Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
'7~6~33
1~
DETERGE~T COMPOUNDS AN~ COMPOSITIONS
Background of the Inven~ion
The present invention relates to amphsteric-fatty acid
complexes. More specifically, the invention relates to
amphoteric-fatty acid complexes which exhibit unexpected
foam properties and low ocular irritancy. The invention
further relates to detergent compositions containing the
novel amphoteric-fatty acid complexes in combination with
other surfactants and/or detergent components.
Nonirritating detergent compositions have been known in
the art and have been in use for some time. United States
Patent Nos. 3,299,069 and 3,055,836 are merely two
representative examples of such prior art nonirritating
detergent compositions. Likewise, amphoteric compounds
have been well known in the art and have been disclosed ln
use with various other detergent compounds. United States
Patent No. 2,528,380, discloses a ring structured
amphoteric compound with a fatty acid attached to the ring
nitrogen. ~one o~ the disclosure.s in the prior art
disclose the amphoterlc-fatty acid complexes o~ the
present invention nor the advantages provided by same.
It is an obiect of the present invention to provide novel
detergent compounds.
It is another objec, of the present invention to provide
novel detergent compounds which exhibit good foam
properties and low ocular irritancy.
.
3~3~3
It is a further object of the present invention to provide
detergent compositions which exhibit good ~oam properties
and low ocular irritancy.
These and other objects of the present invention will
become apparent to one skilled in the art from the
detailed description given hereinafter.
Summary of the Invention
This invention encompasses non-zwitterionic,
amphoteric-fatty acid comp~exes of the formula
[RlC~O~ [R2~1~ A ~
wherein Rl, R2, Al and A2 are as defined below.
Detailed Description of the Inventlon
The present invention relates to novel non-zwitterionic,
amphoteric-fatty acid complexes of the formula
[RlC-O~ [R2~1~ A
wherein
Rl is alkyl or substituted alkyl containing from
about 6 to 18 carbon atoms and mixtures thereof;
R2 is alkyl containing from about 8 to 18 carbon
atoms and mixtures thereof or alkyl amido of the
formula
33
-3-
.
O Z
. ;. -R3-C~-N-Y
wherein
R3 is alkyl 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 containing
from l-to 4 carbon atoms,
Al and A2 are the same or different and are
select~d from the group of anionic salt moieties
consisting of the followiny:
~CH2CH2-cOox]n
~CH2-cOox~n
~CH2C~OH-CH2~sO3x~n
~CH2 CHOH-CH2~OPo3xln
wherein X is a water~soluble cation such as Na+, K+,
CaT~, Mg+~ and the like and n 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 containiny from 1 to 4
carbon atoms.
The non-zwitterionic, amphoteric compounds wh.ich are
useful in the complexes of the present invention are of
the formula:
A
R2-N\
¦ A2
H ,
wherein R2, A1 and A2 are as def ined above.
683
-4-
These compounds can be prepared in accordance with th~
teachings of the art, see for example, United States
Patent NoO 2,970,160.
The fatty acid compounds which are useful in the complexes
of the present invention are of the formula
- O ~
~l-C-O
_
wherein Rl is as defined above. These compounds are
readily available commercially from numerous sources such
as the fatty acids available from Emery Industries Inc.;
Cincinnati, Ohio Procter ~ Gamble, Cincinnati, Ohio and
various other: commercial suppliers.
The amphoteric-fatty acid complexes of the present
invention can be prepared by admixing a suitable
non-zwitterionic amphoteric and a suitable fatty acid,
utilizing heat, i~ nece~sary, to facilitate the blending
and adding water, if needed. The ratio of fatty acid to
amphoteric can be in the range of about 0.5:1 to 1.5:1,
preferably about 1;1. The pH of the resulting complex
should be within the range o 6.5-8.5, pre~erably within
the range of 7.0-7.5, to minimize potential irritation
problems.
Specific examples of the novel amphoteric-fatty acid
complexes of the present invention include:
~ ~ O H C2H40H
~A) LR1-C-O~ C11H23-C-N (CU2) 2 I~C~I2CO~K
wherein Rl is a CllH23 - ClgH37 mixture~
,, .
.i83
--5--
., ~
~ ~ ~,cH2cH2coowa
( }3 )P~l~C-O Cl~H29~N
S _ ~¦~CE~2C~12COONa
wherein Rl i5 an 80%/20% tallow coconut mixture.
