U.S. patent number 3,915,882 [Application Number 05/305,417] was granted by the patent office on 1975-10-28 for soap compositions.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Robert Andrew Gloss, Joseph Peter Nirschl.
United States Patent |
3,915,882 |
Nirschl , et al. |
October 28, 1975 |
Soap compositions
Abstract
Granular laundering compositions comprising a
curd-dispersant-containing soap-based granule, a smectite-type clay
and a quaternary ammonium anti-static agent. The soap and curd
dispersant are formulated in the granule and the clay is attached
to the surface of the granule. The quaternary ammonium compound is
formulated in releasable combination with the granule. The
resulting compositions enhanced solubility and provide
through-the-wash fabric softening and anti-static benefits.
Inventors: |
Nirschl; Joseph Peter
(Cincinnati, OH), Gloss; Robert Andrew (Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
23180693 |
Appl.
No.: |
05/305,417 |
Filed: |
November 10, 1972 |
Current U.S.
Class: |
510/330; 510/307;
510/469; 510/504; 510/515; 510/482; 510/443; 510/308; 510/324;
510/354 |
Current CPC
Class: |
C11D
1/62 (20130101); C11D 9/18 (20130101); C11D
3/001 (20130101); C11D 10/047 (20130101); C11D
17/06 (20130101); C11D 3/126 (20130101) |
Current International
Class: |
C11D
17/06 (20060101); C11D 3/00 (20060101); C11D
3/12 (20060101); C11D 9/04 (20060101); C11D
9/18 (20060101); C11D 1/38 (20060101); C11D
1/62 (20060101); C11D 009/20 () |
Field of
Search: |
;252/8.75,8.6,8.8,110,113,120,131 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3716488 |
February 1973 |
Kolsky et al. |
3765911 |
October 1973 |
Knowles et al. |
|
Primary Examiner: Sebastian; Leland A.
Attorney, Agent or Firm: Witte; Richard C. O'Flaherty;
Thomas H. Schaeffer; Jack D.
Claims
What is claimed is:
1. A fabric laundering composition, comprising:
A. from about 75% to about 96% by weight of 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 curd-dispersing agent;
B. from about 4% to about 25% by weight of an impalpable
smectite-type clay having an ion exchange capacity of at least
about 50 meq/100 grams, attached to the surface of said granular
particles, said composition having a weight ratio of granular
particles to impalpable smectite-type clay of from about 20:1 to
3:1; and
C. from about 0.5% to about 15% by weight of a substantially
water-insoluble quaternary ammonium anti-static agent of the
formula
[R.sub.2 NR.sub.2 '].sub.n X.sup.n.sup.-
wherein each R is a hydrocarbyl group containing from about 10 to
about 22 carbon atoms and each R' is a hydrocarbyl group containing
from about 1 to about 4 carbon atoms, X is an anion and n is an
integer from 1 to 3, the weight ratio of smectite-type clay to
quaternary ammonium compound being in the range of from about 40:1
to about 1:1, said quaternary ammonium compound being in releasable
combination in said composition.
2. A composition according to claim 1:
A. wherein the soap compound is a water-soluble 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 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, 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 3
carbon atoms;
vi. compounds of the formula ##SPC12##
wherein R is an alkyl group of from about 8 to 16 carbon atoms and
X is selected from the group consisting of methyl, ethyl and
.beta.-hydroxyethyl groups;
vii. compounds of the formula ##SPC13##
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.
viii. compounds of the formula ##SPC14##
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 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 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;
ix. compounds of the formula ##SPC15##
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
x. organic amines selected from the group consisting of N-alkyl
monoalkylolamines and N-alkyl dialkylolamines wherein the alkyl
group contains from about 10 to 16 carbon atoms and the alkylol
group contains 2 or 3 carbon atoms; N-alkyl morpholines wherein the
alkyl groups contains from about 10 to 16 carbon atoms and N-alkyl
tris(hydroxymethyl)-aminomethane wherein the alkyl group contains
from about 10 to 16 carbon atoms; and wherein said 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;
C. wherein said impalpable smectite-type clay is selected from the
group consisting of dioctahedral expandable three-layer
aluminum-silicates and trioctahedral expandable three-layer
magensium silicates, and is present to the extent of from about 4%
to about 25% by weight of the total composition; and
D. wherein the quaternary ammonium compound is
ditallowdimethylammonium chloride and is present in releasable
combination with the composition at a concentration of from about
0.5% to about 5% by weight.
