Note: Descriptions are shown in the official language in which they were submitted.
BACKGROUND OF THE INVENTION
.
For many years the primary material used to control
water hardness in detergent products has been sodium tri-
polyphosphate at levels of approximately 50~ by weightof the finished detergent product. Wi~hin the past few
years the use of high levels of sodium tripolyphosphate
has come under scrutiny because of the suspicion that
soluble phosphate species accelerate the eutrophication
or aging process of water bodies. This eutrophication
is ordinarily evidenced by the rapid growth of algae in
the water body.
` Sodium tripolyphosphate exists as a molecule containing
5 atoms of sodium, 3 of phosphorus, and 10 atoms of oxygen.
:~ . - .
., -
lU90~7~
When utilized as a detergent builder the sodium tripolyphosphate
molecule sequesters as a soluble species one mole of
calcium or magnesium cation per mole of tripolyphosphate
anion. In other words, sodium tripolyphosphate se~uesters
calcium and magnesium ions on a 1:1 mole basis. The calcium
or magnesium tripolyphosphate species is relatively stable
in a wash solution, thus preventing the water hardness from
reacting with anionic detergents which in turn gives better
cleaning. The calcium or magnesium tripolyphosphate species
exists essentially as a single trivalent negative anionic
species in the wash solution, This calcium or magnesium
trivalent anion does not precipitate in the course of the
wash.
Sodium pyrophosphate has generally been
considered to be an equivalent ~uilder when compared
to sodium tripolyphosphate. It has also been suspected
that sodium pyrophosphate is the equivalent of
sodium tripolyphosphate in promoting the eutrophication
as has been discussed above.
Sodium pyrophosphate contains one less atom of phosphorus
than does sodium tripolyphosphate. The foregoing is reflected
in the empirical formula of sodium pyrophosphate which is
4 atoms of sodium, 2 atoms of phosphorus and 7 atoms of oxygen.
Sodium pyrophosphate is also ~nown to form a 1:1 molar complex
with calcium or magnesium ions. ~he species resulting from
the sequestration of calcium or magnesium ~y the tetravalent
negative pyrophosphate anion is the calcium or magnesium
divalent negatively charged pyrophosphate complex. ~his calcium
-- 2 --
~090~;7;~
or magnesium pyrophosphate complex is sufficiently stable
in the wash solution to prevent the water hardness cations from
interfering with the detergency process.
The pyrophosphate tetravalent anion has a high associ-
ation constant with the first calcium ion with which it
associates. Association constants are a measure of the
stability of the complex formed. The divalent anion has
a very small association constant with the second calcium
ion for the formation of dicalcium pyrophosphate which is
electrically neutral. In the absence of any material which
makes the dicalcium pyrophosphate more stable,one of the
associated calcium ions will be free to disassociate and to
seek a more stable association such as with body soil on the
fabrics or with the anionic detergent. The main purpose of
controlling calcium ions whether free or associated in a
Weak complex is to prevent the last mentioned reaction with
the detergent or soiled fabric from occurring. As the pyro-
phosphate anion strongly holds one mole of calcium ion per --~
pyrophosphate anion it has been common practice to attempt
the first association (se~uestration~ on a mole for mole
basis. If, however, the pyrophosphate anion can be induced
to strongly associate ~precipitate) with two moles of calcium
ion the pyrophosphate level used could be reduced substantially,
and still maintain the same level of hardness control.
Preferably some free pyrophosphate tetravalent anion will also
be present in the wash for its value in peptizing clay soils.
Thus, in addition to the molecular weight advantage
which allows more moles of the pyrophosphate salt to be
present in a composition at a given fraction of phosphate
1(J90~i72
than tripolyphosphate, the ability of the pyrophosphate to
precipitate as the dicalcium pyrophosphate salt under normal
wash conditions gives a substantially greater advantage. How-
ever, the precipitation of pyrophosphates has ~een viewed as
undesirable in wash solutions as the salt formed has a tendency
to build up on fabrics and exposed machine surfaces. Further-
more the precipitation of calcium pyrophosphate is unpredictable
under normal wash conditions where such factors as the total
hardness, the pH, and the ratio of calcium ions to magnesium
ions may vary from load to load.
Some work has been done in an attempt to ma~e pyrophosphate
a more effective detergency ~uilder. Johnson states in U.S.
Patent 2,381,960 issued August 14, 1945 that water-hardness
may be reduced by.adding pyrophosphates to the solution con-
taining the hardness after a supplemental alkaline materialsuch as sodium orthophosphate, alkali metal hydroxides and
carbonates, soap or sodium silicate having an SiO2:Na2O ratio
greater than 1.5 has been added to the solution. Kepfer in
U.S. Patent 2,326,950 issued August 17, 1943, discloses that
pyrophosphates can be used to control water hardness if the
pyrophosphate is added to the solution containing the hardness
prior to the addition of certain specific supplemental al~aline
materia~s such as sodium borate, sodium metasilicate and
disodium dihydrogen phosphate. ~epfer, in effect, teaches
exceptions to the general rule set forth ~y Johnson. It has
been found that Johnson was wrong, at least in one respect,
as detailed hereinafter.
lV9C~;72
It can thus be seen that pyrophosphate has the
potential of being a much more effective detergency
builder than do the tripolyphosphate salts.
It has now been discovered that alkali metal pyrophos-
phates can be formulated into a detergent composition in a
manner such that the pyrophosphate builds by first associ-
ating with one mole of calcium and then precipitating up
to two moles of calcium per mole of pyrophosphate. An
advantage to the precipitation of pyrophosphate in large
amounts is that the precipitate can be removed from waste
water and used as a fertilizer in the sewerage sludge.
- It is thus an object of the present invention to
more efficiently utilize alkali metal pyrophosphates as
detergent builders.
Percentages and ratios given throughout the applica- -
tion are by weight unless otherwise indicated. Tempera-
tures are in degrees Fahrenheit unless otherwise noted.
The term dry weight basis indicates that the slurry when
dried would have the same weight percentages in a finished
product.
SUMMARY OF THE INVENTION
The present invention relates to an alkaline solid
granular detergent composition consisting essentially of:
(1) from about 20% to 100% of a homogeneous detergent
material containing:
(a) from about 1~ to about 30% by weight of a
si~icate having the formula Si02:M20
wherein M is sodium or potassium or mixtures
thereof and the molar ratio of Si02:M20
is from about 1.6:1 to 4:1;
(b) from 0% to about 60% by weight of a pyrophos-
phate having the formula MXHy(P2O7)
-- 5 --
`` 1090~;7Z
wherein the sum of x and y is 4 and M is
sodium or potassium or mixtures thereof;
~c) from 0% to about 80% by weight of diluent;
and
(d) from about 1% to about 50% by weight of an
anionic, nonionic, zwitterionic, or ampholytic
detergent and mixtures thereof; and
~2) from 0~ to about 60% by weight of an al~aline
sodium or potassium pyrophosphate or mixtures
thereof, to give a detergent composition containing
from about 5% to about 60~ of said pyrophosphate;
and
~ 3) from about 0% to about 80% by weight of a diluent;
said detergent ~1) being dried to an SiO2:H2O molar ratio of
greater than about 0.5, and the total amount of alkali metal
tripolyphosphate present being less than about 20% by weight
of the total pyrophosphate present.
