FR2465725A1 - MONO-AZOIC COMPOUNDS, MONO-AZOIC COLORANTS AND METHOD FOR COLORING POLYESTER FIBERS - Google Patents

Abstract

NEW COLORING MATERIALS OF THE MONO-AZOIC TYPE. MONO-AZOIC COMPOUNDS AND MONO-AZOIC COLORANTS REPRESENTED BY THE FOLLOWING GENERAL FORMULA, AND PROCESS FOR COLORING POLYESTER FIBERS USING MONO-AZOIC DYES OF FORMULA: (CF DRAWING IN BOPI) IN WHICH R AND R EACH REPRESENT ONE HYDROGEN ATOM, A POSSIBLY SUBSTITUTED RADICAL ALKYL, A RADICAL ALCENYL OR A CYCLOHEXYL RADICAL, R REPRESENTS AN ATOM OF HYDROGEN, CHLORINE OR BROMINE, A RADICAL ALKYL, A RADICAL ALCOXY POSSIBLY SUBSEQUENTLY OR SUBSTANTIALLY SUBSTITUTE RADICAL ALCOXY A HYDROGEN, CHLORINE OR BROMINE ATOM, A RADICAL ALKYL, A RADICAL ALCOXY, A HYDROXY GROUP, A RADICAL ACYLAMINE, A RADICAL ALCOXY-CARBONYLAMINE, A RADICAL ARAKYLOXYCARBONYLAMINE OR A RADICAL ARAKYLOXYCARBONYLAMINE OR A UN RADICAL ALKONARBYLAMINE. DYEING POLYESTER FIBERS, AND PRINTING POLYESTER FIBERS BY RESISTANCE OR BY DISCHARGE.

Description

The present invention relates to novel monoazo compounds, in particular

  particular mono-azole compounds usable as dyestuffs. It further relates to a method of coloring polyester fibers

  using such new mono-azo dyes.

  The mono-azo compounds according to the present invention are useful as dyes and, when used as dyes, they are temperature dependent in a favorable manner. When the dyes according to the invention are used for dyeing or dyeing polyester fiber fabrics, the dyed fabrics thus obtained have fewer spots in the white background printing and have satisfactory "fastness", for example a fastness to the

satisfactory sublimation.

  Further, when a resist or discharge printing is applied to polyester fibers using a mono-azo compound according to the invention as a colorant and a base as a resist or discharge printing agent, various designs can be obtained. clean and firmly printed with less damage to the fibers and excellent whiteness in the areas printed by

resistance or discharge.

  It is known that the polyester fibers may be dyed yellow or blue by azo dyes represented by the following general formula

NO. CIN

  Wherein R3 is an alkyl radical, a radical. substituted alkyl or an aralkyl radical; and A is the residue of a coupling component selected from the group consisting of: (1) Five- or six-membered heterocyclic compounds having an amino group, an oxo group or a hydroxy group, (2) optionally substituted naphthols and (3) aromatic amines not having a substituent group at the 4-position with respect to the amino group and

  comprising at least one aliphatic or cyclo-substituted substituent

  aliphatic group on the nitrogen atom of the amino group (see

  Japanese Patent Publication No. NI 17848/1977).

  Mono-azo compounds and mono-

  azo compounds according to the invention are represented by the following general formula: (i)

C) "NN

  Wherein R 1 and R 2 each represent a hydrogen atom, an optionally substituted alkyl radical, an alkenyl radical or a cyclohexyl radical, R 3 represents a hydrogen, chlorine or bromine atom or an alkyl radical; , an optionally substituted alkoxy radical or an alkenyl radical, and R4 represents a hydrogen, chlorine or bromine atom or an alkyl radical, an alkoxy radical, a hydroxyl group, an acylamine radical, an alkoxycarbonylamine radical, an aralkyloxycarbonylamine radical or

an alkylaminocarbonylamine radical.

  In the general formula (I) above, R1 and R2 independently include a hydrogen atom, alkyl radicals such as methyl, ethyl, propyl straight chain or branched, butyl, pentyl, hexyl, heptyl, octyl; lower alkoxyalkyl radicals such as the methoxyethyl radical, the ethoxyethyl radical or the butoxyethyl radical; alkenyloxy-lower alkyl radicals such

  that the allyloxyethyl radical; the alkoxyalkoxy radicals

  lower alkyl such as the methoxyethoxyethyl radical and

  the ethoxyethoxyethyl radical; the alkoxyalkoxy radicals

  lower alkoxyalkyl such as the methoxyethoxy radical

  ethoxyethyl and the ethoxyethoxyethoxyethyl radical; optionally substituted phenoxyalkyl radicals, such as the phenoxyethyl radical and the chlorophenoxyethyl radical; aralkyloxyalkyl radicals, optionally substituted,

  such as the benzyloxyethyl radical and the chloro

  benzyloxyethyl; cyano-lower alkyl radicals such as the cyanomethyl radical and the cyanoethyl radical; optionally substituted hydroxyalkyl radicals, such as the hydroxyethyl radical, the hydroxypropyl radical, the hydroxybutyl radical, the hydroxyhexyl radical and the

