DE1644467A1 - Process for making blue anthraquinone dyes - Google Patents

Description

BADISGHE ANIIIN- & SODA-FABRIK AG

Our reference: OZ 24 785 Hee / Gb Ludwigshafen / Rhein, March 21, 1967

Process for the production of blue anthraquinone dyes

This invention relates to anthraquinone blue dyes in general formula

in the A an endomethylene group-containing cycloaliphatisohen Means radical and the anthraquinone ring in positions 5, 6, 7 and / or 8 can still be substituted.

These new dyes are obtained if you use the general formula in Anthraohinonderi

0 NH ₀

Tl I * -

NHA

is in which A is as defined above and the anthraquinone ring in positions 5 »6, 7 and / or 8 can also be substituted, cleaves SuIfönsäuregruppe in the 2-position by reduction.

The anthraquinone derivatives to be used as starting materials can be in positions 5, 6, 7 and / or 8, preferably in one to two of these positions still have substituents, such as halogen atoms or

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Contain sulfonic acid groups. They contain one in the 4-position eye loaliphatisohen containing endomethylene groups bound via the -NH- bridge A remainder derived from, for example, di- or tetrahydro compounds of di- or trimeric cyclopentadiene or from endomethylene groups cyoloaliphatic Seehsringverbindungen and also substituents, e.g. alkyl groups, such as methyl or May contain ethyl groups, halogen atoms such as chlorine atoms, hydroxyl groups, acetoxy groups or amino groups. For example the following residues A. are mentioned:

and

The preparation of these anthraquinone derivatives is detailed in the German patents (patent application B 82 345 IVc / 22b),

(Patent application B 91 198 IVc / 22b) and (patent application B 91 455 IVc / 22b).

The sulfonic acid group in 2-stälung is removed using methods known per se, for example by reduction in a weakly acidic to alkaline medium, preferably in an aqueous medium, or in water-miscible organic solvents such as alcohols, e.g. methanol, ethanol or glycol, lower carboxylic acid

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amides such as dimethylformamide, formamide or N-methylpyrrolidone,
or in mixtures of these liquids with sodium sulfide, sodium dithionite (sodium hydrosulfite), hydroxyalkyl sulfinic acids, zinc or sodium formaldehyde sulfoxylate, glucose, fructose, galactose or cellulose xanthogenate. The reduction is expediently carried out at a moderately elevated temperature, for example at 20 to 100.degree.

After elimination of the 2-position sulfonic acid dyes formed can if necessary be reoxidized, for example by treatment with hydrogen peroxide or air at temperatures up to 100 ⁰ G. Thus, for dyes of the invention, even in cases in which the treatment with the reducing agents not only the Cleavage of the sulfonic acid group in the 2-position of the anthraquinone nucleus, but also a
Caused reduction in the anthraquinone ring. If necessary
the reaction products are precipitated from their solutions with water or with inorganic salt solutions.

The dyes of the formula are of particular interest

fl I

0 NH-R

in the R one of the remainders

and

means.

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With the new dyes you can do synthetic and semi-synthetic Material, preferably textile material made of polyamide, can be dyed and colored in clear blue tones with very good fastness properties to press. The new dyes can also be used like organically soluble dyes and natural or artificial ones for dyeing Resins, waxes, lacquers and plastic compounds, e.g. from cellulose ethers or esters, for example for spin dyeing acetate silk and for dyeing natural or synthetic Polymers or condensation products suitable. For example, they color polyethylene, polystyrene and its copolymers in clear colors blue tones.

The dyes can also be used as a mixture with one another and as a mixture with other dyes, but especially also as a mixture with the Starting dyes containing sulfone groups, from which the new dyes are produced, can be used.

The parts mentioned in the examples are parts by weight.

example 1

51 parts of the dye of the formula

(produced according to Example 1 of the German patent (patent application B 82 345 IVc / 22b)) are in a mixture of

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1250 parts of water and 50 parts of sodium carbonate were stirred vigorously at normal temperature. A mixture of 25 parts of sodium dithionite and 25 parts of sodium carbonate is added in portions, the mixture is stirred for 2 hours at 40 to 45 ^° C., then for 15 hours at normal temperature, another 10 parts of sodium carbonate and 50 parts of sodium dithionite are added and the mixture is kept at 85 to 45 minutes 95 0. It is then filtered while still warm, washed neutral with water and dried. A dye is obtained in a very good yield which dyes polyamide fabric in clear blue shades with very good fastness properties.