The invention still more specifically relates to a
detergent composition prepared by the process of:
(1) forming an aqueous slurry comprising
(a) from about 1% to about 25% on a dry weight
~asis of an alkali metal silicate having
the formula SiO2:N2o, wherein the SiO2:M2O
weight ratio is ~rom about 1.6:1 to about
2~ 4:1, and M is an alkali metal or mixtures
thereof;
(b) from a~out 0% to about 60% on a dry weight
lOg~;72
basis of an alkali metal pyrophosphate having
the formula MXHy(P2O7) and the sum of
x + y are integers equal to 4; M is an alkali
metal or mixtures thereof;
~c) from about 0.1% to about 80% on a dry weight
basis of a diluent;
(d) from about 1% to about 50% on a dry weight
basis of an anionic, nonionic, zwitterionic,
or ampholytic detergent and mixtures thereof;
then,
(2) drying the slurry of ~1) to a moisture content not
exceeding about 5% by weight; and,
(3) admixing from about 0% to about 60% on a dry `
weight basis of the material described in ~l)(b) -
to give a detergent composition containing from
about 5% to about 60% by weight M4(P2O7)
wherein M is an alkali metal.
The process for forming the compositions are also
within the scope of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The pyrophosphate salts of the finished product in
the present invention have alkali metal cations, such as
sodium or potassium, preferably sodium. Pyrophosphate
salts useful herein may be obtained commercially by
neutralization of the corresponding pyrophosphoric acid
salt. Preferably the pyrophosphate is substantially
free of tripolyphosphate, however, up to about 20%,
preferably less than 10% and most preferably less than
S~, of tripolyphosphates may be present by weight of the
pyrophosphate. Tripolyphosphates tend to inhibit the
-precipitation reaction in which dicalcium
-- 7 --
. f~"~`
1090672
pyrophosophate is formed and thereby diminish the performance
of the composition at high hardness levels. Preferably, the
compositions are substantially free of orthophosphates, i.e.,
no more than 5% or orthophosphate by weight of the pyrophosphate.
Similarly, if tripolyphosphate salts are dried with the pyro-
phosphate the temperature conditions necessary to achieve
the moisture content of the finished product will cause reversion
of the tripolyphosphate, producing some undesired orthophosphate.
The pyrophosphate salts under the conditions expressed in the
present invention do not substantially degrade into the ortho-
phosphate salts upon drying. The pyrophosphates of the present
invention may be either anhydrous or hydrated forms; pre-
ferably the former in a finely divided form to permit rapid
dissolution in the wash.
The alkali metal pyrophosphate is typically added to
the slurry, or formed in situ in the slurry by neutralization
and dried, or added to the product of the dried slurry. The
pyrophosphate acid salts are not effective builders and thus the
finished product must contain from about 5% to about 60~, ordinarily
about 9~ to about 50%, preferably about 12% to about 45%,
and most preferably about 17~ to about 35% on a dry weight basis
of the alkali metal pyrophosphate. If the acid pyrophosphates
are employed the product should contain a source of alkalinity
preferably by using s~dium carbonate as the diluent. Where
none or not all of the alkali metal pyrophosphate is included
in the slurry,additional amounts up to the total in the finished
product are admixed with the dried product of the slurry.
C ' ~ .
1090~7~
The second component of the detergent composition of
the present invention is an alkali metal silicate having the
formula SiO2:M2O wherein M is an alkali metal or mixtures
thereof, such as the sodium or potassium salt, preferably
S sodium. The molar ratio SiO2:~2O is from about 1.6:1 to
about 4:1, ordinarily about 2:1 to about 4:1, preferably from
about 2.4:1 to about 4.1, and most preferably from about
2.75:1 to about 4:1. For the product by process composi-
tions the SiO2:M2O ratios are by weight. `~
The alkali metal silicate is typically present in the
slurry used to form the homogeneous composition at from about
1% to about 30%, preferably from about 1% to about 25%,
more preferably about 2% to about 20%, and most preferably
about 4% to about 15~ on a dry weight basis.
lS The benefits of the invention are most clearly demon-
strated when the weight ratio of the alkali metal silicate to
the alkali metal pyrophosphate in the finished product is from
about 1:60 to about 5:1, preferably from about 1:30 to about
4:1, and most preferably from about 1:15 to about 2:1.
Contrary to the teachings of the prior art, it has
been found that improved performance is obtained if the
pyrophosphate dissolves in the wash solution first. Tt
has been found surprisingly, that when the silicate described
above is dried to a moisture level wherein the SiO2:H2O molar
ratio in the homogeneous composition is greater than about
0.5, pre~erably greater than about 0.6, more preferably
greater than about 0.8 and most preferably greater than about
1.~0, the silicate is converted into a less quic~ly soluble
species which is believed to be a dehydrated polymer. When
C
109~;72
rehydrated, the polymer is broken down into a more readily soluble
species. However, this regeneration occurs sufficiently slowly
when the composition is added to water to form an aqueous
wash solution so that the pyrophosphate is able to provide con-
trol of the hardness, e.g. calcium ions by precipitationbefore too much of the readily soluble interfering species
of silicate is re~ormed. The formation of the polymeric silicate
occurs when the products are dried to at most a 5% by weight
moisture content. Lower moisture levels are desirable when
lower ratio silicates are utilized.
A measure of the degree of polymerization of the
silicate is obtained by dissolving or leaching the composition
in distilled water (1.2 grams/liter at 25C) and after agitating
the sample for one minute, filtering the solution through a
142 mm, five micron Millipore filter in less than about five
seconds normally about three seconds,at 6.8 atmospheres of
nitrogen pressure. The filtrate is then analyzed for SiO2
by any of the following methods herein incorporated by reference.
~1) Hargis, L.G., Anal. Chem., 42, 1494 (1970)
(2) ~argis, L.G., Anal. Chem. Acta, S2, 1 (1970)
(3) Babulak, S.W. and Gildenberg L.~., Am. Oil
Chem. Soc., 50, 296 (1973)
~4) Chalmers, R. A. and Silclair, A. G., Anal.
Chem. Acta, 34, 412 (1966)
(~) Mivelay, W. ~., Advances in Automated Analysis,
Technicon International Congress, II, 36~ (1970)
~ _
1090~;7~
It has been found that a molar ratio of the filtrate SiO2 found
in this solution to the pyrophosphate in the composition of less
than about 0.9:1 indicates that the silicate will not interfere
with pyrophosphate precipitation whereas a ratio of 5:1 will
indicate that the silicate will interfere with the precipitation.
A ratio of equal to or less than about 0.9:1 is preferred, more
preferably less than 0.7:1 and most preferably less than 0.5:1.
The method of formation of the polymer is irrelevant.
