CA1055020A

CA1055020A - Disazo navy blue dyes for nylon

Info

Publication number: CA1055020A
Application number: CA230,766A
Authority: CA
Inventors: James F. Feeman
Original assignee: Crompton and Knowles Corp
Current assignee: Crompton and Knowles Corp
Priority date: 1974-07-10
Filing date: 1975-07-04
Publication date: 1979-05-22
Also published as: CH606307A5; FR2277865A1; DE2530443A1; NL7508075A; IT1039462B; ES439259A1; GB1509737A; BE831126A; FR2277865B1

Abstract

ABSTRACT

The compounds having the structure:

wherein R 13 Cl, -CH3. -C2H5, -OCH3 or -OC2H5; R1 is -H, -Cl, -CH3, -C2H5, -OCH3 or -OC2H5; R2 is -H or -CH3; and M ls -H, -Na, -X, -Li, or -NH4 are useful a water-soluble acid dyes giving navy blue hues on nylon and other polyamide fibers and have good light fast-ness and wash fastness and dye nylon fibers over a wide pH range.
They are capable of dyeing nylon efficiently at neutral and alaka-line pH. They are also useful as dyes for natural polyamides such as silk and wool.

Description

1~550;~0 DISAZO NAVY BLUE DYES FOR NYLON
This invention relates to a new group of disazo compounds which are useful as dyes for polyamide textile fibers and fabricsO
The compounds of this invention have the structure:
R

--N=N ~ N=N ~ ~ NH

Rl SO3M

wherein R is Cl, -CH3, -C2H5, -OCH3 or -OC2H5; Rl is -H, -Cl, -CH3, -C2H5, -OCH3 or -OC2H5; R2 is -H or -CH3; and M is -H, -Na, -K, -Li, or -NH4~
The compounds of this invention are water-soluble acid dyes giving navy blue hues on nylon and other polyamide fibers and have good light fast-ness and wash fastness and dye nylon fibers over a wide pH range. They are capable of dyeing nylon efficiently at neutral and alkaline pHo They are also useful as dyes for natural polyamides such as silk and woolO
Because of their neutral dyeing capability, the compounds of this invention can be used in mixture with direct dyes for cellulose, and mixed fabrics made from polyamide and cellulose fibers can be dyed from a single bath~
The compounds of this invention are made by diazotizing a primary aromatic amine such as o, m, or p-chloroaniline, o, m, or p-toluidine, o, m, or _-anisidine, o, _, or p-phenetidine, o, m, or p-ethylaniline, 2-chloro-4-2a aminotoluene, 4-chloro-2-aminotoluene, 6-chloro-2-aminotoluene; 2,5-dichloro-aniline, 3,4-dichloroaniline, 2,3-dichloroaniline, 2,4-dichloroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,4-xylidine, 3-chloro-2-methoxyaniline,

2-chloro-5-methoxyaniline, 2-chloro-5-ethoxyaniline; coupling the diazonium salt to l-aminonaphthalene-6-sulfonic acid (Cleve's 1,6-), l-aminonaphthalene-7-sulfonic acid (Cleve's 1,7-) or a mixture of Cleve's 1,6- and 1,7-acids (especially the readily available mixed acid that is composed of about 54% of the 1,6-Cleve's and about 46% of the 1,7-Cleve's); rediazotizing the reaction product and coupling the resultant diazonium salt with N-phenyl peri acid or an N-to~lperi acid - usually ~-N-tolyl peri acid;
recovering the dye from the reaction mixture and optionally converting it to another desired salt form by appropriate acidification and/or neutraliza-tionO
The compounds of this invention are usually formed as sodium salts of the sulfonic acids and may be used as such or converted to the free acids by treatment wi~h an inorganic acid; the free acids can then be converted to any of various salts such as -K, -Na, -Li, or -N114 by neutralization with a suitable hydroxide, carbonate or ammoniaO
The compounds of this invention are intended to replace dyes such as C.I. Acid Blue 113, C.I. Acid Blue 114, and C.I. Acid Blue 120, all of which require the use of l-naphthylamine as an intermediate or as the pre-cursor of the intermediate. Such replacement is important because 1-naphthylamine has been declared by Federal authorities to be a hazardous substance with carcinogenic potential. The compounds of this invention are prepared from Cleve's 1,6-, Cleve's 1,7- or Mixed Cleve's 1,6- and 1,7-acids - i.eO, naphthyl compounds that can be prepared from naphthalene with-out using or producing l-naphthylamine.
Somewhat similar dyes (e.g., C.I. Acid Blue 116 or C~Io Acid Blue 118~ prepared from aniline rather than the specified substituted anilines are inferior to the compounds of this invention from the standpoint of neutral dyeability. They cannot be efficiently or economically used to pro-duce deep blue shades unless the pH of the dye bath is on the acid side -i.e., below about 6 during a substantial portion of the dyeing cycleO Fur-ther, the chloro, dichloro and chloroalkyl derivatives of this invention are of greener hue than the compounds prepared from aniline and, therefore, they give dyers still another differently hued self shade blue dye that will sim-plify and facilitate matching shades in an economic manner and without adversely affecting other properties of the dyeingO Thus it will permit shade matching without the need of locating a compatible yellow shading dye that will strike and exhaust at substantially the same rate as the blue from any given bath pH and at any given temperature. Compatibility also requires that the shading dye should not adversely affect the overall properties of the dyeing - particularly light fastness and wash fastness. As the addition of a shading dye in any quantity (in addition to changing hue) will in-variably exert some influence on other properties of the dyeing, and since the influence will be accentuated as the quantity of shading dye is in-creased, it is a distinct advantage to the dyer to have as many as possible different pure self shades in his arsenal; this will reduce the amount of shading dye that must be added in order to match shades specified by his customers and, in some cases, totally eliminate the need to add any shading dye.
The following example illustrates the preparation of representa-tive dyes of this invention, the utilization of the dyes in dyeing polyamides and the novel dyeings thereby produced. In this example, parts and per-centages are by weight and temperatures are in degrees Centigrade unless otherwise stated.

