Note: Descriptions are shown in the official language in which they were submitted.
1~36~S6
DETERGENT COMPOSITION
An aspect of this invention relates to
home washing of clothes, using automatic washing
machines and using a wash water containing dispersed
therein a finely divided water-insoluble alkali
metal aluminum ~ilicate molecular sieve and an
anionic detergent, preferably with an a~kali metal
silicate and a nonionic detergent, too. It has
been found that combinations of a molecular sieve
and water-soluble builders, with relatively large
amounts of sodium silicate, give especially good
results. One particularly suitable added builder
salt for use in such compositions is trisodium 2-
oxa-1,1,3-propane tricarboxylate, the e~fect of --
which, in combination with the molecular sieve and
sodium silicate, is found to exceed that of penta-
sodlum tripolyphosphate. Thus, a particular
preferred composition ~e.g., for use in a washing
machine containing 150 ppm hard water at 0.15%
concentration) contains 10% tridecylbenzenesulfonate,
20~ molecular sieve, 15% alkali metal silicate
(Me20:SiO2 ratio of 1:2.35), 15% alkali metal
2-oxa-1,1,3-propane tricarboxylate, 2% nonionic
detergent, 0.5% sodium carboxymethylcellulose and
the balance sodium ~ulfate and water. In other
embodiments, where phosphate and NTA are unobjec-
tionable, the preferred trisodium
1~P3645~i
2-oxa-1,1,3-propane tricarboxylate (TO~T) is replaced wholly or in part
(ë.g., 1/3 or 1/2 thereof) by pentasodium tripolyphosphate ~TPP) or trisodium
nitrilotriacetate (NTA), with the latter giving particularly good results.
It has been found that an increase in the amount of anionic
detergent permits a corresponding decrease in the amount of sodium silicate.
For instance an increase from 10% to 15% gives a marked improvement even
when the sodium silicate proportion is correspondingly reduced from 20% to
15%, with unchanged proportions of molecular sieve (e.g., 30%) and of the
other constituents (e.g., 2% nonionic detergent, 0.5% sodium carboxymethyl-
cellulose and 35% sodium sulfate).
Instead of the alkylbenzenesulfonate an olefin sulfonate detergent,
e.g., of 15 to 18 carbon atoms, or other suitable anionic detergent may be
used, preferably as a partial replacement only.
According to the present invention, there is provided a detergent
composition in the form of free-10wing hollow beads having a maisture content
of 3~ to 15~ by wcight which comprises spray dried beads of a detergent
composition corltalning at least about 5% by weight of a water-soluble,
synthctic, organ~c~ anionic dotorgent and about 15 to 45% by weight of finely
dlvldod, wntor-insoluble sodium or potassium aluminum silicate molecular
siovc, having the capacity to remove calcium ions from water, the proportion
of said sieve being calculated on an anhydrous basis and being greater than
the proportion of anionic detergent, having a post-added liquid or tacky
nonionic detergent sorbed thereon, the proportion of sorbed nonionic detergent
being at least 1% by weight and the total proportion of nonionic detergent
being~less than 2/3 of the weight of said molecular sieve.
In another aspect, the invention provides a process for preparing
a detergent composition in the form of free-flowing hollow beads which
comprises forming an aqueous slurry of a detergent composition containing at
least about 5% by weight of a water-soluble synthetic, organic, anionic
detergent and about 15 to ~5% by weight of a finely divided, water-insoluble
sodium or potassium aluminum silicate molecular sieve having the capacity to
~ - 2 -
.
~ ~3~i6
remove calcium ion from water, the proportion of said sieve being calculated
on an anhydrous basis and being greater than the proportion of anionic
detergent, and the balance being a water-soluble detergent builder salt
selected from the group consisting of inorganic and organic builder salts;
spray drying said aqueous detergent composition to form free flowing hollow
beads having a moisture content of 3% to 15% by weight; and then blending
said beads with a liquid or tacky nonionic detergent to form free flowing
beads, the amount of nonionic detergent blended therewith being at least 1% by
weight and the total proportion of said nonionic detergent being less than 2/3
of the weight of said molecular sieve.
In general, in the compositions oftthis invention the proportion
of sodium silicate is at least about half the proportion of molecular sieve
tbased on dry weight) and at least about equal to or more than the proportion
of organic detergent. It is also found that the use of such higher
proportions of sodium silicate, in accordance with this invention, gives
wash wat~rs in which the
- 2a -
~ll)364S~
finely divided molecular sieve is more stably
suspended,and improves the deflocculation of
particulate soils.
It is conventional when using household
automatic washing machines of the type employed in
the United States to employ detergent compositions
at a concentration of about 0.15~ in the wash
water. For use in such concentration the propor-
tion of sodium silicate in the formulations of this
invention is in the range of about 12 to 25~,
preferably about 15 to 20% and the proportion of
molecular sieve is in the range of about 15 to 35%,
preferably about 20 to 30%, while the proportion of
anionic detergent is preferably in the range of
about 10 to 20%, more preferably about 10 to 15%.
However, the weights of various components may be
such that the synthetic organic anionic detergent
tincluding soap~) may be at least about 5%, the
molecular sieve may be about 15 to 45% (being more
than that o the anionic detergent), the silicate
content may be almost up to that of the molecular
sieve, the TOPT may be 1/2 to twice the silicate
` and the nonionic may be up to 2/3 the molecular
sieve weight, while still making a free flowing
product.
