U.S. patent number 3,886,075 [Application Number 05/351,678] was granted by the patent office on 1975-05-27 for fabric softening composition containing a smectite type clay.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Lowell Watson Bernardino.
United States Patent |
3,886,075 |
Bernardino |
May 27, 1975 |
Fabric softening composition containing a smectite type clay
Abstract
Detergent-compatible fabric softening and anti-static
compositions containing particular smectite clay materials,
cationic anti-static agents and certain substituted amino
compatibilizing agents are described. The compositions permit the
simultaneous attainment of fabric softening, static-reduction and
cleansing effects of fabrics washed therein.
Inventors: |
Bernardino; Lowell Watson
(Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
27406897 |
Appl.
No.: |
05/351,678 |
Filed: |
April 16, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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337331 |
Mar 2, 1973 |
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Current U.S.
Class: |
510/515;
510/330 |
Current CPC
Class: |
C11D
3/001 (20130101); D06M 13/46 (20130101); D06M
13/342 (20130101); C11D 3/126 (20130101); C11D
3/26 (20130101); C11D 1/10 (20130101); C11D
3/2075 (20130101); D06M 13/402 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); C11D 3/12 (20060101); D06M
13/00 (20060101); D06M 13/46 (20060101); D06M
13/402 (20060101); D06M 13/342 (20060101); C11D
3/26 (20060101); C11D 3/20 (20060101); D06m
013/00 () |
Field of
Search: |
;252/155,8.75,8.8,546,547 |
References Cited
[Referenced By]
U.S. Patent Documents
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3644203 |
February 1972 |
Lamberti et al. |
|
Primary Examiner: Lechert, Jr.; Stephen J.
Attorney, Agent or Firm: Schaeffer; Jack D. Witte; Richard
C. O'Flaherty; Thomas H.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part application of
application Ser. No. 337,331, filed Mar. 2, 1973 now abandoned,
titled: DETERGENT-COMPATIBLE FABRIC SOFTENING AND ANTI-STATIC
COMPOSITIONS, inventor Lowell W. Bernardino.
Claims
What is claimed is:
1. A fabric softening composition comprising:
a. from about 2 to about 90% by weight of a smectite-type clay
having an ion-exchange capacity of at least 50 meq/100 grams;
b. from about 1 to about 40% by weight of a substantially
water-insoluble quaternary ammonium antistatic agent of the
formula: ##SPC5##
wherein R.sub.1 and R.sub.2 represent hydrocarbyl groups containing
from about 10 to about 22 carbon atoms, R.sub.3 and R.sub.4
represent hydrocarbyl groups containing from 1 to about 4 carbon
atoms, X is an anion and n is an integer from 1 to 3; and
c. from about 1 to about 40% by weight of a compatibilizing agent
of the formula: ##SPC6##
wherein R.sub.1 represents an alkyl group containing from 1 to
about 22 carbon atoms; R.sub.2 and R.sub.3 represent alkyl groups
containing from 1 to about 10 carbon atoms or hydrogen, whereby not
more than one of the groups R.sub.2 and R.sub.3 can be hydrogen;
and Y represents --CONH.sub.2 ; --CON(R.sub.4).sub.2 ; or --COOH;
wherein R.sub.4 represents an alkyl group containing from 1 to
about 4 carbon atoms or hydrogen.
2. A composition in accordance with claim 1 wherein the component
(a) smectite-type clay is used in an amount from about 5 to about
90% by weight.
3. A composition in accordance with claim 2 wherein the component
(b) quaternary ammonium component is present in an amount from
about 2 to about 25% by weight.
4. A composition in accordance with claim 3 wherein the component
(a) smectite-type clay is used in an amount from about 8 to about
75% by weight.
Description
BACKGROUND OF THE INVENTION
This invention related to compositions adapted to the provision of
fabric softening and anti-static effects in fabric laundering
operations. More particularly, it relates to the provision of these
effects while simultaneous cleansing fabrics in the presence of
conventional synthetic detergent compounds and organic or inorganic
detergent builders.
