Cross Reference to Related Application
[0001] This application is a continuation-in-part of copending application Serial No. 962,822
for LOW PHOSPHATE DETERGENT COMPOSITIONS, filed November 22, 1978, which is a continuation-in-part
of copending application Serial No. 949,182, Murphy, for LOW PHOSPHATE LAUNDRY DETERGENT
COMPOSITIONS, filed October 6, 1978, which is a continuation-in-part of copending
application Serial No. 943,419, Murphy, for LOW PHOSPHATE LAUNDRY DETERGENT COMPOSITIONS,
filed September 18, 1978, which is a continuation-in-part of copending application
Serial No. 885,931, Murphy, for LOW PHOSPHATE LAUNDRY DETERGENT COMPOSITIONS, filed
March 13, 1978.
Technical Field
[0002] This invention relates to laundry detergent compositions which exhibit surprisingly
effective removal of particulate soils, as well as fabric softening, static control,
color fidelity (i.e., the inhibition of the bleeding of fabric colors into the laundry
solution), and dye transfer inhibition (i.e., the inhibition of the redeposition of
dyes in the laundry solution onto fabrics) capabilities, even in the total absence
of de-ergency builder materials. Specifically, completely unbuilt compositions of
the present invention have demonstrated the ability to remove particulate soils from
fabrics as well, and under some conditions better, than fully-built conventional laundry
detergents. Other detergent compositions which utilize mixtures of selected nonionic
surfactants and cationic surfactants are defined in U.S. Patent Application Serial
No. 919,181, Murphy, filed June 26, 1978, and the parent applications thereof and
U.S. Patent Application Serial No. 919,341, Cockrell, filed June 26, 1978, and the
parent applications thereof, both of which are incorporated herein by reference.
Background Art
[0003] Nonionic surfactants are generally utilized in laundry detergent compositions for
their ability to remove greasy and oily, rather than particulate, soils from fabrics.
Some types of cationic surfactants have been included in detergent compositions, primarily
because they provide adjunct fabric care benefits, and not because they provide any
cleaning advantage. Thus, certain cationic surfactants have been included in detergent
compositions for the purpose of yielding a germicidal or sanitization benefit to washed
surfaces; e.g., U.S. Patent No. 2,742,434, Kopp, issued April 17, 1956; U.S. Patent
No. 3,539,520, Cantor et al, issued November 10, 1970; and U.S. Patent No. 3,965,026,
Lancz, issued June 22, 1976. Other cationic materials, particularly those of the di-long
chain type, have been included in detergent compositions for the purpose of providing
a fabric softening benefit (see U.S. Patent No. 3,607,763, Salmen et al, issued September
21, 1971, and U.S. Patent No. 3,644,203, Lamberti et al, issued February 22, 1972),
or a static control benefit (see U.S. Patent No. 3,951,879, Wixon, issued April 20,
1976, and U.S. Patent No. 3,959,157, Inamorato, issued May 25, 1976).
[0004] The relative insolubility of the di-long chain quaternary ammonium materials has
led formulators of detergent compositions away from their inclusion for the purpose
of yielding a cleaning or whiteness maintenance benefit; this is particularly true
in compositions, such as those described herein, where the relatively low nonionic:cationic
ratios required preclude the use of large amounts of the nonionic surfactant to solubilize
the cationic material. In fact, it is well known in the detergency art that the use
of such di-long chain cationic materials actually causes fabrics laundered with them
to become yellow and dingy. See U.S. Patent No. 3,644,203, Lamberti et al, issued
February 22, 1972; U.S. Patent No. 3,360,470, Wixon, issued December 26, 1967; U.S.
Patent No. 3,676,341, Gerecht and Wixon, issued July 11, 1972; and U.S. Patent No.
3,904,359, Rama- chandran, issued September 9, 1975, which teach ways of avoiding
this yellowing problem caused by the di-long chain cationics. The teachings of patents
such as these makes the whiteness maintenance properties of the present invention,
which result from inhibiting the transfer of dyes in the wash solution, particularly
surprising.
[0005] The compositions of the present invention have outstanding cleaning capabilities
in terms of the removal of particulate soils. In laundry tests, these ccmpositions,
not containing any builder components, have been shown to remove particulate soils
(such as clay) as well, and in some cases dramatically better, than fully-built conventional
laundry detergent compositions. The compositions are relatively insensitive to water
hardness conditions, performing well in both hard and soft water conditions. Finally,
in addition to this cleaning performance, the present invention provides, in a single
detergent product, fabric softening, static control, fabric color fidelity, and dye
transfer inhibition benefits to the laundered fabrics. This well-rounded cleaning
and fabric care performance is the result of a heretofore unrecognized cleaning potential
of the selected di-long chain cationic surfactants defined herein, when they are used
in the presence of certain alcohol ethoxylate nonionic surfactants, within a narrow
range of nonionic:cationic surfactant ratios.
[0006] It is, therefore, an object of this invention to provide low- or no-phosphate laundry
detergent compositions which demonstrate outstanding particulate soil removal capabilities.
[0007] It is another object of this invention to provide laundry detergent compositions,
yielding excellent particulate soil removal, which may conveniently be produced in
a variety of physical forms, such as liquid, solid, paste, granular, powder, or in
conjunction with a carrier, such as a substrate.
[0008] It is a further object of this invention to provide a single composition which provides
outstanding cleaning performance together with fabric softening, static control, color
fidelity, and dye transfer inhibition benefits.
[0009] It is yet another object of this invention to provide a process for laundering fabrics
which yields exceptional particulate soil removal, over a range of water hardness
conditions, using cationic and nonionic surfactant-containing detergent compositions.
