U.S. patent number 3,862,058 [Application Number 05/305,416] was granted by the patent office on 1975-01-21 for detergent compositions containing a smectite-type clay softening agent.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Robert Andrew Gloss, Joseph Peter Nirschl.
United States Patent |
3,862,058 |
Nirschl , et al. |
January 21, 1975 |
DETERGENT COMPOSITIONS CONTAINING A SMECTITE-TYPE CLAY SOFTENING
AGENT
Abstract
Granular, built laundry detergent compositions containing
particular smectite clay materials and quaternary ammonium
anti-static agents. The compositions impart a soft hand and reduce
the static charge of fabrics washed therein.
Inventors: |
Nirschl; Joseph Peter
(Cincinnati, OH), Gloss; Robert Andrew (Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
23180688 |
Appl.
No.: |
05/305,416 |
Filed: |
November 10, 1972 |
Current U.S.
Class: |
510/330; 510/324;
510/334; 510/496; 510/515; 510/504; 510/494; 510/331 |
Current CPC
Class: |
C11D
3/001 (20130101); C11D 1/62 (20130101); C11D
3/126 (20130101) |
Current International
Class: |
C11D
3/12 (20060101); C11D 3/00 (20060101); C11D
1/38 (20060101); C11D 1/62 (20060101); C11d
003/10 () |
Field of
Search: |
;252/8.6,8.8,113,131,528
;8/137 |
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 granular, built laundry detergent composition, comprising:
a. from about 2 percent to about 30 percent by weight of a non-soap
synthetic detergent compound selected from the group consisting of
anionic synthetic detergents, nonionic synthetic detergents,
ampholytic synthetic detergents, zwitterionic synthetic detergents
and mixtures thereof;
b. from about 10 percent to about 60 percent by weight of an
organic or inorganic detergent builder salt;
c. from about 1 percent to about 50 percent by weight of a
smectite-type clay softening agent having an ion exchange capacity
of at least about 50 meg/100 g.; and
d. from about 0.5 percent to about 15 weight of a substantially
water-insoluble quaternary ammonium anti-static agent of the
formula [R.sub.2 N.sup.+R'.sub.2 ].sub.n X.sup.n.sup.-, wherein
each R is a hydrocarbyl group containing from about 10 to about 22
carbon atoms, each R' is a hydrocarbyl group containing from 1 to
about 4 carbon atoms, X is an anion and n is an integer from 1 to
3, at a weight ratio of said smectite-type clay to quaternary
ammonium anti-static agent 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 synthetic detergent compound is an anionic synthetic
detergent and is present at from about 5 percent to about 20
percent by weight;
b. wherein the builder salt is selected from the group consisting
of alkali metal carbonates, alkali metal borates, alkali metal
phosphates, alkali metal polyphosphates, alkali metal
tripolyphosphates, alkali metal bicarbonates, alkali metal
sulfates, water-soluble amino polyacetates, water-soluble salts of
phytic acid, and water-soluble polyphosponates, and is present at
from about 20 percent to about 50 by weight;
c. wherein the smectite-type clay softening agent is selected from
the group consisting of dioctahedral expandable three-layer
alumino-silicates and trioctahedral expandable three-layer
magnesium silicates and is present at from about 5 percent to about
15 percent by weight; and
d. wherein the quaternary ammonium anti-static agent is present at
a concentration of from about 0.5 percent to about 5 percent of the
total composition.
3. A composition according to claim 1 wherein the smectite clay
softening agent is selected from the group consisting of
montmorillonites, volchonskoites, nontronites, hectorites,
sauconites and vermiculites.
4. A composition according to claim 1 wherein the anionic
surfactant is a water-soluble salt of an organic sulfuric reaction
product containing an alkyl group of from about 8 to about 22
carbon atoms and a moiety selected from the group of sulfuric acid
ester moieties and sulfuric acid ester moieties.
5. A composition according to claim 1 wherein the builder salt is
selected from the group consisting of sodium tripolyphosphate,
sodium nitrilotriacetate, sodium mellitate, sodium citrate and
sodium carbonate.
6. A composition according to claim 1 wherein the anti-static agent
is ditallowdimethylammonium chloride.
7. A composition according to claim 6 wherein the smectite-type
clay softening agent is montmorillonite.
8. A composition according to claim 6 wherein the smectite-type
clay softening agent is Gelwhite GP.
9. A composition according to claim 6 wherein the smectite-type
softening agent is Volclay BC.
10. A granular, built laundry detergent composition,
comprising:
a. from about 5 percent to about 20 percent of a mixture, in a
1.22:1 weight ratio, of sodium tallow alkyl sulfate and sodium
linear alkyl benzene sulfonate wherein the alkyl chain of the
sulfonate averages about 12 carbon atoms in length;
b. from about 20 percent to about 50 percent of a sodium
tripolyphosphate builder salt;
c. from about 5 percent to about 15 percent of a member selected
from the group consisting of Gelwhite GP and Volclay BC clay
softening agents; and
d. from about 0.5 to about 5 percent by weight of
ditallowdimethylammonium chloride.
11. A process for simultaneous laundering softening, and providing
anti-static benefits to fabrics comprising contacting said fabrics
with an aqueous medium containing from about 0.02 percent by weight
to about 2 percent by weight of a composition in accordance with
claim 1.
Description
BACKGROUND OF THE INVENTION
The instant invention relates to qranular built laundry detergent
compositions which provide simultaneous laundering, softening and
anti-static benefits on textiles during conventional fabric
laundering operations. Such compositions employ a combination of
synthetic detergent compounds, organic or inorganic detergent
builders, particular smectite clay compounds having particular
cation exchange characteristics and cationic anti-static
agents.
Various clay materials have been utilized in many different types
of detergent systems for widely diverse purposes. Clays, for
example, have been disclosed for utilization as builders (Schwartz
and Perry, Surface Active Agents, Interscience Publishers, Inc.,
1949, pp. 232 and 299); 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 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 copending application of Storm
and Nirschl, Ser. No. 271,943, filed July 14, 1972, and Ohren, Ser.
No. 279,127, filed Aug. 9, 1972, relate to the use of clays as
softeners in laundry compositions.
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.
Commercially acceptable softeners provide anti-static benefits, and
such benefits have come to be expected by the user of such
products. Indeed, fabrics coated with clays, while exhibiting a
soft hand, tend to develop higher levels of static charge than the
uncoated fabrics.