  2-hydroxy-3-methoxypropyl radical; acyloxy radicals

  (lower alkyl), optionally substituted, such as the acetyloxyethyl radical, the chloroacetyloxyethyl radical,

  the chloropropionyloxyethyl radical and the benzoyloxy radical

  ethyl; alkoxycarbonyloxy (lower alkyl) radicals such as the methoxycarbonyloxyethyl radical and the radical

  méthoxyéthoxycarbonyloxyéthyle; carbamoyl radicals

  lower alkyl such as the carbamoylmethyl radical and the

  carbamoylethyl radical; the alkoxycarbonyl radicals

  lower alkyl, optionally substituted, such as

  methoxycarbonylmethyl radical, the ethoxycarbonyl radical

  methyl, methoxyethoxycarbonylmethyl radical, ethoxycarbonylethyl radical and benzyloxycarbonyl] methyl radical; optionally substituted aralkyl radicals, such as

  benzyl radical, the phenethyl radical, the chloro

  benzyl and the nitrobenzyl radical; aryloxy radicals

  carbonyl-lower alkyl such as the aryloxy radical

  carbonylethyl and the aryloxycarbonylmethyl radical; the

  tetrahydrofurfuryl radical; the succinimido radicals

  lower alkyl such as the succinimido-ethyl radical; phthalimido-lower alkyl radicals such as the phthalimido-ethyl radical; cyanoalkoxy-lower alkyl radicals such as the cyanoethoxyethyl radical and the cyanomethoxy-ethyl radical; haloalkyl radicals such as the chloroethyl radical; alkenyl radicals such as the allyl radical, the methallyl radical, and the radical

crotyl; and the cyclohexyl radical.

  Preferred R and R substituents include alkyl radicals having 1 to 8 carbon atoms, lower alkoxyalkyl radicals, lower alkoxyalkoxyalkyl radicals, tetrahydrofurfuryl radical, acyloxy lower alkyl radicals and aralkyl radicals. The substituent R3 comprises the hydrogen atom; the chlorine atom; the bromine atom; alkyl radicals such as the methyl radical, the ethyl radical, the straight or branched chain propyl radical, the butyl radical, the pentyl radical, the hexyl radical, the heptyl radical and the octyl radical; alkoxy radicals such as the radical

  methoxy and the ethoxy radical; the alkoxyalkoxy radicals

  lower such as the methoxyethoxy radical and the ethoxyethoxy radical; lower alkoxyalkoxyalkoxy radicals such

  that the methoxyethoxyethoxy radical and the ethoxy radical

  ethoxyethoxy; halo-lower alkoxy radicals such as the chlorethoxy radical and the bromethoxy radical; the

  cyano-lower alkoxy radicals such as the cyano-

  ethoxy; and alkenyl radicals such as the allyl radical,

  the methallyl radical and the crotyl radical.

  The preferred substituent R3 includes the atom

  of hydrogen and alkoxy radicals.

  The substituent R4 comprises the hydrogen atom; the chlorine atom; the bromine atom; alkyl radicals such as the methyl radical, the ethyl radical, the straight or branched chain propyl radical, the butyl radical, the pentyl radical, the hexyl radical, the heptyl radical and the octyl radical; alkoxy radicals such as the methoxy radical and the ethoxy radical; the hydroxy group; optionally substituted acylamine radicals, such as the acetylamine radical, the chloroacetylamine radical, the radical

  bromoacylamine, the benzoylamine radical, the methoxy-

  benzoylamine, the methylsulfonylamine radical, the benzenesulfonylamine radical and the bromopropionylamine radical; the

  alkoxycarbonylamine radicals such as the methoxy radical

  carbonylamine, the radical ethoxycarbonylamine and the radical

  méthoxyéthoxycarbonylamine; aralkyloxy radicals

  carbonylamine such as the benzyloxycarbonylamine radical; and alkylaminocarbonylamine radicals such as the ethylaminocarbonylamine radical. The preferred R substituent comprises the atom

  hydrogen, alkyl radicals and acylamine radicals.

  The mono-azo compounds and the mono-azole dyes represented by the general formula (I) mentioned above are prepared by reacting the compounds represented by the general formula:

R

NC RC R1

NC _ RNR2 (I)

  in which R1, R2, R3 and R4 have the same definitions as above, with the compound represented by the general formula: (III)

X - CH2CN (III)

  in which X represents a halogen atom, or with the compound represented by the general formula:

D - SO3CH2CN (IV)

  in which D represents a phenyl radical

substituted.

  The sulphonic acid esters represented by the general formula (IV), which form one of the starting materials for the preparation of mono-azo compounds and monoazo dyes according to the invention, include in particular para-toluenesulphonate. cyanomethyl and

cyanomethyl phenylsulfonate.

  On the other hand, the halogenated compounds represented by the general formula (III) include in particular chloroacetonitrile, bromoacetonitrile, iodoacetonitrile, etc. The compounds represented by the general formula (II) are obtained by diazotising 2-amino-4,5-dicyanoimidazole in a conventional manner and combining the diazotized products with the amines represented by the following general formula: R 3

NR2 V

/ \ R2 V

  R4 wherein R1, R3, R3 and R4 have the same definitions as above. The mono-azo compounds and the mono-azo dyes according to the invention can be obtained in a very pure state and with a good yield by heating, between 20 and 200 ° C., the compound represented by the general formula (II) with the compound halogen represented by the general formula (III) or with the sulphonic acid ester represented by the formula (IV), in an aromatic solvent such as chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene,

  ortho-nitrotoluene, an inert solvent, for example an N-

  alkylformamide such as dimethylformamide, an N-alkyl

  pyrrolidone such as N-methylpyrrolidone, a ketone such as acetone or methylethyl ketone, an alcohol such as methanol, a nitrile such as acetonitrile, or in a complex solvent organic solvent such as the mixture water- acetone, the water acetonitrile mixture, the water-methyl ethyl ketone mixture, the etutetrahydrofuran mixture or the water-N-methylpyrrolidone mixture, in the presence of an organic or inorganic base such as pyridine, piperidine, sodium carbonate or potassium carbonate , the oxide

  magnesium, sodium hydroxide or sodium bicarbonate.