Summary of The Invention
[0010] The present invention relates to low- or no-phosphate laundry detergent compositions,
especially beneficial for the removal of particulate soils from fabrics, having a
pH in the laundry solution of greater than about 7, containing no more than about
15% phosphate and no more than about 1C silicate materials, and being substantially
free of ethoxylated cationic surfactants containing more than an average of about
.10 moles of ethylene oxide per mole of surfactant which comprise from about 5% to
about 100%, by weight, of a surfactant mixture consisting essentially of:
(a) a nonionic surfactant having the formula R(OC2H4)nOH, wherein R is a primary alkyl chain containing an average of from about 10 to about
18 carbon atoms and n is an average of from about 2 to about 9, and having an HLB
of from 5 to about 14, or a mixture of such surfactants; and
(b) a quaternary ammonium cationic surfactant having 2 chains which contain an average
of from about 16 to about 22 carbon atoms, or a mixture of such surfactants;
the ratio of said nonionic surfactant to said cationic surfactant being in the range
of from about 2:1 to about 9:1.
Dischosure of The Invention
[0011] The compositions of the present invention comprise, by weight, from about 5 to about
100%, preferably from about 15 to about 90%, and most preferably from about 20 to
about 80%, of a mixture of particularly defined nonionic and cationic surfactants
in the ratios stated herein. Preferred compositions contain at least about 15% of
the nonionic/ cationic surfactant mixture and at least about 1% of the cationic component,
itself, in order to assure the presence of a sufficient amount of both the cationic
surfactant and the nonionic/cationic mixture to provide the desired cleaning and fabric
conditioning benefits.
[0012] The compositions of the present invention contain the nonionic and cationic surfactants,
defined hereinafter, within ratios of nonionic to cationic surfactant of from about
2:1 to about 9:1, preferably from about 3:1 to about 6.5:1, more preferably from about
3.5:1 to about 5.5:1 and most preferably from about 4:1 to about 5:1, in order to
achieve the best particulate soil removal performance. In addition, by using ratios
in the range of from about 3.5:1 to about 5.5:1, the static control performance of
the compositions is not only excellent under typical laundering conditions, but is
particularly impressive under stress conditions, such as relative humidity less than
about 35%, which generally are very difficult conditions under which to obtain any
static control benefits. Preferred compositions may also contain mixed nonionic surfactant
systems.
[0013] It is preferred that the compositions of the present invention are formulated so
as to have a pH of at least about 7 in the laundry solution, at conventional usage
concentrations, in order to optimize their overall cleaning performance, to aid in
their manufacturing and processing, and to minimize the possibility of washing machine
corrosion. Lower product pH's (e.g., as low as 6) are acceptable, but preferably the
composition is not buffered below 7. It is also preferred that the composition pH
be at least about 7.1, especially when a halide, e.g., choride, cationic is used to
avoid corrosion of the equipment used in making the composition. Also, a pH range
of from 7.2 to about 8.0, which is strongly buffered, is desirable if the cationic
material has a substantial level of unquaternized amine, for odor reasons. Alkalinity
sources, such as potassium hydroxide, potassium carbonate, potassium bicarbonate,
sodium hydroxide, sodium carbonate and sodium bicarbonate, may be included in the
compositions for this purpose. Some of the cationic/nonionic systems of the present
invention may attain optimum removal of greasy/oily soils at higher pH's, while attaining
optimum particulate soil removal at relatively lower pH's. In these systems, overall
performance may be enhanced by varying the pH of the wash solution during the laundering
process. Particularly preferred compositions have a pH of at least about 8 in the
laundry solution, in order to optimize the removal of greasy/oily and body soils.
In addition to the higher pH in the laundry solution, these preferred compositions
should also have the ability to maintain a pH in the laundry solution of from about
8 to 11 throughout the washing operation (reserve alkalinity). Such a reserve alkalinity
may be obtained by incorporating compounds which buffer at pH's of from about 8 to
11, such as monoethanolamine, diethanolamine or triethanolamine.
[0014] Preferred compositions of the present invention are also essentially free of oily
hydrocarbon materials and solvents, such as mineral oil, paraffin oil and kerosene,
since these materials, which are themselves oily by nature, load the washing liquor
with excessive oily material, thereby diminishing the cleaning effectiveness of the
compositions.
Nonionic Component
[0015] The nonionic surfactants used in the compositions of the present invention are biodegradable
and have the formula R(OC
2H
4)
nOH, wherein R is a primary alkyl chain containing an average of from about 10 to about
18, preferably from about 10 to. about 16, carbon atoms, and n is an average of from
about 2 to about 9, preferably from about 2 to about 7 These nonionic surfactants
have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 14, preferably
from about 6 to about 13. HLB, an indicator of a surfactant's hydrophilic or lipophilic
nature, is defined in detail in Nonionic Surfactants, by M.J. Schick, Marcel Dekker,
Inc., 1366, pages 607-613, incorporated herein by reference.
[0016] Preferred nonionic surfactants for use in the present invention include the condensation
product of coconut alcohol with 5 moles of ethylene oxide; the condensation product
of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C
12-15 alcohol with 7 moles of ethylene oxide; the condensation product of C
12-15 alcohol with 9 moles of ethylene oxide; the condensation product of C
14-15 alcohol with 2.25 moles of ethylene oxide; the condensation product of C
14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C9-11 alcohol
with 8 moles of ethylene oxide, which is stripped so as to remove unexthoxylated and
lower ethoxylate fractions; the condensation product of C
12-13 alcohol with 6.5 moles of ethylene oxide, and this same alcohol ethoxylate which
is stripped so as to remove unethoxylated and lower ethoxylate fractions. A preferred
class of such surfactants utilize alcohols which contain about 20% 2-methyl branched
isomers, and are commercially available, under the tradename Neodol, from Shell Chemical
Company. The condensation product of tallow alcohol with 9 moles of ethylene oxide
is also a preferred nonionic surfactant for use herein. Particularly preferred nonionic
surfactants for use in the compositions of the present invention include the condensation
product of coconut alcohol with 5 moles of ethylene oxide, the condensation product
of C
12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C
12-15 alcohol with 7 moles of ethylene oxide, the condensation product of C14-15 alcohol
with 7 moles of ethylene oxide, and mixtures of those surfactants.
