DE1813385A1 - Process for dyeing and printing fiber material made from synthetic materials - Google Patents

Description

CASSELLA FARBWERKE MAINKUR Ref. 2854 SHARED COMPANY

6cooFRANKFURT (MAiN) -FECHENHEiM Prankfurt (Main), the k. December 1968

Dr.Rdm / Cz

Process for dyeing and printing fiber goods made of synthetic materials

It has been found that real dyeings and prints are obtained on fibers made of synthetic, hydrophobic materials such as polyacrylonitrile, polyamide, cellulose 2 l / 2-acetate, cellulose triacetate or, in particular, on polyesters, e.g. polyethylene glycol terephthalate ₍ if this fiber is mixed with an aqueous Dispersion of dyes of the general formula

X R-N = N-x ^ _y

HO ^ N- ^ O

Z treated in the

R is the remainder of a group free of water-soluble groups Diazo component of the benzene, naphthalene, diphenyl, diphenylmethane or heterocyclic series,

X is hydrogen, an optionally branched alkyl,

especially a methyl group, a carbalkoxymethylene, a carbalkoxy or an optionally substituted cycloalkyl, aralkyl or aryl group «,

Y hydrogen, a cyano, a nitroso, a nitro,

an optionally branched alkyl, an optionally substituted cycloalkyl, aralkyl, aryl group or the

Radicals -COOR ₁ , -CORg ₁ -CO-N ^ *, -SOgRg or -SO «-N (

where R ₁ and R ₂ «in · optionally branched alkyl group,

009827/1971

Ref. 2854

Rg also an optionally substituted cycloalkyl, Aralkyl or aryl group and R and R are hydrogen, an optionally branched alkyl, hydroxyalkyl, alkoxyalkyl, Cycloalkyl, aralkyl or aryl group, the alkyl radicals R_ and R. also being linked directly or via a heteroatom can,

Z is an optionally branched, substituted alkyl or alkenyl, an optionally substituted cycloalkyl, aralkyl «= or aryl group.

or alkenyl

In the radicals X, Y and Z the alkyl groups have one chain length of preferably 1 to 6 carbon atoms and substituents on the cycloalkyl, aralkyl or aryl groups are, for example or more halogen atoms, alkyl or alkoxy groups, where a phenyl group in the Z position can also be replaced by a Alkylsulfonylalkylene group or by the radicals

-CH ₂ -CH ₂ CH
-CH 2 ~ _y (YH ₃
-CH-CH ₂ ² CH ₂ -
-CH CH, Ih ³ Ch CH ₃
-CH-CH ₂ 2 2 CH ₂
CH ₂ ,
I. -CH ₂ -CH ₂ -CH
ι _{M. 11th} I.
( Γ · ΤΤ \ -CH ₂ - ( co -CH ₂ ^C , ^H 2
. ^CH 2
> CH ₂ - (CH CH ₂ , -CH f ^H 2 CO CH ₂ CHr C.

R R

-COOR ₁ , -COR ₂ , -CO-Nc ^ ³ , -SO ₃ R ₂ or -SO ₂ -N ^ ³ , where η is

^{R R}

0098-27 / 1S71

" ^: """'"" Β !!! ΐρι'ί'"ί: ■ ijf

1813385 Ref. 2854

the numbers 0 to 3 and R, to R ^ the above

/ -substituted meaning can be substituted. As Z-position / alkyl group comes into consideration, for example, a mono- or dialkylaminoalkyl, cyanoalkyl, hydroxyalkyl, aoylhydroxyalkyl, alkoxyalkyl, aryloxyalkyl or an alkyl or arylamino-carbonyloxy-alkyl group.

The dyes which can be used according to the invention are customary Available by coupling diazotized amines R.NH ₂

the benzene, naphthalene, diphenyl, diphenylmethane or hetero- " cyclic series that are free of water-soluble groups are, with 6 ~ hydroxy-2-pyridones of the general formula

in which X, Y and Z have the meaning given above.

Diazo components R.NH ₂ are for example:

Aniline,

2 ~, 3- or 4-amino-töluene, 3-amino-benzotrifluoride, 3 or 4 amino-1,2-dimethylbenzene, 2-, 4- or 5-amino-1,3-dimethylbenzene, 4-amino-1,3 »5-trimethylbenzene, 2-, 3- or 4-amino-anisole, 2-, 3- or 4-aminophenetol, 2-amino-1,4-dimethoxybenzene,

009827/1971

2-amino-l, 4-diethoxybenzene, 2-, 3- or 4-aminophenol <- (ß-hydroxy-ethyl ether), 2-, 3- or 4-aminophenol- (ß-hydroxy- n-propyl ether), 2-, 3-or 4-chloroaniline, 2-, 3- or 4-bromani1ine, 2,3- _> 2,4-, 2,5- ⁱ or 3, ^/ t- ^{dicloroaniline} »2,5-dibromaniline, 2,4,5-, 2,4,6-, 3,4,5- or 3,4,6-trichloroaniline, 3-, 4-, 5- or 6-chlorine -2-aminotoluene, 4-chloro-3-aminotoluene, 2-chloro-4-aminotoluene, 5-chloro-2-aminobenzotrifluoride, 4,5- or 4,6-dichloro- 2 - Amino-toluene, 2,5- or 4,6-dichloro-3-aminotoluene, 2,5- or 3 »5-dichloro-4-aminotoluene _t 4,5» 6-trichloro-2 -amino-toluene, 4-chloro-2-amino-1,3-dimethyl-benzene, 6-chloro-3-amino-anisole, 2-chloro-4-amino-anisole, 3-chloro-4-amino-anisole \ 2-, 3- or 4-nitroaniline, 3-nitro-4-amino-toluene, 5-nitro-4-amino-1,3-dimethylbenzene, 6-nitro-3-amino-ani8ol, 3-nitro- 4-amino-anisole, 5 ~ nitro-2-amino-phenetol, 2-nitro-4-araino-phenetol,

