JPS5833261B2 - Azo dye manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula (in which Dl and D2 are residues of a diazo component having at least one halogen triazine group, and D2 and D2 are both Both have two sulfonic acid groups or carboxylic acid groups, and Y is at least a difunctional group selected from a carbonyl group, a residue of an aliphatic or aromatic dicarboxylic acid, or a residue of a heterocyclic acyl compound. This relates to an azo dye represented by (which is a residue of an acyl compound).

Although the groups D1 and D2 can be the same or different, in a preferred embodiment D1 and D2 are the same group.

These diazo groups D1 and D2 are aromatic groups which themselves can have an azo group, or aromatic groups derived from anthraquinone, nidroaryl, phthalocyanine, stilbene, or the like.

In particular, the diazo group is a benzene or naphthalene group.

The water-soluble ab dyes of formula (1) can have more than one heterocyclic fiber-reactive group, such as a halogen triazine group, on the basis of the groups D1 and D2 of the diazo component.

These ab dyes are substituted in the radicals of the diazo component by groups conferring water solubility, such as sulfonic acid groups, carboxyl groups or quaternized amine groups, and, as is customary, other atoms or groups, such as halogen atoms, hydroxyl group, amine group, alkyl group, aryl group, alkoxy group,
It can be further substituted with an aryloxy group, an acylamino group, a cyan group, an acyl group, a carbalkoxy group, an acyloxy group, a nitro group, or the like.

When the group of the diazo component has a complex-forming group such as an alkoxy group such as a hydroxyl group, an amino group, a carboxyl group, or a methoxy group at the 〇-position of the ab bridge, the formula (1
) can be converted to their heavy metal complexes if desired before or after the introduction of fiber-reactive groups.

Examples of complex-forming metals include iron, manganese, nickel,
Examples include copper, cobalt and chromium.

The above heavy metal complex contains one metal atom and one azo dye of formula (1).
It can have a molecule or two molecules bonded (
1:1-4 or 1:2-complex).

However, in the 1:2 complex, one of the two ligand molecules can also be an azo dye molecule which does not correspond to formula (1), for example an azobenzene type compound with a corresponding complex-forming group.

Fiber-reactive groups are understood to be such groups that are capable of reacting and covalently bonding with the hydroxyl groups of cellulose or the amine groups of polyamides.

In the context of the present invention, such groups are in particular 5- or 6-membered heterocyclic groups substituted with splittable atoms or splittable groups.
A group having a ring member via a carbonyl group or a sulfonyl group, or a triazine group or pyrimidine group substituted with a splittable atom or group and bonded directly via a carbon atom. It is also a group that has a group like this.

The fiber-reactive group is preferably a 6-membered heterocyclic group having a halogen atom and bonded via an amine group, such as a halogen group or a halogenpyrimidine group.

In particular, the fiber-reactive group has the formula %) [In this formula, R1 is a lower alkyl group or preferably a hydrogen atom. Z is a 4,6-dihalogen unisymmetric triazinyl-(2) group or a 4-halogen-6-amino (
or -alkoxy, -phenoxy, -alkylmercapto or monoarylmercapto) unisymmetric triazinyl-(2) group].

In this connection, lower alkyl groups are understood to be alkyl groups having 4 carbon atoms in 1, such as methyl, ethyl, propyl, isopropyl or butyl.

The bridge members Y are in particular groups of aliphatic or aromatic dicarboxylic acids, such as oxalic acid, malonic acid, maleic acid or terephthalic acid groups, or also groups of heterocyclic acyl compounds, such as halogen triazine groups or halogen pyrimidine groups. can be mentioned.

As Y, a group -CO- is preferable.

In the dye of formula (1), Dl and D2 are each halogen monosymmetric triazinylamino-monosulfo- or -
Preferably it is a disulfobenzene group and Y is a group -CO- and Dl and D2 are the same group.

Examples of azo dyes according to preferred embodiments include, for example, azo dyes represented by the formula:

The present invention also relates to a method for producing the ab dye of formula (1).

This method consists of 2-amino-5-hydroxy-naphthalene-7-sulfonic acid, a diazo component represented by the formula % (3) (4), and at least a difunctional acyl compound having a group Y. are joined together by coupling and condensation reactions in any reaction order to form an azo dye of formula (1).