[0017] The compositions of the present invention may contain mixtures of nonionic surfactants
falling within the above nonionic surfactant definition, such as: a mixture of the
condensation product of C
12-13 alcohol with 6.5 moles of ethylene oxide (Neodol 23-6.5) with the condensation product
of C
14-15 alcohol with 7 moles of ethylene oxide (
Neodol 45-7), in a ratio of from about 4:1 to 1:4, a mixture of the condensation product
of C
12-15 alcohol with 7 moles of ethylene oxide with Neodol 45-7, in a ratio of from about
4:1 to about 1:4, preferably about l:l; or a mixture of the condensation product of
C
9-11 alcohol with 8 moles of ethylene oxide, stripped to remove lower ethoxylate and nonethoxylated
fractions, with Neodol 45-7, ih a ratio of higher ethoxylate to lower ethoxylate of
from about 1:6 to about 1:1, preferably about 1:3. The present invention may also
contain mixtures of nonionic surfactants, some of which do not fall within the above
nonionic surfactant definition (such as alcohol ethoxylates having an average of greater
than about 9 ethylene oxide groups per molecule, secondary alcohol ethoxylates, or
alkyl phenol ethoxylates), as long as at least one of the nonionic surfactants contained
in the mixture falls within the above definition of required nonionic surfactants,
and that required nonionic surfactant (mixture) is contained in an amount such that
it falls within the required nonionic/cationic ratio. Where the nonionic surfactant
mixture contains a nonionic surfactant (or surfactants) which falls outside of the
above nonionic definition, it is preferred that the ratio of the surfactant (or surfactants)
within the definition to that which is outside the definition be within the range
of from about 1:1 to about 10:1. A specific example of such a surfactant mixture is
a mixture of the condensation product of C
12-13 alcohol with 6.5 moles of ethylene oxide (e.g., Neodol 23-6.5) and the condensation
product of a secondary Cl5 alcohol with 9 moles of ethylene oxide (e.g., Tergitol
15-S-9), in ratio of lower ethoxylate to higher ethoxylate nonionic of from about
1:1 to about 6:1; or a mixture of Neodol 23-6.5 and the condensation product of nonyl
phenol with 7 moles of ethylene oxide, having a ratio of Neodol to nonyl phenol ethoxylate
of about 4:1.
[0018] Preferred nonionic surfactant mixtures contain alkyl glyceryl ethers in addition
to the required nonionic surfactant. Particularly preferred are glyceryl ethers having
the formulae
wherein R is an alkyl or alkenyl group of from about 8 to about 18, preferably about
8 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbon in the
alkyl chain, and n is from 1 to about 6, together with the nonionic surfactant component
of the present invention, in a ratio of nonionic surfactant to glyceryl ether of from
about 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful
in the present invention are disclosed in U.S. Patent Application Serial No. 904,656,
Jones, filed May 10, 1978 and its parent application,and U.S. Patent 4,098,713, Jones;
issued July 4, 1978, both_of which are incorporated herein by reference.
[0019] Other nonionic surfactants well known in the detergency arts may be used, in combination
with one or more of the required nonionic surfactants, to form useful nonionic surfactant
mixtures. Examples of such surfactants are listed in U.S. Patent No. 3,717,630, Booth,
issued February 20, 1973, and U.S. Patent No. 3,332,880, Kessler et al, issued July
25, 1967, both of which are incorporated herein by reference. Nonlimiting examples
of suitable nonionic surfactants which may be used in conjunction with the required
nonionic surfactants, defined above, are: polyethylene oxide condensates of alkyl
phenols, such as the Igepal surfactants, marketed by the GAP Corporation, and the
Triton surfactants, marketed by the Rohm and Haas Company; condensation products of
aliphatic alcohols with from about 10 to about 25 moles of ethylene oxide, where those
alcohols are of a primary, branched or secondary alkyl chain structure; condensation
products of ethylene oxide with a hydro- - phobic base formed by the condensation
of propylene oxide with propylene glycol, such as the Pluronic surfactants, marketed
by Wyandotte Chemical Corporation; and condensation products of ethylene oxide with
the product resulting from the reaction of propylene oxide and ethylene diamine, such
as the Tetronic surfactants, marketed by Wyandotte Chemical Corporation.
[0020] A preferred group of nonionic surfactants useful herein comprises a mixture of "surfactant"
and "cosurfactant", containing at least one nonionic surfactant falling within the
definition of the nonionic surfactants useful herein, as described in U.S. Patent
Application Serial No. 001, 632, Collins, filed January 8, 1979, and its parent applications,
the disclosure of which is incorporated herein by reference.
[0021] Another preferred mixture of nonionic surfactants comprises C
12-13EO
6-5 and C14-15E07 in a ratio of 4:1 to 1:4. This mixture provides a desirable suds pattern
during the wash and during rinsing as compared to either surfactant by itself.
[0022] Preferred compositions of the present invention are substantially free of fatty acid
polyglycol ether di-ester compounds, such as polyethylene glycol-600-dioleate or polyethylene
glycol-800-distearate. Such additives offer no advantage, and possibly even result
in a disadvantage, in terms of achieving the particulate soil removal and fabric conditioning
benefits provided by the present invention.
Cationic Component
[0023] The cationic surfactants used in the compositions of the present invention are of
the di-long chain quaternary ammonium type, having two chains which contain an average
or from about 16 to about 22, preferably from about 16 to about 18, carbon atoms.
The remaining groups, if any, attached to the quaternary nitrogen atom, are preferably
C
1 to C4 alkyl or hydroxyalkyl groups. Although it is preferred that the long chains
be alkyl groups, these chains may contain heteroatoms or other linkages, such as hydroxy
groups, double or triple carbon-carbon bonds, and ester, amide, or ether linkages,
as long as each chain falls within the carbon atom ranges required given above. Preferred
cationic surfactants are those having the formulae
wherein the R
1 and R
2 groups contain an average of from about 16 to about 22 carbon atoms, preferably as
alkyl groups, and most preferably contain an average of from about 16 to about 18
carbon atoms, R
3 and R
4 are C
1 to C
4 alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected
from the group consisting of halide, hydroxide, methylsulfate, or acetate anions.
