DE69726544T2 - Fluorescent white toner formulation - Google Patents

Description

The present invention relates to fluorescent whitening formulations and especially liquid ones fluorescent whitening formulations, what a solution a fluorescent whitener and of a specific type of nonionic surfactant.

Traditionally, detergent manufacturers have solid detergent products by spray drying an aqueous slurry which the various components of the detergent composition included, including a fluorescent whitener, manufactured. For this purpose, the detergent manufacturers prefer the use of the fluorescent whitening component in the mold a liquid Wording to insert of the fluorescent whitener into the slurry, which are spray dried should be easier. As a result, they become fluorescent whiteners often in the form of an aqueous slurry delivered to the detergent manufacturers. Such watery slurries of fluorescent whitening agents however usually contain size Proportions of water which during the subsequent spray drying needs to be removed and most of the time have problems like forming lumps during of spray drying as well as the instability regarding sedimentation during storage.

It was recently found that the detergent manufacturers the method of manufacturing detergents by application a liquid Formulation of a fluorescent whitener onto a previously spray dried one granulated Mix the remaining detergent components at the end of the Simplify the process for producing the cleaning agent significantly can. For this There is a need to provide the fluorescent application whitener in a liquid Form in which the water content is reduced. In addition, the Detergent manufacturers desire that the fluorescent whiteners in the form of a homogeneous solution, namely in a form that addresses the problems associated with conventional aqueous slurries avoids, available is provided. Yet another requirement is that the viscosity the homogeneous solution is sufficiently low that conventional pumping of the fluorescent Whitener Formulation allows becomes.

Liquid formulations are also known of fluorescent whiteners, what organic solvents use and are essentially anhydrous (e.g. FR-A-2 654 123, EP-A-0 703 293). This liquid However, wording is common highly viscous, and there is a need for them in the cleaning powder using special mixing techniques. US-A-3,953,380 reveals liquid Detergent compositions containing fluorescent whitening agents in the proportion of 0.5–5%, non-ionic detergent in the proportion of 40–75% and water in the proportion of 5-35% include.

Surprisingly it has now been found that anionic fluorescent whitening agents soluble in a mixture which are a predominant amount of a certain type non-ionic surfactant and a lower proportion of water, being stable, clear solutions low viscosity to be provided.

• a) 10–25 Gew.-%, bevorzugt 15–20 Gew.-% eines anionischen fluoreszierenden Weißmachers, basierend auf dem Gesamtgewicht der Formulierung;
• b) 15–35 Gew.-%, bevorzugt 20–30 Gew.-% Wasser, basierend auf dem Gesamtgewicht der Formulierung; und
• c) 45–75 Gew.-%, bevorzugt 50–70 Gew.-%, auf der Basis des Gesamtgewichts der Formulierung, eines nichtionischen Tensids mit der Formel:
  
  worin m 1, 2, 3 oder 4 ist, und wenn m 1 ist, R ein C₈-C₁₈-Alkylrest oder ein C₈-C₁₈-Alkylcarboxyrest ist; wenn m 2 ist, R ein C₂-C₄-Alkylenglykolrest ist, von welchem die zwei Hydroxygruppen entfernt worden sind; wenn m 3 ist, R der Rest von Trimethylolpropan ist, von dem die drei Hydroxygruppen entfernt worden sind; und wenn m 4 ist, R der Rest von Pentaerythritol ist, von dem die vier Hydroxygruppen entfernt worden sind; R₁ Wasserstoff, Methyl oder Ethyl ist; und n eine Zahl im Bereich von 1 bis 40 ist.

Accordingly, the present invention provides a liquid fluorescent whitening agent formulation which is a solution having a viscosity of 50 to 5,000 mPas, preferably 100 to 3,500 mPas, in particular 100 to 1,000 mPas, and which comprises:

• a) 10-25% by weight, preferably 15-20% by weight of an anionic fluorescent whitening agent, based on the total weight of the formulation;
• b) 15-35 wt%, preferably 20-30 wt% water, based on the total weight of the formulation; and
• c) 45-75% by weight, preferably 50-70% by weight, based on the total weight of the formulation, of a nonionic surfactant with the formula:
  
  wherein m is 1, 2, 3 or 4, and when m is 1, R is a C ₈ -C ₁₈ alkyl group or a C ₈ -C ₁₈ alkyl carboxy group; when m is 2, R is a C ₂ -C ₄ alkylene glycol residue from which the two hydroxy groups have been removed; 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 residue of pentaerythritol from which the four hydroxy groups have been removed; R _{1 is} hydrogen, methyl or ethyl; and n is a number 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 group or a C ₈ -C ₁₈ alkyl carboxy group; when m is 3, R is the residue of trimethylolpropane from which the three hydroxyl groups arise were removed; and when m is 4, R is the residue of pentaerythritol from which the four hydroxy groups have been removed; R ₁ is hydrogen, methyl or ethyl; and n is a number ranging from 1 to 40.

The viscosity of the liquid fluorescent whitening formulation according to the present Invention is at a thrust of 100 / s and a temperature of 25 ° C ± 1 ° C.

worin R₂ und R₃ unabhängig OH, 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, NH-Aryl, Morpholino, S-C₁-C₄-Alkyl(aryl), Cl oder OH sind; R₄ H, SO₃M, O-C₁-C₄-Alkyl, CN, Cl, COO-C₁-C₄-Alkyl oder CON(C₁-C₄-Alkyl)₂ ist; M H, Li, Na, K, Ca, Mg, Ammonium, Mono-, Di-, Tri- oder Tetra-C₁-C₄-alkylammonium, Mono-, Di-oder Tri-C₁-C₄-hydroxyalkylammonium oder Ammonium ist, welches di- oder trisubstituiert ist mit einer Mischung aus C₁-C₄-Alkyl- und C₁-C₄-Hydroxyalkylgruppen; und p 0 oder 1 ist.Preferred anionic fluorescent whitening agents for use in the present invention are those having one of the formulas:

wherein R ₂ and R _{3 are} independently OH, NH ₂ , OC ₁ -C ₄ alkyl, O-aryl, NH-C ₁ -C ₄ alkyl, N (C ₁ -C ₄ alkyl) ₂ , N (C ₁ -C ₄ alkyl) (C ₁ -C ₄ hydroxyalkyl), N (C ₁ -C ₄ hydroxyalkyl) ₂ , NH-aryl, morpholino, SC ₁ -C ₄ alkyl (aryl), Cl or OH; R _{4 is} H, SO ₃ M, OC ₁ -C ₄ alkyl, CN, Cl, COO-C ₁ -C ₄ alkyl or CON (C ₁ -C ₄ alkyl) ₂ ; MH, Li, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C ₁ -C ₄ -alkylammonium, mono-, di- or tri-C ₁ -C ₄ -hydroxyalkylammonium or ammonium which is di- or tri-substituted with a mixture of C ₁ -C ₄ alkyl and C ₁ -C ₄ hydroxyalkyl groups; and p is 0 or 1.

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

Preferred compounds of formula (2) are those in which R ₂ and R _{3 are} independently methoxy, phenoxy, NH ₂ , NH-methyl, N (methyl) ₂ , N (methyl) (hydroxyethyl), NH-ethyl, N (hydroxyethyl) ) ₂ , NH-phenyl, morpholino, S-methyl (phenyl), Cl or OH.

Specific examples more preferred Compounds of formula (2) are those with one of the formulas:

Preferred compounds of formula (3) are those wherein R _{4 is} H or Cl and p is 1.

Specific preferred examples of the compounds of formula (3) are those with one of the formulas:

The connection is particularly preferred of formula (10) or a crystal modification thereof as described in EP-A-O 577 557 is described.

If desired, a mixture of two or more anionic fluorescent whiteners as component (a) of the formulation according to the present invention be used.

Component (b) of the formulation according to the present Invention is water. If desired can However, water together with one or more polar co-solvents be used, such as an alkylene glycol, e.g. B. ethylene glycol or 1,2-propylene glycol, or a polyalkylene glycol, especially polyethylene glycol or polypropylene glycol. The amount of any co-solvent is preferably in the range of 0-15% by weight based on the Total formulation weight.

