AZOIC DYES INSOLUBLE IN WATER

COLORANTS AZOIQUES INSOLUBLES DANS L'EAU

English Abstract

ABSTRACT OF THE DISCLOSURE:
Azoic dyes fre of sulphonic groups and having the
following general formula:
<IMG>
wherein R and R1 are the same or different and each represents
hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxyl group, a halogen,
a nitro group, a cyano group, a -SO2CH3 group, a sulphamidic group,
a -NHCOZ group wherein Z is a C1-C4 alkyl group, or a phenylazo
group which may be substituted in the phenyl ring by a C1-C4 ? ?yl
group, with the proviso that when one of the radicals R and R1 is a
halogen, the other cannot represent a cyano group; R2 is hydrogen or
a C1-C4 alkonyl group; R3 and R4 are the same or different and each
represents a C1-C4 alkyl group, a C1-C4 cyanalkyl group, a C1-C4
hydroxyalkyl group, a C1-C4 alkoxyalkyl group, a C1-C4 acyloxyalkyl
group or a carboxyester group having a C1-C4 aliphatic chain; X is
a linear or branched aliphatic or cycloaliphatic chain containing
from 1 to 6 carbon atoms, which may be saturated or contain a double
bond; and n is 1 or 2. These dyes show a high dyeing power for
fibers of cellulosic esters and ethers, for synthetic polyamidic
fibers and for fibers derived from terephthalic esters; moreover,
they have a high resistance to wet treatments and a remarkable
quality especially for materials such as polyamidic fibers, for
which it is hard to find dyes that will simultaneously satisfy
the requirement of covering up the roller streaks due to irregula-
rities in the fiber itself.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. Azoic dyes free of sulphonic groups and having the
following general formula:
<IMG>
wherein R and R1 are the same or different and each represents
hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxyl group, a halogen,
a nitro group, a cyano group, a -SO2CH3 group, a sulphamidic group,
a -NHCOZ group wherein Z is a C1-C4 alkyl group, or a phenylazo
group which may be substituted in the phenyl ring by a C1-C4 alkyl
group, with the proviso that when one of the radicals R and R1 is a
halogen, the other cannot represent a cyano group; R2 is hydrogen
or a C1-C4 alkonyl group; R3 and R4 are the same or different and
each represents a C1-C4 alkyl group, a C1-C4 cyanalkyl group, a
C1-C4 hydroxyalkyl group, a C1-C4 alkoxyalkyl group, a C1-C4 acyl-
oxyalkyl group or a carboxyester group having a C1-C4 aliphatic
chain; X is a linear or branched aliphatic or cycloaliphatic chain
containing from 1 to 6 carbon atoms, which may be saturated or
contain a double bond; and n is 1 or 2.
2. Azoic dye according to claim 1, and having the
following formula:
<IMG>
3. Azoic dye according to claim 1, and having the
following formula:
14

<IMG>
4. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>
5. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>
6. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>

7. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>
8. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>
9. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>
10. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>
16

11. Azoic dye according to claim 1, and having the
following formula:
<IMG>
12. Azoic dye according to claim 1, and having the
following formula.
<IMG>
13. Azoic dye according to claim 1, and having the
following formula:
<IMG>
14. Azoic dye according to claim 1, and having the
following formula:
<IMG>
17

15. Azoic dye according to claim 1, and having the
following formula:
<IMG>
16. Azoic dye according to claim 1, and having the
following formula:
<IMG>
17. Azoic dye according to claim 1, and having the
following formula:
<IMG>
18. Azoic dye according to claim 1, and having the
following formula:
<IMG>
18

19. Azoic dye according to claim 1, and having the
following formula:
<IMG>
20. Azoic dye according to claim 19 and having the
following formula:
<IMG>
21. Azoic dye according to claim 1, and having the
following formula:
<IMG>
22. Azoic dye according to claim 1 and having the
following formula:
<IMG>
19

