JPS61213267A - Mixture of phormazane compounds each containing monochlorotriazinyl group and its production and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to mixtures of formazan compounds containing monochlorotriazinyl groups, processes for their preparation and processes for dyeing or printing using mixtures of these compounds as fiber-reactive dyes.

According to the present invention, a mixture consisting of compound (A) and compound (B), wherein compound (A) and compound (B)
A mixture of compounds characterized in that, in free acid or salt form, corresponds to the following formula (1) (one of the possible tautomeric forms).

rl In the above formula, the sulfo group is in the 4 or 5 position, R3 represents hydrogen, C1-4 alkyl, halogen f, = CI-4 alkyl monosubstituted by hasyan, or C2-4 haloalkyl, R2 is hydrogen , C1-4 alkyl, 1 or 2 halogens, hydroxy, cyano, COOH, 5OsH-.

C substituted by a group selected from 0SO31 (and OR4), ~6 alkyl, phenyl or phenyl substituted by a group selected from 1 or 2 C0-4 alkyl, halogen, COOH, OR4 and -1SOzRs, or R1 and R2 together with the N atom to which they are attached contain 1 to 3 heteroatoms and are further unsubstituted or substituted by 1 to 3 01-4 alkyl groups. may form a 5- or 6-membered saturated ring, R4 represents C1-4 alkyl or Ct-4 hydroxyalkyl, R% represents hydroxy, amino, C1-4 alkyl or phenyl, m represents 0.1.2 or 3, R is each independently halogen, cI~4 alkyl, C+
-a full: J xy, SO, H, C0OH or -NHC
represents OCI-4 alkyl, provided that (i) compound (A) is different from compound (B), and (ii) compound (A) has a sulfo group at the 5-position in formula ■, and m is O; ,R.

is hydrogen and R2 is 4-sulfophenylamino, compound (B) is m in formula 1.
, Rt and the position of the sulfo group are the same as those defined for compound (A), and R is a compound other than the compound in which R is 3-sulfophenylamino.

Preferably, the mixture comprises compound (A) and compound (B)
(A) in a ratio (by weight) of 9:1 to 1:9, more preferably in a ratio of 4:1 to 1:4.
Most preferred are mixtures containing B) in a ratio of 4:1 to 1:1, especially about 1:1.

Preferably, compound (A) differs from compound (B) with respect to the position of the sulfo group (4 or 5) and/or with respect to the one NR+Ih group attached to the chlorotriazinyl group. Most preferably the sulfo group is at the 5 position in both compounds (A) and (B).

Generally, the term halogen is fluorine, chlorine or bromine, preferably chlorine or bromine, most preferably chlorine.

Any alkyl or alkoxy group is linear or branched unless otherwise specified. In any hydroxy- or alkoxy-substituted alkyl group attached to a nitrogen atom, the hydroxy or alkoxy group is attached to a carbon atom other than the CI atom.

The phenyl group optionally substituted by m groups R is
Preferably it is unsubstituted (m-0) or substituted by one or two identical or different radicals R. More preferably, the phenyl group is unsubstituted or substituted by one or two groups R, where each R is independently chlorine, 01-2 alkyl, 01-2 alkoxy, 5O3H or -NHCO
CR*. Furthermore, more preferably, this phenyl group is unsubstituted or one or two groups R1
wherein each Rh is independently chlorine, methyl, methoxy or 5osn. Most preferably the phenyl group is unsubstituted.

R4 is preferably R4m, methyl, ethyl or 2-
hydroxyethyl, more preferably R4 is 2-
It is hydroxyethyl.

R3 is preferably R'1m, hydroxy, amino, methyl or ethyl. More preferably, R3 is R
5m, hydroxy or amino, most preferably R2 is hydroxy.

R3 is preferably Rlm, ie Cl-2 alkyl monosubstituted by hydrogen, methyl, ethyl, chlorine or cyano, or 02-. Hydroxyalkyl or R1
, together with R2 and the nitrogen atom to which they are attached form a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine ring. More preferably, R8 is Rlb, ie hydrogen, methyl, ethyl or 2-hydroxyethyl, or Rlb, together with R2 and the nitrogen atom to which they are attached, forms a morpholine, piperazine or N-methylpiperazine ring. is forming. Most preferably R.

is hydrogen.