Ortho-chloroaniline (12.8 parts) was dissolved in 25 parts of water and 28 parts of 32% hydrochloric acid, ice added to O and diazotization 20 carried out by adding 25 parts of 4 N sodium nitrite solution at O . After stirring 10 minutes a slight excess of nitrous acid was removed by addition of sulfamic acid solution.
The solution of diazonium salt was added gradually in 15 minutes to 22.5 parts of Cleve's 1,6- acid (which had been dissolved in 150 parts of water at 50 and at pH 8.5 and cooled to 5 with ice). The pH of the mix-ture was then raised to 4.0 by adding during 5 minutes 7 parts of sodium bicarbonate. After stirring 18 hours, the pH was raised to 12 and the inter-mediate monoazo compound isolated by adding 5% (based on volume) of sodium chloride and filtering.
The filter cake was pasted in 200 parts of water at 20 and treat-ed with 7.5 parts of NaNO2 as aqueous solution. To the slurry was added 30 parts of 32% hydrochloric acid and ice to 10 . The diazotization mixture :1~)550Z0 was stirred for four hours at 10-15 . Excess nitrous acid was then removed by addin6 sulfamic acid.
To the diazonium salt slurry was added during 15 ~inutes a mixture of 30.3 parts of N-phenyl peri acid in 50 parts of water, 4 parts of sodium hydroxide, 10 parts of sodium bicarbonate, and ice to 10. The coupling was stirred at pH 4 for one hour; then the pH was raised to 11.5 with sodium hydroxide solution. The mixture was heated to 60 7 filtered, and the pre-cipitate dried at 90 .
The product is a dark colored solid which dyes nylon and other polyamide fibers from alkaline, neutral or acidic aqueous baths in navy hues of good wash fastness and good light fastness and has the structure:

N-N ~ N=N ~ NH

Cl ~ ~ S03~a S03Na In the preceding example, replacement of the o-chloro-aniline by m-chloroaniline, ~-chloroaniline, o-anisidine, m-anisidine, ~-anisidine, o-toluidine, m-toluidine, ~-toluidine, o-phenetidine, m-phenetidine, ~-phenetidine, or 2-chloro-4-aminotoluene, 4-chloro-2-aminotoluene, 6-chloro-2-aminotoluene; 2,5-dichloroaniline, 3,4-dichloroaniline, 2,3-dichloroan-iline, 2,4-dichloroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,4-xylidine, 3-chloro-2-methoxyaniline, 2-chloro-5-methoxyaniline, 2-chloro-5-ethoxyaniline; or of the Cleve's 1,6- acid by Cleve's 1,7- acid, or a mix-ture of Cleve's 1,6- acid with Cleve's 1,7- acid, gives dyes which have similar properties to those of the dyes of Example 1 but which have minor variations in hue, the chloro compounds having greenish-navy hues, with the alkyl and alkoxy compounds having slightly redder navy hues on nylon.

Claims

I Claim:

1. A compound having the structure:

wherein R is -Cl, -CH3, -C2H5, -OCH3 or -OC2H5; R1 is -H, -Cl, -CH3, -C2H5, -OCH3 or -OC2H5; R2 is -H or -CH3; and M is -H, -Na, -K, -Li or -NH4.

2. A compound having the structure:

wherein R2 is -H or -CH3; R4 is -H, -Cl, -CH3, -C2H5, -OCH3 or OC2H5; and M is -H, -Na, -K, -Li or -NH4.

3. A compound according to Claim 2 where R2 is -H.

4. A compound according to Claim 3 where R4 is -H.

5. The 6-sulfonic derivative of a compound according to claim 1.

6. The 7-sulfonic derivative of a compound according to Claim 1.

7. A composition of matter comprising a mixture of the derivatives of Claims 5 and 6.

8. A compound according to Claim 1 having the structure:

9. A compound according to Claim 1 having the structure:

10. A compound according to Claim 1 having the structure:

11. The process of dyeing natural and synthetic poly-amide fibers which comprises contacting the fibers with an aqueous dye bath containing a compound according to Claim 1.

12. A polyamide yarn or textile dyed with a compound according to Claim 1.

13. The method of making a compound according to Claim 1 which comprises diazotizing a primary aromatic amine structured to give substituents corresponding to R and R1, coupling the diazonium salt to Cleve's 1,6- acid, Cleve's 1,7- acid, or a mix-ture of Cleve's 1,6- and 1,7- acids; rediazotizing the reaction product and coupling the resulting diazonium salt with N-phenyl peri acid or N-tolyl-peri acid.