US2208932A - Process of producing fast dyeings and the dyed fiber obtained thereby - Google Patents

Description

Patented July 23, 1

UNITED ST TES PATENT OFFICE PROCESS OF PRODUCING FAST DYEINGS AND THE DIED FIBER OBTAINED THERE- No Drawing.

Application February 11, 1939, Se-

No. 255,958. In Germany February 17,

10 Claims.

The present invention relates to a process of producing fast dyeings and to the dyed flber obtained thereby.

We have found that valuable dyeings on cellulose esters and ethers or on hydrophilic artificial highly polymeric bodies, of all kinds, such as fabrics, sheets, moulded articles or latices may be obtained by applying to the highly polymeric body, in an aqueous neutral, acid or alkaline solution or suspension, a condensation product free from sulfonic acid groups, containing a heterocyclic ring, an amino-group capable of being diazotized and a hydroxyl group rendering }5 the coupling possible, and then diazotizing the compound. The self-coupling of the diazo-compound of the amino-hydroxy compound frequently occurs spontaneously; in general, however, it is brought about or completed by a treatment with an agent neutralizing the acid or having an alkaline action.

By the new process it, is, for instance, possible to dye directly sheets from acetyl-, ethylor benzyl-cellulose or from polymerization products the most various shades. Besides the hitherto unknown possibility of dyeing sheets, moulded articles or latices, it is also possible to obtain on fabrics, from the above highly polymeric bodies, particularly acetate silk or acetate silk staple fiber dyeings of good properties of .fastness, the highly polymeric character .of the body being preserved.

As condensation products of theabove-mentioned composition theremay, for instance,-be 35 used the following compounds:

Amino-hydroxy-styryl-quinolines, Amino-aryl-pyrazolones, Amino-hydroxy-benznaphthoxazoles, Amino-hydroxy-naphthobenzoxazoles, Amino-hydroxy-phenylbenzoxazoles, Amino-hydroxy-benznaphthothiazoles, Amino-hydroxy-naphthobenzthiazoles, Amino-hydroxy-phenylbenzthiazoles, Amino-hydroxy-benznaphthimidazoles, Amino-hydroxy-naphthobenzimidazoles, Amino-hydroxy-phenylbenzimidazoles, Amino -arylbarbituric acid. a

The following examples serve to illustrate the 50 invention, but they are not'intended tolimit it thereto: v i

l. 1 kilo of acetate silk yarn is treated for one hour at 85 C., with a suspension in 25 liters of water of 30 grams of finely divided 4-aminobenzal-3-hydroxy-quinaldine l3 hydroxy-2-(4' aminostyryD-quinolinel of the following constitution:

CH=CH N (obtained by condensing 3-hydroxy-quinaldine with paranitrobenzaldehyde in a manner analogous to that described in Berichte der deutschen Chemischen Gesellschaft, volume XX, page 2046, and subsequently reducing the nitro-group). The yarn is then centrifuged and introduced into a batch containing per 30 liters of cold water 30 grams of sodium nitrite and 80 cc. of concentrated hydrochloric acid.

After one hour, the diazotization is complete. The material is again centrifuged and then developed in a bath containing 30 liters of cold water and 80 cc. of ammonia of 25 per cent strength. Thereupon, the material is centrifuged and dried. A deep black dyeing of good fastness to-rubbing and washing is obtained.

Instead of hydrochloric acid there may be used for the diazotization other inorganic acids, such as, for instance, sulfuric acid, or preferably organic acids, such as acetic acid or formic acid.

2. 1 kilo of a sheet prepared from acetyl-cellulose is, according to its thickness, treated, for 1 to 2 hours at 85 C. with a solution containing per 50 liters of water 20 grams of 1-(3'-aminophenyl) -3-methyl-5-pyrazolone and then introduced into a bath containing per 50 liters of water 20 grams of sodium nitrite and 80cc. of formic acid of 85 per cent strength. The base, which has been taken up by the foil is, thereby, diazotized and, for the main part, coupled with itself. After 1 to 2 hours, the diazo-solution is run off, and 50 liters of fresh water and 50 cc. of ammonia of 25 per cent strength are then added. The sheet, which has been dyed a uniform yellow tint ls rinsed with water and dried.

In the same manner, a sheet from ethyl-cellulose is dyed a uniform yellow tint.

