DE2739769A1 - METHOD OF DYING POLYAMIDE FIBERS - Google Patents

Description

BEIL, WOLFF & BEIL

RECHTSANWÄLTE ADELONSTRASSE 58 6230 FRANKFURT AM MAIN 80

Our no. 21 261 Ώ / mä

Aziende Colori Nazionali Affini-ACNA S.p.A. Milan, Italy

Process for dyeing polyamide fibers

Bf) HB 1 1/0786

The present invention relates to the use of dyes, which are free of sulphonic acid or carboxylic acid groups and are characterized by at least one -SOpNH CO group are for uniform dyeing of polyamide fibers.

809811/0786

It is well known that it is difficult to use polyamide fibers in particular to achieve uniform coloring because of the irregularities regarding the chemical nature (no homogeneous distribution of the basic ind groups) or chemical / physika = lic or physical differences in these fibers, e.g. due to more or less crystalline morphological State, different surface structures and different Microporosity, which lead to different distribution of the dye in the fiber, in particular but to different diffusion and absorption behavior in sunlight. The resulting errors will be usually referred to as "streaks".

In general, dyestuffs for textiles have uniform mounting and good fastness properties, in particular at Ness. treatments, requested. These two requirements cannot always be met by one dye at the same time, especially not when dyeing synthetic polyamide fibers.

It can roughly be said that the greater the fastness of a dye in the case of wet treatment, the greater the ability to migrate decreases and with it the compensatory capacity on polyamide fibers, and vice versa.

It is known that fabrics made of polyamide fibers, with SuI = dyes containing fonsäuregruppen are colored, show irregular and streaky colors. These tissues are, however, evenly colored with disperse dyes containing carboxyl groups, see IT-PS 985 593 and

(Italian patent application 19 692 A / 74). Further it is known from FR-P3 2 245 815 that real and uniform colorations can be achieved if one carboxylic acid

8098 1 1/0786

group-containing dyes used in the presence of a tanning agent.

Surprisingly, it has now been found that polyamide fabrics produced by dyes containing sulfonic acid groups are uneven dyed, dyed uniformly if dyes free of sulfonic acid or carboxylic acid groups are used, but which have at least one -SOpNHCO group.

Compared to analogous dyes with carboxyl groups, these dyes are in the dyeing stage against changes in the pH value less sensitive. This property facilitates application and enables deeper, even coloring, since the dyes show no precipitations, as is the case with the aforementioned dyes; Case is.

The wet fastness properties are satisfactorily high, so that no tanning agent is required.

In contrast to the carboxyl group-containing dyes and the conventional disperse dyes, those according to the invention offer provided dyes have the important advantage that no finish treatment is required because they are under are soluble under the conditions of use.

The dyestuffs according to the invention with divalent radicals the formula -SC ^ NHCO- can also be used to dye cellulose = esters or ethers can be used, e.g. of secondary acetate, cellulose triacetate, and of fibers made of terephthalic = esters, e.g. from Terital, Dacron or Trevira.

The dyes according to the invention can be used in an aqueous bath or from baths containing organic solvents app =

8098 11/0786

be licensed. Organic solvents can be used with preferably a boiling point between 40 and 170 ⁰ C, for example aromatic hydrocarbons such as toluene, xylene, halogenated hydrocarbons, in particular halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,1-diehlorethane, 1, 2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloro = ethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1-chloro = propane, 2-chloropropane, 1,2- Dichloropropane, 1,1,1-trichloro-propane, 1-chlorobutane, 2-chlorobutane, 1,4-dichlorobutane, 1-chloro-2-methylpropane or 2-chloro-2-methylpropane, and halogen-containing aromatic hydrocarbons such as chlorobenzene and dichlorobenzene. Tetrachlorethylene, trichlorethylene and 1,1,1-trichloroethane are particularly suitable.

Azo dyes, aniiraequinone dyes, polymethine dyes and nitroamino dyes may be mentioned as examples of dyes with the radical -SO _{2 NHCO-.}

Preferred dyes correspond to the general formula

wherein X is one of the radicals -SO ₂ NHCO-H ₂ or -CONHSO ₂ - R ₁ , wherein R _{1 is} a lower alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl = radicals with 1 to 4 Carbon atoms, chlorine, bromine, the nitro group or cyano group, a radical of the formula -SO ₂ R, in which R is a lower alkyl radical, or -SO ₂ NH ₂ , R. and

8098 11/0786

R ₅ hydrogen, -UCH ₂ GH ₂ OH ₁ halogen, lower alkyl or alkoxy radicals or acylamino radicals, and Rg and R- hydrogen, lower alkyl radicals, -CH ₂ GH ₂ OH, -GH ₂ CH ₂ R, in which R is a lower acyloxy radical denotes -CH ₂ CH ₂ CN or -CH ₂ CH ₂ COOR, in which R denotes a lower alkyl radical;

^R 6

J CHpCHp - X 2) i

R ₂ R ₅

wherein X is one of the radicals -SO ₂ NHCOR ₂ or -CONHSO ₂ R ₁ , R _{1 is} a lower alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ , R, and R. hydrogen, ₄ alkyl radicals with up to 4 carbon atoms, chlorine, Bromine, the nitro group, tri = fluoromethyl group or cyano group, a radical -SO ₂ R, in which R is a lower alkyl radical, -SO ₂ NH ₂ , -CONRSO ₂ -, in which R is hydrogen or a lower alkyl radical, -COOR, in which R is a lower alkyl radical, -CONRR, in which R, R is hydrogen or a lower alkyl radical, or X, R ₅ and R _{6 are} hydrogen, -OCH ₂ CH ₂ OH, halogen, alkyl or lower alkoxy radicals or acylamino and Ry is hydrogen , a lower alkyl radical, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ OR, where R is a lower alkyl radical, -CH ₂ CH ₂ OH or 1-CH ₂ CH ₂ COOR, where R is a lower alkyl * radical, represent;

