Patent GB-219349-A (GB)
Title: Improvements in or relating to the dyeing of cellulose acetate or products made therewith
IPC: C09B67/38
Filed: 1923-01-27
Abstract: Preparations for dyeing cellulose acetate goods are made by treating insoluble or difficulty-soluble dyes with higher fatty acids or their sulpho or other derivatives or salts thereof; sulphoricinoleic acid, or oleic palmitic, or stearic acid or their alkali or ammonium salts are suitable solubilizing-agents.  The dye is dissolved in the fatty acid or salt by stirring and heating, the solution diluted with water, neutralized with alkali if necessary, and added to the dye-bath; highly concentrated or "solid solutions" may be prepared and subsequently dissolved. A large number of suitable dyes are described.  Reference has been directed by the Comptroller to Specification 211,720.ALSO:Preparations for dyeing cellulose acetate goods are made by treating insoluble or difficulty-soluble dyes with higher fatty acids or their sulpho or other derivatives or salts thereof; sulphor ricinoleic acid, or oleic, palmitic or stearic acid or their alkali or ammonium salts are suitable solubilizing-agents. The dye is dissolved in the fatty acid or salt by stirring and heating, the solution diluted with water, neutralized with alkali if necessary, and added to the dye-bath; highly concentrated or "solid solutions" may be prepared and subsequently dissolved. Suitable dyes are insoluble azo dyes containing no sulpho group or dyes of the indophenol, di- or tri-phenylmethane, azine, oxazine, thiaazine, or indigoid series, or basic anthraquinone derivatives, the indophenols or indigoid dyes being employed in the unreduced state and the basic dyes being employed in the form of free base. p   Azo dyes, for use in the above process, are described from the following pairs of components:-nitranilines, dinitranilines, nitrotoluidines, nitroxylidines, anisidines, chloranisidines, nitroanisidines, phenetidines, chlorphenetidines, nitrophenetidines, or chlornitranilines, diazotized and coupled with aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, methylethylaniline, diphenylamine, methyl- or ethyl-diphenylamine, m-toluidine, or p-xylidine: aniline, chloranilines, nitranilines, chlornitranilines, dinitranilines, toluidines, xylidines, nitrotoluidines, nitroxylidines, anisidines, chlor- or nitro-anisidines, phenetidines, or chlor- or nitro-phenetidines, diazotized and coupled with a - or b -naphthylamine, or their methyl, ethyl, dimethyl, diethyl, methylethyl, mono- or di-phenyl, methylphenyl, or ethylphenyl derivatives; a - or b -naphthylamine or their chlor or nitro derivatives diazotized and coupled with aniline or the alkylated or arylated aniline derivatives mentioned above or a - or b -naphthylamine or the alkylated or arylated naphthylamines mentioned above.  The shades given by the following azo dyes are tabulated:-benzene-azo-benzene-azo-b -naphthol, naphthaleneazo-a -naphthol, p-aminobenzene-azo-dimethylaniline, naphthalene-azo-dimethylaniline, m- or p-nitrobenzene-azo-dimethylaniline, benzene-azobenzene-azo-dimethylaniline, 4-nitro-2-methoxy-benzene-1-azo-dimethylaniline, and the corresponding dyes from diethylaniline or diphenylamine, aminoazonaphthalene; in examples, p-nitrobenzene-azo-diphenylamine, benzene-azonaphthalene-azo-phenol, or 2 : 4-dinitrobenzene-1-azo-diethylaniline and dissolved in sodium sulphoricinoleate.  Naphthylamine derivatives.-The methylethyl-a -naphthylamine and ethylphenyl-a -naphthylamine referred to above may be prepared by ethylating methyl- or phenyl-a -naphthylamine; the diphenyl-b -naphthylamine may be made by further phenylation of phenyl-b -naphthylamine.  Reference has been directed by the Comptroller to Specification 211,720, [Class 15 (ii), Dyeing, Processes &c. for].ALSO:The dyeing or colouring of cellulose acetate goods (yarns, threads, filaments, fabrics, films, &c.) is effected by means of insoluble or difficulty-soluble dyes which have been solubilized by pretreatment with higher fatty acids or their sulpho or other derivatives or salts thereof; sulphoricinoleic acid or oleic, stearic, or palmitic acid or their alkali or ammonium salts are suitable solubilizing-agents.  