Note: Descriptions are shown in the official language in which they were submitted.
-` 1062S79
sackground of the Invention
This invention relates to detergent compositions
having improved particulate soil removal capability. More
particularly, this invention relates to detergent compositions
incorporating certain ethoxylated compounds which provide
unexpectedly good clay soil removal.
Zwitterionic surfactants, i.e., those surface active
compounds that contain both positive and negative charge centers
in the same molecule while being electrically neutral, are
10 known. For example, U.S. Patent Nos. 3,668,240 and 3,764,568
to Melvin A. Barbera,.issued respectively on June 6, 1972,
and October 9, 1973, disclose zwitterionic surfactants having
a 2,3-butene moiety between the charge centers. U.S. Patent
No. 3,332,875 to Adriaan Kessler and Phillip Floyd Pflaumer
also discloses mixtures of certain olefin sulphonates with
zwitterlonic detergents in which the charge centers are
separated by a 2-hydroxy propane group. U.S. Patent Nos.
3,452,066 and 2,781,390 to Hans S. Mannheimer, issued res-
pectively on June 24, 1969 and February 12, 1957, outline a
range of z~itterionic surfactants which optionally may be sub-
stituted with a wide variety of oxygen-ccntaining groups between
the positive and negative charge centers. U.S. Patent No.
3,i69,311 to Leonard J. Armstrong and Eldon de Vere Dawald
issued October 3b, 1973, discloses carboxylic compounds having
ethylene oxide groups.between the charge centers but fails to
recognize the effect of the various structural param~ters
on the performance of the molecule in removing soil, especially
particulate soil.
In contrast, the present invention concerns detergent
compositions incorporating certain zwitterionic surfactants in
a polyethenoxy group of a size that permits not only adsorption
1062S79
of the molecule from an aqueous system onto particulate and
other soils, and the subsequent removal of the soil b~ emul-
sification or dispersion but also the continued maintenance
of the removal soil in suspension in the aqueous solution.
However, the present invention is directed to the
discovery that a wider range of zwitterionic compounds,
in combination with certain detergent builder materials can
provide unexpectedly good particulate soil removal and also
good oily soil removal from hard surfaces and textile materials.
The ~thoxylated zwitterionic compounds useful in the present
invention possess an ability to remove particulate soil that
is independent of water hardness over a very wide range or
Ca and Mg levels. Furthermore, this performance is re-
latively insensitive to temperature changes in the range of
70F. - 140F., the normal range for domestic cleaning
functions.
The importance of such a development is readily ap-
parent as it permits a high level of soil removal performance
to be obtained with a range of detergent formulations. Further-
more, the nature ~and level of other components of the for-
mulation can be controlled by the selection of an ethoxylated
zwitterionic material having the appropriate level of per-
formance.
Accordingly, it is an object of the present invention
to provide detergent compositions incorporating ethoxylated
zwitterionic compounds that have good particulate and oily
soil removal performance.
Another object of the preseht invention is the pro-
vision of detergent compositions having improved particulate
and oily soil removal performance in both liquid and granular
forms.
-- 2 --
- 1062579
Summary of the Invention
In its broadest aspect the present invention embraces
a detergent composition comprising:
a) 1% to 99% by weight of the composition of a water-
soluble compound having a formula selected from the group
consisting of: 12
i) 1 1 (C2H4O)yR4X
R3
wherein R1 is selected from the grou~ consisting of straight
and branched chain C8-C30 alkyl and alkenyl moieties and
alkaryl moieties in which the alkyl group has 10-24 carbon
atoms; R2 is selected from the group consisting of straight
and branched chain C8-C21 alkyl and alkenyl moieties, alkaryl
moieties in which the alkyl group has 6-16 carbon ato~s, and .
Cl 4 alkyl and hydroxyalkyl moieties; R3 is selected from the
group consisting of straight and branched chain C8-C21 alkyl
and alkenyl moieties, alkaryl moieties in which the alkyl
group has 6-16 carbon atoms, C1 4 alkyl and hydroxyalkyl moieties
20 and -(C2H4O)XH wherein x has a value of about 3 to about 50;
R4 is selected from the group consisting of Cl-C8 alkylene,
C3-C8 alkenylene, 2-hydroxy C3 alkylene and 2- and 3-hydroxy
C4 alkylene moieties and Cl-C4 alkarylene moieties provided
that where R3 is -(C2H4O~XH then R4 is -CH2-CH2-; X is an
anion selected from the group consisting of sulfate and sul-
fonate radicals; and y has a value in the range of 2-100 provided
that where R3 is -(C2H4O)xH then x + y > 10.
_ ~ +
ii) Rl - N - (C2H4)y-l CH2CH2 M
(C2H40) X--1 -- CH2CH2
106Z579
- wherein Rl is selected from the group consisting of
linear and branched C8-C30 alkyl and alkenyl radicals;
R2 is selected from the group consisting of linear and
branched C8-C30 alkyl and alkenyl radicals and Cl-C4
alkyl and hydroxyalkyl radicals; X is selected from
the group consisting of sulfate and sulfonate;
y and x have values in the range 2-100 provided that
y + x > 12;
M is a cation selected from the group consisting of
alkali metal, ammonium and alkanolammonium ions.
B.) 99% to 1% by weight of the composition of a detergent
builder, which may be organic or inorganic.
In the context of the present invention, ethoxylated
zwitterionic compounds having hydroxy substituents on the carbon
atoms immediately adjacent the nitrogen atom and/or X moiety
are not preferred as they are unstable in water, especially at
pH's other than neutrality, and are extremely difficult to pre-
pare compared to other hydroxy substituted compounds.
