Note: Descriptions are shown in the official language in which they were submitted.
lOS'~Z~
BACKGROUND OF THE INVENTION
It has long been recognized that laundry compositions function
more efficiently in soft water than in water containing significant amounts
of dissolved "hardness" cations such as calcium ion, magnesium ion and
the like. Heretofore, laundry water has been softened prior to use, usually
by passing the water through columns of zeolite or other cation exchange
materials. The use of such zeolitic or other cation exchange materials to
pre-soften water requires a separate tank or appliance wherein the water
can be percolated slowly through the ion exchange material to remove the
undesirable cations. Such pre-softening procedures require an additional
expense to the user occasioned by the need to purchase the softener
appliance.
Another means whereby fabric-~c can be optimally laundered
under hard water conditions involves the use of water-soluble builder salts
and/or chelators to sequester the undesirable hardness cations and to
effectively remove them from interaction with the fabrics and detergent
materials in the laundering liquor. However, the use of such water- soluble
builders necessarily introduces into the water supply certain materials
which, in improperly treated sewerage effluents, may be undesirable.
Accordingly, a means for providing water-softening builders in detergent
compositions without the need for soluble builder additivé`s is desirable.
A variety of methods have been suggested for providing builder
and water-softening action concurrently with the deterging cycle of a home
laundering operation, but without the need for water-soluble detergent ~-
additives. One such method employs a phosphorylated cloth which can be
added to the laundry bath to sequester hardness ions and which can be
removed after each laundering; see U. S. Patent 3, 424, 545.
The use of certain clay minerals to adsorb hardness ions from
laundering liquors has also been suggested; see, for example, Rao, in Soap
Vol. 3 #3 pp. 3-13 (1950); Schwarz, et al. "Surface Active Agents and
Detergents", Vol. 2, p. 297 et seq. (1966).
The zeolites, especially the naturally-occurring aluminosilicate
-2-
~s~zz~
zeolites, have been suggested for use in washing compositions; see UO SO
Patent 2,213,641; also U. S. Patent 2,264,103.
Various aluminosilicates have been suggested for use as adjuncts
to and with detergent compositions; see, for example, U. S. Patents
923,850; 1,419,625; and British Patents 339,355; 461,013; 462,591; and
522~ 097O
From the foregoing it is seen that a variety of methods have been
heretofore employed to remove hardness cations from aqueous laundering ~ ~
systems concurrently with the deterging cycle of a home laundry operation. -
However, these methods have not met with general success, primarily due
to the inability of the art-disclosed materials to rapidly and efficiently
reduce the free polyvalent metal ion content of the aqueous laundering liquor
to acceptable hardness levelsO To be truly useful in laundry detergent
compositions, an ion exchange material must have sufficient cation exchange
capacity to significantly decrease the hardness of the laundry bath without
requiring excessive amounts of the ion exchanger. Moreover, the ion
exchange material must act rapidly, io e., it must reduce the cation hardness
in an aqueous laundry bath to an acceptable level within the limited time
(ca. 10-12 minutes) available during the deterging cycle of a home laundering ~ -
operation. Optimally, effective ion exchange materials should be capable ~
of reducing calcium hardness to about 1 to Z grains per gallon within the ~-
first 1 to 3 minutes of the deterging cycle. Finally, useful cation exchange
builders are desirably substantially water-insoluble, inorganic materials
which present little or no ecological problems in sewage.
It has now been found that certain aluminosilicate materials
have both the high ion exchange capacity and the rapid ion exchange rate
needed for cation exchange builder materials in laundry detergent -~
compositions.
Accordingly, it is an object of the present invention to provide
detergent compositions containing insoluble, inorganic aluminosilicate ion
exchange materials.
It is a further object herein to provide methods for laundering
- 3 _
~os~z~z~
fabrics using the aforesaid detergent compositions.
These and other objects are obtained herein as will be seen
from the following disclosure.
SUMMARY OF THE INVENTION
The instant invention is, in part, based on the discovery that
cleaning and washing compositions capable of rapidly reducing the free
polyvalent metal ion content in laundering liquor can now be prepared
comprising a particular water-insoluble aluminosilicate ion exchange
material in combination with surface active ingredientsO In particular,
the detergent compositions of this invention comprise:
(a) from about 5% to about 95% by weight of a water-insoluble
crystalline aluminosilicate ion exchange material of the
formula
Naz [ (A 1 O2) z . ( SiO2 )y ]XH2
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, preferably
from about 0.8 to 1.0; and x is an integer from about 15 to
about 264, preferably about 27; said aluminosilicate ion
exchange material having a particle size diameter from
about 0.1 micron to about 100 microns; a calcium ion
exchange capacity on an anhydrous basis of at least about
200 mg. eq. /g.; and a calcium ion exchange rate on an
anhydrous basis of at least about 2 grains/gallon/n~inute/gram;
and
(b) from about 5% to about 95% by weight of a water-soluble
organic surface-active agent selected from the group
consisting of anionic, nonionic, ampholytic and zwitterionic
surface-active agents and mixtures thereof.
The above compositions are disclosed and claimed in Canadian
Patent Application 199,507, filed May 10, 1974, of which this application
is a divisional.
In another embodiment, as clai~:ned in the present application,
- 4 -
105'~;~Z~
the invention resides in a water softener composition comprising:
a) from about 5% to about 95% by weight of a water-insoluble
crystalline inorganic aluminosilicate ion exchange material : -
of the formula ~ ~.
Nal2(Al02.sio2)l2-~ H20
wherein x is an integer of from about 20 to about 30, said
ion exchange material being characterized by a particle ~ :~
diameter of from about 1 micron to about 100 microns, a ~.
calcium ion exchange capacity on an anhydrous basis of at
least about 200 mg eq. /g, and a calcium ion exchange rate :
on an anhydrous basis of at least about 2 grains/gallon/
minute /gram; and
b) froIn about 5% to abouS 95% by weight of an auxiliary builder.
In a preferred embodiment herein, the water-insoluble ~ ::
aluminosilicate ion exchange material has the formula ~ .
Na 12 (A1O2 . SiO2 )12 .x H2 - :
wherein x is an integer of from about 20 to about 30 (preferably about 27)~
The detergent compositions herein can contain, in addition to
the ion exchange material and organic detergent compound, various other
20 ingredients commonly
;,
" ', .
_ 5_ 6
. .
l~s~
employed in detergent compositions. In particular,
auxiliary, water-soluble builders can be employed
in the compositions to aid in the removal of calcium
hardness and to sequester magnesium cations in water
where dissolved magnesi~m salts create significant
hardness problems.
Additionally, the compositions herein can
contain pH adjusting agents to ~aintain the pH of
the laundering liauor within a desired range.
. 10 DETAIT.F~D DESCRIPTION OF l~lE INVENTION
The aluminosilicate ion exchange materials
herein are prepared by a pro_ess which results in the
formation of materials which are particularly suitable
for use as detergency builders and water softeners.
Specifically, the aluminosilicates herein have both a
higher calcium ion exchange capacity and a higher
exchange rate than similar mater~als heretofore suggested
as detergency builders. Such highjcalcium ion exchange
rate and capacity appear to be a function of several
interrelated factors which result from the method of
preparing said aluminosilicate ion exchange materials.
One essential feature o~ the ion exchange builder
materials herein is that they be in the "sodium form".
That is to say, it has surprisingly been found, for
example, that the potassium and hydrogen forms of the
instant aluminosilicate exhibit neither the exchange
rate nor '.he exchange capacity necessary for optimal
builder use,
105'~
~ second e~sential feature of the ion exchange
builder material~ herein ~s that they be in a hydrated
form, i.e. contain 10%-28~/o~ preferably 10%-22%~ by
weight of water. Highly preferred aluminosilicates
herein contain from about
18~ to about 22% (wt~) water in their crystal matrix.
It has been found, for example, that less highly
hydrated aluminosilicates, e.g. those with about 6%
water, do not function effectively as ion exchange -~
builders when employed in the context of a laundry
detergent composition.
A third essential feature of the ion exchange
builder materials herein is their particle slze range
Proper selection of small particle sizes results in
fast, highly efficient builder materials.
The method set forth below for preparing the
aluminosilicates herein takes into consideration all
of the foregoing essential elements. Fir~t, the method
avo~ds contamina~ion of the aluminosilicate product by
cations other than sodiu~. For example, product
washing steps involving acids or bases other than
sodium hydroxide are avoided. Second, the process
is designed to form the aluminosilicate in its most
highly hydrated form. Hence, high temperature heating
and drying are avoided. Third, the process is designed
to form the aluminosilicate materials in a finely-
divided state having a narrow'range of small particle
sizes. Of course; additional gr~nding operations can
be employed to st~ll further reduce the particle size.
