Note: Descriptions are shown in the official language in which they were submitted.
-
~13S~OS
Case 1-12162/1+2/=
Process for the production of washing powders of stabilised
ox enhanced appearance which contain fluorescent
whitenin~ a~ents
The present invention relates to a process for the
production of washing powders of stabilised or enhanced
appearance which contain one or more ~luorescent whitening
agents of the bis-styrylbiphenyl type.
It has long been known to add fluorescent whiteners to
detergents. Reference is made in this connection e.g. to
Environmental Quality and Safety, Supplement Volume 4,
Fluorescent Whitening Agents, pages 59-62, ed. by Coulston
Korte, G. Thieme Verlag, Stuttgart 1975; German patent
specification 731 558; and numerous other patent
specifications relating to fluorescent whitening agents.
It is also known to add specific fluorescent whitening
agents to detergents in powder form in order to enhance
the appearance of the detergents (see e.g. J. of Color
Appearance~l (1972), 5, page 46).
Like other fluorescent whitening agents of the stilbene-
sulfonic acid type, the compounds of the formula (1) herein
(known from Briti~sh patent~specification 1 247 934) are
most suitable for~whitening and brightening textiles in a
wash bath. If, 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 washing powder, but irequently
even caus~e a deterioration in its appearance. Unattractive ;
35905
- 2 -
greenish-yellow washing powders of reduced commercial value
are obtained in this manner.
The production of washing powders usually comprises
preparing a slurry from the individual components (surface- ;
active substance, 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 subsequently added to the
dry washing powder. Thus non-ionic surfactants can be
sprayed onto the washing powder and/or certain additives,
e,g. perborate, perfumes, enzymes, dyes and other thermo-
labile substances, blended with the otherwise finished
washing powder. Fluorescent whitening agents are usually
added to the slurry before it is spray dried~ The
unattractive greenish-yellow washing powders reerred to
above are usually obtained by means of this procedure.
Even the later addition of fluorescent whitening agents
is not able to effect any stabilising or enhancement of the
appearance. The s`ame problem arises when incorporating
fluorescent whitening agents of the bis-triazinylamino- -
stilbene-disulfonic acid type. Means of improvements have
already been proposed, such as the addition of various
substances, e,g. alcoholsj sugars, certain surface-active
substances etc. 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 suf~icient to
solve the problem on which this invention is based, and
they effect no adequate stabilising or enhancement of the
appearance of ~he washing powder. ~ -
The present inventlon is based on the surprising observation
that it is possible to obtain an excellent white appearance
by a specific process for producingwashing powders which contain
~13S90~
- 3 -
~luorescent whitening agents, and that particularly good
white effects can be obtained on the textlles washed with
these washing powders.
~he process of the present invention for the production of
washing powders of stabilised or enhanced appearance
which contain one or more 1uorescent whitening agents o~
the formula
x ~ C~=C~ .-C~=C8~ . 3 , (l)
Xl . T . ~ ~1
X2. X2
wherein Xl is hydrogen, chlorine, bromine, or alkyl or
alkoxy, each containing 1 to 4 carbon atoms, X2 is hydrogen
or alkyl of 1 to 4~carbon atoms, and M is hydrogen, an
alkali metal, ammonium or amine salt ion, consists in
first dissolving or dispersing the 1uorescent 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 s~olution 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:sub:sequently drying:~this slurry~, or, :
optionally after the~addition of urth:er:~washing powder
components, spraying~said solution or dispersion onto a:
dried un~i:nished washing powder, or drying the solution
or dispersion contalning the fluores~cent 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.
'` 1135905
Preferred alkali metal ions M in formula (1) are sodium
and potassium ions. Suitable amine salt ions M are
principally those of the formula -H~ lR2, wherein Rl is
hydrogen or unsubstituted or substituted alkyl, and R2 is
unsubstituted or substituted alkyl. Preferred substituted
alkyl radicals, which preferably contain 1 to 4 carbon
atoms, are hydroxyalkyl, cyanoalkyl, haloalkyl and benæyl.
M is preferably hydrogen, sodium, potassium, or ammonium~
It is an essential feature of the process of the invention
that the fluorescent whitening agent is dissolved or
dispersed in the mixture o~ water and a polymer (polyvinyl
alcohol or polyvinyl pyrrolidone, or mixtures of these
polymers), as otherwise the desired effect is not achieved.
