PROCEDE D'OBTENTION DE DETERSIFS EN POUDRE DONT L'APPARENCE EST CONSERVEE OU AMELIOREE ET QUI CONTIENNENT DES AGENTS FLUORESCENTS DE BLANCHIMENT

PROCESS FOR THE PRODUCTION OF WASHING POWDERS OF STABILISED OR ENHANCED APPEARANCE WHICH CONTAIN FLUORESCENT WHITENING AGENTS

Abrégé anglais

- 1 -
Case 1-12163/1+2/=
Process for the production of washing powders of stabilised
or enhanced appearance which contain fluorescent
whitening agents
Abstract of the Disclosure
The invention relates to the production of washing powders
of stabilised or enhanced appearance which contain a
fluorescent whitening agent of the formula
<IMG>
or of the formula
<IMG>
wherein R1 is hydrogen or chlorine, and M is hydrogen, an
alkali metal or ammonium ion. The stabilising or enhancement of the
appearance is effected by first dissolving or dispersing
the fluorescent whitening agent in a mixture of water and
a polyvinyl alcohol or polyvinyl pyrrolidone which is
soluble or is able to swell in water, adding this solution
or dispersion to the washing powder slurry and drying the
slurry. The solution or dispersion can also be subsequently
sprayed onto the dried residual washing powder. The
appearance can be further enhanced by employing a poly-

- 2 -
ethylene glycol, a surfactant containing ethyleneoxy and/or
propyleneoxy groups, and/or a cellulose ether, in addition
to the polymer in the solution or dispersion. The solution
or dispersion comprising fluorescent whitening agent and
polymer can also alternatively be dried, preferably by
spray drying, to produce a preparation which, after it has
been suspended in water, can also be added to the washing
powder slurry. The slurry is then dried, preferably by
spray drying.

Revendications

- 20 -
What is claimed is
1. A process for the production of a washing powder of
stabilised or enhanced appearance which contains one
or more fluorescent whitening agents of the formula
<IMG>
or of the formula
<IMG> ,
wherein R1 is hydrogen or chlorine, and M is hydrogen, an
alkali metal, ammonium or amine salt ion, which process com-
prises first dissolving or dispersing the fluorescent whitening
agent or agents in a mixture of water and a polyvinyl
alcohol or polyvinyl pyrrolidone which is soluble or
swellable in water, and adding the solution or dispersion
so obtained, which may additionally contain a polyethylene
glycol, a surfactant containing ethyleneoxy and/or
propyleneoxy groups, or a cellulose ether, to the washing
powder slurry and subsequently drying this slurry or,
optionally after the addition of further washing powder
components, spraying said solution or dispersion onto a
dried unfinished washing powder, or drying the solution
or dispersion containing the fluorescent whitening agent or
agents to a powder, suspending said powder in water,
adding the resultant suspension to the washing powder
slurry, and subsequently drying this slurry.

- 21 -
2. A process according to claim 1, which comprises
adding the solution or dispersion containing the fluorescent
whitening agent direct to the washing powder slurry and
subsequently drying said slurry, or, optionally after addi-
tion of further washing powder components, spraying said
solution or dispersion onto a dried unfinished washing
powder.
3. A process according to claim 1, which comprises
drying the solution or dispersion containing the fluorescent
whitening agent and suspending the fine powder so obtained
in water, adding this suspension to the washing powder
slurry, and subsequently drying said slurry.
4. A process according to claim 3, which comprises
drying the solution or dispersion by spray drying with
hot air.
5. A process according to claim 1, which comprises
wet grinding the dispersion before it is incorporated in
the washing powder slurry or before it is dried.
6. A process according to claim 5, wherein the wet
grinding procedure is carried out in a ball mill in the
temperature range between room temperature and the boiling
point of the dispersion.
7. A process according to claim 1, which comprises
dissolving or dispersing the fluorescent whitening agent
in a mixture of water and a polyvinyl alcohol having a
degree of hydrolysis of 80 to 100% and a viscosity between
3 and 66 cP, or a polyvinyl pyrrolidone having a molecular
weight of 10,000 to 360,000.

- 22 -
8. A process according to claim 1, wherein the mixture
of water and the polymer contains at least 0.01% by weight
of polymer.
9. A process according to claim 1, wherein the ratio
of fluorescent whitening agent to polymer in the aqueous
solution or dispersion, or in the dried powder obtained
therefrom, is 9:1 to 1:10.
10. A process according to claim 9, wherein the ratio
of fluorescent whitening agent to polyvinyl alcohol is
80:20 to 40:50.
11. A process according to claim 9, wherein the ratio
of fluorescent whitening agent to polyvinyl pyrrolidone
is 1:1 to 1:10.
12. A process according to claim 1, wherein the mixture
of water and polyvinyl alcohol or polyvinyl pyrrolidone, in
which the fluorescent whitening agent is dissolved or dis-
persed, additionally contains a polyethylene glycol, a sur-
factant containing ethyleneoxy and/or propyleneoxy groups,
or a cellulose ether.
13. A process according to claim 12, wherein the mixture
additionally contains a polyethylene glycol having a mole-
cular weight between 100 and 10,000, a cellulose ether, a
copolymer of polyethylene oxide and polypropylene oxide
having a molecular weight of 2000 to 20,000 of the formula
H0(C2H40)x-(C3H60)y-(C2H40)zH ,
wherein the content of ethylene oxide (x + z) is 10 to
85% by weight and the content of propylene oxide (y) is