  The fibers which can be dyed with the mono-azole dyes according to the invention include polyester fibers such as polyethylene terephthalate, products resulting from the polycondensation of terephthalic acid and 1,4-bis- ( hydroxymethyl) cyclohexane, and like products, or mixed fiber products or blended fabrics of natural fibers such as

  cotton, silk and wool with the poly-

ester mentioned above.

  In order to dye the polyester fibers with the aid of the dyes according to the invention, since the dyes represented by the above general formula (I) are insoluble or poorly soluble in water, it is possible to proceed with the dyeing or bleaching. Printing using a dye bath or printing paste which is prepared by dispersing these dyes in an aqueous medium using products of the condensation of naphthalenesulfonic acid with formaldehyde, sulfates of higher alcohols higher alkylbenzene sulfonates, and like products, as dispersing agents, in a conventional manner. In the case of dyeing, the polyester fibers or their blends can be dyed with natural fibers, for example, with excellent fastness to light, by applying a conventional dyeing process such as high temperature dyeing, dyeing using a carrier and dyeing using a thermosol. In this case, better results can be obtained by adding to the dye bath acidic substances such as formic acid, acetic acid, phosphoric acid or ammonium sulphate. The dyes represented by the above general formula (I) and which are intended to be used with the process according to the invention can be used in combination with dyes of the same type or of different types, and satisfactory results can be obtained by for example, an improvement in the colorability, by combining the compounds represented by the formula

  previous general (I) with each other.

  In addition, when applied to poly-

  ester-resistant or discharge printing using, as dyes, monoazo dyes according to the invention and, as a resist or discharge printing agent, at least one base selected from alkali metal hydroxides and alkali metal hydroxides -terrous, weak organic and inorganic acid salts, ammonia and aliphatic amines, one can obtain various clear and firmly printed designs with less damage to the fibers and a satisfactory whiteness in the areas printed by

resistance or discharge.

  Organic or inorganic bases which can be used as resist or discharge printing agents in resist or discharge printing pastes include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metal phosphates such as disodium phosphate, monosodium phosphate, trisodium phosphate and potassium acid phosphate; alkali metal carbonates such as potassium carbonate, sodium carbonate and lithium carbonate; alkali metal bicarbonates such as bicarbonate

  sodium and potassium bicarbonate; trialkyl-

  alkali metal phosphates such as sodium trimethylphosphate and potassium trimethylphosphate; alkali metal borates such as sodium borate and potassium borate; ammonia; and aliphatic amines such as triethylamine, tripropylamine, tributylamine,

  ethanolamine, dimethylethanolamine, diethylethanolamine

  amine, diethanolamine, methyldiethanolamine, ethyl-

  diethanolamine, propyldiethanolamine and triethanolamine.

  Various methods are already known for the resistance or discharge printing of polyester fibers. A first of these methods consists of soaking the polyester fiber fabrics of a dispersion containing the mono-azo dye represented by the preceding general formula (I) and various auxiliary agents, to dry them at a temperature of 80 ° C. to 150 ° C. to print the dyed fabrics thus obtained with a discharge printing paste containing the abovementioned base and various auxiliary agents, to successively apply a heat treatment at a temperature between 100 C and 230 C to decompose the mono-azo dye represented by the aforementioned general formula (I) in the zone in which the fixing paste and discharge printing has been applied, and subsequently applying a post-treatment in a conventional manner. A second

  process consists in printing the fabrics made of

  ester with a resist printing paste and then to print them either after drying at a temperature of 80 ° C to C or directly in the state with a printing paste containing the mono-azo dye represented by the general formula preceding (I) and various auxiliary agents, and then applying a heat treatment at a temperature of 100 ° C to 230 ° C to decompose the mono-azo dye represented by the general formula (I) in the area in which the fixing paste and resistance printing has been applied, and then apply post-processing in a conventional manner. A third method is to first print the polyester fiber fabrics with a printing paste containing the mono-azo dye represented by the above-mentioned general formula (I), to dry at a temperature of 80 ° C to 1500 ° C, then printing them with a discharge printing paste, and then applying a heat treatment at a temperature of 100 ° C to 2300 ° C to decompose the mono-azo dye represented by the general formula (1) in the area in which the fixing and discharge printing has been applied, and to

  then apply a post-treatment in a conventional way.

  When applying the various resist or discharge printing methods described above to polyester fiber fabrics, multicolored patterns can be formed by adding base-resistant dyes as shown below to the printing paste by

resistance or discharge.

  The base-resistant disperse dyes which can be combined with the dyes represented by the above general formula (I) to form multicolored designs are known dyes belonging to the groups of azo dyes, azomethine, quinophthalone,

  nitroso dyes and anthraquinone dyes.

  Several of the examples of these base-resistant dispersed dyes are in particular represented below:

OH 0 N

0 H H OH

O OH

No N O -OH

H2N O OH OCH3

Cx O2N-f O-N = N X -NN-O-N (C2H5) 2

HO O OCH3

  The invention will now be described in more detail by means of preferred embodiments, but

  is not limited to these embodiments.