In forming the dehydrated polymer, the molar ratio of
- the filtrate SiO2 to the total SiO2 from the sodium or potassium
silicate in the composition by the above described test is less
than 3.3:4, preferably less than 3:4, more preferably less than
1.3:2, and most preferably less than 1:2.
Avoidance of rehydration by protection from moisture
is desirable. For example, protective packaging, moisture sinks,
and minimization of surface by use of large particle sizes and
coatings are all desirable. However, normally the product loses
only a small fraction of its effectiveness upon storage.
The slurry to be dried additionally contains a diluent
in an amount from 0% to about 80~, preferably from about 0.1%
to about ~0%, more preferably from a~out 1~ to about 55~, and
most preferably from about 2~ to about 45% on a dry weight
basis. In formulating the present invention it has been found
most desirable to prepare a slurry to be dried with the
al~ali metal p~rophosphate, the detergent and silicate all
present. It has been found, however, that none of the alkali
metal pyrophosphate need be in the dried granule to give
adequate performance. The diluent is normally required to
' give desirable characteristics to the dried product of the
, ~ ,,
10906'7Z
slurry especially when the product is formed by spray drying
as later described. Where no diluent is used the granules
tend to be sticky and not flow freely.
The diluent materials useful in the present inventiOn
are primarily but not necessarily inert in the slurry or the
composition. They are prefera~ly inorganic. For instance a
preferred diluent is sodium carbonate which provides alkalinity
to the composition thus favoring detergency. The sodium
carbonate will also neutralize the acid pyrophosphates
present in the slurry or admixed in dried product thereby
rendering the latter a more effective builder. Additionally
sodium carbonate will control water hardness to a certain extent.
On the other hand sodium sulfat~ also a preferred diluent,serves
only to provide desirable granule characteristics.
The diluents which are suitable alone or in mixtures in
the present invention include natural and synthetic clays, such
as montmorillonite, hectorite, saponite, volchonskoite, non-
tronite, and sauconite; alkali metal carbonates, especially sodium
~090~;7Z
and potassium, and salts of bicarbonates, sesquicarbonates, borates,
perborates, sulfates, chlorides, bisulfates, and aluminates. Also
useful as a diluent in the slurry is calcium carbonate.
The lower limit on the water in the aqueous slurry to
be dried is determined by the amount which is sufficient to
allow the detergent and the silicate with the diluent and/or
pyrophosphate to become thoroughly mixed prior to the drying
step. The upper limit of water in the slurry is effectively
determined by the economics of not having to drive off any
more water than is necessary to achieve the dried product of
. the requisite moisture content. Generally, the amount of
water in the aqueous slurry should be from about 20~ to about
95%, preferably from about 25% to about 75~, and most
preferably from about 30% to about 50~ by weight of the total
composition of the slurry.
Detergent Com~onent
It is believed that the surfactant (detergent) should be in
intimate association with the silicate. This can be conveniently
arranged by drying a slurry containing both the silicate and
the surfactant so that the portion of the composition con-
taining these two ingredients is essentially homogeneous. ~his
is desirable also since the silicate makes the granule crisp
and free-flowing.
When formulating a detergent composition in accordance
with the present invention, any anionic, nonionic, zwitterionic
or ampholytic detergent may ~e employed. Anionic detergents are
preferred since they interfere least with the pyrophosphate
~3
1090~;7Z
precipitation reaction. The following detergents are exemplary
of those which may be used in the present invention.
Preferably the detergent component of the present
invention is a water-soluble salt of: an ethoxylated sulfated
alcohol with an average degree of ethoxylation of about l to 4
and an alkyl chain length of about 14 to 16; tallow ethoxy
sulfate; tallow alcohol sulfates; an alkyl benzene sulfonate
with an average alkyl chain length between ll and 13, preferably
11.2 carbon atoms; a C6-C20 a-sulfocarboxylic acid or ester
thereof having l to 14 carbon atoms in the alcohol radical;
a C8-C24 paraffin sulfonate; a C10-C24 -olefin sulfonate or
mixtures thereof; or other anionic sulfur-containing surfactant.
Such preferred detergents are discussed below.
An especially preferred alkyl ether sulfate
detergent component of the present invention is a mixture
of alkyl ether sulfates, said rnixture having an average
(arithmetic mean) carbon chain length within the range of
about 12 to 16 carbon atoms, pre~erably from about 14 to
15 carbon atoms, and an average (arithmetic mean) degree of
ethoxylation of from about 1 to 4 moles of ethylene oxide,
preferably from about 2 to 3 moles of ethylene oxide.
Specifically, such preferred mixtures comprise
from about 0 to 10% by weight of mixture of C12 13 compounds,
from about 50 to lO0~ by weight of mixture of Cl4 lS compounds,
and from abo~t 0 to 45% by weight of mixture of Cl6 17
compounds, and from about 0 to 10% ~y weight of a mixture
of C18 l9 con~pounds. Further, such preferred alkyl ether
s~lfate mixtures comprise from about 0 to 30~ by weight of
~C ' ~
1090~;7Z
mixture of compounds ha~ing a degree of ethoxylation of 0, from
about 45 to 95~ by weight of mixture of compounds having a
degree of ethoxylation from 1 to 4, from about 5 to 25% by
weight of mixture of compounds having a degree of ethoxylation
from 5 to 8, and from about 0 to 15% by weight of mixture of
compounds having a degree of ethoxylation greater than 8.
The sulfated condensation products of ethoxylated alcohols of
8 to 24 alkyl carbons and with from 1 to 30, preferably 1 to
4 moles of ethylene oxide may be used in place of the preferred
alkyl ether sulfates discussed above.
Another class of detergents which may be used in
the present invention includes the water-soluble salts, particu-
larly the alkali metal, ammonium, and alkylolammonium salts of
organic sulfuric reaction products having in their molecular
structure an alkyl qroup containing ,rom about 8 to about 22
carbon atoms and a sulfuric acid ester group. Examples of
this group of synthetic detergents are the sodium and potassium
alkyl sulfates, especially those obtained by sulfating the
higher alcohols (C8-C18 carbon atoms) produced by reducing
the glycerides of tallow or coconut oil.
Preferred water-soluble organic detergent compounds
herein include alkyl benzene sulfonates (preferably essentially
linear although "hard" ABS may be used) containing from about
9 to 15 carbon atoms in the alkyl group. ExampleS of the above
are sodium and potassium alkyl benzene sulfonates in which the
alkyl group contains from about 11 to about 13 carbon atoms, in
straight chain or branched chain configuration, e.g., those of
the type described in U.S. Patents 2,220,099 and 2,477,383.
Especially valuable are straight chain alkyl benzene sulfonates
in which the average of the alkyl groups is about 11.2 carbon
atoms, abkreviated as Cll 2LAS.
r ~
1090~;7~
Another useful detergent compound herein includes the
water-soluble salts of esters of - sulfonated fatty acids contain-
ing from about 6 to 20 carbon atoms in the fatty acid group and
their esters from about 1 to 14 carbon atoms in the alcohol radical.
