ES2210486T3 - FORMULATION OF FLUORESCENT WHITENING AGENT. - Google Patents

Abstract

THE PRESENT INVENTION PROPOSES A FLUORESCENT WHITENING LIQUID FORMULATION WHICH IS A VISCOSITY SOLUTION BETWEEN 50 AND 5000 MPAS, PREFERENTLY BETWEEN 100 AND 3500 MPAS, ESPECIALLY 100 TO 1000 MPAS AND INCLUDING: A) 10-25%, PREFERENTLY 15-20% IN WEIGHT OF AN ANIONIC FLUORESCENT WHITENING AGENT, BASED ON THE TOTAL WEIGHT OF THE FORMULATION; B) 15-35%, PREVIOUSLY 20-30% BY WEIGHT OF A POLAR SOLVENT, BASED ON THE TOTAL WEIGHT OF THE FORMULATION; AND C) 45-75%, PREFERRED 50-70% BY WEIGHT, BASED ON THE TOTAL WEIGHT OF THE FORMULATION, OF A NON-IONIC SURFACTANT OF FORMULA: WHERE M IS 1, 2, 3 OR 4, AND WHEN M IS 1 , R IS A RENT WASTE C SUB, 8} - C SUB, 18} OR A RENT WASTE C SUBBOX, 8} - C SUB, 18}; WHEN M IS 2, R IS AN ALQUILENGLICOL WASTE FROM WHICH THE TWO HYDROXYL GROUPS HAVE BEEN ELIMINATED; WHEN M IS 3, R IS THE TRIMETHYLPROPANE RESIDUE FROM WHICH THE THREE HYDROXYL GROUPS HAVE BEEN ELIMINATED; AND WHEN M IS 4, R IS THE PENTAERITRITOL RESIDUE FROM WHICH THE FOUR HYDROXYL GROUPS HAVE BEEN ELIMINATED; R SUB, 1} IS HYDROGEN, METHYL OR ETILO; AND N IS A NUMBER BETWEEN 1 AND 40,

Description

Bleaching Agent Formulation fluorescent.

The present invention relates to a formulation of fluorescent whitening agent and, in a way In particular, this refers to a bleaching agent formulation Fluorescent, liquid, comprising a solution of an agent fluorescent bleach in a specific type of non-surfactant ionic.

Traditionally, detergent manufacturers, have been producing solid detergent products, through the spray spray drying of a dispersion aqueous, which contained the various components of the composition detergent, including a fluorescent whitening agent. For this one  purpose, detergent manufacturers prefer to use a component of fluorescent whitening agent, in the form of a liquid formulation, in order to facilitate the incorporation of fluorescent whitening agent, in the suspension to be dried by spray projection (spray). As a result, the fluorescent whitening agents are often supplied to detergent manufacturers, in the form of an aqueous suspension. Such types of aqueous suspensions of fluorescent whitening agent, however, they usually contain large amounts of water, the which must be removed during the subsequent drying stage by spray projection (spray), and are often hampered through problems, such as lump formation, during spray spray drying, as well as instability, tending to sedimentation, during storage.

Recently, the fact that, detergent manufacturers can simplify in a way considerable, the detergent production process, proceeding to apply a liquid formulation of a bleaching agent fluorescent, at the end of the detergent production process, to a mixture in granular form, previously dried by vacuum, of the remaining detergent components. For this application, there is a need for the fact of providing the bleaching agent fluorescent, in a liquid form, in which, the content of Water is reduced. In addition to that, detergent manufacturers, have expressed the wish that, the fluorescent whitening agent, be supplied in the form of a homogeneous solution, namely in a way to avoid the problems associated with dispersions Traditional watery. Still, an additional requirement is that of that, the viscosity of such a homogeneous solution, be as reduced enough to allow conventional pumping of the fluorescent whitening agent formulation.

Liquid formulations of fluorescent whitening agents are also known, which use organic solvents and are substantially anhydrous (see, for example, the French patent application document FA
- A - 2 654 123, and European patent application document EP - A - 0 703 293. These liquid formulations, however, are usually highly viscous, and need to be incorporated into the matter in the form of detergent powder, by means of special mixing techniques. US-A-3,953,380, discloses liquid detergent compositions, comprising a fluorescent bleaching agent, at a percentage of 0.5-5%, 40-75% non-ionic detergent, and 3 - 35% water.