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 applications of Storm
and Nirschl, Ser. No. 271,943, filed July 14, 1972 now abandoned;
Ohren, Ser. No. 279,127, filed Aug. 9, 1972, now U.S. Pat. No.
3,852,211 Nirschl and Gloss, Ser. No. 305,416, filed Nov. 10, 1972
now U.S. Pat. No. 3,862,058; and Gloss and Nirschl, Ser. No.
305,417, filed Nov. 10, 1972; relate to the use of clays as
softeners in laundry compositions.
While clays can provide softening properties, and in the presence
of detergent and builder substances used in the cleansing or
laundering of fabrics, they do not provide anti-static properties.
Commerically-acceptable fabric softeners additionally 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. These compounds, while suitable in
combination with clay materials to provide the anti-static
properties which are not provided by the clays can be inhibited in
their provision of anti-static effects by the presence of anionic
substances conventionally employed in the cleansing of fabrics in
laundering operations.
It is an object of the present invention to provide fabric
softening and anti-static compositions capable of providing their
effects in the presence of conventional detergent compositions to
thereby concurrently launder, soften and impart anti-static
benefits to fabrics.
It is another object of the present invention to provide
compositions containing certain clay fabric softening agents and
quaternary ammonium anti-static agents adapted to use in the
washing cycle of a laundering operation.
These and the objects are obtained herein, as will be seen from the
following disclosure.
SUMMARY OF THE INVENTION
The present invention is based in part upon the discovery that
certain substituted amino compounds, defined hereinafter, will
mitigate the interactive effects of quaternary ammonium anti-static
agents and conventional detergent laundering compositions. These
materials, termed compatibilizing agents hereinafter, can be
employed in combination with quaternary ammonium anti-static agents
and clay fabric-softening materials in fabric-laundering operations
to provide treated textile materials with simultaneous cleansing,
anti-static and fabric-softening effects.
In its composition aspect, the present invention encompasses
fabric-softening compositons containing as essential ingredients a
particular smectite-type clay fabric-softening material, a
quaternary ammonium fabric softening agent and a substituted amino
compatibilizing agent. Such compositions can be conveniently
employed by the housewife or other user by addition to the laundry
washing bath provided by addition to water of a conventional
laundry detergent composition. The present invention also
encompasses as integral formulations compositions containing the
materials hereinbefore-defined in combination with synthetic
detergent compounds and organic or inorganic builder salts. Such
compositions, merely added to water, provide in a single step the
provision of a laundering bath adapted to the provision of
simultaneous cleansing, softening and anti-static effects.
In a method aspect, the invention encompasses a method for
simultaneously cleansing, softening and providing anti-static
effects on fabrics or textiles which comprises treating the fabrics
or textiles in an aqueous laundry bath containing detergent, clay,
quaternary ammonium and compatibilizing agent as defined
herein.
DETAILED DESCRIPTION OF THE INVENTION
Compositions suited herein as additives to the detergent washing
bath of a laundering operation, and termed additive compositions
herein comprise:
a. from about 2 to about 90% by weight of a smectite-type clay
having an ion-exchange capacity of at least 50 meq/100 grams;
b. from about 1 to about 40% by weight of a substantially
water-insoluble quaternary ammonium anti-static agent of the
formula: ##SPC1##
wherein R.sub.1 and R.sub.2 represent hydrocarbyl groups containing
from about 10 to about 22 carbon atoms, R.sub.3 and R.sub.4
represent hydrocarbyl groups containing from 1 to about 4 carbon
atoms, X is an anion and n is an integer from 1 to 3; and
c. from about 1 to about 40% by weight of a compatibilizing agent
of the formula: ##SPC2##
wherein R.sub.1 represents an alkyl group containing from 1 to
about 22 carbon atoms; R.sub.2 and R.sub.3 represent alkyl groups
containing from 1 to about 10 carbon atoms or hydrogen, whereby not
more than one of the groups R.sub.2 and R.sub.3 can be hydrogen;
and Y represents --CONH.sub.2 ; --CON(R.sub.4).sub.2 ; or --COOH,
wherein R.sub.4 represents a alkyl group containing from 1 to about
4 carbon atoms or hydrogen.
