US2013689A - Treatment of textile materials - Google Patents

Description

Patented Sept. 10, 1935 UNITED STATES 2,013,689 TREATMENT or TEXTILE MATERIALS Ernest William Kirk and George Holland Ellis,

Spondon, near Derby, England, assignors to' PATENT ;=OFFICE Celanese Corporation of America, a. corporation l of Delaware.

No Drawing. Application April 14,. 1933, Serial No. 66fi,173. In Great Britain May 12, 1932 7 claims. (oi, s-s) This invention relates to'the production of colorations on textile materials and especially upon materials consisting of or containing cellulose acetate or other cellulose esters or ethers.

In the coloration of textile materials it is frequently found necessary, in order to obtain a particular shade or a particular shade of special 'fastness or other property, to employ mixtures ofcoloring matters. In general however it is necessary procedures in the two cases.

I We have now found that valuable mixed shades may be obtained by applying to or incorporating in textile materials a leuco compound of a vat dyestuil, a 'diazotizableamine and an azo coupling component, and thereafter subjecting the '95 :iterial to treatment to effect diazotization and coupling, and also the oxidation of the leuco compound to the parent vat dyestuff.

Thus, for example, a cellulose acetate material may'be dyed in a green shade by impregnating with a chloraniline and diaceto-acetyl-orthotolidide and the leuco compound of a blue indigoid dyestufi and thereafter treating with nitrous acid in order to diazotizethe. amine and so eiIect coupling, and simultaneously to oxidize the leuco compound of the vat dyestuii. In this way the desired mixed shades of vat and azoic colors may be obtained with little or no more complication of procedure than is normally necessary in the production of azoic colorations on textile mate:

' rials. Moreover, the mixed shades obtainable exhibit a high degree of fastness for the dyeings obtainable by vat or azoic methods in general exhibit exceedingly good fastness properties.

The three components, diazotizable amine, coupling component and leuco vat dyestufi, are conveniently applied to the material simultaneously If desiredhowever they may be applied separately to the materials, though in general less nated material may be subjected to a mild oxidaacid baths suitable for eifecting the diarptization from a single bath vpadding liquid the m -of the amines. When therefore these esters are employed the treatment maybe similar to that tion, for example, by means of air, in order to oxidize the leuco compound, "and thereafter to the action of nitrous acid, followed if necessary by an alkaline treatment, in order to 'eifect diazotization and coupling. Mostconveniently how- 5 ever the diazotization and oxidation of the leuco compound are effected simply by treatment in a nitrous acid bath, the nitrite serving-the dual purpose of di'azotizing agent and oxidizing agent. Following the nitrous acid treatment the mate- 1 rials may be subjected to soaping, preferably in the presence of sodium carbonate, or to other weakalkaline treatmentto ensure completion of the coupling. Further, if desired, the material 'may be subjected to a mild oxidizing treatment 15 to ensure the complete oxidation of the leuco compound of the vat dyestufi.

The diazo component, coupling component and leuco'vat dyestufi', may be applied to the materials either in the free state or in the form of salts, 2 I

according to the character of the material under-.

going treatment and the precise method 01' application employed. Thus, in the case of celllilosic materials the coupling component and the leuco compound are advantageously applied in 25 the form of alkali salts, in which form they exhibit very good aflinity for the material. In the case of animal fibres, for example wool .or silk, and. cellulose acetate or other cellulose ester or ether artificial silks, the components are, with particular advantage, applied in the free state to the materials. In this state the components exhibit very good affinity for these materials, and in consequence dyeings .are obtained possessing very good fastness to rubbing, in addition to other desirable fastness properties.

If desired leuco compounds of the vat dyestufis may be applied to or incorporated in the materials in the form of their sulphuric, phosphdric or other esters, for example the products sold under the name Indigosol or the registered trade-mark Soledon. These sulphuric or other esters of the leuco compounds are readily saponified and oxidized to the vat dyestufl by the nitrous 5 adopted when the leuco vat dyestuffs are em-' ployed in the free state or in the form of alkali '0 .metal salts.

7 'compounds.

1,844,350, Bri ish Patents 396,412 and 404,327.

Likewise coupling .components of widely .varying character may be employed, for example any of those mentioned' in U. S. application S. No. 666,172, for example arylamides of 2:3-oxynaph- 'thoic acids. Particularly useful results may be diaceto-acetyl-orthotolidide and orthochloraniline. Again, purple shades may be obtained by using 5 :7:5:7'-tetrabromindigo, 2:3-oxynaphthoic acid-m-nitranilide and 5-nltro-2-aminoanisole;

The vat dyestuffs employed may be of any desired series, forexample of-the anthraquinone or indigoid series. Further, sulphur dyestuffs may be applied in accordance with the new process, and in fact any of the dyestufis or classes of dyestufl's referred to inU. S. Patent No. 1,960,172 as suitable for application to jcellulose ester and ether materials in the form of their free leuco In the case of cellulose ester or ether materials, particularly useful results may be secured by meansrof dyestuffs of the indigoid series,-or by means of anthraquino ne dyestuffs containing only a single anthraquinone'nucleus.