Azo dyes of formula (1) are prepared using diazo components that already have heterocyclic fiber-reactive groups.

However, in many cases it is also possible to subsequently introduce fiber-reactive groups into the azo compounds obtained.

This introduction can take place after the coupling reaction or after the condensation reaction with the difunctional acyl compound.

In order to introduce a heterocyclic fiber-reactive group, in addition to the diazotizing amino group, an acylatable amino group or a group that can be converted into an acylatable amino group by reduction or saponification, such as a nido tetragroup or This is preferably carried out by acylating the corresponding diazo component which additionally contains an acetylamino group.

Corresponding diazo components suitable for introducing fiber-reactive groups include, for example, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, and (1),4-diaminobenzene-2- Sulfonic acid, 1.4-
Diaminobenzene-2,5-4 or 2,6-disulfonic acid, 1,3-diamino-4-methylbenzene-6=sulfonic acid or their monoacetyl derivatives, 1-amino-4-nitrobenzene, 1-amino -2-chloro-4-nitrobenzene, 6-acetylamino-4-chloro-2-aminophenol, 6-nitro-4-methyl-2-aminophenol, 4-nitro-2-aminephenol-6-sulfonic acid , 6-acetylamino-1-amino-2-naphthol-4-
Examples include sulfonic acid.

Examples of aminoazo compounds into which a fiber-reactive group can be introduced after the coupling reaction include a coupling product of the above diazo component and 2-amino-5-hydroxy-naphthalene-7-sulfonic acid.

If the fiber-reactive group further has a plurality of easily splittable substituents, for example a halogen atom such as a dichlorotriazine group, a reactive hydrogen atom bonding this via a petero atom. (in which case the reactive hydrogen atom can react with the splittable substituent of the fiber-reactive group to form a functional group linked via the petero atom) .

In particular, one chlorine atom on the dichlorotriazine group can be replaced by a corresponding group by reaction with ammonia, amines, alcohols, phenols or mercaptans.

Incidentally, instead of later substituting one halogen atom in the dihalogen triazine group with an amine group, alkoxy group, aryloxy group, or mercapto group, an amino group, alkoxy group, Dihalogen triazines with attached aryloxy or mercapto groups can also be used.

Furthermore, the azo compound of formula (1) has a monohalogen triazine group via an amino group, and this triazine group has one amino group in addition to a halogen atom, and this amine group has another Compounds to which fiber-reactive groups, especially halogen triazine groups, are additionally bonded are of interest.

When this second fiber-reactive group is a halogen triazine group, it is preferably linked to the first triazine group via an alkylene diamine or arylene diamine group.

Therefore, the fiber-reactive amino group present in addition to the halogen atom in the above monohalogen triazine group has the formula (in this formula, R1 and R2 are hydrogen atoms or lower alkyl groups, A is an alkylene group or an arylene group, , Zl is a halogen atom, such as a fluorine, chlorine or bromine atom, and Z2 is a halogen atom, an amine group, an alkoxy group, an aryloxy group, an alkylmercapto group or an arylmercapto group). preferable.

Note that the lower alkyl group in this case has 1 to 4 carbon atoms.
It is often understood that it is an alkyl group with individuals.

A can be a shorter or longer chain alkylene group, such as an ethylene group or a hexylene group, but
Preference is given to benzene groups, such as m- or p-phenylene groups, especially phenylenesulfonic acid groups.

Alkoxy groups include primary, secondary or tertiary alcohol groups, such as methoxy, ethoxy, propyloxy, isopropoxy or 1.1-dimethylethoxy groups, etherified dialcohol groups; For example, ethoxyethoxy or methoxypropoxy groups, unsaturated aliphatic alcohol groups such as allyloxy or propalkyloxy groups, or aliphatic alcohol groups with cyclic groups such as benzyloxy, furfuryloxy or tetrahydrofuryloxy groups. A furyloxy group is mentioned.

Aryloxy groups include phenol or naphthol groups, in particular phenoxy, sulfophenoxy or disulfophenoxy groups.

Examples of the alkylmercapto group or arylmercapto group include a methylmercapto group or a phenylmercapto group.

