JPS5853026B2 - Method for producing liquid preparation of fluorescent whitening dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the production of a novel *liquid preparation of a fluorescent brightener of formula (I).

The compound group of 4,4'-his-substituted triazinylaminostilbene-2,2'-disulfonic acid or its salts represented by formula (I) can be used as a fluorescent whitening dye for cellulosic materials, semi-synthetic materials, or synthetic materials. It is used for brightening dyeing textiles, pulp, paper, etc., or as a brightening agent in detergents, and is indispensable as a means of increasing commercial value because it can significantly improve visual whiteness.

(Formula 0), X and Y are the same or different and are a hydroxy group, an aliphatic hydroxy residue, an aromatic hydroxy residue, an amino group, an aliphatic or aromatic amine residue, a heterocyclic amine residue. represents a group, an alicyclic amine residue, or a halogen atom, and these alcohol or amine residues further have a halogen atom, hydroxy group, sulfamoyl group, carbamoyl group, lower alkoxy group, or sulfonic acid group as a substituent. I can do it.

Moreover, M represents a hydrogen atom or an alkali metal atom.

) Conventionally, liquid products of the fluorescent whitening dye represented by formula (1) are produced by completing the reaction by a known synthesis method, and then adding a large amount of salt to the reaction product solution to perform salting out, or After the precipitated fluorescent whitening dye crystals are separated as a solid by performing acid precipitation by adding an acid, water, a solvent such as ethylene glycol or propylene glycol, an aliphatic alkylamine, or a hydroxyalkylamine are used. If desired, urea or other solubilizing agents may be mixed in to dissolve the dye again, and in some cases, liquid fluorescent whitening dyes may be produced and put into practical use by concentrating the dye until the required concentration is reached. ing.

However, this method requires a large amount of water for troublesome filtration, washing, and take-out operations, resulting in drainage problems, and the time-consuming steps of redissolving and concentrating products. The energy required for this is significantly large.

Furthermore, since the fluorescent whitening dye is poorly soluble in water, it may be difficult to liquefy it due to its low water solubility.

In some cases, the fine dyestuff obtained by drying with a Penules-type or spray-type dryer is used as it is, but this contaminates the environment due to the scattering of fine particles, and is extremely inconvenient to handle. It is a form of

Furthermore, fluorescent whitening dyes with relatively low solubility in water are commercialized in the form of an aqueous paste, which is obtained by mechanically atomizing wet R agglomerates in the coexistence of an anionic or nonionic dispersant. In addition to the separation operation from the reaction solution, a complicated and energy-consuming atomization operation is required, and the products manufactured by this method have poor stability during storage, and the dye raw materials and ingredients There are problems such as salt precipitation and viscosity increase over time.

Furthermore, in the case of so-called paste-type products suspended in water, the problem of crystallinity (transformation) of fluorescent whitening dyes cannot be ignored, and during long storage periods, they convert into crystalline forms with undesirable properties. It gels or becomes extremely thixotropic, losing fluidity and becoming unusable.

In this way, the present inventors have developed a stable, low-viscosity liquid preparation that can withstand long-term storage, in order to easily prepare a liquid preparation of a fluorescent whitening dye that is difficult or extremely time-consuming. As a result of intensive studies, the present invention was arrived at.

That is, the present invention provides a fluorescent whitening dye represented by the formula (I) by adding a nonionic surfactant capable of forming an aqueous two-phase system in the coexistence of a precipitant to an aqueous solution containing a fluorescent whitening dye represented by the formula (I).
1. A method for producing a liquid preparation of a fluorescent whitening dye, which comprises forming a nonionic surfactant layer (coacervate layer) containing the fluorescent whitening dye represented by I) and separating it. .

Representative examples of the fluorescent whitening dye represented by formula (I) according to the present invention include those shown in Table 1.

All of these can be prepared using a conventional method, for example, by dispersing and suspending an acetone solution of cyanuric chloride in cold water, and adding 4,4'-diaminostilbene-2,2 to this in the presence of soda carbonate.
It is obtained by adding dropwise an aqueous solution of '-disulfonate, and then reacting an amino compound and/or a hydroxy compound in the presence of an alkaline agent.

Further, even if acetone is not used or the order of the reactions is changed, the application of the method of the present invention is not affected in any way.

