Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
- 1~l373t~11
DETERGENT COMPOSITIO~S
Technical Field
This invention relates to compositions which provide
static control benefits in fabric laundering operations.
More particularly, it relates to providing these benefits
at reduced antistatic agent levels while simultaneously
cleansing fabrics by means of conventional detergent
compositions and detergency builders.
Background Art
Various quaternary ammonium compounds are known in the
art to possess antistatic properties. These quaternary
ammonium compounds are also known to be generally incom-
patible with anionic surfactants commonly employed in
laundering compositions. The anionic surfactants attack
and inactivate the cationic quaternary ammonium compounds
in the wash-water environment. Thus, larger amounts than
desired of the fairly expensive quaternary ammonium com-
pounds must be added to detergent compositions in order to
avoid total inactivation in wash solution. It therefore
would be highly beneficial from a performance and economic
standpoint, to be able to formulate a surfactant system
more compatible with the quaternary ammonium compounds in
the wash water, without disturbing their effectiveness as
static control agents in the subsequent machine drying
process.
Techniques known in the art for preserving the anti-
static properties of the cationic quaternary ammonium
compounds focused on efforts to physically shield them
from the hostile anionic surfactant environment. For
example, see U.S. Patent 3,936,537, issued to Baskerville
et ai on February 3, 1976, which discloses prilling of
the quaternary ammonium compound with organic dispersion
inhibitors; the McDanald, U.S. Patent 4,141,841 issued
February 27, 1979, which discloses the agglomeration
~3738~
of the above-described prill with certain water-soluble
neutral or alkaline salts, using organic agglomerating
agents; Draper, U.S. Patent 4,184,970, issued January 22,
1980 discloses the water agglomeration of the prill with
water-soluble neutral or alkaline salts; and Draper and
Jones, U.S. Patent 4,272,386 issued June 9, 1981 and
Jones, U.S. Patent 4,265,772 issued May 5, 1981, both of
which disclose the formation of a relatively insoluble
complex constituting at least a portion of the surface
of the quaternary ammonium compound. While delivering
improved static control and softening benefits over
methods then known in the art, the above-described
techniques were only partially effective in shielding the
quaternary ammonium compounds from the hostile environment.
lS The present invention, by contrast, teaches the formu-
lation of an improved surfactant system for use in con-
junction with quaternary ammonium antistatic agents. The
new surfactant system, an anionic, preferably an anionie/
nonionic, surfaetant mixture, substantially free of alkyl
ether sulfates, is more compatible with the quaternary
ammonium antistatic agents and allows a more efficient
delivery of aetive antistatic agent to the dryer than
eompositions eontaining only nonionic surfactants or
eontaining alkyl ether sulfate surfactants. Thus the
total level of antistatic material can be reduced without
a reduction in static control performance.
It is therefore an object of the present invention to
provide a detergent composition capable of concurrently
laundering, softening, and imparting static control
benefits to fabrics washed therewith and subsequently
machine dried, while using a minimum amount of anti-
static fabric-softening agent in the detergent composition.
Summar~ of the Inventio_
The present invention encompasses a detergent
composition for preventing static buildup on textiles and
softening fabrics laundered therewith, comprising:
(a) from about 5% to about 75% by weight of an anionic
surfactant,
1~373~
-- 3 --
(b) up to about 40% by weight of a nonionic surfactant,
(c) from about 0.01% to about 10% by weight of a
quaternary ammonium compound of the formula ~RlR2R3R4N] Y
wherein at least one, but not more than two, of Rl, R2, R3,
and R4 is an organic radical containing a group selected
from a C16-C22 aliphatic radical, or an alkyl phenyl or
alkyl benzyl radical having 10 to 16 carbon atoms in the
alkyl chain, the remaining group or groups being selected
from Cl-C4 alkyl, C2-C4 hydroxyalkyl, and cyclic structures
in which the nitrogen atom forms part of the ring, Y con-
stituting an anionic radical selected from the group
consisting of hydroxide, halide, sulfate, methyl sulfate,
ethyl sulfate and phosphate ions, said quaternary ammonium
compound being intimately mixed with an organic dispersion
inhibitor, which is a solid organic material having a solu-
bility in water of 50 ppm maximum at 25C and a softening
point in the range of 75F to 250F, said material being
selected from the group consisting of paraffinic waxes,
cyclic and acylic mono- and polyhydric alcohols, substi-
tuted and unsubstituted aliphatic carboxylic acids, esters
of the foregoing alcohols and acids, C3-C4 alkylene oxide
condensates of any of the foregoing materials and mixtures
thereof; substantially all of the individual particles of
the intimate mixture having a size of about 10 microns to
about 500 microns, a solubility in water of about 50 ppm
maximum at 25C, and a softening point of from about 75F
to about 250F, and being substantially free of alkyl
ether sulfate surfactants.
_isclosure of the Preferred Embodiments
~0 This invention comprises the discovery of an improved
surfactant system for use in conjunction with quaternary
ammonium antistatic agents. The new surfactant system,
an anionic, preferably an anionic/nonionic, surfactant
mixture, substantially free of alkyl ether sulfates, is
more compa.tible with the quaternary ammonium antistatic
agents and allows a more efficient delivery of active
antistatic agent to the dryer than compositions containing
only nonionic
113738~
surfactants or containing alkyl ether sulfate surfactants.
Thus the total level of antistatic material can be reduced
without a reduction in static control performance.
While not wishing to be bound by theory, it is
believed that the surfactant system herein is more compatible
with the quaternary ammonium antistatic agents because of
less and weaker chemical interaction between the cationic
antistat and the surfactants. Alkyl ether sulfates are
excluded herein because they form strong complexes with
the quaternary ammonium compounds; they readily attack
and inactivate the quat. The antistatic properties of the
quaternary ammonium compounds are preserved, not neutralized,
in the instant compositions.