One particularly good detergent formula-
: tion contains about 10% sodium linear alkylbenzene-
sulfonate, 2% nonionic detergent, 1% soap, 24%
~L~36456
molecular sieve, 15~ sodium silicate, about 1/2 to
1% sodium carboxymethyl cellulose and the balance
sodium sulfate and water (together with small
! amount~ of optical brighteners and conventional
minor adjuvants). Another detergent composition of
I - superior performance i~ otherwise similar but
j contains 20% sodium silicate and 30% molecular
sieve. In a preferred form the weight ratio of
sodium silicate to molecular sieve (on an anhydrous
basis, as usual) is in the range of about 0.5:1 to
0.8:1, more preferably about 3:5 to 3:4. The
silicate,preferably sodium silicate, has an
Na2O:SiO2 ratio o about 1:2 to 1:3.2, preferably
1:2.0 to 1:2.4, e.g., 1:2.35.
lS The following examples are given to
illustrate this invention further~ In this applica-
tion all proportions are by weigh~ unless otherwise
indiaated.
~.~36456
EXAMPLES 1-7
In the tabulated Examples below, the com-
positions are added to the water (e.g., water of
150 ppm hardness having a Ca:Mg ionic ratio of
3:2) used for washing clothes in amount of 1.5
grams of the compo~ition per liter of water. A
suitable washing temperature employed i5, for
example, about 50C; and the period for agitated
washing before spinning (i.e., before centrifuging
to remove the wash water, prior to rinsing) is
about 10 minutes. A standard wash load, such as
3.S kilograms, of mixed laundry (cottons, poly-
esters and blends) are used and washings are for
the usual times, e.g., 15 minutes of a 30 minute
lS machine aycle.
-- 5
,
~at36456
~ u~ I
r~l o o o .
,, ~ ~ o ~
~D ¦ O O O u") t--) N
,I tr7 ~ ~
O ~
Z ~ o o ~
~ ~ o O u~ In ~u~ u~
o a~
~1 I O O 11~ IJl ~`I 1~') U') ~
o a~ o
~1 ~ ~ ~n
~1 1
O ~ ,i 0~
X ~ $
a~ o ~1 u I ~
N ~ 1rl t`
.4 ~ g
a~ o In ~ ~ i O
~1 ~1 0 0 ~ O i~i O P:~
O ~ Z Z
Notes: 1036~56
(1) Sodium linear alkylbenzenesulfonate having
an average of about 13 tspecificaily 12.8) carbon
a~oms in the alkyl chain. The chain length distri-
bution (by weight) is às follows:
No. of carbon 10 11 12 13 14
atoms in chain:
Percentage : 3.2 11.1 15.8 38.4 31.5
j The distribution (by weight) of the position, on
the carbon chain, of the aromatic ring is as
follows:
Position on 2 3 4 5 6 and 7
carbon chain:
Percentage : 16.8 14.3 17.2 26.1 25.6
(2) Sodium olefin sulfonate made from an olefin
mixture containing 78% alpha~olefins, 7-8% internal
olefins, 14-15% olefins having a pendent =CH2
group (i.e., having a vinylidene group) and 0.1~ of
parafins, which mixture contains 1.7% C12
oleins, 6S% C14 olefin , 33.2~ C16 olefins and
0.1~ C18 olefins. The reaction is carried out in
conventional manner: the olefin is sulfonated with
S03 highly diluted with alr, using slightly over 1
mol of S03 per mol of olefin, the resulting acid
mix is made alkaline with excess aqueous NaO~, thus
converting alkenyl sulfonic acids, formed during
sulfonation, to the corresponding sodium salts, and
the resulting alkaline mixture is heated at elevated
~ temperature (e.g., 170C ) at superatmospheric
pressure to convert sultones, formed during the
-- 7
iL03645~;
sulfonation, to the corresponding sodium hydroxy-
alkane sulfonates and alkenyl sulfonates.
(3) Type 4A molecular sieve containing 21~
moisture (proportions of molecular sieve in the
foregoing examples are on an anhydrous basis, i.e.,
in Example 1 the proportion of moisture-containing
molecular sieve actually added is 38.0%), having a
mean particle diameter of 6.4 microns. All the
particles are less than ~8.7 microns in diameter,
98~ are less than 14~4 microns, 94% le~s than 11.0
microns, 69% less than 7.6 microns and 15~ less
than 4.1 microns. The X-ray diffraction peaks of
the molecular sieve are as follows:
-- 8
~36~5~
er
o o CO
o 1~
~o o
~D
", oo ,,
.
N
,~ ~
~ ~ CO CO
r~ ~r co 1` co
u~ o a~
~ ~ o~
r1 N o~
~ ~ CO
D 00 0~ 1` t~
r~
O CO t--'~
r~ o oco
~.0 0 CO O
N (~
r~ N ~D ~1
.. - .. .. .. ..
d, ~ oP
a.~ a~ ~
,~ o
H tJ~ H
H ~C H
In
~36~56
(4) Na2O:SiO2 ratio of ~f 1:2.35, added as
an aqueous solution.
(5) Pentasodium tripolyphosphate.
(6) Triso~ium nitrilotriacetate (added as the
s monohydrate, but proportions given are on an
anhydrous basis).
(7) "Neodol 45-11", reaction product of 11 mols
of ethylene oxide and 1 mol of a mixture of C14
and C15 ~traight chain, normal primary alXanols,
said mixture having an average of about 14-15
(e.g., 14.5) carbon atoms. (This may be added in
the crutcher or, in a preferred embodiment of the
invention may be post-sprayed onto the beads made
from the rest of the formulation or may be added
partly in the crutcher and partly after spray
drylng or other formulation of the rest of the
composition).
