Phosphate-free textile detergent, especially for washing at temperatures of over 75.degree. C.

A pulverulent, phosphate-free textile detergent consisting essentially of: PA0 (a) from 20% to 40% by weight of a water-insoluble, finely-divided, crystalline alkali metal aluminosilicate having a calcium binding power of 50 to 200 mg of CaO/gm on the anhydrous basis; PA0 (b) from 5% to 20% of a surface-active compound of the anionic, nonionic, amphoteric or zwitterionic types; PA0 (c) from 0.05% to 0.75% by weight of a water-soluble substituted alkane diphosphonate or triphosphonic acid or alkali metal salts thereof; PA0 (d) from 10% to 35% by weight of an inorganic per compound; and PA0 (e) from 0 to 50% by weight of other conventional ingredients for detergents of the type; wash alkalis, soil suspension agents, optical brighteners, enzymes, antimicrobial agents, textile softeners, coloring compounds, perfumes, sodium sulfate and water.

BACKGROUND OF THE INVENTION 
Detergents which contain a finely divided, water-insoluble, cation 
exchanging alkali metal aluminosilicate as substitute for phosphate have 
been described in German Published Application (DOS) No. 2,412,837, as 
well as U.S. Patent Application Ser. No. 458,306, filed Apr. 5, 1974, and 
now abandoned in favor of continuation application Ser. No. 800,308, filed 
May 25, 1977, now abandoned in favor of continuation-in-part application 
Ser. No. 956,851, filed Nov. 2, 1978. The cation exchanging properties of 
these aluminosilicates manifest themselves in their calcium binding 
capacity which amounts to at least 50 mg of CaO per gm of anhydrous 
substance, when tested at about 20.degree. C., and more particularly, 
within the range of from 100 to 200 mg of CaO/gm. It is preferred to use 
synthetically produced crystalline aluminosilicates containing bound water 
which have the composition, 0.7-1.5Me.sub.2 O.Al.sub.2 
O.sub.3.1.3-4SiO.sub.2, and in particular those having the composition, 
0.7-1.1Me.sub.2 O.Al.sub.2 O.sub.3.1.3-3.3SiO.sub.2, based in each case on 
their anhydrous form, Me representing an alkali metal such as sodium or 
potassium. The sodium aluminosilicates are generally preferred in 
practice. 
According to the teaching in the aforesaid German Offenlegungsschrift No. 
2,412,837, the cation exchanging aluminosilicates are advantageously used 
in combination with water-soluble complex formers for the purpose of 
improving and speeding up the washing process. 
In German Published Application (DOS) No. 2,540,510, as well as in U.S. 
patent application Ser. No. 505,626, filed Sept. 13, 1974, there is 
described a detergent for cold washing and washing at 60.degree. C. which, 
in addition to containing from 5% to 20% by weight of the cation 
exchanging aluminosilicate defined above, contains mainly a surface-active 
component of paraffin sulfonate and olefin sulfonate and up to 30% by 
weight of sodium silicate and preferably does not contain any soluble 
complex formers, particularly no detergent phosphates. This detergent, 
however, is unsatisfactory in its primary and secondary washing power at 
all temperatures. The properties of this detergent cannot be substantially 
improved by the addition of a compound containing active oxygen or by 
employing it under the conditions of a boiling wash procedure. 
Another phosphate-free textile detergent based on the aluminosilicates 
defined above, so-called wash alkalis, in particular alkali metal 
silicates and carbonates, certain organic complex forming salts from the 
group of alkali metal salts of phosphorus-free polymeric polycarboxylic 
acids and the phosphonic acids, and a surface-active component consisting 
of nonionic surface-active agents and optionally anionic surface-active 
agents has already been proposed. This detergent contains from 0.1 to 2 
parts by weight of the organic complex former to 1 part by weight of the 
water-insoluble aluminosilicate, based on the anhydrous compounds. 
OBJECTS OF THE INVENTION 
An object of the present invention is the development of a pulverulent 
bleaching textile detergent for use at high temperatures, in particular 
for the boiling wash procedure, which, in addition to the bleaching 
component, contains mainly surface-active agents, water-insoluble, cation 
exchanging alkali metal aluminosilicates and a small quantity of certain 
critical water-soluble organic complex formers. 
Another object of the present invention is the further development of the 
substitution of cation exchanging aluminosilicates for phosphates in 
detergents. 
Another object of this invention is that the quantity of water-soluble 
complex formers, whose presence in detergents containing aluminosilicates 
is important for good washing results, should be reduced to such a level 
that it causes no pollution of the effluent. It is also a particular aim 
of the invention to develop a detergent which, while being completely free 
from sodium tripolyphosphate and containing a minimum quantity of soluble 
complex formers, has an efficient primary and secondary washing action and 
is not harsh on fabrics even in a boiling wash in spite of the high 
content of per compounds which is necessary for an efficient bleaching 
action. 
A further object of the present invention is the development of a 
pulverulent, phosphate-free textile detergent consisting essentially of: 
(a) from 20% to 40% by weight of a water-insoluble, finely-divided, 
synthetically-produced, crystalline alkali metal aluminosilicate 
containing at least some combined water and having primary particles in 
the size range of from 100.mu. to 0.01.mu. and a calcium binding power of 
from 50 to 200 mg CaO/gm of anhydrous active substance when measured at 
22.degree. C. by the Calcium Binding Power Test Method described in the 
specification and the formula on the anhydrous basis 0.7-1.5Me.sub.2 
O.Al.sub.2 O.sub.3.1.3-4.0SiO.sub.2 where Me is an alkali metal; 
(b) from 5% to 20% by weight of a surface-active component selected from 
the group consisting of at least one of anionic surface-active compounds, 
nonionic surface-active compounds, amphoteric surface-active compounds and 
zwitterionic surface-active compounds, optionally with up to 50% of the 
surface-active component replaced by foam inhibitors; 
(c) from 0.05% to 0.75% by weight of a water-soluble organic complex former 
selected from the group consisting of (i) diphosphonates having the 
formula 
##STR1## 
wherein X is a member selected from the group consisting of hydroxy and 
amino, Y is a member selected from the group consisting of alkane having 
from 1 to 5 carbon atoms, aminoalkane having from 2 to 5 carbon atoms, 
hydroxyalkane having from 2 to 5 carbon atoms, phenyl, hydroxyphenyl, 
aminophenyl and halophenyl and M is a member selected from the group 
consisting of hydrogen and alkali metal, and (ii) aminotri(lower alkylene 
phosphonic acid) and its alkali metal salts; 
(d) from 10% to 35% by weight of an inorganic per compound releasing 
hydrogen peroxide in water; and 
(e) from 0 to 50% by weight of other conventional ingredients for 
detergents of the type: wash alkalis, soil suspension agents, optical 
brighteners, enzymes, antimicrobial agents, textile softeners, coloring 
compounds, perfumes, sodium sulfate and water. 
A yet further object of the invention is the process of washing textiles in 
aqueous solution at temperatures above 75.degree. C. employing the above 
pulverulent, phosphate-free textile detergent. 
These and other objects of the present invention will become more apparent 
as the description thereof proceeds.

DESCRIPTION OF THE INVENTION 
The above objects have been achieved by the development of a phosphate-free 
detergent or washing composition based on cation exchanging alkali metal 
aluminosilicate when care is taken that in addition to a selected tenside 
component certain critical complex forming, water-soluble, organic 
substituted phosphonates are present in amounts of below 1% by weight 
based on the total weight. 
The invention therefore provides a detergent which contains: 
(a) from 20% to 40% by weight of a water-insoluble, finely-divided, 
synthetically-produced, crystalline alkali metal aluminosilicate which 
contains bound water and corresponds to the formula, 0.7-1.5Me.sub.2 
O.Al.sub.2 O.sub.3.1.3-4.0SiO.sub.2 (based on the anhydrous active 
substance=AS), in which Me represents sodium or potassium, which alkali 
metal aluminosilicate has a calcium binding capacity of from 50 to 200, 
preferably from 100 to 200 mg of CaO/gm of AS; 
(b) from 5% to 20% by weight of a surface-active component consisting of at 
least one anionic, nonionic, amphoteric or zwitterionic surface-active 
agent and optionally foam inhibiting additives; 
(c) from 0.5 to 0.75% by weight, preferably 0.2 to 0.6% by weight, of a 
water-soluble organic complex former which is a substituted alkane di- or 
triphosphonic acid or an alkali metal salt thereof; and 
(d) from 10% to 35% by weight of an inorganic per compound. 
