DE2241392A1 - HYDRO-INSOLUBLE MONOAZO DYES - Google Patents

Description

Ref. 2953 2241392

Water- insoluble monoazo dyes

The present invention relates to valuable water-insoluble monoazo dyes of the general formula I

* I

in the

R. an optionally branched or substituted alkyl group ,,

R _{9 is} an optionally branched or substituted, alkyl, alkoxy or alkylamino group,

R ^ hydrogen, chlorine, bromine, an optionally subsi itated alkyl or alkoxy group,

R. hydrogen or an optionally substituted alkyl or alkenyl group,

Rj- a secondary or branched alkyl group with 3 to 8 carbon atoms

mean.

The warp-nläDgp, leglicher Alkylgrupp ^ n in the R? Th R., R _2, R, and R. is preferably 1 to k carbon atoms, "the chain length of alkt-nylgruppen in Re.st R. is preferably 3 to k Kohlens t (. Ff at ome *

:, 0 9 ■: ^f :: j / 1 no

- 2 - Ref. 2953

The alkyl or alkenyl groups in the radicals R ₁ to R can be substituted, for example, by a halogen atom, in particular chlorine, or a hydroxy, acyloxy, alkoxy, aryloxy, cyano, nitro, alkylsulfonyl or alkylaminocarbonyl group be.

The new dyestuffs are obtained if according to the teachings of the French patent no. 1,524,647, the nucleofugic group of monoazo dyes of the general F · imel II

^SO 2 ^R 1

^ ^H II R-

₂ °

in which R., Rp, R-, H, and R- have the meaning given above we have X means chlorine or bromine, nuoleophilic against Cyan too.

The new dyes are also obtained if, according to the teachings of German Offenlegungsschrift 1 809 921, the nucleofugal groups of monoazo dyes of the general Formula III

QK __. '/ XV-X = N- / ^V ) -N ^ III

NHC

R.

COR ₂

in which R _p , R ,, R. and R_ have the meaning given above and Y signifies chlorine, bromine or a nitro group, nucleophilically exchanges an alkylsulfonyl group.

, 09809/1068

- 3 - Ref. 2953

The compounds of the general formula I can preferably be used, for example, as R.

a methyl, ethyl, η-butyl, sec-butyl, chloromethyl, hydroxyethyl or cyanine thylgruppe, al * R ₂ position

a methyl, ethyl, n-propyl, sec-butyl, chloromethyl, Hydroxyethyl, cyanomethyl, methoxy, methylamino, ethylamino, n-butylamino or alkylamino group, as R,

Methyl, ethyl, methoxy, ethoxy, hydroxyethyloxy, acetoxyethoxy or methoxyethyloxy group, as R ^

a hydrogen or a methyl, ethyl, n-propyl, η-butyl, 2-hydroxyethyl, 2-acetoxyethyl, 2-carbmethoxyethyl, 2-cyanoethyl, 2-chloroethyl, 2-ethylsulfonylethyl, 2-nitroethyl, 2-phenoxyethyl, 3-methoxypropyl, benzyl, phenethyl, allyl, methallyl, buten-2-yl or 3-chloroallyl group and
as R-

contain an isopropyl, sec-butyl, β-pentyl, y ~ - pentyl,> ~ -hexyl, 2-ethylbutyl,) ^ - heptyl, β-octyl or a 2-ethylhexyl group.

The new dyes can be used to make synthetic hydrophobic Materials such as foils, films or textiles such as woven fabrics, knitted fabrics, flocks, threads or fibers made of polyesters, e.g. made of polyethylene glycol terephthalate or polyester

409809/1068

- k - Ref. 2953

from i, ^ - bis (hydroxymethyl) cyclohexane and terephthalic acid! from cellulose triacetate, cellulose-2 l / 2-acetate or from Dye and print polyacrylonitrile in an excellent way.

With the help of the new dyes it is possible to achieve brilliant blue colorations or prints on the materials mentioned, which is characterized by high dye yield, very good structure and duroh excellent fastness properties, in particular very good heat-setting, washing, rubbing and light fastness properties distinguish.