It is also believed that linear alkylbenzene sulfonate
surfactants (LAS) are especially preferred anionic surfact-
ants herein because they are enriched in pi electron ad-
sorption sites at which the quaternary ammonium compounds
adsorb in the wash water. This is believed to result in
increased deposition of the antistatic material on fabrics
laundered with LAS surfactants, thereby increasing static
control performance.
Anionic/nonionic surfactant systems are preferred in
the present compositions, although anionic surfactants
alone are also useful so long as they are substantially
free of alkyl ether sulfates having the formula RO(C2~40)X
SO3M wherein R is alkyl, alkyl phenyl 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 sub-
stituted ammonium. The anionic to nonionic weight ratio
is preferably from about 2:1 to about 15:1, more preferably
from about 2:1 to about 10:1, and most preferably from about
3:1 to about 6:1. Although higher surfactant levels are
permitted, the total surfactant concentration is preferably
from about
~l37;~81
5% to about 25%, and more preferably from about 10% to
about 20%, by weight of the detergent composition.
As a particularly preferred embodiment of the present
invention, the quaternary ammonium compound is intimately
mixed with an organic dispersion inhibitor and formed into
a prill prior to incorporation into the detergent composi-
tion. The dispersion inhibitor adds to the insolubility
and physical integrity of the quaternary ammonium compound
particles, thus minimizing surfactant-quaternary ammonium
compound interactions and further enhancing the antistatic
benefits realized. This development is described in detail
in U.S. Patent 3,936,537, to Baskerville.
As another preferred embodiment of the present inven-
tion, the quaternary ammonium particles or prills are
agglomerated with certain water-soluble neutral or alkaline
salts, especially sodium tripolyphosphate, prior to incorp-
oration into detergent compositions. This development,
which results in improved static control performance, is
described in detail in U.S. Patents 4,141,841 and
4,184,970.
As another embodiment of the present invention, the
quaternary ammonium particles, prills, or agglomerates can
be complexed with certain anionic complexing components
prior to incorporation into detergent composition. The
complexing reaction results in the formation of a rela-
tively insoluble complex constituting at least a portion
of the surface of the quaternary ammonium particle, prill,
or agglomerate. This development, which also results in
improved static control performance, is described in detail
in U.S. Patent 4,272,386.
1~37;~81
The quaternary ammonium compound particles, prills,or agglomerates of the present invention are preferably
admixed or agglomerated with smectite clays, described in
U.S. Patent 4,062,647, Storm et al, issued December 13,
1977 to enhance fabric softening, as described in U.S.
Patent 3,936,537, Baskerville et al. The smectite clays
have an ion exchange capacity of at least 50 meq/lOOg,
preferably at least 60 meq/lOOg, and have a particle size
range of from about 5 microns to about 50 microns. The
smectite clays represent from about 1% to about 15%,
preferably from about 3~ to about 10%, by weight of the
detergent composition. Useful smectite clays include
sodium and calcium montmorillonite, sodium and lithium
hectorite, sodium saponite and mixtures thereof. Sodium
montmorillonite clay having an ion exchange capacity of
at least 60 me~/lOOg is especially preferred.
The detergent composition of this invention can
additionally contain other water-soluble surfactants in
addition to those disclosed herein, such as zwitterionic
surfactants, as long as they are substantially free of
alkyl ether sulfates, and detergency builder salts. The
quaternary ammonium compound provides antistatic benefits
on the fabrics and also adds an increment of softening
benefit to the fabrics, while the detergent surfactant and
builder components provide known cleansing and building
benefits.
The individual particle size of the quaternary ammon-
ium particles or prills lies in the range from about
10 microns to about 500 microns, preferably from about
25 microns to about 250 microns, and most preferably
from about 50 microns to about 100 microns. Further,
the particles or prills should not have a solubility in
water at 25C of greater than 50 ppm (parts per million),
preferably less than 10 ppm. The softening or melting
point of the particles or prills
`` 1J~37381
should lie in the range from about 75F to about 250F,
prefera~ly from about 100F to abou~ 200F, more
preferably from about 150F to about 175F~ The above
specified ranges need not apply to quaternary ammonium
compound particles free of the organic dispersion
inhibitor, although the ranges pre~erably also apply in
this situation. Individual particles of the particu-
late detergent additive can become agglomexated during
processing s~eps. These agglome~ates have a size of
from about 10 microns to about 2S00 micxons. The
agglomerates breakup in the wash water, but the
individual particles remain relati.vely insoluble in the
water-
Anlonic Surfactant
The deterg~t compositiorls o th~ pre~ent il~ventior
comprise ~rom about 5% to about 75%, preferably from
about 5~ to about 25%, by weight of an anionic surfac~ant.
Preferably the total surfactant concentration (anion;c
plus nonionic) is from about 5% to about 25%, more
2~ preferably from about 10% to about 20~, by weight of
the detergent composition.
Water-soluble salts of the higher fatty acids,
i.e. "soaps", are useful as the anionic surfactant
herein. Suitable are ordinary alkali metal soaps such
as the sodium, potassium, ammonium, and alkano3.amm~n;u~
salts of hig~er fatty acids containing from a~out 8 t~
about 24 carbon atoms and preferahly rom ahout 10 to
about 20 carbon atoms. Soaps can be made by direct
saponification of fats and oils or by the neutra]i~a1_ion
of free fatty acids. Paxticularly useflll are the
sodium and potassium salts Oc the mixtures of f2tty
acids derived from coconut oil and tallow, i.e., sodium
or potassium tallow and coconut soaps.
