DE2364475C3 - Process for printing hydrophobic fiber materials according to the transfer printing principle - Google Patents

Description

Y,

N N

Y ₁ R ₁

wherein Y ₁ H, NO ₁ , CN, CF, or CH ₃ , Y ₂ Y ₁ , C or Br, Y ₃ H or Cl, R ₁ and R ₁ H, C, -C ₄ -alkyl PhCHyI-C ₁ -C, -alkyl, cyclopentyl, cyclohexyl, methyl cyclohexyl. C, -C ₄ -chloroalkyl or C ₁ - or C-alkoxy-C, -C ₄ -alk \ l, R ₃ H, C, -C ₄ -alkyl, C, -C ₄ -alkoxy, phenoxy, benzyloxy and R _{4 is} H, CH ₁ , CF 1, C 1 H, Cl, Br or NHCOR ₅ , where R _{5 is} H, C, -C ₄ -alkyl, C, -C ₄ -chloroalkyl, C, -C ₄ -bromoalkyl or Is melhoxy-C ₂ -C ₄ alkyl.

Particularly preferred types of dyes to be used are those of the formula II in which

a) Y, = NO ₂ , Y ₂ = H and Y ₃ = H,

b) Y ₁ = NO ₁ , Y ₂ = NO ₂ and Y ₃ = H,

c) Y ₁ = CN, "Y ₂ = NO ₂ and Y ₃ = H,

d) Y ₁ and Y ₃ = H and Y ₂ = CF ₃ as well as

e) Y ₁ = NO ₂ ; Y ₂ = CF, and Y ₃ = H

and, where R, R ₄ are as defined above. Of these, preference is again given to those where

R ₃ = H, CH ₃ , OCH ₃ or OC ₂ H ₅ and
R ₄ = H, CH ₃ , C ₁ H _5, or Cl.

The dyes of the formula (I) are prepared by processes known per se, by adding a Diazotized aniline of the formula (III)

(CF ₃ ) ,,

NH,

(ΠΙ)

The invention relates to a method for printing on hydrophobic fiber materials the transfer printing principle, which is characterized in that sublimable, sulfo-free Monoazo dyes of the general formula

N == N-

^x >

X ₁

(D

used, in which X ₁ and X _{1 are} hydrogen, optionally _{C 1} -C ₄ -alkyl or C ₅ -C _{7 -cycloalkyl radicals which are substituted by C 1} - or d-alkoxy, F, Cl, Br or phenyl and /; the number 1, 2 or 3, and the ring A by NO ₂ , CN, F, Cl, Br, SO ₂ CH. ,, SO ₂ C ₂ H ₅ , C ₁ -C ₄ - and the diazonium compound with a coupling component of formula (IV) combined.

5 .s X,

(IV)

As a diazo component !! of the formula (III) come into question, for example:

1-A mino-2-trill uormethy! Benzene,
I-amino-4-trirluoromethylbenzene,
(15 I -Amino ^ -chlor- ^ - trifluoromethylbenzene,

l-AiT! ino-2-broin-4-trifluoromethylbenzene,
l-amino-2-methyl-4-trifluoromethylbenzene,
l-amino ^ -trifluoromethyl-chlorobenzene,

1-amino-2-trilliiormethyl-4-methylbi: iizol.

l-amino-2,4-bis-irifluoromethylbeiizole, l-AmiiH> -2,6-bis-trifluoromethylhen / .i> l, l-Ainmo ^ -chlor-S-trilluormethylben / ol, l-Amino-2,5-irinuormethyl-benzc> l, l-amino-2,4,6-tris-trifluoromelhylben / ol, l-amino-2-trilluormethyl-4-nitroben / ol, l-Amino-2-nitro-4-trinii (iimelhylbcn / ol, l-amino-2-trifluoromethyl-4,6-dinilro-ben / ol, l-Amino-2,4-bis-trifluoromelhyl-6-nilio-hen /. (il, 1-amino-2,6-bis-trifluoromethyl! -4-niti () - bcn / ol.

