CA1096557A - Polyester dyed with o-nitrophenylazo-2-naphthol dyes - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Aromatic polyester textile material dyed with an o-nitrophenylazo-2-naphthol compound of the formula:

wherein X1 and X2 are independently hydrogen; carboxy; carbalkoxy (the alkyl portion having 1-4 carbon atoms); chlorine; bromine;
sulfamyl; trifluoromethyl; alkylsulfone (the alkylportion having 1-4 carbon atoms); monoalkylsulfonamido (the alkyl portion having 1-4 carbon atoms) and dialkylsulfonamido (the alkyl portion having 1-4 carbon atoms); and Y1 and Y2 are independently selected from the group consisting of hydrogen;
amino (-HNR, -NRR, where R is alkyl of 1-4 carbons); RCONH-(where R is alkyl of 1-4 carbons) hydroxy; RCOO- (where R is alkyl of 1-4 carbons); chloro; bromo; alkyl of 1-4 carbons;
carboxy; carbalkoxy (the alkyl portion containing from 1-4 carbon atoms); carbalkoxyamino (-NHCOOR, where R is alkyl of 1-4 carbons) and carbamyl in which the nitrogen atom is unsub-stituted, singly substituted with alkyl of 1-4 carbon atoms or phenyl (which, in turn, may be substituted with methyl or ethyl) or doubly substituted with alkyl of 1-4 carbon atoms; are provided. The dyeings are of strong, brilliant orange to red hues of excellent build-up and of unexpectedly outstanding lightfasteness and good sublimation.

Description

Il , BACKGROUND OF THE INVENTION

Field of the Invention Among commercial textile ~ibers, those based on aromatic, polyesters and~ particularly, polyethlene terephthalate, continue ~5 to be the most important although ~ibers based on 1,4-dimethylenecyclohexane terephthalate have become commercially !
available Developments in both homo- and copolyesters have continued and many modified versions of polyethylene terephthalate¦
are now on the marke-t. With the ad~ent of new fibers, ho~ever, the search is continuing for dyes wh~ h build-up on the various types of aromatic polyester fabrics proportionate to the amount . of dye applied, and which are characterized by good lightfastness and good s~blimation properties.
Monoazo compounds, generally, are known to have utility i~ the dyeing o~ synthetic ~ibers. The properties of these dyes, howPver, vary with their structure and the particular substrate I to which they are applied. Att~mpts have been made, therefore, to correlate the structure~o~ monoazo dyes ~ith their properties.
Thus, for example it is reported by Venkataraman~ The Ch~mistry of S~nthetic Dyes, Vol. I, New York, Arademic Press, 1952, p.474, that the position o~ to the azo linkage in the diazo part of such dyes was the most sensitive to the e~fect of a substituent ~ith respect to fastness to light. In a series of monoazo dyes, having~
in the diazo par-t, ortho to the azo linkage, OCH3, phenyl, CH3,0

-2- Botros t~ I
. I

1 Cl, COOH, S03H and N02 substituents, it was found that best ast-ness to light was shown by the o-carboxy dye whereas poorest lightfastness was shown by the o-chloro and o-nitro dyes. The influence on the lightfastness of substituents in ortho position to the azo linkage of certain monoazo dyes is also discussed by Muller in an article entitled "Recent Developments in the Chemistry of Disperse Dyes and Their Intermediates" American Dyestuff Reporter, (March, 1970), 41-43. He arranged the substi-tuents in order of decreasing ~he lightfastness as follows:
CN, Cl, H, CH3, and N02 and reported that the monoazo dye with the N02 group ortho to theazo linkage is 4-~ points poorer in lightfastness than its analag having the ni-trile group~ When monoazo dyes having the above groups ortho to the linkage were tested on Dacron* polyester' fibers, they followed the same order of decreasing the light-fastness as indicated above. Furthermore, the dye with the nitro group ortho ~o the azo linkage gave the lowest lightfast-ness on both Dacron* and nylon.