Anionic synthetic surfactants useful herein include
water-soluble salts, particularly the alkali metal,
ammonium and al~anol~monium salts, of orqanic sulfuric
reaction products having in their molecular structure
an al~yl group containing from about 3 to about 30
1~l3738~
carbon atoms, more preferably from about 8 to about 22
carbon atoms, and a sulfonic acid or sulfuric acid ester
group. (Included in the term "alkyl" is the alkyl portion
of acyl groups.) Examples of this group of synthetic sur-
factants which can be used in the present invention arethe sodium and potassium alkyl sulfates, especially those
obtained by sulfating the higher alcohols (C8-C18 carbon
atoms) produced by reducing the glycerides of tallow or
coconut oil; sodium or potassium C8-C20 paraffin sulfon-
ates; and sodium and potassium alkylbenzene sulfonates, inwhich the alkyl group contains from about 9 to about 18
carbon atoms in straight chain or branched chain configur-
ation e.g., those of the type described in U.S. Patents
2,220,099 and 2,477,383 (especially valuable are linear
straight chain alkylbenzene sulfonates in which the
average of the alkyl groups is about 13 carbon atoms and
commonly ab~reviated as C13 LAS).
Other anionic surfactant compounds useful herein
include the sodium alkyl glyceryl ether sulfonates,
; 20 especially those ethers of higher alcohols derived from
tallow and coconut oil, and sodium coconut oil fatty acid
monoglyceride sulfonates.
Other useful anionic surfactants herein include the
water-soluble salts of esters of alpha-sulfonated fatty
acids containing from about 6 to 20 carbon atoms in the
ester group; water-soluble salts of 2-acyloxy-alkane-1-
sulfonic acids containing from about 2 to 9 carbon atoms
in the acyl group and from about 9 to about 23 carbon
atoms in the alkane moiety; alkene sulfonates containing
from about 10 to 20 carbon atoms in the alkane group; and
beta-alkyloxy alkene sulfonates containing from about 1 to
3 carbon atoms in the alkyl group and from about 8 to 20
; carbon atoms in the alkane moiety.
~3~;~81~
Other useful anionic surfactants utilizable herei.n
are olefin sulfonates having about 12 to a~out 24
carbon atoms. The term "olein sulfonates" is used
herein to mean compounds which can be produced by the
sulfonation of alpha-olefins ~y means of uncomplexed
sulfur trioxide, followed by neutralization of the acid
reaction mixture in conditions such that any sulfones
which have been formed in the reaction are hydrolyzed
to give the corresponding hydroxya~kane sulfona~es.
The sulfur trioxide can be li~uid or gaseous, and is
usually, but not ne~essarily, dilu~ed by iner~ diluents
(for example, by liquid S02, chlorinated hydro~arbons,
etc.), when used in the liquid form, or by ~ir, nitroye~,
gaseous SO2, etc., when used in th~ gaseous fo~n.
~he alpha-olefins from which the olefin sulfona~es
- are derivea are mono-olefins h~ving 1~ to ~4 ~arbon
atoms, preferably 14 to 16 caxbon a-toms. Prefexably
they are straight chain olefins. Examples of suitable
l-olefins include l-dodecene, l-te~radecene, l~hexad~cene,
l-octadecene, l-eicosene, and l-te~racosene.
In addition to the true alken~ sulfonates and a
portion of hydroxyalkane sulfonates, the olefin sulfonate~
can contain minor amounts of other materials, such as
alkene ~isulfonates depending upon the reaction con-
ditions, proportion of reactants, the nature of the
starting olefins and impurities in the olefin stock and
side reactions during the s~lfonation process.
Preferred anionic synth~ic surfac~anl-s are alkali
and alkaline earth metal, ammonium and al~anolammo~ium
salts of line~r ~nd branched C10-C14 alkylben~2ne 5Ul-
fonates, ClQ-C20 alpha-sulfo carboxylic acid salts and
esters in which the alkyl group has ~ to 8 carbon
atoms, Clo~C20 alkane sulfonateS~ C14-C18 olefin
sulfonates, and C10-C18 alkyl sulfates, and mi~tures
thereof.
Alkyl ether sulfates are not compatible with the
quaternary ammonium antistatic compounds and are
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-- 10 --
specifically excluded, except in trace amounts, from the
anionic surfactants useful herein. These materials have
the formula RO(C2H4O)XSO3M wherein R is alkyl, alkyl
phenyl 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.
Nonionic Surfactant
The detergent compositions of the present invention
comprise up to about 40%l preferably from about 1~ to about
30%, by weight of a nonionic surfactant. The nonionic
surfactant is optional, although highly preferred, in the
surfactant systems of interest herein. Also, the total
surfactant concentration (anionic plus nonionic) is from
about 5% to about 25~, more preferably from about 10% to
about 20~, by weight of the detergent composition. The
anionic to nonionic weight ratio is preferably from about
2:1 to about 15:1, more preferably from about 2:1 to about
10:1, and most preferably from about 3:1 to about 6:1.
The nonionic surfactants can be prepared by a variety
of methods well known in the art. In general terms, such
nonionic surfactants are typically prepared by condensing
ethylene oxide with an -OH containing hydrocarbyl moiety,
e.g., an alcohol or alkyl phenol, under conditions of
acidic or basic catalysis.
Nonionic surfactants for use herein comprise the
typical nonionic surface active agents well known in the
detergency arts. Useful nonionic include those described
in U.S. Patent 4,075,118, issued to Gault et al on
February 21, 1978, in U.S. Patent 4,079,078, issued to
Collins on March 14, 1978, and in U.S. Patent 3,963,649,
issued to Spadini et al on June 15, 1976.
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Suitable, water-soluble, nonionic surface-active
agents useful in the detergent composition of the present
invention are:
1. water-soluble, nonionic, tertiary amine oxides as
represented hereinafter by the general formula
RlR2R3Y ~ O
whereby Y represents an N-atom, the arrow is a conventional
representation of a semi-polar bond; Rl represents a
high molecular, straight or branched, saturated or
unsaturated, aliphatic hydrocarbon, hydroxyhydrocarbon, or
alkyloxyhydrocarbon radical, preferably an alkyl radical,
having a total 8 to 24, preferably 12 to 18, most preferably
12 carbon atoms, or a mixture of dodecyl with decyl and
tetradecyl radicals, whereby at least 50% of the radicals
are dodecyl; R2 and R3, which may be the same of different,
represent each a methyl, ethyl, hydroxymethyl, and hydroxy-
ethyl radical.