In a particular embodiment, Z2 represents a chromophore group of the azo dye of formula (1).

Examples of the acylating agent having a heterocyclic fiber-reactive group include the following.

, 4,5-dichloro-1-phenylpyridazone carboxylic acid chloride or -sulfonic acid chloride, 4,5-dichloropyridazone propionic acid chloride, ■, 4-dichlorophthalazine-carboxylic acid chloride or - Sulfonic acid chloride, 2,3-dichloroquinoxaline-carboxylic acid chloride or -sulfonic acid chloride, 2,4-dichloroquinoxaline-carboxylic acid chloride or monosulfonic acid chloride, 2-methanesulfonyl-4-chloro-6-methyl Pyrimidine, 2.4-bis-methanesulfonyl-6-methylpyrimidine, 2.4.6-trichloro- or 2,4,5°6-titrachlor-pyrimidine, 2.4,6-tribromo or 2,4,5゜6-titrabromopyrimidine, 2-methanesulfonyl-4,5-dichloro-6-methylpyrimidine, 2.4.6-dolychlor-5-bromopyrimidine, 2.4,5.6-titrafluoropyrimidine, 4 .6-
Dinoluor-5-chlorpyrimidine, 2.4.6-4 Lifluoro-5-chlorpyrimidine, 2,4,5-4 Lifluoropyrimidine, 2.4.6
- trichlor (or -tribromine or monotrifluoro)-1,3,5-triazine, and 4,6-dichlor (or -dichlor or monodifluoro)-1,3,5-)lyazine (which is 2- of mercapto compounds or hydroxy compounds bonded in position by an aryl or alkyl group, such as a phenyl, methyl or ethyl group, or via an aliphatic or aromatic atom or an oxygen atom, respectively. or in particular by a group -NH2 or by a group of an aliphatic, heterocyclic or aromatic amino compound bonded via its nitrogen atom).

Acylation reactions with heterocyclic fiber-reactive acylating agents and condensation reactions with compounds with reactive hydrogen atoms attached through heteroatoms can be performed using acid binders such as sodium carbonate or sodium hydroxide. under conditions such that one substitutable halogen atom, unsaturated bond, etc. remains in the fiber-reactive groups of the product, i.e., for example in an organic solvent or at a relatively low temperature. It is suitable to carry out in an aqueous medium.

At least bifunctional compounds having the group Y include the following.

Oxalic acid dichloride, chloromaleic anhydride, succinic acid dichloride, terephthalic acid dichloride, 4.5-dichloro-1-phenylpyritasone-carboxylic acid chloride or -sulfonic acid chloride, 2.4.6-tri5 chloride ( or -tribromo)-pyrimidine, 2.4,5,6-tetrachlor (or -tetrabromo)-pyrimidine, 2.4,6-trichlor (or -tribromo or monotrifluor) -1,3,5-triazine, 4. 6-dichloro (also -dibromo or difluoro)-2-amino (or -alkoxy, *.-phenoxy, -alkylthio 1 or monoarylthio)-1,3,
5-triazine, carbonate dichloride, or foscene.

Formula (3) J? The diazo component (4) is diazotized by a method known per se using, for example, hydrochloric acid and sodium nitrite.

This and 2-amino-5-hydroxy-naphthalene-7-
The coupling reaction with sulfonic acid is also carried out in an acidic or weakly alkaline medium by a method known per se.

Furthermore, the condensation reaction with the difunctional acyl compound having the group Y is suitably carried out in the presence of an acid binder.

According to a preferred embodiment, 2-amino-5hydroxy-naphthalene-7-sulfonic acid and at least 2
An intermediate of the formula is prepared from the functional acyl compound and the diazo components of formulas (3) and (4) are coupled thereto.

When Dl and D2 are the same group, these diazo components are coupled to the intermediate of formula (5) in a molar ratio of 2:1.

As the diazo component of formulas (3) and (4), halogen-symmetric triazinylamino-aminobenzene-monosulfonic acid or -disulfonic acid is preferred.

The ab dyes (hexagrams and heavy metal complexes thereof) obtained by the method of the present invention are novel.