  In the Examples and Comparative Examples, the polyester fiber fabrics were printed with printing pastes containing mono-azole dyes according to the invention and various auxiliary agents, and dried, and then applied to them. resistance or discharge printing pastes, containing strong bases, with heat treatment at a temperature of 1000C to 2300C to develop and fix the colors of the dyes, and then subjected to post-treatments in a conventional manner . The resistance print quality or discharge of the paste containing the strong base was then judged, with regard to whiteness in the areas having undergone resistance or discharge printing, by means of

  gray scale (following an indication of 5).

  The temperature dependence was indicated by the color coding density at a temperature of 120 ° C., with reference to 100 the color density at a temperature of 130 ° C. The dyeing temperature is usually 130 ° C. , and the color density decreases as the temperature drops. Sublimation strength was evaluated according to Japanese Industrial Standard JIS 0879-B (1975) by placing test pieces of about 10 cm × 4 cm (printed cloth of primed fiber fabric) between two layers of tetron taffeta. by drying them with an iron (180 C for 30 seconds) and using a

  gray scale (following an indication of 5).

EXAMPLE 1

  30 g of the dye represented by the following structural formula were finely dispersed:

NC - N C2H 5

X, 1fN = N- -N / NC N t \ C H t

CH2CN CH3

  and an imbibition liquid containing 945 ml of water, 20 g of a 10% aqueous solution of FINEGUM LV3 (manufactured by Daiichi Kogyo Seiyaku) and 5 g of citric acid was added thereto. The polyester fiber fabrics were impregnated with this imbibing liquid, wrung out to a 60% absorption rate of the dyeing liquid, and then dried at 80-100 ° C. drying, overprint was applied using a discharge printing paste containing 50 g of sodium carbonate, 50 g of COLOR FINE AD (manufactured by Daiichi Kogyo Seiyaku Co.), 600 g of a 25% aqueous solution TEXPRINT LB (manufactured by GrUinau Co.) and 300 ml of water. After applying a post-treatment of fixing and reduction with superheated vapors at 1750C for 7 minutes, a soaping then a rinse and a drying, one obtained a clear impression of red color with blue shade having satisfactory solidities, in particular excellent fastness to light, sublimation, water and washing. Satisfactory white background printing has been obtained with distinct outlines in the areas where the discharge printing paste containing

  sodium carbonate had been applied.

  The dye used in this example had been

  prepared in the manner indicated below.

  A mixture of 38.3 g of the compound represented by the following formula was stirred at room temperature for 30 minutes.

NC \ -N = N- / \ __X / 2H5

NC H - 'C2H

H CH3 2

  of 8.0 g of sodium bicarbonate, 80 ml of methylethyl

  ketone and 320 ml of water. 16.0 g of chlorine

  acetonitrile, then heated gradually and further stirred at 720C for 20 hours. Then, after cooling to room temperature, 400 ml of methanol were added, stirred at room temperature for 2 hours and the crystals which had settled were collected by filtration. After washing and drying, 35.4 g of dark red crystals of the dye represented by the following formula:

X 9NC-NNN- \ -N \

CH2CN CH3

  This dye had its X max at 530 nm (in acetone). The elemental analytical levels of the dye were in good agreement with the calculated values shown in the table below.

[C24H22N8]

C (%) H (%) N (%)

  Calculated value 68.23 5t25 26.53 Analytical value 68.31 5.19 26.44 Comparative Examples 1-1 to 1-4: Polyester fibers were dyed in the same manner as in Example 1, except that Dyestuffs having the structural formula shown in Table 1 were used to obtain dyed fabrics having a clear blue-red color. Table 1 gives the results of the evaluation for these dyes as well as for

the dye of Example 1.

TABLE 1

  Whiteness, Depth- Solidity impressiondanceà la

  Formula developed from vis-à-vis sublima-

dye charge visions

_____ _-- "the weather

Pérat.

NC 2CN 2 4

  Example 1 N = N N 5 80 4 - 5 NCc / i - - 2H40 4- 2 <

CH 2CN CH3

comparative 1-1

CH2 CH 2CN 3

NCN / C H5

  Example I = N N 2 -3 40 4 Comparative 1-2NC C 1/3 2iccIc 2 S - _

ExempleN

Comfree! gf 1-3NCJ. 60 3-4

CH CH3

Example 1 4-5

NC,% 2H4-

comparative 1-4 47 \

EXAMPLE 2

  Polyester fiber fabrics were printed using a strength printing paste containing sodium carbonate, 60 g COLOR FINE AD (manufactured by Daiichi Kogyo Seiyaku Co.), 600 g aqueous % TEXPRINT LB (manufactured by GrUnau Co.) and 280 ml water, and dried at 80-100 C. After drying, they were overprinted using a printing paste prepared by finely dispersing 30 g of dye represented by the following structural formula:

NC 'ICHC.H = 2

t N = N / / \ -N2H = H

1NC N / C2H4OCH2CH = CH2

CH2CN CH3

  and adding to the dispersion 24 g CELLUCOL PBL-600 (manufactured by Adachi Koryo Co.), 45.5 g KIPROGUM P-20N (manufactured by Nichiden Kagaku Co.), 1.5 g tartaric acid, 2 g of MS POWDER (manufactured by Meisei Kagaku Co.), 30 g of MEIPRINTER Y-75 (manufactured by Meisei Kagaku Co.) and 858.8 ml of water. After applying a fixing and reduction after-treatment with superheated steam at 175 ° C. for 6 minutes, then soaping and then rinsing and drying, a clean red impression having very satisfactory solidities was obtained. especially excellent fastness to light, sublimation, water and washing. A very satisfactory white background printing was obtained with distinct outlines in the areas where the resistive printing paste containing the carbonate

of sodium had been applied.

