Compositions of disulphonic fluorescent whitening agents

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for optic whitening of paper or cardboard. Composition includes at least two fluorescent whitening agents - derivatives of disulphonic bis-triazinylaminostilbenes, containing group -CO2M in aniline rings in para and/or ortho-position to aminogroup, where M is hydrogen, Li, Na, K, Ca, Mg, ammonium or ammonium, which is mono-, di-, tri- or tetra-substituted C1-C4-alkyl or C2-C4-hydroxyalkyl. Described is method of preparing said composition, its application, method of paper whitening and paper resulting from said process.

EFFECT: claimed composition possesses higher whitening ability in comparison with each of separate whitening agents and provides stable concentrated water compositions without addition of auxiliary solubility-improving substances.

25 cl, 1 dwg, 1 tbl, 4 ex

 

AREA of TECHNOLOGY

The present invention relates to compositions of fluorescent whitening agents containing at least two special disulfonate fluorescent whitening agent for whitening of paper or cardboard.

It is well known that the whiteness of paper and cardboard can be improved by the addition of fluorescent whitening agents (FWA). The most significant of fluorescent whitening agents used in the manufacture of paper and cardboard are anilinomethyl bis(triazinyl)derivatives of 4,4'-diaminostilbene-2,2'-disulfonic acid (acid flavone). Among them are known disulfonate, tetrasulfane and hexachlorophene fluorescent whitening agents. Disulfonate fluorescent whitening agents that do not contain sulfoximine groups in the aniline ring, have low solubility in water and high affinity for cellulose fibres. They are particularly well-suited for use in the wet end of the paper production process. Hexachlorophene fluorescent whitening agents containing two sulfoximine groups in each balinova the ring, have a high solubility and a low affinity to cellulose fibres. They are more narrowly specialized products in cases where it is necessary to obtain very high �degree of whiteness. Tetrasulfane fluorescent whitening agents containing one sulfoximine group in each aniline ring, possess intermediate properties between disulfonate and hexachlorophene fluorescent whitening agents and are most commonly used for whitening paper or cardboard.

For ease of handling and dosing in the production of paper and cardboard requires fluorescent whitening agents supplied in liquid form, preferably in the form of a concentrated aqueous solution, which must be stable during prolonged storage in a wide range of temperatures. Due to the low solubility disulfonate fluorescent whitening agents in the water for providing stability during storage of concentrated aqueous solutions disulfonate fluorescent whitening agents currently add improve the solubility of auxiliary substances such as urea, triethanolamine or diethylene glycol, in an amount up to 30%. These improve the solubility of the additive does not have the affinity to cellulose and pollute the waste water of a paper mill, thus being undesirable. In patent document EP-A-1752453 presents sustainable storage solutions disulfonate fluorescent whitening agents containing the specific�s counterions sulfoximine groups in this case, the counterions are derived from specific amino alcohols. In patent document WO 02/055646 A1 discloses concentrated aqueous solutions containing a mixture of two special disulfonate fluorescent whitening agents.

Alternatively known suspensions and dispersions disulfonate fluorescent whitening agents in water, for example, from patent document EP 0884312 B1. However, to facilitate the dispensing of homogeneous compositions in the paper production process usually requires stirring.

Unexpectedly it was found that the problems of the prior art can be overcome by use of mixtures or combinations of special disulfonate fluorescent whitening agents containing aniline rings carboxyl group. Such mixtures when used for whitening paper or paperboard allow you to get a paper or paperboard with improved whiteness. Moreover, disulfonate fluorescent whitening agents can form stable concentrated aqueous compositions or solutions without addition of auxiliary substances that improve the solubility. Moreover, the manner of obtaining such fluorescent whitening agents is more cost-effective compared with the method of obtaining normally used disulfonic about fluorescent�belevush agents since it is possible to do without such time-consuming stages, as selection and filtering.

Thus, the present invention relates to compositions of fluorescent whitening agents (FWA), suitable for optical bleaching of paper or paperboard, where the composition comprises at least two fluorescent whitening agent selected from the fluorescent whitening agents of formula (1), formula (2) and formula (3)

where

R1, R2, R3and R4independently from each other represent hydrogen, a cyano group, C1-C4-alkyl, C2-C4-cianelli, C2-C4-hydroxyalkyl or C1-C4-alkoxyalkyl; or R1and R2or R3and R4independently from each other together with N atom form morpholine, piperidine or pyrrolidine ring; or -(CH2)I-SO3M, where I is 1, 2 or 3; or -(CH2)i-COOR, -(CH2)i-CONHR, -(CH2)i-OR, where i is an integer from 1 to 4, R is C1-C2-alkyl or has the same meaning as M;

M represents hydrogen or one equivalent of a cation, in particular Li, Na, K, Ca, Mg, ammonium, or ammonium, mono-, di-, tri - or tetrasomy C1-C4-alkyl or C2 -C4-hydroxyalkyl.

The invention also relates to a method of producing compositions of fluorescent whitening agents (FWA) and to their use for bleaching of pulp and paper in the mass or on the surface, for example, in the coating or for use in sizing presses. Furthermore, the invention relates to a method of bleaching paper and paper produced using this method. Preferred embodiments of the invention described in the description below, and with the help of graphic materials and claims.