Preferred "olefin sulfonate" detergent mixtures
utilizable herein comprise olefin sulfonates containing from about
10 to about 24 carbon atoms. Such materials can be produced
by sulfonation of ~olefins by means of uncomplexed sulfure
trioxide followed by neutralization under conditions such that
any sultones present are hydrolyzed to the corresponding hydroxy-
alkane sulfonates. The a-olefin starting materials preferably
have from 14 to 16 carbon atoms. Said preferred ~-olefin sul-
fonates are described in U.S. Patent 3,332,880.
The paraffin sulfonates embraced in the present
invention are essentially linear and contain from 8 to 24 carbon
atoms, preferably 12 to 20 and more preferably 14 to 18 carbon
atoms in the alkyl radical.
Other anionic detergent compounds herein include the
sodium alkyl glyceryl ether sulfates, especially those ethers
of higher alcohols derived from tallow and coconut oil;
sodium coconut oil fatty acid mono ~ eride sulfonates and
sulfates; and sodium or potassium salts of alkyl phenol ethylene
oxide ether sulfate containing about 1 to about 10 units of
ethylene oxide per molecule and wherein the alkyl groups
contain about 8 to about 12 carbon atoms.
-16-
1090~7Z
Water-soluble salts of the higher fatty acids, i.e.
"soaps", are useful as the detergent component of the composition
herein. This class of detergents includes ordinary alkali metal
soaps such as the sodium, potassium, ammonium and alkylolammonium
salts of higher fatty acids containing from about 8 to about 24
carbon atoms and preferably from about 10 to about 20 carbon
atoms. Soàps can be made by direct saponification of fats
and oils or by the neutralization of free fatty acids.
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.
Water-soluble nonionic synthetic detergents are
also useful as the detergent component of the instant compos-
ition. Such nonionic detergent materials can be broadly
defined as compounds produced by the condensation of alkylene
oxide groups (hydrophilic in nature) with anorganiC- hydro-
phobic compound, which may be aliphatic or alkyl aromatic
in nature. The length of the polyoxyalkylene group 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
mark "Pluronic sold by Wyandotte Chemicals. These compounds
are formed by condensing ethylene oxide with a hydrophobic
base formed by the
-17-
10901;7;~
condensation of propylene oxide with propylene glycol.
Other suitable nonionic synthetic detergents include
the polyethylen~ 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 strai~ht chain or branched chain
configuration, wlth 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 water-soluble condensation products of aliphatic
alcohols having from 8 to 22 carbon atoms, in either straight
chain or branched 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 fraction
having from 10 to ~4 carbon atoms, are also useful nonionic
detergents herein. Additional nonionics useful herein include
those listed in Canadian patent application 222,185 to Collins
filed March 17, 1975 and in Canadian patent application
218,740 filed January 27, 1975 to LaGasse et al.
Semi-polar nonionic detergents include water-soluble
amine oxides containing one alkyl moiety of from about 10 to
28 carbon atoms and 2 moieties selected from the group consisting
of alkyl groups and hydroxyalkyl groups containing from 1 to
about 3 carbon atoms; water-soluble phosphine oxide detergents
containing one alkyl moiety of about 10 to 28 carbon atoms and
2 moieties selected from the group consisting of alkyl
groups and hydroxyalkyl groups containing from about 1 to 3
~arbon atoms; and water-soluble sulfoxide detergents containing
109~67Z
one alkyl moicty of from about 10 to 28 carbon atoms and a ~oiety
selected from the group consisting of alkyl and hydroxyalkyl
moieties of from 1 to 3 carbon atoms.
Ampholytic detergents include derivatives of aliphatic or
aliphatic derivatives of heterocyclic secondary and tertiary amines
in which the aliphatic moiety can be straight chain or branched
and wherein one of the aliphatic substituents contains from about
8 to 18 carbon atoms and at least one aliphatic substituent
contains an anionic water-solubilizing group.
Zwitterionic detergents include derivatives of
aliphatic quaternary ammonium, phosphonium and sulfonium
compounds in which the aliphatic moieties can 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. ~urther use of zwitterionic detergents are
discussed in Canadian patent applications 231,524 filed July
,15, 1975 and 231,695 filed July 17, 1975.
.. . ....
Other useful detergents include water-soluble salts of
2-acyloxy-alkane-1-sulfonic acids containing from about 2 to
2~ 9 carbon atoms in the acyl group and from about 9 to about 23
carbon atoms in the alkane moiety; ~-alkyloxy alkane sulfonates
containing from about 1 to 3 carbon atoms in the alkyl group
and from about 8 to 20 carbon atoms in the alkane moiety; alkyl
dimethyl amine oxides wherein the alkyl group contains from
a~out 11 to 16 carbon atoms; alkyl-dimethyl-ammonio-propane-
sulfonates and alkyl-dimethyl-ammonio-hydroxy-propane-sulfonates
wherein the alkyl ~roup in both types contains from about 14 to
18 carbon atoms; soaps as hereinabove defined; the condensation
product of tallow fatty alcohol with about 11 moles of ethylene
FRi~ r ,~
1090~;7"
..
oxide; the condensation product of a C13 ~avg.) secondary alcohol
with 9 moles of ethylene oxide; and alkyl glyceral ether sul-
fates with from 10 to 18 carbon atoms in the alkyl radical.
A typical listing of the classes and species of detergent
compounds useful herein appear in U.S. Patent 3,852,211 to
Ohren issued December 3, 1974. The foregoing list of detergent
compounds and mixtures which can be used in the instant com-
positions is representative of such materials, but is not
intended to be limiting.
A particularly useful anionic detergent mixture comprises:
(i) from about 2% to about 15% by weiqht of an alkyl
sulfate wherein the alkyl radical has from 10 to
20 carbon atoms and mixtures thereof the cation
being an alkali metal preferably sodium;
(ii) from about 2% to about 15% by weight of an alkyl `
benzene sulfonate having from 9 to 15 carbon atoms
in the alkyl radical and mixtures thereof the cation
being an alkali metal preferably sodium.
An additional component which may be added to (i) and
(ii) above is:
(iii) from about 2% to about 15~ by weight of an alXyl
ethoxy sulfate having from 10 to 20 carbon atoms
in the alXyl radical and from 1 to 30 ethoxy groups
and mixtures thereof having an alkali metal prefer-
ably sodium cation.
f~
1090~7;~
The detergent is present in the aqueous slurry typically
used to prepare the compositions of this invention at levels
of about 1% to 50%, preferably from about 5% to about 40%,
and most preferably from about 10% to about 30% on a dry
weight basis.
Ad~itional Components
It is to be understood that the compositions of
the present invention may be supplemented by all manner
- of detergent components, either by including such components
in the aqueous slurry to be dried or by admixing such
components with the composition of the invention following the - .
drying step. Soil suspending agents at about 0.1% to 10% by weight
such as water-soluble salts of carboxymethylcellulose, carboxy-
hydroxymethylcellulose copolymers of vinyl ether and maleic
anhydride and preferably polyethylene glycols having a
molecular weight of about 400 to 10,000 are common components
of the present invention. Dyes, pigments, optical brighteners,
and perfumes can be added in varyinq amounts as desired.
