US2132456A - Dyeing cellulose esters and ethers - Google Patents

Description

Patented Oct. 11, 1938 UNITED STATES 2,132,456 DYEING CELLULOSE ESTERS AND ETHERS Harold Blackshaw and Ma 'ce Arthur Thorold Rogers, Blackley, Englan assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. "Application August 4, 1936, Serial 3 Claims.

The present invention relates to the dyeing of textile materials composed of cellulose esters I and ethers by means of triazene compounds, characterized by the presence of the group N=N--N=, both water soluble and water insoluble, in conjunction with suitable coupling components. The amines used for the preparation of the diazo compounds which enter into the formation of the aforesaid triazenes are free from water-solubilizing groups and may be monoor polynuclear.

,We have found that triazene compounds, e. g. that prepared from diazotized 5-chloro-2-toluidine and diethanolamine, are taken up by fibre composed of cellulose ester or ether and are hydrolyzed and developed on the fibre by treatment in a bath containing a coupling component (as for example 2:3-hydroxynaphthoic acid) and an acid (either mineral or organic, as for example, acetic or formic or dilute hydrochloric acid). Alternatively the coupling component, (as for example 2z3-hydroxynaphthoic acid anilide) may be applied to the fibre simultaneously with the triazene compound, and the shade then developed on the fibre by treatment with acid.

The invention, accordingly, has for an object the provision of novel means of producing fast shades on cellulose ethers and esters; a further objectis the production by novel means on cellulose esters and ethers of ice colours; a further object is the production on cellulose esters and ethers of ice colours without application to the fibre of diazotizing baths. Others objects will become apparent as the description proceeds.

Generally speaking those triazene compounds free from water solubilizing groups, e. g. those derived from diazo compounds usually employed in the production of ice colours and from secondary amines free from carboxylic or sulphonic groups are preferred because they have the greatest afiinity for cellulose esters and ethers and yield 'on development the deepest shades. f the water soluble compounds containing carboxylic or sulphonic groups or both the afllnity appears to be dependent to some extent on the chemical constitution. Thus the triazenes derived from cyanamide or cyanamide carboxylic acid usually possess better-affinity than corresponding triazene compounds derived for example irom sarcosine, sulphonanthranilic acid, pipecolinic acid and the like.

In carrying the invention into effect it is usually preferred to mix the triazene compounds with a suitable dispersing agent, as e. g. Turkey-red oil or a salt of the condensation product of naphthalene sulphonic acid and formaldehyde to secure their better distribution in and absorption from the dye bath.

In that embodiment of the invention in which a. triazene compound and a coupling component In Great Britain August 14, 1935 bath containing only acid, it is necessary that the coupling component shall have'aflinity for the cellulose ester or ether. used are such ascontain no solubilizing groups such as sulphonic or carboxylic groups, for instzlnce, the arylamides of 2:3-hydroxynaphthoic acid. If sulphonic groups are present they should preferably be in the form of sulphuric esters, as for instance sulphatoethyl-meta-toluidine.

Hitherto developed shades are acetyl cellulose artificial silk (which is the most widely used substance of those coming within the group of textile materials composed of cellulose esters and ethers) have been obtained by causing a diazotizable base to be absorbed by the fibre in one bath, diazotizing the base on the fibre in another bath, and finally, coupling the thus produced diazo compound with a suitable component in a third bath.

According to thepresent invention no' more than two baths are necessary for the production of a developed dyeing, thus not only is a considerable economy in time and labour effected, but beyond this, by the elimination of a process, the liability to damage of the valuable artificial silk.