009827/1971

3-nitro- k- amino-phenetol, 5-nitro-2-amino-1,4-dimethoxy-benzene, 5-nitro-2-amino-1,4-diethoxy-benzene, 2-chloro-t-nitroaniline , 2-bromo-4-ni trani1in, ^ -chloro ^ -nitraniline, 4-bromo-2-ni trani1in, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-uitraniline, 2,4- Dinitraniline, 6-chloro-2,4-dinitraniline, 6-bromo-2,4-dinitraniline, 2,4,6-trinitraniline, 2-cyano-4-nitroaniline, 4-cyano-3-nitraniline, 2-methylsulfonyl ^ -nitraniline, 4-methylsulfonyl-2-nitraniline, 2-, 3- or 4-amino-acetophenone, 2-, 3- or. 4-Amino-benzophenone, 2-, 3- or 4-amino-benzoic acid ethyl ester, 2-, 3- or 4-amino-benzoic acid n-butyl ester, 2-, 3- or 4-amino-benzoic acid -oyolohexyl ester, 2-, 3- or 4-araino-benzoic acid araid, 2-, 3- or 4-amino-benzoic acid monomethylamide, 2-, 3- or 4-amino-benzoic acid dimethylamide, 2-, 3 - or at-amino-benzoic acid-ethylene amide, 2-, 3- or 4-amino-benzoic acid-ieo-propylamide, 2-, 3- or 4-amino-benzoic acid diethylamide,

009827/1971

2-, 3- or 4-amino-benzoic acid di-n-butylamide, 2-, 3- or 4-amino-benzoic acid morpholide, 2-, 3- or 4-amino-benzoic acid anilide, 2 -, 3- or 4-amino-benzoic acid N -methylanilide, 2-, 3- or 4-aminopheny1-methylsulfone, 2-, 3- or 4-aminobenzyl-methy1sulfone, 2- , 3- or 4-amino-phenethyl-methyl sulfone, 4-amino-phenyl-propyl-methyl-sulfone, 2- (4 ^l- amino-phenyl) -propyl-methyl-sulfone,! - (^ • -aminophenethyl-tetramethylene sulfone, 2-, 3- or 4-aminophenol ~ (^ - methylsulfonylpropyl ether), 2-, 3- or ^ - aminophenyl-methyl-sulfonic acid ester, 2-, 3- or, ^ - amino phenyl-ethyl-sulfenic acid ester, 2-, 3- or 4-areno-phenyl-ß-chloroethyl-sulfonic acid ester, 2-, 3- or 4-aminophenyl-butyl-sulfenic acid ester, 2-, 3-h or 4 -Amino-phenyl-n-hexyl-sulfenic acid ester,

/ ~ phenyl-2-, 3- or 4-amino-phenyy-sulfonic acid ester, 2-, 3- or 4-araino-phenyl- (4'-methyl-phenyl) -sulfenic acid ester, 2-, 3-hzw.4-Amino-phenyl- (4'-methoxyphenyl) -sulfonic acid ester, 2-, 3- or 4-aminophenyl-dimethylsulfamic acid ester, 2-, 3- or 4-aminophenyl-dtäthylsulfamic acid ester, 2-, 3- or 4-aminophenyl-di-n-butylsulfamic acid ester, S - ^ - DZw. ^ - Amino-benzene-sulfonic acid amide, 2-, 3-l) ZW «4 ~ aminobenzenesulfonic acid monomethylamide, 2-, 3 "-l) zw, 4-Amino-benzenesulfonic acid-diniethylamide, 2 «, 3 or» 4-amino-benzenesulfonic acid-ethylene amide, 2-, 3- or 4-amino-benzenesulphonic acid diethylaraid,

00-9827 / 1971

2-y5 - or. 4 — Amino — benzo 1 sulphonic acid — di — n — butyl amide, 2-, 3- or 4-Arainobenzenesulfonsäurθ-morpholide, 2-, 3 ~ or 4-amino-benzenesulphonic acid anilide, 2-, 3- or 4-amino-benzenesulfonic acid-II-methyl-anilide, l-methoxy-2-aminobenzene-4-sulfonsäuΓβamid, l-methoxy-2-aminobenzene-4-sulfonic acid dimethylamide, l-methoxy-2-aminobenzene-4-βlIlfonsäure- J ^ -methylanilid, l-chloro-2-aminobβnzol-4-sulfonsäurθ-dimβthylamid, l ~ chloro-4-aminobenzene-2-sulfonic acid ~ dimethylamide, 2-, 3- or 4-amino-acetanilide,

