Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to glassy phosphate detergent
additives and to processes for preparing detergent compositions
containing glassy phosphate additives.
(2) Prior Art
The utility of glassy phosphates as an adjuvant
to soap has been recognized for years. (U.S. Patent 1,956,515
to Ralph E. Hall, April 24, 1934.)
Glassy phosphates are known to have the property of
sequestering ions of calcium, magnesium, and other polyvalent
metals, and of deflocculating or dispersing certain solids,
e.g., clay soils. However, they have the undesirable property
in aqueous solution of being hydrolyzed to less desirable and
sometimes objectionable lower phosphates, with corresponding
loss of their useful properties. Thus, the incorporation of
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glassy phosphates into detergent compositions without hydrolysis
has been beset with difficulty. For example, U.S. Patent No.
2,568,110 to Irving Beiley et al, September 18, 1951, attempted
to overcome this problem by admixing a concentrated aqueous
solution containing 20% to 65% glassy phosphate with a sub-
stantially hydratable salt. This approach, typical of the
prior art, sought to compensate for the decomposition or
hydrolysis by adding additional glassy phosphates to the com-
position. Specific uses of the glassy phosphates of this
invention are also found in U.S. Patent 3,896,056 issued July
22, 1975 to Benjamin and Connor, and the copending Canadian
application of Francis, Carson and McKay, Serial Number
246,120 filed February 19, 1976.
Throughout the specification and claims percentages
and ratios are by weight and temperatures in degrees
Fahrenheit unless otherwise indicated.
SUMMARY OF THE INVENTION
The present invention is based in part upon the
discovery that the undesirable degradation of glassy phos-
phates used in detergent laundering compositions can be
mitigated by protecting the glassy phosphate from degradation
with a normally solid, organic protective agent.
In the detergent additive aspect of the invention
there is provided a substantially anhydrous detergent additive
comprising 1% to 90%, preferably 1% to 75% and most perferably
1% to 60% by weight, of a glassy phosphate represented by the
general formula (M2O)X(P2O5)y wherein M is an alkali metal, y
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has a value in the range of from 5 to 50, and the ratio of
x:y lies in the range of from about 1:1 to about 1.5:1; and
10~ to 99%, preferably 40% to 99~, by weight of a protective
agent being a normally solid organic material having a melting
point ranging from 100F to 200F; said normally solid
organic material being selected from the group consisting of
the aliphatic carboxylic acids condensed with 20 to 50 ethyl-
ene oxide groups, linear and branched C10-C24 alcohols
condensed with 9 to 50 ethylene oxide groups, aliphatic,
cycloaliphatic, and aromatic amides, polyalkylene glycols
where the alkylene group is ethylene or propylene, C8-C18
alkyl phenols condensed with from 25 to 50 moles of ethylene
oxide, C12-C30 fatty acids, C16-C30 fatty alcohols, and
ethylene oxide-propylene oxide polymers containing 20% to
90% oxyethylene by weight.
In the detergent composition aspect of the invention
there is provided a granular detergent comprising 1 to 15
parts by weight of a detergent additive comprising 1% to 90%,
preferable 1% to 75%, and most preferably 1% to 60% by
weight of a glassy phosphate having a general formula
,, .
M2y+2P2yO6y+l wherein M is an alkali metal and y is as
defined above, and 10% to 99~, preferably AO% to 99%, by
weight of a protective agent being a normally solid organic
material having a melting point ranging from 100F to 200F;
said normally solid organic material being selected from
those defined above; and 85 to 99 parts by weight of
detergent granules comprising 2% to 35% by weight of a
surface-active agent selected from the group consisting of
anionic, nonionic, ampholytic, and zwitterionic surface-
active materials, and 10~ to 65% by weight of a detergent
builder salt.
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DESCRIPTION OF THE INVENTION
The detergent additive of this invention comprises
a glassy phosphate and a normally solid organic material.
The glassy phosphates useful in this invention are des-
cribed in U.S. Patent No. 2,568,110 to Irving Beiley et al,
September 18, 1951, and in _ neral and Inorganic Chemistry,
J.R. Partington, 4th Ed., MacMillan, 1967. Glassy phosphates
~i useful in the present invention can be represented by the
formula
,, 10
,,
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~ 20
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(M2C~X (P2O5)y
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- wherein M is an alkali metal, preferably sodium or potassium,
y lies in the range 5 to 50, preferably 7 to 12, and the
ratio of x:y generally lies in the range 1:1 to 1.5:1. Ratios
of x:y greater than 1.5:1 can be used, but such phosphates
are not completely glassy in nature. The preferred glassy
phosphates suitable for use are those having the general
formula
2y+2 2y6y+1
';
wherein M is an alkali metal and y is as defined above, made
e.g., by fusing together NaPO3 and Na4P2O7 in the desired
,` proportions. The preferred glassy phosphates are the sodium
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glassy phosphates having about (21) twenty-one phosphorus
atoms in the molecule.
d The glassy phosphates are commercially available
as dry powder, fine granules, plates, and coarse granules.
