U.S. patent number 3,852,211 [Application Number 05/279,127] was granted by the patent office on 1974-12-03 for detergent compositions.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Tom H. Ohren.
United States Patent |
3,852,211 |
Ohren |
December 3, 1974 |
DETERGENT COMPOSITIONS
Abstract
Granular laundering compositions comprising a
curd-dispersant-containing, soap-based granule and a smectite-type
clay. The soap and curd dispersant are formulated into the granule
and the clay is attached to the surface of the granule. The
resulting compositions exhibit enhanced solubility and provide
through-the-wash fabric softening.
Inventors: |
Ohren; Tom H. (Cincinnati,
OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
23067734 |
Appl.
No.: |
05/279,127 |
Filed: |
August 9, 1972 |
Current U.S.
Class: |
510/334; 252/179;
310/75R; 510/307; 510/438; 510/443; 510/507; 510/441; 510/326;
510/308; 510/324; 510/354 |
Current CPC
Class: |
C11D
10/047 (20130101); C11D 10/04 (20130101); C11D
17/06 (20130101); C11D 10/042 (20130101); C11D
1/342 (20130101); C11D 1/18 (20130101); C11D
1/523 (20130101); C11D 1/886 (20130101); C11D
1/28 (20130101); C11D 1/92 (20130101); C11D
1/345 (20130101); C11D 1/521 (20130101); C11D
1/29 (20130101); C11D 1/90 (20130101) |
Current International
Class: |
C11D
17/06 (20060101); C11D 9/04 (20060101); C11D
9/18 (20060101); C11D 10/04 (20060101); C11D
10/00 (20060101); C11D 1/02 (20060101); C11D
1/38 (20060101); C11D 1/18 (20060101); C11D
1/28 (20060101); C11D 1/34 (20060101); C11D
1/90 (20060101); C11D 1/92 (20060101); C11D
1/52 (20060101); C11D 1/29 (20060101); C11D
1/88 (20060101); C11d 009/10 (); C11d
003/065 () |
Field of
Search: |
;252/110,109 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Sebastian; Leland A.
Attorney, Agent or Firm: Filcik; Julius P. Allen; George W.
O'Flaherty; Thomas H.
Claims
What is claimed is:
1. A fabric laundering composition comprising
A. granular particles which comprise
i. from about 30% to about 80% by weight of said granular particles
of a soap compound, and
ii. from about 1% to about 30% by weight of said granular particles
of a soap-curd-dispersing agent; and
b. an impalpable smectite clay having an ion exchange capacity of
at least about 50 meg/100 grams, attached to the surface of said
granular particles;
said composition having a weight ratio of granular particles to
impalpable smectite clay of from about 20:1 to 3:1.
2. A composition in accordance with claim 1
A. wherein the soap compound is a salt of a higher fatty acid
containing from about 8 to about 24 carbon atoms and is present in
said granular particles to the extent of from about 40% to about
70% by weight of the granular particles;
B. wherein the soap-curd-dispersing agent is selected from the
group consisting of
i. compounds of the formula ##SPC9##
wherein R.sub.1 is alkyl or alkenyl of about 10 to 20 carbon atoms,
R.sub.2 is alkyl of 1 to about 10 carbon atoms and M is a
salt-forming cation;
ii. compounds of the formula ##SPC10##
wherein R.sub.1 is alkyl of about 9 to about 23 carbon atoms,
R.sub.2 is alkyl of 1 to about 8 carbon atoms and M is a
salt-forming cation;
iii. compounds of the formula
RO(C.sub.2 H.sub.4 O).sub.x SO.sub.3 M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms,
x is 1 to 30 and M is a salt-forming cation;
iv. olefin sulfonates containing from about 12 to 24 carbon
atoms;
v. compounds of the formula ##SPC11##
wherein R.sub.1 is alkyl of about 8 to 18 carbon atoms, R.sub.2 is
selected from the group consisting of alkyl of 1 to about 3 carbon
atoms and hydrogen, R.sub.3 is alkylene of 1 to about 4 carbon
atoms, Z is selected from the group consisting of carboxy,
sulfonate, sulfate, phosphate and phosphonate, and M is a
salt-forming cation;
vi. compounds of the formula ##SPC12##
wherein R.sub.1 is selected from the group consisting of alkyl,
alkenyl, hydroxyalkyl and alkylbenzene groups, all groups
containing from about 8 to about 24 carbon atoms and having from 0
to about 10 ethylene oxide moieties and from 0 to 1 glyceryl
moiety; Y is selected from the group consisting of nitrogen,
phosphorus, and sulfur atoms; R.sub.2 is an alkyl or monohydroxyl
alkyl group containing 1 to about 3 carbon atoms; x is 1 when Y is
a sulfur atom and 2 when Y is a nitrogen or phosphorus atom,
R.sub.3 is alkylene or hydroxyalkylene of from 1 to about 4 carbon
atoms and Z is a group selected from the group consisting of
carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups;
and
vii. compounds of the formula ##SPC13##
wherein R is hydrogen, alkyl or alkylol and R' and R" are each
hydrogen, alkyl, alkylol, or alkylene joined through an oxygen
atom, the total number of carbon atoms in R, R' and R" being from
about 9 to about 25;
and wherein said soap-curd-dispersing agent is present in said
granular particles to the extent of from about 2% to about 20% by
weight of said granular particles; and
C. wherein said impalpable smectite clay is selected from the group
consisting of dioctahedral expandable three-layer
aluminum-silicates and trioctahedral expandable three-layer
magnesium silicates, and is present to the extent of from about 4%
to about 25% by weight of the total composition.
3. A composition in accordance with claim 2
A. wherein the soap is selected from the group consisting of sodium
tallow soap, sodium coconut soap, potassium tallow soap, potassium
coconut soap and mixtures thereof;
B. wherein the soap-curd-dispersing agent is selected from the
group consisting of the sodium salt of the methyl ester of
.alpha.-sulfonated tallow fatty acid; the sodium salt of
ethoxylated tallow alkyl sulfate having an average of about 3
ethylene oxide groups per mole; the sodium salt of ethoxylated
tallow alkyl sulfate having an average of about 6 ethylene oxide
groups per mole; sodium .beta.-acetoxy-hexadecane-1-sulfonate;
sodium .beta.-acetoxy tridecane-1-sulfonate; the sodium salt of
sulfonated 1-hexadecane; sodium hexadecylmethylaminopropionate;
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and
3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein
in both compounds the alkyl group averages about 14.8 carbon atoms
in length; 3(N,N-dimethyl-N-hexadecylammonio)-propane -1-sulfonate;
3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; and
tallow acyl monoethanolamide; and
C. wherein the smectite clay is selected from the group consisting
of montmorillonites, volchonskoites, nontronites, hectorites,
sauconites and vermiculites.
4. A composition in accordance with claim 3
A. wherein the soap-curd-dispersing agent is selected from the
group consisting of the sodium salt of ethoxylated tallow alkyl
sulfate having an average of about 3 ethylene oxide groups per
mole; the sodium salt of ethoxylated tallow alkyl sulfate having an
average of about 6 ethylene oxide groups per mole; and tallow acyl
monoethanolamide; and
B. wherein the smectite clay is a montmorillonite.
5. A composition in accordance with claim 4 wherein the
soap-curd-dispersing agent is the sodium salt of ethoxylated tallow
alkyl sulfate having an average of about 3 ethylene oxide groups
per mole and the smectite clay is a sodium montmorillonite.
6. A composition in accordance with claim 2 wherein the granular
particles contain, in addition to the soap and soap-curd-dispersing
agent, from 1% to 30% by weight of the particle of a conventional,
non-soap-curd-dispersing surfactant and wherein the composition in
addition to the granule particles and impalpable smectite clay,
contains an adhesion-promoting material comprising from about 0.5%
to about 8% by weight of the total composition.
7. A composition in accordance with claim 6
A. wherein the soap is selected from the group consisting of sodium
tallow soap, sodium coconut soap, potassium tallow soap, potassium
coconut soap and mixtures thereof;
wherein the soap-curd-dispersing agent is selected from the group
consisting of the sodium salt of the methyl ester of
.alpha.-sulfonated tallow fatty acid; the sodium salt of
ethoxylated tallow alkyl sulfate having an average of about 3
ethylene oxide groups per mole; the sodium salt of ethoxylated
tallow alkyl sulfate having an average of about 6 ethylene oxide
groups per mole; sodium .beta.-acetoxy-hexadecane-1-sulfonate;
sodium .beta.-acetoxy tridecane-1-sulfonate; the sodium salt of
sulfonated 1-hexadecene; sodium hexadecylmethylaminopropionate;
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and
3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein
in both compounds the alkyl group averages about 14.8 carbon atoms
in length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;
3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
and 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane- 1-sulfonate
and tallow acyl monoethanolamide; and
C. wherein the smectite clay is selected from the group consisting
of montmorillonites, volchonskoites, nontronites, hectorites,
sauconites, saponites, and vermiculites.
