DETERGENT COMPOSITIONS STABLE TO CHLORINE SEPARATION, AND AGENTS FOR PRODUCING SAME

COMPOSITIONS POUR DETERGENT, NE LIBERANT PAS LE CHLORE, ET AGENTS POUR LES PREPARER

English Abstract

CANADIAN PATENT APPLICATION
OF
KRISTER HOLMBERG and INGVAR NILSSON
FOR
DETERGENT COMPOSITIONS STABLE TO CHLORINE SEPARATION,
AND AGENTS FOR PRODUCING SAME
Abstract of the Disclosure:
Detergent compositions stable to chlorine sepa-
ration are described, which as main constituents contain
alkali metal phosphate, alkali metal silicate, a tenside
and granulate chlorinated triazine trione, the granules
of the chlorinated triazine trione being coated with a
thin layer of a hydrophobic substance. The surface-treated
chlorinated triazine trione which constitutes an agent
for producing the composition, is also described as is the
use of the composition as a machine dish washing detergent
or industrial detergent.

Claims

The embodiments of the invention in which an
exclusive property or privilege is claimed are defined
as follows:
1. A detergent composition comprising 25-60%
by weight alkali metal phosphate, 20-70% by weight
alkali metal silicate, 0.5-3% by weight a tenside,
1-10% by weight a chlorinated triazine trione of the
formula
<IMG> (I)
wherein X is C1, Na or K, or when X is Na, the dihydrate
thereof, and optionally conventional additives, character-
ized in that the chlorinated triazine trione of formula
(I) has the form of granules coated with a thin hydro-
phobic layer of a diester of phthalic acid or adipinic
acid with an alcohol having 4 - 18 carbon atoms in an
amount of 3-9% by weight, calculated on the amount of the
chlorinated triazine trione of formula (I).
2. The composition of claim 1, characterized in
that the alcohol is a straight or branched alcohol having
6 - 12 carbon atoms.
3. The composition of claim 1, characterized in
that the hydrophobic layer comprises phthalate 610,
di-(2-ethyl-hexyl) phthalate, diisodecyl phthalate
di-(2-ethyl-hexyl) adipate and/or diisodecyl adipate.
18

4. The composition of one or more of claims
1-3, characterized in that for use as machine dish
washing detergent the composition comprises
25-60% by weight of alkali metal phosphate
30-70% by weight of alkali metal silicate
0.5-3% by weight of tenside
1-5% by weight of chlorinated triazine trione
3-9% by weight of diester, calculated on the amount
of chlorinated triazine trione
0-4 0% by weight of conventional additives.
5. The composition of claims 1, 2 or 3
characterized in that for use as an industrial detergent
the composition comprises
25-60% by weight of alkali metal phosphate
20-70% by weight of alkali metal silicate
0-30% by weight of alkali metal hydroxide
0.5-3% by weight of tenside
1-10% by weight of chlorinated triazine trione
3-9% by weight of diester, calculated on the amount
of chlorinated triazine trione
0-4 0% by weight of conventional additives.
6. An agent for producing the detergent
composition, characterized in that the agent comprises
granules of chlorinated triazine trione of the formula
<IMG>
wherein X is C1, Na or K, or the dihydrate of the triazine
19

trione of formula (I) when X is Na, said granules being
coated with a thin hydrophobic layer of a diester
of phthalic acid or adipinic acid with an alcohol hav-
ing 4-18 carbon atoms in an amount of 3-9% by weight,
calculated on the amount of the chlorinated triazine
trione of formula (I).
7. The agent of claim 6, characterized in that
the alcohol is a straight or branched alcohol having
6-12 carbon atoms.
8. The agent of claim 6, characterized in that
the hydrophobic layer comprises phthalate 610,
di-(2-ethyl hexyl) phthalate, diisodecylphthalate, di-
(2-ethyl hexyl) adipate and/or diisodecyladipate.