l-amino-4-trilluormethyl-2,6-dinitrobenzene / ol, l-amino-2-cyano-4-triflu () rmethylben / ol, l-amino-2-triΠuormethyl-4-cyano-ben / .ol, t-Amiiio-4-trifluoromethyl-2,6-dicyanobenzene, l-amino ^ -trifluoromethyl ^ o-dieyanbcnzol, 1 -A mino-2,6-trifluoromethyl-4-cyano benzene, l-Amino ^ -trifluoromelhyl ^ -nitro-o-cyano-bcnzo !, ] -Amino-2-trifluoromethyl-4-cyano-6-nitro-benzene, l-amino-2-chloro-4,6-bis-trifluoromethylbenzene, ! -Amino ^ -fluor ^ trifluoromethylbenzene, l-amino-2-ΠuoΓ-4,6-bis-trifluoromelhylbenzene, l-Aniino-I.o-dichloM-trifliiormethylaiiilin, l-amino ^ -trifluoromethyl-S-nitrobenzene, l-amino-2-trifluoromethyl-4-methylsulfonylbenzene,

1-Amino ^ -trifluoromethyl ^ -ethylsilfonylbenzene. l-A! ■ nino-2,6-bis-trif ^ uormethyl-4-nitrobenzene, 1-amino ^ -methoxy ^ -nitro-o-trifluonnethylbenzene.

The coupling components of the formula (IV) are included for example in question:

Ν, Ν-dimethylaniline,

Ν, Ν-diethylaniline,

Ν, Ν-di-n-propylaniline,

Ν, Ν-diisopropylaniline,

Ν, Ν-di-n-butylaniline,

N-methyl-N-benzyl-aniline, N-ethyl-N-benzylaniline, N-n-propyl-N-benzylaniline, N-methyl-N-ZJ-phenylethylaniline, N-ethyl-N - ^ - phenylethylaniline, N-n-Butyl-N - ^ - phenylethylaniline, N-methyl-N-cyclopentylaniline, N-ethyl-N-cyclopentyl-aniline, N-methyl-N-cyclohexylaniline, N-ethyl-N-cyclohexylaniline, N-n-butyl-N-cyclohexylaniline, N, N-di-benzylaniline,

N-Benzyl-N-cyclohexyl-aniline, N - ^ - phenethyl-N-cyclohexylaniline, N-methyl-N-Zi-chloro-ethylaniline, N-ethyl-N-ji-chloro-ethylaniline, N-methyl-N - ^ - chloropropylaniline, N-ethyl-N - ^ - chloropropyldniline, N-ethyl-N-y-chloropropylaniline, N-ethyl-N - ^ - bromoethylaniline, N-n-Propyl-N - ^ - chloroethylaniline.

N-propyl-N-y-chloroethyl aniline,

N-Benzyl-N - ^ - chloroethylaniline, N-Cyclohexyl-N-Zi-ehloroethylaniline.

N.N-Bis - ^ - chloroethylaniline, N - ^ - phenylethyl-N-zi-chloroethylaniline.

1- (N, N-dimethylamino) -3-methyl-benzene.

1 - (N.N-diethylamino) -3-methylbenzene.

! -! N, N-di-n-phenylamino) -3-methyl-benzene.

(.0

('S

1- (N ₁ NI) i-isopi- (ipyl-amiiH>) -3-methyl-ben / ol, 1- (N, N-ni-ii-butylaniiiio) -3-diethyl-benzene, 1- (N -Methyl-N-benzyl-amino) -3-methyl-beü / ol, l- (N-Alhyl-N-benzyl-amino) -3-methyl-benzene, l-lN-n-Pi'opyl-N- ben / yl-aniincO - ^ - niethyl-

ben / .ol, l- (N-Melliyl-N- / i'-phünylätliyl-amiiu)) - 3-methyl-

bcn / .ol, I - (N-AlIi \ l-N - // - phuny lälhylamino) -3-melhyl-

benzene, 1 - (N, η ■ butyl-N-zi-phcnylii I hylamino) -3-melh> I -

benzene, l- (N-methyl-N-cyclopentyl-amino) -3-mi; thyl

gasoline, l- (N-ethyl-N-eyclopenlyl-amino) -3-methyl-

benzene,! - (N-methyl-N-cyelohcxyl-amiiioJ-S-methylbenzene,

1- (N "ethyl-N -cyelohexylamino) -3-methylbenzene. l- (N, N-dibenzylamino) -3-methylbenzoi,! - (N-benzyl-N-cyclohexyl-aminoVS-methyl-