Polyamide fabric is dyed with the dye, for example in the following way: 100 parts of polycaprolactam fabric are introduced ^{into a bath at 40 °} C. which contains 2 parts of dye and 1.5 parts of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil in 3000 parts of water. Increasing the temperature of the dyebath for 30 minutes to 95 to 98 ⁰ C and then stained for 90 minutes at 95 to 98 ⁰ G. After the usual completion is obtained a clear blue dyeing having very good fastness properties.

Example 2
10 parts of the dye of the formula

(produced according to example 2 of the German patent (patent application B 82 345 IVc / 22b) ·) are in a mixture of

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250 parts of water and 5 parts of sodium carbonate dissolved warm. A mixture of 5 parts of sodium carbonate and 5 parts of sodium dithionite is then added in portions at normal temperature. The mixture is slowly heated to 35 to 40 ^° C. in about 1 hour and is kept at this temperature for 1 to 2 hours. The dye formed is then filtered off, washed neutral with water and dried. A dye is obtained in good yield which dyes polyamide fabric with good fastness properties in a clear blue.

The procedure for dyeing polystyrene is as follows: 0.2 parts of the dye are dry-mixed with 100 parts of ground polystyrene block polymer in a high-speed mixer. The mixture is melted in a screw press at a cylinder ^{temperature of 200 to 220 °} C. and homogenized. The colored plastic mass is granulated by hot knocking at the nozzle head or by pulling threads with cooling. The granulate obtained in this way is then injected into molded bodies in an injection molding device at 200 to 250 ° or pressed into any desired bodies on presses. Clear blue, transparent injection molded parts of high lightfastness are obtained.

Example 3
41 parts of the dye of the formula

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(prepared according to. Example 2 of the German patent specification (patent application B 82 545 IVc / 22b)) are mixed well in a mixture of 900 parts of water and 40 parts of sodium carbonate. A mixture of 20 parts of sodium carbonate and 20 parts of sodium dithionite is added in portions at 40 to 45 ^{° C. to the mixture.} The mixture is stirred for 2 hours at 40 to 45 ^° C., 15 hours at normal temperature and then heated to 70 to 75 ^° C. At this temperature, a mixture of 40 parts of sodium dithionite and 40 parts of sodium carbonate is added in portions, and the mixture is stirred for 1 hour same temperature, filtered while still warm, washes neutral and dries. A dyestuff is obtained in good yield which dyes textiles made of polyamide in clear blue shades with good fastness properties.

Example 4
To a solution of 10 parts of the dye of the formula

(prepared according to example 1 of the German patent specification (patent application B 82 345 IVc / 22b)) and 5 parts of sodium carbonate in 250 parts of water are added in ^{portions at 60 to 70 °} C. to a mixture of 8 parts of sodium dithionite and 8 parts of sodium carbonate. The mixture is stirred for 1 hour at the same temperature, filtered and washed neutral with water. Receives after drying

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a dye that uses polyamide fabric in good yield dyes clear blue shades with good fastness properties.

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Claims (2)

O.Z. 24,783 patent claims 1. Process for the preparation of blue anthraquinone dyes general formula O MA in which A denotes a cycloaliphatic radical containing endomethylene groups, and the anthraquinone ring can be substituted in positions 5, 6 »7 and / or 8 , characterized in that anthraquinone derivatives of the general formula SO, H 0 NHA in which A has the meaning given above and the anthraohinone ring may still be substituted in positions 5, 6, 7 and / or 8, splitting off the sulfonic acid group in the 2-position by reduction. 2.) Blue anthraquinone dyes of the general formula 0
8 η 0 HHA in dar A an oj'sloaliphatic Ss ~ * ~ tsde ^ et containing endomsthylengruppe and "d $ ^ JLatfor-aofciaonring in s © e stables 5, 6, 7 , -t>'ti"> ■ ■ i:> - ·% Ä Λ ¹ Vi βί- ^ - ^ i- ■ -W. 6 S ::: i-FABRIK AG INSPECTED