Contrary to these teachings, it has now been found according to the present invention that a specific class of monoazo dyes having a nitro group ortho to the azo linkage and pre~ared by coupling an appropriate diazotized amine into a 2-naphthol in an alkali~e medium pxoduce dyeings on aromatic polyester fibers of outstanding lightfastness. The compounds are also desirable

3~

*Trade Mark -3-~ .

1 ~q~;7 l I

in tha they dye polyester fibers in strong, brilliant orange to ~¦ red hues of excellent build-up and good sublimation.
Although nitrophenylazo-2~naphthol compounds and, particularly, o-nitrophenylazo~2-naphthol compounds, are reported in the dye art, they do not appear to be disclosed for use in dyeing aromatic polyester ibers probably in view of the belief . that a nitro group ortho to the azo linkage will adversely ef~ect.
: .the lightfastness on polyester.
. ~ . In the priox art, Pigment Orange 2, C.I. 12060 (Colour `10 Index, Vol. 4, Third Edition, 1971) is o-nitroaniline diazo coupled with 2-naphthol.
: Herzber~ e-t al, United States Patent No. l,038,884, discloses that compounds corresponding ~o the formula:
'`, . .

~15 are insoluble in water and are especially adapted for the manu- .
: facture of pigments which are distinguished by their fastn~ss to light.
Other nitrophenylazo Z-naphthol compounds are disclosed . by DahLen et al, in United States Patent No. 2,135~964 The ZU compounds include those of ~he structure: -

-4- Botros o~ !

I ~ q~i~57 , 'i NHacyl Aryl-N=N

and are shown in the examples of the patent to have utility in the . coloration o~ cotton by printing and dyeing metho1s.

~¦ onoazo dyes of the ionmula:

2 ~ N~N-R

~. wherein X is CH3, OCH3, or CC2H5; and ; ~ R is a coupling component of the naphthalene series I -containing a hydroxyalkyl side chain or hydroxyalkylamino I
side chain;

are disclosed by Mo~by et al, Uni-ted States Patent No. 1~935,657, as having particular ~alue in the dyeing of cellulose acetate or other cellulose esters or ethers. Maphthols are not disclosed as c ouplers in the patent.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided aromatic polye~ter textile material dyed w.ith an

5- Botros ~ I

;557 ~¦o-nitrophenylazo-2-naphthol compound of the formula:

x2 No2 OH
X~y2 wherein XL and x2 are independently hydrogen; carboxy; carbalkoxy (the alkyl portion having 1-4 carbon at~ms); chlorine;
S bromine; sulfamyl;tri~luoromethyl; alkylsulfone (the alkyl portion having 1-4 carbon atoms);
: monoalkylsulfonamido (the alkyl portion havin~ 1-4 carbon atoms) and dialkylsulfonamido (the alkyl portion having ; 1~4 carbon atoms); and L0 yl and y2 are independently selected from the group con-sisting of hydrogen; amino (~HNR, -~RR, where R ;s alkyl o~ 1-4 carbons); RCONH- (where R is alkyl o 1-4 carbon3) hydroxy; RCOOL (where R is aLkyl of 1-4 carbons); ch~oro;
br~mo; alkyl of 1-4 carbons; carboxy; carbalkoxy ~the !5 alkyl por~ion containing from 1-4 carbon atoms);
. carbalkoxyamino (-NHCOOR, where R is alkyl of 1-4 carbons) ; and carbamyl in which the nitrogen atom is unsubs~ituted, ~ singly substituted with alkyl of 1-4 carbon at~ms or : phenyl ~which, in turn, may be substituted with methyl or O ethyl) or doubly substituted with alkyl o~ 1-4 car~
; atoms.

~ -6- Botros .' . I;

¦ I r ~

I
. ' ~
The dyed aromatic polyester textile materials according ~
to the invention are dyed in strong, brilliant orange to red hues ;, of excellent build-up, good sublimation and outstanding lightfast-. ness.

