U.S. patent number 3,925,262 [Application Number 05/493,952] was granted by the patent office on 1975-12-09 for detergent composition having enhanced particulate soil removal performance.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Robert Gene Laughlin, Robert Lee Stewart.
United States Patent |
3,925,262 |
Laughlin , et al. |
December 9, 1975 |
Detergent composition having enhanced particulate soil removal
performance
Abstract
Detergent compositions are disclosed incorporating combinations
of specified ethoxylated zwitterionic compounds with detergent
builders and other types of surfactants to give enhanced
particulate soil removal.
Inventors: |
Laughlin; Robert Gene
(Cincinnati, OH), Stewart; Robert Lee (Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
23962393 |
Appl.
No.: |
05/493,952 |
Filed: |
August 1, 1974 |
Current U.S.
Class: |
510/345; 558/29;
510/336; 510/493; 510/494; 510/359; 510/337; 510/351; 510/352;
510/357; 510/340 |
Current CPC
Class: |
C11D
1/88 (20130101); C11D 1/92 (20130101) |
Current International
Class: |
C11D
1/92 (20060101); C11D 1/88 (20060101); C11D
003/066 (); C11D 001/18 () |
Field of
Search: |
;252/526,545,546,DIG.11,155 ;260/501.12 ;8/26 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
813,502 |
|
Oct 1974 |
|
BE |
|
2,009,802 |
|
Nov 1970 |
|
DT |
|
Primary Examiner: Welsh; John D.
Attorney, Agent or Firm: Filcik; Julius P. O'Flaherty;
Thomas H. Witte; Richard C.
Claims
What is claimed is:
1. A detergent composition comprising
A. 1 to 99% by weight of the composition of a compound having the
formula selected from the group consisting of ##EQU15## wherein
R.sub.1 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.30 alkyl and alkenyl moieties and
alkaryl moieties in which the alkyl group has 10-24 carbon
atoms;
R.sub.2 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
and C.sub.1-4 alkyl and hydroxyalkyl moieties;
R.sub.3 is selected from the group consisting of straight and
branched chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
C.sub.1-4 alkyl and hydroxyalkyl moieties and --(C.sub.2 H.sub.4
O).sub.x H wherein x has a value of about 3 to about 50;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene, and 2-
and 3-hydroxy butylene moieties and C.sub.1 -C.sub.4 alkarylene
moieties provided that where R.sub.3 is --(C.sub.2 H.sub.4 O).sub.x
H then R.sub.4 is --CH.sub.2 --CH.sub.2 --;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals;
and y has a value in the range of 2-100 provided that where R.sub.3
is --(C.sub.2 H.sub.4 O).sub.x H then x + y .gtoreq. 10; and
##EQU16## wherein R.sub.1 is selected from the group consisting of
linear and branched C.sub.8 -C.sub.30 alkyl and alkenyl
radicals;
R.sub.2 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals and C.sub.1
-C.sub.4 alkyl and hydroxyalkyl radicals;
X.sup.- is selected from the group consisting of sulfate and
sulfonate;
y and x have values in the range of 2-100 provided that y + x
.gtoreq. 12;
M is a cation selected from the group consisting of alkali metal,
ammonium and alkanolammonium ions; and
B. 99to 1% by weight of the composition of a detergent builder.
2. A detergent composition according to claim 1 wherein the
detergent builder is an inorganic detergent builder selected from
the group consisting of alkali metal, ammonium, and alkanolammonium
polyphosphates, carbonates, bicarbonates, silicates,
aluminosilicates, borates, and sulfates.
3. A detergent composition according to claim 1 wherein the
detergent builder is an organic detergent builder selected from the
group consisting of alkali metal ammonium and alkanolammonium salts
of ethylene diamine tetra acetic acid, nitrilotriacetic acid,
citric acid, oxydisuccinic acid, carboxymethoxysuccinic acid,
benzene penta- and hexa-carboxylic acid, 1, 3, 5-trihydroxy
benzene-2, 4, 6-trisulfonic acid, and copolymers of maleic
anhydride with vinyl methyl ether and ethylene.
4. A detergent composition according to claim 1 wherein the
zwitterionic compound has the formula ##EQU17## wherein R.sub.1 is
selected from the group consisting of straight and branched chain
C.sub.16 -C.sub.22 alkyl and alkenyl moieties, R.sub.2 is a C.sub.1
-C.sub.3 alkyl group and x + y has a value in the range of
12-50.
5. A detergent composition according to claim 4 wherein R.sub.1 is
selected from the group consisting of straight and branched chain
C.sub.16-C.sub.18 alkyl and alkenyl moieties and x + y has a value
in the range of 15-25.
6. A detergent composition comprising
A. 1-99% by weight of the composition of a compound having the
formula ##EQU18## wherein R.sub.1, R.sub.2, and R.sub.3 are each
selected from the group consisting of branched and straight chain
C.sub.6 -C.sub.16 alkyl and alkenyl radicals;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene, and 2-
and 3-hydroxy butylene moieties and alkarylene moieties in which
the alkyl group contains from 1-4 carbon atoms;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals; and
y has an average value in the range of 6-100; and
B. 99-1% by weight of the composition of a detergent builder.
7. A detergent composition according to claim 6 wherein y has a
value of at least 9.