R2 is preferably R0, ie hydrogen, methyl, ethyl, chlorine, cyano, 01-4 alkyl monosubstituted by C00HSSO3H or 05O3H, C! substituted by 1 or 2 hydroxy groups or by 0Ra-. -4 alkyl, phenyl or phenyl substituted with one or two groups selected from chlorine, methyl and -3O,RS, or R1, is R, and Together with the nitrogen atom, it forms a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine ring. More preferably, R2 is R1, ie hydrogen, C0OH,
C3~ mono-substituted by 5OsH or oso, n
．． Alkyl, 02-. substituted by one or two hydroxy groups or by 0R43. Alkyl, phenyl or 1 or 2 chlorine, methyl and -SO□
phenyl substituted by a group selected from R%b, or Ro together with R3 and the nitrogen atom to which they are attached represents morpholine, piperazine or N
- forms a methylpiperazine ring. Most preferably R2 is Rlc, ie hydrogen or phenyl substituted by methyl and/or sulfo.

Preferred compounds correspond to formula Ia below in one of the possible tautomeric forms.

In the above formula, m represents 0.1 or 2.

A further preferred compound is, in formula Ia, (1)
Compounds where Rlk is hydrogen, (2) Rtb is Rlc
(3) a compound in which Rlb is hydrogen and Rlh
Compounds where is Rlc (4) Compounds (1) to (3) where J is O, (5) Compounds (1) to (4) where the sulfo group is at the 5-position
The compound is .

Preferred mixtures of compounds (A) and (B) are such that compound (A) is of formula I where R1 is hydrogen and R2 is hydrogen or Ct, -4 alkyl (hydroxy or monosubstituted at OR4). It is a compound that
Compound (B) is a compound of formula (A), more preferably a compound of formula 1a, and compounds (A) and (B) are present in a ratio (by weight) of 4:1 to i:4. It's something like this.

Further preferred mixtures are compounds of formula I, more preferably compounds of formula Ia, wherein compound (A) is a compound of formula I in which R1 and R2 are both hydrogen, and compound (B) is different from compound (A). , most preferably compounds of formula Ia in which Rlb is phenyl substituted by methyl and/or sulfo, and compounds (A) and (B) are 4:1 to 1:1 (A): (
It exists in the ratio (weight) of B).

The most preferable mixture is a compound in which R and R2 are both hydrogen, m is 0, and the sulfo group is at the 5-position in formula (2), and compound (B) is compound (A).
is a compound in which the sulfo group is in the 5-position in 71 a, m is 0, Rlk is hydrogen, and Rlk is phenyl substituted by methyl and/or sulfo, and the compound ( A) and (B) are 4
:1 to 1:1 (by weight), especially in a ratio of about 1:1.

If the compound of formula ■ is in salt form in the mixture, the cations of the sulfo and carboxy groups are not important, and the non-chromogenic cations customary in the field of reactive dyes, as long as the corresponding salts are water-soluble. Examples of such cations, which may be any of the following, are alkali metal cations and unsubstituted or substituted ammonium cations, such as lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra- Methylammonium, triethylammonium, mono-, di- and triethanolammonium.

Preferred cations are alkali metal cations and ammonium, with sodium being most preferred.

In the compound of formula (■), the cations of the sulfo group and the carboxy group may be the same or different,
For example, they may be mixtures of the above-mentioned cations, meaning that the compounds of II may be in mixed salt form.

The present invention further provides a method for producing a mixture of compound (A) and compound (B). This method converts one or more compounds corresponding to the following formula (■) in one of the possible tautomeric forms and the following blanks to the following formula (2), ^ [wherein X represents chlorine or -NR+Rt] ], and when X is chlorine, one or more compounds of the following formula
, HNR+ Rt N , provided that at least two different starting compounds of the formulas ■, ■ and/or ■ are used.

The individual condensation steps on the triazine ring can be carried out according to conventional methods.