,
8_
~ . . . . : : . -
lOS'~ZZl '
However, the need for such mechanical reduction steps
is sub~tantially lessened by the procesQ herein.
The aluminosilicates herein are prepared
according to the following procedure:
(a) dissolve qodium aluminate (Na A102) in
water to form a homogeneous solution
having a concentration of Na A~O2 of
- about 16.5% by weight (preferred);
~) add sodium hydroxide to the sodium
aluminate solution of step (a) at a
we~ght ratio of NaOH:Na AlO2 of 1:1.8
(preferred) and maintain the temperature
of the solution at about 50~C until
all the NaOH dissolves and a homogeneous
~olution forms;
(c) add sodium silicate (Na2 SiO3 having a
SiO2:Na2O weight ratio of 3.2 to 1) to
the solution of step (b) to provide a
sol~tion having a weight ratio of
Na2SiO3:NaOH of 1.14:1 and a weight
ratio of Na2SiO3:NaAlO2 of 0.63:1;
(d) heat the mixture prepared in step (c~
to about 90C - 100C and maintain at
this temperature range for about one
hour.
In a preferred embodiment, the mixture of
step (c~ i~ cooled to a temperature below about 25C,
preferably in the range from 17C to 23~C, and main-
t~ned at that temperatur~ for a period from about 25
hours to about S00 hours, preferably from about 75
hours to about 200 hours.
l~)S'~
Tne mixture resulting from step (d) is cooled
to a temperature of about 50C and thereafter filtered
to collect tne desired aluminosilicate solids. If the
low temperature (<25C) crystallization technique is
used, then the precipitate is filtered without addi-
tional preparatory steps. The filter cake can option-
ally be washed free of excess base (deionized water
wash preferred to avoid cation contamination). The
filter cake is dried to a moisture content of 18~ - 22%
by weight using a temperature below about 150C to
avoid excessive dehydration. Preferably, the drying
is performed at 100C - 105~C.
Following is a typical pilot-plant scale - -
preparation of the aluminosilicates herein.
105'~Z2~
: .
.
~ _ .
.
'~ EO~ c, tQ U, a~ . ' '
3 ~ N O
~1
O ~D O a~ ~r
P
W ~ ~ D O
H ~ ~1 111 ~D
3 ~ 0~
~ m :~ u~ ~ O
' E~
, . ~ m O ~ u~ er
o ~a ~ ~ ~ O
Z ~ ~ ~ O~
H ~ ~
~, ~ O ~ O~ O 1`
~ 3 ~ c ~ ~
,, . ~
,,. . o
,." :Z
~ . H U) U~ 1`~ D O
:`'- ~ ~ ~_~
. ~ ~ U~~ pO, ~ U) 0
.' P~
a~
~ Z 0
O - N
~ ~-,1 o
, C: 0 '~
~ t~
O O ~ . ' _
E~ ~ ~0 ~ ~ '
c.) z ~q~ z ~ :
'
.
--11-- "
lOS;~
The sodium alumin~te was dissolved in the water
with stirr~ng and the sodium hydroxide added thereto.
The temperature of the mixture was maintained at 50C
and the sodium silicate was added thereto with stirring.
The temperature of the mixture was raised to 90C - 100C
and maintained wi~hin this range for 1 hour with stirring
to allow formation of Nal2(AlO2-SiO2)12 27 H20. The
mixture was cooled to 50C, filtered, and the filter
cake washed twice with 100 lbs. of deionized water.
The cake was dried at a temperature of 100C - 105C to
a moisture content of 18~/o ~ 22% by weight to provide the
aluminosilicate builder material.
The aluminosilicates prepared in the foregoing
manner are characterized by a cubic crystal structure.
Water-insoluble aluminosilicates having a molzr
ratio of (A102):(SiO2) smaller than 1, i.e. in between
1.0 and about 0.5, can be prepared in a similar manner.
These aluminosilicate ion exchange materials
(A102:SiO2 ~1) are also capable of effectively reducing
the free polyvalent hardness metal ion content of an
aqueous washing liquor in a manner substantially
similar to the aluminosilicate ion exchange material
having a molar ratio of AlO2:SlO,2 = 1 as described
hereinbefore. Examples of aluminosilicates having a -
molar ratio. A102:SiO2 Cli suitable for use in the
instant compositions include:
,
1~)5~
86 [ (A12 ) 86 (Sio2 ) 106 ] ' 264 H2O; and
Na6 [ (A 12 ) 6 (S io2 ) 10 ] ' 15 H2 .
:~os~z21 ,
Although completely hydrated aluminosilicate ion
exchange materials are preferred herein, it is recognized
that the partially dehydrated aluminosilicates having
the general formula given hereinbefore are also excel-
S lently suitable for rapidly and effectiveiy reducing
the water hardnes~ during the laundering operation.
Of course, in the process of preparing the instant
aluminosilicate ion exchange material, reaction- -
crystallization parameter fluctuations can result in
such partially hydrated materials. As pointed out
previously, aluminosilicates having about 6% or less
water do not ~unction effectively for.the intended ..
purpose in a laundering context. The suitability of .
particular..partially dehydrated water-insoluble
15 aluminosilicates for use in the compositions of this
invention can easily be asserted and does only involve
routine testing as, for example, described herein
(Ca-ion exchange capacity; rate of exchange).
The ion exchange properties of the alumino-
silicates herein can conveniently be determined bymeans of a calcium ion electrode. In this technique,
the rate and capacity of Ca uptake from an aqueous
solution containing a known quantity of Ca+~ ion is
determined as a function of the amount of alumino-
silicate ion exchange material added to the solution.
The water-insoluble, inorganic aluminosilicate
ion exchange materials prepared in the foregoing manner
are characterized by a particle size diameter from
-14-
l~)S'~ZZl
a~out ~.1 micron to about 100 microns. Preferred iron exchange
materials have a particle size diameter from about 0.2 micron to
about 10 microns. Additional preferred water-insoluble alumino-
silicates herein are characterized by a particle size aiameter from
about 0.2 micron to about 0.7 micron ~ The term "particle size
diameter" herein represents the average particle size diameter of
a given ion exchange material as determined by conventional
analytical techniques such as, for example, microscopic determin-
ation, scanning electron microscope (SEM).
The aluminosilicate ion exchangers herein are further
characterized by their calcium ion exchange capacity, which is
at least about 200 mg. equivalent of CaCO3 hardness/gram of
aluminosilicate, calculated-on ~n anhydrous basis, and which
generally lies within the range of from about 300 mg. eq./g. to
about 352 mg. eq./g.
The ion exchange materials herein are still further
characterized by their calcium ion exchange rate, which is at
least about 2 grains (Ca+~)/gallon/minute/gram of aluminosilicate
lanhydrous basis), and lies within the range of about 2 grains/
gallon/minute/gram to about 6 grains/gallon/minute/gram, based
on calcium ion hardness. Optimum aluminosilicates for builder
purposes exhibit a Ca~ exchange rate of at least about
4 grainsJgallon/minute/gram.
The foregoing procedure for preparing the
aluminosilicate ion exchange materials herein can ~e
modified in its various process steps, as follows. -
- 15 -
: - . : .
S'~Z~
Step (a) can be modified by u~ing solution concentra-
tions of NaAlO2 of from 5% to 22% by weight; the
optimum concentration is 16% to 16.5%. Step (b) can
be modified by aeletion of the NaOH. Sodium hydroxide
is no~ required to form the aluminosilicates herein
but its use is preferred to initiate the reaction
and to maintain reaction efficiency. Step (b~ can
be further modified by use of temperatures within
the range of from about 30C to about 100C; 50C is
preferred. Step (c) can be modified by varying the
ratio of aluminate to silicate. In order to satisfy
- the 1:1 A102:SiO2 stoichiometry requirements of a
specifically preferred species in the final product,
it is necessary to provide in that particular case at
15 least a 1:1 mole ratio of AlO2:SiO2 (based on NaAlO2
and Na2SiO3) in t.ie mix. In ti~at latter event, it
is highly preferred to employ an excess of NaAlO2,
inasmuch as excess NaAlO2 has been found to promote
the rate and efficiency of the formation reaction of
aluminosilicates having a 1:1 molar ratio of
AlO2:SiO2. Suitable water-insoluble aluminosilicate
ion exchange materials having a molar ratio of
AlO2:SiO2 of less than about 1.0, i.e. from 1.0 to
about 0.5, can be prepared as described hereinbefore
except that the molar amount of SiO2 is increased
~he proper determination of the excess silicate to
be used in the formation reaction can easily be
optimized and does only require a routine investigation.
