JPS602337B2 - Fiber reactive dye and its manufacturing method - Google Patents

Description

Detailed Description of the Invention The present invention is based on the formula (where A is a monoazo-based, disazo-based, metal key salt azo-based, anthraquinone-based, or phthalocyanine-based sulfo group-containing chromophore group, and A2 is a hydrogen atom). or is a colorless aliphatic, cycloaliphatic, aromatic or heterocyclic group, or A2 is a ring directly bonded to the s-triazine group via the nitrogen atom in the formula to which A2 and R4 are bonded. B is an alkylene group or an arylene group, and R, R2, and R3 each independently represent a hydrogen atom or a carbon atom. 1 to 6 alkyl groups or cyclohexyl groups, or when B is an alkylene group, R2 and R3 form a closed aliphatic key, and the bridge member is a double cyclic ring containing 2 nitrogen atoms. It shall be possible to form a ring,
and R4 is a hydrogen atom, an unsubstituted or substituted alkyl group of 1 to 6 carbon atoms, or a cyclohexyl group) and a method for producing the fiber-reactive dyes.

The colorless group A2 includes, in addition to a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a methoxyethyl group, a methoxypropyl group, an ethoxyethyl group, a cyanethyl group, a hydroxyethyl group, cyclohexyl group, methylcyclohexyl group, aryl group such as phenyl group (which may optionally be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl group, alkoxy group such as methoxy group,
Ethoxy group, isopropoxy group, ethoxyshetoxy group,
isopropoxypropoxy groups, acyl groups such as acetyl groups, acetylamino or pennzoylamino groups, ureido groups, carpoxyl groups or sulfo groups and halogen atoms such as chlorine or bromine atoms), Examples include a naphthyl group, a sulfonaphthyl group, and a polycyclic group such as a pyridyl group, a benzthiazolyl group, an oxazolyl group, a thiazolyl group, and a quinolyl group.

Furthermore, A2 can be part of a double cyclic group when A2 and R4 in formula '11 are taken together to form a ring. Therefore, when A2 and R4 are bonded, said moiety is directly bonded to s-triazine via the nitrogen atom. Such post-boundary groups are, for example, piveridyl and morpholyl. The alkylene or arylene group B is derived from an aliphatic or aromatic diamine.

B can therefore be a long chain (for example one carbon atom or more) or a short chain, straight chain or branched alkylene group. Particular mention may be made of alkylene groups having 1 to 6 carbon atoms, such as ethylene, propylene, butylene, hexylene or cyclohexylene. Preferably, B is an aromatic group. For example, naphthylene groups, diphenyl or stilbene groups or especially phenylene groups. These groups can further carry substituents such as halogen atoms, lower alkyl groups, lower alkoxy groups, carboxyl groups and sulfo groups. When B is an alkylene group, R2 and R3 can also be taken together to form an aliphatic chain. Thus, the bridging member represented by the formula, together with the two ring nitrogen atoms in the formula, is a dicyclic ring, such as 1,4-piverazinylene.

B is preferably a phenylene group. R,,R2,
Examples of R3 and R4 include, in addition to hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, or cyclohexyl. R,, R2, R3 and R
4 is preferably a hydrogen atom. Particularly preferable fiber-reactive dyes represented by the formula '1' are those of the formula [wherein A
, and B have the same meaning as in the above formula {11, x is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxyl group, or a sulfo group, and the benzene group D is further substituent, especially a sulfonic acid group. It is a dye represented by

Due to the presence of two removable fluorine atoms in both s-triazines of the dye of formula {l},
This dye becomes fiber [2] tentative.

By fiber-reactive compound is meant one which is capable of reacting by forming covalent chemical bonds with the hydroxyl groups of cellulose or the amino groups of natural or synthetic polyamides. formula'
The fiber-reactive dye represented by 1- is produced by the following method.

A dye represented by the formula (wherein A, and R have the same meanings as above), a compound represented by the formula (wherein A2 and R4 have the same meanings as above), and a compound represented by the formula (wherein A2 and R4 have the same meanings as above); Middle, B, R2 and R
3 has the same meaning as above) and trifluoro-s-triazine represented by the formula are reacted with each other so as to obtain a fiber-reactive dye represented by the formula '1}. (In this case, the order of partial reactions can be freely selected while taking into consideration the starting materials to be reacted with each other.)
and manufacture it.

One of the important variants for producing fiber-reactive dyes of formula m is as follows.

A dye represented by formula '3' and a dye represented by formula '5 are produced such that a fiber-reactive dye represented by formula (wherein A, B, R, and R2 and R3 have the same meanings as above) is produced. } and alkylene diamine or arylene diamine represented by the formula {
6} and trifluoro-s-triazine are reacted with each other (in which case, the order of partial reactions can be freely selected while taking into consideration the starting materials to be reacted with each other), and this formula is expressed as Dye and formula'4
1 (in the formula, and R4 have the same meanings as above).

In the variant described above, which consists of condensing a fiber-reactive dye of formula '7' with a compound of formula {41,
X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxyl group or a sulfo group, and the benzene group D can further have a substituent, particularly an aminobenzene represented by a sulfonic acid group. It is advantageous to use it.

Further, the fiber-reactive dye represented by formula '21 can be obtained by other methods.

That is, the dye represented by the formula is acylated with the phenylaminodifluoro-triazine represented by the formula.

According to another method, a dye component represented by the formula {31 containing an amino group represented by the formula and a compound represented by the formula ■ containing an amino group represented by the formula Acylation is performed with triazine, and the resulting acylated product is reacted with other components and an alkylene diamine or arylene diamine represented by the formula in any order to obtain fiber reactivity represented by the formula [1]. Get the dye.

Preference is given to using starting materials that contain groups that render them water-soluble.

The reaction of difluoro- or trifluoro-triazines with amino/group-containing compounds and dyes or their components is carried out in organic solvents or in aqueous soot at relatively low temperatures using acid binders such as sodium carbonate or sodium hydroxide. It is advantageous to carry out the process inside. In the above reaction, it is preferable that one fluorine atom remains which can be removed per s-triazine ring in the obtained product. As shown in the above formula '1', the dye that reacts with trifluoro-s-triazine represented by the formula '6' is of the formula -NHR, and -NHR4 (where R and R
4 has the above-mentioned meaning) and must contain at least one acylated amino/group.