~ DESCRIPTIOW OF PREFEI~RED E~IBODI~OENTS

The ~onoazo dyes-according to the invention are made in : a usual way by adding an appropriate diazotized a~umatic amine to : an alkaline solution o~ the 2-naphthol coupling ccmponent!
Diazotiza~ion of the ar~matic amine is effected by hea~-¦
ing it (i necessary to achieve solution) in an aqueous solution of strong mineral acid such as hydrochloric acid~ coolin~ the resulting solution to a t~mperature of 0-10C, and adding thereto a quantity of sodium nitrite sligh~ly in excess of the stoichio- ¦
metric re~uirement. An al~ernate method of diazotization involves.
~15 dissolving sodium nitrite in concentrated sulfuric acid, heating . to a temperature of about 60-70 C, cooling the resulting solu~ion to 0-10C and adding thereto the aromatic amine.
The coupling reaction is carried out by adding the diazonium salt to a cold aqueous alkaline solution of the respec-~20 tive coupler, The mixture is allowed to react untiL the coupling is essentially complete, usually in 1-24 hour5 at 0C to ro~m : te~perature and is thereafter filtered and washed with water or water containing dissolved sodium chloride. The product may be reslurried in water which is then made acidic to Congo ~ed paper I -7- Botros , .

.f ~1 ~with hydrochloric or other acid. The mixture is fil~ered and the cake is washed neutral with water. The desired azo produc~ is thus obta;ned in the form of a moist cake. The product may be used in this form or it may be dried be~ore grinding with a suit- i, able agent to oxm a disperse paste or powder as described ~ore fully below Aminobenzenes useful as the diazotizable base in the coupling reaction must, of course, have a nitro group orthoto the amino group. Typical of these aminobenzenes are o-nitroaniline;
4-chloro-2-nitroaniline; 4~5-dichloro-2-nitroaniline;
~onobromo-2-nitroaniline; 4,6-dichloro-2-nitroaniline;
3-nitro-4-aminobenzoic acid~ ethyl-3-nitro-4-aminGbenzoate;
l-amino-2-nitrobenæene-4-N,N-dimethylsulfonamide;
- 4,6-dibromo 2-nitroaniline; 4-trifluoromethyl-2-nitroaniline;
L5 1-a~ino-2-nitrobenzenesulfonamide; 1-amino-2-nitro-4-methylsulfone.l Aside from the re~uirement relating to the nitro group, the choice i of suitable aromatic amines wherein Xl and x2 are as defined above is believed to be limited only by economic considerations and availability.
As suitable 2-naphthol coupling components there ~y be mentioned 2-naphthol; 8-acetamino-2-naphthol, 8-carbethoxya~ino-2-naphthol; 6-bromo-2-naphthol;
8-carbmethoxyethylamino~2-naphthol; 3-(o-toluamido)-2-naphthol;
8-M~N-diethyl~mino-2-naphthol; 8-ethylamino-2~naphthol;
Z5 8-amino-2-naphthol; 2,3-dihydroxynaphthalene; 1 ;:~ ~
~ - -8- Botros ~' . ., I