As examples of triazene compounds adapted for use according to the invention, we mention, for

instance, diazoimino or diazoamino compounds,

prepared from diethanolamine, the tetraand hexaethenoxyamines (which are obtained by condensing four or'six molecular proportions respectively of ethylene oxide with one molecular proportion of 4-toluene-sulphonamide and hydrolyzing the condensation product thus obtained with aqueous sulphuric acid of 60% strength), 6 methyl 2:224 trimethyltetrahydroquinoline, isoindoline, ethylamino-ptoluidine, methylamino p tolui'dine, methylamine-be'nzene-p-sulphonamide, methylamine-benzene-p-dimethylsulphonamide, methylamino p dimethylaminoaniline, p-ethyl amino-benzamide, tetrahydrocarbazole dihydrobenzcarbazole 2 3 -trimethyl-indole, cyclohexylmethylamine,

Hence those preferably was dimethylamine, diethylamine, dipropylamine,- methylhydroxyethylamine, ethylhydroxyethylamine, dicyclohexylamine, methylamino-tetrahydronaphthalene NHC a pyrollidine, methylglucamine, ethylglucamine,

. sarcosine, pipecolinic acid, piperazino acetic acid, the alkali salts of cyanamide or cyanamide car- 1 boxylic acid, sulphcanthranilic acid, aniline disulphonie acid, piperidine sulphonic acid, methyltaurine, hydroxyethyltaurine, dlben zylamine d1- sulphonic acid, methylaniline-p-sulphonic acid,

inethyl-aniline-m-sulphonic acid, methylanilinep-carboxylic acid, ethyl-p-toluidine-sulphonic acid, monoglycinated -sulphoanthranilic acid, diglycolamino acid 4 cmco on compounds suitable for the production of triazene compounds may be prepared we mention among others as suitable bases 4:5-dichloro-2-amino- .methylbenzene, 3 6-dichloro-4-amino methylbenzene, 6-nitro- 1-methoxy-3-amino-methylbenzene, fi-benzoylamino-4-chloro 3-amino -methoxybenzene, 4 6-dich1oro-2-amino-l-methylbenzene, I

2:5-dichloroaniline, 5-nitro-o-toluidine, 4-amino- 5-benzoylamino-m xylene, N-p-amino-benzoyl-' p-toluidine, a-aminoanthraquinone, a-naphthylamine, 4-aminoazob'nzene, 4-amino-5-methoxy- 2'-ethoxyl-2-methylazobenzene, 5-chloro-o-toluidine, 4 -chloro-2-nitroaniline, S-aminowarbazole, tolidine, 1-amino-4-benzoylamino-2:5-diethoxyaniline, o-chloroaniline, 4-ehloro-5-nitro-o-anisidine, m-nitraniline, 4-chloro-o-anisidine, 6-chloro-o-toluidine, 2,.-benzoylamino5- amino-cresol ether.

. By way of illustration of coupling components which may be applied simultaneously with the triazene compound to the fibre or whichmay be added to the acid coupling bath we mention acetoacet-o-tolidide, acetoacet-p-chloraniline, the arylidessof 2:3-hydroxynaphthoic acid, for in stance, the anilide, 4-bromo-o-anilide, 2:5-dimethoxyanilide, a naphthylamide, dianisi de, m-

nitranilide, p-chloranilide, 5-,-methoxy-2- o-anisidide,

uidide,

p-anisidide, p-naphthylamide, 5-

- chloro-2-toluidide, o-phenetidide, m-xylidide, p-.

chloroahilide of 2-hydroxycarbazole-3-Earboxylic acid, o-toluidide of 2-hydroxyanthrac'ene-3-car- 65 boxylic acid, resorcinol, m-phenylene diamine, 4- hydroxydiphenyl-3-carboxylic amide, 3-hydroxydiphenylamine-S-carboxylic amide, 3-hydroxydiphenylamine-4-carhoxylic amide, 3-hydroxydidihydroxynaphthalene 2 6 dlcarbcxylic anilide, hydroxyphenanthrene-o-carboxy1ic 'anilides,

hydroxychrysene-o-carboxylic anilides', arylalkyl-.

pyrazolones, e. g. phenylmethylpyrazolone, u-

.naphthol, p-naphthol, aminonaphthols, 3-hydroxycarbazole, 3-hydroxyfluorene, S-hydroxyfluorene-2-carboxylic-o-to1uidide, 3-hydroxy-di phenylene oxide, 3-hydroxy-diphenylene oxide-2- r carboxylic-p-chloranilide, 1 :5 (hydroxyethylamino) -naph thol, hydroxyanthracenes; hydroxyphenanthrenes but it is to be understood that other suitable coupling components may be employed.