Mixtures of compounds of formula I can be isolated according to known methods, for example by conventional salting out with alkali metal salts, filtration and optionally vacuum drying.By reaction and isolation conditions, compounds of formula I can be isolated. are obtained in free acid form or preferably in salt form or, for example, in mixed salt form containing one or more of the abovementioned cations. It can be converted by conventional means from the free acid form to the salt form or to a mixture of salt forms or vice versa or from one salt form to the other.

Furthermore, the compound mixture according to the invention can be prepared by combining the individual compounds (A) and (B) in free acid form or salt form in a desired ratio (
It can also be produced by simply mixing (by weight).

The starting compounds of formula (1) are known or can be prepared using appropriate starting materials according to known methods. The amines (2) are likewise known or can be prepared analogously to customary methods.

Mixtures of compounds of formula I are useful as fiber-reactive dyes for dyeing or printing hydroxy- or nitrogen-containing organic materials. Preferred substrates are leather and fibrous materials comprising or consisting of natural or synthetic polyamides and especially natural or regenerated celluloses, such as cotton, viscose and spun rayon. The most preferred substrate is a fibrous material containing or consisting of cotton.

Dyeing or printing is performed according to known methods.

However, for mixtures of compounds of formula (1) it is preferred to use exhaust dyeing methods. The advantage is that dyeing with these dyes is not temperature dependent in the usual dyeing temperature range.

Therefore, the dyeing is almost the same at 80°C as at 100°C, without any substantial decrease in fixation rate.
It can be carried out.

The compound mixture according to the invention has good compatibility with other reactive dyes, which by themselves or with similar dyeing properties, for example, a degree of ability to exhaust them from dyebaths onto fibers. , common fastness properties to the dyeings obtained, etc., in combination with suitable fiber-reactive dyes of the same type. The dyeings obtained with such combination mixtures have good fastness properties.

In view of their pronounced fixing power, mixtures of compounds of formula I give high exhaustion and fixation rates. Unfixed dye portions can be easily washed away from the substrate. The dyeings obtained exhibit good light fastness and wet fastness properties such as wash, water, seawater and sweat fastness. They are stable to oxidizing agents such as chlorine water, hypochlorous acid bleaching and peroxide- or perborate-containing cleaning solutions.

The following examples serve to further illustrate the invention.

In the examples, parts and percentages are given by weight or volume, and temperatures are in degrees Celsius.

Example 1 19 parts of cyanuric chloride, 60 parts of a compound of the following formula, 0.5 part of a commercially available wetting agent, 300 parts of water and 30 parts of a
0 parts of water. p) of the solution is increased from 5 to 6 by addition of 15% soda solution until the end point of acylation.
was held at Next, 10 parts of 1-aminobenzene-3-
Sulfonic acid was added. The resulting suspension was heated to 50° and the pH was kept at 7-8 by addition of 15% soda solution. After 3 hours, 15 parts of 25% ammonia solution were added. The reaction mixture was then stirred at 50' for a further period of time until no major acylated product was detected. The dye mixture thus prepared, having the following formula (compounds present in a ratio of approximately 1:1 (by weight)), was salted out with a mixture of sodium chloride and potassium chloride, filtered off and dried. A dark blue dye powder was obtained, which dyed cotton in a distinct blue color. The cotton dyeings had good light and wet fastness properties and were remarkably stable to any oxidizing agents.

Examples 2 to 22 Analogously to the method described in Example 1 and using appropriate starting materials, mixtures of other dye compounds of formula (1) as shown in the table below could be prepared. For these mixtures containing compound (A) and compound (B) in a ratio (by weight) of about 1:1, these The compounds are different and R is hydrogen. These mixtures can be applied to cellulose fibers according to conventional exhaust dyeing methods. The dyeings obtained have a blue color and exhibit good light and wet fastness properties and good stability against oxidative agents.