They are generally prepared by direct oxidation of
appropriate tertiary amines, according to known methods.
Specific examples of tertiary amine oxides are:
dimethyl dodecyl amine oxide, diethyl tetradecyl amine
oxide, bis-(2-hydroxyethyl)-dodecyl amine oxide, bis-
(2-hydroxyethyl)-2~dodecoxy-1-hydroxypropyl amine oxide,
dimethyl 2-hydroxy-dodecyl amine oxide, and diethyl eicosyl
amine oxide;
2. water-soluble, nonionic, tertiary phosphine oxides
as represented hereinafter by the general formula
RlR2R3Y~ O
but whereby Y stands for a phosphorus atom, Rl, R2 and
R3 have the same meaning as hereinbefore, and the arrow is
a conventional representation of a semi-polar bond, and
which can be prepared by alkylating an alkyl phosphine
derivative and oxidizing said reaction product as
described for example in the French patent specification
No. 1,317,586. Specific examples of tertiary phosphine
oxides are: dimethyl dodecyl phosphine oxide,
~'
,,~
~l37;~81-
- 12 -
diethyl tetradecyl phosphine oxide, bis-(2-hydroxyethyl)-
dodecyl phosphine oxide, tetradecyl methyl 2-hydroxyethyl
phosphine oxide, oleyl dimethyl phosphine oxide, and
2-hydroxydodecyl dimethyl phosphine oxide;
3. water-soluble amides as represented hereinafter
by the general formula
R4-CO-N(H)m_l(RsOH)3-m
wherein R4 is saturated or unsaturated, aliphatic hydro-
c~rbon radical having from 7 to 21, preferably from 11 to
17 carbon atoms; R5 represents a methylene or ethylene
group; and m is 1, 2, or 3, preferably 1. Specific
examples of said amides are mono-ethanol coconut fatty
acid amide, diethanol dodecyl fatty acid amide, and
dimethanol oleyl amide;
4. water-soluble condensation products obtained by
condensing from 1 to about 20 moles of ethylene oxide
with one mole of organic, hydrophobic compound, aliphatic
or alkyl aromatic in nature, having 8 to 24 carbon atoms,
and at least one reactive hydrogen atom, preferably a
reactive hydroxyl, amino, amido, or carboxy group.
General examples are:
a. the condensates of ethylene oxide with
aliphatic alcohols of more than 8 carbon
atoms. The alcohols can be derived from the
naturally occurring fatty acids, but also from
various branched-chain higher alcohols. Among
the preferred alcohol-ethylene oxide condensation
products are those made from alcohols derived
from tallow and coconut fatty acids. The alcohols
may be primary, secondary, or tertiary. Most
preferred are condensation products of about 1
to about 12 moles of ethylene oxide per mole of
an aliphatic alcohol having from 9 to about
18 carbon atoms.
b. condensates of ethylene oxide with alkylphenols,
whereby the phenols may be mono- or polyalkylated
and the total number of side-chain carbon atoms
is as low as 5 to as high as 18 carbon atoms.
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The aromatic nucleus bearing the phenolic hydroxyl
may be benzene, naphthalene, or diphenyl, preferably
benzene. Specific examples are condensation products
of one mole nonylphenol with 9 to 15 moles of ethylene
oxide;
c. condensates of ethylene oxide with the fatty acid
esters, preferably mono-fatty acid esters of the sugar
alcohols, sobitol and manitol, and, but less preferred,
of di- and poly-saccharides. Specific examples are
the polyoxyethylene sobitan-monolauric acid esters,
having 20 and more ethylene oxide units; and the
polyoxyethylene derivatives of fatty acid partial
esters of hexitol anhydrides generally known under the
trade mark TWEEN; ICI America, Inc., Wilmington, Del.
d. polyethenoxy esters or esters by reacting ethylene
oxide with carboxylic acids. The acids can be natural
fatty acids or fatty acids made from oxidized paraffin
wax, or mono- or polyalkylated benzoic and naphthenic
acids. Preferred are aliphatic fatty acids having
from 10 to 20 carbon atoms, and benzoic acids with 5
to 18 carbon atoms in the alkyl groups. Specific
examples and preferred condensation products are tall
oilethylene oxide and oleic acid-ethylene oxide
condensation products having 9 to 15 ethylene oxide
units;
e. condensation products of fatty acyl alkanol-amides of
the type C7 17 alkyl-CO-NHC2H4OH, C7_17 alkyl-CO N
(C2H4OH)2 with ethylene oxide. Preferred are condensa-
tion products of one mole coconut-CO-NH-C2H4OH with 5
to 20 moles of ethylene oxide. Specific examples of
polyethenoxy alkanolamides of fatty acids are the
commercial products, marketed under the trade mark
ETHOMID; Armour Chemicals Co., Chicago, Ill.
1~l3738~
f. condensation products of C~ 18 alkyl,
C8_18 alkenyl and C5_18 alkylaryl amines and
ethylene oxide. A specific and preferred
example is the condensation product of one
mole of a dodecylamine with 9-12 moles of
ethylene oxide. Another specific example
has the formula Cll 13 alkyl-CO-NH-C6H4-N-
[(OC2 4)6 ]2
g. condensates of ethylene oxide with a hydro-
phobic base formed by the condensati.on o~
propy~ene oxide with propylene glyGol con- -
stitute another type of noni.oni~ sw:actan~.