Fig.1 is a graph showing the brightness of various fluorescent whitening agents, and mixtures thereof.

According to a preferred embodiment of the invention, the composition of the fluorescent whitening agents is a composition for wet end paper machine, and the method is a method of bleaching paper pulp and the mass or pulp slurry are brought into contact with the said composition. According to another preferred variant implementation, the composition of the fluorescent whitening agents are used to obtain fluid for size press or opaque composition.

According to the invention, the composition or the mixture comprises at least two derivatives of bis-triazinyl�of stilbene the above-described formulas (1), (2) and (3). In the context of the invention, in formulas (1), (2) and (3) the alkyl group can be linear or branched, and the possible substituents of the alkyl group constituting the alkoxy-, cyano - and/or hydroxyl group may be attached at any position of the alkyl chain. According to the present invention, C1-C4-alkoxyalkyl mean C1-C4-alkyl, substituted C1-C4-alkoxyl. According to a preferred embodiment of the, R1, R2, R3and R4independently from each other represent C2-C4-hydroxyalkyl, C1-C4-alkoxyalkyl or C1-C4-alkyl, preferably C2-4-hydroxyalkyl or C1-C4-alkoxyalkyl, in particular, hydroxyethyl or hydroxyisopropyl. Most preferably, R1, R2, R3and R4are hydroxyethyl.

Preferred variants of the implementation of M are hydrogen, Na, K, Ca, Mg, in particular, M represents Na, K or hydrogen, most preferred Na.

Fluorescent whitening agents of formulae (1), (2) and (3) and their mixtures can be obtained in accordance with known techniques. Fluorescent whitening agents used in the form of free acids or their salts, preferably alkali metal salts. In most cases, Conn�tion is produced by interaction of cyanuramide with 4,4'-diaminostilbene-2,2'-disulfonic acid or its salts, 2-aminobenzoic acid and/or 4-aminobenzoic acid and substituted aliphatic amines or heterocyclic compounds. The ratio of 2-aminobenzoic acid and 4-aminobenzoic acid can be selected so that the mixture was the desired ratio of the fluorescent whitening agents of formulae (1), (2) and/or (3). Typical methods are presented in the following examples 3 and 4. In patent document PL 61710 revealed getting some special fluorescent whitening agents described above formulae containing one carboxyl group in the para-position of each aniline ring. In the GDR patent No. 55668 discovered another way of getting some special fluorescent whitening agents of the above formula. Purification of the fluorescent whitening agents of formulae (1), (2) and (3) is easier and, therefore, is more economical than in the case of the commonly used disulfonate fluorescent whitening agents, which eliminates stage of selection. Cleaning can be carried out, for example, using membrane filtration. In contrast to the stages of water evaporation or deposition of salts, disclosed in patent document PL 61710, purification of fluorescent whitening agents can be carried out using membrane filtration, and the resulting product - is�to alisovtsy as such. This is due to unexpectedly higher solubility of the fluorescent whitening agents.

The composition of the fluorescent whitening agents of formulae (1), (2) and/or (3) can be obtained in the form of a mixture having the desired ratio of fluorescent whitening agents. Suitable methods are described in the examples below. Alternatively, the composition may be obtained by preparing separately the fluorescent whitening agents of formulae (1), (2) and/or (3) using methods known in the art and such as described above, followed by stirring or mixing them together in the desired ratio after cooking.

The composition according to the invention comprises at least two, in particular two or three, fluorescent whitening agent selected from the fluorescent whitening agents of formulae (1), (2) and (3). According to one preferred embodiments, the composition comprises the fluorescent whitening agents of formulae (1) and (2). According to another preferred embodiment of the composition comprises the fluorescent whitening agents of formulae (1) and (3). According to another preferred embodiment of the composition comprises the fluorescent whitening agents of the formulae (2) and (3). According to a particularly preferred �the Ariant implementation the composition comprises the fluorescent whitening agents of formulae (1), (2) and (3). The composition may also contain one or more of each of the fluorescent whitening agents of formulae (1), (2) and/or (3). Furthermore, the composition may contain one or more known fluorescent whitening agents based on bis-triethynylbenzene or distributional.

The amount of fluorescent whitening agents in the composition will depend on the number present fluorescent whitening agents, and from which fluorescent whitening agents are present. According to the invention, the composition preferably contains at least one fluorescent whitening agent of formula (1) in an amount of from 0 to 99 mass%, preferably, from 2 to 90 mass%, most preferably, from 5 to 80 wt.%; at least one fluorescent whitening agent of formula (2) in an amount of from 0 to 99 mass%, preferably, from 2 to 90 mass%, most preferably, from 5 to 80 wt.%; and at least one fluorescent whitening agent of formula (3) in an amount of from 0 to 99 mass%, preferably, from 2 to 90 mass%, most preferably, from 5 to 80 wt.%; in each case based on 100 wt.% the total number present fluorescent whitening agents of formulae (1), (2) and/or (3). According to other embodiments be implemented thr�tion, the composition preferably contains at least one fluorescent whitening agent of formula (1) in an amount of from 10 to 80 mass%, in particular, from 20 to 70 mass%, at least one fluorescent whitening agent of formula (2) in an amount of from 10 to 60 mass%, in particular, from 10 to 50 wt.%, and at least one fluorescent whitening agent of formula (3) in an amount of from 10 to 80 mass%, in particular, from 20 to 70 mass%, in each case based on 100 wt.% the total number present fluorescent whitening agents of formulae (1), (2) and/or (3).