23. Azoic dye according to claim 1, and having the
following formula:
<IMG>
24. Azoic dye according to claim 1, and having the fol-
lowing formula:
<IMG>
25. Azoic dye according to claim 1, and having the
following formula:
<IMG>
26. Process for the dyeing and printing of artificial
and synthetic fibers characterized in that the fibers are dyed in
a bath containing azoic compounds according to claim 1.
27. The process of claim 26, in which the fibers dyed
are artificial fibers of the secondary cellulose acetate and cel-
lulose triacetate type.
28. The process of claim 26, in which the fibers dyed
are synthetic fibers of the polyamide, polyester and polyacrylic

type.
29. Artificial and synthetic fibers dyed and printed
by the process of claim 26.
21

Description

~031~8~2
The dyes of the invention, ~ree of sulphonic groups, have
the following general formula:
~ N = ~ ~ / R3
1 (R)n NH-CO-X-COOH
where R and Rl are the same or different and each represents hydro-
gen, a Cl-C4 alkyl group, a Cl-C4 alkoxyl group, a halogen, a nitro-
group, a cyano group, a -SO2C~3 group, a sulphamidic group, a
-NHCOZ group in which Z represents a Cl-C4 alkyl group, or a phenyl-
azo group which may be substituted in the phenyl ring by a Cl-C4
alkyl group, with the proviso that when one of the radicals R and
Rl is a halogen, the other cannot represent a cyano group;
R2 is hydrogen or a Cl-C~ alkoxy group;
R3 and R4 are the same or different and each represents
a Cl-C4 alkyl group, a Cl-C4 cyanalkyl group, a Cl-C4 hydroxyalkyl
group, a Cl-C4 alkoxyalkyl group, a Cl-C4 acyloxyalkyl group or a
carboxyester group having a Cl-C4 aliphatic chain;
X is either a linear or branched aliphatic chain or a
eycloaliphatie group containing from 1 to 6 carbon atoms, which
ehain may be saturated or contain a double bond; and
n is 1 or 2.
The dyes of the general formula (I) show a high dyeing
power for fibers of cellulosie esters and ethers (e.g. secondary
- acetate and triacetate of cellulose), for synthetic polyamidic
fibers (e.g.: Nylon ( ), TJilion ( ), Perlon , Caprolan ( )etc.)
and for the fibers derived from terephthalic esters (e.g. Teri-
tal (R), Dacron ( ), Tergal (R), etc); moreover they are suited
for dyeing in soft or medium shades also polyacrylonitrilic fiber
(e.g.: Leacril 16 ( ), Euroacryl ( ), Orlon ( )).
/ In the foregoing recitation ofspecific fibrous ~a;terials
. -- 1 --

1~38t~;Z
dyeable according -to this i.nvention~ the superscript (R) indica-
tes that -the name given is a trademark~
The dyeing hues obtained by applying the dyes of formu-
la I on the indica-ted materials range from yellow to blue. Their
general fastness is excellent, partic~larly their ~esis-tance to
sublimation, washing and light.
The main characteristic of the dispersed dyes of -this
invention, which makesthem differen-t and distinguishes them from
the dispersed dyes of the prior art, is the high resis-tance to
the wet treatments, remarkable quality especially for such mate-
rials, for i.nstance polyamidic fibers, for which it is hard -to
find dyes that will simultaneously sa-tis~y the requirement of
covering up the roller s~reaks due to irregularities i.n the fiber
itself,
. Although the dyes of this invention can be classified
aæ dispersed dyes, on the basis of their general structure, they
comprise, in a side chain, a free alipha-tic acid group which con-
fers to the struc-ture a certain character of acid dyes. This is
confirmed by the fact that better results .in the dyeing of the po-
lymidic fibers are obtained by starting with the applicatio.n of
aqueous dispersio.n -solutio.ns with a slightly alkaline p~I, and
by then reduci.ng the pH to 5,5 This process consti.-tutes the
procedure for dyei.ng the polyamidic fiber with the Conventional
acid d~es, which normally result in dyeings resistant to wet
treatments but which display apoor equalizing as far as concer.ns -
the covering up of the roller streaks of the manufactured product.
The dyes of this inve.ntion, in comparison wi-th the ana-
logous dispersed dyes of the prior art derived from N,N-dialkyl-
m-amino-acylanilides, show a definitely superior dying power,
especially on polyamidic fi.~ers, a fact that must be a-ttributed
to the anionoid charac-ter of the aliphatic acid chain.
~or the a.pplication of thè dyes of this inven-tion to
-- 2 --

