HK1003161B

HK1003161B - Azo dyes

Info

Publication number: HK1003161B
Application number: HK98101874.2A
Authority: HK
Inventors: Clement Antoine; Tzikas Athanassios
Original assignee: 西巴特殊化学品控股有限公司
Priority date: 1993-05-06
Filing date: 1998-03-06
Publication date: 1998-10-16

Description

The present invention relates to dispersion dyes, their manufacturing processes and their use in the dyeing of textile materials.

Dispersed monoazo dyes are known from EP-A-0 391 121 and differ from the dyes of the invention by the substituents on the diazo component.

The method for staining synthetic fibre materials from organic solvents with dyes which differ from the dyes of the invention by the substituents on the amino nitrogen of the coupling component is known from DE-A-2 308 044.

Dispersion dyes, i.e. dyes which do not contain water-soluble groups, have long been known and used to dye hydrophobic textile material, but the resulting dyes are often not thermally conductive enough.

To overcome this deficiency, special dyes have already been developed with the lowest possible diffusion capacity due to their molecular size and/or bulk. This often makes the application of such dyes difficult, however, as they cannot or only poorly dye after extraction and these dyes usually require undesirably high fixing temperatures even in the thermosol process.

The present invention relates to dispersion dyes which give very thermomigrating dyes but which nevertheless have good structure in the extrusion and thermosol processes as well as in textile printing.

The dyes of the invention are as follows: In which D a remainder of the formula is X hydrogen, methyl, halogen or -NH-CO-R means that R is methyl, ethyl, ethoxy or amino,Y is hydrogen, chlorine or fluorine,R3 is methyl or ethyl,R4 is hydrogen, C1-C6-alkyl or allyl,A1 is hydrogen, chlorine, nitro or cyan,A2 is hydrogen, halogen or cyan,A3 is hydrogen, chlorine, COOCH3 or COOCHCH(CH3) 2) and A4 is nitro or SO2CH3.

In particularly valuable dyes, the formula (1) means X preferably - NH - CO - R or Cl, where R has the meaning defined above.R3 preferably means CH3.R4 preferably means hydrogen or allyl; hydrogen is particularly preferred.A1 preferably means chlorine or cyan.A2 preferably means hydrogen or chlorine.A3 preferably means hydrogen or chlorine.

The new azo dyes of formula (1) can be produced by known processes, for example by diazotizing a compound of formula and attaching it to a coupling component of formula The test shall be carried out on a test vessel with a maximum mass of not more than 10 kg.

The diazotizing of the compounds of formula (3) is carried out in a known way, e.g. with sodium nitrite in an acidic, e.g. hydrochloric or sulphuric, aqueous medium. However, diazotizing can also be carried out with other diazotizing agents, e.g. nitrosyl sulphuric acid. In the process of diazotizing, an additional acid may be present in the reaction medium, e.g. phosphoric acid, sulphuric acid, acetic acid, propionic acid, hydrochloric acid or mixtures of these acids, e.g. mixtures of phosphoric acid and acetic acid.

The coupling of the diazotized compound of formula (3) to the coupling component of formula (4) is also known to occur in a known manner, e.g. in an acidic, aqueous or aqueous organic medium, preferably at temperatures of -10 to 30°C, especially below 10°C. Acids are used, e.g. hydrochloric acid, acetic acid, sulphuric acid or phosphoric acid.

The diazo components of formula (3) are known or can be produced by known means.

The coupling components of formula (4) may also be produced by a known process.

The compounds of the invention of formula (1) may be used as dyes for the dyeing and printing of semi-synthetic and especially synthetic hydrophobic fibre materials, especially textile materials.

The main semi-synthetic textile materials are cellulose 21/2 acetate and cellulose trietric acetate.

Synthetic hydrophobic textile materials consist mainly of linear aromatic polyester, such as those of terephthalic acid and glycols, especially ethylene glycol or condensation products of terephthalic acid and 1,4-bis- ((hydroxymethyl) cyclohexane); polycarbonates, such as those of α,α-dimethyl-4,4'-dihydroxy-diphenyl methane and phosgene, of polyvinyl chloride and polyamide-based fibres.

The compounds of the invention are applied to textile materials by known dyeing processes, for example, polyester fibre materials are dyed by exfoliation from aqueous dispersion in the presence of common anionic or non-ionic dispersions and, where appropriate, common carriers at temperatures between 80 and 140°C. Cellulose-21/2 acetate is preferably dyed at temperatures between about 65 and 85°C and cellulose tetriacetate at temperatures up to 115°C.

The new dyes do not colour wool and cotton present in the dyeing bath at the same time or only slightly (very good reserve), so they can also be used well for dyeing polyester/wool and polyester/cellulose fibre mixtures.

The dyes of the invention are suitable for thermosol dyeing, extrusion and printing processes.

The textile material in question may be obtained in the various forms of processing, such as fibres, yarns or nonwovens, or as woven or knitted fabrics.

It is advantageous to transfer the dyes of the invention to a dye preparation before use. For this purpose, the dye is ground to an average particle size of between 0.1 and 10 microns. The grinding can be done in the presence of dispersants. For example, the dried dye is ground with a dispersant or kneaded into a paste with a dispersant and then dried in vacuum or by serration. The preparations obtained in this way can be used to produce water-based pastes and dyes after addition of water-based presses.

The printing will be made using the usual thickeners, e.g. modified or unmodified natural products such as alginate, British rubber, rubber arabic, crystal rubber, cornmeal, carrier, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products such as polyacrylamides, polyacrylic acids or their copolymers or polyvinyl alcohols.