benzene, 1- (N - /) '- phenylethyl-N-cyclohcxylainino) -

3-methyl-benzene, l- (N-methyl-N - / (- chloroethylamino) -3-mclhyl-

benzene, l- (N-ethyl-N- / i-ehloräthylaiTiino) -3-mf-l.hyl-

benzene, l- (N-methyl-N - / <- chloropropylamino) -3-methyl-

benzene, 1 - (N-AtIi yl-N- / i-chloropmpylamino; -3-methyl-

benzene, l- (N-ethyl-N -) '- chloropropyl-amino) -3-methyl-

benzene, l- (N-ethyl-N- / i-bromoäthylaniino) -3-methyl-

benzene,! - (N-Benzyl-N-zi-chloroethylaminoi-S-melhyl-

benzene,! - (N-Cyclohexyl-N - ^ - chloroethylamino) -

3-methylbenzene, 1 - (N - / * - Phenylethyl-N-zi-chlorathylamino) -3-methylbenzene,

1- (N, N-bis- / I-chloroethylamino) -3-methylbenzene. l- (N, N-dimethylamino) -3-chlorobenzene, 1 - (N, N-Oiäthylamino) -3-chlorobenzene, l- (N-ethyl-N-benzyl-amino) -3-chlorobenzene, l- (N-ethyl-N- / i-phenylethyl-amino) -3-chlorobenzene,

! - (N-Ethyl-N-cyclohexylaminol-S-chlorobenzene, l-fN-ethyl-N-Zi-chloroethylaminol-S-chlorobenzene,

l- (N, N-diethylamino) -3-bromobenzene, l- (N-ethyl-N-benzyl-amino) -3-bromobenzene, l- (N-ethyl-N- / I-chloroethylamino) -3-bromobenzene,

! - (N.N-DimethylaminoJ-S-acetylaminobenzene, l- (N, N-dimethylamino) -3-propionylaminobenzene,

l- (N, N-dimethylamino) -3-formylamino-benzo l- (N, N-dimethylaminoV3-chloroacetylamino-

benzene, l- (N, N-dimethylamino) -3 - /) '- chloropropionylaminobenzene,

l- (N, N-diethylamino) -3-formylaminobenzene, l- (N, N-diethylamino) -3-acetylaminobenzene, l- (N, N-diethylamino) -3-butylamino-benzene, 1- (N.N-diethylamino) -3-chloroacetylaminobenzene.

l- (N, N-ethyl-benzylaniino) -3-; ieetylamino--

benzene,

I- (N-At hyl-N-bcii / ylaniinol-.Vchliirauct viii minobcn / ol,
l- (N-Ethyl-N-benzylamino) -3-rormvlamim> -

benzene,

1- (N, N-dibiitylamino) -3-formylaminohenzene.
HN.N-DihiilylammoKVchlor.icelylamino-

benzene,
l- (N, N-dimethylamino) -2-melhoxy-5-formyl-

a min ο benzene,
l- (N, N-dimethylamino) -2-metlioxy-5-aeelyl-

aminobcnzol,
l- (N, N-diethylainino) -2-rnclhoxy-5-iicctyl-

aminobcnzol,
l- (N, N-diethylamino) -2-ethoxy-5-acclyl-

aininobenzene,
l- (N, N-diethylamino) -2-phenoxy-5-acctyl-

aminobenzene,
1- (N ₁ N-diethylamino) -2-benzyloxy-5-auclyl-

aminobenzene,
l- (N, N-diethylamino) -2-methyl-5-acctyl-

aminobenzene,

l- (N, N-diethylamino) -2-methyl-5-dilorobenzene, I- (N, N-diethylamino) -2,5-dimethylbenzoi,
l- (N, N-diethylamino) -2-ethyl-5-formyl-

aminobenzene,
I - (N, N-diethylamino) -2-propoxy-5-aeetyl-

aminobcnzol,
l- (N, N-diethylamino) -2-methoxy-5-chloro-

acctylaminobenzene,
l- (N-ethyl-N-benzyl-amino) -2-methoxy-

5-acetylaininobenzene,
l- (N-ethyl-N-cyclohexyI-amino) -2-methoxy-

5-acctylaminobenzene,

l- (N, N-ethyl-N- / i-chloroethyl-amino) -2-methoxy-5-acetylaminobenzene,

1- (N, N-ethylamino) -2-methoxy-5-methyl-bcnzo !. 1- (N, N-diethylamino) -2-methoxy-5-chlorobenzene. l- (N-Benzyl-N-n-butylamino) -2-metho \ y-

5-acetylaminobenzene,
l-IN.N-dibenzylamino ^ -phenoxy-S-chloro-

aeetylaminobenzene.