~i i,2,7-dihydroxynaphthalene and 2-hydroxy-3-naphthoic acid. TypicaLly ¦l,preferred 2-naphthol compounds are 2-naphthol;
~-acetamino-2-naphthol; 6-bromo 2~naph~hol;
8-carbèthoxyamino-2-naphthol and 3-(o-toluamido)-2-naphthol because of their brightness and superior lightfastness when coupl~
into o-nitroaminobenzenes.
To prepare the azo c~mpound for application to the synthetic fiber substrates noted hereabove, it must be suita~ly dispersed. This may be done by any of the several well-known methods, e g., milling as in a ball-mill with dispersing agents such as lignin ~.ulonic acid materials. The resultant aqueous dispersion can be dried, as in a spray-dryer~ or preserved and used as a paste. Standardization to any desîred lower strength can be done with inert colorless diluents such as water soluble - inorganic salts, soluble organic materials or additional disper-sants for powders, or wate~ fox pastes. Other materials such as preservatives, oam-con~rol agents, and wetting agents (for powders) may be added as desiredO
Dispersed pastes are made by wet milling the azo materials in conventional equipment in the presence of a dispersing agent, preferably sodium lignin sulfonate or sodium alkylnaphthalene sulfonate. Various other commercially available dispersing agents, such as sodi~um salts of carboxylated polyelectrolytes and the naphthalene sulfonates~ e.g., the condensation products of sulfonated naphtha].ene and fonmaldehyde, .
-9- Botros ! ~f ,- t 1~6S5~ 1 such as sodium dinaphthylmethanedisulEonate, are conveniently ~¦used. The disperse paste may be cut or standardized to a standard strength with water. The final color content of the ~inished paste is usually from 10 to 40% by weight (pure color) active dye bas e.
Disperse powders are prepared by wet milling coLor in the presence of a dispersant~ such as those mentioned hereabove, ; in equipment such as a ball-mill, Werner-Pfleiderer mill or attritor~ The dispersed material is oven or spray dried and micropulverized if necessary to provide the dispersed powder. The color is cut or standardized to a standard strength in a blender with a diluent, such as the same or another dispersant or dextrin. ¦
A wetting agent, such as sodium cetyl sulfate or an alkylphenoxy polyethanol may be added to aid in wet-ting-out the product when it is placed in the dye bath. Disperse powders are usually cut or standardized to 10-50 percent by weight color content (pure color).
The dye, when added to water with or without auxiliary agents, fonms a ~ear colloidal aqueous dispersion ~r~m whic'n .
aromatic polyester fiber or textile material is dyed i~ the con-ventional manner at 40-105C (104-220F) to give a colored fiber containing about 0.01-2 percent by weight dye (100% color basis).
Alternatively, dyeing on polyester may be accomplished without a carrier at temperatures of 100-150 C under pressure.
The dye may also be applied in patterns by conventional printing methods. The printing paste can be thickened with -10- Botros ,,, ,. , I

'5 I . '~ ' ~

customary thickening agents and may also contain other additives conventionally used with printing pastes. The printing paste is expediently applied to the ~abric by a printing block or a roller, whereupon the printed fabric is dried and steamed at a temperature between 105C and 110C. After thP dyeing or printing of the fibers, it is treated with a hot aqueous soap solution, rinsed thoroughly and dried. As suitable dyeing and printing techniques there may be mentioned those described in United States Patent Nos 3,399,027; 3,399,952; 3,492,078; 3,556,709; and 3,360,656.
The dye can also be applied to aromatic polyester iber ¦
by thenmofixation methods, such as the "Thermosol" process. This process, which involves padding the cloth with the diluted dye dispersion followed by drying and heating with dried hot aix or heated contac~ rolls, is convenlently used for dyeing polyester fibers and blends containing these fibers. Fixation temperatures of 180-220 C (356-428 F~ are used for 30 to 90 seconds. If the fabric contains cotton or viscose rayon, apart from synthetic fibers~ there is little danger of damaging cellulosic port~ons, but if wool is present, the temperature must be kept within 180-200 C and the time must be reduced to 30 seconds.
In order to evaluate the effectiveness o a particular ~, ~ dye for a given type of fiber, the dyed fiber is examined for various properties including, for example, substantivity, light- j fastness and resistance of the color to sublimation. Sublimation ~- tests were conducted a~cording to standard M TCC Fastness to Dry -11- Botros ,,. . I
,,, 1 Heat (sublimation) Test No. 117-1974T, p. 119 of the 1974 Technical Manual of the American Association of Textile Chemists and Colorists. Lightfastness tests were conducted according to AATCC Color Fastness to Light Xenon Arc Lamp, Continuous Light Test No. 16E-1974, as detailed on p. 133, of the 1974 Technical Manual of the AATCC. A11 dyeings were made on Type 54, Style 755 Dacron*.
EXAMPLE I

Preparation o~ the Dye:

N=N ~

(M.W. 293) A mixture of 13.8 g o-nitroaniline, 40 g 32% hydrochloric acid, 40 ml water and 2 g Tween* 20 was heated at 55-60C to a smooth slurry. The mixture was drowned hot into 200 g ice and was diazotized at 0C with a solution of 7.2 g sodium nitrite in 50 ml water. The diazo mixture was stirred at 0C for one half ~ hour. Excess nitrous acid was destroyed with a few drops of - sulfamic acid solution and the diazo solution was clarified.
It was then added in small portions at 0C to a clear solution of 14.4 g 2-naphthol dissolved in 500 ml water, 4 g sodium hydroxide beads 3~

*Trade Marks -12-L~

- 1~916~7 1 and 19 g sodium carbonate. Coupling was very rapid. The coupled mass was ~hen filtered and the cake was washed nearly alkali free with water. The moist cake was reslurried in water and was made acidic to Congo Red paper with hydrochloric acid.
After stirring for 2 hours the mass was filtered and the cake was washed neutral with water.
Yièld = 224.2 g moist cake (dry test: 13%) = 29.1 g dry product Theory = 29.3 g Standardization: 200 g of the moist cake (dry test 13%), 19.5 g Lignosol* FTA, 19.5 g Lignosol*
D-10, 21 ml water and 150 g sand were charged to a sandgrinder and the mix-ture was milled until dispersion test was satisfactory.
Yield = 260 g 10% color content paste The dispersed product dyed polyester fabric in brilliant orange shades of excellent depth and build--up. r~he lightfastness was outstanding. There was no break at 20 exposure hours under Xenon light. Sublimation at 3500F was good.

Preparation of the Dye:

=N

(M.W. 372) Br '; ` .
, ' *Trade Mark -13-B

1 A mixture of 21.7 g monobromo-o-nitroaniline (made by mono-bromoinating o-nitroaniline in 32% hydrochloric acid), 40 g 32%
hydrochloric acid and 2 g Tween* 20 was heated to 60C, then stirred to room temperature. The smooth slurry was then drowne~
into 1000 g water-ice mixture and was diazotized at 0C with a solution of 7.1 g sodium nitrite dissolved in 100 ml water.
The diazo mixture was stirred at 0C for one hour. Excess nitrous acid was destroyed with a few drops of sulfamic acid solution and the diazo solution was clarified. It was then ~9 added in small portions at 0C, to a clear solution of 14.4 g 2-naphthol dissolved in 750 ml water, 4 g sodium hydroxide beads and 18.6 g soda ash. Coupling was very rapid. The reaction mass was filtered and the cake was washed nearly alkali free with water. The moist cake was reslurried in water, made acidic to Congo Red paper with hydrochloric acid, filtered and washed neutral with water~
Yield = 106.8 g moist cake (dry test: 22%) = 23.5 g dry product Theory = 37.2 g - When applied to polyester fabrics, the dispersed product produced ,~ brilliant orange shades of more depth and build-up than those :
obtained in Example I. Lightfastness was equally outstanding.

, .

~ ' - 3~

*Trade Mark -14-~B

r 9~57~ -I . ' ` .
EXAMPL~ III

Preparation of the Dye:

CO~

(~.W. 350) Following the procedure outlined in Example I, 13.~ g o~nitroaniline was diazotized ànd the diazo solution was added ; during one hal hour at 0C to a clear solution o~ 20.1 g ~
l-acetylamino-7~naphthol in 500 ml water, 4 g sodium hydroxide beads and 19 g soda ash. The coupling mixture was stirred ~o room ;~ lO temperature overnight. It was then filtered and the cake was washed neutral with water. The product was dried in an ovenr -Yield = 27.6 g ~ Theory = 35~g `; -The di~persed prod~ct dyed polyester fabric in bright yelLowish red shades o excellent bùild-up, The sublimation fastness and ~ 15 lightfastness were outstanding. There was no break at 20 e~posure ;` hours under Xenon ligh~.
. , .

-15- Botros !

