U.S. patent number 3,637,511 [Application Number 04/825,984] was granted by the patent office on 1972-01-25 for detergent formulations.
This patent grant is currently assigned to Ethyl Corporation. Invention is credited to Meiling T. Yang.
United States Patent |
3,637,511 |
Yang |
January 25, 1972 |
DETERGENT FORMULATIONS
Abstract
To obviate eutrophication of water, nonphosphorus detergent
builders are provided. These are the water-soluble salts of
N,N,-di(carboxymethyl)-aspartic acid (e.g., the tetrasodium salt
thereof). Conventional detergent actives may be used with these
builders. Synthesis of the builders is described.
Inventors: |
Yang; Meiling T. (Baton Rouge,
LA) |
Assignee: |
Ethyl Corporation (New York,
NY)
|
Family
ID: |
25245391 |
Appl.
No.: |
04/825,984 |
Filed: |
May 19, 1969 |
Current U.S.
Class: |
510/337; 510/324;
510/357; 510/480; 510/361; 510/352; 510/325; 510/340; 562/571 |
Current CPC
Class: |
C11D
3/33 (20130101) |
Current International
Class: |
C11D
3/33 (20060101); C11D 3/26 (20060101); C11D
3/00 (20060101); C11d 003/30 () |
Field of
Search: |
;252/137,152
;260/534,534C,534E |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Halpern; M.
Claims
I claim:
1. A washing composition consisting essentially of an organic
detergent surfactant selected from the group consisting of anionic
detergents, cationic detergents, nonionic detergents, ampholytic
detergents, zwitterionic detergents, and mixtures of the above
suitable for use in water and, as a builder, a water-soluble salt
of N,N-di-(carboxymethyl)-aspartic acid selected from the group
consisting of alkali metal salts, ammonium salts, and alkyl
ammonium salts, the ratio by weight of the detergent surfactant to
the builder being in the range of about 1:10 to about 3:1.
2. The composition of claim 1 wherein said water-soluble salt is a
sodium salt.
3. The composition of claim 1 wherein said detergent surfactant is
one or a mixture of anionic detergents.
4. The composition of claim 1 additionally containing from about 2
to about 10 percent by weight based on the total weight of the
composition of a water-soluble alkali metal silicate.
5. The composition of claim 1 additionally containing up to about
60 percent by weight based on the total weight of the composition
of an alkali metal sulfate or an alkali metal carbonate, or
both.
6. The composition of claim 1 wherein said detergent surfactant is
one or a mixture of anionic detergents, wherein said salt is the
tetrasodium salt of N,N-di-(carboxymethyl)-aspartic acid, and
wherein the composition additionally contains from about 2 to about
10 percent by weight based on the total weight of the composition
of a water-soluble sodium silicate and from about 10 to about 50
percent by weight based on the total weight of the composition of
sodium sulfate.
7. An aqueous washing system consisting essentially of water, an
organic detergent surfactant selected from the group consisting of
anionic detergents, cationic detergents, nonionic detergents,
ampholytic detergents, zwitterionic detergents, and mixtures of the
above and, as a builder therefor, a water-soluble salt of
N,N-di-(carboxymethyl)-aspartic acid selected from the group
consisting of alkali metal salts, ammonium salts, and alkyl
ammonium salts, the ratio by weight of said detergent surfactant to
said builder being in the range of from about 1:10 to about 3:1,
said system having a pH between about 8 and about 12.
8. The method of washing articles which comprises contacting the
same with an aqueous washing system of claim 7.
9. The composition of claim 7 wherein said detergent surfactant is
one or a mixture of anionic detergents.
10. The composition of claim 7 wherein said water-soluble salt is a
sodium salt of N,N-di-(carboxymethyl)-aspartic acid.
Description
This invention relates to novel nonphosphorus builders for use with
synthetic detergents and to the resultant washing compositions and
their uses.
BACKGROUND
In the manufacture of detergent formulations for laundering and
general purpose washing operations, it is common practice to employ
detergent builders--substances used in combination with
surface-active compounds to aid in cleansing the articles being
washed. The polyphosphates, notably sodium tripolyphosphate and
tetrasodium pyrophosphate, are the commonly used detergent
builders. However, these materials possess certain shortcomings. In
the first place, the polyphosphates are susceptible to hydrolysis
and degradation in aqueous solutions (Canadian Patent 737,422). In
addition, the phosphorus residues resulting from the widespread use
of synthetic detergent formulations containing these
phosphorus-containing builders have been said to contribute to
eutrophication of rivers, lakes, underground streams, and other
bodies of water. ["Detergent Phosphorus Effect on Algae" by Thomas
E. Maloney, Journal of the Water Pollution Control Federation, Vol.
38, No. 1, pp. 38-45 (Jan. 1966)].