The transfer printing process is well known and z. B. in the French patents 23 330 and 13 34 829 have been described. The dyes are z. B. in the form of so-called printing inks, how they z. B. are described in French patent specification 73 698, or as pastes on so-called Auxiliary carriers (paper, other cellulose materials such as cotton or cellophane. Metal foils and the like. B. from French patent specification 15 75 069 are applied). This Printing inks are synthetic resinous dye solutions in suitable organic solvents, such as Benzene, toluene, xylene, chlorobenzene, chloroform, dichloroethane. Trichlorethylene, perchlorethylene, ethanol, isopropanol, benzyl alcohol, cyclohexanone, ethyl acetate or their mixtures. The printing inks and printing pastes can, however, also have an aqueous base, that is to say they represent dispersions of the dyes in water. Which is also the usual dispersing and thickening agent (cf. French Patent 12 23 330 and US Palentschrift 36 47 503). The printing inks can be printed using the usual printing processes (letterpress, gravure, offset ■■ film or Screen printing).

Substrates suitable for transfer printing with dyes are textile materials which are made entirely or predominantly of polyesters, such as polyethylene glycol Ierephthalai, poly-1.4 to hydroxymethylcyclohexane terephthalate or CcIIu lose triacetal and cellulose 2 ^l / 2-i ^l ^ li't 'Hler consist of pol \ - imiden or polyacrylonitrile, but also non-textile plastic articles such as foils, tapes or blocks made of commercially available polymer or odei

ίο polycondensate plastics.

Particularly suitable dyes I sublime in the range from 140 to 250 C, preferably from 160 220 C.

ILs is ids extremely surprising too he / eichs new that the dyes to be used according to the invention. which by the combination of a Cl, group-containing diazo component and a special one Type of aniline coupling components are characterized, so excellent transferring shafts have, as comparable dyes, which formally similar instead of the trifluoromethyl group Remnants z. B. the "normal" methyl group or another common in dye chemistry The remainder mil approximately the same molecular weight z. B. a

2s Br.imsuhstituenl included, less good for the Transfer printing are suitable.

example 1 A) 75 g of the dye of the formula

CF,

O ₁ N

N-N

/ Λ

cn.,

C ₂ FI ₅

CH ₇ ClU

50 g of an anionic dispersant, e.g. B. one Ligninsulfonates or a condensation product of Naphthalenesulfonsäurc and formaldehyde, and 100 ml of water are mixed and finely divided into a ball mill by grinding for 10 hours Form transferred.

The dispersion thus obtained, containing approx. 30% raw paint, is storage-stable.

B. The aqueous dispersion obtained according to A can be processed into a printing paste as follows:

50 to 200 g with 400 g of a 10% so .lohannisbrotkernmehlätherverbindungen and 550 to 400 ml of water made into a paste.

C. This printing paste is used to print a paper using the gravure printing process. If you press this paper for 15 to 60 seconds at 200 "C with a textile made of polyester fibers, a clear, bright red print with good fastness properties.

Example 2

A. 40 to 50 g of the dye used in Example 1 substance with 5 to 10 g of an emulsifier mixture: from atruixylated nonylnhenol (4 to 12 moles of ethylene oxide) made into a paste in water. 10 g of ethyl cellulose and 30 to 40 parts of a maleinate resin are added. to. that by condonsation of ('olopiumiuni mi' 'ν ·; Maleic acid was produced. One kneads at Sl up to 100 C approx. 2 hours and then grinds in one of the usual mills. A fine grain is obtained Dye powder.

B. 200 μ of the dye powder obtained according to A are added with stirring to a mixture of 730 g of ethanol, 50 g of ethyl glycol and 20 g of ethyl cellulose.