2-, 3- or 4-amino- (ß-butoxy-propionylanilide), λ

2 ~, 3- or 4-aminophenoxyacetanilide, 2-, 3- or 4-amino-N-raethyl-acetanilide, N- (4-aminophenethy 1) - ^ buty ro 1 ac t am, N -Methyl-y .- (4-aminophenethyl) -j (-butyrolactam, N-methy1 - »- / 2- (4'-aminophenyl) propyl / - ^ - butyrolactam, N- (4 ~ amino -phenäthyl) - £ -caprolactam, 4-amino-diphenyl ,

Ethyl 4-amino-diphenyl-4'-carboxylate, 4-amino-diphenyl-methane,

4-amino-diphenyl-diraethyl-methane, "

1-amino-naphthaiine,

8-chloro-l-amino-naphthalene,

5-nitro-1-amino-naphthalene,

2-amino-naphthalene, "

5-nitro-2-aminothiazole

009827/1971

Suitable coupling components within the meaning of the above formula are, for example, the following 6-hydroxy-2-pyridones:

l-methyl-ö-oxy - ^ - pyridone,

l-phenyl-6-oxy-2-pyridone,

l ~ methyl-4-methyl-6-oxy-2-pyridone, l-ethyl-4-methyl-6-oxy-2-pyridone, ln- or iso-propyl - ^ - methyl-6-oxy-2- pyridon _f 1-n, iso- or sec-butyl-4-methyl-6-oxy-2-pyridon, 1-n- or. iso-amyl ^ -methyl-o-oxy ^ -pyridon ,, ln-hexyl ^ -methyl-o-oxy ^ -pyridone, 1- (2 ^l -dimethylamino- or diethylamino-ethyl) -4-methyl-6- oxy-2-pyridone, l -. (2 ^t -cyano-ethyl) -4-methyl-6-oxy-2-pyridone, 1- (2'-hydroxyethyl) -4-methyl-6-oxy-2 -pyridone, 1- (2 ^f -acetoxy-ethyl) -4-methyl-6-oxy-2-pyridone, 1- (2 ^f -phenoxy-acetoxy-ethy1) -4-methyl-6-oxy-2-pyridone , 1- (1'-methyl-2'-hydroxy-ethyl) -4-methyl-6-oxy-2-pyridone, 1- (3 ^! -hydroxypropyl) -4-methyl-6-oxy-2- pyridone, l- (2'-phenoxy-ethyl) -4-methyl-6-oxy-2-pyridone, l- (3 »-Methoxypropyl) -4-methyl-6-oxy-2-pyridone, l- Cyclohexyl-4-methyl-6-oxy-2-pyridone, l-benzyl-4-methyl-6-oxy-2-pyridone, I- (31-methyl-benzyl) -4-methyl-6-oxy-2- _f pyridone l-phenyl-4-methyl-6-oxy-2-pyridone, l- (2'-or. k '-methyl-phenyl) -4-methyl-6-oxy-2-pyridone, l- (2 ·, 4'-Dimethy1-phenyl) -4-methyl-6-oxy-2-pyridone, 1- (2 ^l -chloro-4 ^l -methylphenyl) -4-methyl-6-oxy-2-pyridone, l- (2 or 4'-chlorophenyl) -4-methyl-6-oxy-2-pyridone,

009827/1971

1313385

Ref. 2854

1- ( 2'- or h · -methoxyphenyl) -4-methyl-6-oxy-2-pyridone, 1- (2 ', 5 »-dimethyl- * -chlorophenyl) -4-methyl -6-oxy-2-pyridon, 1- ^ V- (3 * -Methyl-sulfonyl-propyl) -phenyl7-4-methyl-6-oxy-2-pyridone from Forael CH _r

IH ₂ -CH ₂ -CH ₂ -SO ₂ -CH ₃

l ~ / k «- (2" -N- £ -Caprolactam) -ethyl / -phenyl-4-methyl-6-oxy-2-pyridone of the formula CH-

-OH ₂ -OH

1- {41- / 2 "- (tC-ir-methyl - ^ - butyrolactam) -ethyl / -phenyl} -4-diethyl-6-oxy-2-pyridone the formula

CH ₂ -CH ₂ -CH-CII ₂ OCCH

I

009827/1971

1 »(2 · -, 3'- or 4'-carbethoxyphenyl) -4-methyl-6-oxy-2-pyridone, 1 - (2 ·, 3 ^% « - or 4 '-Acety 1 -pheny 1) ^ -methyl-o-oxy-2-pyridone, 1- (2 ^! -, 3'- or 4 ^f -Benzoyl-phenyl) -4-methyl-6-oxy-2-pyridone, 1- (2 '-, 3' or 4 · -Dimethy 1-carbamyl-phenyl) -4- «ethyl-6-0xy-2-pyr i 6 one , 1- (2 · -, 3 'or 4 '-Diethy 1-carbamyl-phenyl) -4-HBotliyl-6-oxy-2-pyridone, 1- (2' -, 3 'or 4 -i so-propyl-carbamyl-phenyl) -% - ethyl -6-oxy-2-pyridone, 1- (2 · -, 3 'or. 4 · -Methyl-sulphony 1-pheny 1) -4- «ethyl-6-oxy-2-pyridone«, 1- (2'-13'-or k '-phenyl-sulfony1-phenyl -4- «ethyl-6-oxy-2-pyridone, 1- (2.)' -., 3 'or k' -Dimethy1 -sulfamyl-phenyl) -4h-ethyl-6-oxy-2-pyridone,

-phenyl 1- (2 · -, 3 'or. 4' -iso-propyl-sulfamine ^ l · -4-lιιethyl-6-oxy-2-pyridone, 1- (2 ^f -, 3'- or .4'-Diethy1-sulfamy1-pheny1) -4-ethyl-6-oxy-2-pyriaeone.