~ ID3886~ ~
the polya~ide ~ibers the pH values and the dyeing times may be
suitably varied according to the availab.Le material and to the
color intensity desired, Good results have been obtained by dy-.
eing at-temperatures up to 11 ooa .
r~he applicatio.n of the dyes of this invention on po~y-
es-ter fibers may be carriea out with sllghtly acid a~ueous baths
.~ ~
con-taining suitable dispersants, particularly of the non-ionoge-
nous type,.a-t a temperature o~ 100C9 in the presence of carriers
or swe~ling substances~ or wlthout car.riers, at temperatures ran-
gin~ from 125-135C, under pre~s~re.
rrhe .~ollowing examples are given to illustrate the in-
ventlon and are not i.ntend~d to be limited..
rl'he parts and percentages indicated in the examples àre
expressed as parts and percentaged by weight, if not otherwise
indicated,
~ IP~ 1
2.07 parts of m-nitroaniline were dissolved in 6 ml of
HCl, d=1.18, and 30 ~1 of water. Disazotation followed at about
10C by slowly ~eeding a solutio.n o~ 1 035 parts of Na~0~ in 10
;20 ml of water, rrhis disazo-solu-tion, after clarification, was pour-
ed at 5-10~C over a so,lution of 3~94 parts of N,N-diethyl-m-
~mino-succinylaniline in 20 ml of acetic acid, 8 p. of sodium
acetate in crystals and 50 ~l of water-~ After about 2 hours of
stiring at 5-10C, the mixture was filtered, the precipita-te
washed.with water and then dried. ~hereby were Obtained 5.34
parts of the dye:
DT=DT ~ ~T / C2~5
~T02 ~co-(cH2)2--cooH
- 3 ~

~;0388~2 1
in the form of an oran~e-shaded powder which dyed polyamidic, cel-
lulose es-ter, polyester and polyacrylic fibers in very bright,
~ast and uniform orange shades
- E~AMP~E 2
2.07 parts of p-nitroaniline were diazotized and cou-
pled ~Jith 3.94 parts of N,~-diethyl-m-amino-succinylanilide ac-
cording to the procedu~e of Example 1
Thereby were ob-tained 5.8 parts of -the dye: ~
O ' ,;
C2~5
~x c o- ( aH2 ) 2-COOH
as a red powder that dyes the above mentioned fibers red.
0.35 part of 2-methyl-3-chloroaniline were dissolved
in 1 ml of HCl d=1.18, and 25 ml of water. This solution was
cooled to 0~5C, whereupon there was 510wly admi~ed 0.17 part of
sodiwn nitrite dissolved in 5 ml of water.
A~ter about 15 minutes of stirring, the disaæo solution
was slowly poured, under s-tirring, onto a solution of 0,66 part
of N,N-diethyl-m-aminosuccinylanilide dissolved in ~.4 ml of ace-
tic acid, 8.5 ~1 of ~Yater and 1.~5 parts of crystallized sodium
acetate. ~fter about 2 hours of stirring at 5-10C, this mixtu-
re was filtered, the precipi-tate was washed with water and -then
dried. Thereby were ob-tained 0.5 part of the dye:
~ ~ ~ 0 } ~ 2 5
Cl CH~ N~I-co-(cH2)2-cooH