The radical R in the compounds of the formula (1), when m is 1, is derived from a C ₈ -C ₁₈ -alkyl monoalcohol. Examples of such monoalcohols include naturally occurring monoalcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol, and also synthetic alcohols, such as 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethyl nonyl alcohol, n Decanol, C ₉ -C ₁₃ oxo alcohols, tridecyl alcohol, isodecyl alcohol or linear primary C ₈ -C ₁₈ alcohols. Such linear primary C ₈ -C _{1 8} alcohols are commercially available under the trade name of Alfols, typical examples being Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol (16-18). The name "Alfol" is a registered trademark.

Preferred examples of the compounds of formula (1) wherein m is 1 include e.g. B. Polyadducts of 3-20 moles of ethylene oxide with 1 mole of a C ₈ -C ₁₈ alkyl monoalcohol. Of particular interest are polyadducts of 3-20 moles of ethylene oxide with 1 mole of a C ₁₁ -C ₁₃ oxo alcohol and polyadducts of 8-20 moles of ethylene oxide with 1 mole of a C ₁₂ -C ₁₄ fatty alcohol.

The radical R in the compounds of the formula (1), when m is 2, is derived from a C ₂ -C ₄ alkylene glycol radical from which the two hydroxyl groups have been removed. Examples of such C ₂ -C ₄ alkylene glycols include ethylene glycol, n-butylene glycol and in particular propylene glycol.

worin x und y jeweils ganze Zahlen innerhalb des Bereiches von 1 bis 10, bevorzugt innerhalb des Bereichs von 1 bis 5 sind, wobei die Summe von x und y bevorzugt ungefähr 10 ist.Preferred examples of the compounds of formula (1) wherein m is 2 include e.g. B. Polyadducts of 2-20 moles of ethylene oxide with 1 mole of a C ₂ -C ₄ alkylene glycol, preferably polyethylene glycol ether of propylene glycol, especially those having the formula:

wherein x and y are each integers within the range from 1 to 10, preferably within the range from 1 to 5, the sum of x and y preferably being approximately 10.

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

Preferred examples of the compounds of formula (1) wherein m is 3 include polyadducts of 3-20 moles Ethylene oxide with 1 mole of trimethylolpropane. Are particularly interesting Polyadducts of 7-20 moles Ethylene oxide with 1 mole of trimethylolpropane.

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

Preferred examples of the compounds of formula (1) wherein m is 4 include polyadducts of 4-20 moles Ethylene oxide with 1 mole of pentaerythritol. Are particularly interesting Polyadducts of 5-20 Moles of ethylene oxide with 1 mole of pentaerythritol.

Mixtures of 2 or more of the Compounds of formula (1) can as component c) of the formulation according to the present invention be used.

The compounds of formula (2) to (12) are known and can can be obtained by known methods.

Optional tools, which in of the formulation of the present invention Stabilizers, which are used to adjust the flow properties of the formulation are effective, anti-foaming agents, alkaline agents, fabric softeners, Anti-re-settling agents, anti-oxidants, auxiliary builders, like polyacrylic acid, and fragrances.

Examples of such stabilizers include e.g. B. kaolin, a Mg / Al silicate, especially bentonite, Montmorillonite, a zeolite or a highly disperse silica.

The wording of the present Invention can be made by mixing the fluorescent whitener, of the solvent and the compound of formula (1) along with any optional Auxiliaries and homogenization of the mixture thus obtained are preferred at an elevated Temperature, e.g. B. at 40-100 ° C. become. Mixing is best done using a suitable stirrer causes.

The resulting wording is usually a clear and stable solution. Depending on it, however the formulation may need to be filtered to remove small proportions on insoluble Remove components.

The wording of the present The invention is particularly suitable for incorporation into a dry cleaning composition, usually by adding the required amount of the formulation of the present Invention to a dry cleaning composition and subsequent homogenization the mixture thus obtained. The formulation of the present invention can also be used to produce liquid cleaning agents Add the required amount of the formulation of the present Invention to a liquid Detergent composition and then homogenizing the so obtained mixture can be used.

The following examples illustrate this the present invention further. Parts and percentages, which ones given herein are by weight as long as nothing other is indicated. The viscosity data, which in the examples are expressed in mPas and are given a shear force of 100 / s and a temperature of 25 ° C ± 1 ° C.

example 1

The following materials are placed in a 1 liter flask:
100 g deionized water;
600 g of an adduct of one part of a C ₁₃ oxo alcohol with 9 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula:

The suspension thus obtained is with stirring heated to an internal temperature of 70-80 ° C. After 4-5 hours becomes an approximate clear solution obtained, which contains less than 1 wt .-% undissolved components. The solution is cooled to 40-50 ° C and filtered. A clear yellow solution is obtained with an active substance content of 15 wt .-%, a Water content of 25% by weight and a viscosity of 462 mPas.