Preferably the ethoxylated zwitterionic compound is one
of either ~-(N-C16_18 alkyl, N-Cl 3 alkyl,N- polyethenoxy
ammonio) - 2-polyethenoxyethane-1-sulphonate wherein the total
number of ethylene oxide groups lies in the range 15-25
or
~-(N-C12_18 alkyl,N,N-diCl-C3 alkylammonio) -2-polyethenoxy
ethane-l-sulphonate wherein the number of ethylene oxide groups
in the polyethenoxy chain is in the range 6-12.
~06Z~q9
Performance Testing
_
In this specification the assessment of particulate and
oily soil removal performance both of detergent formulations of
the invention and of comparative formulations is carried out
using the following procedures.
a.) Particulate soil removal testing
This is carried out in either an automatic mini
washing machine (AMW) having a capacity of 4,700 ml.
and a cloth/liquor ratio of 1:30 or a Tergotometer
having a capacity of 1,000 ml. and a cloth/liquor
ratio of 1:140. In both instances the machines are
fitted with horizonally rotating paddle agitators, the
AMW having a speed of 100 RPM, while the Tergotometer
uses a speed of 80 RPM.
The AMW washing procedure involves a 12-minute
wash cycle at 105F in 7 grains per U. S. gallon hard
water (calculated as CaCO3) using a 2:1 ratio of Ca:Mg
salts. The first two minutes of the cycle are used for
product dissolution following which the fabric load is
added and washed for the remaining 10 minutes. A 5-
minute rinse cycle then follows, 2 minutes of which is
with agitation, the remaining 3 minutes being a spin to
remove excess moisture. The fabrics are then tumble-
dried prior to heing graded.
106Z579
~ A similar washing procedure is used for the Tergoto-
meter with the exception that 5.5 grains/gallon water is
employed having a 3:1 ratio of Ca:Mg salts (calculated as
CaCO3). The wash is followed by one rinse cycle of three
minutes in 80F water of the same hardness, level, and
type as for the wash, after which the swatches are
machine-dried before being graded.
The fabric load for particulate soil removal testing
comprises a mixture of white cotton, poly-cotton (65~
DACRO ~/35~/ cotton), and polyester (KODEL~ swatches
which are stained with a standardized illite clay soil.
For the A~, three 5" x 5" swatches of each fabric are
used in each load, while in the Tergotometer, three
2 1/2" x 2 1/2" swatches of each fabric type are employed.
The results (expressed as relative clay removal
index) for each formulation represent a percentage of the
whiteness value achieved by a commercial synthetic de-
tergent standard tested at the same time under identical
conditions. This standard formulation hereinafter
designated as "A" has the following composition by
weight:
1062579
Sodium C12 alkylbenzene sulphona~te 7.55
~ Sodium Tallow alkyl sulphate 9.25
Coconut alcohol + 6 mole EO 0.60
Diethanolamide 1.60
Sodium Tripolyphosphate 50.00
Sodium Silicate solids 5.90
Sodium sulphate 14.20
Moisture 10.00
Miscellaneous 0.30
100. 00
Grading of Performance
Swatches are graded before and after washing on a
Gardner Whiteness meter reading the L, a, and b coordinates.
Whiteness (W) is calculated as:
W = 7L - 4OLb
700
; Performance is determined by finding the difference in whiteness
(~W) before and after washing as:
Q W = Wafter ~ Wbefore
This is compared to the commercial Control Product A by calcu-
lating ~W as a percentage of ~W given by the Control Product in
each batch.
The Relative Clay Removal Index= ~W for Test Samplex 100
~W for Control
Product A
b.) Grease and oil removing testing
Identical equipment and washing conditions
are used to evaluate grease and oil removal perform-
ance. The fabric load comprises a mixture of green
polycotton (65% DACRO ~/35% cotton) and polyester
(KODE ~) swatches, four 2 1/2" x 2 1/2" swatches of
each type being used in the tergotometer.
-- 7 --
1062S79
Two triglyceride stains, namely bacon grease and
vegetable oil, and two hydrocarbon-based stains,
namely dirty motor oil and simulated lipid soil are
employed.
Following washing and drying, the swatches are
graded visually on a scale whose absolute values are
described below:
5. Complete removal
4. Discernible stain remaining
3. Moderate amount of soil remaining
2. Large amount of soil remaining
1. Very large amount of soil remaining
0. No change, original amount of stain remaining
As in the particulate soil removal performance
test, the results are expressed as a percentage of
the soil removal achieved by the standard formulation
A under the same conditions.
DETAILED DESCRIPTION OF THE INVENTION
The compositions of the present invention contain two
essential components, namely the ethoxylated zwitterionic com-
pound and a detergent builder material which may be inorganic
or organic in character. The zwitterionic and detergent builder
may be present in a ratio of from 99:1 to 1:99 by weight,
preferably from 20:1 to 1:10 by weight, and most preferably from
5:1 to 1:5 by weight of the composition. The precise levels of
the zwitterionic and builder components will depend on the
nature of the zwitterionic compound and the type of product to
be formulated. For example, a product intended for prewash
-- 8 --
1062579
treatment of laundry to remove specific stains by direct
iapplication to the fabric will be formulated to contain a lower
level of zwitterionic compound and different optional ingredients
than a product designed as a main wash detergent.
For use as a main wash detergent, the level of ethoxy-
lated zwitterionic compound in the product will lie in the range
5%-35% by weight, preferably 10%-25%, and most preferably 15%-
20%, the level of the detergent builder being in the range 10%-
70%, preferably 10%-60%, and most preferably 20%-45% by weight.
Such a main wash detergent can be formulated as a conventional
granule or as a liquid, paste, flake, ribbon, noodle, pellet, or
tablet. As will be shown hereinafter, this formulation flexi-
bility is due, at least in part, to the ability of the zwitter-
ionic surfactants of the present invention to achieve particulate
soil removal performance equivalent to that of commercial heavy
duty laundry detergents when used in blends with detergent
builder materials.
