Note: Descriptions are shown in the official language in which they were submitted.
." 107~os8
As known, the detergents used in the household, in co~mer-
cial establishments and in industry, frequently con~ain large
quantities of condensed phospha~es, particularly tripolyphosphates.
These are provided to sequester the hardness formers of tap T~ater
and are responsihle to a great extent for increasing the cleaning
power of the capillary-active washing substances. The phosphorus
content o~ these agents has been criticized by the public in con-
nection with questions of the protection of the environment. The
view is frequently expressed that the phosphates, which arrive in
the rivers and lakes after treatment of the sewage, have great in-
fluence on the eutrophication of the waters, and is said to lead
to an increase of the growth of algae and of oxygen consumption.
It has therefore been tried to eliminate phosphate from the wash-
ing and cleaning processes or from the agents used for this pur-
pose, or at least to substantially reduce its proportion.
Copending, commonly-assigned Canadian Patent Applica-
tion Serial No. 197,628, filed April 16, 1974 discloses a process
for the washing, bleaching or cleaning of solid materials, parti-
cularly textiles, by treating these materials with a liquor con-
taining compounds able to bind the cations that make water hard.The process is characterized in that finely-dispersed, water-in-
soluble silicate compounds having calcium-binding capacity of at
~ least 50 mg CaO/gm of anhydrous active substance (AS) and having
i~ the formula I, combined water not shown
(M2/n)x Me203 . (SiO2)y (I)
where M is a cation of the valence n, exchangeable with calcium,
x is a number from 0.7 to 1.5, Me is aluminum or baron, and y is
a number from o.8 to 6, preferably from 1.3 to 4~ are suspended
in the aqueous treatment bath. The process of the patent makes
possible the complete or partial replacement of phosphates that
,
. ~
--1-- ~
,, ... . -: . , .. : .: . . . . .. .
~071Q58
bind calcium ions by complexing and are still being used in the
washing and cleaning process.
The calcium-binding capacity of the above~defined compounds
may reach values of 200 mg CaO/gm AS and is preferably in the
range of 100 to 200 mg CaO/gm AS. The above-derined compounds
capable of binding calcium are referred to as "aluminosilicates"
in the following text, for the sake of simplicity. This applies
particularly to the sodium aluminosilicates that are to be used
preferably. All data given for their preparation and processing
apply accordingly to the totality of the above aluminosilicate
compounds as defined in said earlier application.
The cation M employed is preferably sodium. Ho-~ever, the
same can also be totally or partially replaced by other cations
exchangeable with calcium~ such as hydrogen, lithium, potassium,
ammonium or magnesium, as well as by the cations of water-soluble
organic bases, for example, by those of primary~ secondary or
tertiary alkylamines or alkylolamines with not more than 2 carbon
atoms per alkyl radical, or not more than 3 carbon atoms per
alkylol radical.
The anhydrous active substance (AS) of the alumlnosilicates
- ~ is that reached after one hour of drying at 800C, whenever re-
ference to anhydrous aluminosilicate is made in the ~ollowing text.
. ~ ~ The adhering water as well as the water of retention is removed
partlcally completely by this drying.
Aluminosilicates that are still moist, for example~ from
~their preparation, are used to advantage as starting compounds in
the preparation of washing and cleansing agent compositions con-
tainlng the above-defined aluminosilicates in addition to the con-
ventional components. The moist compounds are at least mixed with
,~ ~ 30 a portion o~ the remaining components of the material to be
''`
' .
` ~ -2-
1071058
prepared, and the mix~ure is incorporated into the finished
washiny and cleansing agent composition to give as the final
product, a product that is a pourable powder.
q'he aluminosilicates are supplied or used, in the
framework of the procedure for the preparation of washing and
cleansiny agent compositions outlined above, as aqueous sus-
pensions or as moist filter cake. Certain improvements of
the suspension characteristics, such as the stability of the
suspension and the transferability of the aluminosilicates
dispersed in the aqueous phase, by pumping, would be desirable.
An object of the present invention is the development
of an aqueous suspension of water-insoluble, calcium-binding
aluminosilicates with an improved stability against settling
consisting essentially of (A) from 20% to 50% by weight on the
anhydrous basis of at least one finely-divided, water-insoluble
~ilicate compound having a calcium-binding power of at least
50 mg CaO/gm of anhydrous active substance and having the
formula, combined water not shown
(M2/n) . Me203 . ~SiO2) y . .- '.
where M is a cation of the valence n, exchangeable with calcium,
x is a number of from 0.7 to 1.5, Me is aluminum or boron, and
i y is a number from 0.8 to 6 and (B) from 0.5% to fi% by weight
of at least one inorganic water-insoluble, but water-swellable
silicate with a laminated structure, as a dispersing agent.
', '
' .
~ B - 3 ~
, . .
1071Q58
We have now found that certain compounds possess to
a special degree, the capability to stabilize suspensions of
the above calcium-binding aluminosilicates so that these,
even with a high solids content, remain stable for a long time,
in fact for a practically unlimited time, and also can stil~
be pumped without problems after long periods of standing.
Surprisingly, it has been found that there are certain compounds
which are capable of keeping suspension of moist aluminosili-
cates which have a bound or adhering water content of 70% or
less, pumpable practically, independent of their standing
period, which was impossible until now.
