CA1135905A - Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents - Google Patents
Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agentsInfo
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- CA1135905A CA1135905A CA000341383A CA341383A CA1135905A CA 1135905 A CA1135905 A CA 1135905A CA 000341383 A CA000341383 A CA 000341383A CA 341383 A CA341383 A CA 341383A CA 1135905 A CA1135905 A CA 1135905A
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- fluorescent whitening
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Abstract
Case 1-12162/1+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
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
Description
-~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 ;
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 ;
- 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~
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
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(~
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 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(~;
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 "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 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 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 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/~;
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~
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
~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
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(~
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 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(~;
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 "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 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 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 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/~;
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~
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(~
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 : ~':,, ~ .
~ ' :
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, ~ -~ :
~ :
, : :: ,.
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(~
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 : ~':,, ~ .
~ ' :
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, ~ -~ :
~ :
, : :: ,.
Claims (39)
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 (1) wherein X1 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, 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 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.
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 addition 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 obtaind 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 or agents 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.
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 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 dispersed, additionally contains a polyethylene glycol, a surfactant 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 molecular 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 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-ORR
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 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.
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 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 accelerated by heating in the temperature range from 40°
to 80°C.
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.
17. A process according to claim 1, which comprises the use of a fluorescent whitening agent of the formula , wherein X'1 is hydrogen or chlorine and M' is hydrogen, sodium, potassium or ammonium, or mixtures of several such fluorescent whitening agents.
18. A process according to claim 17, which comprises the use of a fluorescent whitening agent of the formula wherein M" is hydrogen, sodium or potassium.
19. A process according to claim 17, which comprises the use of a fluorescent whitening agent of the formula wherein M" is hydrogen, sodium or potassium.
20. A process according to claim 17, which comprises the use of a mixture of the fluorescent whitening agents as defined in claims 18 and 19, wherein M" is sodium.
21. An aqueous solution or dispersion containing one or more fluorescent whitening agents of the formula (1) , wherein X1 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, 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.
22. A solution or dispersion according to claim 21, which contains one or more fluorescent whitening agents of the formula (1), 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.
23. A solution or dispersion according to claim 22, which contains one or more fluorescent whitening agents of the formula (1) and a polyvinyl alcohol, the ratio of fluorescent whitening agent to polyvinyl alcohol being 80:20 to 40:50.
24. A solution or dispersion according to claim 22, which contains one or more fluorescent whitening agents of the formula (1) and a polyvinyl pyrrolidone, the ratio of fluorescent whitening agent to polyvinyl pyrrolidone being 1:1 to 1:10.
25. A solution or dispersion according to claim 21, which contains at least 0.01% by weight of the respective poly-mer.
26. A solution or dispersion according to claim 22, which contains a polyvinyl alcohol having a degree of hydrolysis of 90 to 100% and a viscosity of 3 to 10 cP.
27. A solution or dispersion according to claim 21, which, in addition to containing the fluorescent whitening agent or agents and polyvinyl alcohol or polyvinyl pyrrolidone, contains a polyethylene glycol, a surfactant containing ethyleneoxy and/or propyleneoxy groups, or a cellulose ether.
28. A solution or dispersion according to claim 21, which contains a fluorescent whitening agent of the formula wherein M" is hydrogen, sodium or potassium.
29. A solution or dispersion according to claim 21, which contains a fluorescent whitening agent of the formula wherein M" is hydrogen, sodium or potassium.
30. A solution or dispersion according to claim 21, which contains a mixture of the fluorescent whitening agents defined in claims 28 and 29, wherein M" is sodium.
31. A preparation consisting of one or more fluorescent whitening agents of the formula (1) , wherein X1 is hydrogen, chlorine, bromine, or alkyl or alkoxy, each containlng 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, 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.
32. A preparation according to claim 31 consisting of one or more fluorescent whitening agents of the formula (1), 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.
33. A preparation according to claim 32 consisting of one or more fluorescent whitening agents of the formula (1) and a polyvinyl alcohol, the ratio of fluorescent:whitening agent to polyvinyl alcohol being 80:20 to 40:50.
34. A preparation according to claim 32 consisting of one or more fluorescent whitening agents of the formula (1) and a polyvinyl pyrrolidone, the ratio of fluorescent whitening agent to polyvinyl pyrrolidone being 1:1 to 1:10.
35. A preparation according to either of claims 32 or 33, which contains a polyvinyl alcohol having a degree of hydrolysis of 90 to 100% and a viscosity of 3 to 10 cP.
36. A preparation according to claim 31 consisting of one or more fluorescent whitening agents of the formula (1), a polyvinyl alcohol or a polyvinyl pyrrolidone and a polyethylene glycol having a molecular weight between 100 to 10,000, a cellulose ether, a copolymer of poly-ethylene 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 , 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.
37. A preparation according to claim 31, which contains a fluorescent whitening agent of the formula wherein M" is hydrogen, sodium or potassium.
38. A preparation according to claim 31, which contains a fluorescent whitening agent of the formula wherein M" is hydrogen, sodium or potassiam.
39. A preparation according to claim 31, which contains a mixture of the fluorescent whitening agents defined in clalms 28 and 29, wherein M" is sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000341383A CA1135905A (en) | 1979-12-06 | 1979-12-06 | Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000341383A CA1135905A (en) | 1979-12-06 | 1979-12-06 | Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1135905A true CA1135905A (en) | 1982-11-23 |
Family
ID=4115767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000341383A Expired CA1135905A (en) | 1979-12-06 | 1979-12-06 | Process for the production of washing powders of stabilized or enhanced appearance which contain fluorescent whitening agents |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1135905A (en) |
-
1979
- 1979-12-06 CA CA000341383A patent/CA1135905A/en not_active Expired
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