GB2347935A

GB2347935A - Monoazo dyes and mixtures thereof containing both vinylsulphone-type & (halo/pyridinio)-substituted triazine fibre reactive groups

Info

Publication number: GB2347935A
Application number: GB0006242A
Authority: GB
Inventors: Atsushi Inoue; Minoru Uchiyama; Nobuyuki Katsuda
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1999-03-17
Filing date: 2000-03-15
Publication date: 2000-09-20
Anticipated expiration: 2020-03-15
Also published as: GB2347935B; DE10012529A1; GB0006242D0

Abstract

A monoazo compound mixture and monoazo compounds usable as the components of the mixture, and a process for dyeing or printing fiber materials are provide. The monoazo compounds are represented by the following general formula (I): <EMI ID=1.1 HE=39 WI=141 LX=450 LY=999 TI=CF> <PC>[wherein m and n represent 0 or 1; R<SP>1</SP> and R<SP>2</SP> represent a hydrogen atom or a C<SB>1</SB>-C<SB>4</SB> alkyl group (which may be optionally substituted with a hydroxyl group, a cyano group, an alkoxy group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, a sulfamoyl group or a halogen atom); A represents a phenylene group (which may be optionally substituted with one or two substituents selected from C<SB>1</SB>-C<SB>4</SB> alkyl group [which may be optionally substituted with a C<SB>1</SB>-C<SB>4</SB> alkoxy group], C<SB>1</SB>-C<SB>4</SB> alkoxy group, sulfo group and halogen atom) or a naphthylene group (which may be optionally substituted with one sulfo group); Y represents a group: -SO<SB>2</SB>CH=CH<SB>2</SB> or -SO<SB>2</SB>CH<SB>2</SB>CH<SB>2</SB>Z (wherein Z is a group which can be eliminated by the action of an alkali), and in compounds of formula (I-1) X represents a halogen atom and in compounds of formula (I-2) X represents a pyridinio group which may be substituted with one or two substituents selected from a carboxyl group or carbamoyl group. The mixtures comprise at least one monoazo compound of formula (I-1) and at least one monoazo compound of formula (I-2). The following compounds are claimed per se :- <SL> <LI>(i) compounds of formula (I-1) when m is 1, R<SP>1</SP> is hydrogen or methyl and X is chloro or fluoro, subject to the provisos set out in claim 8 and <LI>(ii) compounds of formula (I-2) when m is 1. </SL>

Description

MONOAZO COMPOUND OR MIXTURES THEREOF AND PROCESS FOR DYEING OR PRINTING USING THEM BACKGROUND OF THE INVENTION The present invention relates to fiber-reactive monoazo compounds useful. as reactive dyes or mixtures thereof. The present invention also relates to a process for dyeing or printing onto fiber materials using them.

Various reactive dyes of orange or scarlet color, useful in dyeing, or the like, of the above fiber materials, have been known. For example, JP-A-57-89679 describes compounds for reactive dyes represented by the-following formula ;

wherein R represents a lower alkyl group having up to 4 carbon atoms, Xi and Xi respectively represent hydrogen, chlorine, a methyl group, a methoxy group or a sulfonic acid group and m represents 0 or 1.

Moreover, dyes having a fiber-reactive group of pyridiniotriazine and a fiber-reactive group of vinylsulfone in a molecule, represented by the following formula :

have also been known (JP-A-60-173060).

When, however, fiber materials are dyed with the above known dyes, satisfactory performances can not be obtained. For example, dyeing performance such as exhaustion property, fixation rate, build-up property, color value, easiness of removal by washing of unfixed dye from fiber materials and the like; preservation stability in dried condition, wet condition and dissolved condition; dyeing reproducibility ; solubility in dyeing bath or the like;, compatibility with other reactive dye; dyeing finish in compound dyeing, suitability to more economic dyeing formulation and various fastness such as chlorine resistance, light resistance, perspiration resistance, perspiration-sunlight resistance, acid-hydrolysis resistance, resistance to alkali, washing resistance, peroxide washing resistance and so on are not satisfactory. Therefore, development of fiber-reactive monoazo compounds excellent in various performances described above has been desired.

The present inventors have conducted extensive researches for the development of reactive dyes superior in dyeing reproducibility, level dyeing, washing-off and other dyeing performances, comparing to conventional dyes, capable of dyeing in a lower salt concentration and capable of giving dyed products and printed products which are excellent in various fastness and the like. As the result, they have found the fact that the aim can be attained with monoazo compounds having a specific structure and mixtures thereof. Thus, the present invention has been completed.

SUMMARY OF THE INVENTION The present invention provides a monoazo compound mixture which comprises at least one monoazo compound represented by the following general formula (I-1) :

wherein m and n, independently with each other, represents 0 or 1, RI and R2, independently with each other, represent a hydrogen atom or a C : l-C4 alkyl group which may be optionally substituted with a hydroxyl group, a cyano group, an alkoxy group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, a sulfamoyl group or a halogen atom, A represents a phenylene group which may be optionally substituted with one or two substituents selected from Cl-C4 alkyl group which may be optionally substituted with a C1-C4 alkoxy group, Ci-C4 alkoxy group, sulfo group and halogen atom, or a naphthylene group which may be optionally substituted with one sulfo group, Y represents a group :-SO2CH=CH2 or-SO2CH2CH2Z wherein Z is a group which can be eliminated by the action of an alkali, and X represents a halogeno, or a salt thereof; and at least one monoazo compound represented by the following general formula (1-2) :

wherein m, n, R1, R2, A and Y have the same meaning as above and X'represents a pyridinio group which may be optionally substituted with one or two substituents selected from carboxyl group and carbamoyl group or a salt thereof.

The present invention also provides a monoazo compound represented by the formula (1-1), wherein m is 1, RI represents a hydrogen atom or a methyl group, X represent a chloro or a fluoro, and n, R2, A and Y have the same meaning as above, with the proviso that: when RZ is a hydrogen atom and A is an unsubstituted m-phenylene or when R2 is an ethyl group and A is an unsubstituted p-phenylene group, then X is a fluoro; or a salt thereof.

The present invention further provides a monoazo compound represented by the formula (1-2), wherein m is 1, n, R', R, A, X'and Y have the same meaning as above, or a salt thereof.

The present invention still further provides a process for dyeing or printing a fiber material with the above monoazo compound mixture, or the monoazo compound or a salt thereof.

DETAILED DESCRIPTION OF THE INVENTION In the formula (I-1) and (1-2), m and n may be same to or different from each other. m represents 0 or 1. Preferably, m is 0. n represents 0 or 1. Preferably, n is 0.