~8) ~Sodium carboxyme~hylcellulose, of conventional
detergent grade.
~he foregoi.ng compo~ltions are formed
into hollow spheres or beads by spray drying. In
preparing a mixture for spray drying one blends an
aqueous slurry of the alkylbenzenesulfonate or
other detergent with an aqueous sodium silicate,
adds optical brighteners, sodium carboxymethyl-
* TRADE~IARK
-- 10
~3645~
cellulose, sodium sulfate, nonionic detergent,
soap, and the molecular sieve (containing 18-27~
water, e.g., 20%),all while stirring in a conventional
manner in a crutcher. The moisture content of the
crutcher mix is about 50~ but in variations o~ the
method may be from 35 to 70%. The mixture, at an
elevated temperature of 50 to 90C, e.g., 65C,is then
sprayed into heated air (e.g., countercurrently in
a spray tower into air having a temperature of
100C to 400C, e.g., 230C) under such conditions
that the resulting hollow beads have a moisture
content of about 3 to 15%, preferably 4 to 10%.
Onto the surfaces o~ the hollow beads
made are sprayed an additional 2%, in each case, of
the same nonionic detergent in molten ~orm, while
the bead~ are tumbled. All the products made,
before and after addition of this nonionic, are
good heavy duty detergents as tested in home
washing machines on mixed laundry, using 150 ppm
hardness water, but the compositions containing
more of the nonionic are generally better.
The preferred molecular sieves are
Type 4A molecular ~ieves. The sodium (and potas-
sium) forms of Type A sieves are well known. See,
for instance, U.S. patent 2,882,243 which describes
them as zeolite A. The water-containing hydrated
form of the molecular sieve is preferably the form
incorporated into the detergent composition. The
1].
~36~;6
molecular sieves are preferably of fine particle
size, such as cubic crystals having mean particle
diameters below 8 microns, e.g., 1/2, 1, 2, 4 or 6
microns. The manufacture of such crystals is well
known in the art. Preferably the crystals of
hydrated zeolite A that are formed in the crystal-
lization medium (such as a hydrous amorphous sodium
aluminosilicate gel) are used without the high
temperature dehydration (calcining, e.g., to 2-3%
water content) that is normally practiced in
preparing such crystals for use as catalysts te.g.,
cracking catalysts); that is in the preferred
practice of the invention the molecular sieves are
used in completely or almo~t completely undehydrated
condition, 9uch as i8 obtained by filtering off the
crystals, washing them with wster and drying them
in air 90 that their water content is about 20%.
It has Also been found that the efectiveness of a
moleoular sieve that has been calcined may be
signi~icantly increased by soaking it in water
(e.g., deionized water at room temperature) and
then drying in air at, say, room temperature or
110C, giving a product having a water content of
about 20%. In general, it is preferable to use a
molecular sieve whose rate of calcium ion uptake is
such that when 375 ppm (anhydrous basis) of the
molecular sieve are placed in water at 45C
containing 40 ppm of dissolved calcium ion,while
~(~3~4S6
vigorously stirring, the dissolved calcium ion
content of the water is reduced to below about 8
ppm, preferably below 3 ppm, within 5 minutes.
More preferably the rate of calcium ion uptake is
such that an appreciable effect is also observed
; within 2 minutes, the dissolvad calcium ion content
at that time being preferably less than 12 ppm,
most preferably less than 3 ppm.
In the foregoing test for rate uptake of
calcium ion, the water is deionized water in which
calcium chloride has been dissolved (i.e., 110 ppm
of CaC12 to provide 40 ppm of Ca ion). The stirring
may be effected in a 250 ml beaker with a glass-
encased magnet as the s~irring element (the beaker
being placed, for instance~ on a conventional
Corning hot plate type of magnetic stirring motor,
set ~t moderate speed). Timing is started as soon
as the molecular sieve is added to the water. At
; predetermined times ~e.g., 2 minutes and 5 minutes)
a sample o~ the water is removed and the dispersed
mo~ecular sieve particles in that sample are
removed immediately by vacuum filtration (a procedure
that takes up to about 10 seconds overall). The
filtered water sample can then be analyz~d for its
calcium content (as by a standard EDTA titration
method).
The compositions may contain sodium
carbonate to provide additional alkalinity or as a
! - 13
~Q36gL5~
filler (in place of sodium sulfate) or as a carrier
for liquid, pasty or soft solid ingredients (or for
; any combination of these or other purposes) in such
compositions. It is known that detergent composi-
tions containing sodium carbonate tend to form
insoluble calcium carbonate in the wash water which
can lead to undesirable stiffening ("boardiness")
of the washed fabrics due to interaction of the
hard water and the sodium carbonate. This tendency
is greatly inhibited or substantially eliminated in
compositions containing the molecular sieve. Such
composi~ions,designed for use at concentrations
of about 0.15~ in the wash water,may be like those
of Examples 1-7 but may also contain 10, 15, 20, 25
or 30~ or more o sodium carbonate (i.e., corres-
ponding to a carbonate content of about 80, 130,
170, 210 or 260 ppm or more, in the wash water).
