JPS58174448A - Preparation of concentrated aqueous solution of water- soluble dye or stilbene-type fluorescent brightener - Google Patents

Abstract

PURPOSE:To prepare the titled concentrated solution having excellent storage stability, easily, by reacting a metallic salt of a water-soluble dye or a stilbene- type fluorescent brightener with lower hydroxyalkylamine, and separating the insoluble matters from the reaction mixture. CONSTITUTION:A hardly water-soluble or insoluble metallic salt of a water- soluble dye having anionic group (e.g. azo dye) or a stilbene-type fluorescent brightener is suspended in water, and made to react with a lower hydroxylalkylamine of formula (R and R1 are H, lower alkyl, or lower hydroxyalkyl; R2 is lower hydroxyalkyl) in the presence of an acidic substance. The objective concentrated solution of the dye or the fluorescent brightener can be obtained by separating and removing the insoluble matters from the reaction mixture. The acidic substance is a compound which can separate the metallic cation of the dye or the fluorescent brightener in an aqueous medium, e.g. sulfuric acid, oxalic acid, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to concentrated aqueous solutions of water-soluble dyes or stilbene-based fluorescent brighteners (hereinafter referred to as stilbene-based IFB).

In general, a water-soluble dye or stilbene-based FB membrane is processed through diazotization, coupling, condensation, or other synthetic reactions, and then the desired dye or stilbene-based FB is processed. BA is separated from the reaction mixture by an appropriate method, dried and pulverized to produce a product in the form of powder.

However, recently these dye- or stilbene-based IFBAs have been developed mainly due to their several advantages in terms of improved working product terms and simplification of the manufacturing process.
It is also often provided on the market in the form of a concentrated aqueous solution. In order to obtain such a concentrated aqueous solution, the first condition is that the active ingredients of the dye or stilbene-based FB itself have good solubility in water, and the stability of the concentrated aqueous solution is Needless to say, the final effect depends on the solubility of the active ingredient itself. However, one of the important factors in obtaining a stable concentrated aqueous solution is the impurities coexisting with dyes or stilbene-based 'FB' and the inorganic salts inevitably mixed in during their manufacturing process. One example is to reduce the content of .

Generally, water-soluble dyes or stilbene-based FBams are synthesized by a combination of reactions such as diazotization coupling and expansion condensation, and in many cases, inorganic salts are produced as by-products during these reactions. Furthermore, after the synthesis reaction is completed, in order to precipitate the desired dye or stilbene-based FBum as a corresponding alkali metal salt, it is usually necessary to add a large amount of an inorganic salt such as common salt or mirabilite salt for salting out. However, from the table below, the precipitate of alkali metal salts obtained in this way is generally unfavorable, and the wet cake after filtration contains 9% of water, and this water contains naturally However, it contains considerable concentrations of inorganic salts produced as by-products during the synthesis reaction and inorganic salts used in salting out. If a concentrated aqueous solution is prepared using such a dye or stilbene-based IFB with a high concentration of inorganic salts, it will not be possible to obtain the aqueous solution with a high concentration of active ingredients, and the storage stability will also be unfavorable. Therefore, this inorganic salt must be removed by a suitable method prior to or during the preparation of the concentrated aqueous solution.

In all known methods for producing concentrated aqueous solutions containing water-soluble dyes or stilbene-based FB as active ingredients, unique methods are used to reduce the content of inorganic salts in the aqueous solutions as much as possible. For example, 1. Japanese Patent Publication No. 37-10187 describes a method of dissolving an alkali metal salt of stilbene-based FB with a suitable organic solubility enhancer. During the synthesis of FBum, the initial condensation product of cyanuric chloride and the amine component is filtered, washed with brine and acetone, and then dried in vacuum. In this step, inorganic salts produced as by-products are removed.

2. *Open and Shu No. 52-3627 describes a method of reacting an alkali metal salt or ammonium salt of a stilbene-based FB with a salt of a nitrogen base that imparts hydrophilicity in a water-soluble organic solvent. This method attempts to remove inorganic salts by taking advantage of their low solubility in organic solutions.

& In the specification of German Patent No. 1.794.159, he is a scientist who converted an alkali metal salt or ammonium salt of a stilbene-based IFB into the corresponding free acid using an appropriate acid and separated it. A method has been proposed in which the active ingredient is neutralized with a water-soluble amine in the presence of a water-soluble solubility enhancer, but this method involves first treating the active ingredient as a sparingly soluble free acid, and then adding inorganic substances to the F solution. The purpose is to drain out the salt.