~ U l~3 C~2CHOH~2S03K
~ C ~ Rl-C-O R2 C-N--( CE~2 ) 2--N~
_ _ I CH2CE~O~CH20Po3Na2
wherein Rl is tallow and R~ i~ a
C11~323-C17H2s mix'~ure.
' ~9
r I 1 ~ ~ c~2c~OEcH2so3
(D) LRlC l ~18 37 1 ~ CX2CHOHCH2S03~
wherein Rl is a 70%/30% mixture of laurlc and
myristic acids.
2 5 r u 1 r
( E ) LRlC-O~ C12H25-N-CH2OEI2-COO~a~
. El
where in Rl is tallow .
e ~ ~cH2cH2~OoNa ~
( F ~ C12~5C- Cl4H29-N\
_CH2C~2COONa_
_ ~ (3
1~ 11 1 ~CH2CH2COONa
(G )RlC-O C12~25-N
4 0 _ ¦ ~CH 2CH 2COONa
where in R1 is a C6H13 ~ C18H37 mixture -
--6--
~he amphoteric-fatty acid complexes of the present
invention exhibit excellent surfactant properties. In
particular, these complexes exhibit good foam properties
and low ocular irritancy. me good foam properties are
unexpected because fatty acids do not normally exhibit
such properties. It has further been found within the
p~ range of 7~0-7.2 that the amphoteric-~atty acids
cornplexes exhibit unexpected foam synergism.
These complexes can be utilized in detergent compositions
either alone or in combination with other surfactants in
a range of from about 1.0 to 50.0% by weight of the
total compositions.
The amphoteric surfactants which may be used in the
present invention include betaines, sultaines,
phosphobetaines, phosphitaines, n-alkylamino propionates,
n-alkylimino dipropionates and imidazolines. The betaine
and sultaine surfactants useful in this invention are
described in U.S. Patent No. 3,950,417 issued April 13,
1976. The phosphobetaines and phosphitaines useful in
this invention are described in U.S. Patent ~os
4,215,064 and 4,261,911. The n alkylamino propionates
and n-alkylimino dipropionates are sold under the trade-
name Deriphats by General MillsA The imidazolines which
are useful in the compositions of this invention are
described in UOS~ Patent ~o. 2,970,160.
The preferred betaine amphoteric ~urEactants include
the alkylbetaines such as cocodimethylcarboxymethyl-
betaine, lauryldimethylcarboxymethylbetaine, lauryl-
dimethylcarboxyethylbetaine, cetyldimethylcarboxymethyl
betaine, lauryl-bis-~2-hydroxyethyl~ carboxymethylbetaine,
i
96~3
-7-
oleyldimethyl-qamma-carboxypropylbetaine, lauryl-bis-
(2-hydr~xypropyl)-carboxyethylbetaine, and the like; the
sultaines such as cocodimethylpropylsultaine, stearyldi-
methylpropylsultaine, lauryl-bis-(2-hydroxyethyl)
propylsultaine and the like; and the amidosultaines such
as cocoamidodimethylpropylsultaine, stearylamidodimethyl-
propylsultaine, laurylamido-bis-(2-hydroxyethyl)
propylsultaine, and the like.
The preferred phosphobetaines include laurlc-myristic-
amido-3-hydroxypropylphosphobetaine, cocamldodisodium-
3-hydroxypropylphospho~etaine, lauric-myristicamido-
disodium-3-hydroxypropylphosphobetaine, lauric-myristic-
amidoglyceryl-phosphobetaine, lauric-myristicamidocarboxy-
disodium-3-hydroxypropylphosphobetaine, and the like. The
preferred phosphitaines include cocoamidopropylmonosodium-
phosphitaine, lauric-myristicamidopropylmonosodium-
phosphitaine and the like.
l~he preferred n-alkylamino propionates and n-alkylimino
dipropionates include those having the following
structures:
R - NH2C~2CH2COO
and
~ / H2CH2COO
R NH\
CH2CH2COO ~la
wherein R is from about 8 to 22 carbon atoms and mixtures
thereof.
The amphoteric detergents may be present in an amount from
about 2 to 10% by weight of the total composition.