Built laundry detergent compositions of the invention comprise (a)
from about 2 to about 30% by weight of a synthetic detergent
compound selected from the group consisting of anionic soap and
non-soap detergents, nonionic synthetic detergents, ampholytic
synthetic detergents, zwitterionic synthetic detergents and
mixtures thereof; (b) from about 0 to about 60% by weight of an
organic or inorganic detergent builder salt; (c) from about 1 to
about 50 % by weight of a smectite-type clay softening agent having
an ion exchange capacity of at least about 50/meq/100 g; (d) 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
N.sup.+R'.sub.2 X.sup.-, wherein each R is an alkyl group
containing from about 10 to about 22 carbon atoms and each R; is an
alkyl group containing from about 1 to about 4 carbon atoms and
wherein X is an anion, e.g., F.sup.-, Cl.sup.-, Br.sup.-, OH.sup.-;
and (e) from about 0.5 to about 15% of an amino compound having the
formula: ##SPC3##
wherein R.sub.1 represents an alkyl group containing from 1 to
about 22 carbon atoms; R.sub.2 and R.sub.3 represent alkyl groups
containing from 1 to about 10 carbon atoms or hydrogen, whereby not
more than one of the groups R.sub.2 and R.sub.3 can be hydrogen;
and Y represnts .sub.[CONH.sub.2 ; --CON(R.sub.4).sub.2 ; or
--COOH, wherein R.sub.4 represents an alkyl group containing from
about 1 to about 4 carbon atoms or hydrogen. The weight ratio of
smectite-type clay-to-quaternary ammonium compound in the detergent
compositions herein is from about 40:1 to about 1:1, and is
preferably about 10:1 to 3:1. The quaternary ammonium compound and
amino compatibilizing agent are present in releasable combination
in the compositions herein in a weight ratio of quaternary ammonium
compound to amino compound of from about 1:5 to about 5:1,
preferably from 3:1 to 1:2.
The detergent compositions herein provide a solution pH of from
about 7 to about 12 when dissolved in water at a concentration of
about 0.12% by weight.
The compositions and method of this invention employ three
essential ingredients; the clay softener; the quaternary ammonium
anti-static agent; and the amino compatibilizing agent. The
detergent compositions of the invention additionally will comprise
a water-soluble detergency compound and a detergency builder salt.
The smectite-type clay functions to soften the laundered fabrics
while the quaternary ammonium compound provides anti-static effects
on the fabrics and adds an increment of softening benefits to the
fabrics. The detergent and builder components provide the known
cleansing and building effects. The various components of the
compositions herein are described in greater detail
hereinafter.
CLAY COMPOUNDS
The essential clay component of the present compositions consists
of particular smectite clay materials. These smectite clays are
present in the additive compositions of this invention at levels
from about 2 to about 90%, preferably from 5 to 90% and especially
from 8 to 75%, by weight. In the built detergent composition
embodiments of this invention, the smectite clay is used in an
amount from about 1 to about 50%, preferably from about 5 to about
25% by weight. 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 can be described as expandable, three-layer
clays, i.e., alumino-silicates and magnesium silicates, having an
ion exchange capacity of at least 50 meq/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 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 inventon 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 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 milli-equivalents per 100 g. of
clay (Meq./100 g.). The cation exchange capacity of clays can be
measured in several ways, including by electodialysis, 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, is determined at least in part by the lattice structure,
and the like. The ion exchange capacity of clays varies widely in
the range from about 2 meq/100 g. for kaolinites to about 150
meq/100 g., and greater, for certain clays of the montmorillonite
variety. Illite clays have an ion exchange capacity somewhere in
the lower portion of the range, i.e., around 26 meq/100 g. for an
average illite clay.