A method for removing inorganic salts from an aqueous solution of an alkali metal salt of a stilbene-based FB membrane by electrodialysis is described in Japanese Patent Publication No. 54-12957.

However, these methods require complicated manufacturing steps, require large amounts of expensive organic solvents or organic solubility enhancers, are difficult to perform in the filtration process, require special equipment, and are difficult to concentrate. It has drawbacks such as requiring a lot of time and energy due to the additional process, and cannot be said to be fully satisfactory from the viewpoints of quality, economy, or energy conservation.

As a result of various research into methods for producing concentrated aqueous solutions containing water-soluble dyes, stilbenes, and 1B as active ingredients, the present inventors have found that they can be produced using simple methods, easily available chemicals, and containing active ingredients at high concentrations. We have now discovered a method for producing the water bath liquid, which also has excellent storage stability.

That is, the method of the present invention involves adding a water-soluble dye having an anionic group or a stilbene-based optical brightener to the corresponding water.
II soluble or insoluble metal salts in an aqueous medium in the presence of an acidic substance capable of eliminating the metal cations of the dye or stilbene fluorescent brightener according to the following general formula (wherein R and R1 are hydrogen). a lower alkyl group or a lower hydroxyalkyl group, and R3 represents a lower hydroxyalkyl group), and then separating and removing insoluble substances from the reaction mixture. This is a method for producing a concentrated aqueous solution containing a dye, a stilbene-based fluorescent brightener, and a salt of a lower hydroxyalkylamine as active ingredients.

A more specific explanation of the method of the present invention is as follows. That is, a suitable amount of a water-soluble dye having two or more anionic groups or a metal salt corresponding to a stilbene-based FB, which is sparingly soluble or insoluble in water, is suspended in water Kfa, and mixed with #C while stirring. The dye or Stilpera FBA
a substantial or excessive amount of an acidic substance capable of dissociating the metal cation of the dye or stilbene-based IB;
Add a considerable or excess amount of the lower hydroxyalkylamine represented by the general formula (1) that can form a salt with the anionic component of the hydroxide, and make sure that the reaction mixture is alkaline. , if necessary, by heating to cause a cation exchange reaction of the dye or stilbene-based FB, and the resulting insoluble substances (mainly the anion component of the added acidic substance and the dye or stilbene-based FB)
The process consists of separating and removing the inorganic salt bound to the metal cation released from A from the reaction mixture during heating or cooling, and then adjusting the resulting concentrated aqueous solution so that the active ingredient has the desired concentration. ing.

However, in the method of the present invention, the solubility in water of the inorganic salt produced by the combination of the metal cation of the dye or stilbene-based FB^ used as a raw material in the above-mentioned cation exchange reaction with the anion of the acidic substance is It is necessary to consider the network combination of the metal cations and acidic substances so that the amount is less than αS* (H amount), preferably less than α3-, during cooling over time. Needless to say, this is to avoid mixing inorganic salts into the target concentrated aqueous solution as much as possible, and to maintain good storage stability.

In addition, in order to efficiently obtain a concentrated aqueous solution, it is preferable to use a tortoise shell, from which the inorganic salt produced as a by-product during the cation exchange reaction can be easily separated from the reaction mixture. Therefore, in the method of the present invention, suitable metals constituting the cations of the dye or mystylbene are those in the periodic table of elements including alkaline earth metals such as magnesium, calcium, strontium, and barium. Metals from groups 1 to 2 can be mentioned, but from a comprehensive perspective, considering ease of acquisition, economy, workability, safety, and risk of pollution, the most common metals are alkalis. Earth metals, % calcium are preferred.

In addition, examples of acidic substances that can be used in the method of the present invention include inorganic acids such as sulfuric acid and phosphoric acid, as well as organic acids such as oxalic acid and coke acid.

It is necessary to select an appropriate one in consideration of the solubility of the inorganic salt produced in the cation exchange reaction.

The above general formula (1) that can be used in a cation exchange reaction
Examples of lower hydroxyalkylamines represented by are monoethanolamine and N-methyl (or ethyl) monoethanolamine.

n-propanolamine, mono-1sO-gropanolamine% N-methyl (or ethyl) propatoolamine, n-butanolamine, N-methyl (or ethyl) butanolamine, jetanolamine, di-n-propanolamine toolamine, di-110-propertoolamine,
Di-n-butanolamine, triethanolamine.