It is envisioned that any anionic surfactan~ may be used
in the compositions of the invention such as, for example,
an alkyl sulfate of the formula R-C~2-OSO3X, an
alkylether sulfate of the formula R(OCH2CH2)p-OSO X, an
alkylmonoglyceryl ether sulfonate of the formula
R~OCH2~CH~CH2-sO3xr
OH
an alkylmonoglyceride sulfate of the formula
RCOOCH2-CH-C~120S03X
OH
an alkylmonoglyceride sulfonate of the formula
RCOOCH2CH-CH2S03X
OH
an alkyl sulfonate of the formula
RSO3X
and an alkylaryl sulfonate of the formula
R
~ SO3X
wherein R is alkyl having from 7 to 17 carbon atoms; X is
selected from the group consisting of alkali metal ions,
alkaline earth metal ions, ammonium ions, and ammonium
ions substituted with from 1 to 3 lower alkyls and p is an
integer ~rom 1 to 6.
The anionic detergent may be present in an amount of from
about 2 to 10% by weight of the total composition.
Nonionic detergents which are useful include the alkylene
oxide ethers of phenolsr fatty alcohols, and alkyl
mercaptans; the alkylene oxide esters of fatty acid
amides; the condensation products of ethylene oxide with
partial fatty acid esters, and mixtures thereof. The
polyoxyalkylene chain in such agents may contain rrom 5 to
100 alkylene oxide units in which each alkylene unit has
from 2 to 3 carbon atoms.
~'7~3
The nonionic surfactant may be present in an amount of
from about l to 30% by weight of the tokal composition.
Cationic surfactants suitable in these compositions
include mono- and bis-quaternary ammonium halides, such
as stearyldimethylbenzylammonium chloride, cetyltri-
methylammonium chloride, ~,N-dioctadecyl-N,N,N',~'-
tetramethyl-1,5-(3-oxapentylene) di-ammonium bromide,
tertiary amine salts such as cocoamidopropyldimethyl-
amine hydrochloride stearylamidopropyldimethylaminecitrate' cationic polymers such as hydroxyethyl
cellulose reacted with epichlorohydrin and then
quaternized with trimethylamine (Polymers of this type
are sold by Union Carbide under the tradename Polymer
JR) and specific triesters of phosphoric acid. The
specific triesters of phosphoric acid are described
in Canadian Patent ~o. l,126,750 issued June 29, 1982.
The cationic surfactants should be present in an
amount of from abou-t 0.5 to 3.0% by weight of the total
composition.
The total amount of the active surfactant ingredients
in the present invention should not be greater than
about 50O!o by weight of the total composition i.n orcler
to avoid ocular irritation problems, prefera'bly from
about 5 to 20% by weiy'ht of the total composition with
the proviso that the total amount of anionic surfactant
and amphoteric surfactant should not exceed 20% by
weight of the total composition. In addition, other
ingredients conventionally added to surfactant compo-
sitions for personal use, such as dyes, preservatives,
perfumes, thickeners, opacifiers, conditioners, emol-
lients, buffering agents, and the like, may be added
in minor amounts. Ingredients such as dyes, preserva-
tives and perfumes together usually constitute lessthan 2% by weight of the total composition and
thickeners may be added to the co~position in an
~L~'7~6~33
-10-
amount of from about 1 to about 3~ by weigh~ of the total
composition.
The detergent compositions of the present invention should
have a pH in the range of about 6.5 to 8.5, preferably
from about 7.0-7.5.
Liquid detergent compositions utilizing the complexes of
the present invention can be prepared by admixing the
amphoteric-fatty acid complex with the other surfactant(s)
at room temperature or slishtly 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 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., HCl, or strong base NaOH, as
needed.
Detergent bar compositions utilizing the complexes of the
present invention can be prepared by admixing the
amphoteric - fatty acid complex with the other
surfactan~s) in a steam jacketed rotary mixer at
temperatures within the range of 60-80C. Fillers,
whitening agents and processing oils can be added, as
needed, to the hot slurry. After ade~uate mixing to
assure homogeneity and moisture balance the produc~ is
chill rolled or drum dried înto flakes. Uyes and
fragrances are added to the flakes in a standard
amalgamator together with additional water to provide
- proper bar formation. After adequate mixing the flakes
are milled and plodded into logs which are then cut into
blanks prior to s~amping into bar form.
~t7~ 3
~11
The detergent compositions of the present inven~ion can be
tested for ocular irritation by the following modif ied
Draize Test (J. H~ Draize et al ., Toilet Goods Assn. No. 17 ,
May 1952, No. l, Proc. Sci. Sect. ) .