- 23 -
15 to 90% by weight, an ethoxylated alcohol of the formula
H(C2H4O)a-OR ,
wherein a is an integer between 10 and 200, and R is alkyl
of 12 to 20 carbon atoms, alkenyl of 12 to 18 carbon atoms,
or phenylalkyl, or an ethoxylated alkylphenol of the formula
<IMG> ,
wherein R' is alkyl of 6 to 18 carbon atoms, Z is hydrogen,
-SO3M' or -PO3M', in which M' is hydrogen, an alkali metal
or ammonium ion, and b is an integer between 6 and 30.
14. A process according to claim 2, wherein the solution
or dispersion is added to the washing powder slurry and the
slurry is then dried.
15. A process according to any one of claims 1 to 3,
wherein the dissolving or dispersing of the fluorescent
whitening agent in the aqueous polymer mixture is acceler-
ated by heating in the temperature range from
40° to 80°C.
16. A process according to claim 1, wherein the polymer
is a polyvinyl alcohol having a degree of hydrolysis of
90 to 100% and a viscosity of 3 to 10 cP.

- 24 -
17. A process according to claim 1, which comprises
the use of a fluorescent whitening agent of the formula
<IMG>
wherein M' is hydrogen, sodium, potassium or ammonium.
18. A process according to claim 1, which comprises the
use of a fluorescent whitening agent of the formula
<IMG>
wherein M' is hydrogen, sodium or potassium.
19. An aqueous solution or dispersion containing a
fluorescent whitening agent of the formula
<IMG> (1)
or of the formula
(2),
<IMG>

wherein R1 is hydrogen or chlorine, and M is hydrogen, an
alkali metal, ammonium or amine salt ion, a polyvinyl
alcohol or polyvinyl pyrrolidone which is soluble or
swellable in water, and optionally a polyethylene glycol,
a surfactant containing ethyleneoxy and/or propyleneoxy
groups, and/or a cellulose ether,
20. A solution or dispersion according to claim 19,
which contains a fluorescent whitening agent of the formula
(1) or (2), a polyvinyl alcohol having a degree of hydro-
lysis of 80 to 100% and a viscosity of 3 to 66 cP, or a
polyvinyl pyrrolidone having a molecular weight of 10,000
to 360,000, the ratio of fluorescent whitening agent to
polymer being 9:1 to 1:10.
21. A solution or dispersion according to claim 20,
which contains a fluorescent whitening agent of the formula
(1) or (2) and a polyvinyl alcohol, the ratio of fluores-
cent whitening agent to polyvinyl alcohol being 80:20 to
40:50.
22. A solution or dispersion according to claim 20,
which contains a fluorescent whitening agent of the formula
(1) or (2) and a polyvinyl pyrrolidone, the ratio of
fluorescent whitening agent to polyvinyl pyrrolidone being
1:1 to 1:10.
23. A solution or dispersion according to claim 19,
which contains at least 0.01% by weight of the respective
polymer.
24. A solution or dispersion according to claim 20,
which contains a polyvinyl alcohol having a degree of
hydrolysis of 90 to 100% and a viscosity of 3 to 10 cP.

- 26 -
25. A solution or dispersion according to claim 19, which,
in addition to containing the fluorescent whitening agent
and polyvinyl alcohol or polyvinyl pyrrolidone, contains a
polyethylene glycol, a surfactant containing ethyleneoxy
and/or propyleneoxy groups, or a cellulose ether.

- 27 -
26. A solution or dispersion according to claim 19,
which contains a fluorescent whitening agent of the
formula
<IMG>
wherein M' is hydrogen, sodium or potassium.
27. A solution or dispersion according to claim 19,
which contains a fluorescent whitening agent of the
formula
<IMG>
wherein M' is hydrogen, sodium or potassium.
28. A preparation consisting of a fluorescent whitening
agent of the formula
<IMG> (1)
or of the formula
<IMG> (2) ,

- 28 -
wherein R1 is hydrogen or chlorine, and M is hydrogen, an
alkali metal, ammonium or amine salt ion, a polyvinyl
alcohol or polyvinyl pyrrolidone, and optionally a poly-
ethylene glycol, a surfactant containing ethyleneoxy
and/or propyleneoxy groups, and/or a cellulose ether.
29. A preparation according to claim 28 consisting of
a fluorescent whitening agent of the formula (1) or (2),
a polyvinyl alcohol having a degree of hydrolysis of 80
to 100% and a viscosity of 3 to 66 cP, or a polyvinyl
pyrrolidone having a molecular weight of 10,000 to 360,000,
the ratio of fluorescent whitening agent to polymer being
9:1 to 1:10.
30. A preparation according to claim 29 consisting of a
fluorescent whitening agent of the formula (1) or (2) and
a polyvinyl alcohol, the ratio of fluorescent whitening
agent to polyvinyl alcohol being 80:20 to 40:50.
31. A preparation according to claim 29 consisting of a
fluorescent whitening agent of the formula (1) or (2) and
a polyvinyl pyrrolidone, the ratio of fluorescent whitening
agent to polyvinyl pyrrolidone being 1:1 to 1:10.
32. A preparation according to either of claims 29 or 30,
which contains a polyvinyl alcohol having a degree of hydro-
lysis of 90 to 100% and a viscosity of 3 to 10 cP.
33. A preparation according to claim 28 consisting of a
fluorescent whitening agent of the formula (1) or (2), a
polyvinyl alcohol or a polyvinyl pyrrolidone and a poly-
ethylene glycol having a molecular weight between 100 and
10,000, a cellulose ether, a copolymer of polyethylene