The hydrophobic portion of ~hese compounds
has a molecular weight of ~rom about 3.500 to
18,000 and, of course, exhibi~s water insol~
ubility.
h. condensates of ethyl.ene oxide with the
product resulting from the reaction of
propylene oxi.~e and ethylenediamine are
another type of nonionic surfactant useful
herein. The hydrophobic "base" of these
condensation products consists of the reaction
product of ethylenediami.ne and excess propylene
oxide, said base having a molecular ~eight of
from about 2500 to about 3~00. T~is base
compound is thereafter condensed wi~h ~O to
the extent that the condensation product
contains from about ~0~ to about gO% by
weight of poly-E0 and has a molecular weight
of from about 5,000 to about 11,000.
It is to ~e recognized that mixtures of the fore-
going nonionic surfactants are also useful herein and
are readily available from commercial alcohol mixtures.
Moreover, the degree of ethoxylation can vary somewhat,
inasmuch as average fractional degrees of ethoxylation
occur.
Preferred nonionic surfactants herein are those
obtained by the condensation of from about 1 to 12
~37;~t
- 15 -
moles of ethylene oxide with a C10-C20 aliphatic alcohol
or a C6-C12 alkyl phenol. Rspecially preferred are those
obtained by the condensation of from about 5 to 8 moles of
ethylene oxide with a C12-C15 aliphatic alcohol.
An especially preferred nonionic surfactant is obtained
by the condensation of about 6.5 moles of ethylene oxide
with a C12-C13 aliphatic alcohol.
Quaternary Ammonium Antistatic Agent
The detergent compositions of the present invention
comprise from about 0.01% to about 10~, preferably from
about 1% to about 5%, by weight of a quaternary ammonium
antistatic agent. Suitable quaternary ammonium anti-
static agents are included in U.S. Patent 3,936,537,
Baskerville et al. In the preferred embodiment of the
present invention where the quaternary ammonium compound
is intimately mixed with an organic dispersion inhibitor
and formed into a prill prior to incorporation in the
detergent composition, the quaternary ammonium antistatic
agent will normally be employed at a level of 99.9% to
about 20~ by weight, preferably from about 80~ to about
30% by weight, and most preferably from about 75~ to about
50% by weight, of the intimate mixture.
The antistatic agents useful herein are quaternary
ammonium salts of the formula [RlR2R3R4N] Y wherein Rl
and preferably R2 represent an organic radical containing a
group selected from a C16-C22 aliphatic radical or an alkyl
phenyl or alkyl benzyl radical having 10-16 carbon atoms in
the alkyl chain, R3 and R4 represent hydrocarbyl groups con-
taining from 1 to about 4 carbon atoms, or C2-C4 hydroxy
alkyl groups and cyclic structures in which the nitrogen
atom forms part of the ring, and Y is an anion such as
halide, methyl sulfate, or ethyl sulfate.
In the context of the above definition, the hydrophobic
moietY (i.e., the C16-C22 aliphatic, C10 C16 y p
or alkyl benzyl radical) in the organic
~13738~
- 16 -
radical Rl may be directly attached to the quaternary
nitrogen atom or may be indirectly attached thereto
through an amide, ester, alkoxy, ether, or like grouping.
The quaternary ammonium antistatic 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 "ditallow" quaternaries are made
from alkyl halides having mixed C14-C18 chain lengths.
Such mixed di-long chain quaternaries are useful herein
and are preferred from a cost standpoint. As used herein
"ditallow" is intended to refer to the above-described
ditallowalkyl quaternaries.
The quaternary ammonium antistatic compounds useful
herein include both water-soluble and substantially water-
insoluble materials. Imidazolinium compounds enumerated
in the Baskerville patent possess appreciable water solu-
bility and can be utilized in the present invention by
mixing with the appropriate type and level of organic
dispersion inhibitor to give ultimate particle solutility
in water of less than 50 ppm (parts per million) at 25C.
Relatively water-soluble quaternary ammonium antistatic
agents may also be of the nonring variety, such as diiso-
stearyl dimethyl ammonium chlorides disclosed in U.S.Patent 3,395,100 to Fisher et al. Exemplary quaternary
ammonium imidazolinium compounds are specifically methyl-
l-alkylamidoethyl-2-alkyl imidazolinium methyl sulfates,
specifically l-methyl-l-~(tallow-amido)ethyl]-2-tallow-
imidazolinium methyl sulfate. However, the most usefulquaternary ammonium antistatic agents are characterized
by relatively limited solubility in water.
The following are representative examples of
substantially water-insoluble quaternary ammonium
1~37381
- 17 -
antistatic agents suitable for use in the compositions of
the instant invention. All of the quaternary ammonium
compounds listed can be formulated 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 antistatic agent for use herein by
virtue of its high antistatic activity; ditallowdimethyl-
ammonium chloride is equally preferred because of itsready availability and its good antistatic activity; other
useful di-long chain quaternary compounds are dicetyldi-
methylammonium chloride; bisdocosyldimethylammonium
chloride; didodecyldimethylammonium chloride; ditallowdi--
methylammonium bromide; dioleoyldimethylammonium hydroxide;ditallowdimethylammonium chloride; ditallowdipropylammonium
bromide; ditallowdibutylammonium fluoride; cetyldecyl-
methylethylammonium chloride; bis-[(ditallowdimethyl-
ammonium] sulfate; tris-[ditallowdimethylammonium]
phosphate; and the like.
The preceding description of quaternary ammonium anti-
static compounds is an abbreviated discussion. Description
in further detail is contained in U.S. Patent 3,936,537,
Baskerville et al.
Organic Dispersion Inhibitor
As a preferred embodiment of the present invention, an
organic dispersion inhibitor is intimately mixed with the
quaternary ammonium compound in the form of a prill prior
to incorporation into the detergent composition. The
organic dispersion inhibitor adds to the insolubility and
physical integrity of the quaternary ammonium compound
particles, thus minimizing surfactant-quaternary ammonium
compound interactions and enhancing the antistatic benefits
realized. The organic dispersion inhibitor represents
from about 0.1~ to about 80~
1~3738~
- 18 -
by weight, preferably from about 20~ to about 70~ by
weight, and most preferably from about 25~ to about 50%
by weight of the intimate mixture. The dispersion
inhibitor should have a solubility in water of 50 ppm
maximum at 25C and a softening point in the range of
75-25~F, preferably 125-200~F, and is preferabl~
selected from the group consisting of paraffinic waxes,
cyclic and acyclic mono~ and polyh~dric alcohols,
substituted and unsubstituted aliphatic caxboxylic
acids, esters of the f~Iegoing alcohols and acids, C3-
C4 alkylene oxide condensates of any o~ the foxegoing
materials and mixtures thereof.