The dyes of the invention give the materials, especially the polyester material, uniform hues of very good reliability, such as particularly good thermofixation, pleasing, chlorine and wet proofness, water, sweat and wash resistance; the discolorations are also characterized by very good wear resistance.

The dyes of the invention may also be used to produce mixtures of colours with other dyes, and of course mixtures of the dyes of the invention may also be used with each other.

In addition, the dyes of the invention are also well suited to the dyeing of hydrophobic textile material from supercritical CO2.

The above-mentioned use of the azure compounds of formula (1) is also the subject of the present invention, as is a process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material, particularly textile material, consisting of applying or incorporating one or more compounds of formula (1) onto or into the said material. The said hydrophobic fibre material is preferably textile polyester material. Further substrates which can be treated by the method of the invention and preferred conditions are to be found in the further description of the use of the compounds of the invention.

The invention also relates to hydrophobic fibre material, preferably polyester textile material, dyed or printed by the above-mentioned process.

The dyes of the invention of formula (1) are also suitable for modern recording processes, such as thermal transfer printing.

The following examples illustrate the invention without limiting it to parts and percentages, which refer to weight, unless otherwise stated.

Example 1: 10.7 g m-toluidine, 45 ml 2-chloropropionic acid methyl ester, 10 g sodium carbonate and 0.5 g sodium bromide are stirred for 18 hours at 125°C to 130°C. The reaction mixture is then cooled to room temperature and extracted with acetic acid/water mixture. The acetic acid ester phase is then compressed in the rotary evaporator. 3,3 g 2-cyan-4-nitroaniline are diazotized in concentrated sulphuric acid in the usual way and coupled at a pH between 3 and 5 to an equivalent amount of the coupling components described above. The raw product obtained by filtration is added to 100 ml of methanol, stirred for 2 hours at return temperature and hot filtered. After drying, 6 g of crystals are obtained with a melting point of -177°C. The dye has the formula Other

He dyes polyester textiles in red tones, which are very authentic, and in particular, they are thermally and light-tight.

Example 2: 16.4 g 3-propionamide aniline, 11.7 g baking soda, 1.6 g sodium bromide and 50 ml 2-chloropropionic acid methyl ester are stirred for 5 hours at 120-130°C. The reaction mixture is then cooled to 120°C, filtered hot and washed with 20 ml 2-chloropropionic acid methyl ester. The filtrate is pressed on the rotary evaporator. 17.3 g 2-chloro-4-nitroaniline are diazotized in concentrated sulphuric acid in the usual way and coupled at a pH of 3 to 5 to an equivalent amount of the coupling component described above. The raw product obtained by filtration is added to 100 g of water and stirred for 1 hour at 95 to 97 °C, then cooled to 70 °C and filtered. Other

He colors textile materials made of polyester in bright red hues.

Examples 3 to 47:

The following dyes can also be produced using the method described in examples 1 and 2: they dye textile materials from polyester in the shades shown in the last column of Tables 1 to 8

Claims

A dye of the formula wherein D is a radical of formula
X is hydrogen, methyl, halogen or -NH-CO-R, wherein R is methyl, ethyl, ethoxy or amino;

Y is hydrogen, chloro or fluoro

R₃ is methyl or ethyl;

R₄ is hydrogen, C₁-C₆alkyl or allyl;

A₁ is hydrogen, chloro, nitro or cyano;

A₂ is hydrogen, halogen or cyano,

A₃ is hydrogen, chloro, COOCH₃ or COOCH(CH₃)₂ and

A₄ is nitro or SO₂CH₃.
A dye according to claim 1, wherein R₄ is hydrogen.
A dye according to either claim 1 or 2, wherein X is -NH-CO-R or chloro, where R is as defined in claim 1.
A dye according to any one of claims 1 to 3, wherein R₃ is methyl.
A dye according to any one of claims 1 to 4, wherein Y is hydrogen or chloro and R₃ is methyl.
A dye according to claim 1, wherein A₁ is chloro or cyano.
A dye according to claim 1, wherein A₃ is hydrogen or chloro.
A dye according to claim 1, wherein A₁ is chloro or cyano, A₂ is hydrogen or chloro, A₃ is hydrogen or chloro, and A₄ is nitro or SO₂CH₃.
A dye according to claim 1, of formula
A process for the preparation of a dye of formula (1) according to claim 1, which comprises diazotising a compound of formula and coupling the diazonium salt to a coupling component of formula in which
A₁ is hydrogen, chloro, nitro or cyano;

A₂ is hydrogen, halogen or cyano,

A₃ is hydrogen, chloro, COOCH₃ or COOCH(CH₃)₂,

A₄ is nitro or SO₂CH₃,

X is hydrogen, methyl, halogen or -NH-CO-R, wherein R is methyl, ethyl, ethoxy or amino, and

Y is hydrogen, chloro or fluoro,

R₃ is methyl or ethyl, and

R₄ is hydrogen, C₁-C₆alkyl or allyl.
A process according to claim 10, wherein R₄ is hydrogen.
Use of a dye according to claim 1 for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material, especially textile material.
Use according to claim 12 for dyeing or printing polyester fibre textile material.
A process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material, especially textile material, which comprises applying to, or incorporating in, said material one or more than one compound as defined in claim 1.
A process according to claim 14, wherein the hydrophobic fibre material, preferably textile material, consists of polyester fibres.
The material dyed or printed according to claim 14 or 15.