Particularly advantageous results are obtained with poly-
vinyl alcohol.
" ~
It is preferréd to employ polyvinyl alcohols having a degree
of hydrolysis of 80 to 100 mol.% and a viscosity between 3
and 66 cP, especially those having a degree of hydrolysis
of 9o to 100 mol.% and a viscosity of 3 to 10 cP. In this
specification, all viscosity values indicated for pol~vinyl
alcohol are measured in a 4% aqueous solution at 20C.
Polyvinyl pyrrolidones suitable for the process of the
present invention preferably have a molecular weight of
10~000 to 360,000, especially from 15,000 to 50,000. It
will be appreciated that the term "polyvinyl pyrrolidone" ;~
encompasses not oniy~the polymerisation products of unsub-
stituted vinyl pyrrolidone, but also those of substituted,
e.g.~alkylsubstituted, vinyl pyrrolidones.
:~
The specified polymers form solutions with water~if they
do not have a high molecular weight. However, it suffices
:
~: ,:
~3S~O~
also if the polymers swell or are dispersed in water.
The aqueous mixtures in which the fluorescent whitening
agentis dissolv~ or ~spersed pr~erab:Ly contain atleast 0,01% by
weight, most preferably at least 0.05% by weight, of the
respective polymer. The maximum content of polymer is
determined by the flowability of the mixture obtained and
depends on the molecular weight of the respective polymer.
Where a flowable mixture is obtained, high concentrations
of polymer do not impair the operability o the process.
In practice, suitable concentrations of polymer in the
mixture are preferably between 0.01 and 20% by weight,
especially between 0.05 and 10% by weight.
To enhance the appearance of the finished washing powder `
further, it is possible to add to the mixture of water
and polyvinyl alcohol or polyvinyl pyrrolidone in which
the fluorescent whitening agent is dissolved or dispersed,
a polyethylene glycol, a surface-active substance
containing ethyleneoxy and/or propyleneoxy groups, or a
cellulose ether. An enhanced efect is obtained in particular
with the ~ollowing aubstances:
a) polyethylene glycols,preferably those having a~molecular
weight of 100 to 10,000;
b~ cellulose ethers~,~e.g. hydroxypropyl cellulose, methyl
cellulose, carboxymethyl cellulose, methylhydroxypropyl
cellulose;
c) copolymers of polyethyl e oxide and polypropylene
oxide of the formula
o(c2~4o3x-(c3x6o3y ~(C2H~)z
wherein the content of ethylene oxide (x ~ z)~is 10 to
85% by weight~, a~nd~;that o~ propylene oxide (y)~is 15 :to
90% by weight. The~molecular;weight o~ such polymers~is
between 2000 and 20,000;
~ ~ .
~L~3S90S
- 6 -
d) ethoxylated aliphatic alcohols of the formula
H IC2~4 ) a -OR , .
wherein a is an integer between 10 and 200, especially
between 30 and 200, and R is alkyl of 12 to 20 carbon atoms,
alkenyl of 12 to 18 carbon atoms, or phenylalkyl; - ''
e) ethoxylated alkylphenols o the formula ~
- .
wherein R' is alkyl of 6 to 18 carbon atoms, Z is hydrogen, -'
-S03M' or P03M', in which M' is hydrogen, an alkali metal '' '~'
or ammonium ion, and b is an integer between 6 and 30.
Preferably, the amounts in which the above mentloned ' '~
optional components are added are 1 to 50 ~imes, especially ; '
1 to 20 times, e.g. 1 to 10 times, the amount of polyvinyl ~ -
alcohol or polyvinyl pyrrolidone, or mixtures~thereof,
present in the~aqueous mixture. ~
The fluorescent~whlt~ening a8ent~can~ b~e;~ diss olved or ' '
dispersed e.g~.~at~room temperature~in the~medium consisting
of water and the polymer~specifie~d above~. Frequently, '.
however, it is advantag~eous~to~heat the mixture~, e.~g. to "~
a temperature~ in'the~rànge~from~30;to;100~C,~ pre~erably
from 40~to 80C, es~p'ecially from'~60~to 80C~,~whereby a
more rapid or a~bett;er~solution or~dispersion cf~the flu~
orescent whitener'in the~mixture is~ of~en'achieved. ' ';
If a dispersion~is obtained when~mixing the fluorescent ~ -
whitening agent with~the polymer solution or dispers~ion -
and this:is~usually ~90 -~then lt~can be advantagecus ~to subject ~.