Dispersions of the diazo or coupling components may be obtained by any desired method for example, by fine milling or grinding with or without the aid of dispersators and/or protective colloids, by'precipitation in the presence 0f protective colloids, or by a simple treatment with dispersators, as described for instance in any of U. S.'Patents NOS. 1,613,413, 1,618,414, 1,694,413,,

1,690,481, 1,803,008, 1,840,572, -1,716,721 and 1,928,647 and British Patent;No.-323,788. Disper sion of coupllng'components, especially those of phenolic character or containing the''C0.H:-

group may frequently be-facilitated by the presence of small quantities of alkali, for example, a;

quantity of caustic soda sufficient to yield a solution of about pH'7.2 or even slightly more alkaline.

Vat dyestufis may be vatted' with caustic alkali anda reducing agent and applied to the materials together with or separately from the diazo and coupling components. In the case of animal fibres, cellulose esters or other materials liable to damage by alkali, the excess alkali of .the vat may be neutralized, for example by means of organic acids or there may be used vats of relatively low alkalinity prepared with the aid of ammonia, organic amines or other weak alka- 'lies. Any such organic acids or organic bases 'f should of course be such as do not interfere with the pmduction of the deslredshades, e. g., by coupling with the diazo compound. Where the I leuco compounds are to be ap lied to the-ma.-

terials in thefree state they are advantageously converted into fine suspensions or dispersions,

for example in any of the ways described in U. S.

Patent N0. 1,900,172. ri The various components, whether in free or combined form, may be applied to the materials in any desired manner. Thus, for'instance,

they may be applied by dyeing, padding or other mode of .uniform application, 'or by printing,

stencilling' or other mode. of local'application. For padding, printing and the like the preparations containing the components may contain any desired thickening or other agents to fit them 2,018,689 amines are giv for instance U. S. Patent No.

pfegnated with a mixture of diazotizable amine an dcoupling component, over-printed with a leuco compound of a vat dyestuff or an esterthereof and thereafter diazotized and developed.

In-this way a pattern colored by both dyestuffs" is obtained upon a ground colored only by the (azoic colorations.

- As indicated previously the invention is of especial interest in the coloration. of cellulose ester or ether materials. Such materials may for instance consist of the previously mentioned cellulose acetate or of other cellulose esters or mixed esters, for example cellulose formate, propionate, butyrate,-'a nitroacetate, or acetate-butyrate, or cellulose 'esters obtained by esterifying cellulose while retaining its fibrous form. Again, cellulose ethers, or ether-esters for instance ethyl or benzyl cellulose may be colored. Other natural or artificial materials, for example animal fibres,

'cotton or the regenerated cellulose type of arti-- sisting of cellulose acetate and a cellulosic fibre 40 such as cotton ;or viscose artificial silk, the acetate only may be colored by applying the components in the free-state, under which conditions they possess little or no afiinity for the cellulosic material.

The invention is illustrated the following examples:-

Ezamplei L but not limited by To, dye a brilliant emerald green shade on 10 .50

kilograms of cellulose 'acetate'yarn.

300 grams -oi Algol brilliant green-BK paste (Schultze, 7th Edition; volume 2, page 6) are wetted down with methylated spirit and vatted in about-30 litres of soft water at 60 C. by addition of 50 cos. of monoethanolainine and 100-grams of sodium hydrosulphite powder. In andther vessel 100 grams of ortho-chloraniline are dispersed by heating with 200 grams of Turkey red oil and diluting with hot soft water. Both these solutions are then added to' the dyebath, followed by a; solution of 200 grams of diaceto-acetyl-orthotolidine in sufiicient hot soft water containing 40 grams of caustic soda. A solution of 100 grams of glucose is then added and the bath adjusted to 300 litres. The yam'is entered into the dyebath at 30-40 C. and worked for half-an-hour, during which time .the temperature of the bath is raised to 75 C. and thedyeing' continued at this temperature fora further hour. The yarn is lifted, thoroughly rinsed 011; and entered in adi- L azotization bathxcontainlng 8-grams per litre of glacial acetic acid and 4 grams per litre of sodium nitrite, the temperature not exceeding 15 C. After working in this bath for half-an-hour the yarn is again lifted and thoroughly rinsed, and then entered into a cold bath containing A gram per litre soda ash and 1 gram per litre good textile soap, worked cold for a quarter of an hour, the temperature raised slowly to 75 C. and worked at this point for a further half hour. The yarn is then lifted, rinsed and dried, or otherwise treated as requisite.

Example 2 To. obtain a green printed design on a white ground of cellulose acetate fabric.

The following paste is first prepared:-

1.6 parts 2:5-dichloraniline 3.8 Diacetoacetylorthotolidine. 6.0 Indigosol blue AZG. 10.0 Ethyl lactate. 10.0 Diethylene glycol.

