MXPA99008684A - Procedure for obtaining colorants and / or black preparations - Google Patents

Abstract

Process for obtaining preparations containing dyes and / or bleaches, having at least one SO3H- and / or free COOH group, characterized in that an aqueous suspension is applied, which contains a) dyes and / or bleaches, which at least have a group S03H- and / or COOH- free and b) inorganic synthesis salts, with a microfiltration membrane with a pore diameter of 0.05 to 40

Description

PROCEDURE FOR THE OBTAINING OF COLORANTS AND / OR WHITENING PREPARATIONS.

Field of the invention.

The invention relates to processes for obtaining dyes and / or bleaching preparations.

Description of the prior art.

According to Patent No. EP-A-835 906 disclosures of optical brighteners with SO3H- groups are disclosed for bleaching paper. Since the synthetic salts, which are formed during the manufacture of the bleaches, greatly impair further dissolution with sodium hydroxide solution in terms of the maximum possible concentration of bleaches, the content of the bleaches must also be kept as low as possible. in salts in the aqueous dispersions of optical brighteners with SO3H- groups. In the Patent No. EP-A-835 906 the elimination of the salts is carried out, for example, in such a way that the press cake of the bleach is washed with demineralized water. The drawback of this procedure REF. 85132 resides, on the one hand, in that high losses of product must be suffered when the cakes or press pastes are handled and, on the other hand, in that only conditions of elimination of the moderate and non-reproducible salts are had due to the formation of channels in the press cake, which ensures a good elimination of salts only locally limited.

Detailed description of the invention. - - A process has now been found with which it is possible to eliminate the previously described drawbacks of the state of the art. Thus the invention relates to a process for obtaining dye-containing and / or bleaching preparations, which at least have a group S03H- ~~; / or COOH-free, characterized in that an aqueous suspension is submitted, which contains: a) dyes and / or bleaches, which at least have a group S03H- and / or COOH- free and b) inorganic synthesis salts, to an elimination of the salts with a microfiltration membrane with a pore diameter of 0.05 to 40 μm. The colorants and / or the bleaches with at least one S03H- and / or COOH-free group can obviously also be present together with their salt forms (for example alkali, alkaline earth or ammonium salts). However, it is preferred that at least one dye and / or bleach is present at least 90 mol% in the form of its free acid. The microfiltration membrane used can be operated, for example, in the cross-flow working mode. For membrane filtration with a transverse current, microporous membranes are preferably used in the form of capillaries, tubes or in the form of a spiral wound module. The membranes are produced, for example, from inorganic (for example TIO2 Zr02, A1203) or organic materials (for example polypropylene or partially or fully fluorinated polymers, polysulfone, polyethersulfone), the diameter of the pores being preferably from 0.05 to 3.0. μm. The shape of the cross-flow process is characterized in that the membranes are tangentially swept by the product solution / suspension. In this case, transmembrane pressures of 1 to 10 bar are preferably applied. It is also preferable to carry out a periodic rinsing of the permeate side in order to maintain high permeate yields.