Below is the margin - J - f (Continued) Position of Ishi compound (B) in Todoroki 1sO3H compound (A) -NR, Rz -NR+Rg example
20 parts of Glauber's Salt (calcined) were added after a further 15 minutes. Dyeing continued for 45-60 minutes at the boil. Next, rinse the dyed fabric with heat and boil for 20 minutes.
Soaped in 0.00 parts water and 0.5 parts sodium lauryl sulfonate. After rinsing and drying, a blue cotton dyeing was obtained which had good light and wet fastness properties.

Application Example B 0.5 parts of the dye mixture of Example 1 were dissolved in 300 parts of water. 10 parts of cotton fabric were added and the temperature of the dyebath was raised to 80° within 10 minutes. 15 parts of Glauber's salt (calcined) were added, followed by 30 minutes later 3 parts of sodium carbonate (calcined).

Staining continued for 1 hour at 80°. The dyed fabric was then cold rinsed, then hot rinsed and soaped according to the method described in Application Example A. After rinsing and drying, a blue cotton dyeing with good fastness properties was obtained.

In the same way, the dye mixtures of Examples 2 to 22 could be used for dyeing cotton according to the method described for application examples A or B, and blue dyeings with good fastness properties were obtained.

Maximum absorption wavelength (λ□,) of dye mixtures according to Examples 1 to 22
The measurements, shown below, were carried out using respective aqueous solutions of the dye mixtures.

Procedural amendment (voluntary) June 1, 1986 Michibe Uga, Commissioner of the Patent Office 1, Indication of the case Patent No. 55155 of 1988 4 Name of the invention Mixture of formazan compounds containing a monochlorotriazinyl group , their manufacture and use 3, relationship with the case of the person making the amendment Patent applicant name: Sand Akteengsellschaft 4, agent address: 8-10-5, Toranoto-chome, Higashi-Etsu Minato-ku, 105
Subject of amendment (1) “Claims” column of the description (2)
Column 6 of "Detailed Description of the Invention" of the Specification, Contents of Amendment (1) A general amendment will be made to the scope of the patent claims.

(2) (a) On page 16 of the specification, line 199, "4"-sulfophenylamino" will be corrected to 14-sulfo-7enyl J.

(b) On page 17 of the specification, line 3, "3-sulfophenylamino" will be corrected to "13-sulfophenyl."

←9 Specification page 19, line 3, r R5FiR5,J
Correct it to "rR5 is R5,".

) Insert the following statement after "Added." on page 35 of the specification, line 2.

7.5 parts of sodium carbonate (calcined) were then added. ”L Amended catalog of attached documents Claims 1 copy 2, Claims 1. A mixture consisting of compound (2) and compound (2), in which compound (2) and compound (2) are in free acid form or salt form, and has the following formula! (one of the possible tautomeric forms).

In the above formula, The sulfo group is located at the 4 and I/i5 positions.

R1 is hydrogen, C, ~4 alkyl, C1-4 alkyl substituted with halogen or cyano, or C2
~4 haloalkyl, R2 is hydrogen, C1-4 alkyl, Ir12 halo, H, cyano, COOH, 80, H.

0803H and C1-4 alkyl substituted by groups remaining from OR4, phenyl/I/or 1 or 2 C1-4 alkyl, halogen, C00I! , OR4
and -80215, or R1 and R2 together with the N atom to which they are attached contain 1 to 3 heteroatoms and are further substituted. Rtic alkyl or C2_4 hydroxya4
1-4 represents roxy, R5 represents hydroxy, amino, C1-4 alkyl or phenyl, 1! l represents 0.1.2 or #'i3, R#i each independently represents halogen, C1-4 alkyl, C1-4 alkoxy, So, H, COOH, or C1-4 alkyl; however, (1) Compound (2) is different from compound φ), (10 compounds have a sulfo group in the 5-position, 1m is O, R1 is hydrogen, and R2 is 4-sulfo of the compound, if the compound is phenyl)
In formula I, t! l e The positions of R1 and the sulfo group are the same as those defined for compound (6), fi
, R2 is a compound other than the compound in which R2 is 3-sulfophenyl.

