US2213193A - Process of producing fast dyeings - Google Patents

Description

' Patented Sept. 3, 1940 UNITED STATES PATENT OFFICE PROCESS OF PRODUCING FAST DYEIN N Drawing. Application June 6, 1938, Serial No. 212,134. In Germany June 7, 1937 8 Claims.

The'present invention relates to the production of fast dyeings and 'to the dyed fibre obtained thereby.

I have found that dyeings of good properties of fastness may be obtained by applying to the fibre a sulphonic acid or a sulphonate of a hydroxy-naphtho-oxazole, -thiazole, or -imidazole, substituted at the carbon atom of the heterocyclic ring, by the radical of an aromatic hydrocarbon which contains an amino-group capable of being diazotised and which may contain one or more substituents, then diazotising the compound and coupling it with itself or another diazo compound from an amine of the constitution indicated above which has been applied to the fiber in the same bath. The self-coupling may be performed or completed, for instance, by treating the diazo-bath with an agent neutralising the acid or by passing the fibre through a bathhaving an alkaline action.

As compared with the process of preparing insoluble azo-dyestnffs on the fibre by self-coupling amino-arylides of hydroXy-carboxylic acids as described in German Patent No. 552,926 and 25 with the self-coupling dyestuffs of the 2.3-hydroxy-naphthoic acid arylide series disclosed by J. S. Turski (Melliands Textilberichte, 1937, vol. 18, part 1, page '75), the new process has the considerable advantage that the components can also be brought onto the fibre in a neutral or a feebly acid solution. The process may, therefore, be applied to animal fibres without the fibre being damaged.

The new process is, moreover, distinguished by 35 a high degree of certainty in the dyeing operation. If compounds of the following general formula are used:

Hols

wherein X stands for oxygen, sulphur or the which are distinguished by a very good fastness.

to wet processing and by a good fastness to rubbing.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto:

(1) 1 kilo of mixed yarn consisting of 30 percent. of staple fibre made by the viscose process and '70 per cent. of wool is treated, for one hour at 85 C., with a solution containing per 24 litres of the liquor 30 grams of the ammonium salt of 3' amino C phenyl -1.2-(N) -imidazolo-5.-hydroxynaphthalene-7-sulphonic acid of the following constitution:

HOaS NH:

30 grams of sodium nitrite grams of formic acid of per cent. strength and 30 grams of sodium dibutylnaphthalene-sulphonate in 30 litres of cold water.

The material is then centrifuged and developed in 30 litres of cold water containing 45 cc. of ammonia of 25 per cent. strength and 15 cc. of a solution of 30 per cent. strength of the product obtained by causing ethylene oxide to act upon octodecyl alcohol.

(obtainable according to Example 2 of German Patent No. 165,126) a red tint having the same good properties of fastness is obtained.

(3) 1 kilo of a mixed yarn consisting of 30 per cent. of viscose staple fibre and 70 per cent. of wool, is treated, for one hour at 85 C., with a solution containing per 24 litres of the liquor 15 grams of the ammonium salt of 3'-amino-C- phenyl-1.2-(N) -imidazolo-5 hydroxy naph thalene-l-sulphonic acid,

15 grams of the ammonium salt of 3'-amino-4'- methoxy C phenyl 1.2-(N) -thiazolo-5hydroxy-naphthalene-7-sulphonic acid of the following constitution:

s cQ-ooin (made by the process of German Specification No. 165,126 by causing meta-nitro-para methoxy-benzaldehyde to act in the presence of a polysulphide upon sodium 2.5-aminonaphthol- 7 -sulphonate and transforming the product obtained into the ammonium salt) and grams of ammonium sulphate;

Thereupon, the goods are squeezed, centrifuged or rinsed and treated for half an hour with a solution containing per 30 litres of cold water:

15 cc. of a solution of 30 per cent. strength of the product of the action'of ethylene oxide upon octodecyl-alcohol and 30 grams of sodium carbonate;

the goods are then rinsed and dried. A bluish-red tint is obtained which has very good properties of fastness to washing and fulling and a good fastness to rubbing.