Textiles made from polyesters, such as, for example, polyterephthalic acid glycol esters or those based on terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane, can be dyed with the dyes according to the invention by known processes. The dyeing temperatures for the present in aqueous dispersion dyes are present in normal Druok at 95-100 ⁰ C, preferably at 100 ⁰ C, or under elevated pressure at 104 to 140 ⁰ C. In the application of temperatures around 100 ⁰ C it is recommended that the Add swelling agent (carrier) to the dye bath. As swelling agents, for example aromatic hydrocarbons such as diphenyl, aromatic halogen compounds such as chlorobenzenes, aromatic carboxylic acids such as benzoic acid and salicylic acid, phenols such as o- and p-phenylphenols, esters such as terephthalic acid esters can be used. Instead of dyeing from the bath can be a hot air fixation of padded on the dyed material dyes at temperatures of 200 - 230 ⁰ C to make.

409809/1068

- 5 - Ref. 2955

The printing can be carried out so that the printed product in the presence of a carrier at temperatures between about 8o - 110 ⁰ C or in the absence of a carrier at about 110 - damped l40 ° C or, after the so-called thermofixing process at about 170-230 ⁰ C is treated.

Compared to the dye of the formula IV

IV

the inter alia in the German patent application Az.: P 17.19 066.8 · Is described and compared to the dye of the formula V

? CH, NHCOCH ₃ - ^C 2 ^H 5
^ CH O ₂ N- CN

SO ₂ CH ₃

NHC ₂ H _{5 v} NHCOCH ₃

which is described inter alia in the German patent application Az .: P 20 20 030.0, can be achieved with the new dyes the so-called HT dyeing process a significantly better color structure. According to the so-called thermosetting process stronger colors are achieved even at lower temperatures.

It should be noted that mixtures of the new dyes sometimes have a better color yield than the individual ones Supply dyes.

40980 9/1068

- 6- Ref. 2953

example 1

50.1 g of 2-bromo-4-nitro-6-cyano-1- 4'-N-ethyl-N-ß-pentylamino-2'-acetylamino-phenylazo-benzene, 17 g of zinc methyl sulfinate and 2 g of copper (I) oxide are entered successively in 200 ml of dimethylsulfoxide and heated to 100 ⁰ C. After 15 minutes the mixture is allowed to cool, sharply suctioned off and the residue is washed with a little dimethyl sulfoxide and then with water. This gives 39 g of 2-methylsulfonyl-4-nitro-6-oyan-1-R'-N-ethyl-N-β-pentylamino-2'-acetylamino-phenylazol-benzene, which has a very blue color on polyester results in good light and sublimation resistance.

Example 2

55.6 g of 2-bromo-4-nitro-6-methylsulfonyl-4 '-N-ß-butylamino-2'-acetylamino-5'-ethoxy-phenylazoJ -benzene, 9 g of copper (I) cyanide and 1 g Nntriumcyanid are introduced into 200 ml of dimethylsulfoxide and heated to 9O ⁰ C. After 15 minutes the mixture is allowed to cool, sharply suctioned off and the residue is washed with a little dimethyl sulfoxide and then with water. This gives 44 g of 2-mithylsulfonyl-4-nitro-6-cyano- ¹ -JjI 1 -N-β-butylamino-2-acetylamino-5'-ethoxy-phenylazo-benzene, which has a very good greenish blue color on polyester Results in light and sublimation fastness.

/ »09809/1068

BATH

- 7 - Ref. 2955

The table below shows further dyes according to the invention which are blue on polyester materials Dyeings with also very good ooloristic properties, especially very good light and sublimation fastness properties result.

C. ^R l T a b e 1 1 e CR SO ₂ R ₁ r- / ^ 5N-6O / - N = N - ON NHCOR ₂ No. R ₂ ^R 3 3 CH ₃ H

H H

^R 5

ch;

H H

CH-

H 'H'

CH-

HH ^ ^G bHc

CH ^A °

^: 2 ^H 5

"H H ^ C H_

CH ^ ^{2 5}

H H

CH '

A09809 / 1068

No.