~.~L3~90S
this dispersion to a wet grinding before the addition to
the detergent in order to effect a better dispersion of the ~-
fluorescent whitening agent by reducing the particle si~e.
The wet grinding can be carried out e.g. by adding glass
beads to the dispersion and grinding it in ~ ball mill.
The temperature during the grinding procedure can be in the
range between room temperature and the boiling point of the
dispersion, e.g. between 20 and 80C. Depending on the
desired fineness of the dispersion, the grinding can take
up to several hours, e.g. from 1 to 10 hours.
The amount o~ fluorescent whitening agent to be dissolved
or dispersed depends on the desired amo~nt in the finished
washing powder. It can be e.g. from 0.001 to 10% by weight,
preferably from 0.01 to 5% by weight, especially from
0.05 to 2a/o by weight. Very good results are obtained with
amounts from 0.1 to 0.5% by weight.
',~'
The ratio between the fluorescent whitening agent and the
polymer or polymer mixture in the aqueous solution or
dispersion, or in the dried fluorescent whitener preparation
obtained therefrom, c~an vary within wide limits and depends
on the fluorescent~whitening agent employed and the nature -~
of the polymer or polymers. For example, the ratio of
fluorescent whitening~agent to polymer can he about 9:1 to
lO.~When using~ polyvinyl alcohol, it~is preferably in the
region of 80:20~to 40:50, most preferably of 70:30. When -~
using polyvinyl pyrrolidone, the ratio of fluorescent
whitening agent to~polymer is~e.g~. between l:l and 1:10,
preferably a~out 1:9~
, ;
Withln the scope~of~the process of thls invention, prefsrred
fluorescent whitening;~agents of the formula (l) are those of
the formula
~359(~
X'~ CH=CH~ .-CXsCH~ .-X'l (2)
S03~ S03~
wherein Xl is hydrogen or chlorine and M' is hydrogen,
sodium, potassium or ammonium, or mi~tures of several of
these fluorescent whitening agents, especially those of the
formulae
Cl-~ CH=C~ .-CHsCH ~ -Cl (3) and
3M" S03M"
~ ~ L C~I = C~ C~ ~ C ~
.,
53`~" 50
wherein ~' is hydrogen, sodium or potassium, as well as -~
mixturesof fluorescent~whi~ening agents of the formulae (3)
and (4), especially~those in which M" is~sodium.
The fluoreacent whi~tening agent lS preferably incorporated
in the~detergent by adding the solution~or dispersion
(obtained as~described above;) t~o the~washing~powder slurry
(mixture of the customary~components) and then drying the
slurry containing the~luorescent whitening agent in the
conventional manner. I~ the slurry contains substances
which are~unstable~at~e1evated temperature (e.g.~certain
surfactants,~such as~;those which contain ethyleneoxy
groups)~, then it is dried at low tem*erat~re, e.g. below
3~
g
50C. Normally, however, the slurry is dried at elevated
temperature, e.g. up to 300C, for example by conventional
spray drying or fluidised bed drying.
-The solution or dispersion can, however,
also be sprayed onto the dried washing powder
(e.g. by spray drying in a spray tower) in the conventional
manner employed for obtaining washing powderscontaining
thermolabile substances, e.g. certain surfactants containing
ethyleneoxy groups. This constitutes a very impor~ant
method in practice. It is, however, also possible to mix
the solution or dispersion with suitable detergent
components which are normally adided to the otherwise
finished washing powder at the conclusion of the production
process (e.g. with sodium perborate, bleaching agents such
as chlorine donors, enzymes, parfumes etc.), and then to
apply this mixture to the already existing Fesidual powder.
It is decisive for~the success of the process of the -
invention that the fluorescent whitening agent should be
dissolved or ~inely dispersed in the above described
mixture. The best~results are obtained when the fluorescent
whitening agent is dissolved or very ~inely~dispersed
(e.g. by an additional grinding) in the corresponding
medium.