! All, or part of the sodium carbonate of the composi-
tion may be pre-blended as a dry powder with the
liquid, pasty or waxy non-ionic detergent (such as
molten Neodol 45-11) to form free flowing particles
which may then be post-added to the free-flowing
spray-dried beads of the remainder of the detergent
composition but it i9 often preferred to blend
(e.g., spray) the same nonionic detergent, in
liquid form, with the spray dried or otherwise
hollowed beads while tumbling them. Proportions
of 2, 4 or 6~ of the nonionic can be post-added to
- 14
1~36~56
the spray-dried bead~ made from a detergent crutcher
mixture containing sodium carbonate, which produces
a composition having good flow characteristics
despite its rather high content of nonionic deter-
gent. It is found that the formation of insoluble
calcium carbonate in solutions containing sodium
carbonate is inhibited by the presence of the
molecular sieve and it is thus also within the
broader scope of thi~ aspect of the invention
(relating to the use of sodium carbonate) to reduce
the amount of sodium silicate when carbonate is
employed. The proportion of sodium carbonate
present in the product will generally be 1 eæB than
; the proportion of molecular ~ieve.
In the embodiment of the invention in
which sodium carbonate powder i9 pre-blended with
the nonionic detergent, after which the mix is
blended with the re~t of`the product, the weight
ratlo of the nonionic detergent to sodium carbonate
may be up to about 1:1, such as about 0.1:1, 0.2:1,
0.3:1, 0.5:1, 0.7:1 and 0.9:1. The ~odium carbonate
may be substantlally anhydrous and may be in the
form of a fine powder of about 2 to 10 or 20
microns mean particle diameter which may be simply
mixed mechanically with the nonionic detergent
which coats and/or agglomerates the sodium carbonate
particles (e.g., to form agglomerates which are of
about the same size as the spray-dried beads).
~364~6
The use of sodium carbonate is illustrated
in the following Examples 8-28:
EXAMPLES 8-14
Examples 1-7 are repeated except that the
formulations contain 20% sodium carbonate (added in
anhdrous form in place of part of the sodium
sulfate). The composition~ are spray dried (~rom
an aqueous mixture of all the ingredients thereof)
to form free flowing hollow beads which may then be
blended with the nonionic detergent as described.
The products are good heavy duty detergentSwith
free 10wing characteristics.
EXAMPLES 15-21
; Examples 8-14 are repeated except that
19 the additional nonionic detergent is included in
the ~rutcher instead of being post-sprayed onto the
~pray~dried bead~. Some of the nonionic plumes ~is
lost out the spray tower top) during drying and the
products are less effective detergents due to such
losses.
.
EXAMPLES 22-28
Examples 1-7 are repeated, with the
compo~itions being spray-dried from an aqueous
, mixture o all the ingredients thereof to form ree
flowing hollow beads but not having nonionic
detergent post-blended with them. 6 Parts o
- 16
- ~364S6
anhydrous ~sodium carbonate powder and 5 parts of
the same nonionic detergent are mechanically blended
to form a free flowing granular mixture of agglom-
erated particles and the res~ilting granules are
then added to the spray-dried beads in amounts to
bring the nonionic detergent contents of the
resultin~ products to about 5%, after which the
products may be blended with an additional 2% of
the same nonionic detergent. (The word "blending"
includes post-spraying and tumbling).
It has also been found, unexpectedly,
that the free flowing spray-dried beads of deter-
gent compositions containing the molecular sieves
can carry higher loadings of oversprayed nonionic
detcrgcnt than can powder blends of detergent
components, although normally lower loadings will
bc cmployod. This is illus*rated in Example 29
below. Thus 9uch compositions may contain about 15
to ~5%~ (e.g.~ about 20, 30 or 35%) of the molecular
siovc togethcr with an anionic detergent, usually
present in amo~mt which is at least 5% (such as 10
or 15%) but is generally less than the amount of
molecular sieve. The proportion of nonionic
detergent in the composition may be low, say 2%, or
high (such as the 20% in Example 29, or more) or
intermediate (e.g., 3, 4, 5, 8 or 10%); generally
it will be less than about two-thirds of the
proportion of molecular sieve. It will be appre-
ciated that the post-addition of the nonionic
-17-
16J36~56
~, detergent makes it po~sible to carry out the spray
drying with little or no nonionic detergent presant
(and therefore little or no "pluming" in the
exhaust from the spray drying tower). It is also
within the broader scope of this aspect of the
invention to past-add, similarly, other tacky
materials (such as wash-active oily or waxy addi-
tives) in place of all or part of the nonionic
detergent.
1, 10 EXAMPLE 29
., .
(a) A detergent composition of the following
approximate composition is made by spray drying the
named ingredients, from an ac,~ueous ~lurry thereof:
10~ ~odium linear alkylbenzenesulfonate (as in
Example 1); 2~ nonionic detergent (Alfonic 1618-
65)7 1~ soap (~odium 90ap of 80% tallow atty acids
and 20~ coconut oil fatty acids); 33~ molecular
sieve o Example 1; 7~ sodium silicate (Na20:SiO2
ratlo of 1:2.4)~ 0.$4 ~odium carboxymethylcellulose;
4g (apparent) water; 0.8~ of a mixture of optical
brighteners; and the balance being sodium sulfate.
The sodium silicate is supplied to the mixture, as
an aqueous slurry; the molecular sieve is supplied
to the mixture in hydrated form (i.e., as a powder
containing about 20% moisture). The apparent water
content of 4~ is that measured by adding hydrocarbon
solvent (Skelly V) and distilling off the water at
116-143C; the total water content is about 8% when
- 18
~)36~S~
measured with a DuPon~ moisture analyzer, uRing a
dehydrating temperature of 160C or 200C.