3. A composition according to claim 1
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 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; dimethyldodecylphosphine oxide; sodium
hexadecylmethylaminopripionate;
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonat and
3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; and
tallow acyl monoethanolamide;
C. wherein the smectite-type clay is selected from the group
consisting of montmorillonites, volchonskoites, nontronites,
hectorites, sauconites and vermiculites; and
D. wherein the quaternary ammonium compound is
ditallowdimethylammonium chloride.
4. A composition according to claim 1 wherein the smectite-type
clay is selected from the group consisting of "fooler clay,"
Thixogel No. 1, Gelwhite GP, Volclay BC, Volclay No. 325, Black
Hills Bentonite BH 450, Veegum Pro and Veegum F.
5. A composition according to claim 1 wherein the smectite-type
clay is Volclay BC.
6. A composition according to claim 1 wherein the smectite-type
clay is "fooler clay."
7. A composition according to claim 1 wherein the 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-type clay is Thixogel No. 1.
8. A composition according to claim 1 containing as an additional
component from about 0.5% to about 8% by weight of an
adhesion-promoting material.
9. A composition according to claim 1 containing as an additional
component from about 1% to about 30% by weight of an alkaline
builder salt.
10. A composition according to claim 9 wherein the alkaline builder
salt is sodium tripolyphosphate.
Description
BACKGROUND OF THE INVENTION
The instant invention relates to granular laundering compositions
which provide simultaneous laundering, softening and anti-static
benefits on textiles during conventional fabric laundering
operations. Such compositions employ a combination of a soap and a
curd dispersant in granular form, certain smectite clay compounds
having particular cation exchange characteristics, and certain
cationic anti-static agents.
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 clothing. 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 their 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
agglomerates as a gelatinous material which then deposits in an
unsightly manner on the fabrics being laundered.
As more fully disclosed in the co-pending application of Ohren,
Ser. No. 279,127 filed Aug. 9, 1972, certain smectite-type clay
materials 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.
However, such clay-plus-soap granules, while effective for their
intended purpose, do no impart desirable antistatic benefits to
fabrics laundered therein. That is to say, commercially acceptable
fabric softeners also provide anti-static benefits, and such
benefits have come to be expected by the user of such products. The
present invention discloses a means for providing these desirable
anti-static benefits.
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, Intersicence 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 watersofteners (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 properties thereto. Such clay
deposition is usually realized by contacting fabrics to be so
treated with aqueous clay suspensions (see, for example, U.S. Pat.
Nos. 3,033,699 and 3,594,221). The co-pending application of Storm
and Nirschl, Ser. No. 271,943, filed July 14, 1972, now abandoned,
teaches the use of clays as softeners in detergent
compositions.
Various quaternary ammonium compounds are known in the art which
possess anti-static properties, and the use of clays in combination
with conventional cationic agents for various purposes has been
taught in the prior art. For example, U.S. Pat. No. 3,594,212
teaches that quaternary ammonium compounds affixed to the surface
of clay can enhance clay deposition of fabrics; see, also, U.S.
Pat. No. 3,625,505. However, as will be seen hereinafter, when
quaternary compounds are chemically affixed to clay surfaces in the
manner disclosed in the prior art, the desirable anti-static
benefits are substantially lost. Furthermore, quaternary ammonium
compounds are not generally taught to be useful in combination with
anionic materials such as soap in the manner disclosed herein.
While the use of clays as fabric softeners is described in the
cited art, such clay softeners are not entirely suitable for this
purpose since they do not possess anti-static properties. Indeed,
fabrics coated with clays, while exhibiting a soft hand, tend to
develop higher levels of static change than the uncoated fabrics,
themselves.