ETHOXYLATED ZWITTERIONIC COMPOUNDS
. _ _
Ethoxylated zwitterionic compounds useful in the present
invention may have one or other of the following formulae:
12
i) 1 ,N (C2H4O)y - R4 - X
R3
a.) Mono-long chain derivatives
In this derivative, Rl is a hydrocarbon moiety that can
be a straight or branched chain C8-C30 alkyl or alkenyl group or
an alkaryl group in which the alkyl portion has 10-24 carbon
atoms; R2 and R3 are Cl-C4 alkyl or hydroxyalkyl groups; R4 is
g _
~062579
a Cl-C8 alkylene, C3-C8 alkenylene, 2-hydroxy propylene or 2- or
3- hydroxy butylene group or a Cl -C4 alkarylene group; X is a
sulfonate or sulfate radical; and y has a value in the range
2-100.
In this embodiment, preferred groups for Rl are C12-C18
alkyl, particularly C14-C16 alkyl, while preferred groups for R2
and R3 are Cl_3 alkyl and C2 3 hydroxyalkyl, the most preferred
groups being methyl- and hydroxethyl- radicals. The preferred
range of values for y is 6-50, more preferably 6-25, and most
preferably 9-12.
The synthesis of the above compounds can be achieved
using readily available commercial starting materials. One such
synthetic route is as follows. Sodium hydride is slowly and
stoichiometrically reacted (2:1 molar ratio) with polyethylene
glycol in a solution of tetrahydrofuran under an atmosphere of
an inert gas, e.g., argon. The reaction is carried out over a
period of 4-10 hours in an ice bath to cool the reaction, which
is exothermic. The polyethylene glycol used is the commercially
available material comprising a mixture of compounds having chain
lengths from about 4 to about 100. The resultant product is the
sodium salt represented by
(I) Na (CH2cH2) yCH2CH2 Na
wherein y can be, for example, 3, 21, 32, 67, or 99.
A stoichometric amount of tosyl chloride dissolved in
tetrahydrofuran is then added slowly to reaction product (I),
cooled in an ice bath, and the resultant mixture is stirred for
12 to 20 hours to form
(II) CH3- ~ -So2-o(cH2cH2o)y+l 2 ~ 3
i.e., the polyethylene glycol ditosylate. Pyridine or other
-- 10 --
1062579
suitable base is added to the mixture, and the solution is then
poured into ice water and acidified with HCl to a pH of about
2-3. The aqueous solution is then extracted with chloroform,
rinsed with water and the chloroform extract is dried over
sodium sulfate to give purified polyethylene glycol ditosylate
(II).
The ditosylate (II) is then reacted with a tertiary
amine of the structure
12
(III) Rl - ~
R3
wherein Rl, R2 and R3 are as defined above. The reaction of
(III) with (II) is conveniently carried out neat, or with a
suitable solvent as N,N-dimethyl formamide or CH3CN at
temperatures of 80C to about 100C to produce a mixture of
,R2
(IV) Rl ~+ ~ (C2H4O)y+l 2 ~ - CH3,
R3
3 ~ -SO3-
and
(V) Dicationic ammonium byproducts
The mixture of (IV) and (V) is then dissolved in
methanol and refluxed from 20-40 hours with an aqueous solution
of sodium sulfite. The unreacted (V) and other ionic materials
are removed by contacting the above solution with a mixed bed
ion exchange resin, followed by filtration of the solution and
-- 11 --
1062579
evaporation of the solvent to give, as the predominant zwitter-
ionic product.
I +
(VI) 1 ~ (C2H4O)y C2H4S3
Compound (VI) can optionally be further purified using the
mixed bed resin and tested for purity by thin layer chromatography.
It will be appreciated that zwitterionic compounds of
the general formula (VI) can be prepared using any of a variety
of tertiary amines (III). Moreover, zwitterionic compounds
having any desired, specific degree of ethoxylation (y) can be
prepared by fractionating the polyethylene glycol used in the
reaction and using the desired fraction in the synthesis scheme.
Alternatively, relatively narrowly defined distillation "cuts"
of polyoxyethylene glycol having any desired average degree of
ethoxylation, and containing individual compounds having differ-
ing degrees of ethoxylation within the desired range, can be
used in the reaction. It will be further understood that sodium
salt (I) can be reacted with a variety of epoxy compounds (e.g.,
butylene epoxide) or halohydrins (e.g., 6-chlorohexanol or 8-
bromooctanol) to provide zwitterionics having various R4 groups
within the scope of this invention.
A specific preparation of a mono-long chain ethoxy-
lated zwitterionic compound useful in the present invention was
as follows:
Preparation of 26-dimethyloctadecylammonio-3,6,9,12,15,18,21, 24
octaoxahexacosane-l-sulfonate
Preparation of Nonaethyleneglycol (A). Under nitrogen,
- 12 -
106Z579
46 grams (2 moles) of sodium pellets were added cautiously to2,664 ml (20 moles) of previously dried and distilled tri-
ethyleneglycol. The temperature was kept below 100C. After
all the sodium had reacted, the temperature was adjusted to
100C and 187 grams (1 mole) of 1,2-bis-(2-chloroethoxy) ethane
was added in a slow stream. The mixture was heated overnight
at 100C (still under nitrogen) and then filtered hot to remove
most of the sodium chloride. Excess triethyleneglycol was
stripped under vacuum and the mixture was again filtered while
hot. The material was purified by molecular distillation and
has a b.p. of 170-175C at 0.001 mm.
Preparation of Nonaethyleneglycol ditosylate (B)
The nonaethyleneglycol (A), 300 grams, (0.72 moles) was
dissolved in 800 ml (10.3 moles) of dry pyridine and cooled to
0C. Tosyl chloride (i.e., _-toluene-sulfonyl chloride, 420
grams, 2.2 moles) was added, with stirring, in small portions.