Surprisingly, it has been found now the fact that non-ionic fluorescent bleaching agents, they are soluble in a mixture comprising a predominant amount of a certain type of non-ionic surfactant, and an additional amount reduced water, to provide clear, stable solutions of reduced viscosity

In accordance with the above, the present invention, provides a liquid formulation of agent fluorescent bleach, which is a solution that has a viscosity of 50 to 5000 mPas, preferably, 100 to 3500 mPas, and especially, 100 to 1000 mPas, and which understands:

a) 10-25%, preferably 15-20%, by weight, of an anionic fluorescent bleaching agent, based to the total weight of the formulation;

b) 15-35%, preferably 20-30%, by weight, of water, based on the total weight of the formulation; Y

c) 45-75%, preferably 50-70%, by weight, based on the total weight of the formulation, of a nonionic surfactant having the formula:

one

in which, m, is 1, 2, 3 or 4 and, when m, is 1, R is a C 8 -C 18 alkyl residue, or a C 8 -C 18 alkylcarboxyl residue; when M, is 2, R is an alkylene glycol residue C_ {2} -C_ {4}, from which the two have been removed hydroxy groups; when m is 3, R, is the residue of trimethylolpropane, from which the three hydroxy groups have been removed; and, when m is 4, R is the pentaerythritol residue, of which they have removed the four hydroxy groups; R1, is hydrogen, methyl, or ethyl; and n, is a number within margins ranging from 1 to 40

Preferably, m is 1, 3 or 4 and, when m is 1, R, is a C 8 -C 18 alkyl residue, or a C 8 -C 18 alkylcarboxyl residue; when m, is 3, R the trimethylolpropane residue, of which removed the three hydroxy groups; and, when m is 4, R is the residue of pentaerythritol, from which the four groups have withdrawn hydroxy; R1 is hydrogen, methyl, or ethyl; and n, is a number comprised within margins ranging from 1 to 40.

The viscosity of the liquid formulation of the fluorescent whitening agent in accordance with the present invention, is determined as a shear force of 100 / s, and at a temperature of 25 ± 1 ° C.

Anionic fluorescent whitening agents for use in the present invention, they are those that have a of the following two formulas:

two

or

3

in which, R_ {2} and R_ {3}, are, of a independently, OH, NH2, O-alkyl O-C_ {1} -C_ {{}}, O-aryl, NH-C 1 -C 4 alkyl, N (C 1 -C 4 alkyl) 2, N (C 1 -C 4 alkyl) (hydroxyalkyl C 1 {C 4}), N (hydroxy-alkyl C 1 -C 4) 2, NH-aryl, morpholino, S-alkyl (aryl) -C 1 -C 4, Cl or OH; R 4, is H, SO 3 M, O-alkyl C_ {C} {C4}, CN, Cl, COO-C 1 -C 4 alkyl, or CON (C 1 -C 4 alkyl) 2; M, is H, Li, Na, Ka, Ca, Mg, ammonium, mono-, di-, tri, or tetra-C 1 -C 4 -alkyl - ammonium, mono-, di-, or tri-hydroxyalkyl-C 1 -C 4 -ammonium, or ammonium, which is di-, or tri- substituted with a mixture of groups C 1 -C 4 alkyl and hydroxyalkyl C 1 -C 4; and p is 0 or one.

In the compounds of the formulas (2) or (3), the C 1 -C 4 alkyl groups, are, for example, methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl. Aryl groups, they are, for example, naphthyl or, especially, phenyl.

Preferred compounds of the formula (2), are those in which, R_ {2} and R_ {3}, in a way independent, they are methoxy, phenoxy, NH2, NH-methyl, N (methyl) 2, N (methyl) (hydroxyethyl), NH-ethyl, (hydroxyethyl) 2, NH-phenyl, morpholino, S-methyl (phenyl), Cl or OH.

They are specific examples of the formula (2), those who have one of the formulas:

4

40

5

Y

6

Preferred compounds of the formula (3), are those in which, R4, is H or Cl, and p, is 1.