Suitable bleaches herein include percarbonates, perborates, and
activators therefor.
Additional components which are desirable in the
present invention are the whiteness maintenance additives.
In particular glassy phosphates at levels of from about
0.1% to 4~ having the formula
-r æf
~J ~
1090~;7~
( 2 )X(P2O5)y
wherein M is an alkali metal, preferably sodium; y having a value
of from about 5 to 50, preferably 7 to 25 with the ratio of y:x
from about 1:1 to about 1:1.5 are useful in the present invention
for whiteness maintenance.
Preferred values of y above are such that there are
10, 14, and 21, most preferably 14 and 21 phosphorous atoms in
the compound. A more preferred range of glassy phosphate is from
about 0.5% to about 2.5~ by weight, most preferably from about
1.0% to about 2% by weight of the finished product. Alterna-
tively the formula of the glassy phosphates can be expressed
as M~y + 2Py 6y + 1 wherein M is an alkali metal and y varies
from 7 to 12. -
Other materials such as fluorescers, antiseptics,
germicides, enzymes in minor amounts, anti-caking agents such
as sodium sulfosuccinate, and sodium benzoate may also be added.
Enzymes suitable for use herein include those discussed in U.S.
Patents 3,519,570 and 3,~53,13~ to McCarty and McCarty et al
issued July 7, 1970 and January 5, 1971, respectively.
Additional amounts of water-soluble detergency builders
may be added to the detergent compositions of the present inven-
tion. Such inorganic detergency builder salts include alkali
metal carbonaies, borates, and bicarbonates. Specific examples
of such salts are the sodium and potassium borates, perborates,
bicarbonates, and carbonates.
Examples of suitable organic detergency builder salts
are: (1) water-soluble aminopolycarboxylates, e.g.
-22-
1090672
sodium and potassium ethylenediaminetetraacetates, nitri-
lotriacetates and N-(2-hydroxyethyl)-nitrilodiacetates; (2)
water-soluble salts of phytic acid, e.g. sodium and potassium
phytates -- see U.S. Patent 2,739,942; (3) water-soluble
polyphosphonates, including specifically, sodium, potassium and
lithium salts of ethane-l-hydroxy-l, l-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 the alkali metalsalts of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethane-
diphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-
1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic
acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-
tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid;
and ~4) water-soluble salts of polycarbQxylate polymers and
copolymers as described in U.S. Patent 3,308,067.
A useful detergent builder which may be employed
in the present invention comprises a water-soluble salt
of a polymeric aliphatic polycar~oxylic acid having the following
structural relationships as to the position of the carboxylate
groups and possessing the following prescribed physical charact-
eristics: (a) a minimum molecular weight of about 350 calculated
as to the acid form~ Ib) an equivalent weight of about 50 to
about 80 calculated as to acid form; (c) at least 45 mole
percent of the monomeric species having at least two carboxyl
radicals separated from each other by not more than
-23-
1090~;7;:
two carbon atoms; (d) the site of attachment of the
polymer chain of any carboxyl-containing radical being
separated by not more than three carbon ato~s along the
polymer chain from the site of attachment of the next
carboxyl-containing radical. Specific examples of
the above-described builders include polymers of itaconic
acid, aconitic acid, maleic acid, mesaconic acid, fumaric
acid, methylene malonic acid and citraconic acid and
copolymers with themselves.
In addition, other builders which can be used
` satisfactorily include water-soluble salts of mellitic
acid, citric acid, pyromellitic acid, benzene pentacarboxylic
acid, oxydiacetic acid, carboxymethyloxysuccinic acid, and
oxydisuccinic acid.
The detergent compositions of this invention preferably
contain the water-soluble detergent in a ratio to the total
builder present in a weight ratio of from about 10:1 to about
1:10, preferably from about 3:1 to about 1:3. The amount of
additional builder in the detergent compositions of the present
invention is from about 5% to about 50~, preferably from about
10% to about 25~. These additional builders may be dried with
the aqueous slurry or admixed with the dried product of the
slurry. If desired the additional builder can be the diluent
material and thereby added to the slurry to be dried.
Certain zeolites or alumino silicates when dried with
the components of the slurry enhance the function of the
silicate of the slurry and add building capacity in that the
alumino silicates sequester calcium hardness. When admixed
with the dried product of the slurry the alumino silicates
r ~
7~.
function as a cobuilder to the pyrophosphates. One such
alumino silicate which is useful in the compositions of the
invention is an amorphous water-insoluble hydrated compound
of the formula Nax(xAlO2-ySiO2), wherein x is an integer
of from 1 to 1.2 and y is 1, said amorphous material beinq
further characterized by a Mg++ exchange capacity of from about
50 mg eq. CaCO3/g to about 150 mg e~. CaCO3/g. This ion
exchange builder is more fully described in Ireland published
patent application 1505/74, to B. H. Gedge et al filed
July 16, 1974.
A second water-insoluble synthetic aluminosilicate ion
exchange material useful herein has the formula ~az E ~Al02) z-
(Sio2)y]xH2O, wherein z and y are inteqers of at least 6;
the molar ratio of z to y is in the range from 1.0 to about
lS 0.5, and x is an integer from about lS to about 264; said
aluminosilicate ion exchange material having a particle size
diameter from about 0.1 micron to about 100 microns; a calcium
ion exchange capacity of at least about 200 mg eq./g; and a
calcium ion exchange rate of at least about 2 grains/gallon/
minute gram as described in Belgian Patent 814,874.
The above-described aluminosilicates are employed at
levels of from about 1% to about 40~, preferably about 5% to
about 25~ by weight.
lOgO~;72
Composition Preparation
The detergent compositions of the present invention is
prepared by a process for forming a detergent composition
comprising the steps of:
(1) forming an aqueous slurry comprising
(a) from about 1% to about 30% on a dry
weight basis of an alkali metal silicate
having the formula SiO2:M2O, wherein the
SiO2:N2O weight ratio is from about 1.6:1
to about 4:1, and M is an alkali metal or
mixtures thereof;
(b) from about 0~ to about 60~ on a dry weight
basis of an alkali metal pyrophosphate having
. the formula MXHy(P2O7) and the sum of x + y
are integers equal to 4; M is an alkali
metal or mixtures thereof;
~c) from 0% to about 80% on a dry weight basis
of a diluent;
(d) from about 1% to about 50% on a dry weight
basis of an anionic, nonionic, zwitterionic,
or ampholytic detergent and mixtures thereof;
then
(2) drying the slurry of (1) to an SiO2:H2O m~lar ratio
of greater than about O.S; and,
(3) admixing from about 0% to about 60% on a dry
weight basis of the material described in (l)(b)
to give a detergent composition containing from
~r~ 26`
1090~7'~
about 5% to about 60~ by weight M4(P2O7) wherein
M is an alkali metal, the amount of tripolyphosphate
in said composition being less than 20% by weight
of the amount of pyrophosphate.
