United States Patent [19]
[11]
4,323,465
Downey et al.
[45]
Apr. 6, 1982
['54] STABILIZED SODIUM
[56]
References Cited
SULFATE-HYDROGEN
PEROXIDE-SODIUM CHLORIDE ADDUCT
U'S' PATENT DOCUMENTS
AND ALKALINE BLEACH COMPOSITION
CONTAINING SAME
,
3,308,067~
3,979,312
3/1967 Diehl .............................. .. 252/99 X
9/1976 Nakagawa et a . .
252/95 X
3,979,313
9/1976
1/1977
4,005,182
[75]‘ Inventors:
'
Gale D. Downey, Pennington;
Charles W. Lutz, Princeton, both of
' Ni
-
i
Nakagawa et a]. .
252/99 X
Ito ct a1. ......................... .. 252/94 X
_
Primary Examiner_Mayer wemblatt
Attorney, Agent, or Firm—Robert D. Jackson; Eugene
G. Horsky
[73] Assignee:
FMC Corporation, Philadelphia, Pa.
Y
[57]
ABSTRACT
4Na2SO4.2H2‘O2.NaCl, having improved alkaline stabil
[21] APPL NO-I 256,621
ity, is produced by crystallizing it in the presence of a
stabilizing quantity of a soluble, organic polyphosphon
[22] Filed:
Apr. 23, 1981
ate which is taken up in the crystalline structure of the
-
compound.
[51]
Int. Cl.3 .............................................. .. C11D 7/36
The stabilized product is useful as a peroxygen bleach
[52]
U.S. Cl. .................................... .. 252/102; 252/99;
ing agent in alkaline bleach systems.
V
v
[5.8]
,
252/ 103
Field of Search ........................ .. 252/102, 99, 103
'
19 Claims, No Drawings
4,323,465
1
2
preformed adduct is ineffective. Apparently, the poly
STABILIZED SODIUM SULFATE-HYDROGEN
PEROXIDE-SODIUM CHLORIDE ADDUCT AND
ALKALINE BLEACH COMPOSITION
CONTAINING SAME
phosphonate alters or in some manner in?uences the
crystalline habit of the 4Na2SO4.2H2O2.NaCl as to ren
der it insensitive to alkalies. In this connection, micro
scopic examination reveals differences in the crystalline
con?guration between the phosphonate-treated 4Na2.
This invention relates to hydrogen peroxide adducts,
particularly to sodium sulfate-hydrogen
SO4.2H2O2.NaCl and a control specimen, yet no differ
peroxide-sodium chloride adduct having improved
other hand, preparations with the stabilizing additive
stability in alkaline bleach media.
ences in x-ray diffraction patterns are evident. On the
10
Sodium sulfate-hydrogen peroxide-sodium chloride
have improved thermal stability as the decomposition
temperature of the stabilized samples is 220° C. as com
pared to 180° C or less for unstabilized samples of
adduct of the formula:
4Na2SO4-2H2O2-NaCl.
Polyphosphonates which have been found effective
for stabilizing 4Na2SO4.2H2O2.NaCl are those having
is a known chemical entity which is useful as a peroxy
two or more —-PO3— — functions connected through
gen bleaching agent. The adduct is readily obtained by
their phosphorus atoms by way of an alkylene chain,
reacting in aqueous solution, sodium sulfate, sodium
optionally interrupted by a nitrogen atom or containing
chloride and hydrogen peroxide. It has such desirable
a hydroxyl substituent. As understood herein, the term
characteristics as fast dissolving rate and high solubility 20v polyphosphonate includes the free acid and salts
in cold water and it can be manufactured from low cost
thereof. Exemplary polyphosphonates are the following
non-toxic starting materials. For a detailed description
polyphosphonic acids or their alkali metal salts:
of this prodct, including its preparation and application
in' bleaching, reference is made to US. Pat. Nos.
3,979,312, 3,979,313 and 4,005,182.
Although affording generally excellent bleaching
action, 4Na2SO4.2H2O2.NaCl possesses the deleterious
25
and undesirable property of being unstable in the pres
ence of the caustic salts of the type which are contained
in heavy duty bleaching systems. Such alkaline sensitiv
ity has severely limited the utilization of 4Na1SO4.2
H2O2.NaCl in bleaching, at least from a commercial
standpoint. Manifestly, overcoming the alkaline insta
bility of 4Na2SO4.2H2O2.NaCl would bene?t the
bleaching art.