In the general formulas (1-1) and (1-2), R'and R2 represent a hydrogen atom or a C-C4 alkyl group which may be optionally substituted with a hydroxyl group, a cyano group, an alkoxy group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, a sulfamoyl group or a halogen atom. The alkyl moieties in the alkoxy, alkoxycarbonyl and alkylcarbonyl groups which may be present as substituents on the C,-C4 alkyl groups represented by R'and R are preferably C,-C4 alkyl groups, more preferably methyl or ethyl groups. R'can be the same to or different from R.

R'in the general formulas (I-1) and (I-2) is preferably a hydrogen atom or a methyl group, with a hydrogen atom being particularly preferred.

Specific examples of a Cl-C4 alkyl group as R'and Ruz in the formulas (I-1) and (I-2) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2 cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl, carboxymethyl, 2carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1, 2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2 methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3 methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 2sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3chloropropyl, 3-bromopropyl, 4-chlorobutyl and 4-bromobutyl.

R2 in the formulas (I-1) and (I-2) is preferably a hydrogen atom, a methyl group or an ethyl group, with an ethyl group being particularly preferred.

Ain the formulas (I-1) and (I-2) represents a phenylene group which may be optionally substituted with one or two substituents selected from Cl-C4 alkyl group which may be optionally substituted with a Ci-C4 alkoxy group; Cl-C4 alkoxy group; sulfo group and halogen atom; or a naphthylene group which may be optionally substituted with one sulfo group.

Specific examples of the substituent includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, sulfo, chloro, and bromo.

Preferred A is unsubstitated phenylene or phenylene substituted with one or two substituents selected from Cl-C4 alkyl group which may be optionally substituted with a C1-C4 alkoxy group ; Ci-C4 alkoxy group; sulfo group and halogen atom.

More preferred A is phenylene and a phenylene substituted with one or two substituents selected from methyl, methoxy and sulfo, with 1,4-phenylene being particularly preferred.

Xin the formula (I-1) represents a halogeno. As X, a chloro and a fluoro are preferred. X'in the formula (I-2) represents a pyridinio group which may be optionally substituted with one or two substituents selected from carboxyl group and carbamoyl group. i in the formulas (1-1) and (1-2) represents a group: SO2CH=CH2 or -SO2CH2CH2Z wherein Z is a group which can be eliminated by the action of an alkali.

Z includes, for example, a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, a halogeno group or a pyridinio group which may be optionally substituted with one or two groups selected from carboxyl group and carbamoyl group.

In the formula (1-2), Z is preferably a sulfate ester group, and preferred examples ofY include-SOzCH=CH2 or- SO2CH2CH2OSO3H, with-SO2CH2CHzOSO3H being particularly preferred.

In the formula (1-1), Z is preferably a sulfate ester group, or a pyridinio group which may be optionally substituted with one or two groups selected from carboxyl group and carbamoyl group. In the formula (I-1), preferred examples of Y include-SO2CH=CH2,- SOzCH2CH2OSOsH,-S02CH2CHz-Xo, wherein Xo is a pyridinio group which may be optionally substituted with one or two group selected from carboxyl group and carbamoyl group, with SOzCHzCHzOSOsH being particularly preferred.

Among the monoazo compound of formula (I-1) and the monoazo compound of formula (1-2), those having specific structures exhibit good effects even when they are not used in combination. Therefore, the present invention also provides the monoazo compound of formula (I-1) having specific structure and the monoazo compound of formula (I-2) having specific structure, each of them can be used singly and exhibits good effect.

When the monoazo compound of formula (I-1) is not used in combination with the monoazo compound of formula (I-2), in the formula (I-1), m is 1, RI is a hydrogen atom or a methyl group, preferably a hydrogen atom, and X is a chloro or a fluoro.

Furthermore, when the monoazo compound of formula (I-1) is not used in combination with the monoazo compound of formula (1-2), and when R2 is a hydrogen atom and A is an unsubstituted m-phenylene or when R2 is an ethyl group and A is an unsubstituted p-phenylene group, then X is a fluoro.

When the monoazo compound of formula (1-2) is not used in combination with the monoazo compound of formula (I-1), m in the formula (1-2) is 1. In this case, R1 in the formula (1-2) is preferably a hydrogen atom or a methyl group, with a hydrogen atom being particularly preferred.

Among monoazo compounds of the formula (I-1) or salts thereof, compounds represented by the following general formula (II)-=-

wherein n, RI, X and Y have the same meanings as above, and R3 and R4, independently with each other, represent a hydrogen atom, a methyl group or a methoxy group, or salts thereof are more preferred. Among them, compounds of the formula (II) wherein n is 0, or salts thereof, are particularly preferred.

Preferably, Ra and R4 are hydrogen atoms.

In the monoazo compound mixture of the present invention, the amount of the monoazo compound of formula (1-1) or a salt thereof is preferably 20 to 8Q parts by weight per 100 parts by weight of the sum of the monoazo compound of formula (I-1) or a salt thereof and the monoazo compound of formula (1-2) or a salt thereof.

Among the monoazo compound mixture of the present invention, the mixture comprising one kind of the monoazo compound of formula (1-1) or a salt thereof and one kind of the monoazo compound of formula (1-2) is preferable.

Although the monoazo compounds of the formulas (I-1) and (I-2) or salts thereof of the present invention may be in the form of a free acid form or a mixture of a free acid form and a salt thereof, preferably it is in the form of alkali metal salt, an alkaline earth metal salt and a mixture containing them. A sodium salt, a potassium salt, a lithium salt and a mixture containing them are particularly preferred.

The process for producing the monoazo compounds of the formulas (I-1) and (1-2) or salts thereof of the present invention is not particularly limited. They can be produced, for example, according to the following manner.

The compound of the formula (1-1), wherein X is a chloro or a fluoro, can be produced by condensing, in any desired order, a compound of the following general formula (III) :

wherein n and R1 have the same meanings as above, and a compound of the following general formula (IV) :

wherein R2, A and Y have the same meaning as above, with 2,4,6-trichloro-s-triazine or 2,4,6-trifluoro-s-triazine.

The compound of the formula (1-2) can be produced by condensing, in any desired order, a compound of the formula (III), a compound of the formula (IV) and a raw material compound for introducing the pyridinio group into the triazine ring, with 2,4,6-trichloro-s-triazine or 2,4,6-trifluoro-s-triazine.