^E 5

/ ^E 6

-N- N - <? - «3)

80981 1/0786

wherein X is one of the radicals -CuNHSO ₂ R ₁ or -SO ₂ NHCO H ₁ , wherein R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ » ^R 3 ^{and k} a hydrogen, alkyl = radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group, -SO ₂ NH ₂ , CP ,, -SO ₂ R, where R is a lower alkyl group, -COOR, where R is a lower alkyl group, -CONRR, where R , R is hydrogen or lower alkyl = radical, -CONR-UO ₂ -, where R is hydrogen or lower alkyl, or X, R _{5 is} hydrogen, halogen, alkyl or lower alkoxy and R ₆ and Ry are hydrogen, lower alkyl = radicals, -CH ₂ -CH ₂ OH, -CH ₂ OH ₂ OR, in which R is a lower acyl _{radical, -CH 2} CH ₂ CN or -CH ₂ CH ₂ COOR, in which R is a lower alkyl radical;

It

HO N

wherein X one of the radicals -SONHCO R ₁ or -CONHSO ₂ -R ₁ * R _{1 is} a lower alkyl radical with 1 to 4 carbon atoms or an arylate, R ₂ and R-, hydrogen, lower alkyl radicals, chlorine, bromine, the nitro group or cyano group , -SO ₂ NH ₂ or -SO ₂ R, in which R is a lower alkyl radical, R. is a lower alkyl radical, -CONH ₂ , -CONRR, in which R is hydrogen or lower alkyl, or -COOR, in which R is a lower alkyl radical , and R _{5 represent} a lower alkyl _{radical, -CH 2} CH ₂ OH, an aryl radical which is optionally substituted by a halogen or a nitro group, or -COCH;

809811/0786

L V \ _ N - N -

wherein X is one of the radicals -SO ₂ NHCO - R ₅ or -CONHSO ₂ - R ₅ , R ₁ , R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group or nitro group, -SO ₂ NH ₂ or -SO ₂ R, in which R is a lower alkyl radical, R. is an alkyl radical with 1 to 4 carbon atoms, -CONHp, -COOR, in which R is a lower alkyl radical, or -UONRR, in which R is hydrogen or a lower Al = denotes kyl, and Rf- denotes an alkyl group having 1 to 4 carbon atoms or an aryl group;

wherein X is one of the radicals -SO ₂ NHCO - R ₁ or -CONHSO ₂ - R ₁ , R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine , the cyano group or nitro = group, -SO ₂ NH ₂ or -SO ₂ R, where R is a lower alkyl =

80981 1/0786

means radical, and R. and R ^ represent hydrogen, alkyl radicals having 1 to 4 carbon atoms or -CH ₂ CH ₂ OH;

-N = N

-N = N-

wherein Σ one of the radicals -3O ₂ NHCOR ₁ or -CONHaO ₃ R ₁ , R an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, lower alkyl create, chlorine, bromine, the cyano group or nitro group, -SO ₂ NH ₂ or -SO ₂ R, where R is a lower alkyl radical, R., R ₅ and R _{6 are} hydrogen, alkyl or alkoxy radicals having 1 to 4 carbon atoms and R _{7 is} hydrogen or a lower alkyl radical;

R '"0 R

R.

where X is one of the reagents -CONHSO ₂ -

or -SO ₂ NHCO -

R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group, -SOpNHp or -SO ₂ R, where R is a lower alkyl radical, R The hydroxyl group, amino group or a radical -NHR, in which R is an alkyl radical having 1 to 4 carbon atoms and R ₅ and Rc are the hydroxyl group, amino group, hydrogen or

80981 1/0786

Represent a nitro group, one of the radicals R
Rx- also a remainder

-, R, - or

can mean in which X, ne have meanings;

and R given above

wherein X is one of the radicals -CONHSC ^ - or -SO ₂ NHCO-, R _{1 is} hydrogen, chlorine, an alkyl radical with 1 to 4 carbon atoms or an alkoxy radical with 1 to 4 carbon atoms and R «is hydrogen, chlorine, bromine or an alkyl radical with 1 to 4th
Represent carbon atoms;

R.

-N = N - // \ v - ι

AQ)

wherein X is one of the radicals -3O ₂ NHCO -

or -CONHSO ₂ -

₂ , R ₅ and R _{4 are} hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group or nitro group, -SO ₂ NH ₂ or -SO ₂ R, where R is a lower _{alkyl radical, R 1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical and R ₅ and Rg represent hydrogen or alkyl radicals with 1 to 4 carbon atoms;

B 0 9 8 1 1/0786

11)

wherein X is one of the radicals -SO ₂ NHCO - R ₁ or -CONHSO ₂ - R ₁ , R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, Rp and R ^ are hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group or nitro group, -SO ₂ NH ₂ or -SOpR »in which R is a lower alkyl radical and R. and R _{5 are} alkyl radicals having 1 to 4 carbon atoms or aryl;

12)

wherein X is one of the radicals -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical and R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group or Ni = tro group, -SO ₂ NH ₂ or -SO ₂ R, in which R is a lower alkyl group;

₍ J — N = N - Λ CO - "" *% /

wherein A represents a base capable of coupling; and.