- 29 -
oxide and polypropylene oxide having a molecular weight
of 2000 to 20,000 of the formula
HO(C2H4O)x-(C3H6O)y-(C2H4O)zH ,
wherein the content of ethylene oxide (x + z) is 10 to
85% by weight and the content of propylene oxide (y) is
15 to 90% by weight, an ethoxylated alcohol of the formula
H(C2H4O)a-OR ,
wherein a is an integer between 10 and 200, especially
between 30 and 100, and R is alkyl of 12 to 20 carbon
atoms, alkenyl of 12 to 18 carbon atoms, or phenylalkyl,
or an ethoxylated alkylphenol of the formula
<IMG> ,
wherein R' is alkyl of 6 to 18 carbon atoms, Z is hydrogen,
-SO3m' or -PO3M', in which M' is hydrogen, an alkali metal
or ammonium ion, and b is an integer between 6 and 30.
34. A preparation according to claim 28, which contains
a fluorescent whitening agent of the formula
<IMG>
wherein M' is hydrogen, sodium or potassium.

- 30 -
35. A preparation according to claim 28, which contains
a fluorescent whitening agent of the formula
<IMG>
wherein M' is hydrogen, sodium or potassium.

Description

r~i3fG~
Case 1-12163/1+2/=
Proces~ for the productio~ of wa~3hing powder~ o ~tabili~ed
or enhanced appearance which contain ~luorescen~
The prese~t invention relates to a process for the
production o~ washing powders o stabili~ed and/or enhanced
appearance which con~ain one or more fluoresce~ whitening
agents o~ the bis-triazolylstilbene or naphthotriazolyl-
stilbene type.
It has long been known to add fluorescen~ whi~ener to
deterge~ts. Reference i~ made in this connection e.g. to
~nvironmental Quality and Saety, Suppl~ment Volume 4,
Fluorescent Whitening Agent~, pages 59-62, ed. by C~ulston
+ Korte, G. Thieme Verlag, Stuttgart 1975; German patent
specification 731 558.; and numerous other pa~ent
specifica~ions relating ~o fluoresce~t-whitening agent~. ;
It is al30 known to add ~peci~ic fluorescent w~itening
agents to detergents in powder form in ordex to enhance
the appearance of the deterge~ts (see e.g~ J. of Color
Appearance 1 (1972), 5, page 46).
Like other fluorescent whitening agents of the st~lbene-
sulfonic aeid type, the compsunds of the formula (1~ herein
(known fi~m U~S.patent specifica~ns 2 784 183 and 3 485 831) are
most suitable or whitening and brightening textile~ in a
wash ba h. 1~, however, they are incorporated in solid
washing powders in the customary manner, they have an
exceedingly undesirable drawback: not only do they barely
enhance the appearance of the wsshing powder, but frequently
even cause a deterioration in it~ appearance. Unattractive
j, . . .
,

~ ~ 3~3~ ~
greenish~yellow washing powder~ o r~duced commercial value
are obtained in this manner.
The production of w shing powders usually comprise~
preparing a slurry from the individual componen~s (surfacP-
active substa~ce, salts, builder, water etc.), and then
drying this slurry, preferably by spray drying at elevated
temperature. If desired, various further ingredients which
are resistant to drying at elevated temperature (e.g. in
the range from 200 to 300C) are ~ubsequently added to the
dry wa~hing powder. Thu8 ~on-ionic surfac~an~s can be
sprayed onto the washlng powder and/or cer~in addi~ives~
e.g. perborate, per ume3 9 enzymes, dye~ and other thermo-
labile substance~, ble~ded with the otherwi e finished
washing powder. Fluorescent whitening agents are usually
added to the slurry before it is spray dried. The
unattractive greenish-yel}ow w~shing powder~ reerred to
above ~re usually ob~ained by means of thiY procedure.
Even the la~er addi~ion o~ fluorescent whitening agents
is not able to effect any tabili~in~ ar ~nhancement of the
appearance. This problem arise~ when i~corporating
fluorescent whiteni~g gents of ~he bis-triazinylamino-
stilbene-di ulonic acid typ~. Mean~ of improvements have
already been proposed, e.g. the preparation of special
crystal modifications o the fluorescent whitening agent
or the additicn of substances having a large surace area.
Reference is made in this connection to e.g. German
Auslegeschrift 2 747 088, German Offenlegungsschrit 2 659 675.
With respect to the problem of detergent yellowing arising
with fluorescent whitening agents of the bis-triaæinyl-
aminostilbene-2,2'-disulfonic acid type proposals
have been published ~or enhancing the appearance of the
wa~hing powders, e.g. by the addition of various substances
such as alcohols, sugars, certain surfactants etc.
..