A second variant o~f incorporating the~fluorescent
whitening agent or~agent;s in the washing powder by the
process o~ the~invention consists in drying ~he asueous
solution or dispersion of fluorescent whitener and polymer
to a fine powder,~suspending this powder in wster, and
mixing this suspension with the washing powder slurry and
drying this latter in conventional manner, e.g. that
described above. ~ -~
; .
- ~3~9(~
- 10 -
This second variant is especially advantageous if it is
not possible to dissolve the fluorescent whitening agent
in the aqueous polymer solution or dispersion, and only
a dispersion is obtainRd, In this case, a further enhan-
cement of the appearance of the washing powder can be
achieved by first drying the dispersion. As already
described9 iL iS often advantageous to subject the
dispersion of the fluorescent whitening agent and polymer
or polymers to a wet grinding procedure before drying this
dispersion.
The solution, in particular dispersion, can be dried by
conventional methods. The dispersion can simply be dried in
a drying cabinet, e.g. in the temperature range from 40 to
100C, preferably from 50 to 80C, and the dry substance
obtained is ground to a fine powder. However, it is
advantageous to dry the dispersion with hot air in a spray
tower to produce a fine powder. The powder containing the
fluorescent whitening agent and polymer or polymers is
incorporated in the washing powder by suspending it in
water and adding this suspension to the washing powder
slurry, which is then dried in conventional manner, e.g.
also by spray drying.
A further advantage of the above described second variant
of the process of the invention is that the powder obtained
by drying the dispersion (fluorescent whitener preparation
in powder form) can be easily stored over a prolonged period
of time without discolouration or other diminution of the
quality of the fluorescent whitener. This preparation can
therefore also be used as a commercial formulation of the
respective fluorescent whitening agent. Regardless of where
the preparation is produced, the incorporation in a washing
powder can be effected anywhere.
~ s~
In contradistinction to the variants of the process of the
invention. the addition of the respective polymers and
fluorescent whitening agents, without dissolving or
dispersing them in the aqueous polymer solution or
dispersion, to the washing powde:r separately, does not
ef~ect the desired enhancement of the appearance o~ the
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, then, surprisingly,
there no longer occurs any deterioration in the appearance
of the washing powder during storage, although this would `
be expected because o~ the presence of large amounts of
electrolytes and the attendant "salting out'l action on the
fluorescent whitening agent.
The process of the invention can be used ~or incorporating
the fluorescent whitening agents in any deter~gent composit`ion
in powder form. Such compositions preferably contain the
known mixtures of active detergents, for example soap in
the form o chips and powders, synthetics1 soluble salts of
sulfonic acid hemiesters of higher fatty alcohols, aryl-
sulfonlc acids~ with~higher and/or multiple alkyl substituents,
sulfocarboxylic acid esters of medium to higher alcohols,
i fatty acid acylaminoalkyl- or acylaminoaryl-glycerol
~,
sul~onates-and phosphoric acid esters~of fatty alcohols.
Suitable builders which can be used are,~for example, alkali
metal polyphosphates and polymetaphosphates, alkali metal
pyrophosphates or aluminosilicates, alkali metal salts of
carboxymethylcellulose and other soil redeposition
inhibitors, and also alkali~metal silicates, al~aLi me~al
carbonates, alkali metal sulates,~alkali metal perborates,
nitxilotriacetic acid,~ethylenediaminet2traacetic acid,
and foam~s~tabilisers,~such~as alkanolamides of higher ~atty
acids. The detergents can further contain for example:
~i3~ 5
- 12 -
antistatic agents, fat restorative skin protectives such as
lanolin, enzymes, antimicrobial agents, perfumes, colourants,
and bleaching activators such as tetraacetylethylenediamine
or tetraacetylglycoloril. Examples of suitable detergents
will be fotmd in the illustrative Examples which follow.
Incorporation of the fluorescent whitening agents o the
formula tl) in a washing powder by the process o~ this
invention results at least in a stabilising of the
appearance of the washing powder, i.e. the washing powder
treated with fluorescent whitening agent is at least as
white in appearance as the washing powder without
fluorescent whitening agent. The o~ten observed greenish
or yellowish discolouration of the detergent caused by the
addition of fluorescent whitener can thus be avoided.
Usua~lly, however, the process of the inventioh ef~ects an
enhancement of the appearance of the washing powder, i.e.
the powder treated with fluore5cent whitener has a whiter i.
appearance than one which does not contain whitening agent. ,
The wasKing powders obtained by the process of the invention
are most sùitable for washing textiles to produce a good
white effect on the~w~ashed substrates.