More particularly, the present invention relates to a pulverulent, 
phosphate-free textile detergent consisting essentially of: 
(a) from 20% to 40% by weight of a water-insoluble, finely-divided, 
synthetically-produced, crystalline alkali metal aluminosilicate 
containing at least some combined water and having primary particles in 
the size range of from 100.mu. to 0.01.mu. and a calcium binding power of 
from 50 to 200 mg CaO/gm of anhydrous active substance when measured at 
22.degree. C. by the Calcium Binding Power Test Method described in the 
specification and the formula on the anhydrous basis 
0.7-1.5Me.sub.2 O.Al.sub.2 O.sub.3.1.3-4.0SiO.sub.2 
where Me is an alkali metal; 
(b) from 5% to 20% by weight of a surface-active component selected from 
the group consisting of at least one of anionic surface-active compounds, 
nonionic surface-active compounds, amphoteric surface-active compounds and 
zwitterionic surface-active compounds, optionally with up to 50% of the 
surface-active component replaced by foam inhibitors; 
(c) from 0.05% to 0.75% by weight of a water-soluble organic complex former 
selected from the group consisting of (i) diphosphonates having the 
formula 
##STR2## 
wherein X is a member selected from the group consisting of hydroxy and 
amino, Y is a member selected from the group consisting of alkane having 
from 1 to 5 carbon atoms, aminoalkane having from 2 to 5 carbon atoms, 
hydroxyalkane having from 2 to 5 carbon atoms, phenyl, hydroxyphenyl, 
aminophenyl and halophenyl and M is a member selected from the group 
consisting of hydrogen and alkali metal, and (ii) amino tri(lower alkylene 
phosphonic acid) and its alkali metal salts; 
(d) from 10% to 35% by weight of an inorganic per compound releasing 
hydrogen peroxide in water; and 
(e) from 0 to 50% by weight of other conventional ingredients for 
detergents of the type: wash alkalis, soil suspension agents, optical 
brighteners, enzymes, antimicrobial agents, textile softeners, coloring 
compounds, perfumes, sodium sulfate and water. 
When fabrics were washed with the detergent according to the invention 
under boiling wash conditions (98.degree. C.), it was surprisingly found 
that the properties of protecting the fabric were even more pronounced in 
the detergent according to the invention than in the conventional high 
quality detergents which have a high phosphate content. This finding is 
completely unexpected since it has hitherto been assumed (Lindner, 
Tenside--Textilhilfsmittel--Waschrohstoffe, Vol. II, p. 1422 et seq), that 
it was the presence of the phosphate in the detergent acting in 
combination with stabilizers for the per compounds, in particular 
magnesium silicate and amino polycarboxylic acids such as the Trilon type, 
which was responsible for protecting fabrics when these were washed under 
boiling wash procedures in the presence of bleaching compounds which 
contained active oxygen, in particular sodium perborate. 
The applicant found that, even without the addition of magnesium silicate 
and salts of aminopolycarboxylic acids such as ethylene 
diaminetetraacetate which is known to act as inhibitor of the 
decomposition of peroxide by heavy metal ions, the detergent according to 
the invention had a damaging factor of only 0.1-0.2 after 50 washes. By 
comparison, a high quality detergent which has a high phosphate content 
has a damaging factor of 0.4. As is well known (see Lindner, ibid. p. 
1413), damaging factors below 0.4 are not regarded as harmful and even 
factors of up to about 1.0 are still acceptable. 
It was also observed that even without the addition of magnesium silicate 
the stability of the perborate in the detergents according to the 
invention was greater than in conventional phosphate-containing detergents 
which also contained magnesium silicate. 
The usual additions of 0.1% to 0.5% by weight of an aminopolycarboxylate, 
in particular ethylene diaminetetraacetate, to the usual phosphate based 
detergents suitable for boiling washes is unnecessary in the detergents 
according to the invention. Although this small proportion of 
polyaminocarboxylate in the known detergents cannot be regarded as 
significantly polluting the effluent, the fact that such additions may be 
dispensed with in the preparations according to the invention is of 
importance in the overall assessment of the detergent according to the 
invention, particularly when viewed in conjuction with the surprising 
finding that the special water-soluble organic complex former according to 
(c) used according to the invention, which is also added in only very 
small amounts, substantially below 1%, makes an important contribution to 
the powerful primary and secondary washing action of the detergent 
according to the invention. It may therefore be said viewed purely 
quantitatively, the complex forming salt used according to the invention 
takes the place of the complex forming salts of the amino polycarboxylate 
type hitherto normally used in detergents, and this exchange is therefore 
to be regarded as neutral in its environmental effect with regard to the 
pollution of effluent. With regard to the washing effect, however, the two 
types of complex formers differ from each other according to the teaching 
of this invention. If in the detergents according to this invention, the 
proportion of selected phosphonate according to (c) is replaced by the 
same quantity of an aminopolycarboxylate or of some other complex former 
for heavy metal ions, the important advantageous properties of the 
detergent according to this invention are not found in the resulting 
preparation. Thus, for example, when the detergent according to the 
invention is used for washing cotton textile samples, the remission 
values, which are a measure of the degree of whiteness retained, are 
higher by more than 20 units after 50 such washes than those obtained 
under similar conditions with a detergent which does not contain the 
phosphonate (c) defined above or in which the phosphonate has been 
replaced by an equal quantity of ethylene diaminetetraacetate. The 
remission values obtainable with the detergents according to this 
invention are therefore as high as those obtained with commercial 
phosphate-containing detergents. The phosphonates according to (c) are 
therefore sufficient as substantially the only soluble complex formers in 
the detergents according to the invention. 
Suitable cation exchanging alkali metal aluminosilicates (a) are, in 
principle, the crystalline products described in the above-mentioned 
German Published Application DOS No. 2,412,837, which generally consist of 
particles below 50.mu., mainly below 40.mu. and mostly within the range of 
from 20 to 0.1.mu.. 
In the detergents according to the invention, it is advantageous to use 
crystalline sodium aluminosilicates having the composition, 
0.7-1.1Na.sub.2 O.1.0Al.sub.2 O.sub.3.1.3-2.4SiO.sub.2, which are also 
known as "zeolite NaA", especially those products of this composition and 
crystal structure which have been prepared under carefully selected 
conditions so that the resulting crystals have rounded edges and corners 
and a particle size below 30.mu., with at least 80% of the particles 
measuring from 8 to 0.01.mu. and with the maximum range of the particle 
size distribution curve being from 3 to 6.mu.. Such aluminosilicates with 
rounded edges and corners are described in German Published Application 
DOS No. 2,531,342. 
According to our observations, when the detergent according to the 
invention is used under boiling wash conditions in the washing machine, 
both the calcium ions and the magnesium ions in the wash water, which are 
generally present in proportions of Ca:Mg of approximately 5:1 in water 
with average degrees of hardness, are both bound by the aluminosilicate. 
Problem-free removal of the hardness due to calcium and to magnesium is 
still achieved in artifically prepared hot washing liquors having a degree 
of hardness of 16.degree. and a proportion of calcium to magnesium ions of 
1:1. 
Accelerated removal of the magnesium hardness, already setting in at 
temperatures considerably below boiling, can also be achieved by using a 
sodium aluminosilicate according to (a) which has the composition, 
0.7-1.35Na.sub.2 O.1.0Al.sub.2 O.sub.3.1.3-2.4SiO.sub.2 and which consists 
of a binary mixture of from 40 to 90% of particles of zeolite NaA and from 
10 to 60% of particles of zeolite HS (hydrosodalith). An aluminosilicate 
as defined above has a calcium binding capacity of from 100 to 165 mg of 
CaO/gm and a magnesium bind capacity of from 50 to 110 mg of MgO/gm at a 
temperature of only 50.degree. C. in the washing liquor, the quantities 
given being based on the anhydrous substances. These aluminosilicate 
mixtures, their preparation and their use in detergents and cleaning 
agents have been described in German Published Application DOS No. 
2,543,941. 
The surface active component (b) contained in the detergents according to 
this invention preferably consists, in quantities of from 5% to 17% by 
weight, in particular of from 7% to 12% by weight, of a combination (ba) 
having the following composition: 
(ba1) 1 Part by weight of at least one nonionic surface-active agent which 
is an ethoxylated aliphatic C.sub.10 -C.sub.20 alcohol, preferably an 
alkanol or an alkenol, having a degree of ethoxylation of from 2 to 20; 
(ba2) 0.3 to 1.75, preferably 0.3 to 1.0 parts by weight of a foam 
inhibiting alkali metal soap of C.sub.12 -C.sub.22 fatty acids containing 
more than 50% by weight of alkali metal salts of saturated C.sub.18 
-C.sub.22 fatty acids, which soap may be partly replaced by a 
non-surface-active foam inhibitor in proportions of soap to 
non-surface-active foam inhibitor within the range of from 25:1 to 2:1; 
and 
(ba3) 0.5 to 6, preferably 0.8 to 4, parts by weight of an anionic 
surface-active agent of the sulfonate and/or sulfonate type. 
Detergents according to the invention which contain a surface-active 
component according to (ba) show excellent lather control during the whole 
boiling wash program and rinsing, especially when used in drum type 
washing machines. 
Particularly suitable for removing hydrophobic dirt are those lather 
controlled preparations according to the invention which contain the 
combination (bb) defined below as surface-active component (b), again in 
quantities of preferably from 5% to 17% by weight, more particularly from 
7% to 12% by weight. 
Combination (bb) consists of the following components: 
(bb1) 1 Part by weight of at least one nonionic surface-active agent which 
is an ethoxylated aliphatic C.sub.10 -C.sub.20 alcohol, preferably an 
alkanol or alkenol, having a degree of ethoxylation of from 2 to 20; 
(bb2) 0.05 to 0.75 parts by weight of a foam inhibiting alkali metal soap 
of C.sub.12 -C.sub.22 fatty acids containing more than 50% by weight of 
alkali metal salts of saturated C.sub.18 -C.sub.22 fatty acids; and 
(bb3) 0.05 to 0.3, preferably 0.1 to 0.25 parts by weight of a compound 
corresponding to the following formula I: 
##STR3## 
in which X-A represents a C.sub.10 -C.sub.18 fatty acid acyl residue; or 
X represents a .beta.-hydroxy-(C.sub.8 -C.sub.22)-alkyl residue in the 
terminal or non-terminal position, in which case A represents a simple 
C-N-valency or an aminoalkylene or polyaminopolyalkylene residue which may 
be substituted with polyethylene glycol ether groups; Y represents 
hydrogen or the group --(CH.sub.2 CH.sub.2 O).sub.m H and n and m each 
represent numbers of from 1 to 3. 
