Note: Descriptions are shown in the official language in which they were submitted.
Z~ HOE 89/H 019
he present invention relates to builders for'"'textile
detergents for washing hea~y laundr~, whites and coloreds
in automatic washing machines.
Suitable detergents for automatic washing machines
comprise a combination of surfactants as the active
detergents, bleaches, water glass, dispersants and the
so-called builders which, on the one hand, fulfil the
function of a skeletal substance and, on the other hand,
by binding the hardness of the water, prevent encrusta-
tions of inorganic and organic constituents on the
material being washed and thus extend the life of the
textiles and provide a pleasant feel on the skin when
wearing these.
Suitable builders are alkali metal phosphates, above all
sodium tripolyphosphate, zeolite A and alkali metal
silicates, in particular a crystalline sodium layer
silicate.
In certain regions, alkali metal phosphates are no longer
added to the detergents, because of the risk of eutrophi-
cation of slowly flowing water courses and lakes, even
though precisely alkali metal phosphates have outstanding
builder properties.
In US-A-4,274,975, a detergent composition is described
in which, in particular, the zeolite of the formula
Na12(AlO2 SiO2)1z x H20, in which x is an integer from
about 20 to 30, is used as the builder.
A disadvantage in the use of a zeolite as the builder is
the accelerated degradation of the bleach during tha
storage time of the detergent and encrustation of the
material being washed in the course of several washing
steps by inorganic and organic constituents. The encrus-
tations can be partially suppressed by a relatively high
content of polycarboxylates in zeolite-containing
.
2til7958
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detergents. Instead, however, an undesirably high poly-
carboxylate content in the effluent must be accepted. An
increased polycarboxylate content has no influence on the
degradation of the bleach.
In US-A-4,728,443, detergents are described in which
crystalline layer silicic acids or alkali metal salts
thereof of the formula N2Si~02~1 . y HaOr where x > 7.0, M
= Na, ~ or H ant y = 0 to 25, are incorporated as buil-
ders. The disadvantage of these builders is the low Ca
hardness-binding capacity, which does not adequately
prevent encrustation of the material being washed with Ca
salts. These builders have a very high Mg hardness-
binding capacity.
It is the object of the invention to provide a builder,
by means of whirh a textile detergent can be produced, of
which the bleaching action is largely preserved during
storage, which has an enhanced cleaning action and with
which only slight encrustation on the material being
washed takes place, with a small addition of polycarboxy-
late.
The in~ention, by means of which, surprisingly, the
stated object is achieved and the disadvantages described
are avoided, relates to builders for textile detergents,
which comprise a mixture of 20 to 80% by weight of a
crystalline sodium layer silicate and 20 to 80% by weight
of a zeolite.
Furthermore, the builders according to the invention for
textile detergents can preferably and optionally have the
features that
a) the builder content in the textile detergent is
5 to 60% by weight, preferably 10 to 30% by
weight,
b) a crystalline sodium layer silicate having an
SiO2/Na20 molar ratio of (1.9 to 3.5) : 1 is used,
Z~}1'79~
3 --
c) a zeolite of the formula Nal2(Al02 . sia)l2 -
x H2O, in which x is an integer from 20 to 30, is
used,
d) they are used at a primary particle size from
0.01 to 1000 ~m, in particular from 1 to 20 ~m,
e) they are used together with up to 2.0% by weight
of polycarboxylate, relative to the textile
detergent, as a dispersant co-builder,
f) they are used together with inorganic and/or
organic phosphates and/or phosphonates, borates,
citrates, gluconates, ethylenediaminetetraacetic
acid, nitrilotriacetic acid and/or iminodiacetic
acid or alkali metal salts thereof in quantities
of up to 20~ by weight, relative to the textile
detergent, and
g) they are agglomerated together with the remaining
ingredients of the textile detergent by the
spray-mist mixing process by jetting-on of an
aqueous binder, in particular water glass and/or
a cellulose ether, in the range from 0.25 to
2.5 mm.
Suitable crystalline sodium layer silicates have an ion
exchange capacity of more than 100 mmol of Na~/100 g of
anhydrous substance and can be selected from naturally
occurring alkali metal silicates such as natrosilite
(Na2Si2O5) or revdite (Na2Si2O5 . SH2O). In general, how-
ever, syntheti~ally produced layer silicates are prefer-
: red, in particular those which are obtained in accordance
with EP-A-0,293,640.
Suitable zeolites have an ion exchange capacity of more
than 100 mmol of Naf/100 g of anhydrous ~ubstance, ~uch
as, for example, naturally occurring chabasite
(CatAl2Si~0~2~ . 6 H20), the calcium content of which has
been xchanged for sodium.
In general, however, synthetically produced zeolites are
preferred, in particular those obtained in accordance
.. ~ .' ,.'' :
.