(4) 1 kilo of wool is treated for one hour at 95 C. with 30 grams of the ammonium salt of 3'-amino-C-phenyl-1- (N) -2-oxazolo5-hydroxynaphthalene-'l-sulphonic acid of the following constitution:

Q J) N H:

' HOzS (obtainable according to Examples 2 and 3 of German Patent No. 165,102) and 80 grams of ammonium sulphate in 30 litres of water, rinsed and treated in the cold, for half an hour, with 20 litres of water containing 30 grams of sodium nitrite and 80 grams of formic acid of per cent. strength 50 grams of sulphuric acid of 96 per cent.

strength.

The wool is then squeezed 0r rinsed and developed, within the course of half an hour, in a bath containing 40 cc. of ammonia of 25 per cent. strength in 30 litres of cold Water.

After rinsing and drying, a beautiful scarlet tint of very good fastness to washing and fulling is obtained.

(5) 1 kilo of natural silk is treated, at a temperature of 80 C. with 30 grams of the ammonium or sodium salt of 3'-aminoC-phenyl- 1.2- (N) -imidazolo-5-hydroxynaphthalene-7- sulphonic acid (cf. Example 1) and 300 grams of sodium sulphate in 30 litres of water, squeezed and treated for half an hour with 30 litres of cold water containing 30 grams of sodium nitrite and 80 grams of formic acid of 85 per cent. strength.

The silk is squeezed and then developed, for half an hour, in a bath of 30 litres of cold water containing 45 cc. of ammonia of 25 per cent. strength and 15 cc. of a solution of 30 per cent. str ngth of the product obtained by the action of ethylene oxide upon octodecyl-alcohol.

After rinsing and drying, a beautiful red tint of very good properties of fastness is obtained.

(6) When using, instead of 30 grams of the ammonium salt of 3'-amino-C-phenyl-1-(N )-2- oxazolo-5-hydroxynaphthalene-7-sulphonic acid (of. Example 4) 30 grams of the ammonium salt of 3 amino 4' 4 methoxy-C-phenyl-LZ-(N) thiazolo-5-hydroxynaphthalene-7-sulphonic acid of the following constitution:

diazotizing and developing with 60 grams of sodium carbonate in 30 litres of cold water, a

Bordeaux tint of very good fastness to washing and fulling is obtained.

(7) 1 kilo of viscose staple fibre is treated for one hour at 70 C. with 30 grams of the sodium salt of 3'-amino-C-pheny1-1.2-(N)-imidazolo-5- hydroxynaphthalenefl-sulphonic acid (cf. Example 1) and 600 grams of sodium chloride in 30 litres of water. The fabric is then squeezed and treated for half an hour with 30 litres of cold water containing 30 grams of sodium nitrite and cc. of hydrochloric acid of 20 B.

It is then again squeezed and treated for half an hour in the cold with 30 litres of water containing 60 grams of sodium carbonate and 15 cc. of a solution of 30 per cent. strength of the product obtained by the action of ethylene oxide upon octodecyl alcohol.

After rinsing and drying, a vivid red tint of very good fastness to washing and rubbing is obtained. 4

(8) A fabric of viscose staple fibre or of cotton is printed with a printing paste 1 kilo of printing color containing per 175 grams of solution, 500 grams of wheat starch tragacanth thickening and 25 grams of sodium nitrite, dissolved in 280 grams of water.

Afterv printing and drying, the fabric is steamed for about 10 minutes, in a room containing an acid vapour for instance that obtained by evaporating a mixture of 25 parts of acetic acid of 50 per cent. strength and 5 parts of formic acid of 85 per cent. strength; it is then passed through a bath containing per litre of water 10 grams of sodium carbonate, rinsed, soaped, rinsed again and dried. Alternatively, instead of being steamed or, if desired, after steaming the fabric is passed through a dilute acid solution (for instance, 50 grams of formic acid of 85 percent. strength per litre of water) then exposed to air and treated in a dilute sodium carbonate bath; it is then rinsed, soaped, rinsed again and dried. Beautiful prints of good properties of fastness are obtained.