809811/0786

14 ·)

wherein X is one of the radicals -SO ₂ NHCO - R ₁ or -CONHSO ₂ - R ₁ , R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine , the cyano group or nitro «group, -SOpITH ₂ or -SO ^ R» where R is a lower alkyl = _{radical, R. and R 1} - hydrogen, alkyl radicals with 1 to 4 carbon atoms or the cyano group and Rg hydrogen, a lower alkyl radical or represent an aryl radical.

The dyes of the formulas 1 to 14 · are new and represent therefore a further subject matter of the invention. Furthermore, the invention relates to objects and fabrics made of syn = thetiscben polyamide fibers which have been dyed or printed by the above process, in particular with one of the new ones Dyes of the general formulas 1 to 14,

Example A.

General example of dyeing with isolated dyes

in acid form.

The amount of dye required to achieve a certain depth of color was dissolved in the dyebath, then the Dye in the acid form with the required amount of volatile or fixed alkali (NH.OH, KOH, NaOH or their carbonates) converted into salt form in situ.

The material to be dyed was in the dye bath from 50 to

80981 1/0786

Were introduced 6O ⁰ C and the temperature was gradually increased to the boiling point, which gradually added to low acetic acid levels to be reached in 30 to 40 minutes, dyeing under boiling a pH value that leads to good bath exhaustion. (PH 5.5 to 6 for pale tones, pH 4.5 to 5 for deep tones). As soon as the optimum pH value was reached, staining was continued for a further 20 or 30 minutes.

The colored material was rinsed several times with water and dried in hot air.

Example B.

General example of dyeing with a dye in salt form.

The one required to achieve a certain depth of color The amount of dye was dissolved in a 50 to 6 µg dye bath. Then ammonium acetate was obtained in amounts from 1 to 4 5 * based on the weight of the fiber, after which the material to be dyed was introduced. Then the temperature slowly increased to the boiling point. After boiling for 10 to 20 minutes, small amounts of acetic acid were added, so that after boiling for 30 to 40 minutes the optimum pH value for good exhaustion was reached (515 to 6 for pale tones, 4.5 to 5 for low tones). When the staining was complete (about 1 hour boiling) the material became rinsed several times with water and dried in hot air.

Example C

A pad bath of the following composition was prepared:

bO98 11/0786

-A-

Dye, salt form 10 parts

Water 89O parts "Indalca SH / C · (thickener,

12 ^ -ig) 80 parts

Ammonium oxalate crystall. 20 parts

1000 parts The yellow dye of the following formula was used

^c t ^sibo 4 / r ""'- ij-ii " ^CH 3

H ₀ / \ / '

in salt form. Fabric made of polyamide-66 was made with this provided bath padded using a squeeze = effects of #

The padded material was dried at 70 ⁰ C, for 30 to 40 minutes at 104 to 106 ⁰ C with water vapor (about 1.2 atmospheres), washed thoroughly with water and dried.

In this way a uniform yellow coloration was obtained good lightfastness and fastness to wet treatments achieved.

Example D

Printing process

A printing paste of the following composition was prepared:

B098 11/0786

Dye, salt form 5 parts

Water 335 parts

"Indalca PA / 3" (thickener = medium, 10% liquid solution) 600 parts

Ammonium tartrate 33 ^ 0 ig 60 parts

1000 parts

An orange colored dye of the following formula was used

A structured fabric made of polyamide 66 fibers was printed, dried in the dryer, treated with steam for 30 to 40 minutes at 104 to 106 ° C (1.2 atmospheres), carefully washed with water and dried.

In this way, a uniform orange coloration was achieved, the good lightfastness and fastness to moisture owned.

If you want to apply the corresponding dye with a carboxyl group instead of -SOpNEAc-Reets, you have to use a Use specially purified product to achieve analogous results get.

example 1

2.14 parts of p-aminobenzene sulfonacetamide are in 50 parts Water and 2.5 parts by volume of concentrated hydrochloric acid (36%) solved. The starting material is made in a conventional manner

B098 11/0786

diazotized at 0 to 2 ° C by adding dropwise a solution of 0.69 '-files of sodium nitrate in 15 parts of water. The diazonium salt solution is poured into a solution of 1.74 parts of N-ethyl-N-ß-cyanoethylaniline in 50 parts of water ^{at from 0 to 5 ° C., whereupon sodium acetate is added to a pH of about 3.} When the reaction has ended, it is filtered and the residue is washed with water. 3.82 g of a dye of the formula are obtained

-N ^

Vh ₁ Cn

in the form of an orange-yellow powder that turns polyamide fibers a deep yellow. The dye has good balancing properties, good lightfastness and, in particular, good fastness in potash treatments.

Example 2

2.14 parts of p-aminobenzenesulfonacetamide are dissolved in 50 parts of water and 2.5 parts by volume of concentrated hydrochloric acid (36%). The amino compound is diazotized in a conventional manner at υ ⁰ to 2 C, is added dropwise by a solution of 0.69 parts of sodium nitrite in 15 parts of water.

The diazonium salt solution becomes a solution at 0 to 5 ° G of 2.06 parts of Ν, Ν-diethyl-m-aminoacetanilide, 50 parts Water and 1.5 parts by volume of 36 ^ hydrochloric acid are poured in. Sodium acetate is then added until the pH is about 3 amounts to. When the reaction has ended, it is filtered and washed with water.