35
It is therefore an object of the invention to provide an
alkali stable 4Na2SO4.2H2O2.NaCl and a method of
Jpreparing same. It is also an object of the invention to
provide stable alkaline bleaching compositions and the
The amount of polyphosphonate found to be effec
use thereof containing said alkali stable 4Na2SO4.2
H2O2.NaCl. Other objects and purposes will be made
tive in stabilizing 4Na2SO4.2H2O2.NaCl is quite small
manifest subsequently herein.
>
relative to the adduct itself. Of course, the molecular
weight of the polyphosphonate as well as the number of
adduct as a peroxygen bleach agent in an alkaline
phosphonate functions will influence the degree of sta~
bilization attained, some members of the class being
more effective than others. In general, it has been found
that 4Na2SO4.2H2O2.NaC1 containing from about 0.001
to about 2.0% of a soluble polyphosphonate, based on
bleaching system‘.
the weight of the composition, imparts sufficient stabil
In accordance with the invention, the aforesaid ob
jects are realized by incorporating a soluble organic
polyphosphonate in the crystalline structure of 4Na2.
SO4.2H2O2.NaCl and using the resulting alkali stable
The alkali stable 4Na2SO4.2H2O2.NaCl is conve
niently produced by crystallizing the adduct in the pres
ence of the polyphosphonate. Except for the presence
of the polyphosphonate, the 4Na2SO4.2H2O2.NaCl is
prepared and crystallized in the known manner. In gen
ity to the adduct whereby it can be used as the peroxy
gen bleaching component in heavy duty bleaches and
detergents.
Alkaline bleach compositions containing the stabi
lized 4Na2SO4.2H2O2.NaCl of the invention are typical
of peroxygen bleach systems prepared in the known
eral, the reaction is carried out by combining sodium
sulfate with hydrogen peroxide, in an aqueous solution, 55 manner. The essential ingredients are a peroxygen
at a temperature of from 0° to 50° C. in the presence of
bleaching agent and an alkaline component to provide
an aqueous bleach solution having a pH in excess of 8,
sodium chloride, wherein the concentration of hydro
gen peroxide in the reaction system is from 70 to 800 g/l
preferably in the neighborhood of 10.6. Buffering
and the concentration of sodium chloride is from 20 to
agents may be necessary to maintain the requisite pH
300 g/l, and recovering the crystalline solid from the 60 conditions. Buffering agents suitable for use herein in
reaction system. Introduction of the polyphosphonate
clude any non-interfering compound which can alter
can be made at any convenient time during the prepara
and/or maintain the solution pH within the desired
tion provided it is present during crystallization of the
range, and the selection of such buffers can be made by
4Na2SO4.2H2Oz.NaCl.
referring to a standard text. For instance, phosphates,
So far as can be ascertained, the polyphosphonate 65 carbonates, or bicarbonates, which buffer within the pH
must be incorporated in the crystalline structure of the
range of 8 to 12 are useful. Examples of suitable buffer
4Na2SO4.2H2O2.NaCl in order to render it stable to
ing agents include sodium bicarbonate, sodium carbon
alkalies: merely adding the polyphosphonate to the
ate, sodium silicate, disodium hydrogen phosphate,
3
4,323,465
sodium dihydrogen phosphate. The bleach solution may
also contain a detergent agent where bleaching and
laundering of the fabric is carried out simultaneously.
The strength of the detergent agent is commonly about
4
?te), for example, primary paraf?n sulfonates of about
10-20 preferably about 15-20 carbon atoms; sulfates of
higher alcohols; salts of a-sulfofatty esters (for example,
of about 10-20 carbon atoms, such as methyl a~sulfomy
0.05% to 0.20% (wt) in the wash water. _
ristate or a-sulfotallowate).