It has been determined that illite and kaolinite clays, with their
relatively low ion exchange capacities, are not useful in the
instant compositions. However, smectites, such as nontronite,
having an ion exchange capacity of approxmately 50 meq/100 g.,
saponite, which has an ion exchange capacity of around 70 meq/100
g., and montmorillonite, which has an ion exchange capacity greater
than 70 meq/100 g., have been found to be useful in the instant
compositions 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 meq/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
commercially 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 meq/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 is a
smectite-type clay mineral containing at least 3% of iron
(expressed as Fe.sub.2 O.sub.3) in the crystal lattice, and which
has a very high ion exchange capacity, is one of the most efficient
and effective clays for use in the instant 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 compositions disclosed herein.
ANTI-STATIC AGENT
The quaternary ammonium anti-static agents will normally be
employed in the additive compositions in an amount of from about 1
to about 40% and preferably from about 2 to about 25% by weight.
The quaternary ammonium anti-static agent will normally be present
in the detergent compositions of the invention in an amount of from
about 0.5 to about 15% and preferably in an amount of from about 1
to about 10% by weight. Whether an additive or detergent
composition of the invention is employed in providing an aqueous
laundering bath or liquor, an amount sufficient to provide a
concentration of quaternary ammonium compound in the bath or liquor
of from about 2.5 ppm (parts per million) to about 1500 ppm will
normally be employed. In general, the quaternary anti-stats are
used in either type of composition at a clay-to-quaternary weight
ratio of from about 40:1 to about 1:1, preferably from about 10:1
to about 3:1.
The anti-static agents useful herein 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. When the quaternary anti-static agent is affixed to the
surface of the clay, it does not provide the desired anti-static
effects on fabrics.
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. Dioctadecyldimethylammonium chloride is an especially
preferred quaternary anti-static agent for use herein by virtue of
its high anti-static activity; ditallow dimethyl ammonium chloride
is equally preferred because of its readily availability and its
good anti-static activity; other useful di-long chain quaternary
compounds are dicetyldimethylammonium chloride;
bis-docosyldimethylammonium chloride; didodecyldimethylammonium
chloride; ditallowdimethylammonium bromide,
dioleoyldimethylammonium hydroxide; ditallowdiethylammonium
chloride; ditallowdipropylammonium bromide; ditallowdibutylammonium
fluoride, cetyldecylmethylethylammonium choride,
bis-[ditallowdimethylammonium]sulfate;
tris-[ditallowdimethylammonium]phosphate; and the like.
COMPATIBILIZING AGENT
The essential amino compatabilizing agent is used is an amount of
from about 1 to about 40%, preferably from about 2 to about 20% by
weight of the ternary mixture of essential components, i.e., the
additive compositions of the invention. In the built detergent
embodiments, said compatiblizing agent is used in an amount from
about 0.5 to about 15%, preferably from about 1 to about 10% by
weight. Normally, in either the additive or detergent embodiments
of the invention, an amount of amino compatibilizing agent
sufficient to provide a weight ratio of quaternary ammonium
compound to amino component of from about 5:1 to about 1:5, and
preferably from 3:1 to 1:2, is employed.
The compatibilizing agent can be represented by substituted amino
compounds having the formula: ##SPC4##
wherein R.sub.1 represents an alkyl group containing from 1 to
about 22 carbon atoms; R.sub.2 and R.sub.3 represent alkyl groups
containing from 1 to about 10 carbon atoms or hydrogen, whereby not
more than one of the groups R.sub.2 and R.sub.3 can be hydrogen;
and Y represents --CONH.sub.2 ; --CON(R.sub.4).sub.2 ; or --COOH;
wherein R.sub.4 represents an alkyl group containing from 1 to
about 4 carbon atoms or hydrogen.
Preferred herein because of ready availability and also by virtue
of its high anti-static activity is N-coco-.beta.-amino-propionic
acid.