-16-
: ' ,, - .
iOS'~Z2~
Step (d~ can be modified to employ temper-
~tures from 50C to 110C at ambient pressure~,
90C to 100C is optimal. Of course, higher temperature~
can be employed if high pressure equipment i~ used to
prepare the alum~nosilicates. When the high-temperature
~90-100C) crystalliz~tion technique i~ used, step (d)
will normally require a formation reaction time of
about 1 to 3 hour~. As noted hereinbefore, an addi-
tional po~sibility for preparing the ion exchange
materials resides in modifying step ~d) by cooling the
mixture of step (c) to a temperature below about 25C,
preferably in the range from 17C-23C, and maintaining
said mixture at that temperature for a period from about
25 hour~ to 500 hours, preferably from about 75 hours
to about 200 hours.
Following the formation of the aluminosilicates
by the foregoing procedure, the materials are recovered
and dried. When employed as ion exchange builders, th~
aluminosilicates must be in a highly hydrated form,
i.e. 10% to 28%, preferably 10% to 22%, by weight of
water. Accordingly, drying of the aluminosilicates
must be carried out under controlled temperature condi-
tions. Drying temperatures of from about 90C to
about 175~C can be employed. However, at drying ~ -
temperatures from about 150C to about 175C, the
less highly hydrate~ materials (ca. 10% H20) are
obtained. Accordingly, it is preferred to dry the
alumlnosllicates at 100C to 105C, whereby the optimum
"
--1
.
` 105~'~Zl
builder materials containing 18% to 22% by weight of water are securedO
At these latter temperatures, the stability of the preferred Z7-hydrate
form of the aluminosilicate is independent of drying timeO
The ion exchange materials prepared in the foregoing manner
can be employed in laundering liquors at levels of from about 0. 005% to
about 0O 25% by weight of the liquor, and reduce the hardness level,
particularly calcium hardness, to a range of about 1 to 3 grains/gallon
within about 1 to about 3 minutes. Of course, the usage level will depend
on the original hardness of the water and the desires of the userO Highly
10 preferred detergent compositions herein comprise from about 20% to
about 50% by weight of the aluminosilicate builder and from about 15%
to about 50% by weight of the water-soluble, organic detergent compoundO
In another highly preferred embodiment, the compositions herein comprise
from about 10% to about 50% by weight of the aluminosilicate builder.
DETERGENT COMPONENT
The detergent compositions of the instant invention can contain
all manner of organic, water-soluble detergent compounds, inasmuch as
the aluminosilicate ion exchangers are compatible with all such materials.
A typical listing of the classes and species of detergent compounds useful
20 herein appears in U, S. Patent 3, 664, 961 of Russell Norris, issued May
23, 1972. The following list of detergent compounds and mixtures which ~;
can be used in the instant compositions is representative of such materials,
but is not intended to be limitingO
- 18 -
.
lOS~Z'~
~ater-soluble salts of t~e higher fatty acids,
i.e. ~soapsn, are useful as the detergent component of
the compositions herein. This class of detergents
includes ordinary alkali metal soaps such as the
sodium, potassium, ammonium and alkylolammonium salts
of Aigher 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 saponifi-
cation 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.
Another class of detergents includes water-solu~le
salts, particularly the alkali metal, amm~nium and alkylolammonium
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 ~etergents
~hich form a part of the detergent compositions of the present
invention are the sodium and potassium alkyl sulfates, especially
those obtained by sulfating the higher alcohols (C8 - C
carbon atoms) produced by reducing the glycerides of tallow
or coconut oil; ana sodium and potassium alkyl benzene sulfonates,
in which the alkyl group contains from about 9 to about 15
carbon atoms, in straight chain or branched chain configuration,
-19-
.
e.g. those of the type described in United States Patents
2,22~,099 and 2,477,383. Especially valuable are linear straight
chain alkyl benzene sulfonates in which the average of the
alkyl groups is about 13 carbon atoms, abbreviated as C13 LAS-
. Other anionic detergent 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 1 to about 10 units of ethylene oxideper molecule and wherein the alkyl groups contain about 8 to
about 12 carbon atoms.
Water-soluble nonionic synthetic detergents are also
useful as the detergent component of the instant composition.
Such nonionic detergent materials can be broadly defined
as compounds produced by the condensation of alkylene oxide
groups (hydrophilic in nature) with an organic hydrophobic
compound, which may be aliphatic or alkyl aromatic in nature.
The length of the polyoxyalkylene group which is condensed _
with any particular hydrophobic group ca~ be readily adjusted
to yield a water-soluble compo~nd having the desired degree_s~ -
balance between hydrophilic and hydrophobic elements.
For example, a well-known class of nonionic synthe.tic
detergents is made avai-lable on the market under the trade~
mark of "~luronic.'~ These compounds are formea by condensing - ~
-20-
lOSZ;~Zl
ethylene oxide with a hydrophobic base formPd by the condensa-
tion of propylene oxide with propylene glycolO Other suitable
nonionic synthetic detergents include the polyethylene oxide
condensates of alkyl phenols, e.g., the condensation products of
5 alkyl phenols having an alkyl group containing from about 6 to
12 carbon atoms in either a straight chain or branched chain
configuration, with ethylene oxide, the said ethylene oxide
being present in amounts equal to 5 to 25 moles of ethylene
oxide per mole of alkyl phenol.
The wate~-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 S to 30
mnles of ethylene oxide per mole of coconut alcohol, the
15 coconut alcohol fraction having from 10 to 14 carbon atoms,are
also useful nonionic detergents herein.
Seml-polar nonionic detergents include water-soluble amine
oxides containing one alXyl moiety of from about 10 to - :~
28 carbon atoms and 2 moieties selected from the group
20 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 t~e group consisting
of alkyl groups and hydroxyalkyl groups containing from
25 about 1 to 3 carbon atoms; and water-soluble sulfoxiae ~-
.
.. ..
105~ZZ~
aetergents containing one alXyl iety of from about 10 to 28
carbon atoms and a moiety selected from the group consisting
of alXyl 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 c~ain or branched ana 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 sub-
stituents contains from about 8 to 18 car~on atoms and one
contains an anionic water solubilizing group.
Other useful detergent compounds herein include thewater-soluble salts of esters of a-sulfonated fatty acids con-
taining from about 6 to 20 carbon atoms in the fatty acid group
20 and from about 1 to 10 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; alkyl ether
sulfates containing from about 10 to 20 carbon atoms in the
25 alkyl group and from about 1 to 30 moles of ethylene oxide;
-2a_ .
105~Z~ , ` .
- w~ter-soluble salts ~f olefin sulfonates containing from about
12 to 24 carbon atOmS; and ~-alkyloxy alkane sulfonates con-
taining from about 1 to 3 carbon atoms in the alXyl group and
from about 8 to 20 carbon atoms in the alkane moiety.
Preferred water-soluble organic detergent compounds
herein include linear alkyl benzene sulfonates containing
from about 11 to 14 carbon atoms in the alkyl group; the
tallow range alkyl sulfates; the coconut alkyl glyceryl
sulfonates; alkyl ether sulfates wherein the alkyl moiety
cont~ ns from about 14 to 18 carbon atoms and wherein the
average degree of ethoxylation varies between 1 and 6; the `.
~ulfated condensation products of tallow alcohol with from .
about 3 to 10 moles of ethylene oxide; olefin sulfonates
containing from about 14 to 16 carbon atoms; alkyl dimethyl
amine oxides wherein the alkyl group contains from about 11
to 16 carbon atoms, alXyldimethyl-ammonio-propane-sulfonates
and alkyl-dimethyl-ammonio-hydroxy-propane-sulfonates wherein
the alkyl group in both types contains from about 14 to 18
car~on atoms: soaps, as hereinabove defined; the condensation :
product of tallow fatty alcohol wi~h about 11 moles of e.thylene
oxide; and the condensation product of a C13 (avg.) secondary -
alcohol with 9 moles of ethylene oxide.
. Specific preferred detergents for use herein
include: sodiu~ linear C10 - C18 alkyl benzene sulfonate;
triethanolamine C10 - C18 alkyl benzene sulfonate: sodium
'~'. '
.