The raw material for introducing a pyridinio group into the triazine ring includes, for example, pyridine compounds which may be optionally substituted with one or two groups selected from carboxyl group and carbamoyl group, such as pyridine, picolinic acid, nicotinic acid, isonicotinic acid, quinolinic acid, 2,4 pyridinedicarboxylic acid, isocinchomeronic acid, dipicolinic acid, cinchomeronic acid, dinicotinic acid, nicotinamide, isonicotinamide and cinchomeronamide. Among them, pyridine, nicotinic acid, isonicotinic acid, nicotinamide and isonicotinamide are preferred, and nicotinic acid and isonicotinic acid are particularly preferred, since, as X'in the formula (1-2),. a nicotinio or isonicotinio group is particularly preferred.

The compounds of the formula (1-2) can easily be produced by condensing the compound of the formula (1-1), wherein X is a chloro or a fluoro, produced in the above manner with a raw material compound for introducing the above pyridinio group into the triazine ring, in an aqueous medium at a temperature of 30 to 100 C while controlling pH between 1 and 6.

In the condensation reaction with 2,4,6-trichlorotriazine or 2,4,6-trifluorotriazine, the order of condensation and conditions for respective condensation are not particularly limited. It is preferred that the condensation reaction with an unsubstituted triazine is carried out at a temperature of-10 to 40"C while controlling pH between 1 and 9. The reaction with a monosubstituted triazine is carried out at a temperature of 0 to 70 C while controlling pH between 4 and 10. The reaction with a disubstituted triazine is carried out at a temperature of 10 to 10Q C while controlling pH between 1 and 8.

The process for producing the compounds of the formula (III) is not particularly limited. They can be produced, for example, by diazotizing a compound represented by the general formula (V):

wherein n has the same meaning as above, and subjecting the obtained diazo compound to the diazo-coupling reaction with a compound of the general formula (VI):

wherein R1 has the same meaning as above, to give the compound of the general formula (III).

The monoazo compound mixture of the present invention may be produced by mixing the components, i. e. the compound of formula (1-1) and the compound of formula (1-2). The mixing may be conducted at the same time in the course of production of the components. Alternatively, it may be produced by mixing after the production of the components was completed. In addition, it is also possible to conduct the mixing when used for dyeing. The state of the components to be mixed may be solid such as powders or granules, aqueous solutions or a combination thereof.

The above explained monoazo compounds or a salt thereof and the monoazo compound mixture of the present invention have a vinylsulfone type and a halogenotriazine or pyridiniotriazine type fiber-reactive group in the molecule. Therefore, they can be used as reactive dyes for dyeing or printing onto a fiber material.

The fiber material is not particularly limited as far as it has a hydroxyl and/or amido group. Examples thereof include natural or regenerated cellulose fibers, natural or synthesized polyamide fibers, polyurethane fibers, leathers and mixed materials containing them.

The natural cellulose fibers specifically include cotton, linen, flax, jute, ramie and the like. Preferred one is cotton.

The regenerated cellulose fibers specifically include rayon, polynosic, cupra and products commercialized under the names "Tencel","Tufcel","Modal","Celtima"and the like.

The natural or synthetic polyamide fibers specifically include wool, silk, polyamide-6, 6, polyamide-6, polyamide-11, polyamide-4 and the like.

The mixed materials containing them include textile blend of these fiber materials and textile blend of the fiber material with a synthetic fiber such as polyester, acryl fiber and the like.

The monoazo compound, a salt thereof or a monoazo compound mixture of the present invention can be used for dyeing or printing onto the above described materials, particularly the above described fiber materials, by a method depending on their physical or chemical properties.

Such method specifically include a method for dyeing or printing onto the above described fibers by the exhaustion dyeing method, the cold batch-up method, the continuous dyeing method, the printing method or the like.

For example, when a cellulose fiber is dyed by the exhaustion dyeing method, the method include dyeing at a temperature of about 30 to 100 C in the presence of an acid-binding agent such as sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium hydroxide or the like and, if necessary, adding a neutral salt such as sodium sulfate, sodium chloride or the like and, if further required, using a solubilizing agent, penetration agent, leveling agent or the like. The addition of the acid-binding agent, neutral salt and the like can be carried out in one portion or in divided portions according to the routine method.

When a cellulose fiber is dyed by the old batch-up method, the method include padding using a neutral salt such as sodium sulfate, sodium chloride or the like and an acid-binding agent such as sodium hydroxide, sodium silicate or the like and then standing in a sealed packing material at a determined temperature.

When a cellulose fiber is dyed by the continuous dyeing method, examples of the method include the one-phase padding method in which the fiber is padded according to a known process at room temperature or an elevated temperature in the presence of an acid-binding agent such as sodium carbonate, sodium bicarbonate or the like and then treated by steaming or dryheating. Also included is the two-phase padding method in which the fiber is dipped in a padding solution containing a compound of the present invention dissolved therein, padded with a neutral salt such as sodium sulfate, sodium chloride or the like and an acidbinding agent such as sodium hydroxide, sodium silicate or the like and then treated by steaming or dry-heating.

When a cellulose fiber is printed, examples of the method include a method in which the fiber is printed, in the onze-phase process, with a printing paste containing an acid-binding agentsuch as sodium bicarbonate or the like and then steamed at a high temperature over 80 C. Also included a method in which the fiber is printed, in the two-phase process, with, for example, a neutral or weakly acidic printing paste, passed through an alkaline bath containing an electrolyte or over-padded with an alkaline padding solution containing an electrolyte, and then treated by steaming or dry-heating. The printing paste used here may contain, for example, a size and/or emulsifier such as sodium alginate, starch ether or the like, and if necessary, may further contain, for example, a printing aid and/or dispersing agent such as urea or the like.

When a cellulose fiber is dyed or printed with the compound of the present invention, the acid-binding agent to be used is not particularly limited. Examples include alkali metal hydroxides, water-soluble basic salts formed by an alkali metal or alkaline earth metal with an inorganic or organic acid, compounds which release an alkali in a heated state and the like. Particularly mentioned are alkali metal hydroxides and alkali metal salts with an inorganic or organic acid of weak or medium strength. Among them, sodium or potassium hydroxide and sodium or potassium salts are preferred. As the acid-binding agent, in addition to the above described sodium carbonate, sodium bicarbonate, trisodium phosphate, sodium hydroxide and sodium silicate, potassium hydroxide, sodium formate, potassium carbonate, mono-or disodium phosphate, sodium trichloroacetate and the like canspecifically be used.