2. A mixture according to claim 1, wherein the compound of formula I corresponds to the following formula IaK.

In the above formula, there is a sulfo group Fi4 or #'i5 position, ml is 0.1
or 2, each Rb is independently salt! , methyl, methoxy
' or So, H; R1, represents hydrogen, methyl, ethyl or 2-hydroxyethyl; % or R1, together with R2 and the nitrogen atom to which they are bonded, represents morpholine, piperazine or It may form an N-methylbiperazine ring, R2b is hydrogen: C0OH, 80,H or 080. H
IC is mono-substituted 90, ~3 alkyl: 1 or 11
2m hydroxy group or OR4, C2~. Alkyl; phenyl: t or 1 or 2
represents phenyl polysubstituted with n groups selected from chlorine, methyl and -802R5, or R2b is "1
b and n may be combined with the nitrogen atom to which they are bonded to form a morpholine, piperazine or N-methylbiperazine ring, and 841 represents methyl, ethyl or Fi2-hydroxyethyl.

Rsb represents hydroxy or amine.

3. In formula Ia, Rlb is hydrogen and R2b is R2
3. A mixture according to claim 2, wherein c is nine phenyl substituted with hydrogen or methyl and/or sulfo.

4. Claim 2 in which m is 0 in formula Is
Also, the mixture described in Fi section 3.

5. The mixture according to any one of claims 1 to 4, wherein the sulfo group is located at the 5-position in both of compound object) and (B).

6, to the compound) and (B) the ratio of t-4:1 to 1:4 (
6. The mixture according to any one of claims 1 to 5, comprising: (by weight).

7. Compound (4) has formula I in which R1 is hydrogen and R
2 is hydrogen or C2-4 alkyl monosubstituted by OH or OR4, and ) of the compound is a compound different from compound (4) in formula I, and compound object) and (119 is 4=1- Mixture according to claim 1 or 6, present in a ratio (by weight) of 1:4.

8. Compound (g) is a compound of formula (■) in which R1 and R2 are both hydrogen, and compound (ω) is compound (1)
is a compound of formula I different from
The mixture according to claim 1, wherein li amount) c' is present.

9. A compound of formula 1m defined in claim 2, wherein ) of the compound is different from compound (5). A mixture according to claim 2 or 8.

10. In the compound of formula 1 m, R2b is phenyl di-substituted with methyl and/or sulfo. A mixture according to claim 9.

11. Compound ■ is a compound of formula ■ in which both R1 and R2 are hydrogen, m is 0, and the sulfo group is at the 5 position, and ) of the compound is different from the compound In the formula 1m specified in Range 2, the sulfo group is at the 5-position, ml is O, "1b is hydrogen," 2b is phenyl di-substituted with methyl and/or sulfo. For a large number of compounds such that the compounds (■ and
2. A mixture according to claim 1 or 2, wherein the mixture is present in a weight range (by weight).

12. The mixture of claim 11, wherein the ratio (A):(E) is about 1:1.

13. A mixture consisting of a compound and a compound (B), wherein the compound (A) and the compound (B) are in free acid form or salt form, and have the following formula I (possible tautomeric form [in the above formula, The sulfo group is at the 4 or 5 position, R1 is hydrogen, 01-4 alkyl, )) or cyano substituted with 90, -4 alkyl,
~4 represents haloalkyl.

R2 is hydrogen, C1-4 alkyl, 1 or 2
? ':/,! )'l:I-? C, ”/7), C0O
H, 80, H.

di-substituted by a group selected from 080, H and OR4 n
C1-6 alkyl, phenyl or 1 or 2 C
1-4 alcohol, halogen, COOH, OR4 and -
SO□Represents 7enyl substituted by a group selected from R5, or B, and 8□ together with the N atom to which they are bonded represent 1 to 3 may form a 5- or 6-membered saturated ring containing a heteroatom and further unsubstituted or disubstituted by 1 to 3 C1-4 alkyl groups, R is C Alkyl or 02-4 hydroxya 4 1
~4 alkyl; R5 represents hydroxy, amino, C1-4 alkyl or phenyl;

Represents mJI'io, 1, 2 or 3.