8. A detergent composition comprising
A. 1-99% by weight of the composition of a compound having the
formula: ##EQU19## wherein R.sub.1 and R.sub.2 are each selected
from the group consisting of branched and straight chain C.sub.6
-C.sub.21 alkyl and alkenyl radicals;
R.sub.3 is selected from the group consisting of C.sub.1 -C.sub.4
alkyl and hydroxyalkyl moieties;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene, and 2-
and 3-hydroxy butylene moieties and alkarylene moieties in which
the alkyl group contains 1-4 carbon atoms;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals; and
y has an average value in the range of 6-100;
B. 99-1% by weight of the composition of a detergent builder.
9. A detergent composition according to claim 1 wherein the
compound has the formula: ##EQU20## wherein R.sub.1 is selected
from the group consisting of branched and straight chain C.sub.8
-C.sub.30 alkyl and alkenyl radicals; R.sub.2 and R.sub.3 are each
selected from the group consisting of C.sub.1 -C.sub.4 alkyl and
hydroxyalkyl moieties; and R.sub.4 is selected from the group
consisting of C.sub.1 -C.sub.8 alkylene, C.sub.3 -C.sub.8
alkenylene, 2-hydroxy propylene, and 2- and 3-hydroxy butylene
moieties and alkarylene moieties in which the alkylene group has
1-4 carbon atoms; and y has a value of from about 6 to about
20.
10. A detergent composition according to claim 9 wherein R.sub.1 is
a C.sub.12 -C.sub.18 alkyl moiety; R.sub.2 and R.sub.3 are
independently selected from C.sub.1 -C.sub.3 alkylene and
hydroxyalkylene moieties; R.sub.4 is a --CH.sub.2 CH.sub.2
--moiety; and y has a value from about 6 to about 12.
11. A composition according to claim 1 incorporating an organic
detergent selected from the group consisting of anionic, nonionic,
ampholytic, and zwitterionic surfactants.
Description
BACKGROUND OF THE INVENTION
This invention relates to detergent compositions haveing improved
particulate soil removal capability. More particularly, this
invention relates to detergent compositions incorporating certain
ethoxylated compound 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 neurtral, are known. For example,
U.S. Pat. Nos. 3,668,240 and 3,764,568 to Melvin A. Barbera, issued
respectively on June 6, 1972, and Oct. 9, 1973, disclose
zwitterionic surfactants having a 2, 3-butene moiety between the
charge centers. U.S. Pat. No. 3,332,875 to Adriaan Kessler and
Phillip Floyd Pflaumer also discloses mixtures of certain olefim
sulphoneates with zwitterionic detergents in which the charge
centers are separated by a 2-hydroxy propane group. U.S. Pat. Nos.
3,452,066 and 2,781,390 to Hans S. Mannheimer, issued respectively
on June 24, 1969and Feb. 12, 1957, outline a range of zwitterionic
surfactants which optionally may be substituted with a wide variety
of oxygen-containing groups between the positive and negative
charge centers. U.S. Pat. No. 3,769,311 to Leonard J. Armstrong and
Eldon de Vere Dawald issued Oct. 30, 1973, discloses carboxylic
compounds having ethylene oxide groups between the charge centers
but fails to recognize the effect of the various structural
parameters 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 of the molecule
from an aqueous system onto particulate and other soils, and the
subsequent removal of the soil by emulsification or dispersion but
also the continued maintenance of the removed soil in suspension in
the aqueous solution.
Some of these compounds are effective in the absence of
conventional detergent additives such as builders, surfactants etc.
and form the subject of the commonly assigned co-filed Ser. No.
493,951, filed Aug. 1, 1974 Applications by Robert G. Laughlin,
Eugene P. Gosselink, William A. Cilley, and Vincent P. Heuring and
Robert G. Laughlin, Eugene P. Gosselink, and William a. Cilley Ser.
No. 493,956, filed of even date (Attorney's Docket No. 2102), both
Applications being entitled "Detergent Compounds." The disclosures
of both said Applications are hereby incorporated herein by
reference.
However, the present invention is directed to the discovery that a
wider range of zwitterionic compounds, of the type disclosed in the
above identified Applications, 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 ethoxylated zwitterionic
compounds useful in the present invention possess an ability to
remove particulate soil that is independent of water hardness over
a wide range of Ca .sup.+.sup.+ and Mg.sup.+.sup.+ levels.
Furthermore, this performance is relatively insensitive to
temperature changes in the range of 70.degree.-140.degree.F, the
normal range for domestic cleaning functions.
The importance of such a development is readily apparent as it
permits a high level of soil removal performance to be obtained
with a range of detergent formulations. Furthermore, the nature and
level of other components of the formulation can be controlled by
the selection of an ethoxylated zwitterionic material having the
appropriate level of performance.
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 present invention is the provision of
detergent compositions having improved particulate and oily soil
removal performance in both liquid and granular forms.