To appreciate the magnitude of the problem, it has been estimated
that over two billion pounds of salts of condensed phosphates are
used in detergents each year in the United States. The
phosphorus-containing builders can therefore be properly termed
ubiquitous.
The desirability of providing an efficacious detergent builder
which does not suffer from the foregoing limitations is deemed to
be self-evident.
Accordingly, an object of this invention is to provide efficacious
detergent builder systems which are hydrolytically stable and
devoid of the eutrophic characteristics exhibited by the
polyphosphates and other phosphorus builders. Another object is to
provide washing compositions which are devoid of
phosphorus-containing builders but which possess the advantageous
characteristics of washing compositions which presently contain the
polyphosphate builders.
Other important objects of this invention will become apparent from
the ensuing description and appended claims.
THE INVENTION
In accordance with this invention it has been found possible to
reduce--indeed, eliminate--the phosphorus-containing builders in
detergent formulations without sacrifice of cleaning power and
brightness by employing as a detergent builder a water-soluble salt
of N,N-di(carboxymethyl)-aspartic acid. This acid has the
formula:
The preferred salts are the alkali metal salts with potassium and
especially sodium being particularly preferred. Other suitable
salts include the ammonium and substituted ammonium salts.
An embodiment of this invention involves the provision, as new
compounds, of N,N-di(carboxymethyl)-aspartic acid and the
water-soluble salts thereof, the sodium and potassium salts being
preferred. Another embodiment is a process for producing such
compounds.
The builders of this invention may be prepared by reacting an
alkali metal salt of nitrilodiacetic acid with an alkali metal salt
of a monohalosuccinic acid in an alkaline aqueous system:
For best results, the reaction is conducted at mildly elevated
temperatures (e.g., 60.degree.-90.degree. C., preferably
70.degree.-75.degree. C.) using alkali metal hydroxide in amount
sufficient to keep the reaction solution alkaline but insufficient
to cause the pH to exceed 10. Treatment of the resultant organic
acid salt with mineral acid (e.g., HC1) or acidic ion-exchange
resin liberates the free acid.
The builders of this invention can be advantageously used with a
wide variety of detergent actives or surfactants, including those
known in the art as anionic, cationic, nonionic, ampholytic, and
Zwitterionic detergents as well as any suitable mixture of such
detergents. When the resultant washing compositions are used in
aqueous washing systems, the cleaning power of the formulation is
enhanced in much the same way as when the commonly used
polyphosphate builders are employed. Yet the present builder
systems are more resistant to hydrolytic degradation than the
polyphosphates and do not contribute to the eutrophication problems
characteristic of phosphorus-containing builders.
Accordingly, this invention provides, inter alia, a washing
composition composed of an organic detergent surfactant suitable
for use in water and, as a builder, a water-soluble salt of
N,N-di-(carboxymethyl)-aspartic acid. Although the proportions may
be varied to suit the needs of the occasion, the weight ratio of
the detergent surfactant to the builder of this invention will
normally fall within the range of about 1:10 to about 3:1. The
preferred ratios are within the range of about 1:5 to about
3:2.
As noted above, the builder of this invention is generally employed
in the form of a water-soluble salt, notably an alkali metal salt,
an ammonium salt, or an alkyl ammonium salt. The alkali metal salts
can involve one or a mixture of alkali metal salts although the
potassium or sodium salts, especially the tetrasodium salt of
N,N-di-(carboxymethyl)-aspartic acid, are preferred because of
their relatively low cost and enhanced effectiveness. Because the
detergent formulations are generally used in alkaline aqueous
systems, it is entirely feasible to use in their manufacture either
N,N-di-(carboxymethyl)-aspartic acid itself or the partially
neutralized free acid. The free acid group(s) will be converted to
the appropriate salt at least as soon as the formulations are put
to use in an alkaline environment.
For best results, the formulations of this invention will provide
in aqueous solution a pH between about 8 and about 12.
As noted above, the builders of this invention can be used with a
wide variety of detergents including those classed in the art as
anionic detergents, cationic detergents, nonionic detergents,
ampholytic (i.e., amphoteric) detergents, and Zwitterionic
detergents, and any suitable mixture of two or more of these
(whether from the same class or from different classes). The
anionic surface-active compounds are generally described as
compounds which contain hydrophilic and lyophilic groups in their
molecular structure and which ionize in an aqueous medium to give
anions containing the lyophilic group. Typical of these compounds
are the alkali metal salts of organic sulfonates or sulfates, such
as the alkali metal alkyl aryl sulfonates and the alkali metal
salts of sulfates of straight chain primary alcohols. Sodium
dodecylbenzene sulfonate and sodium lauryl sulfate are typical
examples of these anionic surface-active compounds (anionic
synthetic detergents). For a further amplification of anionic
organic detergents which can be successfully built in accordance
with this invention, reference should be had to U.S. Pat. No.