Ref. 2953

10 CH, 11 12

CH

Br

OCH

OC,

CH ₂ ClT

CH,

CH-CH: CH '

Hj

14th

¹ p

CH '

CH-

16 17

OCH

OCH ^

19 20

OC ₂ H

Cl

CH

CH

/.09809/ 1068

No. 21

'3

Ref. 2953

CH

22nd

23 24

26th 27

it '

28 C ₄ H ₉ 29 • CH
CH ^ ^?
^ C ₀ H 30th 2
CH ₂ Cl 31 C ₂ H ₄ OH

H H H H H

H H

2> V, DD

C ₂ H ₅

'C ₄ H ₉

/ ^C 2 ^H 5 "C ₄ H ₉

CH '

CH-

CH-

'C ₂ H ₅

409809/1068

No. R ₁

32 CH ₂ CN

33 CH.

CH '

'CH.

CH ₂ Cl

- 10 -

Ref. 2953

Ri

CH

^ C ₂ H ₅

CH ^ '■ ^ C

C ₃ H ₇

CH ₂ CN

OCH,

40 It NHCH ₃ H 41 Il NHC ₂ H ₅ H 42 Il NHC ₄ H ₉ H

CH ₃

, CH.

CH '

CH

-C ₃ H ₇

409809/106 8

No. R ₁

NHCHgCH = CHg

C ₂ H ₅

OCH ₂ CH ₂ OH

CH,

Ref. 2953

^R 5

^ CH, CH

OCH ₂ CH gOCH ₃ CH ₅ OCH ₂ CH ₂ OCOCH, dd H X ₁ -C ₅ H ₇ H CH ₂ CH = CH ^

H
H

CHgC = CH ₂

CH ₂ CH = CHCH ₃

CHgCH = CHCl

* 2 N,

809/10 68

Ref. 2953

No. 54

55 56 57 58 59

6ο 61

62 63

CH-

H H H H H

H H

H H

CH CH OH CH,

² 2 _rxi ^

CHgCHgOCOCH, <J

CHgCHgCOOCH "

CHgCHgCN "

CHgCHgCl "

CHgCH ₂ SOgCgH

CHgCHgNOg

CHgCHgO- (O

CH CH CH OCH-

^ CH "

CHg-

CHgCHg

H ₀ CH

409809/1068

■ - 15 - Ref. 2953

Example 65

In a dye liquor which finely dispersed 1 g of a commercially available dispersant and 0.5 g in 1 liter of water Dye of the formula VI

VI

and adjusted _{to P u} 5 with acetic acid

at 50 - 60 ⁰ C. 25 g of a yarn from Polyterephthalsäureglykol ester introduced, the dye bath within 45 minutes to 1 ^ 0 ⁰ C HEATER-t and held for 90 minutes at this temperature. The material thus colored is ^{reductively aftertreated for 20-30 minutes at 60-70 °} C. with 4 ml / l sodium hydroxide solution (38 ^° Be) and 2 g / l dithionite. Then it is rinsed warm, acidified with acetic acid and rinsed again.

A blue dyeing with excellent fastness properties is obtained.

Example 66

With a padding liquor, which is 2 - 3 g per liter of water of an ethylene oxide addition product as a dispersant, 20 g of a thickener based on polyacrylic acid and 2 g of finely dispersed dye of the formula VII

OC ₂ H ₅
ViT "" ^ 2 TII

A09309 / 106

BATH

- l4 - Ref. 295)

contains a fabric of PoIyterephthalsäureglykol- is' ester padded at 4o ° C, dried and subjected to thermosol treatment for 60 seconds using hot air at 200 ⁰ C. After a reductive post-treatment with 4 ml / 1 of sodium hydroxide solution (3 ° Be) and 2 g / l of dithionite during 2C minutes at 60 - 7O ⁰ C, the material is rinsed, acidified and rinsed again.

A blue dyeing with excellent fastness properties is obtained.

