DE1644399C - Process for the preparation of azo dyes and new monoazo dyes and their use - Google Patents

Description

NH

Y ¹ Π)

NO ₁

Y ²

IO

Synthetic polyester fibers, of which the polyethylene terephthalate the best known are mostly dyed or printed with disperse dyes; these dyes are practically insoluble in water and are water-based on the fiber Dye applied in a state of fine distribution containing dispersions. Many of the present The disperse dyes used volatilize when textiles are heat-treated in an undesirable extent, so that colored fabrics such. B. when ironing undesirable and uneven Changes in color tint suffer and adjacent white fabric parts and those for ironing equipment used can become stained. The same difficulties can arise if at high "5 Disperse dyes which volatilize at high temperatures for dyeing and printing synthetic materials Fibers can be fixed by heating the dry tissue.

Nitro derivatives of diphenylamine, e.g. B. 4-Amino-4 ', 4'-dinitrodiphenylamine (CI Disperse Yellow 9) are used as. Disperse dyes used for yellowing synthetic fibers. Although such relatively simple dyes to "build quickly" and deep yellow staining revealed they have ² S "yoke technical disadvantage that they sublime at those applied to the above mentioned heat treatment temperatures.

Monoazo compounds, which are very sparingly soluble in water, are largely used to achieve scarlet and purple hues used, but many otherwise suitable yellow and orange hues Monoazo compounds show such an undesirable photoiropy that they are not useful. Other yellow and orange monoazo compounds, which do not have the disadvantage of phototropic, evaporate at the temperatures in question for the thermal finishing treatment of thermoplastic fibers comes. Other yellow and orange dyes of different chemical structure, their volatility low are available, but their build-up ability is limited so they are at the usual Dyeing and printing conditions do not result in deep tints. As a result, it is not yet possible been, deep golden yellow and orange tints. which are sufficiently strong on polyethylene terephthalates and similar polyester fibers.

It has been found that the dyes of the formula below are used to dye fiber materials made from polyethylene terephthalate and cellulose triacetate to give orange-brown, golden-yellow and yellow-brown or scarlet shades, and that these dyes sublime to an insignificant extent at the temperatures required for ironing, fixing and similar processes come into question for treating textiles; these dyes have the general formula:

_ _N _ _N _ ^ when Y ¹ denotes hydrogen, and in whichX denotes a nitro group or the group-SO, ■ NR'R> denotes in which R ¹ and R ^{2 are} hydrogen or alkyl groups, particularly 1 to 4 carbon atoms, are lower alkyl groups which not substituted or substituted e.g. B. can be through a hydroxyl group, or the group SO ₂ AIk in the AIk denote an alkyl group containing at most carbon atoms and ^ denotes the remainder of an aromatic hydroxy or aromatic amine coupling component.

The invention now relates to a process for the preparation of new dyes of the general formula I. · _A ■ given above

It is characterized in that one uses an aminonitrodiphenylamine the general formula

NH

Z ¹ (II)

NO ₁

diazotized, in which X has the meaning given above, Z ^{1 is} hydrogen or an NH ₂ group, and Z ^{2 is} hydrogen when Z ^{1 is} NH ₂ , and an NH ₂ group when Z ^{1 is} hydrogen, and the thus formed diazo compounds with an aromatic hydroxy or aromatic amine coupling component.

Suitable aromatic hydroxy components are phenolic compounds, e.g. B. phenol, naphthols, especially /? - Naphthol, the cresols and the phenylphenols. These coupling components result in golden yellow Disperse dyes.

Suitable aromatic amine coupling components are e.g. B. those that have the general formula

(III)

in which Y '- N - N - A or hydrogen, Y ^{1 is} hydrogen. if Y ¹ - N = NA, and have, in which R is hydrogen or a low molecular weight alkyl group, especially methyl, R ^{3 is} hydrogen, a low molecular weight alkyl group, especially ethyl, a low molecular weight Hydroxylalkylgruppc, especially a hydroxyethyl group, a low molecular weight Cyatialkylgruppe, especially a cyanoethyl group, or a

- (CH ₂ J _n - O - C - R * group
O

means in which / 1 is an integer from I to 4, especially 2, and R ^{5 is} a monovalent hydrocarbon radical, especially a low molecular weight alkyl * group, such as methyl, and R ^{4 is} hydrogen,

a low molecular weight hydroxylalkyl radical, especially hydroxyethyl, or a

added in 500 parts of water.
AzofarbstolT of the formula

The so educated

- (CH ₂ ), - O - C - R ⁵ radical
O

is of the type indicated above.

The invention also relates to a method for dyeing or printing fiber material made of synthetic ! isic polyesters or of cellulose triacetate, in which a disperse dye of the above-mentioned general formula I is used.

