U.S. patent number 3,844,952 [Application Number 05/249,815] was granted by the patent office on 1974-10-29 for detergent compositions.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Gary Edwin Booth.
United States Patent |
3,844,952 |
Booth |
October 29, 1974 |
DETERGENT COMPOSITIONS
Abstract
Laundry detergent and fabric softener compositions containing
various detergent-compatible disubstituted polyol softeners and, in
a preferred embodiment, polyalkyleneimine anti-static agents.
Inventors: |
Booth; Gary Edwin (Cincinnati,
OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
22945133 |
Appl.
No.: |
05/249,815 |
Filed: |
May 3, 1972 |
Current U.S.
Class: |
510/333; 510/324;
510/505; 510/515; 510/527; 510/506; 510/501; 510/325; 510/327;
510/499; 510/328; 510/332 |
Current CPC
Class: |
C11D
3/3723 (20130101); C11D 3/2093 (20130101); D06M
15/53 (20130101); D06M 13/48 (20130101); C11D
3/001 (20130101); C11D 3/2065 (20130101); C11D
3/221 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); D06M 15/53 (20060101); D06M
15/37 (20060101); D06M 13/00 (20060101); D06M
13/48 (20060101); C11D 3/37 (20060101); C11D
3/20 (20060101); D06m 013/16 (); D06m 013/18 ();
C11d 001/00 () |
Field of
Search: |
;252/8.6,8.9,540,559,8.75,89,108,109,525,544,DIG.1
;117/139.5C,139.5Q ;260/410,615R,410.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Guynn; Herbert B.
Attorney, Agent or Firm: Schaeffer; Jack D. O'Flaherty;
Thomas H. Witte; Richard C.
Claims
1. A detergent composition consisting essentially of: (1) from
about 5 to about 30 percent by weight of a water-soluble organic
detergent compound; (2) from about 25 to about 75 percent by weight
of a water-soluble detergency builder; (3) from about 2 to about 15
percent by weight of an .alpha.,.omega.-disubstituted derivative of
a non-cyclic, hygroscopic polyol, said derivative having the
formula ##SPC10##
wherein x is an integer of from 3 to 7 and each R is an alkyl or
alkanoyl group containing at least 16 carbon atoms; and (4) from
about 0.5 to about 1.5 percent by weight of a polyalkyleneimine
compound containing the moiety ##SPC11##
wherein y is an integer from 1 to 4, z is an integer greater than
1, and R.sup.1 is selected from the group consisting of hydrogen
and alkyl and alkanoyl substituents containing from about 1 to
about 22 carbon atoms, said polyalkyleneimine having from about 5
to about 100 percent of the nitrogen atoms substituted with said
alkyl or alkanoyl substituents, the polyalkyleneimine having a
molecular weight of from about 200 to 1
2. A composition according to claim 1 wherein the organic detergent
compound is a water-soluble salt of an organic sulfuric acid
reaction product having in the molecular structure an alkyl
substituent containing about 8 to about 22 carbon atoms and a
substituent selected from the group consisting of sulfonic and
sulfuric acid ester moieties; and the polyalkyleneimine has from
about 10 to about 60 percent of the nitrogen atoms substituted with
the alkyl or alkanoyl substituents and has a
3. A composition according to claim 1 wherein the organic detergent
compound is an alkali metal salt of a fatty acid containing from 8
to 24 carbon atoms; and the polyalkyleneimine has from about 10 to
about 60 percent of the nitrogen atoms substituted with the alkyl
or alkanoyl
4. A composition according to claim 1 wherein the organic detergent
compound is sodium linear dodecylbenzene sulfonate; and the
5. A composition according to claim 4 wherein the disubstituted
polyol is a member selected from the group consisting of
1,6-distearoyl sorbitol,
6. A composition according to claim 5 wherein the polyalkyleneimine
has the
7. A composition according to claim 1 wherein the polyalkyleneimine
compound is polyethyleneimine having a molecular weight in the
range from
8. A composition according to claim 1 wherein the water-soluble
detergency builder is selected from the group consisting of sodium
nitrilotriacetate,
9. A fabric softening composition consisting essentially of: (1)
from about 10% to about 50 percent by weight of an
.alpha.,.omega.-disubstituted derivative of a non-cyclic,
hygroscopic polyol, said derivative having the formula
##SPC12##
wherein x is an integer of from 3 to 7 and each R is an alkyl or
alkanoyl group containing at least 16 carbon atoms; and (2) from
about 50 to about 90 percent by weight of a water-soluble carrier
selected from the group consisting of sodium carbonate, sodium
bicarbonate, sodium silicate,
10. A composition according to claim 9 wherein the disubstituted
polyol is a member selected from the group consisting of
1,6-distearoyl sorbitol,
11. A composition according to claim 9 containing as an additional
component from about 0.5 to about 2 percent by weight of a
polyalkyleneimine compound containing the moiety ##SPC13##
wherein y is an integer from 1 to 4, z is an integer greater than
1, and R.sup.1 is selected from the group consisting of hydrogen
and alkyl and alkanoyl substituents containing from about 1 to
about 22 carbon atoms, said polyalkyleneimine having from about 5
to about 100 percent of the nitrogen atoms substituted with said
alkyl or alkanoyl substituents, the polyalkyleneimine having a
molecular weight of from about 200 to 1
12. A composition according to claim 11 wherein the
polyalkyleneimine has a molecular weight of from about 200 to 2000
and from about 15 to 40 percent
13. A process for softening fabrics consisting essentially of
adding an .alpha.,.omega.-disubstituted derivative of a non-cyclic,
hygroscopic polyol, said derivative having the formula
##SPC14##
wherein x is an integer of from 3 to 7 and each R is an alkyl or
alkanoyl group containing at least 16 carbon atoms to an aqueous
laundry bath containing fabrics at a concentration of at least
about 20 ppm, and
14. A process according to claim 13 wherein the disubstituted
polyol is
15. A process according to claim 13 wherein the disubstituted
polyol is a member selected from the group consisting of
1,6-distearoyl sorbitol,
16. A process according to claim 13 wherein a polyalkyleneimine
compound containing the moiety ##SPC15##
wherein y is an integer from 1 to 4, z is an integer greater than
1, and R.sup.1 is selected from the group consisting of hydrogen
and alkyl and alkanoyl substituents containing from about 1 to
about 22 carbon atoms, said polyalkyleneimine having from about 5
to about 100 percent of the nitrogen atoms substituted with said
alkyl or alkanoyl substituents, the polyalkyleneimine having a
molecular weight of from about 200 to 1 million, and being
water-soluble or water-dispersible is added to the laundry bath
concurrently with the disubstituted polyol at a concentration
17. A process according to claim 16 wherein the polyalkyleneimine
has a molecular weight of from about 200 to 2000 and from about 15
to 40 percent of the nitrogen atoms are substituted with stearoyl
substituents.
Description
BACKGROUND OF THE INVENTION
The present invention relates to laundering compositions containing
certain disubstituted polyol fabric softeners and certain polyamine
anti-static agents. These materials can be used in the presence of
detergents to soften fabrics concurrently with laundering.
Textile softeners and anti-static agents are used commercially to
improve the handle of fabrics and to reduce the annoyance of static
electrical charges on fabric surfaces. A variety of cationic
materials, such as the dimethyl-di(hydrogenated tallow)ammonium
halide salts, are widely used in the textile industry for this
purpose. Similar cationic fabric softener and antistatic
compositions are available for home use and usually consist of a
solution or suspension of a cationic nitrogen compound similar to
those used industrially. It has long been recognized that these
cationic materials, although highly effective when properly
applied, are incompatible with the anionic organic detergent
compounds widely used in home laundering processes. For this
reason, the user of such materials has heretofore been constrained
to wait until the final rinse of the laundering process before
adding the fabric softening and anti-static material to the
laundering bath, or washing machines having specially designed
fabric softener dispensers have had to be developed.
The aforementioned problem regarding the stepwise use of fabric
softening agents in laundering operations would be obviated were
fabric softening and anti-static agents which are compatible with
modern built anionic detergent compositions available. Such agents
could then be added to the laundering bath in conjunction with the
detergent as a mixed composition to provide fabric cleansing,
softening and anti-static benefits concurrently. Since this problem
is widely recognized by the formulators of detergents and fabric
softeners, a variety of materials have been suggested for use as
detergent-compatible fabric softeners and anti-static agents. For
example, U.S. Pat. No. 3,454,494 discloses a textile softener
composition which is compatible with anionic detergents comprising
an acid salt of a condensation product of a fatty acid and an
aliphatic polyfunctional amine co-condensed with a polyoxyalkylene
compound. South African application 69/3923 discloses fabric
softeners comprising certain N-2-hydroxy higher alkyl amines said
to be suitable for use as detergent-compatible fabric softeners.