. ............... . . ~ . ~ .............. . . . .
' ' ' '' ~ . . : ,, ,
105~
tallow alkyl sulfate; sodium coconut alkyl glyceryl ether
sulfonate; the sodium salt of a sulfated con~ensation product
-~ of a tallow alcohol with from about 3 to about lO moles of
ethylene oxide~ the condensation product of a coconut fatty
alcohol with about 6 m~les of ethylene oxide; the condensation
product of tallow fatty alcohol with about ll moles of ethylene
oxide; 3-(N,N-dimethyl-N-coconutalkylammonio).-2-hydroxypropane-
l-sulfonate; 3-(N,~-dimethyl-N-coconutalkylammonio-propane-l-
sulfonate; 6-(N-dodecylbenzyl-N,~-dimethylammonio)hexanoate; :~
10 dodecyl dimethyl amine oxide; coconut alkyl dimethyl amine ~.
oxide; and the water-soluble sodium and potassium salts of ~.
higher fatty acids containing 8 to 24 carbon atoms.
It is to e reoognized that any of the foregoing
~ .
detergents can be used separately herein or as mixtures.
15 Examples of preferred detergent mLxtures herein are as follows. ~.
An especially preferred alkyl ether sulfate detergent
component of the instant compositions is a mixture of alkyl -.-
ether sulfates, said mixture having an average (arithmetic mean)
carbon chain length within the range of from about 12 to 16
..
carbon atoms, preferably from about 14 to lS carbon atoms, and
:
an average (arith~etic mean) degree of ethoxylation of from
. about 1 to 4 moles of ethylene ~xide, preferably from about
2 to 3 moles of ethylene oxide.
J . ---
.25 __
~ ,
, , . . - . ' ., '~
-2
~ ,. . . .
Specifically, such preferred mixtures comprise from
about 0.05% to 5% by weight of mixture of C12 13 compounds,
from about 55% to 7~/O by weight of mixture of C14 15 compounds,
from about 25% to 4~O by weight of mixture of C16 17 compounds
and from about 0.1% to 5% by weight of mixture of C18 19
compounds. Further, such preferred alkyl ether sulfate mixtures
comprise from about 15% to 25% by weight of mixture of compounds
having a degree of ethoxylation of 0, from about 50% to 65% by
weight of mixture of compounds having a degree of ethoxylation
from 1 to 4, from about 12% to 22% by weigh~ of mixture of
compounds having a degree of ethoxylation from 5 to 8 and
from about 0.5% to l~/o by weight of mixture of compounds having
a degree of ethoxylation greater than 8.
Examples of alkyl ether sulfate mixtures falling
within the above-specified ranges are set forth in Table I.
.
-
~oszzz~ ~
.
. ~ I ~
~:> ~ 1~ 00 N . CO 11'1 ~ U7
XH ~ 11~ ~ t-l --~ Il) t`l Z
H
~ . . .-
. . ,', ~ '
Ed dP , tlP
~H CO dP dP d~ dP 11'3 0~ --I 0
1~ H ~ '1 ~1 . t~ 7 t~l O Z
H ~ ~o ~ . t~ ~ ~1
. , _
12 0~ ~
~ ~ W dP d~ ~ ~ dP ~
:~: H ~ ~ ~ . _1 ~ 1` ~ Z
E l ~ ~D r~ N ~ 11'1 _I
. E" _l
H --
~ . '
~ ~ ~D dP d~ d~ dP OD dP dP dP dP
E~ :~; H 'r ~ U-) ~ ~ '~ ~
. ~S _l U~ _l ~ `J .,
_ ~ ~
. , dP dP -
dP J~ J~
~ 3 3 3
_ __ ~ ~. 3 _
dP dP dP dP ~1 _ ~ a
.... x ~a ~ a)
O ~ 1
H 3 . 3 3 :~c .C ^ ~ X X -~
E~ C:^ _ j_ _ _ ~ 0 ~1 O O X
tl~ -~ U~ . ~ ~:1 X O
H ~ ~ tr~ O C) O
~ s O ~ ~
E~ ~ o, 1 0 0 0 O CJ au a) CJ
El ~C ~: !~ ~ IJ _I ' ~
~> ~ I~ ~U Oa~
~ O U ~ ~ ~
P~ .~:a ~ ~ ~ ~ ~ s
~ ~ o o o o ~ ~ a) a~
:~ ~ o ~ ~ 5~ ~ . g) o ~ a
o o z ~ ~ z a) L~ ~0
_ ~ _ ~ .
w a) ~ .) a) u~
tr: ~ ~ ~ ~ O O _~
::) ~ ~ ~ ~ O ~ O
E- h b~ ~1 ~ I ~rl O E~
X Q~ ~ I I ~ I I ~ ~ ~
H ~ 0 t~ ~ ~D 0 ~ 0 I I ~ 1~
~: ''S-:l ~ 1 ~ O ~ 1~ O~ ~a
U~ O U~
--2 6-
- ` .
105i~Z2~L
- Preferred "olefin sulfonate" detergent mixtures
utilizable herein comprise olefin sulfonates containing from
a~ou~ 10 to about 24 carbon atoms. Such m~terials can be
produced by sulfonation of Q-olefins by means of uncomplexed
sulfur dioxide followed by neutralization under conditions.
such that any sultones present are hydrolyzed to the corres-
ponding hydroxy-alXane sulfonates. The a-olefin starting
materials preferably have from 14 to 16 carbon atoms. Said
preferred ~-olefin sulfonates are described in U. S. Patent ;
3,332,880 of Ressler et al., issuea July 25, 1967.
., , ~,
~ Preferred ~-olefin sulfonate mixtures-herein
consist essentially offrom about 30/O to about 7~/O by weight
of a Component A, from about 2~/o to about 70/O by weight of a
Component B, and from about 2% to about 15% of a Component C,
15 wherein
(a) said Component A is a mixture of double-bond
positional isomers of water-soluble salts of
alkene-l-sulfonic acids containing from
about 10 to about 24 carbon atoms, said
mixture of positional isomers including about
l~/o to about 25% of an alpha-beta unsaturated
isomer, about 30/O to about 70/O of a beta-
gamma unsaturated isomer, about 5~O to about
25% of gamma-delta unsaturated isomer, and about
5% to about l~/o of a delta-epsilon unsaturated
-27-
:~.
l~S'~Z'~l
isomer;
.(b~ said Component B is a mixture of water-soluble
salts of bifunctionally-substituted sulfur-
containing saturated aliphatic compounds
containing from about 10 to about 24 carbon
atoms, the functional units being hydroxy
- .- ana sulfonate groups with the sulfonate ;~
groups always being on the terminal - - ;
carbon and the hydroxyl group being attached
to a carbon atom at least tw~ carbon atoms
removed.from the terminal carbon atoms at
least 90/O of the hydroxy ~roup substitutions
being in 3, 4, and 5 positions; and
~c) said Component C is a mixture.comprising from
about 30/O-95% water-soluble salts of alkene
. disulfonates containing from about 10 to about 24
carbon atoms, and from about 5% to about
7~% water-soluble salts of hydroxy disulfonates
containing from about 10 to about Z4 carbon
atoms, said alkene disulfonates containing a
sulfon.ate group attached to a terminal carbon
atom and a second sulfonate group attached
to an internal carbon atom not more than about
six carbon atoms removed from said terminal
2~ carbon atom,.the alkene double bond being dis-
tributea between the terminal carbon atom and
-- .
b t th lU~ h~l '
disulfonates being saturated aliphatic compounds
having a sulfonate group attached to a
terminal carbon, a second sulfonate group
attached to an internal carbon atom not more
than about six carbon atoms removed from said
~erminal carbon atom, and a hydroxy group
attached to a carbon atom which is not more-
than about four carbon atoms removed from the
.site of attachment of said second sulfonate group.
. ~OS'~Z21
Auxiliarv Builders
A~ noted hereinabove, the detergent composition3
of the present invention can contain,in addition to the
aluminosilicate ion exchange builders, auxiliary,water-
soluble builders such as those taught for use in
detergent compositions. Such auxiliary builders can be
employed to aid in the seguestration of hardneqq ionq
and are particularly useful in combination with the
aluminosilicate ion exchange builaers in qituations
where magnesium ions contribute significantly to w~ter
hardness. Such auxiliary buil~erq can be employed in
concentrations of from about 5% to about 50%
by weight, preferably from about 10% to about 35%
by weight, of the detergent compositions herein to
provide their auxiliary builder activity The auxiliary
builders herein include any of the conventional inorganic
and organic water-soluble builder salts.