The composition of the fluorescent whitening agents can be presented in liquid form, in particular in the form of a solution or in powdered form. According to a preferred implementation options, the compositions contain water, in particular in an amount of from 20 to 90 mass%, on the basis of 100 wt.% of the total number of fluorescent whitening agents and water. Such aqueous compositions of fluorescent whitening agents or mixtures presented in liquid form, in particular in the form of a solution. Preferably, they contain crystalline particles of bleach, in particular, their hydrated forms.

Compositions of fluorescent whitening agents, in particular, aqueous compositions can contain small amounts of auxiliary substances. This can be especially important �La compositions of fluorescent whitening agents used in cold regions, to increase the stability of the compositions to the cold. According to a preferred embodiment of the aqueous composition of the fluorescent whitening agents contain less than 30 wt.%, preferably less than 20 wt.%, more preferably, less than 15 wt.%, in particular, less than 10 wt.% components, different from the fluorescent whitening agents and water, for example, can be added subsidiary of the formulation, such as standardizing agents, surface-active composition, defoamers, organic thickeners, preserving agents and/or electrolytes. However, due to environmental reasons, aqueous composition of the fluorescent whitening agents preferably contains only a small number of components, for example, organic additives or auxiliary substances, in particular, a total of less than 3 mass%, in particular, less than 1 wt.%, on the basis of 100 wt.% aqueous compositions of fluorescent whitening agents. Particularly preferably, the composition does not contain organic co-solvents and/or urea. According to another preferred variant implementation, the composition comprises or essentially consists of fluorescent whitening agents and water.

The aqueous composition of the fluorescent whitening agents are preferably received�Ute the addition of fluorescent whitening agents of formulae (1), (2) and/or (3) or their mixture in the desired ratio in powdered form or in the form of concentrated solution in water. During or after mixing it optionally can be added to any excipients.

The composition according to the invention, can be used for whitening paper or paperboard, preferably in the pulp slurry (paper weight) or in the pulp mass, in particular in the wet end process. Or the composition may be used for whitening the surface of the paper. When used in the wet end of a papermaking machine of the composition can be added anywhere in the pulp cycle, for example, in pulp pools or pipelines, prior to forming sheets. Depending on the method of manufacture of the paper composition may be added during the paper manufacturing process also in diluted form, where the composition was diluted to the desired concentration by adding water and/or excipients. According to a preferred embodiment of the composition, preferably aqueous, fluorescent whitening agents are added, optionally after dilution with water into a pulp mass or slurry of pulp. The composition may be added continuously or discretely. The application is well suited to�for the pulp and to the masses, containing wood and cellulose mass without wood, in particular for pulp mass containing wood. When the surface coating composition can be used for preparation of fluids for sizing presses or for the preparation of coating compositions.

Aqueous compositions of fluorescent whitening agents have a high storage stability and ease of use. At the same time they provide high affinity (substantive) to fibers and high performance bleaching.

The invention also relates to a method of bleaching paper, which includes obtaining pulp or pulp slurry;

the add compositions of fluorescent whitening agents, as described above, in the pulp and the mass or pulp suspension, preferably in an amount of from 0.01 to 5 mass%, more preferably, from 0.02 to 2 mass%, on the basis of 100 wt.% dry pulp; manufacture of a sheet of paper from pulp; and drying the sheet. According to one of embodiments of this method, the composition is added, after dilution with water and/or auxiliary substances, in particular, after dilution with water into a pulp mass or slurry of pulp.

Paper obtained by using the compositions of fluorescent whitening Agay�tov according to the invention, has a higher degree of whiteness compared to paper produced using commonly used disulfonate fluorescent whitening agents.

The degree of whiteness of the resulting paper can be characterized by the CIE whiteness. When evaluated according to the CIE whiteness of different fluorescent whitening agents can be compared with each other in terms of saturation. In other words, if you are using a larger amount of the fluorescent whitening agent is not observed further increase the degree of whiteness, it is characterized as a state of saturation, and the use of even large amounts can adversely affect the whiteness. The saturation effect is also known as darkening. The limit of darkening, i.e. the point at which the increase in the number of used fluorescent whitening agent in fact does not lead to any further increase in whiteness can be obtained, for example, in diagram a*-b*, where a* and b* are the color coordinates in the system CIE-L*a*b*.

The following examples illustrate the invention and show preferred variants of implementation without limiting the scope of the claims.