For example, Hexaphos ~ and Glass H ~ are brands of glassy
phosphate manufactured by the FMC Corporation, these phosphates
respectively having approximately 13 and 21 phosphorus atoms.
`', Glass H ~ is the preferred material of this range of glassy
~ phosphates. Polyphosphates which have empirical formulae
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Nal6P14O43 and 12 10 31
are sold by the Hooker Chemical Corporation, Niagara Falls,
New York.
The detergent additive of the present invention also
~; comprises a normally solid organic material used as a protective
agent. In this context "normally solid" means solid at normal
ambient temperaturés, i.e., below about 90F. The normally
solid organic materials of this invention melt or soften
sufficiently to become fluid between a temperature of about
100F and about 200F, preferably between 110F and 175F,
and most preferably between 120F and 150F. A wide variety
of materials fitting the above criteria and compatible with
the glassy phosphates of this invention are useful in the con-
text of the present invention. Preferred materials are those
having appreciable solubility in water, particularly nonionic
` surfactant materials.
;~ Specific examples of solid organic protective
materials suitable for use in this invention are:
(1) The condensation products of one mole of a
saturated or unsaturated, straight or branched chain carboxylic
acid having from about 10 to about 18 carbon atoms with from
about 20 to about 50 moles of ethylene oxide, which liquefy
between thetemperatures of about 110F and about 200F
. and are solid at temperatures below about 100F. The acid
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moiety can consist of mixtures of acids in the above delineated
carbon atom range or it can consist of an acid having a
specific number of carbon atoms within this range. The con-
densation product of one mole of coconut fatty acid having the
approximate carbon chain length distribution of 2~ C10, 66%
C12, 23% C14, and 9~ C16 with 35 moles of ethylene oxide is a
specific example of a nonionic containing a mixture of dif-
ferent chain length fatty acid moieties. Other specific
examples of nonionics of this type are: the condensation
10 products of one mole of palmitic acid with 40 moles of
ethylene oxide; the condensation product of one mole of
myristic acid with 35 moles of ethylene oxide; the condensation
product of one mole of oleic acid with 45 moles of ethylene
oxide; and the condensation product of one mole of stearic
acid with 30 moles of ethylene oxide.
(2) The condensation products of one mole of a
saturated or unsaturated, straight or branched chain alcohol
having from about 10 to about 24 carbon atoms with from about
- 9 to about 50 moles of ethylene oxide, which liquefy between -
20 the temperatures of about 110F and 200F and are solid at
temperatures below about 110F. The alcohol moiety can
consist of mixtures of alcohols in the above-delineated carbon
atom range or it can consist of an alcohol having a specific
number of carbon atoms within this range. The condensation
product of one mole of coconut alcohol having the approximate
chain length distribution of 2% C10, 66% C12, 23~ C14, and
9~ C16 with 45 moles of ethylene oxide (CNAE45) is a specific
and highly preferred example of a nonionic containing a
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mixture of different chain length alcohol moieties. Other
specific examples of nonionics of this type are the condensa-
tion products of one mole of tallow alcohol with 20 moles of
ethylene oxide; the condensation products of one mole of
lauryl alcohol with 35 moles of ethylene oxide; the conden-
sation products of one mole of myristyl alcohol with 30
moles of ethylene oxide; and the condensation products of
one mole of oleyl alcohol with 40 moles of ethylene oxide.
(3) Two specific examples of nonionic surface
active agents suitable for use in this invention and not
specifically classified herein are polyoxyethylene glyceride
esters having a hydrophilic-lipophilic balance (HLB) of 18.1
and polyoxyethylene lanolin derivatives having an HLB of
17:0. Both nonionics are manufactured by Atlas Chemical
Industries, Inc.; the trademark of the former is "G-1300"
and the trademark of the latter is "G-1795".
(4) Amides which have a melting point between about
100F and 200F are also suitable for use in this invention.
Specific examples are propyl amide, N-methyl amides having
an acyl chain length of from about 10 to about 15 carbon
atoms, pentyl anilide and anilides having a carbon chain
length of from about 7 to about 12 carbon atoms, oleamide,
- amides of ricinoleic acid, N-isobutyl amides of pelargonic
acid, capric acid, undecanoic acid and lauric acid, N-(2-
hydroxyethyl) amides having a carbon chain length of from
about 6 to about 10 carbon atoms, N-cyclopentyllauramide
; and N-cyclopentylstearamide.