Polyalkyleneimine fabric softeners can be used in built anionic
detergent compositions.
Nonionic fabric softeners are compatible with anionic detergents
inasmuch as there are no functional groups in such compounds which
are capable of interacting with the anionic portion of the
detergents. For example, Canadian Patent No. 871,667 discloses the
use of 1,2-alkanediols as fabric softeners in conjunction with
anionic detergents. However, these nonionic fabric softeners
provide only marginal fabric softening benefits and are incapable
of providing the anti-static benefits which are an important
consideration to the user of such products.
U.S. Pat. No. 2,409,056 relates to non-alkylated polyamines and
their use in soap to prevent rancidity. U.S. Pat. Nos. 2,296,226;
2,382,185; 2,185,480; and 2,272,489 describe the preparation of
various alkylated and alkanoylated polyamines and suggest their use
as fabric softeners in textile processing, but do not suggest the
use of these materials in conjunction with anionic detergents and
detergency builders.
To date, however, no truly effective fabric softener and
anti-static material which is compatible with the widely used
anionic detergent compounds and detergency builders has been
suggested and the prior art materials disclosed for this purpose
suffer from a variety of disadvantages. For example, the use of
polyalkyleneimine softeners exclusively can lead to yellowing of
some white fabrics. 1,2-Diglycol based softeners do not provide
substantial anti-static benefits. Many of the detergent-compatible
softeners suggested in the art are excessively water-soluble, and
good deposition on the fabrics is not achieved with such materials.
Accordingly, it is an object of this invention to provide improved
built laundry detergent compositions which possess significant
fabric softening and anti-static properties. A further object
herein is to provide a process for simultaneously washing and
softening fabrics while neutralizing static charge on said fabrics.
These and other objects are obtained by the present invention as
will become apparent from the following disclosure.
SUMMARY OF THE INVENTION
The present invention encompasses fabric softening laundry
detergent compositions comprising: (1) from about 5 to about 85
percent, preferably from about 5 to about 30 percent, by weight of
a water-soluble organic detergent compound as hereinafter detailed;
and (2) from about 2 to about 15 percent, preferably about 3.5 to
about 10 percent, by weight of an .alpha., .omega.-disubstituted
derivative of a non-cyclic, hygroscopic polyol, said derivative
having the formula ##SPC1##
wherein x is an integer of at least 3, preferably 4, and each R is
an alkyl or alkanoyl group containing at least 16, preferably 18 to
22, carbon atoms. In a preferred embodiment, the above-disclosed
detergent composition also contains as a detergent- and
builder-compatible anti-static component from about 0.5 to about
1.5 percent by weight of a polyalkyleneimine compound containing
the moiety ##SPC2##
wherein y is an integer from 1 to 4, preferably 2, z is an integer
greater than 1, preferably from about 20 to about 10,000, and
R.sup.1 is selected from the group consisting of hydrogen, and
alkyl and alkanoyl substituents containing from about 1 to about 22
carbon atoms, preferably from about 12 to about 18 carbon atoms,
said polyalkyleneimine having from 5 to about 100 percent,
preferably about 10 to about 20 percent, of the nitrogen atoms
substituted with said alkyl or alkanoyl substituents.
Especially preferred detergent compositions herein contain as an
additional component about 85 percent, preferably 25 to 75 percent
by weight, of a water-soluble detergency builder salt. Optionally,
a minor amount of laundry adjuncts such as optical brighteners,
enzymes, perfumes and the like can be present in the compositions
herein.
In addition, this invention encompasses a method of softening
fabrics in aqueous laundering baths containing built organic
detergent compositions, especially those containing anionic
detergent compounds, comprising adding an
.alpha.,.omega.-disubstituted polyol of the type disclosed herein
to said bath at a concentration of disubstituted polyol of at least
about 20 ppm, preferably from about 75 ppm to about 300 ppm. Fabric
softening is thereby provided concurrently with cleansing. In a
preferred method, a polyalkyleneimine compound of the type
disclosed above is concurrently added to the laundering bath at a
concentration of polyalkyleneimine of at least about 5 ppm,
preferably 10 ppm to about 20 ppm, to provide an anti-static fabric
finish concurrently with the cleansing and softening.
The foregoing benefits can also be achieved by adding the herein
described disubstituted polyol and polyalkyleneimine materials to a
substantially detergent-free aqueous laundry rinse bath at the
concentrations noted above.
DETAILED DESCRIPTION OF THE INVENTION
The disubstituted (a term which includes dialkylated and
dialkanoylated)polyol softeners of this invention are derivatives
of linear, hygroscopic polyols and have the general formula
##SPC3##
wherein x is an integer of at least about 3, preferably 3 to 7,
most preferably 4, and each R is an alkyl or alkanoyl group
containing at least 16 carbon atoms. The above formula depicts the
.alpha.,.omega.-disubstituted polyols which are preferred
herein.
The disubstituted polyols herein have two aspects of criticality in
addition to the limitations on x and R noted above. First, they
must have a substantially linear (i.e., non-cyclic) configuration
in the polyol portion of the molecule; substituted cyclic polyols
(e.g., the "Sorbitans") have been found not to be useful as fabric
softeners. Apparently, the linear configuration of the
disubstituted polyols herein allows them to interact more strongly
with fabric surfaces than the cyclic polyols and provide the more
complete surface coating necessary to impart softness.
Secondly, the disubstituted polyols herein must be derivatives of
unsubstituted polyol compounds which are, themselves, hygroscopic,
i.e., those which absorb 20 to 100 percent by weight of water on
standing at a temperature of about 70.degree.F and a relative
humidity of about 20 to 99 percent.
As noted above, the .alpha.,.omega.-disubstituted polyols useful
herein are limited to those which are derivatives of hygroscopic
linear polyols. There are a variety of such polyols (polyhydric
alcohols; also termed alditols) which can be prepared, for example,
by the reduction of naturally-occurring sugars, e.g., using sodium
amalgam, electrolysis and the like. The existing polyols include
four unbranched pentitols of the formula HOCH.sub.2 (CHOH).sub.3
CH.sub.2 OH derived from D-arabinose, L-arabinose, ribose and
xylose.
There are 10 hexitols of the formula HOCH.sub.2 (CHOH).sub.4
CH.sub.2 OH prepared, for example, from glucose, altrose, tallose,
galactose, idose, talose and mannose.
There are 16 straight chain heptitols of the formula HOCH.sub.2
(CHOH).sub.5 CH.sub.2 OH, which can be prepared from the 32
naturally-occurring aldoheptoses. In addition, there are various
straight chain octitols and nonitols which can be prepared by
controlled cleavage of complex natural sugars, followed by
reduction of aldehyic and ketonic functionalities to alcohol
groups.
It is to be understood that, of the foregoing linear polyhydric
alcohols, only those which are hygroscopic are suitable for use in
the preparation of the .alpha.,.omega.-disubstituted polyol fabric
softeners herein. Thus, the requisite hygroscopic nature of the
polyol provides a basis for selection of appropriate polyols which
can be converted to di-substituted polyol fabric softeners in the
manner hereinafter described. Preferred hygroscopic polyols for
this purpose include sorbitol (most preferred), xylitol, and
iditol.
The disubstituted (which includes dialkylated and dialkanoylated)
derivatives of the foregoing polyols suitable for use as fabric
softeners in the present invention are prepared by standard
procedures well-known in the art. For example, the dialkylated
polyols herein can be prepared by reacting 20 moles of an alkyl
halide with 1 mole of polyol, preferably in the presence of a metal
catalyst such as magnesium or copper, in the general manner of the
Williamson ether synthesis. For this purpose, alkyl chlorides,
bromides, and iodides having from about 16 to about 22 carbon
atoms, preferably 18 to 22 carbon atoms, in their molecular
structure are suitable.