The azo dye compounds containing at least one monoNHR group, which are used as starting products, can be obtained by various methods. One method consists of diazotizing an aromatic primary amine and coupling the diazo compound thus obtained with a coupling moiety containing one NHR group.

Examples of aromatic primary amines that can be used in the above method to obtain aminoazo compounds are as follows. Aniline, o-, m- and p-toluidine, o-, m- and p-anisidiso, o-, m- and p-chloroaniline, 2,5-dichloroaniline, Q- and B-naphthylamine, 2・5-dimethylaniline "5"
Nitro-2-aminoanisole, 4-aminodiphenyl, aniline-2,3- and -4-carboxylic acids, 2-ami/diphenyl ether, 2-, 3- or 4-aminobenzenesulfonamide or -sulfomonomethyl-
or -ethylamide or -sulfonedimethyl- or -sulfonediethylamide, dehydrothio-p-toluidine monosulfonic acid or dehydrothio-p-toluidine disulfonic acid, aniline-2-, -3- and -4
-sulfonic acid, aniline-2,4- or -2,5-disulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3-aminobenzotrifluoride-4-sulfonic acid, 4-chloro-5-methylaniline-2- Sulfonic acid, 5-chloro-4-methylaniline-2-sulfonic acid,
Sulfoanthranilic acid, 3-acetylaminoaniline-
6-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloraniline-2-sulfonic acid, 3.
4-dichloroaniline-6-sulfonic acid, 4-methylaniline-2-sulfonic acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, and 5
-Methoxyaniline-2-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, 2-naphthylamine-4
・8- and 1-6,8-disulfonic acid, 1-naphthylamine-2-, 1-4-, 15-1, 16-1 or 17-monosulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 2-naphthylamine- 1-sulfonic acid, 2-naphthylamine-1,5-1, 3,6-1 and 1-5,7-disulfonic acid, 2-naphthylamine-3,6,8-trisulfonic acid, m- and p-nitroaniline, 4-nitroaniline-2-sulfone 3-nitroaniline-6-sulfonic acid, m- or p-aminoacetamide and 4-amino-2-acetylaminotoluene-5-sulfonic acid. Examples of coupling components that can be used include the following. 2-amino and 2-methylamino-5 naphthol-7-sulfonic acid, 2-amino and 2-methylamino-8 naphthol-6-sulfonic acid, 1-amino and 1-
ethylamino-8-naphthol-6-sulfonic acid and the corresponding 3,6- and 4,6-disulfonic acids, 1-(
3'-1- or 4'-aminobenzoylamine/)-8-naphthol-3,6- and -4,6-disulfonic acid, aniline, o- and m-anisidine, o- and m-toluidine, 2,5-dimethylaniline , 3-aminomethoxytoluene, 2,5-dimethoxyaniline, N-methylaniline, N-ethyl-o-toluidine, N-methyl-m-anisidine, 3-methylamino-4-methoxytoluene, 1-(3'-aminophenyl)-3-methyl, -carboxy and - Carpoethoxy-5-pyrazolone, 1-(4'-aminophenyl)-3-methyl-, mono-carpoxy and -carboethoxy-5-pyrazolone and 1-(4'-aminophenyl)-3-methyl-S -pyrazolone, 3-aminoacetanilide, and 3-aminophenyl urea.

The aminoazo compound that can be used in the method of the present invention has an azo group of 1
It is not limited to only compounds containing only 1. The disazo compound can be obtained by, for example, tetrazotizing an aromatic diamine containing two primary amino groups, and coupling the thus obtained tetrazo compound with 2 moles of one of the coupling components, or by coupling two moles of one of the coupling components. It can be obtained by coupling 1 mole of each type of coupling component, or by coupling 1 mole of one type of the coupling component with 1 mole of a coupling component that does not contain an amino group. Examples of such aromatic diamines are as follows. Penzidine, 3,3'-dimethoxybenzidine, benzidine-2,2-disulfonic acid, benzidine-3,3'-dicarboxylic acid, benzidine-3,3'-diglycolic acid and 4,4'-diaminostilbene-2
- A disazo compound or a polyazo compound can be obtained by using a primary aromatic amine or diamine which is 2-disulfonic acid and further contains an azo group. Examples of primary aromatic amines or diamines containing these azo groups include 4-aminoazobenzene-4'-sulfonic acid, 4'-amino-2-methylphenylazo2-naphthalene-4,8-disulfonic acid, 4-aminoazobenzene-4'-sulfonic acid, Mention may be made of 5-methoxy-2-methyl-4'nitro-2-sulfobenzene. Instead of using an amine that does not contain one NHR group, one can optionally couple a coupling moiety that does not contain an -NHR group with a diazonium compound that contains one NHR group.

Said diazonium compounds can be obtained by known methods of diazotizing a primary or aromatic amine containing another amino group or a monosubstituted amine/group. Examples of the first aromatic amine include p-phenylenediamine, 1,4-phenylenediamine-12-sulfonic acid,
1,4-phenylenediamine-2-carboxylic acid, 1,4
-diaminonaphthalene-2-sulfonic acid. Examples of coupling components that can be used in the method described above include, in addition to the coupling components described above, the following. 8 naphthol, 2-
Naphthol-6- or -7-sulfonic acid, 2-naphthol-3,6- or -6,8-disulfonic acid, 1-naphthol-4-sulfonic acid, 1-phenyl-3-methyl-5-pyrazolone, 1-(4'- sulfophenyl)-3
-Methyl-5-pyrazolone, 1-(2',5-dichloro-ysulfophenyl)-3-methyl-5-pyrazolone, 2-benzoylamino-5-naphthol-7-sulfonic acid, 1-benzoylamino-8-naphthol- 3.6
-4,6-disulfonic acid, phenol, p-cresol, acetoacetanilide, acetoacetate-2-methoxyaniline-5-sulfonic acid, 3-aminocarbonyl-4-methyl-6-hydroxypyridone-2, 1-ethyl-3-cyan- or 3-chloro-4-methyl-6-hydroxypyridone-2, 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone-2,
2,4,6-triamino-3-cyanopyridine, 2-(
3′-sulfophenylamino)-4,6-diamino-3
-cyanpyridine, 2-(2-hydroxyethylamino)-3-cyan-4-methyl-6-aminopyridine, 2
-6-bis-(2-hydroxyethylamino)-3-cyan-4-methylpyridine.