Various quaternary ammonium compounds known in the art possess
anti-static properties, and the use of clays in combination with
such 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
enhances clay deposition on 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 benefit of
the quaternary compounds is lost. Furthermore, such quaternary
ammonium compounds are not generally taught to be useful in
combination with anionic surfactants in the manner disclosed
herein.
U.S. Pat. No. 2,819,288 discloses clays in combination with
cationic surfactants as dry emulsifiers; however, these
compositions do not contain detergent compounds suitable for
laundering fabrics.
Accordingly, while effective for their intended uses, the prior art
compositions containing clay-plus-quaternary ammonium compounds are
not suitable for laundering fabrics while concurrently imparting
softness and anti-static benefits thereto.
The concurrently filed application of Nirschl and Gloss, entitled
"Soap Compositions", Ser. No. 305,417, filed Nov. 10, 1972,
discloses the use of clays and quaternary salts in soap
compositions.
It is an object of the present invention to provide compositions
which can be employed to concurrently launder, soften, and impart
anti-static benefits to fabrics.
It is a further object of this invention to provide combined
laundering, softening and anti-static compositions in the form of
granular formulations which are readily dispersible in aqueous
laundry baths.
These and the objects are obtained herein, as will be seen from the
following disclosure.
SUMMARY OF THE INVENTION
The present invention encompasses granular built laundry detergent
compositions comprising: (a) from about 2 to about 30 percent by
weight of a non-soap synthetic detergent compound selected from the
group consisting of anionic synthetic detergents, nonionic
synthetic detergents, ampholytic synthetic detergents, zwitterionic
synthetic detergents and mixtures thereof; (b) from about 10 to
about 60 percent by weight of an organic or inorganic detergent
builder salt; (c) from about 1 to about 50 percent by weight of a
smectite-type clay softening agent having an ion exchange capacity
of at least about 50 meq/100 g; and (d) from about 0.5 to about 15
percent by weight of a substantially water-insoluble quaternary
ammonium anti-static agent of the formula, [R.sub.2 N.sup.+R'.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
and werein X is an anion, e.g., halide, hydroxide, sulfate,
carbonate, phosphate, etc. In the above formula, the superscript n
indicates the charge on the anion; n can be 1 to 3 in the compounds
herein. The weight ratio of smectite-type clay to quaternary
ammonium compound in the compositions herein is from about 40:1 to
about 1:1, and is 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 compound are independently
suspended in the aqueous medium.
The compositions herein preferably provide a solution pH of from
about 7 to about 12 when dissolved in water at a concentration of
about 0.12 percent by weight.
In a method aspect, the invention encompasses methods for
concurrently cleansing, softening and providing antistatic effects
on fibers and fabrics comprising laundering said fibers or fabrics
in an aqueous laundry bath containing an effective amount (e.g.,
from about 0.02 to about 2 percent by weight) of a laundry
detergent composition as described above.
DETAILED DESCRIPTION OF THE INVENTION
The compositions and processes of this invention employ four
essential ingredients: the water-soluble detergency compound; the
detergency builder; the clay softener; and the quaternary ammonium
anti-static agent. The detergency compound functions in standard
fashion to remove soil from fabrics being laundered. The detergency
builder functions both to enhance the cleansing action of the
detergency compound and to uniformly disperse the clay softener.
The smectite-type clay functions to soften the laundered fabrics.
The quaternary ammonium compound provides anti-static effects on
the fabrics and adds an increment of softening benefits to the
fabrics. 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 percent, preferably from about 0.5 to about 5 percent 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 N.sup.+R'.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, sulfate, carbonate, phosphate, etc.
The charge on the anion is designated as n-, where n is 1-3. The
number of cationic ammonium groups, n, will equal the charge, 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 preferred anionic surfactants. When the
quaternary anti-static agent is affixed to the surface of the clay,
or has reacted with the anionic surfactant, it does not provide the
desired anti-static effects on fabics.
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 now 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 compounds are not generally considered to be
useful in combination with anionic surfactants since the opposite
charges on these two types of compounds cause them to react and
precipitate from solution. Yet, the anionics are a preferred class
of surfactants for laundering fabrics. Surprisingly, it has now
been found that the desirable anti-static effects of the insoluble
quaternary ammonium compounds used herein are not negated when
employed in combination with anionic surfactants. Apparently, the
insoluble nature of the di-long chain quaternary compounds renders
them somewhat compatible with anionics; whatever the reason, the
quaternary ammonium anti-stats herein perform their anti-static
function when used in combination with clays and anionic
surfactants.
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
counter-ion 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 anti-static 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.
Synthetic Detergent
From about 2 to about 30 percent by weight, preferably from about 5
to about 20 percent by weight, of the instant compositions comprise
a non-soap synthetic detergent selected from the group consisting
of anionic synthetic detergents, nonionic synthetic detergents,
ampholytic synthetic detergents, and zwitterionic synthetic
detergents. Examples of synthetic detergents of these types are
described as follows:
Anionic Detergents
Anionic synthetic detergents include water-soluble salts,
particularly the alkali metal salts, of organic sulfuric reaction
products having in their molecular structure an alkyl group
containing from about 8 to about 22 carbon atoms and a moiety
selected from the group consisting of sulfonic acid and sulfuric
acid ester moieties. (Included in the term alkyl is the alkyl
portion of higher acyl moieties.) Examples of this group of
synthetic detergents which form a part of the preferred built
detergent compositions of the present invention are the sodium and
potassium alkyl sulfates, especially those obtained by sulfating
the higher alcohols (C.sub.8 -C.sub.18 carbon atoms) produced by
reducing the glycerides of tallow or coconut oil; sodium and
potassium alkyl benzene sulfonates, in which the alkyl group
contains from about 9 to about 20 carbon atoms in straight chain or
branched-chain configuration, e.g., those of the type described in
U.S. Pat. Nos. 2,220,099 and 2,477,383 (especially valuable are
linear straight chain alkyl benzene sulfonates in which the average
of the alkyl groups is about 11.8 carbon atoms and commonly
abbreviated as C.sub.11.8 LAS); sodium alkyl glyceryl ether
sulfonates, especially those ethers of higher alcohols derived from
tallow and coconut oil; sodium coconut oil fatty acid monoglyceride
sulfonates and sulfates; sodium and potassium salts of sulfuric
acid esters of the reaction product of one mole of a higher fatty
alcohol (e.g. tallow or coconut oil alcohols) and about 1 to 6
moles of ethylene oxide; sodium and potassium salts of alkyl phenol
ethylene oxide ether sulfates with about 1 to about 10 units of
ethylene oxide per molecule and in which the alkyl groups contain
from about 8 to about 12 carbon atoms.