  The dye used in this example had been

prepared as follows.

  A mixture of 41.9 g of the compound represented by the following formula was heated at 80 ° C.

NC N C 2H4OCH2CH = CH2

\> - N = N -N

NCIICI C H OCH 2CH = CH

H CH3

  of 8.0 g of chloroacetonitrile and 200 ml of N-methyl-

  pyrrolidone and, after 3 hours, added

  gradually, in 8 hours, 8.4 g of sodium bicarbonate.

  After stirring for 10 hours, 3.0 g of chloroacetonitrile was added and stirring was continued for a further 8 hours. Then, after cooling to room temperature, the mixture was poured into one liter of water and

  collected by filtration the crystals which had been deposited.

  These crystals were washed and dried to obtain 38.5 g of dark red crystals of the dye represented by the following general formula: ## STR1 ##

NC XXNC H OC HCH = CH

f 2 42 2

CH2CN CH3

  This dye had its A max at 523 nm (in acetone).

  Comparative Examples 2-1 to 2-4 Polyester fibers were dyed in the same manner as in Example 2 except that the dyes having the developed formulas shown in Table 2 below were used for obtain tissues with a clear red color. Table 2 gives the results of the evaluation for these dyes as well as for the dye of

Example 2

TABLE 2

EXAMPLE 3

  Tissue was dyed in the same manner as in Example 1, 30 g of the dye represented by the following:

A> N = N O-NC N

  polyester fibers except that we used developed formula

/ C2H4OCOCH3

NC '-' - IN C2H4 OCOCH

I r 2 4 3

CH2CN NHCOCH

2 HOC3

  instead of 30 g of the dye of Example 1. A clear blue-blue print was obtained with very satisfactory solidities, in particular excellent fastness to light, sublimation, water and washing, and a very satisfactory white background printing with distinct outlines in the areas where the dough

  discharge printing had been applied.

  The dye used in this example had been

prepared as follows.

  A mixture of 46.6 g of the compound represented by the following formula was stirred at room temperature for 30 minutes. NC NC 2 H OCOCH 3

N = N / 24 3

NC N - \ C2H4OCOCH3

H NHCOCH3

  8.0 g of sodium bicarbonate and 250 ml of acetonitrile.

  24.0 g of chloroacetonitrile and 0.5 g of potassium iodide were added. The temperature was gradually increased and the mixture was stirred at 81 ° C for 16 hours. Then, after cooling the reaction solution to room temperature, it was poured into a mixture of 500 ml of methanol and 500 ml of ice and water, stirred at 0-50 ° C. for one hour, and The crystals which had settled were then collected by filtration. These crystals were washed and dried to obtain 47.8 g of dark red crystals of the dye represented by the following formula

NC 1-NC H OCOCH

XF N = N- -N 2 4 3

NC - tH OCOCH

NC 2 4 3

/

CH2CN NHCOCH3

  This dye had its X max at 538 nm (in acetone).

  Comparative Examples 3-1 to 3-4 Polyester fibers were dyed in the same manner as in Example 3 except that the dyes having the developed formulas shown in Table 3 below were used to obtain clearly colored tissues in red. Table 3 gives the results of the evaluation for these dyes as well as for the dye

of Example 3.

TABLE 3

  Whitening dye developed formula, printing

by de-

  charge NCyN = N '/ C H OCOCH3 ExemplX 3 NCNN 4 3 Example 3 NC> NN NHCOH' C2H4OCOCH3 5 80 CH2CN NC-N i C2H4OCOCH3 Example NC C24 3 3 55 4 comparative 3-1 NHCOCH

CH2CH CN

_ _ _ _ _ _ _ _ 2 2

NC H OCOCH

NC-- N = '/ WC2H4OCOCH 3

\ A & 2 4 3 5

  EXAMPLE NC 2 Comparative 3-2 HCOCH 2 4 3

CH2CHC2H5

gH.

NC XN C2 4 OCOCH

1> ÀN = N_ / \ 1C 2

  Example NC ## STR1 ## Comparative 3-3 NHCOCH 2 4 3 C2H5

NC N C H OCOCH

  EXAMPLE N C H OCOCH 2 EXAMPLE N 3 - NHCOCH C 2 H 4 COOCH 3 1 4 - 5 Comparative 3-4 CH 3 3

2 \ 3

EXAMPLE 4

  Polyester fiber fabrics were dyed in the same manner as in Example 1, except that 30 g of the dye represented by the following structural formula were used: Sublimatic strength

dependent

dance

Visa-

screw

the time

  Pérat. OCH3 $ n -N = N- -i-C2H4COOC H

* NCO- N1

I NHCOCH3

  CH2CN instead of 30 g of the dye of Example 3. There was thus obtained a clear impression in violet having very satisfactory solidities, in particular excellent fastness to light, sublimation, water and washing, and a very satisfactory white background printing with distinct outlines in the areas where the discharge printing paste

had been applied.

  The dye used in this example had been

prepared as follows.