As examplesof cellulose esters and ethers to which the process of the invention maybe applied we mention acetyl, formyl, propionyl and butyryl cellulose, benzyl, methyl, ethyl, propyl and butyl cellulose.

The following examples illustratebut do not limit the invention. 'The parts are by weight.

k Example 1 The triazene compound used made as tollowsz 7 parts of p(p'-aminophenylazo) -a-naphthylamine are dissolved in 50 parts of water and 11 parts of hydrochloric acid, sp. gr. 1116, cooled to 0 C. and treated with 25 parts of sodium nitrite solution (14%). The solution thus obtained is in this example is run into a solution containing '7 parts of second- 3 ary hexaethenoxyamine (prepared by condensing six molecular proportions of ethylene oxide with 1 molecular proportion of 4-tolue ne'sulphonamide ,andhydrolyzing the resultant product with sulphuric acid) and a large excess of sodium car- 3 bonate. The black precipitate which is formed is filtered off and ball-milled with 25% of its weight calculated as dry compound, of the sodium salt of the condensation product of naphthalene sulphonic acid and formaldehyde and 10% water.

A bath is made up from 32parts of this mixture, 2- parts of soda ash and 3000 parts of water. Into this bath at ordinary .temperature there is in troduced 100 parts of acetate rayon. The temperature is gradually raised to 50 C., which is maintained for hour.

The colour is developed in a bath consisting of 3000 parts of water, 5 parts of p-hydroxy-.

naphthoic acid .(liberated from its sodium salt by acetic acid) and 10 parts of acetic acid (30%) washed and dried. A black shade is obtained.

Example 2 The triazene compound used in prepared as follqwsav 7.6 parts of aminoazotoluene are diazotized by stirring for hour with 11.1 parts of hydrochloricacid (sp. gr.,1.16) 50 parts oi water and 25 parts of sodium nitrite solution (14%) the o at 85 c. ,for /2 hour. The material is {then aqueous solution is then filtered and run slowly with agitation into a solution containing 14 parts aforesaid and an excess of sodium carbonate; a thick dark coloured oil separates, which readily gives a clear solution in water in the presence of one of the usual dispersing agents, such as phenylether-5-carboxylic amide, 2:4-dihydroxyd quinoline, 2:4-hydroxybenzquinoline, 1-Jhydroxy--v naphthyl d-phenylketone, 1:5-hydroxynaphthol, 1 :5 p hydromethylaminonaphthol, 6 chlorozz3 -hydroxynaphthoic amide, 6 ethoxy 2:8- hydroxynaphthoic a ni 11 d e, 2 6- dihydroxnaphthalene 3 g 7 dicarboxylic anilide, 3:6-

Acetate rayon is dyed a bright yellow bymeans of the above triazene in the manner described in Example 1. The shade rapidly develops in a bath of beta-hydroxynaphthoic acid made acid with acetic acid and heated to 80 C. to violet or purple shades.

of secondary hexaethenoxyamine prepared as thlsexample is Example 3 The triazene compound used in this example is prepared as follows:--

'93 parts of aniline are diazotized and slowly added to 85 parts of piperidine in 200 parts of velopment is effected by treatment with a hot (80 C.) solution of the sodium salt of 2:3-hydroxynaphthoic acid acidified with acetic acid. A brilliant scarlet shade is obtained.