After the addition was complete, the temperature increased to
10C and the clear reaction mixture became cloudy. The mixture
was stirred at 0-10C for an additional 3 hrs., then poured into
an equal volume of ice water and acidified to pH 2-3 with 6N
HCl. The aqueous solution was then extracted 3 times with
CHC13. The CHC13 was washed with water, sodium bicarbonate
solution, and again with water, then dried over anhydrous sodium
sulfate. Evaporation of the CHC13 gave 520 grams of a slightly
yellow oil. Thin layer chromatography indicated an impurity
which remained at the origin. The oil was dissolved in warm
benzene (40C) and extracted with warm water to remove the
polar impurity. The benzene was dried, filtered and concentrated
to yield 423 grams of a yellowish oil (B).
1062S79
Preparation of dimethyloctadecyl-26-tosyloxy-3,6,9,12,
15,18,21,24 octaoxahexacosylammonium tosylate (C). The
ditosylate (B) 86.7 grams (0.12 mole) and 35.8 grams of distilled
dimethyloctadecylamine were heated at reflux for 5 hrs. in 400
ml of acetonitrile. The solvent was then removed to give 120
grams of a mixture consisting of the monoquaternary tosylate (C),
diquaternary ammonium by-product (D) and some unreacted
ditosylate (B),
Preparation of 26-dimethyloctadecylammonio-3,6,9,12,
15,18,21,24 octaoxahexacosane-l-sulfonate. The mixture of
monoquat (C) and diquat (D) prepared above was dissolved in 1
liter of methanol. Sodium sulfite (100 grams, 0.79 moles) was
added and the reaction mixture was refluxed with stirring for 5
hours. Additional methanol was added and the insoluble salts
were filtered. The solvents were removed to yield a solid
product.
Purification. The above solid reaction product was
dissolved in 1 liter of methanol and stirred with 386 grams of
a mixed bed (Rexyn ~ 300 H-OH, commercially available from the
Fisher Scientific Co.) resin for 5 hours. The solution was then
passed through a column of fresh resin (350 grams of Rexyn ~ 300)
at a rate of 2 liters per 7 hours. The methanol solution was
then concentrated to yield 31.8 grams of a light yellow oil
which was recrystallized from acetone to give a white crystal-
line, hygroscopic product. This product was identified as the
title compound (E in the following schematic).
The following sequence sets forth the above procedure
in abbreviated form to clarify the structures of compounds
prepared thereby. In the sequence, the dimethyloctadecylamine
can be replaced by dimethylhexadecylamine, dimethylnonadecyl-
amine, dimethyleicosylamine, and dimethyldocosylamine,
- 14 -
~06257'~
respectively, and the corresponding compounds wherein R1 is C16,
Clg, C20, and C22 are secured, respectively.
106Z579
HO~C2H40)3H ~ Na O (C2H40)3H (ClCH2CH20)2C2H4
,
(A) ~(F2H4)9H ~
S020 (C2H40) 9 - 2S ~CH3
18~37N(CH312
- C
~C) . C18H37 1 - (C2H4o) 9 - 02S~CH Na2S3
,
CH3~S
,; . . . .
(D) Diquaternary ammo~ium byproduct
CIH3
(E) C18H37 ~ ~ (C2H4o)8 C2H4503 - -
C 3
~F) 2 CH3 ~ S03 , Na
~, .
~A !
;_,,, .1
1062579
b.) Di-long chain derivatives
; In this derivative, both Rl and R2 are hydrocarbon
moieties that can be straight or branched chain C6-C21 alkyl or
alkenyl groups; R3, R4, and X are as in (i) (a.) above and y
has an average value in the range 6-100. Preferably Rl and R2
are identical and comprise alkyl groups each having 10 to 16
carbon atoms, most preferably alkyl groups each having 10 to 24
carbon atoms. Preferred values for y lie in the range 9 to 50,
most preferably in the range 12 to 25.
A specific preparation of a di-long chain alkyl
ethoxylated zwitterionic compound useful in the present invention
was as follows:
Methylation of di-n-octylamine was accomplished by
slowly mixing 50 grams of the secondary amine with, first,
formic acid (30.03 grams), and then formaldehyde, at 0C. The
reaction mixture was kept at 80C for 24 hours, then adjusted
to pH 8-9 with 10~ NaOH solution. The resulting tertiary amine
was extracted with CHC13 and dried over Na2SO4. The tertiary
amine (25.6 grams, 0.10 mole) was then refluxed with 72 grams
(0.10 mole) of nonaethylene glycol ditosylate (compound B, pre-
pared as in the previous procedure) in acetonitrile for 6 hours.
The solvent was evaporated and the resulting mixture of mono-
and diquaternary compounds was dissolved in methancl and re-
fluxed with 100 grams of sodium sulfite (predissolved in water)
for 16 hours. Excess sulfite and other salts were filtered and
the filtrate was stirred for 16 hours with 500 grams of a mixed
bed resin (Rexyn ~ 300). A second treatment with fresh resin
was necessary to remove all impurities. The solvents were
evaporated to complete dryness and the product, 22 grams of a
light yellow viscous oil, was identified as
1062579
fH3
8 17 1 (CH2cH2)8cH2cH2s3
C8H17
or 26-dioctylmethylammonio-3,6,9,12,15,18,21,24-octaoxahexa-
cosane-l-sulfonate.
c.) Tri-long chain derivatives
In this derivative, Rl, R2, and R3 are all hydrocarbon
moieties that can be straight or branched chain C6-C16 alkyl or
alkenyl groups; R4 and X are as in (i) (a.) and (b.) above and
10 y has a value in the range 6-100. Preferably Rl, R2, and R3
are each identical and each comprise an alkyl group having 8-16
carbon atoms in the chain. Most preferably each chain contains
8-12 carbon atoms. y has a preferred value in the range 9-50,
most preferably in the range 12-50.