R each independently represents halogen, C4-4 alkyl, C1
~4 alkoxy, 5o3H, COOH or -NHCO
represents C1-alkyl, provided that (i) the compound is different from the compound ω);
(ii) When compound (4) is a compound of formula I in which the sulfo group is at the 5-position), m is 0, R1 is hydrogen and R2 is 4-sulfophenyl, the compound ( B) In the Fi formula (■), the positions of m, R1 and the sulfo group are the same as those defined for the compound), and R
2 is 3-sulfophenyl] In one of the possible tautomeric forms, the following formula In the formula, R, m and the position rIL of the sulfo group are the same as defined above.] One or more compounds corresponding to the following formula ], and when X is chlorine, the following formula ■HNR, R21V ] A method comprising reacting with one or more compounds corresponding to formulas ■, ■ and /l or ■
A method using at least two different starting compounds of the compounds.

14, a mixture consisting of a compound (6) and a compound (0), in which the compound (6) is in a free acid form or a salt form, and has the following formula (1) (one of the possible tautomeric forms).

I- [In the above formula, The sulfo group is in the 4 or 5 position.

R1 is hydrogen, C1_4 alkyl, )10rn or C1_4 alkyl monosubstituted by cyano, t or 02
~4 haloalkyl, R2 is hydrogen, C1-4 alkyl, 1t or 2 a
yy, hydroxy, cyano, C0OH, 803H.

080 H and polysubstituted n by groups left from OR4
C1-6 alkyl, phenyl or 1 or 2 C
1-4 alkyl, /% r:s P N, C0OH#
represents phenyl polysubstituted by groups selected from OR4 and ``5o2R5, or R1 and R2 together with the N atom to which they are attached contain 1 to 3 heteroatoms; Further unsubstituted h or polysubstituted with 1 to 3 C1-4 alkyl groups may form a 5- or #-1l:6-membered saturated ring, R is C alkyl or C2-4 Hydroxia 4 1
~4 alkyl; R5 represents hydroxy, amino, C1-4 alkyl or phenyl;

m represents 0.1.2 or 3, R each independently represents halogen, C1-4 alkyl, C1
~4 alkoxy, So, H, C0OH or one old ■C1
-4 alkyl, provided that (i) compound (4) is different from compound ), and (ii) compound (4) is represented by formula (■) in which the sulfo group is 5
There is a reed in the position, m is 0, R1 is water-based, 'R2
is 4-sulfophenyl, the position of m, R1 and the sulfo group is the same as defined for the compound in formula (), and R2 is 3-sulfophenyl. A method for dyeing or printing a hydroxy group- or nitrogen-containing organic substrate, the method comprising applying a mixture corresponding to the above as a dyeing or printing agent.

15. The method according to claim 14, wherein the base material is a fibrous material containing or consisting of cotton.

Claims (1)