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(5) The polyethylene glycols and polypropylene
glycols having a molecular weight of from about 1400 to about
30,000. For example, Dow Chemical Company manufactures these
nonionics in molecular weights of 20,000, 9500, 7400, 4500,
3400, and 1450. All of these nonionics are waxlike, solids
which melt between 100F and 200F.
(6) The condensation products of one mole of alkyl
phenol wherein the alkyl chain contains from about 8 to about
18 carbon atoms with from about 25 to about 50 moles of
ethylene oxide. Specific examples of these nonionics are the
condensation products of one mole of decyl phenol with 40 moles
of ethylene oxide; the condensation products of one mole of
dodecyl phenol with 35 moles of ethylene oxide; the condensa-
tion products of one mole of tetradecyl phenol with 35 moles
of ethylene oxide; the condensation products of one mole of
hexadecyl phenol with 30 moles of ethylene oxide.
(7) Fatty acids containing from about 12 to about
30 carbon atoms which melt between 100F and 200F. Specific
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examples of these nonionics are lauric acid, myristic acid,
palmitic acid, stearic acid, tallow acid or mixtures of tallow
acid and coconut acid, arachidic acid, behenic acid and -
lignoceric acid. Fatty acids are nonionic when utilized as
a conglutinating agent. When the finished granules are
utilized in alkaline solutions, however, the fatty acids
are saponified to soap, an anionic surface active agent.
Fatty acids having from 12 to 18 carbon atoms are preferred
for use herein. -
(8) Fatty alcohols containing from about 16 to about
30 carbon atoms which melt between 100F and 200F. Specific
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examples of these nonionics are l-hexadecanol, l-octadecanol,
l-eicosanol, 3-docansanol, l-tetracosanol, and l-octaosanol.
(9) The condensation products of ethylene oxide
with a hydrophobic base formed by the condensation product
of propylene oxide with propylene glycol. The hydrophobic
portion of these compounds has a molecular weight of from
about 950 to 4000 and of course exhibits water insolubility.
The addition of polyoxyethylene moieties to this hydrophobic
portion tends to increase the water-solubility of the molecule
as a whole, and the liquid character of the product is re-
tained up to the point where the polyethylene content is
about 50% of the total weight of the condensation product.
Examples of compounds of this type include certain of the
commercially available Pluronic ~ surfactants which are
defined in the booklet "The Wonderful World of Pluronic
Polyols," ~ 1971 BASF ~yandotte Corporation.
- Normally solid organic materials other than those
listed above can also be used as protective agents in this ~
invention provided they are compatible with the glassy ;
phosphate and are of nature sufficient to protect the glassy
phosphate from decomposition. Preferred organic materials
have a low hygroscopicity; for example, polyethylene glycols ~ -
of molecular weight 4000 to 6000 are reported in Kirk Othmer
Encyclopedia of Chemical Technolog~, 2nd edition, volume 10,
page 652, as kaving a comparative hygroscopicity of 1, relative
to 100 for glycerol. This is conveniently measured by means
- of a hair hygrometer as disclosed in Ibid, volume 2, pages
692 and 693.
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Protected glassy phosphate additives are produced
by a process comprising the steps of (a) heating a normally
solid nonionic material to a temperature sufficient to melt
the material; (b) mixing into the melted material a glassy
phosphate and thereby forming a suspension of the phosphate
in the melt; and (c) cooling the suspension to form a solid
material. The solid material can take several forms, e.g.,
flakes, prills, or a partial coating on other detergent
particulates.
According to this invention, the glassy phosphate
and the normally solid organic material are made into a
suspension or slurry by heating the normally solid material
to a temperature sufficient to melt it and mixing therewithin
the glassy phosphate material. The slurry should be sub-
stantially anhydrous, i.e., it should contain less than 0.1%
by weight of water. Amounts of water greater than this give
~ rise to problems in handling the slurry on account of the
- water take-up by the glassy phosphate. The glassy phosphate
concentration of the slurry and product made therefrom can
vary over a wide range. A range of from 1% to 60~, pre-
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ferably 10% to 60%, and most preferably 35% to 55% on a total
slurry weight basis of glassy phosphate dispersed within the -
` slurry has been found suitable for this invention.
After the glassy phosphate and melted material are
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thoroughly mixed, the slurry is next cooled ana manipulated
to form solidified material, e.g., by prilling as set out in
U.S. Patent No. 3,749,671 issued July 31, 1973, to Burton H.
Gedge. Alternatively, the solidified material can be formed
into particulates by grinding or flaking using conventional
30 techniques.