809811/0786

The dye, which is obtained as an orange-red powder, possesses following formula

CIl CONHSO

0.5 parts of the dye so prepared are with the Dissolved the required amount of ammonium hydroxide and added to a dyebath circulating in the dyeing device. Then 100 parts of nylon 66 fabric are introduced and the temperature is slowly raised to the boiling point. After boiling for 10-20 minutes, the pH is gradually adjusted to 4.5-5 with acetic acid. The coloring takes place with further boiling for 40 to 50 minutes, then the colored material is washed and tumble dried dried.

It turned out to be an orange, well-exhausting and well-balanced one Dyeing of good levelness and good lightfastness and wetfastness achieved.

Replace the dye described above with the equivalent amount of an unfinished dye following formula

NHCOCH

80981 1/0786

in an analogous procedure, dye precipitates are obtained which lead to deposits on the surface to be colored Material and lead on metal parts of the dyeing device. The coloring obtained in this way is compared with the former Color paler, less even and less resistant to scrubbing. If parallel dyeings are carried out with both dyes, but with the rapid addition of acetic acid, it is observed that the precipitation in the dye with carboxyl groups increases noticeably, while the dye with Ac NH SOp-Grruppec no precipitation takes place and the usual good properties described are retained. In the case of the carboxyl group-containing Dye also precipitates when the unfinished product is replaced by a product, that was refined beforehand.

Example 3

2.14 parts of p-aminobenzenesulphonacetamide are used in 50 hours Dissolved water and 2.0 parts by volume of concentrated hydrochloric acid. The amino compound is used in conventional

Manner diazotized at 0 to 2 ⁰ C., is added dropwise to a solution of 0.69 parts of sodium nitrite in 15 parts of water.

The diazonium salt solution is poured at 0 to 5 ° C in a solution of 1.76 parts of i-phenyl ^ -methyl-S-pyrazolone, 50 parts of water and 1.5 parts by volume of a 40 $ strength sodium hydroxide solution. After the reaction, hydrochloric acid is added until reaching pH of about 3, then 30 iainuten to 50 to 60 ⁰ C is heated, filtered and washed with water. The dye obtained as a yellow powder has the following formula

8098 11/0786

CH CONHSO ₀ - L Λ - N = N -

Part of the dye thus obtained is required in the ! «Close ammonium hydroxide is dissolved and the solution is added to the dyebath circulating in a dyeing device.

100 parts of a fabric of polyamide-66 are introduced into the dye bath of from 50 to 6O ⁰ C, then the temperature is slowly raised to boiling temperature. After boiling for 10 to 20 minutes, acetic acid is slowly added until the pH is 4-5-5. The color was boiled for 40 to 50 minutes, then the material was washed and dried in the dryer.

A well exhaustive, uniform yellow coloration was achieved, which is characterized by good levelness, lightfastness and Clarity was excellent.

If the dye described above is replaced by an equivalent Amount of a raw dye of the following formula

HOC) C- (ν A-M = W-

80981 1/0786

replaced, whereby the application takes place in the same way, one observes dye precipitation during the dyeing « which lead to deposits on the material to be colored and the metal parts of the coloring device. The bathroom will not thoroughly exhausted, unlike bathing with the dye previously described. The dye with carboxyl » group provides a paler coloration, which is less even and less rub-resistant in the areas with deposits is.

If parallel dyeings are carried out with the two dyes, but with the more rapid addition of larger amounts of Egaetic acid, so the precipitation only increases in the case of the carboxyl group-containing Dye noticeably too. The bath exhaustion remains incomplete. The precipitation occurs with the carboxyl group-containing Dye even if the unfinished product is first microfinished.

The following dyes were also prepared according to the instructions in the preceding examples:

809811/0786

3a

Example diazo component couplinga = component

"coloring on polyamide

-NH,

SO ₉ NHCOCH

• CH

yellow

^ 1 p
-N

yellow

O ^, Cl] CN

yellow

-κ '

orange-yellow

CJCN
L 4

CH.

yellow

yellow

- 4th

yellow

80981 1/0786

Beiap. Diazo component coupling component

Coloring on polyanide

NHCOCH

reddish yellow

^NC 2 ^H 5

12) 13) 14) 15)

16) 17)

13)

yellow

ff w -r ^{2 4}

'C H.OCOCH
m. j

^C 2 ^H 4 ^CN

yellow

P ₇ CH OH -n / ^{2 4}

η oh
4th

yellow

-N

CH OCOCH 1 3 ^!

C "H .OCOCH 4th

yellow

₀ W

OH

CIl CONH

yellow

orange-yellow

CH CH OH

OH

greenish-yellow

CH-

19)

20)

21)

Example diazo component

-NH,

SO.NHCOCH.

Clutch component

¹ N- CU,

Coloring on polyamide

yellow

yellow

yellow

22)

N ¹ H

CH C - ■ = O

^ CN

MO

yellow

yellow

»U 9 8 1 1/0786

At 3p.

2> p

Diazo components

-NH,

Sl) NHCOCH

Coupling component

HO

A. /

- CH.

rar ou ng ti tu polyamide

yellow

25)

26)

Hü N '

- CONH,

yellow

yellow

Dr

27) CHCONHO ₂ S- ^ y -NH ₂

Br

KCOCH

28)

^C 9 ^H

NHCOCH

29) CH-CONH-SO ₂ - /

-OH

809811/0786 yellow

yellow

orange-yellow

Ex.

26th

Diazo component

Coupling component

30) CH-CONH-SO,

OCH ₃ ^ Y =,

CH.

