US1643233A - Dyeing and printing with phenylamihb- black - Google Patents

Description

v ride FeClr either alone or Patented Sept. 20, 1927. i I

U N B? I ST tars IGYUILIIJEBMO liaison n noEiioivA, sPaIn.

DYEING' AND PRINTING WIT Fen anvtaiinuun BLACK.

No Drawing. Application filed Februarym, 1 922, Serial No. 537 087,'a11t1 in Spain March I, 1921.

I invention Vrelates to the dyeing and printing oftextile fibres with aniline black and the object of the invention is an improved process byvwhich a considerable econ- =omy is effected in thedyeing and printing over-themethods hitherto employed. My invention consists essentially in adding to 'theydyei-ngbath'or to the printing bath, a smalquantityof an azo-derivative of ordinary aniline oil orzof any one of its com ponents H or -methylat1on,; etc., derivatives.

The'presence of this smallquantity of azo-' V derivativegreatlyincreases the aflinity between the color and the fibres, so that, it is possibletoobtain-a fixed intensity of black,

while using smaller quantities of aniline oil and auxiliary chemicals 'than' with the method-usuallyemployed These azo-derivatives are products so cheap that'the cost of the small qu'antityemployed in this inven 'tion is negligible. l v v I To carry out my invention 'the base may be prepared; using instead, of vthe ordinary rivative of any of those substances obtained by sulphonation, methylation or by theintroduction of groups belonging" to {another order, into the anilinr P These azo-deriv'atives may 'bepf an aoid,

basic orneutral character; being all of them distinguished by the general aso-l1nkage it doesnot amount to 2% of the quantity In carrying out my invention, 1' may em a ploy any of the known metallic compounds for "transferring orcarrying oxygen but a greater economyis obtained by using as oxygen-transferring agent the ferrous chloa'ssociat'ed" with volatile compounds:

aniline oilfaniline oil, containing a small proportion of an azo-deriv'atlve ofthe same, 1

toluidi'ne'or xylidine"as'well as an a'zo-detion is industrial aniline oil;

I Very many'azo-derivativesmay be used to carry out this process. amples are mentioned:

Y A zoderivatives from aniline V C H NH Azobenzene,

Amido-azo-benzene,

I o H N=N o 'H .NH v 'Az'o-oXy-benzene, 7

e 5 O ,f 6 5 V s and their derivatives by methylation or by Introduction of groups belonging to another order." Y 1 Azo-derivatives of toluidine' may also be used. They are-homologous compounds of the above mentioned bases, where the group (J E 1S substituted by G H CH Y AZ O(l11Va;t1V- S of Xylidine and their lsomersand derivatives. They are homologous compounds of the first above mentioned series where the group 0 H is sub-- stituted by (1 H (CH The quantity of azo-derivative which is necessary in order to produce the. above mentioned increase of affinity is very small;

affect the total vcost of the dyeing process.

' The most appropriate vehicle for the application of azo-derivatives for black oxida- By the pre- The following BX- v vious manufacture or preparation of aniline 7 or dyeing pastes, or it may contain a larger arately.

quantity of it, and in this case it must be diluted with aniline oil in order to produce an az o-oil of the concentration suitable for operating with it either in dyeing or printing: or toradding that diluting aniline sep-.

In, this invention the composition of the baths'for dyeing or printing with an azoderivative is not solely characterized by the ingredients it contains. It is also characterized by the appearance shown by the products employed whic'liare characterized by -1 the yellow color of azo-derivatives of anilines, toluidines and Xylidines; and it is likewise characterized by the aspect of the material that is to be dyed or printed during the course of the manufacture.

With the usual baths; when not much used or when recently prepared, the material on being impregnated with ordinary anilineblack remains white or a dirty white, or a slightly greenish if made with black prussiate, and so it remains until oxidation begins. In printin it is usual to add an auxiliary color (methyl-violet, for instance) in order to render the printing Visible on being done. 7

With aniline-black with; the. addition; of azo-derivatives the. dyed or printed material is of yellow-color, and has the peculiarity that before oxidation begins (before assuming. the emerald green color.) it shows a' char acteristic vivid pink color. The azoeoil (whatever its concentration may as well as the dyeing bathsor printing pastes, dye

I textile fibres; or the human skin (so that it can be tested for instanceon ones hand) a yellow color turning into light red or vivid pin-k by the action of an acid- (hydroehloricr acid for instance).