Examples of sulfates of higher alcohols are sodium
Although the herein stabilized 4NaZSO4.2H2O2.NaCl
can be employed generally in alkaline bleaching, the
lauryl sulfate, sodium tallow alcohol sulfate; Turkey
adduct is conveniently included as a peroxygen bleach
Red Oil or other sulfated oils, or sulfates of mono- or
ing agent in heavy duty, alkaline cleansing composi
diglycerides of fatty acids (for example, stearic mono
tions. Typically, these contain on a 100% basis by
weight (a) about 3% to about 70% of the herein stabi
glyceride monosulfate), alkyl poly(ethenoxy) ether sul
lized 4Na2SO4.2H2O2.NaCl; (b) about 30% to about
80% of an alkaline inorganic builder salt; (0) about 0%
to about 20% of a surfactant; ((1) about 0% to about
ethylene oxide and lauryl alcohol (psually having 1 to 5
ethenoxy groups per molecule); lauryl or other higher
50% ofa neutral or alkaline salt as a filler. The composi
ether sulfates such as the sulfates of the condensation
fates such as the sulfates of the condensation products of
alkyl glyceryl ether sulfates; aromatic poly(ethenoxy)
tion may contain about 0% to about 2% of various
products of ethylene oxide and nonyl phenol (usually
optional materials commonly added to laundering and
cleansing compositions. Such adjuncts as perfumes,
having 1 to 20 oxyethylene groups per molecule, prefer
ably 2—l2).
optical brighteners, ?llers, anti-caking agents, fabric
The suitable anionic detergents include also the acyl
softeners, and the like can be present to provide the
usual benefits occasioned by the use of such materials in
sarcosinates (for example, sodium lauroylsarcosinate),
the acyl ester (for example, oleic acid ester) of isethion
ates, and the acyl N-methyl taurides (for example, po
tassium N-methyl lauroyl or oleyl tauride).
Other highly preferred water-soluble anionic deter
detergent compositions. Enzymes, especially the ther
mally stable proteolytic and lipolytic enzymes used in
laundry detergents, also can be dry-mixed in the compo
sitions herein.
25 gent compounds are the ammonium and substituted
Surfactants suitable for use in accordance with the
ammonium (such as mono-, di- and triethanolamine),
present invention encompass a relatively wide range of
alkali metal (such as sodium and potassium) and alkaline
materials and may be of the anionic, nonionic, cationic
earth metal (such as calcium and magnesium) salts of
or amphoteric types.
the higher alkyl sulfates, and the higher fatty acid
The anionic surface active agents include those sur 30 monoglyceride sulfates. The particular salt will be suit
face active or detergent compounds which contain an
ably selected depending upon the particular formulation
organic hydrophobic group and an anionic solubilizing
and the proportions therein.
group. Typical examples of anionic solubilizing groups
Nonionic surface active agents include those surface
are sulfonate, sulfate, carboxylate, phosphonate and
active or detergent compounds which contain an or
phosphate. Examples of suitable anionic detergents
35
As examples of suitable synthetic anionic detergents
45
ganic hydrophobic group and a hydrophilic group
which fall within the scope of the invention include the
which is a reaction product of a solubilizing group such
soaps, such as the water-soluble salts of higher fatty
as carboxylate, hydroxyl, amido or amino with ethylene
acids or rosin acids, such as may be derived from fats,
oxide or polyethylene glycol.
oils, and waxes of animal, vegetable or marine origin,
As examples of nonionic surface active agents which
for example, the sodium soaps of tallow, grease, coco 40 may be used there may be noted the condensation prod
nut oil, tall oil and mixtures thereof; and the sulfated and
ucts of alkyl phenols with ethylene oxide, for example,
sulfonated synthetic detergents, particularly those hav
the reaction product of octyl phenol with about 6 to 30
ing about 8 to 26, and preferably about 12 to 22, carbon
ethylene oxide units; condensation products of alkyl
atoms to the molecule,
thiophenols with 10 to 15 ethylene oxide units; conden
the higher alkyl mononuclear aromatic sulfonates are
preferred, particularly the LAS type such as the higher
alkyl benzene sulfonates containing from 10 to 16 car
bon atoms in the alkyl group, for example, the sodium
salts such as decyl, undecyl, dodecyl(lauryl), tridecyl,
sation products of higher fatty alcohols such as tridecyl
alcohol with ethylene oxide; ethylene oxide conden
sates of monoesters of hexahydric alcohols and inner
ethers thereof such as sorbitol monolaurate, sorbitol
mono-oleate and mannitol monopalmitate, and the con
50
densation products of polypropylene glycol with ethyl
tetradecyl, pentadecyl, or hexadecyl benzene sulfonate
ene oxide.
and the higher alkyl toluene, xylene and phenol sulfo
nates; alkyl naphthalene sulfonate, ammonium diamyl
naphthalene sulfonate, and sodium dinonyl naphthalene
Such agents are those surface active detergent com~
Cationic surface active agents may also be employed.
pounds which contain an organic hydrophobic group
sulfonate.