3,422,021, particularly the passage extending from column 11, line
47 through column 12, line 15, including the references therein
cited, which passage is incorporated herein as if fully set out in
this specification.
The cationic detergents are those which ionize in an aqueous medium
to give cations containing the lyophilic group. Typical of these
compounds are the quaternary ammonium salts which contain an alkyl
group of about 12 to about 18 carbon atoms, such as lauryl benzyl
dimethyl ammonium chloride. Compounds of this nature are used in
detergent formulations for special purposes, e.g., sanitizing and
fabric softening.
Nonionic surface-active compounds are generally described as
compounds which do not ionize in water solution. Oftentimes these
possess hydrophilic characteristics by virtue of the presence
therein of an oxygenated chain (e.g., a polyoxyethylene chain), the
lyophilic portion of the molecule being derived from fatty acids,
phenols, alcohols, amides or amines. Exemplary materials are the
poly-(ethylene oxide) condensates of alkyl phenols (e.g., the
condensation product formed from one mole of nonyl phenol and ten
moles of ethylene oxide), and the condensation products of
aliphatic alcohols and ethylene oxide (e.g., the condensation
product formed from 1 mole of tridecanol and 12 moles of ethylene
oxide). Reference should be had to U.S. Pat. No. 3,422,021,
especially the passage extending from column 12, line 16 through
column 13, line 26 where a fairly extensive discussion and
exemplification of nonionic synthetic detergents is set forth.
Inasmuch as the nonionic synthetic detergents set forth in that
passage can be successfully built in accordance with this
invention, the foregoing passage is incorporated herein as if fully
set out in this specification.
The ampholytic surfactants are compounds having both anionic and
cationic groups in the same molecule. Exemplary of such materials
are derivatives of aliphatic amines which contain a long chain of
about eight to about 18 carbon atoms and an anionic water
solubilizing group, e.g., carboxysulfo, sulfo or sulfato. Examples
of ampholytic detergents are sodium-3 -dodecylamino-propionate,
sodium-3 -dodecylaminopropane sulfonate, sodium N-methyl taurate,
and related substances such as higher alkyl disubstituted amino
acids, betaines, thetines, sulfated long chain olefinic amines, and
sulfated imidazoline derivatives.
Zwitterionic synthetic detergents are generally regarded as
derivatives of aliphatic quaternary ammonium compounds, 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 one contains an anionic water-solubilizing group,
e.g., carboxy, sulfo, or sulfato. Examples of compounds falling
within this definition are
3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate and
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate.
For a still further appreciation of surface-active compounds
(synthetic detergents) which can be employed in the practice of
this invention reference may be had, for example, to the
disclosures of U.S. Pat. No. 2,961,409 and French Patent
1,398,753.
The detergent builders of this invention have been found to perform
exceedingly well with anionic surface-active compounds and
therefore this constitutes a preferred embodiment of the
invention.
Another preferred embodiment of this invention is a washing
composition comprising an organic detergent surfactant, a
water-soluble monovalent salt of N,N-di-(carboxymethyl)-aspartic
acid as a builder, and about 2 to about 10 percent by weight based
on the total weight of the composition of a water-soluble alkali
metal silicate. The cleaning efficacy of these preferred
compositions is at least comparable to commercially available
household and laundry formulations. Moreover, the soluble silicates
of such alkali metals as sodium and potassium serve as effective
corrosion inhibitors. In accordance with this preferred embodiment
it is desirable to employ one or more silicates of sodium or
potassium, or both, wherein the weight ratio of SiO.sub.2 :M.sub.2
O (M=Na or K) is in the range of from about 1:1 to about 2.8:1.
Sodium silicates wherein this ratio is in the range of about 1.6:1
to about 2.5:1 are especially useful because of their low cost and
effectiveness.
Another preferred embodiment of this invention involves including
with the mixture of the organic detergent surfactant and the
N,N-di-(carboxymethyl)-aspartic acid builder (e.g., the tetrasodium
salt, the tetrapotassium salt, or the mixed sodium-potassium salts
thereof) an alkali metal sulfate, preferably sodium sulfate, or an
alkali metal carbonate, preferably sodium carbonate, or both.
