JPS62273266A - Fluorescent brightener composition - Google Patents

Abstract

PURPOSE:To provide the titled composition capable of giving a concentrated aqueous solution of stilbene fluorescent brightener of extremely good storage stability, containing little metal ion, comprising a salt made from a stilbene derivative anion and specific quaternary ammonium ion. CONSTITUTION:The objective composition comprising, as the active component, a salt made from (A) a stilbene derivative anion of formula I [X<1> and X<2> are each of formula II, formula III, etc.; Y<1> and Y<2> are each -OCH3, of formula IV (R<1> is H, -COO<->, etc.), etc.] and (B) a quaternary ammonium ion of formula [(CH3)pN(R<7>)<q>] (R<7> is -CH2CH2OH, -CH2CH2CH2OH, etc.; p and q are each 1, 2, or 3; where p+q=4). Said salt can be prepared, for example, by reaction, in an aqueous medium, between a water-soluble metal salt of the anion of the formula I and a water-soluble salt of the quaternary ammonium ion mentioned above.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to fluorescent brightener compositions used in the textile or paper industry.

[Conventional technology]

Fluorescent brighteners used in the textile and paper industries are now available as concentrated liquid products instead of the powder products used in the past, in order to save labor in dissolving, weighing, transporting, etc. in the workplaces where they are used. It is.

A large number of methods have been proposed for producing concentrated aqueous solutions of stilhen-based fluorescent brighteners.
No. 23262 claims that stilchen derivative A (in the formula R, R
', R'' and R3 each represent an alkyl group having 1 to 4 carbon atoms, which may be the same or different.) A fluorescent whitening compound formed from a tetraalkylammonium compound having a group represented by It has been reported that the agent exhibits an excellent whitening effect in an aqueous fluorescent whitening method and also has extremely good solubility in water, making it suitable for the production of highly concentrated stock solutions.

[Problem that the invention seeks to solve]

The inventors discovered that the stability of the concentrated aqueous solution of the stilhen fluorescent brightener produced according to the method described in JP-A-57-123262 was not necessarily sufficient, and that the active ingredient could precipitate during storage. Therefore, we sought to create a concentrated aqueous solution with even higher storage stability.

[Means for solving the problem] The inventors replaced the tetraalkylammonium compound used in JP-A-57-123262 with the general formula %) (wherein R1 is -CH2CH20H, (jlzcHzcH
zOH or -CH2011)ICH□, p is 1
, 2 or 3, q represents 1.2 or 3, p+
q is 4. The present invention was carried out based on the discovery that a concentrated aqueous solution of a stilbene-based fluorescent brightener with extremely excellent storage stability can be obtained by using quaternary ammonium represented by the following formula.

That is, the present invention is based on the general formula % [wherein X1 and X2 are the same or different, or
Represents I3, Yl and Y2 are the same or different - 0C
R3, (wherein R1 is a hydrogen atom, -000- or COOR2
and R2 represents a lower alkyl group. ), -N
(In the formula, R3 and R4 are the same or different hydrogen atoms, lower alkyl groups, hydroxyl-substituted lower alkyl groups, C
H2CH2COO-1CHzCHzCN.

CHzCI (zcOORS or -GHzGHzCON
(R') represents 2, and R5 represents a lower alkyl group.

), (in the formula, R6 is a hydrogen atom, a lower alkyl group, -CH201
1, -CIl□COO- or -C1lzCHzCOO
- represents. ) represents. A fluorescent brightener composition containing a salt formed from a stilbene derivative anion represented by This is a fluorescent brightener composition obtained by dissolving in.

Specific examples of the stilbene derivative anions represented by the general formula (1) are shown in Table 1, but the stilbene derivative anions of the present invention are not limited to these.

l l l
l l-N's
The size! ^N
ω Lo 7==== z z
z zl
1 1 1-CVJ
ω To prepare a salt formed from a stilbene derivative anion represented by the general formula (1) and a quaternary ammonium ion represented by the general formula (n), a water-soluble metal salt of the anion is prepared. Alternatively, an ammonium salt (hereinafter represented by sodium salt) may be reacted with a water-soluble salt (for example, chloride, bromide or iodide) of the quaternary ammonium ion using water as a medium, or The acid and the quaternary ammonium base may be reacted in an aqueous medium.