The anionic surface-active agents of the sulfonate and/or sulfonate type in 
the surface-active component (ba) preferably consist of alkylbenzene 
sulfonates and/or alkane sulfonates. The use of alkanesulfonates as 
washing agents in this surface-active component is particularly preferred 
in view of their rapid and complete biological degradation in the effluent 
and their low toxicity. It has surprisingly been found that, in detergents 
according to this invention, which contain a surface active component (ba) 
in which both an alkanesulfonate and optical brightening agents are 
present, the problems mentioned German Published Application DOS No. 
2,504,276 of the incompatibility of alkanesulfonates with the usual 
optical brighteners of the type of 
4,4'-bis(triazinylamino)-stilbene-2,2'-disulfonic acids used in 
detergents, which results in a greenish yellow to greyish yellow 
discoloration of the detergent powder in storage, does not occur. The use 
of alkanesulfonates as anionic surface-active agents in the detergent 
according to the present invention therefore does not require the use of 
special optical brighteners which are compatible with alkanesulfonates. 
When the detergent according to the invention containing a surface-active 
component (ba) is used for boiling washes in drum washing machines, the 
protection against excessive foam formation during washing and rinsing is 
still provided if up to one third of the given quantities of alkylbenzene 
sulfonate and/or alkanesulfonate is replaced by more strongly foaming 
anionic surface-active agents of the type of .alpha.-sulfo fatty acid 
esters, olefin sulfonates, fatty alcohol sulfates and fatty alcohol 
polyglycol ether sulfates, which also have good biological degradability 
and low toxicity. 
The nonionic surface-active agents contained in combinations (ba) and (bb) 
which are ethoxylated aliphatic C.sub.10 -C.sub.20 alcohols having a 
degree of ethoxylation of from 2 to 20 preferably consist of binary 
mixtures of separately prepared ethylene oxide addition products which 
have average degrees of ethoxylation of, on the one hand, 2 to 7 mols EO 
(ethylene oxide) and, on the other hand, 8 to 20 mols EO and a ratio of 
compound with a low degree of ethoxylation to compound with a higher 
degree of ethoxylation within the range of from 3:1 to 1:3. 
Preferred nonionic surface-active agents are those in which the aliphatic 
group is derived from primary alkanols and alkenols and which are obtained 
from natural and synthetic sources. Particularly preferred on account of 
their efficient biological degradability combined with ease of 
accessibility are the ethoxylation products of natural fatty alcohols, 
particularly those with C.sub.12 -C.sub.18 alkyl and alkenyl groups. 
Ethoxylation products of so-called oxoalcohols which are obtained from 
olefins by hydroformylation and hydrogenation and which are primary 
aliphatic alcohols containing an .alpha.-methyl branch, which does not 
impair biological degradability, are also preferred. The removal of 
hydrophobic dirt is improved if, in the two surface-active components (ba) 
and (bb) defined above, an ethoxylated fatty alcohol is replaced by an 
equal quantity of an ethoxylated oxo alcohol which contains the same 
proportion of hydrophobic to hydrophilic parts in the molecule. 
Compounds (bb3) of formula I in the surface-active component (bb) are 
addition products of 1 mol of a low molecular weight amine having from 1 
to 9 carbon atoms, and 1 to 4 nitrogen atoms and at least one labile 
hydrogen atom, in particular a mono- or di-ethanolamine, ethylene diamine, 
diethylene triamine or triethylene tetramine, and 1 mol of a C.sub.8 
-C.sub.22 epoxyalkane, in particular a C.sub.10 -C.sub.18 epoxyalkane, 
having the epoxy group in either a terminal or non-terminal position, 
which addition products may also be ethoxylated. These compounds 
corresponding to formula I have already been proposed as additions to 
detergents to increase the washing power. Also to be included among 
compounds (bb3) of formula I are the ethanolamides of C.sub.8 -C.sub.18 
fatty acids, in particular the monoethanolamides. These compounds of 
formula I are therefore also to be regarded as nonionic surface-active 
agents in their widest sense. 
The water-soluble organic complex formers from the group consisting of 
substituted alkane di- and triphosphonic acids according to (c), which 
also include heterocyclic substituted compounds, include in particular 
those alkane di- and triphosphonic acids and their alkali metal salts in 
which the alkane group has been substituted by hydroxyl, amino or phenyl 
groups or by a phenyl group which carries hydroxyl, amino or halogen 
groups. More particularly, these compounds are selected from the group 
consisting of (i) diphosphonates having the formula 
##STR4## 
wherein X is a member selected from the group consisting of hydroxy and 
amino, Y is a member selected from the group consisting of alkane having 
from 1 to 5 carbon atoms, aminoalkane having from 2 t 5 carbon atoms, 
hydroxyalkane having from 2 to 5 carbon atoms, phenyl, hydroxyphenyl, 
aminophenyl and halophenyl and M is a member selected from the group 
consisting of hydrogen and alkali metal, and (ii) aminotri-(lower alkylene 
phosphonic acid) and its alkali metal salts. Particularly preferred alkane 
di- and triphosphonates are 1-hydroxyethane-1,1-diphosphonic acid, 
1-aminoethane-1,1-diphosphonic acid; 
3-amino-1-hydroxypropane-1,1-diphosphonic acid, 
1-amino-1-p-chlorophenylmethane-1,1-diphosphonic acid; 
1-hydroxy-1-p-chlorophenylmethane-1,1-diphosphonic acid, 
1-hydroxy-1-phenylmethane-1,1-diphosphonic acid; 
1-hydroxybutane-1,1-diphosphonic acid and aminotri-(methylene phosphonic 
acid) in the form of their alkali metal salts, in particular their sodium 
salts. Among these compounds, the sodium salts of 
1-hydroxyethane-1,1-diphosphonic acid (HEDP), 
1-hydroxybutane-1,1-diphosphonic acid (HBDP) and aminotri-(methylene 
phosphonic acid) (ATMP) are particularly preferred. 
The inorganic per compounds (d) serving as bleaching agents in the 
detergent according to the invention are compounds which release hydrogen 
peroxide in water, primarily sodium perborate tetrahydrate 
(NaBO.sub.2.H.sub.2 O.sub.2.3 H.sub.2 O) and sodium perborate monohydrate 
(NaBO.sub.2.H.sub.2 O.sub.2). Other borates which release hydrogen 
peroxide are also suitable, e.g. perborax Na.sub.2 B.sub.4 O.sub.7.4 
H.sub.2 O.sub.2. These per compounds may be partly or completely replaced 
by other compounds which contain active oxygen, for example, peroxy 
carbonate (Na.sub.2 CO.sub.3.1.5 H.sub.2 O.sub.2). 
As already mentioned above, the perborate-containing detergents according 
to this invention have a higher perborate stability, even without the 
usual stabilizers recommended for perborate-containing detergents, than 
the usual detergent compositions based on sodium tripolyphosphate which 
contain perborate and stabilizer. The stability of the perborates in the 
detergents according to the invention is hardly affected even by the 
presence of heavy metal ions such as copper ions which may occur in the 
washing liquor due to corrosion for example, in the water pipes. 
The detergents according to the invention may in addition contain up to 7% 
by weight, preferably from 2% to 5% by weight, of water-soluble sodium 
silicates of the composition Na.sub.2 O.sub.2.1-3.5 SiO.sub.2 as corrosion 
inhibitors, particularly those in which the proportion of Na.sub.2 
O:SiO.sub.2 is in the range of from 1:2 to 1:3.35. 
The complete formulations of the detergents according to the invention 
generally contain from 1 to 50% by weight of other conventional additives 
which improve the use properties of the detergents, in particular soil 
suspending agents such as carboxymethylcellulose, enzymes, antimicrobial 
agents, optical brighteners, fabric softeners, coloring and perfuming 
substances, sodium sulfate as fillers, as well as water which is bound in 
the crystals of the water-soluble salts and particularly in the 
aluminosilicates and which may amount to about 2% to 18% by weight of the 
pourable washing powder. 
Preferably detergents according to this invention generally correspond to 
the following composition: 
(a) from 25% to 35% by weight of the water-insoluble, cation exchanging 
sodium aluminosilicate defined above, in particular one having the 
composition, 0.7-1.1 Na.sub.2 O.Al.sub.2 O.sub.3.1.3-2.4 SiO.sub.2 ; 
(b) from 5% to 17% by weight, in particular 2% to 12% by weight of one of 
the surface-active components (ba) or (bb) defined above; 
(c) from 0.2% to 0.6% by weight of the water-soluble organic complex former 
from the group consisting of substituted alkane di- and triphosphonates 
according to the definition given above; 
(d) from 15% to 30% by weight, in particular 20% to 25% by weight of sodium 
perborate, preferably in the form of the tetrahydrate; 
(e) from 2% to 5% by weight of sodium silicate, Na.sub.2 O.1-3.5 SiO.sub.2 
; 
(f) from 1% to 50% by weight of other conventional detergent additives from 
the group consisting of soil suspension agents, enzymes, antimicrobial 
agents, optical brighteners, fabric softeners, coloring and perfuming 
substances, sodium sulfate and water. 