55 and a cationic solubilizing group. Typical cationic solu
Other anionic detergents are the ole?n sulfonates,
bilizing groups are amine and quaternary groups.
including long chain alkene sulfonates, long chain hy
droxyalkane sulfonates or mixtures of alkenesulfonates
and hydroxyalkanesulfonates. These ole?n sulfonate
detergents may be prepared, in known manner, by the
reaction of S03 with long chain ole?ns (of 8—25 prefera
bly 12-21 carbon atoms) of the formula RCH:CHR1,
where R is alkyl and R1 is alkyl or hydrogen, to produce
As examples of suitable synthetic cationic detergents
there may be noted the diamines such as those of the
type RNHC2H4NH2 wherein R is an alkyl group of
60 about 12 to 22 carbon atoms, such as N—2—aminoethyl
stearyl amine and N-2-amino-ethyl myristyl amine;
amide-linked amines such as those of the type
R1CONHC2H4NH2 wherein R is an alkyl group of
about 9 to 20 carbon atoms, such as N-2-amino ethyl
a mixture of sultones and alkenesulfonic acids, which
mixture is then treated to convert the sultones to sulfo 65 stearyl amide and N-amino ethyl myristyl amide; qua
nates. Examples of other sulfate or sulfonate detergents
ternary ammonium compounds wherein typically one
are paraf?n sulfonates, such as the reaction products of
of the groups linked to the nitrogen atom are alkyl
alpha ole?ns and bisul?tes (for example, sodium bisul
groups which contain 1 to 3 carbon atoms, including
5
4,323,465
6
such 1 to 3 carbon alkyl groups bearing inert substitu
herein include, for example, water-soluble salts of phos
ents such as phenyl groups, and there is present an anion
phates, pyrophosphates, orthophosphates, polyphos
phates, metaphosphates, silicates, carbonates, zeolites,
such as halide, acetate, methosulfate, etc. Typical qua
ternary ammonium detergents are ethyl-dimethyl-stea
including natural and synthetic and the like. Speci?c
examples of inorganic phosphate builders include so
ryl ammonium chloride, benzyl-dimethyl-stearyl am
monium chloride, benzyl-dimethyl-stearyl ammonium
chloride, trimethyl stearyl ammonium chloride, trime
dium and potassium tripolyphosphates, pyrophos
phates, orthophosphates, and hexametaphosphates. So
thylacetyl ammonium bromide, dimethyl ethyl dilauryl
dium tripolyphosphate is an especially preferred, water»
soluble inorganic builder herein.
Non-phosphorus containing sequestrants can also be
ammonium chloride, dimethyl-propyl-myristyl ammo
nium chloride, and the corresponding methosulfates
and acetates.
selected for use herein as detergency builders. Speci?c
Examples of suitable amphoteric detergents are those
examples of non-phosphorus, inorganic builder ingredi
containing both an anionic and a cationic group and a
hydrophobic organic group, which is advantageously a
higher aliphatic radical, for example, of 10-20 carbon
atoms. Among these are the N-long chain alkyl amino
5
ents include water-soluble inorganic carbonate, bicar
bonate, and silicate salts. The alkali metal, for example,
sodium and potassium, carbonates, bicarbonates, and
silicates are particularly useful herein.
Water-soluble, organic builders are also useful herein.
carboxylic acids, for example, of the formula:
For example, the alkali metal, ammonium and substi
tuted ammonium polyacetates, carboxylates, polycar
boxylates and polyhydroxysulfonates are useful builders
the N-long chain alkyl iminodicarboxylic acids (for
in the present compositions and processes. Speci?c
examples of the polyacetate and polycarboxylate
example, of the formula RN(R’COOH)2) and the N
long chain alkyl betaines, for example, of the formula:
builder salts include sodium, potassium, lithium, ammo
nium and substituted ammonium salts of ethylenedi
25
aminetetraacetic acid, nitrilotriacetic acid, oxydisuc
cinic acid, mellitic acid, benzene polycarboxylic (that is,
penta- and tetra-) acids, carboxymethoxysuccinic acid
and citric acid.