A specific preparation of a tri-long chain alkyl
ethoxylated zwitterionic compound was as follows:
Tri-n-octylamine was distilled to insure purity and 42
grams of the purified product (0.12 mole) was reacted with 87
grams (0.12 mole) of the ditosylate of nonaethylene glycol
(compound B in the mono-long chain preparation) in dry N,N-
dimethylformamide at 100C for 2 hours. The dimethylformamide
was removed and the mixture of mono- and diquaternary material
was dissolved in methanol. This mixture was refluxed for 16
hours with 100 grams of Na2SO3 predissolved in water. The in-
soluble salts were filtered and the filtrate was stirred with 500
grams mixed bed resin (Rexyn ~ 300 H-OH) for 24 hours. An
additional treatment with 500 grams fresh resin was used to
further purify the product. Thin layer chromatography still
- 18 -
106Z579
indicated an impurity, which was subsequently removed by dis-
solving the product in H2O, acidifying to pH 4, and extracting
with CHC13. The CHC13 extract was rinsed with sodium bicarbonate,
dried and evaporated to give a light yellow viscous oil,
identified as
1 8H17
8H17 ~ ~ (CH2cH2)8 CH2CH2S3
C8H17
or trioctylammonio-3,6,9,12,15,18,21,24-octaoxahexacosane-1-
sulfonate
' " R2
ii) Rl - ~ - (C2H4O)y_l ~ CH2CH2 X (I)
( 2 4 ) x
In this structure, R1 can be a linear or branched
C8-C22 alkyl or alkenyl group, preferably a C16 18 alkyl or
alkenyl group; R2 can be a C8-C30 alkyl or alkenyl group or can
be a Cl-C4 alkyl or hydroxyalkyl group, preferably a methyl group;
and X can be a sulfonate or sulfate radical.
The number of ethylene oxide groups in each chain can
20 be from 1 to 100 but their sum should be greater than 10.
Normally there will be approximately the same number in each
chain, the sum of the groups in both chains preferably having a
value in the range 12-50 and most preferably in the range 12-25.
The preparation of zwitterionic compounds of this type
is accomplished using commercially available starting materials.
-- 19 --
1062579
A typical starting material is marketed under the trademark
Ethoquad, by the Armak Company of the Armour Company. Ethoquad
is a mixture of quaternary ammonium compounds whose predominant
component is a di-ethoxylate of the structure
Rl 2 4 )Y
2 ( 2H4)xH
wherein y and x are each non-zero integers whose average sum is,
for example, 5, 10, 15, 50, depending on the "cut" selected, and
1 2 e C12 C18 alkyl and Cl-C3 alkyl, respectively
In general terms, the compounds herein are prepared by
dissolving Ethoquad in pyridine or other suitable base and
cooling the mixture to a temperature of about 0C. Tosyl
chloride is slowly added to the Ethoquad mixture at a 1:1
stoichiometric ratio while the reaction mixture is kept at about
OC-5C in an ice bath. The mixture is then stirred for about
24 hours at OC-5C. At the end of that time the reaction mix-
ture is poured into water and acidified to a pH of 2-3 with HCl.
The foregoing acidified reaction mixture is then ex-
tracted with chloroform and the extract is rinsed first with
sodium bicarbonate solution, then with water; the extract is
then dried over anhydrous sodium sulfate. After evaporation of
the chloroform extract, an oily residue is obtained. This is the
mono-tosylate ester of the structure
- 20 -
106Z579
18 37 (C2H4O)y - O2S ~ CH3
N / , Cl
CH3 / (C2H4)xH
wherein y and x are as above.
The foregoing tosylate ester is then dissolved in
methanol and refluxed for about 24 hours with about a lO molar
excess of sodium sulfite predissolved in H2O. The reaction
mixture is cooled and excess sodium sulfite and sodium tosylate
are removed by filtration. The filtrate is stirred with a
mixed bed (anion-cation) resin to purify the product. A second
resin treatment can optionally be used to remove substantially
all traces of all cationic and anionic impurities. The purified
mono-sulfonate corresponding to (I) above is recovered by
evaporating the solvent. The product can optionally be re-
crystallized from acetone.
N ~ C2H4O)y 1 ~ CH2CH2 ~ X ~ M (II)
(C2H40) X-l - CH2CH2
where Rl, R2, and X are as in (ii) and y and x each
have a value in the range l-lO0 provided that the sum of
y + x > 10. Preferred values for the sum of y + x will
lie in the range 12-50 and most preferably in the range
15-25. The cation M can be alkali metal, ammonium, and
alkanolammonium, e.g. ethanolammonium or methanolammonium
but is most preferably sodium.
- 21 -
106Z579
The disulfonate (II) is prepared in the same manner as
the mono-sulfonate (I), but using excess tosyl chloride (about
3:1 mole ratio, or greater) in the first step and a larger excess
of sodium sulfite (20:1 mole ratio) in the second step. If a
cation, M, other than sodium is desired in the final product,
the corresponding sulfite can be used in the second step.
Alternatively, the sodium form of compound (II) can be ion-
exchanged in standard fashion to any desired cation, M. The
resin purification treatment is unnecessary when preparing the
disulfonate.
The sulfates of the type (I) and (II) are easily pre-
pared by reacting one or two moles of chlorosulfonic acid with
the Ethoquads, respectively. The same consideration with regard
to selection of cation M holds true for the sulfates as for the
sulfonates.
It will be appreciated that a variety of diethoxylated
amino starting materials can be employed in the foregoing re-
action scheme. For example, Ethoquad derivatives having
variations in groups Rl and R2 are commercially available, e.g.,
compounds wherein Rl is an average C12 cut. Moreover, precursor
compounds having varying sums of y and x (within the recited
range) can be selected according to the desires of the user.
Compounds wherein y and x are of approximately equal length, the
sum of y and x being from about 12 to about 25, most preferably
from 15 to about 25, are especially useful herein.
It will be further appreciated that a variety of other
starting materials can be employed to prepare various di-
ethoxylated precursors of the present zwitterionic compounds.
