ITRM960342A1 - DYES FOR MONOAZO DISPERSION (CASE 150-5866). - Google Patents

Description

DESCRIPTION of the industrial invention entitled:

DYES FOR MONOAZO DISPERSION

DYES FOR MONOAZO DISPERSION

It has been found that the monoazo dyes for dispersion of formula I

in which

R means phenyl, optionally substituted, or a group of formula R'-O-,

R 'means C3-4-alkenyl, C3-4-alkynyl, phenyl or C1-8-alkyl with one or two substituents, Ri means hydrogen or C1-2-alkyl,

R2 means hydrogen or halogen,

R3 means hydrogen or C1-3-alkyl, e

R4 means hydrogen, linear or branched C1-8-alkyl with optionally a substituent, or an amino group with optionally a substituent,

since the dye is devoid of groups for solubilization in water, and mixtures of said dyes, they are very suitable for dyeing or printing fibers or threads or materials produced by them, while the fibers, threads or materials comprise hydrophobic organic substances, completely or partially synthetic.

If R is phenyl, it can be substituted, for example with chlorine, -OCH3, -CH3 or N02.

A suitable substituted amino group is for example -NHC6.

In form I, preferably

R means unsubstituted phenyl or the R'-O- group,

R 'means C1-8-alkyl, preferably C1-4-alkyl with a substituent belonging to the compound series. from halogen and C1-4-alkoxy; phenyl; phenyl-C1-3-alkyl or phenoxy-C1-2-alkyl, in which the phenyl nuclei can have a substituent belonging to the series consisting of chlorine, bromine, nitro, C1-2-alkyl or C1-2-alkoxy; tetrahydrofurfuryl; C3-4-alkenyl, C3-4-alkynyl or 1-phenyl-propenyl,

R1 and R2 mean hydrogen,

R3 means methyl, e

R4 means hydrogen, C1-6-alkyl or C 1 -4-alkoxy-C2-3-alkyl.

Particularly preferred are the dyes of formula I, and their mixtures, in which: R is phenyl, o

R 'is benzyl, phenoxyethyl and the Cl- radical (CH2- e;

R1 and R2 are hydrogen,

R3 is methyl, e

R4 is C1-6-alkyl or C1-4-alkoxypropyl.

The dyes of formula I and their mixtures, in which R4 means a linear or branched C 1-6 alkyl radical, are the most preferred. Preferably the alkyl radical is not substituted. When there are substituents, they are preferably selected from the group consisting of C6H5-, Cl1 or -OCOCH3.

The production of these dyes is carried out either by coupling a diazotized amine of formula II

with an amine of the formula

or by condensation of a substance of formula IV

(IV)

with a substance of formula V.

(V)

Diazotization and coupling are carried out using generally known procedures.

By halogen we mean fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, and especially chlorine.

Similarly, the condensation of the substances of formula IV with those of formula V is carried out in a familiar way for an expert in the field, preferably in an organic solvent and in the presence of a basic substance that binds the hydrogen halide that is formed.

Substances having formulas II to V are known or can be readily produced in a manner familiar to one skilled in the art.

The processing of the new substances of formula I, obtainable by means of one of the aforesaid processes, to obtain preparations for dyeing, is carried out in a generally known manner, for example by grinding in the presence of dispersing agents and / or fillers. The dyeing, fularding or printing can take place for example in a so-called long or short bath, after the addition of water, using the preparations optionally dried according to traditional methods, for example vacuum drying, spray drying or using a fluidized bed granulator.

The dyes of the present invention, or mixtures thereof, therefore demonstrate excellent dyes when an aqueous suspension of the dye or mixture thereof is used to treat textile materials comprising high molecular weight, hydrophobic and wholly or partially synthetic organic materials. They are particularly suitable for dyeing or printing textile material consisting of linear aromatic polyesters, as well as cellulose-21⁄2 -acetate and cellulose triacetate.

The dyeing or printing is carried out with known processes, for example those described in the French patent application number 1.445.371.

The dyed or printed pieces thus obtained have a good overall resistance; particularly noteworthy are the resistance to thermo-migration, the resistance to light, the resistance to heat setting, sublimation and creasing, as well as the excellent resistance in water (particularly when measured with the M&S C4A washing test), particularly after treatment thermal.