'
30 ' Highly preferred non-phosphorus builder materials
(both organic and inorganic) herein include sodium
carbonate, sodium bicarbonate, sodium silicate, sodium
where R is a long chain alkyl group, for example, of
about 10-20 carbons, R’ is a divalent radical joining the
amino and carboxyl portions of an amino acid (for ex
ample, an alkylene radical of 1-4 carbon atoms), H is
hydrogen or a salt-forming metal, R2 is a hydrogen or
citrate, sodium oxydisuccinate, sodium mellitate, so
dium nitrilotriacetate, and sodium ethylenediaminetet
raacetate, and mixtures thereof.
Other preferred organic builders herein are the poly
carboxylate builders set forth in US. Pat. No. 3,308,067,
another monovalent substituent (for example, methyl or
other lower alkyl), and R3 and R4 are monovalent sub
incorporated herein by reference. Examples of such
stituents joined to the nitrogen by carbon-to-nitrogen
materials include the water-soluble salts of homo- and
bonds (for example, methyl or other lower alkyl substit
uents). Examples of speci?c amphoteric detergents are
40
N-alkyl-beta-amino-propionic acid; N-alkyl-beta
iminodipropionic acid, and N-alkyl, N,N-dimethyl gly
cine; the alkyl group may be, for example, that derived
from coco fatty alcohol, lauryl alcohol, myristyl alco
hol (or a lauryl~myristyl mixture), hydrogenated tallow
alcohol, cetyl, stearyl, or blends of such alcohols. The
substituted aminopropionic and iminodipropionic acids
are often supplied in the sodium or other salt forms,
which may likewise be used in the practice ofthis inven
tion. Examples of other amphoteric detergents are the
fatty imidazolines such as those made by reacting a long
chain fatty acid (for example, of 10 to 20 carbon atoms)
with diethyleue triamine and monohalocarboxylic acids
having 2 to 6 carbon atoms, for example, l-coco-S
copolymers of aliphatic carboxylic acids such as maleic
acid, itaconic acid, mesaconic acid, fumaric acid, aconi
tric acid, citraconic acid and methylenemalonic acid.
The builders aforesaid, particularly the inorganic
types, can function as buffers to provide the requisite
45
alkalinity for the bleaching solution. Where the builder
does not exhibit such buffer activity, an alkaline react
ing salt can be incorporated in the formulation.
The neutral inorganic salt in the compositions of the
invention is normally a water-soluble, alkali metal salt
such as sodium chloride and sodium sulfate, the latter
being especially preferred. Alkali inorganic salts are.
generally of the class alkali metal carbonates with so
dium carbonate being the preferred member.
containing a sulfonic group instead of the carboxylic
group; betaines in which the long chain substituent is
joined to the carboxylic group without an intervening
nitrogen atom, for example, inner salts of Z-trime‘
An activating agent can also be included among the
ingredients of the herein compositions and in this con
nection reference is made to those activators capable of
reacting with hydrogen peroxide in an aqueous solution
and thus forming an organic peracid, for example, 0
acylated products such as glucose pentaacetate, octa
hydroxyethyl-?-carboxy-methyl-imidazoline; betaines
thylamino fatty acids such as Z-trimethylaminolauric
acetylated sucrose, triacetin, acetoxybenzenesulfonates
acid, and compounds of any of the previously men
tioned types but in which the nitrogen atom is replaced
and triacetylcyanurate, N-acylated products such as
by phosphorus.
and acid anhydrides such as phthalic anhydride and
succinic anhydride, and mixtures of activating agents.
The mixing ratio of the activating agent to the hydro
gen-peroxide adduct of the formula (1), 4NagS()4.2—
H202.N21Cl, is not critical in this invention, but in gen
eral, the mixing ratio of activating agent/adduct is from
The instant compositions contain a detergency
builder of the type commonly added to detergent for
mulations. Useful builders herein include any of the
conventional inorganic and organic water-soluble
builder salts. Inorganic detergency builders useful
tetraacetylethylenediamine and tetraacetylglycoluril,
4,323,465
7
99/1 to l/99, preferably from 7/3 to 1/20 parts by
8
at ambient conditions and then dry blended in the
weight.
bleach formulation of Example 1.