3~ 6~
Attention is drawn in this regard to Japanese patent
publications Sho 51-5308, 51-6687, 46-35273 and
49-967. However, all these means are not suficient to
solve the problem on which this invention is based, and
they effect no adequate stabilising or enhancement of the
appearance of the washing powder.
The present invention is based on the surprising observation
that it is possible to obtain an excellent white appearance
by a5pe~ffl~ process ox produ~ng wash ~ p~ers which contain
fluorëscent whitening agent~, and that particularly good
white effects can be obtained on the textiles washed with
these washing powders~
The proces~ of the pre~ent invention for the production of
washing powders of stabili~ed or enhanced appearance
which contain one or more fluorescent whitening agen~s of
the ~ormula
~ CH=C3~ N
or of the forrnula ~~
~0
~ -C~oC~ N ~
wherein Rl is hydrogen or chlorine, and M is hydrogen, an
alkali metal, ammonium or amine salt ion, con~ists in
' ' , ' ~ ~ '`
.. ~ ,. .

-- 4 --
first dissolving or dispersing the fluore~cent whi~ening
agent or agents in a mix~ure o water and a polyvinyl
alcohol or polyvinyl pyrrolidone which is soluble or
swellable in water, and adding the solution or dispersion
so ob~ained, which may additionally contain a polya~hylene
glycol, a surfactant containing ethyleneoxy and/or
propyleneoxy groups, or a cellulose ether, to the washing
powder slurry and subsequently drying thi.s slurry, or,
optionally after the addition o further washing powder
component3, spraying said solution or dispersion onto a
dried unfinished washing powder, or drying the solution
or dispersion to a powder, suspending said powder in water7
adding the resultant suspension to the washing powder
slurry, and subsequently drying this slurry.
Preferred alkali metal ions M in formula (1) are sodium
and potassium ionsO Sui~able amine salt ion~ M are
principally those of the ormu~a - ~ 1R2, wh~rein Rl is
hydrog~n or unsubs~ituted or substi~uted alkyl, and ~ is
unsubstitu~ed or subs~i~uted alkyl. Pr~erred substituted
alkyl radicals, which preferably co~tain 1 to 4 carbon
atoms, are hy roxyalk~l, cyanoalkyl~ haloalkyl and benzyl.
M is preerably hydrogen, sodium, potassium, or ammonium.
It is an e~ser~tial feature of the proces~ of the invention
that the fluorescent whit~ning agent is dissolved or ~~
dispersed in ~he mix~ure of water arld a polymer (polyvinyl
alcohol or polyvinyl pyrrolîdone, or mix~ures o~ these
polymers~, as otherwise the desired effect is not achieved.
Particùlarly advantageous results are obtained with poIy-
vinyl alcohol.
It is preferreia to employ polyvinyl alcohols having a degree
o~ hydrolysis of 80 to 100 mol.% and a viscosity between 3
~:,' , :

~ 5 --
and 66 cP, especially those having a degree o hydroly~is
of 9o to 100 mol.% and a viscosity of 3 to 10 cP. In this
specifica~ion, all viscosity values indicated for pol~vinyl
aleohol are measured in a 4% aqueous solutlon at 20C~ . -
.
Polyvinyl pyrrolidone~ ~uitable for the process o~ the
present invention preferably have a molecular weight of
10~000 to 360~000, especially ~ro~ 15,0~0 to 50,000. It
will be appreciated that the term "polyvinyl pyrrolidone"
encompasses not only the polymeri~ation products o~ unsub-
stituted vinyl pyrrolidone, but also those o~ substitut~d,
e.g. alkylsubstitutedg vinyl pyrrolidones.
The specified polymers form solutions with water i~ ~hey
do not have a high molecular weight. However, it sufices
al~o if the polymers ~well or are dispersed in water.
The aqueou~ m~xture~ in which the fluorescent whitening agent
is ~ ~olved or ~sp~sed prefe ~ ly contain at least 0.01% by
weight, ~08~ preferably at leas~ 0.05~--by weight, of the
respective polymer. The m~x~mum eontent of poly~er is
determi~ed by the flowability of the mlxture ob~ai~d and
depe~ds on the mol@cular w~gh~ of Ehe respecti~e polymer.
~here a flowable mlx~ure i~ ob~ained, high concentration~
of polymer do not impair the operability of the proces~.
In practice, sultable concentration~ of polym~r in the ~~~
mixture are preferably between 0.01 and 20% by wei~ht,
especially b~ cn O.Q5 and 10% by weight.
To enhance ~he appearance of the f~nished washing powder
further, it is possible to add ~o ~he mi~tur~ of wa~r
and polyvin~l alcohol or polyvinyl pyrrolidorle in whlch
the ~luore~ce~t whi~enlng ager~'c i5 dissolved or dispersed,
a polyethylene glycol, a surface-actlve ~ubstance
.