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:
##EQU1## wherein R.sub.1 is selected from the group consisting of
straight and branched chain c.sub.8 -C.sub.30 alkyl and alkenyl
moieties and alkaryl moieties in which the alkyl group has 10-24
carbon atoms;
R.sub.2 is selected from the group consisting of straight and
branched chain C.sub.8 -c.sub.21 alkyl and alkenyl moieties,
alkaryl moieties in which the alkyl group has 6-16 carbon atoms,
and C.sub.1-4 alkyl and hydroxyalkyl moieties;
R.sub.3 is selected from the group consisting of straight and
branced chain C.sub.8 -C.sub.21 alkyl and alkenyl moieties, alkaryl
moieties in which the alkyl group has 6-16 carbon atoms, C.sub.1-4
alkyl and hydroxyalkyl moieties and --(C.sub.2 H.sub.4 O).sub.x H
wherein x has a value of about 3 to about 50;
R.sub.4 is selected from the group consisting of C.sub.1 -C.sub.8
alkylene, C.sub.3 -C.sub.8 alkenylene, 2-hydroxy C.sub.3 alkylene
and 2- and 3-hydroxy C.sub.4 alkylene moieties and C.sub.1 -C.sub.4
alkarylene moieties provided that where R.sub.3 is --(C.sub.2
H.sub.4 O).sub.x H then R.sub.4 is --CH.sub.2 --CH.sub.2 --;
X.sup.- is an anion selected from the group consisting of sulfate
and sulfonate radicals; and
y has a value in the range of 2-100 provided that where R.sub.3 is
--(C.sub.2 H.sub.4 O).sub.x H then x + y .gtoreq. 10. ##EQU2##
wherein R.sub.1 is selected from the group consisting of linear and
branched C.sub.8 -C.sub.30 alkyl and alkenyl radicals; R.sub.2 is
selected from the group consisting of linear and branched C.sub.8
-C.sub.30 alkyl and alkenyl radicals and C.sub.1 -C.sub.4 alkyl and
hydroxyalkyl radicals;
X.sup.- is selected from the group consisting of sulfate and
sulfonate;
y and x have values in the range 2-100 provided that y + x .gtoreq.
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.sup.- moiety are
not preferred as they are unstable in water, especially at pH's
other than neutrality, and are extremely difficult to prepare
compared to other hydroxy substituted compounds.
Preferably the ethoxylated zwitterionic compound is one of either
.omega.-(N--C.sub.16-18 alkyl, N--C.sub.1-3 alkyl,N-polyethenoxy
ammonio)-2-polyethenoxyethane-1-sulphonate wherein the total number
of ethylene oxide groups lies in the range 15-25 or
.omega.-(N--C.sub.12-18 alkyl,N,N--diC.sub.1 -C.sub.3
alkylammonio)-2-polyethenoxy ethane-l-sulphonate wherein the number
of ethylene oxide groups in the polyethenoxy chain is in the range
6-12.
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
105.degree.F in 7 grains per U.S. gallon hard water (calculated as
CaCO.sub.3) 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 tumbled-dried prior to being
graded.
A similar washing procedure is used for the Tergotometer with the
exception that 5.5 grains/gallon water is employed having a 3:1
ratio of Ca:Mg salts (calculated as CaCO.sub.3). The wash is
followed by one rinse cycle of three minutes in 80.degree.F 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, polycotton (65% DACRON/35% cotton), and
polyester (KODEL) swatches which are stained with a standardized
illite clay soil. For the AMW, three 5 .times. 5 inch swatches of
each fabric are used in each load, while in the Tergotometer, three
21/2.times. 21/2 inch 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 detergent standard tested at the same
time under identical conditions. This standard formulation
hereinafter designated as A has the following composition by
weight:
Sodium C.sub.12 alkylbenzene sulphonate 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: ##EQU3## Performance is determined by finding the
difference in whiteness (.DELTA.W) before and after washing as:
This is compared to the commercial Control Product A by calculating
.DELTA.W as a percentage of .DELTA.W given by the Control Product
in each batch. ##EQU4## b. Grease and oil removing testing
Identical equipment and washing conditions are used to evaluate
grease and oil removal performance. The fabric load comprises a
mixture of green polycotton (65% DACRON /35% cotton) and polyester
(KODEL) swatches, four 21/2.times. 21/2 inch swatches of each type
being used in the tergotometer. 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 compound and a
detergent builder material which may be inorganic or organic in
character. Thw 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 treatment of laundry to remove specific stains
by direct application 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 ethoxylated
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 flexibility is due, at
least in part, to the ability of the zwitterionic 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: ##EQU5## a.
Mono-long chain derivatives
In this derivative, R.sub.1 is a hydrocarbon moiety that can be a
straight or branched chain C.sub.8 -C.sub.30 alkyl or alkenyl group
or an alkaryl group in which the alkyl portion has 10-24 carbon
atoms; R.sub.2 and R.sub.3 are C.sub.1 -C.sub.4 alkyl or
hydroxyalkyl groups; R.sub.4 is a C.sub.1 -C.sub.8 alkylene,
C.sub.3 -C.sub.8 alkenylene, 2-hydroxy propylene or 2- or 3-
hydroxy butylene group or a C.sub.1 -C.sub.4 alkarylene group;
X.sup.- is a sulfonate or sulfate radical; and y has a value in the
range 2-100.