When employing an activator for the 4Na2SO4.2
H2O4.NaC1, the combined sum of these in the bleaching
formulation aforesaid is from about 25% to about 70%
Storage Stability
The alkaline bleach formulations of the examples
by weight.
containing the polyphosphonate treated 4Na2SO4.2
Sufficient 4Na2SO4.2I-I2O2.NaCl to provide from
H202.N3Cl of the invention were tested for storage
stability. The procedure used is known as the acceler
about 2 ppm to about 2000 ppm active oxygen in solu
tion is used. For home bleaching applications, the con
centration of active oxygen in the wash water is desir
ated storage stability test. This consists of placing the
test formulation in a 4 oz. jar provided with a semi
ably from about 5 to 100 ppm, preferably about 15 to 60
ppm. The actual concentration employed in a given
bleaching solution can be varied widely, depending on
permeable closure and allowing the containers to stand
at about 40° to 50° C. and about 90% R.H. for a period
of 5 days. The formulations were then assayed to deter
mine their active oxygen content.
the intended use of the solution.
Reference is now made to the following non-limiting
A set of comparison formulations, prepared identi
cally to the examples except for the polyphosphonate,
were likewise included in the storage stability testing.
examples.
EXAMPLE 1
The test results on the examples and comparison formu
lations are set forth in Table I. As is readily apparent,
4N82SO4.2H202.N3C1 was prepared by evaporating
under reduced pressure at room temperature a 20%
the bleaching composition containing the polyphos
phonate stabilized 4Na2SO4.2H2O2.NaCl bleaching
H202 solution containing 28% Na2SO4, 3% NaCl and
0.03% nitrilo tris(methylene) triphosphonic acid (DE
agent of the invention exhibits superior storage stability
compared to like compositions containing 4Na2SO4.2
QUEST@2000) until only a crystalline product re
mained. This product was then dried at room tempera
H2O2.NaC1 without the polyphosphonate treatment. It
ture after which it was dry blended with a spray dried 25
will be noted that Examples 1, 4 and 5 show particularly
high storage stability. This is believed to be attributable
to the fact that in these examples, the 4Na2SO4.2H2O2.
NaCl was crystallized more slowly in the presence of
the polyphosphonate than in the other examples.
alkaline detergent base to give a bleach formulation
having the following ingredients:
20% 4Na2SO4.2H2O2.NaCl
38% Sodium Carbonate
14% Sodium Linear A1ky1(C12average)benzene Sul
fonate (LAS)
TABLE I
14% Sodium Silicate
8% Sodium Sulfate
5% Moisture
STORAGE STABILITY RESULTS
% A.O.
Remain
1% Carboxymethylcellulose (CMC)
ing In
35
Bleach
EXAMPLE 2
Example polyphosphonate
4NagSO4.2H2O2.NaCl was prepared by sequentially
No.
adding 9 g of NaCl and 190 g of Na2SO4 to 250 ml of
31% H202 solution containing 0.045% nitrilo tris(
40
methylene) triphosphonic acid (DEQUEST @2000).
The solution was then stirred for 30 minutes at 25° C.,
?ltered and the adduct dried at ambient conditions and
then dry blended in the bleach formulation of Example
1.
45
1
Comp.
2
Comp.
3
Comp.
4
Comp.
5 .
EXAMPLE 3
Additive
DEQUEST®
None
DEQUEST®
None
DEQUEST®
None
DEQUEST®
None
2000
2000
2010
2000
DEQUEST® 2000
Accelerated Storage
Mixture
Test Conditions: 5
After
Days in Semi-Perme
Storage
able Containers at
87%
7%
22%
4%
20%
4%
73%
38%
49°
49°
41°
41°
41°
41°
49°
49°
C.,
C..
C.,
C.,
C..
C.,
C.,
C.,
90%
90%
86%
86%
86%
86%
90%
90%
RH.
RH.
RH.
R.H.
RH.
R.I-I.
RH.
R.H.
88%
41° C., 86% RH.
Comp.
The procedure of Example 2 was repeated except the
polyphosphonic acid was hydroxyethylidene-1,l
diphosphonic acid (DEQUEST @2010) at a concentra 50
tion of 0.065% in the reaction solution.