Other methods for preparing azo dye compounds containing one -NHR group which can be used in the process of the invention include reducing nitro group-containing dyes or hydrolyzing one or more acylamides/groups. It consists of treating an azo or polyazo compound containing at least one acylamino group with an aqueous acid or an aqueous alkali.

Said azo or polyazo compounds can be obtained from a primary aromatic amine containing an acylamino group and/or a coupling component. Examples of the above-mentioned first aromatic amine include monoacylbenzidine, 4-amino-1-
Acetylaminonaphthalene-6-sulfonic acid, 4-amino-4'-acetylaminodiphenyl-3-sulfonic acid, 4-amino-3-sulfoacetanilide, 3-amino-4-sulfoacetanilide and 4-amino-4'-acetylaminostilbene-2. Mention may be made of 2-disulfonic acid, and examples of the aforementioned coupling components include 2-acetylamino-5naphthol-7-sulfonic acid, 2-N-acetyl-N-methylamino-5naphthol-7-sulfonic acid, 2- Mention may be made of acetylamino- and 2-N-acetyl-N-methylamino-8-naphthol-6-sulfonic acids and 1-acetylamino-8-naphthol-3,6- and -4,6-disulfonic acids. Examples of anthraquine dye compounds which can be used as starting products in the process of the invention include:

First, on the alkylamino or arylamino group bonded to the - position of the anthraquinone nucleus, the formula -N
It is an anthraquinone compound that has an HR group.

Examples of such anthraquinone compounds include the following. 1-amino-4-(4'-aminoaniline)-anthraquinone-2,3'-disulfonic acid and the corresponding 2,3',5-, 2,3,6- and 2,3,7-trisulfonic acids, 1-amino- 4-(4″
-amino-4'-penzoylaminoaniline)-anthraquinone-2,3-disulfonic acid and the corresponding 12-
3,5-trisulfonic acid, 1-amino-4-[4'-(
4″-aminophenylazo)-anilino]-anthraquinone-2, 2″, 5-trisulfonic acid, 1-amino-4
-(4'-amino-3'-carboxyanilino)-anthraquinone-2,5-disulfonic acid, 1-amino-4-
(3'-aminoanilino)-anthraquinone-2,4'
・5-trisulfonic acid and the corresponding 2,4-disulfonic acid, 1-amino-4-[4'-(4''-aminophenyl)-anilino]-anthraquinone-2,3'',5-trisulfonic acid, 1-amino-4-(4 '-Methylamino)-anilinoanthraquinone-2,3'-disulfonic acid and the corresponding 2,3,5-trisulfonic acid, 1-amino-4-(4'-n-butylamino)-anilinoanthraquinone-2,3-disulfonic acid, 1-aminoanthraquinone-2,3-disulfonic acid, /-4-(
4'-methylamino-3'-carpoxyanilino)-anthraquinone-2-sulfonic acid, 1-amino-4-(
3'-8-hydroxyethylamino)-anilinoanthraquinone-2,5-disulfonic acid, 1-(4'-amino-anilino)-anthraquinone-2,3-disulfonic acid and 1-ami/141(4 '-Amino-2-methoxyanilino)-anthraquinone-2,3-disulfonic acid.

The above-mentioned anthraquinone dye compounds are obtained from anthraquinone compounds having a halogen atom or a nitro group bonded to the Q-position of the corresponding anthraquine nucleus, or from 1,4-dihydroxy-, monodiamino- or -aminohydroxyanthraquinones. can be obtained from the corresponding anthraquinone compound by reacting it with at least 1 mol of an aliphatic or aromatic diamine.

The phthalocyanine dye compounds that can be used in the method of the invention preferably contain metal-containing phthalocyanines, such as at least one water-solubility imparting group, such as a sulfonic acid group, and at least one group represented by the formula -NHR as described above. It is a steel phthalocyanine. One or more -NHR groups can be bonded directly or via a divalent bridge member to the benzene ring of the phthalocyanine nucleus. 2
Examples of valent crosslinking members include -phenylene, -CO-phenylene, -S○2-phenylene, -NH-phenylene, -S-phenylene, -101 phenylene, -CH2
S-phenylene, 1C ratio○-phenylene-, 1C5-phenylene, 1SC ratio-phenylene-, 1S○2CH2
17th Engineering Niren, 1S○2NR. -Phenylene-, -CH2-, -S〇2NR, -Arylene-, NR,CO
-Phenylene-, NR, S02-Phenylene-, -S〇2〇-Phenylene-, C ratio-, -CH2NR, -Phenylene-, -CH is H-CO- -Phenylene-, -SQR
, -Alkylene, 1 C string NR, 1 Alkylene, 1 CO
R, -phenylene-, -CONR, -arylene-, -S02- or -CO- bridge member.

In the above formula showing the divalent crosslinking member, R is a hydrogen atom,
An arylene group which is a divalent aromatic group optionally substituted with an alkyl or cycloalkyl group, e.g. a halogen atom, an alkyl group or an alkoxy group, in which the bond ends are on the same or different nuclei. ), and alkylene groups which are divalent aliphatic radicals in which a heteroatom such as nitrogen may be interposed in the atomic chain, e.g.
One CH2 group. Examples of the divalent aromatic group described above as the arylene group include the following.
Aromatic nuclei such as benzene, naphthalene, acridine and carbazole nuclei can further carry substituents. (In the formula, the benzene ring can have a further substituent, and 1D- is a bridging group). 1NH1, 1S-, 101, SQ-,
-NO=N-, -N=N-, -NH-CO-NH-CO
-NH1, 10-CH2CQ○- or.

Examples of phthalocyanine dye compounds that can be used in the method of the present invention include the following.