[Scope of Claims] 1. A mixture consisting of compound (A) and compound (B), wherein compound (A) and compound (B) are in free acid form or salt form, and have the following formula I (possible tautomerism). A compound mixture characterized in that it corresponds to one of the sex forms). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I In the above formula, the sulfo group is at the 4 or 5 position, and R_1 is hydrogen, C_1_-_4 alkyl, C_1_-_4 alkyl monosubstituted by halogen or cyano, or C_2_- _4 represents haloalkyl, R_2 is hydrogen, C_1_-_4 alkyl, 1 or 2 halogens, hydroxy, cyano, COOH, SO_3
C_1_-_6 alkyl, phenyl or 1 substituted with a group selected from H, OSO_3H and OR_4
or 2 C_1_-_4 alkyl, halogen, CO
represents phenyl substituted by a group selected from OH, OR_4 and -SO_2R_5, or R_1 and R_2 together with the N atom to which they are attached contain 1 to 3 heteroatoms and are further substituted. or may form a 5- or 6-membered saturated ring, which is substituted with 1 to 3 C_1_-_4 alkyl groups, and R_4 is C_1_-_4 alkyl or C_2_-_4
represents hydroxyalkyl, R_5 represents hydroxy, amino, C_1_-_4 alkyl or phenyl, m represents 0, 1, 2 or 3, R each independently represents halogen, C_1_-_4 alkyl, C_1_-_4 alkoxy, SO_3H , COOH or -NHCOC_1_-_4 alkyl, provided that (i) compound (A) is different from compound (B), (ii) compound (A) has a sulfo group in the 5-position in formula I, and m is 0, R_1 is hydrogen,
In the case of a compound in which R_2 is 4-sulfophenylamino, compound (B) has m, R_1 in formula I.
and a compound other than a compound in which the position of the sulfo group is the same as that defined for compound (A) and R_2 is 3-sulfophenylamino. 2. The mixture according to claim 1, wherein the compound of formula I corresponds to the following formula Ia. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I a In the above formula, the sulfo group is at the 4 or 5 position, m_1 represents 0, 1 or 2, and R_b each independently represents chlorine, methyl, methoxy or SO_3H. , R_1_b represents hydrogen, methyl, ethyl or 2-hydroxyethyl, or even if R_1_b together with R_2_b and the nitrogen atom to which they are attached form a morpholine, piperazine or N-methylpiperazine ring. Often R_2_b is hydrogen; COOH, SO_3H or OSO
C_1_-_3 alkyl mono-substituted by_3H;
by 1 or 2 hydroxy groups or OR_4_a
C_2_-_3 alkyl substituted by; phenyl;
or 1 or 2 chlorine, methyl and -SO_2R
represents phenyl substituted by a group selected from _5_b, or R_2_b may be taken together with R_1_b and the nitrogen atom to which they are bonded to form a morpholine, piperazine or N-methylpiperazine ring, R_4_a represents methyl, ethyl or 2-hydroxyethyl, R_5_b represents hydroxy or amino. 3. In formula I a, R_1_b is hydrogen and R_2
3. A mixture according to claim 2, wherein _b is R_2_c, ie hydrogen or phenyl substituted by methyl and/or sulfo. 4. The mixture according to claim 2 or 3, wherein m_1 is 0 in formula Ia. 5. The mixture according to any one of claims 1 to 4, wherein the sulfo group is at the 5-position in both compounds (A) and (B). 6. Compounds (A) and (B) in a ratio of 4:1 to 1:4 (
6. The mixture according to any one of claims 1 to 5, comprising: (by weight). 7. Compound (A) is a compound of formula I in which R_1 is hydrogen and R_2 is hydrogen or C_2_-_4 alkyl monosubstituted by OH or OR_4,
Compound (B) is a compound different from compound (A) in formula I, and compounds (A) and (B) are 4:1 to 1:
7. A mixture according to claim 1 or 6, present in a ratio (by weight) of 4. 8. Compound (A) is R_1 and R_2 in formula I
are both hydrogen, compound (B) is a compound of formula I different from compound (A), and compound (A
) and (B) are present in an (A):(B) ratio (by weight) of from 4:1 to 1:1. 9. The mixture according to claim 2 or 8, wherein compound (B) is a compound of formula Ia as defined in claim 2, which is different from compound (A). 10. The mixture according to claim 9, wherein in the compound of formula Ia, R_2_b is phenyl substituted by methyl and/or sulfo. 11, Compound (A) has R_1 and R_ in formula I
2 are both hydrogen, m is 0, and the sulfo group is at the 5-position, and the compound (B) is different from the compound (A), the formula I a as defined in claim 2 , the sulfo group is at the 5 position, m_1 is 0,
R_1_b is hydrogen, R_2_b is methyl and/
or phenyl substituted with sulfo, and compounds (A) and (B) are 4:1 to 1:
3. A mixture according to claim 1 or 2, which is present in a ratio (A):(B) (by weight) of 1. 12. The mixture of claim 11, wherein the ratio (A):(B) is about 1:1. 13. A mixture consisting of compound (A) and compound (B), wherein compound (A) and compound (B) in free acid form or salt form have the following formula I (one of the possible tautomeric forms) , ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I [In the above formula, the sulfo group is at the 4 or 5 position, and R_1 is hydrogen, C_1_-_4 alkyl, C_1_-_4 alkyl monosubstituted with halogen or cyano, or C_2_~_4 represents haloalkyl, R_2 is hydrogen, C_1_~_4 alkyl, 1 or 2 halogens, hydroxy, cyano, COOH, SO_3
C_1_-_6 alkyl, phenyl or 1 substituted with a group selected from H, OSO_3H and OR_4
or 2 C_1_-_4 alkyl, halogen, CO
represents phenyl substituted by a group selected from OH, OR_4 and -SO_2R_5, or R_1 and R_2 together with the N atom to which they are attached contain 1 to 3 heteroatoms and are further substituted. or may form a 5- or 6-membered saturated ring, which is substituted with 1 to 3 C_1_-_4 alkyl groups, and R_4 is C_1_-_4 alkyl or C_2_-_4
represents hydroxyalkyl, R_5 represents hydroxy, amino, C_1_-_4 alkyl or phenyl, m represents 0, 1, 2 or 3, R each independently represents halogen, C_1_-_4 alkyl, C_1_-_4 alkoxy, SO_3H , COOH or -NHCOC_1_-_4 alkyl, provided that (i) compound (A) is different from compound (B), (ii) compound (A) has a sulfo group in the 5-position in formula I, and m is 0, R_1 is hydrogen,
In the case of a compound in which R_2 is 4-sulfophenylamino, compound (B) has the same positions of m, R_1 and the sulfo group as defined for compound (A) in formula I, and R_2 is In producing a mixture corresponding to the compound other than the compound that is 3-sulfophenylamino, one of the possible tautomeric forms is the following formula II, ▲ mathematical formula, chemical formula, table, etc. ▼II [In the above formula, the positions of R, m and the sulfo group are the same as defined above] One or more compounds corresponding to the following formula III
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼III [In the above formula, X represents chlorine or -NR_1R_2], and when X is chlorine, further The following formula IV, HNR_1R_
2IV [In the above formula, R_1 and R_2 represent the same as defined above] A method comprising reacting with one or more compounds corresponding to formula II, III and/or
A method using at least two different starting compounds of the compounds of IV. 14. A mixture consisting of compound (A) and compound (B), wherein compound (A) and compound (B) in free acid form or salt form have the following formula I (one of the possible tautomeric forms) , ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I [In the above formula, the sulfo group is at the 4 or 5 position, and R_1 is hydrogen, C_1_-_4 alkyl, C_1_-_4 alkyl monosubstituted with halogen or cyano, or C_2_~_4 represents haloalkyl, R_2 is hydrogen, C_1_~_4 alkyl, 1 or 2 halogens, hydroxy, cyano, COOH, SO_3
C_1_-_6 alkyl, phenyl or 1 substituted with a group selected from H, OSO_3H and OR_4
or 2 C_1_-_4 alkyl, halogen, CO
represents phenyl substituted by a group selected from OH, OR_4 and -SO_2R_5, or R_1 and R_2 together with the N atom to which they are attached contain 1 to 3 heteroatoms and are further substituted. or may form a 5- or 6-membered saturated ring, which is substituted with 1 to 3 C_1_-_4 alkyl groups, and R_4 is C_1_-_4 alkyl or C_2_-_4
represents hydroxyalkyl, R_5 represents hydroxy, amino, C_1_-_4 alkyl or phenyl, m represents 0, 1, 2 or 3, R each independently represents halogen, C_1_-_4 alkyl, C_1_-_4 alkoxy, SO_3H , COOH or -NHCOC_1_-_4 alkyl, provided that (i) compound (A) is different from compound (B), (ii) compound (A) has a sulfo group in the 5-position in formula I, and m is 0, R_1 is hydrogen,
In the case of a compound in which R_2 is 4-sulfophenylamino, compound (B) has the same positions of m, R_1 and the sulfo group as defined for compound (A) in formula I, and R_2 is a compound other than the compound that is 3-sulfophenylamino] A method for dyeing or printing a hydroxy group- or nitrogen-containing organic substrate, comprising applying a mixture corresponding to the following as a dyeing or printing agent. 15. The method according to claim 14, wherein the base material is a fibrous material containing or consisting of cotton.