The present invention therefore relates to aqueous
suspensions of water-insoluble, calcium-binding aluminosili-
cates, suitable for use as stock suspensions and transferable
by pump, with an improved stability, characterized by the
fact that, based on the total weight of the aqueous suspension,
they contain
A) at least 20%, preferably 20% to 53% and especially
20%, to 42% by weight on an anhydrous basis of
29 finely-divided, water-insoluble compounds,
capable of binding calcium, of the general
; formula, combined water not shown
: .
(M2/nO) X . Me203 . (si2) y
.
in which the symbols have the meaning given above,
and
B) at least one inorganic water-insoluble, but water-
swellable silicate with à laminated structure, as
!
a dispersing agent.
.~ , , .
l . .
I dg/~
. . ~ . . . ~ , .. .
:............................................ .
1071(}S8
: More particularl~, the invention relates to an : :
aqueous suspensioll o~ water-insoluble, calcium-binding
aluminosilicates with an improved stability against settling
con.sisting essentially of
(A) from 20~ to 50~ by weight on the anhydrous
basis of at least one finely-divided, water-insoluble silica~e
compound havlng
' '
dg/,~ 4a
.
31~Q~58
a calcium-binding power of at least 50 mg CaO/gm of anhydrous
active substance and having the formula, combined water not shown
( 2/n)x . Me23 (SiO2)
where M is a cation of the valence n, exchangeable with calcium,
x is a number of from 0.7 to 1.5, Me is aluminum or boron, and y
is a number from G.8 to 6, and (B) from 0.5% to 6% by weight of
at least one inorganic water-insoluble, but water-swellable sili-
cate compound having a laminated structure, as a dispersing agent.
The pH of the suspensions is generally between about 7 and 12, pre-
ferably between 8.5 and 11.5, and usually below 11.
The condition of the aluminosilicate reached after one hour
of drying at 800C is the basis on which all data of "concentra-
tion of the aluminosilicates", "solids content" or content of
"active substance" (AS) are based. The adhering water and water
of retention is removed practically completely by this drying pro-
cedure.
All data in percentages are referring to percent by weight.
The above-mentioned components A and B are discussed in more
detail below.
The aluminosilicates of component A to be used according
to the invention may be x-ray amorphous or crystalline products,
with the use of mixtures of amorphous and crystalline products as
well as partially crystallized products being permissible. The
aluminosilicates may be naturally occurring or synthetically pro-
duced products, however, the synthetically prepared products are
preferred. Their preparation can be carried out for example,
by reacting water-soluble silicates with water-soluble aluminates
. '
"- "
- 1~71Q58
in thc p~-es~nce o~ watcr~ Pref~rably sodium si,licates and
sodium aluminates are employed. For thls purpose/ aqueous
solutions of the starting materials can be mixed or one
component in solid form can be reacted with the other component
prescnt in an aqueous solution. The desired aluminosi~icates
may also be obtained by mixing the two components in solid
form, in the presence of water. ~luminosilicates are also
produced by reacting Al(OH)3, A12O3 or SiO2 with alkali ~etal
silicate or alkall metal aluminate solutions respectively.
The preparation may be carried out according to other well- ~'' - '
known processes, also. The invention refers, in particular,
to alu~inosilicates possessing, in contrast to the largered
silicate structure of montmorillonite, a three-dimensional
spatial lattice structure.
The preferred calcium-binding capacity, wilich is in
the range of 100 to 200 mg CaO/gm ~S and mainly about 100 to
180 mg CaO/gm AS, is found principally in compounds of the
followiny composition:
0.7 - 1.1 Na2O ~123 1.3 - 3.3 SiO2.
This formula includes two different types of crystal structures
(or their non-crystall-'ne precursors) that differ also in
their formulas:
` a) 0.7 - 1.1 Na2O A123 1.3 - 2.4 SiO2
b) 0 7 - 1.1 Na2O A123 ~2.4 -,3.3 SiO2., ,
The different crystal structures become apparent in the x-ray
diffraction diagram.
The amorphous or crystalline aluminosilicate,
I pxesent in an aqueous suspension can be separated from the, ,~
'~ 30 remaining aqueous solution by filtration and drying at temper-
; atures of 50 to 400C. The product contains a larger or -'
smaller amount o combined water, dep'ending on the drying , ,'
~ .
dg/B~ ~ -6- ~
1, ' ' . ,
.~ ... , . . - ~ .~ . . . . . . . .
~; . . . . - .. . .
1071(:~58
COJldi tions .
Thc higher drying temperatures ~re not general]y
recommended. It is preferable that a temperature of 200 C
is not exceeded in drying, when the aluminosilicate is to be
used in washing and cleansing agent compositions. However, the
aluminosilicates do not have to be dried at all after their
preparation, if they are used for the preparation a suspension
according to the invention. On the contrary, and this is
especially advantageous, an aluminosilicate that is still
moist from its preparation may be used. Also suitable for the
preparation of suspensions according to the invention are
aluminosilicates that are dried at intermediate temperatures
of 80 to 200C, until the adhering liquid water is removed.
The partic],e size of the aluminosilicate particles
may vary between 0.1 ~ and 0.1 mm. This is based on the
primary particle size, i.e. to the size of the particles
obtai.ned by precipitation and, i desired, subsequent crystal-
liæation. Especially advantageous is the use of aluminosili-
cates consisting to at least 8~% by weight of particles
measuring 10 to 0.01~, particularly 8 to 0.1 ~. It is prefer-
ab].e that these aluminosilicates do not contain any primary ''
or secondary particles with a diameter above 30 ~. Secondary
particles are particles that are produced by the agglomeration
of primary particles into larger forms. Most important is the
range between ca. 1 ~nd 10 ~.
