JPS5827288B2 - Stilbene azo mataha Stilbene azoxysenryouno - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel stilbene azo or stilbene azoxy dye containing a sulfonic acid group; Stilbene azo or stilbene azoxy dye salts are provided in which one cation is a tetraalkylammonium cation (the alkyl group may be substituted).

That is, the present invention provides a method for producing the above-mentioned novel salts, which comprises the following formula I: [wherein R represents a substituted or unsubstituted alkyl group,
mA is not otherwise substituted] in the presence of tetraalkylammonium hydroxide (the alkyl group may be substituted).

If necessary, the resulting dye may be reduced to reduce its nitro groups to amino groups.

The alkyl group R may be a lower alkyl group containing mainly 1 to 6, preferably 1 to 2 carbon atoms.

This alkyl group may preferably be substituted with a hydroxyl group, a cyano group, a halogen atom or an aryl group, preferably a phenyl group.

It is preferable to use an excess of tetraalkylammonium hydroxide.

Rather than using the compound of formula ■ initially in the salt form, it is used in the form of the free sulfonic acid, which is added to an excess molar amount of tetraalkylammonium hydroxide to form the salt of this compound in the same reaction system. is preferable.

Therefore, the cation in the compound of formula (1) preferably corresponds to tetraalkylammonium hydroxide.

The reaction is preferably carried out in an aqueous medium at a pH of 7.5 to 14;
It is particularly preferably carried out at a pH of 11 to 13.

The reaction is preferably carried out at an elevated temperature, preferably at a temperature from 30 DEG C. to the boiling point of the reaction mixture, particularly preferably from 45 DEG to 70 DEG C.

The reaction time under preferred conditions is 15 minutes to 2 hours.

Generally, this reaction produces a mixture of salts.

If necessary, these may be separated using conventional methods.

If it is necessary to reduce the resulting dye salt to the primary amino derivative, the usual methods are used, for example dextrose hydrate, alkali metal sulfites or sulfides, glycerin, hydroxyalkylamines or aldehydes in aqueous solution; It may be carried out, for example, in the presence of sodium sulfite, sodium sulfide, hydroxymethylamine or acetaldehyde. or by reacting with an ammonium salt, at least one cation of the sulfonic acid groups present in one molecule is a tetraalkylammonium cation, and other sulfonic acid groups in the molecule are in the form of alkali metal or ammonium salts. It may be modified into salts of certain stilbene azo or stilbene azoxy dyes.

The formation of such lithium, sodium, potassium or ammonium salts may be carried out in conventional manner, for example using halides of these cations, especially chlorides, sulphates, acetates or phosphates.

This reaction is preferably carried out in an aqueous medium at an elevated temperature, preferably between 50 and 100<0>C, more preferably between 70 and 85<0>C.

Among the salts according to the present invention, particularly preferred salts are salts represented by the following formulas (1), (2), (2), (2), (2) and (2).

[In the above formula, R1 represents -5O3H or -8030(CH3)4N'', and the molecule contains at least one tetramethylammonium cation].

[In the above formula, M represents a hydrogen atom or a tetramethylammonium cation, and the molecule contains at least one tetramethylammonium cation].

[In the above formula, R7 is the same as defined above and contains at least one tetramethylammonium ka**thione in the molecule].

[In the above formula, M is the same as defined above and contains at least one tetramethylammonium cation in the molecule].

[In the above formula, R1 is the same as defined above and contains at least one tetramethylammonium ka**thione in the molecule].

[In the formula, M is as defined above and contains at least one tetramethylammonium cation in the molecule].

Dyes represented by these formulas (1) to (2) can be produced by the method of the present invention.

Mixtures of dyes of formulas 1 to 2 may be prepared.

The present invention also includes specific salts represented by formulas (1), (2) and X below.

[In the above formula, Z is LiyNa+, -NH4 or N(CH
3) represents 4 and contains at least one ** N (CH3)4 cation in the molecule].

[In the above formula, Z is the same as defined above and contains at least one -N(CH3)4 cation in the molecule**.

] [In the above formula, Z is the same as defined above and contains at least one -N(CH3)4 cation in the molecule].

Mixtures of dyes of formulas 1 to 1 can also be prepared.