8. A composition in accordance with claim 7
A. wherein the conventional non-soap-curd-dispersing surfactant is
selected from the group consisting of sodium linear alkyl benzene
sulfonate wherein the alkyl group averages from about 10 to 18
carbon atoms in length, sodium tallow alkyl sulfate, and
B. wherein the adhesion-promoting material is selected from the
group consisting of non-ionic surfactants produced by the
condensation of an alkylene oxide moiety with an organic
hydrophobic compound, fatty acids containing from about 10 to about
22 carbon atoms and fatty alcohols containing from about 10 to 22
carbon atoms.
9. A composition in accordance with claim 8
A. wherein the soap-curd-dispersing agent is selected from the
group consisting of the sodium salt of ethoxylated tallow alkyl
sulfate averaging about 3 ethylene oxide groups per mole; the
sodium salt of ethoxylated tallow alkyl sulfate averaging about 6
ethylene oxide groups per mole; and tallow acyl
monoethanolamide;
B. wherein the smectite clay is a montmorillonite;
C. wherein the conventional non-soap-curd-dispersing surfactant is
sodium linear alkyl benzene sulfonate wherein the alkyl group
averages about 12 carbon atoms in length; and
D. wherein the adhesion-promoting material is selected from the
group consisting of coconut alcohol ethoxylate containing 6
ethylene oxide units per molecule; tallow alcohol ethoxylate
containing 11 ethylene oxide units per molecule; coconut fatty acid
mixtures; tallow fatty acid mixtures, the condensate of one mole of
ethylene oxide with 1-dodecanol; and the condensate of one mole of
1-dodecanol with ethylene oxide hexamer, said adhesion-promoting
material being present to the extent of from about 1% to about 4%
by weight of the total composition.
10. A composition in accordance with claim 9
wherein the adhesion-promoting material is selected from the group
consisting of tallow alcohol ethoxylate containing 11 ethylene
oxide units per molecule and coconut fatty acid mixtures.
11. A composition in accordance with claim 10 wherein the
soap-curd-dispersing agent is the sodium salt of ethoxylated tallow
alkyl sulfate averaging about 3 ethylene oxide groups per mole and
the smectite clay is a sodium montmorillonite.
12. A composition in accordance with claim 4 wherein the granular
particles, in addition to the soap and soap-curd-dispersing agent,
contain from about 1% to about 30% by weight of the granular
particles of an alkaline builder salt.
13. A composition in accordance with claim 12 wherein the alkaline
builder salt is sodium tripolyphosphate.
14. A composition in accordance with claim 13 wherein the
soap-curd-dispersing agent is tallow acyl monoethanolamide and the
smectite clay is a sodium montmorillonite.
15. A composition in accordance with claim 12 which, in addition to
the granular particles and impalpable smectite clay, contains an
adhesion-promoting material comprising from about 0.5% to about 8%
by weight of the total composition.
16. A composition in accordance with claim 15 wherein the alkaline
builder salt is sodium tripolyphosphate and the adhesion-promoting
material is selected from the group consisting of coconut alcohol
ethoxylate containing 6 ethylene oxide units per molecule; tallow
alcohol ethoxylate containing 11 ethylene oxide units per molecule;
coconut fatty acid mixtures; tallow fatty acid mixtures, the
condensate of one mole of ethylene oxide with 1-dodecanol; and the
condensate of one mole of 1-dodecanol with ethylene oxide hexamer,
said adhesion-promoting material being present to the extent of
from about 1% to about 4% by weight of the total composition.
17. A composition in accordance with claim 16 wherein the
soap-curd-dispersing agent is tallow acyl monoethanolamide and the
smectite clay is a sodium montmorillonite.
Description
BACKGROUND OF THE INVENTION
The instant invention relates to granular laundering compositions
which provide simultaneous laundering and softening of textiles
during conventional fabric laundering operations. Such compositions
employ a combination of a soap and a curd dispersent in granular
form and certain smectite clay compounds having particular cation
exchange characteristics.
Laundry soaps, i.e., the water-soluble salts of fatty acids,
provide the user with good fabric cleansing coupled with product
mildness. In addition, soaps deposit on many types of fabrics in
the form of a "curd" and thereby provide desirable softening
benefits. However, the buildup of heavy soap curd on fabrics
eventually results in loss of fabric brightness. Furthermore, soap
curd has been found to interfere with the flame retardant finishes
commonly applied to children's chothing. That is to say, flame
retardant fabrics coated with a heavy soap curd exhibit decreased
levels of flame retardancy which, on removal of the soap curd, are
restored to its original level.
From the foregoing, it can be seen that the use of soap-based
laundering products presents a dilemma. The soap provides desirable
fabric cleaning and through-the-wash fabric softening, but can
eventually detract from fabric appearance and decrease the efficacy
of the flame retardant finishes present on modern fabrics.
One method for preventing curd buildup on fabrics laundered with
soap is to include a curd dispersant in the laundering bath. While
this method achieves the desired result, the laundered fabrics no
longer have the desirable softening benefits imparted by soap. More
importantly, granular laundering compositions which contain both
soap and significant amounts of curd dispersant are difficult to
dissolve in aqueous laundering baths. When such products are added
to water, the soap tends to undergo a phase transition and
agglomerate as a gelatinous material which then deposits in an
unsightly manner on the fabrics being laundered.
It has now been found that smectite-type clay material can be
attached to the surface of soap-based detergent granules containing
certain curd dispersants to substantially enhance the solubility of
the granules. Furthermore, once the granules have dissolved, the
clay is dispersed throughout the laundry liquor and deposits on the
fabric surfaces to provide softening. Thus, the problem of excess
curd buildup on fabrics is solved without losing the desirable
softening benefits of soap-based compositions.
Various clay materials have been utilized in many different types
of detergent systems for widely diverse purposes. Clays, for
example, have been disclosed for use as builders (Schwartz and
Perry, Surface Active Agents, Interscience Publishers, Inc., 1949,
p. 233 and Schwartz, Perry and Berch, Surface Active Agents and
Detergents, Vol. II, Interscience Publishers, Inc., 1958, pp.
297-300); as water-softeners (British Pat. No. 461,221); as
anti-caking agents (U.S. Pat. Nos. 2,625,513 and 2,770,600); as
suspending agents (U.S. Pat. Nos. 2,594,257, 2,594,258 and
2,920,045); and as fillers (U.S. Pat. No. 2,708,185).
It is also well known that some clay materials can be deposited on
fabrics to impart softening and antistatic properties thereto. Such
clay deposition is generally realized by contacting the fabrics to
be so treated with aqueous clay suspensions (See, for example, U.S.
Pat. No. 3,033,699 and 3,594,212). The co-pending application of
Storm and Nirschl, entitled "Detergent Compositions"; Ser. No.
271,943, filed July 14, 1972, discloses the use of clay softeners
in built, non-soap detegent compositions.
However, it has been heretofore unrecognized that clay minerals of
the type used in the present invention can be attached to the
surface of soap-based detergent granules, especially those
containing curd dispersants, to enhance the solubility of the
granules in water while concurrently providing fabric
softening.
Accordingly, it is an object of the present invention to provide
compositions which can be employed to yield simultaneous fabric
laundering and fabric softening without interfering with flame
retardancy.
It is a further object of the present invention to provide
soap-based laundering and softening compositions containing curd
dispersants in the form of granular formulations which can be
easily dissolved in water over a wide temperature range.
It has surprisingly been discovered that by attaching smectite-type
clays having particular cation exchange characteristics to the
surface of curd-dispersant containing, soap-based detergent
granules, the above objectives can be realized and granular fabric
laundering and softening compositions can be obtained which are
unexpectedly superior to similar compositions known to the prior
art.
SUMMARY OF THE INVENTION
The present invention encompasses fabric laundering compositions
comprising: (A) a granular particle which comprises: (i) from about
30% to about 80% by weight of said particle of a soap compound,
and; (ii) from about 1% to about 30% by weight of said granular
particle of a curd-dispersing agent; and (B) an impalpable
smectite-type clay having an ion exchange capacity of at least
about 50 meq/100 g. of clay, attached to the surface of said
granular particle. The compositions have a weight ratio of granular
particles to smectite clay in the range of from about 20:1 to about
3:1.
DETAILED DESCRIPTION OF THE INVENTION
The fabric laundering compositions of the present invention contain
two essential components -- granular soap-based particles and an
impalpable smectite-type clay material attached to the surfaces of
such particles. The composition of the granular particles and the
nature of the clay material is described more fully as follows.
The Granular Particles
The granular particle component of the instant laundering
composition comprises two essential ingredients (1) a soap compound
and (2) a curd-dispersing agent.
Soap Compound
The granular particles of the instant invention comprise from about
30% to about 80%, preferably from about 40% to about 70%, by weight
of the particles of a soap compound. Useful soap compounds include
the ordinary alkali metal soaps such as the sodium, potassium,
ammonium and alkanolammonium salts of higher fatty acids containing
from about 8 to about 24 carbon atoms, preferably from about 10 to
about 20 carbon atoms. Suitable fatty acids can be obtained from
natural sources such as, for instance, plant or animal esters
(e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil,
tallow, whale and fish oils, grease, lard, and mixtures thereof).