Anionic phosphate surfactants are also useful in the present
invention. These are surface active materials having substantial
detergent capability in which the anionic solubilizing group
connecting hydrophobic moieties is an oxy acid of phosphorus. The
more common solubilizing groups, of course, are --SO.sub.4 H and
--SO.sub.3 H. Alkyl phosphate esters such as (R--O).sub.2 PO.sub.2
H and ROPO.sub.3 H.sub.2 in which R represents an alkyl chain
containing from about 8 to about 20 carbon atoms are useful
herein.
These phosphate esters can be modified by including in the molecule
from one to about 40 alkylene oxide units, e.g., ethylene oxide
units. Formulae for these modified phosphate anionic detergents are
##SPC1##
in which R represents an alkyl group containing from about 8 to 20
carbon atoms, or an alkylphenyl group in which the alkyl group
contains from about 8 to 20 carbon atoms, and M represents a
soluble cation such as hydrogen, sodium, potassium, ammonium or
substituted ammonium; and in which n is an integer from 1 to about
40.
Another class of suitable anionic organic detergents particularly
useful in this invention includes salts of
2-acyloxyalkane-1-sulfonic acids. These salts have the formula
##SPC2##
where R.sub.1 is alkyl of about 9 to about 23 carbon atoms (forming
with the two carbon atoms an alkane group); R.sub.2 is alkyl of 1
to about 8 carbon atoms; and M is a water-soluble cation.
The water-soluble cation, M, in the hereinbefore described
structural formula 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-, and trimethyl-
ammonium 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 beta-acyloxy-alkane-1-sulfonates, or
alternatively 2-acyloxy-alkane-1-sulfonates, useful herein 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
sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the potassium
salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the sodium salt
of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of
2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of
2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of
2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of
2-propionyloxy-docosane-1-sulfonic acid; the 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 of
about 12 to about 16 carbon atoms, these salts being preferred from
the standpoints of their excellent cleaning properties and ready
availability.
Typical examples of the above described beta-acetoxy
alkanesulfonates are described in the literature: Belgium 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 DeGroote disclose certain salts of beta-acetoxy
alkanesulfonic acids. These references are hereby incorporated by
reference.
Another preferred class of anionic detergent compounds herein, both
by virtue of superior cleaning properties and low sensitivity to
water hardness (Ca++ and Mg++ ions) are the alkylated
.alpha.-sulfocarboxylates, containing about 10 to about 23 carbon
atoms, and having the formula ##SPC3##
wherein R is C.sub.8 to C.sub.20 alkyl, M is a water-soluble cation
as hereinbefore disclosed, preferably sodium ion, and R' is
short-chain alkyl, e.g., methyl, ethyl, propyl, and butyl. These
compounds are prepared by the esterification of .alpha.-sulfonated
carboxylic acids, which are commercially available, using standard
techniques. Specific examples of the alkylated
.alpha.-sulfocarboxylates preferred for use herein include:
ammonium methyl-.alpha.-sulfopalmitate,
triethanolammonium ethyl-.alpha.-sulfostearate,
sodium methyl-.alpha.-sulfopalmitate,
sodium ethyl-.alpha.-sulfopalmitate,
sodium butyl-.alpha.-sulfostearate,
potassium methyl-.alpha.-sulfolaurate,
lithium methyl-.alpha.-sulfolaurate,
as well as mixtures thereof.
A preferred class of anionic organic detergents are the
.beta.-alkyloxy alkane sulfonates. These compounds have the
following formula: ##SPC4##
where R.sub.1 is a straight chain alkyl group having from 6 to 20
carbon atoms, R.sub.2 is a lower alkyl group having from 1
(preferred) to 3 carbon atoms, and M is a water-soluble cation as
hereinbefore described.
Specific examples of .beta.-alkyloxy alkane sulfonates, or
alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness
(calcium ion) sensitivity useful herein to provide superior
cleaning levels under household washing conditions include:
potassium-.beta.-methoxydecanesulfonate,
sodium 2-methoxytridecanesulfonate,
potassium 2-ethoxytetradecylsulfonate,
sodium 2-isopropoxyhexadecylsulfonate,
lithium 2-t-butoxytetradecylsulfonate,
sodium .beta.-methoxyoctadecylsulfonate, and
ammonium .beta.-n-propoxydodecylsulfonate.
Other synthetic anionic detergents useful herein 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 alkyl or alkenyl of about 10 to
about 20 carbon atoms, x is 1 to 30, and M is a watersoluble cation
as defined hereinbefore. The alkyl ether sulfates useful in the
present invention 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 6, molar proportions of ethylene oxide and the
resulting mixture of molecular species, having, for example, an
average of 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 triethylene glycol ether sulfate; and sodium tallow
alkyl hexaoxyethylene sulfate.
Preferred herein for reasons of excellent cleaning properties and
ready availability are the alkali metal coconut- and tallow-alkyl
oxyethylene ether sulfates having an average of about 1 to about 10
oxyethylene moieties. The alkyl ether sulfates of the present
invention are known compounds and are described in U.S. Pat. No.
3,332,876, to Walker (July 25, 1967), incorporated herein by
reference.
Additional examples of anionic non-soap synthetic detergents which
come within the terms of the present invention are the reaction
product of fatty acids esterified with isethionic acid and
neutralized with sodium hydroxide where, for example, the fatty
acids are derived from coconut oil; sodium or potassium salts of
fatty acid amides of methyl tauride in which the fatty acids, for
example, are derived from coconut oil. Other anionic synthetic
detergents of this variety are set forth in U.S. Pat. Nos.
2,486,921; 2,486,922; and 2,396,278.
Additional examples of anionic, non-soap, synthetic detergents,
which come within the terms of the present invention, are the
compounds which contain two anionic functional groups. These are
referred to as di-anionic detergents. Suitable di-anionic
detergents are the disulfonates, disulfates, or mixtures thereof
which may be represented by the following formulae:
R(SO.sub.3).sub.2 M.sub.2, R(SO.sub.4).sub.2 M.sub.2,
R(SO.sub.3)(SO.sub. 4)M.sub.2,
where R is an acyclic aliphatic hydrocarbyl group having 15 to 20
carbon atoms and M is a water-solubilizing cation, for example, the
C.sub.15 to C.sub.20 disodium 1,2-alkyldisulfates, C.sub.15 to
C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium
1,9-hexadecyl disulfates, C.sub.15 to C.sub.20
disodium-1,2-alkyldisulfonates, disodiuum 1,9-stearyldisulfates and
6,10-octadecyldisulfates.