Example 4 3.5 parts of the re-dispersible diazoimino preparation, made as described in Example 8 are pasted with 1.75 parts of Turkey-red oil (50% soda finished) and added to the dye vessel which contains parts of trisodium' phosphate,'20 parts of common salt and 3000 parts of water. 100 parts of acetate rayon is worked in this bath as described in Examples 8, 9 and 10.

The treated material is developed in a bath at 80 C. containing 6 parts of'acetic acid (50% aqueous solution), 6 parts of a 25% paste of sodium N-oleyli-amino-1-methoxy-benzene-2-sulphonate, and 3000 parts of water, to which has been-added 2 parts of the anilide of 2:3-hydroxynaphthoic acid mixed with 7.5 parts of a 10% glue solution.

Development is complete in half an hour, and the dyeing is then rinsed well. A bright scarlet shade is obtained.

Example 5 A triazene compound is prepared as follows:- 6.3 parts of the azo dyestuff condensation product of naphthalene sulphonic acid and formaldehyde and the resulting paste dried andground thoroughly.

2.1 parts of the above ground powder are stirred into a dyebath containing water (5000 parts) and soda ash (2 parts), 100 parts of acetate rayon entered, worked for 1 hour at a temperature 0f'80-85" C., then rinsed in cold water and developed for'ha'lf "an hour in a bath containing 5000 parts of water, 5 parts of 2:3-hydroxynaphthoic acid and lOparts of -acetic acid (30%) for /g'hour. I

A bright blue shade is obtained.

Example 6. p

A bath isprepared containing 10% on the weight of materialto be treated of an equimolecular mixture of the diazoimino compound preparedirom diazotized 5-chloro-o-toluidine and secondary hexaethenoxyamine, prepared as described in Example 1, and the sodium salt of 2:3-hydroxynaphthoic anilide. Acetate rayon is treated in this bath at 80 C. for 10 minutes. It takes up both compounds. The almost colourless material is lightlyrinsed with water and developed by immersion for half an hour at 80 C. in a bath containing 10% of acetic acid 30% (calculated on the weight of material). A brilliant red shade is obtained.

Example '7 In 1000 parts of a dyebath containing 1.25 parts of the diazoimino compound of p(p-aminophenylazo) -u-naphthylamine and secondary hexaethenoxyamine, prepared as described in Example 1, and 1 part of the sodium salt of sulphatoethyl-meta-toluidine, acetate rayon parts) is introduced and manipulated as previously described. When immersed in a bath at 80 C., containing 10% acetic acid (calculated on the weight of material), a deep reddishbrown is developed.

Example 8 A triazene compound is prepared as follows:-

282 parts of 5,-chloro-2-toluidine are diazotized in the usual manner, and the diazo solution is run slowly into a well stirred solution of 172 parts of diethanolamine in 2500 parts of water, made alkaline by the addition of 500. parts of soda ash. The addition of some solid condensation product from a previous preparation before addition of the diazo solution is advisable to prevent the diazoimino compound separating out as an oil which may take some time to solidify.

- The thus obtained solid product is filtered and washed with cold water. The paste is mixed with 1500 parts of a 50% aqueous solution of the sodium salt of the condensationproduct of naphthalene sulphonic acid and formaldehyde, and ball-milled for two hours. The paste so obtained is dried at 50 C. and ground to a very fine powder.

Such a powder disperses readily in cold water and dissolves to a clear solution in warm water.

8.5 parts of the above powder is pasted with 1.75 parts of Turkey-red oil soda finished) and 35 parts oi water at a temperature of C. added. 2.0 parts of the 5-chloro-2toluidide of 2:3-hydroxynaphthoic acid are pasted with 0.33

parts of the sodium salt of the acid sulphuric' ester of the alcohols obtained by the saponification of sperm oil and diluted with 20 parts of water at a temperature of 40 C. The above are added to the bath which contains 6 parts of trisodium phosphate, 10 parts of sodium chloride and 3000 parts of water at a temperature of 40 C. 100 parts of acetate rayon yarn are entered and worked for A hour during which time the temperatureof the bath is raised to 80 C. and

dyeing continued for hour. The almost colourless material is then well rinsed in cold water and treated in a bath at 80 C. prepared by the additionof 60'parts of acetic acid'(50%) to 3000 parts of water, worked for /2 hour at this temperature and well rinsed in cold or warm (40 C.) water.- It is then soaped in a'bath containing 3 parts ofsoapfiakes per 1000 parts of water.