containing ethyleneoa;y and/or propyleneoxy group3, or a
cellulo~e ether. An enharlced efect is obtained iTI particular
with the ollowing substance~
a) polyethylene glyc:ols, prefer~ly those having a molecular
weight o 100 'co 10 ,000;
b) cellulose ether~, e.g. hydroxypropyl ~ellulo~e, methyl
cellulose, carboxymethyl cellulose, methylhydroxypropyl
cellulo~e;
c) copolymer o~ polyethylene oxide and pol~rpropylene
oxide oi~ ~che formula
~olc2~l4v)X (C3~6)y (C2~ ) Z
wherein the content of @thylene oxide (~ + z) is lO to
85% by weight, and that o propylene oxide (y) i~ 15 to
90% by weigh~. The molecular weigh~ of such polymers is
between 2000 and 20 ,000;
d) ethoxylated alipha~ic alcohol~ of the formllla
E~ ~C2E140) a ~
wherein a i9 an integer between 10 and 200, e~pecially
betwee~ 30 a~d 200, and R is alkyl of L2 to 20 carb~r~ a~om~,
alkenyl of 12 to 18 carbo~ atom~, or phenylalk~l
e) ethoxylated alkylpheraols o the formula
-C1 ( C~2C~20 ) b Z
~=,~
wherein R' is alkyl of 6 I:o 18 carbon ato~, Z is hydrogen,
-S03~' or P03~f', in which Ms is hydrogen, an alkali metal
or ammonium ion, and b is an integer between 6 a~d 30.
Preferably, ~he amou~ in which the abo~e rnentioned
optional compone~ts are added a~e 1 to 50 timeg, especially
1 ~o 20 timeq, e.g. 1 to lO time~, the amoun~ of polyvinyl
,. , : ,
. ;" ~ . ,.:
: : , . ..

~ ~ 3~
alcohol or polyvi~yl pyrrolidone. or mixture~ thereo~,
present in the aqueou mixtu~e.
The 1uorescent whitening agent can be dissolved or - :
dispersed e.g. at room temperature i~ the medium consis~ing
of water and ~he polymer specified above. Frequen~ly,
h~wPver, it i~ advantageou to h~at the mixture, e.g. to
a temperature in the range ~rom 30 to 100C, preferably
from 40 to 80C, e~pecially from 60 to 80C, whereby a
more rapid or a better solu~ion or dispersion o~ the 1u-
orescent whi~ener in the mix~ur~ i~ of~en achieved,
If a di~persion i9 ob~ained wh~n mixing the ~luorescen~
whitening agent with the polymer solution or disper~ion ~ . .
and this is usually so - then it can be advantageou~ to subj~
this dispersion to a wet grinding before the additio~ to
the detergent in order to effect a bet~er disper~ion o the
~luorescen~ whi~ening agent by reducing ~he par~icle ~ize.
The wet grinding can be carried out e.g. by adding glas~
bead~ to ~he dispersion and grinding. it in a ball mill.
The temperature during the grindi~g procedure can be m ~he
ran~e between room tempera~ure and the boiling poin~ of the
dispersio~, e.g. be~ween 20 ~nd 80C. Dependisg on the
de~ired finene~ o ~he di per8ion, the grinding can ~ake
up to ~everal hour~, e.g. ~r~m 1 to 10 hours.
The amou~t of fluores~e~t whi~ening agent to be dissolved
or dispersed d~pends on the desixed ~mount i~ the inished
washing p~wder. It can be e.g. from 0.001 to 10% by weigh~.
preferably fro~ 0~01 to 5% by welgh~, e~p~cially from
0.05 to 2% bylweigh~. Very good resul~s are ob~ined wi~h
amou~ts from 0.1 to 0.5% by weigh~.
:,
~-:
',

~ ~ 3~
The ratio between the fluorescent whitening agent and the
polymer or polymer mixture in the aqueous solution or
dispersion, or in the dried 1uorescent whitener preparation
obtained therefrom, can vaxy wit:hin wide limlts and depends
on the fluorescent whitening a~en t employed and the nature
o~ the polymer or polym~rs. For e~ample, ~he ra~io of
fluorescent whitening agent to polymer can be about 9:1 to
1:10. When using polyvinyl alcohol, it is pre~erably in the
region of 80:20 to 40:50, most preferably of 70:30. When
using polyvinyl pyrrolidone, the ratio of fluorescent
whitening a~ent to polymer is e.g. between 1:1 and 1:10,
preferably about 1:9.
Within the scope o the proce~ of this invention, praferred
fluorescent whitening agents are those of the ~ormulae
CH=CH~ N ~ I I (3) and
So3~ . --
I$ ~ c~=c~ .-N
SO3M' S~3M'
wherein M' is hydrogen, sodium or potassium.
The fluore~cen~ whitening age~t is preferably incorporated
in the de~ergent by adding the solution or dispersion
(o~tained as d~escribed above) to the washing powder slurry
(mixture of thle customary components) and the~ drying the
. : . ....................... : :; . ~ .
- ,. , ,:: . . . . .
.