The aliphatic portion of the disulfates or disulfonates is
generally substantially linear, thereby imparting desirable
biodegradable properties to the detergent compound.
The water-solubilizing cations include the customary cations known
in the detergent art, i.e., the alkali metals, and the ammonium
cations, as well as other metals in group IIA, IIB, IIIA, IVA and
IVB of the Periodic Table except for boron. The preferred
water-solubilizing cations are sodium or potassium. These dianionic
detergents are more fully described in British Letters Patent
1,151,392 which claims priority on an application made in the
United States of America (No. 564,556) on July 12, 1966.
Still another anionic synthetic detergents include the class
designated as succinamates. This class includes such surface active
agents as disodium N-octadecylsulfosuccinamate; tetrasodium
N-(1,2-dicarboxyethyl)-N-octadecylsulfo-succinamate; diamyl ester
of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic
acid; dioctyl esters of sodium sulfosuccinic acid.
Other suitable anionic detergents utilizable herein 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 in conditions such that any sultones which have
been formed in the reaction are hydrolyzed to give the
corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be
liquid or gaseous, and is usually, but not necessarily, diluted by
inert diluents, for example by liquid SO.sub.2, chlorinated
hydrocarbons, 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 sulfonates 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, proportion of reactants, the nature
of the starting olefins and impurities in the olefin stock and side
reactions during the sulfonation process.
A specific anionic detergent which has also been found excellent
for use in the present invention is described more fully in the
U.S. Pat. No. 3,332,880 of Phillip F. Pflaumer and Adrain Kessler,
issued July 25, 1967, titled "Detergent Composition", the
disclosure of which is incorporated herein by reference.
Of all the above-described types of anionic surfactants, preferred
compounds include sodium linear alkyl benzene sulfonate wherein the
alkyl chain averages from about 10 to 18, more preferably about 12,
carbon atoms in length, sodium tallow alkyl sulfate;
2-acetoxy-tridecane-1-sulfonic acid; sodium
methyl-.alpha.-sulfopalmitate; sodium
.beta.-methoxyoctadecylsulfonate; sodium coconut alkyl ethylene
glycol ether sulfonate; the sodium salt of the sulfuric acid ester
of the reaction product of one mole of tallow alcohol and three
moles of ethylene oxide; and mixtures thereof.
Nonionic Synthetic Detergents
Most commonly, nonionic surfactants are compounds produced by the
condensation of an alkylene oxide (hydrophilic in nature) with an
organic hydrophobic compound which is usually aliphatic or alkyl
aromatic in nature. The length of the hydrophilic of
polyoxyalkylene moiety which is condensed with any particular
hydrophobic compound can be readily adjusted to yield a
water-soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements. Another type of nonionic
surfactants are the so-called polar nonionics derived from amine
oxides, phosphine oxides or sulfoxides. Examples of suitable
nonionic surfactants 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, the 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 may 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 products of aliphatic alcohols with ethylene
oxide. The alkyl chain of the aliphatic alcohol may 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 1,500 to 1,800 and of course exhibits water
insolubility. 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 ethylene diamine 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
percent 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.
5. Surfactants having the formula R.sup.1 R.sup.2 R.sup.3
N.fwdarw.O (amine oxide surfactants) wherein R.sup.1 is an alkyl
group containing from about 10 to about 28 carbon atoms, from 0 to
about 2 hydroxy groups and from 0 to about 5 ether linkages, there
being at least one moiety of R.sup.1 which is an alkyl group
containing from about 10 to about 18 carbon atoms and no ether
linkages, and each R.sup.2 and R.sup.3 is selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from
1 to about 3 carbon atoms,
Specific examples of amine oxide surfactants include:
dimethyldodecylamine oxide, dimethyltetradecylamine oxide,
ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,
dimethylstearylamine oxide, cetylethylpropylamine oxide,
diethyldodecylamine oxide, diethyltetradecylamine oxide,
dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide,
bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,
(2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine
oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the
corresponding decyl, hexadecyl and octadecyl homologs of the above
compounds.
6. Surfactants having the formula R.sup.1 R.sup.2 R.sup.3 P.fwdarw.
O (phosphine oxide surfactants) wherein R.sup.1 is an alkyl group
containing from about 10 to about 28 carbon atoms, from 0 to about
2 hydroxy groups and from 0 to about 5 ether linkages, there being
at least one moiety of R' which is an alkyl group containing from
about 10 to about 18 carbon atoms and no ether linkages, and each
R.sup.2 and R.sup.3 is selected from the group consisting of alkyl
groups and hydroxyalkyl groups containing from 1 to about 3 carbon
atoms.
Specific examples of the phosphine oxide detergents include:
dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide,
ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide,
dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide,
diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide,
dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide,
bis-(hydroxymethyl)-dodecylphosphine oxide,
bis-(2-hydroxyethyl)dodecylphosphine oxide,
(2-hydroxypropyl)methyltetradecylphosphine oxide,
dimethyloleylphosphine oxide, and
dimethyl-(2-hydroxy-dodecyl)phosphine oxide and the corresponding
decyl, hexadecyl, and octadecyl homologs of the above
compounds.
7. Surfactants having the formula ##SPC5## (sulfoxide surfactants)
wherein R.sup.1 is an alkyl group containing from about 10 to about
28 carbon atoms, from 0 to about 5 ether linkages and from 0 to
about 2 hydroxyl substituents, at least one moiety of R.sup.1 being
an alkyl group containing no ether linkages and containing from
about 10 to about 18 carbon atoms, and wherein R.sup.2 is an alkyl
group containing from 1 to 3 carbon atoms and from zero to two
hydroxyl groups. Specific examples of sulfoxide surfactants include
octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl
methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide,
3-methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl
methyl sulfoxide, octadecyl 2-hydroxyethyl sulfoxide, and
dodecylethyl sulfoxide.
Of all the above-described types of nonionic surfactants, preferred
nonionic surfactants include the condensation product of nonyl
phenol with about 9.5 moles of ethylene oxide per mole of nonyl
phenol, the condensation product of coconut fatty alcohol with
about 6 moles of ethylene oxide per mole of coconut fatty alcohol,
the condensation product of tallow fatty alcohol with about 11
moles of ethylene oxide per mole of tallow fatty 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
fatty alcohol.