The use of aluminosilicates still moist from their
preparation, for the production of suspensions according to
the invention, has been especially advantageous with respect to
the agglomeration of primary particles into larger forms, ',
since it was found that a formation of secondary particles is
practically completely prevented by the use of these moist product~.
The more detailed description o~ the compounds used
as component B according to the invention follows.
..
dg~r'~^ ~7~ ' ' '
~ 1~)7:~58
The dispersing agents which are suitable according to the
invention as component B are the water-insoluble, but water-swell-
able silicates having a laminated structure, of the type of clays.
These have a laminated structure in ~ontrast to the aluminosilic-
ates of component A to be suspended according to the invention,
which have a three-dimensional lattice structure. The water-swell-
able silicates having a laminated structure are known as smectites.
These are compounds of the general formula
2(si2o5)2(oH)2 and Mg3(si25) (OH)
Examples are bentonite, montmorillonite, volchonskoite, nontronite~
hectorite, saponite, sauconite and vermiculite. Depending on the
origin, these clays, capable of swelling in water, also possess
catlons such as sodium, potassium or calcium, since they are cap-
able of cation exchange. Naturally occurring and synthetically
produced substances are equally suitable, with the synthetic pro-
ducts frequently offering the advantage of being purer. The
particle size of these laminated silicates is mainly below about
50 ~. Particularly suitable are types containing little calcium,
which are capable of binding calcium. ~ -
Aqueous suspensions especially preferred in the invention
consist mainly of at least 20% of component A. The upper limit of
the content of the aluminosilicate component A is determined by
the limit of the flow characteristics, which lies generally at
about 42% by weight. Concentrations between 25% and 40% by weight,
especially between about 28% and 38% by weight, are preferred.
The range of 30% to 38% by weight is the most important for
practical application.
The amount of component B to be used depends mainly on the
desired degree of stabllization of the suspensions. In general,
--8--
- 1071058
the concentration of component B of the suspensions accor~ing
to the invention ]ies between abol1t 0.5% to 6~, more oEten
from 0.8% to 6% by weight, calculated on the total weight of
the aqueous suspension. It is preferably in the range of about
1% to 4% by weight and in most cases about 1.3% to 3% by
weigllt, as a matter of practicality. T~e desired viscosity
can be taken into consideration in the selection of the
concentration of component B, if necessary, since the viscosity
of the suspensions is influenced by the content of component B.
Smaller amounts of component B are used for the
stabilization of the finer aluminosilicates than of coarser
products. For example, aluminosilicate suspensions containing
90~ or more of particles measuring between 1 and 8 ~ can be
stabilized equally well by a content of from 0.5% to 1% by -
weight of dispersing agent, as products with intermediates
size particles of 10 to 12 ~ which are stabilized ~y 1% to
2% of dispersing agent. These data are only guidelines. The
suitable amount of component B must be determined for the
definite requirements of the individual case.
Especially preferred aqueous suspensions in the
invention consist mainly of at least 20% of component A, at
least about 0.5% preferably at least about 0.8% of component
B and water.
Inorganic salts or hydroxides from the precipitation
or other processes for the preparation of the aluminosilicates
are present in addition to the mentioned components. That
is, small amounts of excess sodium hydroxide, or sodium
carbonate or bicarbonate formed from it by absorption of carbon
dioxide may be present, or the sulfate ion, if aluminum sulfate
was used as the al~inum-containing starting material for the
pxeparation of aluminosilicate.
: .
d~ f~ ~9~
.
lVS8
Basically, the aqueous suspensions also may contain addi-
tional substances in relatively small amounts besides the mentioned
components A and B and, if necessary, substances remaining from the
starting materials for the preparation of tnese comp~nents. Where
the suspensions for washing agents and detergents are to be pro-
cessed further, the additionally present substances are preferably
substances suitable as components of washing and cleansing agent
compositions.
An indication of the stability of the suspensions is pro-
vided by a simple test, in which an aluminosilicate suspension is
prepared of the desired concentration, such as 31%, and containing
a dispersing agent according to the invention as well as optionally
other substances, and/or detergent components such as pentasodium
tripolyphosphate, in varying amounts. The influence of the added
substances can be observed visually by the precipitation char-
acteristics of the suspension. A preferred suspension generally
should not have settled beyond the point where the clear supernat-
ant liquid, the solution free from silicate particles, amounts to -
more than 20%, preferably more than 10%, especially more than 6%,
Of the total height, after standing for 24 hours. In general, the
amount of additives should be adjusted so that the suspension can
be readily transferred again by pumping after standing for 12 hours,
preferably 24 hours and especially also after 48 hours of standing
in the storage tank and pipes or tubes. The settling characteris-
tics of the suspensions containing further components, if desired,
is tested at room temperature, at an overall height of 10 cm for
the suspension. If the height of the clear supernatant liquid of
especially preferred suspensions stays within the given range, even
after 4 and especially after 8 days, they can be pumped without any
problem after 4 and after 8 days. These data concerning the
stability of the suspension again are guidelines. The desirable
--10--
:~7~C3 58
stability for the suspension must be determined for each individual
case. When using the suspensions according to the invention as
stoc-k suspensions for extended storage in a tank; from which it can
be removed by pumping, it may be advantageous to keep the portion
of other components of washing and cleansing agent compositions,
low or to eliminate them completely.