It is a further object of this invention~to provide the -~
aqueous solutions or dispersions~which contain one or more
fluorescent whitening agents of~the ormula (1), a polyvinyl
aIcohol or~p~lyvinyl~p ~ olidone;which isw~er-solubleor swells in water~
and optiona~y a polyethylene glycol, a surfactant containing
ethyleneoxy and/or~propyleneoxy~groups, and/or a cellulose
ethèr, and which can~be incorporated in washing powders
by the process~of the invention. The composition and
preparatlon ofi~these solutions~or dlsper~slons, as~ well as
the preferred~embodiments of these solutions or d~ispersions,
are described~above.
~35~9(~;
- 13 -
It is yet a further object of the invention to provide the
preparations obtained from the solutions or dispersions
described above and which comprise one or more fluorescent
whitening agents of the formula (1), a polyvinyl alcohol
or polyvinyl pyrrolidone, and optionally a polyethylene
glycol, a surfactant containing ethyleneoxy and/or
propyleneoxy groups, and/or a cellulose ether.
.
These dry preparations comprise one or more fluorescent
whitening agents of the formula (1) and a polyvinyl alcohol
having a degree of hydrolysis of 80 to 100% and a viscosity
of 3 to 66 cP, or a polyvinyl pyrrolidone with a molecular
weight of 10~000 to 360,000, the ratio of fluorescent
whitening agent to polymer being preferably 9:1 to 1:10,
when using polyvinyl alcohol especially from 80:20 to 40:50,
preferably 70:30, and when using polyvinyl pyrrolidone,
especially 1:1 to 1:10.
,
Most preferably, in addition to containing the fluorescent
whitening agent, 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 of the formula (4), especially those
of the formula (3),~ and mixtures therèof.
The following Examples illustrate th~e process of the
invention in mo~re detail, without implying any~restriction
to what is described~therein, as well as the solutions or
dispers~lons employed~in this~process and the dry preparations~
obtained therefrom.
3~5
~ E~ 20 mg of the fluorescent whitening agent of
the formula (3), wherein M" is sodium, together with 20 mg
of polyvinyl alcohol (degree of hydrolysis 99%; viscosity
28 cP) are dissolved at 60C in 20 ml of deionised water.
A homogeneous paste is obtained by stirring this solution
at room temperature with 20 g of a detergent of the
following composition in 20 ml of deionised water:
alkylarylsulfonate 17.5%
fatty alcohol sulfate3.7%
coconut fatty acid mono
ethanolamide 2.7%
sodium tripolyphosphate39.0%
sodium silicate 4.0%
magnesium silicate 2.0%
carboxymethyl cellulose1.0%
sodium ethylenediaminetetra-
acetate 0.5~/0
water 6.7%
sodium sulfate to make up 100.0% ~;
This paste (slurry) is spread on a porcelain dish, dried
for 10 hours at 80C under 150 torr in a vacuum drying
cabinet. 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 determining the
appearance. The washing powder so obtained has an attractive
white appearance.
`
,, : , :
~; ~ 3i:~E9~ Th~ proc~dure or Exar~'e 1 ls repeated using
lOO mg of the~fluorescent whitening agent of the formula (4),
wherein M" is sodium, and 100 mg of polyvinyl alcohol. A washing
' powder with an attractive~white appearance is likewise obtained.
,~
- ~1359C~S
Example 3: 20 mg of the fluorescent whitening agent of the
formula (3), wherein M" is sodium, are dissolved in a mixture
of 20 mg of polyvinyl alcohol (v:iscosity 5 cP; degree of
hydrolysis 97-99%), 100 mg of polyethylene glycol (mol. wt.
about 400), and 20 ml o~ water. A homogeneous paste is
obtained by stirring this solution at room temperature with
20 g of a detergent of the compo~3ition of Example 1 in 20 ml
of deionised water. This paste is dried for 2 hours at 80C
in vacuo and then pulverised. A washing powder with a pure
white appearance is obtained.
Example 4: White washing powders are also obtained by
repeating the procedure of Example 3 and substituting the
substances listed in Table 1 for polyethylene glycol.