Also suitable are the pyridones, which in the 4-position instead of the methyl group are ethyl, n-hzw.iso-propyl, n-, iso- or. sec.Butyl, n- or iso-amyl, n-hexyl, cycloalkyl, benzyl, phenyl, 4 ¹ -methyl-phenyl, carboxyethyl or the best -CH ₀ -COOCH. also contain the derivatives of these pyridones, such as those that are in the 3-position by a cyano, nitroso, nitro, methyl, ethyl, n- or iso-propyl, n-, iso-hzw. sec-butyl, n- or iso-amyl, n-hexyl, cycloalkyl, benzyl or aryl groups are substituted or contain the following radicals in the 3-position:
3-carboxylic acid methyl ester,
3-carboxylic acid-ethyleter, 3-carboxylic acid-n- or iso-propyl-8ter, 3-carboxylic acid-n-, iso- or seo-butyl ester, 3-carbonette-n- or iso-ethyleeter, 3-carbonic acid-n -hexyleeter,

009827/1971

3-acetyl, 3-propionyl, 3-capronyl, 3-capryl, 3-hexahydrol> enxoyl, 3-phenacetyl, 3-benzoyl, 3_ (4ι-methyl-benzoyl), 3- (2 ", h ♦ -diaethyl- benzoy1), 3- ( Ί'- methoxy-benaoyl), 3_ (41-chlorobensoyl),

Ref. 2854

3-Carbonsätireaeid _y 3-Carbonsätire-HBono-Hiethylamid, 3-Carbonsäere-dimethyla *id, 3-Carbonsäure-Sthylenamid, 3-Carbonsäure-HBono-Ethy 1 amid, 3-Carbonsäure-HBOno-iso-propylamid, 3- Carboxylic acid diethylaid, 3-carboxylic acid piperidide, 3-carbonic acid-cyclobexylamide, 3-carbonic acid-cyclobexylamide, 3-carbonic acid-HBorpholide * -benxylaeid, 3-Carboneäure-enllid _y 3-Carboneäere - (% ^l - «ethyl-anilid),

009827/1971

3-cart) on acid- (N -methyl-anilide),

3-methylsulfonyl,

3-ethylsulfonyl,

3-n- or iso-propylsulfonyl, 3-n-, iso- or sec-butylsulfonyl, 3-n- or iso-amylsulfonyl, 3-n-Hexy1sulfony1,

3-benzylsulfonyl,

3-phenylsulfonyl,

3- ( k '-Methyl-phenyl) -sulphony1, 3- (2', k -dimethyl-phenyl) -sulphonyl, 3 - (^ '- methoxyphenyl) -sulphonyl, 3- ( h ' -chloro- pheny1) -sulfony1,

3-sulfonic acid arid,

3-sulfonic acid-raonoraethylamide, 3-sulfonic acid-dimethylamide, 3-sulfonic acid-ethylene araid, 3-sulfonic acid-monoethylamide, 3-sulfonic acid-mono-iso-propylamide, 3-sulfonic acid-diethylamide, 3-sulfonic acid-mono-oxethylamide, 3- Sulfonic acid mono- {f ^/ -methoxy-propylamide, 3-sulfonic acid morpholide, 3-sulfonic acid piperidide, 3-sulfonic acid cyclohexylamide, 3-sulfonic acid benzylamide, 3-sulfonic acid anilide,

009827/1971

3-sulfonic acid- (4'-methyl-anilide),
3-sulfonic acid- (N -methyl-anilide).

The dyes which can be used according to the invention are very suitable for dyeing and printing structures made of synthetic materials, such as polyacrylonitrile, polyamide, cellulose-2 l / 2-acetate, Cellulose triacetate and especially polyester materials such as polyethylene glycol terephthalate. You then deliver according to the usual Dyeing and printing processes strong, clear, yellow to red dyeings and prints with very good fastness properties, in particular very good good fastness to light and sublimation. -

Dyes of the type characterized above, which are in the 3-position possess a cyano group, provide dyeings and prints with particularly favorable coloristic properties.

The dyeing of the said materials is advantageously carried out from an aqueous suspension in the presence of carriers between about 80 ° and 110 ° C, in the absence of carriers between about 110 ° to 140 ⁰ C, and by the so-called thermofixing process at about 170 ° to 230 ⁰ C. the printing can be carried out so that the printed goods steamed of a carrier at temperatures of "between about 80 ° and 100 ⁰ C or in the absence of a carrier at about 110 ° to 140 ⁰ C in the presence or also by the so-called thermofixing process at about 170 ° to 230 ° C is treated «

009827/1971

Example 1;

1.0 part by weight of the finely dispersed dye of the formula

are stirred into 2000 parts by weight of water. It is adjusted to a pH of 5 to 6 with acetic acid and mixed with k g of ammonium sulfate and 2 g of a commercially available dispersant based on a naphthalenesulfonic acid-formaldehyde condensate. In the dyeing liquor thus obtained 100 parts by weight brings a polyester fabric based on polyethylene glycol terephthalate and dyeing is a 1 1/2 hours at 120 ° to 130 ⁰ C. After subsequent rinsing, reduction treatment at a 0.2 $ solution of alkaline sodium dithionite for 15 minutes 60 ° to 70 ⁰ C, rinsing and drying, it is in particular a very good lightfastness is obtained a greenish yellow dyeing having very good fastness properties.