Such auxiliary builders can be, for example, water-
soluble salts of phosphates, pyrophosphates, orthophosphates,
polyphosphates, phosphonates, carbonates, polyhydroxysulfonates,
silicates, polyacetates, carboxylates, polycarboxylates and
succinates. Specific examples ~f inorganic phosphate builders
include sodium and potassium tripolyphosphates, pyrophosphates,
phosphates, ana hexametaphosphates. The polyphosphonates specif-
ically include, for example, the sodium and potassium salts of
ethylene aiphosphonic acid, the sodium and potassium salts ofethane l-hydroxy~ diphosphonic acid and the sodium and
potassium salts of ethane-1,1,2-triphosphonic acid. Examples of
_30_
1~)5'~ZZl
these and other phosphorus builder compounds are disclosed in
U.S. Patents 3,-159,~81,--3,213,030, 3,422,021, 3,422,137"
` 3,400,176 and 3,400,148.
~ on-phosphorus containing .~equestrants can also
bc selected for use herein as auxiliary builders.
Specific examples of non--phosphorus, inorganic auxi- ;
liary aetergent builder ingredients include water-soluble
inorganic carbonate, bicarbonate, ana silicate
saltq. The al~ali metal, e.g., soaium ana pota~-
3ium, carbonate , bicarbonates, and silicates are
particularly useful herein.
Water-soluble, organic auxiliary builders are also
u~eful herein. For example, the alXali metal, ammonium ~;
and substituted ammonium polyacetateY, carboxylates, --
polycarboxylates and polyhydroxysulfonates are useful auxiliary :
builders in the present compositions. Specific example~
of the polyacetate and polycarboxylate builder sa~ts - -
include sodium, potassium, lithium, ammonium and substituted
ammonium salts of ethylene diamine tetraacetic a~id
nitril~triacetic acid, oxydisuccinic acid, mellitic acid,
benzene polycarboxylic acids, and citric acid.
Highly preferred non-phosp~orus auxiliary builder
~ . materials herein include sodium carbonate, sodium bicarbonate,
sodium silicate, sodium citrate, soaium oxydisuccinate,
sodium mellitate, sodium nitrilotriacetate, and sodium
ethylenediaminetetraacetate, and-mixtures thereof.
Other highly preferred auxiliary builders herein are
the polycarboxylate builders set forth in U.S. Patent 3,30~,067, -
- 105'~
Diehl, issued March 7, 1967. Examples of such
material~ include the water-soluble salts of homo- and
co-polymerq of aliphatic carboxylic acidq such as m~leic
acid, itaconic acid, meqaconic acid, fumaric acid, aconitic
acid, citraconic acid, methylenemalonic acid, 1,1,2,2-ethane
tetracarboxylic acid, dihydroxy tartaric acid and keto~malonic
acid.
Additional, preferred auxiliary builders herein
include the water-qoluble saltq, especially the ~odium and
potasqium ~altq, of carboxymethyloxymalonate; carboxymethyl-
oxysuccinate, cis-cyclohexanehexacarboxylate, ciq-cyclopenta-
netetracarboxylate and phloroglucinol tri~ulfonate.
Specific examples of highly preferred phosphorus con-
taining auxiliary builder salts for use herein include alkali
pyrophosphates whereby the weight ratio of ion exchange
material to pyrophosphate is within the range from about 1:2
to about 2:1. Additional preferred auxiliary co-builders
such as the alkali salts of sodium tripolyphosphates and
nitrilotriacetic acid provide equally superior performance
for a weight ratio of ion exchange material to`,auxiliary
builder salt in the range from about 1:1 to abdut 1:3.
The ion exchange aluminosilicates in combination with citrate
auxiliary builder salts will provide superior free metal ion
depletion in washing li~uor when the zeolites used have a
25 molar ratio of AlO2:SiO2 of 1:1. It is understood that in
the above preferred ranges of auxiliary builder to alumino-
silicate the builder component can be represented~by mixtures
of said builders.
The detergent compositions herein containing the
aluminosilicate ion exchange builder and the auxiliary, water-
_32-
,
105~2~1
soluble builder are useful by virtue of the fact that the
aluminosilicate preferentially adsorbs calcium ion in
the presence of the auxiliary builder material. Accordingly,
the calcium hardness ions are primarily removed from solu-
tion by the aluminosilicate while the auxiliary builderremains free to sequester other polyvalent hardness ions,
such as magnesium and iron ions.
The deter~ent compositions herein can contain all
manner of a~ditional materials commonly found in laundering
10 and cleaning compositions. For example, such compositions
can contain thickeners and soil suspending agents such as
carboxymethylcellulose and the like; Enzymes, especially
the proteolytic and lipolytic enzyme~ commonly used in
laundry d~tergent compositions,can also be present herein.
15 Various perfumes, optical bleacheQ, filler~, anti-caking
agent3, fabric softeners and the like can be present in the
compositions to provide the usual benefits occasioned by
the use of such materials in detergent composition~. It
is to be recognized that all such adjuvant materials are
20 useful herein inasmuch as tney are compatible and stable - -
in the presence of the aluminosilicate ion exchange
builders.
The granular detergent compositions herein can also
advantageously contain a peroxy bleaching component in an
25 amount from about 3% to about 40% by weight, preferably from
about 8% to about 33~ by weight. Examples of suitable
peroxy bleach components for use herein include perborates,
-33-
l(~S;~2Z~
persulfates, persilicates, perphosphates, percarbonates
and more in general all inorganic and organic peroxy
bleaching agents which are known to be adapted for use in
the subject compositions.
The detergent compo~itions o this invention can be
prepared by any of the several well known procedures for
preparing commercial detergent compositions. For example, the
compositions can be prepared by simply admixing the
alumin~ilicate ion exchange material with the water--
soluble organic detergent compound. The adjuvant builder
material and optional ingredient~ can be simply admixed
therewit~, as desired. Alternatively, an aqueous slurry of the
aluminosilicate on exchange ~ilder containing the dissolved,
water-soluble organic detergent compound and the optional
15 and auxiliary materials can be spray-dried in a tower
to provide a granular composition. The granules of such
spray-dried detergent compositions contain the alumino-
~ilicate ion exchange builder, the organic detergent
compound and the optional and auxiliary materials.
Alternatively, the aluminasilicate ion exc~ange
materials herein can be employed-separately in aqueous laundry
and/or rinse baths to reduce hardneQ~ cations. When
. 80 employed, the user can simply admix an effective
amount, i.e., an amount sufficient to lower the hardness
25 to about 1 to 2 grains per gallon, to the aqueGus
bath ana thereafter add any commercial detergent compo~ition -~
-3
105'~ZZ~ ,
of choice. Generally, when employed in this manner the
aluminosilicate will be added at a rate of about 0 005% to about
0.25h by weight of the aqueous bath.
The ion exchange alumino~ilicates herein can also
5 be employed in combination with standard cationic fabric
~ofteners in fabric rinses. When so employed, the alumino-
silicates remove the hardnes~ cations and result in a softer
feel on the softened fabrics Typical cationic fabric
softeners useful in combination with the alumin~silicate
10 ion exchangers include tallowtrimethylammonium ~romide,
tallowtrimethylammonium chloride, ditallowdimethylammonium
bromide, ana ditallowdimethylammonium chloride. Aqueous fabric
softener compositions containing the aluminOsilicate ion
exchangers comprise from about 5~O to about 95%
15 by weight of the aluminosilicate and from about 1%
to about 35% by weight of the cationic fabric softener.
~ he detergent compositions herein are employed in
a~ueous liguors to cleanse surfaces, especially fabric
surfaces, using any of the standard laundering and cleansing
20 techniques. For example, the compositions hérein are
particularly suit~d for use in standard automatic washing
machines at concentrations of rom about 0.01% to about
0.50% by weight. Optimal results are obtained when the
compositions herein are employed in an aqueous lzundry
25 bath at a level of at least about 0.10% by weight. As
_
~ 35
lOS;~2;~1
in the case of most commercial laundry detergent composi-
tion~, the dry compo-qitions herein are usually added to a
conve~tional aqueous laundry solution at a rate of about
1.0 cup/17 gallons of wash water.