Specific preferred examples of the formula (3), are those that have one of the formulas:

7

Y

8

In a specific way, the compound of the formula (10) or a crystalline modification thereof, as described in the patent application document European EP - A - 0 577 557.

If desired, a mixture of two or more fluorescent, anionic bleaching agents, such as make up a) of the formulation in accordance with this invention.

The component b) of the formulation, in Concordance with the present invention is, preferably, Water. If desired, however, water can be used in conjunction with one or more polar solvents, such as the alkylene glycol, for example, ethylene glycol or 1,2-propylene glycol, or a polyalkylene glycol, especially, polyethylene glycol or polypropylene glycol. The amount of any co-solvent, is found preferably, within a range of 0 - 15%, by weight, based on the total weight of the formulation.

The radical R, in the compounds of the formula (1), when m, is 1, is derived from an alkyl monoalcohol C_ {8} -C_ {18}. Examples of such monoalcohols, include naturally occurring monoalcohols, such like lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol, as well as alcohols synthetics, such as 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, n-decanol, C 8 -C 13 oxoalcohols, tridecyl alcohol, isodecyl alcohol, or primary alcohols, linear c 8 {-C 18}. Such types of linear primary alcohols in C_ {8} -C_ {18}, are commercially obtainable, in the market, under the trade name Alfols, being examples typical of this one, the Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol) 16-18). The name "Alfol" is a name corresponding to a registered trademark.

Preferred examples of the formula (1), wherein, m, is 1, include, for example, polyaducts of 3-20 moles of ethylene oxide, with 1 mole of a C 8 -C 18 alkyl monoalcohol . They are specifically interesting, the polyaducts of
3-20 moles of ethylene oxide, with 1 mole of a C 11 C 13 oxoalcohol, and polyaducts of 8-20 moles of ethylene oxide, with 1 mole of C 12 -C 14 fatty alcohol }

The radical R, in the compounds of formula (1), when m is 2, it is derived from an alkylene glycol residue C_ {2} -C_ {4}, from which the two have been removed hydroxy groups Examples of such types of ethylene glycol C 2 -C 4, include ethylene glycol, n-butylene glycol and, especially, propylene glycol.

Preferred examples of compounds of the formula (1), in which m is included, for example, polyamides of 2-20 moles of ethylene oxide with one mole of one C 2 -C 4 alkylene glycol, preferably, polyethylene glycol ethers of propylene glycol, in particular, those who have the formula:

9

in which, x and y, are each of them a integer, within ranges ranging from 1 to 10, preferably, within a range ranging from 1 to 5, being, the sum of x and y, in a way preferable, about 10.

The alkyl radical R, in the compounds of Formula (1), when m is 3, is derived from trimethylolpropane.

Examples of preferred compounds of the formula (1), in which, m is 3, include polyaducts of 3-20 moles of ethylene oxide, with 1 mole of trimethylolpropane Especially interesting are the polyducts 7-20 moles of ethylene oxide, with 1 mole of trimethylolpropane

The alkyl radical R, in the compounds of the Formula (1), when m is 4, are derived from pentaerythritol.

Preferred compounds of the formula (1), in which, m is 4, include 4-20 polyducts moles of oxide and ethylene, with 1 mole of pentaerythritol. They are especially interesting, the polyducts of 5-20 moles of ethylene oxide, with 1 mol of pentaerythritol.

As compound C), of the formulation in in accordance with the present invention, mixtures may be used of two or more compounds of formula (1).

The compounds of formula (2) to (12) are known, and can be obtained by procedures that are well known.

The optional auxiliaries that can be found present in the formulation of the present invention, include a the stabilizers that are effective in adjusting the fluidity properties of the formulation, agents anti-foaming agents, alkaline agents, softeners tissues, anti-redeposition agents, antioxidants, auxiliary formers, such as polyacrylic acid, and fragrances

Examples of such types of stabilizers, include, for example, kaolin, Mg / Al silicate, especially bentonite, montmorillonite, a zeolite or a silicic acid highly dispersed

The formulation of the present invention can be produced by mixing fluorescent whitening agent, solvent, and the compound of the formula (1), together with optional auxiliaries, and homogenizing the mixture in this way obtained, preferably, at a high temperature, by example, at 40-100 ° C. Mixing is done in a way convenient, by an appropriate agitation device.