The suspensions can be prepared by the simple mixing of .
their components, in which.process the aluminosilieates may be used
as is or moist, optionally from their preparation, or in aqueous ~
10 suspension. Especially advantageous is the addition of alumino- :
sili¢ates that are still moist, as filter cakes, to a dispersion
of component B in water. This dispersion of component B is pre- -
ferably warmed, to 50 to 70C.
Dried aluminosilicates, for example, substances from which
the adhering water has been removed, but.that contain bound water,
can also be used in the preparation of stable suspension.
. In an especially suitable process for the preparation of .-
.the suspensions according to.the invention, aluminosilicate is
precipitated by mixing sodium.aluminate and sodium silicate solu-
20 ti0ns. These solutions are more alkaline, thus containing more
, . theoretical sodium hydroxide than.is necessary.for the formation
.~ of the final aluminosilicate, so that an ex¢ess of sodium hydroxide
is presen.t.in the aluminosilicate suspensi.ons,..the immediate pro-
-' duct of.pre¢ipitation. This suspension is concentrated by filter-
t ing off part of the supernatant mother liquor, and subsequently
freed from a sufficient amount of the excess sodium hydroxide
.. ~ .present by rinsing with water, so that the sodium hydroxide content
... . of the suspension is below about 5%, preferab.ly.below 3% or even
below 2% by weight. The remaining sodium hydroxide is neutralized
by the addition of an acid, particularly aqueous sulfuric acid, to
-
` '
-` '~' -11- ; .
.
~(~71a!58
such a degree that the obtained suspension has a pH between about
7 and 12, particularly between about 8.5 and 11.5. The amount of
dlspersing agent necessary to achieve the desired degree of stabi-
lization is added to the suspension. This addition may be made :
before, during or after the partial neutralization step. ~
The suspensions according to the invention are characterized ..
by high stability and other advantages. Their stabilizing effect :
is particularly valuable for-aluminosilicates with a particle size
of 5 to 30 y- They can be pumped, permicting the easy handling of :
moist aluminosilicates. The suspensions can be moved without any
problem by pumping, even after longer interruptions in the pumping
process. Due to their high stability, the suspensions can be trans- .-
ported in regular tank trucks and drum trucks without formation of .:
useless or interfering residues.. The suspensions are therefore
exceptionally suitable as a form.in which aluminosilicates can be .
delivered to detergent manufacturers, for example.
The suspensions can be stored.at room temperature or highertemperatures, and transported through pipe lines, pumps or other
means. The suspensions are usual.ly handled.betwee.n room tempera-
20 ture, most preferably, and about 60C. .
Particularly suitable are the suspensi.ons according to theinvention for the processing of flowing or triekleable products
with.a dry appearance, and.for.the.preparation of powdery water
softeners, through spray-drying. Thus, the suspensions have con-
siderable..value for the preparation of.powdery al.uminosilicates.
No troublesome res.idues are found dur.ing the feeding of the aqueous :~
suspension into the drying equipment. It.was also observed that
the suspensions of the invention~can be processed into extremely
~ dust-free products.
.
-12-
~ .. ~ . - , . ~. .. . .
os~
Because of their special stability, the suspensions accord-
ing to the invention can be used as they are, without further
process compounding and with or without further additives possess-
ing a cleansing, bleaching and/or washing effect, for example as
water softeners, washing or cleansing agents and particularly as
liquid scouring products with increased suspension stability.
An especially important use of the suspension is in the
further conversion into pourable or trickleable washing and cleans-
ing agents and containing other compounds in addition to the com-
ponents of the suspension.
The suspensions according to the invention are especiallysuitable for the preparation of washing and cleansing agent com-
positions described in the Canadian Patent Application Serial Nos.
197,628, 198,561 and 198,560, all filed April 16, 30 and 31, 1974,
and all data for their preparatlon, their composition components
and for the proportions of the components are applicable corres-
pondingly.
Thus the invention also concerns a process for the prepara-
tion of pourable powdery products with a content of water-insoluble
aluminosilicates, as defined above, in which a pourable product is
~ produced in the usual manner by starting with an aqueous, flowing
; solution of a premix of individual components of the products. The
process is characterized by the fact that the aluminosilicates are
used in the form of the suspensions according to the invention.
The suspensions according to the invention can be converted into
the solid, pourable washing and cleansing agent compositions by
well~known processes.
Powdered, trickleable washing and cleansing agent composi-
tions according ~o the invention are prepared in such a manner that
-
~ -13-
a suspension according to the invention, from a storage tank, is
mixed with at least one washing, bleaching or cleaning component
of the product to be prepared, and that the mixture is subsequently
converted into a powdered product by a customary process. A se-
questering agent, a compound capable of binding the alkaline earth .
metal ions that make the water hard, particularly the magnesium ~:
and calcium ions, is added to advantage. ..
In general, the suspension according to the invention is
combined preferably with at least one water-soluble surface-active
compound ortensidef~r the preparation of washing and cleansing agent
compositions according to the invention.