Of course, the sodium salt of the anion can be separated from the reaction solution in which it was synthesized by cooling, salting out, concentration, etc.;
The quaternary ammonium salt may be added to the solution itself after the reaction is completed.

The ratio of the quaternary ammonium compound to the stilbene derivative for producing the composition of the present invention is preferably at least equivalent to the amount of -3O1- contained in the stilbene derivative; When C00- is contained, it is preferably at least an equivalent amount to the total amount of -303- and -COO-. However, it is not always necessary to use an equivalent amount or more, and the amount can be reduced depending on the intended use of the composition.

Even if an equivalent amount of quaternary ammonium salt is applied to the sodium salt of the stilhene derivative anion, all of the sodium in the sodium salt is removed from the quaternary ammonium salt in an amount equivalent to the acid group contained therein.
Although it is difficult to replace the quaternary ammonium salt with quaternary ammonium salt in many cases, this substitution rate can be increased by increasing the proportion of quaternary ammonium salt used. When the stilbene derivative is a free acid, a stilbene derivative almost completely bound to quaternary ammonium ions can be obtained by treating the acid with an equivalent amount of quaternary ammonium base.

The composition of the present invention has high solubility in water, and by using an appropriate solubilizing agent in combination, it can be made into a stable, highly concentrated aqueous solution that can withstand long-term storage.

Well-known solubilizers are used, such as monoethanolamine, jetanolamine, triethanolamine, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, urea, and sucrose, but are not limited to these. It's not a thing.

Further, in the paper manufacturing industry, there is a demand for a fluorescent brightener with a low content of metal ions, and the composition of the present invention satisfies such a demand.

〔Effect of the invention〕

A stilhen derivative composition represented by the general formula (I) with excellent solubility in water can be obtained, a concentrated solution with excellent storage stability can be produced, and a fluorescent whitening composition with a low content of metal ions can be obtained. A composition for use can be provided.

Example 1 15 g of cyanuric chloride and 7.5 g of sodium hydrogen carbonate were added to 65 ml of methanol and heated at a temperature of 20 to 25°C.
After continuing to stir for an hour, the mixture was poured into cold water and the precipitate was collected by filtration.

4. Dissolve 13.9 g of 4'-diaminostilbene-2,2'-disulfonic acid and 6.5 g of sodium hydroxide in water, bind the total amount to 500 m/m, add the filtered material from above, and make 55 to 60 g of sodium hydroxide. Stirring was continued for 1 hour at a temperature of .degree. Next, 5.3 g of anhydrous sodium carbonate and 9.1 g of aniline were added and the reaction was continued for 1 hour under reflux to synthesize the sodium salt of m8 stilbene in general formula (I) having Xl and X2.

To the above reaction solution was added 11.4 g of choline chloride dissolved in water, and when the mixture was cooled, precipitation of a candy-like substance began at a temperature of around 80°C, and upon cooling to room temperature, 60 g of a candy-like substance was obtained.

This candy-like substance was dissolved in 300 mf of water and spray-dried to obtain +1.

A pale yellow powder was obtained, the main component of which was

This powder was found to contain approximately 25% sodium salt of the same stilbene derivative as a result of ash content measurement.

Example 2 The same synthesis reaction as in Example 1 was carried out, and after the reaction was completed, the temperature was 80°C.
When the mixture had cooled down to , choline chloride was added in the same manner as in Example 1. The sodium salt of the stilbene derivative, which had already begun to precipitate, was once dissolved by the addition of choline chloride, and as the temperature decreased, a candy-like substance began to precipitate.

Cool to room temperature, take out the candy-like substance that has precipitated out, and add 1 part of water.
00nj! Added triethanolamine 35.0 g
Then, 13.0 g of urea was added and dissolved by heating, and water from which a trace amount of insoluble matter had been filtered was added to bring the total amount to 130 g. The composition thus obtained was a slightly viscous light yellowish brown liquid, and no precipitates were observed even after storage for two years at room temperature.

Comparative Example 1 The same experiment as in Example 2 was conducted using tetramethylammonium chloride instead of choline chloride used in Example 2.

When the obtained liquid composition was stored at room temperature,
Precipitation started after about 3 months, and a large amount of yellow precipitate had been deposited after 4 months.