The concurrently filed application of Nirschl and Gloss, entitled
"Detergent Composition;" Ser. No. 305,416, filed Nov. 10, 1972
discloses the use of clay-plus-quat softeners and anti-static
agents in built, non-soap detergent compositions.
U.S. Pat. No. 2,819,228 discloses the use of clays in combination
with cationic surfactants as dry emulsifiers; however, these
compositions do not contain detergent compounds suitable for
laundering fabrics.
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, and combined with specific quaternary ammonium
compounds to provide soluble soap granules having combined fabric
softening and anti-static benefits.
Accordingly, it is an object of the present invention to provide
compositions which can be employed to achieve concurrent fabric
laundering, fabric softening, and anti-static effects without
interfering with flame retardancy.
It is a further object of the present invention to provide
soap-based laundering, softening and anti-static compositions
containing curd dispersants in the form of granular formulations
which can be easily dissolved in water over a wide temperature
range.
These and other objects ae obtained herein, as will be seen from
the following disclosure.
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; (B) an impalpable smectite-type clay
having an ion exchange capacity of at least about 50 meg/100 g. of
clay, attached to the surface of said granular particle; and (C)
from about 0.5% to about 15% by weight of a substantially
water-insoluble quaternary ammonium anti-static agent of the
formula
[R.sub.2 NR.sub.2 '].sub.n X,.sup.n.sup.-,
wherein each R is a hydrocarbyl group containing from about 10 to
about 22 carbon atoms and each R' is a hydrocarbyl group containing
from 1 to about 4 carbon atoms, and wherein X is an anion, i.e.,
halide, hydroxide, carbonate, phosphate, etc. In the above formula,
the integer, n, indicates the charge on the anion; n can be 1 to 3
in the compounds herein. The compositions have a weight ratio of
granular particles to smectite clay in the range of from about 20:1
to about 3:1. The weight ratio of smectite-type clay-to-quaternary
ammonium compound in the compositions herein is from about 40:1 to
about 1:1, preferably about 5:1. The quaternary ammonium compound
is present in releasable combination with the compositions herein.
By "releasable combination" is meant that, on admixture with water,
the soluble components of the composition granules dissolve and the
clay and quaternary compounds are independently suspended in the
aqueous medium.
The compositions herein preferably provide a solution pH of from
about 6 to about 11 when dissolved in water at a concentration of
about 0.12% by weight.
In a method aspect, the invention encompasses methods for
concurrently cleansing, softening and providing anti-static effects
on fibers and fabrics comprising laundering said fabrics in an
aqueous laundry bath containing an effective amount (e.g., from
about 0.02% to about 2% by weight) of a laundry composition as
described above.
DETAILED DESCRIPTION OF THE INVENTION
The compositions and processes of this invention employ three
essential ingredients: the soap-based granule; the clay; and the
quaternary ammonium anti-static agent. The soap granule dissolves
and functions in standard fashion to remove soil from fabrics being
laundered. The curd dispersant contained in the granule prevents
curd build-up on the laundered fabrics. The smectite-type clay
functions to soften the laundered fabrics and to help dissolve the
soap-plus-curd dispersant granule. The quaternary ammonium compound
provides anti-static effects on the fabrics and adds an increment
of softening benefit thereto. These various components are
described in greater detail hereinafter.
Anti-Static Agent
The quaternary ammonium anti-static agents are employed in the
instant compositions at a concentration of from about 0.5% to about
15%, preferably from about 0.5% to about 5% by weight, and are
therefore present in the laundering liquors at levels from about 5
ppm to about 150 ppm. In general, the quaternary anti-stats are
used at a clay to quaternary weight ratio of from about 40:1 to
about 1:1, preferably about 5:1.
The anti-static agents of this invention are quaternary ammonium
salts of the formula
[R.sub.2 NR.sub.2 '].sub.n X.sup.n.sup.-
wherein each R group is a hydrocarbyl (i.e., alkyl or alkenyl)
group containing from about 10 to about 22 carbon atoms and each R'
group is a short-chain hydrocarbyl group containing from 1 to about
4 carbon atoms. X in the above compounds can be any salt-forming
anion, e.g., halide, hydroxide ion, sulfat, carbonate, phosphate,
etc. The charge on the anion is designated an n.sup.-, wherein n is
1-3. The number of cationic ammonium groups, n, will equal the
change, n, on the anion to provide electrical neutrality.