There are several variations of the preparation of washing :~
and cleansing agent compositions. For example, the suspension
according to the invention can be combined w.ith substances capable
: . of adding water of crystallization, preferably by spraying the sus-
pension onto the anhydrous or partially anhydrous compounds cap-
able of adding water of crystal].ization, placed in a mixer, so that
.with constant m,xing a finally solid product of dry appearance is
obtained. However, the suspensions according to the invention are
preferably mixed into a slurry, and spray-dried.with at least one
additional washing, bleaching or.cleansing substance. Additional, .
. surprising advantages of the claimed.aluminosilicate suspensions
. are observed herein. It has been found that highly dust-free pro-
ducts can be obtained through the use of the suspensions according
to the invention for spray-drying. The products of spray-drying
. ....have a~high capaci.ty for binding calcium and are readily wettable. .~:
` ; Washing.agent compositons according to the invention, that ~.
:, ls washing agent compositions that can be prepared with the use of
the suspensions described above, may have various compositions.
3 Generally, they contain at least one tenside. The washing and .
j cleansing agent compositions of the invention can be in general
. agreement with the overall formulations of the above-mentioned, .~
-14- :
l~. . . . . .. - : , . .
71~5E~
prior patent applications. They contain an aluminosilicate, de-
fined as above, as a calcium-binding compound, in addition to at
least one other inorganic or organic compound that has a washing,
bleaching or cleansing effect. Furthermore, such products may
contain other conventional additives and ad~uncts found mainly in
smaller quantities. The above mentioned, prior patent applications
should be consulted for further details. The data also apply to
thesecases.
The content of aluminosilicates of such products may be from
5% to 95%, preferably from 15% to 60% by weight.
The compositions according to the invention may also con-
tain sequestering or precipitating agents for calcium, preferably
with contents of 2% to 15% by weight, depending on the chemical
nature of the agents.
The substantially phosphorus-free washing agent compositions
should have a content of inorganic phosphates and/or organic phos-
phorus compounds not exceeding a total content of 6% P, preferably
of 3% P.
The additional components with a washing, bleaching or
cleansing effect contained in the washing and cleansing agent com-
positions are surface-active compounds, surface-active or non-sur-
face-active foam stabilizers or inhibitors, textile softeners,
neutral or alkaline builders, chemically active bleaches as well as
stabilizers and/or activators. Other additives and ad~uncts are
usually~present in smaller amounts, such as corrosion inhibitors,
antimicrobial agents, soil suspension agents, enzymes, optical
brighteners, dyes and perfumes.
The composition of typical washing agent composition to be
used at temperatures between 50 and 100C is in the range of the
following formulation.
1~7~S8 ~
3~ to 30%, preferably 5% to 30%, of anionic and/or amphoteric
and/or nonionic surface-active compounds;
5% to 70~O of aluminosilicates (¢alculated for AS), including -:
the laminated structure silicates of the invention;
2~ to 45% of sequesterin~ agents for calcium; .:
0 to 50% of wash alkalis not capable of forming complexes
(alkaline builders;
0 to 50% of bleaching a~ent components as well as other ad;uncts
mainly found in smaller amounts in textile washing
agent compositions.
~ ollowing is an enumeration of compounds suitable for use
in the products according to the invention.
The surface-active compounds or tensides contaln in the
molecule at least one hydrophobic or~anic moiety and one water-
solublllzlng, anionic, nonionic or amphoteric group. The hydro-
: phoblc molety ls mostly an aliphat.ic hydrocarbon radical with 8 to
- 26, preferably 10 to 22 and particularly 12 to 18 carbon atoms or
an alkyl aromatic radical, such.as.alkylphenyl, with 6 to 18, pre-
ferably 8 to 16 aliphatic carbon atoms.
~2 20 Among the anionic surface-active compounds, are, for example,
.- soaps of natural or syntheti-c,.p~eferably saturated, fatty acids,
optionally, also, soaps of: resinic or naphthenic.acids. Suitable
- synthetic anionic tensides are those of the type of the sulfonates,
sulfates and synthetic carboxylates.
. $uitable tensides of the sulfate type are the sulfuric acld
. monoesters of primary aleohols (e.g. from coconut fatty alcohols,
.tallow.fatty alcohols or olely alcohol) and.those of secondary
i ~ alcohols. Also suitable are sulfated.Patty acid.alkanolamides,
,` sulfated fatty acld monoglycerides or sulfated reaction products
`l 30 o~ l to 4 mols of ethylene oxide with primary or secondary fatty
.~ alcohols or alkylphenols. .
;
: -16-
~0~71f~58
Nonionic tensides are mainly the addition products of 9 to
40, preferably 9 to 20 mols of ethylene oxide onto 1 mol of a fatty
alcohol. -
Suitable nonionic surface-active eompounds or tensides are
the addition products of 4 to 40, preferably 4 to 20 mols of ethy-
lene oxide to 1 mol of a fatty alcohol, alkylphenol., fatty acid,
fatty amine, fatty acid amide or. alkane-sulfonamide. Particularly
important.are the addition products of 5 to 16 mols of ethylene
oxide to coconut fatty alcohols or tal.low fatty alcohols, to oleyl
alcohol or to secondary alkanols with 8 to 18, preferably 12 to 18
carbon atoms, as well as monoalkylphenols or dialkylphenols with
6 to 14 carbon atoms in the alkyls. In.a~dition to these water-
soluble nonionics, polyglycol ethers.with 1 to 4 ethylene glycol
ether radicals.in the molecule,which are insoluble or not completely
water-soluble are also of interest, particularl.y lf they are used
. together with water-soluble nonionic or anlonic tensides.