  A mixture of 42.4 g of the compound represented by the following formula was stirred at room temperature for 30 minutes: OCH

N 3NH

I _N = N- 4NCHCOOCH

NC 24 2 5

H NHCOCHJ

H 3

  of 9.0 g of sodium bicarbonate and 300 ml of methyl

  ethyl ketone. 40.0 g of phenylsulfonic acid cyanomethyl ester were added. The mixture was gradually heated and stirred at 80 ° C. for 20 hours. Then, after cooling the reaction solution to room temperature, it was poured into a mixture of 500 ml of methanol and 500 ml of ice and water. After stirring for 1 hour at 05 ° C., the crystals which had settled were collected by filtration. They were washed and dried to obtain 43.2 g of dark red crystals of the dye represented by the following formula:

  This dye had its X max at 560 nm (in acetone).

  Comparative Examples 4-1 to 4-4 Polyester fibers were dyed in the same manner as in Example 4, except that dyestuffs having the developed formulas shown in Table 4 below were used for obtain clearly dyed tissues in red with a blue shade. Table 4 gives the results of the evaluation for these dyes as well as for the

dye of Example 4.

TABLE 4

EXAMPLE 5

  Polyester fiber fabrics were dyed in the same manner as in Example 1 except that dye represented by the following structural formula was used:

NC X N C H2 4

NCDN = N "-NH 25H

  N22 instead of 30 g of the dye of Example 1. A clear red impression was thus obtained with extremely satisfactory solidities, in particular excellent fastness to light, sublimation, water and washing, and a very satisfactory white background printing with distinct outlines in the areas on which

  had applied the printing paste by discharge.

  The dye used in this example had been

prepared as follows.

  To a mixture composed of 30.9 g of the compound represented by the following formula

NOT

NC X N C2H4OH

H

  of 5.3 g of sodium carbonate, 80 ml of tetrahydro-

  furan and 300 ml of water, 17.0 g of iodine were added.

  acetonitrile. The mixture was gradually heated and stirred at 660C for 8 hours. Then, after cooling the reaction solution to room temperature, 300 ml of methanol was added and after stirring for one hour at room temperature, the crystals which had settled were collected by filtration. They were washed and dried to obtain 31.7 g of dark red crystals of the dye represented by the following formula

NC N C2H5

/2.5

I NH4OH

NC N 2

CH 2 CN

  This dye had its X max at 523 nm (in acetone).

  Comparative Examples 5-1 to 5-4 Polyester fibers were dyed in the same manner as in Example 5, except that dyestuffs having the structural formulas given in Table 5 below were used for obtain clearly dyed fabrics in yellow red. Table 5 gives the results of the evaluation for these dyes as well as for

the dye of Example 5.

TABLE 5

  Whiteness, Depth, Solidity, or color printing by color sublimation. screw

the time

_.érat.

NC N N = N 2 5

Example 5

  Example S NW N [f \ COH O 255 90 4 - 5

I 2

  ## STR2 ## EXAMPLE X-N-3-4 70 4 Comparative 5-1 NC NC 2H4

CH2CH2CN

NZ.N% 225

  OH Example. 2 Comparative 5-3 CN - W: 1224 1 - 2 75 2 - 3 2H5 Exerple I N = N - 2 3 10 404 Comparative 5-4NC 'CN - H, 2 4OH IH22

EXAMPLE 6

  Polyester fiber fabrics were dyed in the same manner as in Example 1 except that dye represented by the following structural formula was used:

NC N / A C2H4OCH3

2CN NHCO-E I

  instead of 30 g of the dye of Example 1. This gave a distinct blue-red print with extremely good fastness, particularly excellent fastness to light, sublimation, water and washing. , and a very satisfactory white background printing with distinct outlines in the areas on which

  had applied the printing paste by discharge.

  The dye used in this example had been

prepared as follows.

  A mixture comprising 47.2 g of the compound represented by the following formula was stirred at 81 ° C for 20 hours.

NC N C HOCE

NXN / N 2 4 3

-NC N <2H40 H3

I ÉNCOtj

  8 g of pyridine, 300 ml of acetonitrile and 24.0 g of

  acetonitrile. Then, after cooling the reaction solution to ambient temperature, it was poured into a mixture of 400 ml of methanol and 700 ml of ice and water, stirred at 0-50 ° C. for one hour, and then

  collected by filtration the crystals which had been deposited.

  These crystals were washed and dried to obtain 48.3 g of dark red crystals of the dye represented by the following formula:

NC N /; - / C OCH

"l N / N \ / C 2H4 OCH3

NC XN> N / 24H

N 2 4 H3

uCH2C N NHC O

  This dye had its X max at 530 nm (in acetone).

  Comparative Examples 6-1 to 6-4 Polyester fibers were dyed in the same manner as in Example 6 except that the dyes having the developed formulas shown in Table 6 below were used for obtain clearly dyed fabrics in red. Table 6 gives the results of the evaluation

  for these dyes as well as for the dye of Example 6.

TABLE 6

  Whiteness, Depth-Solidity to Formula of the impressiondance the by screw-to-sublimation dye discharge screw of

the time

  Pérat. Example 6 ## STR2 ## Example ## STR1 ## NC $ Ny N / 2 H4 47 3 comparative 6-NC. V CHOCH3 2 -3 50

CH2CH2CN NHCO-n.