The re~ulting hollow spray dried beads
are found to have generally spherical form; when
viewed with the electron scanning microscope the
particles of molecular sieve are seen to be concen-
trated internally, i.e., near the internal walls of
the beads.
11 Grams of molten nonionic detergent
(Neodol 45-11) are poured gradually onto 50 grams
of the 3pray dried bead~ at room temperature while
stirring the mixture. The resu ting product is a
free flowing granular mixture that retains its
granular form when a mass of the particles i9
between one' B ingers. (In contrast, when the same
amount of molten nonionic detergent is added to
conventlonal spray-dried detergent beads containing
abouk 33~ pentasodium tripolyphosphate in place o
the approximately 32% of molecular sieve, the
resultlng produat is caky and forms a coherent lump
when pressed between one's fingeri.) The granular
product contains (by calculation) about 8% sodium
alkylbenzenesulfonate, about 20% nonionic detergent
I and about 27~ molecular sieve,and is a good detergent.
`~ 25 A similar effective product is made when the
; corresponding potassium form of the molecular sieve
is used instead of part or all of the sodium form.
A similar change is also made in the silicate
- 19
; ~36~S~i
cation without difficulty.
(b) Example 29(a) is repeated except that
the proportion of molecular sieve is decreased to
about 25~, the proportion of sodium silicate is
increased to about 15%, and the proportion of
sodium carboxymethyl cellulos~ is increased to
about 1%.
The product resulting from the pouring
of 11 grams of molten nonionic detergent on*o 50
gr~ms of spray dried beads i~ ~omewhat tacky or
caky and not as free-flowing as desired but when
the proportion of added molten nonionic detergent
is decreased to 5 grams (to SO grams of spray dried
beads) the product is a ree flowing granular
detergent composition.
~c) Example 29(a) is repeated except that
the proportion of molecular sieve is decreased to
about 30%, the proportion o~ alkylbenzene sulfonate
i~ increased to about 15~, the proportlon o sodium
8iliaate i~ increased to about 20~ and the propor-
tion of sodium carboxymethyl cellulose is increased
to about 1%, while the proportion of sodium -~ulfate
is correspondingly decreased. A free flowing
granular detergent product is obtained.
The bulk specific gravities of the spray-
dried beads used in Examples 29(a),29~)and 29(c)
are about 0.37, 0.33 and 0.31,respectively.
As is conventional in the art, the
- 20
1~36~56
spray-dried detergent compo3itions used in this
invention will generally be made up of beads of
such size that substantially all ~by weight) passes
through a 6 mesh screen (a~l screen sizes given
herein are U.S. Standard) and substantially all (by
weight) is retained on a 200 mesh screen (i.e.,
ranging from about 0.75 mm, to about 3.3 mm in
particle size). Preferably the particle si~e
distribution can range from about all through a 14
mesh screen to about all retained on a 100 mesh
screen (i.e., ranging in particle size from 0.14
mm to 1.5 mm). Another particularly useful size
distribution is not more than about 30% retained on
a 16 mesh screen and not more than about 7~ through
a 100 mesh screen. U~ually the major portion of
the spray-dried product i9 made up of beads having
partiale diameters below 1 mm, preferab~y below
0.9 mm. The bulk specific gravity of the spray-
dried product is usually below about 0.8, more
generally below about 0.6, preferably below about
0.6 and still more preferably at least about 0.3
and in the range of about 0.3 to 0.4.
The nonionic surfactants having the most
desirable detergency properties are usually viscous
liquids or unctuous pa~ty or tacky ~olids at room
temperature, ~uch as those having melting points
below about 40C. and having significant volatility
under commercial spray drying conditions. Typical
`- 1(1136~56
nonionic detergent~ are polyoxyethylene and poly-
oxypropylene derivatives that are usually prepared
by the addition or ethylene oxide and/or propylene
oxide to compounds having a hydrophobic hydro-
carbon chain and containing one or more active
hydrogen atoms, such a~ alkylphenols, fatty alcohols,
fatty acids, fatty mercaptans, fatty amines, fatty
amides and polyols, e.g., fatty alcohols having an
8 to 20, typically 10 to 18 carbon atoms alkyl
chain and ethoxylated with an average of about 3 to
20, typically 5 to 15 ethylene oxide units.
Commercially available ethoxamers falling into this
category are NEODOL 45-11, which is an ethoxylation
product ~having an average of 11 ethylene oxide
units) of a 14 to 15 carbon straight chain fatty
alcohol (Shell Chemical Company); NEODOL 25-7, a 12
to 15 carbon chaln fatty alcohol ethoxylated with
an average o~ about 7 ethylene oxlde units; ALFONIC*
1618-65, which is a 16 to 18 carbon alkanol ethoxy-
lated with an avera~e o~ 10 to 11 ethylene oxide
units tCont~nental Oil Company); and Pluronlc ~-26,
having a 12 to 13 carbon alcohol etherified with
ethylene oxide and propylene oxide tBASF-Wyandotte
Chemical Company).
2S The reason for the superior ability of
the spray-dried beads made with the molecular
sieves to carry otherwise tackifying materials such
as nonionic surfactants is not clearly understood.