Description

9 ~ ~
DETERGENT COMPOSITIONS_STABLE TO_CHLORI~E SEPARAT~L
AND AGENTS FOR PRODUCING SAME
This invention relates to detergent compositions stable
to chlorine separation for use as machine dish washing de-
tergents or industrial detergents, and to agents for pro-
ducing said compositions.
Machine dish washing detergent compositions for exam-
ple consist mainly of
- alkali metal phosphate
- alkali metal silicate
- tenside
- organic chlorine compound.
The alkali metal phosphate, usually sodium tripoly-
phosphate, primarily serves as complexing agent for cal-
cium and magnesium ions.
The alkali metal silicate normally is a sodium sili-
cate having a molar ratio SiO2 : Na2O of 3.50 to 0.75.Usually,use is made of so-called sodium metasilicate,
which implies that said ratio lies about 1. The purpose
of the silicate is to provide a high pH, which is needed
int.al. for hydrolysis of edible fat rests, and to have
a corrosion preventing effect.
The sodium metasilicate may be either practically
anhydrous or be present as a hydrate with crystal
bound water. The commercially most usual hydrate is
the crystalform called pentahydrate. This product is
usually writtenas SiO2 . Na2O 5H2O, but actually is
a tetrahydrate of the salt Na2H2SiO4. This crystal form
is hereinafter called "pentahydrate".
The pentahydrate offers several advantages over the
anhydrous sodium metasilicate in machine dish washing
detergent compositions, int.al. because it is more
readily soluble and considerably cheaper. The introduc-
tion of water into a machine dish washing detergent
composition in powder for~ however, as experience has
~. 1.,.~,

1 1~89~8
shown, entails problems regarding the stability of the
organic chlorine compounds. These readily hydrolyzed
compounds in fact give off chlorine gas in a moist
environment, which amounts to a considerable technical
problem. For these reasons, use is preferably made of
anhydrous sodium metasilicate in said products.
The tenside usually is a low-foaming non-ionic ten-
side, preferably a block polymer of ethylene and pro-
pylene oxide. Its task is to contribute to wetting
and emulisification simultaneously as it shall have
an antifoaming effect on for example proteins.
The organic chlorine compound or chlorine carrier
functions as an oxidative bleaching agent which has the
task of attacking deposits of int.al. coffee, tea and
fruit juices. The economically most favourable chlorine
carrier is trichloroisocyanuric acid, but it is very
instable and gives off chlorine too easily to permit
being used in practice. Salts of dichloroisocyanuric
acid are therefore used in most cases and the sodium
salt has, primarily for economical reasons, been most
widely utilized.
Apart from the above-mentioned main components,
machine dish washing detergents often also contain
varying quantities of alkalimetal carbonates and bi-
carbonates, corrosion inhibitors, dyes and perfume.
What has been said above about machine dish washingdetergents is also true, in a~plicable parts,to indus-
trial detergent compositions generally.
There have been made great efforts to stabilize the
organic chlorine compounds in detergent compositions and
thereby to reduce the problem of a premature chlorine
gas development. It has been tried, by addition of re-
ducing agents (cf. German Patent 1,111,198) or by adjust-
ment of pH with the aid of a combination of boron oxide
and soda (cf. French Patent 1,537,311) to reduce the
tendency of chlorine separation in alkali salts of di
chloroisocyanuric acid. There is also described a method