NCJN \ \ / C2 H4OCH3

Example NCX N H OCH

NC 2 45 3

comparative 6- 45 4

I NHCO-- -

CH2CHC2H5

OH

NC -N C2H4OCH3

  Example --N / 24 3 -comparative 6-3 NCN - 2 413 2 4 3 i 60 3-4

NC_ JN C2H4OCH3

C> H5N = N N

  Example N N 3 10 4 Comparative 6-4 H 2 4 3 1 CH 2 NHCO

2 \ 0

EXAMPLE 7

  Polyester fiber fabrics were dyed in the same manner as in Example 1, except that the dyes indicated in Table 7 below were used instead of the dye of Example 1. thus obtained bright impressions and very satisfactory quality, such as

shows Table 7.

TABLE 7

NC) fN) N = N N

NC HF C / 4N

CH 2 CN. '

  R1 R2 R3 R4 Color stain (polyester fibers) red at 1 C H (n) C H (n) H CH red4 1 C4H9 4H9) H CH3 blue shade534 2 C2H5 CH2CHC4H9 (n) "531: 2H $ .5

3 CH3 CH3. "" 527

4C2H5 2 C5292H5

  C3H7 (i) C3H7 (i) C13H9 (i) C3H7 (i) C13H9 (i) C13H9 (i) C13H9 (i) 532 C5H11 (n) C5H (n) 535 No. 535 No. X max of the dye, in nm (in acetone) OO 0% Ln U o * VI TABLE 7 (continued)

I 1-

  C6H13 (n) C6H13 (n) H Red CH3 535 C7H15 () CH (n) 536 C7 15 CH2 CH4H (n) CH2 HC4H9 (n) l 537

C2H5 C2H5

12 C2H5 C4H (n) 530

2 "" 4 93

  13, C5H11 (n) 530 14 C6H13 (n) 530 6 133 1.C7H15 (n) 531 and 531 7 15. C8H17 (n) 531 17-CH2-O-OCH3 n 529

._. CH ....

CH2CH2CH2- 531

w A o LA '6ZS HD = HD HD zHD = eHO

6 ZS ,, HD = HDEH HO HO = HOZ HO L

  SES 9 ILL HO 0Z SZS ,, ,,,, (U) 6HDO HzO (U) 6HDOgHrZSE EZS, ,, HO-HO = HDOHOO HD EHO-HO = HD HO H OD Pz ES mi ai HO HO HO

E. ,, __ ,,,

E S, HHO ,,, Z

  ## STR5 ## wherein: ## STR2 ## (U) 6HDD61 Cu o- -Iro (a, 4Tns) LVISIUVI ZZa5 to OO-H l to O-O-OtH'D tLE l., Ab -OvHEo.-OHzD 9u bzu HDO HzDOvHzDOH HOD

HHE HO úH

9Z, CH ,,, EDOH 0HDHD HDOH'HDHDPE

  SZS ",,,,, EHDO HEDOTHHDOHHDO7HzD úEC SZS ,,,,, EHDOYHD HzDO HED ZE

S6S E.O HDO HEOuH? HD = O TE

  ZS ,, l.l ,, l ZH HD = C HO an9Tq ate EEE

6ZSI 1HOH HODH = HJHDCHDHD = HD HDH 6Z

(alTns) LfoE Ldo 4, CMJ CN

  LIS ,,, D HHDODOHED 6DEHD HHOODO HD: 9V

  LTS -., DZHODODOVH) D D HOODO OHZDS9 HD L HDODO D HDODO HD V

* OE * H.HDSHD H DHD HOúÀ

  HO OEc.s ,,. * EHOHH ZHD EHDH ZHDZP ZE ,,, HOHZHDH zHD HOzHDZHDZHDTV 6zS, H,, H, D HO HzDOP SZ5.i ZO -ZH3OHO O -ZHDO HzD6E

ToSZenu? aSno: T EO-

  (.TFns) L al'qn Ln CNj 1- r> o i4. co. here

, ..., ,,

  Sz Z ni l "(N bH Z N: 8K H Z acuenu ig abnoq_. O NH ú H ZZS B6no. Ux ND H DO'H D ND H OO1HZD ZS

HO HI

6ES H = ODD. H1.

6ZS ,, ,,,, 3H: DOHH IH S

DH H1

  ## STR2 ## wherein: ## STR2 ## 9% ZI there H = H: aH; OZH0HDHO HD-HD HOZ HOH; HO 681

HO HO

  9Z.ln) q úHO H úHDOZHDHZHO EHDOZHDHDZH3 LtP has reached V aenox U% N N Ln% O (9, 4Tns) L avaiavi bE S., SDO H DO H; ## EQU1 ##

,, HDOHDOHD HDOHEDO'HD 1 9

  Sz. (T) 6HDOOHD (T) 6H DO HD09 LI 6zs ,, ,,,, u HDOD HD 6HD S 6Z, z = ozH ZH = HO S 6Z SanaTlq * 'H, = D = HH HD = l: HDLs iceuvnu. abno "

  . JI..DTD: 01S K 3HOOO ZHZ) HDOOQ HO9S

  ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 63C2H40C2H4oC4H9 (n) C2H4oC2H4oC4H9 (n) H CH3 blue in color524 blue shade 524

64 CH C3CH

1 i 3

C2H4C-OCH C2H4C24-OCH3 4526

24d 524

CH 3 CH.

  C H OC H OC H OC H C2H4oC2 4H2 40C2H5 524

2 42 4 2 42 5 4 2HOC H4

  66C2H42424oc7 (n) C2H4oc2H4OC2H.4OC3H7 (n) 524 CH4OC24C43H (n) "1" "67C2H4OC2H4OC2H4 oC4H9 (n) C2H42H40Cl2H4OC4H9 (n) 524

2. 424 ..