An 0.1 ml. sample of a neutral composition under test is
dropped into one eye o~ an albino rabbit, the other eye
serving as a control. Six rabbits are employed for each
composition. Observations are made ater 1, 24, 48, 72
and 96 hours and 7 days after initial instillationi 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 of the rabbit's
eye after 7 days to severe irritation and/or complete
corneal opacity. Ocular lesions are scored for the
cornea, iris and conjunctiva with a higher number
indicating greater ocular irritation and ~he scores are
added to give a total numerical v~lue for each reading for
six rabbits and averayed. The averaged score is an
indication of the irritation potential of the composition
under test. 3ased on the averaged score, descriptive
irritation evaluation may be given, e.g., none, slight,
moderate, severe as the case may be~
Deter~ent compositions of the invention provide high foam
volume and moreover outstanding oam stability as measured
by an adaption oE the well-known Ross-l~iles ~oam test
principle "Oil and Soap" 18.9-102 (1941) .
Lanolin, anhydrous, cosmetic grade is mixed with dioxane
(technical grade) in the proportion o~ 2.5 grams lanolin
and 100 grams of dioxane. The lanolin is rirst mixed with
25 cc. o 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
36~3
-12
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.
~_~,t7~6~
~20.2 grams (.19g/moles) of a 24% active solution of an
amphoteric of the ormula
0 H C2H4OH
CllH23~C-~- ( CH2 ) 2 1~CH2COOK
are mixed with 47 grams (.24 g/moles) of premelted coconut
fatty acids of the following chain length percentage
distribution: C~-0.3, Cg~7.3~ C10-6-5~ C12-5-7
C14-18.g, C16-8.6, C18-7-7-
The resulting product is an opaque, viscous slurry
containina 34~ solids with a pH of 7.1 and is an
amphoteric-fatty acid complex of the structure shown as
compound G in the specification. The complex foams
copiously in both soft and hard water and is a slight
ocular irritant.
Exam~le II
The slurry obtained in Example I is freeze-dried by known
procedures to yield abouk 95% solids. The solids are
ground to a slightly tacky powder which can be utilized to
form a bar soap and is a slight to moderate ocular
irritant.
Example_III
Following the procedures of Example I, the amphoteric or
Example I is mixed with stripped hydrogenated coconut
fatty acids of the following chain length percentage
distribution: C8-1, C10-1~ C12-56~ C14-24
C16~12~5 an~ Clg-5; to form an
amphoteric~-fatty acid complex shown as compound A in the
~14-
~pecification. ~he resultant dried powder is ~ound to be
a sli~ht ocular irritan-t.
., .
Example IV
Following the procedures of Example I, 227 grams
(.15 g/moles) of a 22% active solution of tetradecyl -
iminodicarboxylate are dissolved in 450 grams of deionized
water at a temperature of about 50-60Co 30 grams
(.15 g/moles) OL the coconut fatty acid of Example I are
- 10 added to form the resulting amphoteric-~atty acid complex
which is a moderate irritant and is of the following
structure:
1S [ U ] r CH2cH2c~ONal
C14H29-N
_ I ~ CH2CH2COONa
_ H
~0 wherein Rl is a C6H13-C1gH37 mixture~
EXAM~LE V
..
300 grams ~0.07 g./moles) of an 11.1% activ~ solution
of an amphoteric of the ~ormula
- O C2H40H 0
ll H
CllH23~C~N~(CH2)2-l-CH2CHOHC~2SO3Na
30 _ H
are mixed with 14.1 grams ~0.07 g./moles) of premelted
coconut fatty acids having the alkyl chain length
distribution set forth in Example I. The resulting
3S product is a hazy solution containing 1~ solids, having a
83
-15-
p~ of 7.3 and is an a~photeric-fatty acid complex of the
formula:
[ r o c2~40~
I Cll}323-c-N-(cJ~2~2-N-cH2c~IoHcH2so3Na
~X~MPLE VI
360 grams (~.19 g./moles) of a 19.1~ active solution
of an amphoteric of the formula
r fH2cOONa 1
R~ - N
~ ~C~2COONa
_ H _
wherein Rl has an alkyl chain length percent distribution
as follows: Clo-2, C12-53~ C14-24~ C16-11
Clg-l~i are mixed with 40 grams (0.19 g./mo}es) of
: premelted coconut fatty acids having the alkyl chain
length distribution set forth in Example I. The resulting
product is a hin, opaque slurry containing 27% solids
havi~g a pH o~ 7~5 and is an amphoteric ~a~ty acid complex
of the ~ormula.