4~7
3_
of adding pararin oil to compositions based on these
ch]orine compounds (cf. U.S. Patent 3,390 092). Tri-
cllloroisocyanuric acid also has been s-tabi]ized for in-
s-~ance by mfians of an oleiin having a car}on--carbon double
bond one carbon a,o~n of said double bord being tertiary
(cf. Bl-itisll Patent ~8,397). Co~lon to all of these
metl^~oc's is t]-~at even though they imply a certain improve-
ment as to stability to chlorine separation, the result is
far from sa-tisfactory. With the use of sodium metasilicate
]0 pentahydrate in detergellts an uncontrolled discharge of
chlorine gas therefore still is a production-technical
problem for the industries producing the detergents and
also an important practical problem for the consumer because
of chlorine smell and lower bleaching effects.
It has now been fourld that the tendency of chlorine
separation in organic chlorine compounds can be reduced and
a surprisingly good result be reached by surface-treating
said chlorine compounds in granular form with a hydrophobic
substance. ~lowever, a prerequisite is that the chlorine
compounds ar~ p-esent in granulated form, with a particle
size of about 0.5 to 5 mm. Pulverulent compounds cannot
be surface-tr2ated in this way since caking of the product
will result from such a treatment~ Machine dish washing
detergents and :industrial detergents based on surface-treated
organic chlorine compounds show a high degree of stability
to chlorine separation. Surface-treated trichloroisocyanuric
acid also gives acceptable results when used in machine dish
washing detergents and industrial detergents.
A considerable reduction of the chlorine losses is
obtained not only at the storing of the finished machine
dish washing detergent but also in the production thereof
when use is made of a chlorine compound surface-treated in
accordance with the present invention.
This invention thus relates to a detergent composition
comprising 25-60~ by weight alkali netal phosphate, 20-70~
~.~1~'' '

1 ~894~
,~
by weight alkali metal silicate, 0.5-3~ by weight a ten-
side, 1-10% by weight a chlorinated triazine trione of
formula (I) X
O ~\~0
~`C C (I)
N
\C
o
wherein X is Cl, Na or K, or when X is Na, the dihydrate
thereof, and opti.onally conven-tional additives. Said
composition is characterized in that the chlorinated
triazine trione of formule (I) is in the Eorm of granules
coated with a thin hydrophobic layer of a diester of phthalic
acid or adipinic acid with an alcohol having 4-18 carbon
atoms in an amount of 3-9% by weight, calculated on the
amount of chlorinated triazine trione of formula (I).
The invention further relates to an agent for pro-
ducing the detergent composition, said agent being character-
ized in that it consists of granules of chlorinated triazine
trione of formuLa (I) X
~C~ ~
N ~ ~ (I)
Cl ~ Cl
wherein X is CL, Na or K, or the dihydrate of the triazine
trione of formula (I) when X is Na, said granules being
coated with a thin hydrophobic layer of a diester

1 1689~
of phthalic acid or adipinic acidwithan alcohol hav-
ing 4-18 carbon atoms in an amount of 3-9~ by weight,
calculated on the amount of the chlorinated triazine
trione of formula (I).
Different embodiments of the composition according
to the invention comprise a machine dish washing de-
tergent composition and an industrial detergent compo-
sition, respectively.
The surface-treatment of the chlorinated triazine
trione is preferably performed such that the hydrophobic
substance in liquid form or dissolved in a readily
volatile solvent is added by portions under some kind
of agitation to the granulate chlorinated triazine
trione which is thereby coated with a thin film of
hydrophobic material effectively protecting the labile
chlorine compound from contact with water.
The hydrophobic film-forming substances utilized
in the surface-treatment are diesters of certain car-
boxylic acids, particularly phthalic acid or adipinic
acid, which surprisingly have proved to yield excel-
lent results.
The diesters preferably utiliæed in the invention
are diesters of phthalic acid or adipinic acid with
an alcohol having 4-18 carbon atoms, preferably a
straight or branched alcohol having 6-12 carbon atoms.
The following diesters have proved to be particularly
useful:
phthalate 610
di-(2-ethyl hexyl)phthalate
diisodecyl phthalate
di-(2-ethyl hexyl)adipate
diisodecyl adipate
~phthalate 610 is the trade nameof a fraction of di-
esters of phthalic acid and alcohols having 6-10 car-
bon atoms.