The fatty acids also can be synthetically produced (e.g., by the
oxidation of petroleum, or by hydrogenation of carbon monoxide by
the Fischer-Tropsch process). Resin acids are suitable such as
rosin and those resin acids in tall oil. Naphthenic acids are also
suitable. Sodium and potassium soaps can be made by direct
saponification of the fats and oils or by the neutralization of the
free fatty acids which are prepared in a separate manufacturing
process. Particularly useful are the sodium and potassium salts of
the mixtures of fatty acids derived from coconut oil and tallow,
i.e., sodium tallow soap, sodium coconut soap, potassium tallow
soap, potassium coconut soap and mixtures thereof.
The Curd Dispersing Agent
As noted above, it is well known that the use of soap in hard water
results in the formation and precipitation of insoluble fatty acid
salts, more commonly referred to as lime soaps. which have a
tendency to coagulate and form a sticky curd. To prevent formation
of such curd in laundering solutions containing the compositions of
the instant invention, the granular particles in addition to the
soap component contain from about 1% to about 30%, preferably from
about 2% to about 20%, by weight of the particle of a
curd-dispersing agent.
Such curd dispersing agents either prevent the formation of large
particles of insoluble lime soaps or prevent such soaps from
flocculating so that they are flushed away with the washing or
rinsing liquid and do not adhere to fabrics or to surfaces of
washing vessels.
The effectiveness of particular materials as curd-dispersing agents
can be ascertained by a simple procedure testing the ability of the
test material to peptize lime soaps. Such a procedure is outlined
in Schwartz and Perry, Surface Active Agents, Interscience
Publishers, Inc., 1949 at pp. 326 and 327, and is summarized as
follows.
The general method consists of preparing a series of mixtures
containing varying proportions of sodium oleate and the curd
dispersing agent being tested. These mixtures contain approximately
10% total soap-plus-curd dispersant in distilled water. Five
milliliters of each mixture are then added to 45 milliliters of
hard water (usually 200 ppm hardness as CaO). This is called the
first dilution, and it usually results in a turbid but
well-dispersed sol. Five milliliters of the first dilution are then
added to 45 milliliters of hard water, forming the second dilution.
This is a severe test since there is now more than enough lime
present to precipitate all the soap. Furthermore, the total
soap-plus-curd dispersant concentration is of the order of 0.1%.
The results are expressed as the percentage of dispersant in the
soap-curd dispersant mixture which is just sufficient to prevent
flocculation on the second dilution. The more effective the curd
dispersing agent, the lower is the percentage value. For purposes
of the instant invention a "curd-dispersing agent" is any material
which produces a percentage value in the above-described lime soap
peptizing procedure of about 39% or less. A conventional non-curd
dispersant surfactant for purposes of this invention is a
surfactant providing a percentage value greater than 39% in the
above-described lime soap peptizing procedure.
Examples of suitable curd-dispersing agents include certain
anionic, semipolar nonionic, ampholytic and zwitterionic materials
as well as certain amides and amines. Classes of these
curd-dispersing agents are more fully described as follows.
1. Anionic organic detergents which are alkali metal, ammonium and
substituted-ammonium salts of esters of .alpha.-sulfonated fatty
acids in which the esters contain about 12 to about 25 carbon
atoms.
These detergent compounds have the following structure:
##SPC1##
wherein R.sub.1 is an alkyl or alkenyl moiety of about 10 to about
20 carbon atoms (forming with the two carbon atoms a fatty acid
group); R.sub.2 is alkyl of 1 to about 10 carbon atoms; and M is a
salt-forming moiety.
The salt-forming moiety M in the hereinbefore described structural
formula is a water-solubilizing cation and can be, for example, an
alkali metal cation (e.g., sodium, potassium, lithium), ammonium or
substituted ammonium cation. Specific examples of substituted
ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and
triethanolammonium cations and quaternary ammonium cations such as
tetramethyl ammonium and dimethyl piperidinium cations and those
derived from alkylamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof and the like.
Specific examples of this class of compounds include the sodium and
potassium salts of esters where R.sub.2 is selected from methyl,
ethyl, propyl, butyl, hexyl and octyl groups and the fatty acid
group (R.sub.1 plus the two carbon atoms in the structure above) is
selected from lauric, myristic, palmitic, stearic, palmitoleic,
oleic, linoleic acids and mixtures thereof. A preferred ester
material herein is the sodium salt of the methyl ester of
.alpha.-sulfonated tallow fatty acid, the term tallow indicating a
carbon chain distribution approximately as follows: C.sub.14 -
2.5%, C.sub.16 - 28%, C.sub.18 - 23%, palmitoleic - 2%, oleic -
41.5%, and linoleic - 3% (the first three fatty acids listed are
saturated).
Other examples of suitable salts of .alpha.-sulfonated fatty esters
utilizable herein include the ammonium and tetramethylammonium
salts of the hexyl, octyl, ethyl, and butyl esters of
.alpha.-sulfonated tridecanoic acid; the potassium and sodium salts
of the ethyl, butyl, hexyl, octyl, and decyl esters of
.alpha.-sulfonated pentadecanoic acid; and the sodium and potassium
salts of the butyl, hexyl, octyl, and decyl esters of
.alpha.-sulfonated heptadecanoic acid; and the lithium and ammonium
salts of the butyl, hexyl, octyl, and decyl esters of
.alpha.-sulfonated nonadecanoic acid.
The salts of .alpha.-sulfonated fatty acid esters of the present
invention are known compounds and are described in U.S. Pat. No.
3,223,645, issued Dec. 14, 1965 to Kalberg, this patent being
hereby incorporated by reference.
2. Anionic organic detergents which are salts of
2-acyloxy-alkane-1-sulfonic acids.
These salts have the formula: ##SPC2##
where R.sub.1 is alkyl of about 9 to about 23 carbon atoms; R.sub.2
is alkyl of 1 to about 8 carbon atoms; and M is a salt-forming
moiety as hereinbefore described.
Specific examples of .beta.-acyloxy-alkane-1-sulfonates, or
alternatively, 2-acyloxy-alkane-1-sulfonates, utilizable herein to
provide superior curd dispersion include the sodium salt of
2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of
2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of
2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of
2-pentanoyloxy-pentadecane-1-sulfonic acid; the ammonium salt of
2-hexanoyloxy-hexadecane-1-sulfonic acid; the sodium salt of
2-acetoxy-hexadecane-1-sulfonic acid; the dimethylammonium salt of
2-heptanoyloxy-tridecane-1-sulfonic acid; the potassium salt of
2-octanoyloxy-tetradecane-1-sulfonic acid; the dimethylpiperidinium
salt of 2-nonanoyloxytetradecane-1-sulfonic acid; the sodium salt
of 2-acetoxyheptadecane-1-sulfonic acid; the lithium salt of
2-acetoxyoctadecane-1-sulfonic acid; the dimethylamine salt of
2-acetoxyoctadecane-1-sulfonic acid; the potassium salt of
2-acetoxynonadecane-1-sulfonic acid; the sodium salt of
2-acetoxy-eicosane-1-sulfonic acid; the sodium salt of
2-propionyloxy-docosane-1-sulfonic acid; and isomers thereof.
Preferred .beta.-acyloxy-alkane-1-sulfonate salts herein are the
alkali metal salts of .beta.-acetoxy-alkane-1-sulfonic acids
corresponding to the above formula wherein R.sub.1 is an alkyl
moiety of about 12 to about 16 carbon atoms, these salts being
preferred from the standpoint of their excellent curd-dispersing
properties and ready availability.
Typical examples of the above described .beta.-acetoxy
alkanesulfonates are described in the literature: Belgian Pat. No.
650,323 issued July 9, 1963, discloses the preparation of certain
2-acyloxy alkanesulfonic acids. Similarly, U.S. Pat. Nos. 2,094,451
issued Sept. 28, 1937, to Guenther et al. and 2,086,215 issued July
6, 1937 to De Groote disclose certain salts off .beta.-acetoxy
alkanesulfonic acids. These patents are hereby incorporated by
reference.
3. Anionic organic detergents which are alkyl ether sulfates.
These materials have the formula RO(C.sub.2 H.sub.4 O).sub.x
SO.sub.3 M wherein R is an alkyl or alkenyl moeity of about 10 to
about 20 carbon atoms, x is 1 to 30, and M is a salt-forming cation
as defined hereinbefore.
The alkyl ether sulfates useful in the present invention as curd
dispersants are condensation products of ethylene oxide and
monohydric alcohols having about 10 to about 20 carbon atoms.
Preferably, R has 14 to 18 carbon atoms. The alcohols can be
derived from fats, e.g. coconut oil or tallow, or can be synthetic.