r ~ 1 ~cH2cOoNa ~
LRl ~ ~ ~ R - N
~I CH2COONa
_ ~
~1~7'~3~3
-16-
Example VII
A clear ~el hair care product is prepared as follow~; 200
grams of deionized water are charged to a vessel equipped
with an agitator and steam. 50 grams of a phosphate ester
hydrotrope are added and the pH is adjusted to 7Ø lS0
grams of Compound A are added and the solution is mixed
until clear. 20 grams of polyethylene glycol 6000
distearate are added and heat is applied to the solution
to 70C for twenty minutes. The solution is cooled to
25-30C and l.0 grams of preservative, 2.0 grams of
fragrance and sufficient deionized water is added to bring
the total weight to lO00 gcams.
15 The resulting product has the following compositions;
wt./wt.%
Compound A li.00
phosphate ester hydrotrope 5.00
polyethylene glycol 6000 distearate 2.00
preservative 0.10
fragrance 0.~0
deionized water q.s. to 100
Example VIII
-
An opaque liquid soap is prepared having the following
formulation:
wt.~wt.%
Compound A 15.00
- 30 Compound C lS.00
Cabosi' (tradename for colloidal silica, 3.50
available from Cabot Corp., Boston,
Mass.)
isopropanol 0.10
fragrance 0.30
deionized water q.s. to 100%
3 ~ ~ 3
-17-
The pH of the above formulation is adjusted to 6.5 with
citric acid.
Example IX
5 A clear, liquid hair cleanser composition is prepared
having the following formulation:
wt./wt.
Compound A 5.00
polyoxyethylene 80 sorbitan monolaurate 10.00
Deriphat~(tradename for salt of N-alXyl 5.00
beta-iminopropionic acid available from
General Mills Inc.~ Kankekee, Illinois)
polyethylene glycol 6000 distearate2.00
benzyl alcohol 0.10
Dowicil 200 (tradename for the cis isomer 0.10
or 1~(3-chloroalkyl)-3,5,7-triaza-1-
azoniaadamantine chloride)
fragrance 0.20
deionized water q.s. to lO0~
The above ~ormulation is adjusted to a pH or 7.l with 15%
HCl and has a viscosity of 413 cps. at 25C and is a
slight ocular irritant. The formulation aiso exhibits
good foam properties.
Example X
A detergent bar composition is prepared as follows: 50
parts of Compound A are mixed with 20 parts o~ Deriphat in
a steam jacketed mixer at a temperature of 70C. After
the slurry is homogeneous, lO parts of polyoxyethylene (80)
sorbitan monopalmitate are added followed by the addition
of lO parts each of talc and dextrin. The batch is mixed
20 minutes, cooled, milled into ribbons and pressed into
detergent bars.
~.:1'7~6~3
-18-
The resulting bars have the following formulation.
~t./wt.%
Compound A 50.00
Deriphat 20.00
polyoxyethylene (80) 10.00
sorbitan monopalmitate
talc lO.00
dextrin lO.00
100 . 00
and has a pH o~ 7~0. This product is a moderate irritant
and exhibits excellent foaming properties.
EXAMPLE XI
In order to demonstrate the synergism of the amphoteric-
fatty acid complexes of the present invention with
respect to foam characteristics, compounds A and B, the
amphoteric portion thereof and the coconut fatty acid
portion thereof were individually tested in accordance
with the modified Ross-Miles foam test set forth
hereinbefore.
The results are shown in Table I below:
33
--19--
TABLE I
Initial foam Height (mm)
-Normal Water Ha~d Water
Compound % Activ and Grease 200 ppm CaCO3
amphoteric of
compound A 5.0295 343
coconut fatty acid 5.0 0 0
compound A 5.0353 358
amphoteric of
compound B 5.0 - 295
coconut ~atty acid 5.0 - 0
compound B 5.0 - 360
2~
In addition to the preferred embodiments described herein,
other embodiments, arrangements and variations within the
spirit of the invention and the scope of the appended
claim will occur to those skilled in the art.