The preferred disubstituted polyols used herein are those wherein
each R group is alkanoyl. These can be prepared in standard fashion
by reacting 2 moles of a carboxylic acid or acid halide with 1 mole
of a polyol. When acid halides are employed the reaction is
preferably done in the presence of an organic base (e.g., pyridine,
morpholine and the like) so that the reaction proceeds with the
formation of the desired disubstituted polyol and the base
hydrohalide. Acid chlorides, bromides, and iodides are suitable for
this purpose; acid chlorides are preferred. Alternatively, lower
alkyl esters of acids can be admixed at a mole ratio of 2:1 with
the polyols and heated with the liberation of a lower alcohol and
the formation of the disubstituted polyol. For this purpose, the
methyl, ethyl and propyl esters of acids having an alkyl carbon
chain of from about C.sub.16 to about C.sub.22, preferably about
C.sub.18 to about C.sub.22, are suitable herein.
Disubstituted polyol materials prepared in the foregoing manner
will have two substituent groups in the molecule; substitution can
occur at any of the hydroxyl groups of the polyol. However, the
major products of such reactions have been found to be
disubstituted polyols wherein the .alpha. and .omega. hydroxyl
groups are substituted. It is to be understood that while the
.alpha.,.omega.-disubstituted polyols are the preferred fabric
softeners herein, they may be contaminated with minor portions of
the other disubstituted polyols. This in no way limits their use
herein. However, the major proportion of the substituted polyols
must be .alpha.,.omega.-disubstituted.
Exemplary acids, esters acid halides and alkyl halides suitable for
preparing the disubstituted polyols herein include palmitic acid
and its acid halides, ethyl palmitate, stearic acid and its acid
halides, ethyl stearate, eicosanoic acid and its acid halides,
methyl eicosanate, docosanoic acid and its acid halides, and ethyl
docosanate. Alkyl halides suitable herein include 1-hexadecyl
chloride, 1-octadecyl bromide, 1-eicosyl chloride, 1-docosyl
bromide, 1-octadecyl chloride, 1-eicosyl iodide, 1-octadecyl iodide
and eicosyl chloride. Stearic acid and its acid chloride are
preferred herein from an economic standpoint. Eicosanoic acid and
docosanoic acid are preferred from the standpoint of preparing
disubstituted polyols which exhibit optimum softening
performance.
From the foregoing it can be seen that a variety of alkyl halides,
organic acids and acid halides and esters having from about
C.sub.16 to about C.sub.22, preferably from about C.sub.18 to about
C.sub.22, carbon atoms in the alkyl or alkanoyl groups can be used
with linear, hygroscopic polyols of the formula HOCH.sub.2
(CHOH).sub.x CH.sub.2 OH, wherein x is an integer as defined above,
to provide disubstituted polyols of the type used herein. Exemplary
disubstituted polyols suitable for use in the present invention
include the diesters: 1,6-distearoyl sorbitol, 1,6-bis-eicosanoyl
sorbitol, 1,6-bis-docosanoyl sorbitol, 1,5-distearoyl xylitol,
1,5-bis-eicosanoyl xylitol, 1,5-bis-docosanoyl xylitol,
1,6-distearoyl iditol, 1,6-bis-eicosanoyl iditol and
1,6-bis-docosanoyl iditol. Exemplary diether-type disubstituted
polyols useful herein include: 1,6-distearyl sorbitol,
1,6-bis-eicosanyl sorbitol, 1,6-bis-docosanyl sorbitol,
1,5-bis-eicosanyl xylitol, 1,5-distearyl xylitol, 1,5-bis-docosanyl
xylitol, 1,6-distearyl iditol, 1,6-bis-eicosanyl iditol and
1,6-bis-docosanyl iditol. The preferred
.alpha.,.omega.-disubstituted polyol softeners herein are
1,6-distearoyl sorbitol, 1,6-bis-eicosanoyl sorbitol and
1,6-bis-docosanoyl sorbitol. From a cost standpoint, the
1,6-distearoyl sorbitol is most preferred. From a performance
standpoint, the 1,6-bis-eicosanoyl and 1,6-bis-docosanoyl sorbitols
are preferred.
While the disubstituted polyols herein provide superior fabric
softening benefits, they provide only marginal anti-static effects
to the treated fabrics. Accordingly, in a preferred embodiment
herein a detergent- and builder-compatible compatible anti-static
agent is used concurrently with the disubstituted polyol and the
desired softening and antistatic benefits are thereby provided. The
polyalkyleneimines having the hereinabove disclosed formula are
employed herein as the detergent-compatible fabric anti-static
agents. These materials comprise a polyalkyleneimine "backbone"
having pendant alkyl or alkanoyl groups on at least 5 percent of
the nitrogen atoms. These polymers are difficult to describe in
other than a qualitative manner. For example, one of the more
useful polyalkyleneimines used herein is alkylated or alkanoylated
polyethyleneimine. It is believed that the structural formula of
polyethyleneimine is ##SPC4##
wherein y is an integer greater than 1, usually about 2 to 100,000,
and R.sup.1 represents hydrogen and alkyl or alkanoyl groups, as
noted above. Branched chains occur along the polymeric backbone,
and the relative proportions of primary, secondary and tertiary
amino groups present in the polymer will vary, depending on the
manner of preparation. The distribution of amino groups in a
typical polyethyleneimine is approximately as follows:
--CH.sub.2 CH.sub.2 --NH.sub.2 30%
--CH.sub.2 --CH.sub.2 --NH-- 40%
--CH.sub.2 --CH.sub.2 --N-- 30%
The polyethyleneimine can only be characterized in terms of
molecular weight. Such polymers can be prepared, for example, by
polymerizing ethyleneimine in the presence of a catalyst such as
carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide,
hydrochloric acid, acetic acid, etc.
Specific methods are described in U.S. Pat. Nos. 2,182,306;
3,033,746; 2,208,095; 2,806,836; and 2,553,696.
The alkylated and alkanoylated polyethyleneimines used herein are
obtained by heating alkyl halides or organic acids or acid halides
with the polyethyleneimine in the manner described in U.S. Pat.
Nos. 2,296,226; 2,272,489; and 2,185,480, incorporated herein by
reference. Other polyalkyleneimines are prepared in like fashion.
In the case of the alkanoylated polyalkyleneimines, the alkanoyl
groups are attached to the polymer backbone by amide linkages.
Various ratios of alkylating or alkanoylating agent to
polyalkyleneimine "backbone" can be employed so that varying
percentages of the nitrogen atoms are thereby substituted.
Polyalkyleneimines having various percentages of the nitrogen
functionalities substituted with alkyl or alkanoyl groups are
designated hereinafter as "20 percent stearoylated
polyethyleneimine," "50 percent docosylated polybutyleneimine,"
etc., according to the percentage of nitrogen groups in the polymer
which are substituted. The percentage nitrogen substitution can be
determined, for example, by an examination of the proton magnetic
resonance or the infrared spectrum of the polymer. The alkylated
and alkanoylated polyalkyleneimines, having molecular weights in
the range of about 200 to about 1 million, are useful herein. The
lower molecular weight, less highly substituted polyalkyleneimines
of this group are substantially water-soluble while the higher
molecular weight members are water-dispersible; both the
water-soluble and water-dispersible polyalkyleneimines are suitable
for the present use. Preferred herein are alkylated and
alkanoylated polyalkyleneimines, especially polyethyleneimines,
having a molecular weight in the range of about 600 to 100,000,
wherein from about 10 to about 60 percent of the nitrogen groups
are alkylated or alkanoylated. Polyethyleneimine having a molecular
weight range of about 200 to 2,000, most preferably 600 to 1,200,
and which is from about 15 to about 40 percent stearoylated, most
preferably 20 percent stearoylated, is especially preferred for use
herein as the detergent compatible anti-static agent.
The .alpha.,.omega.-disubstituted polyol fabric softeners described
above are simply admixed with the polyalkyleneimines and are
employed with all manner of soap and organic detergent compounds in
conjunction with all manner of detergency builder salts to provide
the softening, cleansing and anti-static compositions of this
invention. Surprisingly, although the disubstituted polyols and
polyalkyleneimines compete for deposition on the fabric surface, a
portion of both kinds of materials apparently deposits thereon to
provide the desired softening and anti-static benefits
concurrently. The following describes typical soaps, synthetic
organic detergent compounds and builder salts suitable for use with
the disubstituted polyol softeners of this inventon or with the
combination of disubstituted polyols and polyalkyleneimines, but is
not intended to be limiting thereof.