OH

L ι 4-su-oabg on polyamide

orange

31) CH -CONHSO / yHH

> CH

orange-yellow

32)

. 33) 34) 35) 36)

' ^C 2 ^H 5 I orange-yellow

'2 5

^ Λ-ίΓ ' ² " ⁵

O -ι /

C, H ₁ OH

₀ H "4

orange

orange

orange-yellow

orange-yellow

80981 1/0786

3V

Seisp. Diazo component coupling component

CH-CONHSO- / V ^NH 3 *

Coloring on polyamide

orange-yellow

NHCOCH.

i

^K ~ ' ^X CH ₁ OCOCH

orange-yellow

40) 41)

-N

(»Μ

'' orange-yellow

\ ι

C "H. OCOCH,

H.OM

orange-yellow

OCOCH.

,

orange-yellow

43)

C H CN '

( ^{2 4}

orange-yellow

yellow

80981 1/0786

Example diazo component

CII-CONIISO _{9 y}

NIL coupling component

N-CH

Coloring on polyamide

yellow

ClI

yellow

47)

4S)

49)

CH.

Il
c

NH,

- NH ^y

C = O

-CH.

HO

CONH.

yellow

yellow

yellow

yellow

8098 1 1/0786

Example diazo component

CH CONHSO ^ -f \\ - NH., 3 ^ώ coupling component

ι r ^CH

YY--

Coloring on polyamide

• yellow

I.
COCH,

51) \ 7 S (/ "NHCOCH,

OCH

NMlCOCH,

orange

52)

yellow

53) 54) 55)

N-CU.

CH

Il

- NH

80981 1/0786 yellow

yellow

yellow

Ex.

56)

57)

-Vf-

HO

Diazo component

Cl

\\ - NH "

SO NHCOCH

Coupling 8-component

^CH 3
"CN

Coloring on polyamide

yellow

yellow

59)

60)

61) CH ₁ SO NHCO

HO '

CH

ι COCH.

i

-CONH

OCH

yellow

2H5

NHCOCH

yellow

yellow

orange

80981 1/0786

62)

Beep. Diazo component

Coupling component

Coloring on polyamide

yellow

63) 64)

I.

-CH

C OC H,

example

0.5 parts of a dye of the formula

yellow

yellow

are applied according to general procedure A. One achieves a blue dye of excellent levelness and very good light and wet fastness.

example

The following materials are poured into a reaction vessel :

80981 1/0786

-yr-

320 parts of butyl alcohol, 27 parts of quinizarine, 27 parts of leuco-quinizarine, 163 parts of p-aminobenzenesulfonacetamide and 27 parts of boric acid. The mixture is heated reflux for 12 hours, fed at 8O ⁰ C and washed with 320 parts of butanol at 8O ⁰ C. The filter cake is distilled in a stream of water vapor, filtered off and dried.

100 parts of a dye of the following formula are obtained:

NHCOCH,

¹ 3

'/ VsO., NHCOCH,

\ = / ^λ 3 _ι

which dyes greenish-blue on polyamide fibers, whereby levelness and eye hexes were good

In the same way, dyes of the following formulas can be used:

Ö0981 1/0786

69) 70) 71)

Example dye

0 NH

0 NHCOCH 2 3

0 NHCK

Coloring on polyamide fibers

blue

SO MMCOCH

HCH

SO ₀ NH (TOCH, i

0 Oi:

0 OH , VSO ₂ NHCOCH,

SO NHCOCH,

^m \ J blue

blue

reddish blue

reddish blue

80981 1/0786

Example 72

0.5 part of the dye of the following formula

NO

NH

are applied according to method A. A yellow dyeing of good levelness and very good light and wet fastness is obtained.

Example 73

According to Method A, 0.5 part of a dye becomes as follows formula

= N-

-SO NHCOCH 2 » 3

applied. A yellow dyeing of good levelness and very good lightfastness and wetfastness is obtained.

Example 74

0.5 parts of a dye of the formula

XI = ν J \\ - N.,

C., H.

NHCOCH

are applied according to method A. A red dyeing of excellent levelness and very good light- and naughtiness.

The dye of this example was made as follows:

80981 1/0786

At a temperature below 15 ° C 11 parts by volume of a 1: 5-tremischs of propionic acid and acetic acid with a solution of 0.70 parts of sodium nitrite in 5 * 5 parts by volume of concentrated sulfuric acid mixed · at a temperature below 5 ⁰ C, 2 parts of 5- Amino-1,2-benzoisothiazolone-1,1-dioxide and then a further 11 parts by volume of the 1: 5 acid mixture are added, after which the reaction mixture is stirred at 0 to 5 ° C. for 2 hours.

2.06 parts of m-diethylaminoacetanilide are in 75 ml of the 1: 5 acid mixture dissolved, the solution is cooled with ice, and then the solution of the diazonium salt is added · The resulting The mixture is buffered with sodium acetate and stirred for one hour. A dye precipitates when water is added the formula

NHCOCH,

which is washed with water and dried.

The following dyes were used in the same way:

80981 1/0786

Beep. Diazotizable base coupling component dyeing on polyamide fibers

HN

-Nil X = / ^ CH ₀ CH ₀ CN

orange

t ' Λ-Ν'

NHCOCH. - ^C » ^H 5

-C ₀ H ₁ -OCOCH,

! Scarlet fever

-NII

Scarlet fever

Scarlet fever

Scarlet fever

orange

80981 1/0786

Example: Diazotizable base coupling component

81)

HN

CO -

^s v

-NH,

Coloring on polyamide fibers

Scarlet fever

82) 83) 84)

CH _n CONH

K -CH OCOCH.