The concentration of the fluorescent whitening dye in the aqueous solution or aqueous suspension is not substantially limited, but in the case of readily water-soluble fluorescent whitening dyes it is advantageous to preferably be below its water saturation solubility. .

In this case, a completely transparent liquid preparation is obtained.

Furthermore, the aqueous solution or aqueous suspension does not necessarily have to be neutral; in the case of a fluorescent whitening dye that is alkaline or neutral and has high water solubility, it is preferably alkaline or neutral to completely dissolve it.

The nonionic surfactant capable of producing an aqueous two-phase system as used in the present invention refers to a nonionic surfactant that can contain a dye in a coacervate layer by the so-called coacervation method and be separated from an equilibrium solution by the effect of a precipitant such as a salt. An ionic surfactant.

The coacervation method is f(,G, Bungenb
erg de jong &H.

R, Kruyt; prod, Acad, Sci.
, Amsterdam.

Volume 32, page 849 (1929) Ori.

G. Dervichian: Re5earch,
2, p. 210 (1949), and the phenomenon in which a dye is encapsulated in a coacervate layer is also known from R, Ca.
5ty: American, Dyestuff,
Reporter, volume 49, page 952 (1960
) is known.

However, this method of producing a liquid preparation of dyed stings directly from an aqueous solution or aqueous suspension containing a water-soluble fluorescent whitening dye by the effect of a precipitant such as a salt is completely new.

Nonionic surfactants that can be used for such purposes only need to have the above-mentioned performance, but representative examples include polyethylene glycol type higher alcohols, higher thioalcohols, and alkylphenols as hydrophobic base materials. , polypropylene glycol, higher fatty acids,
A polymer or copolymer obtained by reacting a higher amine or a higher aliphatic acid amide with an alkylene oxide as a hydrophilic base material, such as ethylene oxide or propylene oxide, to an appropriate degree of polymerization; called a polyhydric alcohol fatty acid ester type. An ester or partial ester of a higher fatty acid as a hydrophobic base material and glycerin or sorbitan norbitol as a hydrophilic base material; or a polyhydric alcohol which can be said to be a polyhydric alcohol ester ether type having a chemical structure that is in between the above two. Examples include ethylene oxide polymers of higher fatty acid esters.

Further, the precipitant as used in the present invention is one that assists in the precipitation and separation of the above-mentioned coacervate layer, and refers to electrolytes such as inorganic salts and organic salts.

Examples of inorganic salts include sodium chloride, sodium sulfate,
Examples of organic salts include ammonium chloride, calcium chloride, potassium sulfate, sodium phosphate, and sodium acetate.

Next, embodiments of the method of the present invention will be described.

First, a fluorescent whitening dye, a nonionic surfactant capable of forming an aqueous two-phase system, and a precipitant are added to water and dissolved or suspended by stirring.

At this time, the addition order may be arbitrary, but preferably the fluorescent whitening dye, the nonionic surfactant, and the precipitant are added in this order.

In addition, when the fluorescent whitening dye is obtained by a synthesis reaction in an aqueous solution, it is industrially advantageous to directly add the nonionic interface to the reaction finished liquid without separating the fluorescent whitening dye from the reaction mixture after the completion of the reaction. An activator is added and, if necessary, a precipitant is added.

Usually, the reaction-completed solution contains a large amount of salt such as common salt, which acts as a precipitant, so in this case, much less precipitant is needed, and L. has the advantage of not being necessary.

The aqueous solution or suspension furthermore advantageously has a surfactant that is greater than the base point of the nonionic surfactant used, preferably from 80 to 100
C. for 10 minutes to 3 hours, preferably 30 minutes to 1 hour.

The nonionic surfactant layer (coacervate layer) containing the fluorescent whitening dye is separated into an upper layer or a lower layer depending on the amount of precipitant used before heating, during heating, or during cooling after heating.

Any known method may be used for the separation operation, but decantation is advantageously used.

According to the process of the invention, a hygienic and easy-to-handle liquid preparation of the fluorescent whitening dye of the formula (I) is obtained with industrial advantage.

In addition, this liquid preparation has the advantage of having high concentration and low viscosity, excellent transparency, and little or no change over time, but its whitening properties are not impaired in the slightest. It's not a thing.

In addition, this liquid preparation, like conventional products, can be applied to dyeing fields such as pulp dyeing, detergent base whitening, and washing whitening.