Ampholytic Synthetic Detergents
Ampholytic synthetic detergents can be broadly described as
derivatives of aliphatic or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical may be
staight chain or branched and wherein one of the aliphatic
substituents contains from about 8 to 18 carbon atoms and at least
one contains an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfato. Examples of compounds falling within this
definition are sodium 3-(dodecylamino)-propionate, sodium
3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl
sulfate, sodium 2-(dimethylamino)octadecanoate, disodium
3-(N-carboxymethyldodecylamino)-propane-1-sulfonate, disodium
octadecyl-iminodiazetate, sodium
1-carboxymethyl-2-undecylimidazole, and sodium
N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. Sodium
3-(dodecylamino)propane-1-sulfonate is preferred.
Zwitterionic Synthetic Detergents
Zwitterionic surfactants can be broadly described as derivatives of
secondary and tertiary amines, derivatives of heterocyclic
secondary and tertiary amines, or derivatives of quaternary
ammonium, quaternary phosphonium or tertiary sulfonium compounds.
The cationic atom in the quaternary compound can be part of a
heterocyclic ring. In all of these compounds there is at least one
aliphatic group, straight chain or branched, containing from about
3 to 18 carbon atoms and at least one aliphatic substituent
containing an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfato, phosphato, or phosphono. Examples of various
classes of zwitterionic surfactants operable herein are described
as follows:
1. Compounds corresponding to the general formula ##SPC6##
wherein R.sub.1 is alkyl, alkenyl or a hydroxyalkyl containing from
about 8 to about 18 carbon atoms and containing if desired up to
about 10 ethylene oxide moieties and/or a glyceryl moiety; Y.sub.1
is nitrogen, phosphorus or sulfur, R.sub.2 is alkyl or
monohydroxyalkyl containing 1 to 3 carbon atoms; x is 1 when
Y.sub.1 is S, 2 when Y.sub.1 is N or P; R.sub.3 is alkylene or
hydroxyalkylene containing from 1 to about 5 carbon atoms; and Z is
a carboxy, sulfonate, sulfate, phosphate or phosphonate group.
Examples of this class of zwitterionic surfactants include
3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
2-(N,N-dimethyl-N-dodecylammonio)acetate;
3-(N,N-dimethyl-N-dodecylammonio)propionate;
2-(N,N-dimethyl-N-octadecylammonio)ethane-1-sulfate;
3-(P,P-dimethyl-P-dodecylphosphonio)propane-1-sulfonate;
2-(S-methyl-S-tert-hexadecylsulfonio)ethane-1-sulfonate;
3-(S-methyl-S-dodecylsulfonio)propionate;
4-(S-methyl-S-tetradecylsulfonio)butyrate;
3-(N,N-dimethyl-N-4-dodecenylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-2-diethoxyhexadecylammonio)propane-1-phosphate;
and 3-(N,N-dimethyl-N-4-glyceryldodecylammonio)propionate.
Preferred compounds of this class from a commercial standpoint are
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate;
3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate; the
alkyl group being derived from tallow fatty alcohol;
3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-tetradecylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-alkylammonio-2-hydroxypropane-1-sulfonate, the
alkyl group being derived from the middle cut of coconut fatty
alcohol;
3-(N,N-dimethyldodecylammonio)-2-hydroxypropane-1-sulfonate;
4-(N,N-dimethyl-tetradecylammonio)butane-1-sulfonate;
4-(N,N-dimethyl-N-hexadecylammonio)butane-1-sulfonate;
4-(N,N-dimethyl-hexadecylammonio)butyrate;
6-(N,N-dimethyl-N-octadecylammonio)hexanoate;
3-(N,N-dimethyl-N-eicosylammonio)-3-methylpropane-1-sulfonate; and
6-(N,N-dimethyl-N-hexadecylammonio)hexanoate.
Means for preparing many of the surfactant compounds of this class
are described in U.S. Pat. Nos. 2,129,264, 2,774,786, 2,813,898,
2,828,332 and 3,529,521 and; German Pat. No. 1,018,421 all
incorporated herein by reference.
2. Compounds having the general formula: ##SPC7##
wherein R.sub.4 is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl
group containing from 10 to 20 carbon atoms; M is a bivalent
radical selected from the group consisting of aminocarbonyl,
carbonylamino, carbonyloxy, aminocarbonylamino, the corresponding
thio groupings and substituted amino derivatives; R.sub.5 and
R.sub.8 are alkylene groups containing from 1 to 12 carbon atoms;
R.sub.6 is alkyl or hydroxyalkyl containing from 1 to 10 carbon
atoms; R.sub.7 is selected from the group consisting of R.sub.6
groups R.sub.4 --M--R.sub.5 .sup.-, and --R.sub.8 COOMe wherein
R.sub.4, R.sub.5, R.sub.6 and R.sub.8 are as defined above and Me
is a monovalent salt-forming cation. Compounds of the type include
N,N-bis(oleylamidopropyl)-N-methyl-N-carboxymethylammonium betaine;
N,N-bis(stearamidopropyl-N-methyl-N-carboxymethylammonium betaine;
N-(stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine;
N,N-bis(oleylamidopopyl)-N-(2-hydroxyethyl)-N-carboxylmethylammonium
betaine; and
N-N-bis-(stearamidopropyl)-N-(2-hydroxyethyl)-N-carboxymethylammonium
betaine. Zwitterionic surfactants of this type are preparing in
accordance with methods described in U.S. Pat. No. 3,265,719 and
DAS 1,018,421.
3. Compounds having the general formula: ##SPC8##
wherein R.sub.9 is an alkyl group, R.sub.10 is a hydrogen atom or
an alkyl group, the total number of carbon atoms in R.sub.9 and
R.sub.10 being from 8 to 16 and ##SPC9##
represents a quaternary ammonio group in which each group R.sub.11,
R.sub.12 and R.sub.13 is an alkyl or hydroxyalkyl group or the
groups R.sub.11, R.sub.12 and R.sub.13 are conjoined in a
heterocyclic ring and n is 1 or 2. Examples of suitable
zwitterionic surfactants of this type include the .gamma. and
.delta. hexadecyl pyridino sulphobetaines, the .gamma. and .delta.
hexadecyl .gamma.-picolino sulphobetaines, the .gamma. and .delta.
tetradecyl pyridino sulphobetaines and the hexadecyl
trimethylammonio sulphobetaines. Preparation of such zwitterionic
surfactants is described in South African patent application
69/5788.