3. 1 kilo of an aqueous emulsion of about 50 per cent strength of polyvinyl acetate is intimately mixed with a solution containing per 100 cc. of hot water 10 grams of 1-(3'-aminopheny1)- 3-methyl-5-pyrazolone and the whole is heated to 50 C. to 60 0.; nitrous acid gas is then introduced. The base is thus diazotized, self-coupling simultaneously occurring and a yellow dyestuif being formed. As soon as the depth of color of the emulsion no longer increases, the introduction of gas is interrupted and the excess of nitrous acid is removed by introduction or air. A yellow emulsion is thus obtained which may be further worked up in the usual manner.

The following table illustrates a. number of other dyeings obtainable by self-coupling according to the present invention:

Parent material Shade OH-OH N obtainable by condensing 3-hydroxyquinaldine with meta-nitmbenraldeh de in a manner analogous to that described in erichte der Deutschen Chemischen Gesellschait," volume XVI, page 2000, and subsequenti reducing the nitro-grou 2. l- 4'-aminop enyl)-3-meth?l-5-pyrazo one 3. 1- '-amino-6-chloropheny )-3-methyl-5-pyrazolone...

- obtainable by condensing para-nitrobenzoylchloride with l-amino-ZJ-dihydroxynaphthalene and subsequently reducing the nitro-group.

*uiQ,

Brown.

0 range. Yellow.

Ited.

Scarlet.

obtainable by reducing meta-nltrophenyl-Mrydroxy- N-(D-naphthoxazole, which is prepared by condensing metanitrobanzoyl chloride with 1-amino-2.5- dlhydroxynaphthalene.

Brownorange.

obtainable by reducing the condensation product trom meta-nitro-cinnamic acid chloride and 1.2- diaminoa'i-hydroxynaphthalene.

Brown.

obtainable by reducing the condensation product from para-nitro-cinnamic aldehyde and 1.2-diamin hydroxy-naphthalene.

NH Cl N N NE,

obtainable by condensing 2.3-hydroxynaphthoic acid chloride with 2.4 dinitro-chloro-l-aniline, and subsequently reducing the nitro-groups, the imidazole being simultaneously formed.

Blueish red.

Parent material Shade obtainable by condensing 2.3hydro1'ynaphthoic acid chloride with 1.2-diamino-4-nitroben1-ene and reducing the nitro-imidazole derivative formed.

N NE:

obtainable by condensing 2.3-hyrdoxynapbthoic acid chloride with 2-an1ino-4-nitro-1-hydrorybenzene, and subsequently reducing the nitro-group.

Red.

(JO-CH:

HIN N\ /C O O O-NH obtainable by condensing paranitrmiaphenyl urea with malonic acid and subsequently ucing the nitrogroup.

Orange.

We claim:

1. The process which comprises applying to materials of the group consisting of cellulose esters and ethers and hydrophilic artificial highly polymeric bodies, in an aqueous medium, an aminoaryl-pyrazolone of the following constitution:

wherein X stands for a member of the group consisting of hydrogen and halogen, then diazotizing the compound on the material and causing the diazo-compound to combine with itself.

2. The process which comprises applying to materials of the group consisting of cellulose esters and ethers and hydrophilic artificial highly polymeric bodies, in an aqueous medium, an aminoaryl-pyrazolone of the following constitution:

x-- NH:

aminoaryl-pyrazolone oi the following constitution:

wherein X stands for a member of the group consisting of hydrogen and halogen, then diazotizing the compound 'on the material and causing the diam-compound to combine with itself by passing the diazotized goods through a. bath having an alkaline action subsequently to the discotization process. 4

4. The process which comprises applying to cellulose esters, in an aqueous medium, 1-(3'- aminophenyl) -3-methy1-5-pyrazolone, then diazotizing the compound on the fiber and causing the diazo-compound to combine with itself by an alkaline treatment.

5. The process which comprises applying to cellulose esters and ethers dyed with an ace-- compound obtainable on the fiber by the process claimed in claim 1.

'l. Fibrous material of the group consisting oi cellulose esters and ethers dyed with an azocompound obtainable on the flber by the process claimed in claim 2.

8. Fibrous material of the group consisting of cellulose esters and ethers dyed with an azocompound obtainable on the fiber by the process claimed in claim 3.

9. Fibrous material or the group consisting o! cellulose esters and ethers dyed with an azucompound obtainable on the fiber by the process claimed in claim 4.

10. Fibrous material of the group consisting of cellulose esters and ethers dyed with an azo-compound obtainable on the fiber by the process claimed in claim 5.

GEORG mlinzmm. WERNER KIRST. CARL JOSE]? mm