Preparation of the detergent according to the invention may be carried out 
by the usual methods, in the simplest case by thoroughly mixing all of the 
components at room temperature. 
When preparing the detergents according to the invention the 
aluminosilicates (a) are preferably used in the still moist state from 
their preparation, for example as aqueous suspensions or moist filter 
cakes, and these moist aluminosilicates are preferably converted into 
stable, pumpable suspensions, optionally with further addition of water 
and with the addition of the dispersing agent. These pumpable suspensions 
contain from 25% to 40% by weight of the aluminosilicate, based on the 
quantity of anhydrous substance, and from 0.3% to 4% by weight of the 
dispersing agent. 
In principle, the dispersing agents used are preferably compounds which are 
themselves effective detergent constituents, especially those which are 
already provided as components of the detergent according to the 
invention. Particularly preferred in the present invention as stabilizers 
for aqueous suspensions of aluminosilicates are the ethoxylated aliphatic 
C.sub.10 -C.sub.20 alcohols with an average degree of ethoxylation of from 
2 to 7 mols EO which are preferably contained in the surface-active 
components (ba) and (bb) or the compound of formula I used as constituent 
(bb3) in the combination (bb). Pumpable stable aluminosilicate suspensions 
containing, inter alia, ethoxylated alcohols such as tallow alcohol plus 5 
mol of ethylene oxide or fatty acid ethanolamides such as lauric acid 
monoethanolamide as dispersing agents are described in detail in German 
Published Application DOS No. 2,527,388 and U.S. Pat. No. 4,072,622. The 
adducts of epoxyalkanes and low molecular weight amines corresponding to 
formula (I) defined above, which adducts may be ethoxylated, have also 
already been proposed as dispersing agents for aluminosilicate 
suspensions. 
The suspensions prepared by mixing aluminosilicate, water and dispersing 
agent are distinguished by their high stability. They may be stored at 
room temperature or higher temperatures and transported through pipes or 
in tank trucks or by other means before they are processed into the 
detergents according to the invention. This processing into pourable, 
pulverulent detergents according to the invention is generally carried out 
by adding to the previously prepared suspensions of aluminosilicate, the 
other components of the detergent according to the invention with the 
exception of those components which are not stable to heat and moisture, 
particularly the sodium perborate, subjecting the resulting aqueous, fluid 
preliminary mixture to a process of spray drying and then mixing the 
resulting powder product with the perborate and optionally other 
constituents which are suitably not present during the process of spray 
drying, such as enzymes and perfumes. If the aliphatic alcohols with a low 
degree of ethoxylation which constitute part of the surface-active 
components and the compounds of formula I of the surface-active component 
(bb) have not been completely used for preparing the suspension, it is 
advisable, in view of the fact that in most cases they have a viscous 
liquid consistency, to add them subsequently to the powder product, either 
by spraying them into the powder which has been prepared by spray drying 
or by using the sodium perborate as carrier for these compounds. 
Another preferred variation of the method of preparing the detergents 
according to the invention consists of using the aluminosilicates 
according to (a) in the form of a powder which feels dry but contains 
varying quantities of bound water, depending on the drying temperature 
employed, optionally together with sodium perborate, as solid carrier for 
the liquid or viscous constituents of the detergent according to the 
invention, in particular for the nonionic surface-active agents according 
to (ba1) or (bb1) and the compounds according to (bb3). These compounds 
are converted into pourable preliminary mixtures by spraying their 
solutions in volatile organic solvents or their solvent-free melts on to 
the solid carriers, and these preliminary mixtures are then mixed in the 
usual manner with the other pulverulent constituents of the detergent 
which is to be produced. Such preliminary mixtures and methods of 
preparing them are described in detail in German Published Application DOS 
No. 2,507,926, corresponding to U.S. Pat. No. 4,136,051. 
As already mentioned above, the aluminosilicates used are synthetic 
crystalline products, although mixtures of crystalline and amorphous 
products or partly crystalline products may, of course, also be used for 
the purpose of this invention. 
Preparation of the aluminosilicate may be carried out by, for example, 
reacting water-soluble silicates with water-soluble aluminates in the 
presence of water. For this purpose, aqueous solutions of the starting 
materials may be mixed together or one component in the solid state may be 
reacted with the other component used as aqueous solution. The desired 
aluminosiliates may also be obtained by mixing the two solid components in 
the presence of water. Aluminosilicates may also be prepared from 
Al(OH).sub.3, Al.sub.2 O.sub.3 or SiO.sub.2 by reaction with alkali 
silicate or alkali metal aluminate solution, respectively. The preparation 
may also be carried out by other known methods. 
Preferred aluminosilicates have a calcium binding capacity approximately 
within the range of from 100 to 200 mg CaO/gm AS, in most cases 
approximately 100 to 180 mg CaO/gm AS. This is found mainly in compounds 
having the composition, 0.7-1.1 Na.sub.2 O.Al.sub.2 O.sub.3.1.3-3.3 
SiO.sub.2. 
This overall formula covers two types of crystal structures which differ 
from each other by their separate overall formulae, as follows: 
EQU 0.7-1.1 Na.sub.2 O.Al.sub.2 O.sub.3.1.3-2.4 SiO.sub.2 (i) 
EQU 0.7-1.1 Na.sub.2 O.Al.sub.2 O.sub.3.&gt;2.4-3.3 SiO.sub.2. (ii) 
The different crystal structures show up in the X-ray diffraction diagram. 
For the preparation, identification and use for washing and cleaning 
purposes of these types of aluminosilicate also known as zeolites NaA and 
NaX, see German Published Application DOS No. 2,412,837. 
The aluminosilicates still moist or wet with water from their preparation, 
which may be in the form of aqueous suspensions or moist filter cakes, may 
be converted into dry powders by the usual method of first removing part 
of the water mechanically and then drying them, e.g. at temperatures of 
from 50.degree. to 400.degree. C. The powder product, which outwardly 
seems dry, contains varying quantities of bound water, in most cases from 
5% to 35% by weight, depending on the conditions employed from drying. The 
temperatures employed for drying preferably do not exceed 200.degree. C., 
if the aluminosilicate is intended to be used in washing and cleaning 
agents. However, the aluminosilicates need not be dried at all after they 
have been prepared if, according to the teaching of U.S. Pat. No. 
4,072,622 they are converted into a stable suspension by treatment with a 
certain dispersing agent and water and this suspension is then used for 
further processing into detergents. Apart from the saving in energy due to 
elimination of the drying stage, this method of processing eliminates 
virtually completely the agglomeration of primary particles to undesirably 
large particles (secondary particles), which is observed when the usual 
methods of drying are employed, which therefore necessitate subsequent 
milling and screening. 
All the figures given for the water content, solids content and amount of 
active substance (=AS) in the aluminosilicates are based on the 
composition of the aluminosilicate after one hour's drying at 800.degree. 
C. This heat treatment removed virtually all of the bound water and water 
adhering to the aluminosilicate. This reference value of aluminosilicate 
dried for one hour at 800.degree. C. is particularly important for 
determing the calcium binding capacity. 
The calcium binding capacity of the aluminosilicates is determined by 
adding 1 gm of aluminosilicate (based on the quantity of AS) to 1 liter of 
an aqueous solution which contains 0.594 gm of CaCl.sub.2 (=300 mg 
CaO/l=30.degree. dH) and which has been adjusted to pH 10 with dilute 
sodium hydroxide, and then vigorously stirring the suspension for 15 
minutes at a temperature of 22.degree. C., 50.degree. C. and 90.degree. 
C., respectively. After removal of the aluminosilicate by filtration, the 
residual hardness x of the filtrate is determined. The calcium binding 
capacity of the aluminosilicate is calculated from this value as (30 - 
x).10 mg CaO/gm AS. For shorthand purposes this test procedure will be 
referred to as the Calcium Binding Power Test Method. 
The magnesium binding capacity is determined in similar manner on an 
aqueous solution containing 1.0877 gm of MgCl.sub.2.6 H.sub.2 O per liter 
(=215 mg MgO/l=30.degree. d MgO). The magnesium binding capacity is 
calculated as (30 - x).7.19 mg of MgO/gm AS. For shorthand purposes this 
test procedure will be referred to as the Magnesium Binding Power Test 
Method. 
The particle sizes of the aluminosilicates may be determined by, for 
example, sedimentation analysis. 
The surface-active agents or tenside contained in the detergents according 
to this invention have at least one hydrophobic organic residue and one 
water-solubilizing anionic, amphoteric or zwitterionic or nonionic group 
in the molecule. The hydrophobic residue is, in most cases, an aliphatic 
hydrocarbon residue, such as alkyl or alkenyl, having from 8 to 26, 
preferably from 10 to 22 and more particularly from 12 to 18 carbon atoms, 
or an alkylaromatic residue, such as alkylphenyl or alkylnaphthyl, having 
from 6 to 18, preferably from 8 to 16, carbon atoms in the alkyl. 
Particularly suitable synthetic anionic surface-active agents are those of 
the sulfonate and sulfate type. 