Furthefrmore, the water-soluble addition products of 20 to :~
2.50 mols of ethylene-oxide to polyoxypropylene glycol containing
10 to 100 propylene glycol ether groups (Pluronics f~f ), to
ialkylenediamine-polyoxypropylene~glycol (Tetronics ~f ), and to
, ,
ll alkylpolyoxypropylene gly~ols with 1 to.l.0 carbon atoms in the
f~ alkyl chain, can also be used.wher~ the polyoxy.propylene glycol
chaln ac.ts as a.hydrophobic radical. ~ . .
f,` Nonionic tensides of the type of the amine oxides or sul-
foxides can also be used.
~The amphoteric surfaee-active eompounds or tensides are of
.~ : the type of the carboxybet.aines or~sulfobetaines. :~.
I Compounds capable of~bindin~.cal¢ium as.a complex, as well
a8 th0se that do not possess this property, are suitable as builders. : .
The alkali metal bicarbonates,.oarbonates, borates or silicates, or
. . .
~: -17-
~ ' '
, . '-. .. :
. . . . - , ~ .. .. ~ . .. .
SB
wash alkalis, the alkali metal sulfates as well as t~e alkali
metal salts of organic sulfonic acids, carboxylie acids and sul-
foncarboxylic acids that do not possess any surface activity and
contain 1 to 9 carbon atoms are examples of the non-complexing
builders. Specific examples are the water-soluble salts of benzene,
toluene or xylenesulfonic acid as well as the water-soluble salts
of sulfoacetic acid, sulfobenzoic aci~ or of sulfodicarboxylic
acids. The complexing builders are the alkali metal tripolyphos-
phates, as well as a large number of the known or~anic complexing
agents of the type of the polycarboxylic acid, also including poly-
meric carboxylic acids, of the aminocarboxylic acids, phosphonic
acids, phosphonocarboxylic acids, hydroxycarboxylic acids, carboxy-
alkyl ethers, etc.
Suitable bleachin~ agents are compounds that release H2O2
in aqueous solution, such as alkali metal perborates, or substarlces
releasing active chlorine. Other additives, present mainly in
small amounts, are foam stabilizers or inhibitors, textile softeners,
stabilizers and/or activators for bleaching agents, corrosion in-
hibitors, antimicrobial compounds, soil suspension agents, enzymes,
optical brighteners, dyes and perfumes.
The products prepared according to the in~ntion can be used
for the various cleaning tasks in numerous technical areas and in
the household. Examples of such areas of application are the
cleaning of tools, vessels of wood, plastics, metal, earthenware,
glass etc. in the industry or in commercial establishments, the
cleaning of furniture, walls, floors, objects of earthenware, glass,
metal, wood, plastics, the cleaning of polishing or shellacked sur-
faces in the household, etc. An especially important area of appli-
catlon is the washing of textiles of all types in the industry, in
commercial cleaning establishments and in the household.
18-
1071C~58
The following specific embodiments all illustrative
of the invention without being limitative in any respect.
EXAMPLES
Preparation of aluminosilicates
First, the synthesis of aluminosilicates used in
the suspensions according to the invention is described for
which no invention is claimed. The description is purely
illustrative; other well-known processes for the preparation of
aluminosilicates can be used as described in the Canadian
Patent Application Serial Nos. 197,628, 198,561 and 198,560,
all filed April 16, 30 and 31, 1974.
~) The sodium aluminate solution was reacted with -the calculated amount of sodium silicate solution under
vigorous agitation in a 15 liter vessel (temperature of the
solutions 20 to 80C). A sodium aluminosilicate that was
x-ray amporphous was produced as primary precipitation product
in an exothermic reaction. After ten minutes of vigorous
agitation the suspension of the precipitation product was either -
1. processed further directly, i.e. without
crystallization, or
2. heated at 80C for 3 to 6 hours for crystalliza-
tion, or aging, after which products were obtained completely
crystalllne according to x-ray structural analysis.
~) The mother liquor was filtered off from the
suspensions obtained above. The remaining filter cake was
washed with deionized water and then mixed with deionized water
, to form the suspension ~1 (from ~1) or ~2 (from ~2).
y) A microcrystalline aluminosilicate was prepared
~ ..
,~ 30 by reacting the aluminate solution, diluted with deionized
j~ water, with the 8ilicate solution, with vigorous agitation with
¦ a high-speed agitator (10,000 rpm; "Ultraturrax" made by
'~: . ' .
* trademark -19-
dg/f~..J
~, . .. . . .. . . . . . . .. . .
071058
Janke & Kun]~el IK~-Werk, StauEfen/Breisgau, Federal Repuhlic
of Germany). After ten minutes of vigorous agitation, the
suspensioll of the amorphous precipitation product was trans-
ferred to a crystallization vessel, wh~re the formation of
larc3e crystals was prevented by agitating the suspension.
~fter the removal of the liquor from the crystal mass by suction
and washing with deionized water until the collected wash water
had a pll of about 10, the filter residue was dried, then
pulverized in a ball mill and separated into two fractions by
io a centrifugal sifter ("Microplex" air sifter by Alpine,
Augsburg, Federal Republic of Germany). The finer fraction
did not contain any particles above 10 ~. From the finer
fraction, a suspension in deionized water (yl) was prepared.