Dyes in the form of lithium salts of formulas ■, ■ and ■ are covered by British patent no.
, No. 114,944, and is used for coloring paper.

The tetraalkylammonium salts of these compounds have surprisingly high cold water solubility compared to the common powdered commercial stilbene azo dyes disclosed in the above patents.

Furthermore, the new salts have a considerably higher coloring strength for paper coloring than the dyes of the above-mentioned patents.

Although dried dye salts in the form of pure lithium salts, ie completely free of water from the dyes of the above-mentioned British patent, have good solubility in water, these salts are extremely hygroscopic.

For this reason, it is impossible or extremely difficult to make it into granules.

The tetraalkylammonium salt according to the present invention can be made into granules much more easily than this.

Another advantage of the tetraalkylammonium salts is that they can be spray dried very easily.

In the case of the dyes of the British patent mentioned above, they are too hygroscopic to be spray dried.

The novel salts according to the invention are primarily suitable for coloring unsized paper in stock solutions prior to sheet formation.

These salts can also color paper by the dipping method.

These new dyes have excellent solubility, especially in cold water.

The degree of coloration of the residual liquid during paper manufacturing is very slight;
Therefore, wastewater treatment is extremely easy.

These dyes do not stain the paper unevenly or cause color differences between the front and back sides, and are extremely insensitive to pH conditions.

These dyes produce colored papers with bright tones and excellent lightfastness.

Prolonged exposure to sunlight will only cause the hue to fade.

Pigmented papers are generally moisture resistant not only to water, but also to milk, fruit juices, soft drinks and alcoholic beverages, and their resistance to alcohol is generally very good.

These dyes can be added directly to the paper stock as dry powder or granules without being pre-dissolved, without reducing brightness or color intensity.

Post-treatment with a cationic fixative gives almost complete wettability and alcohol fastness.

Colored papers can be bleached by oxidative and/or reductive methods, which is important for the recycling of waste paper.

These new dyes can be made into concentrated liquid preparations that are stable for long periods of storage and are also preferred for use because of this storage stability.

The production of concentrated liquid preparations of this type is disclosed, for example, in Belgian Patent No. 718,007.

It is likewise practical to use granular or powdered solid dye preparations as described above.

Such preparations can be manufactured by well-known methods, for example the method disclosed in French Patent No. 1,581,900.

The following examples serve to further illustrate the invention.

In addition, "part" and "percentage" of the owner are expressed by weight.

In the examples, as the press cake of 4-nitrotoluene-2-sulfonic acid, 80.4 parts of 10
A solution containing 0% 4-nitrotoluene-2-sulfonic acid and 2.55 parts of sulfuric acid was used.

Example 1 A dye mixture containing a dye represented by the following formula a: [wherein X represents a group represented by the formula -(CH3)4] can be produced by the following method.

11.9 parts of 4-nitrotoluene-2-sulfonic acid in the form of a wet presscake were weighed out and 40 parts of 25% aqueous tetramethylammonium hydroxide solution were added dropwise.

A bluish-red solution formed and the temperature rose to about 45°C.

The solution was heated to 55° C. with stirring and held at this temperature for 1 hour.

The resulting reddish-brown suspension is then cooled to approximately 4.7
The mixture was neutralized with 30% hydrochloric acid.

The suspension was dried in a drying oven to obtain 17 parts of a reddish-yellow dyestuff having the above formula.

λmaX (measured using 1% acetic acid solution/same below) =
431nm.

For neutralization of the condensation product, sulfuric acid, phosphoric acid, acetic acid or formic acid or their ammonium salts could be used instead of 30% hydrochloric acid.

**Example 2 A dye mixture containing a dye represented by the following formula b: (1) [In the above formula, X represents a group represented by the formula -N(CH3)4] can be produced by the following method.

12.2 parts of 2-nitrotoluene-2-sulfonic acid in the form of a wet filter cake were weighed out and 40 parts of 20% tetramethylammonium hydroxide solution were added dropwise.

The resulting bluish-red solution was heated at 40°C with stirring.
and stirred at this temperature for 2 hours.

Next, 3.3 parts of dextrose hydrate were added and the solution was stirred for a further 2 hours at 40° C. After this reduction, a precipitate crystallized from the solution.