- 9 -
slurry containing the fluore~cent whitening agent in ~he
conventional manner. If the slurry contains substances
which are unstable at ele~a~ed t:empera~ure (e.g. car~ain
surfactants, such as those which contain ethyleneoxy
groups), then it is dried at l~i temperature9 e.g. bel~w . -
50C. Normally, however, ~he sll~ry is dried a~ ~levated
temperature, e.g. up to 300C. i.or example by conventlonal
spray drying or 1uidised bed drying.
The solutlon or dispers~on can, however,
also be sprayed onto the dried washin~ powder
(e.g. by spray drying in a pray tower) in the co~en~ional
man~er employed ~or obtalning washing powd~ containi~g
~hermolabile ~ub~ta~c~, e.g. certai~ su~fac~ants con~ai~l~g
e~hyleneoxy groups. This con~titu~e3 a very lmpor~an~
method ln practic~ i3, however, also po~ble to m~x
the solution or dLspersion with suitable detergent
componen~s which are r~ally added to the o~herwis~
~ini~hed wa~hing p~wder a~ the co~lusion of ~he production
process (a.g. with sodium perborate, bleachi~g agents such
as chlorin~ donor~, e~z~mes, parfum~ etc,)~ and then to
apply thi~ mlx~ure ~o ~he already ex~ing re~idual p~wde~.
It is decisive for the success of the proces~ o the
invention th~t the 1uorescent whitening agent should be
dissolved or .inely dispersed in the above described
mixture. The best results are obtainet when the fluoresc~nt
whitening agent is dissolved or very inely dispersed
(e.g. by an additional grinding~ in the corresponding
medium.
A second variant of incorporating the fluoreseent
whitening agent or agents in the washing powder by the
process of the invention consis~s in drying the aqueous
., ,-
,
,- : . , ,: :

~5~
- 10 -
solution or dispersion o fluore cent whitener and polymer
to a ine powder, suspending this powder in water, and
mixing this suspension with the washing powder slurry and
drying ~his latter in conventional manner, e~g. tha~ :
described above.
This second vaxiant i~ e~pecial:Ly advantageou~ i~ it i~
not possible to dissolve the flllorescent whitening agent
in the aqueous polymer solution or disper~ion, and only
a dispersion is obtained. In this case, a further enhan-
cement o the appearance o ~he washing powder can be
achieved by irst drying the dispersion. As already
described, it is often advantageous ~o subject the
di persion of the fluorescent whitening agent and polymer
or polymers to a wet grinding procedure before drying this
disper~ion.
The solution, i~ partlcular di~persio~7 can be dried by
conventional methods. The disper~ion can simply be dried in
a drying cab~net~ e.g,, in the temperature range ~rom 40 to
100C, pre:erably from 50 ~o 80C, and the dry substance
obtained i~ ground to a fine powd~rO However, it is
advantageous to dry the dispersion with hot air in a spray
tower to produca a fine powder. The powder containing the
~luorescent whitening agent and polymer or pslymers is
incorporated in the wa~hi~g powder by suspending it in -~-
w~ter a~d adding this suspension to the washing powder
slurry, which is then dried in conventional manner, e.g.
al~o by spray drying.
A further advcmtage af ~he above described second variant
o the process o the invention is that the powder obtained
by drying the dispersion (fluorescent whitener preparation
in powder fo~l) can be easily stored over a prolonged period
.. . . . ~ . .. . . ..
. . ~ . . . . .
,! , ' ;, ,~ ~'
, . . ~ , , . . .

~3~
of time without dis~olouration ~r other diminution of the
quality o the fluorescent whitener. This preparation can
therefore also be used as a commercial formNlation of the
respective fluorescent whitening agent. Regardless of where
the preparation is produced, the! incorporation in a wa~hing
powder can ba e~ected anywhere.
In contradistinction to the variant~ of the proce~9 o the
lnvention, the addition o~ the respective polymQrs and
fluorescent whi~ening agents, without disqolving or
dispersing them in the queou~ polymer solution or
dlspersion, to the washing powder ~eparately, doe~ not
efect the desired ~nhancement of ~he appear~nce of ~he
washing powder (attention is also drawn in this connection --
to the Examples). However, if the washing powder is produced
in the manner according to the invention~ the~, surprisingly,
~here no longer occurs any deter~oration in ~he appearance
of the washing powder during storage, although this would
be expected because of ~he presence o large amounts of
elee~roly~e~ and ~he attendant "~al~ing ou~" action on the
fluorescen~ whi~ening agent.
The proceYs of th~ i~venti~n can b2 used for incorpora~ing
the fluore~c~nt whi~rli~ agen~ in any de~ergenP co~pc)~ltion
in powder for~. Such composition~ preferably contain the
kn~wn mixtures of acti~e detergen~s, for example ~oap in ~~~
the for~ of chips and po~ders, sy~thetics. soluble salts o~
sulfonic acid hemies~er~ o higher ~at~y alcohols, xyl-
~ulonic acids with higher and/or mul~iple alkyl ~ubs~ituent~,
sulfocarbo~li.c acid esters of mediwm to higher alcohols.
fa~ty acid ac~laminoalkyl- or acylami~oaryl-glycerol
sulfona~e~ and pho~phoric acid esters o~ fat y alcohol~.
Suitable builders which oan be us~d axe, for exa~ple, alkali
metal polypho~phates a~d polymetaphosphates, alkali metal
:,'
.
~ . . .
~ ' , :' ' " , ~- ,
,, ,~ . . .
'
' '