CH ₂ CH ₂ OH

Red

Red

Scarlet fever

80981 1/0786

-yf-

Example 85

6.12 parts of 1-amino-2-chloro-benzene-4-methylaulfon are added over one hour to 15 parts by volume of nitrosyl sulfuric acid 2N at 10 ⁰ C, then an hour is stirred and the resulting solution is in 60 parts water and 60 Poured parts of ice.

The cloudy diazo solution is poured at 0 ⁰ C in a solution consisting of 12.72 parts of the compound of formula

NHCONH

-SO NHCOCH,

150 parts of water and 3.0 parts of 36% hydrochloric acid. When the reaction has ended, sodium acetate is added to pH 4.7, then it is filtered and washed with water. The dye obtained in the form of a red powder has the following formula:

_ N = N-

- ^N

NHCONH

A part of the dye thus obtained is brought into solution with the required amount of ammonia and the solution is mixed into a dyebath circulating in the dyeing device. Then, 100 parts of tissue to be introduced polyamide-66 at 50 to 60 ⁰ C in the dyeing bath, after which the tempera-

809811/0786

-38Γ-

temperature is slowly brought to the boil. After boiling for 10 to 20 minutes, acetic acid is slowly added until the pH is 4.5 to 5. Staining is carried out with boiling for 40 to 50 minutes, then the material is washed and dried in the dryer.

In this way, a well-exhausting, uniformly red coloration is achieved, which is achieved through good levelness and good Light and wet fastness is marked.

The following dyes were also used in the above manner manufactured:

Example diazo component

88 '

CN

Qym_

CN

Cl-ί Q V-NH

Cl

Vn

, CN

Coupling component staining on

polyamide

do.

do. do. do.

C H

* ⁵

NHCONH- (O) "SO" HM \ / ² I

CH

KO

Red

Red

Red

blue

blue

809811/0786

Example diazo component

Coupling component coloring on polyamide

NO

CH t 2 5

C H 5

NH CONH

'~ \ OV SO ₂ NHCO

CH

violet

egg

nh

Cl orange

egg

NH

CN

Cl

Cl

O N-2

. -NH

'

CH
/ 3

do

I.

CH

Red

Red

Red

blue

80981 1/0786

Example diazo component

Coupling component coloring on polyamide

: o ν «,

CH CH

NHCONH-Zq Y-SO NH

CH CH Cl 2

Red

do.

orange

809811/0786

Example 99

1.61 parts of 2,5-dichloroaniline become a solution of 20 Parts of water and 2.5 parts of 36% hydrochloric acid were added. The amino compound is set in a conventional manner at 0 to 2 ° C diazotized by a solution of 0.69 parts of sodium nitrite in 15 parts of water is added dropwise. The diazonium = salt becomes a solution of 2, B4 parts of the compound of the formula

CONHSO CH, Z

50 parts of water, 50 parts of ice and one part of 365% hydrochloric acid admitted. After the reaction has ended, the pH is adjusted to 4.7 with sodium acetate and then filtered and washed with water.

The dye obtained in the form of a yellow-orange powder had the following formula:

ei _ ... ■ - = ■ I

N = N -

CH

\ /. CH ₂ -CH-CONHSO CH

. j

A part of the dye thus obtained was added with the required Amount of ammonia brought into solution and then added to the dyebath circulating in a dyeing device.

In this dyeing bath, 100 parts of tissue were incubated at 50 to 6O ⁰ C

Ö09811 / 0786

53

Introduced from polyamide-66, whereupon the temperature slows down was increased to boiling temperature. After boiling for 10 to 20 minutes, acetic acid was slowly added until the pH was 4-5-5.

They were colored with boiling for a further 4 © bis 50 minutes, then the colored material was washed and dried in the dryer. A well-exhausting, uniform red coloration was achieved, which was achieved through good levelness and good Light and wet fastness was excellent *

Example- diazotizable base 100)

co

s sP> - NH,

Coupling component coloring

on polyamide

Red

CH CH CONHSO CH! 2 2 2 3

101) 102)

103)

Cl

CN

do.

do.

do.

Red

Red

Red

809811/0786

COPV

Beiap. Diazotizable base

Coupling component coloring on polyamide

104)

CH.

/ 25 i

K '

CH CH CONHSO CH \
2 2 3 i

Red

105)

CN

106)

107)

, Cl

CH CONHSO

^CH o

/ 3

CONHSO-,

_r NH ₂ do.

NH,

Red

108)

Cl /

CH ^ CON-SO -

3 ι

^CH

Cl

3,

Red

CONHSO CH

Red

Red

80981 1/0786

Beep. Diazotizable base coupling component coloring on polyamide

109)

^CH 3 ^SO 2 -

Ci

^{c H 2}

110)

111)

CF

NH

Red

yellow

Cl

112).

yellow

.Cl

113) 'NC-Zq

NH

Red

80981 1/0786

Example 114

staining in a solvent

0.5 part of the dye according to Example 2 in salt form is dissolved in 40 parts of water and the solution is added to a dyebath which is in a pressure vessel and consists of 100 parts of perchlorethylene, 2 parts of acetic acid and 20 parts of a mixture of 84.0 ? ί Setrol 0 and 16 ^ Setroles 0. Then it was diluted with 2900 parts of perchlorethylene. At 20 ⁰ C, 100 parts of a fabric of polyamide fibers = 66 inserted, then C is heated in the course of 30 minutes at 100 ^0th This temperature is obtained 45 Aiinuten long upright, then is cooled in the course of 20 minutes at 20 ⁰ C, the dyed material is washed with perchlorethylene and dried. A uniform orange coloration is obtained, which is distinguished by good levelness and good light and wet fastness. Replacing the above dye with an equivalent amount of the dye of the following formula