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The protected glassy phosphates of this invention
can be added to a wide variety of washing formulations. For
instance, they can be incorporated into a presoak laundry
product, a laundry detergent, or an automatic dishwashing
product, the level of glassy phosphate in the product being
in the range of from 0.1% to 10%, preferably 1% to 5% by
weight.
The protected glassy phosphate detergent additive
of this invention is preferably incorporated into detergent
formulations by spraying the slurry of glassy phosphate and
melted material directly onto detergent granules in a rotating
drum, pan granulator, fluidized bed, or the like. A two-
fluid nozzle system with hot air as an atomizing agent is
preferably used to spray the slurry onto the detergent granules.
~nother method of spraying is by simple pressure atomization.
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Surfactant
In the detergent composition aspect of the invention
the glassy phosphate additive can be incorporated into con-
ventional granular detergent formulations together with a wide
range of surfactants and detergent builder salts. ~he level
of additive in the product is normally in the range of 1% to
15~ by weight of the total composition, preferably from 2% to
5~, and is adjusted to deliver the desired amount of glassy
phosphate to the product.
From about 1% to about 50~ by weight, preferably
about 5% to about 25% by weight, and most preferably from about -
10% to about 20% by weight of the detergent compositions can
comprise an organic surfactant selected from the group con-
sisting of anionic, nonionic, ampholytic, and zwitterionic
detergents and mixtures thereof. Examples of organic sur-
< factants of these types are described in U.S. Patent -~
; 3,579,454; column 11, line 45 to column 13, line 64.
~; Water-soluble salts of the higher fatty acids, i.e.,
"soaps" are useful as the anionic surfactant herein. This
class of surfactants 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. Soaps can be made by direct saponification
of fats and oils or by the neutralization of free fatty
5, 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
soaps.
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Another class of anionic surfactants includes water-
soluble salts, particularly the alkali metal, ammonium and
alkanolammonium salts, of organic sulfuric reaction products
having in their molecular structure an alkyl group containing
from about 8 to about 22 carbon atoms and a sulfonic acid or
sulfuric acid ester group. (Included in the term "alkyl" is
the alkyl portion of acyl groups.) Examples of this group
of synthetic surfactants which can be used in the present in-
vention 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; and sodium and potassium alkyl benzene sul-
fonates, 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.
Patents 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 11.8 carbon atoms and
commonly abbreviated as Cll 8LAS).
Other preferred detergents for use herein are
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alkyl ether sulfates. These materials have the formula
;; RO(C2H4O)XSO3M 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 such as alkali metal, ammonium, and substituted
ammonium. 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
3~ be synthetic. Lauryl alcohol and straight chain alcohols -
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derived from tallow are preferred herein. Such alcohols are
' reacted with 1 to 30, and especially l to 6, molar proportions
of ethylene oxide and the resulting mixture of molecular
; species, having for example, an average of 3 moles of ethylene
- oxide per mole of alcohol, is sulfated and neutralized.
Specific examples of fat-derived alkyl ether sul-
fates of the present invention are sodium coconut alkyl
ethylene glycol ether sulfate; sodium tallow alkyl trioxy-
~;~ ethylene ether sulfate; and sodium tallow alkyl hexaoxyethylene
sulfate.
Examples of alkyl ether sulfates of synthetic
origin in which the starting alcohol is a narrow-cut olefin `
feed stock include sodium C14 15 alkyl trioxyethylene ether
sulfate and C15_l6 alkyl trioxyethylene ether sulfate.
Other anionic surfactant compounds herein include
the 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; and sodium or potassium salts of alkyl phenol
ethylene oxide ether sulfate containing about l to about 10
units of ethylene oxide per molecule and wherein the alkyl
groups contain from about 8 to about 12 carbon atoms.
Other useful anionic surfactants herein include
, the water-soluble salts of esters of ~-sulfonated fatty
acids containing from about 6 io 20 carbon atoms in the ester
group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic
acids containing from about 2 to 9 carbon atoms in the acyl
group and from about 9 to about 23 carbon atoms in the alkane
moiety; alkene sulfonates containing from about 10 to 20
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carbon atoms in the alkane group; and ~-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.
Other preferred 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 sulfonation of ~-olefins by
means of uncomplexed sulfur trioxide, followed by neutraliza-
tion 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-alkane sulfonates. The
sulfur trioxide can be liquid or gaseous, and is usually,
but not necessarily, diluted by inert diluents, for example
by liquid SO2, chlorinated hydrocarbons, etc., when used in
the liquid form, or by air, nitrogen, gaseous SO2, etc.,
when used in the gaseous form.
; The ~-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 l-olefins
include l-dodecane, l-tetradecene, l-hexadecene, l-octadecene,
l-eicosene, and l-tetracosene.