The new dyes or mixtures thereof are also particularly suitable for modern fast dyeing processes, for example the Foron <®> fast dyeing process.

The new dyes or mixtures thereof are also suitable for modern imaging predictions, for example thermal transfer printing.

In the following examples, the parts and percentages are expressed by weight. Temperatures are expressed in degrees Celsius.

EXAMPLE 1

28.1 parts of 4-amino-benzoic acid (1-carbobenzyloxy) -methyl ester are stirred in 30 parts of water and 30 parts of 30% hydrochloric acid for 2 hours, and after 30 parts of ice are added 22 parts of a 4N sodium nitrite solution at 5-10 °. After adding another 30 parts of ice and stirring for 30 minutes, the slight excess of nitrous acid is decomposed with amidosulfonic acid, and the resulting diazonium salt solution is filtered. The cold, filtered solution of diazonium salt is slowly poured into a solution of 21 parts of N-butyl-3-cyano-4-methyl-pyridone-2 in 110 parts of water, which has been brought to pH 7 - 7.5 and has been mixed, as a crystallization germ, with some crystals of the dye of formula I, while during the coupling the temperature range of 15 - 20 ° is maintained by adding ice and the interval is maintained pH 3 - 5 by adding sodium acetate. After stirring for 2 hours, the resulting yellow suspension is filtered and the cake obtained by filtration is washed in portions with 300 parts of water at 50 ° until it is neutral and free of salt. The crude dye is dried under vacuum at 60 ° and can be further purified by recrystallization or column chromatography (eluent: toluene /

ethylmethylketone).

The dye thus obtained has the following formula I

(1)

It colors polyester fibers (PES) (PES 100%), as well as mixed PES / cotton (CO) fabrics in bright yellow-green shades with good resistance, particularly resistance in water after heat setting (180 °, 30 min).

λ-max (dimethylformamide, DMF): 433 nm.

EXAMPLE 2

43.4 parts of the dye of formula 2 with a title of 93%

obtained by diazotization of p-aminobenzoic acid in hydrochloric acid diluted with 4N nitrite solution and coupling with the coupling component of example 1, they are suspended in 123 parts of dimethylformamide, while adding 30.3 parts of K2C03. 28 parts of benzyl ester monochloroacetic acid are then added in drop form at 60-65 DEG, and the resulting yellow reaction suspension is stirred for 30 minutes. After dilution with 300 parts of 93% ethyl alcohol and cooling to 15 - 20 °, the precipitated dye is collected by filtration under suction, to then wash it with 200 parts of 93% ethyl alcohol at 10 - 13 ° and subsequently with 300 parts of water at 60 °. The dye is dried under vacuum at 60 ° and is structurally identical to that of example 1 and can similarly be purified by recrystallization or column chromatography (eluent: toluene / ethylmethylketone).

EXAMPLE 3

If 28.5 parts of the amine of formula 3 are used

instead of 28.1 parts of 4-amino-benzoic acid- (1-carbobenzyloxy) -methyl ester in example 1, while the process otherwise remains the same as that described in example 1, a dye of formula 4

Similarly to the dye of the above example 1, this substance colors the polyester fibers (PES) (PES 100%), in addition to the mixed fabrics PES / cotton (CO) in bright yellow-green shades having excellent resistance, particularly resistance in water after heat setting. (180 °, 30 min).

Table 1 below shows further dyes of formula I, produced in a manner similar to that of the procedures reported in the preceding examples.

R is always R'-O-, R1 is always hydrogen, with the exception of examples 41 and 42, in which it is methyl.

Except where it is stated otherwise, all the alkyl and alkylene radicals have a straight chain, R2 is hydrogen and R3 is methyl.

All dyes color the polyester fiber material in yellow shades with excellent resistance.