They can be applied to a variety of materials, such as silk, leather, wool, synthetic fibers consisting of superpolyamides and superpolyurethanes, polyhydroxylated materials, cellulose-containing materials of fibrous structure, such as linen, stable fibers, regenerated cellulose, rice noodles, etc. Suitable for dyeing and printing.

Note that non-metalized water-soluble azo dyes are particularly important as these dyes.

These dyes can be applied to nitrogen-containing fibers such as superpolyamides,
Superpolyurethanes, silk, inverses and especially wool are dyed, for example from weakly acidic, neutral or slightly alkaline baths, if desired with the addition of customary auxiliaries such as ethylene oxide condensation products of higher amines, or especially celluloses. The material, in particular the noodles, can be processed, for example, by a padding method (according to which the article is impregnated with an aqueous dye liquor, which may also contain salt, and the dye is fixed by an alkali treatment or optionally by heating in the presence of an alkali) or It is particularly suitable for dyeing from alkaline aqueous baths, which may also contain salts, by exhaustion methods from dilute dye baths.

In addition, these azo dyes are also suitable for printing, especially for printing noodles, and also for printing nitrogen-containing fibers such as wool, silk, or wool-containing materials.

Azo dyes of the formula (1) with a halogen-unisymmetric triazinyl group as the fiber-reactive group are particularly suitable for the exhaustion process, in which they can be added in smaller amounts than would normally be the case with salts. It also shows good dyeing and very high fixation.

The dyeings and prints thus obtained are characterized by very pure and vivid tones, which are interesting and valuable.

These dyeings and prints have high acid and alkali resistance, high stability to synthetic resin finishes, high sunlight fastness and especially pronounced wet fastness on sheets.

Furthermore, it is worth mentioning that the degree of fixation is high and the removal of unfixed dye is easy.

In order to improve the dyeing properties and the wet fastness of the prints thus obtained, they are thoroughly treated with cold and hot water, if desired with the addition of auxiliaries having a dispersing action and promoting the diffusion of unfixed constituents. We recommend rinsing.

Next, the present invention will be explained in more detail with reference to Examples.

In these embodiments, it is assumed that both the parts and the kesa are based on weight, and the relationship between parts by weight and parts by volume is the same as that of 2 to cc.

Example 1 25.3 parts of aniline-2,5-disulfonic acid and 250 parts of water
Dissolve in a neutral state while adding caustic soda solution.

18.5 parts of cyanuric chloride is added to this and condensation is carried out at about 5°C.

In this case, the pH value of the reaction mixture is maintained at 4 by adding caustic soda solution.

When cyanuric chloride is no longer detected, 1.
21 parts of the sodium salt of 3-phenylenediamine-4-sulfonic acid dissolved in 150 parts of water are added and heated to 30°C.

The acid liberated in this condensation reaction is neutralized by adding caustic soda solution.

After the condensation is completed, diazotization is carried out using hydrochloric acid and sodium nitrite at 0 to 5°C in a conventional manner.

The azo solution obtained in this way was dissolved in 300 parts of water.
Pour 27.4 parts of the disodium salt of 5'-dihydroxysinaphthalin-2,2'-ylurea-7'7'-disulfonic acid into the residue, stirring thoroughly, and adjust the pH of the solution to the addition tube. Keep the value between 7 and 8.

Thus Cup I. When the dye is finished, add potassium chloride and apply the dye.

When this is filtered and dried, an orange dyed semi-powder is obtained.

However, the dye can be isolated by evaporating the entire reaction mixture without adding salt.

This stuff dyes momen noodles in a firm color (orange color).

The λmax of this dye is 488 nn.

Click on the method in this example and add the amines in column 1 of the following table.

Condensation with cyanuric chloride followed by condensation with the 5 amines in column (2), diazotization and coupling with the force nibbling component described above dyes fibers made of cellulose material in the tones shown in column (2). More dye is obtained.

Dissolve 77.3 parts of the trisodium salt of an azo dye represented by
1 part and 25 parts of 4N sodium nitrite solution to diazotize.

Disodium salt of 5,5'-dihydroxysinaphthalin-2,2'-ylurea-7°7'-disulfonic acid, in which the diazo compound thus produced was dissolved in 300 parts of water27.
The coupling reaction was brought to pH 7 by pouring into 4 parts of the solution.
Do it in 5.