Tallow alcohol is pref~red becaus~ o ready
availability, but useful dispersion inhibitors in~lude
other fatty alcohols in the ~14-C~6 range, ~uch as
myristyl alcohol, cetyl alcohol, stearyl alcohol,
arac;nidyl alcohol, benenyl alGoho7, ana mixtures th~reo~.
Saturated fatt~ acids hav~ng 12 to 24 carbon atoms in
the alkyl chain can be used, such as: lauric acid,
myristic acid, palmitic acid, stearic acid, arach;dic
acid, and behenic acid, as well as mixtures of these,
particularly those derived from naturally occurring
sources such as tallow, coconut, and marine oils.
Esters of the aliphatic alcohols and fatty acids are
useful dispersion inhibitors, provided they have a
total of more than 22 carbon atoms in the acid and
; alkyl radicals. Long chain C22-C30 paraffinic hydro-
carbon materials such as the saturated hydrocarbon
octacosane having 28 carbon atoms can also be used.
3n When fatt~ acids are used as dispersion inhibitors as
hereinabove described, the anionic surfactant may not
include soaps.
Another preferred class of materials useful in the
present invention are the water-insoluble sorbitan
esters which comprise the reaction product of C12-C26
fatty acyl halides or fatty acids and th2 COlllpleX
~37;~
-- 19 --
mixtures of cyclic anhydrides of sorbitol collectively
known as "sorbitan". The reaction sequence necessary to
produce such sorbitan esters from sorbitol is set out in
the Baskerville patent. The sorbitan esters are, in turn,
complex mixtures of mono-, di-, tri-, and tetra-ester
forms, of which the tri- and tetra- are the least water-
soluble and hence the most preferred for the purposes
of the present invention. Typical fatty acids that are
suitable for the alkyl portion of the ester are palmitic,
stearic, docosanoic, and behenic acids and mixtures of any
of these. These sorbitan esters, particularly the triand
tetra- esters, provide a degree of fabric softening in
addition to their function as dispersion inhibitors.
The previous discussion of organic dispersion inhib-
itors is an abbreviated one. Further discussion in detail
is set out in U.S. Patent 3,936,537, Baskerville et al.
Other Optional Ingredients
Other ingredients which are conventionally used in
detergent compositions can be included in the detergent
compositions of the present invention. These components
include detergency builders, such as those enumerated in
the Baskervil]e patent from column 13, line 54 through
column 16, line 17, as well as color speckles, bleaching
agents and bleach activators, suds boosters or suds sup-
pressors, anti-tarnish and anti-corrosion agents, soil
suspending agents, soil release agents, dyes, fillers,
optical brighteners, germicides, pH adjusting agents,
alkalinity sources, hydrotropes, enzymes, enzyme-stabiliz-
ing agents, perfumes, alkyl polyethoxylate nonionic
surfactants, and other optional detergent compounds.
The detergent compositions of the instant invention
can contain a detergency building in an amount from
about 5% to about 70% by weight, preferably from about
15% to 60~ by weight, and most preferably from about
~1373~3~
- 20 -
20% to about 40~ by weight of the entire de~ergent
composition.
As used herein, all percentages, parts and ratios
given are "by weight", unless otherwise specified
The following nonlimiting examples illustrate the
additives and compositions of th~ present in~ention.
As discussed hereinafter in the examples, the words
"comparable results" and substantially similar results"
are intended to indicate that static control benefits,
at reduced antistatic agent levels r can also be obtained
using the compositions descrlbefl.
XAMPL~ I -
The-detergent composi~on of ~his exam~le was
prepared as follows:
.. . . ..
Ingredient W~. ~
. .
Dimethyl di-hydroger~ated tallow 75
allcyl ~mmcni~-~ chlorid~ ~95~ active
powder)
Tallow alcohol 25
100
The dimethyl di-hydrogenated tallow ammonium
chloride (DTDMAC) and tallow alcohol were melted
together to form a clear solution at 250~. ~`his
molten solution was atomized at 1600 psi in~o a chambeL
with zmbient temperature air passin~ through the
chamber. The atomized droplets froze into solid
particles in the size ~ange of about 20 microns to
about 150 microns. The softening point o the DT~MAC/
tallow alcohol mixtur~ was about 165F. The DTD~AC/
tallow alcohol mixture had a solubility of substantially
less than 10 ppm in 25C water. The prills in all the
subse~uent examples have essentially the same character-
istics.
Sodium tripolyphosphate (Sl'P), the DTD~C/tallow
alcohol prills, and a dextrin ~lue solution we-e fed
into a Schugi mixer (Flexomix 160) where they were
thoroughly admixed. The sodium tripolyphosphate was a
dry, anhydrous, powder with at least ~0~ passing throu~h
a 100-mesh Tyler sieve.
~13738~
- 21 -
The STP/prill agglomerated mixture was discharged from
the Schugi Flexomi ~ 160 mixer onto a pan agglomerator
and there mixed with sodium montmorillonite clay of good
fabric softening performance and having an ion exchange
capacity of about 63 meq/100 g. (available from Georgia
Kaolin Co. USA under the trade mark Brock), which was also
discharged onto the pan agglomerator. The resulting mix
was aged for approximately one hour, mixed with silica
to increase flowability, and then admixed, by dry mix
addition, with a conventional detergent composition com-
prising surfactants, builders and other optional detergent
ingredients, forming the following detergent composition.