In addition to the true alkene sulfonates and a
portion of hydroxy-alkane sulfonates, the olefin sulfonates
can contain minor amourts 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 sulfonation
process.
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A specific anionic detergent which is useful in
the present invention is described more fully in U.S. Patent
3,332,880 of Phillip F. Pflaumer and Adrian Xessler, issued
July 25, 1967, titled "Detergent Composition".
Preferred nonionic surfactants useful in the
present invention are those obtained by the condensation
of one to twelve ethylene oxide moieties with a C10-Cl8
aliphatic alcohol. The alcohol may be completely linear
as occurs in materials derived from natural feedstocks such
as vegetable oils and animal fats, or may be slightly
branched as occurs in petroleum-derived alcohols made by
oxo-type synthesis. Particularly preferred materials are
C14-C15 alcohol condensed with an average of seven ethylene
oxide groups, C12-C13 alcohol condensed with an average of
about four ethylene oxide groups and then subjected to
stripping to remove unethoxylated and low ethoxylated
materials, to leave an ethoxylate having a mean of 4.5
ethylene oxide groups.
Preferred zwitterionic materials are derivatives
of quaternary ammonium compounds containing an aliphatic
straight chain group of 14-18 carbon atoms and a sulfate
or sulfonate anionic solubilizing group. Specific examples
include 3-(N,N-dimethyl-N-hexadecyl ammonio-2-hydroxypropane-
l-sulfonate; 3-(N,N-dimethyl-N-tallowyl ammonio)-2-hydroxy-
propane-l-sulfonate; 3-(N,N-dimethyl-N-tetradecyl ammonio)-
propane-l-sulfonate; and 6-(N,N-dimethyl- N-hexadecylammonio)-
hexanoate.
- 16 -
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Detergency Builders
Detergent compositions comprising the glassy phos-
phate additive of the instant invention normally contain a
detergent builder in an amount from about 5% to 95g by
weight, preferably from about 15~ to 60~ by weight of the
composition. Useful builders therein include any of the
conventional inorganic and organic water-soluble builder
salts as well as various water-insoluble and so-called
"seeded" builders. In these compositions these water-
soluble builder salts serve to maintain the pH of the laundry
solution in the range of from about 7 to about 12, pre-
ferably from about 8 to about 11. Furthermore, these builder
salts enhance the fabric cleaning performance of the overall
compositions while at the same time they serve to suspend
particulate soil released from the surface of the fabrics
and prevent its redeposition on the fabric surfaces.
Suitable detergent builder salts useful herein can
be of the polyvalent inorganic and polyvalent organic types,
or mixtures thereof. Non-limiting examples of suitable water-
soluble, inorganic alkaline detergent builder salts include
the alkali metal carbonates, borates, phosphates, polyphos-
phates, tripolyphosphates, bicarbonates, silicates, and
sulfates. Specific examples of such salts include the sodium
and potassium tetraborates, bicarbonates, carbonates, tri-
polyphosphates and pyrophosphates. Of course, mixtures are
also useful. ~
Examples of suitable organic alkaline detergency -
builder salts are: (1) water-soluble amino polyacetates,
e.g., sodium and potassium ethylenediaminetetraacetates,
nitrilotriacetates, and N-(2-hydroxyethyl)nitrilodiacetates;
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(2) water-soluble salts of phytic acid, e.g., sodium and
potassium phytates; (3) water-soluble polyphosphonates,
including, sodium, potassium and lithium salts of ethane-l-
hydroxy-l,l-diphosphonic acid; sodium, potassium, and lithium
salts of methylenediphosphonic acid and the like.
Additional organic builder salts useful herein in-
clude the polycarboxylate materials described in U.S. Patent
2,264,103, including the water-soluble alkali metal salts of
mellitic acid. The water-soluble salts of polycarboxylate
polymers and copolymers such as are described in U.S. Patent
3,308,067 are also suitable herein. It is to be understood
- that while the alkali metal salts of the foregoing inorganic
and organic polyvalent anionic builder salts are preferred
for use herein from an economic standpoint, the ammonium,
alkanolammonium, e.g., triethanolammonium, diethanolammonium,
and the like, water-soluble salts of any of the foregoing
builder anions are useful herein.
. :, .
Mixtures of organic and/or inorganic builders can
be used herein. One such mixture of builders is disclosed
in Canadian Patent 755,038, e.g., a ternary mixture of
sodium tripolyphosphate, trisodium nitrilotriacetate, and
trisodium ethane-l-hydroxy-l,l-diphosphonate.
Another type of builder useful herein includes
various substantially water-insoluble materials which are
capable of reducing the hardness content of laundering
liquors, e.g., by ion-exchange processes. Examples of such
builder materials include the phosphorylated cloths disclosed
in U.S. Patent 3,424,545 to Bauman issued January 28, 1969,
- 18 -
.