ORGANIC DETERGENTS
The organic detergent compounds which can be utilized with the
combination of detergent- and soap-compatible
.alpha.,.omega.-disubstituted polyols and polyalkyleneimines in the
laundering compositions and processes encompassed by this invention
include the following:
A. Anionic Soap and Non-Soap Synthetic Detergents
This class of detergents includes ordinary alkali metal soaps such
as the sodium, potassium, ammonium and alkanolammonium salts of
higher fatty acids containing from about 8 to about 24 carbon atoms
and preferably from about 10 to about 20 carbon atoms. Suitable
fatty acids can be obtained from natural sources such as, for
instance, plant or animal esters (e.g., palm oil, coconut oil,
babassu oil, soybean oil, castor oil, tallow, whale and fish oils,
grease, lard, and mixtures thereof). The fatty acids also can be
synthetically prepared (e.g., by the oxidation of petroleum, or by
hydrogenation of carbon monoxide by the Fischer-Tropsch process).
Resin acids are suitable such as rosin and those resin in tall oil.
Naphthenic acids are also suitable. Sodium and potassium soaps can
be made by direct saponification of the fats and oils or by the
neutralization of the free fatty acids which are prepared in a
separate manufacturing process. Particularly useful are the sodium
and potassium salts of the mixtures of fatty acids derived from
coconut oil and tallow, i.e., sodium or potassium tallow and
coconut soap.
This class of detergents also includes water-soluble salts,
particularly the alkali metal salts, of organic sulfuric reaction
products having in their molecular structure an alkyl substituent
containing from about 8 to about 22 carbon atoms and a sulfonic
acid or sulfuric acid ester moiety. (Included in the term alkyl is
the alkyl portion of higher acyl substituent.) Examples of this
group of synthetic detergents which form a part of the preferred
built detergent compositions of the present invention are the
sodium or potassium alkyl sulfates, especially those obtained by
sulfating the higher alcohols (C.sub.8 -C.sub.18 carbon atoms)
produced by reducing the glycerides of tallow or coconut oil;
sodium or potassium alkyl benzene sulfonates, in which the alkyl
group contains from about 9 to about 15 carbon atoms in straight
chain or branched chain configuration, e.g., those of the type
described in U.S. Pat. Nos. 2,220,099 and 2,477,383 (especially
valuable are linear straight chain alkyl benzene sulfonates in
which the average of the alkyl groups is about 13 carbon atoms and
commonly abbreviated as C.sub.13 LAS); sodium alkyl glyceryl ether
sulfonates, especially those ethers of higher alcohols derived from
tallow and coconut oil; sodium coconut oil fatty acid monoglyceride
sulfonates and sulfates; sodium or potassium salts of sulfuric acid
esters of the reaction product of 1 mole of a higher fatty alcohol
(e.g. tallow or coconut oil alcohols) and about 1 to 6 moles of
ethylene oxide; sodium or potassium salts of alkyl phenol ethylene
oxide ether sulfate with about 1 to about 10 units of ethylene
oxide per molecule and in which the alkyl radicals contain about 8
to about 12 carbon atoms.
Anionic phosphate surfactants are also useful in the present
invention. These are surface active materials having substantial
detergent capability in which the anionic solubilizing group
connecting hydrophobic moieties in an oxy acid of phosphorus. The
more common solubilizing groups, of course, are --SO.sub.4 H,
--SO.sub.3 H, and --CO.sub.2 H. Alkyl phosphate esters such as
(R-O).sub.2 PO.sub.2 H and ROPO.sub.3 H.sub.2 in which R represents
an alkyl chain containing from about 8 to about 20 carbon atoms are
useful.
These esters can be modified by including in the molecule from one
to about 40 alkylene oxide units, e.g., ethylene oxide units.
Formulae for these modified phosphate anionic detergents are
##SPC5##
in which R represents an alkyl group containing from about 8 to 20
carbon atoms, or an alkylphenyl group in which the alkyl group
contains from about 8 to 20 carbon atoms, and M represents a
water-soluble cation such as hydrogen, sodium, potassium, ammonium
or substituted ammonium; and in which n is an integer from 1 to
about 40.
Another class of suitable anionic organic detergents particularly
useful in this invention includes salts of
2-acyloxyalkane-1-sulfonic acids. These salts have the formula
##SPC6##
where R.sub.1 is alkyl of about 9 to about 23 carbon atoms (forming
with the two carbon atoms an alkane group); R.sub.2 is alkyl of 1
to about 8 carbon atoms; and M is a water-soluble cation.
The water-soluble cation, M, in the hereinbefore described
structural formula can be, for example, an alkali metal cation
(e.g., sodium, potassium, lithium), ammonium or
substituted-ammonium cation. Specific examples of substituted
ammonium cations include methyl-, dimethyl-a and trimethyl-
ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperidinium cations and those
derived from alkylamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like.
Specific examples of .beta.-acyloxy-alkane-1-sulfonates, or
alternatively 2-acyloxy-alkane-1-sulfonates, useful herein to
provide superior cleaning levels under substantially neutral
washing conditions include the sodium salt of
2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of
2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of
2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of
2-pentanoyloxy-pentadecane-1-sulfonic acid; the sodium salt of
2-acetoxy-hexadecane-1-sulfonic acid; the potassium salt of
2-octanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of
2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of
2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of
2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of
2-acetoxy-uncosane-1-sulfonic acid; the isomers thereof.
Preferred .beta.-acyloxy-alkane-1-sulfonate salts herein are the
alkali metal salts of .beta.-acetoxy-alkane-1-sulfonic acids
corresponding to the above formula wherein R.sub.1 is alkyl of
about 12 to about 16 carbon atoms, these salts being preferred from
the standpoints of their excellent cleaning properties and ready
availability.
Typical examples of the above-described .beta.-acetoxy
alkanesulfonates are described in the literature: Belgium Patent
No. 650,323 discloses the preparation of certain 2-acyloxy
alkanesulfonic acids. Similarly, U.S. Pat. Nos. 2,094,451 and
2,086,215 disclose certain salts of .beta.-acetoxy alkanesulfonic
acids. These patents are hereby incorporated by reference.
Another preferred class of anionic detergent compounds herein, both
by virtue of superior cleaning properties and low sensitivity to
water hardness (Ca++ and Mg++ ions) are the alkylated
.beta.-sulfocarboxylates, containing about 10 to about 23 carbon
atoms, and having the formula ##SPC7##
wherein R is C.sub.8 to C.sub.20 alkyl, M is a water-soluble cation
as hereinbefore disclosed, preferably sodium ion, and R' is
short-chain alkyl, e.g., methyl, ethyl, propyl, and butyl. These
compounds are prepared by the esterification of .alpha.-sulfonated
carboxylic acids, which are commercially available, using standard
techniques. Specific examples of the alkylated
.alpha.-sulfocarboxylates preferred for use herein include:
ammonium methyl-.alpha.-sulfopalmitate,
triethanolammonium ethyl-.alpha.-sulfostearate,
sodium methyl-.alpha.-sulfopalmitate,
sodium ethyl-.alpha.-sulfopalmitate,
sodium butyl-.alpha.-sulfostearate,
potassium methyl-.alpha.-sulfolaurate,
lithium methyl-.alpha.-sulfolaurate,
as well as mixtures thereof.
A preferred class of anionic organic detergents are the
.beta.-alkyloxy alkane sulfonates. These compounds have the
following formula: ##SPC8##
where R.sub.1 is a straight chain alkyl group having from 6 to 20
carbon atoms, R.sub.2 is a lower alkyl group having from 1
(preferred) to 3 carbon atoms, and M is a water-soluble cation as
hereinbefore described.
Specific examples of .beta.-alkyloxy alkane sulfonates, or
alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness
(calcium ion) sensitivity useful herein to provide superior
cleaning levels under household washing conditions include:
potassium-.beta.-methoxydecanesulfonate,
sodium 2-methoxytridecanesulfonate,
potassium 2-ethoxytetradecylsulfonate,
sodium 2-isopropoxyhexadecylsulfonate,
lithium 2-t-butoxytetradecylsulfonate,
sodium .beta.-methoxyoctadecylsulfonate, and
ammonium .beta.-n-propoxydodecylsulfonate.