103B86Z
in -the Porm of a yellow powder -that dyes -the above me.n-tio.ned fi-
ber yellow.
~XAMP~ 4
0.35 part of 2-methyl-4-chloroaniline were diazotized
and coupled wi-th 0.66 part of N7N-diethy.l-m-aminosucci.nylanilide~
according to the procedures described in ~ample 3
Thexeby were obtained 0,5 part of the dye:
,.
Cl ~ ~ ~ C2~l5
C~.I3 ~ ~rH-ao (a~I2 ) 2-COOH r;
in the form oP a yellow powder tha-t dyed the above mentioned fi-
bers to a yellow shade more reddish than -that obtained by using
the dye of E~ample ~.
~AMP~ 5
. _ '
~o 0.87 part of 2-chloro-4-nitroaniline dissolved i.n
4.6 parts oP sulphuric acid, d=1.84 there were gradually added
while cooli.ng, 3 ~1 oP water. ~o the suspe.nsion thus Pormed
there was added a-t between 0 and 5C 0.4 part of sodium .nitri-te
dissolved i.n 1 ml of wa-ter. After about 1 hour of stirring at
5-10C, the mixture was filtered and the diazo solutio.n was.slow-
ly poured onto a solu-tion, at 10C, oP 1.32 parts of N9~T-diethyl-
m-ami.no-succinylanilide dissolved i~ 10 parts ofacetic acid and
10 parts oP water. During the loading of the .diazo, the p~ was
maintained at a value not lower than 4 by the additio.n of crystal-
lized sodium acetate.
After about 1 hour after the end oP the pouring of the
diazo, -the precipitate was Piltered, washed and then was dried.
~hereby were obtained 2.05 par-ts oP the dye: ~
-- 5 ~

1038~6~ ' `
2~ ~ `I = ~ ~ ` ~ C~l~
NH-CO- ( aH2 ) 2-Ct)OH
in the form of a dark ~lue powder that dyes the fibers violet
~XAMP~E 6
A solution consisting of 0 82 part of 2-cyano-4-ni-tro- ;
aniline in 10 pa~ts of acetic acid, 2 parts of propionic aoid
and one part of water, was cooled down to 5-10C, whereupo.n there
were slowly charged i.nto it, under stirring, at the abo~e cooling
temperature, 5.5 ml of I N nitrosyl~ulphuric acid. After about 1
hour of further stirring at 5~-10a, the diazo-solutio.n was slow-
ly poured, under stirring, o.nto a solution at 5~-10C of 1,32
.~ parts of N,N-diethyl-m-amino-succinylani:lide i-n 10 par-ts of ace-
tic acid and 30 parts of water.
Duri.ng coupling, the pH of the mixture was buf~ered to
a value of .not less than 4, by adrnixture of crystallized sodium
. 20 acetate.
Once the pouring o~ the diazo was comple-ted, the mixtu-
re was maintained under stirring :Eor about 1 hour, whereupon lt
was filtered, washed with wa-ter and finally dried, ~hereby were
obtained 1.5 parts of the dye:
,
02N - ~ N = N ~ - N
CN NH-C0-(CH2)2-COOH
in the form of a violet powder that dyes fibers of the materials
mentioned herein viole-t,