* TRADE MAR~S
~ 22
A~ ~
~364~6
It may be due to the structure of the bead, or to
an increased internal surface area owing to the
presence of the small insoluble particles of
molecular sieve; see the interior of the broken
bead illustrated in FIG. 1 (which is a
photomicrograph made with a scanning electron
microscope, the scale being indicated next to the
photomicrograph, of a spray-dried bead prior to the
post-addition of nonionic detergent). When viewed
with an ordinar~ light mlcroscope the walls of
the beads appear to become less opaque after
treatment with the nonionic detergent, which
indicates that the latter has been sorbed into the
bead material. It also appears that the presence
of the ~inely divided insoluble solid particles,
particularly when they are distributed ~as a
porous, bonded aggregate) through much of the
interior of the bead, provides beads which are
stronger or le~ likely to de~orm under pre~sure
and therefore have lesser tendencles to aggregate
together or to interfere wlth flow. It i~ there-
fore within the broader scope of this aspect of the
invention to replace a part of the molecular sieve
by other water-insoluble solid particles, prefer-
ably of similar sizes, shapes and characteristics,
to obtain similar free flowing and effective heavy
duty detergents.
As indicated in Examples 1-7, for instance,
the anionic detergent may be an alkylbenzenesulfonate
- 23
-
3L~36~
or an olefin sulfonate. In the alkylbenzene-
sulfonate the number of carbons in the alkyl group
may be, for instance, in the range of about 10 to
16; preferably the alkyl i9 a straight chain
radical of an average length of about ll to 13 or
14 carbon atoms. Preferably, the alkylbenzene-
sulfonate has a high content of 3- (or higher)
phenyl isomers and a correspondingly low content
(well below 50~) of 2- (or lower) phenyl isomers;
in other terminology, the benzene ring is prefer-
ably attached in large part at the 3 or higher
(e.g., 4, 5, 6 or 7) position of the alkyl group
and the content of isomers in which the benzene
ring i9 attached at the 2 or l position is corres-
pondingly low. One suitable type of suoh detergent
i8 described in U.S. Patent 3,320,174 to Rubinfeld.
Olefin sulfonate detergents are well
known ln the art. Generally they contain long
chain alken yl sulfonate~ or long chain hydroxy-
alkane sulfonates ~with the OH being on a caxbon
atom whlch i8 not directly attached to the carbon
atom bearing the -SO3 group). More usually, the
olefin sulfonate detergent comprises a mixture of
these two types of compounds in varying amounts,
often together with long chain disulfonates or
sulfate-sulfonates. Such olefin sulfonates are
descxibed in many patent~, such a~ U.S. patents
No's. 2,061,618; 3,409,637; 3,332,880; 3,420,875;
3,428,654; 3,506,580; British patent No.
_ 24
lQ36~S~;
1,139,158; and in the article by Baumann et al. in
Fette-Seifen-Anstrichmittel,Vol. 72,No. 4, pp.
24i-253 (1970). All the above-mentioned disclosures
are incorporated herein by reference. As indicated
in these patents and the published literature, the
olefin ~ulfonates may be made from straight chain
alpha-olefins, internal olefins, olefins in which
the unsaturation is in a vinylidene side chain
(e.g., dimers of alpha-olafins), etc., or more
usually, from mixtures of such compounds, with the
alpha-olefin normally being the major constituent.
The sulfonation i8 usually carried out with ~ulfur
trioxide under low partial pressure, e.g., S03
highly diluted with inert gas such as air, nitrogen
or S03 under vacuum. This reaction generally
yields an alkenyl sulfonlc acid, often together
with a sultone7 the resulting aci~ic material is
generally then made alkaline and i9 treated to open
the sultone ring to ~orm hydroxyalkane sulfonate
and alkenyl sul~onate. The number of carbon atoms
in the olefin is u~ually within the range of 10 to
; 35, more commonly 12 to 20, e.g., a mixture
principally of C12, C14 and C16 having an average
of about 14 carbon atoms or a mixture principally
of C14, C16 and C18 having an average of about 16
carbon atoms. The preferred olefin sulfonates are
sodium salts but it is within the broader scope of
the invention to use other water-soluble salts such
-
6456
as ammonium or potassium salts thereof.
The anionic detergent may be a paraffin
sulfonate, e.g., of 10 to 20 carbon atoms; these
may be the primary paraffin sulfonates made by
reacting long chain alpha-olefins and bisulfites
(e.g., sodium bisulfite) or paraffin sulfonates
having the sulfonate groups di3tributed alcng the
paraffin chain, such as the products made by
reacting a long chain paraffin with sulfur dioxide
and oxygen under ultraviolet light, followed by
neutralization with NaOH or other suitable base (as
in U.S. Patents 2,503,280; 2,507,088; 3,260,741;
3,372,188; and German Patent 735,096).
Other anionic detergents are water-
soluble soaps of, or instanca,h~gherfatty acids
; such as lauric, myristic, stearic, oleic, elaidic,
iso~tearic, palmitic, undecylenic, tridecylenic,
pentadecylenic, 2-lower alkyl higher alkanoic (such
as 2-methyl tridecanoic, 2-methyl pentadecanoic or
2-methyl heptadecanoic) or other saturated or
unsaturated atty acid of 11 to 20 carbon atoms~
Soaps o dicarboxylic acids may also be used, such
as the soaps of dimerized linoleic acid. Soaps o
such other higher molecular weight acids such as
resin or tall oil acids, e.g., abietic acid, may
also be employed. Specific examples of suitable
soaps are the sodium soaps of mixture~ of tallow
fatty acids and coconut oil fatty acids (e.g.,
3~1 and 4:1 ratios). Soaps may also be used in
- 26
645~
small amounts as foam-decreasing agents.