When a synthetic or natural polyamide fiber or a polyurethane fiber is dyed by the exhaustion dyeing method, the -compound of the present invention is exhausted into the fiber in an acidic or weakly acidic dyeing bath while controlling pH, which is then changed to neutral or alkaline nature. If necessary, a leveling agent such as a condensation product of cyanuryl chloride with aminobenzenesulfonic acid, a condensation product of cyanuryl chloride with aminonaphthalenesulfonic acid, an addition product ofstearylamine with ethyleneoxide or the like, or other agent may be used.

The monoazo compound of the present invention and the monoazo compound mixture of the present invention can be used, if necessary, in admixture with another dye insofar as the feature of the invention is adversely affected, in order to obtain a desired color tone. The dye usable in admixture is not particularly limited as far as it is a reactive dye. Examples include dyes having, as the reactive group, at least single group from at least one selected from sulfatoethylsulfone group, vinylsulfone group, monochlorotriazine group, monofluorotriazine group, mononicotinatetriadine group, dichlorotriazine group, difluoromonochloropyrimidine group and trichlorotriazine group, (kiml or dyes commercialized under group names of Sumifi Sumifix/ ra Supra, Sumifix/HF,RemazoL(LevafixProcionCibacronBasilen/ Drimarene/Kayacion, Kayacelon React and the like, dyes disclosed in JP-A-50-178, JP-A-56-9483, JP-A-56-15481, JP-A-56-118976, JP-A-56-128380, JP-A-57-236S, JP-A-B7 89679, JP-A-57-143360, JP-A-59-15451, JP-A-58-191755, JP-A-59-96174, JP-A-59-161463, JP-A-60-6754, JP-A-60-123559, JP. A-60-229957, JP-A-60-260654, JP-A-61-126175, JP A-61-1B5469, JP-A-61-225256, JP-A-63-77974, JP-A-63-225664, JP-A-1-185370, JP-A-3-770, JP-A-6-32907, JP- A-6-11753S, JP-A-5-247366 and JP-A-6-287463, dyes represented by C. I. Reactive Blue. 19 and C. I. Reactive Black 5.

The monoazo compound or a salt thereof of the present invention and the monoazo compound mixture of the present invention are characterized in that they exhibit an excellent performance in dyeing and printing onto fiber materials.

Particularly, they are suitable for dyeing and printing onto cellulose fibers. The dyed product and printed product obtained with these compounds have a light good resistance, perspirationsunlight resistance, chlorine resistance, moisture resistance, such as washing resistance, peroxide washing resistanc, perspiration resistance, acid-hydrolysis resistance and alkali resistance, and further, a good abrasion resistance and ironing resistance.

In addition, the monoazo compound or a salt thereof of the present invention and the monoazo compound mixture of the present invention are excellent in solubility and dyeing ability such as build-up property, level dyeing property, washing-off property, exhaustion property and fixation property, and particularly in the dyeing ability in deep color and the dyeing ability at a lower salt concentration. In addition, they are not liable of being affected by changes in the temperature, the amounts of the dyeing aid such as the salt or alkaline agent and bath ratio, and allow giving dyed products of a steady quality.

Furthermore, they are excellent in that the obtained dyed products are not liable to have a change in color during the fixing treatment or resin processing, and not liable to have a change upon contact with a baeic substance during storage.

EXAMPLES The present invention will now be described in more detail by means of Examples, wherein"part (s)" means part (s) by weight.

Example 1 By condensing 53.35 parts of a monoazo intermediate, the free acid form of which is represented by the formula (1)

synthesized by the conventional process, with 18.44 parts of 2,4,6-trichloro-s-triazine at a pH of 3 to 8 and a temperature of 10 to 40 C, a compound, the free acid form of which is represented by the formula (2)

was obtained.

This compound was condensed with 28.13 parts of aniline 4-ss-sulfatoethylsulfone at a pH of 3 to 8 and a temperature of 10 to 60 C in an aqueous medium to give a compound, the free acid form of which is represented by the formula (3). When a cotton product was dyed with this compound (kmax in an aqueous solution : 504 nm), a dyed product of scarlet color was obtained.

Example 2 When the synthesis in Example 1 is repeated except that the order of reaction of the monoazo intermediate represented by the formula (1) and aniline-4--sulfatoethylsulfone with 2,4,6trichloro-s-triazine is changed, the compound, the free acid form of which is represented by the formula (3), can also be obtained.

Example 3 By carrying out a similar synthesis as those in Example 1 or Example 2 with exception that compounds shown in column 2, compounds shown in column 3 and compounds shown in column 4 in the following Table are used in place of the monoazo intermediate (1), aniline-4-p-sulfatoethylsulfone and 2, 4,6-trichloro-s-triazine used in Example 1 and Example 2, respectively, corresponding monoazo compounds can be obtained. When a cotton product is dyed with these compounds, dyed products of scarlet color are obtained.

Table 1

F Column 1 | StH Oh | COIUmll 3 | Column 4) Column 1Column 2Column 3Column 4 OH CIYNCI o- Q-SOCH.

L, HC) H03 y gp, H CI COOH The same as above H2NtSOaCzH4OSO3H The same as above CH3O CH6 3 The same as above H2 S02CAOS03H The same as above CH, CHO The s une as bove | H2NoS0, 0, H, O5O3H S j CH, o FFvNYF Y, zr F Y F Table 2

Column 1 Column 2 Column 3 Column 4 ~ SO, OH F~N9F /=\ 1 " < 6 o i i NH, /x 4 Y S03"F 82Nm 7 The same as above The same as above S02C2H4OSO3H rS CI=NrCI HN 8 The same as above HN NyN SO2C2H40SO3H Cl SOH ON L H--SC. C , HOTS O ; H HAN 10 The same as above The same as above So2C&num;l4OCOC Table 3

Column 1 Column 2 Column 3 Column 4 ;OH CH30 N=N Y,-Y H td. SO H SO H N N d 1 HO S I N'i /2Cz a a HOTS GI SO, H s F., N F I N N 12 The same as above HN SO2C2H, OSOyN -F CI N Ct N-N 13 The same as above * N. N vV Ct CH3 H'The same as H 14 The same as aboie soZc2H,, oso, N a bove so, H oH cif3o N=H ICH3 H2N S02CH=Cii2 The same as 15) &num;mu SO, H Example 4 Into 200 parts of water were dissolved 0.3 part of the monoazo compounds obtained in Example 1, and 20 parts of sodium sulfate was added to the respective solutions. Then, 10 parts of cotton was added thereto, and the temperature was raised to 60 C.