EXAMPLE 4
A.O. : Active Oxygen
What is claimed is:
1. A 4Na2SO4.2H2O2.NaC1 composition, having im
proved storage stability in alkaline formulations, com
prising 4Na2SO4.2H2O2.NaCl having incorporated in
4Na2SO4.2I-I2O2.NaCl was prepared by evaporating
its crystalline structure a stabilizing amount of an or
under ambient conditions 400 ml of 20% H2O; solution 55 ganic polyphosphonate compound wherein the poly
phosphonate compound contains 2 or more —PO3— —
containing 200 g Na2SO4, 20 g NaCl and 0.10% nitrilo
functions connected through their phosphorous atoms
by way of an alkylene chain optionally interrupted by a
nitrogen atom or containing a hydroxy substituent.
formed, the solution was ?ltered, the recovered product
2. The composition of claim 1 wherein the polyphos
dried at ambient conditions and dry blended in the 60
phonate is:
bleach formulation of Example 1.
tris(methylene)
triphosphonic
acid
(DE
QUEST @2000). After suf?cient product crystals had
EXAMPLE 5
4Na2SO4.2I-I2O2.NaC1 was prepared by evaporating
at ambient temperatures 170 ml of 30% H202 containing 65
0.13% nitrilo tris(methylene)triphosphonic acid (DE
QUEST @2000) to which 5.9 g NaCl and 50 g Na2SO4
was added. The product crystals were ?ltered off, dried
or an alkali metal salt thereof.
4,323,465
3. The composition of claim 1 wherein the polyphos
10
13. The detergent composition of claim 7 wherein the
4Na2SO4.2I-I2O2.NaCl is stabilized with the polyphos
phonate of claim 6.
14. An alkaline peroxygen bleach composition having
phonate is:
a pH in excess of 8 when dissolved in aqueous media
wherein the peroxygen bleaching agent in the composi
tion is 4Na2SO4.2H2O2.NaCl having incorporated in
the crystalline structure thereof an effective amount of
or an alkali metal salt thereof.
10
4. The composition of claim 1 wherein the polyphos
an organic polyphosphonate wherein the polyphos
phonate contains 2 or more —PO3— — functions con
nected through their phosphorous atoms by way of an
phonate is:
alkylene chain optionally interrupted by a nitrogen
atom or containing a hydroxy substituent to stabilize the
(H203PCH2)2N(CH2)2N(CH2P03H2)2
4Na2SO4.2H2.O2.NaCl in said alkaline bleach composi
15 tion.
or an alkali metal salt thereof.
15. The bleach composition of claim 14 wherein the
polyphosphonate is:
5. The composition of claim 1 wherein the polyphos
phonate is:
(H2O3PCHZ)ZN(CHZ)6N(CHZPO3HZ)Z
20
Or an alkali metal salt thereof.
-,6. The composition of claim 1 wherein the polyphos
25 or an alkali metal salt thereof.
phonate 1s:
16. The bleach composition of claim 14 wherein the
polyphosphonate is:
(H203PCH2)ZNCHgCl-IglIICH2CH2N(CH2PO3H2)2
CH2
PO3H2
30
or an alkali metal salt thereof.
7. An alkaline detergent composition having a pH in
or an alkali metal salt thereof.
excess of 8 when dissolved in aqueous media, compris
17. The bleach composition of claim 14 wherein the
ing (a) about 3% to about 70% of the polyphosphonate 35 polyphosphonate is:
stabilized 4Na2SO4.2H2O2.NaCl of claim 1; (b) about
10% to about 80% of a detergent builder; (0) about 0%
' tojiabout 20% of a surfactant and \(d) about 0% to about
50% of a neutral or alkaline ?ller salt.
8. The detergent composition of claim 7 wherein the
4Na2SO4.2H2O2.NaCl is stabilized with the polyphos
phonate of claim 1.
9. The detergent composition of claim 7 wherein the
4N'a2SO4.2H2O2.NaCl is stabilized with the polyphos
or an alkali metal salt thereof.
40
45 or an alkali metal salt thereof.
19. The bleach composition of claim 14 wherein the
polyphosphonate is:
phonate of claim 2.
10. The detergent composition of claim 7 wherein the
4Na2SO4.2H2O2.NaCl is stabilized with the polyphos
phonate of claim 3.
i 11. The detergent composition of claim 7 wherein the
18. Therbleach composition of claim 14 wherein the
polyphosphonate is:
50
. 4Na2SO4.2I-IgO2.NaCl is stabilized with the polyphos
..
$111
phonate of claim 4.
PO3HZ
12. The detergent composition of claim 7 wherein the
4Na2SO4.2H2O2.NaCl is stabilized with the polyphos 55 or an alkali metal salt thereof.
'
*
*
*
*
phonate of claim 5.
60
65
*