While the aluminosilicate ion exchange builder
materialq herein function to remove calcium hardness ions
over a wide pH range, it ix preferred that detergent
compositions containing such materials have a pH in the
range of from about 8.0 to about 11, preferably about 9.5
10 to about 10.2. As in the case of other standard deterge~
compositions, the compositions herein function optimally
within the basic pH range to remove soils and triglyceride
solls and -~tains. While the aluminosilicate~ herein
inherently provide a baqic solution, the detergent compo-
sitions comprising the aluminosilicate and the organicdetergent compound can additionally contain from about
5% to about 25% by weight of a pH adjusting agent. Such
compositions can, of cour~e, contain the auxiliary builder
materials and optional ingredients aq hereinbefore ae-qcribed
The pH adjusting agent used in such compositions are--selected
such that the pH of a 0.05/0 by weight aqueous mixture of--
said compo~ition iq in the range of from about 9.5 to
about 10.2.
. .
-
~)5~
The optional pH adjusting agent~ u~eful herein include any
o~ the water-solu~le, basic m~terials commonly employed in
detergent compositions. Typical examples of such water-soluble
materials include the sodium phosphates; sodium silicates,
especially those having a silicon dioxidP:sodium oxide
weight ratio of from akout 1:1 to about 1:3.2,
preferably from about 1:1.7-to about L:2.3; sodium hydroxide:
pota~sium hydroxide; triethanolamine; diethanolamine;
ammonium hydroxide and the like. Preferred pH adjusting
10 agents herein include sodium hydroxide, triethanolamine
and sodium ilicate.
The following examples are typical of the detergent
compositions herFin, but are not intended to be limiting
thereof.
(~ :
.
... ' 105~
o
~ .
J~ , ~, .
~q ,
o
u
3 t~l 'r e~ ~ . . .
O
_~ ~ a~ ,
O ~ ,.~
- , ,.. :
~ '
.C 4~ ,
~IJ . ~ ~ :,
11 ' O :.
O ~ ' :.,'
~1 -rl ~ U ` U
:~ ~ U~
O
0
~ ~ O ~
H h 3 a ~: ~ a) ..
1~R. O -~:
dP d -~1
x ~n a~ ~r a) :
W
O
.~ ~
~ a) a) a~ :
",~
~q d O ~ ~ a) o
O ~ 0 ~ .~ '
0 0 0 IJ X U~
O ~ l ~ O . --1
U Ul ~ ~i5.C
u ~ ~ a) o
e ~ ~0) ~ ~ 3 a) 1 ~
b- O I~ 0 ~
~, u ~o,les ~ ~
n~ 3-U 0 0 ~ ~ `
e o
O
0 o ~ o
~a ~ ~ ~ ~ o o
_I ~ ~~ O o s~
,~ o ~ :~ ~ s ~ _I
o U o
~1 U
o ~ oO O ~, U~
~) ~ 0 ~ a~
~''. ':
.
j
.' ~',,
.~,~, . .
U~
_, . :
_38_ :
1 . .' .
.
S;~Z;~l
` The foregoing composition provides excellent fabric
laundering performance when employed under conventional home
laundering conditions in a laundering liquor-of 7 grains gallon
hardness with a composition concentration in the laundering liquor
of about 0.12% by weight. Under such conditions sudsing and
cleansing performance of the Example I composition compares
favorably with that of conventional, fully built, high-sudsing
anionic detergent formulations. Such a composition-is pourable and
is prepared with conventional spray-drying apparatus.
Compositions of substantially similar performance quality
are secured when, in the above-desçribed Example I composition,
the sodium tallow alkyl sulfate is replaced with an equivalent
amount of potassium tallow alkyl sulfate, sodium coçonut alkyl
sulfate, potassium coconut alkyl sulfate, sodium decyl benzene
sulfonate, sodium undecyl benzene sulfonate, sodium tridecyl
benzene sulfonate, sodium tetradecyl benzene sulfonate, sodium
tetrapropylene benzene sulfonate, potassium decyl-~enzene sulfonate
potassium undecyl benzene sulfonate,-potassium tridecyl-benzene
sulfonate, potassium tetradecyl benzene sulfonate and potassium
tetrapropylene benzene sulfonate, respectI~ely.
Compositions of substantially similar performance
quality, physical characteristics and processability are secured ~:
when in the above-described Example I composition, the conaensation ;~
product of the 15 carbon atom secondary
~ 39 -
105~
alcohol with 9 moleq of ethylene oxide is replaced with an
equivalent amount of the condensation product of tridecyL
alcohol with about 6 moles of ethylene oxide (HLB = 11.4);
the conden~ation product of coconut fatty alcohol with
about 6 moles of ethylene oxide (HLB = 12.0); "Neoa~ol
23-6.5n* (HLB = 12); "Neodol 25-9"** (HLB = 13.1); and
"Tergitol 15-S-9~*** (HLB = 13.3), respectively.
* Trademark
** Trademark
*** Trademark
:~ (
l(~5;~
EX~MPLE II
A spray-dried detergent composition useful in
water containing both Ca~ and Mg++ hardness is prepared
having the following composition:
. Wt.%
Component 24 7% . ~'
Surfactant system comprising:
Sodium linear alkyl
benzene sulfonate
wherein the alkyl
group averages about
11.8 carbon atoms in
length
Condensation product ( anionic/
o one mole of coco- ~ nonionic =
nut fatty alcohol 4 26 1
with about 6 moles
of ethylene oxide
. -~5.0%
*Nal2~AlO2 sio2~12 27 2 15.0
Sodiùm silicate (Na~O/SiO2
~t. ratio = 1:2.4 20.0%
Sodium citrate
5.0
. Sodium Acetate
2.0%
Sodium toluene sulfonate
. 4.0
Water
Balance
Minors
*prepared in the mdninemreter 7.5 microns
~I~
105'~Z2~
The composition of Example II provides excellent fabric
cleansing performance when employed under conventional home laundering
conditions in a laundering liquor of 7 grains/gallon mixed Ca+fand Mg++
hardness with a composition concentration in said laundering liquor of
about 0. lZ% by weightO The composition pH in solution is caO 10.2 at
this concentrationO Under such conditions, sudsing performance of the : -
Example II composition compares favorably with that of conventional,
fully-built, high-sudsing anionic detergent formulationsO Such a
composition is readily pourable and storage stable and is prepared with
conventional spray-drying apparatusO
Compositions of substantially similar performance quality,
physical characteristics and processability are secured when, in the
above composition, the sodium citrate is replaced by an equivalent amount
of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium ~:
silicate, sodium oxydisuccinate, sodium mellitate, sodium nitrilo-
triacetate, sodium ethylenediaminetetraacetate, sodium polymaleate,
sodium polyitaconate, sodium polymesaconate, sodium polyfumarate,
sodium polyaconitate, sodium polycitraconate, sodium polymethylene-
malonate, and mixtures thereof, respectivelyO
A composition of substantially similar performance quality,
physical characteristics and processability is
- 42 - :
. . :. .
securea when, in the above described Example II compo~i-
tion, there i9 incorporated about 3% by weight of ~odium
perborate solid~ with all other components remaining in
~he same relative proportions. Such perborate composi-
tions are particularly adapted for u~e under the wa~hingconditions commonly encountered in Europe.
In the above composition the total surfactant
system is replaced by an equivalent amount of the alkyl
ether sulfate mixtures I, II, III and IV appearing in
Table I, respectively, and excellent detergency performance
is secured.
In the above composition the Nal2(A102 SiO2)12-27H20
is replaced with Nal2(A10? SiO2)12 2
Nal2(A12'SiO2)12'30H20, respectively, and equivalent re~ults
are secured.
(
-
105;~
EXAMPLE III
A phosphorus-free detergent composition is
prepared having the following composition:
.
Component . Wt.%
-
*Surfactant System . 35%
Triethanolamine (pH-adjusting 7% .
agent) :
NaO~ (p~-adjusting agentj . 0.5%
**Nal2(AlO2-sio2)l2 27 ~2
Sodium Citrate 15~
Water and Minors Balance -.
:, .
*The Surfactant System comprises an ~-olefin sulfonate ~
mixture consisting essentially of from about 30% to ~ :
about 70% by weight of a Component A, from about 20% . -
to about 70% by weight of a Component B, and from
about 2~ to about 15% of a Component C, wherein ` :
(a) said Component A is a mixture of double-
bond positional isomers of water-so.luble
salts of alkene-l-sulfonic acids con- -. :
taining from about 10 to about 24 carbon
atoms, said ~ixture of positional isomers
including about 10~ to about 25~ of an
alpha-beta unsaturated isomer, about 30% to
about 70% of a beta-gamma unsaturated isomer,-
about 5~ to about 25% of a gamma-delta un-
saturated isomer, and about 5% to about 10~ : -
of a delta-epsilon unsaturated isomer; : -
(b) said Component B is a mixture of water-soluble
salts of bifunctionally-substituted sulfur-
containing saturated aliphatic compounds
containing from about 10 to about 24 CarDOn
atoms, the functional units being hydroxy and
sulfonate groups with the sulfonate groups ~ .
always being on the terminal carbon and the . -
hydroxyl group being attacned to a carbon atom
at least two carbon atoms removed from the
terminal car~on atoms, at least 90% of the
nydroxy group su~stitutions being in 3, 4, ana
5 positions; and ~ .