Copper monophthalocyanine-4-N-(4-amino-3-sulfophenyl)-sulfonamide 4', 4", 4"'-
Trisulfonic acid, cobalt phthalocyanine-4,4'-di-N-(4'-amino-4'-sulfophenyl)-carbonamide 4'',4...-dicarboxylic acid and copper-4
-(4'-amino-3'-sulfobenzoyl)-phthalocyanine.

Mixtures of aminophthalocyanines can also be used.

For example, a mixture of approximately equal parts of copper phthalocyanine-N-(4-amino-3-sulfophenyl)-sulfonamide trisulfonic acid and copper phthalocyanine-N-(4-amino-3-sulfophenyl)-sulfonamide disulfonic acid can be used. Aminophthalocyanines bearing sulfonic acid are made either by sulfonation of known phthalocyanines bearing primary or secondary amino groups, or by synthesis from mixtures of phthalic acid derivatives and sulfonated phthalic acid derivatives. be able to.

As sulfonating agent, use is made, for example, of fuming sulfuric acid, for example a 20% solution of sulfur trioxide in sulfuric acid. In addition, suitable derivatives of sulfonated phthalic acids and substituted phthalic acids can be prepared in a conventional manner, such as 4-sulfophthalic anhydride and 41p nitro-penzoyl phthalic anhydride, urea, It can be obtained by heating a mixture of steel (0) chloride and ammonium molybdate in o-dichlorobenzene to about 150 °C. Alternatively, the corresponding primary and secondary amines may be sulfonated or the primary
(or a second N-alkyl or cycloalkyl)
It can also be obtained by reacting nitroaniline with a phthalocyanine having a chloromethyl group and a sulfonic or carboxylic acid group, and the phthalocyanine can be used as a starting material. Furthermore, the above-mentioned aminophthalocyanine can be obtained by reacting a phthalocyanine having a chlorosulfonyl group with a monoacetyl alkylene diamine or amino-N-pendylacetamide in the presence of water, and the product thus obtained (this is a product containing a sulfonamide group and a sulfonic acid A lid containing a chloromethyl group and a sulfonic or carboxylic acid group is treated with an aqueous alkali to hydrolyze the acetylamine/group. It can be obtained by reacting cyanine with monoacetyl alkylene diamine and treating the product thus obtained with an aqueous alkali to hydrolyze the acetylamino group. Alternatively, anhydride, urea and catalyst can be combined with an organic compound, for example, by direct sulfonation or by appropriate heating of a suitable carboxy- or sulfophthalic acid derivative combination with a substituted phthalic acid derivative. By reducing the nitrophthalocyanine sulfonic acid or carboxylic acid thus obtained by heating in a solvent, or by hydrolyzing the acylaminophthalocyanine sulfonic acid or carboxylic acid thus obtained, or having a carboxylic acid chloride group By reacting a phthalocyanine compound with diaminobenzenesulfonic acid or carboxylic acid, aminobenzoic acid or aminobenzenesulfonic acid having a nitro group and reducing the nitro compound thus obtained, or with a phthalocyanine compound having a carboxylic acid chloride group. N
-aminobenzylacetamide and then hydrolyzing the product thus obtained with aqueous alkali. As examples of dye compounds having at least one -NHR group which can be used as starting materials in the process of the invention, mention may be made of the following classes of compounds:

'1' class: Formula (in the formula, D is at most a bicyclic aryl group that does not contain an azo group and -NHR group, and one NHR group is located at the 6-1, 7- or 8-1 position of the naphthalene nucleus) A monoazo compound represented by (preferably, a sulfonic acid group is bonded to the naphthalene nucleus) and may have a sulfonic acid group at the 5-1 or 6-position of the naphthalene nucleus.

Therefore, D,' is a naphthalene or benzene group having no azo substituent, such as a stilbene group, diphenyl group, benzthiazoylphenyl group or diphenylamine group.

Also in this class, instead of one NHR group being attached to the naphthalene nucleus, the 6-, 7- or 8-
Modified dyes with penzoylamino or anilino groups attached at positions are also conceivable. Particularly valuable starting dyes are D, a sulfonated phenyl or naphthyl radical, in particular the abovementioned radicals with an --S03 radical in the ortho-position to the azo bond.

The phenyl group can be further substituted, for example by halogen atoms such as a chlorine atom, alkyl groups such as a methyl group, acylamino groups such as an acetylamino group and alkoxy groups such as a methoxy group. [Type 2-: In the above formula (■), D is an azobenzene-based, azonaphthalene-based, or phenylazonaphthalene-based group, and the naphthalene nucleus is formed by one NHR group and optionally a sulfonic acid group, as in the above m group. A disazo compound of the formula which is substituted with .

[3' class: Formula (in the formula, D, at most bicyclic aryl group, for example [1
The benzene nucleus is preferably a disulfonaphthyl group or a stilbene group, and the benzene nucleus may further have a halogen atom or a substituent such as an alkyl group, an alkoxy group, a carboxylic acid group, or an acylamino group. A monoazo compound represented by

'4}: Formula (wherein D is an arylene group, such as an azobenzene-based, azonaphthalene-based, or phenylazonaphthalene-based group, or preferably an at most bicyclic arylene group of a benzene-based or naphthalene-based group; , K is a naphtholsulfonic acid group or a genolized or henolizable ketomethylene compound such as acetoacetarylide or 5-bilazolone with an OH group in the ortho position to the azo group; Disazo compound.

D is preferably a benzene group having a sulfonic acid group. '5} type: Formula DI-N: N-K2-NHR
■ [In the ceremony, D. is [1} and [
2}, K2 is a ketomethylene compound that can be phenolated, such as acetoacetarylide or 5-pyrazolone, and has one OH group in the ortho-position to the azo group. A mono- or disazo compound represented by

■Class: In the above formulas ■ and ■, D, , K and K
2 has the same meaning as above, and a group that can be metallized, such as a hydroxyl group, a lower alkoxy group, or a carboxylic acid group, is D,
metal salt compounds of dyes represented by the formulas (1) and (2) in the ortho-position to the azo group, such as copper rust salts, chromium salts and cobalt salts. '7' class: Formula (wherein the anthraquinone nucleus can further have a sulfonic acid group at the 5-, 6-1, 7- or 8-position, and Z' is a bridge member, preferably a benzene-based 2 Anthraquine compounds represented by a valent group such as a phenylene group, a diphenylene group or a 4,4'-stilbene group or an -azobenzene group.