Various printing effects may also be obtained by padding the fabric in the presence of sodium nitrite with an alkali salt of a compound of the following constitution:

wherein X and R have the meaning indicated above, printing it with a non-volatile acid and passing it through an alkaline bath or printing it with a reducing agent, if desired together with a vat-dyestuif and steaming, then steaming in the presence of an acid or passing it through an acid bath and subsequently through an alkation:

H038 NR2 (obtainable according to German Patent Specification No. 172,319 by causing meta-nitro-paramethoxybenzoyl chloride to act-upon 1.2-diamino- '5-hydroxynaphthalene-7-sulphonic acid and reducing the nitro compound formed). The whole is then cooled to about 70 C., by adding 600 grams of sodium sulphate dissolved in 6 litres of cold water. It is allowed to stand, at the said temperature, for about one hour, then rinsed and .allowed to stand at falling temperature.

treated for half an hour in a fresh bath contain ing:

30grams of sodium nitrite 80 grams of formic acid of 85 per cent. strength and 30 grams of sodium dibutylnaphthalene-sulphonate in 30 litres of cold water.

To this bath 230 cc. of an ammonia solution of 25 per cent. strength are added and the whole is further treated in the same bath for another half an hour. The material is then rinsed and dried; a beautiful Bordeaux tint of very good fastness to rubbing, washing, fulling, perspiration and sea-water is obtained. 1

(10) 1 kilo of mixed yarn consisting of 30 per cent. of viscose staple fibre and 70 per cent. of wool is treated, for one hour at 85 0., with a solution containing per 24 litres of the liquor 30 grams of ammonium sulphate and 30 grams of the sodium salt of 4-aminobenzoyl-3'-amino-C- phenyl 1.2 (N) imidazolo-5-hydroxynaphthalene-7-sulphonic acid of the following constitu- Hols H (obtainable by causing 3-amino-C-phenyl-1.2- (N) -imidazolo hydroxynaphthalene 7 sulphonic acid of Example 1 to react with para-nitrobenzoyl chloride and reducing the nitro compound obtained according to German Specification No..240,827). The whole is then cooled to about 70 C., by addng 600 grams of sodium sulphate dissolved in 6 litres of cold water and is The material is then centrifuged and treated in the cold for half an hour in a fresh bath containing 30 grams of sodium nitrite 80 grams of formic acid of 85 per cent. strength and 30 grams of sodium dibutylnaphthalene-sulphonate in 30 litres of cold water The material is then centrifuged and developed 30 litres of cold water containing 80 cc. of ammonia of 25 per cent, strength and 15 cc. of a 30 per cent. solution of the product of the action of ethylene oxide upon octodecyl alcohol.

NH-C

' t HOaS NIELCO Hons (obtainable by causing 3'-amino-4'-methoxy-C- phenyl- 1.2- (N) -imidazolo-5hyroxynaphthalene- 7-sulphonic acid described in Example 9 to react with para-nitro-benzoyl chloride and reducing the nitro compound obtained), or 30 grams of the sodium salt of 3"-amino-benzoy1-3'-amino- 4-methoxy-C -phenyl- 1.2 -(N) -imidazolo- 5 -hydroxynaphthalene-7-sulphonic acid of the following constitution:

HOaS

(obtainable by causing 3'-amino-4-methoxy-C- phenyl 1.2-(N)-imidazolo-B-hydroxynaphthalene-7-sulphonic acid described in Example 9 to react with meta-nitro-benzoyl chloride and subsequent reduction), or 30 grams of the sodium salt of 3"-amino-benzoyl-4'-amino-C-phenyl- 1.2 (N) imidazole-5-hydroxynaphthalene-7- sulphonic acid of the following constitution:

I H NHEOQ H I NH:

HOaS N (obtainable by causing 4-amino-C-phenyl-1.2- imidazolo -5- hydroxynaphthalene-'7-sulphonic acid to react with meta-nitro-benzoyl chloride and subsequently reducing), or 30 grams of the sodium salt of 3"-amino-4"-methoxybenzoyl-4'- amino C-phenyl1.2-(N) -imidazolo-5-hydroxy naphthalene-'Z-sulphonic acid of the following constitution:

NH-T-ONELCOQO 0H: bi NH:

HOQS

(obtainable by causing 4'-amino-C-phenyl-1.2- (N) imidazolo 5-hydroxynaphthalene-'7-su1- phonic acid to react with meta-nitro-paramethoxy-benzoyl chloride and reducing the nitro compound).