[0024] Mixtures of the above surfactants are also useful in the present invention. These
cationic surfactants may also be mixed with other types of cationic surfactants, such
as sulfonium, phosphonium, and mono- or tri-lorg chain quaternary ammonium materials,
as long as the amount of required cationic surfactant contained in the composition,
falls with the nonionic:cationic ratio requirements specified herein.
[0025] Examples of cationic surfactants which may be used together with those required herein,
include those described in U.S. Patent Application Serial No. 919,181, Murphy, U.S.
Patent Application Serial No. 919,341, Cockrell, U.S. Patent Application Serial No.
919,344, Letton, and U.S. Patent Application Serial No. 919,343, Letton, all of which
were filed on June 26, 1978, and their parent applications all of which are incorporated
herein by reference.
[0026] Preferred cationic surfactants include ditallowalkyl- dimethyl (or diethyl or dihydroxyethyl)
ammonium chloride, ditallowalkyldimethylammonium methyl sulfate, dihexadecylalkyl
(C
16; also known as distearyl) dimethyl (or diethyl, or dihydroxyethyl) ammonium chloride,
dioctadecylalkyl (C
18)- dimethylammonium chloride, dieicosylalkyl-(C
20) dimethylammonium chloride, methyl (1) tallowalkyl amido ethyl (2) tallowalkyl imidazolinium
methyl sulfate (commercially available as Varisoft 475 from Ashland Chemical Company),
or mixtures of those surfactants. articularly preferred cationic surfactants are ditallowalkyldimethylammonium
chloride, ditallowalkyldimethylammonium methyl sulfate, methyl (1) tallowalkyl amido
ethyl (2) tallowalkyl imidazolinium methyl sulfate, and mixtures of those surfactants,
with ditallowalkyldimethylammonium chloride being especially preferred.
[0027] Another particularly useful class of cationic surfactant is that in which the two
long chains of the cationic surfactant contain a significant amount of unsaturation,
such as where at least about 20%, preferably at least about 30%, of the long chains
contain at least one double bond. By increasing the percentage of chains containing
the double bonds, the performance benefits of these cationic materials are increased.
Compounds of this type have the formula
wherein R
1 and R 2 contain an average of from about 16 to about 22 (most preferably from about
16 to about 18) carbon atoms, and at least about 20% of these chains contain at least
one double bond; R 3 and R
4 are C
1 to C
4 alkyl or hydroxyalkyl groups, and X is any compatible anion, particularly one selected
from the group consisting of halide, hydroxide, methylsulfate or acetate anions. Thus,
for example, a preferred cationic surfactant is di-partially hydrogenated tallow dimethylammonium
halide (especially chloride or methyl sulfate), which is also known as di-softened
tallowalkyl dimethylammonium halide. A commercially available compound of this type
is Adogen 470, sold by Ashland Chemical Company, wherein about 30c of the tallow chains
are oleyl in character. Another method of forming similar cationic materials is to
synthesize a di-oleyl quaternary ammonium compound and hydrogenate it to the level
of unsaturation desired. Compositions made with these cationics show several significant
advantages over those made with more conventional cationics (such as ditallowalkyldimethylammonium
chloride, only about 2% of the long chains of which contain double bonds); particularly
these compositions show improved particulate soil removal, especially at low wash
temperatures, improved static control and remain in a stable single phase at temperatures
down to about 40°F.
[0028] The cationics of this invention are preferably low in unquaternized amine content.
If they contain more than about 1% unquaternized amine or amine salt the pH of the
formula is desirably kept below about 8 to avoid the amine odor. Also, for odor reasons,
it is preferable to use a solvent for the amine quaternization reaction which does
not have an objectionable odor, e.g., a liquid nonionic detergent material, ethyl
alcohol, etc.
[0029] The compositions of the present invention must be formulated so as to be substantially
free of ethoxylated cationic surfactants which contain more than an average of about
10, and preferably free of those which contain more than an average of about 7, moles
of ethylene oxide per mole of surfactant. These compounds tend to be relatively non-biodegradable,
do not enhance the cleaning or fabric conditioning benefits provided by the compositions
and may, in some circumstances, decrease the overall laundering performance provided
by them. It is to be noted that polyethoxylated cationic surfactants having relatively
low levels of ethoxylation, i.e., those with less than 10, and particularly less than
7, ethylene oxide groups exhibit better biodegradability characteristics and may be
advantageously included in the compositions of the present invention.
[0030] In particularly preferred embodiments of the present invention, the detergent compositions
additionally contain from about 2 to about 25%, preferably from about 2 to about 16%,
and most preferably from about 2 to about 10% of a fatty amide surfactant, such as
ammonia amide(e.g.,coconutalkyl ammonia amide, diethanol amides, and ethoxylated amides).
The amides are water-soluble or at least water dispersible. In relation to the nonionic/cationic
surfactant system, the ratio of the cationic/nonionic mixture to the amide component
in the composition is in the range of from about 5:1 to about 50:1, preferably from
about 8:1 to about 25:1. The addition of the amide component results in a composition
which exhibits improved antiredeposition of both clay and greasy/oily soils. This
development is described in greater detail in U.S. Patent Application Serial No. 811,419,
Cambre, filed June 29, 1977, and U.S. Patent Application Serial No. 919,340, Cambre,
filed June 26, 1978, both of which are incorporated herein by reference. Preferred
amides are CS-C20 monoethanol amides, CS-C20 diethanol amides, and amides having the
formula
wherein R is a C
8-C
20 alkyl group, and mixtures thereof. Particularly preferred amides are those where
the alkyl group contains from about 10 to about 16 carbon atoms, such as coconut alkyl
monoethanol or diethanol amide. Such compounds are commercially available under the
tradenames Superamide GR, from Onyx Chemical Co., Jersey City, N.J., Superamide F-3
from Ryco, Inc., Conshohocken, Pa., and Gafamide CDD-518, available from GAF Corp.,
New York, N.Y.