Example 3 135 g of water, 210 g of ice, 30.0 g of cyanuric chloride, and a small amount of surfactant were vigorously stirred in a 40-liter flask for 30 minutes, and while cooling on ice, 28.0 g of sulfanilic acid was added.
Aqueous solution 180II of 1 g neutralized with sodium hydroxide
1 liter was added dropwise over 1.5 hours.

The temperature was gradually raised to 15° C., during which time the reaction solution was kept almost neutral using an aqueous sodium hydroxide solution.

Next, a solution of 28.9 g of 4,4'-diaminostilbene-2,2'-disulfonic acid and 6.3 g of sodium hydroxide dissolved in 200 mJ of water was added, and while neutralizing with an aqueous solution of sodium hydroxide, the Stirring was continued for 1 hour at a temperature of °C.

Next, 24.0 g of jetanolamine was added, and the mixture was heated at a temperature of 100° C. for 1 hour while being neutralized with an aqueous solution of sodium hydroxide.
Continuing the reaction for a time, XI and Y2 in formula (1) become -N
The sodium salt of the anion (CHzCHzOH) 2 was synthesized.

A trace amount of suspended matter was filtered off from this reaction solution, and 45.4 g of choline chloride was added to the filtrate. No precipitates were observed even after cooling. This liquid was filtered using a laboratory Tijin PBrL tubular pressure filtration device (manufactured by Teijin Engineering Co., Ltd.).
A semipermeable membrane made of polybenzimidacylon is used.

See Japanese Patent Application Laid-open No. 158266/1983. ) until almost no chloride ions are observed in the solution, and then spray-dry to obtain 125g of pale yellow powder.
I got it.

This powder was heated and incinerated with sulfuric acid according to a conventional method, and the sodium content was measured.
Approximately 1.5/4 of the total 303- with O3-
was found to be bound to sodium. Therefore, 2.5/4 of all-5O1- is ((CHz) 3NGHzG
HzOH).

Example 4 A synthetic experiment similar to that in Example 3 was carried out using methanic acid instead of the sulfanilic acid used in Example 3.
In general formula (1), XI and -N (CH2CH
Synthesize the sodium salt of the anion that is 2OH) t,
Choline chloride was added in the same manner as in Example 3. Desalting and concentration was performed using the same pressure reduction device as in Example 3 until the salt concentration in the liquid became 1.0%, and 30.0 g of urea was added.
300 g of a pale yellow-brown solution containing 25% bistriazinylaminostilbene derivative were obtained. Even when this solution was left at room temperature for 6 months, no precipitates were observed.

Example 5 14.05 g of sulfanilic acid and 14.0 g of metanilic acid instead of 28.1 g of sulfanilic acid in Example 3
A bistriazinylaminostilbene derivative was synthesized in the same manner as in Example 3 using 5 g of the mixture. As a result of analysis by liquid chromatography, the bistriazinylaminostilbene derivative obtained here was found to be an anion in the general formula (I) in which XI and Y2 are -N(CHzCHzOH)z, and Xl and Y2 are -N(CHzCHzOH). 2
anion, and Xl is and Yl and Y2
3 of the anion where -N (CHzCHzOH) z
It was found that the mixture was based on species anions in a ratio of approximately 22:29:49.

Choline chloride was added to this synthesis reaction in the same manner as in Example 4, followed by desalting, addition of urea, and concentration to obtain a concentrated solution of a stilbene derivative. Even when this concentrated solution was left at room temperature for 6 months, no precipitates were observed.

In addition, the results of quantifying the amount of sodium corresponding to the stilbene derivative anion in the solution before adding urea were as follows:
The amount corresponded to approximately 1.6/4 of the total amount. Therefore, 2.4/4 of the total 503- is choline salt.

Example 6 A mixture of sodium salts of three types of stilbene derivatives was synthesized by carrying out the same reaction as in Example 5, and 120 g of choline chloride was added to this reaction solution, followed by stirring at a temperature of approximately 100° C. for 60 minutes. After cooling and removing a trace amount of suspended matter by filtration, desalination was carried out in the same manner as in Example 5 until almost no chlorine ions were observed. The pale yellow solution thus obtained was spray dried to obtain a pale yellow powder. When this powder was heated and incinerated, there was only a trace amount of ash. That is, in this powder, most of the -503- ions in the mixture of three stilbene derivatives having the same composition as that obtained in Example 5 are choline salts.