Preferably they are prepared by a process for preparing
a detergent composition comprising the steps of:
(l) forming an aqueous slurry comprising
(a) from about 1% to about 25~ on a dry
weight basis of an al~ali metal silicate
having the formula SiO2:M2O, wherein the
SiO2:M2O weight ratio is from about
1.6:1 to about 4:1, and M is an alkali
metal or mixtures thereof;
(b) from about 0% to about 60~ on a dry weight
basis of an alkali metal pyrophosphate having
mula MXHy(P2O7) and the sum of x + y
are integers equal to 4; M is an alkali
metal or mixtures thereof;
(c) from about 0.1~ to about 80% on a dry weight
basis of a diluent;
(d~ from about 1~ to about 50% on a dry weight
basis of an anionic, nonionic, zwitterionic,
or ampholytic detergent and mixtures thereof:
then
(2) drying the slurry of (~) to a moisture content not
exceeding about 5~ by weight; and
(3) admixing from a~out 0~ to about 60~ on a dry
109067Z
weight basis of the material described in (l)(b)
to give a detergent composition containing from
about 5% to about 60~ by weight M4(P2O7) wherein
M is an alkali metal~
Preferably, the moisture content of the product immediately
following the drying operation will contain moisture at a
level of from about 0.1% to about 3.5~, more preferably from
about 0.4~ to about 3% and most preferably from about 1.5%
to about 2.5% by weight of the total solids present in the
composition.
The product may partially rehydrate to higher moisture
levels. However, the amount of rehydration is normally not
enough to cause substantial performance loss.
The lower limit on the moisture content of the detergent
composition of the present invention will be determined partly
by the economics involved in that the more the granule is dried
the more costly the drying operation and that charring may
result from the oxidation of the organic components if the
drying temperature is too high.
The moisture content of the dried product may be ~`
determined by any convenient method. One such method is
to weigh a sample of the product following the drying step
and to then heat the product at a substantially higher
temperature than that employed in the drying operation and
determining the amount of moisture which is driven off in the
second heating step. This figure is thus expressed as a
percentage of the total solids present.
The detergent compositions of the present invention can
be prepared ~y drying the slurry to a solid product o~
the re~uisite moisture content ~y any convenient means.
r ~ _~
1090~i7,.
Preferably, the drying to a solid is carried out as a
single operation in spray-drying towers such as those described
in U.S. Patents 3,6~9,951 and 3,629,955, both of which were
issued to Robert P. Davis et al, December 28, 1971. Other
methods of drying the compositions of the present invention
include freeze drying, drum drying, and oven drying. The product
may also be formed in a series of steps, such as by agglom-
eration as described in ~.S. Patent 2,895,916 followed by
drying the agglomerated product.
Preferably the preparation of the detergent composi-
tion comprises the steps of adding the alkali metal silicate,
the detergent, the pyrophosphate and diluent as well as other
compatible ingredients, to an aqueous slurry and thoroughly
mixing (crutching) the composition. The thoroughly miY.ed
slurry is then dried such as by the previously mentioned spray-
drying operation. The slurry temperature may vary according
to the solubility of the components. If kept aboVe about
180F the pyrophosphate, if present in the slurry, will be
anhydrous when dried. ~here freeze drying is used it may be
necessary to further dry product down to the requisite
moisture content by additional steps such as oven drying.
The product of the present invention is desirably in granular
form. Thus if the product is formed in large irregular chun~s
it is ground to form the desired size granules. The products
may be formed into detergent ~ars as described in U.S. Patent
3,17~,370 issued April 13, 1965 and British Patent 1,054,414
issued April 5, 1967 both to Oke-nfuss herein incorporated by
reference.
.. ._ . ...
1090~;7Z
Granular products in the present invention are preferably
prepared by spray drying. The spray-drying operation can be
caxried out in countercurrent or cocurrent drying towers,
preferably in countercurrent towers. In its simplest
S aspect the products of the present invention are spray dried
by pumping the slurry which has been crutched to the spray-
drying tower where the slurry is fed through a series of atomizing
nozzles in a~direction opposite to the flow of the hot drying
gases. The temperature of the hot air mixture should be in
the range of from about 150 to about 1500F, preferably
from about 200 to about 1000F, and most preferably from about
220 to about 700F.
The temperature range within which the granules of
the present invention reach is from about 120F to about 300F,
preferably from about 140F to about 275F, and most preferably
from about 150F to about 250F.
When a multilevel spray-drying apparatus is employed
such as described in the Davis et al patent, previously
incorporated herein by reference, the product is suitably spray
dried with the remaining conditions listed therein.
The detergent composition prepared in accordance with the
present invention is preferably used in solid form product, pref-
erably a granule. However, the respective products can be ground-
up to preferably a colloidal size and suspended in an appropriate
medium such as watei and packaged as a liquid composition.
The compositions of the present invention are preferably
used at concentrations of from about O.OS% to about 1.5% by
weight. Wash temperatures range from 50F to 130F however,
under European conditions the product is often used at about
200~ and at higher concentrations than those listed.
The following are Examples of the present invention.
a ~0
10!~0~;72
EXAMPLE I
Spray-dried products are formulated in A and B
below:
A B
9.9% sodium tallow alcohol sulfate 9.2
8.1 sodium alkyl ~11.8 average) 7.6
benzene sulfonate*
10.1 sodium silicate (SiO2:Na O
3.2:1) 2
~ sodium silicate (SiO2:Na2O 5.9
26.2 sodium pyrophosphate
- sodlum tripolyphosphate 49.4
0.8 moisture 10.0
42.0 sodium sulfate 14.2
minors** to 100%
Composition A is made in accordance with the present
invention with all components spray dried to the listed moisture
content. Composition B is spray dried to the listed moisture
content with all components in the slurry. Performance of the
products is measured by a Hunter-Whiteness meter as Hunter
Whiteness Units (HWU hereafter) on Dacron ~ Polyester fabrics
soiled with clay. The fabrics are washed in 100~ water at
* Sodium alkyl (11.8 average) benzene sulfonate indicates that
the averaqe chain length to the alkyl portion of the molecule
was 11.8 carbon atoms.
**Minors include for example brighteners, perfumes, bleaches, and
soil anti~edeposition agents such as those previously discussed.
~a ~,
109067Z
a product level of 0.12% by weight in the wash.
Hardness A~HWU) B(HWU)
.
9 grains ~3:1/ 35.6 34.3
11 ~rains (3:1/ 22.6 24.2
Ca +:Mg+~)
Least Significant Difference LSDo oS = 2.0
This test shows composition A of the present invention
performing equivalently On clay soil removal to a product
~B) containing substantially more phosphate.
The moisture content of the detergent product is determined
by boiling distillation. The boiling distillation or B.D. method
is carried out by placing a 25 gram sample of the dried
detergent product into a 500 ml. round bottomed flask.