After 30 minutes from the time when the temperature reached to 60 C, 4 parts of sodium carbonate was added and dyeing was carried out for 1 hour at the same temperature. Then, washing with water and soaping were performed. Washing-off during washing with water and soaping was good and coloring of wastewater from dyeing was little. The obtained dyed products had an even deep color. In the course of the dyeing, the compounds showed a good solubility, an excellent exhaustion, a high fixation rate and a high color value. The obtained dyed products were good in various fastness including light resistance, perspiration resistance, perspiration-sunligt resistance, chlorine resistance, hydrolysis resistance, alkali resistance, washing resistance and peroxide washing resistance.

Example 5 Into 200 parts of water are dissolved 0.3 part of the respective monoazo compounds obtained in Examples 2 and 3, and 20 parts of sodium sulfate is added to the respective solutions.

Then, 10 parts of cotton is added thereto, respectively, and the temperature is raised to 60 C. After 30 minutes from the time when the temperature reaches to 60 C, 4 parts of sodium carbonate is added and dyeing is carried out for 1 hour at the same temperature. Then, washing with water and soaping are performed.

During the washing with water and soaping, coloring of wastewater from dyeing is little. The obtained dyed products have an even deep color and are excellent in various fastnesses. such as washing fastness.

Example 6 The dyeing in Examples 4 or 5 is repeated except that the amount of sodium sulfate is changed from 20 parts to 10 parts.

The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 4 or 5.

Example 7 The dyeing in Examples 4 ord 5 is repeated except that the amount of sodium sulfate is changed from 20 parts to 4 parts. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 4 or 5.

Example 8 The dyeing in Examples 4 to 7 is repeated except that the temperature is changed from 60 C to 70 C. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 4 to 7.

Example 9 The dyeing in Examples 4 to 8 is repeated except that the temperature is changed from 60 C to xOoc. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 4 to 8 Example 10 The dyeing in Examples 4 to 8 is repeated except that 0.06 part of sodium salt of a condensation product (degree of sulfonation : 110%, average degree of polymerization: 1.8) of methylnaphthalenesulfonic acid and formaldehyde is used in addition to 0.3 parts of the monoazo compound. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 4 to 8.

Example 11 The dyeing in Examples 5 to 10 is repeated except that the amount of the monoazo compound is changed from 0.3 parts to 0.1 part or 0.6 part. The obtained dyed products using 0.6 part have a substantially deep color as compare with the products in Examples 5 to 10 in which 0.3 part of the compounds is used, and the respective monoazo compounds exhibit good build-up property.

Example 12 Color pastes having the following compositions are prepared using respective monoazo compounds obtained in Examples 1 to 3. compositionofc < olorpaste: Monoazo compound 5 parts Urea 5 parts Sodium alginate (5%) stock paste 50 parts Hot water 25 parts Sodium bicarbonate 2 parts Balance (water) 13 parts Total 100 parts The color pastes are printed onto a cotton broad cloth treated for mercerization. The printed cloth is intermediately dried, steamed at 100 C for 5 minutes, washed with hot water, soaped, washed again with hot water and finished by drying. The obtained dyed products respectively have an even deep color and good in various fastness.

Example 13 Into hot water are respectively dissolved 30 parts of the monoazo compounds obtained in Examples 1 to 3 and the solutions are cooled to 25 C. To these dye solutions are added 15 parts of 32.5% aqueous sodium hydroxide solution and 150 parts of 50 Baume water glass. Then, water is added at 25 C to make the total volume is 1,000 parts. Then, immediately, cotton cloths are padded using the obtained solutions as the padding solution. The cotton cloths after padding are rolled up, sealed with a polyethylene film, left at the room temperature of 25 C for 20 hours. Then, the cloths are washed with water according to the usual manner and dried to give finished products-All the obtained dyed products have an even deep color. In addition, all the obtained dyed products are good in various fastness.

Example 14 Into hot water are respectively dissolved 20 parts of the monoazo compounds obtained in Examples 1 to 3 and the solutions are cooled to 256C. To these dye solutions are added 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate. Then, water is added at 25 C to make the total volume is 1,000 parts. Then immediately, cotton cloths are padded using the obtained solution as the padding solution. The cotton cloths after padding are dried at 120 C for 2 minutes and steamed at 100 C for 5 minutes to fix the dyes. All the obtained dyed products have an even deep color. In addition, all the obtained dyed products are good in various fastness.

Example 15 A compound, the free acid form of which is represented by the formula (3), obtained in the same manner as in Example 1, was condense with 12.31 parts of nicotinic acid at a pH of 1 to 6 and a temperature of 30 to 100 C in an aqueous medium to give a compound, the free acid form of which is represented by the formula (4) shown below. When a cotton product was dyed with this compound (Xmax in an aqueous solution: 510 nm), a dyed product of scarlet color tone was obtained.

(4) Example 16 When the synthesis in above Example 15 is repeated except that 2,4,6-trifluoro-s-triazine is used in place of 2, 4, 6-trichloro- s-triazine, the compound, the free acid form of which is represented by the formula (4), can be obtained.

Example 17 When the syntheses in above Example 15 and Example 16 are repeated except that the order of reaction of the monoazo intermediate (1), aniline-4--sulfatoethylsulfone and nicotinic acid with 2,4,6-trichloro-s-triazine is changed, the compound, the free acid form of which is represented by the formula (4), can be obtained.

Example 18 By carrying out a synthesis in a similar manner as in Example 15 and Example 16 with exception that compounds shown in column 2, compounds shown in column 3 and compounds shown in column 4 in the following Table are used in place of the monoazo intermediate (1), aniliiwe-4- -sulfatoethylsulfone and nicotinic acid used in Example 15 and Example 16, respectively corresponding monoazo compounds can be obtained. When a cotton is dyed with these compounds, dyed products of orange or scarlet color tone are obtained.

Table 4

Column 1 Column 2 Column 3 Cvlurnn 4 SOH oH /Hfi f w tit% H2N-. o-SO2C. 4mCHz ~., I SO, H COOL 2 The same as above H2N SO. C2H.-I-ookf The same as Theab above CH30""-3 The sauie as above H2N S02C2H4oSo3H The same as 3 The same as above"v y-'' ..---CHabove CH3 4 The salue as ahove H2 < SO2CzH4OSO3H The same as 4 The a. amea. 8 above'v y""" CO C2H.