9~038~ 2
~ ,11 parts of 2-chloro-4-me-thylsulphonylamiline suspe.n-
ded i.n 14 ml of hydroch~oric acid~ d=1.18, and 8 ml.o:E water,
were diazotized by slowly addi.ng~ at 5-10C, a solution of 1,5
parts of sodium .nitrite in 5 ml water, Af`ter abou-t 30 minutes
of stirring at 5-10C, -the solution thus obtained was clarified
and filtered and the filtrate was the.n slowly admixed, ~t 5-10C9
to a solution of 5028 parts o~ M,l~-diethyl-m-amino-succinylanili-
de in 35 parts of icy acetic acid and 70 parts of water.
Duri.ng the pouring, the pH of the ~oupling mass was
mai.ntai.ned at ralues.not lower than 4 by the addition of the ~ne-
ces~ary quantity of cry~tallized sodium ac~tate.
After about 1 hour of stlrring, -the precipitate thus
formed was filtered, washed with water on the f~l-ter, and dried.
~hereby were obtai.ned 6.~ parts of the dye:
' " ' '
H3C2S~ /C2H5
, ~/ C2H5
NH C0-(C~I2)2-~OOH
i.n the form of a red powder that dyes fibers of the aforementio.n~
ed materials -to a scarlet hue, ` -
~X~IPIE 8
4 8 par-ts of 2,5-dichloro-4-methylsulphonylanili.ne were
diazotized and coupled with 5.38 parts of N,N-diethyl-rn-ami.no-
succinylanilide, by following the procedures of ~xamp~e 7, There-
by were obtained 6.2 parts of the dye:
- 7 -
. .

386Z
H3CO~S ~ N = ~ ~ \ C215
Cl NH~Co-taH2)2-cooH
, .
in the form of a red powder that dyes the fibers red~
EXAMPIE 9
1 1 parts of 4-chloro-6-methylsulphonyl-o-tolUidi.ne
dissolved in 5 ml of hydrochloric acid1 d=1.13, and 5 ~1 of water
were diazotized at 0-5C by the addition of a solution of 0.35
.: parts of sodium .nitrite in 5 ml o~ water. After 1 hour of stir
ri.ng, the dia~o solu-tion was poured, at 5-10C, onto a solutio.n
of 1.32 parts of N,N-diethyl-m c~mino-succi.nyl-anilide dissolved
i.n 15 parts o~ acetic acid and 15 ml of wa-ter.
Duri.ng the pouring of the diazo solution, the pH of
the coupling mass was maintalned a-t values not lower than ~, by
the gradual additio.n of the necessary quantity of crystallized
sodium acetate.
After about 1 hour of stirring, the precipitated dye
was filtered, washed with water and then dried~ Thereby were ob-
tained 2.25 parts of t~e dye:
CH3
Cl ~ ~ / 2N5
S2CH3 l`l~I-CO-t~H2)2-COOH
i.n the form of a yellow-orange powder tha~ dyes fibers of the
aforementioned materials orangeO
EXAMPLE 10
11 par-ts of 2-chloro-~ methylsulphonylanilîne were

103~386Z
diazo-tized a~d coupled with 5,24 pc~rts of N,N~diethyl-m-c~mi.no-
maley:L-anilide, by following the procedures described in E~ample
7. ~hereby were obtained 6.1 parts of the dye:
_~Cl j C2H5
X3C02S~ ~~`~ C H
~H-CO-CH=aH-aOOH
in -the :~orm o~ a red powder that dyes .the fibers scarlet.
Other dyes prepared as described in the preceeding ex-
c~mples are reported in the ~ollowing table.
~xc~ple No. ~or~ul~ color shade o~ f~ber
~ OCH3 / ~2I~5
11 H3co2s ~ FN - N- ~ C2 5
~I-aO-(CH2 ) 2COO:H
.
,~ ~aH3 /a~H5 i,
H3aO25 ~ O ~ A - ~ a2 5 ruby
- ~Eaoc~=aI-Icoo~
/C21~5
3 13 ~r - a2fI5 violet
NI-I-CO-aH2-~H2-aOOH
_ g _

8862
xal[lple No. Formula_ color shad of fiber
1~ 02N--CO~ = N~ / blue
NFL-CO- CH2--G~I2-GOOH , '
~- ,
..
<~CII N/ reddleh blue
C2~I5
CO_CI~=C~I-aOOH
.
~;G'I ~O~H3 a H
C2~I5
CO-aII2-aH2-aOOI-I
OCH
- 02N- (~--N = N--~O~ N
17 . \~J \C II gree.nish bluc
NH-aO-aH =CH-COOH
~0
_ 10 -