'
Zl~1'7'358
4 -
with US-A-4,274,975. --
The layer silicate and the zeolite as builder mixturesexert a synergistic effect, by means of which, on the one
hand, the decomposition of the bleach during storage of
detergent formulations based thereon is greatly retarded
and, on the other hand, enc Nstation of the material
being washed with calcium and magnesium salts is effec-
tively prevented.
The surfactants which have proved suitable in the textile
detergent according to the invention are carboxylates
(soaps), alkanesulfonates, laurylbenzenesulfonate,
dodecylbenzenesulfonate, alkylphenol polyglycol ethers or
the condensation product of polypropylene glycol with
8 mol of ethylene oxide.
Suitable bleaches are sodium perborate tetrahydrate
(NaBO3 . 4 H2O), sodium perborate monohydrate (NaBO3 . H2~)
or sodium percarbonate (2 Na2CO3 . 3 H2O2).
Textile detergents with the builder according to the
invention are equally suitable for any water hardness,
depending on the dosage, on the assumption that the total
hardness consists to the extent of 70 to 85% of Ca
hardness and to the extent of 30 to 15% of Ng hardness.
The primary washing effect of the textile detergent was
determined at 60C on various test fabrics (EMPA tSwiss
Materials Testing Institute] Standard lO1 Cotton; ENPA
Standard 104 2 : 1 polyester/cotton, C-WF~ Standard 10
cotton, C-WFR Standard 20 2 : 1 polyester~cotton) accord-
ing to DIN 44983, Sheet 1 (January 1968) Section 4.1, by
determining the differential reflection which results
from the difference of the reflection of the test fabric
before and after the wash.
The secondary washing effect was determined at 90C on
various test fabrics (EMPA Standard 101 cotton, cotton
... .
2~}1~7~S8
_ 5 _
terry fabric) according to DIN 44983 (4.4). ..
The total hardness of the washing water was 18 German
hardness (hardness range III). The CaO: MqO ratio varied
between 2 : 1 and 5 : 1.
In the washing tests, 115 g of detergent were added in
the pre-wash, and 135 g of detergent in the main wash.
The invention is further illustrated by the examples
which follow.
Examples 1 to 9.
The detergent formulations were prepared from the indi-
vidual components given below by the spray-mist mixing
process familiar to those skilled in the art (Table 1).
.. . . .. . ~ .. . . _ ..... ~ .. . . .. .. .. ... .. .. . . .. . ... .. ..... .. .. . . . . . .
Z~ 58
a~ u~ O.- I O O. O. I ,
. ~ 1~ et' U'') N
U~ U~ ~ O
. ~` 11~ ~ ~ O ~ O O O
~ ~o ~ ~n ~ ~
U~ U~ ~ O, O.
t- ~ d' CO
~ ~r u~ u~ u~ I ~ ~ _
. ~
~ U~ ~ U~ O O .
E~ ~ r r~ ~ Y a n
. ~ t~ ~ ~ _1 ~9
~ ~ L~
~D
........................ ,................ ~ ...... ........ . .
2lt 117~ r
_ I ~ O I O .
o~ 1o ~J O ~i I_ I
* ~1 ..
~ ~ ~o~ ~ '- .
~1
~ ~ '
~' '", '
~:11'7~
The primary washing results are shown in Table 2 as
differential reflection, the bleach action on the PE/
cotton fabric tea soiling being listed separately in
Table 3. The differential reflection was determi~ed
a~cording to DIN 44983 (4.1).
Table 2
Primary washing results at 60C
determined as % differential reflection
Example E~PA WFK
Cotton/ PE/ Cotton/ PE/
(11) cotton(104) (lOC) Icotton(20C
1 25 35 27 15
2 25 35 26 15
3* 29 39 32 19
4* 30 40 32 19
5* 28 37 29 17
6* 27 37 30 16
7 25 32 26 15
8* 26 36 26 15
. 9 21 30 24 13
* Textile detergent with builder according to the
invention
,
2~795f;'~
g _ .
Table 3
Bleach action
Example % washing power l
j 1 l 42 .,
2 41
3* 38
. 4* 38
S* 39
6* 39
7 36
8* 37
9 36
. .
* Textile detergent with builder according to the
invention
... . .. _ .. ~.. ~ .. ...... ... ... ....... ... . .. .. . . . .. ....... . .. . . . .. . .
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Table 4
Encrustation in % by weight
.
Example Test fabric
WFR terry EMPA cotton .,
1 1.6 1.8
2 1.8 2.0
3* 1.0 0.9
4* 1.2 1.3
5* 1.5 1.6
6* 1.7 1.8
7 2.9 3.0
. 8* 23 5 l 23 63
* Textile detergent with builder according to the
invention
......... .. ..... ... . .. . . . . . .. ...... . ..... ....... ...... ........ ........ ............