[0031] These amide components may also be added in small amounts, i.e., from about 2% to
about 5%, to act as suds modifiers. Specifically, they tend to boost the sudsing in
an active system which exhibits relatively low sudsing, and depress the sudsing in
an active system which exhibits relatively high sudsing.
[0032] The compositions of the present invention may also contain additional ingredients
generally found in laundry detergent compositions, at their conventional art-established
levels, as long as these ingredients are compatible with the nonionic and cationic
components required herein. For example, the compositions may contain up to about
15%, preferably up to about 5%, and most preferably from about 0.001 to about 2%,
of a suds suppressor component. Typical suds suppressors useful in the compositions
of the present invention include, but are not limited to, these described below.
[0033] Preferred silicone-type suds suppressing additives are described in U.S. Patent 3,933,672,
issued January 20, 1976, Bartolotta et al., incorporated herein by reference. The
silicone material can be represented by alkylated polysiloxane materials such as silica
aerogels and xerogels and hydrophobic silicas of various types. -The silicone material
can be described as a siloxane having the formula:
wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups,
especially methyl, ethyl, propyl, butyl and phenyl. Polydimethylsiloxanes (R and R'
are methyl, having a molecular weight within the range of from about 200 to about
200,000, and higher, are all useful as suds controlling agents. Additional suitable
silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed
alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples
of such ingredients include diethyl-, dipropyl-, dibutyl-, methylethyl-, phenylmethyl-polysiloxanes
and the like. Additional useful silicone suds controlling agents can be represented
by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica.
Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
A preferred silicone suds controlling agent is represented by a hydrophobic silanated
(most preferably trimethylsila- nated) silica having a particle size in the range
from about 10 millimicrons to 20 millimicrons and a specific surface area above about
50 m
2/gm intimately admixed with dimethyl silicone fluid having a molecular weight in the
range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica
of from about 19:1 to about 1:2. The silicone suds suppressing agent is advantageously
releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active,
detergent-impermeable carrier.
[0034] Particularly useful suds suppressors are the self- emulsifying silicone suds suppressors,
described in U.S. Patent 4,136,045, Gault et al., issued
January 23, 1979,incorporated herein by reference. An example of such a compound is
DB-544, commercially available from
Dow Corning, which contains a siloxane/glycol copolymer together with solid silica
and a siloxane resin.
[0035] Microcrystalline waxes having a melting point in the range from 35°C-115°C and a
saponification value of less than 100 represent additional examples of a preferred
suds regulating component for use in the subject compositions, and are described in
detail in U.S. Patent 4,056,481, Tate, issued November 1, 1977, incorporated herein
by reference. The microcrystalline waxes are substantially water-insoluble, but are
water-dispersible in the presence of organic surfactants. Preferred microcrystalline
waxes have a melting point from about 65°C to 100°C, a molecular weight in the range
from 400-1,000; and a penetration value of at least 6, measured at 77°F by ASTM-D1321.
Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline
petrolatum waxes: Fischer-Tropsch and oxidized
Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba
wax.
[0036] Alkyl phosphate esters represent an additional preferred suds suppressant for use
herein. These preferred phosphate esters are predominantly monostearyl phosphate which,
in addition thereto, can contain di- and tristearyl phosphates and monoleyl phosphates,
which can contain di- and trioleyl phosphates.
[0037] The alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly,
a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g.
monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to
about 5 mole percent of trialkyl phosphate.
[0038] Other adjunct components which may be included in the compositions of the present
invention, in their conventional art-established levels for use (i.e., from about
0 to about 40%), include semi-polar nonionic (such as amine oxides), anionic, zwitterionic
and ampholytic cosurfactants; detergency builders; bleaching agents; bleach activators;
soil release agents (particularly copolymers of ethylene terephthalate and polyethylene
oxide terephthalate, such as Milease T sold by ICI, United States, as disclosed in
U.S. Patent Application Serial No. 895,682, Nicol, filed April 12, 1978, incorporated
herein by reference); soil suspending agents; corrosion inhibitors; dyes; fillers;
optical brighteners; germicides; pH adjusting agents; alkalinity sources; hydrotropes;
enzymes; enzyme-stabilizing agents; perfumes; solvents; carriers; suds modifiers;
opacifiers; and the like. However, because of the numerous and diverse performance
advantages of the present invention, certain conventional components, such as cosurfactants
and detergency builders, as well as fabric softening and static control agents, will
not generally be necessary in a particular formulation, giving the compositions of
the present invention a potential cost advantage over conventional detergent/softener
compositions. In fact, because the compositions of the present invention give such
outstanding clay removal performance, even in a builder-free environment, and across
the range of water hardness conditions, for environmental reasons the compositions
of the present invention contain less than about 15% phosphate materials. Preferred
compositions contain less than 7% phosphate, and may even be substantially, or totally
free of such phosphate materials, without decreasing the performance of the composi--
tions. Further, in order to achieve optimal particulate soil removal performance,
the compositions of the present invention contain less than 10%, and are preferably
substantially free of, silicate materials. Preferred compositions of the present invention
are also substantially free of carboxymethylcellulose in order to optimize the clay
removal performance of the system. Finally, while the compositions of the present
invention may contain anionic materials, such as anionic surfactants and hydrotropes
(e.g., alkali metal toluene sulfonates), it is preferred that particular anionic materials
be contained in amounts sufficiently small such that not more than about 10%, preferably
not more than about 5%, of the cationic surfactant, contained in the laundry solution,
is complexed by the anionic material. Such a complexing of the anionic material with
the cationic surfactant, decreases the overall cleaning and fabric conditioning performance
of the composition. Suitable anionic materials may be selected based on their strength
of complexation with the cationic material included in the composition (as indicated
by their dissociation constant). Thus, when an anionic material has a dissociation
constant of at least about 1 x 10
-3 (such as sodium toluene sulfonate), it may be contained in an amount up to about
40%, by weight, of the cationic surfactant; where the anionic material has a dissociation
constant of at least about 1 x 10
5, but less than about 1 x 10
-3, it may be contained in an amount up to about 15%, by weight, of the cationic surfactant;
and where the anionic material has a dissociation constant of less than about 1 x
10
-5 (such as sodium C
11-8 linear alkylbenzene sulfonate), it may be contained only in amounts up to about 10%,
by weight, of the cationic surfactant. Preferred compositions are substantially free
of such anionic materials.