DESCRIPTION of embodiments of the INVENTION

Example 1 (R1, R2, R3, R4=-CH2CH2OH)

Stage 1: Reaction of cyanuramide with Dean�rievas salt of 2,2'-disulfo-4,4'-sterbenden

In a flask with a capacity of 2 l, equipped with stirrer, pH electrode, thermometer and reflux condenser was loaded with 600 ml of water at a temperature of 8°C and 100 g (0,542 mol) of cyanuramide. After lowering the pH to 4.5 dropwise added a solution of 112,2 g (0.27 mole) of the disodium salt of 2,2'-disulfo-4,4'-stillbelieve in 835 g of water. At the same time to maintain a pH of 4.5 in the reaction mixture was dropwise added 10 wt.% a solution of sodium hydroxide (222 g), while stirring the reaction mixture to a temperature of 16°C. After the addition of reagents, the reaction mixture was stirred at 16°C for 1 hour, maintaining the pH value of 4.5.

Stage 2: reaction of the intermediate of step 1 with 4-aminobenzoic acid

296,1 g of 25 wt.% solution of 4-aminobenzoic acid (0,54 mol) was added in aqueous suspension with stage 1 within 45 min. the pH Value was maintained constant (pH=6,8) simultaneous addition of a 10% solution of sodium hydroxide, at the same time gradually increasing the temperature to 60°C. the reaction mixture was stirred at 60°C and pH 6.8 to complete consumption of the sodium hydroxide solution.

Stage 3: Reaction of the intermediate stage 2 with diethanolamine

67,8 g (0,54 mol) of diethanolamine was added in aqueous suspension with stage 2 for 20 minutes. The pH value was maintained constant (pH=8) simultaneous addition of a 10% solution of hydroxide NAT�Oia, at the same time gradually increasing the temperature to 100°C. Then the reaction mass is stirred at a temperature of 100°C and pH 8 for 3 hours. The resulting solution was cooled to a temperature of approximately 50°C and clarified by filtration and then obtained the solution of a compound of formula 1 (88,7%), as shown below.

Example 2 (R1, R2, R3, R4=-CH2CH2OH)

Stage 1: the requirements are the same as stage 1 of Example 1

Stage 2: reaction of the intermediate of stage 1 with 2-aminobenzoic acid

296,1 g of 25 wt.% solution of 2-aminobenzoic acid (0,54 mol) was added in aqueous suspension with stage 1 within 45 min. the pH Value was maintained constant (Ph=6,8) simultaneous addition of a 10% solution of sodium hydroxide, at the same time gradually increasing the temperature to 60°C. Then the reaction mass is stirred at a temperature of 60°C and pH 6.8 to complete consumption of the sodium hydroxide solution.

Stage 3: Reaction of the intermediate stage 2 with diethanolamine 67,8 g (0,54 mol) of diethanolamine was added in aqueous suspension with stage 2 for 20 minutes. The pH value was maintained constant (pH=8) simultaneous addition of a 10% solution of sodium hydroxide, at the same time gradually increasing the temperature to 100°C. Then the reaction mass is stirred at a temperature of 100°C and pH 8 for 3 hours. The obtained Sol�R is cooled to a temperature of approximately 50°C and clarified by filtration, then obtained the solution of a compound of formula 3 (of 89.4%), as shown below.

Example 3 (R1, R2, R3, R4=-CH2CH2OH)

Stage 1: the requirements are the same as stage 1 of Example 1

Stage 2: reaction of the intermediate of stage 1 with a mixture of 4-aminobenzoic acid and 2-aminobenzoic acid (4:1, mass./mass.)

296,1 g (0,54 mol) mixture of 4-aminobenzoic and 2-aminobenzoic acid (4:1, mass./mass.) was added to a 25 wt.% solution in aqueous suspension with stage 1 within 45 min. the pH Value was maintained constant (pH=6,8) simultaneous addition of a 10% solution of sodium hydroxide, at the same time gradually increasing the temperature to 60°C. the reaction mixture was stirred at 60°C and pH 6.8 to complete consumption of the sodium hydroxide solution.

Stage 3: Reaction of the intermediate stage 2 with diethanolamin

67,8 g (0,54 mol) of diethanolamine was added in aqueous suspension with stage 2 for 20 minutes. The pH value was maintained constant (pH=8) simultaneous addition of a 10% solution of sodium hydroxide, at the same time gradually increasing the temperature to 100°C. Then the reaction mass is stirred at a temperature of 100°C and pH 8 for 3 hours. The resulting solution was cooled to a temperature of approximately 50°C and clarified by filtration and then obtained the solution of the mixture of compounds 1 (65%), 2 (30,3%) and 3 (4,7%), as shown in a total yield of 84.3%.

Example 4 (R1, R2, R3, R4=-CH2CH2OH)

Stage 1: the requirements are the same as stage 1 of Example 1

Stage 2: reaction of the intermediate of stage 1 with a mixture of 4-aminobenzoic and 2-aminobenzoic acid (1:1, mass./mass.)

296,1 g (0,54 mol) mixture of 4-aminobenzoic and 2-aminobenzoic acid (1:1, mass./mass.) was added to a 25 wt.% solution in aqueous suspension with stage 1 within 45 min. the pH Value was maintained constant (pH=6,8) simultaneous addition of a 10% solution of sodium hydroxide, at the same time gradually increasing the temperature to 60°C. the reaction mixture was stirred at 60°C and pH 6.8 to complete consumption of the sodium hydroxide solution.