Salt is added to this solution to precipitate the dye, filtered and dried.

This dye dyes the noodles a firm ruby color.

Example 14 Click on Example 1 and replace 5,5'dihydroxysinaphthalin-2,2'-ylurea 7,7'-disulfonic acid with terephthalic acid-di(5,5'-dihydroxy-7, 7'-disulfo)naphthylamide30.
If 5 parts are used, an orange dye is likewise obtained.

Furthermore, by using the coupling components shown in the following table, an additional orange dye can be obtained.

Example 20 A diazo component is prepared and diazotized by the method described in Example 1.

This diazo solution is added dropwise to a solution of 26.1 parts of the sodium salt of 6-amino 1-naphthol-3-sulfonic acid, the pH value of the coupling solution being maintained at 7 by simultaneous addition of sodium bicarbonate. .

Once the coupling is complete, the solution is warmed to 40 DEG -45 DEG C. and, while maintaining a neutral OpH value, phosgene is introduced into the solution at 1, when no more starting material is detected.

Then potassium chloride is added to precipitate the dye, filtered off and dried.

This is the same as the dye according to Example 1. Example 21 24.6 parts of 6-acetylamino-2-aminophenol 4-sulfonic acid is diazotized by a conventional method, and when the diazotization is complete, the acetyl group is saponified by heating at 50 DEG C. for 1 hour in a hydrochloric acid solution.

The diazo solution obtained in this way was dissolved in 300 parts of water.
'-dihydroxysinaphthalin-2,2'-yl urea-
In addition to a solution of 27.4 parts of 7,7'-disulfonic acid, pH
Coupling with 8.

After the coupling is completed, 100 parts by volume of IN steel sulfate solution is added to the solution and stirred at 50-60°C and pH 8 for 2 hours.

The violet dye solution thus formed is cooled to 0° C. and mixed with 18.5 parts of freshly precipitated cyanuric chloride.

The acid liberated by this condensation reaction is neutralized by adding caustic soda solution dropwise.

Next, add 25 parts by volume of condensed ammonia water to 35-40°C.
Stir and stir for another 3 hours.

Add sodium chloride to precipitate the dye.

This dyes cellulosic materials a fast violet color.

Example 22 26.8 parts of 1,4-phenylenediamino-2,5-disulfonic acid are dissolved at pH 8 in 300 parts of ice water without addition of caustic soda solution.

Add 18.5 parts of cyanuric chloride to this and
A big one.

At this time, caustic soda is added to maintain the pH value at 5-6.

The condensation product thus obtained is immediately diazotized without isolation by adding 25 parts by volume of ION hydrochloric acid and 50 parts by volume of 2N sodium nitrite solution.

The diazonium salt solution thus obtained is neutralized to pH 6 by adding sodium carbonate.

At the same time, add ice to keep the temperature between 0 and 5°C.

5,5'-dihydroxysinaphthalin-2,2'-yl urea-7,7' was added to the thus neutralized diazonium salt solution.
Dissolve 27.4 parts of disodium disulfonate in 250 parts of water, add and complete the coupling.1) H value is 7.
Keep at ~7.5.

Next, 25 parts by volume of 24 volumes of aqueous ammonia were added to this orange solution, and the reaction mixture was stirred for 3 hours at a temperature of 30 to 50°C.
Zeru.

When salt is added to this orange dye solution, the dye represented by the formula precipitates out.

If this is filtered, dried and ground, a reddish-brown dye powder is obtained which dyes momen noodles in red tones from an aqueous solution.

Dyeing Example 1 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water together with 0.5 part of sodium m-nitrobenzenesulfonate.

A noodle fabric is also impregnated with this solution to a weight gain of 75 threads and dried.

Sodium hydroxide 5? The dyeing thus obtained was impregnated with a warm solution at 20°C containing 1/l and 300 S'/7 of sodium chloride and squeezed with a weight increment of 1 of 75 φ.
Steam for 1 minute at 0-101°C, rinse, soap for 15 minutes at boiling temperature in a 0.3-polymer solution of non-ionic detergent, rinse and dry.

Staining example 2 2 parts of the dye obtained according to Example 1 are dissolved in 100 parts of water.