. - . I

~Q~ 7 1 EXA~LE IV
Preparation of the Dye:

Cl~N=N
.~ ~
(M.W. 327.5) A mixture of 17.3 g 4-chloro-2-nitroaniline, 40 g 32% hydro- -lO chloric acid, 40 ml water and 2 g Tween* 20 was stirred to 70C, then drowned hot into 200 g ice and 100 ml water. The fine slurry was then diazotized at 0C with a solution of 7.2 g sodium nitrite in 50 ml water. The diazo mixture was stirred at 0C for one hour. Excess nitrous acid was destroyed with a few drops of sulfamic acid solution and the diazo solution was clarified. It was then added during one half hour at 0C to a ,~ clear solution of 14.4 g 2-naphthol in 500 ml water, 4 g sodium hydroxide beads and 19 g soda ash. The reaction mixture was filtered and the cake was washed neutral with watar.
Yield = 144.4 g moist cake (dry test: 22%) = 31.7 g dry product Theory - 32.8 g The dispersed product dyed polyester fabric in bright orange shades of excellent build-up. The lightfastness was outstanding *Trade Mark -16-D
l L~

l There was no break after 20 exposure hours under Xenon light.

EXAMPLE V

Preparation of the Dye:

HOOC ~ N=N ~

(M.W. 337) 22.4 g 3-nitro-4-acetaminobenzoic acid (made by mononitrating p-acetaminobenzoic acid with 40~ mixed acid) was dissolved in 100 g 66Bé sulfuric acid. The clear solution was diluted with 34 ml water, and the mass was heated at 95-100C for 3 hours.

Then it was drowned into 700 g ice, 100 ml water, 25 g 32%

hydrochloric acid and 2 g Tween* 20. The slurry was diazotized ,~ .
with a solution of 7.5 g sodium nitrite dissolved in 50 ml water.
;' The diazo solution was stirred at 0C for one hour. Excess ~- nitrous acid was destroyed with a few drops of sulfami~ acid solution and the diazo solution was clarified. It was then 2~ added at 0C during one and one half hour to a clear solution of 14.4 g 2-naphthol, 500 ml water, 4 g sodium hydroxide beads and l10 g soda ash~ Coupling was very rapid. The reaction mass was filtered and ~he cake was reslurried in water and made acidic to Congo Red paper with *Trade ~ark -17-il hydrochloric acid. After filtration, the cake was ~ash d acid free with water and sucked dry.

Yield = 95.2 g mois~ cake (dry test: 38%) = 36 g dry product Theory = 33.7 g I ;

The dispersed product dyed polyester fibers in brilliant yellowish¦
orange shades by the carrier method and pressure method. The thermofixation dyeings, however, were weaker. Light~astness and sublimation were outstanding. There was no break at 20 exposure hours under Xenon light.

XAMPLE VI

Preparation of the Dye:

' C~)OC2H5 -(M.W, 380) Following the procedure outlined in Example I, 13.8 g o-nitroanili~e was diazotized and the diazo solution was added at 0C during one hal~ hour to a clear solution o~ 23.1 g 8 carbethoxyamino-2 n~phthol (made by condensation o~
8-amino-Z-naphthol with ethyl chloroEormate) in 500 ~1 water, ~18- Botros ~
I ., I

5~

1 4 g sodium hydroxide beads and 19 g soda ash.- The coupled reac-tion mass was filtered and the cake was washed neutral with water.
Yield = 53.7 g moist cake (32% dry test) = 17.2 g dry product ~ Theory = 38 g ,; The dispersed product dyed polyester fibers in strong scarlet shades of superior sublimation and lightfastness. There was hardly any mark off on the undyed fabric at 400F in the sublima-;-. 10 tion test. Also, there was no break after 20 exposure hours - under Xenon light.
~, EXAMPLE VII
,`: ` .
, ~ Preparation of the Dye:
NO OH