In this embodiment, preferred groups for R.sub.1 are C.sub.12
-C.sub.18 alkyl, particularly C.sub.14 -C.sub.16 alkyl, while
preferred groups for R.sub.2, and R.sub.3 are C.sub.1-3 alkyl and
C.sub.2-3 hydroxyalkyl, the most preferred groups being methyl- and
hydroxyethyl- 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
tetrahyydrofuran 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
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 ##SPC1##
i.e., the polyethylene glycol ditosylate. Pyridine or other
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 ##EQU6## wherein R.sub.1, R.sub.2 and R.sub.3 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 CH.sub.3 CN at temperatures of 80.degree. to about
100.degree.C to produce a mixture of ##SPC2##
and
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 evaporation of the
solvent to give, as the predominant zwitterionic product, ##EQU7##
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 differing 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 R.sub.4 groups within the scope of
this invention.
A specific preparation of a mono-long chain ethoxylated
zwitterionic compound useful in the present invention was as
follows:
Preparation of 26-dimethyloctadecylammonio-3,6,9,12,15,18,21,24
octaoxahexacosane-1-sulfonate
Preparation of Nonaethyleneglycol (A)
Under nitrogen, 46 grams (2 moles) of sodium pellets were added
cautiously to 2,664 ml (20 moles) of previously dried and distilled
triethyleneglycol. The temperature was kept below 100.degree.C.
After all the sodium had reacted, the temperature was adjusted to
100.degree.C and 187 grams (1 mole) of 1,2-bis-(2-chloroethoxy)
ethane was added in a slow stream. The mixture was heated overnight
at 100.degree.C (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.degree.-175.degree.C 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 0.degree.C.
Tosyl chloride (i.e., p-toluene-sulfonyl chloride, 420 grams, 2.2
moles) was added, with stirring, in small portions. After the
addition was complete, the temperature increased to 10.degree.C and
the clear reaction mixture became cloudy. The mixture was stirred
at 0.degree.-10.degree.C 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 CHCl.sub.3.
The CHCl.sub.3 was washed with water, sodium bicarbonate solution,
and again with water, then dried over anhydrous sodium sulfate.
Evaporation of the CHCl.sub.3 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 (40.degree.C)
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).
Preparation of dimethyloctadecyl-26-tosyloxy-3,6,9,12,15,18,21,24
octaoxahexacosylammonium(C) 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 byproduct (D) and some unreacted ditosylate
(B).
Preparation of 26-dimethyloctadecylammonio-3,6,9,12,15,18,21,24
octaoxahexacosane-1-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 te
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 crystalline, 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, dimethylnonadecylamine,
dimethyleicosylamine, and dimethyldocosylamine, respectively, and
the corresponding compounds wherein R.sub.1 is C.sub.16, C.sub.19,
C.sub.20, and C.sub.22 are secured, respectively. ##EQU8## b.
Di-long chain derivatives
In this derivative, both R.sub.1 and R.sub.2 are hydrocarbon
moieties that can be straight or branched chain C.sub.6 -C.sub.21
alkyl or alkenyl groups; R.sub.3, R.sub.4 and X.sup.- are as in (i)
(a.) above and y has an average value in the range 6-100.
Preferably R.sub.1 and R.sub.2 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 0.degree.C. The reaction mixture
was kept at 80.degree.C for 24 hours, then adjusted to pH 8-9 with
10% NaOH solution. The resulting tertiary amine was extracted with
CHCl.sub.3 and dried over Na.sub.2 SO.sub.4. The tertiary amine
(25.6 grams, 0.10 mole) was then refluxed with 72 grams (0.10 mole)
of nonaethylene glycol ditosylate (compound B, prepared 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 methanol and refluxed 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 ##EQU9##
or
26-dioctylmethylammonio-3,6,9,12,15,18,21,24-octaoxahexacosane-1-sulfonate
.
c. Tri-long chain derivatives
In this derivative, R.sub.1, R.sub.2, and R.sub.3 are all
hydrocarbon moieties that can be straight or branched chain C.sub.6
-C.sub.16 alkyl or alkenyl groups; R.sub.4 and X.sup.- are as in
(i) (a.) and (b.) above and y has a value in the range 6-100.
Preferably R.sub.1, R.sub.2, and R.sub.3 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
100.degree.C 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
Na.sub.2 SO.sub.3 predissolved in water. The insoluble 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 indicated an impurity, which was
subsequently removed by dissolving the product in H.sub.2 O,
acidifying to pH 4, and extracting with CHCl.sub.3. The CHCl.sub.3
extract was rinsed with sodium bicarbonate, dried and evaporated to
give a light yellow viscous oil, identified as ##EQU10## or
trioctylammonio-3,6,9,12,15,18,21,24-octaoxahexacosane-1-sulfonate.
##EQU11##
In this structure, R.sub.1 can be a linear or branched C.sub.8
-C.sub.22 alkyl or alkenyl group, preferably a C.sub.16-18 alkyl or
alkenyl group; R.sub.2 can be a C.sub.8 -C.sub.30 alkyl or alkenyl
group or can be a C.sub.1 -C.sub.4 alkyl or hydroxyalkyl group,
preferably a methyl group; and X.sup.- can be a sulfonate or
sulfate radical.