Stage 3: Reaction of the intermediate stage 2 with diethanolamine

67,8 g (0,54 mol) of diethanolamine was added in aqueous suspension with stage 2 for 20 minutes. The pH value was maintained constant (pH=8) simultaneous addition of a 10% solution of sodium hydroxide, at the same time gradually increasing the temperature to 100°C. Then the reaction mass is stirred at a temperature of 100°C and pH 8 for 3 hours. The resulting solution was cooled to a temperature of approximately 50°C and clarified by filtration and then obtained the solution of the mixture of compounds 1 (25,9%), 2 (48,1%) and 3 (26%), as shown below, with a total output 92,6%.

Were derived fluorescent whitening agents, t�the cue as pictured below. Shown below comparative FWA used in the Sample application.

Comparative FWA

Example 1

Example 2

Example 3

Example 4

These fluorescent whitening agents and mixtures used in the following Example application.

Application example

The effectiveness of the whitening fluorescent whitening agents and their mixtures were studied using the following test procedure.

Non-wood paper pulp (pulp suspension) consisted of 85 parts (parts by weight) wood pulp and 30 parts of long fibers with a fineness of 40° SR (Schopper-Riegler).

800 ml of 0.625% of the paper pulp was weighed in a beaker to prepare manually sheet 5 g density ~120 g/m2for each experimental series. With the help of distilled water was prepared a solution of a fluorescent whitening agent with a concentration of 0.1 wt.%. The amount of a fluorescent whitening agent shown in Table 1 below, were obtained by adding appropriate amounts of 0.1 wt.% R�target of a fluorescent whitening agent with a pipette to the stirred suspension of pulp, which was stirred for another 10 minutes after adding the fluorescent whitening agent. The amount of the fluorescent whitening agent in Table 1 are designed for the active ingredient based on 100 wt.% dry pulp.

On the net lithophragma device was placed wet filter paper, lithophragma device inflicted mass and filtered. Obtained by a manual sheet protected with the help of additional dry filter, pressed and dried on the calender at a temperature of 100°C. the resulting sheets were manually maintained in a controlled atmosphere chamber at standard conditions overnight and then analyzed with a spectrophotometer Datacolor (ISO2469 measuring the CIE L*, a* and b*, using the light source in accordance with the standard ISO2469.

The results are presented in Table 1 and further shown in Fig.1.

to -0.05
Table 1
FWAAmount (wt.%) FWACIE whitenessL*a*b*
Example 10,1923,8191,87 0,0112,12
0,2826,58of 91.960,0511,58
0,3729,4392,050,0711,03
0,4632,1192,200,0410,30
Example 20,19of 22.34of 91.85-0,04of 12.43
0,2827,4592,020,03of 11.43
0,3729,5492,040,0211,18
0,4630,1492,100,0110,90
Example 30,1923,8491,8712,12
0,2827,5491,990,0711,40
0,3730,1492,050,1010,88
0,4631,7692,090,0810,55
Example 40,1926,1592,030,0411,72
0,2829,3692,090,1011,07
0,3730,7292,060,09representation stands at 10.97
0,46there was obtained 31.0592,030,10of 10.67
Comparative FWA0,1922,09of 91.8512,48
0,2824,5991,910,0311,98
0,3726,60of 91.960,0611,69
0,4628,4192,050,08of 11.25

Thus, the compositions of fluorescent whitening agents according to the invention have better bleaching efficiency than single disulfonate fluorescent whitening agents.

1. The composition of the fluorescent whitening agents optical whitening of paper or paperboard, containing at least two fluorescent whitening agent selected from the fluorescent whitening agents of formula (1), formula (2) and formula (3)



where
R1, R2, R3and R4independently from each other represent hydrogen, a cyano group, C1-C4-alkyl, C2-C4-cianelli, C2-C4-hydroxyalkyl or C1-C4-alkoxyalkyl; or R1and Rsub> 2or R3and R4independently from each other together with N atom form morpholine, piperidine or pyrrolidine ring; or -(CH2)I-SO3M, where I is 1, 2 or 3; or -(CH2)i-COOR, -(CH2)i-CONHR, -(CH2)i-OR, where i is an integer from 1 to 4, R represents C1-C3-alkyl or has the same meaning as M;
M represents hydrogen or one equivalent of a cation, in particular Li, Na, K, Ca, Mg, ammonium, or ammonium which is mono-, di-, tri - or terazosina C1-C4-alkyl or C2-C4-hydroxyalkyl.

2. A composition according to claim 1, characterized in that R1, R2, R3and R4independently from each other represent C2-C4-hydroxyalkyl or C1-C4-alkoxyalkyl.

3. A composition according to claim 1, characterized in that R1, R2, R3and R4are hydroxyethyl.

4. A composition according to claim 2, characterized in that R1, R2, R3and R4are hydroxyethyl.

5. A composition according to claim 1, characterized in that it comprises the fluorescent whitening agents of formula (1), formula (2) and formula (3).