It appears preferable that Z' has a sulfonic acid group on each of the aforementioned benzene rings. '8) Type: formula [wherein Pc is a phthalocyanine nucleus, preferably steel phthalocyanine, is -OH and/or -N ratio, and Z' is a crosslinking member, preferably aliphatic, lipophilic or aromatic group bridge member, and n and m are each 1, 2 or 3
and can be the same or different, n0m
shall not be greater than 4].

Examples of starting dyes belonging to the above-mentioned dye classes include the following.

'1-Class: 6-amino-1-hydroxy-2-(2-sulfophenylazo)naphthalene-3-sulfonic acid, 6-methylamino-1-hydroxy-2-(4'-acetylami/1-2-sulfophenylazo)naphthalene -3-sulfonic acid, 8-amino-1-hydroxy-2-(2-sulfophenylazo)-naphthalene-3,6-disulfonic acid, 8
-amino-1-hydroxy-2-(4'-chloro-2-sulfophenylazo)-naphthalene-3,5-disulfonic acid, 7-amino-2-(2,5-disulfophenylazo)-1-hydroxynaphthalene- 3-sulfonic acid, 7
-Methylamino-2-(2-sulfophenylazo)-1
-Hydroxynaphthalene-3-sulfonic acid, 7-methylamino-2-(4'-methoxy-2'-sulfophenylazo)-1-hydroxynaphthalene-3-sulfonic acid,
8-(3'-aminobenzoylamino)-1-hydroxy-2-(2'-sulfophenylazo)naphthalene-
3,6-sulfonic acid, 8-amino-1-hydroxy-2
・Z-azonaphthalene-1', 3, 5, 6-tetrasulfonic acid, 8-amino-1-hydroxy-2, 2-azonaphthalene-1', 3, 6-trisulfonic acid, 6-amino-1-hydroxy-2, 2-azonaphthalene-1 '・3
・6-trisulfonic acid, 6-methylamino-1-hydroxy-2-Z-azonaphthalene-1', 3,5-trisulfonic acid, 7-amino-1-hydroxy-2,2-azonaphthalene-1', 3-disulfonic acid, 8-amino-1
-Hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)-naphthalene-316-disulfonic acid, 6-amino-1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)-naphthalene-3・6-disulfonic acid.

Class ■: 8-amino-1-hydroxy-2-[4'-(2''-sulfophenylazo)-Z-methoxy-5-methylphenylazo]naphthalene-3,6-disulfonic acid, 8-amino-1-hydroxy-2 -[4'-(4"-methoxyphenylazo)-2-carboxyphenylazo]naphthalene-316-disulfonic acid, 8-amino-1-hydroxy-2-[4'-(2"-hydroxy-3"/6")
-disulfo1''-naphthylazo)-2'-carponylphenylazo]naphthalene-3,6-disulfonic acid,
4.4′-bis-(8″-amino-1″-hydroxy-3″・6″-disulfo-2″naphthylazo)-3.3
1-dimethoxydiphenyl, 6-amino-1-hydroxy-2-[4'-〆-sulfophenylazo)-2-methoxy5'-methylphenylazo]naphthalene-3,6
-Disulfonic acid.

■Class: 2-(4'-amino-2-methylphenylazo)naphthalene-4,8-disulfonic acid, 2-(4'-amino-2-acetylaminophenylazo)naphthalene-5.
7-disulfonic acid, 4-nitro-4'-(4"-methylaminophenylazo)-stilbene-2,2-disulfonic acid, 4-nitro-4'-(4"-amino-2"-methyl-5"-toxyphenylazo) )-Stilbene-2
・2-disulfonic acid, 4-amino-4'-(4''-methoxyphenylazo)-stilbene-2-di-disulfonic acid, 4-amino-2-methylazobenzene-2,5'-
Disulfonic acid.

■Class: 1-(2,5-dichloro-4'-sulfophenyl)-3
-methyl-4-(3''-amino-6''-sulfophenylazo)-5-pyrazolone, 1-(4'-sulfophenyl)-3-carboxy-4-(4''-amino-2''-sulfophenylazo)-5-pyrazolone, 1-(2'-methyl-5'-sulfophenyl)-3-methyl-4-(4''
-amino-2″-sulfophenylazo)-5-pyrazolone, 1-(2-sulfophenyl)-13-methyl-4-(
3″-amino-6″-sulfophenylazo)-5-pyrazolone, 4-amino-(3″-methyl-1″-phenyl-4″-pyrazole-5″-onylazo)-stilbene-2,2′-disulfonic acid, 4-amino-4′-(
2″-Hydroxy-3″/6″-disulfo-1″-mephthylazo)-stilbene-2,2-disulfonic acid, 8-acetylamino-1-hydroxy-2-(3′-amino-6′-sulfophenylazo)naphthalene-3/6 −
Disulfonic acid, 7-(3'-sulfophenylamino)-1-hydroxy-2-(4'-amino-2-carpoxyphenylazo)-naphthalene-3-sulfonic acid, 8-phenylamino-1-hydroxy-2-(4' -Amino-
2-sulfophenylazo)-naphthalene-3,6-disulfonic acid, 6-acetylamino-1-hydroxy-2-(5'-amino-Z-sulfophenylazo)naphthalene-3-sulfonic acid.

'5' class: 1-(3'-aminophenyl)-3-methyl-4-(2
・5-disulfophenylazo)-5-pyrazolone, 1-(3'-aminophenyl)-3-lupoxy-4-(2
-carboxyi-sulfophenylazo)-5-pyrazolone, 4-amino-[3″-methyl-4″-(2 rivers, 5 skins-disulfophenylazo)-1″-pyrazole-5″-onyl]-stilbene -2,2-disulfonic acid,
1-(3'-aminophenyl)-3-hydroxy-4-[4''-(2'''・5-disulfophenylazo)-12''-methoxy5''-methylphenylazo]-5-pyrazolone.