Base Finished
Granule Admix Product
Ingredients Parts Parts 18.6~ Admix
Sodium tC13) linear14.74 - 12.0
alkylbenzene sulfonate
(C13 LAS)
C12_13 (E)6 5 * 3.69 - 3.0
Sodium silicate (2.0r) 14.74 _ 12.0
Sodium tripolyphosphate 24.32 24.5 24.4
Sodium sulfate 34.46 - 28.0
Sodium toluene sulfonate 1.23 - 1.0
Tallow fatty acid 0.61 - 0.5
Brightener 0.06 - 0.05
Moisture 6.00 12.6 7.2
Perfume 0.15 - 0.15
DTDMAC - 16.1 3.0
Tallow alcohol - 5.4 1.0
Sodium montmorillonite - 33.4 6.2
clay (ion exchange capa-
city about 63 meq/100 g,
commercially available
from Georgia Kaolin Co.,
USA, under the trade
mark ~ROCK)
Dextrin glue - 6.2 1.2
Miscellaneous (dyes, etc.) - 1.8 0.3_
100 . O100 . O 100 . O
1~3738J.
- 22 -
*Condensation product of C12 13 alcohol with 6.5 moles
of ethylene oxide,-stripped to remove lower ethoxylate
E~ and non-ethoxylated fractions, commercially available
.~ as Neodol~ 23-6.5T, fro~ Shell Chemical Corporation.
EXAMPLE II
The following detergent composition was produced,
using the method described in Example I.
Base Finished
. .... . ...............Granule Admix Product
Ingredient Parts PartsParts
Sodium ~C ) linear 14.3 - 12.0
alkylben~ne sulfonate
C12_13(EO)6 5 3.6 - 3.0
Sodium aluminosilicate23.9 - 20.0
(hydrated Zeolite A,
particle diameter 1-10
microns)
Sodium silicate (2.Or)14.3 _ 12.0
Sodi~m sulfate 22.3 24.6 22.7
Sodium carbonate 11.~ ~ 10.0
Brightener .06 - .05
Moisture 6.0 - 5.0
Sodium acetate 3.6 - 3.0
DTDMAC - - 18.4 3.0
Tallow alcohol - 6.2 1.0
Sodium montmoril.lonite - 38.~ 6.5
clay (ion exchange capa-
city about 63 meq/100 g,
commercially available
from Georgia Kaolin Co.,
USA, under the trade
name BROCK)
Speckles (nil phosphate~ - 11.8 ~.0
The cG~positions of Ex~mp1 2S I and II provide s~od
~abric cleaning and static control at DTD~AC leve~s
lower than those required in prior art.
EXAMPLE III
The indicated detergent compositions were prepared
according to the procedure of Example I and tested as
follows.
~37~8~
, .
- 23 -
Ingredient Parts
Surfactant system as indicated below
- 3:1 DTDMAC:tallow alcohol prills as indicated below
Sodium montmorillonite clay 10.9
Sodium tripolyphosphate 24.4
Sodium sulfate 25.0
Sodium silicate 12.0
Moisture g.o
Miscellaneous tincludes
brighteners, perfume, and
processing aids) balan~e
A series of fabrics ~mixed bundles contai.ning
cotton, polyester and polyester/cotton) were washed in
these respective com~ositions (1-1/4 cups usage), usi.ng
a normal washing cycle, at a wash water temperature of
about 1~0F and at a water hardness of about 2 grai.ns
per gallon, ana then d~.ied l?nder ordinar~ machine
; drying corlditions and at a dew point of from about 42F
to 49F. These were full-scale washer and dryer loads
using conventional fabric bundles. The fabrics wexe
then measured for average volts per square yard using a
Faraday cage apparatus and for number of clings.
The results were as follows:
... .. .. ... . Avg. V/ Av~.
Sample Surfactant System ~ DTDMAC sq. ~d. - Clin~s
A 12 parts C 2 LAS/ 2.0 6.3 8
6 parts so~lum
C14 15 alkyl 3.5 2.7 3
polyethoxylate (1.1)
sulfate
B 18 parts C13 ~AS 2.0 2.4 4
3.5 1.0 0
C 10 par~s C13BA~ 2.d 1.0 0
5 parts C14_15(E)7 3 5 1.2 o
These results demonstrate that Sample C compositions,
containing a preferred anionic/nonionic surfactant
system, demonstrated acceptable static control at 2.0
and at 3.5% DTDMAC, whereas Sample B compositions,
~l373~
- 24 -
containing only an anionic surfactant, gave acceptable
static control only at 3.5% DTDMAC. ~urther, Sample
. A compositions, having a surfactant system representative
of that disclosed in the prior art, containing an alkyl
ether sulfate anionic surfactant, did not have accept-
able static control at either 2.0~ or 3.5% DTDMAC.
Sample Surfactant System ~ DTDMAC ~v~sq.yd. Clings
D 10 parts C13LAS/ 2.0 4.0 6
5 parts C14_15(EO)7 3.0 1~ 0
4.0 ~.5 0
5.~ 1.5 2
6.0 ~.0
E12 parts C14_15(EO)7 2-0 3-4 3
3.0 2 6 3
4.0 ~.~ 4
5.0 4.~ 9
6.0 5.3 11
These results demonstrate that Sample D composi~iolls,
containing a preferred anionic/nonionic surfactant
system, controlled static better than Sample E compositions
containing only a nonionic sur~actant, which did not
have acceptable static control.
Substantially similar results are obt:ained when
the anionic surfactants above are replaced with other
anionic surfactants selected from the group consisting
of alkali and alkaline earth metal, ammonium and
alkanolammonium salts of linear and branched C10-C14
alkylbenzene sulfonates, C -C
20 alpha-sulfo carboxylic
acid salts and esters i.n which the alkyl group has 1-
~
3~ ~arbon atoms, C10-C20 alkane sulfonates, C14-C18 oïefin
sulfonates, and C10-Cl8 alkyl sulfates, and mixtures
thereof.