6. A composition according to claim 2, characterized in that it comprises the fluorescent whitening agents of formula (1), formula (2) and formula (3).

7. A composition according to claim 3, characterized in that contains the fluorescent whitening agents of formula (1), formula (2) and formula (3).

8. A composition according to claim 1, characterized in that it comprises at least one fluorescent whitening agent of formula (1) in an amount of from 0 to 99 mass%, at least one fluorescent whitening agent of formula (2) in an amount of from 0 to 99 wt.% and at least one fluorescent whitening agent of formula (3) in an amount of from 0 to 99 mass%, in each case based on 100 wt.% the total quantity of compounds of formulas (1), (2) and/or (3).

9. A composition according to any one of claims.2-7, characterized in that it comprises at least one fluorescent whitening agent of formula (1) in an amount of from 0 to 99 mass%, at least one fluorescent whitening agent of formula (2) in an amount of from 0 to 99 wt.% and at least one fluorescent whitening agent of formula (3) in an amount of from 0 to 99 mass%, in each case based on 100 wt.% the total quantity of compounds of formulas (1), (2) and/or (3).

10. A composition according to claim 1, characterized in that it contains water, in particular in an amount of from 20 to 90 mass%, on the basis of 100 wt.% the total number of fluorescent whitening agents and water.

11. A composition according to claim 2, characterized in that it contains water, in particular in an amount of from 20 to 90 mass%, on the basis of 100 wt.% the total number of fluorescent whitening agents and water.

12. A composition according to claim 3, characterized in that it comprises water, h�particular, in an amount of from 20 to 90 mass%, on the basis of 100 wt.% the total number of fluorescent whitening agents and water.

13. A composition according to claim 4, characterized in that it contains water, in particular in an amount of from 20 to 90 mass%, on the basis of 100 wt.% the total number of fluorescent whitening agents and water.

14. A composition according to claim 5, characterized in that it contains water, in particular in an amount of from 20 to 90 mass%, on the basis of 100 wt.% the total number of fluorescent whitening agents and water.

15. A composition according to claim 6, characterized in that it contains water, in particular in an amount of from 20 to 90 mass%, on the basis of 100 wt.% the total number of fluorescent whitening agents and water.

16. A composition according to claim 7 or 8, characterized in that it contains water, in particular in an amount of from 20 to 90 mass%, on the basis of 100 wt.% the total number of fluorescent whitening agents and water.

17. A composition according to any one of claims.10-15, characterized in that the composition containing water, contains less than 30 wt.%, in particular less than 20 wt.%, other components.

18. A method of preparing a composition according to any one of the preceding paragraphs, including the interaction of cyanuramide with 4,4'-diaminostilbene-2,2'-disulfonic acid or its salts, 2-aminobenzoic acid, 4-aminobenzoic acid and related substituted aliphatic amines or heterocyclic�climate connections.

19. Use of the composition according to any one of claims. 1-17 for optical bleaching of paper or cardboard.

20. The use according to claim 19, wherein the composition is used in the pulp slurry or pulp mass.

21. The use according to claim 20, wherein the composition is used in the pulp mass, containing no wood or cellulose mass containing wood, in particular in the pulp mass, containing wood.

22. The use according to claim 19 for the optical bleaching of paper on the surface, in particular, by covering or coating the sizing press.

23. Method of bleaching paper, including the production of pulp or pulp suspension, adding the compositions of fluorescent whitening agents described in any one of claims. 1-17, in cellulose mass or slurry of pulp, manufacture of paper sheet and drying the sheet.

24. A method according to claim 23, characterized in that the composition is added to the pulp mass or a suspension of pulp after dilution with water and/or auxiliary substances.

25. Paper, obtained using the method according to claim 23 or 24.



 

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25 cl, 2 dwg, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention includes (a) at least one optical bleaching agent of formula (1) , wherein R1 denotes hydrogen or SO3M, R2 denotes hydrogen or SO3M, R3 denotes hydrogen or CH2CO2M, R4 denotes CH2CO2M, CH(CO2M)CH2CO2M or CH(CO2M)CH2CH2CO2M, where M denotes hydrogen, a cation of an alkali metal, ammonia, mono-methyl-di-C2-C3-hydroxyalkylammonium, dimethyl-mono-C2-C3- hydroxyalkylammonium, ammonium, which is mono-, di- or trisubstituted with a C2-C3 hydroxyalkyl radical, or a mixture of said compounds, (b) a magnesium salt or (c) binder, which is selected from a group consisting of natural starch, enzyme-modified starch, and chemically modified starch, wherein there are 0.1-15 parts of component (b) for one part of component (a). The invention also relates to a method of bleaching paper using said composition.

EFFECT: composition is a more efficient means of achieving high paper whiteness.