For example, the Ethomeens (a trademark of a class of compounds
marketed by the Armak Company, a division of the Armour Company)
- 22 -
1062S~9
can be quaternized to produce variations of the commercial
Ethoquads. Thus, Ethomeens of the general formula R-N(C2H40)X
H(C2H40)yH, when R is alkyl, can be reacted with excess alkyl
iodide or hydroxy-substituted alkyl iodide (CH3I, C2H5I, etc.)
to produce a quaternary ammonium compound which can be sulfated
or sulfonated on one or both ethylene oxide groups in the manner
disclosed above.
It should be appreciated that mixtures of any of these
zwitterionic compounds in any proportions may be used in the
compositions of the present invention. Such mixtures may be
produced intentionally by blending individual species or may
arise as a result of the choice of feedstocks or as a result of
the
- 23 -
1062579
processing s~eps involved.
Th~ ethoxylated zwitterionic compounds useful in
the present invention desirably display appreciable
solubility in aqueous media. A solubility in water
at 25C of at least 50 ppm, preferably more than 75 ppm
appears to be necessary for satisfactory particulate
~oil removal performance, but the preferred materials
have solubilities in water of 10/~-30C/~ by weight.
The second essential component of a composition in
accordance with the present invention is a detergent builder
material. This can be present at a level of from 1%-~9/~ by
weight of the composition, the actual level being dependent on
the end use of the composition and its desired physical form.
Inorganic detergent builders that are useful in
compositions in accordance with the present invention are the
alkali metal, ammonium and alkanolammonium, polyphosphates
(exempllfied by the tripolyphospnates, pyrophosphates, and
glassy polymeric meta-phosphates), phosphonates, silicates,
carbonates (including bicarbonates and sesquicarbonates),
sulphates, borates, and aluminosilicates.
Specific examples of polyphosphates of value in the
present invention are the alkali metal tr-ipolyphosphates, sodium,
gotassium ànd ammonium pyrophDsphate, sodium and potassium
orthophosphate, sodium polymeta phosphate in which the degree
of polymerization ranses from about 6 to about 21. Particularly
preferred are the alkali metal tripoly- and pyro- phosphates.
Examples of suitabie phosphonate builder salts are
the water-soluble salts of ethane l-hydroxy-l, l-diphosphonate
particularly the sodium and potassium salts, the water-soluble
- 24 -
~i
~062579
salts of methylcne diphosphonic acid e.g. the trisodium and tri-
potassium salts and the water-soluble salts of substituted
methylene diphosphonic acids, such as the trisodium and tri-
potassium ethylidene, isopropylidene benzylmethylidene and halo
methylidene phosphonates. Phosphonate builder salts of the
aforementioned types are disclosed in U. S. Patent Nos.-
3,159,581 and 3,213,030 issued December l, 1964 and October
19, 1965,to Diehl; U. S. Patent No. 3,422,021 issued January
14, 1969, to Roy; and U. S. Paten~ Nos. 3,400,148 and 3,422,137
lG issued September 3, 1968, and Janury 14, 1969 to Quimby.
Preferred silicate builders are the alkali metal
silicates, particularly those having a SiO2:Na2O ratio in the
range 1-6:1 to 3-2:1. However, other silicates may also be
useful-such as for example magnesium silicate, which can serve
as a crispening agent in granular formulations as a stabilizing
agent for oxygen bleaches such as sodium perborate, and as a
component of suds control systems.
Examples of preferred carbonate builders include
sodium carbonate and sesquicarbonate and mixtures thereof with
ultra-fine calcium carbonate as disclosed in German Patent
Application DOS No. 2,321,001 published on November 15, 1973.
Alkali metal borates which are of value in the present
invention include sodium tetraborate, decahydrate, and potassium
pentaborate tetrahydrate.
Aluminosilicate builder salts found to be useful in
the present invention have the general formula:
Nazt~A102)z (SiO2)~,] X H20
~''
106Z579
wherein z and y are integers of at least 6, the molar
ratio of z to y is in the range from 1.0 to about 0.5,
and x is an integer from about 15 to about 264. Such
aluminosilicates also should have a particle size
diameter in the range 0.1 to 100 microns, a calcium ion
exchange capacity of at least about 200 milligram equiva-
lent/gram and a calcium ion exchange rate of at least
about 2 grains/U.S. gallon/minute/gram. Detergent com-
positions incorporating aluminosilicate builder salts of
this type are disclosed in Canadian patent 1,035,234,
issued July 25, 1978.
Organic detergent builders suitable for the purposes
of the present invention include, but are not restricted to,
alkali metal, ammonium and alkanolammonium, salts of ethylene
diamine tetraacetic acid, nitrilo triacetic acid, phytic acid,
mellitic acid, and mixtures thereof with benzene penta carboxylic
acid, benzene 1, 3, 5-tricarboxylic acid and 1, 3, 5-trihydroxy
benzene-2, 4, 6-trisulphonic acid, citric acid, itaconic acid,
oxydisuccinic acid, carboxy-methyloxysuccinic acid, poly maleic
acid, and copolymers of maleic anhydride with ethylene or vinyl
methyl ether. Specific disclosures of these and other suitable
organic detergent builders occur in U. S. Patent No. 3,308,067
issued March 7, 1967, to Diehl; Japanese Patent Application No.
73,703 filed May 24, 1971, and published January 8, 1973;
U. S. Patent Nos. 3,699,159, 3,758,420, and 3,812,044 issued
October 17, 1972, September 11, 1973, and May 21, 1974 in the
names of Connor and Krummel; and U. S. Patent No. 3,635,830
issued January 18, 1972 in the names of Lamberti and Konort.
Mixtures of any of the above detergent builders can
also be used, several particularly advantageous combinations
- 26 -
106Z579
being disclosed in U. S. Patent Nos. 3,356,613 and 3,392,121
issued respectively on December 5, 1967 and July 9, 1968 to
Gedge.