Other synthetic anionic detergents useful herein are alkyl ether
sulfates. These materials have the formula RO(C.sub.2 H.sub.4
O).sub.x SO.sub.3 M wherein R is alkyl or alkenyl of about 10 to
about 20 carbon atoms, x is 1 to 30, and M is a water-soluble
cation as defined hereinbefore. The alkyl ether sulfates useful in
the present invention are condensation products of ethylene oxide
and monohydric alcohols having about 10 to about 20 carbon atoms.
Preferably, R has 14 to 18 carbon atoms. The alcohols can be
derived from fats, e.g., coconut oil or tallow, or can be
synthetic. Lauryl alcohol and straight chain alcohols derived from
tallow are preferred herein. Such alcohols are reacted with 1 to
30, and especially 6, molar proportins of ethylene oxide and the
resulting mixture of molecular species, having, for example, an
average of 6 moles of ethylene oxide per mole of alcohol, is
sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention
are sodium coconut alkyl ethylene glycol ether sulfate; lithium
tallow alkyl triethylene glycol ether sulfate; and sodium tallow
alkyl hexaoxyethylene sulfate.
Preferred herein for reasons of excellent cleaning properties and
ready availability are the alkali metal coconut- and tallow-alkyl
oxyethylene ether sulfates having an average of about 1 to about 10
oxyethylene moieties. The alkyl ether sulfates of the present
invention are known compounds and are described in U.S. Pat. No.
3,332,876, incorporated herein by reference.
Additional examples of anionic non-soap synthetic detergents which
come within the terms of the present invention are the reaction
product of fatty acids esterified with isethionic acid and
neutralized with sodium hydroxide where, for example, the fatty
acids are derived from coconut oil; sodium or potassium salts of
fatty acid amides of methyl tauride in which the fatty acids, for
example, are derived from coconut oil. Other anionic synthetic
detergents of this variety are set forth in U.S. Pat. Nos.
2,486,921; 2,486,922; and 2,396,278.
Additional examples of anionic, non-soap, synthetic detergents,
which come within the terms of the present invention, are the
compounds which contain two anionic functional groups. These are
referred to as di-anionic detergents. Suitable di-anionic
detergents are the disulfonates, disulfates, or mixtures thereof
which may be represented by the following formulae;
R(SO.sub.3).sub.2 M.sub.2, R(SO.sub.4).sub.2 M.sub.2, R(SO.sub.3)
(SO.sub.4)M.sub.2,
where R is an acyclic aliphatic hydrocarbyl group having 15 to 20
carbon atoms and M is a water-solubilizing cation, for example, the
C.sub.15 to C.sub.20 disodium 1,2-alkyldisulfates, C.sub.15 to
C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium
1,9-hexadecyl disulfates, C.sub.15 to C.sub.20
disodium-1,2-alkyldisulfonates, disodium 1,9-stearyldisulfates and
6,10-octadecyldisulfates.
The aliphatic portion of the disulfates or disulfonates is
generally substantially linear, thereby imparting desirable
biodegradable properties to the detergent compound.
The water-solubilizing cations include the customary cations known
in the detergent art, i.e., the alkali metals, and the ammonium
cations, as well as other metals in group IIA, IIB, IIIA, IVA and
IVB of the Periodic Table except for boron. The preferred
water-solubilizing cations are sodium or potassium. These dianionic
detergents are more fully described in British Letters Patent No.
1,151,392.
Still other anionic synthetic detergents include the class
designated as succinamates. This class includes such surface active
agents as disodium N-octadecylsulfosuccinamate; tetrasodium
N-(1,2-dicarboxyethyl)-N-octadecyl-sulfo-succinamate; diamyl ester
of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic
acid; dioctyl esters of sodium sulfosuccinic acid.
Other suitable anionic detergents utilizable herein are olefin
sulfonates having about 12 to about 24 carbon atoms. The term
"olefin sulfonates" is used herein to mean compounds which can be
produced by the sulfonate of .alpha.-olefins by means of
uncomplexed sulfur trioxide, followed by neutralization of the acid
reaction mixture in conditions such that any sultones which have
been formed in the reaction are hydrolyzed to give the
corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be
liquid or gaseous, and is usually, but not necessarily, diluted by
inert diluents, for example by liquid SO.sub.2, chlorinated
hydrocarbons, etc., when used in the liquid form, or by air,
nitrogen, gaseous SO.sub.2, etc., when used in the gaseous
form.
The .alpha.-olefins from which the olefin sulfonates are derived
are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16
carbon atoms. Preferably, they are straight chain olefins. Examples
of suitable 1-olefins include 1-dodecene; 1-tetradecene;
1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.
In addition to the true alkene sulfonates and a proportion of
hydroxy-alkanesulfonates, the olefin sulfonates can contain minor
amounts of other materials, such as alkene disulfonates depending
upon the reaction conditions, proportion of reactants, the nature
of the starting olefins and impurities in the olefin stock and side
reactions during the sulfonate process.
A specific anionic detergent which has also been found excellent
for use in the present invention is described more fully in the
U.S. Pat. No. 3,332,880, incorporated herein by reference.
B. Nonionic Synthetic Detergents
Nonionic synthetic detergents may be broadly defined as compounds
produced by the condensation of alkylene oxide groups (hydrophilic
in nature) with an organic hydrophobic compound, which may be
aliphatic or alkyl aromatic in nature. The length of the
hydrophilic or polyoxyalkylene radical which is condensed with any
particular hydrophobic group can be readily adjusted to yield a
water-soluble compound having the desired degree of balance between
hydrophilic and hydrophobic elements.
For example, a well known class of nonionic synthetic detergents is
made available on the market under the trade name of "Pluronic."
These compounds are formed by condensing ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with
propylene glycol. The hydrophobic portion of the molecule which, of
course, exhibits water insolubility, has a molecular weight of from
about 1500 to 1800. The addition of polyoxyethylene radicals to
this hydrophobic portion tends to increase the water solubility of
the molecule as a whole and the liquid character of the product is
retained up to the point where polyoxyethylene content is about 50
percent of the total weight of the condensation product.
Other suitable nonionic synthetic detergents include:
1. The polyethylene oxide condensates of alkyl phenols, e.g., the
condensation products of alkyl phenols having an alkyl group
containing from about 6 to 12 carbon atoms in either a straight
chain or branched chain configuration, with ethylene oxide, the
said ethylene oxide being present in amounts equal to 5 to 25 moles
of ethylene oxide per mole of alkyl phenol. The alkyl substituent
in such compounds may be derived from polymerized propylene,
diisobutylene, octene, or nonene, for example.
2. Compounds derived from the condensation of ethylene oxide with
the product resulting from the reaction of propylene oxide and
ethylene diamine. For example, compounds containing from about 40
to about 80 percent polyoxyethylene by weight and having a
molecular weight of from about 5,000 to about 11,000 resulting from
the reaction of ethylene oxide groups with a hydrophobic base
constituted of the reaction product of ethylene diamine and excess
propylene oxide, said base having a molecular weight of the order
of 2,500 to 3,000, are satisfactory.
3. The condensation product of aliphatic alcohols having from 8 to
22 carbon atoms, in either straight chain or branched chain
configuration with ethylene oxide, e.g., a coconut alcohol-ethylene
oxide condensate having from 5 to 30 moles of ethylene oxide per
mole of coconut alcohol, the coconut alcohol fraction having from
10 to 14 carbon atoms.
4. Nonionic detergents include nonyl phenol condensed with about 10
to about 30 moles of ethylene oxide per mole of phenol; the
condensation products of coconut alcohol with an average of either
about 5.5 or about 15 moles of ethylene oxide per mole of alcohol,
and, the condensation product of about 15 moles of ethylene oxide
with one mole of tridecanol.
Other examples include dodecylphenol condensed with 12 moles of
ethylene oxide per mole of phenol; dinonylphenol condensed with 15
moles of ethylene oxide per mole of phenol; dodecyl mercaptan
condensed with 10 moles of ethylene oxide per mole of mercaptan;
bis-(N-2-hydroxyethyl)lauramide; nonyl phenol condensed with 20
moles of ethylene oxide per mole of nonyl phenol; myristyl alcohol
condensed with 10 moles of ethylene oxide per mole of myristyl
alcohol; lauramide condensed with 15 moles of ethylene oxide per
mole of lauramide; and di-isooctylphenol condensed with 15 moles of
ethylene oxide.