The number of ethylene oxide groups in each chain can 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. A
typical starting material is marketed under the tradename 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 ##EQU12## 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 R.sub.1 and R.sub.2 are
C.sub.12 -C.sub.18 alkyl and C.sub.1 -C.sub.3 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 0.degree.C. Tosyl chloride is slowly
added to the Ethoquad mixture at a 1:1 stoichiometric ratio while
the reaction mixture is kept at about 0.degree.-5.degree.C in an
ice bath. The mixture is then stirred for about 24 hours at
0.degree.-5.degree.C. At the end of that time the reaction mixture
is poured into water and acidified to a pH of 2-3 with HCl.
The foregoing acidified reaction mixture is then extracted 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 ##EQU13## 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 10 molar excess of sodium
sulfite predissolved in H.sub.2 O. 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 recrystallized from acetone.
##EQU14## where R.sub.1, R.sub.2, and X.sup.- are as in (ii) and y
and x each have a value in the range 1-100 provided that the sum of
y + x .gtoreq. 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.sup.+ can be alkali metal, ammonium, and alkanolammonium,
e.g. ethanolammonium or methanolammonium but is most preferably
sodium.
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 prepared 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 reaction
scheme. For example, Ethoquad derivatives having variations in
groups R.sub.1 and R.sub.2 are commercially available, e.g.,
compounds wherein R.sub.1 is an average C.sub.12 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 tradename of a class of compounds marketed by the
Armak Company, a division of the Armour Company) can be quaternized
to produce variations of the commercial Ethoquads. Thus, Ethomeens
of the general formula R--N(C.sub.2 H.sub.4 O).sub.x H(C.sub.2
H.sub.4 O).sub.y H, when R is alkyl, can be reacted with excess
alkyl iodide or hydroxy-substituted alkyl iodide (CH.sub.3 I,
C.sub.2 H.sub.5 I, 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 processing steps involved.
The ethoxylated zwitterionic compounds useful in the present
invention desirably display appreciable solubility in aqueous
media. A solubility in water at 25.degree.C of at least 50 ppm,
preferably more than 75 ppm appears to be necessary for
satisfactory particulate soil removal performance, but the
preferred materials have solubilities in water of 10-30% 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 1-99% 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 (exemplified by the
tripolyphosphates, 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 tripolyphosphates, sodium, potassium
and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium polymeta phosphate in which the degree of polymerization
ranges from about 6 to about 21. Particularly preferred are the
alkali metal tripoly- and pyro- phosphates.
Examples of suitable phosphonate builder salts are the
water-soluble salts of ethane 1-hydroxy-1, 1-diphosphonate
particularly the sodium and potassium salts, the water-soluble
salts of methylene diphosphonic acid e.g. the trisodium and
tripotassium salts and the water-soluble salts of substituted
methylene diphosphonic acids, such as the trisodium and
tripotassium ethylidene, isopyropylidene benzylmethylidene and halo
methylidene phosphonates. Phosphonate builder salts of the
aforementioned types are disclosed in U.S. Pat. Nos. 3,159,581 and
3,213,030 issued Dec. 1, 1964 and Oct. 19, 1965, to Diehl; U.S.
Pat. No. 3,422,021 issued Jan. 14, 1969, to Roy; and U.S. Pat. Nos.
3,400,148 and 3,422,137 issued Sept. 3, 1968, and Jan. 14, 1969 to
Quimby, said disclosures being incorporated herein by
reference.
Preferred silicate builders are the alkali metal silicates,
particularly those having a SiO.sub.2 :Na.sub.2 O 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 Nov. 15, 1973, the disclosure of which is
incorporated herein by reference.
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:
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
equivalent/gram and a calcium ion exchange rate of at least about 2
grains/U.S. gallon/minute/gram. Detergent compositions
incorporating aluminosilicate builder salts of this type are
disclosed in the commonly assigned copending application Ser. No.
450,266 of Corkill, Madison, and Burns filed Mar. 11, 1974, which
disclosure is incorporated herein by reference.
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. Pat. No. 3,308,067 issued Mar. 7, 1967, to
Diehl; Japanese Pat. No. 73,703 filed May 24, 1971, and published
Jan. 8, 1973; U.S. Pat. Nos. 3,699,159, 3,758,420, and 3,812,044
issued Oct. 17, 1972, Sept. 11, 1973, and May 21, 1974 in the names
of Connor and Krummel; and U.S. Pat. No. 3,635,830 issued Jan. 18,
1972 in the names of Lamberti and Konort, which disclosures are
hereby incorporated by reference.
Mixtures of any of the above detergent builders can also be used,
several particularly advantageous combinations being disclosed in
U.S. Pat. Nos. 3,356,613 and 3,392,121 issued respectively on Dec.
5, 1967 and July 9, 1968 to Gedge, which disclosures are also
incorporated herein by reference.