Ctlo ab ove C2H5 The same as above J Hl The same as above Table 5

Column I Column 2 Column 3 Column 4 S% if ON N *4 ;., o, HCOOH "- f" Cool COOL N HN 7 The saine as above SO2C2H40SO3H O ; Ns N s 8 The same as above T : ! & S02C2H4OSO3H HOOC COOH so, oN N CN, O j Nat t a w, N, H SOZCH=Ctlz 9 i i HN / Ho, s COOH SD3H N) 10 The same as above ; SO2C2H40COCHJ CON Table 6

Column 1Column 2Column 3Column 4 so, H oH 11. CH, O NN 1 i i NH HO, S H05 = COOH SO, H~ CZH-CN HN The same as 12 The same as So2cH=cH2 awbove N HaN / 13 The same as above T COOH j Hy H 14 The same as above HNa YCONH2 , SO2C2L0SO3H COF on N c imi N=N N C. 43 SOJA SOIN Example 19 Into 200 parts of water were dissolved 0.3 part of the monoazo compounds (4) obtained-in Example 15, and 20 parts of sodium sulfate was added to the respective solutions. Then, 10 parts of cotton was added thereto, and the temperature was raised to 60 C. After 30 minutes from the time when the temperature reached to 60 C, 4 parts of sodium carbonate was added and dyeing was carried out for 1 hour at the same temperature. Then, washing with water and soaping were performed. Washing-off during washing with water and soaping was good and coloring of wastewater from dyeing was little. The obtained dyed products had an even deep color. In the course of the dyeing, the compounds showed a good solubility, an excellent exhaustion, a high fixation rate and a high color value. The obtained dyed products were good in various fastness including light resistance, perspiration resistance, perspiration-sunligt resistance, chlorine resistance, hydrolysis resistance, alkali hydrolysis resistance, washing resistance and peroxide washing resistance.

Example 20 Into 200 parts of water are dissolved 0.3 part of the respective monoazo compounds obtained in Example 18, and 20 parts of sodium sulfate is added to the respective solutions. Then, 10 parts of cotton is added thereto, respectively, and the temperature is raised to 60 C. After 30 minutes from the time when the temperature reaches to 60 C, 4 parts of sodium carbonate is added and dyeing is carried out for 1 hour at the same temperature. Then, washing with water and soaping are performed. In any cases of the respective compounds, washing-off during washing with water and soaping is good and coloring of wastewater from dyeing is little. The obtained dyed products have an even deep color. In the course of the dyeing, the compounds show a good solubility, an excellent exhaustion, a high fixation rate and a high color value. The obtained dyed products are good in various fastness.

Example 21 The dyeing in Example 19 is repeated except that the amount of sodium sulfate is changed from 20 parts to 10 parts. The obtained dyed products have a comparative quality to those of the dyed products obtained in Example 19.

Example 22 The dyeing in Example 19 is repeated except that the amount of sodium sulfate is changed from 20 parts to 4 parts. The obtained dyed products have a comparative quality to those of the dyed products obtained in Example 19.

Example 23 The dyeing in Examples 19 to 21 is repeated except that the temperature is changed from 60 C to 70 C The obtained dyed products are good in various fastness.

Example 24 The dyeing in Examples 19 to 21 is repeated except that the temperature is changed from 60 C to 80 C. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 19 to 22.

Example 25 The dyeing in Examples 19 to 23 is repeated except that 0. 06 part of sodium salt of a condensation product (degree of sulfonation : 110%, average degree of polymerization : 1. 8) of methylnaphthalenesulfonicacid and formaldehyde is used in addition to 0. 3 parts of the monoazo compound. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 19 to 23.

Example 26 The dyeing in Examples 19 to 24 is repeated except that the amount of the monoazo compound is changed from 0.3 parts to 0.1 part or 0.6 part. The obtained dyed products using 0.6 part have a substantially deep color as compare with the products in Examples 19 to 24 in which 0.3 part of the compounds is used, and the respective monoazo compounds exhibit good build-up property.

Example 27 Color pastes having the following compositions are prepared using respective monoazo compounds obtained in Examples 15 to 18.

(composition of color paste : Monoazo compound 5 parts Ures 5 parts Sodium alginate (5%) stock paste 50 parts Hot water 25 parts Sodium bicarbonate 2 parts Balance (water) 13 parts Total 100 parts The color pastes are printed onto a cotton broad cloth treated for mercerization. The printed cloth is intermediately dried, steamed at 100 C for 5 minutes, washed with hot water, soaped, washed again with hot water and finished by drying.The obtained dyed products respectively have an even deep color and good in various fastness.

Example 28 Into hot water are respectively dissolved 30 parts of the monoazo compounds obtained in Examples 15 to 18 and the solutions are cooled to 25 C. To these dye solutions are added 15 parts of 32.5% aqueous sodium hydroxide solution and 150 parts of 50 Baume water glass. Then, water is added at 25 C to make the total volume is 1,000 parts. Then, immediately, cotton cloths are padded using the obtained solutions as the padding solution. The cotton cloths after padding are rolled up, sealed with a polyethylene film, left at the room temperature of 25 C for 20 hours. Then, the cloths are washed with water according to the usual manner and dried to give finished products. All the obtained dyed products have an even deep color. In addition, all the obtained dyed products are good in various fastness.

Example 29 Into hot water are respectively dissolved 20 parts of the monoazo compounds obtained in Examples 15 to 18 and the solutions are cooled to 25. To these dye solutions are added 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate.

Then, water is added at 25 C to make the total volume is 1,000 parts. Then immediately, cotton cloths are padded using the obtained solution as the padding solution. The cotton cloths after padding are dried at 120 C for 2 minutes and steamed at 100 C for 5 minutes to fix the dyes All the obtained dyed products have an even deep color. In addition, all the obtained dyed products are good in various fastness.

Example 30 A monoazo compound mixture was obtained by sufficiently mixing 50 parts of the compound, the free acid form of which is represented by the following formula (5):

(hapax in an aqueous solution : 504 nm) and the compound, the free acid form of which is represented by the following formula (6) :

(Bmazc in an aqueous solution: 512 nm).

Into 200 parts of water were respectively dissolved 0.1,0.3 and 0.6 parts of the mixture. Then, 10 parts of sodium sulfate and 10 parts of cotton were added thereto, respectively, and the temperature was raised to 60 C. After adding 4 parts of sodium carbonate and dyeing for 1 hour, washing with water, soaping, washing with water and drying were successively performed.

During washing with water and soaping, coloring of wastewater from dyeing was little. All the obtained dyed products had an even deep color.

The dyed product obtained with 0.6 part of the monoazo compound mixture had a substantially deeper color than the dyed product obtained with 0.3 part. Similarly, the dyed product obtained with 0.3 part of the monoazo compound mixture had a substantially deeper color than the dyed product obtained with 0. 1 part. The results indicate that the build-up property of the monoazo compound mixture is good.