{Class 61: Steel key salt of 8-amino-1-hydroxy-2-(2-hydroxy-5''-sulfophenylazo)naphthalene-3,6-disulfonic acid, 6-amino-1-hydroxy-2
Copper rust salt of 1-(2-hydroxy-5'-sulfophenylazo)naphthalene-3-sulfonic acid, 6-amino-1-
Copper rust salt of hydroxy-2-(2-hydroxy-5'-sulfophenylazo)-naphthalene-3,5-disulfonic acid, 8-amino-1-hydroxy-2-(2'-hydroxy-3'-chloro-5'-sulfophenylazo) Steel salt of naphthalene-3,6-disulfonic acid, 6-methylamino-1-hydroxy-2-(Z-carboxy 5'
-sulfophenylazo)naphthalene-3-sulfonic acid copper key salt, 8-amino-1-hydroxy-2-[4'-〆-sulfophenylazo)-2-methoxy5'-methylphenylazo)naphthalene-3,6-disulfone Copper mirror salt of acid, steel salt of 6-amino-1-hydroxy-2-[41-(〆・5″-disulfophenylazo)-12-methoxy5′-methylphenylazo)naphthalene-3,5-disulfonic acid , 1-(3'-amino-4'-sulfophenyl)-13-methyl-4-[4"-1(2"'・5
″′-disulfophenylazo)-2″-methoxy5″
-methylphenylazo]-5-pyrazolone copper key salt, 7
-(4'-ami/-3'-sulfoanilino)-1-hydroxy-2-[4''-(2'''・5M-disulfophenylazo)-2''-methoxy-5''-methylphenylazo]-naphthalene Steel mirror salt of 3-sulfonic acid, 61 (4'
-amino-3'-sulfoanily/)-1-hydroxy-2-(2''-carboxyphenylazo)naphthalene-
Steel rust salt of 3-sulfonic acid, 7-amino-6' nitro-1, 2-dihydroxy-2, r-azonaphthalene-3,
1,2-chromium mirror salt of 4'-disulfonic acid, 1,2-chromium key salt of 6-amino-1-hydroxy-2-(2-carpoxyphenylazo)naphthalene-3-sulfonic acid, 8-amino-1-hydroxy-2-( 4'Nitro-2-hydroxyphenylazo)naphthalene-3,6-
1,2-chromium mirror salt of disulfonic acid, 6-(4'-amino-3'-sulfoanilino)-1-hydroxy-2-(
1,2-cobalt key salt of 5″-chloro-hydroxyphenylazo)-naphthalene-3-sulfonic acid, 1-(
1,2-chromium salt of 3'-amino-4'-sulfophenyl)-3-methyl (2''-hydroxy-4''-sulfo-1'' naphthylazo)-5-pyrazolone, 7-
(4'-sulfoanilino)-1-hydroxy-2-(4
1,2-chromium key salt of ``-amino-2''-carboxyphenylazo)naphthalene-3-sulfonic acid, 1-(3
-aminophenyl)-1,2-chromium mirror salt of 3-methyl-4-(4'-nitromer-carpoxyphenylazo)-5-piozolone.

Class '71: 1-amino-4-(3-amino-4'-sulfoanilino)-anthraquinone-2-sulfonic acid, 1-amino-4-(4'-amino-3'-sulfoanilino)
-Anthraquinone-2,5-disulfonic acid, 1-amino-4-[4'-(4''-amino-3'-sulfophenyl)-anilino]-anthraquinone-2,5-disulfonic acid, 1-amino-4-[4'-(4 ″-amino-2″-sulfophenylazo)-anilino]-anthraquinone-
2,5-disulfonic acid, 1-amino-4-(4'-methylamino-3'-sulfoanilino)-anthraquinone-2-sulfonic acid.

{Class 81: 3-(3'-amino-4'-sulfophenyl)-sulfamyl steel phlocyanine tri-3-sulfonic acid, D4
-(3'-amino-4'-sulfophenyl)-sulfamyl steel phthalocyanine-di-4-sulfonic acid, 3-(3
'-aminophenylsulfamyl)-3-sulfamyl steel phthalocyanine-di-3-sulfonic acid.

The novel dyes described above can be separated and prepared into useful dry dye formulations.

Separation is preferably carried out by salting out and filtration at as low a temperature as possible. The filtered dye can be dried, optionally with Coupage and/or buffering, for example by adding a mixture of equal parts monosodium phosphate and disodium phosphate; the drying is not expensive. Preference is given to carrying out at temperature and under reduced pressure. In some cases, it is also possible to produce dry formulations according to the invention directly, ie, by omitting intermediate separation operations of the dye, by spray drying the entire product mixture. The dyes according to the invention can be applied to a variety of materials such as silk, leather, wool, superpolyamide fibers and superpolyurethanes, especially cellulose-containing materials with a fibrous structure, such as flax,
Used for dyeing and printing cellulose, regenerated cellulose and especially cotton. Said dyes are used in particular for dyeing by the exhaustion method from the alkaline and optionally strongly salt-containing aqueous nature of long dye baths and by the padding method in which the material is impregnated with an aqueous dye solution optionally containing salts. The dyes are fixed by alkali treatment or in the presence of an alkali, optionally under the action of heat. The dyes of the invention are used not only for printing cotton, but also for printing nitrogen-containing fibers, such as wool, silk or wool-containing blends.

The dyes of the invention have a very good reactivity, so that dyeings can be obtained at lower temperatures or with shorter fixing operations than are customary with corresponding dyes.

Other advantageous features include good dye transfer ability and therefore high dye strength, good bond stability between dye and fiber, as well as good wash-off of unfixed areas and good build-up. Can list abilities.

The dyeings and prints obtained are very deep in color and have excellent light and wet fastness properties, including washfastness. In order to improve the wet fastness properties, it is appropriate to thoroughly wash dyeings and prints with cold and hot water, optionally with the addition of reagents which have a dispersing action and promote the diffusion of unfixed parts. It is.

The present invention will be described in more detail below based on Examples, where parts are parts by weight, percentages are percentages by weight, and temperatures are degrees Celsius unless otherwise specified.

The relationship between parts by weight and parts by volume is the same as the relationship between grams and cubic centimeters. Example 1 30.5 parts of the dye represented by the formula were dissolved in 600 parts by volume of water, and 2,4,6-trifluoro-
Condensation with 7.4 parts of 1,3,5-triazine.