A further class of insoluble builder salts is the
type which functions ~y cation exchange to remove polyvalent
mineral hardness and heavy metal ions from solution. A
preferred builder of this type has the formulation
Naz (AlO2)z (SiO2)y x H2O wherein z and y are integers
of at least 6, the molar ratio of z to y is in the range
from 1.0 to about 0.5 and x is an integer from about 15 to
about 264 said aluminosilicate having 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.
Compositions incorporating builder salts of this type are
the subject of Canadian Patent 1,035,234 of John Michael
Corkill, Bryan L. Madison, and Michael E. Burns, granted
- July 25, 1978, said patent being entitled "Detergent Composi-
tion", and also the subject of Netherlands Patent Application
No. 74/06306 published on November 13, 1974.
Another type of detergency builder material useful
in these compositions and processes comprises a water-soluble
material capable of forming a water-insoluble reaction product
with water hardness cations in combination with a crystalliza-
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tion seed which is capable of providing growth sites for said ~- -
- reaction product. "Seeded builder" compositions of this type
~- are described in Belgian Patent No. 798,856 published on
October 29, 1973.
:
More particularly, the seeded builders useful herein
comprise a crystallization seed having a maximum particle
dimension of less than 20 microns, preferably a particle
diameter of from about 0.01 micron to about 1 micron, in
combination with a material capable of forming a water-
insoluble reaction product with free metal ions.
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119
A seeded builder comprising a mixture of sodium
carbonate and calcium carbonate is especially preferred
herein. A highly preferred seeded builder comprises a
30:1 to 5:1 (wt. Na2CO3:CaCO3) mixture of sodium carbonate
and calcium carbonate wherein the calcium carbonate has
an average particle diameter from 0.01 micron to 5 microns.
The following examples are illustrative of the
present invention. All parts, percentages, and ratios set
forth herein in the preceding specification and in the
claims are by weight unless otherwise specified.
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Optional ingredients that may also be incorporated
in detergent compositions of the present invention include
enzymes for removal of protein-based or carbohydrate-based
stains. Enzymes for removing protein-based stains are
proteolytic in nature such as those sold under the trademarks
"Alcalase" and "Esterase" by Novo Industries A/S Denmark or
under the trademarks "Maxatase" and "AZ Protease" by Gist-
Brocades N.V. The Netherlands. These materials are normally
incorporated at levels of up~to 1% by weight, preferably
0.25% to 0.75% by weight, and are preferably coated or prilled
with inert additives to minimize dust formation and improve
storage stability. A wide range of enzyme materials and
means for their incorporation into synthetic detergent
granules is disclosed in U.S.P. 3,553,139 issued on January 5,
1971, to McCarty, Roald, DeOude, Blomeyer, and Cracco.
A further ingredient that may be incorporated to
improve product performance is a bleaching agent of the
halogen or oxygen-containing type. Examples of the hypohalite
, bleach type include trichloro isocyanuric acid and the sodium
and potassium dichloroisocyanurates and N-chloro and N-bromo
alkane sulphonamides. Such materials are normally added at
0.5%-10% by weight of the finished product, preferably 1%-5%
by weight.
Examples of oxygen-containing bleaches include sodium
perborate, sodium percarbonate, and potassium monopersulphate
'~J that are incorporated at levels of 5-30%, preferably 10-25%
, by weight of the final product. The inclusion of organic
bleach activators such as phthalic anhydride, tetra acetyl
ethylene diamine, tetra acetyl methylene diamine or tetra
acetyl glycouril lead to the in situ production during the
washing process of the corresponding organic peroxy acids
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which have enhanced low temperature bleaching performance.
Activators of this type are normally used with sodium per-
borate, at usage levels of 5-15% by weight of the final pro-
duct.
Materials to boost or modify the sudsing pattern of
the compositions of the present invention may also be included.
Examples of suds boosters include coconut and tallow mono- and
di-alkanolamides, particularly ethanolamides and C12 15 alkyl
di-lower alkyl amune oxides. Typical suds depressors include long
chain fatty acids such as those disclosed in U.S. Patent
2,954,347 issued September 27, 1960, to Wayne St. John and
combinations of certain nonionics therewith as disclosed in
U.S. Patent 2,954,343 issued September 27, 1960, to Eugene
Schwoeppe.
Other optional ingredients in granular products
include hydrotropes and anticaking additives such as salts
of lower alkyl-aryl sulphonic acids, salts of ~-sulphosuccinic
.