Suitable sulfonate type surface-active agents are, above all, the 
alkylbenzene sulfonates containing C.sub.9 -C.sub.15 alkyl groups and 
alkanesulfonates which are obtainable from C.sub.12 -C.sub.18 alkanes by 
sulfochlorination or sulfoxidation followed by hydrolysis or 
neutralization or by bisulfite addition to olefins. Other suitable 
surface-active agents of the sulfonate type include esters of 
.alpha.-sulfo-fatty acids, e.g., .alpha.-sulfonated methyl or ethyl esters 
of hydrogenated coconut, palm kernel or tallow fatty acids as well as 
olefin sulfonates, i.e., mixtures of alkene sulfonates and hydroxyalkane 
sulfonates, as well as alkane disulfonates, such as may be obtained, for 
example, from monoolefins having a double bond in a terminal or 
non-terminal position by sulfonation with gaseous sulfur trioxide followed 
by alkaline or acid hydrolysis of the sulfonation products. 
Suitable surface-active agents of the sulfate type include sulfuric acid 
monoesters of naturally occurring or synthetic primary alcohols, 
particularly alkanols and alkenols, i.e., fatty alcohols such as coconut 
fatty alkanols, tallow fatty alkanols, oleyl alcohol, lauryl alcohol, 
myristyl alcohol, palmityl alcohol or stearyl alcohol, or C.sub.10 
-C.sub.20 oxo alcohols as well as secondary alcohols which have this chain 
length, such as C.sub.10 -C.sub.20 sec. alkanols. 
Sulfuric acid monoesters of ethoxylated aliphatic primary alcohols which 
have been ethoxylated with 1 to 6 mols of ethylene oxide and of 
ethoxylated secondary alcohols or ethoxylated alkylphenols are also 
suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid 
monoglycerides may also be used. 
The anionic surface-active agents may be in the form of their alkali metal 
salts, such as sodium and potassium, or ammonium salts or soluble salts of 
organic bases, such as mono-, di- or triethanolamine. 
The nonionic surface-active agents which may be used according to the 
invention are addition products of from 1 to 40, preferably 2 to 20, mols 
of ethylene oxide to 1 mol of an aliphatic compound having a replaceable 
hydrogen atom and containing in the main 10 to 20 carbon atoms, taken from 
the group consisting of alkanols, alkenols, alkylphenols, alkanoic acids 
and alkenoic acids. Particularly important are the addition products of 
from 8 to 20 mols of ethylene oxide to primary fatty alcohols, such as 
coconut fatty alcohols or tallow fatty alcohols, oleyl alcohol or oxo 
alcohols of the same chain lengths or to corresponding secondary alkanols 
or to monoalkyl or dialkylphenols having from 6 to 14 carbon atoms in the 
alkyl groups. Apart from these water-soluble nonionic surface-active 
agents, polyalkylene glycol ethers which are insoluble or not completely 
soluble in water and which have from 2 to 7 ethylene glycol ether groups 
in the molecule are also of interest, particularly if they are used in 
combination with water-soluble nonionic or anionic surface-active agents. 
Ethoxylation products of primary aliphatic alkanols and alkenols are 
particularly interesting from a practical point of view on account of 
their good biological degradability. 
Typical representatives of nonionic surface-active agents with an average 
degree of ethoxylation of 2 to 7 which may be used according to the 
invention include, for example: 
coconut fatty alcohol+5 EO (EO-ethylene oxide) 
tallow fatty alcohol+5 EO 
oleyl/cetyl alcohol+5 EO (iodine number 30 to 50) 
tallow fatty alcohol+7 EO 
synthetic C.sub.12 -C.sub.16 fatty alcohol+6 EO 
C.sub.11 -C.sub.15 -oxo alcohol+3 EO 
C.sub.14 -C.sub.15 -oxo alcohol+7 EO 
i-C.sub.15 -C.sub.17 -alkanediol+5 EO (i=nonterminal vicinal position) 
and sec.-C.sub.11 -C.sub.15 -alkanol+4 EO. 
Examples of nonionic surface-active agents having an average degree of 
ethoxylation from 8 to 20, in particular from 9 to 15, include the 
following compounds: 
coconut fatty alcohol+12 EO 
synthetic C.sub.12 -C.sub.14 -fatty alcohol+9 EO 
oleyl/cetyl alcohol+10 EO 
tallow fatty alcohol+14 EO 
C.sub.11 -C.sub.15 -oxo alcohol+13 EO 
C.sub.15 -C.sub.18 -oxo alcohol+15 EO 
i-C.sub.15 -C.sub.17 -alkanediol+9 EO 
C.sub.14 -C.sub.15 -oxo alcohol+11 EO 
and sec. C.sub.11 -C.sub.15 -alkanol+9 EO. 
Water-soluble addition products containing from 20 to 250 ethylene glycol 
ether groups and from 10 to 100 propylene glycol ether groups and obtained 
by the addition of ethylene oxide to polypropylene glycol, to alkylene 
diamine-polypropylene glycol and to alkyl polypropylene glycols which have 
from 1 to 10 carbon atoms in the alkyl chain may also be used as nonionic 
surface-active agents. In these compounds, the polypropylene glycol chain 
functions as hydrophobic residue. Nonionic surface-active agents of the 
aminoxide or sulfoxide type may also be used, for example, N-coconut 
alkyl-N,N-dimethyl-aminoxide, 
N-hexadecyl-N,N-bis-(2,3-dihydroxypropyl)-aminoxide, and N-tallow 
alkyl-N,N-dihydroxyethyl-aminoxide. 
The amphoteric surface-active agents are compounds which contain both an 
anionic and a cationic group in the same molecule. Suitable compounds 
include derivatives of aliphatic C.sub.8 -C.sub.18 amines which contain a 
water-solubilizing group, e.g., a carboxyl, sulfo or sulfate group. 
Typical representatives of amphoteric surface-active agents include the 
sodium salts of 2-dodecylamino-propionic acid and 3-dodecylaminopropane 
sulfonic acid and similar compounds, e.g., sulfated imidazoline 
derivatives. 
The zwitterionic surface-active agents used are preferably derivatives of 
aliphatic quaternary ammonium compounds in which one of the aliphatic 
groups is a C.sub.8 -C.sub.18 group and another contains an anionic, 
water-solubilizing carboxyl, sulfo or sulfate group. The following 
compounds are examples of typical representatives of such surface-active 
betaines: 
3-(N-hexadecyl-N,N-dimethyl-ammonio)-propanesulfonate 
3-(N-tallow alkyl-N,N-dimethyl-ammonio)-2-hydroxypropanesulfonate 
3-[N-hexadecyl-N,N-bis-(2-hydroxyethyl)-ammonio]-2-hydroxypropylsulfate 
3-[N-coconut alkyl-N,N-bis-(2,3-dihydroxypropyl)-ammonio]-propanesulfonate 
N-tetradecyl-N,N-dimethyl-ammonio-acetate 
N-hexadecyl-N,N-bis-(2,3-dihydroxypropyl)-ammonio-acetate. 
The foam inhibiting additives may be foam suppressing soaps and 
non-surface-active foam inhibitors. The foam suppressing action of soaps 
generally increases with the degree of saturation and the number of carbon 
atoms in the fatty acid residue, so that soaps of natural and synthetic 
origin which contain a high proportion of C.sub.18 -C.sub.22 fatty acids 
are particularly suitable as foam inhibiting soaps, for example, the 
derivatives of hydrogenated fish train oils and rape oils. In practice, 
one would generally use fatty acid mixtures containing from C.sub.12 
-C.sub.22 carbon chains, at least 50% of which consist of C.sub.18 
-C.sub.22 fatty acid salts (iodine number &lt;5). 
The non-surface-active foam inhibitors which may be used alone or together 
with the foam inhibiting soaps are generally water-insoluble compounds, in 
most cases containing aliphatic C.sub.8 -C.sub.22 carbon residues. 
Suitable non-surface-active foam inhibitors include, for example, 
N-alkylaminotriazines, i.e., reaction products of 1 mol of cyanuric 
chloride with 2 to 3 mols of a monoalkylamine or dialkylamine containing 
mainly 8 to 18 carbon atoms in the alkyl group. Propoxylated and/or 
butoxylated aminotriazines are also suitable, for example, the reaction 
products of 1 mol of melamine with 5 to 10 mols of propylene oxide and in 
addition 10 to 50 mols of butylene oxide, as well as aliphatic C.sub.18 
-C.sub.40 alkanones, such as stearone, fatty ketones of hardened train oil 
fatty acid or tallow fatty acid, etc. as well as paraffins and halogenated 
paraffins with melting points below 100.degree. C. and polymeric organic 
silicon compounds of the type of silicone oils. 
In the detergents according to the invention which contain the 
surface-active combination (bb), the compounds corresponding to Formula I, 
insofar as they are hydroxyalkylamines (in Formula I, X represents a 
.beta.-hydroxyalkyl group and A a single C--N bond) are mainly compounds 
which have been prepared by a single stage or two-stage reaction from 
terminal or non-terminal epoxyalkanes by first reacting these with mono- 
or diethanolamine or mono- or di-isopropanolamine or with ammonia, an 
alkylene diamine, a polyalkylene polyamine or a hydroxyalkylpolyamine and 
then optionally ethoxylating the resulting addition products in a second 
reaction stage. 