The resulting formulation is normally a clear and stable solution. Occasionally, however, it may be it is necessary to filter the formulation, in order to eliminate smaller amounts of insoluble components.

The formulation of the present invention is particularly suitable for incorporation into a composition dry detergent, in a convenient way, proceeding to add the required amount of the formulation of the present invention, to a dry detergent composition and then proceeding to homogenize the mixture in this way. The formulation of the present invention, however, can also be used for production of liquid detergents, by adding the required amount of the formulation of the present invention, at a liquid detergent composition and then homogenizing the mixture thus obtained.

The examples given below, further illustrate the present invention. The parts and percentages indicated in them, refer to weight, unless expressly specified otherwise. The data from viscosity, in the examples, is expressed in mPas, and determined at a shear force of 100 / s, and at a temperature of 25 ° C ± 1 ° C.

Example 1

The following materials are loaded in a 1 liter flask:

100 g of deionized water;

600 g of a 1 part adduct of oxoalcohol C 13 with 9 parts of ethylene oxide; Y

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula:

10

The suspension thus obtained is heats, with stirring regime, at an internal temperature within a range of 70-80 ° C. After a After 4 to 5 hours, a solution is obtained almost clear, which contains less than 1%, by weight, of components not dissolved. The solution is cooled to a temperature comprised within a range of 40-50 ° C, and filtered. You get one clear, yellow solution, which has a substance content active of a percentage of 15%, by weight, a water content of 25%, by weight, and a viscosity of 462 mPas.

Example 2

Using the procedure described in the Example 1, we proceeded to prepare solution formulations additional of the compound of formula (10), proceeding to vary the quantities of the respective components and / or varying the number of parts of ethylene oxide, in the condensation product. The results, are shown in the table given to continuation.

TABLE

Example Cpd (10) Cake Water Parts from Percentage Appearance Viscosity from pressing % in weigh OE in the in weigh of the of the product mPas % in weight adduct adduct% to 25ºC two 30 fifteen 9 55 Slightly 506 opalescent

Example 3

The following materials are loaded in a 1 liter flask:

100 g of deionized water;

600 g of a 1 part adduct of oxoalcohol C 13 with 11 parts of ethylene oxide; Y

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained, which is a solution clear, at a temperature of 25 ° C, and a viscosity of 397 mPas.

Example 4

The following materials are loaded in a 1 liter flask:

100 g of deionized water;

420 g of a 1 part adduct of oxoalcohol C 13 with 8 parts of ethylene oxide;

180 g of a 1 part adduct of oxoalcohol C 13 with 15 parts of ethylene oxide; Y

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained, which is a solution clear, at a temperature of 25 ° C, and a viscosity of 434 mPas.

Example 5

The following materials are loaded in a 1 liter flask:

150 g of deionized water;

385 g of a 1 part adduct of oxoalcohol C 13 with 8 parts of ethylene oxide;

165 g of a 1 part adduct of oxoalcohol C 13 with 15 parts of ethylene oxide; Y

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained, which is a solution clear, at a temperature of 25 ° C, and a viscosity of 550 mPas.

Example 6

The following materials are loaded in a 1 liter flask:

50 g of deionized water;

455 g of a 1 part adduct of oxoalcohol C 13 with 8 parts of ethylene oxide;

195 g of a 1 part adduct of oxoalcohol C 13 with 15 parts of ethylene oxide; Y

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained, which is a solution clear, at a temperature of 25 ° C, and a viscosity of 540 mPas.

Examples 7 to 10

The following materials are loaded in a 1 liter flask:

100 g of deionized water;

600 g of a 1 part adduct of fatty alcohol C 12 -C 14 with 15 parts of oxide ethylene;

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained (example 7), which is a clear solution, at a temperature of 25 ° C, and a viscosity of 1600 mPas.

Similar good results are obtained, when 1 part of fatty alcohol is replaced C 12 -C 14 with 15 parts of oxide ethylene, using a 1 part adduct of fatty alcohol C 12 -C 14, with 20 parts of ethylene oxide (Example 8, viscosity, 3261 mPas); or through a 1 part adduct of C 12 -C 14 fatty alcohol, with 8 parts of ethylene oxide (Example 9, viscosity, 829 mPas), or when not use non-deionized water and the amount of cake pressed (with a 50% content, by weight, of active substance) of the agent fluorescent bleach, which has the formula (10), is increased in an amount of 10 g (Example 10; viscosity, 2417 mPas).