[0039] Examples of cosurfactants and detergency builders which may be used in the compositions.
of the present invention are found in U.S. Patent No. 3,717,630, Booth, issued February
20, 1973, and U.S. Patent Application Serial No. 919,181, Murphy, filed June 26, 1978,
both of which are incorporated herein by reference. However, these components, particularly
the anionic surfactants, should be checked with the particular nonionic/cationic surfactant
system chosen, and used in an amount, so as to be certain that they will be compatible
with the nonionic/cationic surfactant system.
[0040] Compositions of the present invention may contain from about 0.0u5% to about 3%,
preferably from about 0.01% to about 1% of an optical brightener. Nonionic brighteners
are preferred because of their compatibility with the nonionic and cationic surfactants
utilized herein. Suitable and preferred brighteners are disclosed in the copending
U.S. Patent Application of Lowell W. Bernardino and Joseph McGrady for BRIGHTENER
CONTAINING LAUNDRY DETERGENT COMPOSITIONS, Serial No. 003,567, filed January 15, 1979,
said application being incorporated herein by reference. Nonionic brighteners include
those of the coumarin and benzoxazole classes; a particularly preferred brightener
being 4-methyl-7-diethyl amino coumarin, commercially available under the tradename
Tinopal SWN from Ciba-Geigy Corp., Ardsley, N.Y., Hiltamine Arctic White SOL, available
from Hilton-Davis Chemical Co., Cincinnati, Ohio, and Calcofluor White SD, available
from American Cyanamid, Wayne, N.J. Other brighteners useful herein include bis (benzoxazol-2-yl)triophenes,
1,2-bis(benzoxazol-2-yl) ethylenes, l,4bis(benzoxazol-2-yl)naphthalenes, 4,4'-bis
(benzoxazol-2-yl)-stilbenes, 2-(styryl)benzoxazoles, 2 (styryl)naphthoxazole, or 2-(4-phenylstilben-4'-yl)-5-tertbutyl
benzoxazole.
[0041] Preferred compositions of the present invention contain from about 0.05% to about
1.5%, preferably from about 0.05% to about l%,.and most preferably from about 0.1%
to about 0.8%, of polyacids capable of forming water-soluble calcium complexes, such
as organo-phosphonic acids, particularly alkylene-polyamino-polyalkylene phosphonic
acids. These materials include ethylenediamine tetramethylene phosphonic acid, hexamethylene
diaminetetramethylene phosphonic acid, diethylene triaminepentamethylene phosphonic
acid, and amino-trimethylene phosphonic acid.
[0042] Other preferred embodiments of the present invention include an alkaline proteolytic
enzyme having an iso-electric point of greater than about 8. The enzyme is present
in an amount from 0.001% to about 2%, preferably from about 0.005% to about 0.8%,
especially from about 0.02% to about 0.2%, and are particularly useful when used in
conjunction with the polyacids, described above. The most preferred proteolytic enzyme
preparations for use in this invention are derived from bacillus subtilis, such as
ALCALASE, manufactured by Hovo Industri A/S, and MAXATASE, manufactured by Gist-Brocades
N.V. These most preferred enzyme species have an iso-electric point in the range from
about 8.5 to about 9.2.
[0043] These polyacid and enzyme components, as well as the benefits they provide, are discussed
in detail in U.S. Latent 4,100,262, Arnau et al., issued August 29, 1978, and U.S.
Patent 4,111,855, Barrat et al., issued September 5, 1978, both of which are incorporated
herein by reference. Compositions which include these components are particularly
useful for the hand-laundering of fine fabrics, such as wool.
[0044] The compositions of the present invention may be produced in a variety of forms,
including liquid, solid, granular, paste, powder or substrate compositions. Preferred
substrate articles may be formulated according to U.S. Patent Application Serial No.
781,378, Flesher et al, filed March 25, 1977, incorporated herein by reference. In
a particularly preferred embodiment, the compositions of the present invention are
formulated as liquids and contain up to about 20% of a lower alkyl (C
l to C
4) alcohol, particularly ethanol. Liquid compositions containing lower levels of such
alcohols (i.e., about 7 to 12%) tend to exhibit less phase separation than compositions
containing higher alcohol levels.
[0045] The compositions of the present invention are used in the laundering process by forming
an aqueous solution containing from about 0.01 (100 parts per million) to about 0.3%
(3,000 parts per million), preferably from about 0.02 to about 0.2%, and most preferably
from about 0.03 to about 0.15%, of the nonionic/cationic detergent mixture, and agitating
the soiled fabrics in that solution. The fabrics are then rinsed and dried. When used
in this manner, the compositions of the present invention yield exceptionally good
particulate soil removal, and also provide fabric softening, static control, color
fidelity, and dye transfer inhibition to the laundered fabrics, without requiring
the use of any of the other conventionally-used fabric softening and/or static control
laundry additives.
[0046] All percentages, parts, and ratios used herein are by weight unless otherwise specified.
[0047] The following nonlimiting examples illustrate the compositions and the method of
the present invention.
EXAMPLE I
[0048] The particulate soil removal performance of the present invention was tested against
a built, commercially-available heavy duty laundry detergent composition, in the manner
described below. Composition A, a liquid composition of the present invention, was
formulated by mixing together the components given below; Control 1 is a more conventional
granular detergent formulation.