(13) 1 kilo of mixed yarn consisting of 30 per cent. of viscose staple fibre and I0 per cent. of wool is treated, for 1 hour at 85 C.,' in a bath containing per 24 litres of the liquor grams of ammonium sulphate and 30 grams of the ammonium salt of 3'.'-amino-4"-methoxybenzoyl- 3' amino-C phenyl-1.2(N) -imidazolo-5hydroxynaphthalene-7-sulphonic acid, 600. grams of sodium sulphate dissolved in 6 litres of water are then added to the bath and the whole is treated, for another hour at 70 C., in the same bath.

The material is squeezed, diazotised in. the cold, the proportion of the goods to the liquor being 1:30, with 30 grams of sodium nitrite and 80 cc. of formic acid of 90 percent. strength; it is then squeezed and developed in the cold in a fresh bath with 80 cc. of ammonia of 25 per cent. strength, the proportion of the goods to the liquor being 1:30. The material is rinsed hot and cold; there is obtained a bluish-red of very good fastness to wet processing which, when treated at 90 C. with 3 per cent. of copper sulphate and 2 per cent. of acetic acid, turns to a Bordeaux tint.

The following table shows the tints of a number of other dyeings obtainable according to the present invention:

Parent component Tint 3' amino 4' ethylsulphonyl C phenyl 1.2 (N) imidazolo 5 hydroxynaphthalenc -7 sulphonic acid (obtainable by causing 3-nitro- 4-ethyl-sulphonyl-benzoyl chloride to act upon l.Z-diemino-S-hydroxynaphtha1ene-7-sulphonic acid and reducing the nitro-compound) 3-amino-4-mcthylsulphonyl-O-phenyl-l .2- (N) imidezolo-5-hydroxynaphthaienc-7-sulphonic acid (obtainable by causing 3-nitro4-methylsulphonyl-bcnzoyl chloride to act upon l-2.diamino-5-hydroxynaphthalcnc-7-suipl1onic acid and reducing the nitro compound).

3"-amino'4-methylsulphonyl-bcnzoyl-y-aminm C -pheny1-l.2- (N) -imidazolc-5-hydroxynapl1- thalene-7-sulphonic acid (obtainable by causing 3-amino-C-phenyl-l.2-(N) -imidnzolo- 5- hydroxynaphthalene-Tsul honic acid to react with 3-nitro-4-methy1sulp onyl-bcnzoyl chloride and reducing the nitro-compound).

3"-amino-4"-ethylsulphonyl-benzoyl3-amino- C-phenyl-l.2-(N )-imidazolo-5-l1ydroxy-nnphthalcne-7-snlpl1onic acid (obtainable by causing 3'-amino-C -phenyl-l.2- (N) -imidnzolo-5- hydroxynaphtbalene-Wsulphonic acid to react with 3-nitro-4-ethyl-sulphonyl-benzoyl chloride and reducing the nitro compound).

Brown-orange.

Yellowish-red.

(14) 1 kilo of mixed yarn consisting of 50 per cent. of wool and 50 per cent. of viscose staple fibre is treated in 24 litres of water, for one hour at C. with 20 grams of ammonium sulphate and 50 grams of a compound of the following constitution NH(|,iOH=H CONH:

(obtainable by causing 1.2-di'amino-5-hydr0xynaphthalene-'i-sulphonic acid to react with para-nitro-cinnamic aldehyde and subsequently reducing the nitro-compound). 600 grams of sodium sulphate dissolved in 6 litres of cold water, are then added and the material is further treated for one hour at 70 C. centrifuged and 30 grams of sodium nitrite.

30 grams of sodium dibutylnaphthalene-sulphonate and 80 cc. of hydrochloric acid of 20 B. in 30 litres of cold water.

The material is then centrifuged and developed for half an hour in the cold with 80 cc. of an ammonia solution of 25 per cent. strength in 30 litres of water. After rinsing and drying a reddish black of very good fastness to rubbing and to wet processing is obtained.