-HÖÖC-

in this way a coloring with a significantly lower depth of color is obtained

For: Aziende Colori Nazionali Affini ACNA SpA
Milan, Italy

Dr.H.cfr.Beil Lawyer

8098 11/0786

Claims (23)

Patent claims: 1. Process for even and true dyeing of synthetic polyamide fibers from aqueous or organic! = * Shem solvent, characterized by the use of dyes derived from sulfonic acid or Car = acid groups are free and at least one own. 2. The method according to claim 1, characterized by the use of monoazo or polyazo dyes, the are free of sulfonic acid or carboxylic acid groups and have at least one -SO ^ HCO group. 3. The method according to claim 1, characterized by the use of anthraquinone dyes !!, which of sulfonaäu = re or carboxylic acid groups are free and have at least one -SOgNHCO group. 4. The method according to claim 1, characterized by Use of nitroamino dyes derived from sulfone = acid or carboxylic acid groups are free and have at least one -SOgNHCO group. 5. The method according to claim 1, characterized by the use of azamethine dyes which are free of sulfonic acid or carboxylic acid groups and have at least one -SO ₂ NHCO group. 6. Azo dyes of the general formula 809811/0786 ORIGINAL INSPECTED ■ rfi- where X
where R one of the radicals -SO ₂ NHCOR ₁ or -CC ι an alkyl radical with 1 to 4 carbon atoms men or an aryl radical, R ₂ and water substance, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the nitro or cyano group, a radical of the formula -SO ₂ R ^ where R is an alkyl radical iait 1 to 4 carbon atoms, or -SO ₂ NH ₂ , R. and R ₅ hydrogen, halogen, the radical -OCH ₂ CH ₂ OH, alkyl radicals with 1 to 4 carbon atoms, alkoxy radicals with 1 to 4 carbon atoms or acylamino and Rg and R ₇ hydrogen, Al = alkyl radicals with 1 to 4 carbon atoms, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ O-acyl, -CH ₂ CH ₂ CN or -CH ₂ CH ₂ COOR, in which R is an alkyl radical having 1 to 4 carbon atoms. 7. Azo dyes of the general formula - = N H_CH -X JL wherein X is one of the radicals -S or - a lower alkylreat with 1 to 4 carbon atoms or an aryl radical, R ₂ , R * and R. Hydrogen, alkyl = radicals with 1 to 4 carbon atoms, chlorine, bromine, the 809811/0786 Nitro group, trifluoromethyl group or cyano group, a radical of the formula -SO ₂ R, in which R is a lower alkyl radical, -SO ₂ NH ₂ , -CONRSO ₂ -, in which R is hydrogen or a lower alkyl radical, -COOR, in which R is a lower alkyl radical means, -CONRjR ₁ , WOrInRtR ₁ mean hydrogen and a lower alkyl radical, or X, R ₅ and R ₆ mean hydrogen, the radical -OCH ₂ CH ₂ OH, halogen, alkyl or lower alkoxy radicals or acylamino and R ₇ hydrogen, a lower one Alkyl radical, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ OR, in which R is a lower acyl radical, -CH ₂ CH ₂ CN or -CH ₂ CH ₂ COOR, in which R is a lower alkyl radical. 8. Azo dyes of the general formula N = N wherein X is one of the radicals -CONHSO ₂ R ₁ or -SO ₂ NHCO R ₁ , R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ , R, and R. is hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, Bromine, the cyano group, one of the radicals -SO ₂ NH ₂ , -C? ,, -SO ₂ R, in which R is a lower alkyl radical, -COOR, in which R is a lower alkyl radical, CONRR, in which R ₁ R is hydrogen and a lower alkyl radical, -CONR-SOp- »where R is hydrogen or a lower alkyl radical 809811/0786 -χΓ- (j. 273976b or X, R _{5 is} hydrogen, halogen, an ajl = alkyl radical or lower alkoxy radical and Rg and H _{7 are} hydrogen, lower alkyl create, -CH ₂ -CH ₂ OH, -CH ₂ CH ₂ OH, where R is a lower alkyl radical, -CH ₂ CH ₂ CN or -CH ₂ CH ₂ COOR, in which R is a lower alkyl radical. 9 · Azo dyes of the general formula -M = N- 'γ' - R wherein X is one of the radicals -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , wherein R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the nitro group or cyano group, -SO ₂ NH ₂ or -SO ₂ R, where = rin R is an alkyl radical having 1 to 4 carbon atoms, R. is an alkyl radical having 1 to 4 carbon atoms, -CONH ₂₁ -CONRR, where R is hydrogen or a Denotes alkyl radical with 1 to 4 carbon atoms, or -COOR, in which R denotes an alkyl radical with 1 to 4 carbon atoms, and R ₁ - an alkyl radical with 1 to 4 carbon atoms, -CH ₉ CHpOH or an optionally substituted by Halo- or / —— ■ ^: ν gen s, the nitro group or -COCHy substituted aryl radical represent.
10. Azo dyes of the general formula 809811/0786 -R wherein X is one of the radicals -SO ₂ NHCOR ₅ or -CONHSO ₂ R ₅ , where R _{5 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₁ , R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms , Chlorine, bromine, the cyano group or nitro group, -SO ₂ NHp or -S0 ₂ R, in which R is an alkyl radical with 1 to 4 carbon atoms, and R- is an alkyl radical with 1 to 4 carbon atoms, -CONH ₂ , -COOR, in which R denotes an alkyl radical having 1 to 4 carbon atoms, or -CONRR, in which R denotes hydrogen or an alkyl radical having 1 to 4 carbon atoms. 11. Azo dyes of the general formula Ii Ü = N - CH Il ο - O wherein X is one of the radicals -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , Where rin R ₁ denotes an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, 80981 1/0786 the nitro group or cyano group, -SO ₂ NH ₂ or -SO ₂ R, where R is an alkyl radical with 1 to 4 carbon atoms, and R. and R ₁ - hydrogen, alkyl radicals with 1 to