TABLE 1

EXAMPLE 45

25.5 parts of 4-amino-benzoic- (1-benzoyl) -methyl ester are vigorously mixed in 30 parts of 30% hydrochloric acid, and after 25 parts of ice and 25 parts of water have been reached, a solution of 3.8 parts of sodium nitrite in 15 parts of water at 5 - 10 ° over the course of 30 minutes. The mixture is stirred for 2 hours at 15-20 <®>, the slight excess of nitrous acid is decomposed with amidosulfonic acid, and the mixture is filtered to clarity. The resulting diazonium salt solution is then poured continuously, under stirring, into a mixture of 9.7 parts of N-propyl- and 10.3 parts of N-butyl-3-cyano-4-methyl-pyridone- 2 in 100 parts of water at pH 7.5, while the mating temperature is maintained at 15-20 ° by spraying small quantities of ice. A pH value> 4 is maintained by adding about 5 parts of sodium acetate. After stirring for 2 hours, the pH is brought to 5 with a 30% caustic soda solution, the mixture heated to about 75 °, stirred for 1 hour and filtered. The yellow cake obtained from filtration is washed in portions with lukewarm water, until it is free of salt, and dried under vacuum at 60 °.

The dye obtained corresponds to the following formula:

(1: 1)

and colors polyester fiber fabrics in bright yellow-green shades = 433 (DMF)] with excellent resistance, particularly excellent resistance in water after heat setting (180 ° 30 min).

Table 2 shows further examples of yellow dyes that can be produced, for example in accordance with example 45. 1 dyes correspond to the following formula

TABLE 2

Application example 1

17.5 parts of the dye according to example 1 in the form of wet pressed cake are ground in the wet state with a known method with 32.5 parts of a commercial dispersing agent based on lignin sulphonates, and reduced to poor. 1.2 parts of this coloring preparation are added to 2000 parts of demineralized water at 70 °, containing 40 parts of ammonium sulphate; the pH value of the dye bath is brought to 5 with 85% formic acid. 100 parts of washed polyester fiber fabric are placed in this dye bath, the container is closed, heated to 130 ° in the course of 20 minutes, and dyeing continues for another 40 minutes at this temperature. After cooling, the polyester fiber fabric is removed from the dye bath, rinsed, soaped and cleaned by reduction with sodium hydrosulfite in the usual manner. After thermo-fixing (180 °, 30 min), a bright yellow colored piece is obtained with excellent overall resistance, particularly resistance to light and sublimation, in particular excellent resistance in water. The dye of Examples 2 to 61 can be used in a similar manner, and bright yellow colored pieces with excellent overall strength are obtained.

Claims (10)

PATENT CLAIMS 1. Dye for monoazo dispersion of formula I in which R means phenyl, optionally substituted, or a group of formula R'-O-, R 'means C3-4-alkenyl, C3-4-alkynyl, phenyl or C1-8-alkyl with one or two substituents, R1 means hydrogen or C1-2-alkyl, R2 means hydrogen or halogen, R3 means hydrogen or C1-3-alkyl, e R4 means hydrogen, linear or branched C1-8-alkyl with optionally a substituent, or an amino group with optionally a substituent, the dye being devoid of groups for solubilization in water, and mixtures thereof. 2. Dye according to claim 1, wherein R4 is an unsubstituted linear or branched C1-6-alkyl radical. 3. Process for the production of dyes for monoazo dispersion of formula I, according to claim I, characterized in that a diazotized amine of formula II it is coupled with an amine of formula IIΙ while R1, R2, R3 and R4 have the meanings reported above in claim 1. 4. Process for the production of dyes for monoazo dispersion of formula I, according to claim I, characterized in that a substance of formula IV is condensed with a substance of formula V (V) wherein Hai is a halogen atom and R ,, R2, R3 and R, have the meanings reported above in claim 1. 5. Use of the monoazo dispersion dye of formula I, or of mixtures thereof, according to claim 1 or 2, for dyeing or printing fibers or threads or materials produced therefrom, comprising hydrophobic, fully or partially synthetic organic materials. 6. Use of the monoazo dispersion dye of formula I or mixtures thereof, according to claim 1 or 2, for thermal transfer printing. 7. Use of the monoazo dispersion dye of formula I or mixtures thereof, according to claim 1 or 2, in a rapid dyeing process. 8. Textile material colored with a dye of formula I or mixtures thereof, as claimed in claim 1 or 2. 9. Dye for monoazo dispersion according to claim 1 or 2, obtainable by means of a process according to claim 3. 10. Dye for monoazo dispersion according to claim 1 or 2, obtainable by means of a process according to claim 4.