Amounts up to about 60 percent by weight of the total formulation
are suitable. These formulations are effective, economical
mainstays of finished detergent formulations for laundry, household
and/or industrial use. In the preferred compositions the amount of
alkali metal sulfate and/or alkali metal carbonate is generally
from about 10 to about 50 percent by weight based on the total
weight of the formulation.
Finished detergent formulations of this invention may contain minor
amounts of other commonly used materials in order to enhance the
effectiveness or attractiveness of the product. Exemplary of such
materials are soluble sodium carboxymethyl cellulose or other soil
redeposition inhibitors; benzotriazole, ethylene thiourea, or other
tarnish inhibitors; perfume; fluorescers; dyes or pigments;
brightening agents; enzymes; water; alcohols; other builder
additives, such as the water-soluble salts of
ethylenediaminetetraacetic acid,
N-(2-hydroxyethyl)-ethylenediaminetriacetic acid, nitrilotriacetic
acid and N-(2-hydroxyethyl)-nitrilodiacetic acid; and pH adjusters,
such as sodium hydroxide and potassium hydroxide. In the built
liquid detergent formulations of this invention, the use of
hydrotropic agents may be found efficacious. Suitable hydrotropes
include the water-soluble alkali metal salts of toluene sulfonic
acid, benzene sulfonic acid, and xylene sulfonic acid. Potassium
toluene sulfonate and sodium toluene sulfonate are preferred for
this use and will normally be employed in concentrates ranging up
to about 10 or 12 percent by weight based on the total
composition.
It will be apparent from the foregoing that the compositions of
this invention may be formulated according to any of the various
commercially desirable forms. For example, the formulations of this
invention may be provided in granular form, in liquid form, in
tablet form, or in the form of flakes or powders.
The relative proportions and absolute quantities of the several
ingredients of the finished compositions of this invention are
susceptible to variation and in most cases will vary depending upon
such factors as the nature of the particular ingredients being
utilized, the end use for which the composition is intended to be
put, the relative costs of the ingredients, and the like. For
example, the total concentration of the detergent formulations of
this invention in water will normally range below about 0.3 percent
by weight although it is entirely feasible to utilize higher
concentrations where the circumstances warrant or justify the use
of higher concentrations. In most cases the aqueous washing
solutions of this invention will contain from about 0.05 to about
0.25 weight percent of combined detergent active(s) and builder.
The preferred compositions of this invention are phosphorus free
although it may be desired to include therein reduced quantities of
conventional phosphorus-containing materials such as sodium
tripolyphosphate, tetrasodium pyrophosphate, salts of substituted
methylene diphosphonic acids, long chain tertiary phosphine oxides,
or the like.
The invention is not to be limited to any particular method of
mixing the builder and the detergent. The builder may be
mechanically mixed in, crutched in the detergent in the form of a
slurry, or dissolved in a solution of the detergent. In addition,
the builder system may be admixed with the detergent in any of the
forms in which the detergent is manufactured, as well as being
added simultaneously or separately to an aqueous solution. In any
event, the present builder system is intended to be used with the
detergent at the time of application as a cleansing agent .
In order to still further illustrate the practice of this
invention, the following examples are presented.
EXAMPLE I
Disodium nitrilodiacetate, HN(CH.sub.2 COONa).sub.2 .sup.. H.sub.2
O, 20 grams (0.1 mole), was dissolved in 50 ml. of water in a 500
ml. three-necked flask equipped with a mechanical stirrer, a
combination pH electrode and a dropping funnel. Bromosuccinic acid,
20 grams (0.1 mole), was neutralized with 8 grams of NaOH in 100
ml. of water and the resulting solution was added to the flask.
While the flask was immersed in an oil bath at 70.degree. C., 4
grams of NaOH in 50 ml. of water was added dropwise at such a rate
that the pH of the reaction mixture always remained below 10. The
mixture was stirred for 2 more hours.
The reaction mixture was concentrated to 50 ml. at 70.degree. C.
After cooling, 150 ml. of methanol was added. The taffylike
material was separated and blended with four 100 ml. portions of
methanol. The solid thus obtained still showed positive bromide
test. It was dissolved in 50 ml. of water and passed through a
2.5.times. 100 cm. column of an ion-exchange resin (Dowex 50W-X1,
50/100 mesh), the resin initially being in the acid form. Water was
used as the eluent and the following acidic effluent fractions were
collected and evaporated;
Residue Fractions Volume pH of fraction After evaporation
__________________________________________________________________________
1 125 ml. 2.5 Trace, brownish 2 125 1.5-2.0 Trace, brownish 3 225 1
12 g., light green 4 225 2.5-4 None 5 300 4.0-4.5 Trace 6 1300 3.0
0.9 g. 7 100 4 None
__________________________________________________________________________
The residue from fraction 3 gave a negative bromide test. It was
recrystallized from water to yield, after drying, 9.3 grams of
N,N-di-(carboxymethyl)-aspartic acid, a colorless solid. The
gas-liquid chromatogram of its methyl ester exhibited only one peak
in the product region and was devoid of peaks due to starting
materials. The free acid melted with decomposition at 146.degree.