C. The printing ink thus obtained can be used for gravure printing on paper. Of these printed Papers can be used in the transfer process, textiles made of cellulose triacetate or polyamide, e.g. B. Knitted fabrics, print and receive strong red prints.

The dye of Example 1 was prepared in the following way: 60 parts of finely powdered 1-amino-2-trifluoromethyl-4-nitrobenzene are concentrated with stirring in 300 parts. Dissolved sulfuric acid, whereby the temperature should not exceed 20 "C. Then is cooled to 0 'C, and at this temperature gradually becomes one by dissolving 20 parts Sodium nitrite in 80 parts conc. Sulfuric acid produced nitrosylsulfuric acid was added dropwise. It will Stirred for about 2 hours at 0 "C. The diazonium chloride solution thus prepared is now at 0 5" C below Good stirring gradually to a solution of 58 parts of I - (N - ethyl - N - // - chloroethyl - amino) -3-methyl-benzene in 2000 parts of water and 50 parts of koiu. Hydrochloric acid, to which one 10 parts sulfamic acid added. The clutch works immediately. You can do this by buffering the solution pH 4 5 can be accelerated by means of sodium acetate. When the coupling is complete, the resulting azo dye is used filtered off, washed salt-free with water and dried. 116 parts of a red one are obtained Dye powder.

The table below shows other dyes which are obtained when the diazo component is used of column 2 and diazotized with the coupling component of column 3 to the azo dye combined, as well as the nuances thus obtainable according to the method given in Example 1.

example
No. Diazo component F., C " Nl 3 O, N \ ^V "·

Coupling component

Shade on polyester

the same

the same

- N (CH,);

N (C ₂ HO ₂
C ₂ H ₅

Red Red

Red

ClI ₂

the same

Feces

C ₂ IU

the same

Red

the same

N (C., II,),

RoI

N (IiC ₁ Il ,,),
Ii -C ₁ II ₁ .

dcsj'.l

ik'Sgl

CII,
CH,

Red

RoI

Srliarlai'li

ClI, CII.Cl

Kort set / U η ι »

Example diazo component

12 O ₂ N- <

13 the same.

CF ₃

NH,

Coupling component

f Vn '

-N

CH ₅

Vn ₂ CH ₂ Cl C ₂ H ₅

Vh ₂ - ch

Cl

10

N'lance on l'olyester

Scarlet fever

Scarlet fever

14 the same

15 the same.

16 the same

17 the same.

N scarlet fever

CH ₂ - CH ₂ - CH ₂ Cl

-N

CH ₂ CH ₂ Br CrI

C ₂ W,

> ■■ N

CH ₂ CH-OCH,

Scarlet fever

Red

Red

IH the same

^ N

Feces

I ') the same.

20 the same

CH ₂ / V

V11., CII, OC, N (C ₂ II ₅ ),

Feces

Hlauslichigrot

21 the same.

^X N (C, 11 ₁ ),

Hlaiistiehigrol

11th

■ oilsel / imii

Seispid
Mr.

Diazo companiesU ¹

C) ₁ N

Cl-,

Nile,

Coupling coniponcmc

N (Ii-C ₄ H-):

Nuance on I'olyei

ßlaustichim'ol

dcsul.

24 the same.

CH.,

- N

C ₂ II ₅

-N

Bluish red

Blue tinted red

likewise. C ₂ H ₅

V-N

CH,

Bluish red

the same. VN

CW ₁ CW ₂

■ * X

Bluish red

27 desg !.

the same

the same

Yn ₂ cn cn,

Cl

c. 11

YlI, CH, CII, C

CII.,

VlI.CIHKMI,

Red

Feces

C, IU

■ N Uot

VlI, CII, CII, CiI, Cl

purple iisl ic h ίμιο

13th

Oilset / unu

U

licispicl Hiii / okompoiKMHc

Coupling component

Shade on polyester

31 Ο, Ν- ν ■ Nil,

NK MU).

Bluish red

COl ₅

32 the same.

WM.,),

Red

Cl

33 the same.

N (C ₂ HO;

RoI

Cl

34 the same.

N (CMlO-

Red

Mr

the same

Cl

ClUClUCl

üelhstiehigrol

N (C, 1 Ub

Cielbsliehi red

37 the same.