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 performance in the absence
of builder is not particularly good. The results 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 compound
combinations for a range of zwitterionic compound structures is
demonstrated in Table III. It can be seen that a combination
incorporating the C.sub.8 alkyl dimethyl derivative (Run No. 4)
does not provide good particulate soil removal performance (c.f.
C.sub.12 alkyl and C.sub.14 alkyl materials in Table II) but that
performance improves slightly for the di-C.sub.8 derivative (Run
No. 5) and then shows a marked increase for the derivative in which
total substitution of the methyl side chains by C.sub.8 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 used at
recommended concentrations.
Grease and oil removal performance results for combinations of
ethoxylated zwitterionic compounds and detergent builders are set
out in Table V. Combinations using the C.sub.16 dimethyl
octaethenoxy compounds, the C.sub.14 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.
TABLE I
__________________________________________________________________________
CLAY SOIL REMOVAL PERFORMANCE OF ETHOXYLATED ZWITTERIONIC COMPOUNDS
IN COMBINATION WITH DETERGENT BUILDERS Conditions: 10 Minute Wash
in Tergotometer, Mineral Hardness 7 grains/gallon (Ca:Mg = 2:1),
Temp. 105.degree.F RELATIVE ETHOXYLATED LEVEL LEVEL CLAY REMOVAL
INDEX ZWITTERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO. COMPOUND
SOLUTION TYPE SOLUTION COTTON COTTON ESTER
__________________________________________________________________________
1 (N-C.sub.16 H.sub.33 N,N-bisCH.sub.3 ammonio) 250 -- -- 75 96 95
(CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 2 " 125 --
-- 62 88 77 3 " 250 Na.sub.5 P.sub.3 O.sub.10 250 104 100 101 4 "
125 Na.sub.5 P.sub.3 O.sub.10 250 100 97 105 5 " 250 Na.sub.4
P.sub.2 O.sub.7 250 111 102 112 6 " 125 Na.sub.4 P.sub.2 O.sub.7
250 92 90 106 7 " 250 Na.sub.12 (AlO.sub.2.SiO.sub. 2.).sub.12
27H.sub.2 O 500 104 94 107 8 " 125 " 500 65 93 93 * 9 " 250
CaCO*.sub.3 /Na.sub.2 CO.sub.3 100/200 93 95 104 10 " 125 " 100/200
63 93 99 11 " 250 Sodium NTA 180 117 98 122 12 " 125 Sodium NTA 180
98 97 116 13 " 250 Sodium citrate 300 88 94 101 14 " 250
CH(COONa).sub.2 OCH.sub.2 COONa 300 111 103 106 15 " 125
CH(COONa).sub.2 OCH.sub.2 COONa 300 104 101 104 * 16 " 250 Na.sub.2
CO*.sub.3 /Na.sub.2 SiO.sub.3 200/200 92 106 109 17 (N-C.sub.21
H.sub.43 N,N-bisCH.sub.3 ammonio) 250 -- -- 90 95 101 (CH.sub.2
CH.sub.2 O).sub.5 CH.sub.2 CH.sub.2 SO.sub.3 18 " 250 Na.sub.2
CO.sub.3 /Na.sub.2 SiO.sub.3 * 200/200 94 107 115
__________________________________________________________________________
*SiO.sub.2 : Na.sub.2 O = 3.2:1 **CaCO.sub.3 surface area 100
m.sup.2 /gram (.apprxeq.0.02.mu.)
TABLE II
__________________________________________________________________________
CLAY SOIL REMOVAL PERFORMANCE OF ETHOXYLATED ZWITTERIONIC COMPOUNDS
IN COMBINATION WITH DETERGENT BUILDERS Conditions: 10 Minute Wash
in Tergotometer, Mineral Hardness 7 grains/gallon (Ca:Mg = 2:1),
Temp. 105.degree.F RELATIVE ETHOXYLATED LEVEL LEVEL CLAY REMOVAL
INDEX ZWITTERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO. COMPOUND
SOLUTION TYPE SOLUTION COTTON COTTON ESTER
__________________________________________________________________________
1 (N-C.sub.14 H.sub.29 N,N-bisCH.sub.3 ammonio) 250 -- -- 53 69 46
(CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 2 " 125 --
-- 41 52 24 3 " 250 Na.sub.5 P.sub.3 O.sub.10 250 94 90 98 4 " 125
Na.sub.5 P.sub.3 O.sub.10 250 62 73 39 5 " 250 Na.sub.4 P.sub.2
O.sub.7 250 94 88 99 6 " 125 Na.sub.4 P.sub.2 O.sub.7 250 77 80 80
7 " 250 Na.sub.12 (AlO.sub.2.SiO.sub.2.).sub.12 27H.sub. 2 O 250 85
92 88 8 " 125 " 250 61 75 44 * 9 " 250 CaCO*.sub.3 /Na.sub.2
CO.sub.3 100/200 92 96 84 10 " 125 " 100/200 70 78 44 11 " 250
Sodium NTA 180 100 94 109 12 " 125 Sodium NTA 180 55 65 33 13 " 250
CH(COONa).sub.2 OCH.sub.2 COONa 300 98 103 99 14 " 125
CH(COONa).sub.2 OCH.sub.2 COONa 300 86 84 55 * 15 " 250 Na.sub.2
CO*.sub.3 /Na.sub.2 SiO.sub.3 200/200 80 92 75 16 (N-C.sub.12
H.sub.25 N,N-bisCH.sub.3 ammonio) 250 -- -- 50 46 33 (CH.sub.2
CH.sub.2 O).sub.5 CH.sub.2 CH.sub.2 SO.sub.3 17 " 250 Na.sub.2
CO.sub.3 /Na.sub.2 SiO.sub.3 * 200/200 68 67 41
__________________________________________________________________________
*SiO.sub.2:Na.sub.2 O = 3.2:1 **CaCO.sub.3 surface area 100 m.sup.2
/gram (.apprxeq.0.02.mu.)?