After the acylation is complete, 130 parts by volume of an aqueous solution containing 10.5 parts of 1,3-diami/benzene-4-sulfonic acid (Na salt) are reacted with the dye solution, and the temperature is then raised to 20°C. The base value of the reaction mixture is 4. with sodium carbonate solution.
Keep it at 5. After the reaction is complete, the dye is precipitated with sodium chloride, filtered and dissolved while still wet in 150 evacuation parts of water to a nominal value of 5.5. 2・4・at pH value 4.5 at 0-2℃
After further condensation with 7.4 parts of 6-trifluoro-1,3,5-triazine, 5.4 parts of 2-methylaniline are added to the reaction mixture.

The feed value is kept at 7.5 during the condensation by adding sodium carbonate solution dropwise and the temperature is raised to 20o. After the reaction is completed, sodium chloride and a buffer salt are added to precipitate the dye represented by the formula, which is then filtered and washed. After drying, a light brown powder precipitates out, which dyes the cotton in a golden shade. The maximum loading of this dye is 424 nM. Instead of using 2-methylaniline, ammonia, methylamine, N-methylpropylamine, cyclohexylamine,
4-methoxyaniline, 4-acetylaminoaniline,
4-aminobenzoic acid, 2-chloroaniline, aniline-3-sulfonic acid, aniline-4-sulfonic acid, 2-amino/-5-sulfobenzoic acid, 1-naphthylamine-5-sulfonic acid or 1-naphthylamine-4,7-disulfonic acid, etc. Even when used in large quantities, a useful dye is obtained which dyes cotton golden yellow.

Furthermore, dyes can also be obtained by condensing chromophore diamines and amines with 2,4,6-trifluoro-1,3,5-triazine in the order arranged in the following table.

Regarding the representative examples of dyes listed in the above table, their input ma.
The x values are as follows. For typical examples of the dyes listed in the above table, their Pamax values are as follows. Example 22 - Aminobenzenesulfonic acid 86
5 parts, the multiplication value was set to 7 by adding caustic soda solution,
Soluble in water.

Add 5 parts of sodium hydrogen carbonate to the resulting solution and
and then 2,4,6-trifluoro-1,315
7.4 parts of triazine are added dropwise, after the end of the condensation, 114
- An aqueous solution of 10.5 parts of sodium salt of phenylenediamine-2-sulfonic acid is added and condensed at 5 to 1 oo.Hydrogen fluoride, which is continuously generated during the condensation, is neutralized by adding a solution of caustic soda. sum up After the condensation condensation is completed, it is cooled again to 00, and further multiplied by 6 to 7.
7 parts of 6-trifluoro-1,3,5-triazine are added dropwise. After completion, 25.4 parts of an aqueous solution of the dye represented by the formula is added, the solution is flooded twice, and the hydrogen fluoride liberated during the condensation is neutralized by adding sodium hydroxide solution. .

After the condensation is complete, add sodium chloride to precipitate the dye,
Filter, add buffer salt and dry. It dyes cotton a solid yellow shade. The max of this dye is 39. If 1,4-phenylenediamine-12-sulfonic acid is replaced by an equivalent amount of 1,3-phenylenediamine-4-sulfonic acid, dyes with very similar properties are obtained.

Even more useful dyes can be obtained by replacing the aminoazo dyes with the amino group-containing chromophores described in Example 1 above and in the tables that follow. The color tones obtained on the cellulose fibers are also as described in Example 1 above.
Dyeing Example A Two parts of the yellow dye described in Example 1 are dissolved in 100 parts of water.

A cotton fabric is slop-padded with this dye solution and then wrung out under pressure until the pick-up level is 80%. The dyed material was intermediately dried at 500 ml of sodium chloride in 100 parts by volume of water.
Treat with a solution of 1 part by volume of 30% caustic soda solution and then heat at 1000 °C for 18 minutes. After washing, a washfast golden-yellow color is obtained. Instead of steaming, a nearly identical waxy dyeing can be obtained by leaving it for 2 minutes at room temperature.

B No. in the table above. Dissolve 3 parts of blue dye No. 33 in 10 parts of water. A cotton cloth is furalized with this solution at room temperature and then dried at 50o. The dyed material thus obtained is immersed for 1 hour in a solution of 25 parts of sodium chloride and 3 parts of 30% caustic soda solution in 100 parts of water, heated to 3 parts. Then wash with cold and hot water. A clear blue dyeing is obtained that is resistant to washing and light. C No. in the above table in 100 eave volume parts of water. 2
A cotton cloth is impregnated with a solution of 25 parts of clear color dye of No. 0, 2 parts of sodium carbonate and 30 parts of sodium sulfate, and squeezed to give a weight gain of 70%. The impregnated fabric is left wet for 4 hours at 25°C and then thoroughly washed. A light color wash with good washability is obtained. D No. in the above table. 1 part of reddish yellow dye No. 11 and 3 parts of sodium chloride are dissolved in 1000 parts by volume of water.

Five pieces of cotton cloth that have been slightly warmed to 40o are placed in this dye bath, and the material to be dyed is dyed while being constantly moved.
At this time, after 15 minutes have elapsed, an additional 3 parts of sodium chloride are added. Next, add 2 parts of anhydrous sodium carbonate and add 40
Stain for an additional 60 minutes at 0. The obtained dyed product is washed cold and hot, centrifugally dehydrated and dried. A strong yellow dyeing with excellent properties is obtained. 8 N in the above table
o. A slot badging solution is made from 3 parts of No. 33 dye, 1 part of urea, 5 parts of sodium bicarbonate, and 82 parts of water.

A mercerized cotton fabric is impregnated with this slot badging solution, squeezed out under pressure, and heated at 160° for 6 minutes. After washing, a ropey blue stain is obtained. Printing Example In a printing paste thickener consisting of 73 ml of a 3% aqueous alginate solution, 20 ml of urea and 1 part of sodium bicarbonate, No. 1 in the above table was added. Sprinkle 15 dyes and 5 anchors,
and melt it.