5. A detergent having the formula R.sup.1 R.sup.2 R.sup.3 N.fwdarw.
O (amine oxide detergent) wherein R.sup.1 is an alkyl group
containing from about 10 to about 28 carbon atoms, from 0 to about
2 hydroxy groups and from 0 to about 5 ether linkages, there being
at least one moiety of R.sup.1 which is an alkyl group containing
from about 10 to about 18 carbon atoms and 0 ether linkages, and
each R.sup.2 and R.sup.3 are selected from the group consisting of
alkyl radicals and hydroxyalkyl radicals containing from 1 to about
3 carbon atoms.
Specific examples of amine oxide detergents include:
dimethyldodecylamine oxide, dimethyltetradecylamine oxide,
ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,
dimethylstearylamine oxide, cetylethylpropylamine oxide,
diethyldodecylamine oxide, diethyltetradecylamine oxide,
di-propyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine
oxide, bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,
(2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleyamine
oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the
corresponding decyl, hexadecyl and octadecyl homologs of the above
compounds.
6. A detergent having the formula R.sup.1 R.sup.2 R.sup.3 P.fwdarw.
O (phosphine oxide detergent) wherein R.sup.1 is an alkyl group
containing from about 10 to about 28 carbon atoms, from 0 to about
2 hydroxy groups and from 0 to about 5 ether linkages, there being
at least one moiety of R.sup.1 which is an alkyl group containing
from about 10 to about 18 carbon atoms and 0 ether linkages, and
each of R.sup.2 and R.sup.3 are selected from the group consisting
of alkyl radicals and hydroxyalkyl radicals containing from 1 to
about 3 carbon atoms.
Specific examples of the phosphine oxide detergents include:
dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide,
ethylmethyltetradecylphosphine oxide, catyldimethylphosphine oxide,
dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide,
diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide,
dipropyldodecylphosphine oxide, bis(hydroxymethyl)dodecylphosphine
oxide, bis-(2-hydroxyethyl)dodecylphosphine oxide,
(2-hydroxypropyl)methyltetradecylphosphine oxide,
dimethyloleylphosphine oxide, and
dimethyl-(2-hydroxydodecyl)phosphine oxide and the corresponding
decyl, hexadecyl, and octadecyl homologs of the above
compounds.
7. A detergent having the formula ##SPC9##
(sulfoxide detergent) wherein R.sup.1 is an alkyl radical
containing from about 10 to about 28 carbon atoms, from 0 to about
5 ether linkages and from 0 to about 2 hydroxyl substituents at
least 1 moiety of R.sup.1 being an alkyl radical containing 0 ether
linkages and containing from about 10 to about 18 carbon atoms, and
wherein R.sup.2 is an alkyl radical containing from 1 to 3 carbon
atoms and from 1 to 2 hydroxyl groups: e.g., octadecyl methyl
sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide,
3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl
sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl
2-hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.
C. Ampholytic Synthetic Detergents
Ampholytic synthetic detergents can be broadly described as
derivatives of aliphatic or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical may be
straight chain or branched and wherein one of the aliphatic
substituents contains from about 8 to 18 carbon atoms and at least
one contains an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfato. Examples of compounds falling within this
definition are sodium 3-(dodecylamino)propionate, sodium
3-(dodecylamino)propane-1sulfonate, sodium 2-(dodecylamino)ethyl
sulfate, sodium 2-(dimethylamino)octadecanoate, disodium
3-(N-carboxymethyldodecylamino)propane-1-sulfonate, disodium
octadecyl-iminodiazetate, sodium
1-carboxymethyl-2-undecylimidazole, and sodium
N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
D. Zwitterionic Synthetic Detergents
Zwitterionic synthetic detergents can be broadly described as
derivatives of aliphatic quaternary ammonium and phosphonium or
tertiary sulfonium compounds, in which the cationic atom may be
part of a heterocyclic ring, and in which the aliphatic radical may
be straight chain or branched, and wherein one of the aliphatic
substituents contains from about 3 to 18 carbon atoms, and at least
one aliphatic substituent contains an anionic water-solubilizing
group, e.g., carboxy, sulfonate, sulfato, phosphato, or phosphono.
Examples of compounds falling within this definition are
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate,
3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate,
2-(N,N-dimethyl-N-dodecylammonio)acetate, 3-(N,N-dimethyl
N-dodecylammonio)-propionate,
2-(N,N-dimethyl-N-octadecylammonio)ethyl sulfate,
2-(trimethylammonio)ethyl dodecylphosphonate, ethyl
3-(N,N-dimethyl-N-dodecylammonio)propylphosphonate,
3-(P,P-dimethyl-P-dodecylphosphonio)propane-1-sulfonate,
2-(S-methyl-S-tert-hexadecyl-sulfonio)ethane-1-sulfonate,
3-(S-methyl-S-dodecylsulfonio)propionate, sodium
2-(N,N-dimethyl-N-dodecylammonio)ethyl phosphonate,
4-(S-methyl-S-tetradecylsulfonio)butyrate,
1-(2-hydroxyethyl)-2-undecylimidazolium-1-acetate,
2-(trimethylammonio)octadecanoate, and
3-N,N-bis-(2-hydroxyethyl-N-octodecylammonio)-2-hydroxypropane-1-sulfonate
. Some of these detergents are described in the following U.S. Nos.
2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332. The
ammoniopropane sulfonates containing about 8 to about 21 carbon
atoms are one class of detergent compounds preferred herein by
virtue of their relatively low calcium ion (hardness)
sensitivity.
Builder Salts
The detergent compositions herein can contain water-soluble
detergency builder salts, either of the organic or inorganic types,
and these are wholly compatible with the
.alpha.,.omega.-disubstituted polyol softeners and the
polyalkyleneimine antistatic agents, and with the hereinabove
disclosed organic detergent compounds to provide the combined built
detergent-fabric softener-anti-static compositions of this
invention.
Non-limiting examples of suitable water-soluble inorganic alkaline
detergency builder salts are the alkali metal carbonates, borates,
phosphates, polyphosphates, bicarbonates, silicates and sulfates.
Specific examples of such salts are sodium and potassium
tetraborates, perborates, bicarbonates, carbonates,
tripolyphosphates, pyrophosphates, orthophosphates and
hexametaphosphates.
Examples of suitable organic alkaline detergency builder salts are:
(1) water-soluble aminopolyacetates, e.g., sodium and potassium
ethylenediaminetetraacetates, nitrilotriacetates and
N-(2-hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of
phytic acid, e.g., sodium and potassium phytates - see U.S. Pat.
No. 2,739,942; (3) water-soluble polyphosphonates, including
specifically, sodium potassium and lithium salts of
ethane-1hydroxy-1,1-diphosphonic acid, sodium potassium and lithium
salts of methylene diphosphonic acid, sodium, potassium and lithium
salts of ethylene diphosphonic acid, and sodium potassium and
lithium salts of ethane-1,1,2-triphosphonic acid. Other examples
include these alkali metal salts of
ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic
acid, carbonyldiphosphonic acid,
ethane-1-hydroxy-1,1,2-triphosphonic acid,
ethane-2-hydroxy-1,1,2-triphosphonic acid,
propane-1,1,3,3-tetraphosphonic acid, and
propane-1,1,2,3-tetraphosphonic acid, and
propane-1,2,2,3-tetraphosphonic acid; water-soluble salts of
polycarboxylate polymers and copolymers as described in U.S. Pat.
No. 3,308,067.
The polycarboxylate materials described in U.S. Pat. No. 2,264,103,
are also suitably employed herein. For example, aconitic acid,
mellitic acid and the tetra- and penta-carboxylic acids prepared by
the malonic acid synthesis are also suitable for use herein as
builders, as are the phloroglucinoltrisulfonates, (ethylenedioxy)
diacetates, and oxydisuccinates. Especially preferred are the
water-soluble alkali metal salts of these compounds.
Mixtures of organic and/or inorganic builders can be used and are
generally desirable. One such mixture of builders is disclosed in
Canadian Patent No. 755,038, e.g., ternary mixtures of sodium
tripolyphosphate, trisodium nitrilotriacetate and trisodium
ethane-1-hydroxy-1,1diphosphonate. The above-described builders can
also be utilized singly in this invention. Preferred builders
herein include sodium tripolyphosphate, sodium citrate, sodium
nitrilotriacetate and sodium mellitate. (The term "sodium"
encompasses di-sodium, tri-sodium, etc., depending on the number of
anionic counterion groups in the anionic portion of the builder
molecular.)