~ acid, and ~-sulphobenzoic acid, and urea, normally utilized
. .
at levels of 0.5% to 5% by weight of the final product,
preferably at levels of 1%-3% by weight. C12-C18 alkyl acid
phosphates and their condensation products with ethylene
oxide may also be incorporated at similar levels for control
, of crutcher mix viscosity. Antiredeposition agents such as
~ . .
carboxymethyl cellulose, hydroxyethyl cellulose, and their
derivatives may also be incorporated.
Advantageously, ingredients may also be included to
minimize the wrinkling of fabrics that occurs during con-
ventional drying processes. Detergent products incorporating
starch and other particulate materials useful as fabric con-
ditioning agents are diclosed in Belgian Patent No. 811,082
published August 16, 1974. A non-limiting example of such a
- 22 -
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fabric conditioning agent is corn starch, which can be added
at a level of 0.1-5.0% by weight of the composition, pre-
ferably 0.25-1.0%.
Anti-tarnish and anti-corrosion agents, perfume and
colour may also be included, the last ingredient being con-
veniently added either as a general colour or in the form of
a speckle applied to a separate granule fraction of the entire
formulation or to a granulate of one or more of the ingredients.
The pH of detergent formulations in accordance with
- 10 the present invention can lie anywhere within the range 5-12
but is preferably chosen to fall within the range 8.0-10.5 as
this provides a slight particulate soil removal benefit on
synthetic fabrics. However, the use of specific optional
components such as enzymes may require the selection of a
product pH that will permit optimum functioning of the com-
ponent concerned.
The following examples illustrate the production, ~:
according to this invention, of glassy phosphate additives
. and their inclusion in detiergent compositions.
-' 20
~ EXAM2LE I
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A detergent base granule having the formulation
shown below was prepared using conventional techniques
~: of mixing in a crutcher and spray drying.
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Base Granule Parts by Weight
Linear alkyl benzene sulfonate
(average alkyl chain of 11.8) 14.0
Alkyl ethoxylate sulfate
(average alkyl chain of C15 and
average ethoxylation of 3.0) 6.0
Sodium tripoly/pyro/orthophosphate 11.1/11.0/2.0*
Sodium silicate (SiO2:Na2O ratioof 2:1) 12.0
Sodium sulfate 36.0
Water 6.0
98.1
Additives
PEG 4000
Glassy phosphate (Glass H) 1.0
~' 100 . O
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~; *The final distribution of phosphate salts. When the preformed
detergent granules were made, a portion of sodium tripoly-
phosphate was degraded under normal processing conditions.
- 90 grams of a polyethylene glycol of molecular
-~ 20 weight 6000 were heated to a temperature of about 150F in a
stirred container. 100 grams of Glass H ~ , a glassy phosphate
having approximately 21 phosphorus atoms per molecule, were
added and a slurry was formed containing 52.6% glassy phosphate.
The base granules were tumbled in an inclined pan
gra~ulator and the heated slurry sprayed onto the tumbling
mass by means of a heated two-fluid nozzle using heated air
as the second fluid. The spray on was adjusted to give a level
of additive in the product of 1.9% by weight. The resultant
glassy phosphate-containing granules were then cooled to pro-
vide a free-flowing product.
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For comparison purposes, a similar composition was
made up in which the glassy phosphate was added at the
crutcher and exposed to the conventional mixing and spray-
drying steps used to manufacture spray-dried synthetic
detergent granules. Samples of this material and that made
in accordance with the invention were then analyzed for
initial glassy phosphate content and subjected to storage
testing. Results of this comparison are shown in the following
table.
% Glass H
Time Storage Remaining
Elapsed ConditionCrutching Spray-On
0 (After 40% 100%
Processing)
7 days 80F, 60RH 0% 100%
21 days 80F, 60RH 0% 100~ -
21 days South Florida 0% 100%
Cycle
35 days 80F, 60RH 0% 85.7%
35 days South Florida 0% 85.7%
2q Cycle
42 days 80F, 60RH 0% 85.7%
,
The S~uth Florida cycle is a storage condition
~: simulating climatic conditions in South Florida. Typically,
the temperature cycles between 80F and 92F and the humidity
- varies independently between 50~ Relative Humidity and 87
- Relative Humidity over a period of 24 hours.
It can be seen that the glassy phosphate-containing
granules prepared in accordance with the invention display
a resistance to degradation on storage which cannot be
achieved when the glassy phosphate is incorporated in the ~-
conventional manner. It can also be seen that the glassy -- ~
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- 25 -
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phosphate reverts (i.e., degrades to lower phosphate species)
during processing, most of this reversion occurring in the
spray-drying tower. In contrast, little or no degradation
of the glassy phosphate incorporated in accordance with the
invention occurred either in processing or storage under
the same conditions.