Other useful compatibilizing agents include:
Octadecylamino-propionic acid
Methylamino-bispropionamide
Tallow alkyl-amino-dipropionic acid
Dodecylamino-diacetic acid
Hexadecylamino-bisacetamide
Hexylamino-bisbutyramide
N-hexadecyl-.alpha.-aminoacetic acid
Dodecyl-aminodiacetic acid
N-octyl-.beta.-amino acetamide
Butylamino-pelargonamide
Ethylamino-dicaproamide
Methylamino-di-n-heptylamide
DETERGENT
From about 2 to about 30% by weight, preferably from about 5 to
about 20% by weight, of the detergent compositions comprise an
organic detergent selected from the group consisting of anionic,
nonionic, ampholytic and zwitterionic detergents and mixtures
thereof. Examples of organic detergents of these types are
described in U.S. Pat. No. 3,579,454; incorporated herein by
reference, column 11, line 45 to column 19, line 64.
Preferred for use herein are the water-soluble salts of 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). Suitable cations include alkali metals (sodium,
potassium, lithium) ammonium and substituted ammonium (mono, di and
tri-ethanol and methanol amines) neutralizing agents.
Another preferred detergent for use herein include 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 water-soluble
cation such as alkali metal, ammonium and substituted ammonium. The
alkyl ether sulfates useful in the present invention are
condensation products of ehtylene 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 1 to 6,
molar proportions of ethylene oxide and the resulting mixture of
molecular species, having, for example, an average of 3 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; sodium
tallow alkyl trioxyethylene ether sulfate; and sodium tallow alkyl
hexaoxyethylene sulfate.
Other preferred 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-alkane-sulfonates. 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 portion 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 Adrian Kessler,
issued July 25, 1967, titled "Detergent Composition", the
disclosure of which is incorporated herein by reference.
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 released 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 laundering 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 detergent
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
ethylenediaminetetraacetates, 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., triethanolammonium, diethanolammonium, 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, c.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 0
to about 60%, preferably 20 to 50%, by weight of the detergent
compositions of this invention.
The clay-containing compositions of this invention are in granular
form. The compositions can be conveniently prepared in standard
fashion by admixing the clay and detergent, builder and optional
ingredients, if any, in a crutcher anad spray-drying the mixture to
form granules.
Following this, the quaternary ammonium anti-static agent and amino
compatibilizing 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 and at least a portion
of the amino compatibilizing agent to spray onto the granules. The
compositions are then added to water, or to a detergent bath as the
case may be, to provide a laundering liquor. Soiled fabrics are
added to the laundering liquor and cleansed in the usual manner.
The effective amount of the additive or 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
prepared thereby provide adequate cleaning, softening and
anti-static benefits with soiled fabrics, especially cotton and
cotton/polyester blends.
It will be appreciated that the method of simultaneously cleansing,
softening and reducing static build-up on laundered textiles can be
conveniently practiced by providing an aqueous treating liquor in a
number of ways. A suitable washing liquor can be prepared by
adding, for example, a commercially-available built anionic-based
laundry detergent composition into a washing machine at a
concentration of about 0.12% and separately, adding an additive
composition of the invention as defined hereinbefore. Suitable
treating liquors will normally contain:
Smectite clay 5 to 5000 ppm Quaternary ammonium compound 2.5 to
1500 ppm Amino compatibilizing agent 2.5 to 1500 ppm Detergent 10
to 3000 ppm; and Builder 0 to 6000 ppm, whereby
the weight ratio of quaternary ammonium compound to amino
compatibilizing component is normally in the range from about 5:1
to about 1:5.
The additive and built detergent compositions and processes of the
instant invention are illustrated by the following examples.
EXAMPLE I
A through-the-wash cycle fabric-softening detergent composition
which imparts imultaneous cleansing, softening and anti-static
properties to fabrics treated therewith having the following
formula is prepared:
Component Weight Percent ______________________________________
Anionic surfactant* 16.6 Sodium tripolyphosphate 43.3 Sodium
silicate 5.8 Sodium sulfate 10.0 Gelwhite GP (smectite) 9.8
Dioctadecyl dimethyl ammonium chloride 2.0 N-coco-.beta.-amino
propionic acid 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.