Finally, the invention also relates to the particularly "valuable dyes used in the following Examples are described in more detail.

example 1

There were 15 parts of 4-amino-2 ', 4'-dinitrodiphenylamine, 200 parts of water and 82.5 parts of aqueous hydrochloric acid (35%) at U to 5 ° C in a suitable, with glass-lined Behjilter stirred together.

A solution of 4 parts of sodium nitrite in 60 parts of water was then slowly added over about 2 hours. The reaction mixture was stirred for 12 hours during which time the temperature was allowed to rise to 15 ° C; then 500 parts of water were added and the yellow diazo solution was freed from insoluble impurities by filtration. The filtered solution was then slowly, with rapid stirring, a ^{solution, cooled to 0 °} C. by adding ice, of 10 parts of ortho-phenylphenol and 30 parts of sodium hydroxide O, N

N = N

NO ₂

separated as an orange precipitate, which was filtered off, washed and treated with a formaldehyde / Grind the cresol sulfonic acid condensation product would.

The dye can be used to dye polyester fibers, it gives golden yellow colors, namely from a boiling water bath, which is used as a carrier z. B. contains dichlorobenzene, or in under Pressure vessels at 125 to 140'C or by padding an aqueous dispersion on the fabric, which is dried and then 30 to 60 seconds is heated to 200 ° C.

Example 2

It was made of 15 parts of 4-amino-2'-nitrodiphenylamine-4'-sulfon-n-butylamide, 54 parts of concentrated hydrochloric acid and 150 parts of water Stirring at 0 "C prepared a solution and then 30 parts of an aqueous IO% sodium nitrite solution added. After stirring for 12 hours, 150 parts of cold water were added, the diazo solution filtered and in a cooled to 0 C solution of 5 parts of para-cresol and 22 parts of sodium hydroxide run in 500 parts of water.

The separating monoazo dye formula

H ₃ C - CH ₂ - CH ₂ - CH ₂ - NH - SO ₂ OH

NH

colors polyester and cellulose acetate fibers golden yellow.

Example 3

15 parts of 4-amino-2'.4'-dinitrodiphynylamine were contained. 5 parts of sodium acetate were then added diazotized as in Example I, and the filtered given and the mixture stirred well and a The slide solution quickly became an aqueous, ice-cold sodium hydroxide solution which was long-chilled to 0C Solution of 8.6 parts of N-ethyl-N-hydroxy-55 sam added to bring the pH to 5-6.

g g yyy

üthyl-m-toluidine in 600 parts of water added, the 12 parts concentrated hydrochloric acid (36%)

g, p g

The precipitating monoazo dye of the formula

O, N

NH

'v- N = N

NO,

CH,

C ₂ H ₅

C ₂ H ₄ OH

dyes polyester fibers oraitgobnuin.

Example 4

If in Example I instead of 4-amino-2 \ 4'-dinilrodiphenylamine 15 parts of 3-amino-2 ', 4'-dini'rodipheny | - amine are used, a similar golden yellow dye is obtained. He has the formula

Claims (6)

Patent claims: 1. Process for the preparation of azo dyes, characterized in that one an aminonitrodiphenylamine of the general form NH means, when Z ^{1 is} hydrogen, diazotized and the diazo compound thus formed with an aromatic hydroxy or aromatic amine coupling component to form a dye of the general formula NH ζ ² αϊ) wherein X denotes a nitro group or the group -SO ₂ NR ¹ R ² in which R ¹ and R ^{2 are} hydrogen or substituted or unsubstituted alkyl groups or the group SO ₂ AIk in which Alk is an alkyl group having at most 4 carbon atoms. Z ^{1 is} hydrogen or an NH ₂ group, Z ^{2 is} hydrogen when Z ^{1 is} an NH ₂ group, and an NH ₂ group 2. Monoazo dye of the formula NO ₂ Y ² wherein X has the meaning given above and Y ^{1 is} - N = NA or hydrogen, Y ^{2 is} hydrogen when Y ^{1 is} -N = NA, and - N = N - - A is when Y ^{1 is} hydrogen, where A means the residue of an aromatic hydroxy or aromatic amine coupling component, couples. NO 3. Monoazo dye of the formula H ₃ C - CH ₂ - CH ₂ - CH ₂ - NH - SO ₂ 4. Monoazo dye of the formula OH NH NO ₂ S. monoazo dye of the formula C ₂ H ₄ OH 6. Process for dyeing or printing fiberglass made from synthetic polyesters or made from colulosctriaccliii. characterized in that the dyes b / \ v prepared according to claim I are kissed. the dyes gcmiiü claim 2 to S used.