Example 2

Using the method described in Example 1, further solution formulations of the compound are prepared by varying the amount of the corresponding components and / or by varying the amount by weight of ethylene oxide in the condensation product. The results are as follows shown in the table.

table

Example 3

The following materials are placed in a 1 liter flask:
100 g deionized water;
600 g of an adduct of 1 part of a C ₁₁ oxo alcohol with 11 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method, a liquid formulation is obtained, which is a clear solution at 25 ° C is and a viscosity of 397 mPas.

Example 4

The following materials are placed in a 1 liter flask:
100 g deionized water;
420 g of an adduct of 1 part of a C ₁₃ oxo alcohol with 8 parts of ethylene oxide;
180 g of an adduct of 1 part of a C ₁₃ oxo alcohol with 15 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method, a liquid formulation is obtained, which is a clear solution at 25 ° C represents and a viscosity of 434 mPas.

Example 5

The following materials are placed in a 1 liter flask:
150 g deionized water;
385 g of an adduct of 1 part of a C ₁₃ oxo alcohol with 8 parts of ethylene oxide;
165 g of an adduct of 1 part of a C ₁₃ oxo alcohol with 15 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method, a liquid formulation is obtained, which is a clear solution at 25 ° C represents and a viscosity of 550 mPas.

Example 6

The following materials are placed in a 1 liter flask:
50 g of deionized water;
455 g of an adduct of 1 part of a C ₁₃ oxo alcohol with 8 parts of ethylene oxide;
195 g of an adduct of 1 part of a C ₁₃ oxo alcohol with 15 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method, a liquid formulation is obtained, which is a clear solution at 25 ° C represents and a viscosity of 540 mPas.

Examples 7 to 10

The following materials are placed in a 1 liter flask:
100 g deionized water;
600 g of an adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 15 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method is a liquid formulation (example 7) Get a clear solution at 25 ° C is and a viscosity of 1600 mPas.

Similar good results are obtained when the adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 15 parts of ethylene oxide by an adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 20 parts of ethylene oxide (Example 8; viscosity 3261 mPas) ; or is replaced by an adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 8 parts of ethylene oxide (Example 9; viscosity 829 mPas); or if no deionized water is used and the amount of the moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10) is increased to 400 g (Example 10; viscosity 2417 mPas).

Examples 11 and 12

The following materials are placed in a 1 liter flask:
100 g deionized water;
420 g of an adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 8 parts of ethylene oxide;
180 g of an adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 15 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method is a liquid formulation (example 11), which after filtering a clear solution Represents 25 ° C and a viscosity of 732 mPas.

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

Examples 13 and 14

The following materials are placed in a 1 liter flask:
150 g deionized water;
385 g of an adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 8 parts of ethylene oxide;
165 g of an adduct of 1 part of a C ₁₂ -C ₁₄ fatty alcohol with 15 parts of ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method is a liquid formulation (example 13; viscosity 807 mPas), which after filtering provides a clear solution Is 25 ° C.

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

Examples 15 to 17

The following materials are placed in a 1 liter flask:
600 g of an adduct of 1 part pentaerythritol with 5 parts ethylene oxide; and
400 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method is a liquid formulation (example 15; viscosity less than 500 mPas), which is a clear solution Is 25 ° C.

Similar good results are obtained when the adduct of 1 part of pentaerythritol with 5 parts of ethylene oxide through the adduct of 1 part of trimethylolpropane with 7 parts of ethylene oxide (Example 16; viscosity 446 mPas); or through that Adduct of 1 part of trimethylolpropane with 20 parts of ethylene oxide (example 17; Viscosity 558 mPas) is replaced.

Examples 18 to 20

The following materials are placed in a 1 liter flask:
100 g deionized water;
600 g of an adduct of 1 part pentaerythritol with 5 parts ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

Using the example 1 described method is a liquid formulation (example 18; viscosity less than 500 mPas), which is a clear solution Is 25 ° C.