Lauryl alcohol and straight chain alcohols derived from tallow are
preferred herein. Such alcohols are reacted with 1 to 30, and
especially 3 or 6, molar proportions of ethylene oxide and the
resulting mixture of molecular species, having, for example, an
average of 3 or 6 moles of ethylene oxide per mole of alcohol, is
sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention
are sodium coconut alkyl ethylene glycol ether sulfate; lithium
tallow alkyl trialkylene glycol ether sulfate; sodium tallow alkyl
hexaoxyethylene sulfate; and ammonium tetradecyl octaoxyethylene
sulfate.
Preferred herein for reasons of excellent curd-dispersing
properties and ready availability are the alkali metal coconut- and
tallow-alkyl oxyethylene ether sulfates having an average of about
3 to about 10 oxyethylene moieties. The alkyl ether sulfates of the
present invention are known compounds and are described in U.S.
Pat. No. 3,322,876 to Walker (July 25, 1967) incorporated herein by
reference.
4. Anionic organic detergents which are olefin sulfonates having
about 12 to about 24 carbon atoms.
The term "olefin sulfonates" is used herein to mean compounds which
can be produced by the sulfonation of .alpha.-olefins by means of
uncomplexed sulfur trioxide, followed by neutralization of the acid
reaction mixture using conditions such that any sultones which have
been formed in the reaction are hydrolyzed to give the
corresponding hydroxy-alkanesulfonates. The sulfur trioxide may be
liquid or gaseous, and is usually, but not necessarily, diluted by
inert diluents, for example by liquid SO.sub.2, chlorinated
hydrocarbon, etc., when used in the liquid form, or by air,
nitrogen, gaseous SO.sub.2, etc., when used in the gaseous
form.
The .alpha.-olefins from which the olefin sulfates are derived are
mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16
carbon atoms. Preferably, they are straight chain olefins. Examples
of suitable 1-olefins include 1-dodecene; 1-tetradecene;
1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.
In addition to the true alkene sulfonates and a proportion of
hydroxy-alkanesulfonates, the olefin sulfonates can contain minor
amounts of other materials, such as alkene disulfonates depending
upon the reaction conditions, proportions of reactants, the nature
of the starting olefins and impurities in the olefin stock and side
reactions during the sulfonation process.
A preferred embodiment herein are those olefin sulfonates which are
described completely in U.S. Pat. No. 3,332,880 issued July 25,
1967, to Kessler et al., hereby incorporated by reference.
5. Nonionic organic detergents which are semipolar detergent
compounds.
These include, for example, long chain tertiary phosphine oxides
having the structure: ##SPC3##
wherein R.sub.1 is alkyl, alkenyl, or monohydroxyalkyl of about 8
to about 18 carbon atoms having from 0 to about 10 ethylene oxide
moieties and from 0 to 1 glyceryl moiety and R.sub.2 and R.sub.3
are each alkyl or monohydroxyalkyl groups containing from 1 to
about 3 carbon atoms. The arrow in the formula is a conventional
representation of the semi-polar bond.
Examples of suitable phosphine oxides are:
dodecyldimethylphosphine oxide,
tetradecyldimethylphosphine oxide,
tetradecylmethylethylphosphine oxide,
3,6,9-trioxaoctadecyldimethylphosphine oxide,
cetyldimethylphosphine oxide,
3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl)-phosphine oxide,
stearyldimethylphosphine oxide,
cetylethylpropylphosphine oxide,
oleyldiethylphosphine oxide,
dodecyldiethylphosphine oxide,
tetradecyldiethylphosphine oxide,
dodecyldipropylphosphine oxide,
dodecyldi(hydroxymethyl)phosphine oxide,
dodecyldi(2-hydroxyethyl)phosphine oxide,
tetradecylmethyl-2-hydroxypropyl phosphine oxide,
oleyldimethylphosphine oxide, and
2-hydroxydodecyldimethylphosphine oxide.
6. Nonionic organic detergents which are certain organic
sulfoxides.
Such compounds have the general formula: ##SPC4##
wherein R is an alkyl group of 8 to 16 carbon atoms and X is
selected from the group consisting of methyl, ethyl and
.beta.-hydroxyethyl groups. Such compounds are described in U.S.
Pat. No. 3,232,879 hereby incorporated by reference.
7. Ampholytic synthetic detergents which are derivatives of
aliphatic secondary and tertiary amines in which the aliphatic
group can be straight chain or branched and wherein one of the
aliphatic substituents contains from about 8 to about 18 carbon
atoms and one contains an anionic water solubilizing group, e.g.,
carboxy, sulfonate, sulfate, phosphate, or phosphonate.
These detergents have the formula ##SPC5##
wherein R.sub.1 is alkyl of about 8 to 18 carbon atoms, R.sub.2 is
alkyl of 1 to about 3 carbon atoms or is hydrogen, R.sub.3 is
alkylene of 1 to about 4 carbon atoms, Z is carboxy, sulfonate,
sulfate, phosphate or phosphonate and M is a salt-forming cation,
as hereinbefore described. Examples of compounds falling within
this definition are sodium 3-dodecylaminopropionate; sodium
3-dodecylaminopropane sulfonate; N-alkyltaurines such as the ones
prepared by reacting dodecylamine with sodium isethionate according
to the teaching of U.S. Pat. No. 2,658,072; sodium salts of
N-higher alkyl aspartic acids such as those produced according to
the teaching of U.S. Pat. No. 2,438,091; and the products sold
under the trade name "Miranol" and described in U.S. Pat. No.
2,528,378.
8. Zwitterionic synthetic detergents which are derivatives of
aliphatic quaternary ammonium, phosphonium and sulfonium compounds,
in which the aliphatic groups can be straight chain or branched,
and wherein one of the aliphatic substituents contains from about 8
to 18 carbon atoms and one contains an anionic water solubilizing
group, e.g., carboxy, sulfonate, sulfate, phosphate, or
phosphonate. A general formula for these compounds is: ##SPC6##
wherein R.sub.1 is an alkyl, alkenyl, hydroxyalkyl or alkylbenzyl
group containing from about 8 to about 24 carbon atoms and having
from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl
moiety; Y is selected from the group consisting of nitrogen,
phosphorus, and sulfur atoms; R.sub.2 is an alkyl or monohydroxy
alkyl group containing 1 to about 3 carbon atoms; x is 1 when Y is
a sulfur atom and 2 when Y is a nitrogen or phosphorus atom,
R.sub.3 is an alkylene or hydroxy alkylene group of from 1 to about
4 carbon atoms and Z is a member selected from the group consisting
of carboxylate, sulfonate, sulfate, phosphonate, and phosphate
groups.
Examples include:
4-[N,N-di(2-hydroxyethyl)-N-octadecyl-ammonio]-butane-1-carboxylate;
5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;
3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phos
phate;
3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-1-phosphonate;
3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulfonate;
4-[N,N-di(2-hydroxyethyl-N-(2-hydroxydodecyl)ammonio]
-butane-1-carboxylate;
3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;
3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate;
S-[n,n-di(3-hydroxypropyl)-N-hexadecyl-ammonio]-2-hydroxypentane-1-sulfate;
3-(dodecylbenzyldimethylammonio)propane-1-sulfonate; and
2-(dodecylbenzyldimethylammonio)ethane-1-sulphate.
Examples of compounds falling within this definition also include
3-(N,N-dimethyl-N-hexadecyl-ammonio)propane-1-sulfonate and
3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulfonate
which are especially preferred herein for their availability and
curd dispersant characteristics. Some of the compounds of this type
as well as their use as dispersing agents are more fully described
in U.S. Pat. Nos. 2,699,991 and 3,660,470 herein incorporated by
reference.
9. Organic carboxylic acid amides.
Such amide compounds include those aliphatic amides of the general
formula: ##SPC7##
wherein R is hydrogen, alkyl, or alkylol and R' and R" are
hydrogen, alkyl, alkylol, or alkylene joined through an oxygen
atom, the total number of carbon atoms in R, R' and R" being from
about 9 to about 25.
Amides of this general type which are of special utility are those
aliphatic carboxylic acid alkanolamides of the formula:
##SPC8##
in which RCO is the acyl group of a soap-forming carboxylic acid
having from about 10 to about 18 carbon atoms, R' and R" are each
selected from the group consisting of hydrogen, alkyl, and alkylol
substituents, and R'" is an alkylol substituent, the total number
of carbon atoms in R', R" and R'" being from 1 to 7.
Some specific amides coming within the scope of the invention
are:
lauric ethanolamide;
stearic ethanolamide;
dimethyl lauramide;
lauramide;
lauryl lauramide;
myristic N-methyl ethanolamide;
butyl capramide;
capric butanolamide;
dibutyl capramide;
dibutyl myristamide;
stearic acid amide of tris(hydroxymethyl)amino methane;
myristic glycerylamide;
N-lauroyl morpholine;
lauric glycerylamide;
palmitic acid amide of 2-amino-2-methyl-1,3-propanediol;
lauryl hydroxy-acetamide;
myristyl formamide;
lauric isopropanol amide; and
myristic acid amide of 3-amino-3-methyl-2,4-pentanediol.
Especially preferred is tallow acyl monoethanolamide.
Such amides, their preparation and use as dispersing agents are
discussed more fully in U.S. Pat. No. 2,527,076, hereby
incorporated by reference.