The process according to the invention works in a particularly advantageous manner when the pH value of the suspension to be released from the salts is between 1 and 6, especially between 2 and 5. It is also advantageous that the acid form (S03H and / or COOH) ) of the dye or of the bleach has a solubility in water of less than 5 g / 1, preferably less than 1 g / 1 under the corresponding process conditions. . The process according to the invention will preferably be applied for the removal of dye and / or bleach salts, especially whiteners, containing SO3H- groups. The amount of dye and / or preferred bleach in the aqueous suspension to be released from the salts amounts to 100 to 500 g / 1, especially 150 to 400 g / 1 of the aqueous suspension to be released from the salts. In this case, the salt content in the suspension is, before the removal of the salts, in general from 1 to 25, preferably from 2 to 8% by weight, based on the suspension. The content of inorganic salts to be preferably adjusted by means of the process according to the invention is <1% by weight, especially less than 0.5% by weight. The inorganic synthesis salts are preferably constituted by halides, sulfates or alkali hydrogensulphates. The removal of the salts according to the invention is preferably carried out at a temperature of 25 to 70 ° C, especially 30 to 50 ° C. The removal of the salts can be carried out in this case by concentration or diafiltration. In the case of diafiltration, the permeate formed by completely desalinated water will be continuously replaced. It is particularly preferable that those of the formulas (I), (II) and / or (III) will be used in the process according to the invention as optical brighteners, wherein M means H, Ri and R-2 / independently from each other, mean -NH2, -NHCH3, -NHC2H5, -N (CH3) 2, -N (C2H5) 2, -NHCH2CH2OH, -NHCH2CHzCH2OH, -N ( CH2CH2OH) 2, -N (CH2CH2CH2OH) 2, -N (CH3) (CH2CH2OH), -NHCH2CH2OCH2CH2OH, - HCH2CH2CH2S03H, -OH, -OCH3, -OCH (CH3) 2, -OCH2CH2OCH3, ' where M has the meaning indicated above; or the formula wherein R3 signifies hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen or S03H, and R4 signifies hydrogen or alkyl having 1 to 4 carbon atoms and M has the meaning indicated above; also the formula in which M has the meaning indicated above and R5 and R6, independently of each other, mean hydrogen, CH3, R5 and R6 together signify the complementary part for a benzene ring. Particularly preferred are those bleaches of the formula (I), especially those of the formula (la) lia) It is also advantageous to combine the process according to the invention with a concentration, for example by eliminating the water by means of membrane technology. If necessary, the size of the particles of the dye or bleach suspension can be adjusted before, during or after the process according to the invention by means of a wet comminution process, such as, for example, grinding with Cavitron, disperser technology. to jet, grinding with pearls etc. The dye and / or bleach dispersions obtained according to the process of the invention can be mixed or homogenized, for example after addition of other additives such as polyvinyl pyrrolidone, commercially available anionic dispersing agents such as, for example, condensates of formaldehyde-naphthalene acid sulphonic or other condensation products consisting of aromatic sulfonic acids and formaldehyde or starch decomposition products, such as, for example, anionic polyhydroxy compounds, preferably xanthan, and can then be used for dyeing or bleaching paper pulp in the manufacture of paper and for bleaching or dyeing the masses for brush application in the brush application usually employed in the paper industry, the latter being paper pulps and masses for brush application not pigmented or, preferably, pigmented. However, other additives may also include reducing agents and preservatives. The bleaches are preferably applied in three ways in papermaking: Mass: This is the cellulose suspension before the paper is made. In this case, bleaches with two sulfo groups are preferably used. Masses applicable to brush, paint: In this case a coating is applied after the drying part on the finished paper. The masses applicable to brush contain, in addition to the optical brighteners, preferably those with 6 sulfo groups, among other pigments (chalk, kaolin), latex type binders, coagglutinants and dispersing agents. Gluing press: After the drying part the almost finished paper passes through the gluing press, which can be constituted for example by rollers that rotate in opposite directions, which in turn rotate through a liquid containing starch and optical brightener. The application can, however, also be carried out via Foulard or sprayed, after which a drying part is preferably found. During the application of the dye and / or bleach dispersions prepared according to the process of the invention, an alkaline pH value is desirable for a perfect solution. In the case of the masses applicable to the brush, this pH value must be above all in the range of 8 to 11 and in the case of the masses above all from 7.5 to 9. The desired pH value can be adjusted, for example by means of addition of NaOH preferably adjusting this pH value in the dispersion of the dye or in the mass applicable by brush already before the addition of the bleach dispersion.

When alkaline fillers such as precipitated or natural calcium carbonate are used, the addition of alkalis may be abandoned.

