US1877318A - Process of producing azo dyestuffs on the fiber - Google Patents

Description

Patented Sept. 13, 1232 Y UNITED STATES- PATENT OFFICE EBWIN HOFFA .AND CARL SEIB, OF FRANKFORT-ON-THE-MAIN-HOGHST, GERMANY,

.ASSIGNORS '10 GENERAL ANILINE WORKS, INC., 01? NEW YORK, N. Y., A CORPORA- TION OF DELAWARE PROCESS OF PRODUCING AZO DYETUFFS ON TH E FIBER f No Drawing. Application filed June ii, 1928, SerialNo. 288,126, and in Germany June 18, 1927.

Our present invention relates to a process of producing azo dyestuffs on the fiber.

It is based on the discovery that diazoninm horofluorides as well as tetrazoniumborofluor- 8 ides of amines of the aromatic series, including those which already possess dyestufl' character, are extremely suitable for producing dyestufis on the fiber and that dyeings'oi? very good properties of fastness are obtained 1 by dyeing or printing by means of the said diazonium compounds on vegetable or animal fibers which have been pre-treated with any couplin component, for instance a naphthol or a. ody of similar action, such as 2: 3-hydroxynapl1thoic acid arylides, yrazolones, dipyrazolones, acetoacetic (acid ides or diacetoacetic (acid) diaminodiarylcompounds. The dyeings thus obtained are in many cases distinguished by a particular brillianc in comparison with those which are pro need by means of the "usual diazo solutions. r The following examples illustrate the 1nvention, it being understood that-they are in no way limitative: I Example 1.Example for the production of the dyestulf from 2:3-hydroxynaphthoic acid-2'-methyl-1-ani1ide and phenyldiazonium horofluoride when the material is dyed in lots of 25 kilos, treated with a grounding liquor in the open vat and subsequently dyed in the tureen.

There is first prepared in a vat holding 50 liters a rounding bath containing 7 5 grams of 2: 3- ydroxynaphthoic acid-2-methyl-1- anilide per liter and composed as follows:

3. 75 kilos of 2 -hydr.oxynaphthoic acid-2-methyl-1'- an e 7. 5 liters of 'Turkey red oil of 50 per cent. strength, 5.7 liters of caustic soda solution of 34 B L0 3. 75 liters of formaldehyde of 33 per cent strength;

made up to 500 liters of liquor.

To this bath is subsequently added for 25 kilos of material to be dyed, 0.375 kilos of 2: 3-hydroxynaphthoic acid-2"-methyl-1'-anilide. The yarns are treated with the grounding liquor for hour and freed from water by hydro-extraction.-

For the development of the dyestufl there is used a chassis holding 30 liters of liquor,

. which contains 3.85 grams of phenyldia'zonium horofluoride per liter. There is first prepared a bath with 115. 5 grams of phenyldiazonium borofluoride 1. 5 kilos of sodium chloride 0. 02 liters of acetic acid of 50 per cent. strength,-ma de up to 30 liters of liquor.

To this bath is subsequently added for 26 kilos of material to be dyed, 0.300 kilos of phenyldiazonium borofluoride contained in 12.5 liters of liquor composed as follows:

300 grams of phenyldiazonlum borofiuoride 0. 5 kilo of sodium chloride 0. 08 liters pf acetic acid of 50 per cent. strength; made 12. 5 liters of liquor.

The grounded yarns are once passed through the bath in hanks of 1 kilo.

For

every 1 kilo of yarn, liter of additional liquor is to be added. After the development is complete, the material is rinsed several times and soaped at a temperature of about 60 C.'for hour with 2 grams of soap per liter, finally it is'rinsed and dried. In this manner a vivid reddish-orange tint is obtained which is much clearer than that of the dyeing obtainable byusing the phenyldiazonium chloride. The dyestufi has the following formula:

Us. bonn Example 2.There .is first prepared in a vat holding 500 liters a grounding bath containing 5 grams of 2:3-hydroxynaphthoic acid-4-chloro-2'-methyl-1'-anilide per liter, the bath being composed of 2.5 kilos of- 2:3-hydroxynaphthoic acid-4-chloro-2- methyl-1'-anilide 5 liters of Turkey red oil of 50 per cent. strength 5 liters of caustic soda solution of 34 B.

2.5 liters of formaldehyde of 33 per cent. strength;

made up to Y loo ' tained. The dyestufi has For the development of the dyestuif is used First a bath prepared as indicated in Ex ample 1, but instead of 115.5 grams of phenyldiazonium borofluoride 144 grams of t-chloro- 2-methyl-1-phenyldiazonium borofluoride are used.

Into this bathare subsequently introduced 376 grams of 4-chloro-2-methyl-l-phenyldiazonium borofluoride instead of 300 grams used-in Example '1.

The method of working being the same as that in Example 1, a vivid bluish-red is obthe following formula:

By using 5-chloro-2-methyl1-phenyld nium borofluoride a vivid red dyeing is ob tained with a somewhat yellower hue, the dyestufi' having the following formula:

01. QN=N on;

n; H oonncol Example 3.For printing cotton there is first prepared a ground ng bath composed of: grams I of 2 3-hydroxynaphthoic acid-4'-ch1oro-2'- methyl-1-anilide grams of monopol soap 1: 1

500 cc. of boiling water cc. of caustic soda solution of 34 36., made up to 1 liter.

The printing paste from 24 grams of 4.-chloro-2-metliy1-1-phenyldiazonium borofluoride, which is dissolved in .thickened with to be used is prepared 476 grams of water, the solution being grams of tragacanth (100:1000) 1 liter.