The ratio of water-soluble organic detergent compound: builder in
the built detergent compositions herein can be in the range of from
about 1:100 to 1:1 (wt.), preferably about 1:10 to 1:20 (wt.).
As noted above, it is a method aspect of this invention to add a
composition comprising a .alpha.,.omega.-disubstituted polyol of
the type disclosed above, preferably containing a polyalkyleneimine
as herein described, to aqueous, detergent-containing laundering
baths in concentrations of disubstituted polyol of about 20 ppm,
and greater, and concentrations of polyalkyleneimines of about 10
ppm, and greater, to achieve simultaneous fabric cleansing,
softening and anti-static benefits. In this method aspect, the
combination of disubstituted polyol and polyalkyleneimine is
preferably added as a component of a detergent composition, as
herein detailed. However, fabric softener compositions comprising
from about 10 to about 50 percent by weight of the
.alpha.,.omega.-disubstituted polyol, from about 50 to about 90
percent of a solid or liquid carrier, and preferably from about 0.5
to about 2 percent by weight of the polyalkyleneimine, can also be
added to laundry baths containing built or unbuilt detergent
compositions to provide the desired softening and anti-static
benefits. Such compositions are also encompassed by this invention.
Useful carriers in such compositions include liquids in which the
disubstituted polyols and polyalkyleneimines are stable as
solutions or suspensions. Inert solid carriers (preferably
water-soluble) can also be employed. Such carriers must be
compatible with laundry detergents, builders, bleaches and like
materials employed in common laundering operations. Exemplary
liquid carriers suitable in such compositions include water
(preferred), the lower alcohols, e.g., methanol, ethanol, propanol,
iso-propanol and the like, the lower ketones, e.g., acetone, and
mixtures thereof. Solid carriers include sodium carbonate, sodium
bicarbonate, sodium silicate, sodium phosphate, sodium
tripolyphosphate, as well as any of the other water-soluble solid
materials disclosed hereinabove as builders. Such
softener-anti-static compositions are stable and effective when
added to laundering baths containing any of the hereinbefore
detailed detergents and builders.
The detergent compositions of this invention can be in any of the
usual physical forms for such compositions, such as powders, beads,
flakes, bars, tablets, pastes and the like. The instant
compositions can contain other materials commonly used in laundry
detergents in minor amounts. For example, various soil suspending
agents, corrosion inhibitors, dyes, proteins, fillers, optical
brighteners, suds boosters, suds depressants, germicides,
anti-tarnishing agents, cationic materials, enzymes and the like,
well-known in the art for use in detergent compositions can be used
herein; water can also be present. The compositions are prepared
and utilized in the conventional manner.
Built detergents and soaps are used in the basic pH range, usually
from about pH 8 to 11.5. Some detergent materials can be employed
in the acid pH range. The pH of the washing system is immaterial
for the purposes of this invention in that the softener and
anti-static compositions of this invention function well over the
entire range of acidity and basicity. Most generally, the pH of the
aqueous laundry baths in which the compositions herein are used is
in the range from about pH 5 to pH 12.
Laundering bath temperatures are likewise immaterial in that the
compositions of this invention can be used at all common laundry
temperatures from about 50.degree.F to 212.degree.F, most
preferably 80.degree.F to 125.degree.F, with good results.
The following illustrates the preparation of a typical
disubstituted polyol fabric softener of the type used in this
invention.
Preparation of 1,6-distearoyl Sorbitol
182.17 g. (1.0 mole) of sorbitol (commercial grade) and 599.02 g.
(2.0 moles) of methyl stearate are admixed in the presence of about
1 liter of methanol. 0.1 Mole of sodium methoxide is added and the
mixture is stirred and refluxed for 48 hours. The methanol is
evaporated and the resulting pasty mass, which comprises > 90
percent 1,6-distearoyl sorbitol, is suitable for use as a fabric
softener herein.
In the above procedure, the methyl stearate is replaced by an
equivalent molar amount of the methyl esters of eicosanoic acid and
docosanoic acid, respectively, and 1,6-bis-eicosanoyl sorbitol and
1,6-bis-docosanoyl sorbitol are secured.
1,6-Distearyl sorbitol is prepared by admixing 2 moles of octadecyl
bromide with one mole of sorbitol in the presence of copper filing
and heating the mixture until HCl evolution ceases. The resulting
mass is water-washed and the water evaporated to yield
1,6-distearyl sorbitol.
In the above procedure the the sorbitol is replaced by an
equivalent amount of xylitol and 1,6-distearyl xylitol is
secured.
The following examples are typical combined built
detergent-softener and detergent-softener-antistatic formulations
containing the .alpha.,.omega.-disubstituted polyols and the
substituted polyalkyleneimines described hereinabove. The
formulations are for the purposes of illustration and are not
intended to be limiting to the types of formulations encompassed by
this invention.
Composition A ______________________________________ Weight Percent
7.8 sodium linear dodecylbenzenesulfonate 9.5 sodium
tallowalkylsulfate 49.4 sodium tripolyphosphate 5.9 sodium silicate
13.7 Na.sub.2 SO.sub.4 0.2 sodium carboxymethylcellulose 2.2
nonionic suds controlling agents 7.0 1,6-distearoyl sorbitol bal.
moisture ______________________________________
The above composition is used in an aqueous laundry bath at a rate
of 1.5 cups (.apprxeq.77 g.) per 10 gallons of water and
concurrently cleanses and softens nylon, polyester and cotton
fabrics.
Composition B ______________________________________ Weight Percent
5.0 dimethyldodecylphosphine oxide 10 condensation product of 11
moles of ethylene oxide with 1 mole of coconut fatty alcohol 10
tetrasodium methylenediphosphate 60 sodium tripolyphosphate 0.5
sodium carboxymethylcellulose 4.0 sodium silicate 9.0
1,6-bis-eicosanoyl sorbitol bal. moisture
______________________________________
The above composition is used as a rate of 1 cup/10 gallons of
water and cleanses and softens white cotton men's shirts without
yellowing.
The following examples illustrate the detergent-softener
compositions herein containing the polyalkyleneimine anti-static
agents.
Composition C ______________________________________ Weight Percent
______________________________________ 16.5 sodium linear
dodecylbenzenesulfonate 38 sodium tripolyphosphate 13 sodium
sulfate 11 sodium nitrilotriacetate 7.0 sodium silicate 2.0 sodium
toluenesulfonate 6.0 1,6-distearoyl sorbitol 3.0 20% stearoylated
polyethyleneimine (Mol. wt. of polyethyleneimine 600-1200) 1.0
additives* (optional) (approx.) bal. moisture
______________________________________ * Including perfumes,
enzymes and optical brighteners.
The above composition is used at a rate of 1 cup/10 gallons of
water and concurrently cleanses, softens and neutralizes static
charge on cotton, linen, nylon and polyester fabrics.
Composition D ______________________________________ Weight Percent
______________________________________ 30 sodium salt of 20:80
coconut:tallow fatty acids 10 sodium silicate (builder) 40
tetrasodium pyrophosphate (builder) -6.0 sodium chloride 4.0
1,6-distearoyl sorbitol 1.0 20% stearoylated - 10% methylated poly-
butyleneimine (avg. mol. wt. 20,000) 0.05 additives* (optional)
bal. moisture ______________________________________ * Including
perfumes and optical brighteners.
The above composition is used at a concentration of 1.5 cups/10
gallons of water and cleanses and provides antistatic and softening
benefits to cotton, nylon, polyester and cotton/polyester blend
fabrics.
In the above composition the builders are deleted and replaced by
an equivalent amount of the sodium salt of coconut: tallow fatty
acids. The unbuilt composition is used at a concentration of 1.5
cups/10 gallons of water and cleanses, softens and provides
anti-static benefits to nylon, and polyester fabrics.
The following compositions are used at a rate of about 70 g./10
gallons of water to provide cleansing and softening of cotton,
nylon and polyester fabrics while concurrently providing an
anti-static effect:
Composition E ______________________________________ Weight Percent
______________________________________ 7.0 sodium tallow alkyl
sulfate 7.0 sodium linear dodecylbenzenesulfonate 50 sodium
tripolyphosphate 10 sodium carbonate 10 sodium sulfate 5.0
potassium dichlorocyanurate (bleach) 5.5 1,6-bis-eicosanoyl
sorbitol 1.5 20% stearoylated polyethyleneimine (avg. - mol. wt.