Cl- ',

(IU

C iclbs

3S dvsi'l.

CIUClUCl

3 ·) des) "l.

Cielbslicliij'.red

CU ₁

cn,

■ in desi'.l.

(ielbstichigrot

(irtM.'1 / uiiü

15th

16

ikukv iill! In the

O ₂ N

12 dc style.

dcsül.

the same

46 the same

47 the same.

48 the same

49 the same.

50 the same.

51 desiil.

> - NlI,

CH,

ClI,

CH,

'' ■ '. y - N (CH,),

Nile CHO

^{/ y} V- N (CH,),

NI ICOCH,

■ f VN (CH ₁ J ₁

V- --y

NIICOCH ₂ Ci

y ~ N (CHO ₂ HOLE ₁ CH ₁ Cl

<_ ^ N (C ₂ H ₅ J ₂ NHCHO

^ VN (C ₂ H ₅ J ₂

NHCOC ₄ H,

N (C ₂ H ₅ );

NH COC H, Cl

' ¹ S h

C ₂ H ₅

CH,

NHC0CH, CH, CI

NHCOC ₄ H ₁ ,

NHCOCMi-

QH ₅

CH ₂ CH ₂ - <

C, H ₇

CH ₁

Blue limedimiot

Bluish red

Bluish tint

Bluish red

Bluish red

Bluish tint

Bluish tint

Bluish tint

Bluish tinted euro

! hispid
Jr.

53 the same.

54 the same.

55 the same.

56 the same.

57 the same.

58 the same.

59 the same.

60 the same.

17th

CF,

O ₂ N <;> -NII,

/ fO

is

coupling () ( , pom · ,, i _s ). Ή .. Ί1Ο N (C, I NHC OC - '( OCH, N (C, I NHC

<t ^v · -N (Ii-C ₄ Hy),

NHCOCH,

OCH,

<\ - N (C ₂ H ₅ ),

OCH ₁
^ - N (C ₂ H ₅ ) ₂

CH ₂ CH ₂ Cl

CH ₂ CH ₂ Cl
CH ₂ CH ₂ Cl

CH ₂ CH ₂ Cl

OCH ₃

CH ₂ CH ₂ Cl

/ ,, CH ₂ CHXl

OCH,

■ N

NHCOCH,

CH ₁ CHXI

CHXHXl

Nu.iiiLi 'mil ΙΊ

Rol \ ii) lcti

Red-violet

Bordo

Bordo

Scarlet fever

Yellowish tinge

Red

Bordo

19th

nrt'xt / ιιημ

_L .j _S | iif | l »i; i / () koniptiin ^- nlL ·

O ₁ N <'-> NIK

62 the same.

63 O ₂ N-

NH ₂ NO,

the same.

66 the same.

67 the same

68 the same.

69 the same

70 the same.

23 64 47

20th

OCIl ₁

NHC OC -y ' H ₁ ., H ₇ Il ₅ 5 H,- OC OC,
/ C. 2 H / /
/ / /
- n ' C. V- \ \ 'H ₂ NHC

- N (CH ₃ ),

/ V-

N (C ₂ H ₅ I ₂

N (Ii-C ₄ H ₉ ),

C ₂ H ₅

-N

CH ₂
C ₁ H,

^ CH ₂ CH ₂ Cl

f Vn

Vh ₂ CH ₂ CH ₂ CI
, QH ₅

^X CH ₂ - CH - CH ₃
Cl

CH ₁

\
CH ₂ CH ₂ Cl

iUiIiCC mil l'iilycslci

Colviolet

Red-violet

violet

violet

violet

violet

Bordo

Bordo

Bordo

Bordo

21

l'oilsL'1 / ιιημ

Ik'ispii'l I) i; i / () k () nip (iiiL'iiU '

71 O ₂ N <ζ V- N

NO ₂

72 the same.

73 the same

74 the same.

75 the same

76 the same

77 the same

78 the same

79 the same.

SO that.