If'the acetate rayon'is lustrous, it is worked at a temperature of C. for hour. "If delustered material is used, thetemperature may be raised "to -98 C.

good iastness towashing.

' Example 9 are added slowly to a boiling mixture of 300 parts of water and 12 of 10 N hydrochloric acid,

and boiling is continued until a clear solution is obtained. This solution is cooled to 5 C. with stirring, a further 16 parts of 10 N hydrochloric acid added and the suspension 'diazotized witha saturated solution containing 6.9 parts of sodium nitrite. The filtered diazo solution is run slowly into 11.5 parts of diethanolamine dissolved in 150 parts of 2N-sodium carbonate solution, which is seeded during theearly part of the addition with. solid product obtained from a previous preparation. A brown granular precipitate is obtained which is filtered from the liquor, washed with cold water, and ball-milled for 3 hours with 40 parts of the condensation "product of sodium naphthalene sulphonateand formaldehyde, 100 parts of waterand 20 parts of a 25% paste of sodium N-oleyl-4-aminod-rnethoxybenzene-Z- sulphonate. The product is dried at 50 C. and ground, giving a readily dispersible powder.

3.5 parts of the above powder are pasted with 1.75 parts of Turkey-red oil (50% soda finished). The paste is diluted with 35 parts of water at a temperatureof 60 C. Further, 1.0 part ofthe 2,182,450 ,4 L A bright bluish-red shade is obtained of very veloprnent performed as described in Example 8.

A bright greenish-blue shade of good Iastness properties is obtained. g

Example 10 A triazene compound is prepared as follows:

' droxynaphthoic acid are pasted with 2.5 parts of a 33% aqueous paste of the sodium salt of the acid sulphuric ester of the alcoholsobtained by the sulphonation of sperm oil, and diluted with 50 parts of water at a temperature of 60 C. and; i

together with the. dispersed diazoimino compound, added to the dye vessel which contains 6 parts of trisodium phosphate, 30 parts of sodium chloride and3000 parts of water at a temperature of 40 C.

Dyeing and further procedure may carried v out as described in Example 8.

An orange shade of; good fastness is obtained. The following table illustrates further combinations and shades obtained therefrom when applied according to the invention.

Coupling component No. Diazotized base 1 Combined with- Shade 1 5-chl0ro-2-toluidine Diethanolamine 4:4-diacetoa0et-2-t0lidide'.- Bright greenish yellow. 2 do CH;CH,0CH CH,OH 4-chl0r0amlide of 2-hydroxy- Deep brown.

HN.CH CH; carbazole-3-carboxyl1c acid. 3 4 benzoylamino 2:5 Diethanolamine 2-t0iuidide of 2-hydroxyap- Bright bluish green.

diethoxyaniline. thrgcene 3 carboxylicaci 4 do Morpholine Anilide of 2:3 hydroxynaph- Blue.

7 7 their: acid. 5 Aniline d Scarlet. 6 -chloro-2-toluidine. 2'naphthol Bright reddish orange. 7 6-chloro-2-toluidine 2Pmtroanilide oi 2:3-hydroxy- Yeliowish red.

, naphthoic acid. 8 o Aminoazo-toluenmu Secondary hexaethenoxy- 4-chloroanilideof2-hydroxy- Deep brown.

\ amine. I carbazolei-carboxyhc acid. 9 3-chloroaniline. Secondary tetmethenoxy- 5-chloro-2-toluid1de o! 1 2:3- Yellowish scarlet.

amine. hydroxynaphthoic acid. 10 4-chloro-2-toluidine Diethanolamine B-nitroamlide oi 2:3-hydroxy- Red.

