: be utilized such as other anionics, nonionics,
~` amphoterics, cationics and the like. In addition to such
other surfactants, other ingredients conventionally added
to detergent and cleansing compositions for personal use,
such as dyes, preservatives, perfumes, thickeners,
"
~.'
:, ,1
'~";
~., ' ;
., ' .' ~.
. .
':,
'~
`
'' ' ~ ': `
: ' ~
, `:` .~
733~4
,.
--10--
,
~ opacifiers, conditioners, emollients, buffering agents and
$ the like, may be added in minor amounts. Ingredients such
c` as dyes, preservatives and perfumes together usually
i ~ constitute less than 2% by weight of the total composition
S in an amount of from about l to about 3~ by weight of the
i~ total composition.
~; ' '
The detergent and cleansing compositions of the present
~~ invention may be in the form of liquid detergent
compositions or detergent bar co~lpositions, as desired.
~ '.
s Liquid detergent formulations utilizing the compositions
of the present invention can be prepared by admixing the
~; amphoteric-fatty acid complex and anionic surfactant at
room temperature or slightly elevated temperatures (about
50C) and then sufficient deionized water is added to
bring the composition to about three quarters of its
intended weight. Other ingredients such as other
surfactants, various detergency adjuncts, fillers,
carriers, perfumes, preservatives, gelling agents and the
like are added as required followed by the balance of the
water. The pH is then adjusted to within the desired
range by the addition of strong acid, e.g., ~ICl, or strong
base ~aOH, as needed.
Detergent bar formulations utilizing the compositions of
the present invention can be prepared by admixing the
amphoteric-fatty acid complex and the anionic surfactant
! in a steam jacketed rotary mixer at temperatures within
the range of 60-80C. Other surfactants, fillers,
; whitening agents and processing oils can be added, as
needed, to the hot slurry. After adequate mixing to
assure homogeneity and moisture balance the product is
chill rolled or drum dried into flakes. Dyes and
fragrances are added to the flakes in a standard
amalgamator together with additional water to provide
. .
,:,
:
733~
- 1 1-
~.'
proper bar formation. After adequate mixing the flakes
are milled and plodded into logs which are then cut into
blanks prior to stamping into ~ar form.
, :...-
The detergent compositions of the present invention can be
~`~` tested for ocular irritation by the Eollowing modified
Draize Test (J.H. et al., Toilet ~ood~ Assn. No. 17, May
1952, No. 1, Proc. Sci. Sect.).
.~
An O.1 ml. sample of a neutral composition under test i5
dropped into one eye of an albino rabbit, the other eye
serving as a control. Six rabbits are employed for each
composition. Observations are made after 1, 24, 48, 72
~~ and 36 hours and 7 days after initial instillation; second
and third instillations are made after the 24 and 48 hour
- readings. Results may vary from substantially no change
or only a slight irritation in the appearance o~ the
rabbit's eye after 7 days to severe Lrritation and/or
complete corneal opacity. Ocular lesions are scored for
the cornea, iris and conjunctiva with a higher number
~`~ indicating greater ocular irritation and the scores are
added to give a total numerical value for each readin~ for
~- six rabbits and averaged. The averaged score is an
indication of the irritation potential of the composition
~ ~ 25 under test. Based on the averaged score, descriptive
j irritation evaluation may be given, e.g., none, slight,
`- moderate, severe, as the case may be.
,s
Detergent compositions of the invention provide high foam
" ";,! 30 volume and moreover outstanding foam stability as measured
by an adaption of the well-known Ross-Miles foam test
principle "Oil and Soap" 18.9-102 (1941):
~":
Lanolin, anhydrous, cosmetic grade is mixed with dioxane
(technical grade) in the proportion of 2.5 grams lanolin
and 100 grams of dioxane. The lanolin is first mixed ~ith
.,
'
.:
3 3 2 ~
. -12-
`'
25 cc. of dioxane. This mixture is heated over a steam
bath to 45C in order to dissolve the lanolin in the
dioxane. The remainder of the dioxane is then added and
mixed. This lanolin dioxane solution, which is stored in
an amber bottle, should be prepared fresh on the day that
the tests are run.
The composition to be tested is diluted by adding 376 cc.
of distilled water to 4 grams of the composition, and then
by adding 20 cc. of the lanolin dioxane solution described
above while mixing. Heat is produced when the lanolin
dioxane solution is added to the solution of the
composition in water and care must be taken in adjusting
the temperature of this solution to 24-25C. Both of
these intermediate solutions should therefore be adjusted
to 23C before mixing. The cooling of the lanolin dioxane
solution should be gradual in order to avoid precipitation
of the lanolin. This will produce a final solution with a
temperature of 24-25C.
The final solution of the composition to be tested, water,
dioxane and lanolin described above, is then run in a
modified Ross-Miles foam column in the usual way. All
tests are conducted in duplicate, and the average of the
two results is taken. Foam stability is determined by
measuring the decay in foam height after two minutes,
expressed as a percentage of the original height.