9 cl, 4 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a compound of formula (1) where R1 denotes hydrogen or SO3, R2 denotes hydrogen or SO3, R3 denotes hydrogen or CH2CO2, R4 denotes CH2CO2, CH(CO2)CH2CO2 or CH(CO2)CH2CH2CO2, and where M denotes a stoichiometric cation equivalent required to balance the anionic charge in formula (1) and is a combination of Mg2+ with at least 1 additional cation. The additional cations are selected from a group consisting of H+, a cation of an alkali metal, a cation of an alkali-earth metal other than Mg2+, ammonium, mono-C1-C4 alkyl-di-C2-C3-hydroxyalkylammonium, di-C1-C4-alkyl-mono-C2-C3-hydroxyalkylammonium, ammonium, which is mono-, di- or trisubstituted with a C2-C3 hydroxyalkyl radical, and mixtures thereof. The invention also relates to versions of the method of producing said compound and use of said compound in binding compositions for bleaching paper.

EFFECT: compound is a more efficient paper bleaching agent.

8 cl, 4 tbl, 10 ex

FIELD: textiles, paper.

SUBSTANCE: in one of the aspects, the invention is directed to a method which enables mainly to maintain (or even increase) the brightness and/or whiteness of paper with increased degree of grinding the cellulose pulp, where the said method comprises grinding of the cellulose pulp till the freeness value of about 100 CSF and adding the composition OVA and a polymeric carrier to the paper surface in the size press in amounts sufficient to increase brightness and/or whiteness of the paper obtained. In another aspect, the invention is directed to a method of making paper from grinded cellulose pulp, which comprises grinding the suspension of cellulosic fiber to reduce the freeness up to about 100 CSF and mixing the cellulosic fiber with at least one optical bleaching agent (OBA) during or after the grinding stage and prior to adding any additional chemical ingredients of the wet stage of production.

EFFECT: effective maintenance or increase of brightness and whiteness of paper from the grinded cellulose pulp.

13 cl, 14 tbl, 34 dwg

FIELD: textiles, paper.

SUBSTANCE: method comprises the following steps: a) adding a known amount of one or more surface additives to a papermaking process in a known proportion with a known amount of one or more inert fluorescent markers, and the inert fluorescent markers are selected from the group consisting of fluorescein or derivatives of fluorescein and rhodamine, or derivatives of rhodamine, b) measuring the fluorescence of one or more inert fluorescent markers in the point after adding the surface additives and after the web formation, at that fluorescence is measured with a fluorometer of reflective type, c) establishing the correlation between the fluorescence value of the inert fluorescent markers on the web and the concentration of surface additives in the coating on the web and/or coating thickness on the web.

EFFECT: use of the proposed method enables paper machine to control the rate of adding at very low levels, with ability to assess quickly and regulate statically rate of adding beyond the technical specifications.

17 cl, 1 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: described is an aqueous solution of an optical brightener, containing (a) 10-50 wt % optical brightener of formula (I): where: M is hydrogen, an alkali metal atom, ammonia or an amine cation; R1 is hydrogen, C1-C4-alkyl or C2-C4-hydroxyalkyl; R2 - C1-C4-alkyl which can be substituted with -CN- or -CONH2-group or C2-C4-hydroxyalkyl; or R1 and R2 together with a nitrogen atom close a morpholine ring; (b) 0.5-9 wt % polyvinyl alcohol, having degree of hydrolysis 71-85.2% and Brookfield viscosity 3-5.4 mPa·s; and (c) water. The invention also describes use of said solution in a coating composition for paper and a method of obtaining paper coated with said coating composition.

EFFECT: disclosed aqueous solutions of optical brighteners have low viscosity, can be used directly by paper manufacturers and can be fed by a pump directly into the coating composition to provide a coating on paper with high whiteness.

10 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: described is water solution of optic bleach, which contains from 10 to 40 wt % of compound, described by formula (1) [M+]n [(CH3)2NH+CH2CH2OH]2-n, where R is hydrogen or methyl, M+ represents Li, Na or K+, n is smaller or equals 1.5, and from 0.05 to 5 wt % of citric, glycolic, acetic or formic acid, method of claimed solution obtaining and its application for optic bleaching textile, paper, cardboard and non-woven materials and methods of paper bleaching.

EFFECT: water solution of optic bleach is stable in storage and does not require application of additional solubilising additives.

10 cl, 8 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: composition contains at least one fluorescent bleaching agent from bis-triazinylaminostilbene compounds containing taurine groups in a triazine nucleus, having formulae (1), (2) and (3). The composition is used to bleach paper in a wet process, in a gluing press or by coating.

EFFECT: increased whiteness.

25 cl, 2 dwg, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to solutions of optical bleaching agents which are stable during storage, based on defined salt forms of aniline-substituted bis-triazinyl derivatives of 4,4'-diaminostilbene-2,2'-disulphonic acid of formula where R denotes a hydrogen atom, R1 denotes a β-hydroxyalkyl radical having 2-4 carbon atoms, R2 denotes a hydrogen atom, M+ denotes Na+, n is less than or equal to 1.5; which do not require additional dissolution promoting additives.

EFFECT: high stability of the compounds during storage.