Gum arabic thickening to 100.0 parts Example 3 To dye a fast green shade on 10 kilograms of silkyam.

100 grams of 5:7:5':7' tetrabromindigo are vatted by warming to C. with 200 grams of monoethanolamine, 200 gramsTurkey red oil and 100 grams of sodium 'hydrosulphite in 5 litres of soft water. 100 grams of 2:5-dichloraniline are dispersed by warming with 300 cos;

of Turkey red oil and diluting with 1 litre of boiling soft water, and 200 grams of (ii-acetoacetyl-orthotolidine are dissolved with 50 grams of caustic soda and 5 litres of hot soft water. These dispersions are then added to the dyebath which already contains 100 grams of glucose and which-is adjusted to a volume of 300 litres, and the previously degummed silk yarn entered. The temperature is then slowly raised to 75 C. and kept at this for an hour and a half the silk meanwhile being well turned. The yarn is then lifted and rinsed, and entered directly into the diazotiz ing bath which contains 6 grams of sodium nitrite and 12 cos. of glacial acetic acid per litre. After diazotization for 15 minutes, the yam is lifted.

rinsed, and soaped to shade as in Example 1- pling component and a compound selected from the group consisting of the free leuco compounds of vat dyestuffs and the salts of the free leuco compounds of vat dyestuffs, and thereafter simultaneously effecting diazotization and coupling and conversion or the leuco derivative to the parent vat dyestufl with nitrous acid.

2.Pi'ocess for the production-of mixed shades on textile materials containing organic derivatives of cellulose, which comprises applying thereto a diazotizable amine, 'an arylamide of 2.3-oxynaphthoic acid, and a compound selected from the group consisting of the free leuco compounds ,5

of vat dyestuiis and the salts of the free leuco compounds of vat dyestuffs, and thereafter simultaneously effecting diazotization and coupling and conversion of the leuco derivative to the par-- ent vat dyestui! with nitrous acid. 10 3. Process for the production of mixed shades on textile materials containing organic derivatives of cellulose, which comprises apply n to the materials a diazotizable amine, an azo coupling component, and a compound selected from the group 15 consisting of the free leuco compounds of vat dyestufi's and the salts of the free leuco compounds of vat dyestuffs, and thereafter simultaneously eflecting diazotization and coupling and conversion of the leuco derivative to the parent vat dye- 20 stuff with nitrous acid.

4. Process for the production of mixed shades on textile materials containing cellulose acetate,

.which comprises applying thereto a diazotizable amine, a diacyl-acetyl derivative of an; aromatic 25 diamine, and a compound selected from the groupconsisting of .the free leuco compounds of vat dyestuifs and the salts of the free leuco compounds of vat dyestuffs, and thereafter simultaneously effecting diazotization' and coupling and 30 conversion of the leuco derivative to the parent vat dyestufl with nitrous acid.

5. Process for the production of mixed shades -on textile materials containing organic derivatives of cellulose, which comprises applying to the 35 materials a diazotizable amine, an azo coupling component and a compound selected from the group consisting of the free leuco compounds of anthraquinone vat dyestuffs containing a single anthraquinone nucleus, and the salts of said free 40 leuco compounds, and thereafter simultaneously effecting diazotization and coupling and conversion of the leuco derivative to the parent vat azotizable amine, an an) coupling component and a compound selected from the group consisting of the free leuco compounds of anthraquinone vat 50 dyestuffs containing a single anthraquinone nucleus, and the salts of said free leuco compounds, and thereaftersimultaneously efl'ecting diazotization and coupling and conversion of the leuco derivative to'the parent vat dyestuif with nitrous acid.

7. Process for the'production of mixed shades on textile materials containing cellulose acetate, which comprises applyi to the materials a diazotizable amine, a diacyl-acetyl derivative of an 00 aromatic diamine, and a compound selected from the group consisting of'the free leuco compounds of anthraquinone vat dyestufls containing a 1 gle anthraquinone nucleus and the salts of said free leuco compounds, and thereafter effecting di- 65 azotization and coupling simultaneously with conversion of the leuco derivative to the parent vat dyestuif with nitrous acid.

I above numbered patenflreg'uiring correction as follows:

. CERTIFICATE OIf'CORREGTION, Pateht -Np. Z-,.013 689 I 1 EkN sT WILLIAM KIRK, TYALL 4 It is hereby certified thatferror' appears in theprinted specification of the Page-2, first cwlumn, .l 'ines 5 and 6, for -"U.S 'Application S. No. 666,172" read British Patent-N0. 404,327; and that the said Letters Patent should be readwiththis correction therein that the same mayeonform 'tothe record (if the ease in the Patent Office. Signed and sealedthis 8th day" of OctOber AI 1935'. K

. 'r L'eslie Frazer (Seal) Acting Commissio er of Patents.

September 10, 1935.-