10. Organic alkyl and alkanol amines.
Such amine compounds include N-alkyl monoalkylolamines and N-alkyl
dialkylolamines in which the alkyl group has from 10 to 16 carbon
atoms and the alkanol group has 2 or 3 carbon atoms; N-alkyl
morpholines in which the alkyl group has from 10 to 16 carbon
atoms; and N-alkyl tris(hydroxymethyl)aminomethane in which the
alkyl group has from 10 to 16 carbon atoms.
Specific examples of such compounds include
N-dodecylmonoethanolamine,
N-dodecyl-tris(hydroxymethyl)aminomethane, N-dodecyl
isopropanolamine, N-tetradecyl monoethanolamine, N-dodecyl
diethanolamine, N-tetradecyl diethanolamine and N-dodecyl
morpholine. Compounds of this type and their use as curd-dispersing
agents are described more fully in British Pat. No. 1,006,836,
incorporated herein by reference.
Of all of the above-described types of curd-dispersing agents, the
compounds preferred for use in the granular particles of the
instant composition include the sodium salt of the methyl ester of
.alpha.-sulfonated tallow fatty acid; the sodium salt of
ethoxylated tallow alkyl sulfate having an average of about 3
ethylene oxide groups per mole; the sodium salt of ethoxylated
tallow alkyl sulfate having an average of about 6 ethylene oxide
groups per mole; sodium .beta.-acetoxyhexadecane-1-sulfonate;
sodium .beta.-acetoxy tridecane-1-sulfonate; the sodium salt of
sulfonated 1-hexadecene; dimethyldodecylphosphine oxide; sodium
hexadecylmethylaminopropionate;
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and
3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein
in each propane sulfonate compound the alkyl group averages about
14.8 carbon atoms in length;
3(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;
3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
3-(N-dodecylbenzene-N,N-dimethyl ammonio)-propane-1-sulfonate and
tallow acyl monoethanolamide.
Highly preferred curd dispersing agents herein are the sodium salt
of ethoxylated tallow alkyl sulfate averaging about 3 ethylene
oxide groups per mole, the sodium salt of ethoxylated tallow alkyl
sulfate averaging about 6 ethylene oxide groups per mole, and
tallow acyl monoethanolamide.
Optional Granule Components
Besides the above-described soap and curd-dispersing components,
the granular particles of the instant compositions can contain a
wide variety of optional components generally found in conventional
fabric laundering formulations. Such optional components include,
for example, conventional anionic or nonionic surfactants which are
not particularly useful as curd dispersants and alkaline builder
salts. Such non-curd-dispersing surfactants are those having a
percentage value in the above-described lime soap peptizing test
greater than 39% and include the sodium salts of linear alkyl
benzene sulfonic acid wherein the alkyl group average about 10 to
18 carbon atoms in length, sodium tallow alkyl sulfate, the
condensation product of coconut fatty alcohol with about 6 moles of
ethylene oxide per mole of alcohol, and the condensation product of
a secondary fatty alcohol containing about 15 carbon atoms with
about 9 moles of ethylene oxide per mole of alcohol. When employed,
such conventional non-curd-dispersing surfactants generally
comprise from about 1% to 30% by weight of the granular
particle.
Typical alkaline builders include sodium tripolyphosphate, sodium
citrate, sodium nitrilotriacetate, sodium carbonate and sodium
mellitate. When employed, such conventional builders generally
comprise from about 1% to 30% by weight of the granular
particle.
Other optional granule components include the various
soil-suspending agents such as carboxymethylcellulose, corrosion
inhibitors, dyes, fillers such as sodium sulfate and silica,
optical brighteners, bleaches such as sodium perborate, suds
boosters, suds depressants, germicides, anti-tarnishing agents, pH
adjusting agents such as sodium silicate, enzymes, and the like,
well known in the art for use in detergent compositions. Bound
water can also be present in said compositions.
The soap-based granules herein can be prepared in standard fashion,
e.g., by blending the soap, curd dispersant and optional
ingredients of the granules in a crutcher, and subsequently blowing
the mix in standard spray-drying equipment.
Clay Compounds
The present compositions contain, as an essential ingredient,
particulate smectite-type clay materials which increase the
solubility of the combined soap-curd dispersant granules and
provide fabric softening concurrently with fabric cleansing. These
smectite clays are present in the detergent compositions at
concentrations from about 4% to about 25%, preferably from 5% to
15% by weight, of the total composition. The weight ratio of clay
to the soap-based granules is from about 20:1 to about 3:1 by
weight.
The clay minerals used to provide the solubility and softening
properties of the instant compositions can be described as
impalpable, expandable, three-layer clays, i.e., alumino-silicates
and magnesium silicates, having an ion exchange capacity of at
least about 50 meq/100 g. of clay. The term "impalpable" as used to
describe the clays employed herein means that the individual clay
particles are of a size that they cannot be perceived tactilely.
Such particle sizes are within the range below about 50 microns. In
general, the clays herein will have a particle size within the
range of from about 5 microns to about 25 microns. The term
"expandable" as used to describe clays relates to the ability of
the layered clay structure to be swollen, or expanded, on contact
with water. The three-layer expandable clays used herein are those
materials classified geologically as smectites.
There are two distinct classes of smectite-type clays. In the
first, aluminum oxide is present in the silicate crystal lattice;
in the second class of smectites, magnesium oxide is present in the
silicate crystal lattice. The general formulas of these smectites
are Al.sub.2 (Si.sub.2 O.sub.5).sub.2 (OH).sub.2 and Mg.sub.3
(Si.sub.2 O.sub.5) (OH).sub.2, for the aluminum and magnesium oxide
type clay, respectively. It is to be recognized that the range of
the water of hydration in the above formulas can vary with the
processing to which the clay has been subjected. This is immaterial
to the use of the smectite clays in the present invention in that
the expandable characteristics of the hydrated clays are dictated
by the silicate lattice structure. Furthermore, atom substitution
by iron and magnesium can occur within the crystal lattice of the
smectites, while metal cations such as Na+, Ca++, as well as H+,
can be co-present in the water of hydration to provide electrical
neutrality. Except as noted hereinafter, such cation substitutions
are immaterial to the use of the clays herein since the desirable
physical properties of the clays are not substantially altered
thereby.
The three-layer, expandable alumino-silicates useful herein are
further characterized by a dioctahedral crystal lattice, while the
expandable three-layer magnesium silicates have a trioctahedral
crystal lattice.
As noted hereinabove, the clays employed in the compositions of the
instant invention contain cationic counterions such as protons,
sodium ions, potassium ions, calcium ion, magnesium ion, and the
like. It is customary to distinguish between clays on the basis of
one cation predominantly or exclusively absorbed. For example, a
sodium clay is one in which the absorbed cation is predominantly
sodium. Such absorbed cations can become involved in exchange
reactions with cations present in aqueous solutions. A typical
exchange reaction involving a smectite-type clay is expressed by
the following equation:
smectite clay (Na) + NH.sub.4 OH .fwdarw. smectite clay (NH.sub.4)
+ NaOH Clays,
Since in the foregoing equilibrium reaction, one equivalent weight
of ammonium ion replaces an equivalent weight of sodium, it is
customary to measure clay cation exchange capacity (sometimes
termed "base exchange capacity") in terms of milliequivalents per
100 g. of clay (meq/100 g.). The cation exchange capacity of clays
can be measured in several ways, including by electrodialysis, by
exchange with ammonium ion followed by titration, or by a methylene
blue procedure, all as fully set forth in Grimshaw, The Chemistry
and Physics of Clays, Interscience Publishers, Inc. pp. 264-265
(1971). The cation exchange capacity of a clay mineral relates to
such factors as the expandable properties of the clay, the charge
of the clay, which, in turn, is determined at least in part by the
lattice structure, and the like. The ion exchange capacity of clays
varies widely in the range from about 2 meq/100 g. for kaolinites
to about 150 meg/100 g., and greater, for certain clays of the
montmorillonite variety. Illite clays have an ion exchange capacity
somewhere in the lower portion of the range, i.e., around 26
meq/100 g. for an average illite clay.
It has been determined that illite and kaolinite clays, with their
relatively low ion exchange capacities, are not useful in the
instant compositions. Indeed, such illite and kaolinite clays
constitute a major component of clay soils and, are, in fact,
removed from fabric surfaces by means of the instant compositions.
However, smectites, such as nontronite, having an ion exchange
capacity of approximately 50 meq/100 g., saponite, which has an ion
exchange capacity of around 70 meq/100 g., and montmorillonite,
which has an ion exchange capacity greater than 70 meq/100 g., have
been found to be useful in the instant compositions. This is so
since such smectites, if attached to the granule surface, increase
composition solubility while, once added to laundering liquor,
deposit on the fabrics to provide softening. Accordingly, clay
minerals useful herein can be characterized as impalpable,
expandable, three-layer smectite-type clays having an ion exchange
capacity of at least about 50 meq/100 g.