Quaternary ammonium compounds wherein n=1 are commercially
available and are preferred herein for this reason.
The quaternary ammonium anti-static agents herein are characterized
by their limited solubility in water. That is to say, such
quaternary salts are essentially insoluble in water, existing
therein in what appears to be the mesomorphic liquid crystalline
state. The insolubility of the quaternary salts used herein is a
critical aspect of this invention inasmuch as water-soluble
quaternary salts become chemically affixed to the surface of the
clay, or react with the soap or curd dispersant. When the
quaternary anti-static agent is affixed to the surface of the clay,
or has reacted with the soap or curd dispersant, it does not
perform the desired anti-static function.
The cause of the solubility properties of the particular class of
quaternaries found to be useful herein is not known with certainty.
While not intending to be limited by theory, it appears that the
two extended hydrocarbyl chains (C.sub.10 -C.sub.22) present in the
molecules serve to lower their solubility and probably account for
their existence as liquid crystals. In any event, it has been found
the di-long chain quaternaries can be used in releasable
combination with compositions containing clays. That is to say, the
quaternary compound and the clay are independently suspended in the
washing liquor and the quaternary compound does not appear to
substantially affix itself to the clay surface by an ion exchange
mechanism.
Quaternary ammonium compound are not generally considered to be
useful in combination with anionic materials such as soaps since
the opposite charges on these two types of materials cause them to
react and precipitate from solution. Surprisingly, it has been
found that the desirable anti-static benefits of the insoluble
quaternary ammonium salts used herein are not negated when employed
in combination with soaps or the anionic curd dispersants.
Apparently, the insoluble nature of the di-long chain quats renders
them somewhat campatible with such anionic materials. Whatever the
reason, the quaternary ammonium anti-stats herein perform their
anti-static function when used in combination with clays and
anionics such as soap and curd dispersants.
The quaternary ammonium anti-static agents used in this invention
can be prepared in various ways well-known in the art. Many such
materials are commercially available. The quaternaries are often
made from alkyl halide mixtures corresponding to the mixed alkyl
chain lengths in fatty acids. For example, the "di-tallow"
quaternaries are made from alkyl halides having mixed C.sub.14
-C.sub.18 chain lengths. Such mixed di-long chain quaternaries are
useful herein and are preferred from a cost standpoint.
As noted above, essentially any anionic group can be the counterion
in the quaternary compounds used herein. The anionic groups in the
quaternary compounds can be exchanged, one for another, using
standard anion exchange resins. Thus, quaternary ammonium salts
having any desired anion are readily available. While the nature of
such anions has no effect on the compositions and processes of this
invention, chloride ion is the preferred counter-ion from a cost
standpoint.
The following are representative examples of substantially
water-insoluble quaternary ammonium antistatic agents suitable for
use in the compositions and processes of the instant invention. All
of the quaternary ammonium compounds listed can be formulated in
releasable combination with the detergent compositions herein, but
the compilation of suitable quaternary compounds hereinafter is
only by way of example and is not intended to be limiting of such
compounds. Ditallowdimethylammonium chloride is an especially
preferred quaternary anti-static agent for use herein by virtue of
its low cost, low solubility and high-anti-static activity; other
useful di-long chain quaternary compounds are
dicetyldimethylammonium chloride; bis-docosyldimethylammonium
chloride; didecyldimethylammonium chloride;
ditallowdimethylammonium bromide; dioleoyldimethylammonium
hydroxide; ditallowdiethylammonium chloride;
ditallowdipropylammonium bromide; ditallowdibutylammonium fluoride,
cetyldecylmethylethylammonium chloride,
bis-[ditallowdimethylammonium]sulfate;
tris-[ditallowdimethylammonium]-phosphate; and the like.