Examples include N-methyl (or ethyl) getanolamine, triproparturamine, and N-methyl (or ethyl) dibrobanolamine.

The water-soluble dye having an anionic group used in the present invention is a known water-soluble dye used for ordinary dyeing or coloring, and particularly preferred among them are azo dyes such as monoazo, disazo, and polyazo. Dyes, anthraquinone dyes, or phthalocyanine dyes.

In addition, the Sderpey-based IFB is '34.4'-bis-substituted-triazinylaminostilbene-2,2'-disulfonic acid 1lI as represented by the following general formula (A).
5! nose body, or 4 as represented by ) in the following general formula:
4'-bis-substituted-triazolylstilbene-2,2'
-disulfonic acid conductor, bis-substituted stilpenesulfonic acid derivatives, and the like.

Substituent x that meets the general formula),! ! and Y,! .

may be the same or different, for example -IIH goose
, -MIKCTI,, -MHO11'
i1. -N(01!3) Goose--M(MFIm) Mushroom.

-I(OsH*)*, -M(0411[s) snow,
-IHOH Tomi CH Yuki OR.

-m(aII鵞aBcmg)鵞, , -11101
! Snow aI! lan win (3B.

11 -MUCH will 01! , OH Goose 001'11. -N(
CII, OH Tomi and Goose aH) Goose.

-I(OHsOB,OH,Clll1.0II),,
lT101! ,Cooe.

If the substituent R3 and R4 in the general formula -) is represented by a group such as 1'.:, ', then the general formula (C)
Substituents RsFi, H, -at, -0H1e -ell, -o
It is represented by groups such as ooe, -so, and e.

On the other hand, the water-insoluble metal salt of dye or stilbene-based IB used as a raw material can be easily produced as follows.

That is, dyes synthesized by known methods or aqueous suspensions (undiluted solutions after the synthesis reaction) of alkali metal salts of stilbene-based PB, metal compounds satisfying the above conditions (for example, calcium chloride, tt (barium chloride, etc.) is added to produce water K.
N-soluble or insoluble metal salts are separated from the reaction mixture by filtration or the like. The nine-filtered cake obtained in this way can be subjected to a cation exchange reaction in its original form, but if not necessary, water-soluble impurities (mainly inorganic salts) can be washed away by further washing with water. I can do it.

In the above-mentioned cation exchange reaction, the dye or the poorly soluble or insoluble metal salt of the stilbene type IB, the acidic substance, and the lower hydroxyalkylamine can be mixed in any order.

That is, in addition to the mixing order described above, a dye or a sparingly soluble or insoluble metal salt of a stilbene-based FBum may be added to the aqueous solution of the acidic substance and lower hydroxyalkyl. Alternatively, an acidic substance may be added to the aqueous suspension of the metal salt of the dye or stilbene-based FB, and the primary lower hydroxyalkylamine component may be added, and further,
The dyestuff can be prepared by adding an acidic substance to a mixture of a stilbene film containing an aqueous suspension of the metal salt and a lower hydroxyalkylamine.

The concentrated aqueous solution of the present invention obtained in this manner may contain, for example, a surfactant, a sequestering agent, etc., within a range that does not affect the dyeing property, whitening effect, or fluidity or stability of the concentrated aqueous solution.
Known additives such as preservatives, antifreeze agents, and, if necessary, dissolution enhancers can be added. In addition, when the active ingredient is a Bam 81W conductor, it is possible to mix aqueous solutions containing different types of active ingredients with a concentration higher than knee. The concentration of the active ingredient in the concentrated aqueous solution prepared by the method of the present invention is about 20 to 50 Is, preferably about 25 to 40 Is, as each amine salt.

The concentrated aqueous solution prepared in this way has good fluidity and excellent storage stability, and hardly changes over time. For example, we compared the properties of the concentrated aqueous solution prepared in Example 1, which will be described later, immediately after its preparation and the properties of the concentrated aqueous solution after it had been stored in a brown opaque polybottle (with an inner lid and a screw-type outer lid) for more than three years. The concentration change of the active ingredient measured by optical density (0, D value) was 100 immediately after preparation, and the change rate after storage was 10 (L7gi). Almost no quality deterioration was observed in terms of color, primary color, transparency, dyeability, brightening effect, etc.

The method of the present invention will be explained below in more detail with reference to Examples, but the present invention is not limited only to these Examples.