Examples 11 and 12

The following materials are loaded in a 1 liter flask:

100 g of deionized water;

420 g of a 1 part adduct of fatty alcohol C 12 -C 14 with 8 parts of oxide ethylene;

180 g of a 1 part adduct of fatty alcohol C 12 -C 14 with 15 parts of ethylene oxide; Y

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in 1, obtains a liquid formulation (Example 11), which, after filtration is a clear solution, at a temperature of 25 ° C, and which has a viscosity of 732 mPas.

Similar good results are obtained, when the amount of adduct, 1 part of fatty alcohol C 12 -C 14, with 8 parts of oxide ethylene, is reduced to 300 g and, the amount of adduct of 1 part of C 12 -C 14 fatty alcohol, with 15 parts of ethylene oxide, increases to 300 g (Example 12; viscosity, 893 mPas).

Examples 13 and 14

The following materials are loaded in a 1 liter flask:

150 g of deionized water;

385 g of a 1 part adduct of fatty alcohol C 12 -C 14 with 8 parts of oxide ethylene;

165 g of a 1 part adduct of fatty alcohol C 12 -C 14 with 15 parts of ethylene oxide; Y

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300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained (example 13; viscosity 807 mPas), which, after filtration, is a clear solution, at a temperature of 25 ° C.

Similar good results are obtained, when the amount of adduct, 1 part of fatty alcohol C 12 -C 14, with 8 parts of oxide ethylene, is reduced to 275 g and, the amount of adduct of 1 part of C 12 -C 14 fatty alcohol, with 15 parts of ethylene oxide, increases to 275 g (Example 14; viscosity, 913 mPas).

Examples 15 a 17

The following materials are loaded in a 1 liter flask:

100 g of distilled water;

600 g of a 1 part adduct of pentaerythritol with 5 parts of ethylene oxide; Y

400 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained (example 15; viscosity less than 500 mPas), which, after filtration, It is a clear solution, at a temperature of 25 ° C.

Similar good results are obtained, when the amount of the adduct, 1 part of pentaerythritol, with 5 parts of ethylene oxide, it is replaced by an amount of adduct of 1 part of trimethylolpropane, with 7 parts of ethylene oxide, (Example 16; viscosity, 446 mPas); or with the adduct of 1 part of trimethylolpropane, with 20 parts of ethylene oxide (Example 17, viscosity; 558 mPas).

Examples 18 a twenty

The following materials are loaded in a 1 liter flask:

100 g of distilled water;

600 g of a 1 part adduct of pentaerythritol with 5 parts of ethylene oxide; Y

300 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

Using the procedure described in the formula 1, a liquid formulation is obtained (example 18; viscosity less than 500 mPas), which, after filtration, It is a clear solution, at a temperature of 25 ° C.

Similar good results are obtained, when the amount of the adduct, 1 part of pentaerythritol, with 5 parts of ethylene oxide, it is replaced by an amount of adduct of 1 part of trimethylolpropane, with 7 parts of ethylene oxide, (Example 19; viscosity, 101 mPas); or with the adduct of 1 part of trimethylolpropane, with 20 parts of ethylene oxide (Example 20, viscosity; 206 mPas).

Examples 21 a 22

The following materials are loaded in a 1 liter flask:

100 g of distilled water;

300 g castor oil with 40 parts of oxide of ethylene; Y

400 g of pressed cake, moist (with a content 50%, by weight of active substance) of the bleaching agent fluorescent, which has the formula (10).

The suspension thus obtained is heats, under agitation, at an indoor temperature of 70-80 ° C. After a period of 4-5 hours, you get an almost clear looking solution, which contains less 1%, by weight, of undissolved components. The solution is it is then cooled to a temperature of 50-60 ° C, and filtered. A clear, yellow solution is obtained, which has a content of active substance of a percentage of 15%, by weight, a content of water of 25%, by weight, and a viscosity of 3000 mPas. The solution, remains clear, after remaining at rest, during A time course of 2 days.