Cotton cloth is printed with this printing paste and then dried. It is fixed by steaming at 1000 for 2 minutes and then washed. A strong yellow print is obtained. Instead of applying heat, a textile with the same dyeing rate can be soaked for 2 days at 900 ml in a bath consisting of 25 parts of sodium chloride and 3 parts of 30% caustic soda solution in 1000 parts of water. It can be fixed. Although the present invention has been described in detail above,
Another specific example of the configuration of the present invention is summarized as follows. '1 - A fiber-reactive dye according to claim 1, substantially as described in the Examples herein. (2) The fiber-reactive dye according to claim 1, which is obtained by the method according to any one of claims 3 to 8. '3} The dyeing method and the printing method described in the dyeing example and the textile printing example described in this specification.

{41. A method of using the fiber-reactive dye according to claim 1 or 2 and the fiber-reactive dye obtained by the method according to any one of claims 3 to 8 for dyeing and printing.

■ Dyeing and printing cellulose fibers using the fiber-reactive dye according to claim 1 or 2 and the fiber-reactive dye obtained by the method according to any one of claims 3 to 8. The method described in the previous section '411. [6' A dyeing preparation and a printing preparation containing the dye according to claim 1 or 2.

{71 A dyed or printed material obtained by the method described in any one of the preceding items [31 to {5}.

Claims (1)

[Claims] 1 Formula ▲ Numerical formulas, chemical formulas, tables, etc. , A_2 is a hydrogen atom or a colorless aliphatic, alicyclic, aromatic or heterocyclic group, or A_2 is attached to an s-triazine group via the nitrogen atom in the formula to which A_2 and R_4 are bonded. It is a ring that is directly bonded and constitutes a part of the heterocyclic group formed by closing A_2 and R_4, B is an alkylene group or an arylene group, and R_1, R_2, and R_3 are each independently hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclohexyl group, or when B is an alkylene group, R_2 and R_3 form a closed aliphatic chain to form a crosslinking member ▲ Numerical formula, chemical formula, table, etc. ▼ can be a heterocyclic ring containing two nitrogen atoms, and R_4 is a hydrogen atom, an unsubstituted or substituted alkyl group of 1 to 6 carbon atoms, or a cyclohexyl group. A fiber-reactive dye represented by 2 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A_1 and B have the same meaning as in the previous item 1, and
The fiber-reactive dye according to item 1 above, which is a carboxyl group or a sulfo group, and the benzene group D can further have a substituent, particularly a sulfonic acid group. 3 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A_1 is a monoazo-based, disazo-based, metal complex azo-based, anthraquinone-based, or phthalocyanine-based sulfo group-containing chromophore group, and A_2 is a hydrogen atom or is a colorless aliphatic, cycloaliphatic, aromatic or heterocyclic group, or A_2 is a ring directly bonded to the s-triazine group via the nitrogen atom in the formula to which A_2 and R_4 are bonded; B is an alkylene group or an arylene group, and R_1, R_2, and R_3 each independently represent a hydrogen atom, a carbon atom 1 to 6 alkyl groups or cyclohexyl groups, or when B is an alkylene group, R_2 and R_3 form a closed aliphatic chain to form a crosslinking member ▲ Numerical formula, chemical formula, table, etc. ▼ is a nitrogen atom and R_4 is a hydrogen atom, an unsubstituted or substituted alkyl group of 1 to 6 carbon atoms, or a cyclohexyl group). In producing fiber-reactive dyes, there are formulas such as mathematical formulas, chemical formulas, tables, etc. (in the formula, A_1 and R_1 have the above meanings), and the formula ▲ mathematical formulas, chemical formulas, tables, etc. There are compounds represented by ▼ (in the formula, A_2 and R_4 have the above meanings), and formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, B, R_2 and R_3 have the above meanings) ) and trifluoro-s-triazine represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. A fiber-reactive dye represented by the above formula (1), which is characterized by reacting (the order of partial reactions can be freely selected in consideration of the starting materials to be reacted with each other). manufacturing method. 4 The dye represented by the formula (3) described in the preceding section 3 and the formula (5
) and the trifluoro-s-triazine represented by formula (6) are reacted with each other (in this case, the order of partial reactions can be freely selected while taking into account the starting compounds to be reacted with each other). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A_1, B, R_1, R_2, and R_3 have the same meanings as in the previous section 3]. Then, the dye represented by this formula (7) and the formula (4)
The method according to item 3 above, wherein the fiber-reactive dye represented by the formula (1) is produced by condensing the compound represented by the formula (1). 5 Compounds represented by the formula (4) described in 4 above include the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein, X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxy group, or a sulfo group and the benzene group D can further have a substituent, particularly a sulfonic acid group). 6 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A_1 and B have the same meaning as in the previous section 3, and
A carboxyl group or a sulfo group, and the benzene group D can further have a substituent, particularly a sulfonic acid group. -s-triazine, a dye represented by the formula A_1-NH_2 (9), and an alkylene diamine or arylene diamine represented by the formula H_2N-B-NH_2 (10) are condensed to form the formula ▲mathematical formula, chemical formula, table, etc. A dye represented by ▼ is produced, and trifluoro-s-triazine represented by formula (6) is condensed with aminobenzene represented by formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ to form a dye represented by formula ▲
There are chemical formulas, tables, etc. Phenylamino-difluoro-s-triazine represented by ▼ is produced, and the formula (1
3. The method according to item 3, wherein the dye represented by formula (1) is acylated with phenylamino-difluoro-s-triazine represented by formula (12) to produce the fiber-reactive dye represented by formula (2). 7 A dye component represented by the formula (3) described in the preceding section 3 [this shall include an amino group represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.] and the formula (4)
) [This is a formula ▲ mathematical formula, chemical formula,
containing an amino group represented by ▼] with trifluoro-s-triazine represented by formula (6), and the acylated product thus obtained and an alkylene diamine represented by formula (5) or 3. The method according to item 3, wherein the fiber-reactive dye represented by the formula (1) is produced by reacting the arylene diamine and other components (partial reactions are carried out in any order). 8. The method according to any one of items 3 to 7 above, wherein the reaction with difluoro- or trifluoro-s-triazine is carried out in an aqueous solution.