Substantially similar results are obtained when
the nonionic surfactants above are replaced with other
nonionic surfactants obtained by the condensation of
from about 1 to about 12 moles of ethylene oxide with a
~373~
C10-C20 aliphatic alcohol or a C6-C12 alkyl phenol.
Substantially similar results are obtained when
the weight ratio of anionic to nonionic surfactat is
varied anywhere from about 2:1 to about 15:1.
EXAMPLE IV
The indicated detergent compositions were prepared
according to the procedure of Example I and tested as
follows.
. . . .. ...
Ingredient Parts
Surfactant system as indicated below
3:1 DTDMAC:tallow alcohGl prills as indi~ated below
Sodium montmorillonite clay as indicated ~low
Sodium tripolyphosphate 24.~
Sodium sulfate 25.0
Sodium silicate ~2.0
Moisture g o
Miscellaneous (~ncludes
brlghteners, perfume, and
processing aids) balance
Desized cotton terry washcloths were washed ~n
aqueous solutions ha~ing dissolved therein 1~ cups
of the detergent compositions of this Example.
The terry swatches were washed for 10 minutes in a
miniature agitator containing 1-1/2 gallons of ~ashing
liquor at 100F and 7 gr/gal. artificial hardness. The
swatches comprised 4% by weight of the washing liquor.
After washing, the swatches were spun dry and rinsed
with 1-1/2 gallons of water at 100F and 7 gr/gal.
artifi~ial hardness. Swatches were then dried in a
minature electric dryer.
After several treatment cycles, the test ar.d
control swatches were graded tactilely for softness by
a panel of three judges making paired comparisons of
all swatches. Graders assigned an integer grade of
from ~ to 4 on a linear scale to the softer treatment
of each pair, assigning the higher grades to corre-
sponding larger differences in softness. The data
obtained were analyzed statisticall~ to obtain mean
~13738~
- 26 -
softness grades (panel score units) for each treatment
and a statistical estimate of the least significant
difference (LSD) was 0.25 at the 95% confidence level.
The results were as follows:
Sample -Surfactant System Grade
(Modified
Softness Units)
Test 1 (5X DTDl~AC, 10.9 parts
sodium montmorillonite clay
p 14-15( 77 0.51
B 15 parts C13LAS 1.07
C 12 parts C 2LAS/6 parts sodium 1.00
c(~4l~s al~yl poly~thoxy].ate
15Test 2 (5% DTDMAC, 10.9 paxts
sodium montmorillonite clay)
D 12 parts C14~15(E)7 0.20
E 15 parts C13LAS 0.93
F 10 parts C 3LA-~/5 ~a~'s l.C2
C14-15~ ~7
~ hese resu~ts demonstrate that surfactant systems
containing only nonionics do not provide acceptable
levels of softening ~as measured against composition C
which is representative of that disclosed in prior
art), and that anionic/nonionic systems of the present
invention provide acceptable ~oftening which is direc-
tionally better than that ~rovided by anionics alone.
Grade (Modified
Softness Units at
listed washing
5ample Surfactant System temperatures) _
(~ DTD,~C, 5.5 parts sodium
montmorillonite clav) 70~F l~O~F 130F
G 12 parts C12LAS/5 parts sod 0.64 0.71 0.85
ium C14 ~ polyetho~ylate
(1.1) suI~ate
H 10 parts C13LAS/5 parts 0.41 0.76 0.58
14-15( )7
I 12 parts C13LAS/3 parts 0.65 0.78 0.85
C14-15( )7
These results demonstrate that a 4:1 weight ratio
of anionic to nonionic i5 preferred for softening
performance over a 2:1 ratio. ~he 4:1 ratio is required
~37;~8~
- 27 -
to match the softening performance o~ the composition
G, which is representative of compositions disclosed in
prior art.
Substantially similar results are obtained when
the anionic, nonionic and weight ratio of anionic to
nonionic surfactants are varied as describe~ in Example
III.
EXAMPLE V
The indicated detergent compositions were prepared
according to the procedures of Example I and tested as
follows.
ngredient Parts
Surfactant system as indicated below
3:1 DTDMAC:tallow alcohol prills 3~ DTDMAC
Sodium montmorillonite clay 5.5
Sodium tripolyphosphate 24.4
Sodi~ sulfate 25.0
Sodium silicate 12.0
Moisture g.o
Miscellaneous (includes
brightener, perfume, and
processing aids) balance
Sudsing he ght was determined by a statistical
average of 64 separate full-sc~le washer runs, using
mixed consumer soiled clothes. Ranges in the washing
conditions were as follows: water hardness, from 0 to
16 gr./gal.; water temperature, from 60~F to 150F; and
product usage, from 60% to 160% of standard 1-1/4 cup
usage. Sudsing height was measured in inches one
minute into the wash cycle. The results were as
follo~s:
Sample Su factant Syst~One minute suds
height (in.)
A 10 parts C 3LAS/5 parts1.08
C14-15~~7
B 12 parts C 3LAS~3 parts1.18
14-15(EO~7
C 12 parts C 3LAS~3 parts1.40
12-15( ~7
~373~t
- 28 -
D 12 parts C 3LAS~3 parts 1.44
C12-13~E0~6 5
E 12 parts C12LAS/6 parts 1.~0
sodium C alk~l poly-
ethoxyla~e ~.1) sulfate
(5% DTDMAC, 10.9 parts sodium montmorillonite clay)
These results demonstrate that sudsing can be
improved by increasing the anionic to nonionic weight
ratio from 2:1 to 4:1 and by decreasing the alcohol
chain lengths. Sample D, an especially preferred
composition, provldes sudsing performance be~er than
that of composition E, which is representative of
compositions disclosed in prior art.
Substantially similar results are obtained when
the anionic, nonionic, and weight ratio of anionic to
nonionic surfactants are varied as described in Example
III.