EXAMPLE II
A detergent base granule having the formulation
shown in Example I was prepared using conventional techniques.
270 pounds of "Carbowax 4000"*, a polyethylene
glycol having an average molecular weight of 4000, was melted
to a temperature of about 150F in an agitated container. To
this melt was added 300 pounds of Glass H ~ and a slurry
, p! was formed containing 52.6% glassy phosphate.
The slurry was pumped to a two-fluid spray nozzle
located in a rotating mix drum at the base of the spray-drying
tower used to form the base detergent granule. The spray
nozzle had an orifice of 0.1" diameter and used hot air as
' 20 the second fluid. Detergent granules were fed into the
rotating drum and were exposed to the slurry spray which was
adjusted to give a level of additive in the product of 1.9%.
` The resultant glassy phosphate-containing detergent granules
were then cooled to provide a free-flowing product. No
reversion took place on processing. Product made in this
manner displays a similar storage stability to that of the
product of Example I.
The following examples are of slurry compositions -
that, when cooled and flaked, prilled, or as in Example I,
sprayed on~o detergent granules, produce protected glassy
phosphate additives useful in detergent compositions.
- 26 -
- * Trademark
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EXAMPLE III
Condensation product of one mole
of coconut alcohol and 45 moles
of ethylene oxide (heated at 135F
to melt) 50 lbs.
Glassy phosphate (Glass H ~ ) 35 lbs.
EXAMPLE IV
"Carbowax 6000"1 (heated to 150F
to melt) 50 lbs.
Glassy phosphate (Glass H ~ ) 1 lb.
EXAMPLE V
"Carbowax 4000" 50 lbs.
Sodaphos ~ (defined above) 25 lbs.
EXAMPLE VI
"Carbowax 6000" (heated to 150F
to melt) 90 lbs.
Glassy phosphate tGlass H ~ ) lO lbs.
EXAMPLE VII
. _
' "Carbowax 6000" (heated to 150F
-i 20 to melt) l lb.
Glassy phosphate (Glass H ~ ) 99 lbs.
"Carbowax 6000" is a polyethylene glycol of molecular weight
6000 to 7500 made by the Union Carbide Corporation. ("Carbowax
6000" is a trademark).
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Satisfactory additive products in accordance with
the invention are also obtained when the following materials
are substituted, either wholly or in part, for the above
exemplified, normally-solid organic materials:
'. the condensation product of one mole of coconut fatty acid
. having the approximate chain length distribution of 2% C10,
66% C12, 23% C14, and 9% C16 with 35 moles of ethylene oxide;
the condensation product of one mole of palmitic acid with
40 moles of ethylene oxide; the condensation product of one
- 10 mole o~ myristic acid with 35 moles of ethylene oxide; the
condensation product of one mole of oleic acid with 45 moles
of ethylene oxide; and the condensation product of one mole
of stearic acid with 30 moles of ethylene oxide, the conden-
sation product of one mole of 2-methyl tetradecanoic acid
with 45 moles of ethylene oxide; the condensation product
of one mole of tallow alcohol with 20 moles of ethylene
oxide; the condensation product of one mole of lauryl
- alcohol with 35 moles of ethylene oxide; the condensation - ~
' product of one mole of myristic alcohol with 30 moles of -~ -
ethylene oxide; the condensation product of one mole of
2-methyl tetradecanol with 45 moles of ethylene oxide;
the condensation product of one mole of oleyl alcohol with
40 moles of ethylene oxide; polyoxyethylene glyceride esters,
having a hydrophile-lipophile balance of about 18:1;
polyoxyethylene lanolin derivatives having a hydrophile-
lipophile balance of about 17.0; polyethylene glycols having
a molecular weight of from about 1400 to about 30,000, e.g.,
20,000, 9,500, 7,500, 4,500, 3,400, 1,450; mixtures of
polyethylene glycols and polypropylene glycols; the corre-
sponding product of one mole of alkyl phenol wherein the
alkyl chain contains 8, 10, 12, 15, 16, or 18 carbon atoms
- 28 - .
. ` ' '
~O~ 19
with 25, 35, 45, or 50 moles of ethylene oxide; water-soluble
amides having a melting point between 110F and 200F, e.g.,
propyl amide, N-methyl amides having an acyl chain length of
10, 12, 14, or 15 carbon atoms, pentyl anilide and anilides
having a carbon chain length of 7, 8, 10, or 12 carbon atoms,
oleamide, amides of ricionoleic acid, N-isobutyl amides of
pelargonic acid, capric acid, undecanoic acid, and lauric
acid, N-(2-hydroxy ethyl) amides having carbon chain lengths
of 6, 8, or 10 carbon atoms, N-cyclopentyllauramide, and
N-cyclopentylstearamide.
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