Other anionic detergents are sulfates of
higher alcohols, such a~ sodium lauryl sulfate,
~odium tallow alcohol sulfate, Turkey Red Oil or
other sulfated oils, or sulfates of mono- or
diglycerides of fatty acids (e.g., stearic mono-
glyceride monosulfate), alkyl poly(ethenoxy) ether
sulfates such as the sulfates of the condensation
products of ethylene oxide and lauryl alcohol
(usually having 1 to 5 ethenoxy groups per molecule);
lauryl or other higher alkyl glyceryl ether sulfonates; and
aromatic poly(ethenoxy) ether sulfates ~uch as the
~ulfates of the condensation produats of ethylene
oxide and nonyl phenol (usually having 1 to 20
oxyethylene groups per molecule, preferably 2-12).
The ether sul~ate may also be one having a lower
alkoxy ~e.g., methoxy) substitutent on a carbon
clo~e to that carrying the sulfate group, such as a
monomethyl ether monosulfate of a long chain
vicinal glycol (e.g., a mixture of vicinal alkane-
diols o~ 16 to 17, 18 or 20 carbon atoms in a
~traight chain).
Other anionic detergents include also the
acyl sarcosinates (e.g., sodium lauroyl sarcosinate)
the acyl e~ters (e.g., oleic acid ester) of i80-
thionates, and acyl N-methyl taurides (e.g.,
potassium N-methyl lauroyl- or oleyl tauride).
Another type of anionic detergent i9 an alkyl
- 27
~ 31~45~;
phenol disulfonate such as one having an alkyl
group having some 12 to 25 carbon atoms, preferabl~
a linear alkyl of about 16 to 22 carbon atoms,
which may be made by sulfonating the corresponding
alkyl phenol to produce a product containing in
excess of 1.~, preferably about 1.8 (e.g., 1.8 to
1.9 or l.9S) So3H groups per alkyl phenol molecule.
The disulfonate may be one whose phenolic hydroxyl
group is blocked, as by etherification or
e~terification. Thus, the ~ of the phenolic OH
may be replaced by an alkyl ~e.g., ethyl) or
hydroxyalkoxyalkyl [e.g., a -(C-~2CH20)XH group
in which x is one or more, such as 3, 6 or 10,
and the resulting alcoholic ~H may be esterified
to form a sulateJ.
Most commonly the anionic detergents are
employad as ~odium salts but other alkali metal
salts, or ammonium or even alkaline earth metal
~c.g., magnesium salts) may be used. Mixtures o
~0 ~arious anionic detergent~, e.g., a mixture o~ a
sodium alkylbenzenasulfonate and a sodium ole~in
sulfonate, may be employed. Any of the described
anionic detergents may be ~ubstituted for the
anionics in the Examples to produce useful heavy
duty detergents.
The composition preferably also contains
a fluorescent brightener in small amount. Such
brightenexs are well known. They may be coumarin
types, as illustrated in U.S. patents 2,590,485;
- 28
~36~56
2,600,375; 2,610,152; 2,647,132; 2,647,133;
2,791,564; and 2,882,186; triazolyl stilbene types,
as illustrated in U.S. phtents 2,668,777; 2,684,966;
2,713,057; 2,784,183; 2,784,197; 2,817,665;
2,907,760; 2,927,866; and 2,993,892; stilbene
cyanuric types, as illustrated in U.S. patents
2,473,475; 2,526,668; 2~595,030; 2,618,636;
2,658,064; 2,658,065; 2,660,578; 2,666,052;
2,694,064; and 2,840 F 557; acylamino stilbene types,
as illu~trated in U.S. patents 2,084,413;
2,468,431; 2,521,665; 2,528,323; 2,581,057;
2,623,064; 2,674,604; and 2,676,982; or miscel-
laneous types, 3uch as are shown in U.S. patents
2,911,415 and 3,031,460. The amount of brightener
employed may be, for instance, in the range of
about 1/20~ to 1%, e.g., 1/10% to 1/2%. A suitable
combination of brighteners in¢ludes (a) a naph-
thotriazola stilbene sulfonate brightaner, sodium
2-~ul~o-4-t2-naphtho-1,2-triazolyl) stilbene, (b)
another ~tilbene brightener, bi~-tanilino diethanol~
amino triazinyl) stilbene disulfonic acid, ~c)
another stilbene brightener, ~odium bis-(anilino
morpholino triazinyl) stilbene disulfonate and
(d) an oxazole brightener, havinq a l-phenyl 2-
benzoxazole ethylene structure, 2-styryl naphtha
[1, 2 d]-oxazole, in the relative proportions,
a:b:c:d, of about 1:1:3:1.2.
Other ingredients which may be included
_ 29
1~36~5~
are foam-suppressing agent~; for this purpose
soaps, or high molecular weight amide or amine foam
suppressors, Yuch as N,N-dilauryl (or dicoco
alcohol) amine, may be employed in small amounts,
e.g. 1/2 to 8~ of the total composition.
Optionally the compositions of the
Examples contain minor proportions (e.g., about 5
to 15%) of ~odium per~orate for its bleaching
effects.