TABLE III
__________________________________________________________________________
CLAY SOIL REMOVAL PERFORMANCE OF A RANGE OF ETHOXYLATED
ZWITTERIONIC COMPOUNDS IN COMBINATION WITH A CARBONATE/SILICATE
BUILDER SYSTEM (SILICATE RATIO SiO.sub.2 :Na.sub.2 O = 3.2:1)
Conditions: 10 Minute Wash in Tergotometer, Mineral Hardness 7
grains/gallon (Ca:Mg=2:1), Temp. 105.degree.F RELATIVE CLAY REMOVAL
INDEX ETHOXYLATED LEVEL LEVEL ZWITTERIONIC PPM IN BUILDER PPM IN
POLY- POLY- NO. COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER
__________________________________________________________________________
1 (N-C.sub.18 H.sub.37 N,N-bisCH.sub.3 ammonio) 250 -- -- 94 98 98
(CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 2 " 250
Na.sub.2 CO.sub.3 /Na.sub.2 SiO.sub.3 200/200 104 103 113 3
(N-C.sub.16 H.sub.33 N,N-bisCH.sub.3 ammonio) 250 " 200/200 91 99
109 (CH.sub.2 CH.sub.2 O).sub.5 CH.sub.2 CH.sub.2 SO.sub.3 4
(N-C.sub.8 H.sub.17 N,N-bisCH.sub.3 ammonio) 250 " 200/200 46 53 39
(CH.sub. 2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 5
(N,N-bisC.sub.8 H.sub.17 N-CH.sub.3 ammonio) 250 " 200/200 52 62 33
(CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 6
(N,N,N-trisC.sub.8 H.sub.17 ammonio) 250 " 200/200 82 92 101
(CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 7
(N,N-bisC.sub.10 H.sub.21 N-CH.sub.3 ammonio) 250 " 200/200 101 95
109 (CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 8
[N-C.sub.18 H.sub.37 N-CH.sub.3,N-(CH.sub.2 CH.sub.2 O).sub.y 250 "
200/200 73 87 95 ammonio] (CH.sub.2 CH.sub.2 O).sub.x CH.sub.2
CH.sub.2 SO.sub.3 where x+y=15 9 (N-C.sub.18 H.sub.37
N,N-bisCH.sub.3 ammonio) 250 " 200/200 58 93 112 (CH.sub.2 CH.sub.2
O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 10 " (predissolved in methanol)
250 " 200/200 104 109 114
__________________________________________________________________________
TABLE IV
__________________________________________________________________________
EFFECT OF VARIATIONS IN LEVEL OF ETHOXYLATED ZWITTERIONIC COMPOUND
AND BUILDER ON CLAY SOIL REMOVAL PERFORMANCE Conditions: 10 Minute
Wash in Tergotometer, Mineral Hardness 7 grains/gallon (Ca:Mg =
2:1), Temp. 105.degree.F RELATIVE ETHOXYLATED LEVEL LEVEL CLAY
REMOVAL INDEX ZWITTERIONIC PPM IN BUILDER PPM IN POLY- POLY- NO.
COMPOUND SOLUTION TYPE SOLUTION COTTON COTTON ESTER
__________________________________________________________________________
N-C.sub.18 H.sub.37 N,N-bisCH.sub.3 250 -- -- 94 98 98 (EO).sub.8
CH.sub.2 CH.sub.2 SO.sub.3 2 " 250 Na.sub.2 CO.sub.3 /Na.sub.2
SiO.sub.3 * 200/200 104 103 113 3 " 13 Na.sub.5 P.sub.3 O.sub.10
250/200/200 51 -- 42 Na.sub.2 CO.sub.3 Na.sub.2 SiO.sub.3 * 4 " 50
" 250/200/200 63 -- 81 5 " 125 " 250/200/200 85 103 106 6 " 125 "
125/200/200 73 -- 108 7 " 125 " 50/200/200 75 -- 104 8 " 63
Na.sub.12 (AlO.sub.2 SiO.sub.2).sub.12 27H.sub.2 600 75 101 106
Na.sub.2 CO.sub.3 /Na.sub.2 SiO.sub.3 * 200/200 9 " 125 " 600 90
109 107 " 200/200
__________________________________________________________________________
*SiO.sub.2 :Na.sub.2 O = 3.2:1
TABLE V
__________________________________________________________________________
GREASE & OIL REMOVAL PERFORMANCE FOR COMBINATIONS OF
ETHOXYLATED ZWITTERIONIC COMPOUNDS AND DETERGENT BUILDERS
Conditions: 10 Minute Tergotometer Wash at 100.degree.F in 5.5
grains/U.S. gallon Mineral Hardness (Ca:Mg=3:1) ETHOXYLATED LEVEL
LEVEL ZWITTERIONIC PPM IN BUILDER PPM IN POLYCOTTON POLYESTER NO.