~388~2
E~cam~_ No. :Formula_ co.lor shade fiber
18 ~ // 2 5 blUiSh red
02N--~ N = N--~O~
~, a,~II5
CO_CII=CH- COOH
oaH3
~; 19 02N~--N = 1~--(0~--N/ vi
., ~. a~l5
NII-CO_aH =O:H-COOH
,
.'~ ' . :
Z 02N--C~N = N--~ N/ bluish red
C~I2 2
1 2
., HOOC-CH~c~,I ,}12
~_< S02C:~3 /02H5
21 02N ~N = N--~ 2~5
NH-CO- (CH2) 2 CO~
_ 11 -
!

38862 ~
~xamPle No. Formula color shade ~iber
02~ CH3 ~ / C2~l5
C2H5
c o_ ( CE2 ) 2'-C~
' .
2~ 2H5
NH-CO-(OH2) 2-COOH
a~ CH3
24 ~ -N=~- ~ -N=~_ ~ N < red
-CO(CH2)2 C0
~XMAP~E 25
.
0.5 g of a dye obtained by the procedure of Examples 1
to 24, and suitably micronized in a ball mill, were dispersed
-thoroughly in water, and this dispersion was then added to a dy-
eing bath containing 1 g/lt of surfact~nt of the non-ionogenous
type (e.g.: oxyethylated castor oil, ~mulsion ~l*typé) as well
as small quantities of ammonia salts so as to obtai.n a pH-8-8.5.
~0 The dyeing of 100 g of polyamidic fabric was started at
70~ and the temperature was the.n gradually brought up to the
boiling point. The deying wascarried onat theboilingtemperature.
_ 12 -
* Trademark

~033~386;~
for 30-40 minutes~ whereupon the gradual addi-tion o~ acetic acid
was begun and con-tinued; a ~inal pH o~ 5.5-5, useful ~or obtain-
ing a satisfactory exhaus-tion of -the dyeing ba-th was obtained.
The dyed material was then abundantly rinsed with wa-
ter and dried with ho-t air~
~M~IE 26
0O5 g o~ dye obtained accordingto ~he procedure des-
; cribed in Examples 1 to 24 and suitably micronized in a ~all
mill, was dispersed in a little wa-ter and then added to a dyeiMg
bath co.ntaining 1 g/lt o~ a .no.n-io.noge.nous sur~actant (eJg.:
oxyethylate castor oil; ~l E~ulsion) as well as 6 g/lt o~ non-
volatile swelling age.nt (e.g.: swelli.ng a~e.nt:RWM) ~ ~he bath
. was the.n brought up to a pII=5-5,5 by means o~ organic acid.
The applica-tion of the bath to 100 g o~ polyester fibers
was carried out in a jigger apparatus by suitably gradual mixing
o~ the dye and increase in the temperature.
The dyeing was carried on ~or 2 ho~us at boiling tem-
perature. Thereafter, -the dyed material was soaped, rinsed and
dried with hot air.
~ P~.~ 27
0.5 ~ of dye.obtained according to the procedures des-
cribed in ~xamples 1-24 was suitabLy micronized i~ a ball mill;
the micronized dye was then thoroughly dispersed in a little.wa-
ter and mixed with a bath co.ntaining 1 g/lt of .no.n-ionogenous
dispersant (e.g.: oxyethylated castor oil~ at a temperature o~
betwee.n 50 and 60~ and at a pH of 5-5.5 obtai.ned by ~ormic acid,
in a pxessuri~ed apparatus.
The applicatio.n o~ the dye on 100 g of polyester ~ibers
wa~ carried out at 130C ~or S0 minutes, a~ter a gradual increa-
se in the temperature.
~he dyed material was -then rinsed, soapecl, rinsed again
and dried ~n hot airO
- 13 -