~3,~
- 12 -
pyrophospha~Q~ or alumino3ilicat~, alkali metal salt~ o~
carboxgmeth~lcellulose and other soil redeposicion
inhibitors, and also alkali metal. ~ilicates, al~li metal
carbonate , alkali metal sul:eates, alkali metal perborates,
nitrilotriacetic acid, ethylenedi.aminetetraacetic acid,
and foam s~ibilisers, such as alkanolamide of higher atty
acid3. The deter~ent~ can further contain for example:
a~tis~a~c agents, fat res~orati~e skln pro~eetives uch a~
la~olin, en2ym~s, antimicrobial agents, perfum@~, coloura~t~,
and bleaching activator~ ~uch as tetraacetylethylenediamine
or tetraaec~ylglycoloril. Examples o~ sui~able de~ergen~s
will be fou~d in the illu~tra~ive Examples whieh follow.
Incorporation o~ the 1uore~cent whltening a8en~ o the
formulae (1) or (2) in a washing powder by the process of this
inNention r~ults a~ lea~ i~ a stabilising of ~he
appearance of the w~shing p~wd~r, i.e. the washlng powd~r
trcated wi~h fluoresc~nt whitening agan~ is at lea~t as
white in appearance as the washing powder wi~hout
fluorescent whi~ening ageTI~. The of~en.obse~ved greenish
or yellowish diss::olouration of the de~ergent caused by the
addition of fluor~scent w~iteuer can thu3 be a~ro~ded.
Usually, however, the proces~ of ~he invention ef~ec~s a~
enhancemen~ of the appearallcP of the ~ashi~g powder, i~e.
the powder treated wL~h fluoreYcen~ whi~ener has a whlter
appearance han one whi~h does not contain white~ing agent.
The washiry3 powderx ob~c~ined by the process of the iTrven~ion
are most suitabl0 for washing textlles to produce a good
white effec~ orl ~che washed sub~1:rat~.
It is a further obj ect of this inventio~ to provide the
aqueous solutions or dispersions which contain osle or more
fluorescent whitening agents of th~ :Eormulae (1) or (2)~ a polyvinyl
.
~..

- 13 -
alcohol or po~vin~Jl ~ one which ~ ~r-so~bleor sw~ ~ ~ ~r,
and op~on~ly apolyethylene glycolg a surfactant containing
ethyleneoxy and/or propyleneoxy groups, and/or a cellulose
ether9 and which can be incorporated in washing powders
-by the process of the invention. The composition and
preparation o~ these ~olutions or dispersions, as well as
the preerred embodiments o~ these ssLutions or dispersions,
are described above.
It is yet a further ob; ect of the invention to provide the
preparations obtained from the solutions or disp~rsions
desc~ibed above l:~y drying and ~ comprise one or ~re ~orescen'c
whitQning agentæ of the ~ormulae (1~ or (2), a polyvinyl al~ohol
or polyvinyl pyrrolidone, and optionally a polye~hylene ~
glycol, a surfactan~ containing ethyleneo~y and/or
propyleneox~ group~, and/or a cellulose ~ther.
These dry preparations ~erab~ compr~e one or more fluorescent
whitening agen~s of the formulae (1~ or ~2)and a poly~nylak~hol
having a degrae of hydroly~is cf 80 to 100% and a viscosi~y
of 3 to 66 cP, or a polyvinyl pyrrolidone with a molecular
weight of lO~000 to 360,000, the ratio of fluoresee~t
whitening agent to polymer being preferably 9:1 to 1:10,
when using poly~inyl alcohol especially ~rom 80:20 ~o 40:50,
preferably 70:30, and when using polyvinyl pyrrolidone7
especially 1:1 to 1:10.
Most preferably~ in addition to containin~ the fluore~cent
whitening agerlt, such a preparation contains a polyvinyl
alcohol having a degree of hydrolysis of 90 to 100% and a
viscosity of 3 to lOcP.
Preferred fluorescent whitening agents in the above
preparations are those o the formula (4), especially those
of the formula (3), and mixtures thereof.
: . . , ~, : .
.

The following Examples illu~trate the proce~s of the
invention in more detail, without implying any resl:riction
to what is d~scribed therein, as well a~ the solutions or
dispersions employed in this process and the dry preparations .
obtained therefrom.
... . . . . . . . . . ..
. ..... ~ . ~ .

~ ~ 3
- 15 -
ç~ 40 mg of the fluorescent whitening agent of
the formula (3), wherein M' is sodium, are dispersed at
60C in a mixture of 0.2 g of polyvinyl alcohol (viscosity
4 cP, degree of hydrolysis 98%) and 20 ml of water. A
homogeneous paste is obtained by stirring this suspension
at room temperature with 20 g of a detergent of the
following composition in 20 ml of deionised water:
alkylarylsulfonate 17 9 5%
fatty alcohol 3ulfa~e 3.7
coconut ~at~y acid mono-
etha~olamide 2.7%
sodium tripolyphoYphate39.0%
sodium 5ilicate 4.0%
magne9i~m ~ilicate 2.0%
carboxymethyl cellulosel~OV/o
sodium ethylenediami~e~etra-
acetate 0.5%
water 6.7
sodium sulfate to make up 100.0%
This paste (slurry) is spread on a porcelain dish, dried
for 12 hours a~ 30C under 500 torr in a vacuum drying
cabinet, then loosened with a spatula, and subsequently
dried for a further 8 hours at 30C/200 torr. The detergent
is then pressed through a sieve with a 0.8 mm mesh, beneath _
which there is a second sieve with a 0.315 mm mesh.
On this sieve there remains a powder of uniform particle
size which is used for determing the appearance~ The washing
powder so obtained has an attractive white appearance.
Example 2: 30 mg of the fluorescent whitening agent of
the formula (4),wherein M' is potassium, are dissolved