This solution is added to 3900 parts of cold water, 80 parts of sodium chloride are added thereto, and 100 parts of the woven fabric are introduced into the dyebath.

Increase temperature to 75°C for 45 minutes.

In this case, after 30 minutes, trina l-IJium 4
Add 0 parts.

The temperature is maintained at 75° C. for 30 minutes, rinsed and the dyeing thus obtained is soaped for 15 minutes at boiling in a 0.3 multi-solution of non-ionic detergent, rinsed and dried.

In this way an orange dyeing is obtained which is fast to the buttons and fast to light.

Two parts of the dye prepared according to Example 1 were mixed with 45 parts of sodium alkinate thickener, 32 parts of water, and 20 parts of urea.
Add to 100 parts of thickener stock solution containing 1 part of sodium nitrobenzenesulfonate and 2 parts of sodium bicarbonate while stirring quickly.

Using the printing paste thus obtained, a noodle fabric is printed on a roll-up printing machine, and the print thus obtained is steam-treated in saturated steam at 100° C. for 8 minutes.

The thus printed fabric is thoroughly rinsed in cold and hot water.

Although the present invention has been described in detail above, specific examples of the configuration of the present invention can be summarized as follows.

(1) The method according to the above claims, in which the same diazo components in formulas (3) and (4) are used.

(2) A method according to the preceding claims, in which an at least difunctional heterocyclic acyl compound is used as the at least difunctional acylating agent having a group Y.

(3) The method according to the above item (2), in which an at least difunctional symmetrical triazine is used as the at least difunctional heterocyclic acyl compound.

(4) The method according to the preceding item (1), wherein a halogen monosymmetric triazinylamino-aminobenzene monosulfonic acid or monodisulfonic acid is used as the diazo component, and phosgene is used as the at least difunctional acyl compound.

(5) 2-amino-5-hydroxy-naphthalene 7
- A method according to the preceding claims, in which a sulfonic acid is condensed with an at least difunctional acyl compound having a group Y.

(6) The method described in the preceding item (5), in which the diaz component is coupled to the compound of formula (5) at a molar ratio of 2:1.

(7) Aniline-2,5-disulfonic acid, cyanuric chloride, and 1,3-diaminobenzene-4-sulfonic acid or 1,4-diaminobenzene-2-sulfonic acid are reacted to form a compound represented by the formula Then, this compound was converted into 2-amino-5-hydroxy-naphthalene-7*sulfonic acid 2
The method described in the preceding item (6), wherein the compound represented by the formula obtained by reacting 1 mole of phosgene with 1 mole of phosgene is coupled at a molar ratio of 2:1.

(8) Compounds obtained according to Examples herein.

(9) The method described in the Examples of this specification.

(10) The scope of claims button and the preceding paragraphs (1) to (
7) A compound obtained by the method described in any one of 7).

(11) The method described in the dyeing cartwheel and printing examples of this specification.

(12) Statement of the scope of the claims and the preceding paragraphs (1) to (7)
Use of the compound obtained by the method described in any of the above as a dye.

(13) Dyeing or printing methods using the dyes described in the preceding paragraph (1).

(14) The method described in (13) above for dyeing cellulose fibers.

Alpha-based A dyeing or printing formulation comprising a compound obtained by the method described in the claims and any one of the preceding items (1) to (7).

Materials dyed or printed by the method described in (13)-i or (14) above.

Claims (1)

[Claims] Formula 1 (In this formula, Dl and D2 are residues of a diazo component having at least one halogen triazine group, and both Dl and D2 are residues of a diazo component having at least two sulfone groups. Y is at least a bifunctional acyl compound residue selected from a carbonyl group, a residue of an aliphatic or aromatic dicarboxylic acid, or a residue of a heterocyclic acyl compound. In producing the azo dye represented by
5-Hydroxy-naphthalene-7-sulfonic acid, a diazo component represented by the formula % formula % (3) and a diazo component represented by the formula DI NH2 (4) and at least a difunctional acyl compound having a group Y in any reaction order. Formula (1) above, characterized in that they are bonded to each other by coupling and condensation, or finally (or further) a halogen triazine group is introduced by acylating with an acylating agent having a halogen triazine group. The manufacturing method of the azo dye shown.