The accompanying Tables illustrate the particulate
soil removal performance given by combinations of ethoxylated
zwitterionic compounds useful in the present invention and
various detergent builders.
Table I shows the effect of a variety of builders both
inorganic and organic, on the clay soil removal performance of
two ethoxylated zwitterionic compounds that show good performance
on their own. At a zwitterionic compound usage level of 250
ppm, an overall performance improvement is seen for addition of
any builder, with marked benefits on cotton and polyester fabrics.
At a zwitterionic compound usage level of 125 ppm, the addition
of builder restores the level of performance in most instances
to that provided by 250 ppm ethoxylated zwitterionic compound
alone and in some instances exceeds it.
Table II shows a similar result for two ethoxylated
zwitterionic compounds whose particulate soil removal perform-
ance in the absence of builder is not particularly good. Theresults show that certain detergent builders can raise the clay
removal performance of these "poorer" materials to the level
achieved by the ethoxylated zwitterionic compounds that have
good performance on their own and can in some instances even
match the performance of the control product A at its higher
usage concentration (1400 ppm).
The efficacy of builder-ethoxylated zwitterionic com-
pound combinations for a range of zwitterionic compound
structures is demonstrated in Table III. It can be seen that a
combination incorporating the C8 alkyl dimethyl derivative
- 27 -
106Z5~9
(Run No. 4) does not provide good particulate soil removal per-
formance (c.f. C12 alkyl and C14 alkyl materials in Table II)
but that performance improves slightly for the di-C8 derivative
(Run No. 5) and then shows a marked increase for the derivative
in which total substitution of the methyl side chains by C8
alkyl groups has taken place (Run No. 6). Runs 9 and 10
illustrate the desirability of exceeding a given solubility in
water, where it can be seen that the prior solubilization in
methanol of a compound having a low water solubility (cir. 50 ppm
by weight) provided some increase in performance but was not
essential in obtaining an appreciable level of particulate soil
removal. The influence of builder and ethoxylated zwitterionic
level is shown in Table IV where it can be seen that the use of
a builder combination having efficient mineral hardness removal
characteristics can permit the level of ethoxylated zwitterionic
to be lowered considerably (Runs 8 & 9). The use of less
efficient builder systems do not provide the same degree of
formulation flexibility in that the particulate soil removal
performance correlates more directly with the level of the
ethoxylated zwitterionic compound (Runs 3, 4, & 5).
The particulate soil removal results demonstrate that
for those ethoxylated zwitterionic compounds having inherently
good performance, combination with a detergent builder permits a
substantial reduction in the zwitterionic level, the reduction
being associated with the efficacy of the builder in controlling
mineral hardness. For those ethoxylated zwitterionic compounds
that do not have such good particulate soil removal performance,
combination with detergent builders at a zwitterionic level of
125 ppm in solution provides an improvement that in most cases
matches and even exceeds the performance of the control product
- 28 -
1062579
used at recommended concentrations.
Grease and oil removal performance results for combin-
ations of ethoxylated zwitterionic compounds and detergent
builders are set out in Table V. Combinations using the C16
dimethyl octaethenoxy compounds, the C14 homologue, and 1:1
blends of these two materials all show an overall improvement in
grease and oil removal for the incorporation of a detergent
builder but the effect varies both with the fabric and stain
type. In general, a noticeable improvement is seen on polyester
fabrics for both types of stain but the effect is more variable
on poly-cotton blends, particularly with triglyceride-type
stains.
In summary, the addition of a detergent builder to
the ethoxylated zwitterionic compounds of the present invention
improves grease and oil removal on synthetic fabrics, while
having an effect on cotton blends which is dependent on the
stain type and the nature of the builder combination.
106Z579
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1062579
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1062579
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-- 32 --
106Z579
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-- 33 --
10~2579
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-- 34 --
1062579
Optional Components
In addition to the ethoxylated zwitterionic compound
and the detergent builder, the detergent compositions of the
present invention may also contain other ingredients convention-
ally employed in such products. The principal optional component
is a cosurfactant which may be nonionic, zwitterionic, ampholytic,
anionic, or cationic. Nonionic, zwitterionic, and ampholytic
cosurfactants may be present in amounts ranging from 5-95% by
weight of a composition containing the ethoxylated zwitterionic
detergent builder combination. Cationic surfactants containing
a hydrophilic moiety in the molecule (e.g. hydroxy, hydroxyalkyl,
and ethenoxy groups) can also be utilized at these levels, but
cationic surfactants not possessing such groupings serve to de-
press the particulate soil removal performance of the ethoxylated
zwitterionic compounds. Anionic cosurfactants are preferably
incorporated in amounts not exceeding 100% by weight of the
ethoxylated zwitterionic compound for similar reasons.
Specific cosurfactant-ethoxylated zwitterionic com-
pound mixtures are disclosed in U.S. Patent 3,929,678, issued
December 30, 1975.
Another optional ingredient that may be incorporated is
an enzyme for removal of protein-based or carbohydrate-based
stains. Enzymes for removing protein-based stains are prote-
olylic in nature, such as those sold under the trade mark
"Alcalase" and "Esterase" by Novo Industries A/S Denmark or under
the trade mark "Maxatase" and "AZ Protease" by Gist-Brocades N.V.
the Netherlands. These materials are normally incorporated at
levels of up to 1% by weight, preferably 0.25% to 0.75% by weight,
and are preferably coated or prilled with inert additives to
minimize dust formation and improve storage stability. A wide
range of enzyme materials and means for their incorporation into
- 35 -
1062579
synthetic detergent granules is disclosed in U.S.P. 3,553,139
issued on January 5, 1971, to McCarty, Roald, DeOude, Blomeyer,
and Cracco.