The detergent product in the round bottomed flask is then
covered with 250 ml. of toluene. Instead of toluene any
inert distïllation fluid such as kerosene or xylene may be
used. The round bottomed flask is then heated from 1~0
to 200C and the vapors emitted are refluxed through a
water cooled condenser which is sealed from the atmosphere.
The volatile materials which are evaporated are collected
in a graduated side arm of the condenser. The distillation
process is carried out until no further change is observed
in the a~ueous layer of the distillate. The amount of
~&. ~
109067Z
moisture is determined by converting the volume of water
oollected in the distillation flask to a given weight of
moisture by an appropriate density factor. If volatiie
materials are present in the composition which are miscible
in the aqueous layer of the distillate the Karl Fischer
method of moisture determination may be used to accurately
determine the moisture content. Composition A has an SiO2:H20
molar ratio of 2.88.
.... ... . ... ... . ..
; , ., . :
., . ~ . ,
' . , ' ' ~ . ,, :,
.. .. . - ";
- :....... - . ..
:. ~ : . : , . ...
109~67Z
EXAMPLE II
The following products are prepared (C and D):
C D
5,5% sodium tallow alcohol sulfate 5.5%
5 7.0 sodium alkyl ~11.8 average) 7.0 .:
benzene sulfonate
5.5 sodium alkyl (C 4-C16)* 5.5 :
triethoxy sulfa~e -~ ~
10.1 sodium silicate (SiO2:Na O 10.1 ~ -
3.2:1) 2 -
42.0 sodium sulfate 42.0 ..
1.0 moisture 1.0 ~ -
26.2 sodium pyrophosphate
- sodium tripolyphosphate 24.4 ~ ~-
minors to 100%
All of the ingredients except the polymeric phosphate
are spray dried to the moisture listed and the polyphosphates ~`
as granules are admixed to give a phosphorus content in each
composition of 6.1%.
Compositions C and D are used as in Example I at the
:~ ~ same temperature, concentration, hardness ratios and on Dacron
: Polyester swatches soiled with clay.
:~ * A mixture of alkyl ethoxy sulfates wherein the alkyl chain
varies between 14 and 16 carbon atoms and the ethoxylate
distribution averages 3 moles of ethylene oxide per mole
~ of alcohol.
- , .
~ -
. .
I ¢, _ ~ ~
1090~i7Z
The results of washing are:
Hardness C(HWU~ D(HWU)
9 gra~ns 39.3 5-7
11 qrains 24.5 4.8
o.o5 2.3
Example II shows equal phosphorus contents for C and
D but with superior performance for pyrophosphate (C) over
tripolyphosphate (D). Composition C has an SiO2:H2O molar
ratio of 2.3.
EXAMPLE III
. _ _
~ompositions E and F are prepared by spray drying all
the components:
E F
5.5% sodium tallow alcohol sulfate 5.5%
7.0 sodium alkyl (Cll 8) benzene 7.0
5.5 sodium (C14-C16) triethoxy sulfate 5.5
40.0 - sodium sulfate 37.0
12.0 sodium silicate ~SiO2:~a2O12.0
2.4:1)
26.2 sodium pyrophosphate
- sodium tripolyphosphate 24.4
2.5 moisture 6.0
minors to 100%
~ 35--
. . . ,~
109067Z
The products are tested as in Examples I and II with
the following results:
Hardness E(HWU) F~HWU)
.
9 grains 33 12 ~ -
11 grains 23 12 `
LSDo.os = 1-9
The product prepared by the present invention (E)
shows that silicate ratio is lowered without substantial
performance loss relative to C of Example II and F with
all products at equal phosphorus contents (6.1%) and dried
to the respective moisture contents.
EXAMPLE IV
Products G, H, and J are prepared by spray drying all
the components. Products G and H are identical to Product
A in Example I except that G is dried to 1.7% moisture and
H is only dried to 5.5% moisture. Product J is identical to
Product B* in Example I.
Products G, H, and J are tested by washing Dacron Polyes-
ter fabric swatches at lOO~F at product levels of 0.12% by
weight of the wash solution. ~he fabrics have been soiled
with clay and the wash water contains 9 grains per gallon
.
*,Product B in Example I at 9 grains gave 34.3 HWU whereas
Product J above is 25.8 HWU at 9 grains the difference
arises in the amount of clay used and differences
in the bolts from which the swatches were cut.
1090~;7~:
hardness with Ca+~:Mg+~ at 3:1. The results are:
G(HWU) H(HWU) J(HWU)
21.6 10.8 25.8
0.05 1-8
s Product G prepared by the present invention performs
significantly better than Product H where the moisture content
is higher. Product G ha~ing a much lower phosphorus content
than Product J performs similar to Product J. In Example I
where Product A (G here) performed better but with in
~0 the LSDo oS limits than Product B (J here) the moisture
content of Product A was less than Product G (0.8 versus 1.7
respectively. Products G and H have SiO2:H2O molar ratios
of 1.27 and 0.39 respectively. The approximate molar ratio
of the filtrate silicate to the total pyrophosphate in the
alkaline product are 0.36 and 1.0 respectively for Products
G and H while the approximate molar ratio of the filtrate
SiO2 to the total SiO2 from the sodium silicate are 0.56:2
and 3.4:4 respectively.
EXAMPLE V
: .
Products ~ L , and M were prepared by spray drying
the following compositions:
'~
,.. ~ . . . . . . ..
~` ~090~;7Z
K L M
sodium tallow alcohol sulfate 9.9% 9,9% 9.9%
sodium alkyl (11.8 average) 8.1 8.1 8.1
benzene sulfonate
sodium pyrophosphate 26.2 26.2 26.2
sodium silicate (SiO2:Na 0 10.1 - -
3.2:1) 2
sodium silicate ~SiO2:Na20 - 10.1
2.4:1)
sodium silicate (SiO2:Na20 - - 10.1
2.0:1)
sodium sulfate 42.0 42.0 42.0
moisture 2.0 2.0 2.0
minors to 100% -~
Products K~ L, and M are used at 0.12% of the wash
solution to clean clay soiled Dacron PolyeSter fabrics at a
wash temperature of 100F.
The results at 9 grains (Ca++:Mg++ 3:1) are:
K~HWU) L(HWU) M(HWU)
24.8 - 18.0 16.9
0.10 ' 9
The results show Product K versus B and M descend in perform-
ance as the SiO2:Na20 ratio is lowered. Product B (Example I)
at a much higher phosphorus content as sodium tripolyphosphate
in this test scored 27.4. The SiO2:H20 molar ratios for
Products R, L, and M are 1.14, 1.05, and 1.0 respectively.
I~r ~ .
-
10901;7Z
EXAMPLE VI
Products N and P are prepared as follows Both N
and P are prepared in an aqueous slurry, N is spray dried to
the stated moisture while P remains unprocessed. The
nominal compositions are:
N P
sodium tallow alcohol sulfate5.5% 5.5%
sodium alkyl (11.8 average)7.0 7.0
benzene sulfonate
sodium alkyl (C14-C16) triethoxy 5.5 5.5
alcohol sulfate
sodium pyrophosphate 26.2 26,2
sodium sulfate 42.0 42.0
sodium silicate (SiO2:Na2O 3.2:1) 10.1 10.1
moisture 2.0 - *
minors to 100% **
The products are tested as in Example I with the following
results at 9 grains (Ca++:Mg+ 3:1):
N(HWU) P(HWU)
30.9 15.6
SDo.05 2,0
-
* moisture omitted as the product is in an a~ueous slurry.