Next, examples of the present invention will be described.

Example 1 Dried fluorescent whitening dye product 41 represented by formula (I) was added to 10,001 liters of water, and while stirring, the pH of the liquid was adjusted to 9 using 10% caustic soda water to completely dissolve.

Polyoxyethylene nonylphenol (P) is added to this aqueous solution.
OE Base 10) Add 8f, and then add 4 ml of anhydrous sodium sulfate.
The solution was heated at 80° C. for 1 hour, cooled to room temperature and allowed to stand, and the nonionic surfactant of the fluorescent whitening dye, which had settled into a lower layer, was separated by a decantation method.

Fluorescent whitening dye liquid with good fluidity and transparency 16'?
was gotten.

This product was completely stable even after long-term storage, and no changes were observed.

The upper aqueous layer was almost colorless and transparent, with almost no fluorescence observed and did not contain any fluorescent whitening dye.

Add 1.02 ml of the liquid preparation obtained here to 50 liters of boiling water while stirring well, and then add water to bring the total volume to 500 ml (
undiluted solution).

Add 5 TIL of this stock solution to 450 ml of pulp disintegration solution (10 cm of dry pulp that has been torn into thin pieces in advance and 450 ml of water in a mixer and process for 2 minutes) while stirring with an electric stirrer, then add water to make a total volume of 5001 rL, and leave for 15 minutes at room temperature. Stained.

Sizing, dilution, paper making, footing, compression, and drying were performed by conventional methods.

The obtained paper sheet had good white discoloration.

Example 2 Cyanuric chloride (2.02 molar* ratio), sulfanilamide (2.0 molar ratio), and jetanolamine (2.0 molar ratio) were added to sodium diaminostilbendisulfonate (1.0 molar ratio) in an aqueous solution. ) was reacted by a known method to obtain a reaction-completed solution containing a fluorescent whitening dye represented by formula (1) of Example 10.

The polyoxyethylene nonylphenol used in Example 1 (POE group number 10)
130 g was added, and the mixture was heated and stirred at 80° C. for 1 hour.

After cooling to room temperature and standing still, 250 g of the nonionic surfactant layer that had settled and separated into the lower layer was separated by a decantation method.

The obtained lower layer liquid product had good fluidity, was stable even during long-term storage, and no precipitates were observed.

The upper water layer was transparent and almost no fluorescence was observed.

Example 3 Example 1 was performed except that polyoxyethylene lauric acid ester (POE number of groups 15) was used instead of polyoxyethylene nonylphenol (POE number of groups 10) for the fluorescent whitening dye used in Example 1. When treated in the same manner as above, a transparent liquid preparation with good fluidity was obtained.
There was no change at all even after long-term storage.

Example 4 A dried fluorescent whitening dye 4y represented by the formula (2) was used as a fluorescent whitening dye, and polyoxyethylene polypropylene glycol (molecular weight of polypropylene unit 2000, content of ethylene oxide chain 20) was used as a nonionic surfactant. %) 8f was used, and the same procedure as in Example 1 was carried out to obtain a liquid preparation of a fluorescent whitening dye with good fluidity.

This substance did not change even when stored for a long time.

Add 0.32 r of the liquid preparation obtained here to 20 ml of boiling water at 70'C. In addition to this, detergent 4゜? has the following composition. was added and kneaded at 65°C for 30 minutes.

The detergent obtained after drying had an excellent white discoloration.

Claims (1)

[Claims] 1. A nonionic surfactant capable of forming an aqueous two-phase system is added to an aqueous solution containing a fluorescent whitening dye represented by formula (I) in the coexistence of a precipitant. 1. A method for producing a liquid preparation of a fluorescent whitening dye, which comprises forming a nonionic surfactant layer (coacervate layer) containing a photowhitening dye and separating this layer. (In formula (1), X and Y are the same or different, a hydroxy group, an aliphatic hydroxy residue or an aromatic hydroxy residue, an amino group, an aliphatic or aromatic amine residue,
It represents a heterocyclic amine residue, an alicyclic amine residue, or a halogen atom, and these hydroxy residues or amine residues further represent a halogen atom, a hydroxy group, a sulfamoyl group, a carbamoyl group, a lower alkoxy group, or a sulfonic acid group. It can be included as a substituent. Moreover, M represents a hydrogen atom or an alkali metal atom. ).