When applying this invention it is necessary to modify any of the apparatus already in use'in the industry and: the manipulations need not bechan'ged. 7

I111 printing, powerfulwashi n machines maybe dispensed with, because in the most delicate case, that oi designs surcharged ona white .ground,with a simple washing of the fabric (spreadto itstullwidth) after the of bichromate, very pure whites are" ta e 4 With the pmseneeot azoederivatives, all

the aniline present in. the dyeing or printing bath is transformed into black fixed on In the dyeing of pieces in the foulard manner, it is advisable to dissolve all the products in water contain ng about six grams per litre of stareh, 'gum mucilage or This explains the purity of the analogous compositions with the object of givin more stability to the solution.

I s all now discuss the improvements or aniline-black oxidation due; as stated in the beginning, to the employment of chloride of iron FeGl as the 0x gen-transferring agent. This compound as already been proposed tor producing black oxidationy but it has not been adopted'in industrial prac-v tiee, notwithstanding all itsadvantages, be:

cause of its not having been used under favorable conditions it has. never been.

used in presence of azorderivative s. of aniline and its homologues.

In print'ng, it has beenernployed in pres ence of excessive quantities. ofa'acid this: is, at

least a quantity of acid equal to that-of ant.

line; Under these conditions the rapid'oxis elation of the fabric ,(ste'am-black) cannot be brought about because greatly deteriorated.

The present inventien embraces, the. iin-I provement of obtaining,- the. aniline black the fibre becomes 7 employing chloride oi iron FeGlpasthe oxy gen-transferring" agent; in the presence of a'zo-derivativeeot industrial aniline and in direct printing, operating with basic salt of aniline; Under these conditions-and with-1 out employing any other fixed metallic comi pounds, blacks of excellent quality either in printing or in dyeing can be. produced in the most ecenomieailimahner,

qnantityofalkaline salts; totally, inert for oxidation; are for-media the midst of the y mg rmperatimr h refemi bla kprussiate ought t0 bef oxidiiiedat a very high and persistent temperature This does not, occur when chloridieofiiron is used instead f. pl ie te- Fer his-t s s t x da i n of the black is possible at alower temperature and more rapidly Theox-idatiio'n is also deeper, thus saving insuper'oxidizer later on.-

When prussiate's (are employed a. great Throughoutthe elaims iwliere' the't'erm the homologues and; substitution. derivatives as above indicated. The term industrial aniline Israeli in its ordinary sense-min}.

aniline is used, I intend *9 cover thereby tity of acid necessary to form these basic compounds is half of the acidtheoretically requlred to form a neutral salt.

.I claim:

1. In the art of dyeingwith anilin black, the step of treating the textile to be dyed, with a bath containing both anilinand an azo aromatic compound, the latter being present in amount not substantially over 2%- of the former.

2. In the process of claim 1, the step of treating the textile with a mixture of industrial anilin and an .azo compound derived therefrom. p

3. Inthe process of dyeing or printing with anilin black, treating the textile with a bath containing anilin, a small amount of an azoaromatic body and hydrochloric acid,

the amount of the latter being only sufficient to form basic compounds with the dye stuff.

4. In the production of aniline black on the fibres, the addition to the anilin bath of a small quantity of an azo-derivative' from industrial aniline, and conducting the operation in. the presence of iron chloride as an oxygen-transferring agent.

5. In the production of aniline black on the fibre, the process which comprises ap-' plying to the fibre a composition containing aniline, aniline hydrochloride, an azo-derivative of an aromaticamino compound of the benzene series, and an oxygen-transferring agent.

I 6. In the production of anilin-e. black on the fibre, the process which comprises applying to the fibre aniline oil with which has been incorporated an azo-derivative of an aromatic ammo compound of thebenzene series.

7 In the dyeing of textile fibres with aniline black, a dyeing bath comprising, instead of the usual aniline Oll mixture, amlme 011 with which has been incorporated an oxygen-transferring agent and less than 2%, based on the aniline present, of an azoderivative of a constituent of industrial aniline oil.

8. In the printing of fabrics with aniline black, a printing paste comprising, instead of the usual aniline oil, an aniline oil in which has previously been incorporated both ferrous chloride as an oxygen-transferring agent, and less than 2% of an azo derivative of a constituent of industrial aniline oil.

9. In the production of aniline black on the fibre, the process which comprises applying to the fibre aniline hydrochloride with which has been incorporated ferrous chloride and an azo-derivative of an aromatic amino compound of the benzene serles.

10. A composition suitable for use in the production of aniline black on the fibre, comprising aniline hydrochloride, an oxygen-transferring agent,.and an azo-derivative of an aromaticamino compound of the benzene series.

11. A. composition as defined in in Which the oxygen-transferring ferrous chloride.

12. A composition as defined in in which the azo-derivative is an zene.

13. A composition suitable for use in the production of aniline black on the fibre, comprising aniline, aniline hydrochloride, ferrous chloride, and an azo-derivative of aniline.

In testimony whereof I aflix my signature claim 10 agent 13 claim 10 azo-ben-