Composition A
[0049]
1Condensation product of C
12-13 alcohol, having about 20% 2-methyl branching, with 6.5 moles of ethylene oxide, commercially
available from Shell Chemical Company.
Control 1
[0050]
[0051] For each test, 3 cotton and 3 polyester fabric swatches were used. The swatches were
stained with a slurry of clay in water; the 6 swatches containing a total of about
1.5 grams of the clay material. For each treatment, the 6 swatches were run through
one cycle (which includes pre- dissolve, wash, rinse, and spin steps) of a 1.5 gallon
capacity automatic mini-washer. Composition A was used in the washer at a concentration
of about 1800 parts per million (an active concentration of 620 ppm), while Control
1 was used at a concentration of about 1,500 parts per million. The swatches were
machine dried, and the particulate soil removal for each treatment was determined
using a Hunter Whiteness Meter. The results, given below, are in filtered Hunter Whiteness
Units, with higher numbers indicating better particulate removal. The above procedures
were carried out using 100°F wash water containing 7 and 12 grains per gallon of mixed
calcium and magnesium hardness, and using a wash temperature of 125°F, at a hardness
of 7 grains per gallon.
[0052] These data demonstrate the superior particulate soil removal performance, over a
range of wash temperature, water hardness and fabric conditions, of the compositions
of the present invention when compared with a more conventional laundry detergent
formulation. It must be emphasized that Composition A, a totally unbuilt composition,
demonstrated these benefits, in spite of the fact that Control 1 contains significant
amounts of phosphate builder materials.
[0053] Similar cleaning results are obtained when the cationic surfactant in Composition
A is replaced, in whole or in part, by ditallowalkyldimethylammonium methyl sulfate,
ditallowalkyldimethylammonium iodide, dihexadecylalkyldimethylammonium chloride, dihexadecylalkyldihydroxylethylammonium
methyl sulfate, dioctadecylalkyldimethylammonium chloride, dieicosylalkyl methyl ethyl
ammonium chloride, dieicosylalkyl dimethylammonium bromide, methyl (1) tallowalkyl
amido ethyl (2) tallowalkyl imidazolinium methyl sulfate, or mixtures of these surfactants.
[0054] Substantially similar results are also obtained where the nonionic surfactant in
Composition A is replaced, in whole or in part, by the condensation product of C14-15
alcohol with 2.25 moles of ethylene oxide; the condensation product of C
14-15 alcohol with 7 moles of ethylene oxide; the condensation product of C
12-15 alcohol with 9 moles of ethylene oxide; the condensation product of C12-13 alcohol
with 6.5 moles of ethylene oxide, which is stripped so as to remove lower ethoxylate
and nonethoxylated fractions; the condensation product of coconut alcohol with 5 moles
of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene
oxide; the condensation product of C
12-15 alcohol with 7 moles of ethylene oxide; the condensation product of tallow alcohol
with 9 moles of ethylene oxide; a 1:1 by weight mixture of the condensation product
of C
12-15 alcohol with 7 moles of ethylene oxide and the condensation product of C
14-15 alcohol with 7 moles of ethylene oxide; and other mixtures of those surfactants.
[0055] Excellent cleaning results are also obtained where the ratio of nonionic surfactant
to cationic surfactant used in Composition A is about 2:1, 3:1, 3.5:1, 4.5:1, 5:1,
6:1 or
EXAMPLE II
[0056] The dye transfer inhibition properties of Composition A of Example I were compared
to those of a more conventional, built laundry detergent composition in the following
manner.
Control 2
[0057]
While a full size automatic washing machine was filling with 100°F water, having a
mixed calcium/magnesium hardness of 7 grains per gallon, the detergent compositions
were added to the wash solution. In one set of runs, Composition A was used at a level
of 1400 parts per million (an active concentration of 500 ppm), while in the second
set of runs Control 2 was used at a concentration of about 1500 parts per million.
After the washing machine was filled with water, four white cotton terry fabrics and
one piece (9" x 20") of navy blue sweatshirt were added to the wash solution. After
one complete washing cycle, the fabrics were removed and dried.
[0058] Upon visual inspection it was seen that while the fabrics washed with Composition
A were still white, those wasched in Control 2 had a noticeable blue tinge. To confirm
these visual results, a Hunter Whiteness Meter was used to determine the "b" value
of the laundered fabrics. This ''b" value indicates the amount of blue color in the
fabric; with 0 indicating no blue color present, and increasingly negative numbers
denoting increasing amounts of blue color in the fabric. On two runs with Composition
A, the Hunter "b" readings were 0 on each run. However, on two runs using Control
2, Hunter "b" readings of -4 and -5, indicating a definite presence of blue color
in the fabrics, were obtained. These data demonstrate that Composition A, a composition
of the present invention, was able to inhibit the transfer of dye from the blue sweatshirt
fabric onto the white cotton terry fabrics, while Control 2, a more conventional laundry
detergent composition, was not able to effectively do so.
EXAMPLE III
[0059] Using the method described in Example II, the dye transfer inhibition properties
of a composition of the present invention were tested against a similar composition
which included a mono-long chain quaternary ammonium surfactant, rather than the required
di-long chain quaternary ammonium surfactant.
[0060] Before the test procedud was begun, the white cotton terry fabrics used were found
to have a Hunter Whiteness "b" value of -0.78. One set of terries was washed using
Composition A, of Example I, at a usage concentration of about 1400 parts per million,
while a second set of cotton terries was washed in a similar composition containing
a mixture of Neodol 23-6.5 and tallowalkyltrimethylammonium chloride, in a nonionic;cationic
ratio of 4:1, at a usage concentration of about 1400 parts per million. After washing
in the presence of the blue sweatshirt material and drying, the terries washed with
Composition A were found to have a Hunter Whiteness "b" value of -0.79; a value essentially
equivalent to the value of the terries prior to the wash. The terries washed with
the tallowalkyltrimethylammonium chloride composition were found to have a Hunter
Whiteness "b" value of -2.13. These data demonstrate that the compositions of the
present invention, which utilize di-long chain quaternary ammonium materials, offer
a dye transfer inhibition benefit which is far superior to that offered by similar
mixtures of nonionic and cationic surfactants, which utilize a conventional mono-long
chain quaternary ammonium surfactant of similar chain length.