' ~ F3 ~ N=N

HN

(M.W. 418) A mixture of 20.6 g 3-nitro-4-aminobenzotrifluoride, 40 g 3Z%
hydrochloric acid, 40 ml water and 2 g Tween* 20 was heated to a ~ine slurry at 65~70C then drowned into 100 g ice and 100 ml water. The slurry was diazotized at 0C with a solution of 7 . 2 g 3~

*Trade Mark -19-B

I
1, I
I ¦sodium nitrite dissolved in 50 ml water. The diazo mixture was stirred at 0C for one hour. Excess nitrous acid was des,roye~ I ;
with a few drops of sulfamic acid and the diazo solution was clarified. It was then added at O C to a clear solution of 20.1 g!
8-acetylamino-2-naphthol in 500 ml water, 4 g sodium hydroxide beads and 19 g soda ash Couplng was very rapid. The reaction mass was iltered and the cake was washed neutral with water.

Yield = 40.2 g moist cake (44% dry test) ~- = 17.7 g dry product Theory = 41.8 g The dispersed product dyed polyester in a rather weak scarlet shades of excellent lightfastness and outstanding sublimation.

EX~MPLE VIII

; Preparation of the Dye:

~ nd ; (M.W. 372) Following the procedure outlined in Example I~ 13.8 g o-nitroaniline was diazotized, and the diazo solution was added -20- Bo~ros 1 ~ Qq6t~
. , I
,, ; ! , I
during ten minutes at O C to a clear solution of 22.3 g

6-bromo-2-naphthol (made according to the procedure in Org Synth,-,l~ Collective Vol. II, p.132), 1000 ml water, 4 g sodium hydroxide beads and 19 g soda ash. Coupling ~as complete after stirring at 0-5C for one and one hal hour. The mixture was filtered and ,` the cake was washed neutral with water.

Yield = 10507 g moist ~ake (dry test 32%) ~` = 33.8 g ~ Theory = 37.2 g ,!lo The dispersed product dyed polyester fibers in brilliant golden orange shades of outstanding build-up and very good sublimation and lightfastness. There was only a trace of a break after 20 e~posure hours under Xenon light.

EXAMPLE IX

Preparation of the Dye:

3 ~ ~0 S ~ ~ ~

(M.W. 400) ' , , -21- Botros 1 A nitrosyl sulfuric acid mixture was prepared by dissolving at ; 10-15C 7 g sodium nitrite in 100 g 660Bé sulfuric acid. Then :~ there was added below 10C a mixture of 83.3 g glacial acetic acid and ]6.7 g propionic acid, followed by a portionwise addition of 24.5 g 1-amino-2-nitrobenzene-4-(N,N-dimetheylsulfon-amide). The diazo mixture was stirred at 5-10C for two hours, then drowned into 500 g ice, 5 g Tween* 20 and a few drops of fulfamic acid solution. The clear diazo solution was added at 0C during one hour to a clear solution of 14.4 g 2-naphthol, ~i~ 10 1000 ml water, 4 g sodium hydroxide beads and 272.5 g soda ash.
~; The coupling mixture was s~irred tc room temperature overnight~
~he-mass was then filtered and the cake was washed neutral with water.
Yield = :93.8 g moist cake (dry test: 42%~
= 39.4 g Theory = 4~ g 'rhe dispersed product ~yed polyester fibers in-bright orange shades of good-strength and outstanding sublimation. There was a slight break at 20 exposure hours under Xenon light.
~0 *Trade Mark -22-i B

~ i7 '" ., COMPA:RATIVE EXAMPLE I - II j Following the general procedures of the foregoing examples, monoazo compounds corresponding to the following struc-: . tures were prepared:

¦OH OH
H3C ~ N=N ~ ~13C ~ N-N ~ .

. , N2 <~) N2 ~
.

(I~ (II) The dye (I)~ which i~ structurally analogous to those shown in Herzber~ et al~ United States Patent No. 1,038,884, when applied to aromatic polyester fibers by the carrier method provided weak `10 orange shades of poor build-up and with li.ghtastness much in~eri~
to that of the c~mpound of Example I.
The dye (lI~ is a bright red on polyester. The colox almost disappeared, however, at 20 exposure hours undex Xenon light. -COMPARATIVE EX~MPLE III

Following the general procedures of the foregoinJ
~ examples, a monoazo c~mpound corresponding to the follo~ing I ~23- Botros ¦ . - !