In the course of the dyeing, the mixtures showed an excellent exhaustion, solubility and leveling performances and showed a high fixation rate. In addition, the obtained dyed products were good in various fastness (light resistance, perspiration resistance, perspiration-sunlight resistance, chlorine resistance, acidhydrolysis resistance, alkali resistance, washing resistance and peroxide washing resistance).

Example 31 The dyeing in Example 30 is repeated except that the amount of sodium sulfate is changed from 10 parts to 4 parts. The obtained dyed products have a comparative quality to those of the dyed products obtained in Example 30.

Example 32 The dyeing in Examples 30 to 31 is repeated except that the temperature is changed from 60 C to 70oC. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 30 to 31.

Example 33 The dyeing in Examples 30 to 32 is repeated except that 0.06 part of sodium salt of a condensation product (degree of sulfonation : 110%, average degree of polymerization: 1 8) of methylnaphthalenesulfonic acid and formaldehyde is used in addition to 0.1,0.3 or 0.6 part of the monoazo compound. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 30 to 32.

Example 34 Color pastes having the following compositions are prepared using the monoazo compound mixture obtained in Example 30.

Compositionofco,lor paste color Monoazo compound mixture 5 parts Urea 5 parts Sodium alginate (5%) stock paste 50 parts Hot water25 parts Sodium bicarbonate 2 parts Balance (water) 13 parts Total 100 parts The color paste is printed onto a cotton broad cloth treated for mercerization. The printed cloth is intermediately dried, steamed at 100 C for 5 minutes, washed with hot water, soaped, washed again with hot water and finished by drying. The monoazo compound mixture shows good build-up property. The obtained dyed products have an even deep color and good in various fastness and preservation stability.

Example 35 Into hot water is dissolved 30 parts of the monoazo compound mixture obtained in Example 30 and the solution is cooled to 25 C.

To the dye solution are added 15 parts of 32.6% aqueous sodium hydroxide solution and 150 parts of 50 Baume water glass Then, water is added at 25 C to make the total volume is 1, 000 parts.

Then, immediately, cotton cloths are padded using the obtained solution as the padding solution. The cotton cloths after padding are rolled up, sealed with a polyethylene film, left at the room temperature of 25 C for 20 hours. Then, the cloths are washed with water according to the usual manner and dried to give finished products. The monoazo compound mixture shows good build-up property. All the obtained dyed products have an even deep color. In addition, all the obtained dyed products are good in various fastness and preservation stability.

Example 36 Into hot water is respectively dissolved 20 parts of the monoazo compound mixture obtained in Example 30 and the solution is cooled to 25 C. To the dye solution are added 1 part of sodium alginate, 10 parts of sodium metanitrobenzenesulfonate and 20 parts of sodium bicarbonate. Then, water is added at 25 C to make the total volume is 1,000 parts. Then immediately, cotton cloths are padded using the obtained solution as the padding solution. The cotton cloths after padding are dried at 120 C for 2 minutes and steamed at 100 C for 5 minutes to fix the dyes. The monoazo compound mixture shows good build-up property. All the obtained dyed products have an even deep color. In addition, all the obtained dyed products are good in various fastness and preservation stability.

Example 37 The dyeing in Examples 30 to 36 is repeated except that a mixture of the compounds in column 2 in the following Table are used in place of the mixture of the compound of formula (5) and the compound of formula (6) and that the compositions are changed to the ratios shown in column 3. The obtained dyed products have a comparative quality to those of the dyed products obtained in Examples 30 to 36, respectively.

Table 7

Column 1 Column 2 Column 3 50 on Ho, s t v/ 'r sosc, H. oso, H a OM CliO N=N f w N-~-~~ 5 0~ ~ H g i NH-r y-N \/ N 50 O H OS H IICLDO" I COON H & N cH, o N=N.. I, 2 i Nf1-r-H \/ N, N 2 : C, N, OSON "3 98 S 9 8 Clap N ; H HgS'//HHNI- \/ NH C O$ ! 1 N L 9QaM OH-~--- 3. cl CItO N ; N Hn \ 90, C=H, SOH A HOOC''COOM 0, H oM 1109 1 11 N-N11 1 no'si-70 NM Y SO, C=H, O & O, N N [\' v'CON ? i= SO '4 cH, o , rN.. ~ 30 SO, HOH* YN F cHO N-N w w ~ (i/NH-H1-HH SO : WoN -NYH N w 9 COON Table 8

Column 1 Column 2 Column 3 OU 5 c", v " 25 5 CHS ON L\/A 26 zdacl 0) 1 -11yin C00 /'' N ~ 20 wo, '* ''= < COOL ou nu 50 -roi N, FUN W n su i i NN N NN \/ Et a ow N H""'11 N iN Ouzo N 1 60 1 Clio k= H I NvCN N s =ns Y o o h . on a0 1= W 40 no, HH-IW \ l N i ta Y su K -\ cl OL Table 9

Column 1 Column 2 Column 3 N 9 9 CIW b N + 30 oye a SC OM mo-ocli ut am 04 xi chat, son c -"HO,jar-N a N N / B N, < Ct 4sN cl 55 A 6 eooM 1 CN 55 Y so, ccri, cooH in NO, KH-ri ; ZrN- Or i Nli N i Y a UHtCPOD 80 Wi.. rYN 11 / N. tti OH < N++ 20 ow : : soc^osom MM. MO ON ON 20 as' 11 / w N 50psp, 1 00 Table 10

Column 1 Column 2 Column 3 so, H , 13o-, t 25 " . 25 i -soattOH S 13 M ca% 25 Hnu eus i 3020=CH6 N N . K oli COON m 14 cH. v h-.. ' 50 14 ut 50 ~D l~Nb CI so, n w"= i'50 so, c. oso, . L- 50 MUA" OU out 15CH60-6k=N He 45 N YN .