4. Compounds having the general formula ##SPC10##
wherein R.sub.14 is an alkarylmethylene group containing from about
8 to 24 carbon atoms in the alkyl chain; R.sub.15 is selected from
the group consisting of R.sub.14 groups and alkyl and hydroxyalkyl
groups containing from 1 to 7 carbon atoms; R.sub.16 is alkyl or
hydroxylakyl containing from 1 to 7 carbon atoms; R.sub.17 is
alkylene or hydroxyalkylene containing from 1 to 7 carbon atoms and
Z.sub.1 is selected from the group consisting of sulfonate, carboxy
and sulfate. Examples of zwitterionic surfactants of this type
include 3-(N-dodecylbenzyl-N,N-dimethylammonio)propane-1-sulfonate;
4-(N-dodecylbenzyl-N,N-dimethylammonio)butane-1-sulfonate;
3-(N-hexadecylbenzyl-N,N-dimethylammonio)propane-1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate;
4-(N-hexadecylbenzyl-N,N-dimethylammonio)butyrate;
3-(N-tetradecylbenzyl-N,N-dimethylammonio)propane-1-sulfate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate;
3-[N,N-di(dodecylbenzyl)-N-methylammonio]propane-1-sulfonate;
4-[N,N-di(hexadecylbenzyl)-N-methylammonio]butyrate; and
3-[N,N-di(tetradecylbenzyl)-N-methylammonio]-2-hydroxypropane-1-sulfonate.
Zwitterionic surfactants of this type as well as methods for their
preparation are described in U.S. Pat. Nos. 2,697,116; 2,697,656
and 2,669,991 and Canadian Pat. No. 883,864, all incorporated
herein by reference.
5. Compounds having the general formula: ##SPC11##
wherein R.sub.18 is an alkylphenyl cycloalkylphenyl or
alkenylphenyl group containing from 8 to 20 carbon atoms, in the
alkyl, cycloalkyl or alkenyl moiety; R.sub.19 and R.sub.20 are each
aliphatic groups containing from 1 to 5 carbon atoms; R.sub.21 and
R.sub.22 are each hydrogen atoms, hydroxyl groups or aliphatic
groups containing from 1 to 3 carbon atoms and R.sub.23 is an
alkylene group containing from 2 to 4 carbon atoms.
Examples of zwitterionic surfactants of this type include
3-(N-dodecylphenyl-N,N-dimethylammonio)propane-1-sulfonate;
4-(N-hexadecylphenyl-N,N-dimethyl)butane-1-sulfonate;
3-(N-tetradecylphenyl-N,N-dimethylammonio)-3,3-dimethylpropane-1-sulfonate
and
3-(N-dodecylphenyl-N,N-dimethylammonio)-3-hydroxypropane-1-sulfonate.
Compounds of this type are described more fully in British Pat.
Nos. 970,883 and 1,046,252, incorporated herein by reference.
Of all the above-described types of zwitterionic surfactants,
preferred compounds include
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;
(N-dodecylbenzyl-N,N-dimethylammonio)acetate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate;
6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and
(N,N-dimethyl-N-hexadecylammonio)acetate.
Builder Salts
The detergent compositions of the instant invention contain, as an
essential component, an alkaline, poly-valent anionic detergent
builder salt. In the present compositions these water-soluble
alkaline builder salts serve to maintain the pH of the laundry
solution in the range of from about 7 to about 12, preferably from
about 8 to about 11. Furthermore, these builder salts enhance the
fabric cleaning performance of the overall compositions while at
the same time serve to suspend particulate soil release from the
surface of the fabrics and prevent its redeposition on the fabric
surfaces. Surprisingly, although the detergency builder salts serve
to suspend clay soils of the kaolinite and illite types and prevent
their redeposition on fabrics, they do not appear to interfere with
the deposition on fabric surfaces of the smectite-type clay
softeners used herein. Furthermore, these polyanionic builder salts
have been found to cause the smectite-type clays present in the
granular detergent formulations of the invention to be readily and
homogeneously dispersed throughout the aqueous landering medium
with a minimum of agitation. The homogeneity of the clay dispersion
is necessary for the clay to function effectively as a fabric
softener, while the ready dispersability allows granular detegent
compositions to be formulated.
Suitable detergent builder salts useful herein can be of the
poly-valent inorganic and poly-valent organic types, or mixtures
thereof. Non-limiting examples of suitable water-soluble, inorganic
alkaline detergent builder salts include the alkali metal
carbonates, borates, phosphates, polyphosphates, tripolyphosphates,
bicarbonates, silicates and sulfates. Specific examples of such
salts include the sodium and potassium tetraborates, perborates,
bicarbonates, carbonates, tripolyphosphates, orthophosphates and
hexametaphosphates.
Examples of suitable organic alkaline detergency builder salts are:
(1) water-soluble amino polyacetates, e.g., sodium and potassium
ethylenediamine tetraacetates, nitrilotriacetates and
N-(2-hydroxyethyl)nitrilodiacetates; (2) water-soluble salts of
phytic acid, e.g., sodium and potassium phytates; (3) water-soluble
polyphosphonates, including, sodium, potassium and lithium salts of
ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium and
lithium salts of methylenediphosphonic acid and the like.
Additional organic builder salts useful herein include the
polycarboxylate materials described in U.S. Pat. No. 2,264,103,
including the water-soluble alkali metal salts of mellitic acid.
The water-soluble salts of polycarboxylate polymers and copolymers
such as are described in U.S. Pat. No. 3,308,067, incorporated
herein by reference, are also suitable herein. It is to be
understood that while the alkali metal salts of the foregoing
inorganic and organic poly-valent anionic builder salts are
preferred for use herein from an economic standpoint, the ammonium,
alkanolammonium, e.g., triethanol ammonium, diethanol ammonium, and
the like, water-soluble salts of any of the foregoing builder
anions are useful herein.
Mixtures of organic and/or inorganic builders can be used herein.
One such mixture of builders is disclosed in Canadian Pat. No.
755,038, e.g., a ternary mixture of sodium tripolyphosphate,
trisodium nitrilotriacetate and trisodium
ethane-1-hydroxy-1,1-diphosphonate.