(15) 1 kilo of mixed yarn consisting of 50 per cent. of wool and 50 per cent. of viscose staple fibre is treated for one hour at 95 C. in 24 litres of water with 80 grams of ammonium sulphate and 30 grams of a compound of the following constitution NHILCH=H Q (obtainable by causing 1.2-diamino--hydroxynaphthalene-7- sulphonic acid to react with meta-nitroecinnamic acid chloride and subsequently reducing the nitro compound). 600 grams of sodium sulphate, dissolved in 6 litres of cold water, are then added and the material is further treated for one hour at about 77 C. The material is centrifuged, diazotised and developed as indicated in Example 14; a brown of very good properties of fastness is obtained.

(16) If there are used in Example 1 instead of the compound described therein, 30 grams of the sodium salt of 3"-amino-4"-methoxybenzoyl- 3- amino-C-phenyl 1.2 -(N) imidazolo 5 hydroxy-naphthalene-7-sulphonic acid of the following constitution:

NM NH.

N Ii m HOaS NH:

(obtainable by causing meta-nitro-para-chlorobenzaldehyde or meta-nitro-para-chloro-benzoyl chloride to react with 1.2-diamino-5-hydroxynaphthalene-'Z-sulphonic acid and reducing the nitro compound obtained), a yellowish-red tint is obtained.

(18) A bluish-red tint is obtained by using in Example 10 instead of the compound described therein, 30 grams of the sodium salt of 3'-amino- 4'- methyl C phenyl-LZ -(N) imidazolo-5-hydroxynaphthalene-l-sulphonic acid of the following constitution:

NEE-EQCHa H0: NH:

of 5 hydroxy-'I-sulpho 1.2 naphtho-oxazoles,

5-hydroxy-7-su1pho-1.Z-naphthothiazoles and 5-hydroxy-7-sulpho1.2-naphtho-imidazoles sub-' stituted at the carbon atom of the heterocyclic ring by an aromatic radical containing an amino group capable of being diazotised, then diazotising the compound on the fibre and coupling it with itself.

2. The process which comprises applying to the fibre anamino compound of the group consisting of 5-hydroxy-7-sulpho-1.2-naphtho-oxazoles, 5-hydroxy-7-sulpho 1.2 naphtho-thiazoles and 5 hydroxy 7 sulpho 1.2 naphtho-imidazoles substituted at the carbon atom of the heterocyclic ring by a radical of the benzene series containing an amino group capable of being diazotised, then diazotising the compound on the fibre and coupling it with itself.

3. The process which comprises applying to the fibre an amino compound of the group consisting of 5 hydroxy '7 sulpho-1.2-naphtho-oxazoles, 5-hydroxy '7 sulpho-1.2-naphtho-thiazoles and 5-hydroxy-7-su1pho-1.2-naphtho-imidazoles substituted at the carbon atom of the heterocyclic ring by a radical of the benzene series containing an amino group capable of being diazotised, then dia'zotising the compound on the fibre and coupling it with itself by adding to the diazo bath an agent neutralising the acid.

4. The process which comprises applying to the fibre an amino compound of the group consisting of 5 hydroxy '7 sulpho-1.2-naphtho-oxazoles, 5-hydroxy 7 sulpho-1.2-naphtho-thiazoles and 5-hydroxy-7-sulpho-1.2-naphtho-imidazoles substituted at the carbon atom of the'heterocyclic rinig by a radical of the benzene series containing an amino group capable of being diazotised, then diazotising the compound on the fibre and coupling it with itself by passing the fibre through a bath having an alkaline action.

5. The process which comprises applying to the fibre an amino compound of the following constitution:

wherein X stands for one of the group consisting of sulphur and the imino group and R for a radical of the benzene series which contains an amino group capable of being diazotised, then diazotising the compound on the fibre and coupling it with itself.

6. The process which comprises applying to the fibre an amino compound of the following constitution:

NH(IJQO CH3 moss H:

then diazotising the compound on the fibre and coupling it with itself.

7. The process which comprises applying to the then diazotising the compound on the fibre and coupling it with itself.

8. The process which comprises applying to the fibre an amino compound of the following constitution:

1i NRC 000 CH:

NaOaS then diazotising the compound on the fibre and coupling it with itself.

WERNER KIRST.