1 ~689~a
The most important physical property required in
the diesters utilized for the sur~ace-treatment is that
they shall be sufficiently water-repellent in order
that also a thin layer of the diester shall provide
S a fully satisfactory moisture protection for the en-
closed chlorine compound. Further, it is advantageous
if the diester is liquid at room temperature or has
a melting point not too far above said temperature,
preferably below 70C. ~se can also be made of diesters
having a higher melting point, in which case these are
first dissolved in a volatile solvent whereupon the
surface-treatment proper is performed and the solvent
is finally driven off by heating of the granulate sur-
face-treated product.
Naturally,it is also of great importance for the
diesters to have a good adhesion to the granulate chlo-
rine compound.
The chlorinated triazine compounds of formula I
comprise
Na-dichloroisocyanurate
Na-dichloroisocyanurate dihydrate
K-dichloroisocyanurate
~richloroisocyanuric acid.
A complex between K-dichlorocyanurate and trichloro-
isocyanuric acid is also well suited for use with thepresent invention.
The surface-treatment provides an effect already
at astonishingly small amounts of the hydrophobic sub-
stance. For most of the substances tested a content
of 3-9% by weight calculated on the chlorinated triazine
trione has proved to be sufficient. In most cases it
has even been found disadvantageous to exceed that
amount as this results in the surface-treated product
becoming sticky and having a tendency of aggregating.
A machinedishwashing detergent composition being
an embodiment of the present invention has the ~ollowing
constitution as regards its essential components (the

~ 168~
percentages are percentages by weight):
- alkalimetal phosphate in an amount of 25-60%, prefer-
ably 40-50~,
- alkalimetal silicate in an amount of 30-70%, preferably
40-60%, molar ratio SiO2 : Na2O (K2O) of 3.50 - 0.75,
preferably about 1, and a water content of 0 - 60%,
preferably 0 - 5% or 35 - 45%,
- a low foaming non-ionic type tenside in an amount of
0.5 - 3%, preferably 1 - 2%,
- a chlorinated triazine trione of formula (I~, sur-
face-treated with a hydrophobic substance in an amount
of 1 - 5%, preferably 1 - 3 % (the amount of hydro-
phobic substance is 3 - 9 %, preferably 5 - 8 %, cal-
culated on the chlorinated triazine trione),
- conventional additives in an amount of 0 - 40%, pre-
ferably 0 - 20 %.
An industrial detergent composition ~eing another
embodiment of the present invention has the following
constitution (the percentages are percentages by wei~ht):
- alkalimetal phosphate in an amount of 25 - 60 %, pre-
ferably 40 - 50 ~,
- alkalimetal silicate in an amount of 20 - 70 %, pre-
ferably 25 - 45 ~, molar ratio SiO2 : Na2O(K2O) of
3.50 - 0.75, preferably about 1, and a water content
of 0 - 60 %, preferably 0 - 5 % or 35 - 45 %,
- alkalimetal hydroxide in an amount of 0 - 30 %, pre-
ferably 10 - 20~,
- a low foaming non-ionic type tenside in an amount of
0.5 - 3 %~ preferably 1 - 2 %,
- a chlorinated triazine trione of fo~lula (I), sur-
face-treated with a hydrophobic substance, in an amount
of 1 - 10 %, preferably 2 - 5 ~ (the amount of hydro-
phobic substance is 3 - 9 %, preferably 5 - 8 %, cal-
culated on the chlorinated triazine trione),
- conventional additives in an amount of 0 - 40 %, pre-
ferably 0 - 20 %.
As will appear from Example 3 below, it is possible