While any of the foregoing alkaline poly-valent builder materials
are useful herein, sodium tripolyphosphate, sodium
nitrilotriacetate, sodium mellitate, sodium citrate and sodium
carbonate are preferred herein for this builder use. Sodium
tripolyphosphate is especially preferred herein as a builder both
by virtue of its detergency builder activity and its ability to
homogeneously and quickly disperse the smectite clays throughout
the aqueous laundry media without interfering with clay deposition
on the fabric surface. Sodium tripolyphosphate is also especially
effective for suspending illite and kaolinite clay soils and
retarding their redeposition on the fabric surface.
The detergent builders are used at concentrations of from about 10
percent to about 60 percent, preferably 20 percent to 50 percent,
by weight of the detergent compositions of this invention.
Clay Compounds
The fourth essential component of the present compositions consists
of particular smectite clay materials to provide fabric softening
concurrently with fabric cleansing. These smectite clays are
present in the detergent compositions at levels from about 1
percent to about 50 percent, preferably from 5 percent to 15
percent by weight, of the total compositions. The clays used herein
are "impalpable," i.e., have a particle size which cannot be
perceived tactilely. Impalpable clays have particle sizes below
about 50 microns; the clays used herein have a particle size range
of from about 5 microns to about 50 microns.
The clay minerals used to provide the softening properties of the
instant compositions can be described as expandable, three-layer
clays, i.e., alumino-silicates and magnesium silicates, having an
ion exchange capacity of at least 50 meg/100 g. of clay. 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 subsitutions
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
futher 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 compositons 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
(HN.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 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", pp. 264-265, Interscience (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, in 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 clays of the montmorillonite
variety. Illite clays have an ion exchange capacity somewhere 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, as noted above, are
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 in that they
are deposited on the fabrics to provide the desired softening
benefits. Accordingly, clay minerals useful herein can be
characterized as expandable, three-layer smectite-type clays having
an ion exchange capacity of at least about 50 meg/100 g. A
smectite-type clay known as "fooler clay," found in a relatively
thin vein above the Black Hills, also has the requisite ion
exchange properties characteristic of the clays useful herein and
such fooler clay is also encompassed by the term " smectite-type
clay," as used herein.
The smectite clays used in the compositions herein are all
commerically available. Such clays include, for example,
montmorillonite, volchonskoite, nontronite, hectorite, saponite,
sauconite, and vermiculite. The clays herein are available under
various tradenames, for example, Thixogel No. 1 (also,
"Thixo-Jell") and Gelwhite GP from Georgia Kaolin Co., Elizabeth,
New Jersey; Volclay BC and Volclay No. 325, from American Colloid
Co., Skokie, Illinois; Black Hills Bentonite BH450, 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 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 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 is an extremely white
form of smectite clay and is therefore preferred when formulating
white granular detergent compositions. Volclay BC, which a
smectite-type clay mineral containing at least 3 percent 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 product performance. On the other
hand, certain smectite clays 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, taken in combination with
exchange capacity measurements performed in the manner noted above,
provides a basis for selecting particular smectite-type minerals
for use in the granular detergent compositions disclosed
herein.
Optional Components
The detergent compositions disclosed herein can contain other
materials commonly used in such compositions. For example, various
soil-suspending agents such as carboxymethylcellulose, corrosion
inhibitors, dyes, fillers such as sodium sulfate and silica,
optical brighteners, 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, can also be employed herein. Bound water
can also be present in said detergent compositions.
Composition Preparation
The clay-containing detergent compositions of this invention are in
granular form. The compositions can be conveniently prepared in
standard fashion by admixing the detergent compound, clay and
optional ingredients in a crutcher and spray-drying the mixture to
form granules. Following this, the quaternary ammonium anti-static
agent can be sprayed on the granules from a melt. It is a critical
aspect of this invention to avoid affixing the quaternary compound
to the surface of the clay by an ion exchange mechanism;
accordingly, it is preferable to avoid spraying the detergent
granules with an aqueous solution or suspension of the quaternary
compound. The ion-exchange problem is avoided by employing a melt
of the quaternary compound to spray the granules. The compositions
are then added to water to provide a laundering liquor containing
the instant compositions to the extent of from about 0.02 percent
to about 2 percent by weight. Soiled fabrics are added to the
laundering liquor and cleansed in the usual manner. The effective
amount of the detergent compositions to be used will depend to an
extent on the weight of clothes being laundered and their degree of
soiling. Aqueous laundering baths containing said compositions
provide adequate cleaning, softening and anti-static benefits with
soiled fabrics, especially cotton and cotton/polyester blends. The
suspended clay material in the laundering liquor also serves to
adsorb fugitive dyes in solution, thereby reducing or inhibiting
dye transfer.
The granular built detergent compositions and processes of the
instant invention are illustrated by the following examples. The
following test is used to assess through-the-wash anti-static
efficacy of the test products.
Anti-Static Test
A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35
polyester/cotton blend; 17% nylon; 18% Dacron.sup.R) is washed for
10 minutes in a miniature agitator containing two gallons of
aqueous washing liquor containing the test laundry compositions (as
set forth, below). The laundering temperature is 100.degree.F;
water hardness 7 gr/gal. artificial hardness. The bundle comprises
5% by weight of the washing liquor. The bundle is spun dry and
rinsed for two minutes in two gallons of water at 100.degree.F and
7 gr/gal. hardness. The fabrics are then dried in a commercial
dryer for 50 minutes.
The static charge on each fabric is then measured by a standard
electrostatic technique. The sum of the absolute values of the
charges on all fabrics in the bundle, divided by the sum of the
area (yards.sup.2) of the total fabric surface (2 sides of the
fabric) is then computed. This so-called "static value", in
volts/yd..sup.2, correlates with gross observations of the effects
of static charges on fabric surfaces, i.e., electrical shocks,
fabric clinging, etc. Depending on the fabric bundle tested, no
static cling is exhibited by fabrics having a static value of less
than about 1.5 v./yd.sup.2 ; substantial static cling is noted in
fabrics having a static value above about 4.5 v./yd..sup.2.