The pale yellow-brown solution obtained by dissolving 5.0 g of this powder and 2.0 g of urea in water and adjusting the total amount to 20.0 g was stable with no precipitates even after being left at room temperature for 6 months. Ta.

Example 7 A mixture of sodium salts of three types of stilchene derivatives was synthesized in the same reaction as in Example 5, and 80% of β-methylcholine iodide was added to the reaction solution. After adding Og, desalting treatment, addition of urea, and concentration were performed in the same manner as in Example 5 to produce a concentrated solution of a stilbene derivative. This concentrated solution was heated to room temperature for 6 hours.
Even after being left for several months, no precipitates were observed.

Example 8 In the general formula (1), XI and X2 are 10 CI+3, and Yl and Y2 are -NHCHzCHzOH. 30.0 g of powder of sodium salt of a stilbene derivative is heated and dissolved in 600 ml of water, and hydrochloric acid (1: 1) was added to adjust the pH to 2.0 to precipitate the acid form of the stilbene derivative, and the precipitate was filtered and separated, and further washed thoroughly with hot water. This acid form of the stilbene derivative was suspended in 200 m# of water, and 8.2 g of choline was added to adjust the pH to 10.0, resulting in a transparent solution. This solution was spray-dried to obtain 31.0 g of choline salt of stilbene derivative 1 as a pale yellow powder.

When this pale yellow powder was heated and ashed, almost no ash remained. That is, it is considered that there is substantially no sodium salt in this pale yellow powder, and that the stilbene derivative is almost completely choline salt.

Claims (1)

[Claims] 1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, X^1 and X^2 are the same or different ▲ Numerical formula,
There are chemical formulas, tables, etc.▼ or -OCH_3, where Y^1 and Y^2 are the same or different -OCH_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is a hydrogen atom, - COO^- or -COO
R^2 represents a lower alkyl group. )
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3 and R^4 are the same or different, hydrogen atoms, lower alkyl groups,
Hydroxyl group-substituted lower alkyl group, -CH_2CH_2COO
^-, -CH_2CH_2CN, -CH_2CH_2C
OOR^5 or -CH_2CH_2CON(R^5)
_2 and R^5 represents a lower alkyl group. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^6 is a hydrogen atom, a lower alkyl group, -CH_2
OH, -CH_2CH_2OH, -CH_2CH_2S
CH_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH
Represents _2COO^- or -CH_2CH_2COO^-. ) represents. ] and the general formula [(CH_3)_pN(R^7)_q](II)(
In the formula, R^7 is -CH_2CH_2OH, -CH_2CH
Represents _2CH_2OH or -CH_2CHOHCH_3, p represents 1, 2 or 3, and q represents 1, 2 or 3
, and p+q is 4. ) A fluorescent brightener composition containing a salt formed from a quaternary ammonium ion represented by 2) A fluorescent brightener composition according to claim 1, wherein the composition is a highly concentrated aqueous solution of the salt described in the preceding claim. 3) The fluorescent brightener composition according to claim 1 or 2, wherein the quaternary ammonium ion is a trimethyl-β-hydroxyethylammonium ion. 4) X^1 and X^2 in formula (I) are ▲formula,
The fluorescent brightener composition according to any one of claims 1 to 3, wherein the chemical formula, table, etc. are ▼, and Y^1 and Y^2 are -OCH_3. . 5) X^1 and X^2 in formula (I) are ▲formula,
There are chemical formulas, tables, etc. ▼, and Y^1 and Y^2 are -N(CH_2CH_2OH)_2. Whitening agent composition. 6) X^1 and X^2 in formula (I) are ▲formula,
There are chemical formulas, tables, etc. ▼, and Y^1 and Y^2 are -N(CH_2CH_2OH)_2. Whitening agent composition. 7) The stilbene derivative anion is X in formula (I)
^1 and X^2 are ▲There are mathematical formulas, chemical formulas, tables, etc.▼
and Y^1 and Y^2 are -N(CH_2CH_2O
H) An anion where _2, X^1 and X^2 are ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and an anion where Y^1 and Y^2 are -N(CH_2CH_2OH)_2 and X^1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and X^2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and Y^1 and Y^2 are -N (CH_2CH_2O
The fluorescent brightener composition according to any one of claims 1 to 3, which is a mixture containing the anion H)_2.