EXAMPLE IV
[0061] The static control benefits of a liquid detergent composition of the present invention,
having the specific formulation given below, were demonstrated in the following manner.
The composition was formulated by combining the ingredients in the proportions stated.
[0062] A load of clothing was washed in a full size washing machine, using the composition
given above at a usage concentration of about 1400 parts per million in 22 gallons
of 100°F water, having a hardness of about 7 grains per gallon. The composition had
a pH of about 8 in the laundry solution. The load consisted of about 33 pieces of
clothing and contained cotton, polyester/cotton, nylon and polyester materials. The
washed load was subsequently placed in an automatic dryer, the drum of which had been
cleaned with an alcohol-soaked cloth, and dried for a period of 60 minutes. The fabric
load was then removed from the dryer and placed in a grounded Faraday Cage. The overall
charge reading of the materials in the Faraday Cage was read and recorded as individual
items were removed from the Cage. When all the fabrics had been removed, the total
voltage charge for the fabric load could be determined. This value was then divided
by the total area of the fabric load (18.5 sq. yds.) to determine the voltage per
square yard of the load.
[0063] The composition, described above, gave a voltage per square yard reading of 0.95,
with no individual clings of fabrics observed as they were removed from the Faraday
Cage. Conventional laundry detergent compositions, tested in the same manner, generally
give voltage per square yard readings of between about 4 and 10 volts per square yard,
with numerous individual clings being observed, depending upon the relative humidity
at the time the test is carried out. Thus, it is seen that the compositions of the
present invention give excellent static control performance when compared to conventional
laundry detergent compositions.
EXAMPLE V
[0064] A heavy duty liquid laundry detergent composition, having the formula given below,
is made by combining the ingredients in the proportions specified.
[0065] This composition demonstrates outstanding removal of particulate soils, and fabric
softening, static control, and dye transfer inhibition benefits when used to launder
fabrics. The composition may also contain relatively small amounts of conventional
opacifiers, such as about 0.05% of Ti0
2, to enhance its appearance.
EXAMPLE VI
[0066] A liquid laundry detergent product of the present invention is formulated by combining
the components given below in the proportions specified.
[0067] This composition gives excellent removal of particulate soils, as well as static
control, fabric softening and dye transfer inhibition benefits, in the automatic laundering
process. This composition may also be adsorbed onto a finely divided water-insoluble
carrier,. such that the carrier constitutes about 20% by weight of the total composition,
in order to form a particulate detergent product. Further, the composition may be
coated onto a woven or nonwoven substrate sheet, dried, and used in the laundering
process.
EXAMPLE VII
[0068] A liquid laundry detergent composition, having the formulation given below, is made
by combining the components in the proportions specified.
[0069] This composition provides excellent cleaning of particulate soils, as well as static
control, fabric softening and dye transfer inhibition benefits, when used in the conventional
automatic laundering process.
[0070] Substantially similar results are also obtained where the above composition contains
lauramide in place of the coconut ammonia amide.
[0071] Excellent cleaning results are also obtained where the above composition additionally
contains monoethanolamine, diethanolamine or triethanolamine, as an alkalinity source.
[0072] Similar performance is also obtained where the suds suppressor component in the above
composition is replaced, in whole or in part, by a silicone suds suppressor selected
from the group consisting of trimethyl-, diethyl-, dipropyl-, dibutyl-, methylethyl-,
phenylmethyl polysiloxane, and mixtures thereof; a petrolatum or oxidized petrolatum
wax; a Fischer-Tropsch or oxidized Fischer-Tropsch wax; ozokerite; ceresin; montan
wax; beeswax; candelilla; or carnauba wax.
[0073] Substantially similar performance is also obtained where the above composition additionally
contains sodium silicate, at an amount of about 3% of the total composition.
EXAMPLE VIII
[0074] A heavy duty liquid laundry detergent composition, having the formula given below,
is made by combining the ingredients in the proportions specified.
[0075] This composition demonstrates outstanding removal of particulate soils, and fabric
softening, static control, and dye transfer inhibition benefits when used to launder
fabrics.
EXAMPLE IX
[0076] A heavy duty liquid laundry detergent composition, having the formula given below,
is made by combining the ingredients in the proportions specified.
[0077] This composition demonstrates outstanding removal of particulate soils, and fabric
softening, static control and dye transfer inhibition benefits when used to launder
fabrics.
[0078] Substantially similar results are obtained where the coconutalkyl monoethanol amide
is replaced, in whole or in part, by coconutalkyl diethanolamide or an amide having
the formula
wherein R is a coconutalkyl group or a C
16 alkyl group.
[0079] Excellent results are also obtained where the amide and brightener components in
the above composition are removed, and are replaced by water.
EXAMPLE X
[0080] A heavy duty liquid laundry detergent composition, having the formula given below,
is made by combining the ingredients in the proportions specified.
[0081] This composition demonstrates outstanding removal of particulate soils, and fabric
softening, static control and dye transfer inhibition benefits when used to launder
fabrics. In addition, the composition provides benefits over similar compositions
utilizing more conventional cationic components, such as ditallowalkyldimethylammonium
chloride, in terms of improved static control and particulate soil removal (especially
at lower wash temperatures) and better processing characteristics, in that it forms
a single phase product which remains stable at lower storage temperatures.
EXAMPLE XI
[0082] A heavy duty liquid detergent composition.
EXAMPLE XII
[0083] A liquid detergent composition which is particularly useful in cleaning and softening
in the hand-washing of fine fabrics.