The composition of Example I, employed at a concentration of 0.12%
by weight, provides simultaneous cleansing, softening, and
anti-static effects when employed in the washing cycle of a
conventional home laundering process.
Substantially similar detergency, softening and anti-static
benefits are obtained when the anionic surfactant mixture of
Example I is replaced by an equivalent amount of: sodium tallow
alkyl trioxyethylene ether sulfate; sodium coconut alkyl ethylene
glycol ether sulfate; sodium tallow alkylhexaoxyethylene sulfate;
olefin sulfonates produced by means of uncomplexed sulfur trioxyde
sulfonation of 1-dodecene; 1-tetradecene; 1-hexadecene;
1-octadecene; 1-eicosene and 1-tetracosene and sodium linear
dodecyl benzene sulfonate.
Substantially similar detergency, softening and anti-static
benefits are obtained when the clay softening agent in Example I is
replaced with an equivalent amount of volchonskoit, nontronite;
nectorite; sauconite; and vermiculite, respectively, all such clays
having an ion exchange capacity of at least about 50 meq./100
g.
Substantially similar detergency, softening and anti-static
benefits are obtained when the quaternary ammonium anti-static
agent in Example I is replaced by ditallowdimethylammonium
chloride; ditallowdimethylammonium bromide; ditallowdiethylammonium
chloride; dioctadecyldimethylammonium chloride; and
ditallowdimethylammonium hydroxide, respectively.
Substantially similar detergency, softening and anti-static
benefits are also obtained when the N-coco-.beta.-amino propionic
acid is substituted with an equivalent amount of:
octadecylaminopropionic acid; methylamino-bispropionamide; tallow
alkyl-aminodipropionic acid; dodecylamino-diacetic acid;
hexadecylaminobisacetamide; hexylamino-bisbutyramide;
N-hexadecyl-.alpha.-aminoacetic acid; dodecyl-aminodiacetic acid;
N-octyl-.alpha.-amino acetamide; butylamino-pelargonamide;
ethylamino-dicaproamide; methylamino-di-n-heptylamide.
EXAMPLE II
Through-the-wash-cycle fabric softener additive compositions having
the following formulas are prepared:
Components Formula (IN parts)
______________________________________ Sodium bicarbonate 7 13
Ditallow dimethyl ammonium chloride 8 4 N-coco-.beta.-amino
propionic acid 4 2 Sodium montmorillonite 21 21 Extender granules*
60 60 Parts *Sodium linear dodecyl benzene sulfonate 6 Sodium
silicate solids (ratio SiO.sub.2 (Na.sub.2 O = 2.0) 12 Sodium
carbonate 12 Sodium sulfate 28 Minors 2
______________________________________
When employed in conjunction with a commercially-available
anionic-based built detergent composition in a conventional
laundering process, the foregoing additive composition provides
fabric softening and anti-static effect.
The extender granules employed in the composition of Example II are
replaced with any inert or compatible filler materials such as
sodium, sulfate, starch, or the like with similar results.
EXAMPLE III
A through-the-wash cycle fabric-sfotener composition having the
following formula is prepared:
Ingredients Compositions in Parts
__________________________________________________________________________
Thixogel No. 1 (smectite clay) 10 N-coco-.beta.-aminopropionic acid
2 Dioctadecyldimethylammonium chloride 2 Detergent base granules 86
Detergent base granule Ingredients Parts Sodium dodecyl linear
alkyl benzene sulfonate 14 Sodium tallow alkyl trioxyethylene
sulfate 6 Sodium tripolyphosphate 25 Sodium sulfate 23 Silicate
solids (ratio SiO.sub.2 /Na.sub.2 O = 2.0) 12 Moisture and minor
ingredients Balance to 86
__________________________________________________________________________
The composition of Example III when used in a conventional laundry
operation at a product concentration of 0.12% by weight provides
fabric-softening, cleansing and anti-static benefits which are
substantially similar to what can be obtained from a conventional
laundry operation in combination with the subsequent
rinse-softening treatment.
* * * * *