14 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of treating and modifying materials. Described is a method of preparing materials which protects said materials from UV radiation and ozone using a modifier, involving obtaining the modifier by reacting a stilbene derivative in form of 4,4'-bis(s-triazinyl-)diamine-2,2'-disulphostilbene at temperature of up to 55°C in the presence of water with diamine of carbonic acid in amount of 0.5-55 wt % with respect to weight of said stilbene derivative, and material such as foamed or foamable plastic, cement or concrete is then directly treated with the prepared modifier, and/or active radicals of said modifiers are introduced into the surface of said materials. Described also is a method of preparing materials for their protection from UV radiation and ozone using a modifier, involving obtaining the modifier by inoculating a stilbene derivative in form of 4,4'-bis(s-triazinyl-)diamine-2,2'-disulphostilbene with solid diamine of carbonic acid with crystal size less than 40 mcm at 55°C in the absence of water, by grinding the modifiers in a mill and homogenisation at ambient temperature for more than 4 hours, with amount of diamine of carbonic acid of 0.1-45 wt % with respect to the solid stilbene derivative, and material such as foamed or foamable plastic, cement or concrete is then directly treated with the prepared modifier, and/or active radicals of said modifiers are introduced into the surface of said materials.

EFFECT: elimination of negative effect of UV radiation and ozone on surface of materials.

2 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to concentrated aqueous solutions of hexa-sulfonated stilbene used optical brighteners. Description is given of an aqueous solution of hexa-sulfonated stilbene optical brightener which is stable during storage with over 0.214 mol/kg content thereof in the solution. The solution does not contain a soluble agent, for example urea. By removing salts formed during synthesis of the optical brightener, its concentration of up to 0.35 mol/kg can be achieved without losing stability during storage. Also described is a method of preparing an aqueous solution of the said optical brightener and its use for bleaching paper or cellulose materials.

EFFECT: high concentration solutions of the said optical brightener do not show crystallisation signs after 2 weeks at 5°C and enables formation of coating compositions with low water content, which reduces energy consumption on drying and reduces penetration of water and adhesive into the paper layer.

10 cl, 1 dwg, 1 tbl, 3 ex

FIELD: chemistry, textiles, paper.

SUBSTANCE: present invention relates to new amphoteric bis-triazinylaminostilbene fluorescent whitening agents for fluorescent whitening of organic materials, particularly paper. Description is given of use of compounds with formula (5) for fluorescent whitening of paper.

EFFECT: compounds have high bleaching power; fluorescence is not prevented by cation-active polymers or anion-active fluorescent whitening agents contained in the paper.

2 cl, 2 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: invention concerns fluorescent bleach containing a mix of two asymmetrically substituted and one symmetrically substituted triazinylaminostilbene disulfone acid, a new symmetrically substituted derivative, method of their obtaining, and application of the mix in synthetic or natural organic material (especially paper) bleaching and in fluorescent bleaching and sun resistance boost of textile.

EFFECT: high substantivity and light resistance of the claimed fluorescent bleaches and their mixes, and better water solubility of the claimed mixes in comparison to the solubility of each individual bleach.

15 cl, 2 tbl, 12 ex

FIELD: organic chemistry, paper industry.

SUBSTANCE: invention relates to compositions used for coating paper covers. Invention describes a composition for coating paper cover comprising whitening pigment comprising: (a) product of melamine formaldehyde or phenol-formaldehyde polycondensation, and (b) water-soluble fluorescent whitening agent of the formula:

wherein R1 and R2 represent independently of one another -OH, -Cl, -NH2, -O-(C1-C4)-alkyl, -O-aryl, -NH-(C1-C4)-alkyl, -N-(C1-C4-alkyl)2, -N-(C1-C4)-alkyl-(C1-C4-hydroxyalkyl)- -N-(C1-C4-hydroxyalkyl)2 or -NH-aryl, for example, anilino-, anilinemono- or disulfonic acid or aniline sulfone amide, morpholino-, -S-(C1-C4)-alkyl(aryl) or radical of amino acid, for example, aspartic acid or iminoacetic acid that is replaced with radical in amino-group; M means hydrogen, sodium, potassium, calcium, magnesium atom or ammonium, mono-, di-, tri- or tetra-(C1-C4)-alkylammonium, mono-, di- or tri-(C1-C4)-hydroxyalkylammonium, or ammonium di- or tri-substituted with a mixture of (C1-C4)-alkyl and (C1-C4)-hydroxyalkyl groups. Covers prepared on coating paper elicit high photostability and enhanced whiteness degree.

EFFECT: improved method for preparing, improved properties of covers.

7 cl, 1 tbl, 3 ex

The invention relates to an improved process for the preparation of finely granulated optical brighteners creatinineclearance number used for optical bleaching of textile materials

FIELD: textiles, paper.

SUBSTANCE: composition comprises at least one bis-triasinylaminostilbene compound containing alkylsulfoacid groups, as a fluorescent bleaching agent, a salt of a divalent cation, the carrier, and water. The invention also relates to a method of bleaching paper, which consists in the fact that the pulp sheet is contacted with the said composition, and to the paper obtained by this method.

EFFECT: method enables to obtain paper with improved whiteness, at that the obtained paper has improved printing performance.

25 cl, 3 dwg, 3 tbl, 3 ex

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