Not only can the production of dyes or bleach preparations containing S = 3H- or COOH- be improved, but also the manufacture of their salts, especially their aqueous solutions. The water-soluble organic bleaches or dyes are obtained at the end of the synthesis in general in the form of dilute aqueous solutions, which are contaminated as by-products which also contain, as a function of the synthesis, inorganic salts, for example chloride sulfates of alkali metals. In order to manufacture ready-to-market preparations from such raw solutions, they have to be concentrated and released as broadly as possible from the salts and by-products. A high salt content has, above all, a negative effect on the preservation of the liquid formulations, while the secondary products, which frequently also have their own color, can lead to a displacement of the color tone. Processes corresponding to the technology of the membranes for the purification of the corresponding salts of the dyes or of the bleaches are already known. In general, solutions are employed, that is to say with comparatively low concentrations, preferably membranes with sufficient retention for the dissolved species (UF, NF) being used. The ultrafiltration (UF) or nanofiltration (NF) membranes require working pressures greater than 10 bar and therefore result in high operating costs. EP-A 107 006 already describes methods for the purification of corresponding suspensions of dyes and bleaching agents. Disadvantage: we work with a membrane procedure with two stages with different WWCO's. The high residual solubility of the alkali metal salts used (anionic colorants / bleaches) requires, for the application of UF + NF, membranes with the disadvantages described above. The task of the present invention is to improve the existing separation procedures. First of all, a high speed of passage is sought with reduced working pressures, improved performance in the elimination of salts and, in general, high safety at work. The invention therefore also relates to a process for the preparation of dye and / or anionic bleach preparations, having at least one group S03H- and / or a group COOH-, wherein M = means alkali or ammonium, because i) an aqueous suspension, containing a) dyes and / or bleaches, having at least one -S03H- and / or COOH- free group and b) inorganic synthesis salts is subjected to a removal of the salts with a membrane of microfiltration with pore diameters from 0.05 to 40 μm AND ii) after the elimination of the salts, the dyes and / or suspended bleaches are dissolved, by the addition of hydroxides, carbonates and / or alkali or ammonium bicarbonates, and / or amines and iii) the dye and / or bleach solution obtained according to ii) is freed from the colloidal and / or insoluble components, if necessary after addition of other additives, especially solvents, with a microfiltration membrane with diametre. of pores from 0.05 to 40 μm. For the stage i) of this process, the same preferred ranges as in the case of the process according to the invention for obtaining dyes or bleaches containing groups are valid.

S03H- or COOH-. For step ii) of the process according to the invention, preference is given to using NaOH, LiOH, KOH, K2CO3, Na2CO3, NR2R3R4OH, NR2 R2R3, where R1 R2, R3 and 4 mean H, alkyl, aryl (optionally substituted) ), for the solution of the colorant or of the dispersed bleach. KOH are preferred, LiOH, N (CH3) 40H, H2NCH2CH2OH, HN (CH2CH2OH) 2 and H2NCH2CH2NHCH2CH2? H. If desired, one or more solvents may be added in step ii), for example e-caprolactam, urea, triethylene glycol, polyethylene glycol, propanediol, l-ethoxy-2-propanol and / or diethylene glycol. By choosing the base (s) used, the counterion for the dye or the anionic bleach can be determined. For step iii) of the process according to the invention, preferably those which have already been described above will be used as microfiltration membranes. The membranes used in steps i) and iii) are in this case independent of one another. These may be identical but they do not have to be. Thus, another material and / or another form of construction of the module can be used perfectly than in the case of step i). Preferably, the membranes used for step iii) have, however, pore sizes that are above the size of the optical brighteners, or of the anionic dyes or their aggregates in solution. Stage iii) is preferably carried out as dead-end filtration. The "dead-end" mode means that the membrane or that. The membrane filter is not tangentially traversed for most of the permeation time. For example, transverse current devices can be used in the indicated manner when the side of the retentate is completely closed and only opens periodically for a short period of time, for the discharge of the retained particles. The separation of the colloidal and / or insoluble components is preferably carried out at a temperature of from 40 to 100 ° C, preferably from 50 to B0 ° C. By the corresponding choice of membrane for stage iii) preferably with pore diameter <; 0.2 μm, this filtration can also be carried out as a sterile filtration. The dye or bleach solution obtained after step iii) of the process according to the invention can be dried, optionally after addition of auxiliary agents of the formulation, by elimination of the water to give a dye or bleacher preparation. solid, (powder or granulate) and, if necessary, after the addition of auxiliary agents of the formulation such as solubilizers (urea, urea derivatives, glycols, polyglycols, alkanolamines, lactams such as e-caprolactam, etc.), can be used subsequently as stable liquid formulations.