:,
Specific embodiments of the present invention are
illustrated by the following representative examples. It
will be understood, however, that the invention is not
confined to the specific limitations set forth in the
individual examples, but rather to the scope of the
appended claims.
;.. ~ ' :
~: .
~",,
. .
3 ~ ~
- 13 -
; Examples I-IX
The following compositions are prepared by admixing the
surfactant components, adjusting the pH to 7.2+.2 with
dilute acid or base as required and adding deionized
water to 1.00%:
. .
o/O W-t/wt.
EXAMPLES
I II III IV V VI VII VIII IX
Compound B 5.0 2.5 2.5 2.5 2.5
lauryl succinnic
- acid 5.0 2~5
disodium sulfo-
- cocoate 5.0 2~5
lauryl ether (4)
15 carboxylate 5.0 2.5
:~ lauryl disodium
, sulfosuccinate 5.0 2.5
deionized water q.s. to 100%
'',
Ex mple X
The compositions prepared in Examples I-IX are tested
,.. ~ for hard water foam properties using the modified Ross-
~- Miles procedure set forth hereinbefore and the results
i are as follows:
~: Initial Foam Height in mm -
~, 25 Example 200 ppm hard water
I . 358
II
III 348
IV 330
V 330
: VI 365
VII 375
VIII 368
IX 378
~ ;' 'r~
,.~ ~ , ` .
. '' ` i . .
'
~" ' .
~1~3~
-14-
As can be readily seen from the results above, thecompositions containing a mixture of the speciic
amphoteric - fatty acid complexes and the anionic
surfactants of the present invention tExamples VI-IX)
exhibit a synergistic increase in initial foam height. It
is also observed that the quality of the foam generated by
the compositions of the present invention is superior to
that of the other compositions in that it is denser and
creamier. A generated foam of this nature i5 not only
perceived to be better by the consumer, but is also
capable of supporting and suspending soils in a manner
superior to the more open, lace-like foam of the
compositions of Examples I-IV and thus these soils are
more easily removed
Example XI
A detergent bar composition is prepared by charging to a
steam-jacketed rotary mixer 23.7 parts by weight stearic
acid, 13.3 parts by weight dextrin, 35.1 parts by weight
disodium -sulfococoate, 14,2 parts by weight compound A,
0.2 parts titanium dioxide and L0.0 parts water. The
mixture is heated to 50-60~C and mixed until homogeneous
and the pH is adjusted to 7.2+.2 with 50~ NaO~ solution.
The resulting product is chilled, rolled in flakes,
25 milled, plodded and stamped into bars having the following
composition:
% wt/wt
stearic acid 23.7
dextrin 13.3
disodium -sulfococoate 35.1
Compound A 14.2
TiO2 0.2
50% NaOH 5.2
deionized water 8.3
100.0
3~2~
-15~
The resulting bar foams copiously in hard and soft wa~er
and free of lime soap deposits and is also found to be a
slight ocular irritant when tested.
Example XII
A low pH detergent bar composition is prepared in
accordance with the procedure of Example XI and has the
following formulation:
% wt/wt
Compound ~ 20.00
stearic acid lS. ao
polyethylene glycol 4000 5.00
dextrin 10.00
talc ~o,oo
lS disodium lauryl sulfosuccinate 35.00
deionized water _ 5.00
100.Qo
..
Example XI I I
: 20 A liquid cream soap product is prepared as follows: ~7.5
parts by weight of compound C and 20.0 parts by weight of
lauryl succinic acid are char~ed to a vessel equipped with
a stirrer and steam and are heated to 45C. The pH is
adjusted to 7.0+.2 with dilute NaOH followed by the
addition of 1 part of propylene glycol and 95 grams of
deionized water. The mass is cooled to 30C and 2 parts
of a fragrance are added prior to illing into tubes.
The resulting product has the following formulation:
; % wt/wt
Compound C ~2.57
lauryl succinate 9.73
propylenc glycol 0.4a
fragrance 0.97
deionized water q.s. to 100%
35 The product is a smooth opaque mild cream gel easily
dispensed from tubes.
332~
-16-
Example XIV
An opaque liquid soap is prepared having the following
formulation.
% wt/wt
Compound D 30.0
- lauryl sarcosinate 20.0
polyethylene gLycol 6000 distearate 3.0
deionized water q.s. to 100
The pH of the above formulation is adjusted to 6.0 with
dilute HCl.
Example XV
. An opaque liquid soap is prepared having the following
formulation:
.` 15
;. ~ wt/wt
sulfosuccinate 3.00
Compound A 2.50
ammonium lauryl (3) ether sulfate3.00
polyoxye~hylene 80 sorbitan monolaurate 5.00
: preservative .10
dye and fragrance .25
deionized water q.s. to 100
The pH of the above formulation is adjusted to 6.0 with
dilute HCl.
In addition to the preferred embodiments described herein,
other embodiments, arrangements, and variations within the
spirit oE the invention and the scope of the appended
claims will occur to those skilled in the art.
.~ . .
,: ~