The epoxyalkanes used as starting materials are prepared from the 
corresponding olefins or olefin mixtures by known methods. 
The terminal epoxyalkanes used for the preparation of hydroxyalkylamines of 
Formula I preferably have chain lengths of from C.sub.12 -C.sub.18. 
Preferred non-terminal mono-olefins used to make the non-terminal 
epoxyalkanes are of a C.sub.11 -C.sub.14 fraction and a C.sub.15 -C.sub.18 
fraction had the following chain length distribution: 
C.sub.11 -C.sub.14 Fraction: 
C.sub.11 -olefins about 22% by weight 
C.sub.12 olefins about 30% by weight 
C.sub.13 olefins about 26% by weight 
C.sub.14 olefins about 22% by weight; 
C.sub.15 -C.sub.18 Fraction: 
C.sub.15 olefins about 26% by weight 
C.sub.16 olefins about 35% by weight 
C.sub.17 olefins about 32% by weight 
C.sub.18 olefins about 7% by weight. 
The following compounds are examples of typical hydroxyalkylamines 
corresponding to Formula I (turbidity points determined in aqueous butyl 
diglycol according to DIN 53917): 
(1) The reaction product of a non-terminal C.sub.11 -C.sub.14 epoxyalkane 
and diethanolamine; turbidity point &lt;0.degree. C. 
(2) The reaction product of a non-terminal C.sub.11 -C.sub.14 epoxyalkane 
and monoethanolamine; turbidity point 34.degree. C. 
(3) The reaction product of a non-terminal C.sub.11 -C.sub.14 epoxyalkane 
and bis-hydroxyethoxyethylamine; turbidity point 44.degree. C. 
(4) The reaction product of a non-terminal C.sub.11 -C.sub.14 epoxyalkane 
and diethanolamine, in addition ethoxylated with 1 mol of ethylene oxide; 
turbidity point 32.degree. C. 
(5) The reaction product of a non-terminal C.sub.11 -C.sub.14 epoxyalkane 
and diethanolamine, in addition ethoxylated with 2 mols of ethylene oxide; 
turbidity point 45.degree. C. 
(6) The reaction product of a non-terminal C.sub.11 -C.sub.14 epoxyalkane 
and ethylenediamine, in addition reacted with 4 mols of ethylene oxide; 
turbidity point 72.5.degree. C. 
(7) The reaction product of .alpha.-epoxyoctane and ethylene diamine; 
turbidity point 15.degree. C. 
Those compounds corresponding to Formula I in the surface-active 
combination (bb) which are fatty acid ethanolamides (in Formula I, X-A 
denotes a fatty acid residue) are preferably fatty acid monoethanolamides 
obtained from individual fatty acids or from fatty acid mixtures, 
particularly those with chain lengths of from C.sub.10 -C.sub.18. These 
fatty acids or mixtures may be of natural or synthetic origin. The fatty 
acids may be saturated or unsaturated. Monoethanolamides of mixed fatty 
acids obtained from natural sources are particularly suitable, for 
example, the monoethanolamides of coconut fatty acids, palm kernel fatty 
acids or tallow fatty acids. The following compounds are examples of such 
fatty acid monoethanolamides: 
lauric acid monoethanolamide 
coconut fatty acid monoethanolamide 
myristic acid monoethanolamide 
palmitic acid monoethanolamide 
stearic acid monoethanolamide 
oleic acid monoethanolamide 
and tallow fatty acid monoethanolamide. 
The detergents may contain optical brighteners for cotton, in particular, 
derivatives of diaminostilbenedisulfonic acid or alkali metal salts 
thereof. Suitable compounds include, for example, salts of 
4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilbene-2,2'-d 
isulfonic acid or compounds which have a similar structure but carry a 
diethanolamino group, a methylamino group or a 2-methoxyethylamino group 
instead of the morpholino group. Suitable brighteners for polyamide fibers 
include those of the 1,3-diaryl-2-pyrazoline type, for example, the 
compound 1-(p-sulfamoylphenyl)-3-(p-chlorophenyl)-2-pyrazoline and 
compounds having a similar structure but containing, instead of the 
sulfamoyl group, e.g., the methoxycarbonyl, 2-methoxyethoxycarbonyl, 
acetylamine or vinyl sulfonyl group. Substituted aminocoumarins are also 
suitable polyamide brighteners, e.g., 4-methyl-7-dimethylaminocoumarin or 
4-methyl-7-diethylaminocoumarin. 
1-(2-Benzimidazolyl)-2-(1-hydroxyethyl-2-benzimidazolyl)-ethylene and 
1-ethyl-3-phenyl-7-diethylamino-carbostyryl may also be used as polyamide 
brighteners. Compounds which are suitable brightening agents for polyester 
and polyamide fibers include 2,5-di-(2-benzoxazolyl)-thiophene, 
2-(2-benzoxazolyl)-naphtho-[2,3-b]-thiophene, and 
1,2-di-(5-methyl-2-benzoxazolyl)-ethylene. Brighteners of the substituted 
4,4'-distyryl-diphenyl type may also be present, e.g., 
4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl. Mixtures of the brightening 
agents mentioned above may also be used. 
The preparations may also contain soil suspension agents which prevent 
greying by keeping the dirt which has been released from the fibers in 
suspension in the washing liquor. Water-soluble colloids, mostly of an 
organic nature, are suitable for this purpose, for example, water-soluble 
salts of polymeric carboxylic acids, glue, gelatin, salts of ether 
carboxylic acids or ether sulfonic acids of starch or of cellulose or 
salts of acid sulfuric acid esters of cellulose or of starch. 
Water-soluble polyamides which contain acid groups are also suitable for 
this purpose. Carboxymethylated cellulose or starch in the form of its 
sodium salts are preferred. Soluble starch preparations and starch 
products other than those mentioned above, e.g., degraded starches and 
aldehyde starches, are also suitable, and polyvinyl pyrrolidone may also 
be used. 
The following examples are illustrative of the invention without being 
limitative in any respect. 
EXAMPLES 
One method of preparation for the aluminosilicates is first given. Other 
known methods of preparing aluminosilicates may also be employed. 
The sodium silicate solution was added to the sodium aluminate solution 
with vigorous stirring in a vessel having a capacity of from 15 to 20 
liters. A stirrer with dispersing disc rotating at 3000 revs/min was 
employed. Both solutions were at room temperature. An exothermic reaction 
took place and a sodium aluminosilicate which was amorphous according to 
X-ray analysis was formed as primary precipitation product. After ten 
minutes of stirring, the suspension of the precipitation product was 
transferred to a crystallization vessel where it was crystallized by 
heating to 80.degree. C. to 130.degree. C. for one to 24 hours with 
stirring (250 to 500 revs/min). After separation of the crystal paste from 
the liquor by suction filtration and washing with deionized water until 
the wash waters from the paste had a pH of about 10 to 11, the filter cake 
was either dried, e.g., at 100.degree. C. for 24 hours, and then crushed 
to a fine powder or the aluminosilicate was used in the form of an aqueous 
paste, preferably an aqueous suspension, to prepare the detergent or 
cleaning agent. Specific data for the temperature, heating time and method 
of working up are given below in the methods of preparation for the 
individual types of aluminosilicates given as representative examples. 
______________________________________ 
Aluminosilicate Im: 
Reaction mixture for 
preparing the precipi- 
tate: 2.985 kg of aluminate solution 
having the following composition: 
17.7% Na.sub.2 O 
15.8% Al.sub.2 O.sub.3 
66.5% H.sub.2 O 
0.150 kg caustic soda 
9.420 kg water, and 
2.445 kg of a 25.8% solution of 
sodium silicate of the 
composition 1 Na.sub.2 O . 6 SiO.sub.2 
freshly prepared from a 
commerical waterglass and a 
readily alkali-soluble 
silicic acid 
Precipitation: The suspension of amorphous pre- 
cipitation product was stirred 
with a high speed stirrer (10,000 
revs/min) for ten minutes. 
Crystallization: 
Six hours at 90.degree. C. 
Drying: 24 hours at 100.degree. C. 
Composition: 0.9 Na.sub.2 O . 1 Al.sub.2 O.sub.3 . 2.04 SiO.sub.2 . 
4.3 H.sub.2 O (= 21.6% H.sub.2 O). 
Degree of crystal- 
lization: Completely crystalline. 
Calcium binding 
capacity at 22.degree. C.: 
170 mg CaO/gm AS. 
Particle size (by 
sedimentation analysis): 
100% below 40 .mu. 
85% to 95% below 10 .mu.. 
Maximum range of par- 
ticle size distribution: 
3 to 6 .mu.. 
Aluminosilicate R1: 
Precipitation: 7.63 kg of an aluminate solution 
having the composition: 
13.2% Na.sub.2 O 
8.0% Al.sub.2 O.sub.3 
78.8% H.sub.2 O 
2.37 kg of sodium silicate 
solution having the composition: 
8.0% Na.sub.2 O 
26.9% SiO.sub.2 
65.1% H.sub.2 O 
Molar ratios in the 
reaction mixture: 
3.24 Na.sub.2 O, 1.0 Al.sub.2 O.sub.3 
1.78 SiO.sub.2, 70.3 H.sub.2 O. 
Crystallization: 
6 hours at 90.degree. C. 
Drying: 24 hours at 100.degree. C. 