-4 ~
. .
~()5~
(c) said Component C is a mixture comprising
from about 30%-95~ water-soluble salts of
alkene disulfonates containing from about
10 to about 24 carbon atoms, and from about
5% to about 70~ water-soluble salts of
hydroxy disulfonates containing from about
10 to about 24 car,bon atoms,,said alkene
disulfonates containing a sulfonate group
attached to a terminal carbon atom and a
second sulfonate group attached to an
internal carbon atom not more than about
six carbon atoms removed from said terminal
carbon atom, the alkene double bond being
distributed between the terminal carbon
atom and about the seventn carbon atom, '-
said hydroxy disulfonates'being saturated
aliphatic compounds having a sulfonate
group attached to a terminal carbon, a
second sulfonate group attacned to an
internal carbon atom not more than about
six carbon atoms removed from said terminal
carbon atom, and a hydroxy group attached
to a carbon atom which is not more than
about four carbon atoms removed from the
site of attachment of said second sulfonate
group.
**Prepared as disclosed hereinabove. Average
particle diameter 12 microns.
~OS~,ZZl
The composition of Example III is added to an aqueous
bath at 110F at a rate of 0.15% by weight and used to launder
oily fabrics. Excellent cleaning results are secured under
initiai water hardness conditions of 7-12 gr./gallon mixed
hardness.
In the above composition the Surfactant System is
replaced by an equivalent amount of sodium linear C10 - C18
alkyl benzene sulfonate; sodium tallow alkyl sulfate: sodium
coconut alkyl glyceryl ether sulfonate; the sodium salt of a
sulfated condensation product of a tallow alcohol with from
about 3 to about 10 moles of ethylene oxide; the condensation
product of a coconut fatty alcohol with about 6 moles of ethy-
lene oxide; the condensation product of tallow fatty alcohol
with about 11 m~les of ethylene oxide; 3-~N,N-dimethyl-N-
coconutalkylam~onio)-2-hydroxypropane-1-sulfonate; 3-(N,N-
dimethyl-N-coconutalkyla D nio-propane-l-sulfonate 6-(N-dodecyl-
benzyl-N,N-dimethyla D nio)hexanoate; dodecyl dimethyl amine
oxide; coconut alkyl dimethyl amine oxide; and the water-soluble
sodium and potassium salts-of higher fatty acids containing
8 to 24 carbon atoms, and mixtures thereof, respectively, and
equivalent resul~s are secured.
In the above composition the Surfactant System ~s
replaced by an equivalent am~unt of a mixture of alkyl ether
. .
sulfate compounds comprising: from about 0.05% to 5% by weight
of mixture of C12_13 compounds, from about 55% to 7~ by weight
of mixture of C14 15 compounds, from about 25% to 4~0 by weight
o~ mixture of C16 17 compounds, from about 0.1% to 5% by weight
.~ .
__ _ . _
- \ ~
~ 05' '`'~1
of mixture of C18 19 compounds from a~ut 15~ to 25% by w~ight
of mixture of compounds ha~ing a degree of ethoxylation of ~,
from about 5~O to 65% by weight of mixture of eompounds hav;.ng
~`a degree of ethoxylation from 1 to 4, from about l~/o to 22% by
weight of mixture of compounds having a degree of ethoxylation
from S to 8 an~ from about 0.5% to l~o by ~eight of mixture of
eompounds having a degree of ethoxylation greater than 8, and
equivalent results are secured.
In the above composition the sodium citrate is
replaced by an equivalent amount of sodium carbonate, sodium
bicarbonate, sodium silicate, sodium oxydisuccinate, sodium
mellitate, sodium nitrilotriacetate, and the polymerie car-
boxylates set forth in U.S. Patent 3,308,067, and mixtures
thereof, respectively, and effective hard water detergeney
is secured.
- In the above composition the sodium eitrate is suecessiYely
replaced by an equivalent amount of the sodium and potassium
salts of carboxymethyloxymalonate, carboxymethyloxysuccinate,
eis-cyclohexanehexacarboxylate, eis-cyclopentanetetraearboxyl-
ate and phloroglucinol trisulfonate, respectively ande~fective hard water detergency is secured.
(
. .
10~
EXAMPLE IV
A soap-based laundry granule is prepared having
the following composition:
- Component Wt.
Sodium soap(l) 42.6
Potassium soap(l) 11.2
TAE3S( ) 10.7
Cll 8LAS(3) 8.8
Sodium silicate 8.9
Sodium~citrate 11.9
Brightener 0.57
Perfume - 0.17
Water 3.4~~ -
Miscellaneous Balance
.
(1) Soap mixtures comprising 90% tallow an~ 10%
coconut soaps.
(2) Sodium salt of etnoxylated tallow alkyl
sulfate having an average of about 3
etnylene oxide units per molecule.
(3) Sodium salt of linear alkyl benzene sulfonate
having an average alkyl chain length of about
12 carbon atoms.
(
Seventy-five partS by weight of the soap-based
granules prepared above are admixed with 25 parts by
12( 12 SiO2)12 27H20 (prepared in the
manner disclosed hereinabove; 25 micron size). The compo-
sition is employed at 0.12% of weight of laundering liquor and
,
provides excellent fabric cleanqing and sudqing propertiesin 10 gr/gallon hard water.
The composition of Example IV is modified by the
addition of.3 part~ by weight of sodium perborate and
excellent hot water (12~F. - 180F.) cleaning performance
is secured.
(
-\
l~S~ZZ~ '
A~ can be seen by the foregoing, the aluminosilicate
ion exchange builaer materials herein can be employed in all
m~nner of aetergency compositions. Moreover, the aluminosilicate
builders in combination with water-soluble auxiliary builder~ which
sequester magnesium, iron and other polyvalent water hardnesq
cations can also be em~ oyed in comb~nation with all manner of
detergent compositions. Depending upon the desires of the user,
it is, of course, useful to add the alumino~ilicate builder
or aluminosilicate-plus-auxiliary builder materials to a laundry
or rinse liquor separately from the detergent compositions.
Such separate use provides flexibility in the selection of the deter-
gent compo~ition employed by the uSOE while providing the d~sirable
benefits of the builder materials herein. Separate use of the
aluminosilicate builders and aluminosilicate-plus-auxiliary
builder compositions herein to soften water are fully con-
templated by this invention.
Inasmuch as most hard water contains polyvalent
m~tal ions in addition to caicium ions, the use of the
aluminosilicate builders as water softeners is preferably -
carried out i~ the presence of an auxiliary builder of thetype hereinbefore disclosed. Such auxiliary builders can be
any of the phosphorus-containing builders, or, in regions where
such builaers are unacceptable, any of the hereinabove disclose~
non-phosphorus builder materials. The aluminosilicate builders
and the auxiliary builaers can, of course, be separately aAded
to water to exert their softening function. However, it is more
convenient to add such materials simultaneously to the water
_50-
1.05'~2Zl
~o be treated. Accordingly, there are provided to the user
compositions comprislng from about 5% to about 95% by
weight of the aluminosilicate builder materials herein, and
from a~out 5 ~ to about 95 % by weight of an auxiliary
builder of the type hereinabove disclosed. Preferably, such
-compositions wqll contain a weight ratio of.aluminosilicate
builder:auxiliary builder of from about 5:1 to about
1:5_ Such compositions can be provided to the user in any
of the physical forms convenient for u~e as laundry
builders, such as dry powders, tablets, pre-measured
. packets, or in water-soluble packages which can simply be
added to the aqueous so~ution to be softened. Various
adjunct material-~ ~uch as bleache~, bluing, fabric softeners,
sud~ control agent~, perfumes, sanitizers and the like can
be optionally incorporated into such compositions to provide
desirable additional benefit.~
. . The highly desirable speed and ion exchange capacity
of the aluminosilicate materials herein is readily recognized
when such materials are used to presoften laundry liquors.