The Granular Particles
The granular particle component of the instant laundering
compositions comprises two essential ingredients (1) a
water-soluble soap compound and (2) a curd-dispersing agent. In
addition, as will be set forth more fully hereinafter, the
quaternary ammonium antistatic agent can comprise a third component
of the granules, but is more preferably applied to the surfaces of
said granules by spraying after the base granules are formed.
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 mixture 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 lim 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 and 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 moety 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-hexadecane1-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-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of
2-acetoxy-octadecane-1-sulfonic acid; the dimethylamine salt of
2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of
2-acetoxy-nonadecane-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. Pats. No. 2,094,451
issued Sept. 28, 1937, To Guenther, et al., and No. 2,086,215
issued July 6, 1937 to De Groote disclose certain salts of
.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 0).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 by
synthetic. Lauryl alcohol and straight chain alcohols derived from
tallow are preferred herein. Such alcohols are reacted with 1 to
30, and especially 3 to 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.-hydyroxyethyl 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 one
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##
where 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 and 2 when Y is a nitrogen or phosphorus atom, R.sub.3 is
an alkylene or hydroxy alkylene group of 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-3,6,9trioxatetracosanephosphonio]-2-hydroxypropane-1-phosp
hate;
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-(2hydroxydodecyl)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-1sulfate;
3-(dodecylbenzyldimethylammonio)propane-1-sulfonate; and
2-(dodecylbenzyldimethylammonio)ethane-1-sulphate.
Examples of compounds falling within this definition also includes
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 60 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 the above-described types of curd-dispersing agennts, 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 average 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 sulfonac acid where 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, antitarnishing 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 meg/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 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 .revreaction. smectite clay
(NH.sub.4) + NaOH
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 (meg/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 meg/100 g. for kaolinites
to about 150 meg/100 g., and greater, for certain clay of the
montmorillonite variety. Illite clays have an ion exchange capacity
somehwere in the lower portion of the range, i.e., around 26
meg/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 meg/100 g., saponite, which has an ion
exchange capacity of around 70 meg/100 g., and montmorillonite,
which has an ion exchange capacity greater than 70 meg/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 characerized as impalpable,
expandable, three-layer smectite-type clays having an ion exchange
capacity of at least about 50 meg/100 g.
The smectite clays used in the compositions herein are all
commercially available. Such clays include, for example,
montmorillonite, volchonskoite, nontronite, hectorite, spaonite,
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 (also,
"Thixo-Jell") 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 discreet 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% 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 smectite-type clay
minerals for use in the granular detergent compositions disclosed
herein.
COMPOSITION PREPARATION
The compositions herein can be formulated by simply preparing
granules comprising the soap, curd dispersant, and any of the
optional ingredients mentioned hereinabove. The granules are then
sprayed with a quaternary ammonium compound from a melt and then
contacted with the smectite-type clay. When this procedure is used,
the clay can then be simply admixed, e.g., by tumbling, with the
soap-based granules and blended. When this method is employed, the
clay is attached to the soapbased granules mainly by 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. Following this, the quaternary ammonium
anti-static agent can be added to the compositions, e.g., by
spraying from a melt.
Whatever the method chosen for admixing the soap-based granules,
clay and anti-static agent, it is necessary to insure that the
quaternary anti-static agent is not affixed to the surface of the
clay by chemical bonding. That is to say, if the clay and quat
combine by an ion exchange mechanism, the quat is not released to
perform its desirable anti-static function when the composition are
admixed with water. The preferred way to avoid ion exchange
reactions between the quat and clay is to add the quat to the
compositions from a melt, rather than from a solution or suspension
in water.
The materials which can be optionally used herein to promote the
adhesion of the clays to the surface of the granules can be any
water-soluble or water-disperable 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 hygroscopic.
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, a 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-isooctylphenol 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 product 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. Examles 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
Protector and 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 1,500 to 1,800. 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 2,500 to about
3,000. 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
promotoer 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, softening, and anti-static purposes, the
compositions of the instant invention are added to an aqueous
laundering liquor to the extent of from about 0.02% to about 2% by
weight, preferably from about 0.1% to about 1% by weight. Addition
of such compositions provide a laundering liquor pH of from about 6
to 11.