**minors in Product P are present at the same level as in N.
~.
1090672
Product N performs significantly better when dried to
the stated moisture than the components not dried (P) when
used to wash the fabrics at the same dry weight concentrations
(0.12% by weight). The SiO2:H2O molar ratio is 1.14 for Product
N and the filtrate SiO2:pyrophosphate molar ratio is about 0.6
and the filtrate SiO2:sodium silicate molar ratio is about 0.5.
EXAMPLE VII
Products R and S have the following compositions:
sodium tallow alcohol sulfate5.5% 5.5%
sodium alkyl (11.8 average)7.0 7.0
benzene sulfonic acid
sodium alkyl (C14-C16) triethoxy 5 5 5 5
sodium pyrophosphate 26.2 26.2
sodium silicate (SiO2:Na2O 3.2:1) 10.1 10.1
sodium sulfate 42.0 42.0 -~
moi5ture 2.0 1.3
minors to 100%
Product R is spray dried in accordance with the present
invention. Product S is spray dried without the silicate and
pyrophosphate present. The compositions are tested as in
Example I at 9 and 11 grains. The dried granule of Product S
is added to the wash solution simultaneously with granular
pyrophosphate and liquid silicate in the amounts described
above. The results are: ~
~$~
1(1~0l;7~
Hardness R(HWU) S(HWU)
9 grains 9.3 1.0
11 grains 3.4 0
LSDo . o 5 = 2
S The above test shows that the silicate must be dried in
the slurry to achieve the benefits of the invention.
EXAMPLE VIII
The following compositions are prepared in accordance
with the present invention by spray drying to the final composi-
tion given:
T U
Nal2rAlo2 sio2]12 27 H2O 1.0% 40.0%
sodium pyrophosphate 60.0 5.0
sodium silicate (SiO2:Na2O 2.4 1) 3.0 2.0
sodium alkyl (13 average) benzene 1.0 50.0
sulfonate
sodium carbonate 16.0 1.0
calcium carbonate 16.0 -
moisture 3.0 2.0
Products T and U perform satisfactorily in cleaning.
l f~ ,,,
109{~;7~,
EXAMPLE IX
The following are variations of the present invention: -
W X Z
sodium alkyl ~C -C18) 14.9~ 40.0% 5.0% 3.0%
triethoxy sulfa~e
sodium pyrophosphate 60.0 15.0 60.0 12.0
sodium silicate (SiO :Na2O 25.0 - 1.0
1.6:1) 2
sodium silicate (SiO2:Na O - lS.0 - 3.0
4.0:1) 2
clay - - 33.6
sodium aluminate - - - 80.0
sodium borate - 28.0
moisture 0.1 2.0 0.4 2.0
.
Products V and W are prepared by aggiomeration and
then drying. Product X is prepared by freeze drying followed
by oven drying and Z by oven drying alone.
Products V, W, X, Z perform satisfactorily.
EXAMPLE X
A detergent bar is prepared by drying and extruding and
stamping the following composition:
.
. ~. .
lV90~i7~
sodium alkyl benzene sulfonate (hard ABS) 15%
sodium pyrophosphate 20
calcium carbonate 50
sodium silicate (SiO2:Na2O 3.2 1) 13.
moisture 2
EXAMPLE XI
A detergent product is prepared by spray-drying a
slurry having the following dry weight composition: 1l
sodium alkyl (C14-C16)*triethoxy sulfate 5.5% ..
sodium alkyl (Cll 8)* LAS** 7 0-
sodium tallow alcohol sulfate 5.5
sodium pyrophosphate . 24.9
;. sodium silicate ~SiO2:Na2O 3.2:1)10.1
sodium sulfate 42.0
polyethylene glycol (M.W. 6000) 1.0
moisture 2.0
Glass H*** 1.0
minors (perfumes and brightener) balance
~20 EXAMPLE XII
The following product is prepared by spray-drying
an aqueous slurry having the following components on a
finished product dry weight basis:
.. _ ....
* Approximate alkyl chain length
** Linear alkyl benzene sulfonate
*** A glassy phosphate admixed into the dried product
having 21 phosphorous atoms
r !
~ ~ .
_~_
lvsn~;7~
sodium tallow alcohol sulfate 5.S~
sodium alkyl (11.8 average) benzene 7.0
sulfonate
sodium alkyl ~Cl4-Cl6) triethoxy sulfate 5.5
sodium silicate (SiO2:Na2O 3.2:1)8.0
sodium pyrophosphate 13.0
sodium carbonate 18.0
sodium sulfate . 20.0
moisture 3.0
The dried product of the slurry is thereafter admixed
with:
Nal2 [AlO2-siO2]12 27 H2O
to give a finished product containing 20% by weight of the
alumino-silicate. The product cleans efficiently.
1090672
EXAMPLE XIII
The following products are prepared by spray drying
and show the relationship of performance in clay soil removal,
moisture, SiO2:H2O molar ratio and the filtrate SiO2:pyro-
phosphate mola.r ratio.
Component BB CC DD EE FF GG
_ _
~ Sodium pyro-
: phosphate 26.2 26.2 26.2 26.2 26.2 26.2
Sodium silicate
(SiO2 :Na2)
2.0 10.0 10.0 _ _ _ _ :
2.58 _ _ 10.0 10.0 _ _
3.2 _ _ _ _ 10.0 10.0
Sodium tallow
alcohol sulfate 5.5 5.5 5.5 5.5 5.5 5.5
Sodium Cll 2 alky
benzene sulfonat 7.0 7.0 7.0 7.0 7.0 7.0
Sodium C16 alkyl
. triethoxy sulfat 5.5 5.5 5.5 5.5 5.5 5.5
Sodium sulfate 2.0 38.0 42.0 38.0 2.0 38.0
Moisture 1.8 6.1 2.3 6.1 1.8 7.7
~ Minors to 100~- ~
SiO2:H2O (molar) 1.1~ 0.33 0.94 0.35 1.2~ 0.30
Filtrate SiO :
pyrophosphate ~ lar) O.5~ O.96 O.53 1.15 O.36 1.09
Filtrate SiO2: 0.5 0.85 0.4 0.94 0.2 0.84
total SiO2 frcm ~e
sodium or potassium
silica~ (m~lar)
Dacron polyester 0.2 4.5 46.4 29.2 52.5 28.1
HWU* (9 gr/gal) .
* Hunter Whiteness Units
~, C ~ ~S -
lO~`'v, ~
In the above table, compositions BB, DD, and FF are
of the present invention. The filtrate silicate to the total
silicate and the pyrophosphate molar ratio, and the moisture
contents are determined as hereinbefore described.
C - ~