Composition of the 
dried product: 0.99 Na.sub.2 O . 1.0 Al.sub.2 O.sub.3 . 1.83 
SiO.sub.2 . 4.0 H.sub.2 O (= 20.9% H.sub.2 O). 
Crystal form: Cubical with strongly rounded 
edges and corners. 
Average particle dia- 
meter (for the range 
0 to 30 .mu.) 5.4 .mu.. 
Maximum range of par- 
ticle size distribution: 
Below 3 .mu.. 
Calcium binding capacity 
at 22.degree. C.: 
172 mg CaO/gm AS. 
Aluminosilicate F1 
Precipitation: 7.31 kg of aluminate having the 
composition: 
14.8% Na.sub.2 O 
9.2% Al.sub.2 O.sub.3 
76.0% H.sub.2 O 
2.69 kg of silicate having the 
composition: 
8.0% Na.sub.2 O 
26.9% SiO.sub.2 
65.1% H.sub.2 O 
Molar ratios in the 
reaction mixture: 
3.17 Na.sub.2 O 1.0 Al.sub.2 O.sub.3 
1.82 SiO.sub.2 62.5 H.sub.2 O. 
Crystallization: 
6 hours at 90.degree. C. 
Composition of the 
dried product: 1.11 Na.sub.2 O . 1.89 
SiO.sub.2 . 3.1 H.sub.2 O (= 16.4% H.sub.2 o). 
Crystal structure: 
Mixture of zeolite NaA and zeolite 
HS in proportions of about 1:1. 
Crystal form: Rounded crystallites. 
Average particle dia- 
meter (for the range 
0 to 30 .mu. 5.6 .mu.. 
Maximun range of par- 
ticle size distribution: 
Below 3 .mu.. 
Calcium binding capacity: 
105 mg CaO/gm AS at 50.degree. C., 
120 mg CaO/gm AS at 90.degree. C. 
Magnesium binding 
capacity: 15 mg MgO/gm AS at 22.degree. C., 
96 mg of MgO/gm AS at 90.degree. C. 
______________________________________ 
Now follows the description of the washing and cleaning detergents 
according to the invention. The salt type constituents of the detergents 
mentioned in the Examples, i.e. surface-active agents in the form of salts 
and other organic salts as well as inorganic salts, are the sodium salts 
unless specifically indicated to be otherwise. All percentages are 
percentages by weight. In the examples of detergents, the quantity of 
aluminosilicate given is based on "active substance", i.e. on the 
anhydrous product. The proportion of water bound in the aluminosilicate is 
included with the remaining water content of the detergent. The terms and 
abbreviations used in the Examples have the following meaning: 
______________________________________ 
"ABS": The salt of an alkylbenzene 
sulfonic acid having from 10 to 15, 
in most cases from 11 to 15 carbon 
atoms in the alkyl chain, obtained 
by the condensation of straight 
chain olefins with benzene followed 
by sulfonation of the resulting 
alkylbenzene. 
"Alkanesulfonate": 
A sulfonate obtained by sulfoxida- 
tion of C.sub.12 --C.sub.18 paraffins. 
"Fs-ester sulfonate": 
A sulfonate obtained from the 
methyl ester of hydrogenated palm 
kernal fatty acid by sulfonation 
with SO.sub.3. 
"Olefin sulfonate": 
A mixture of hydroxyalkane sulfo- 
nates, alkene sulfonates and 
alkane disulfonates obtained by 
the sulfonation of .alpha.-olefins 
having from 12 to 18 carbon atoms 
with sulfur trioxide and hydroly- 
sis of the sulfonation product 
with sodium hydroxide solution. 
"Coconut alcohol sulfate": 
A sulfate obtained by sulfo- 
nating the C.sub.12 /C.sub.14 fraction 
of coconut fatty alcohol. 
"Tallow alcohol+3-EO- 
A sulfate obtained by sul- 
sulfate": fating an ethoxylated tallow 
fatty alcohol having an average 
degree of ethoxylation of 3. 
"TA+x EO", "KA+x EO", 
The addition products of x 
"OCA+x EO", mols of ethylene oxide (EO) 
"OXO+ EO": with 1 mol of commerical tallow 
fatty alcohol (TA) or of 
coconut fatty alcohol (KA) or 
of oleyl/cetyl alcohol (iodine 
number 50) (OCA) or of a 
C.sub.14 /C.sub.15 oxo alcohol having a 
degree of .alpha.-methyl branching 
of ca. 20%(OXO). 
"Soap": A soap (iodine number = 1) 
prepared from a hardened mix- 
ture of equal parts by weight 
of tallow fatty acid and rape 
oil fatty acid. 
"Foam inhibitor": 
Silicone oil "SAG 100".RTM. of 
Union Carbide and Carbon. 
"i-11-14-DAA": The reaction product of a non- 
terminal C.sub.11 --C.sub.14 -epoxyalkane 
and diethanolamine. 
"i-11-14-MAA": The reaction product of a non- 
terminal C.sub.11 --C.sub.14 -epoxyalkane 
and monoethanolamine. 
"i-11-14-DAA+1 EO": 
The reaction product of a 
non-terminal C.sub.11 --C.sub.14 -epoxy- 
alkane and diethanolamine in 
addition reacted with 1 mol 
of ethylene oxide. 
"HEDP": The salt of 1-hydroxyethane- 
1,1-diphosphonic acid. 
"HBDP": The salt of 1-hydroxybutane- 
1,1-diphosphonic acid. 
"Perborate": A commerical product having 
the approximate composition: 
NaBO.sub.2 . H.sub.2 O.sub.2 . 3 H.sub.2 O. 
"Waterglass": A sodium silicate having the 
composition: 
Na.sub.2 O . 3.35 SiO.sub.2. 
"CMC": The salt of carboxymethylcellulose. 
"EDTA": The salt of ethylenediamine- 
tetraacetic acid. 
"ATMP": The salt of aminotri-(methylene 
phosphonic acid). 
"Brightening agent": 
The salt of 4,4'-bis-(2-anilino- 
4-morpholino-1,3,5-triazin-6- 
yl-amino)-stilbene-2,2'-disul- 
fonic acid. 
"Enzyme": A commerical enzyme mixture of 
proteases and amylases 
(Maxatase.RTM.). 
______________________________________ 
EXAMPLE 1 
This example describes the determination of the average degree of 
polymerization (DP-degree) and the damaging factor resulting therefrom. 
This damaging factor is a measure of the extent to which a detergent 
protects the fabric after repeated washing. Washing tests were carried out 
in the form of so-called strand washing tests. The test fabrics used were 
samples, amounting to 10 gm or 20 gm, of a bleached nettle cloth from 
which the finish had been removed, and an equal quantity of a strand of 
rayon flock was used as filling material. The washing tests were carried 
out in beakers under boiling conditions. Bath ratio 1:10, hardness of 
water 12.degree. dH (German hardness), washing time 15 minutes at boiling 
temperature. The samples were washed 50 times with detergent doses of 5.0 
gm/l. They were rinsed three times with water of the same hardness and 
rung out by hand. 
After drying of the strips of cotton samples, the average degree of 
polymerization was determined by viscosity measurements by the Cuoxam 
method (Melliand Testilberichte, XXXIII, 1952, pages 153-156) and the 
damaging factor was calculated from the average degree of polymerization 
(Melliand Textilberichte, XXII, 1941, pages 424-426). 
The tests were carried out using a detergent of the following composition 
(Detergent 1 a): 
5.5% by weight ABS, 
2.0% by weight TAt14 EO, 
2.5% by weight soap, 
30.0% by weight aluminosilicate R 1, 
4.0% by weight waterglass, 
0.2% by weight HEDP, 
20.0% by weight perborate, 
1.0% by weight CMC, 
Remainder sodium sulfate and water. 
The results were compared with those obtained with a phosphate-containing 
detergent which, instead of 30% by weight of aluminosilicate, contained 
25% by weight of sodium tripolyphosphate and 5% by weight of sodium 
carbonate (detergent 1 b) and with a detergent which had the same 
composition of 1 b but in addition contained 1% by weight of magnesium 
silicate (detergent 1 c). The results were also compared with those 
obtained with a conventional commercial boiling detergent containing about 
40% by weight of sodium tripolyphosphate, 25% by weight of perborate, 2% 
by weight of magnesium silicate and about 10% by weight of surface-active 
agents (detergent 1 d). The figures for the calculated damaging factors 
given in the Table below show the surprising result that the damaging 
factor of detergent 1a according to the invention is far below that of 
comparison preparations 1 b and 1 c and that it is even more advantageous 
than that of the fabric-protecting preparation 1 d. 
TABLE 1 
______________________________________ 
Detergent according 
to Example 1 1 a 1 b 1 c 1 d 
Damaging factor s 
0.18 1.95 0.94 0.40 
______________________________________ 
EXAMPLE 2 
In this example, the degree of whiteness retention of cotton test fabrics 
after 50 washes is tested with detergent 2 a according to the invention, 
which has the following composition: 
Detergent formulation 2 a 
5.5% by weight alkane sulfonate, 
2.0% by weight KA+12 EO, 
2.5% by weight soap, 
30.0% by weight aluminosilicate Im, 
4.0% by weight waterglass, 
0.5% by weight HEDP, 
20.0% by weight perborate, 
1.0% by weight CMC, 
Remainder: sodium sulfate and water. 