The above dye can be prepared in the following way:

21.6 parts by weight of 3-amino-phenyl-dimethylsulfamidsäureester are dissolved in 300 parts by weight of water with the addition of 36 Gewiohtstellen 30% hydrochloric acid and zotiert at 0 to +5 ⁰ C with a solution of 7 _f 7 Nominal scarring sodium nitrite in 50 Gewiohtsteilen water di * _o You let slide solution in

009827/1971

-15- 1813385 Ref. 2854

a solution of 18.0 parts by weight of 1-methyl-3-oyan-4-methyl-6-oxy-2-pyridone in 400 parts by weight of water, 18.2 parts by weight Pour in sodium hydroxide solution 33 ° Be and 36.0 parts by weight of sodium acetate and keeps the Realctionstenperatur during the coupling by adding 500 parts by weight of ice at 0 to + 5 ° C. Of the The resulting dye is filtered off with suction after the coupling has ended, washed neutral with water and dried. He puts a yellow Powder that has a reddish yellow color in conc. Sulfuric acid dissolves. The dye melts at 196 to 197 ° C.

The l-methyl - ^ - eyan - ^ - methyl- % 6-oxy-2-pyridone required as an intermediate can be prepared, for example, by condensation of methyl acetoacetate with monomethyl cyanoacetamide in an aqueous alkaline medium at room temperature. It is a colorless powder, melting at 280 ° to 282 ⁰ C.

In the following Table further usable according to the present invention, dyes as well as the color tones of the dyeings or prints thus available on polyester materials are given, which is also very good fastness properties loading * sit.

009827/1971

Ref. 2854

Table i

R-N = N

No. R.

X ϊ

Color shade on polyester

1. H H-O

O ₂ N-

O ₂ N

O ₂ N

Br

CN

-H »CN / ~ \ yellow

-CH ₃ -CN -CH ₃ yellow

-CH ₃ -CN -CH ₃ yellow

-CH ₃ -CN -CH ₃ yellow

-CH ₃ -CN

yellow

/ NO ₂ SO

-CH ₃ -CN -CH ₃ yellow

-CH ₃ -CN -CH ₃ yellow

-CH, -CN -CH

yellow

9. H ₃ CO ₂ S-HpC

-GH,

10. H ₃ CO ₂ SH ₂ CH ₂ CH ₂ C- ^ V-

-CH

-CN -CH.

-CN -CH- yellow

009827/1971

No. R.

Colors-η hoof polyps i) he

11. HC ₂ OOC -CH ₃ -CN -CH ₃

yellow

12. (H) -0OC- / V- -

N /

CH, -CN -CH, 3

-CN -CH,

yellow yellow

-CH ₃ -CN -CH ₃

yellow

-CH,

yellow

16. H ₂ CH ₂ C-CO ² | ² >

-CH, -CN -CH,

yellow

H ₂ CH "C

- CH-CO

HH ₂ CH ₂ C- / 'Vs -CH- -CN -CH,

H, yellow

18. H ₃ C-OC-:

-CH ₃ -CN

19. H ₃ C-OC-HN- / V- -CH ₃ -CN -CH,

-CH,

yellow

orange

20. H ₃ C-OC-N ₁ -CH ₃

-CH ₃ -CN -CH ₃ -CH ₃ -CN -CH ₃

yellow

orange

009827/1971

No.

Y Z hue up

polyester

22

23

24.

H ^ G GH,

° 2 ^N -i _s ./ ^C -

-CH, -CN -CH, yellow

-CH- -CN -CH ₃ red -CH ₃ -CN -CH ₂ -CH ₂ -CH ₂ -CH ₃ yellow

25th

26. H.

³ Vo _n SOA

H ₃ C -CN

-CH ₃ -CN

27 * -CH ₃ -CN

28. R ₇ C

29

30. H ₅ C ₂ OOC

-CH ₃ -CN -CH ₂ -.CH ₃ -CN -CH ₂ -CH ₂ -OH

-CH ₃ -CN

32 «

33.

01 -CH ₃ -CN

008827 / 1Θ71

No. R.

x y shade on polyester

Br

u O ₂ NfA

-CH ₃ -CN -CH ₂ -CH ₂ -OH

yellow

35. Cl ..// \\ -CH ₃ -CN ν
Cl 36. Cl- / Λ -CH ₃ -CN Cl 37. Cl-) " Λ -CH ₃ -CN

-CH ₃ -CN -CH ₂ -CH ₂ -CH ₂ -OCH ₃

39. / ⁷ V- 0C _ / ^ \ _ -CH- -CN

. H_C

H ₃ (T.

41. H,

H ₃ C

-CH ₃ -CN

-CH ₃ -CN

42. H-C

-CH ₃ -CN

43. HC

^N N-0 _o S-0- (\ y-CH- -CN

-CH ₀ -CH ₀ -O-CO-CH

44. H ₃ CO ₂ SO- / V> - -CH ₃ -CN -CH ₂ -CH ₂ -O-CO-CH ₂ -O- / Λ ^w

009827/1971

No. R.