, naphthoic acid. 1i 4-nitro-2-aminoanido 0 Bright bluish-red. so 0. t

12 4 benzoylamino 2:5 do Anilide ol 2:3-hydroxynaph Bright reddish-blue.

diethoxyanilin thoic acid. Dianisidine do 4:4 diacetoaoet 2 tolidide. Deep gold. 14 u-naphthylamine do 3-nitr0anilide oi 2:3-hydroxy- Light bordeaux.

i naphthoic acid. 15 3 benzoylamino- 4 do 5-chloro -2- tolidide of 2:3- Bright reddish blue.

- methoxyaniline. hydroxynaphthoic acid. l6 ,&chloro-24oluidine N-carbethoxypiperazine o v.-. Do. 17.' 1 amino anthraqui- Diethanelamine -J... Anilide oi 2:3-hydroxyneph- Bright red.

none. thoic acid. 18 2 benzoylamino 4 .do 2-anisidide oi 2:3-hydroxy- Rich violet. chloro 5 aminonaphthoic acid.

anisoie. v 19 do do 5 methoxy 2 tolidide .of Violet. 2:3-hydroxynaphthoic acid.

20 2:5-dichloroaniiine. Cyanamide-- 5-chl0ro-2-toiidide of 2:3- Orange. hydroxynaphthoic acid.

21 Animln dn 4-bromo-2-anisidide of 2:3- Dull yellowish red.

' hydroxynaphthoic acid. A 22 4 chloro 2 nitroani- .-.do B-nitroanilide of2z3-hydroxy- Red.

- line. na phthoic acid.- Z3 5-nitro-2-aminoanl-. N ethylaniline 4 suln Dull red.

sole. phonic acid.-

anilide or 2:3-hydroxynaphthoic acid are pasted coupling component are added to the 'dye vessel which contains 2.4 partsot soda ash, 10 of sodium chloride and 3000 parts of water at a temperature of 403 C. 100 parts of acetaterayon yam are entered and the dyeing and de- The amino derivative in the secorid column ot the second example in the table is prepared by reacting N-ethyl-u-naphthylamine' or N-.

ethylaniline with ,2 molecular proportions of ethylene oxide, converting into the 4-nitroso "compound with nitrous acid, and hydrolyzing with hot aqueous caustic soda.

. We claim:

1. A process or dyeing cellulose ester and ether materials which comprises applying to the material a bath containing a triazene compound of a diazo saltfrom the triazene compound'but an 'insuflicient quantity and concentration of base to saponify said material, and then developing in the presence of an azo dye coupling component by applying an acid bath.

2. The process of dyeing cellulose ester and ether material which comprises applying to the material a bath containing a triazene compound prepared from a diazotized arylamine which upon acidification yields a diazo salt, said bath being alkaline and containing sufiicient base to prevent the splitting-off of a diazo salt from the triazene eompoundbut an insuflicient quantity and concentration of base to saponify cellulose ester and ether materials, and then developing by applying an acid bath of an azo dye coupling component.

' 3. In the process of. dyeing in which a compound capable of coupling with a diazo compound and atriazene compound prepared from a diazotized primary aryl amine which is capable of yielding a 'diazo salt upon acidification are applied to cellulose ester and ether materials which are to be dyed and the dye is developed by acidification, the steps which comprise first immersing said material in an alkaline dyeing medium comprising the triazene compound, a

-coupling component having afiinity for said material, a dispersing agent and a solution of a base which contains an insuflicient quantity and concentration of the base to saponify the cellulose ester and ether material and to convert the coupling component to its alkali metal sait but suI- ficient base to prevent the regeneration of a diazo salt from the triazene compound, and thereafter developing byapplying a solution containing an acid which is effective toregenerate a diazo salt from the triazene compound.