~:
- Table 1
Additive ~ Amount Appearance of the resultant
mg) washin~ powder
polyethylene glycol~ ~ ;
4000 (mol. wt. = about
4000) ~ ~ ~ 200 ~ white
"Pluronlc;L 92"*~ ~ 200 ~whlte
"Pluronlc F 68~'i* ~ 200 ~ ~ white
; "Pluronic F 108"~ 200 white
polyethylene oxide
(mol. wt. - about;
4000) ~ ~ 140 ~white
The substances liste~d~in Table l under the name "Pluronic" *
are polymerisation products of the~formula
0~(c2H4o)x-(c3H6o) -(C2H40) H
* Trade ~ark~
~ ~ 3~9 0 5
- 16 -
"Pluronic L 92" has about a 20% content of ethylene oxide
and a molecular weight of about 3500; "Pluronic F 68" has
abo-ut an 80% ethylene oxide content and a molecular weight
of about 9000; and "Pluronic F 108" has about an 80% ethylene
oxide content and a molecular weight of about 17,000.
Example 5: 20 mg of the fluorescent whitening agent of
the ormula (3)~ wherein M" is sodium, are dissolved in a
mixture of 20 mg of polyvinyl alcohol (degree of hydrolysis
97-99%; viscosity ~8 cP) and 140 mg of polyethylene glycol
400 (mol. wt. about 400), and 20 ml of water. The mixture
is processed to a slurry and the slurry is dried as in
Example 3. A washing powder with a very white appearance
is obtained.
By dispensing with the addition of 140 mg of polyethylene
glycol 400, the resultant white washing powder has a faintly
greenish hue.
~: ~
Example 6: The procedure of Example 5 is repeated,
substituting the substances listed in Table 2 for 140 mg o
-
polyethylene glycol~400. Washing powders with a very white
appearance are also obtained.
: ~ : : :
:
3S~5
- 17 -
Table 2
Additive Amount Appearance o the resultant
(m~)washing powder
hydroxypropyl cellulose
(mol. wt. about 60000) 200 white
methylhydroxypropyl
cellulose 200 white
methyl cellulose 200 white
coconut fatty acid
diethanolamide 200 white
C-decylbetaine 200 white
~. :
If the procedure of this Example is repeated without the
addition of polyvinyl alcohol, the washing powders obtained
are yellow in appearance.
Example 7: 100 mg of the 1uorescent whitening ~gent of
the formula (4), wherein M" is sodium, are dissolved in a
mixture of 1 g of polyvinyl pyrrolidone K 25 (mol. wt. about
24,0Q0) and 20 ml of water. A paste (slurry) is prepared
with this solution as described in Example 3 and then
dried. The resultant washing powder has a pure white
appearance.
~:
Example 8: 20 mg o~the fluorescent whitening agent of the
formula (3), wherein M" is sodium, are dissolved in a mixture
of 1 g of polyvlnyl;~pyrrolidone K 25 (mol. wt. about 24,~0C03
and 20 ml~of ~a~er. The s~lution is stirred with 20 g o~ a
washing powder of the composition indicated in Example 1 and - ;
the paste~so obtained is~drled for 2 hours in a vacuum
cabinet at 80C. After~it~has been pulverised, the washing
powder is sieved and the granulate havlng a particle size
: :: : ~ :
3~359
- 18 -
between 0.3 and 0.8 mm is evaluted visually. The washing
powder has a pure white appearance.
~xample 9: The procedure of Example 8 is repeated,
substituting equal amounts of the polyvinyl pyrrolidones
listed in Table 3 for polyvinyl pyrrolidone K 25. Washing
powders with a very white appearance are also obtained.
Table 3
Polyvinyl pyrrolidone molecular Appearance of the ;
weight (approx.~ washing powder
KlO 10,000 white
K30 40,000 white
K60 160,000 white
K90 360,000 white
,
Example 10: 20 mg of the fluorescent whitening agent of
the formula (3), wherein M" is sodium, are dissolved in a
mixture of 100 mg of polyvinyl pyrrolidone K 25 (mol. wt.
about 24,000) and 20 ml of water. The solution is stirred
to a paste with 20;g of a washing powder of the following
composition:
alkanoylbenzenesulfonate~ 8%
ethoxylated fatty alcohol 2.9%
soap 3.5%
sodium tripolyphosphate ~ 43.8%
sodium si]icate ~ 7.5~
carboxymethyl cellulose1.2%
sodium ethylenediaminetetra-
acetate~ ~ ~ 0.2%
: :
~L3S9V5
- 19 -
sodium sulfate 21.2%
water to make up 100.0%
After addition of 60 ml of water, the suspension is dried
in a spray tower with hot air (about 200C). The washing
powder so obtained has a pure white appearance.