C. The NMR and IR verified its chemical structure and it was shown
by Karl-Fisher titration to contain one mole of water of hydration
per molecule.
EXAMPLE II
A preferred built formulation of this invention had the following
composition:
Weight percent Dodecylbenzene sulfonate (a typical linear alkyl
benzene sulfonate 20.0 Sodium silicate (ratio SiO.sub.2 :Na.sub.2 O
of 2.4:1) 6.0 Sodium carboxymethyl cellulose 0.6 Sodium sulfate
33.4 Tetrasodium salt of N,N-di- (carboxymethyl)-aspartic acid
40.0
The performance of this detergent composition was evaluated by use
of the standard Launder-Ometer test. In particular, the formulation
was dissolved in water to a concentration of 0.15 weight percent
and the pH of the solution adjusted to 9.5 with small amounts of
sodium hydroxide solution. The water had a hardness of 150 p.p.m.
(Ca/Mg 3/2). Swatches of standard artificially soiled cloth were
subjected to the washing procedure. The Launder-Ometer bath
temperature was fixed at 120.degree. F. and the washing span was 10
minutes. After washing, the samples were removed from the washing
solution and thoroughly rinsed with pure water. After drying, the
whiteness of the cloths was ascertained by use of a standard
commercially available reflectance photometer. The identical
procedure also was employed with a formulation identical to that
described above with the exception that sodium tripolyphosphate was
used in lieu of the tetrasodium salt of
N,N-di-(carboxymethyl)-aspartic acid.
In these tests it was established that the formulation of this
invention was as effective as the corresponding sodium
tripolyphosphate formulation. In particular, the cloths washed with
the formulation of this invention had a whiteness of 105 as
compared to the whiteness of the same kind of soiled clothes washed
in the sodium tripolyphosphate formulation (assigned the value of
100 percent).
EXAMPLE III
Some illustrative solid heavy duty laundering formulations of this
invention are as follows (percentages being weight
percentages):
Surface-active agent (See note 1) 10-125% Tetrasodium salt of
N,N-di- (carboxymethyl)-aspartic acid 10-25% Sodium metasilicate
(anhydrous) 2-10% Sodium carboxymethyl cellulose 1% Optical
brightener (fluorescent dye) 0.1% Perfume 0.1% Sodium sulfate (See
note 2) Balance to 100%
__________________________________________________________________________
.sup.1 One or a combination of the following: sodium alkyl aryl
sulfonate, sodium alkyl sulfonate, sodium alkane sulfonate, sodium
alkenyl sulfonate, octyl phenol ethoxylate, nonyl phenol
ethoxylate, fatty alcohol ethoxylate, fatty acid amide, alkanol
amide, tall oil ethoxylate. .sup.2 The sodium sulfate may be
totally or partially replaced by one or more of the following:
borax, soda ash, sodium bicarbonate, sodium chloride, sodium
sesquicarbonate.
EXAMPLE IV
Typical liquid laundering formulations of this invention are as
follows (percentages being weight percentages):
Surface-active agent (See note 1 above) 10-15% Tetrasodium salt of
N,N-di- (carboxymethyl)-aspartic acid (See note 3) 10-20% Potassium
metasilicate 2-10% Sodium carboxymethyl cellulose 1% Sodium benzene
sulfonate (See note 4) 5-10% Optical brightener (fluorescent dye)
0-1% Water Balance to 100%
__________________________________________________________________________
.sup.3 The tetrasodium salt N,N-di-(carboxymethyl)-aspartic acid
may be totally or partially replaced by the tetrapotassium salt of
N,N-di-(carboxymethyl)-aspartic acid. .sup.4 The sodium benzene
sulfonate may be totally or partially replaced by potassium benzene
sulfonate, sodium toluene sulfonate, sodium xylene sulfonate,
etc.
It is not intended that this invention be unduly limited by the
exemplifications herein provided.
Besides being effective detergent builders,
N,N-di-(carboxymethyl)-aspartic acid and its water-soluble salts
are highly effective sequesterants for calcium in aqueous
systems.
* * * * *