Example 1 Stilbene-based FB whose anion component is represented by the above formula
Converting the calcium salt of Mu to its dry powder weight is 4 & 2.
Approximately sol filter cake containing f? 2.4fK2(L2f
After confirming that the pH of the mixture was alkaline, the mixture was heated to 80-90°C for about 5 hours. The ingredients were combined, and K and water were added to adjust the concentration of the active ingredient to 55%.

In this way, the active ingredient is the jetanolamine salt of the stilbene FBA whose anionic component is represented by the above formula, and the yellowish-brown transparent surface is highly soluble in water and has good dilutability. It can be done easily.

The calcium salt cake used in this example is obtained as follows. That is, 2 molecules of siatal chloride, 1 molecule of 4,4'-diaminostilbe'7-2,2'-disulfonic acid, 2. A reaction product liquid containing a sodium salt whose anion component is represented by the above formula is obtained by reacting methanyl acid in an e-proportion and jetanolamine in a diproportion by a known method, and filtering it while hot. After removing undissolved substances by adding a considerable amount to an excess of calcium chloride to the p-liquid, the resulting calcium salt III#! Separate the precipitate by F. If necessary, the kernels can be further washed with water to wash away soluble inorganic salts contained in the filter cake. Furthermore, the filter cake of kernels can be further dried and used as a powder.

Example 2 Calcium salt powder of stilbene-based FB whose anion component is represented by the above formula 4 & 2t & 9t of monoethanolamine, 411t of 20% barium salt of stilbene-based FB whose anion component is represented by the above formula Convert it to its dry powder coulance and convert it to 48F, so that it is about s o -ya
Take the filter cake, mix with it bis-n-propertoolamine 2 & 5f and 20ml sulfuric acid 4' (15f), raise the temperature to 80-90°C with stirring, and react for about 1 hour.Then, the produced insoluble Separate the precipitate in a hot furnace, wash this precipitate with about 10% water, combine the washed F solution with the above-mentioned main F solution, and adjust the concentration of active ingredients to 30% by adding water. did.

The barium salt V filter cake used in this example was obtained by using barium chloride in place of the calcium chloride used in the production of the calcium salt filter cake in Example 1 above.

ψExample 5 N(C40T1aOH), M(C%04
42.51 of a stilbene-based νB calcium salt powder whose 0H% anion component is represented by the above formula was added to a mixture of 2 (12F jetanolamine, 39.2F 209G sulfuric acid, and 40% water). It is added at room temperature for about 3.0 minutes, and the reaction is allowed to proceed for about 1 hour while stirring.Then, the formed insoluble precipitate is separated from V, and this precipitate is washed with about 10% water, and this washing solution F is mixed with the above-mentioned solution. Combine the main liquids and adjust the concentration of the active ingredient to 30-.

Stilbene-based FB whose anion component is represented by the above formula
Add the same amount of water to 6t of calcium salt powder of 100g of aluminum, and add this mixture 1 (2a2f of jetanolamine and 39.2f of jetanolamine).
Add a mixture consisting of 2F 20-sulfuric acid. After confirming that the pH of the entire mixture was alkaline, he adjusted it to 8.
The temperature is raised to 0 to 90°C and the reaction is carried out for about 1 hour. The generated insoluble substances are heated and washed with a small amount of water, the two F solutions are combined, and water is added to adjust the active ingredient concentration to 30-.

In this example, the substituents R3 and R4 in the stilbene-based FB group whose anion component is represented by the above formula are the following groups (R@=-C
If a similar treatment is performed using a stilbene-based IFB calcium salt powder represented by R4--0RB, a stable concentrated aqueous solution with a 1:1 ratio of anionic components having each group as active ingredients can be obtained. can get.

1:<l' lll Example 7 Stilbene-based FB whose anion component is represented by the above formula
The same amount of water is mixed with 27.5 F of calcium salt powder of 2.5 F, and a mixed solution consisting of 3 & 2 F of triethanolamine and 39.2 F of 2091 sulfuric acid is added thereto. After confirming that the -pH of the entire mixture is alkaline, the temperature is raised to 80 to 90°C and reacted for about 1 hour.

The generated insoluble substances are separated by heating, the remaining residue is washed with a small amount of water, the two filtrates are combined, and water is added to bring the active ingredient concentration to 3.
Adjust so that it becomes 0-.

In this way, a stable concentrated aqueous solution containing the stilbene FBA of the above formula as an active ingredient was obtained.