Example 67

25 g of cellulose triacetate fabric are added to a dye liquor prepared according to Example 65 at 50-60 ° C. the dye bath to 125 - 15G ° C within 45 minutes heated and left at this temperature for 90 minutes. The further treatment takes place as described in Example 65. A blue color results.

Example 68

In one with acetic acid to P "6 - 7 set dyeing liquor to 1 titer of water 1 g of a commercially available dispersing agent, and 0.5 g of finely dispersed dye of Example 66 includes, at 40 - 50 ⁰ C 25 g of cellulose acetate (1: 2 / 2-acetate) introduced, the dyebath slowly heated to 75 ° C and held at this temperature for 60 minutes. Then it gets cold and warm. flushed. A blue color is obtained.

/, 09809/1068

GiFfG OA0 BAD ORIGINAL

- 15 - Ref. 2953

Example 69

A dye liquor prepared analogously to Example 68 at j50 - 40 ° cr 25 g of polyamide fabric added, the dye bath within 30 minutes Brought to boiling temperature and held at this temperature for 60 minutes. After dyeing is rinsed cold and warm. This gives a blue color.

Example 70

A fabric made of polyester is printed on a blind printing machine with a tearing paste of the following composition printed:

50 g lO '& Lger dye dough, the. contains the dye of Example 66 in finely dispersed form, 250 g of starch Troganth thickening, 250 g of Kristallgurnmi thickening and. ^ 50 g water or thickening. 60 seconds at I90 - - After printing and drying, the tissue either 3 * 0 is thermosoled 210 ⁰ C or 10 - 20 minute at 1 - damped atm. 2 Brilliant blueprints are obtained with both methods.

4 Q 9 8 0 9/1 0 6 8

BAD ORIQlNAt

Claims (7)

- 16 - Ref. 2953 Pa te n tans check * c he • ti 1. Water-insoluble monoazo dyes of the general formula Γ SO ₂ R ₁ CN NHCOR ₂ in the R _{1 is} an optionally branched or substituted one Alkyl group,
Rp is an optionally branched or substituted one Alkyl ,. Alkoxy or alkylamino group, R, hydrogen, chlorine, bromine, one optionally substituted alkyl or alkoxy group, Rji, hydrogen or an optionally substituted one Alkyl or alkenyl group,
Rc is a self-circular or branched alkyl group with 3 to 8 carbon atoms. 2. Water-insoluble monazo dyes of the formula I given in claim 1, in which the chain length of any alkyl groups in the radicals R., R ₂ , R, and H ₁ ^ is preferably 1 to 4 carbon atoms, the chain length of the alkeny group is preferably 3 to " 4 carbon atoms and the chain length of the alkyl group in the radical Rc is preferably 4 to 6 carbon atoms. 409809/1068 ^{= 1} T "Ref. 2953 3 · Water-insoluble monoazo dyes of claim 1 given general formula I, in which the alkyl or alkenyl group by a chlorine atom or a Hydroxy, alkanoxy, alkoxy, aryloxy, cyano, nitro, alkylsulfonyl or alkylaminocarbonyloxy group are substituted. 4. A process for the preparation of "water-insoluble monoazo dyes of the formula I given in claim 1, characterized in that the nucleofugal group X of monoazo dyes of the general formula II II in which R- ,, Rp, R ₁ , R 1, and R are as defined above, and X is chlorine or bromine, nucleophilically exchanged for cyano. 5. Process for the preparation of water-insoluble monoazo dyes of the formula I given in claim 1, characterized in that the nucleofugal group Y of monoazo dyes of the general formula III III in which Rp, R ^, R ₁ , and R ₁ - have the meaning given above, and Y is chlorine, bromine or the nitro group, nucleophilically exchanged for an alkylsulfonyl group, 409809/1068 - 18 - Ref. 2953 6 .. Process for dyeing and printing synthetic hydrophobic materials, characterized in that a dye of the general formula given in claim 1 is used. 7. With a dye of the general formula given in claim 1 dyed or printed synthetic hydrophobic materials. 409809/1068