A corresponding suspension was also prepared without the drying ~ -
process and the separation into two fractions. The moist
filter cake o~ variable moisture content was added to water.
The suspension ~btained is called y2. The separation of the
~ silicates from the larger portion of the originally present
3 water was carried out by centrifuging instead of filtration
in some cases.
The aluminosilicates obtained had the approximate
composition calculated for anhydrous products (AS):
1 Na2O Al2O3 . 2 S~O2
,~ . . .
The calcium binding power of the precipitation
products was 150 to 175 mg CaO/gm active substance. The
calcium~binding power was determined as follows. One liter of -
an aqueous solution containing 0.594 gm CaC12~300 mg CaO~l =
j 30 30 dH) and adjusted to pH 10 with dilute NaOH was reacted with
1 gm of the aluminosilicate (on the anhydrous basis, AS). Then,
the æuspension was agitated vigorou91y for 15 minutes at a
- trademark
dg/~ J -20-
i .,.;,:., : , , , ~ . ;
: ~ : . .. . , . ~ . . .. . .. . . ..
107~(~S8
temperature of 22C ~ 2C. After filtering the aluminosi]lcate,
the residual hardness x of tlle filtrate was determined. The
calcium binding power was calculated from this in mg CaO/gm AS,
using the formula
(30 ~ x) . 10.
Production conditions for aluminosillcate I:
Precipitation: 2.985 kg of all aluminate solution of the
composition: 17.7% Na20, 15.8% A1203,
66-6% H20
0.15 kg of sodium hydroxide ~;
9.420 kg of water
2.445 kg of a 25.8~ sodium silicate solution
of the composition 1 Na20 . 6.0 SiO2,
prepared freshly from commercial water- -
glass and easily alkali-soluble silica
Cxystallization: 24 hours at 80C
Drying: 24 hours at 100 C
Composition: 0.9 Na20 1 A123 2.05 SiO2 4.3 H20
(= 21.6~ H20)
Degree of crystallization: Fully crystalline
Calcium binding power: 150 mg CaO/gm AS.
~ If the product obtained was dried for 1 hour at 400C,
I an aluminum silicate Ia was obtained of the composition:
0.9 Na20 1 A123 2-04 Si2 . 2-0 l~2 ( 2
which is likewise suitable for the purposes of the invention.
I Product conditions for aluminosilicate II:
Precipitation: 2.115 kg of an aluminate solution of the
composition: 17.7% Na20 15.8% A1203, 66.S% H20
0.585 kg of sodium hydroxide
9.615 kg of water
2.685 kg of a 25.8~ sodium silicate
s~lution of the composition: 1 Na20
6 SiO2 (prepar~d as under I)
.
d~/~t~ 21-
. , , .. , . , , . , ~, .
1071(~58
Crystallization: 24 hours at 80C
Drying: 24 hours at 100C and 20 torr.
Composition: 0.8 Na2O 1 A12O3 2.655 SiO2 5.2 H2O
Degree of crystallization: Fully crystalline
Calcium binding power: 120 mg CaO/gm AS.
This product too can be dehydrated by drying (for 1
hour at 400C) to the composition:
0.8 Na2O 1 A12O3 2.65 SiO2 0.2 H2O
This dehydration product IIa is likewise suitable for the ~-:
purposes of the invention.
The aluminosilicates I and II show in the x-ray
diffraction diagram the following interference lines.
d - values, recorded with Cu-K~ - radiation in A
I II -
12.4
~ . 8.8
8.6
-
7.0 _ -
~ 20 ~ 4-4 (+)
t 4.1 (+)
_ 3.8 (+)
i 3.68 (+)
-~ 3.38 (+) ~
3.26 (+)
. 2.96 (+) - ~-
! - 2.88 (+)
. ~ ~ - . 2-79 (+)
. 2.73 ~+)
_ 2.66 (+)
; 2.60 (+)
1 .
~ , ,
'~ ~ ' . ' .
.~ : d~ -22-
~` ` , .
1071QS8
It is qu.ite possible that not all these interference
lines wi.ll appear in thc x-ray diffraction diagram, partic-
ularly if the aluminosilicates are not fully crystallized.
For this reason, the d-values which are the most important
for the characterization of these types are identified by
a "~
Product.ion conditions for aluminosilicate VIII
Precipitation: 2.115 kg of an.aluminate solution of the
composition 17.7% Na2O, 15.8%
Al2O3l 66-5% H2
0.585 kg of sodium hydroxide
9.615 kg of water
2.685 kg of a 25.8% sodium silicate
solution of the composition~
1 Na2O . 6 SiO2 (prepared as in I)
Crystallization: not carried out
; Drying: 24 hours at 100C
Composition: 0-8 Na2 1 ~12O3 2-65 Si2 4 ~2
Degree of
Crystallization: x-ray amorphous -
Calcium binding
power: 60 mg CaO/gm AS.
Production conditions for aluminosilicate IX:
Precipitation: 3.41 kg of an aluminate solution of the
composition 21.4% Na2O, 15.4%
A12O3, 63.2~ H2O, 10.46 kg of water,
1.13 kg of a 34.9~ sodium silicate
solution of the composition:
2 . 2
Crystalliæation: not carried out;
Drying: 24 hours at 100C;
Composition: 1 Na2O 1 A12O3 1 SiO2 1.4 l-12O;
.