The mixture was cooled and neutralized with 2.9 parts of 30% hydrochloric acid,
This was diluted with water to make 150 parts.

This gave a clear, concentrated solution containing an orange dye with the above formula.

λmax=420nm Example 3 The following formula C is obtained from (2-hydroxyethyl)trimethylammonium hydroxide (choline) by the following method.
: represents the group shown] It is possible to prepare dye mixtures containing dyes of the following formula.

27.6 parts of 4-nitrotoluene-2-sulfonic acid in the form of a wet presscake were mixed with 50 parts of water with stirring.

60 parts of a 50% aqueous choline solution were added dropwise over 15 minutes and the mixture was heated to 75°C and held at this temperature for 1 hour.

Next, 20 parts of ice are added and this cooled solution is mixed with 11 parts of ice.
, 7 parts of 30% hydrochloric acid.

A clear, concentrated solution was obtained containing a reddish-yellow dye having the above formula.

* *λmax=428 nm Example 4 The following formula d: [In the above formula, M represents sodium or tetramethylammonium.

However, sodium and tetramethylammonium are 2.8
:1 can be prepared.

5 parts of powdered dye obtained by the same method as described in Example 1 were added to 35 parts of water with stirring.

To the resulting clear dark red solution was added 10 parts of I-IJ chloride.
Upon addition of um, the dye precipitated quantitatively.

After continued stirring for 30 minutes, the suspension was heated to 70° C. and filtered with suction.

A wet presscake was obtained containing a reddish-yellow dye such that in formula d above M was present as sodium and tetramethylammonium cations in a ratio of 2.8:1.

λmax-431nm. Example 5 If, in the treatment described in Example 4, 10 parts of ammonium chloride, lithium chloride or potassium chloride are used instead of 10 parts of sodium chloride, then in formula d M is the ammonium, lithium or potassium cation and tetramethylammonium. A wet presscake was obtained containing the dye as cationic in a ratio of 0.75:1.

λma) (=431 nm Tetraalkylammonium salts of dyes a, b and C,
In order to convert into the corresponding alkali metal salt or ammonium salt by the treatment described in Example 4 or 5, a sulfate, acetate, phosphate, etc. of the corresponding alkali metal ion or ammonium ion is used in place of the chloride. be able to.

Furthermore, in place of the reducing agent dextrose hydrate mentioned in Example 2, an equivalent amount of an alkali metal sulfite or sulfide, glycerin, hydroxyalkylamine or aldehyde can be used.

To determine the proportion of cations, the salt of the dye is separated from the excess salt by dialysis, dried and the percentage of cations determined by conventional analytical methods (titration, gravimetry, flame spectroscopy, etc.).

Dyeing Example A A suspension of 70 parts of chemically bleached sulfite pulp (from softwood) and 30 parts of sulfite pulp (from birch) in 2000 parts of water was beaten in a Hollander beater. .

0.2 part of the salt of the dye mentioned in Example 1 is sprinkled into this suspension and after mixing for a further 200 minutes, the suspension is mixed to give a reddish-yellow colored hygroscopic I cut it out on a piece of paper.

The remaining liquid was almost colorless. Dyeing Example B 0.5 parts of the salt of the dye mentioned in Example 1 were dissolved in 100 parts of hot water.

The solution was cooled to room temperature and added to a suspension of 100 parts of chemically bleached sulfite pulp suspended in 2000 parts of water and beaten in a Hollander beater.

After 5 minutes of mixing, the liquor was sized and paper was produced from it with a medium reddish-yellow color and good moisture resistance.

Staining example C Continuous hygroscopic unsized paper, dye solution at 40-50°C.

Salt of the dye described in Example 1 Starch Composition: 0.5 parts 0.5 parts Water 99.0 parts An excess of the dye solution was squeezed out with a pair of rollers and the paper was dried.

A reddish-yellow colored paper was obtained.

Claims (1)

[Claims] 1 A compound represented by the following formula ■: [In the above formula, R represents a substituted or unsubstituted alkyl group, and ring A is not otherwise substituted.] at least one sulfonic acid group and at least one tetraalkylammonium in one molecule, comprising condensation in the presence of an alkyl ammonium oxide (the alkyl group may be substituted). A method for producing a stilbene azo or stilbene azoxy dye containing a cation (the alkyl group may be substituted).