Similar results are obtained when the Adduct amount, 1 part castor oil, is replaced by an adduct of 1 part of castor oil, with 11 parts of ethylene oxide.

Claims (36)

1. A liquid formulation of bleaching agent fluorescent, which is a solution that has a viscosity comprised within margins ranging from 50 to 5000 mPas, and the which includes: a) 10-25%, preferably 15-20%, by weight, of an anionic fluorescent bleaching agent, based to the total weight of the formulation; b) 15-35%, preferably 20-30%, by weight, of water, based on the total weight of the formulation; Y c) 45-75%, preferably 50-70%, by weight, based on the total weight of the formulation, of a nonionic surfactant having the formula: eleven in which, m, is 1, 2, 3 or 4 and, when m, is 1, R is a C 8 -C 18 alkyl residue, or a C 8 -C 18 alkylcarboxyl residue; when M, is 2, R is an alkylene glycol residue C_ {2} -C_ {4}, from which the two have been removed hydroxy groups; when m is 3, R, is the residue of trimethylolpropane, from which all three groups have withdrawn hydroxy; and, when m is 4, R is the pentaerythritol residue, of which the four hydroxy groups have been removed; R_ {1}, is hydrogen, methyl, or ethyl; and n, is a number within margins ranging from 1 to 40 2. A formulation according to claim 1 in which, m, is 1, 3 or 4 and, when m is 1, R, is an alkyl residue C 8 -C 18, or an alkylcarboxyl residue C 8 -C 18; when m, is 3, R is the residue of  trimethylolpropane, from which all three groups have withdrawn hydroxy; and, when m is 4, R is the pentaerythritol residue, of which the four hydroxy groups have been removed; R_ {1}, is hydrogen, methyl, or ethyl; and n, is a number within some margins ranging from 1 to 40. 3. A formulation according to claim 1 or 2, which has a viscosity within a range ranging from 100 to 3550 mPas. 4. A formulation according to claim 3, the which has a viscosity within a range that They range from 100 to 1000 mPas. 5. A formulation, according to any one of the preceding claims, which contains a percentage of a 15-20%, by weight, of an anionic fluorescent bleaching agent, based on the total weight of the formulation. 6. A formulation, according to any one of the preceding claims, which contains a percentage of a 20-30%, by weight, of a polar solvent, based on the total weight of the formulation 7. A formulation, according to any one of the preceding claims, which contains a percentage of a 50-70%, by weight, of a non-ionic surfactant, which has the Formula 1). 8. A formulation, according to any one of the preceding claims, in which the bleaching agent fluorescent, anionic, has one of the following two formulas: 12