1 M ru v < ~..

16 O4N48 2 0 SOZ Y xi co $ON 1 i N-i 20 Hp, s "N' SOC, i, 9o, N SO, H NYN a X f "COOH lOaN YN N 'cOOH Table 11

Column 1 Column 2 Column 3 so, n M--~ ~ HOZS NHS ENOSOXC} H*OSOTH Ngs I N! 1-f Nr-N 60tC1, OSOr1 NH Ci C! [0 N-N w W ~ "I-"v SH. oso, h 75 Hgs YN N 90aN oH C 4 0 a H 1$ CO) XNX 2 0 N 8O2C^oxH N iN í SOACH, ""a, coo" H ' i i NH./ han T SO, CAO$0, H sa"-om C^ 18 ~-~ 2 0 -Cl CH Y so, cH, OSO, H I N ~ 30 CH. o \6 : N .. noirs N N li Cl t COpH

Claims

CLAIMS 1. A monoazo compound mixture which comprises at least one monoazo compound of formula (I-1) :

wherein m and n independently represent 0 or 1, R'and R2 independently represent a hydrogen atom or a C-C4 aLkyl group which may be optionally substituted with a hydroxyl group, a cyano group, an alkoxy group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, a sulfamoyl group or a halogen atom, ~ A represents a phenylene group which may be optionally substituted with one or two substituents selected from C-C4 alkyl group which may be optionally substituted with a Cl-C4 alkoxy group, Cl-C4 alkoxy group, sulfo group and halogen atom, or a naphthylene group which may be optionally substituted with one sulfo group, Y represents a group :-SO2CH=CH2 or-SO2CH2CH2Z wherein Z is a group which can be eliminated by the action of an alkali, and X represents a halogen atom, or a salt thereof; and at least one monoazo compound of formula (1-2) :

wherein m, n, R', R, A and Y are as hereinbefore defined and X'represents a pyridinio group which may be optionally substituted with one or two substituents selected from carboxyl group and carbamoyl group, or a salt thereof.
2. A mixture according to claim 1 wherein the amount of the monoazo compound of formula (I-1) or salt thereof is 20 to 80 parts by weight per 100 parts by weight of the sum of the monoazo compound of formula (1-1) or salt thereof and the monoazo compound of formula (1-2) or salt thereof.
3. A mixture according to claim 1 or 2 wherein A is phenylene or a phenylene substituted with one or two substituents selected from methyl, methoxy and sulfo.
4. A mixture according to any one of claims 1 to 3 wherein n is 0.
5. A mixture according to any one of claims 1 to 4 wherein R'is a hydrogen atom.
6. A mixture according to any one of claims I to 5 wherein R2 is an ethyl group.
7. A mixture according to any one of claims 1 to 6 wherein X'is a nicotinio or isonicotinio group.
8. A monoazo compound of formula (I-l) :

wherein mis 1, nisOorl, R'represents a hydrogen atom or a methyl group, RI represents a hydrogen atom or a Cl-C4alkyl group which may be optionally substituted with a hydroxyl group, a cyano group, an alkoxy group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, a sulfamoyl group or a halogen atom, A represents a phenylene group which may be optionally substituted with one or two substituents selected from Cl-C4 alkyl group which may be optionally substituted with a Cl-C4 alkoxy group, Cl-C4aoxy group, sulfo group and halogen atom, or a naphthylene group which may be optionally substituted with one sulfo group, Y represents a group :-SO2CH=CH2 or-SO2CH2CH2Z wherein Z is a group which can be eliminated by the action of an alkali, and X represents a chlorine or fluorine atom, with the proviso that: when RI is a hydrogen atom and A is an unsubstituted m-phenylene group or when R2 is an ethyl group and A is an unsubstituted p-phenylene group, then X is a fluorine atom; or a salt thereof.
9. A monoazo compound of formula (II) :

wnerem n is v or i, R'represents a hydrogen atom or a methyl group, Y represents a group :-SO2CH=CH2 or-SO2CH2CH2Z wherein Z is a group which can be eliminated by the action of an alkali, X represents a chlorine or fluorine atom, and R3 and R4 independently represent a hydrogen atom, a methyl group or a methoxy group, or a salt thereof.
10. A monoazo compound or salt thereof according to claim 8, wherein n is 0.
11. A monoazo compound or salt thereof according to claim 8 or 10, wherein RI is a hydrogen atom.
12. A monoazo compound or salt thereof according to claim 9, wherein R3 and R4 are hydrogen atoms.
13. A monoazo compound of formula (1-2) :

wherein m is 1, n is 0 or 1, R'and R2 independently represent a hydrogen atom or a C-C4 alkyl group which may be optionally substituted with a hydroxyl group, a cyano group, an alkoxy group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, a sulfamoyl group or a halogen atom, A represents a phenylene group which may be optionally substituted with one or two substituents selected from C,-C4 alkyl group which may be optionally substituted with a C,-C4 alkoxy group, C,-C4 alkoxy group, sulfo group and halogen atom, or a naphthylene group which may be optionally substituted with one sulfo group, Y represents a group-SO2CH=CH2 or-SO2CH2CH2Z wherein Z is a group which can be eliminated by the action of an alkali, and X'represents a pyridinio group which may be optionally substituted with one or two substituents selected from carboxyl group and carbamoyl group, or a salt thereof.
14. A monoazo compound or salt thereof according to claim 13, wherein n is 0.
15. A monoazo compound or salt thereof according to claim 13 or 14, wherein R' is a hydrogen atom.
16. A monoazo compound or salt thereof according to any one of claims 13 to 15, wherein R2 is a hydrogen atom.
17. A monoazo compound or salt thereof according to any one of claims 13 to 16, wherein A is phenylene or phenylene substituted with one or two substituents selected from Cl-C4 alkyl group which may be optionally substituted with a C-C4 alkoxy group, C,-C4 alkoxy group, sulfo group and halogen atom.
18. A monoazo compound or salt thereof according to any one of claims 13 to 17, wherein A is a 1,4-phenylene group.
19. A process for dyeing or printing a fiber material which comprises applying a monoazo compound mixture according to any one of claims 1 to 7 to the fiber material.
20. A process for dyeing or printing a fiber material which comprises applying a monoazo compound or salt thereof according to claim 8,10 or 11 to the fiber material.
21. A process for dyeing or printing a fiber material which comprises applying a monoazo compound or salt thereof according to claim 9 or 12 to the fiber material.
22. A process for dyeing or printing a fiber material which comprises applying a monoazo compound or salt thereof according to any one of claims 13 to 18 to the fiber material.
23. A fiber material dyed or printed using a monoazo compound mixture according to any one of claims 1 to 7 or a monoazo compound or salt thereof according to any one of claims 8 to 18.
24. A monoazo compound mixture according to claim 1 substantially as hereinbefore described in any one of the Examples.
25. A process for preparing a monoazo compound or salt thereof according to claim 8,9 or 13 substantially as hereinbefore described.
26. A process according to any one of claims 19 to 22 substantially as hereinbefore described in any one of the Examples.
27. A fiber material according to claim 23 substantially as hereinbefore described in any one of the Examples.