DE2506098A1 - NEW DIOXAZINE DYES, THEIR PRODUCTION AND USE - Google Patents

Description

New dioxazine dyes, their production and use

The present invention relates to new dioxazine dyes of the formula

HO ₃ S-Ar-B

B-Ar-SO ₃ H

(D

wherein

X chlorine or bromine,

Z hydrogen, chlorine or br on,

B is an oxygen atom and - · - -. ·

Ar is an arylene radical.

Arylene radicals are mainly benzene, Understood naphthalene or diphenyl series. The symbol Ar thus denotes radicals such as α- or ß-naphthylene, diphenylene and preferably optionally substituted phenylene radicals.

As a substituent of the latter are low molecular weight Alkyl radicals, cycloalkyl, in particular cyclohexyl and methylcyclohexyl, Aralkyl, especially benzyl, phenyl as well

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To name halogen atoms. With "low molecular weight" Denotes radicals with 1 to 4 carbon atoms: and the term "halogen atoms" here includes fluorine and, in particular, chlorine and bromine.

The new dyes are produced according to the invention, by making a compound of the formula

sulfonated.

The sulfonating agent used is oleum or concentrated sulfuric acid, preferably sulfuric acid monohydrate. The reaction is generally carried out at from 10 to 30 ^° C., preferably around room temperature.

The dyes are expediently isolated in the form of their salts, in particular as alkali salts.

The starting compounds of the formula (2) are obtained in a known manner if a 2,5-diarylaminobenzoquinone is used the formula

, Z.

B-Ar-H (4)

where V is hydrogen, alkoxy, aralkoxy, alkyl mercapto, aryloxy, aralkyl mercapto cd he is aryl mercapto and X, Z, B and Ar have the meaning given, subject to a ring closure leading to dioxazines. Because of their easy accessibility, those are dyes

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preferred in which the symbols X, Z, B and Ar have the following Have meanings:

X: chlorine atom
Z: hydrogen atom B: oxygen atom

Ar: optionally substituted by low molecular weight alkyl, in particular methyl Phenyl radical.

The new dioxazine dyes are suitable for dyeing and printing a wide variety of materials, especially for natural or especially synthetic polyamide materials such as wool, silk, leather and especially nylon, also for

Synthetic fibers made from casein or polyurethane. One obtains in particular on synthetic polyamides with the new dyes have strong, brilliant, fluorescent shades, especially orange to red tones, which cannot be achieved with azo dyes.

They are particularly suitable for combination dyeing. So By combining it with other dyes, e.g. a non-fluorescent yellow, a fluorescent one can be created Achieve orange.

The dyes generally have good fastness properties such as fastness to light, rubbing, decaturation and carbonization, but above all high wet fastness (fastness to washing, water, sea water, alkali, perspiration). The high degree of extension should be emphasized and the good leveling capacity for dyeing on polyamide. In particular, a good covering of the Achieve streakiness on synthetic polyamide. The new dyes have good stability. You own

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is also suitable for high-temperature dyeing and for differential dyeing in carpet dyeing. In the following examples, unless otherwise stated, parts are parts by weight, percentages are percentages by weight and temperatures are given in ⁰ C. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.

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CLBA-GEIGY AG example 1

One carries 20 parts of the compound of the formula

Cl

Cl

at a temperature of 20-22 ° in 180 parts of sulfuric acid monohydrate and then stirs the bright blue solution obtained for 4 hours with the same Temperature. The solution is then poured onto a mixture of 300 parts of ice and 200 parts by volume of 25% sodium chloride solution. The precipitated dye is filtered off and washes the filter material twice with 5% sodium chloride solution. The filter material is now taken in 250 parts by volume Water and adjusts the pH of the slurry by adding dilute sodium hydroxide solution to 7, with a Precipitation of the sodium salt of the dye is obtained. It is filtered off and dried in vacuo at 70 °. The obtained dye of the formula

SO well. dyes synthetic polyamide from weakly acidic bath in

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very brilliant yellow-tinged red tones. The colorations are good wet-fast and are characterized by an intense fluorescence.

If, with otherwise the same procedure, equivalents are used instead of the dioxazine compound listed at the outset Amounts of the dioxazines listed in Table 1 below, this gives dyes with similar properties.