~i,, ~: ~ ~
$, structure was prepared:

OH

/ ~ ~ ~N0 .~. , . I

The compound which is structurally a~.alogous to the azo dyes of Mosby et al, United States Patent No. 1,935,657, when suitably , dispersed and applied to aromatic polyester fabrics by the carrier method provide negligible build-up between 3% and 6% dyeings.
Additionally, there was a distinct different in hue between dyeings on the ar~matic polyester by the carrier method~ the thermofixation method and the pressure method. Also, lightfastn~c was much inferior to that of the compound of Example I.
.
' CLn~,,~K ~LrS IV _V

: To demonstrate the cxiticality of the positioning of the ni~ro group in the diazo por~ion of the monoazo c~pou~dS the ~ollowing compounds were prepared fQllowing the general proce~ures I5 of the foregoing examples.

2 ~ OH
~N=N ~ 02N ~ N=N

-24- Botros ~':
:~' i7 ;
1 These compounds were compared with the compound of Example I.
The dyes not having the nitro group ortho to the azo linkage were found to be inferior in lightfastness as compared to the com-pound of Example I.
COr~ARATIVE EXAM~LE VI
The importance of the ortho positioning ~with respect to the azo linkagel of the hydroxy group of the coupling portion of the compounds employed according to the present invention was demonstrated by preparing the compound:

~N.=N~ OH

according to the general methods of the foregoing examples and comparing to the compound of Example I, The lightfastness of i the compound when compared to that of the cQmpound of Exa~ple I
was much inferior and the shade too dull to be a practical import-ance, Although the invention has been descri~ed in conjunc-tion with the foregoing examples, it is not to be limited thereto, but instead includes all those Qm~odiments witnin the scope and spirit of the appended claims.

: -25-,,~;,.

Claims (7)

WHAT IS CLAIMED IS:

1. Aromatic polyester textile material dyed with a monoazo compound of the formula:

wherein X1 and X2 are independently hydrogen; carboxy; carbalkoxy, the alkyl portion having 1-4 carbon atoms; chloro; bromo;
sulfamyl; trifluoromethyl; alkylsulfone,the alkyl portion having 1-4 carbon atoms; monoalkylsulfonamido, the alkyl portion having 1-4 carbon atoms; and dialkylsulfonamido, the alkyl portion having 1-4 carbon atoms; and Y1 and Y2 are independently selected from the group consisting of hydrogen; amino; -HNR, where R
is alkyl of 1-4 carbons; -NR2, where R is alkyl of 1-4 carbons; RCONH-, where R is alkyl of 1-4 carbons;
hydroxy; RCOO-, where R is alkyl of 1-4 carbons; chloro;
bromo; alkyl of 1-4 carbons; carboxy; carbalkoxy, the alkyl portion containing from 1-4 carbon atoms; -HNCOOR, where R is alkyl of 1-4 carbons; and carbamyl in which the nitrogen atom is unsubstituted or singly substituted -26- Botros with alkyl of 1-4 carbon atoms or phenyl or doubly sub-stituted with alkyl of 1-4 carbon atoms.

2. The dyed aromatic polyester textile material of Claim 1 wherein the monoazo compound is of the formula:

.

3. The dyed aromatic polyester textile material of Claim 1 wherein the monoazo compound is of the formula:

.

-27- Botros

4. The dyed aromatic polyester textile material of Claim 1 wherein the monozao compound is of the formula:

.

5. The dyed aromatic polyester textile material of Claim 1 wherein the monoazo compound is of the formula:

.

6. The dyed aromatic polyester textile material of Claim 1 wherein the monoazo compound is of the formula:

.

-28- Botros

7. The dyed aromatic polyester textile material of Claim 1 wherein the monoazo compound is of the formula:

.

-29- Botros