The laundering 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 mixture
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 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.
The foregoing soap-plus-clay granules are sprayed with melted
ditallowdimethylammonium chloride anti-stat; a total of 5% by
weight of the final composition comprises said anti-stat.
The foregoing composition is added to an aqueous laundering liquor
at 100.degree.F at a concentration of about 0.12% by weight. The
composition rapidly dissolves and the clay and anti-stat are
uniformly and independently dispersed throughout the laundering
liquor. Fabrics laundered in said liquor are concurrently cleansed,
softened and provided with an anti-static finish; substantially no
curd buildup occurs.
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% cocounut 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.
The foregoing granular product is then sprayed with a melt of
ditallowdimethylammonium chloride to a total of 5% by weight of the
granules.
Eighty-eight and four-tenths parts by weight of the soap-based
granules coated with the ditallowdimethylammonium chloride prepared
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. The
admixed clay and soap-based granules are sprayed with liquid
coconut fatty acid and mixing is continued to provide uniform
soap-plus-curd dispersant-plus-quat granules having the clay
attached to the surface. Enough coconut fatty acid is employed to
provide about 3% by weight of the total composition.
The foregoing composition is a stable laundry detergent formulation
having excellent water dispersability and providing excellent
fabric laundering, fabric softening, and fabric anti-static
characteristics when added to laundering liquors 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.
The foregoing soap-based granules are admixed with a melt of
ditallowmethylammonium chloride anti-stat. The quantity of said
anti-stat is adjusted to provide a coating comprising 5% by weight
of the total granules.
Ninety-five parts by weight of the soap-based granules coated with
the anti-stat 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. Such admixture provides a composition comprising the
soap-plus-curd dispersant plus anti-stat granules having the clay
attached to the surface.
The foregoing composition provides excellent fabric laundering and
has desirable solubility, fabric softening and anti-static
characteristics when used to launder fabrics in an aqueous liquor
at concentrations of about 0.7% by weight.
EXAMPLE IV
A soap-based laundry granule is prepared having the following
composition:
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 meq/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.
The foregoing composition is then uniformly admixed with impalpable
particles of ditallowdimethylammonium chloride anti-stat. The final
concentration of anti-stat in the composition is 7% by weight.
The composition is added to an aqueous laundry bath at 90.degree.F
at a concentration of 0.5% by weight. Said laundering bath provides
excellent fabric laundering and imparts desirable fabric softening
and anti-static characteristics to nylon, cotton, polyester and
polyester/cotton blends laundered therein.
It is to be recognized that various substitutions for the
components of the compositions set forth hereinabove can be made
without obviating the advantageous properties of said compositions.
For example, substantially similar results are obtained when, in
the above-described compositions, 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
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, respectively.
Substantially similar results are obtained, when in the
above-described compositions, 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, respectively.
Substantially similar results are obtained when, in the
above-described mixes, 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, respectively.
Substantially similar results are obtained when, in the
above-described compositions, 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, respectively.
Subsequently similar results are obtained when, in the
above-described compositions, the coconut fatty acid
adhesion-promoting agent of the Example II and Example IV
compositions is replaced with an equivalent amount of coconut
alcoholethoxylate 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, respectively.
Equivalent anti-static results are obtained in the above-described
compositions when the ditallowdimethylammonium chloride is replaced
by an equivalent amount of ditallowdimethylammonium bromide;
ditallowdimethylammonium hydroxide; ditallowdiethylammonium
chloride; dioctadecyldibutylammonium iodide;
oleoyldecylmethylbutylammonium chloride;
bis-[ditallowdibutylammonium]carbonate and
tris-[ditallowdiethylammonium]phosphate, respectively.
As seen from the foregoing, compositions comprising from about 75%
to about 96% by weight of a soap-based granule containing a curd
dispersant, from about 0.5% to about 15% by weight of a quaternary
ammonium anti-static agent and from about 4% to about 25% by weight
of a smectite-type clay, provide excellent through-the-wash fabric
cleansing, softening and anti-static benefits.
* * * * *