While it is not intended that the instant invention be limited by
theory, it appears that the advantageous solubility, softening (and
potentially dye scavenging) benefits of the instant compositions
are ascribable to the physical characteristics and ion exchange
properties of the clays used herein. That is to say, experiments
have shown that non-expandable clays such as the kaolinites and the
illities, which are both classes of clays having ion exchange
capacities below 50 meq/100 g., do not provide the beneficial
aspects of the clays employed in the instant compositions.
Furthermore, the unique physical and electrochemical properties of
the smectite clays apparently cause their interaction with, and
dispersion of, the mixture of soap and curd dispersant used in the
instant compositions. Thus, it has now been found that, rather than
agglomerating to form viscous gels when contacted by water, the
soap-plus-curd dispersant granules having the smectite-clay
attached thereto used herein can be added to aqueous laundry baths
over a broad temperature range to yield homogeneous soap solutions
containing homogeneous, stable clay suspensions. The problems of
gelling and agglomeration usually encountered when such non-clay
containing, soap-curd dispersant granules are added to aqueous
media in solid form are alleviated by the presence of the clay.
Apparently, the negative electrical charges on the clay particles
serve to repulse the aggregates which tend to form when the
granular compositions herein are contacted by water thereby
providing the desired homogeneous soap solution. whatever the
reason for the advantageous co-action of the soap-based granules
and smectite clay used herein, the attachment of the expandable,
three-layer, dioctadedral alumino-silicates and expandable,
three-layer, trioctahedral magnesium silicates to the surface of
the granules in the manner of this invention provides a means
whereby the water solubility of the granules is greatly improved
while additionally providing a homogeneous clay dispersion which
provides effective fabric softening.
The smectite clays used in the compositions herein are all
commercially available. Such clays include, for example,
montmorillonite, volchonskoite, nontronite, hectorite, saponite,
sauconite, and vermiculite. The clays herein are available under
commercial names such as "fooler clay" (clay found in a relatively
thin vein above the main bentonite or montmorillonite veins in the
Black Hills) and various tradenames such as Thixogel No. 1 and
Gelwhite GP from Georgia Kaolin Co., Elizabeth, N.J. Volclay BC and
Volclay No. 325, from American Colloid Co., Skokie, Ill; Black
Hills Bentonite BH 450, from International Minerals and Chemicals;
and Veegum Pro and Veegum F, from R. T. Vanderbilt. It is to be
recognized that such smectite-type minerals obtained under the
foregoing commercial and tradenames can comprise mixtures of the
various discrete mineral entities. Such mixtures of the smectite
minerals are suitable for use herein.
While any of the impalpable smectite-type clays having a cation
exchange capacity of at least about 50 meg/100 g. are useful
herein, certain clays are preferred. For example, Gelwhite GP and
fooler clay are extremely white forms of smectite clays and are
therefore preferred when formulating white, granular compositions.
Volclay BC, which is a smectite-type clay mineral containing at
least 3% of iron (expressed as Fe.sub.2 O.sub.3) in the crystal
lattice, and which has a very high ion exchange capacity, is one of
the most efficient and effective clays for use in laundry
compositions and is preferred from the standpoint of fabric
softening performance. Likewise, Thixogel No. 1, is a preferred
clay herein from the standpoint of both product solubility and
through-the-wash fabric softening performance. On the other hand,
certain smectite clays, such as those marketed under the name
"bentonite", are sufficiently contaminated by other silicate
minerals that their ion exchange capacity falls below the requisite
range, and such clays are of no use in the instant
compositions.
Appropriate clay minerals for use herein can be selected by virtue
of the fact that smectites exhibit a true 14A X-ray diffraction
pattern. This characteristic pattern, together with exchange
capacity measurements performed in the manner noted above, provides
a basis for selecting suitable impalpable semctite-type clay
minerals for use in the granular detergent compositions disclosed
herein.
Composition Preparation
The compositions herein are formulated by simply preparing granules
comprising the soap, curd dispersant, and any of the optional
ingredients mentioned hereinabove, and then contacting the granules
with the smectite-type clay. The clay can then be simply admixed
with the soap-based granules and blended. In this precedure, the
clay is attached to the soap-based granules mainly by electrostatic
surface forces between the clay and soap granules.
In a preferred method for attaching the clay to the granules, the
soap-based granules are coated with a material of the type
hereinafter disclosed which promotes adhesion of the clay particles
to the surface of the granules. When an adhesion-promoting material
is used, the substantially dry soap-based granules can be first
sprayed with said material in liquid form and then admixed with the
clay. The clay and sprayed granules are then thoroughly blended to
provide good contact and optimum coating of the granules with the
clay. In an alternate procedure, the clay and granules are
concurrently admixed and sprayed with the adhesion-promoting
material. Mixing of the clay and granules can be achieved using a
standard drum mixer.
The materials used herein to promote adhesion of the clays to the
surface of the granules can be any water-soluble or
water-dispersable organic materials, preferably those which are
liquids or are liquifiable at convenient temperatures for spraying,
i.e., at temperatures from about 60.degree. F to about 150.degree.
F. Of course, the adhesion-promoting materials used herein should
not be toxic or deleterious to fabrics. Since most soap
compositions are desirably white in color, colorless organic
materials are preferred herein for attaching the clay to the
soap-based granules. Preferably, the materials used herein have
sufficient hydrophilic character that they are easily dissolved or
dispersed in water, but they are preferably not hydroscopic.
A variety of liquid and liquifiable organic compounds are useful
herein for attaching the clay to the surface of the soap-based
granules. For example, all manner of common ethoxylated nonionic
surfactants can be used for this purpose. Nonionic surfactants
produced by the condensation of an alkylene oxide moiety
(hydrophilic in nature) with an organic hydrophobic compound which
is usually aliphatic or alkyl aromatic in nature can be used. The
length of the hydrophilic or polyoxyalkylene moiety which is
condensed with any particular hydrophobic compound can be readily
adjusted to yield colorless, liquid or liquifiable, water
dispensable, organic, nonionic surfactants which are useful
adhesion promoters herein. Examples of nonionic surfactants which
can be used as the adhesion-promoting materials herein include:
1. The polyethylene oxide condensates of alkyl phenols. These
compounds include the condensation products of alkyl phenols having
an alkyl group containing from about 6 to 12 carbon atoms, in
either a straight chain or branched chain configuration, with
ethylene oxide, said ethylene oxide being present in amounts equal
to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The
alkyl substituent in such compounds can be derived, for example,
from polymerized propylene, diisobutylene, octene, or nonene.
Examples of compounds of this type include nonyl phenol condensed
with about 9.5 moles of ethylene oxide per mole of nonyl phenol,
dodecyl phenol condensed with about 12 moles of ethylene oxide per
mole of phenol, dinonyl phenol condensed with about 15 moles of
ethylene oxide per mole of phenol, di-isooctyl-phenol condensed
with about 15 moles of ethylene oxide per mole of phenol.
Commercially available nonionic surfactants of this type include
Igepal CO-610 marketed by the GAF Corporation; and Triton X-45,
X-114, X-100 and X-102, all marketed by the Rohm and Haas
Company.
2. The condensation products of aliphatic alcohols with ethylene
oxide. The alkyl chain of the aliphatic alcohol can either be
straight or branched and generally contains from about 8 to about
22 carbon atoms. Examples of such ethoxylated alcohols include the
condensation product of about 6 moles of ethylene oxide with 1 mole
of tridecanol, myristyl alcohol condensed with about 10 moles of
ethylene oxide per mole of myristyl alcohol, the condensation
product of ethylene oxide with coconut fatty alcohol wherein the
coconut alcohol is a mixture of fatty alcohols with alkyl chains
varying from 10 to 14 carbon atoms and wherein the condensate
contains about 6 moles of ethylene oxide per mole of alcohol, and
the condensation product of about 9 moles of ethylene oxide with
the above-described coconut alcohol. Examples of commercially
available nonionic surfactants of this type include Tergitol 15-S-9
marketed by the Union Carbide Corporation, Neodol 23-6.5 marketed
by the Shell Chemical Company, and Kyro EOB marketed by The Procter
& Gamble Company.
3. The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene
glycol. The hydrophobic portion of these compounds has a molecular
weight of from about 1500 to 1800. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the
water-solubility of the molecule as a whole, and the liquid
character of the product is retained up to the point where the
polyoxyethylene content is about 50% of the total weight of the
condensation product. Examples of compounds of this type include
certain of the commercially available Pluronic surfactants marketed
by the Wyandotte Chemicals Corporation.
4. The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylene
diamine. The hydrophobic base of these products consists of the
reaction product of ethylenediamine and excess propylene oxide,
said base having a molecular weight of from about 2500 to about
3000. This base is condensed with ethylene oxide to the extent that
the condensation product contains from about 40% to about 80% by
weight of polyoxyethylene and has a molecular weight of from about
5,000 to about 11,000. Examples of this type of nonionic surfactant
include certain of the commercially available Tetronic compounds
marketed by the Wyandotte Chemicals Corporation.
The fatty acids are another class of materials which can be used to
promote the attachment of the clays to the surface of the granules.