The invention also relates to the bleaches of the formula la in the form of Bis-TN (CH 3) 4 (Ib) salt as well as in the form of Bis-TH 2 N (CH 2 CH 2 OH) 2 (le) salt. The invention also relates to the use of the bleach of the formula la in salt form Bis-eH3NCH2cH2OH (Id) as well as salt Bis-H3®NCH2CH2NHCH2CH2? H (le) for the bleaching of cellulose materials, especially paper. The salts of the bleaches according to the invention Ib and it as well as the salts of the bleaches used according to the invention Id and are suitable for bleaching paper pulps in papermaking, for example cellulose, pulp (chemical pulp) and mechanical) and for the bleaching of the applied brush masses usually used in the paper industry and specifically the bleaching of paper pastes and masses applicable to non-pigmented brush, especially however pigmented. The known brush compositions contain, as binders, inter alia, dispersions of synthetic materials based on copolymers consisting of butadiene-styrene, acrylonitrile-butadiene-styrene, esters of acrylic acid, ethylene-vinyl chloride or ethylene-acetate. vinyl or based on homopolymers, such as polyvinyl chloride, polyvinylidene chloride, polyethylene, polyvinyl acetate or polyurethanes. A preferred binder is constituted by copolymers of styrene-butyl acrylate or of styrene-butadiene, acrylic acid, other polymer latices have been described, for example, in US Pat. No. 3 265 654. For the pigmentation of brush-applied masses They usually serve as aluminum silicates, such as China clay and kaolin, as well as barium sulfate, satin white, titanium dioxide and calcium carbonate (chalk). The brush compositions according to the invention preferably contain from 5 to 70% by weight of a white pigment. The binder will preferably be used in an amount that is sufficient for the dry content of the polymer compound to be from 1 to 30% by weight, preferably from 5 to 25% by weight, of white pigment. The amount of the bleach dispersion according to the invention is calculated in such a way that the bleach is present in amounts of 0.005 to 1% by weight, especially 0.01 to 0.55% by weight, based on the white pigment. The brush-applied mass according to the invention can be manufactured by mixing the components, in any order, at temperatures of 10 to 100 ° C, preferably 20 to 80 ° C. The components in this case also include the usual auxiliary agents, which can be used for the regulation of the rheological properties, such as viscosity and water retention capacity, of the masses applicable by brush. Such auxiliary agents are, for example, natural binders, such as starches, casein, protein or gelatins, cellulose ethers, such as carboxyalkylcellulose or hydroxyalkylcellulose, alginic acid, alginates, polyethylene oxide or polyethylene oxide alkyl ethers, copper oxide copolymers. ethylene and propylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble condensation products deformdehyde with urea or melamine, polyphosphates or salts of polyacrylic acids. The bleaches to be used according to the invention of the formula Ib, Ie, Id and I are incorporated well in the mass applicable to a finished brush or in one of the components of the mass applicable by brush. The brush-applied mass according to the invention can be used for the coating of paper, wood, sheets such as, for example, cellulose, cellulose triacetate, textile products, etc. It is especially preferred to use on paper and cardboard as well as on photographic papers. The brush-applied mass can be applied to the substrate by any of the traditional methods, for example with a pneumatic knife, with a scraper blade, with a brush, with a roller, with a doctor blade or with a rod, after which the coating is dried for example with an infrared dryer and / or with a hot air dryer at temperatures of the surface of the substrate in the range from 70 to 200 ° C, preferably from 90 to 130 ° C, to a residual moisture of 3 to 6% by weight. By means of the use of the brush-applied masses according to the invention, the coatings obtained by an optimal distribution of the optical brightener over the entire surface and by an increase, caused by it, by the degree of whiteness as well as by a high light fastness are characterized .

EXAMPLES Example 1. 30 kg of a synthesis suspension of a disulfonic optical brightener of the formula (la) are concentrated with a dry matter content of 13% and a sodium chloride content of 5.5% at pH 3 to 4.5. a microfiltration facility and are released from the salts. Polymer membranes composed of polyvinylidene fluoride (PVDF) are used in the form of tubular modules with a diameter of 1/2"The membrane has a pore width of 0.1 μm, the module has a surface area of 0.3 m2. salts / concentration First, 15 kg of permeate is removed starting at 20 ° C and with an inlet pressure in the 5. bar module, before the diafiltration is carried out by removing 60 kg of permeate and continuous addition of 60 kg of completely desalinated water In this case, the working temperature is increased to 40 ° C. By removing 8 kg of permeate, the final concentration is carried out.The retentate has a dry matter content of 33%. in NaCl it is approximately 0.1%.