Color shade on polyester

45. HC

yellow -CH, -CN -CH ₀ -CH ₀ -O-CO-NH- (CH ₀ ) ^ - Ch,

46. H ₃ CO ₂ SO- ^ V

-CH

-CN -CH ₂ -CH ₂ -O-CO-NH - / ^) yellow

₂ -CH ₂

47. H, C

NO ₀ SO

-CH

JCH-
-CN -CH ₀ -CH ₀ -NC

48. H ₅ C ₂ OOC - ^ / V_ -CH, -CN -

-CN -CH ₂ - / V \

yellow

Cl

50. O ₀ N - / "^

-CH ₃ -CN yellow

H ₃ C

NO ₂ S-

52. H ₃ CO gS-

-CH ₃ -CN -CH ₂ - / vs

-CH ₃ -CN

CH

yellow

yellow

56. O ₂ N

-CH, -CN

-CH, -CN

-CH, -CN

-CH, -CN

- / Λ

yellow yellow

yellow yellow

0 0 9 8 2 7/1971

Hue on

57. HC ⁵

-CH, -CN / T \

yellow

-CH ₃ -CN / y \

yellow

-CN

-CN

CH.

CH,

yellow

yellow

61. H ₃ CO ₂ SO- /

-CH ₃ -CN

.CH ₃ -CN

CH,

CIL

yellow

yellow

-CH ₃ -CN

\\ - OCH,

yellow

64. H-C

H ₃ C

-CH ₃ -CN

OCH ₃ yellow

-CH ₂ -CH- -CN -CH ₃ yellow

66th HC ^5th

H ₃ C

67. H ₅ C ₂ OOC./

-CH ₂ -CH ₃ -CN -CH ₂ -CH ₂ -CH ₂ -OCH ₃ yellow

-CH ₂ -CH- -CN

-CH ₄

yellow

009827/1971

Ref. 2854

Color on polyester

68. Λ V-OC- / 'V- -CH ₂ -CH, -CN 69 · BLC ₂ OOC- /

-CH ₂ -COOCH ₃ -CN

-CH.

yellow

yellow

70. H-C

H ₃ C

71. HC ⁵

H ₃ C

-CN -CH ₂ -CH ₂ -OH

-CN -CH ₂ -CH ₂ -CH ₂ -OCH ₃ yellow

-CH

yellow

73. H-C

yellow

A Geweb® polyethylene glycol terephthalate is padded on the pad mangle at 30 ⁰ C with zeal liquor containing 20.0 Gewlohtsteile of n in fine distribution g®Tbraoht @ dye ier formula

H ₅ C ₂ OOC

i) ^f .fi? 27/1071

1.0 part by weight of polyacrylamide with a K value of 120 and 0.5 part by weight of a polyglycol ether of oleyl alcohol and 978.5 parts by weight of water. After drying, 60 seconds at 210 ° C fixed in the thermosetting frame. After subsequent rinsing and finishing, as described in Example 1, Paragraph 1, is obtained a greenish yellow dyeing with excellent fastness properties.

The above dye can be prepared in the following Veise: 16.5 parts by weight of 4-arenobenzoic acid ethyl ester are dissolved in 300 parts by weight of water with the addition of 36 parts by weight of 30% strength hydrochloric acid, as described in Example 1, paragraph 2, diazotized with 24 , 9 parts by weight of l-phenyl ^ -oyane - ^ - methyl-eoxy-2-pyridone coupled and the resulting dye isolated · The dye is a yellow powder with a reddish yellow color in conc. Sulfuric acid dissolves. It melts with decomposition at 269 ⁰ C.

The 1-phenyl-3-cyano-% methyl-6-oxy-2-pyridone required as an intermediate is obtained by condensation of acetoacetic anilide with methyl cyanoacetate or of methyl acetoacetate with cyanoacetic anilide in ethyl alcohol with the addition of caustic potash at 85 ^° C. The "pyridon" is a colorless substance that appears at 31; melts up to 315 ° C with decomposition

The following table contains further dyes which can be used according to the present invention and whose dyeings and prints on polyester material also have very good flatness properties.

009827/1971

Ref. 2854

Table 2

RN = N
HO

No. R.

Color shade on polyester

2. HC

H ₃ C

-CH ₃ -COOC ₂ H-

-CH.

-CH ₃ -COO (CHg) ₅ -CH ₃ -CH ₃

yellow

yellow

3. H ₃ C-OC- / y. -CH ₃ -CO-CH ₃ -CH,

yellow

k. H ₃ CO ₂ SO- / V ^
NO,

;. C1- / V

-CH ₃ -CQ - //

-CH ₃ -CO-NH ₂

-CH,

-CH,

yellow

yellow

6. H ₃ C-OC

Cl

-CH,

₃ -CO-N ^

CH, -CH.

i3H «« - CHo -CO-N /

N / ^X CH "- -0 -CH,

yellow

yellow

8. H ₅ C ₂ OOC

NO,

-CII

-CH

-CH

-CH,

yellow

yellow

0 09827/1971

Η PI "ρ ρ

1813385 Ref. 2854

No.

Faro rcm on polyester

Cl

10. / 7 ~ \

-CH.