~3~
- 16 -
in a mi~ture of 0.8 g of polyvinyl alcohol (viscosity
4 cP, degree of hydrolysis 98%) and 20 ml of deionised
water. This solution is processed to a paste with a de~en~
of the composition described in Example 1, afording
a washing powder with an attractive white appearance.
Example 3- 30 mg of the fluorescent whitening~agent of
the formula (4), wherein M' is potassium, are dissolved
in a mixture of 20 mg of polyvinyl alcohol (degree of
hydrolysis 97-99%; viscosity 5 cP), 100 mg of polyethylene
glycol 4000 (mol. wt. about 4000) and 20 ml of water.
This solution is processed to a paste with a detergent of the
composition des~bed in Eæampleland the paste is then dried,
a~fording a washing powder with an attractive white
appearance.
The paste (~lurry) can also be dried by spray drying.
Example 4: 30 mg of the fluorescent whitening agent of
the formula (4)7 wherein M' is potassi~m,are dissolved in
a mixture o~ 1 g of polyvinyl p~rrolidone K25 (mol. wt.
about 24,000) and 20 ml of water. This solu~ion is
processed to a paste with 20 g of a detergentofthe composition
described in Example 1 and the paste is dried in the usual
manner and pulverised, affording a washing powder with a
pure white appearance.
Example 5: 30 mg of the fluorescent whitening agent of
the formula (3), wherein M' is potassium, are dissolved
at 80C in a mixture o 200 mg of polyvinyl pyrrolidone
K25 (mol. wt. about 24,000) and 20 ml of water. This so~tion
is stirred to a paste with 20 g of a detergent of the compo-
sition described in Example 1 and the paste is dried in the
-
.. : '. .' ' . ' : ' . ; ' ' :

3L~ 3~r~
- 17 -
usual manner and pulverised, afording a washing powder
with a pure white appearance.
A similar result is obtained using 1000 mg of polyvinyl
pyrrolidone K25.
Example 6: Example 5 is repeated using 1000 mg of poly-
e~hylene glycol 400 (mol. wt. about 400) instead o~ 200 mg
of polyvinyl pyrrolidone K25. A washing powder with an
attractive white appearance is likewise obtained.
Comparl n Example A: 30 mg of the 1uorescent whitening
agentof the formula (3)wh~ein ~ is sodium are stir ~ at20C m 20ml
~ d~sed water which contains about 1 g of a detergent of
the composition indicated in Example 1. Then a further
19 g of the detergent are added and mixed until a homo-
geneous paste is obtained. This paste is spread on a
porcelain dish and dried for 4 hours a~ ~0C/400 torr in
a vacuum drying cabinet, then loosened with a spatula, and
subsequently dried for 3 hours at about 80C under 250 torr~
The washing powder is reduced to small particles and its
appearance determined as described in Example 1. The
washing powder so obtained has an unattractive greenish
appearance which is poorer than that of the washing powder
which does not contain fluorescent whitener.
A washing powder of a greenish hue is likewise o~tained by
substituting the fluorescent whitening agent of the
formula (4), wherein M' is potassium, for that o~ the
formula (3)wherein M' is sodium, and repeating the above
procedure.
: - . .; , .
'.

~ ~ 33 ~O~
- 18 -
Comparison Exam~le B- To the detergent slurry o Comparison
Example A which contains the 1uorescent whitening agent
of the formula (3), wherein M' is sodium, or (4), wherein
M' is po~assium,is additionally mixed, before drying, 0,2 g
of polyvinyl alcohol (viscosity 4 cP, degree of hydrolysis
98%). The slurry is then dried and pulverised as described
in Comparison Example A. The washing powder so obtained
has about as unattractive an appearance as ~hat~of
Comparison Eæample A
This Example shows that it is not suficient to add the
polymers to be employed in the process of the invention to
the detergent, but that the fluorescent whitening agent
must be dissolved or dispersed beforehand in th~
appropriate medium. A subsequent solution or dispersion
in the detergent itself is obviously not possible.
Example 7: A suspension o 50 g of the fluorescent
whitening agent-of the formula (4),~herei~ k~ is ~dium,in 75mlofwater
is dispersed in a solution of 21 g of polyvinyl alcohol
(degreee of hydrolysis 98%j viscosity 4 cP) in 100 ml of
water. The dispersion is ground in a ball mill for 5 hours
at 50C with 250 g of g~ss beads (diame~er lmm). The g~s beads
are then removed and the dispersion is dried by spray
drying with hot air. A white powder is obtained. The
dispersion can also be dried at 50C in a drying cabinet
with subsequent pulverisation of the dry preparation.
The above powder is incorporated in a washing powder by the
following procedure: 70 mg of the dry powder obtained in
this ~xample are suspended in water and this suspension
is added to 25 g of a detergent of the composition as
indicated in Example 1 in 25 ml of water. The resultant
.. . . . .
, . , . ~

~3.~'3
- 19 ~
paste (slurry) is dried either by the method of Example 1
or in a spray tower with hot air. In both cases the
resultant washing powder has a pure white appearance which
it also retains ater storage in moist air.
.
-
,. . . : . ~ . .
. .
- ; ' ~ . : ' ~.
: . . . -
~,. .
. . ..