In this example, the anion component is replaced with the stilbene-based νBm represented by the above formula, and the substituents US and -803° in the general formula (0) are replaced by the following groups and -R-
0)! Nutyl pene-based FB groups occupying the position relative to the - group.

Bow, 1゜a) R@m El 2-801eb)
If the same treatment is performed using the calcium salt powder of Rs-4-OH2g (') Rs-4R5-4 -CNzd)IIIO202-80se, the triethanolamine salt of the bis-stilbene derivative having each group will be treated as the active ingredient. A stable concentrated aqueous solution is obtained.

Thereafter, the following concentrated aqueous solutions were prepared in the same manner.

X and ! in the above general formula The components, metal cation components, amine components of general formula (I), and acidic substances are listed in the following table.

=33: Example 8 The anion component was a dye represented by the above formula (0,1,A
c1d R@a 112 ) force kV um salt powder 7
Suspend 4,6F in the same amount of water, raise the temperature to 60-70℃, and add jetanolamine 442f into the suspension while stirring.
A solution consisting of 20-107f of sulfuric acid is added, and after confirming that the reaction mixture is alkaline, the mixture is stirred at the above temperature for about 1 hour to carry out a cation exchange reaction. The insoluble material produced is then filtered out, and the insoluble material is washed with 20 liters of water. This cleaning solution and the above-mentioned main F solution were combined and further adjusted to have an active ingredient concentration of 150-.

Example 9 The anionic component was a dye represented by the above formula (a,
1r@ct Yellow 72 ) calcium salt powder 74.4 F to triethanolamine 6! L6t
and 70~ in a mixed solution consisting of 107f of 20-sulfuric acid.
Add slowly at 80°C. The mixture was further stirred at the above temperature for about 1 hour to complete the cation exchange reaction, and then the formed insoluble precipitate was separated.

This precipitate is washed with approximately 20 g of water. The kernel washing liquid and the above-mentioned main filtrate are combined, and the concentration of the active ingredient is further adjusted to 50-.

Thereafter, concentrated aqueous solutions containing the following dyes as active ingredients were prepared in the same manner. The dye components are listed in the first table in the same format as the previous table, except that they are expressed by Generic Name in the Co1our index.

Dyes shown in the table above.

The structural formula of is as follows. be.

(Re C engineering FOO (L Yellow 7 (2) 0 engineering M
qraant Yellow 8(5)C Moraa
nt Yellow 26 (4) C engineering Aci<L B
blue 2K' (5) CI Ac1d Blue
45Nu 0 0H (6) CIA61d Blue 249' 0u
-Phthalocyanine tetra su'
1 foniccid (7) 'OX Mucia Violet 58
, OH0H (8) CI Direct Orang 29 (9
) CID1rect Orange 102ノ(10) ON Direct Re(151(11)
) 0IDirect Re675(12)' c
Engineering Dir@ct Blue 14 (1!S) C
1rect Blue 860u-Phthal
ocyanine disulfonic aei
airi 1rect from C 'Violet 35 (1
5) CI engineering 1) direct Vlolet 4
7 (16) CID1r@ct Green 55 (
18) ir@ct Brown 95' from 0: (19) C3X I)ir*ct Brown 1
12(20) OX Direct Black
38 (21) (!I Direct Black
8G (22) O Engineering Pigment 'Violet
20 0H Kazuo Wakasugi, Commissioner of the Japan Patent Office1, Indication of the case Patent Application No. 54470 of 19822, Title of the invention Water-soluble dye 19 is a method for producing a concentrated aqueous solution of a stilbene-based fluorescent brightener 3, amended Relationship with the patent applicant (name: 4, agent address: Toramon-chome, Minato-ku, Tokyo) No. 24-11, Minato-ku, Tokyo Amend the detailed description of the subject matter of the amendment a to the attached document do.

(No change in content)

Claims (1)

[Scope of Claims] A water-soluble dye having an anionic group or a corresponding sparingly water-soluble or insoluble metal salt of the dye or stilbene-based fluorescent brightener in an aqueous medium. In the presence of an acidic substance capable of removing the metal cation of The above-mentioned dye is prepared by reacting a lower hydroxyalkylamine represented by [alkyl] with a stilbene-based fluorescent brightener and a lower hydroxyalkylamine, and then separating and removing insoluble substances from the reaction mixture in step i. A method for producing a concentrated aqueous solution containing a salt with an alkylamine as an active ingredient.