EXAMPLE I
Composition A ______________________________________ Component
Weight Percent ______________________________________ Anionic
surfactant* 16.6 Sodium tripolyphosphate 43.3 Sodium silicate 5.8
Sodium sulfate 10.0 Gelwhite GP 9.8 Ditallowdimethylammonium
chloride 2.0 Miscellaneous minors** ca. 3.5 Moisture Balance
______________________________________ *1.22:1 ratio of sodium
tallow alkyl sulfate:sodium C.sub.11.8 linear alkyl benzene
sulfonate **Including brighteners, carboxymethylcellulose, coconut
alcohol ethoxylate and perfume
Composition A is prepared by admixing all components except the
ditallowdimethylammonium chloride in a crutcher and spray-drying to
form granules consisting of the surfactant, builder, clay, etc. The
granules are then uniformly sprayed with a melt of the
ditallowdimethylammonium chloride.
Composition A is admixed with water at a concentration of 0.12
percent by weight and used to launder soiled fabrics in standard
fashion. The fabrics are cleansed and softened and the static
charge, as measured by the foregoing test, is substantially
reduced.
The ditallowdimethylammonium chloride of Composition A is replaced
by an equivalent amount of dioleoyldimethylammonium bromide,
bis-[ditallowdimethylammonium] carbonate and
tris-[ditallowdibutylammonium] phosphate, respectively, and
equivalent cleansing, softening and anti-static results are
secured.
EXAMPLE II
Composition B ______________________________________ Component
Weight Percent ______________________________________ Anionic
surfactant* 12.8 Sodium tripolyphosphate 37.8 Sodium silicate 4.5
Sodium sulfate 10.8 Volclay BC 11.5 Ditallow dimethyl ammonium
chloride 0.92 Miscellaneous minors** 4.2 Moisture Balance
______________________________________ *1.22:1 sodium tallow alkyl
sulfate:sodium C.sub.11.8 linear alkyl benzen sulfonate **Including
perfume, brighteners, carboxymethylcellulose and coconut
hexaethoxylate ca. 0.6%
Composition B (prepared in the same manner as Composition A, above)
was employed in the anti-static test set forth hereinabove. In this
test, Composition B was used at a solution concentration of 0.131
percent by weight. Fabrics laundered in the aqueous bath containing
Composition B were tested for static charge following each of two
wash-rinse-drying cycle. After one cycle, fabrics laundered in
Composition B had a static value of 1.2; after two cycles the
static value was 1.7. As a point of comparison, fabrics laundered
in a built, anionic detergent composition without clay or
quaternary ammonium salt had a static value of 8.0 after the first
cycle and 8.6 after the second cycle. Fabrics laundered in a built,
anionic detergent composition containing a clay softener had a
higher static value than fabrics laundered in liquors without
clay.
As can be seen from the foregoing examples, the compositions herein
provide substantial softening and anti-static benefits.
Furthermore, the compositions herein overcome the problem
associated with increased static charge buildup on fabrics
laundered with detergents containing clay softeners, alone.
Compositions A and B of the instant invention also provide
excellent cleaning and detergency when employed in washing
solutions at the specified concentrations.
Substantially similar detergency, softening and anti-static results
are obtained when the anionic surfactant mixture in Compositions A
and B is replaced with an equivalent amount of
2-acetoxy-tridecane-1-sulfonic acid; sodium
methyl-.alpha.-sulfopalmitate; sodium
.alpha.-methoxyoctadecylsulfonate; sodium coconut alkyl ethylene
glycol ether sulfonate; and the sodium salt of the sulfuric acid
ester of the reaction product of one mole of tallow fatty alcohol
and three moles of ethylene oxide, respectively.
Substantially similar detergency, softening and antistatic benefits
are obtained when the anionic surfactant mixture in Compositions A
and B is replaced with an equivalent amount of the condensation
product of nonyl phenol with about 9.5 moles of ethylene oxide per
mole of nonyl phenol; the condensation product of coconut fatty
alcohol with about 6 moles of ethylene oxide per mole of coconut
fatty alcohol; the condensation product of tallow fatty alcohol
with about 11 moles ethylene oxide per mole of tallow fatty
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 fatty alcohol, respectively.
Substantially similar detergency, softening and anti-static
benefits are obtained when the anionic surfactant mixture in
Compositions A and B is replaced with an equivalent amount of
3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate or
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-hydroxypane-1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate;
3-(N-dodecylbenzyl-N,N-dimethylammonio)acetate;
3-(N-dodecylbenzyl-N,N-dimethylammonia)propionate;
6-(N-dodecylbenzyl-N,N,dimethylammonio)hexanoate;
(N,N-dimethyl-N-hexadecylammonio)-acetate; and sodium
3-(dodecylamino)-propane-1-sulfonate, respectively.
Substantially similar detergency, softening and anti-static
benefits are obtained when the sodium tripolyphosphate builder in
Compositions A and B is replaced with an equivalent amount of
sodium nitrilotriacetate; sodium mellitate; sodium citrate; and
sodium carbonate, respectively.
Substantially similar detergency, softening and antistatic benefits
are obtained when the clay softening agent in Compositions A and B
is replaced with an equivalent amount of volchonskoite; nontronite;
hectorite; sauconite; and vermiculite, respectively, all such clays
having an ion-exchange capacity at least about 50 meg./100 g.
Substantially similar detergency, softening and anti-static
benefits are obtained when the quaternary ammonium anti-static
agent in Compositions A and B is replaced by
ditallowdimethylammonium bromide; ditallowdiethylammonium chloride;
dioctadecyldibutylammonium chloride; and ditallowdimethylammonium
hydroxide, respectively.
In addition to the fabric softening and anti-static benefits which
the built laundry detergent compositions of this invention provide,
the compositions provide still other advantages. For example, the
dye-transfer inhibition noted above is a significant advantage not
commonly shared by ordinary laundering and fabric softening
compositions.
Moreover, the particular class of clays described herein which are
deposited on the fabrics provide a soil-release benefit. The clays
are adsorbed by the fabrics being washed providing an improved
soil-release surface. The benefit from this treatment is that
during subsequent washings, stains and soils are more easily
removed from the fabrics as compared to a fabric which has not
previously been exposed to a treatment by the clay-containing
compositions of this invention. Furthermore, all of these benefits
are enjoyed without impairing the water-absorbent qualities of the
treated fabric. This is in marked contrast with ordinary
quanternary ammonium fabric softeners which reduce the
water-absorbent property of treated fabrics after several fabric
treatments.
It is especially significant that each of the benefits described
above in no way impairs or interferes with the general overall
cleaning effectiveness of the detergent composition, even in
compositions containing anionic surfactants. The fact that these
benefits are attained during the relatively brief span of a short
washing cycle, for example about 6 to about 15 minutes, is
especially noteworthy.
* * * * *