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- ir

Table I *

Dioxazine compounds nuance on polyamide

Cl Cl

CH,

H,

Cl Cl

Cl Cl

Cl

Red

bluish red

yellowish red

Red

I blue ig-. Red

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Table I (continued)

Dioxazine compounds nuance on polyamide

^ci

egg

Cl

Cl

^CH

Cl Cl

yellowish red

Red

bluish red

yellowish red

Red

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Table I (continued)

Ί Cl X ^H 3 ^C CH bluish tint
Red Cl N j ^
Cl γΤ
^ 0 yellowish
Red ■ Γ 3
CH ₃ yellowish
Red ' ^H 3 ^G H ₃ C ^ yellowish
Red H ₃ C CH,
ι T v * i- cede yellowish
Red H ₃ C I.
Cl Y] Cl Ύ ° - "^ CH ₃ / ^ CR ₃ Γ
CH ₃

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Table I (continued) _% / fö »

CH,

HC

'XX

CH _Q
ι j

H "CC
r '

^H 3 ^C

Cl

Cl

Cl

Cl

Cl

Cl

Cl

^C1

Cl

CH- CH-

J

CH ₃

Cl

yellowish red

yellowish red

bluish red

Red

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Example 2

In a 40 ° warm solution, containing 5000 parts by volume Water 1.0 part of the dye of the formula

2.0 parts of a dyeing aid (mixture of dodecyldiphenyl ether sulfonate and the addition product of 20 mol of ethylene oxide with stearlyamine, quaternized with dimethyl sulfate, in a mixing ratio of 10: 1), which has been adjusted to pH 5.0 with acetic acid / sodium acetate, is added to 100 Parts of a jersey made of textured! Polyamide 6,6. With constant movement of the dye liquor, the bath is heated to boiling within 45 min Hour at boiling temperature. Then the material to be dyed is rinsed thoroughly with cold water and, dry it. You get a scarlet color of perfect levelness, which has very good wet fastness properties.

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Example 3

In a 40 ° warm solution, containing 5000 parts by volume Water 0.40 parts of the dye of the formula

1.10 parts of the yellow azo dye of the formula

and 2.0 parts of a dyeing aid (mixture of dodedyl diphenyl ether sulfonate and the adduct of 20 mol of ethylene oxide with stearylamine, quaternized with Dimethyl sulfate, in a mixing ratio of 10: 1), which has been adjusted to pH 5.0 with acetic acid-Na acetate, is added 100 parts of a jersey made of textured polyamide-6,6. With constant agitation, the bath is heated to the boil over a period of 45 minutes with dye liquor and the dye is dyed for 1 Hour at boiling temperature. During the dyeing process, the same orange shade is observed from the beginning coloration obtained at the end. You then rinse the dye

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- ', 12-

Rait kai tern water well thoroughly and dry it. An orange coloration of perfect levelness is obtained, which has very good wet fastness properties »

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Claims (12)

CfBA-GEEGYAG Claims 1. Dioxazine dyes of the formula HO S-Ar-B worm _f X chlorine or bromine, Z hydrogen, chlorine or bromine, B is an oxygen atom and Ar is an arylene radical. 2. Dioxazine dyes according to claim 1, wherein Ar is an optionally substituted phenylene radical. 3. Dioxazine dyes according to Claims 1 and 2, wherein X is a chlorine atom. 4 «Dioxazine dyes according to Claims 1 to 3, where Z is hydrogen. 5 »Dioxazine dyes according to claims 1 to 4 of the formula Cl (3) wherein Y is a low molecular weight alkyl radical or hydrogen. 5 0 9 8 3 4/0 CLBA-GEIGY AG 6. Process for the production of dioxazine dyes the formula HO ₃ S-Ar-B CD in which. X chlorine or bromine, Z hydrogen, chlorine or bromine, B is an oxygen atom and
Ar is an arylene radical, characterized in that one is a compound of the formula H-Ar-B B-Ar-H (2) reacts with a sulfonating agent. 7. The method according to claim 6, characterized in that \ draws that one starts from compounds of the formula (2) in which Ar is an optionally substituted phenyl radical is. 8. The method according to claims 6 and 7, characterized characterized in that one starts from compounds of the formula (2) in which X is a chlorine atom. 9. The method according to claims 6 to 8, characterized in that one of compounds of the formula (2) 50 9834/0876 75.11.329 CIBA-GEIGY AG starts out, wherein Z is hydrogen. 10. The method according to claims 6 to 9, characterized in that one of compounds of the formula starts out, wherein Y is a low molecular weight alkyl radical or hydrogen. 11. A process for dyeing and printing using those defined according to claims 1 to 5 or according to Claims 6 to 10 obtained dyes. 12. The dyed or printed material obtained according to claim 11. 509834/0876