The bleached cotton material is padded with the grounding. liquor on a suitable apparatus at a temperature of about35 G. and dried in the hot flue. It is then printed with the printing color and 'after drying washed and soaped at boiling temperature. The dyestufl has the following constitution:

I Example 4.There is first prepared a grounding bath-having the following ingredients: 1

4. 5 graggil of 12 3-hydroxynapht11oyl-5-chlbro 2'dcoluidine 9 cc. of fldrkey red oil of 50 per cent. strength T liter.

to which are finally added 4.5 cc. of formaldehyde of 30 per cent. strength.

the following formula:

cc. of caustlc soda solution of 34 B., made up to 7 The material is treated with this grounding. liquor for -hour. I

There is then prepared a dye-bath as follows:

2. 37 grams of 2-nitrophenyldiazonium borofluoride are made into a paste with 1.6 cc. of acetic acid 01550 per cent. strength and some warm water, and the paste is dissolved in 200 cc. 3f grater atv 50-60 C. there are then added a on 250 cc. of sodium chloride solution (1:10) and the whole is made up to 1 liter.

The material is dyed for hour, then rinsed and soaped at boiling temperature.

' In this manner a lively bluish-red tint is obtained on the fiber. The dyestuif has the following formula:

CH: I H0 ONEO-Gl e Example 5.There is first prepared a grounding liquor in the manner stated in Example 4.

The dye-bath is also made up like that of Example 4., except that there is substituted for the Q-nitrophenyldiazonium borofluoride the same quantity of 4-nitrophenyldiazonium The material is rinsed and soaped at a boiling temperature. Thus a bluish-red dyeing.

is obtained on the fiber. The dyestufii' has the following constitution: v

Example 6.-There is first prepared a grounding-bath with the following ingredients: 5

grams of 2 3-hydroxynaphthoyl-aniline 14 cc. of Turkeyvred oil of 50 per cent. strength 10. 5 cc. of caustic soda solution of 34 136., made up to- 1 liter.

to which are finally added 7 cc; of formaldehyde of30 per cent. strength.- The materialis treated with this groundingliquor for A;

Example 7.There is first prepared a Example 9.There is first prepared agrounding bath with the following ingredients:

grams of. 2: 3 -hydroxynaphthoy1- 2' anisidine (OCH',=1) I cc. of Turke red oil of 50 per cent. strength 7. 5 cc. of caust c soda solution of 34 36., made up to 1 liter.

to which are finally added 5 cc. of formaldehyde of per cent. strength. The material ihs treated with this grounding liquor for our.

The dye-bath is prepared as described. in

Example 4, except that for 2-nitrophenyldia-f zonium borofluoride there are substituted 2.75 grams of 2:5-dichloro-4-methylphenyldiazonium borofluoride' The material is dyed, rinsed and'soaped at boiling temperature; a vivid scarlet is obtained on the fiber. The lowing formula:

grounding bath having the following ingredients: 3. 5 grazgiglpf 21:8-hydroxynaphthoyl-5-chIoro-2-an1sidine 7 cc. of Tiifirey red 011' of per cent. strength 8. 8 cc. of caustic soda solution of 34 Be., made up to 1 liter.-

to which are finally added 35cc. of formaldehyde of 30 per cent. strength. The material is treated with this grounding liquor for hour. v

The dye-bath is prepared as described in Example 4, but for the 2-nitrophenyldiazonium borofluoride there are substituted 2.75

resembles Turkey red. The dyestuif has the following formula:

OH N=N I OOH! H OO.NH O1 dyestuif has the fol-- a diazonium borofluoride of grounding bath having the following ingredientsz 2. 5 grams of hydroxynaphthoyl l'-naphthylamine v5 cc. of Turkey red oil of 50 per cent. strength 7. 5 cc. of caustic soda solution of 34 B., made up to 1 liter.

to which are finally added 2.5 cc. of formaldehyde of 30 per cent. strength. The material is treated with this liquor for hour.

The dye-bath is prepared as described in Example 4, but in place of 2-nitrophenyldiazonium borofluoride, 1.91 gram of 4:4'-di- (diazonium borofluoride)-diphenylamine is used. The material is dyed for hour, then rinsed, acidified with hydrochloric acid, then rinsed cold and hot and soaped at boiling temperature, whereby a black dyeing is obtained. The dyestuff has the following formula:

Weclaim: j 1. The process of producing azo dyestuffs on the fiber which comprises treating ahydroxynaphthoic acid arylide on the fiber with the following general formula:

. [R-N BF wherein R stands for an aromatic residue.

2. The process of producing azo dyestuffs on the fiber which comprises treating a hydroxynaphthoic acid 'arylide on the fiber with a diazonium borofluoride of the following general formula:

wherein It stands for a benzene residue which may be substituted by alkyl, O-alkyl, halogen or the nitro group.

3. The process of producing azo dyestufl's 0 the fiber which comprises treating a hydroxynaphthoic acid arylide on the fiber with a diazonium borofluoride of the followiiig general formula:

wherein one X stands for N0 and the other Xs stand. for hydrogen.

4. The process of producing azo dyestuffs on the. fiber which comprises treating a, hydroxynaphthoic acid arylide on the fiber with a diazonium borofluoride of the following 7 formula 5. The process of producing an azo dye stufi' on the fiber whlch comprises treating 2.3-hydroxynaphthoic acid-2'-n1ethyl-1'-anim lide on the fiber with the diazonium borofluoride of the following formula:

6. The process of producing an azo dyestuff on the fiber which comprises treating 2.3-hydroxynaphthoic acid-2-methoxy-1'- anilide on the fiber with the diazoniuin borofluoride of the following formula:

In testimon whereof, we afiix our signa-