-CH,

yellow

11. HC

H ₃ C

12. Cl

-CH,

-COOC ₂ H ₅

NO _f

V_ -CH ₃ -CO-NH ₂ yellow

- (CH ₂ ) ₅ -CH ₃ yellow

~~ V -CH ₃ -COO (CH ₂ J ₃ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -O-CH ₃ yellow

NO

Cl

-CH ₃ -CO-NH ₂

-CH ₃ -SO ₂ -CH ₃ yellow

yellow

yellow

17. ci ~ /

-CH ₃ -CO-NH ₂

yellow

18. H ₃ CO

Cl

-CH ₃ -COOC ₂ H ₅

-CH ₃ -CO-NH ₂

yellow

yellow

ooc- / ⁷ V

OCH.

yellow

009827/1971

No. . R.

Color shade on polyester

-ί .. ' es Q ₇ I

22nd

-CH ₂ -CH,

O ₂ S-

Cl

23

24. H ₃ CO ₂ SO

-CO-NH,

-CH,

yellow

-COOC ₂ H ₅ ".CH ₂ -CH ₂ -CH ₂ -O-CH ₃ yellow -CO-UH,

-CH,

yellow

-CO-CH ₅ -CH ₂ -CH ₂ -CH ₂ -O-CH ₃ yellow

Example 3:

30 parts by weight of the dye (based on 1000 g of printing paste)

the formula

in the

H ^ C

CN

CH ₂ -CH ₂ -CH ₂ -OCH ₃

are incorporated in fine distribution of a _{Driiolcpast © s} which contains 45.0 parts by weight of locust bean gum, 6.0 parts by weight of 3- "nitro = - 'benzenesilphonate of sodium and 0.50 parts by weight of citrus aerase. With this printing paste, after printing on polyester fabric , you can fix it in a fixing frame

^ 5 feteÄdön at 21 ^ CIg Sfllaa nBi f © j? TlgatQilnag _f as in l.'iji 1, / Vseiftfez 1 tie8otai & fe ©? I ₀ oisaesa gE ~ ilao-fei © kig yellow druol ■ from ββϊΐΓ fpttc ·. ;;

G09327 / 1871

-27- 1813 38b _{Ref # 2854}

The dye provides when printing tri-acetate fabric when it is used in the form of the above printing paste and the printed After drying, the fabric is steamed, rinsed, soaped, rinsed again and dried for 10 minutes at 1.5 atmospheres, a greenish yellow print of high lightfastness.

The above dye can be prepared in the following way:

21.6 parts by weight of 4-amino-phenyl-dimethyl-sulfamic acid ester are, as described in Example 1, paragraph 2, diazotized, with 24.4 parts by weight of 1- (3'-methoxypropyl) -3-cyano-4-methyl- 6-oxy-2-pyridone coupled and the resulting dye isolated. The dye is a yellow powder with a reddish yellow color in conc. Sulfuric acid dissolves It melts at 178 to 182 ⁰ C.

The 1- (3'-methoxy-propyl) -3-cyano-4-methyl-6-oxy-2-pyridone required as an intermediate product for the preparation of the above dye is obtained, for example, by condensation of methyl acetate with (3'-methoxy) propylamide) in ethyl alcohol with the addition of caustic potash at 85 ° C. It is a colorless powder "which melts at 198-199 ^0C.

In the table below are others in accordance with the present invention Usable dyes as well as the color tones of the dyeings or prints available on polyester materials are indicated, which also have very good integrity properties.

009827/1971

Ref. 2854

Tabel

R-N = N

No. ft

Color shade on polyester

-H

-CH,

-CH,

-CH,

-H

-H

-CH,

-H -CH ₂ -CH ₂ -CH ₂ -O-CH ₃

-H

yellow

yellow

yellow

yellow

H ₃ C

-CH ₃ -CH ₂ -CH ₃ -CH,

yellow

CH ₃ - (CH ₂ J ₅ -CH ₃ -CH ₃

yellow

7. H ₃ CO ₂ S-

-CH

-CH,

yellow

8. H ₅ C ₂ OOC- / '

-CH

NO, -CH,

yellow

CH ₃ -CH ₂ -CH ₂ -CH ₂ -CH ₃ -CH ₂ -CH ₂ -OH yellow

0098 27/1971

No. . RZ color au,
polyester

10. H-C

H, C

-CH ₃ -CH ₂ -CH ₂ -CH ₂ -CH ₃ CH ₂ -CH ₂ -CH ₂ -O-CH ₃ yellow

-CH

11.

12 «

O ₂ S

-CH,

13th

. Cl-

NO,

Cl NO,

-CH,

-CH ₂ -CH ₃

-CH ₂ -CH ₃ -CII ₂ -CH ₂ -CH ₂ -CH ₂ - yellow

-CH

-CH,

-CH,

-CH ₂ -CH ₃

-H

-H

CH ₂ -CH ₃

-CH

-CH,

-CH,

16. H ₃ CO ₂ SO ^

CH ₂ -CH ₃ -CH ₂ -CH ₂ -CH ₂ -O-CH ₃ yellow

-CH -NO

-CH,

yellow

yellow

... ^N0

19. H ₃ C - / ~~ V

-CH

-NO ₂ -CH ₂ -CH ₂ -CH ₂ -OCH ₃ yellow

20th H.