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or 13 in which, R_ {2} and R_ {3}, are, of a independently, OH, NH2, O-alkyl C 1 -C 4, O-aryl, NH-C 1 -C 4 alkyl,  N (C 1 -C 4 alkyl) 2, N (C 1 -C 4 alkyl) (hydroxyalkyl  C 1 {C 4}), N (hydroxy-alkyl C 1 -C 4) 2, NH-aryl, morpholino, S-alkyl (aryl) -C 1 -C 4, Cl or OH; R 4, is H, SO 3 M, O-alkyl C_ {C} {C4}, CN, Cl, COO-C 1 -C 4 alkyl, or CON (C 1 -C 4 alkyl) 2; M, is H, Li, Na, Ka, Ca, Mg, ammonium, mono-, di-, tri, or tetra-C 1 -C 4 -alkyl - ammonium, mono-, di-, or tri-hydroxyalkyl-C 1 -C 4 -ammonium, or ammonium, which is di-, or tri-substituted with a C 1 -C 4 alkyl group mixture C 1 -C 4 hydroxyalkyl; and p is 0 or one. 9. A formulation according to claim 8 in which, R_ {2} and R_ {3}, are, in an independent way the one with respect to the other, methoxy, phenoxy, NH2, NH-methyl, N (methyl) 2, N (methyl) (hydroxyethyl), NH-ethyl, N (hydroxy-ethyl) 2, NH-phenyl, morpholino, S-methyl (phenyl), Cl or OH. 10. A formulation according to claim 8 or 9, in which, the compound of the formula (2), has one of the following formulas: 14 fifteen or 16 11. A formulation according to claim 8, in which, in the compounds of formula (3), R 4, is H or Cl, and  p, is 1. 12. A formulation according to claim 8 or 11, in which, the compound of formula (3), has one of the formulas: 17 18 13. A formulation according to claim 12, in which, the compound of the formula (3), is the compound of the formula (10) or a crystalline modification of the compound of the formula (10). 14. A formulation, according to any one of the preceding claims, in which, as component a) of the formulation, a mixture of two or more agents is used fluorescent, anionic bleaches. 15. A formulation according to claim 1, in which, water is used, in conjunction with one or more polar co-solvents. 16. A formulation according to claim 15, in which, the polar cosolvent, is an alkylene glycol or a polyalkylene glycol. 17. A formulation according to claim 16, in which, the alkylene glycol, is ethylene glycol or 1,2-propylene glycol. 18. A formulation according to claim 16, in which, the polyalkylene glycol, is polyethylene glycol or polypropylene glycol 19. A formulation, according to any one of the claims 15 to 18, wherein, the amount of any co-solvent, is included within margins of 0-15%, by weight, based on the total weight of the formulation. 20. A formulation, according to any one of the preceding claims, in which, the compound of the formula (1), m, is 1 and, the compound, is a polyduct of 3-20 moles of ethylene oxide, with 1 mole of monoalcohol C 8 -C 18 alkyl. 21. A formulation according to claim 20, in which, the polyaduct, is a polyamide of 3-20 moles of oxide of ethylene, with one mole of an alcohol alcohol C_ {11} -C_ {13} or a pliaduct of 8-20 moles of ethylene oxide with 1 mol of a fatty alcohol C_ {12} -C_ {14}. 22. A formulation, according to any one of the claims 1 to 19, wherein, in the compound of the formula (1), m, is 2 and, the compound, is a pliaduct of 2-20 moles of ethylene oxide with 1 mol of an alkylene glycol C_ {2} -C_ {4}. 23. A formulation according to claim 22, in which, the C 2 -C 4 alkylene glycol, is ethylene glycol or n-butylene glycol. 24. A formulation according to claim 22, in which, the C 2 -C 4 alkylene glycol, is propylene glycol. 25. A formulation according to claim 24, in which, in the compound of the formula (1), it has the formula: 19 in which, x and y, are each of them a integer, within ranges ranging from 1 to 10, 26. A formulation according to claim 25, in which, x and y, are each an integer that is It is within a range of 1 to 5. 27. A formulation according to claim 26, in which, the sum of x and y, is 10. 28. A formulation, according to any one of the claims 1 to 19, wherein, in the compound of the formula (1), m, is 3 and, the compound, is a polyaduct of 3-20 atoms of ethylene oxide with 1 mol of trimethylolpropane. 29. A formulation according to claim 28, in which the compound is a polyamide of 7-20 moles of oxide of ethylene with 1 mol of trimethylolpropane. 30. A formulation, according to any one of the claims 1 to 19, wherein, in the compound of the formula (1), m, is 4 and, the compound, is a polyamide of 4-20 atoms of ethylene oxide with 1 mol of pentaerythritol. 31. A formulation according to claim 30, in which the compound is a polyamide of 5-20 moles of oxide of ethylene with 1 mol of pentaerythritol. 32. A formulation, according to any one of the preceding claims, in which, as component c) of the formulation, a mixture of two or more of the compounds is used of the formula (1). 33. A formulation according to any one of the preceding claims, in which one or more auxiliaries selected from among stabilizers that are effective in adjusting the fluidity properties of the formulation, antifoaming agents, alkaline agents, are also present. fabric softeners, agents
anti-redeposition, antioxidants, auxiliary formers and fragrances. 34. A procedure for the production of a formulation according to claim 1, comprising mixing the fluorescent, anionic bleaching agent, and the compound of the formula (1), together with any auxiliaries, and the homogenization of the mixture in this way obtained. 35. A method according to claim 34, in which, the procedure, is conducted at a temperature within a range of 40-100 ° C. 36. A procedure for the production of a detergent, which comprises adding the required amount of the formulation of claim 1, to a detergent composition and, then homogenize the mixture in this way.