Clear filtration. Once the elimination of the salts and the concentration is finished, the pressure is reduced to 0 bar. Then 10% by weight of diethylene glycol and 3% of diethanolamine are added. It is heated to 55 ° C and dissolved by the addition of a) potassium hydroxide solution at pH 9.5. The transmembrane pressure is then increased to 10 bar and the clear solution of the bleach is obtained as permeate. After normalization (combination with completely desalinated water until the 1% solution in water has an extinction of 135, layer thickness 1 cm, wavelength 348 nm) results in a highly concentrated liquid formulation, with no precipitation, etc, even after 5 months of storage at room temperature and at 0 ° C. b) of sodium hydroxide solution at pH 9.5. The transmembrane pressure is then increased to 10 bar and the clear bleach solution is obtained as permeate. After normalization, a liquid formulation results from which product crystals are deposited only after 3 months of storage at 0 ° C. c) of lithium hydroxide at pH 9.5. The transmembrane pressure is then increased to 10 bar and the clear bleach solution is obtained as permeate. After normalization, a liquid formulation results from which the first product crystals are released after one week at room temperature.

Example 2. 30 kg of a synthesis suspension of the disulfonic optical brightener of the formula la are concentrated with a dry matter content of 14% and a sodium chloride content of 4.5%, at pH 3 to 4.5 in an installation, of microfiltration that undergoes the elimination of salts. A ceramic capillary module with a channel height of 4 mm, a membrane surface of 0.059 m2 and a pore width of 0.5 μm is used.

Elimination of salts / concentration. First, 18 kg of permeate are removed at 25-30 ° C and with an inlet pressure of 2.0 bar, as a step prior to the diafiltration, by removing 30 kg of permeate and continuously adding 30 kg of completely desalinated water. By eliminating 3 g of permeate, the final concentration is carried out. The retentate has a dry matter content of 29%. The residual content in NaCl is approximately 0.2%.

Clear filtration. Once the elimination of the salts and the concentration is finished, the pressure is reduced to 0 bar. Then 10% by weight of triethylene glycol and 3% of triethanolamine are added. It is heated to 60 ° C and dissolved by the addition of potassium hydroxide solution to pH 9. The transmembrane pressure is now increased to 3 bar and the clear bleach solution is maintained as a permeate. After normalization, a highly concentrated liquid formulation, stable to storage, results.

Example 3. 12 kg of the same bleach suspension as in Example 2 is prepared using a tubular module made of polypropylene with a membrane surface of 0.036 m2 and a pore width of 0.2 μm. Unlike example 2, the module is rinsed periodically with permeate.

Elimination of salts / concentration. First, 5 kg of permeate is removed at 30 ° C and with an inlet pressure in the module of 2.0 bar, before the diafiltration is carried out by removing 21 kg of permeate and continuously adding 21 kg of water completely desalinated By eliminating 2 kg of permeate, the final concentration is carried out. The retentate has a solid content of 27%. The residual content in NaCl is approximately 0.1%. The specific flow of permeate is, in this case, with an approximate value of 400 kg / (m2 / h), approximately double that in the case of the first example.

Clear filtration. Once the elimination of the salts and the concentration is finished, the transmembrane pressure is reduced to 0 bar. Then 10% by weight of triethylene glycol is added and heated to 50 ° C. At this temperature, it is previously dissolved by the addition of potassium hydroxide solution at pH 9. The transmembrane pressure is now increased up to 3 times and the clear bleach solution is obtained as a permeate, which, after normalization, provides a highly concentrated and stable liquid formulation. storage .

Example 4. The retentate from Example 3 is heated, once the salt removal and concentration is complete, to 55 ° C and is extensively dissolved by the addition of tetramethylammonium hydroxide to pH 9.4. By means of the clear filtration through a 1.2 μm membrane filter according to the dead-end working method, a clear solution is obtained which has an extremely good storage stability in relation to that of the corresponding alkaline salt formulations (electrolyte content) comparable strangers).

Example 5. The retentate from Example 3 is heated, after the elimination of the salts and the concentration at 55 ° C and is largely dissolved by the addition of ethanolamine at pH 8.7. By means of a clear filtration through a membrane filter of 1.2 μm according to the dead-end work form, less insoluble components are separated. The clear solution has a good storage stability compared to example 4.

Example 6. The retentate from example 3 is combined, once the elimination of the salts is finished, and the concentration, with 20% of diethylene glycol and is widely dissolved, at room temperature, by the addition of 2- (2-aminoethylamino). -ethanol at pH 9.5. By means of a clear filtration through a 5 μm membrane filter according to the dead-end working method, the soluble components are separated. The clear solution has an excellent storage stability.

Example 7. A solution almost free of foreign salts, containing the lithium / sodium salt (approximate molar ratio 1: 1) of Phthalocyanine dye Direct Blue 199 is combined with sulfuric acid at pH 1.0. The suspension is released from the salts by means of a tubular membrane with a pore width of approximately 50 nm, twice via diafiltration.