Instaad of using a Type 4A molecular
~ieve in the Examples, in which sodium i9 the
cation, one may employ a Type 3A having a potassium
cation or the molecular sieve may contain both
sodium and potassium cations in various relative
atomic proportions, e.g., 1:9, 1:1, 9:1, or other
cationsmay be sub~tituted (e.g., Li or NH4 ) in
whole or part, preferably only in part, e.g., up to
30%. All or part of the Type A sieve may be
replaced by another molecular sieve capable of
exchangin~ calcium,such as Type X ~e.g., in sodium
form). Useful molecular sieves of various types
are well known in the art; see, for instance, the
book "Zeolite Molecular Sieves" by Donald W. Breck,
published in 1973 by Wiley-Interscience. The
zeolites that are used in the Examples are prefer-
ably in a form which is hydrated and substantially
free of water-insoluble binder.
This invention can be used to provide
- 30
1~369~i6
hlghly effective substantially phosphate-free high
performance heavy duty household laundry detergent
compositions which are highly effective against a
wide variety of soils for a wide variety of fabrics,
including cotton, nylon, polyester (e.g., poly-
ethylene terephthalate), etc. They may be used in
automatic washing machines of the type (common in
the U.S.) in which the wash water i5 centrifugally
driven through the clothes (during the "spin"
portion of the washing cycle) without cauaing
signi~icant deposition o~ the particles on the
clothes, which i~ surprising, aGnsidering the
insolubility characteristics of the zeolite
molecular sieves. The wash water may be hot (e.g.,
50C, 60C or higher) or cool (e.g., 40C, 25C, 20C
or lower). The water may be soft or hard (e.g.,
having a hardness, expressed as CaCO3,of 50, 100,
150 or 200 ppm).
A~ wa~ indicated above, the bulk specific
gravlty o~ the ~pray-dried be~d~ in Example 29 i~
ln the range of about 0.3 to 0.4. The bulk speci-
fic gravity of the molecular sieve in that Example
is about 0.25, but other useful molecular sieves
may be of varying bulk specific gravitie~, e.g.,
about 0.2 to 0.5, such as about 0.25 to 0.45. The
true specific gravity of the molecular sieve-~ is
usually about 2, such as within the range of 1.5 to
2.5.
- 31
~L~a6~6
In Example 3 the use o trisodium-2-oxa-
1,1,3-propane tricarboxylate (a builder sold by
Monsanto Chemical~ i3 described. Compositions of
this type in variations of the described example
and in the otXer ~xample~ ma~ contain, for instance,
an amount of trisodium-2-oxa-1,1,3-propane tri-
carboxylate which is at least about 1/2 the weight
of sodium silicate, preferably not more than about
twice the weight of the latter, such as about 15 to
20~ of trisodium-2-oxa-1,1,3-propane tricarboxylate,
about 20 to 30~ o~ the molecular sieve and about 10
to 20~ of the sodium silicate, twith the proportion
of organic anionic detergent etc., being, for
instance, as described on pages 3 and 4, above)
when intended or use in the wash water at 0.15%
concentration, for instance. In another aspect of
the invention it is ound that built detergent
compositions in which the sole or predominant
builders are approximately e~ual amounts of the
tri90dium-2-oxa-1,1,3-propane tricarboxylate and
the sodium silicate (such as about 20~ of each of
these two ingredients), without as much molecular
sieve, give unexpectedly good fabric-washing
results (again, with proportions of the other
ingredients being, for instance, as described on
pages 3 and 4, above and a~ in ~xamples 2, 5 and
6).
_ 32
3~@~6~S6
As indlcated above, another material
whlch may be included in the blend of molecular
sieve, sodium silicate and anionic detergent, if
otherwise unob~ectionable, is trisodium
nitrilotriacetate For instance (as illustrated in
Example 4, above) one may employ about 10 or 15 to
20~ of this ingredient in the composition (with the
proportions of the other ingredients being as
; described on pages 3 and 4 above, for instance) and
. 10 a eood heavy duty detergent i8 produced.
Further, as stated heretofore, it should be
understood that this invention broadly relates to
detergent compositions in the form of spray dried
beads comprising at least 5~ by weight of a water-
soluble anionic organic detergent in combination with
a detergent builder system which includes a water-
insoluble alumlnum silicate molecular sieve in a pro-
portion at lea~t e~ual to that of the detergent and
havin~ an oily, waxy or tacki~ying material sorbed
~0 onto the beads. While the pre~erred sorbed material
is a liquid or pasty nonionic detergent such as primary
and secondary ethoxylated alkanols, other suitable oily,
waxy and ordinarily tackifylng materials which may be
used to enhance the properties of the detergent composl-
25 tion include, for example, concentrated aqueous slurries
of water-soluble salts of anionic sulfonated or sulfated
materials such as high alkyl sulfates, olefin sulfonates
-
~6~5~;
and alkane sulfonates, and higher alkyl polyethenoxy
ether sulfates; cationic quaternary ammonium fabric
softeners, C8-C18 acyl alkanolamides, and aqueous or
non-aqueous dispersions of halohydrocarbon and non-
ionic polyether textile treating agents. Such
materials can usually be convenient applied by
spray atomization onto a moving bed of the spray-
dried beads. After aging, effective washing composi-
tions in the form of free-flowing hollow beads are
produced.
The invention provides highly effective
detergent compositions having ralatively low phosphate
contents, e.g., water-soluble phosphate contents well
below 20~, preferably below 15~, such as 10% or less,
e.g., 5~, and most preferably they are substantially
free o~ phosphates. They may also be ~ree of carbonates
and I~TA in some preferred embodiments.
34-