Example 11: 20 mg of the fluorescent whitening agent o~
the formula (3), wherein M" is sodium, are dissolved in a
mixture of 1 g of an alkylated polyvinyl pyrrolidone
copolymer and 20 ml of water. This solution is incorporated
in a washing powder as described in Example 1 and the
resultant slurry is dried. A washing powder of very white
appearance is obtained.
Example 12: 20 mg of the fluorescent whitening agent of
the formula (3j, wherein M" is sodium, are dissolved at 60C
in a mixture of 20;mg of polyvinyl alcohol (degree of ~`
hydrolysis~100%, viscosity 66 cP), 100 mg of the surfactant
of the formula
Hl9C9 \ /--o(c~2c~2o)9so3Na
and 20 ml o deionised water. This solution is stirred to
a paste at~room temperature wlth 20~g of a detergent of the
compositlon Oe Example~ The paste is subsequently dried
for lO~hours at 80C~under 100 torr. The detergènt~is
pulverised and evaluated as in Example l. The resultant
washing powder ~as~an attractive;white appearance.
~1359/~;
- 20 -
Example 13: 20 mg of the fluorescent whitening agent o
the formula (3), wherein ~' is sodium, are dissolved in
a mixture of 20 mg of polyvinyl alcohol (degree of
hydrolysis g8%; viscosity 4 cP), 200 mg of a polyethylene
oxide cetyl ether of the formula H(C2H40)30-0-C16H33, and
20 ml of water. This solution is stirred to a paste at
room temperature with 20 g of a detergent composition as
described in Example 1. This paste is subsequently dried
for 2 hours at 80C in a vacuum drying cabinet. The residue
is pulverised and the washing powder is sieved. The
granulate having a particle size between 0.3 and 0.8 mm is
evaluated visually. It has an attractive white appearance.
A washing powder with a pure white appearance is likewise
obtained by substituting a polyethylene o~ide cetyl ether
of the formula H(C2H4)80--C16H33
formula H(C2H4)30--C16H33'
,
Comparison Example~A:~ 20 mg of the fluorescent whitening
agent of the formula (3)~ wherein ~' is sodium~ are stirred
at 20C in 20 ml of deionised water which contains about
1 g of a detergent of~the composition~indica~ed in Example 1.
Then a further 19 g of the detergent are added and mixed
until a homogeneous paste is obtained. This paste is spread
on a porcelain dish and dried or 4 hours~ at;80C/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 whitening agent.
~:
3S~O~
- 21 -
Comparison Example B: To the detergent slurry of
Comparison Example A which contains the 1uorescent
whitening agent of the formula (3), wherein M" is sodium,
is additionally mixed, before drying, 20 mg of polyvinyl
~lcohol (viscosity 28 cP, degree of hydrolysis 99%). 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 that o Comparison
Example A.
This Example shows that it is not sufficient 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 the appropriate
mediumO A subsequent solution in the detergent itself is
obviously not possible.
.
Example 14: A suspension of 70 g of the fluorescent
whitening agent of the formula (3), wherein M" is sodium,
in 130 ml of water is dispersed in a solution of 30 g of
polyvinyl alcohol (degree of hydrolysis 98%; viscosity 4 cP)in ~ -
lOOml of water.The dispersionis groundin a ~1 mill for8hours at80C
with 350 g of glass beads (diameter l mm). The glass beads
are removed and the dispersion is then dried by spray dry-
ing with hot air. The resultant powder has a brilliant pure
white appearance.
~ ~ .
The above powder is incorporated in a washing powder by the
following procedure: I00 mg of the dry powder obtained in : i
this Example are suspended in~water and this suspension
is added to 70 g of a~detergent of the composition as
indicated in Example l in 70 ml of water. The resultant
~paste (slurry) is dried either by the method of Example 1
or in a spray tower with hot alr.~In both cases the~
. ,
.3~i90~
- 2~ -
resultant washing powder has a pure white appearance which
it also retains after storage in moist air.