The detergent was compared with a phosphate-containing detergent which 
contained 25% by weight of sodium tripolyphosphate and 5% by weight of 
sodium carbonate instead of the 30% by weight of aluminosilicate; as well 
as the 0.5% by weight of HEDP had been replaced by the same quantity of 
EDTA (detergent 2 b). It was also compared with a detergent which had the 
same composition as preparation 2 a except that it contained 0.5% by 
weight of EDTA instead of 0.5% by weight of HEDP (detergent 2c). 
The washing tests were analogous to the strand washing tests described in 
Example 1. To assess the greying of the fabric, dilute Indian ink (1:100) 
was added in a quantity of 2 cc per liter before each wash as "dirt". The 
degree of whiteness of the washed fabrics was then determined with a 
remission measuring instrument (Elrepho manufactured by Zeiss, Oberkochen, 
Germany). The results given in Table 2 below are average values obtained 
from four results. The figures given in this table show that with the 
addition of only 0.5% by weight of HEDP, a remission value results which 
differs only slightly from that obtained with the phosphate containing 
detergent tested for comparison, whereas the remission value obtained with 
the product which is free from HEDP is lower by more than 30 units. 
Similar effects are also obtained when HEDP is replaced by an equal 
quantity of HBDP or the other substituted diphosphonates which may be used 
according to the invention. 
TABLE 2 
______________________________________ 
Detergent according 
to Example 2 2a 2b 2c 
% Remission after 
50 washes 
(Elrepho Filter 6) 
89.8 93.6 58.3 
______________________________________ 
EXAMPLE 3 
To determine the stability of perborate, a detergent 3a according to the 
invention, which is identical to detergent 1a in Example 1, was compared 
with a detergent 3b which was similar in composition to detergent 3a but 
in addition contained (instead of 1% of sodium sulfate) 1% of magnesium 
silicate. A washing liquor containing 5 gm/l of preparation 3a or 3b, in 
which the water had a degree of hardness of 12.degree. dH, was heated from 
20.degree. C. to 90.degree. C. for 30 minutes and maintained at 90.degree. 
C. for 15 minutes. The active oxygen content of the solution was 
determined at 50.degree. C., 75.degree. C., 80.degree. C. and 90.degree. 
C. and after 15 minutes at 90.degree. C. In both cases, the values of 100% 
had merely dropped to 98% at 90.degree. C. whereas in a washing liquor 
which contained 5 gm/l of preparation 1c (see Example 1), the final value 
for the active oxygen content was 92%. In a preparation which had a 
similar composition but was free from magnesium silicate, the final value 
was 67%. This comparison clearly shows that the preparations according to 
the invention which have no magnesium silicate content have a higher 
stability of perborate than the phosphate-containing preparations compared 
with them, both with and without magnesium silicate. 
When 0.2 mg of copper ions (in the form of copper sulfate) were added per 
liter of washing liquor, preparation 3a according to the invention was 
found to have a residual active oxygen content of about 80%, which is 
still clearly above that obtained for formulation 1c when not contaminated 
with copper ions. 
EXAMPLE 4 
This example demonstrates the primary washing power of a composition (4a) 
according to the invention compared with that of a phosphate-containing 
detergent which contains the same surface-active component (4b). The 
washing tests were carried out in a launderometer. The tests were carried 
out with a liquor ratio of 1:12.5 at 90.degree. C. with 5 gm/l of 
detergent in water having a degree of hardness of 12.degree. dH, and 
continued for 30 minutes, 20 minutes of which were taken up with heating 
up. Artificially soiled polyester/cotton or cotton fabrics which had not 
been finished were used as the samples. To assess the washing power, the 
degree of whiteness of the washed textile samples was determined in a 
color filter measuring instrument RFC 3 of Zeiss, Germany, using a R46 
filter. The remission values obtained, which are entered in the Table 
below, show that the detergent according to the invention is at least 
equal in its primary washing power to the commercial preparation. 
______________________________________ 
Formulation 
4 a 4 b 
______________________________________ 
ABS 5.5 5.5 
OXO+7EO 1.7 1.7 
OXO+11EO 3.0 3.0 
Waterglass 4.0 4.0 
Aluminosilicate R 1 30.0 -- 
Sodium tripolyphosphate 
-- 25.0 
Sodium carbonate -- 5.0 
HEDP 0.2 -- 
EDTA -- 0.2 
Perborate 25.0 25.0 
CMC 1.0 1.0 
Remainder: Sodium sulfate 
and water 
______________________________________ 
TABLE 3 
______________________________________ 
% Remission 
unfinished cotton, 
polyester/cotton 
washing temperature 
fabric, washing 
90.degree. C.; concentration: 
temperature 90.degree. C.; 
Formulation 
5 gm/l concentration: 5 gm/l 
______________________________________ 
4 a 62.1 63.8 
4 b 63.1 58.1 
Significance LSD.sub.95 
Significance LSD.sub.95 
= 1.4 = 0.9 
______________________________________ 
The following examples as presented in Tables 4 and 5 give various recipes 
of detergents according to the invention. 
TABLE 4 
______________________________________ 
% by weight of component in detergent 
Detergent according to Example 
component 5 6 7 8 9 10 11 
______________________________________ 
ABS 5.5 -- 4.0 4.0 -- 5.5 5.5 
Alkane sulfonate 
-- 6.0 -- -- -- -- -- 
Fs-ester sulfo- 
nate -- -- 2.0 -- -- -- -- 
Olefin sulfonate 
-- -- -- -- 5.0 -- -- 
Coconut alcohol 
sulfonate -- -- -- 2.0 -- -- -- 
Tallow alcohol+3- 
EO-sulfate -- -- -- -- -- 2.5 -- 
TA+14 EO 3.0 -- -- -- 2.0 -- -- 
OCA+10 EO -- -- 2.5 1.5 -- -- -- 
KA+12 EO -- -- -- -- -- -- 3.5 
OXO+11 EO -- 2.0 -- -- -- 2.5 -- 
TA+ 7 EO -- -- -- 2.5 1.5 -- -- 
OXO+ 7 EO -- 2.0 -- -- -- -- -- 
TA+ 5 EO 1.5 -- -- -- -- -- -- 
KA+ 3 EO -- -- 1.5 -- -- -- -- 
Soap 3.5 3.0 2.0 3.5 3.0 2.5 3.0 
Foam inhibitor 
-- -- 0.4 -- -- 0.2 -- 
Aluminosilicate 
R1 30.0 30.0 28.0 32.0 30.0 29.0 30.0 
Waterglass 4.5 2.0 3.0 2.5 3.0 2.0 3.5 
HEDP 0.25 -- 0.3 -- -- 0.55 -- 
HBDP -- 0.25 -- 0.5 -- -- -- 
ATMP -- -- -- -- 0.25 
-- 0.4 
Perborate 25.0 25.0 28.0 22.5 23.0 25.0 25.0 
CMC -- 1.0 1.0 1.0 1.0 0.8 0.9 
Brightening 
agent 0.25 0.25 0.2 0.25 
0.22 
0.22 
0.22 
Enzyme 0.4 0.4 -- -- 0.4 -- -- 
Remainder: Color- 
ing and perfuming sub- 
stances, sodium 
sulfate and water 
______________________________________ 
TABLE 5 
______________________________________ 
% by weight constituent in the 
Detergent detergent according to Example 
constituent 12 13 14 15 16 17 
______________________________________ 
TA+14 EO 3.0 -- 4.5 -- 2.0 -- 
KA+12 EO -- -- -- 4.0 -- -- 
OCA+10 EO -- -- -- -- 2.5 5.0 
OXO+11 EO -- 2.5 -- -- -- -- 
TA+5 EO 3.0 -- 3.5 -- -- 2.0 
KA+3 EO -- -- -- 3.0 -- 1.5 
OCA+5 EO -- -- -- -- 3.5 -- 
OXO+7 EO -- 3.5 -- -- -- -- 
Soap 2.5 3.0 1.0 1.5 2.0 1.5 
i-11-14-DAA -- 1.5 -- -- -- -- 
i-11-14-MAA -- -- -- --1.0 
-- 
i-11-14-DAA+1 EO 
-- -- 1.2 1.5 -- -- 
Coconut fatty acid 
monoethanolamide 
2.0 -- -- -- -- 1.0 
Waterglass 4.5 3.5 2.0 2.5 3.5 3.0 
HEDP 0.25 0.25 -- 0.1 -- -- 
HBDP -- -- 0.3 -- 0.4 -- 
ATMP -- -- -- 0.2 -- 0.5 
Perborate 25.0 28.0 22.0 24.0 25.0 25.0 
Aluminosilicate 
R1 30.0 30.0 32.0 28.0 29.0 30.0 
CMC 1.0 1.0 1.0 1.0 0.8 0.9 
Brightening agent 
0.25 0.25 0.20 
0.22 
0.25 
0.22 
Enzyme 0.4 -- -- 0.4 -- 0.4 
Remainder: 
Coloring and 
perfuming sub- 
stances, sodium 
sulfate and water 
______________________________________ 
The detergent compositions of Table 4 contain the surface-active agent 
combination ba and the detergent compositions of Table 5 contain the 
surface-active agent combination bb. 
The preceding specific embodiments are illustrative of the 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 invention or the scope of the appended 
claims.