The dye is dissolved in the fatty acid or salt by stirring and heating, the solution diluted with water, neutralized with alkali if necessary, and added to the dye-bath; highly concentrated or "solid solutions" may be prepared and subsequently dissolved.  Suitable dyes are insoluble azo dyes containing no sulpho group, or dyes of the indophenol, di- or tri-phenylmethane, azine, oxazine, thiazine, or indigoid series, or basic anthraquinone derivatives, the indophenols or indigoid dyes being employed in the unreduced state and the basic dyes being employed in the form of free base.  Azo dyes are described from the following pairs of components: nitranilines, dinitranilines, nitrotoluidines, nitroxylidines, anisidines, chloranisidines, nitroanisidines, phenetidines, chlorphenetidines, nitrophenetidines, or chlornitranilines, diazotized and coupled with aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, methylethylaniline, diphenylamine, methyl- or ethyl-diphenylamine, m-toluidine, or p-xylidine; aniline, chloranilines, nitranilines, chlornitranilines, dinitranilines, toluidines, xylidines, nitrotoluidines, nitroxylidines, anisidines, chlor- or nitro-anisidines, phenetidines, or chlor- or nitro-phenetidines, diazotized and coupled with a - or b -naphthylamine, or their methyl, dimethyl, ethyl, diethyl, methylethyl, mono- or di-phenyl, methylphenyl, or ethylphenyl derivatives; a - or b -naphthylamine or their chlor or nitro derivatives diazotized and coupled with aniline or the alkylated or arylated aniline derivatives mentioned above or a - or b -naphthylamine or the alkylated or arylated naphthylamines mentioned above.  The shades given by the following azo dyes are tabulated: - benzene-azo-benzene-azo-b -naphthol, naphthalene-azo-a -naphthol, p-aminobenzene-azo-dimethylaniline, naphthalene-azo-dimethylaniline, m- or p-nitro-benzene-azo-dimethylaniline, benzene-azo-benzene-azo-dimethylaniline, 4-nitro-2-methoxybenzene-1-azo-dimethylaniline, and the corresponding dyes from diethylaniline or diphenylamine, aminoazonaphthalene; the last-mentioned dye may be diazotized on the fibre and developed with resorcin, dimethylaniline, or b -oxynaphthoic acid.  The following dyes of the other types referred to are specified:-Rosaniline base or its alkyl or aryl derivatives, Pararosaniline base, Malachite green base, safronine base, aminoanthraquinones, aminooxyanthraquinones, 1-oxy-4-p-toluidoanthraquinone, or 1-p-toluido-4-methylaminoanthraquinone.  The process may also be applied in the formation of azo dyes on the fibre by using corresponding solutions of the amino bases, such as p-nitra niline, m-nitraniline, benzidine, dianisidine, dimethylaniline, a -naphthylamine, or diphenylamine.  Mixed goods containing cellulose acetate together with cotton, silk, wool, or cellulose artificial silks, may be dyed; in many cases the solubilized azo dyes dye the acetate fibres but not the other fibres, which may be dyed to uniform or contrasting shades by apprepriate dyes in the same or separate baths; a similar selective effect is shown in developing azo dyes on the material from the solubilized amino bases.  The solutions, mixed with the usual thickening agents, may be employed for printing or stenciling cellulose acetate goods or mixed goods containing acetate. According to examples:-p-nitrobenzene-azo-diphenylamine is well stirred with sodium sulphoricinoleate, diluted, boiled, and filtered into the dye-bath; the goods are dyed at 60-75 DEG  C., an orange shade being obtained; a gold shade is obtained similarly from benzene-azo-naphthalene-azo-phenol; aminoazobenzene is dissolved in sodium sulphoricinolcate, the goods are impregnated with the dye-bath, diazotized, and developed in a bath containing a similar solution of dimethylaniline, giving a scarlet; a bluish-red shade is obtained with Rosaniline dissolved with sodium sulphoricinoleate, and a blue with Indophenol; a mixed fabric of cellulose acetate and cotton is first dyed bluish-red in the acetate portion with 2 : 4-dinitrobenzene-1-azo-diethylaniline dissolved in sodium sulphoricinoleate, and the cotton portion is then dyed blue with Chlorazol fast blue 2B.  According to one of the Provisional Specifications, cellulose acetate may be dyed with indophenols reduced to their leuco compounds with hydrosulphite, stannous salts, &c., followed by oxidation by air, hypochlorites, peroxides, &c. Reference has been directed by the Comptroller to Specification 211,720.