Similar good results are obtained when the adduct of 1 part of pentaerythritol with 5 parts of ethylene oxide through an adduct of 1 part of trimethylolpropane with 7 parts of ethylene oxide (Example 19; viscosity 101 mPas); or through that Adduct of 1 part of trimethylolpropane with 20 parts of ethylene oxide (example 20; Viscosity 206 mPas) is replaced.

Examples 21 and 22

The following materials are placed in a 1 liter flask:
100 g deionized water;
600 g of an adduct of 1 part castor oil with 40 parts ethylene oxide; and
300 g of a moist press cake / filter cake (containing 50% by weight of active substance) of the fluorescent whitening agent with the formula (10).

The suspension thus obtained is with stirring heated to an internal temperature of 70-80 ° C. After 4-5 hours becomes an approximation clear solution obtained, which contains less than 1 wt .-% undissolved components. The solution is cooled to 50-60 ° C and filtered. A clear yellow solution is obtained with an amount of active substance of 15 wt .-%, a Water content of 25% by weight and a viscosity of 3000 mPas. The solution remains clear within 2 days after standing.

Similar good results are obtained when the adduct of 1 part castor oil with 40 Parts of ethylene oxide by an adduct of 1 part of castor oil with 11 Parts of ethylene oxide is replaced.

Claims (36)

A liquid fluorescent whitening formulation which is a solution having a viscosity of 50 to 5000 mPas and which comprises: a) 10-25% by weight of at least one anionic fluorescent whitening agent based on the total weight of the formulation; b) 15-35% by weight water based on the total weight of the formulation; and c) 45-75% by weight, based on the total weight of the formulation, of at least one nonionic surfactant of the formula:

wherein m is 1, 2, 3 or 4, and when m is 1, R is a C ₈ -C ₁₈ alkyl group or a C ₈ -C ₁₈ alkyl carboxy group; when m is 2, R is a C ₂ -C ₄ alkylene glycol residue from which the two hydroxy groups have been removed; 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 residue of pentaerythritol from which the four hydroxy groups have been removed; R _{1 is} hydrogen, methyl or ethyl; and n is a number ranging from 1 to 40. A formulation according to claim 1, wherein m is 1, 3 or 4 and, if m is 1, R is a C ₈ -C ₁₈ alkyl group or a C ₈ -C ₁₈ alkyl carboxy group, if m is 3, R is the group of trimethylolpropane from which the three hydroxy groups have been removed; and when m is 4, R is the residue of pentaerythritol from which the four hydroxy groups have been removed; R _{1 is} hydrogen, methyl or ethyl; and n is a number ranging from 1 to 40. A formulation according to claim 1 or 2 which is a viscosity from 100 to 3500 mPas. A formulation according to claim 3, which has a viscosity of 100 up to 1000 mPas. Formulation according to at least one of the preceding Expectations, containing 15-20 % By weight of an anionic fluorescent whitener, based on the total weight the wording. Formulation according to at least one of the preceding Expectations, containing 20-30 % By weight of a polar solvent, based on the total weight of the formulation. Formulation according to at least one of the preceding Expectations, containing 50-70 % By weight, based on the total weight of the formulation, of a nonionic Surfactants of the formula (1). A formulation according to any one of the preceding claims, wherein the anionic fluorescent whitening agent is either the formula

in which R ₂ and R _{3 are} independently OH, NH ₂ , OC ₁ -C ₄ alkyl, O-aryl, NH-C ₁ -C ₄ alkyl, N (C ₁ -C ₄ alkyl) ₂ , N ( C ₁ -C ₄ alkyl) (C ₁ -C ₄ hydroxyalkyl), N (C ₁ -C ₄ hydroxyalkyl) ₂ , NH-aryl, morpholino, SC ₁ -C ₄ alkyl (aryl), Cl or OH are; R _{4 is} H, SO ₃ M, OC ₁ -C ₄ alkyl, CN, Cl, COO-C ₁ -C ₄ alkyl or CON (C ₁ -C ₄ alkyl) ₂ ; MH, Li, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C ₁ -C ₄ -alkylammonium, mono-, di- or tri-C ₁ -C ₄ -hydroxyalkylammonium or ammonium , which is di- or tri-substituted with a mixture of C ₁ -C ₄ alkyl and C ₁ -C ₄ hydroxyalkyl groups; and p is 0 or 1. A formulation according to claim 8, wherein R ₂ and R ₃ independently of one another methoxy, phenoxy, NH ₂ , NH-methyl, N (methyl) ₂ , N (methyl) (hydroxyethyl), NH-ethyl, N (hydroxyethyl) ₂ , NH- Are phenyl, morpholino, S-methyl (phenyl), Cl or OH. A formulation according to claim 8 or 9, wherein the compound of formula (2) has one of the following formulas:

A formulation according to claim 8, wherein in the compounds of formula (3) R _{4 is} H or Cl and p is 1. A formulation according to claim 8 or 11, wherein the compound of formula (3) has one of the formulas:

The formulation of claim 12, wherein the compound of formula (3) the compound of formula (10) or a crystal modification the compound of formula (10). Formulation according to at least one of the preceding Expectations, being a mixture of two or more anionic fluorescent whiteners is used as component a) of the formulation. The formulation of claim 1, wherein water is together is used with one or more polar co-solvents. The formulation of claim 15, wherein the polar Cosolvent is an alkylene glycol or polyalkylene glycol. The formulation of claim 16, wherein the alkylene glycol Is ethylene glycol or 1,2-propylene glycol. The formulation of claim 16, wherein the polyalkylene glycol Is polyethylene glycol or polypropylene glycol. Formulation according to at least one of claims 15 to 18, the amount of co-solvent in Range from 0-15 % By weight is based on the total weight of the formulation. A formulation according to at least one of the preceding claims, wherein in the compound of formula (1) m is 1 and the compound is a polyadduct of 3-20 moles of ethylene oxide with 1 mole of a C ₈ -C ₁₈ alkyl monoalcohol. A formulation according to claim 20, wherein the polyadduct is a polyadduct of 3-20 moles of ethylene oxide with 1 mole of a C ₁₁ -C ₁₃ oxo alcohol or a polyadduct of 8-20 moles of ethylene oxide with 1 mole of a C ₁₂ -C ₁₄ fatty alcohol. Formulation according to at least one of claims 1 to 19, wherein in the compound of formula (1) is m 2 and the compound is a polyadduct of 2-20 moles of ethylene oxide with 1 mole of C ₂ -C ₄ alkylene glycol. The formulation of claim 22, wherein the C ₂ -C ₄ alkylene glycol is ethylene glycol or n-butylene glycol. The formulation of claim 22, wherein the C ₂ -C ₄ alkylene glycol is propylene glycol. The formulation of claim 24, wherein the compound of formula (1) has the formula:

where x and y are each an integer within the range of 1 to 10. The formulation of claim 25, wherein x and y are each are an integer within the range of 1 to 5. The formulation of claim 26, wherein the sum of x and y is 10. Formulation according to at least one of claims 1 to 19, wherein in the compound of formula (1) is m 3 and the compound a polyadduct of 3–20 Moles of ethylene oxide with 1 mole of trimethylolpropane. The formulation of claim 28, wherein the compound a polyadduct of 7-20 Moles of ethylene oxide with 1 mole of trimethylolpropane. Formulation according to at least one of claims 1 to 19, wherein in the compound of formula (1) m is 4 and the compound a polyadduct of 4-20 Mole of ethylene oxide with 1 mole of pentaerythritol. The formulation of claim 30, wherein the compound a polyadduct of 5-20 Mole of ethylene oxide with 1 mole of pentaerythritol. Formulation according to at least one of the preceding Expectations, wherein a mixture of two or more of the compounds of Formula (1) is used as component c) of the formulation. Formulation according to at least one of the preceding Expectations, one or more aids also being selected Stabilizers, which are used to adjust the flow properties the formulation are effective, anti-foaming agents, alkali agents, Fabric softeners, anti-redeposition agents, antioxidants, Auxiliary builders and fragrances. Process for the preparation of a formulation according to Claim 1 comprising mixing the anionic fluorescent whitening agent, solvent and the compound of formula (1), together with any auxiliary agents and homogenizing the mixture thus obtained. 35. The method of claim 34, wherein the method is carried out at a temperature in the range of 40-100 ° C. Process for the production of a detergent, comprising adding the required amount of the formulation according to claim 1 to a detergent composition and then homogenizing the mixture thus obtained.