To be suitable for such use, the materials must not be so_.
slow as to require an extensive waiting period prior $o
addition of a laundry detergent composition to the laundering
liquor. Moreover, it is likewise undesirable to require the
user to utilize material~ of such l~w ion exchange quantity
that an unduly large qua-ntity is required to effectively -_
sequester hardness ions. For these reasons,.the aluminosilicates
herein are particularly adapted for such bu~der ana water-
softening purposes.
-5~-
l(~S~
The following is an example of a builder composition
of this invention which is suitable for use in water containing
all ma~ner of polyvalent hardness cations.
1~)5~
EXAMPLE V
Component Wt.%
.
*Nal2(Al02 SiO2)12 27 H2
Sodium Citrate 50
*Prepared as described herein.
Partlcle diameter 100 micr~ns.
~OS~Z~:l
The above composition is provided as a granular
powder. The pow~er is adaed at a rate of 2 oz. per 20 gallons
of wash water and agitated for V2-minute. During -this time,
haraness cations are su~stantially reduced to a level of about
1 - 2 gr/gal (starting with 7 grain/gallon hard water). A
comm~rcial laundry detergent composition is thereafter adde~
to the aqueous bath. Fabrics laundered in such pre-softened
water are more effectively cleansed than in water which has
not been pre-softened.
In the above compositiOn, the Nal2(A102 SiO2)12 27H20
i~ replaced by an equivalent amount of Nal2(A1~2-SiO2)12 20H20
and ~al2(A12 SiO2)12 30H2o, prepared as disclosed herein,
respectively, and equivalent results are secured.
In the above composition the sodium citrate is replaced
1~ by an ~quivalent amount of sodium tripolyphosphate, sodium
carbonate, sodium bicarbonate, sodium silicate, sodium
oxydisuccinate, sodium mellitate~ sodium nitrilotriacetate,
sodium ethylenediaminetetraacetate, sodium polymaleate,
sodium polyitaconate, sodium polymesaconate, sodium polyfumarate,
sodium polyaconitate, sodium polycitraconate, sodium poly-
methylenemalonate, sodium carboxymethyloxymalonate, sodium
carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate,
cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate,
and mixtures thereof, respectively, and cffective hard water
dctergency is securcd.
The foregoing compositions are employed at concentrations
of 0.005% to 0.25% by weight and effectively softcn water
containing polyvalent cations.
-5
The aluminosilicate builderq and alumino~ilicate-plus~
auxiliary builder mixtur~s h~rcin are useful in all mann~r of
cleaning compo~ition~. In addition to the foregoing, they
can be effectively used in detergent-containing floor
clean~ers, scouring cleansers and the like, wherein water
hardness also presents detergency problem~. Typical scouring
clean~ers can comprise, for example, from about 25% to
about 95% by weight of an abraYive (e.g., silica), from
about 10% to about 35% by weight of an aluminosilicate
builder aq disclosed herein, from about 0% to about 20%
by weight of an auxiliary builder as disclosed herein,
and from about 0.2% to about 10% by weight of an organic
detergent compound.
10~
. EXAMPLE VI
A detergent base granule having the following
composition was prepared by conventional spray-drying.
,
Ingredient . Parts by Weight
.
(1~ ' .
TAE3S 14.5
Sodium tallow alkyl sulfate 2.5
Silicate solids 13.0
~ratio: Na20/SiO2 = 2.0)
Sodium sulfate 15.0
Minor ingredients including 5.0
sodium toluene sulfonate,
trisodium sulfosuccinate,
moisture, etc.
(1) Sodium salt of ethoxylated tallow alkyl sulfate
having an average of about 3 ethylene oxide units
per molecule.
105;~ZZl
.
A mixture was then prepared containing the above
detergent base granule and a builder component listed
hereinafter in the proportions specified. The composi-
tion so obtained was used for cleaning polyester F
swatches which had been stained with a clay soiling
composition. To tnat end, the swatches were laundered
- for ten minutes at 105F in a laundering liquor con-
taining 0.12% by weight of the above detergent composition. i
The hardness and calcium-magnesium ratio were varied as
indicated. After being laundered, tihe swatches were
rinsed, removed from the washer and dried. The cleaning
performance was expressed as a summation of Hunter
Whiteness readings for 0, 2, 4, 6, 8, 10 and 12 grains
hardness/gallon (Ca/Mg = 2/1) whereby the Hunter Whiteness
equals 0 when 0.06~ by weight sodium sulfate is used
instead of .he builder mixture and equals 100 when 0.06%
;~ by weight sodium tripolyphosphate is used as builder
component. The 0.06% replacement level relates to the
amount of said inqredients in the laundering liquor.
The builder component was represented by a
mixture of an aluminosilicate having the formula
Nal2(AlO2 sio2)12 27 ~2
prepared as described hereinbefore and having an average
particle diarleter of 3 microns and an auxiliary builder
selected from sodium pyropnosphate, sodium tripoly-
phosphate, sodium nitrilo-triacetate and sodium citrate.
The base detergent granule represented 0.06% by
weignt of the laundering liquor; the remaining 0.06% by
, ' ' . ,
-57-
- \
weight was represented by a builder component as indicated.
The whiteness resuits were:
. ~ .
. Sodium Hunter
Aluminosilicate~l) Pyrophosphate(lj Whiteness
0.02 o.b4 117
0.03 0.03 102
0.04 0.02 . g4
(1) in % by weight of laundering liquor.
~05'~ZZl
Sodium citrate was evaluated as auxiliary builder
in lieu of sodium pyrophosphate thereby using the testing
conditions set forth. In addition, the Ca/Mg hardness
level was varie~ as indicated. Tne Hunter Whiteness
readings were as foll~ws:
- - , ::
~ ~,
Sodium Hunter
Ca:Mg Aluminosilicate(l) citrate(l) Whiteness
. :
1:1 0.04 0.02 35
. 0.03 0.03 61
0.02 0.04 51 ::
.
2:1 0.04 0.02 38
. 0.03 0.03 52
. , 0.02 ~.04 53
J
' 3:1 0.04 0.02 37
0.03 0.03 54
0.02 ; 0.~4 50
.
~ (1) In ~ by weight of laundering liquor.
,
' : ':.
--5 ~
10~'~2'~ .
The sodium salt of nitrilotriacetic acid and
sodium tripolyphosphate were also evaluated as auxiliary
builders in substitution for the sodium pyrophosphate
builder thereby using the testing conditions set forth
above. The Ca:Mg ratio was 2:1. The Hunter ~niteness
readings were as follows: .
Alumino- Sodium-nitrilo Sodium tri- Bunter
silicate(l) triacetate(l) Polyphosphate(l) Whiteness .
., . .
L 0.02 0.04 108
0.03 0.03 82
0.04 0.02 . 64
0.02 : . . 0.04 95
0.03 0.03 91
0.04 . 0.02 -79
(1) In % by weight of laundering liquor.
-60-
lOS'~
The foregoing testing data hiyhlight the superior
cleaning perormallce derived from the use of specific
combinations of aluminosilicates and auxiliary builder
salts in detergent context.
Compositions capable of providing substantially
similar performance are obtained when the sodium salt .
of.the ethoxylated tallow alkyl sulfate is substituted
by a substantially equivalent amount of sodium tallow
alkyl sulfate, sodium coconut alkyl sulfate and sodium
decyl benzene sulfonate.
Substantially similar results are also obtained
when the Nal2(A12-Si2)12'27 H2O is replaced with an
equivalent amount of Nal2(AlO2-SiO2)12-20 H2O;
l~a (AlO SiO2)12 30 H2O~ Na861(A12)86( 2 106 2
and Na6[(AlO2)6(SiO2)10]-15 H2O, respectively.
~)S;~
EXAMPLE VII
A granular detergent composition is provided
having the following composition:
InqredientParts by Weight
TAE3S( ) - 14.~
Sodium tallow alkyl sulfate2.1
Sodium tripolyphosphate 24.0
Nal2(AlO2~sio2~l2 27 2 18.0
Sodium sulfate ~ 36.6
Brightener 0.9
Moisture 5.0
(1) Sodium salt of ethoxylated tallow alkyl sulfate
having an average of about 3 ethylene oxide u~its
per molecule.
(2) Prepared as described herein. Average particle
size diameter 3-5 microns.
.
~ A
lOS;~
The above composition is capable of securing
excellent soil removal and cleaning performance
during conventional laundering when using water
naving a high initial water hardness, for example
from 7 to 14 grains per gallon of Ca/Mg nardness.