Fatty acids useful herein are those C.sub.10 to C.sub.22 straight
chain and branched chain aliphatic carboxylic acids which can be
obtained, for example, by the saponification of triglycerides. Both
saturated and unsaturated fatty acids are useful herein. Mixtures
of fatty acids obtainable from certain designated fats, e.g.,
tallow fatty acids, obtainable from tallow; coconut fatty acids,
obtainable from coconut oil and; palm fatty acids, obtainable from
palm oil, are also useful herein. The C.sub.12 to C.sub.20
aliphatic fatty acids, and mixtures thereof, are preferred members
of this class of adhesion-promoting materials herein.
Exemplary fatty acids which can be employed herein to affix the
clay to the soap-based granules include lauric, myristic, palmitic,
stearic, elaidic, oleic and eicosanoic acids, and mixtures
thereof.
The fatty alcohols having C.sub.10 to C.sub.22 hydrocarbon chains
are also useful herein as adhesion promoters. These materials can
be obtained in a variety of ways well known in the art, e.g., from
various triglyceride oils such as palm oil and coconut oil.
Exemplary alcohols useful herein include 1-dodecanol,
1-tetradecanol, 1-hexadecanol and 1-octadecanol.
Preferred materials which can be used herein to attach the smectite
clays to the surfaces of the soap-plus-curd dispersant granules
include; coconut alcohol ethoxylate containing 6 ethylene oxide
units per molecule; tallow alcohol ethoxylate containing 11
ethylene oxide units per molecule, i.e., tallow ethylene oxide
(11); coconut fatty acid mixtures; tallow fatty acid mixtures, the
condensate of one mole of ethylene oxide with 1-dodecanol; and the
condensate of one mole of 1-dodecanol with ethylene oxide hexamer.
Especially preferred adhesion promoters herein include coconut
fatty acids and tallow ethylene oxide (11).
In addition to providing good attachment of the smectite-type clays
to the surface of the soap-based granules herein, the optionally
employed adhesion-promoting materials serve the additional function
of providing an unexpected additional increment of solubility to
the compositions. That is to say, while the soap-plus-curd
dispersant granules herein exhibit poor solubility in laundering
baths on the range of from about 60.degree. F. to 120.degree. F.,
the surface coating of the adhesion-promoting materials enhances
this solubility. while the soap-plus-curd dispersant granules
coated with the adhesion-promoting materials are not rendered
sufficiently soluble to be optimally useful for cool water washing
(i.e., at about 80.degree. F), the added increment of solubility
imparted by the adhesion-promoting materials complements the
substantial increase in solubility afforded by the smectite-type
clays. Accordingly, the soap-based granules coated with the
adhesion promoter and having the smectite-type clays attached to
the surface have a water solubility comparable to that of the
better commercial synthetic detergent compositions over a wide
temperature range.
In addition to providing optimal attachment of the smectite clays
to the soap-based granules and enhancing the water solubility of
the compositions herein, the optionally-employed,
adhesion-promoting materials serve to decrease product dust levels.
The decreased product dust levels afforded by the adhesion
promoters aids in processing and provides a more acceptable product
for the consumer.
When the adhesion-promoting materials herein are employed to attach
the smectite-type clays to the surface of the soap-based granules,
they are preferably used in an amount sufficient to provide said
granules with at least a monolayer coating of said materials. For
most purposes, the adhesion-promoting material can comprise from
about 0.5% to about 8%, preferably 1% to about 4%, by weight of the
total composition. Of course, higher proportions of the adhesion
promoters can be employed, but this represents an economic waste in
that such increased proportions are not required to affix the clay
to the granules and do not further increase product solubility to
any substantial degree.
Use of the clay-to-soap-based granules ratio noted hereinabove
results in compositions wherein a substantial proportion of the
surface of the granules are coated with the clay. Of course, when
the adhesion-promoting materials are additionally employed, greater
coverage of the granules is more easily achieved. While soap-based
granules having about 10%, and greater, of their surfaces coated
with the clay exhibit the desirable solubility properties disclosed
herein, it is preferred that the clay coat at least about 40% of
the granule surface. Such higher degrees of surface coating are
most readily achieved by use of the adhesion-promoting materials
disclosed above.
For fabric laundering and softening purposes, compositions of the
instant invention are added to aqueous laundering liquor to the
extent of from about 0.02% to about 2% by weight, preferably form
about 0.1% to about 1% by weight. Addition of such compositions
provide a laundering liquor pH of from about 7 to 12.
The detergent compositions of the instant invention are illustrated
by the following examples
EXAMPLE I
A soap-based laundry granule is prepared having the following
composition:
Component Wt.% ______________________________________ Sodium
soap.sup.(1) 42.6 Potassium soap.sup.(1) 11.2 TAE.sub.3 S.sup.(2)
10.7 C.sub.11.8 LAS.sup.(3) 8.8 Sodium silicate 8.9 Sodium sulfate
11.9 Brightener 0.57 Perfume 0.17 Water 3.4 Miscellaneous Balance
______________________________________ .sup.(1) Soap mixtures
comprising 90% tallow and 10% coconut soaps .sup.(2) Sodium salt of
ethoxylated tallow alkyl sulfate having an averag of about 3
ethylene oxide units per molecule. .sup.(3) Sodium salt of liner
alkyl benzene sulfonate having an average alkyl chain length of
about 12 carbon atoms.
The foregoing ingredients are mixed in a crutcher and spray-dried
to provide a granular, soap-based composition.
Eighty-eight and four-tenths parts by weight of the soap-based
granules prepared above are admixed with 11.6 parts by weight of an
impalpable sodium montmorillonite clay having an ion exchange
capacity greater than 50 meq/100 g. marketed under the tradename
Thixogel No. 1. Such admixture provides a composition comprising
the soap-plus-curd dispersant granules having the clay attached to
the surface of the granules.
such a composition is a stable laundry detergent formulation
providing excellent fabric laundering and as noted below also has
desirable solubility and fabric softening characteristics when
added to laundering liquor to the extent of about 0.12% by
weight.
EXAMPLE II
A soap-based laundry granule is prepared having the following
composition:
Component Wt. % ______________________________________ Sodium
soap.sup.(1) 42.6 Potassium soap.sup.(1) 11.2 TAE.sub.3 S.sup.(2)
10.7 C.sub.11.8 LAS.sup.(3) 8.8 Sodium silicate 8.9 Sodium sulfate
11.9 Brightener 0.57 Perfume 0.17 Water 3.4 Miscellaneous Balance
______________________________________ .sup.(1) Soap mixtures
comprising 90% tallow and 10% coconut soaps .sup.(2) Sodium salt of
ethoxylated tallow alkyl sulfate having an averag of about 3
ethylene oxide units per molecule. .sup.(3) Sodium salt of linear
alkyl benzene sulfonate having an average alkyl chain length of
about 12 carbon atoms.
The foregoing ingredients are mixed in a crutcher and spray-dried
to provide a granular, soap-based composition.
Eighty-eight and four-tenths parts by weight of the soap-based
granules above are admixed with 8.6 parts by weight of impalpable
sodium montmorillonite clay having an ion exchange capacity greater
than 50 meq/100 g., marketed under the tradename, Thixogel No. 1.
Such admixture of clay and soap-based granules is sprayed with
liquid coconut fatty acid and mixing is continued to provide
uniform soap-plus-curd dispersant granules having the clay attached
to the surface of the granules. Enough coconut fatty acid is
employed to provide about 3% by weight of the total
composition.
Such a composition is a stable laundery detergent formulation
providing excellent fabric laundering and, as noted in greater
detail below, also has desirable solubility and fabric softening
characteristics when added to laundering liquor to the extent of
about 0.12% by weight.
EXAMPLE III
A soap-based laundry granule is prepared having the following
composition:
Component Wt. % ______________________________________ Sodium
soap.sup.(1) 51.8 Tallow monoethanolamide 2.5 Sodium
tripolyphosphate 11.5 Sodium ethylenediamine tetraacetate 0.21
Sodium silicate 5.50 Carboxymethylcellulose 0.33 Sodium perborate
15.6 Perfume, brightener, moisture & misc. Balance
______________________________________ .sup.(1) A mixture of tallow
and coconut soaps comprising 80% tallow soap and 20% coconut
soap.
The foregoing ingredients are mixed in a crutcher and spray-dried
to provide a granular, soap-based composition.
Ninety-five parts by weight of the soap-based granules prepared
above are admixed with 5 parts by weight of an impalpable sodium
montmorillonite clay having an ion exchange capacity of about
85-100 meq/100 g. marketed under the tradename Volclay BC. Such
admixture provides a composition comprising the soap-plus-curd
dispersant granules having the clay attached to the surface of the
granules.
Such a composition is a stable laundry detergent formulation
providing excellent fabric laundering and as noted below also has
desirable solubility and fabric softening characteristics when
added to laundering liquor to the extent of about 0.7% by
weight.