1 1~8~8
to produce with the aid of the above-described surface-
treating method a detergent composition based on sodium
metasilicate pentahydrate wnicn is at least e-lually stable
to chlorine separation as a corres~onding proauct based
on anhydrous sodium metasilicate and a non-treated or-
ganic chlorine compound. The amount stated of hydro-
phobic material for the surface treatment, usually 5 - 8 %
of the amount of organic chlorine compound, usually
constitutes but 0.05 - 0.25 % of the total detergent
composition. The additional cost of said raw product
and of the extra operation the surface treatment in-
volves, is small compared with the savings in raw ma-
terial costs realized by turning from anhydrous meta-
silicate to the pentahydrate thereof.
lS Especially astonishing is that very good results
are also obtained with trichloroisocyanuric acid (see
Example 2).
Another advantage gained by the surface-treating
method indicated thus resides in the possibility of
being able to replace the anhydrous metasilicate in
detergents with the corresponding pentahydrate, retaining
the stability to chlorine separation of t~e detergents.
An alternative application of the surface-treating
method is to provide compositions based on anhydrous
metasilicate and a surface-treated organic chlorine
compound, said compositions being extremely stable to
chlorine separation However, such a formulation will
be relatively exl~ensive and may probably be used only
for special purposes.
The following Examples are meant to illustrate the
invention without restricting it in any way.
EXAMPLE 1
The effect of a surface-treatment of Na-dichloro-
isocyanurate for machine dish washing detergents stored
at 30C/85% relative moisture was examined. The samples
were stored in board cartons treated with polyethylene.
The chlorine content was determined by titration accord-

1 16~948
ing to the iodine-thiosulphate method.
The following machine dish washing detergent com-
position was used in the tests:
sodium tripolyphosphate 40.0 parts
5 sodium metasilicate pentahydrate 50.0 "
non-ionic tenside (block polymer of
ethylene and propylene oxide) 2.0 "
surface-treated sodium dichloro-
isocyanurate 2.0 "
10 water 6.0 "
A great many different substances were tested as
surface-treating agents. The substances most useful in
practice are indicated in Table 1.
The surface-treating agent was added by portions
under vigorous agitation to the granulate chlorine com-
pound. After finished addition the agitation was con-
tinued for a further 2 - 3 minutes. Low viscous sub-
stances were added at room temperature whereas high
viscous substances as well as solid compounds were
first heated to suitable viscosity. The surface treat-
ing agent was added in an amount of 7 %, and in some
cases also 5 %, calculated on the chlorine compound.
A reference test was made, in which the surface-treat-
ing agent was replaced by soda which is totally inert
in this connection.
The chlorine content of the various dish washing
detergent compositions which thus differ only with re-
gard to the surface-treatment of sodium dichloroisocya-
nurate, was determined as a function of the storage
time.
The results of the tests are given in Table 1.

~ 168948
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3 168948
11
EXAMPLE 2
The effect of a surface-treatment of trichloro-
isocyanuric acid for machine dish washing detergents
stored at 30/85 % relative moisture was examined. The
samples were stored in board cartons treated with poly-
ethylene. The chlorine content was determined by ti-
tration according to the iodine-thiosulphate method.
The following machine dish washing detergent com-
position was used in the tests:
10 sodium tripolyphosphate 40.6 parts
sodium metasilicate pentahydrate 50.0 "
non-ionic tenside 2.0 "
surface-treated trichloroisocyanuric acid 1.4 "
water 6.0 "
A great many different substances were tested as
surface-treating agents. The substances most useful in
practice are indicated in Table 2.
The surface-treating agent was added by portions
under vigorous agitation to the granulate chlorine
compound. After finished addition agitation was con-
tinued for a further 2 - 3 minutes. Low viscous sub-
stances were hereby added at room temperature whereas
high viscous substances as well as solid compounds
were first heated to a suitable viscosity. The surface-
treating agent was added in an ~,~ount of 6 %, calculat-
ed on the chlorine compound. A reference test was
made in which the surface-treating agent had been
replaced by soda which is entirely inert in this con-
nection.
The chlorine content of the different machine dish
washing detergent compositions which thus differ only
with regard to the surface-~reatment of trichloro-
isocyanuric acid, was determined as a function of the
storage time.
The results of the tests are indicated in Table 2.

