US3479332A

US3479332A - Disazo dyestuffs containing an n,n-dicyanoethyl group

Info

Publication number: US3479332A
Application number: US471447A
Authority: US
Inventors: Marcel Jirou; Jean Marie Louis Leroy
Original assignee: Kuhlmann
Current assignee: PRODUITS CHIMIQUES UGINE KUKLMANN; Produits Chimiques Ugine Kuhlmann; Pechiney Ugine Kuhlmann SA
Priority date: 1964-07-16
Filing date: 1965-07-12
Publication date: 1969-11-18
Anticipated expiration: 1986-11-18
Also published as: FR1409796A; DE1469683A1; GB1117938A

Description

United States Patent M Int. or. 0691) 31/04 US. Cl. 260186 2 Claims ABSTRACT OF THE DISCLOSURE Disazo dyestuffs having one of the following formulae C 112- C Hz- C N C Hz- 0 H2- 0 N Y X in which Y Y Y and Y each represents a hydrogen or halogen atom or a methyl, methoxy or ethoxy group and X represents a hydrogen or chlorine atom or a methyl or methoxy group. These disazo dyestuffs are suitable for dyeing synthetic fibers and more especially polyesters and cellulose triacetate fibers.

The present invention relates to new disazo dyestuffs suitable for dyeing synthetic fibres, and more especially polyester and cellulose triacetate fibres, in brilliant shades ranging from yellow to brownish red. In addition to an excellent fastness to light, these dyestuffs are exceptionally fast to sublimation. The problem of fastness to light is generally solved for polyester fibres by the use of dyestuffs of the anthraquinone series. However, this series is limited in the field of yellow and orange shades.

The problem of sublimation assumes prime importance for the dyeing of polyester and cellulose triacetate fibers because of the high temperatures to which these fibres are subjected. Especially during the heat-fixing, the sublimed dyestuff is liable to be deposited on the cold parts of the apparatus.

It has now been found according to the present invention that dyestuffs of the general formula:

CHzCHgCN i CH2CH2CN in which X represents a hydrogen or chlorine atom or a CH or OCH group, Ar represents a benzene or naphthalene nucleus and the nuclei A and Ar may, if desired, be substituted by halogen atoms or CH OCH or O-C H groups, possess an excellent aflinity and enable full-bodied yellow to red brown shades with very great fastness to light, sublimation, over-dyeing, washing, seawater, perspiration, combustion gases, heat-fixing and folding to be obtained.

These dyestuffs may be synthesised, for example, by coupling an aminobenzene, which may be substituted, with the sulpho omega methyl derivative (i.e. the sulpho group is at the end of the chain) of another aminobenzene or of an alpha aminonaphthalene, which may be Patented Nov. 18,1969

substituted, saponifying the monoazo derivative obtained, diazotising and coupling in acid medium, with or without neutralisation, with a dicyanoethyl derivative of the formula:

in which X has the meaning given above.

As the first constituent there may be used, for example aniline, a chloraniliue, a bromaniline, a toluidine, a anisidine, a chlorotoluidine, a dichloraniline, or a xylidine; as the intermediateconstituent there may be used; for example, aniline, orthoor meta-toluidine, orthoor metaanisidine, meta-chloraniline, para-xylidine, the dimethyl or diethyl ethers of aminohydroquinone, 2,5-dimethylaniline or other similar bases; as the final constituent there may be used, for example, dicyanoethylaniline, metatoluidine, meta-anisidine or meta-chloraniline.

The dyeing'may be effected by known methods, for example, at temperatures below C. with a vehicle or above 100 C. under pressure. i

Compared with the disazo dyestuffs of'similar constitution which carry one or two hydroxyethyl groups, the dyestuffs according to the invention are much faster to light.

By way of indication, the fastness of the dyestufi":

on polyester fibres, measured on the fadeometer, is 1 to 2. while that of the dyestuff:

CHzCHzCN at the same depth of colour, is 5 to 6.

The dyestuif of the formula:

CHzCHzCN and its use for dyeing cellulose acetate have already been described, but this dyestuff has only a very weak affinity for this fibre and poor fastness to light. From this fact it could not be foreseen that the dyestuffs of the invention which have both an excellent fastness to light and an excellent affinity and are very fast to sublimation, could be used on polyester fibres. Several patents mention the use of dicyano ethyl derivatives of aniline and its homologues, but in none of them is the preparation of disazo compounds mentioned. The latter represent an advance on account of their better fastness to sublimation.

The following examples illustrate but do not limit the invention.