EXAMPLE IV
A soap-based laundry granule is prepared having the following
composition:
Component Wt. % ______________________________________ Soap.sup.(1)
53.5 Tallow monoethanolamide 2.6 Sodium tripolyphosphate 11.8
Sodium ethylenediamine tetraacetate 0.22 Sodium silicate 5.7
Carboxymethylcellulose 0.34 Sodium perborate 16.0 Perfume,
brightener, moisture and miscellaneous Balance
______________________________________ .sup.(1) A mixture of tallow
and coconut soaps comprising 80% tallow soap and 20% coconut
soap.
The foregoing ingredients are mixed in a crutcher and spray dried
to provide a granular, soap-based composition.
Ninety-two parts by weight of the soap-based granules prepared
above are admixed with 5 parts by weight of an impalpable sodium
montmorillonite clay having an ion exchange capacity of about
85-100 meg./100 g. marketed under the tradename Volclay BC and 3
parts by weight of a liquid coconut fatty acid. Mixing is continued
to provide uniform soap-plus-curd dispersant granule having the
clay attached to the surface of such granules.
Such a composition is a stable, laundry detergent formulation
providing excellent fabric laundering and, as noted in greater
detail below, also has desirable solubility and fabric softening
characteristics when added to laundering liquor to the extent of
about 0.7% by weight.
Solubility Test
The water solubilitiy of foregoing compositions is assessed, as
follows
Automatic mini-washers each containing about 1-1/2 gallons of water
(7 gr/gal. hardness) and loaded with 6 blue cotton terry towels (14
.times. 14 inches; ca. 250 grams) are employed in the tests.
Machine settings are "wash-wear", i.e., gentle agitation. After the
water and terry towels are in the machines, test product is poured
uniformly into the machine in an amount equivalent to 1 cup per
17-19 gallons, and agitation is begun. After 15 seconds agitation,
the machine is stopped and a product lumping grade is assigned.
This grade is a visual assessment of the tendency of the product to
coagulate or to form large particles. Small particles are not
considered when assigning a lumping grade. Using this visual
procedure, a grade of 1 indicates many large lumps; a grade of 10
indicates no large lumps.
A second measurement is then taken which measures the length of
time unitl all product is dissolved, up to a maximum time of 4
minutes. One unit is substracted from the grade if the time for
dissolution of the product is greater than one minute.
Lumping is assessed at temperatures of 80.degree. F., 100.degree.
F. and 120.degree. F. A TOTAL SOLUBILITY INDEX is then assigned as
follows: Lumping Grade at 80.degree. F. .times. 0.2 + Lumping Grade
at 100.degree. F. .times. 0.4 + Lumping Grade at 120.degree. F.
.times. 0.4 = TOTAL SOLUBILITY INDEX.
In the above test, the TOTAL SOLUBILITY INDEX of the compositions
of Examples I, II, III and IV above, is substantially greater than
that of compositions comprising soap-plus-curd dispersant granules
without the attached clay.
Substantially similar solubility results are obtained when, in the
above-described tests, the ethoxylated tallow alkyl sulfate curd
dispersing agent of the Example I and II compositions or the tallow
monoethanolamide curd-dispersing agent of the Example III and IV
compositions is replaced with equivalent amounts of the sodium salt
of the methyl ester of .alpha.-sulfonated tallow fatty acid; the
sodium salt of ethoxylated tallow alkyl sulfate having an average
of about 6 ethylene oxide groups per mole; sodium
.beta.-acetoxy-hexadecane-1-sulfonate; sodium .beta.-acetoxy
tridecane-1-sulfonate; the sodium salt of sulfonated 1-hexadecene;
dimethyldodecylphosphine oxide; sodium
hexadecylmethylaminopropionate;
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and
3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein
both compounds the alkyl group averages 14.8 carbon atoms in
length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;
3(N,N-dimethyl-N-hexadecylammonio)-2-hyroxypropane- 1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate;
methyl-.beta.-hydroxydodecyl sulfoxide; stearic ethanolamide or
N-dodecymonethanolamine.
Substantially similar solubility results are obtained, when in the
above-described tests, the Thixogel No. 1 clay of the Example I and
II compositions or the Volclay BC of the Example III and IV
compositions is replaced with an equivalent amount of fooler clay,
Gelwhite GP, Volclay No. 325, Black Hills Bentonite BH 450, Veegum
Pro or Veegum F.
Substantially similar solubility results are obtained when, in the
above-described tests, the sodium linear alkyl benzene sulfonate
non-curd-dispersing surfactant of the Example I and II compositions
is replaced with an equivalent amount of sodium tallow alkyl
sulfate, the condensation product of coconut fatty alcohol with
about 6 moles of ethylene oxide per mole of alcohol or the
condensation product of a secondary fatty alcohol containing about
15 carbon atoms with about 9 moles of ethylene oxide per mole of
alcohol.
Substantially similar solubility results are obtained when, in the
above-described tests, the sodium tripolyphosphate builder of the
Example III and IV compositions is replaced with an equivalent
amount of sodium citrate, sodium carbonate, sodium mellitate or
sodium nitrilotriacetate.
Substantially similar solubility results are obtained when, in the
above-described tests, the coconut fatty acid adhesion-promoting
agent of the Example II and Example IV compositions is replaced
with an equivalent amount of coconut alcohol ethoxylate containing
6 ethylene oxide units per mole; tallow alcohol ethoxylate
containing 11 ethylene oxide units per mole; tallow fatty acid
mixtures, the condensate of one of ethylene oxide with 1-dodecanol;
the condensate of one mole of 1-dodecanol with ethylene oxide
hexamer; or the condensate of 9.5 moles of ethylene oxide with
nonyl phenol.
Softness Test
The through-the-wash fabric softening performance of the laundering
compositions herein is assessed by laundering cotton and
cotton/polyester swatches in aqueous laundry baths containing 0.1%
by weight of the compositions of Examples I and II, and 0.7% by
weight of the compositions of Example III and IV above. After two
complete laundering cycles and drying in an automatic dryer, fabric
softness is assessed tactilely by experienced graders. Fabric
softness of products laundered in the compositions herein is
comparable to that of fabrics laundered in a commerical laundry
detergent employing a commercial fabric softener in the rinse
cycle. Microscopic examination of the swatches indicates that
substantial amounts of the clay are deposited on the fabric, but no
substantial amount of curd is found on the fabric surface.
Substantially similar fabric softening results are obtained in the
above-described tests when the ethoxylated tallow alkyl sulfate
curd-dispersing agent of the Example I and II compositions or the
tallow monoethanolamide curd-dispersing agent of the Example III
and IV compositions is replaced with an equivalent amount of the
sodium salt of the methyl ester of .alpha.-sulfonated tallow fatty
acid; the sodium salt of ethoxylated tallow alkyl sulfate having an
average of about 6 ethylene oxide groups per mole; sodium
.beta.-acetoxy-hexadecane-1-sulfonate; sodium .beta.-acetoxy
tridecane-1-sulfonate; the sodium salt of sulfonated 1-hexadecene;
dimethyldodecylphosphine oxide; sodium
hexadecylmethylaminopropionate;
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and
3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein
in both compounds the alkyl group averages 14.8 carbon atoms in
length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;
3(N,N-dimethyl-N-hexadecylammonio)- 2-hydroxypropane-1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate;
methyl-.beta.-hydroxydodecyl sulfoxide; stearic ethanolamide or
N-dodecylmonoethanolamine.
Substantially similar fabric softening results are obtained, when
in the above-described tests, the Thixogel No. 1 clay of the
Example I and II compositions or the Volclay BC of the Example III
and IV compositions is replaced with an equivalent amount of fooler
clay, Gelwhite GP, Volclay No. 325, Black Hills Bentonite BH 450,
Veegum Pro or Veegum F.
Substantially similar fabric-softening results are obtained when,
in the above-described tests, the sodium linear alkyl benzene
sulfonate non-curd-dispersing surfactant of the Example I and II
compositions is replaced with an equivalent amount of sodium tallow
alkyl sulfate, the condensation product of coconut fatty alcohol
with about 6 moles of ethylene oxide per mole of alcohol or the
condensation product of a secondary fatty alcohol containing about
15 carbon atoms with about 9 moles of ethylene oxide per mole of
alcohol.
Substantially similar fabric-softening results are obtained when,
in the above-described tests, the sodium tripolyphosphate builder
of the Example III and IV compositions is replaced with an
equivalent amount of sodium citrate, sodium carbonate, sodium
mellitate or sodium nitrilotriacetate.
Substantially similar fabric softening results are obtained when,
in the above-described tests, the coconut fatty acid
adhesion-promoting agent of the Example II and IV compositions is
replaced with an equivalent amount of coconut alcohol ethoxylate
containing 6 ethylene oxide units per mole; tallow alcohol
ethoxylate containing 11 ethylene oxide units per mole; tallow
fatty acid mixtures, the condensate of one mole of ethylene oxide
with 1-dodecanol; the condensate of one mole of 1-dodecanol with
ethylene oxide hexamer; or the condensate of 9.5 moles of ethylene
oxide with nonyl phenol.
* * * * *