1 1~8~8
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1 :~68g4~
13
EX~PLE 3
The effect of the surface-treatment of the organic
chlorine compound for machine dish washing detergents
based on anhydrous metasilicate and the pentahydrate
S thereof, respectively, was tested and compared with regard
to stability to chiorine sep~ration. Wse was maae as sur-
face-treating agent of di-(2-ethyl hexyl)phthalate in
an amount of 7 ~ calculated on the organic chlorine
compound. The following formulations were usea:
A B
sodiumtripolyphosphat 40.0 parts 40.0 parts
sodium metasilicate,
anhydrous - 40.0
1 sodium metasilicate,
5 pentahydrate 50.0 "
non-ionic tenside
(block polymer of
ethylene and propylene
oxide) 2.0 " 2.0 "
~o surface-treated sodium
dichloroisocyanurate2.0 " 2.0 "
water 6.0 " 10.0 "
soda - 6.0 "
Reference tests were made for the two formulations
(reference A and reference B, respectively), in which
the di-(2-ethyl hexyl)-phthalate was replaced by soda.
The procedure applied at the surface-treatment like the
execution and evaluation of the tests were analogous
with those in Example 1.
The results of the examination will appear fror,
Table 3. As is evident, the surface treatment had a
positive effect in both cases. It also appears from the
Table that a machine dish washing detergent based on
metasilicate pentahydrate and surface-treated chlorine
compound (R) will be at least equally stable to chlo-
rine separa~ion as a ae~ergent based on anhydrous rneta-
silicate and untreated chlorine cornpound (B).

1 ~6~9~8
14
TABLE 3
Residual chlorine (in ~)
Formulation Storage time (months)
0 1 2 4
A 1.16 0.94 0.92 0.90
reference A1.15 0.86 0.72 0.48
B 1.25 1.18 1.12 1.08
reference B1.25 1.05 0.93 0.81

4 8
EXAMPLE 4
The effect of a surface-treatment of sodium dichlo-
roisocyanurate for detergents stored at 30C/85 ~ re-
lative moisture was examined. Tne sa,~ples are stored in
board cartons treated with polyethylene. The chlorine
content was determined by titration according to the
iodine-thiosulphate method.
The following detergent composition was used in
the tests:
10 sodium tripolyphosphate 45 parts
sodium metasilicate pentahydrate25 "
sodium hydroxide 15 "
non-ionic tenside 2 "
surface-treated sodium dichloroisocyanurate 4 "
lS soda 9 "
A great many different substances were tested as
surface-treating agents. The substances most useful
in practice are indicated in Table 2.
The surface-treating agent was added by portions
under vigorous agitation to the granulate chlorine
compound. After finished addition agitation was con-
tinued for a further 2 - 3 minutes. Low viscous sub-
stances were hereby added at room temperature whereas
high viscous substances as well as solid compounds were
first heated to a suitable viscosity. Tne surface treating
agent was added in an amount C)L 7 ~, calculatea on the
chlorine compound. A reference te~t W.3, r.iade, in whicn
the surface treating agent was replaced by soda which is
entirely inert in this connection.
The chlorine content of the different detergent com-
positions which thus differed only with regard to the sur~
face-treatment of sodium dichloroisocyanurate, was deter-
mined as a function of the storage time.
The results of the tests are indicated in Table 4.

~ 16~9d~8
16
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1' ~
a~ ~ ~ ~
r~ X~ X~
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~ I I V
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l ~ ~ O
a~ Q) a
~ I I a
S~ I I
~ .,1 rl a~
U~ ~ C~

ll689~a
EXAMPLE 15
18.6 kg of granulate sodium dichloroisocyanurate
were charged into a Lodiger mixer of 50 1. Under vigorous
agitation 1.4 kg of di-(2-ethyl-hexyl)phthalate was
added through a fine nozzle. The time of supply amounted
to 3 - 5 minutes. After finished supply agitation was
continued for a further few minutes, whereupon the mixer
was emptied.