place. 4 carbon atoms or the radical -CH ₂ CH ₂ OH- 12. Azo dyes of the general formula R. N = N = N - (/ '% * - OR \ = fc = / wherein X is one of the radicals -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , wherein R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the nitro group or üyangruppe, -SO ₂ NH ₂ or-SOpR, where R is an alkyl radical with 1 to 4 carbon atoms, R ^, Rc and Rg hydrogen, alkyl radicals with 1 to 4 carbon atoms or alkoxy radicals with 1 to 4 carbon atoms and R ^ hydrogen or represent an alkyl radical with 1 to 4 carbon atoms. 13 · Azo dyes of the general formula - N - N - // ■■% wherein X is one of the radicals -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , where- 80981 1/0786 rin R ₁ denotes an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ , R, and R. hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group or nitro group, -SO ₂ NH ₂ or-SOgR, where R is an alkyl radical having 1 to 4 carbon atoms, and R ₅ and Rg are hydrogen or alkyl radicals having 1 to 4 carbon atoms. 14. Azo dyes of the general formula N = N wherein X is one of the radicals -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , where = rin R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, Bromine, the cyano group or nitro group, -SO ₂ NH ₂ or -SOgR, in which R is an alkyl radical having 1 to 4 carbon atoms, and R and R _{c are} alkyl radicals having 1 to 4 carbon atoms or aryl radicals. 15. Azo dyes of the general formula N-N-A wherein A is a coupling base of the formula 80981 1/0786 wherein R ₁ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, alkoxy radicals with 1 to 4 carbon atoms, -OCH ₂ CH ₂ OH, acylamino or halogen and R ₂ and Rj hydrogen, alkyl radicals with 1 to 4 carbon atoms, -CH ₂ GH ₂ OH, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ O-acyl or -CH ₂ CH ₂ -COOR, where R is an alkyl radical with 1 to 4 carbon atoms, or of the formula , wherein R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ 0-acyl or -CH ₂ CH ₂ CH ₂ NHCONHC ₂ H _5, R ₂ is hydrogen, a Alkylreat with 1 to 4 carbon atoms, acylamino, halogen or alkoxy and R _{1, R 4} and R _{5 represent} hydrogen or alkyl radicals having 1 to 4 carbon atoms. 16. Azo dyes of the general formula 809811/0786 -Xi- K _n -J / V> - N = N- wherein X is one of the radicals -SO ₂ NHCOR ₁ or - _21, wherein R ₁ represents an alkyl group having 1 to 4 carbon atoms or an aryl radical, R ₂ and R, is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine, bromine, the cyano group or Nitro group, -SO ₂ NH ₂ or -SOpR, where R denotes an alkyl group with 1 to 4 carbon atoms, R. and R ₅ denotes hydrogen, alkyl groups with 1 to 4 carbon atoms or the cyano group and Rg denotes hydrogen, an alkyl group with 1 to 4 carbon atoms or represent an aryl radical. 17 · Anthraquinone dyes of the general formula wherein X is one of the radicals -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , wherein R _{1 is} an alkyl radical with 1 to 4 carbon atoms or an aryl radical, R ₂ and R, hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group or nitro group, -SOJCiH ₂ or 80981 1/0786 where R is an alkyl radical having 1 to 4 carbon atoms, R. is the hydroxyl group, amino group or a radical -NHR, where R is an alkyl radical having 1 to 4 carbon atoms, and R ₁ - and Rg are hydrogen, the hydroxyl group, amino group or nitro group, or one 4 » ^R 5 the radicals R ₄ , R _c or R _c also represent the radical Λ ~ 7 Oi represent. 18. Nitroamino dyes of the general formula wherein X is one of the radicals -SO ₂ NHGO- or -CONHSO ₂ -, R _{1 is} hydrogen, chlorine, an alkyl radical with 1 to 4 carbon atoms or alkoxyreat with 1 to 4 carbon atoms and R _{2 is} hydrogen, chlorine, bromine or an alkyl radical with 1 to Represent 4 carbon atoms. 19 «azamethine dyes of the general formula CH, -N = CII-CH wherein X is one of the best -SO ₂ NHCOR ₁ or -CONHSO ₂ R ₁ , wherein R _{1 is} an alkyl radical having 1 to 4 carbon atoms or 80981 1/0786 denotes an aryl radical, and Bp ^{un (} * ^ 3 hydrogen, alkyl radicals with 1 to 4 carbon atoms, chlorine, bromine, the cyano group or nitro group, -SO ₂ NH ₂ or -SO ₂ R, in which R is an alkyl radical with 1 to 4 Carbon atoms means represent. 20. By the method of claim 1 dyed or printed polyamide material. 21. Dyed or printed by the method of claim 1 synthetic polyamide fibers. 22. By the method of claim 1 with one of the dyes of claims 6 to 17 colored or printed polyamide material. 23. According to the method of claim 1 with one of the dyes of claims 6 to 17 colored or printed syn = synthetic polyamide fibers. 80981 1/0786