25,000) 0.05 perfume bal. moisture
______________________________________
Composition F (liquid) ______________________________________
Weight Percent ______________________________________ 6.0
sodium-3-dodecylaminopropionate 6.0 sodium linear
dodecylbenzenesulfonate 20 potassium pyrophosphate 8.0 potassium
toluenesulfonate 3.8 sodium silicate 0.3
carboxymethylhydroxethylcellulose 15 1,6-distearyl sorbitol 5.0 60%
stearoylated polyethyleneimine (avg. mol. wt. 15,000) 0.05
additives* (optional) bal. water
______________________________________ * Including perfumes and
optical brighteners.
In the above composition the distearyl sorbitol is replaced by an
equivalent amount of dipalmityl sorbitol, biseicosyl sorbitol and
bis-docosyl xylitol, respectively, with equivalent results.
Composition G (liquid) ______________________________________
Weight Percent ______________________________________ 6.0 sodium
linear dodecylbenzenesulfonate 6.0 dimethyldodecylamine oxide 10
trisodium ethane-1-hydroxy-1,1- diphosphonate 10 tripotassium
toluenesulfonate 3.8 sodium silicate (ratio SiO.sub.2 :Na.sub.2 O
of 2:1) 5.0 potassium dichlorocyanurate (bleach) 0.3 sodium
carboxymethylcellulose 0.20 3-morpholino-2,5-diphenylfuran (optical
brightener) 7.5 1,6-bis-docosanoyl sorbitol 1.5 50% docosanoylated
polypropyleneimine (avg. mol. wt. 10,000) 0.10 perfume bal. water
______________________________________
Composition H ______________________________________ Weight Percent
______________________________________ 10 sodium salt of SO.sub.3
-sulfonated tetradecene 10 dimethyl coconutalkylammonio acetate 60
trisodium ethane-hydroxy triphosphonate 10 sodium carbonate 6.0
1,6-distearyl sorbitol:1,5-distearyl iditol (90:10 wt. mixture) 1.0
50% hexanoylated polybutyleneimine (avg. mol. wt. 200,000) bal.
moisture ______________________________________
Composition I ______________________________________ Weight Percent
______________________________________ 7.5 sodium linear
octadecylbenzenesulfonate 2.0 sodium tallowalkylsulfate 2.2
hydrogenated marine oil fatty acid suds depressant 30 sodium
tripolyphosphate 20 trisodium nitrilotriacetate 10 sodium silicate
(ratio SiO.sub.2 Na.sub.2 O of 2:1) 13 sodium sulfate 10
1,6-bis-docosanoyl xylitol 3.0 20% docosylated polymethyleneimine
(avg. mol. wt. 3,000) 0.20 perfume bal. moisture
______________________________________
Composition J ______________________________________ Weight Percent
______________________________________ 10 sodium linear
dodecylbenzenesulfonate 10 condensation product of 1 mole of nonyl
phenol with 12 moles of ethylene oxide 10 sodium tripolyphosphate
30 trisodium ethane-1-hydroxy-1,1- diphosphonate 10 trisodium
nitrilotriacetate 6.0 sodium silicate (ratio of SiO.sub.2 :Na.sub.2
O of 2:1) 10 trisodium phosphate 0.5 sodium carboxymethylcellulose
4.0 1,6-bis-docosanoyl sorbitol 1.0 40% stearoylated
polyethyleneimine (avg. mol. wt. 25,000) 0.1
3-phenyl-2,5-diphenylthiophene (optical brightener) 0.2
3-diethanolamino-2,5-di-p-methoxyphenylfuran (optical brightener)
bal. moisture ______________________________________
______________________________________ Composition K (For Cool
Water Use) ______________________________________ Weight Percent
______________________________________ 5.0 sodium
tallowalkylsulfate 12 3(N,N-dimethyl-N-dodecylammonio)-
2-hydroxy-propane-1-sulfonate 5.0 sodium salt of SO.sub.3
-sulfonated .alpha.-tridecene 25 sodium tripolyphosphate 15
trisodium nitrilotriacetate 10 sodium silicate (SIO.sub.2 :Na.sub.2
O = 1.6:1) 10 sodium sulfate 0.3 sodium
carboxymethylhydroxyethylcellulose 10.0 10:1 mixture of
1,6-distearoyl sorbitol and 1,5-distearoyl sorbitol 2.0 5%
stearoylated polyethyleneimine (avg. mol. wt. 20,000) 0.1
3-deca(oxyethylene)-2,5-diphenylfuran 0.05 perfume bal. moisture
______________________________________ Composition L (For Cool
Water Use) ______________________________________ Weight Percent
______________________________________ 5.0 sodium octyl sulfate 5.0
3(N,N-dimethyl-N-hexadecylammonio)- propane-1-sulfonate 10
dimethyldodecylphosphine oxide 5.0 trisodium ethane-1-hydroxy-1,1-
diphosphonate 10 trisodium nitrilotriacetate 10 sodium
tripolyphosphate 10 sodium silicate (Na.sub.2 O:SiO.sub.2 = 1:2.5)
0.3 sodium carboxymethylcellulose 10 sodium sulfate 20
1,6-dipalmitoyl sorbitol 5.0 25% stearoylated polyethyleneimine
(avg. mol. wt. 1,000,000) bal. moisture
______________________________________
The following example illustrates a typical fabric softener
composition of this invention.
Composition M ______________________________________ Weight Percent
______________________________________ 50 1,6-distearoyl sorbitol
50 sodium tripolyphosphate (carrier)
______________________________________
The above composition is added to laundry baths containing a
commercial anionic laundry detergent at a rate of 0.5 oz./10
gallons of water and cotton, nylon and polyester fabrics are
softened concurrently with washing.
In the above composition the 1,6-distearoyl sorbitol is replaced by
an equivalent amount of 1,6-bis-eicosanoyl sorbitol and
1,6-bis-docosanoyl sorbitol, respectively, and equivalent results
are secured.
The following examples illustrate the preferred combined fabric
softening and anti-static compositions of the instant invention
which can be added to laundry baths containing detergent
compositions.
Composition N ______________________________________ Weight Percent
______________________________________ 2 20% stearoylated
polyethyleneimine (mol. wt. of polyethyleneimine 600-1200) 50
1,6-distearoyl sorbitol bal. sodium carbonate (carrier)
______________________________________
The above composition is added to a laundry bath containing
compositions A through L, above, respectively at a rate of about 1
oz./16 gallons of water and nylon, polyester and cotton fabrics are
softened and provided with an anti-static finish concurrently with
washing.
In the above composition, the sodium carbonate is replaced by an
equivalent amount of sodium sulfate, sodium tripolyphosphate and
sodium nitrilotriacetate, respectively, and equivalent results are
secured.
In the above composition, the 20 percent stearoylated
polyethyleneimine is replaced by an equivalent amount of 60%
stearoylated polyethyleneimine, 100 percent stearoylated
polyethyleneimine and 50 percent hexanoylated polybutyleneimine,
respectively, and equivalent results are secured.
Composition O ______________________________________ Weight Percent
______________________________________ 25 1,6-distearoyl sorbitol
1.0 polyethyleneimine (PEI) 1.0 20% stearoylated polyethyleneimine
(mol. wt. of polyethyleneimine 600-1200) (20% SPEI) bal. water
(carrier) ______________________________________
The 1,6-distearoyl sorbitol, PEI, and 20% SPEI are suspended in the
water. The composition is shaken and admixed with a laundering bath
containing a commercial laundry detergent at a rate of about 1 oz.
of the said composition to about 10 gallons of water. Cotton,
polyester, nylon and polyester-cotton blended fabrics in the
laundering bath are concurrently cleansed and softened. The static
electric charge on the fabrics is neutralized.
In the above composition the 1,6-distearoyl sorbitol is replaced by
an equivalent amount of 1,6-bis-docosanoyl xylitol,
1,6-bis-docosanoyl iditol, 1,6-bis-palmitoyl sorbitol,
1,5-bis-palmitoyl iditol, 1,6-bis-palmityl sorbitol,
1,5-bis-palmityl iditol and 1,6-bis-eicosanoyl xylitol,
respectively, and equivalent results are secured.
* * * * *