Example 15: A suspension o~ 50 g of the fluorescent
whitening agent of the formula (3), wherein M" is sodium,
in 130 ml of water is dispersed in a solution o SO g of
polyvinyl alcohol (degree of hydrolysis 98%; viscosity
4 cP) in 100 ml of water. The dispersion is ground for
8 hours at 30C in a ball mill with 350 g of glass beads
(diameter 1 mm). The glass beads are removed and the dispersion
is then dried at 50C in a drying cabinet and subsequently
pulverised. A pure white powder is obtained,
The above powder is incorporated in a washing powder by the
following procedure: 100 mg of the dry powder obtained in ~;
this Example are suspended in water and this suspension is
added to SOg of a detergent of the composition~as indicated
in Example 1 in SO ml of water. The resultant paste (slurry)
is dried either by the method of Example l or in a spray
tower with hot air. In both cases the resultant washing
powder has a pure white appearance which it also retains
after storage in moist air.
Example 16:~ A suspension o~ 41 g of~the fluorescent
whitening agent o~ the formula (3), wherein M" is sodium
and 28 g of the fluorescent whitening agent of the formula
(4), wherein ~' is sodium, in 80 ml of water, is dispersed
in a solution of 31 g of~polyvinyl alcohol (degree of ~-
hydrolysis 98%; viscosity 4 cP) in 100 ml of water. The ~
:
dispersion is dried with hot air in a spray tower. The
resultant powder contalning fluorescent whitening agent
and polyvlnyl alcohol~ has a brilliant white apperance.
~L13S9(~
- 23 -
The above powder is incorporated in a washing powder bg the
following procedure: 100 mg of the dry powder obtained in
this Example are suspended in water and this suspension
is added to 70 g of a detergent of the composition as
-indicated in Example 1 in 70 ml of water. The resultant
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 after storage in moist air.
Example 17: A suspension of 41 g o the fluorescent
whitening agent of the formula t3), wherein M" is sodium,
and 28 g of the fluorescent whitening agent of the formula
(4), wherein M" is sodium, in 80 ml of water, is dispersed
in a solution of 31 g of polyvinyl alcohol (degree of
hydrolysis 98%; viscosity 4 cP) in 100 ml of water. The
dispersion is ground in a ball mill for 8 hours at 50C ~ -
with 350 g of glass beads. The glass beads are then
removed and the dispersion is dried by spray drying with
hot air. The dispersion can also be dried at 50C in a
drying cabinet with subsequent pulverisation of the dry
preparation. In each case the powder containlng fluorescent
whitening agent and polyvinyl alcohol has a pure white
~ appearance.
::~: :
The incorporation~of the powder in the washing powder is
carried out as described in Example 16.
:~ ' "
Example 18: Example 16 or 17 is repeated using a mixture
.
of 20 g of polyvinyl alcohol and 11 g of sodium tripoly-
phosphate instead of 31 g of~polyvinyl alcohol. A powder
of pure white appearance is likewise obtained. The addition
: ~':,, ~ .
~ ' :
3S 9
- 24 -
o~ sodium tripolyphosphate facilitates the spray drying
of the dispersion.
The incorporation of the preparation in a washing powder
is effected as described in the preceding ~xamples,
.
Example 19: A suspension of 10 g of the fluorescent
whitening agent of the formula (3), wherein M" is sodium,
in 20 ml of water is dispersed in a solution of 90 g of
polyvinyl pyrrolidone K25 (molecular weight about 24,000)
in 180 ml of water. The dispersion i9 dried by spray
drying with hot air or in a drying cabinet at 50C~ In
the latter case, the dry powder is additionally pulverised.
The resultant powder of polyvinyl pyrrolldone and fluor-
escent whitening age~t has a pure white appearance.
;:
The above powder is incorporated in a washing powder by
the following procedure: 100 mg of the dry powder obtained
in this Example are suspended in water and this suspe~sion -~
is added to 10 g of a detergent of the composition as
indicated in Exampl~e 1 in 10 ml of water. The resultant
paste (slurry) is dri~ed either by the method of Example 1
or in a spray tower with hot air, In each case the
resultant washing powder has a pure white appearance which
it also retains after storage in molst air, ~ -
~ :
~ :
,
: :: ,.
