DE1444568A1 - Process for the production of new metallized dyes - Google Patents

Description

Patent application

ffcompany Aaiende Colori Nazionali Affini ACNA SpA, Milan

concerning

procedure for the production of new metallized dyes

The present invention, the 1st additional patent to the main patent Hr. · ...'..- ■ (Application A 42 248 IVo / 22a) relates to a process for the production of a new class of metallized dyes with a blue shade, which are particularly suitable for coloring synthetic or natural polyamide materials.

In the parent patent a process for the production of metallized Dyes claimed that differ from azo compounds of the formula

OH

OH

HHH

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where B is an alkyl radical with a low molar weight, derive *

Ea has now been found that monoazo dyes are obtained the dyes that are particularly valuable in metallization for dyeing natural and synthetic polyamide materials in the neutral bath result when a derivative of 1-naphthol is used as coupling agent, which has a chlorine atom in position 4.

The present invention therefore relates to a process for the production of metallized dyes, the sioh of monoazo compounds the general formula

NHH

derive, in which B is an alkyl radical having 1-4 carbon atoms.

In particular, the cobalt complex (ratio of cobalt to monoazo dye of 1: 2) is the monoazo compound

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OH

OH

N = N

Eq

CHgCH,

CHgCH,

a dye which has a brilliant bluish-red hue (eee blue) colors and the excellent properties in terms of purity, affinity in the neutral bath for natural and synthetic Polyamide fibers and good reserve effects (acetate silk and cotton). It is also fast to moisture good and very satisfactory.

According to this process, the monoazo compounds (are obtained by coupling the diazonium compounds of the disulfamide bases with the 4-chloro-1-naphthol) previously dried in the anhydrous phase with a mixture of organic compounds, such as urea dimethylformamide, Urea-ethylene glycol, and the desired metallizing agent (e.g. a cobalt salt such as the acetate or the sulfate, etc.) treated approximately in stoichiometric amount.

The reaction temperature for metallization is kept between about 100 and HO ^{0 C.}

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The metallization time is very short, generally between 30 and 100 minutes. After the end of the metallization, the melt becomes poured into water or diluted with water, an alkali metal hydroxide optionally being added, and the dye obtained is separated by known methods and. dried.

Although the metallization preferably carried out in an anhydrous phase, it can also be carried out in aqueous phase, in the presence of cobalt salts or cobalt complexes voh organic hydroxy acids, at a temperature of 70-90 ° C, preferably at 80 ⁰ C, during 2-3 hours , but the results are not as good as when the metallization is carried out in the anhydrous phase. If the metallization is carried out in the aqueous phase, the dye obtained has a lower solubility and its concentration is lower.

The following examples are intended to illustrate the present invention tern, but without this being limited to this »

example 1

32.5 g of 3, ij-bis-N-ethylsulfamido ^ -amino-phenol are indirectly diazotized at 0-5 ° C by pouring the solution of the sodium salt into dilute hydrochloric acid after adding 6.9 g of sodium nitrite. The whole is neutralized against Congo red by means of a fig sodium carbonate solution; the solution is in an alkaline solution containing 18.7 g of 4-chloro-1-naphthol

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ORIGINAL INSPECTED

ι ι —r r

(* 105 % of the theoretical value) cast. The temperature is between 0 and 5 ° C (volume about 1500 ml; pH about 9.5). After the end of the coupling the monoazo compound is filtered off and dried at .8O ⁰ C.

The dried monoazo compound is at 100 ⁰ C in a micro eohung of 100 g of urea, poured 50 ml of dimethylformamide and 0.05 g of cobalt acetate Mole; the whole is heated ^{to 120 °} C. and kept at this temperature for 1 1/2 hours in order to complete the metallization. The melt is poured into 1 1 water \ ser, were to which 50 ml 36 ⁰ Be NaOH. The dye is precipitated from the solution by salting out at 10% and lowering the pH by adding 45 g of sodium bicarbonate and is then filtered off at 65.degree.

After drying at 80 ⁰ C, a dark blue powder is obtained which natural and synthetic polyamide fibers in blaurötlichem .Farbton (sea blue) dyes, the stain better properties shows fastness to moisture and light respect, than those produced using an aqueous phase Dye was achieved.

Example 2

0.1 g mole of monoazo compound, prepared as described in Example 1, is brewed in the form of a paste in a three-necked flask containing 1000 ml of water and 50 ml of sodium hydroxide.

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The whole thing is stirred until it is completely dissolved. The solution · is acidified exactly against Congo red, by the slow and dropwise addition of 21 ⁰ Be hydrochloric acid; the solution is stirred for 1 hour and then ^{heated to 70 0} G; then 0.05 g mole of cobalt chloride (in a 6% solution) and then sodium hydroxide solution drop by drop are added until there is a slight change in color to phenolphthalein.

The solution is heated to 80-85 ° C and left at this temperature for about 2 hours to complete the metallization reaction. Then the mass in 1 1 of cold water is poured, salted out with 10 $> with sodium chloride, filtered and washed with a 10 $> salt solution. The collected precipitate is dried at 80 ⁰ C.

A dark blue powder is obtained which contains wool and polyamide fibers in a neutral or weakly acidic bath with very good general fastness, in particular light fastness, dyes.

Godparent claims

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ORIGINAL INSPECTED

Claims (9)

Claims 1. Process for the production of new metallized dyes the formula N = N NHH where R is an alkyl radical with 1-4 carbon atoms, according to patent no. ..... (application A 42 248 IVc / 22a), characterized in that the coupling of the diazonium compound the monoazo compound obtained from the sulfamide base of 4-chloro-1-naphthol dried and then treated with the desired metallizing agent, preferably in the presence of a Mi-Bohung from urea and dimethylformamide or ethylene glycol. 2. The method according to claim 1, characterized in that a cobalt salt in a stoichiometric amount as a metallizing agent is used. 3. The method according to claim 2, characterized in that cobalt chloride is used. 909838/1327 _ ₈ _ UU568 4 »Method according to claim 2, characterized in that cobalt acetate is used. 5. The method according to one or more of the preceding claims, characterized in that the metallization reaction in anhydrous Phase is carried out. 6. The method according to claim 5, characterized in that the metallization reaction is carried out at a temperature between approximately 100 and 140 ^° C. 7. The method according to one or more of the preceding claims, characterized in that the metallization reaction is carried out in the 'aqueous phase. 8. The method according to claim 7, characterized in that the metallization reaction at a temperature between 70 and 90 ⁰ C, preferably at 8O ⁰ C, is carried out. 9. The method according to claims 7 and 8, characterized in that the. Metallization reaction using cobalt salts or cobalt complexes of organic hydroxy acids. 909838/1327