A further ingredient that may be incorporated to im-
prove product performance is a bleaching agent of the halogen or
oxygen-containing type. Examples of the hypohalite bleach type
include trichloro isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane sulphon-
amides. Such materials are normally added at 0.5%-10% by weight
of the finished product, preferably 1%-5% by weight.
Examples of oxygen containing bleaches include sodium
perborate, sodium percarbonate, and potassium non-opersùlphate
that are incorporated at levels of 5-30%, preferably 10-25% by
weight of the final product. The inclusion of organic bleach
activators such as phthalic anhydride, tetra acetyl ethylene
diamine, tetra acetyl methylene diamine or tetra acetyl glycouril
lead to the in situ production during the washing process of the
corresponding organic peroxy acids which have enhanced low
temperature bleaching performance. Activators of this type are
normally used with sodium perborate, at usage levels of 5-15% by
weight of the final product.
Materials to boost or modify the sudsing pattern of the
compositions of the present invention may also be included.
Examples of suds boosters include coconut and tallow mono- and
di-alkanolamides, particularly ethanolamides and C12 15 alkyl
di-lower alkyl amine oxides. Typical suds depressors include
long chain fatty acids such as those disclosed in U. S. Patent
2,954,347 issued September 27, 1960, to Wayne St. John and com-
binations of certain nonionics therewith as disclosed in U. S.
Patent 2,954,348 issued September 27, 1960, to Eugene Schwoeppe.
- 36 -
~06Z57~
Other optional ingredients in granular products include
hydrotropes and anticaking additives such as salts of lower alky-
aryl sulphonic acids, salts of a -sulphosuccinic acid, and
~ -sulphobenzoic acid, and urea, normally utilized at levels of
0.5% to 5% by weight of the final product, preferably at levels
of 1%-3% by weight. C12-C18 alkyl acid phosphates and their con-
densation products with ethylene oxide may also be incorporated
at similar levels for control of crutcher mix viscosity. Antire-
deposition agents such as carboxymethyl cellulose, hydroxyethyl
cellulose, and their derivatives may also be incorporated.
Anti-tarnish and anti-corrosion agents, perfume and
color may also be included, the last ingredient being conveniently
added either as a general color or in the form of a speckle applied
to a separate granule fraction of the entire formulation or to a
granulate of one or more of the ingredients.
The pH of detergent formulations in accordance with the
present invention can lie anywhere within the range 5-12 but is
preferably chosen to fall within the range 8.0 -10.5 as this pro-
vides a slight particulate soil removal benefit on synthetic
fabrics. However, the use of specific optional components such
as enzymes may require the selection of a product pH that will
permit optimum functioning of the component concerned.
Granular formulations embodying the compositions of the
present invention may be formed by any of the conventional
techniques i.e., by slurrying the individual components in water
and then atomizing and spray-drying the resultant mixture, or by
pan or drum granulation of the components.
Liquid formulations embodying the compositions of the
present invention may contain builders or may be unbuilt. If the
compositions are unbuilt, they will conventionally contain
- 37 -
1062S79
approximately 30-50% total surfactant, from 1-10% of an organic
base such as mono, di, or tri-alkanolamine, a solubilization
system such as alkali metal halide and a lower primary alcohol
such as ethanol or isopropanol and approximately 30%-40% water.
Such compositions will normally be homogeneous single phase
liquids of low viscosity (approximately 100-150 centipoises at
75F).
- 38 -
1062579
Built liquid detergent compositions may also be
single phase liquids provided that the builder can be solu-
bilized in the mixture at its level o~ use. Such liquids
conventionally contain 10%-25% total surfactant, 1~o~20%
builder which may be organic or inorganic, 5%-1~/o oE a
~ydrotrope system and 5~o~6~o of water. Liquids of this
type also have low viscosity (100-150 c.p.s. at 75F) ~
Built liquid detergents incorporating components that form
heterogeneous mixtures or levels of builder that cannot be
completely dissolved can also embody the compositions of the
present invention. Such liquids conventionally employ viscosity
modifiers to produce systems having plastic shear character-
istics to maintain stable dispersions and to prevent phase
separation or solid settlement.
~he following examples serve to illustrate the
present invention:
EXAMPLE 1 -
A concentrated detergent formulation having the
consistency of a thick paste was prepared having the following
composition by weight:
w-(hexadecyl dimethyl ammonio)- 38.4
2-octaethenoxy ethane-l-sulphonate
Sodium Carbonate 30.8
Sodium Silicate (SiO2:Na2O = 3 2:1) 30.8
100,. 0% .
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- 1062579
Cotton, polycotton, and polyester cloth swatches that
had been soiled with a standardized illite clay soil were given
a ten minute wash with this product in the tergotometer at 105F
using water of mineral hardness 7 grains~gallon (Ca:Mg = 2:1).
Product concentration was adjusted to give 250 ppm of zwitter-
ionic compound in solution. Following rinsing and drying, ths
swatches were then graded instrumentally for clay soil removal
ùsing a Hunter Color Difference meter. The results, expressed
as a percentage of the performance achieved by the Standard
Formulation A used at 0.10~ concn. by wt. under the same condi-
tions, were as follows:
- Cotton Polycotton Polyester
92% 106~ 109%
Example II
A solid powdered formulation was prepared having
the following composition:
~ -(N-octadecyi, N-methyl, N-polyethenoxy 27.8%
ammonio)-2-polyethenoxy ethane-l-sulphonate
wherein the total number of ethylene oxide
groups in the molecule was 14
. Sodium Tripolyphosphate 27.8
Sodium Carbonate 22.2
Sodium Silicate (SiO2:Na2O = 3-2:1) 22.2
. _
'100.0
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Using the product concen~rations and adopting-the
Testing Procedure set out in Example I, the following results
were obtained,expressed as a percentage of the performance of
the Control Product A under the same conditions:
CottonPolycotton Polyester
104% 99% 106%
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