EXAMPLE 1 19.8 parts of 4-amino-azobenzene are made into a paste in 40 parts of 20 B. hydrochloric acid, diluted and diazotised for 2 hours with a solution of sodium nitrite. On the other hand, 22 parts of N,N-dicyanoethyl-meta-toluidine are dissolved in 50 parts of ethyl alcohol and poured into the solution of the diazo compound. After stirring for several hours, the dyestuff obtained is filtered off and washed. The paste is mixed with a dispersing agent, for example sodium dinaphthylmethanedisulphonate, dried and ground. The dyestuff obtained dyes polyester or cellulose triacetate fibres in shades of yellow orange.

The following table gives some other examples prepared the fibre and does not migrate to the cold parts of the m an analogous manner to Example 1. apparatus.

Example First constituent Intermediate constituent Final constituent Shade Aniline Aniline N ,N-dicyanoethyl aniline Reddish-yellow. 3 4-chloro-2-methylaminobenzene Meta-anisidine o Yellow-orange. Ortho-broman1l1ne D o.

6 Meta chloran11me Meta-anisidine. 0.-

An ine Alpha naphthylammm ,N-dicyanoethyl-meta-toluidine Brownish-red 8..- 2,4-d1chloroanil1ne Meta-anisidlne o Oran ge Brownish-red.

d n Aminohydroquinone dimethylether do 2,5 dich1oroan1line eta-toluldin do. Orange. n Meta-chloranllme do Yellow-orange.

Red-orange.

13.- 2,4-xyl1dme Meta-toluidme -do. 14 Ortho-toluidine Ortho-toluidine do Orange-red. gntillineh .1 1 1\A/lniizlirltfff .l N ,bg-dicyanoethyl meta-anisidine gedprange. 1 -0 orani 1ne e 31-0 013 111G O I 17 Meta-toluidine Meta-anisidine ..do Rei i fange. 1g gngkllmeifivn ffln aniline id," N,Ndicyanoethyl-meta-ehloraniline geddish-yellow.

1 0-0 oranl 1ne e arau s e O T811 e. 20 r Ortho-toluidine Ortho-toluidine do Ye1lo%v-orange.

EXAMPLE 21 We claim: A printing paste of the following composition is 20 1. Disazo dyestuffs having one of the formulae: ared: U X P Parts I /OHCH2CN 4 Dyestufi of Example 15 1o -N=N@-N=N N Sodium dinaphthylmethane-disulphonate 14 25 v CH1CH2CN Ethylene glycol monoethyl ether 50 Y 2 Water 300 Aqueous solution of sodium chlorate containing 300 CH CHgCN g. per litre @N: A-N=N N Starch tragacanth thickener 600 30 CH CH2CH2CN This paste is applied on a grooved roller to a fabric of 3 polyester fibres, previously desized at 45 C. by alkaline washing. The colour is fixed by steaming under pressure at 130l40 C. The fabric is rinsed and treated in the hot with an alkaline reducing bath containing 1 to 2 g. per litre of a nonylphenol-ethylene oxide condensate. The fabric is coloured a red-orange shade of excellent fastin which U and V each represent a hydrogen or chlorine atom, V is fixed on the position 4 or 5. X represents 5 a hydrogen atom or a methyl or methoxy group, and Y and Z each represent a hydrogen or chlorine atom or a methyl or methoxy group.

2. Disazo dyestuifs according to claim 1 in which U and ness; the reserved parts being white. V are hydrogen atoms 40 EXAMPLE 22 References Cited A foularding bath of the following composition is pre- UNITED STATES PATENTS pared Parts 2,821,526 1/1958 Boyd 260 20s Rh ner 260205 Dyestuif of Example 6 30 2,941,992 6/1960 y Sodium dinaphthylmethane-disulphonate 7 3092616 6/1963 Gaetam 260 186 Starch tragacanth thickener 5 CHARLES B. PARKER, Primary Examiner DONALD M. PAPUGA, Assistant Examiner Water 58 A strip of polyester fabric is foularded several times in this dispersion and heat-fixed for one minute at 200 C. U.S. Cl. X.R. Since the dyestuif is fast to sublimation, it remains on 841, 260-191 IN THE UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 479, 322 Dated Nov. 18, 1969 A. H. Peterson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the patent, Col. 3, line 36 "marco" should read macro Col. 4, line 2 "monotrnor" should read -montmc Col. 4, line 35 "primer" should read --trimer-- SIGNED fiND SEALED JUN 2 gm (SEAL WIN-1AM E. $080M I Edn 1 mm In Comissioner of la'bntl