The Direct Blue 199 has the formula Analogously, the corresponding ethanolammonium salts were obtained by using the following ethanolamines instead of LiOH. 6a: H2N CH2CH2OH 6b: HN (CH2CH2OH) 2 6c: N (CH2CH2OH) 3.

The salts of the dyes according to Example 6 are excellently suited for dyeing and printing paper, especially for printing according to the inkjet method. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (13)

1. Process for obtaining preparations containing dyes and / or bleaches, which at least have a group S03H- and / or free COOH, characterized in that an aqueous suspension is applied, which contains a) dyes and / or bleaches, which at least have a group S03H- and / or COOH- free and b) inorganic synthesis salts, with a microfiltration membrane with a pore diameter of 0.0b to 40 μm.

2. A method according to claim 1, characterized in that the microfiltration membrane is made to work or operate according to a cross-flow operating mode.

3. Process according to claim 1, characterized in that the suspension to be released from the salts has a pH value of 1 to 6, especially 2 to 5.

4. Process according to claim 1, characterized in that the solubility of the dye and / or bleach containing groups S03H, and / or COOH-free, in water, is, under the process conditions of less than 5 g / liter, preferably less than 1. g / liter.

5. Process according to claim 1, characterized in that the process is carried out at a temperature of 25 to 70 ° C, preferably at 30-50 ° C.

6. Process according to claim 1, characterized in that the content of inorganic salts is reduced to < 1, preferably a < 0.5% by weight, based on the suspension released from the salts.

7. Process according to claim 1, characterized in that the suspension to be liberated from the salts contains at least one bleach of the formulas (I), (II) and / or (III), characterized in that M means H, Ri and R2 independently of each other, denote -NH2, -NHCH3, -NHC2H5, -N (CH3) 2, -N (C2H5) 2, -NHCH2CH2OH, -NHCH2CH2CH2OH, -N (CH2CH2OH) 2, -N (CH2CH2CH2OH) 2, -N (CH3) (CH2CH2OH), -NHCH2CH2OCH2CH2OH, -NHCH2CH2CH2S03M, -OH, -OCH3, -OCH (CH3) 2 -OCH2CH2OCH3, where M has the meaning indicated above; or the formula wherein R3 signifies hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, halogen or S03M, and R4 means hydrogen or alkyl having 1 to 4 carbon atoms and M has the meaning indicated above; also the formula in which M has the meaning indicated above and R5 and R6, independently of each other, mean hydrogen, CH3, , R5 and R6 together signify the complementary part for a benzene ring.

8. Process for obtaining preparations of dyes and / or anionic bleaches, having at least one group S03H and / or COOM-, where M = means alkali or ammonium cation, characterized in that i) an aqueous suspension is applied, which contains dyes and / or bleaches, which have at least one group -S03H- and / or COOH- free and b) inorganic synthesis salts with a microfiltration membrane with pore diameters of 0.05 to 40 μm and ii) after the elimination of the salts dissolve the suspended dyes and / or bleaches, by the addition of hydroxides, carbonates and / or alkali or ammonium bicarbonates, and / or amines and iii) the dye and / or bleach solution obtained according to i) is released of the colloidal and / or insoluble components, optionally after addition of other additives, especially solvents, with a microfiltration membrane with pore diameters of 0.05 to 40 μm.

9. Process for obtaining preparations according to claim 2, characterized in that the microfiltration membrane is periodically rinsed.

10 Compounds of the formula where M means? N (CH3) 4 or H2FN (CH2CH2OH) 2.

11. Use of the compounds according to claim 10, as well as the following compound of formula where M means H3TNCH2CH2OH or H3TNCH2CH2NHCH2CH2OH, for the rinsing of cellulose materials, especially paper,

12. Masses applicable to a brush containing 5 to 70% by weight of white pigment and 0.005 to 1% by weight of a bleach, based on the white pigment, of the formula where M means FN (CH3) 4, H2FN (CH2CH2OH) 2, H3FNCH2CH20H or H3FNCH2CH2NHCH2CH20H.

13. Compounds of the formula where CuPc means a phthalocyanine copper moiety, M = 0.5 to 2.5 N = 0.5 to 2.0 M means H3FNCH2CH2OH, H2FN (CH2CH2OH) 2, H? N (CH2CH2OH) 3 or LiF.