  68 C2H4OCH22 2 C2H4OCH2CH "2 n red 523

H3 CH3

  69CH2H (nCHHCH O2C HgCH (n) ,, red with shade 69CH2CHCH2OC4H9 (nl) o "n blue 526

OH OH

  CH2 HCH2OCH2CH = CHCH3CH2HCH2OCH2CH = CICH3 526

OH H

  TABLE 7 (continued) 71CH2COOC2H5CH2COOC2H5H CH3 red 510 72 C2H4OCO-O. C2 HOCO4n _ '507 73C2 H5 CH CH C HOCHE't Coug 5 3 1 2 5 2 213 CH3 blue 531 CE3

, ...... . . _,

7 4 C2H 4oC 2 oc H (n) "52 8 CH3

"CH2 -XC4 __H 29

77 2H4 COCH3 "" 523

78 nC 2Hn NOOCH5 3 3

77 "C2H40COCH3 523 5

  red with blue shade 79 "" "HOCC4H9 (n)" 533

  _ _ _ _ _ _ _ _ _ _ _ _ _ _ _. . , _ _ _ _ _ _, _ ,,

  w -j r-J ut 615 H; a 06 OSaaau to aa 68 TZS aaaiaia 8 TZS úHoOHN The

61. H. 98

  ozs 0o 5H O 5H58 sú1 HO HO HOO H aa LTS a # H 'ú8E LIS a i'. "68a IZ.l",, l ,,. ,,,, 88

r ... 1, iiii, i ...... i ...

S6S NO Ha jDHDH H T "8

,, .. /. 8

anae [q got 9

OZS * .T;) ,, SHZ;) SHZ;) S8,

  ## STR2 ## wherein: ## STR2 ## ' Z 8 Sl S: fn 1; Sl 2H; CD 1.DTD: F ,,,,,

  /-.al aDT S ,,,,,,, STr SwaS no: zHD ,, :), H

i ..... i, ....

  ## EQU1 ## ## STR2 ## wherein ## STR5 ## wherein ## STR5 ## U) 6HbD ,, ú 6

LZS çS 0H D Z6

  ana) qoaDUenU v Z 8E Z sS ano-. HDODHN.HE HDOOD HD LA in% CI <- (aens) L iflvar / aT 0C5,,,, OT, 0 º G5D, l ú H ZO SHN "SHZD SH D 0 6 0 1 L 7g S ,, CHDHNODHN O ,, T, _ ... .... i 8Spq5 aIaq'H DHNODHN R HDODO H ED HOODO H DLO Duenu e ab5no: Ca5noa HO H ,, 90

0995 5HZ: O9HZ; DO., S OT

  .... i 0I99 úHDO EHDO 'Hz P' OT O9 5, l "Ü1HDo tHZDo 11. 11.ú0l '" "' '..DTD: ,, HEDO C úOT

  ## STR1 ## U%% r such o TABLE 7 (cont.) H3 H CH3red 520

3 3,520

I-b 0% A -14 N UT

Claims (4)

  A mono-azo compound represented by the following general formula: R3 CH2CN R   in which R1 and R2 each represent a hydrogen atom, an optionally substituted alkyl radical, an alkenyl radical or a cyclohexyl radical, R3 represents a hydrogen, chlorine or bromine atom, an alkyl radical or an optionally substituted alkoxy radical; or an alkenyl radical, and R4 represents a hydrogen, chlorine or bromine atom, an alkyl radical, an alkoxy radical, a   hydroxyl group, an acylamine radical, an alkoxy radical   carbonylamine, an aralkyloxycarbonylamine radical or a alkylaminocarbonylamine radical.   2. A mono-azo dye represented by the following general formula: R3 NC N R1 > -N = N - 2 NC CH2CN R   in which R and R each represent a hydrogen atom, an optionally substituted alkyl radical, an alkenyl radical or a cyclohexyl radical, R3 represents a hydrogen, chlorine or bromine atom, an alkyl radical or an optionally substituted alkoxy radical; or an alkenyl radical, and R4 represents a hydrogen, chlorine or bromine atom, an alkyl radical, an alkoxy radical, a group   hydroxy, an acylamine radical, an alkoxycarbonyl radical   amine, an aralkyloxycarbonylamine radical or an alkylaminocarbonylamine radical. A process for coloring or dyeing polyester fibers, characterized in that the polyester fibers are colored using a mono-azo dye represented by the following general formula: R 3 NC N1 NC C H2C R1   In which R 1 and R 2 each represent a hydrogen atom, an optionally substituted alkyl radical, an alkenyl radical or a cyclohexyl radical, R 3 represents a hydrogen, chlorine or bromine atom, an alkyl radical or an alkoxy radical; optionally substituted or an alkenyl radical, and R4 represents a hydrogen, chlorine or bromine atom, an alkyl radical, an alkoxy radical, a   hydroxyl group, an acylamine radical, an alkoxy radical   carbonylamine, an aralkyloxycarbonylamine radical or a alkylaminocarbonylamine radical.   4. Method according to claim 3, for forming various printing patterns on polyester fiber fabrics, characterized in that the impression is applied to the polyester fibers by discharge or resistance using, as agent for resistance or discharge printing, at least one base selected from the group consisting of alkali metal and alkaline earth metal hydroxides, salts of weak organic acids and weak mineral acids, ammonia and aliphatic amines.