COMPOUND SOLUTION TYPE SOLUTION TG % HC % TG HC
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% 1 (N-C.sub.16 H.sub.33 N,N-bisCH.sub.3 ammonio) 250 -- -- 91 132
75 102 (CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 2 "
250 Na.sub.5 P.sub.3 O.sub.10 250 97 143 98 109 3 " 500 Na.sub.12
(AlO.sub.2.SiO.sub.2.).sub.12 27H.sub.2 O 500 8 121 99 115 4
(N-C.sub.14 H.sub.29 N,N-bisCH.sub.3 ammonio) 250 -- -- 100 75 80
99 (CH.sub.2 CH.sub.2 O).sub.8 CH.sub.2 CH.sub.2 SO.sub.3 5 " 250
Na.sub.5 P.sub.3 O.sub.10 250 76 122 100 126 6 " 250 Na.sub.12
(AlO.sub.2.SiO.sub.2.).sub.12 27H.sub.2 O 500 63 93 88 111 7
C.sub.16 /C.sub.14 compound mixture 125/125 -- -- 91 121 77 91 8 "
125/125 Na.sub.5 P.sub.3 O.sub.10 250 127 86 112 123 9 " 125/125
Na.sub.12 (AlO.sub.2.SiO.sub.2.).sub.12 27H.sub.2 O 500 78 121 104
117
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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 conventionally
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 depress 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 compound mixtures
are disclosed in the commonly assigned cofiled Application of
Robert G. Laughlin and Vincent P. Heuring, Ser. No. 493,953, filed
Aug. 1, 1974, the disclosures of which are hereby incorporated by
reference.
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 proteolylic in nature, such
as those sold under the trade names "Alcalase" and "Esterase" by
Novo Industries A/S Denmark or under the trade names "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 synthetic detergent granules is
disclosed in U.S. Pat. No. 3,553,139 issued on Jan. 5, 1971, to
McCarty, Roald, DeOude, Blomeyer, and Cracco which disclosure is
hereby incorporated by reference.
A further ingredient that may be incorporated to improve 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
sulphonamides. 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 nonopersulphate 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 C.sub.12-15 alkyl
di-lower alkyl amine oxides. Typical suds depressors include long
chain fatty acids such as those discarded in U.S. Pat. No.
2,954,347 issued Sept. 27, 1960, to Wayne St. John and combinations
of certain nonionics therewith as disclosed in U.S. Pat. No.
2,954,348 issued Sept. 27, 1960, to Eugene Schwoeppe, both
disclosures being incorporated herein by reference.
Other optional ingredients in granular products include hydrotropes
and anticaking additives such as salts of lower alkyaryl sulphonic
acids, salts of .alpha.-sulphosuccinic acid, and
.alpha.-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. C.sub.12 -C.sub.18 alkyl acid phosphates and
their condensation 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 or 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 provides 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
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
75.degree.F).
Built liquid detergent compositions may also be single phase
liquids provided that the builder can be solubilized in the mixture
at its level of use. Such liquids conventionally contain 10-25%
total surfactant, 10-20 % builder which may be organic or
inorganic, 5-10% of a hydrotrope system and 50-60% of water.
Liquids of this type also have low viscosity (100-150 c.p.s. at
75.degree.F). 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 characteristics
to maintain stable dispersions and to prevent phase separation or
solid settlement.
The 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:
.omega.-(hexadecyl dimethyl ammonio)- 38.4% 2-octaethenoxy
ethane-1-sulphonate Sodium Carbonate 30.8 Sodium Silicate
(SiO.sub.2 :Na.sub.2 O = 3.2:1) 30.8 100.0%
Cotton, polycotton, and polyester cloth swatches that had been
soiled with a standardized illite clay soil were given a 10 minute
wash with this product in the tergotometer at 105.degree.F using
water of mineral hardness 7 grains/gallon (Ca:Mg = 2:1). Product
concentration was adjusted to give 250 ppm of zwitterionic compound
in solution. Following rinsing and drying, the swatches were then
graded instrumentally for clay soil removal using 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 conditions, were as follows:
Cotton Polycotton Polyester ______________________________________
92% 106% 109% ______________________________________
EXAMPLE II
A solid powdered formulation was prepared having the following
composition:
.omega.-(N-octadecyl, N-methyl, N-polyethenoxy 27.8%
ammonio)-2-polyethenoxy ethane-1-sulphonate wherein the total
number of ethylene oxide groups in the molecule was 14 Sodium
Tripolyphosphate 27.8 Sodium Carbonate 22.2 Sodium Silicate
(SiO.sub.2 :Na.sub.2 O = 3.2:1) 22.2 100.0%
Using the product concentrations 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:
Cotton Polycotton Polyester ______________________________________
104% 99% 106% ______________________________________
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