-CH,

-NO ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₃ yellow

009827/1971

No. R X Y Z hue

polyester

21 ο Λ yoc / ⁷ \ -CH ₂ -CH ₃ -NO ₂ -CH ₃ yellow

-CH ₃ -NO -CH, yellow

^ J · 11 (.UpUULi-C y- -Oa ₃ -JMU -OUg- Ollg-OMg-OH- gel D

Example k \

30 parts by weight of the dye (based on 1000 g of printing paste) the formula

are finely divided into a printing paste that is 16.0 parts by weight an alginate thickener and 20.0 parts by weight of a starch ether. With this printing paste you get on one Polyester fabric after printing, drying and fixing in the thermal

during _t
fixi err ahmen / So secondary at 220 C, rinsing and finishing as described in example 1, paragraph 1, a greenish yellow print

very good fastness properties

The above dye can be prepared in the following way:

26.2 parts by weight of 3-amino-benzene-8ulfonic acid »f -methyl * anil id are, as shown in Example 1, paragraph 2 besotirleben, diazotized and coupled. The isolated dye represents a yellow «powder

009827/1971

Ref. 285 *

represents, which is in conc. Dissolves sulfuric acid with a greenish yellow color. It melts at 253 to 255 ° C.

The following table contains further dyes which can be used according to the present invention, the dyeings and prints of which on polyester material likewise have very good fastness properties.

Tabel

No. R.

Color shade on polyester

N - O ₂ S,

Ö-

3. H ₂ N-

k. H ₂ N-

-0C - / \

-H -CN

-CN

-CH- -CN

-CH- -CN

-CH,

-CH,

-CH,

yellow

yellow

yellow

yellow

5. H-C-HN-OC-C

-C

-CN

-CH,

yellow

6. HC ,,

^y > H-OC- ('

^H 5 ^C

! Η,

-CN

-CH,

yellow

009827/1971

No. R.

Hue on
polyester

7. H ₃ C

H-C

-CH- -CN

3 ^U Ζ '\\

-CH,

applies »

8. H ₂ NO ₂

-CII, -CN

9. HC-HN-O ₀ S -CH, -CN

^{3 2} K ³

-OIL

yellow

yellow

^ N-O,

η /

-CN -CH,

yellow

11./ "V-HN-O ₂ S -CH ₃ -CN

12. H ₂ NO ₂ SL /

-CH ₃ -CN

-GH »,

-CH,

yellow

yellow

13. H,

< V -CH ₃ -CN -CH ₂ -CH ₂ -CH ₂ -O-CH ₃

H ₃ C

yellow

H ₂ C

H ₃ C

-CH ₃ -CN -CH ₂ -CII ₂ -CH ₂ -CII ₃

-CH ₃ -CN

N-OC

H ₃ C

-CH ₂ -CH ₃ -CN -CH

yellow

yellow

yellow

009827/1971

"'■■' ^i: "! ■ " iiiiiiii ι in

33 - Ref. Ί> 3? 4

No. R.

Pari n
Polvest

-CN -CH,

yellow

19. H, CH ₃ C

/ Λ

-CH ₃ -CN

-CH ₃ -H -CO-CII.

-CH.

-CH ₃ -H -CH ₂ -CH ₂ -CH ₂ -O-CH ₃

yellow

yellow

yellow

- r- %

21. H ₂ NO ^ S / \ _ -CH ₃ -H -CH ₂ -CH ₂ -CH ₂ -CH ₃

yellow

22. H ₃ C

-NO ₂ S

H ₃ C

-CH ₃ -NO ₂ -CH,

yellow

NO ₁

H ₃ C

-CH ₃ -NO -CH,

yellow

009827/1971

Claims (2)

Pat ent claims Yo f ^ iiren for dyeing and printing fiber goods j tbetisehen _t hydrophobic materials, such as polyacrylonitrile, polyamide, polyesters insfoesondere Celluloseestern and Z ^ ₉ B., PolyäthylenglykoIterephthalat, characterized ₉ that here dyes d © r general formula used in the R is the remainder of a group free of water-solubilizing groups Diazo component of the benzene, naphthalene, diphenyl, Dipheny! Methane «* or heterocyclic Eeiiae, X is hydrogen, an optionally branched alkyl, in particular a Metlfcy! group, a carbalkoxymethylene, a cartalkosy or an optionally substituted one Cycloalkyl, aralkyl or aryl group ,, Y is hydrogen, a Cyem- ₉ is a nitroso, nitro, a gegebeneBfalls branched alkyl © "a © optionally substituted cycloalkyl, aralkyl" ?, aryl group or the- R- Jl- Residues -COOR ₁₉ -COIg ,, -CO-H <^ ^J _$ -SOgEg or -SOg-N ^ ^J _% ¹ V ⁿ k ¥ 0ib-3i Rj uni 1 "an optionally branched alkyl" group, Rn also optionally substituted 0 0 9 8 2 7/1 9.7 T Cycloalkyl, aralkyl or aryl group and R, and R. hydrogen, an optionally branched alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl, aralkyl or aryl group, where the alkyl radicals R, and R. also directly, or via a heteroatom can be connected Z is an optionally branched, substituted alkyl or alkenyl, an optionally substituted cycloalkyl, Means aralkyl or aryl group. 2. Dyed or printed fiber material made of synthetic, hydrophobic Materials such as polyacrylonitrile, polyamide, cellulose esters and especially polyesters, e.g. polyethylene glycol terephthalate, which is colored with dyes of the formula given in claim 1. 009827/1971