~ dg//~ 23~
107~()S8
Deyree of crystal~
lization: x-ray amorphous
Calcium binding
power: 120 mg CaO/gm AS.
Product.~on conditions for aluminosilicate XXm:
Precipitation: 0.76 kg of an aluminate preparation of the
composition: 36.0% Na2O, 59.0%
A12O3, 5.0% H2O,
0.94 kg of sodium hydroxide,
io 9.49 kg of water,
3.94 kg of a co~nercial sodium silicate --
solution of the composition: 8.0~ ~-
Na2O, 26.9~ SiO2, 65.1% H2O
Crystallization: 12 hours at 90C;
Drying: 12 hours at 100 C;
Composition: 0.9 Na2O 1 A123 3.1 SiO2 . 5 H2O;
Degree of
Crystallization: completely crystalline
Calcium binding
20 power: 110 mg CaO/gm AS.
The abbreviations used in the following text mean:
TA + EO an addition product of x mols ethylene ox.ide tEO) per
mol of mainly saturated fatty alcohol mixture with
. varying carbon-atoms, prepared by the reduction of
7 ' a tallow fatty acid. The fatty alcohol mixture has
¦ the following approximate distribution:
C12: 0 - 2%
i Cl~ 4 _ 7%
.l C16 25 - 35%
18 60 - 67%
C20: 0 - 2%
; ~ dg/l~ -24- ;`
3~71~1~i8
EDTA the salt of ethylenediaminetetraacetic acid;
CMC the salt of carbox~methyl cellulose;
Sodium silicate a sodium silicate (Na20 : SiO2, theoretically
1 : 3.35)-
Perborate a technical grade product of the approximate com-
position NaBO2 H22 3 H2O-
All salt-like compounds were used in the form of sodium salts.
Suspensions according to the Invention
' '
EXAMPLE 1
10The suspensions according to the invention are illustrated
in the examples with the microcrystalline aluminosilicates pre-
pared according to y2, since these are preferred for the prepara- ;
:~~ tion according to the invention of washing and cleaning products.
The suspensions according to the invention can be prepared also
correspondingly with the suspensions ~ 2 and yl or with
corresponding aluminosilicates isolated as solids.
' :
i EXAMPLE 2
,,:
l A moist aluminosilicate of the formula Na20 . A1203. 2 SiO2
i and containing 50% water was added to suspensions of bentonite in
water. The stabilized suspensions had an AS content of 33% and a
content of 2% or 4% bentonite. The bentonite used was a commer-
`! cial product marketed under the name "Aktive-Bentonite" by
Erbsloh, ~.R of Germany.
Analytlcal composition:
S10256.8%
A12320.1%
234.8%
' ~ , .
~ .... . ; . , . .... , . . .. ...... ., ,. . . .. , , . . ~ :
- 10710S8
CaO 1.8~
MyO 4.0%
K2O 0-7%
Na2O3.1%
loss on
ashing 8.7%
"Montigel F" a bentonite by Sudchemie AG, F.R. of
Germany, can also be employed.
The naturally occurring products or the products
prepared from naturally occurring substances generally contain
iron contaminants as well as silicate contaminants.
Commercial products which can be employed in addition
to the mentioned "Aktive-Bentonite" are 'IVolclay" (Bentonite
Internationai), "Eurogel" ~Amberger Kaolinwerke). Synthetic
products can be obtained from Lange & Co., Bremen, which are
also useful in the preparation of the suspensions of the
invention.
I EXAMPLE 3
¦ Washing agents as described in the copending commonly-
assigned Canadian patent~application Serial No. 197,621 filed
April 16, 1974 can be prepared, as there described with
aluminosilicate suspensions which, however, are stabilized
; w~th bentonite or a synthetic, swellable-silicate of the
Smectite-type, by combining the stabilized gu~pension with the
remaining components of the washing agent to be produced by
forming a slurry which still contains, for example, about 50~ -
~ by weight of water, and then drying the said slurry in a hot ~ :
t ~ stream of air.
; For e~ample, a product can be produced which cor- ~ -
~30 responds to the following recipe:
trademark
~: .
1, ` ~ : '" '"
:
~ .
~ dg//tl~' ~26-
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1071058 ~ ~
TA + 10 EO 3.0%
TA + 5 ~O 2.0%
Sodium tripolyphosphate 20.0%
Sodium carbonate 5.3%
Sodium silicate 3.o%
CMC 1.8%
Aluminosilicate 18.0~ (AS) -
Bentonite 1.1%
EDTA 0.5%
~gSiO3 2.5%
Perborate 28.0%
Soap 2.5%
Remainder waber and
2S4
by admlxing a suspension of the alumi.nosilicate, which contains 2%
I bentonite, with the remaining washing agent components, with the
ji exception of the perborate, to form a slurry which is spray-dried
;, in conventional manner in a hot stream of air, and then admixing
¦ the powder thus obtained with the perborate.
~ 20 All of the suspensions described in the examples were
Z ~
clearly improved with respect to their stability and flow proper-
tles.
~h~ The preceeding specific embodlments are illustrative of the
Z ~ :practice of the invention. It is to be understood however, that
other expedients known to those skilled in the art or disclosed
herein? may be employed without departing from the spirit of the
, . ~ . . .
l invention or the scope of the appended claims.
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