22nd

(Ή,

CH,

CU,

C, 11,

CII ;, <f

> -N (CH ₂ CH ₂ C (J ₂

CH,

CMl ₅

Vh ₂ CH ₂ CI
CMI ₅

CH,

N (CMU) ₂

Cl

N (PC ₄ Ho) ₂

NHCOCH,

NHCOCH ₂ Cl OC ¹ H,

CH,

OC ₂ H ₅

Niiiiiia · .ml

Rotsticliigbhiu

Reddish blue

lilauviolctl

Blue violet

Reddish blue

Red

Reddish blue

Reddish blue

Blue violet

Blue violet

CH,

23

continuation

Example diazo component

81 O, N- <V-NH ₂

82 the same.

NO ₁

83 of the iil.

84 the same.

85 the same.

Kd desul.

24

CH,

K uplungskonipoiienu ·

OCH ₂ - <(y

N (C ₂ H ₅ J ₂

OCH,

- N (C ₂ H ₅ ),

NHCHO

OCH.,

> -N (C ₂ Hs) ₂ NHCOCH.,

NHCHO

OCH,

C ₂ II ₅

NIICOCHa

OC ₁ H ₇

CIl ₂

N (C-II.,) ;.

NlICOCH,

Nuance to l'o

Blaiivioletl

blue

blue

blue

blue

blue

S 7

88 the same.

«») The same,

Nile, N (C.11.,) - C. IU

CII; ·,

C..IU CII, CII, C

yellowish orange

yellowish orange

yellowish (»range

25th

continuation

example

Diazo component

Cl,

90 I ₃ C \> -NH,

the same

92 the same.

93 the same

94 the same.

95 the same.

Coupling component

\ "- N (C ₂ H ₅ ),
NH-COCH,

/ VN (C ₂ H ₅ ),
CH,

VN (C ₂ H ₅ ),

% same

-N (CH ₃ ),

- N (CH ₂ CH ₂ Cl) ₂

CXH,

€ > - N (C ₂ H ₅ ),

NlICOCH,

OCH ₁

26th

Nuance av

iDlslichi Oraime

O ran iie

orange

orange

orange

Red

Red

97 the same.

the same

99 I -., I "\

KK) the same.

NII.

CII.,

Vn, · _χ - ■ ei

C, ll _s

CH, ClI, Cl

NIICOCII.CII.CI

N (C-H,),

CII,

orange

orange

orange

rotsticl orange

27

continuation

example

Diazo component

CN

F ₃ C -

NH ₂

102 the same.

103 the same

104 the same.

105 the same .1 106 the same NH ₂ y 107 \ /
\ \ Ci
/ > - Cl

H) K desgl.

reads·!.

IK) the same.

the same

Coupling component

C ₂ H ₅

CH ₁ CH ₁ CI

N (C ₂ H ₅ J ₂

NHCOCH ₃

NH-COCH ₂ Cl OCH ₃

-N (C ₂ H ₅ ), NH-COCH ₃

N (CH ₃ ),

Cl

N (C ₂ H ₅ J ₂

J "\

cn.,

NIICOCH ₁

V ₁ W,

C ¹ M ₂ CM ₂ C C-II,

CtI, ν

OC, 11,

e, iu

Nuance on polyesle

reddish orange

yellowish Ro

yellowish Ro

Red

Orange orange

reddish gel

yellowish orange

yellowish orange

orange

Red

NIlCOCH,

29

I-ortsct / Linu

Example 1) ia / okoniponente

C I-,

NU,

CF.,

113 the same.

CH.,

N (C ₂ H ₅ ),

30th

Nuance on pole ve

Zieuclrot

reddish bi

114 O ₁ N <ζ V-NH ₁

egg·,

115 Ο, Ν <f

ilcsul.

NH,

V- N

^ - N

CIUCH ₁ CI

C ₂ H ₅

CIUCIUBr

C ₂ H ₅

^> N

yellowish brick red

reddish bi

reddish bi

HK

O, N

Nile.

CN CN

120 Ι ·, ('' ■ NII,

NO. LHI lU'Sül.

CH, ·.

CIUCIUCI

■ N (C., I Ij, Nil COClUCI

CIUCIUCI

'' ■■ · N

Cl ₁ CIUCIUCI

■ N (C-IIJ ..

N (C, 1I ₅ ),

reddish bi

Red-brown

Violelt

MiuiNlieliijzos llorilo

reddish violet

31

OrlM. '1 / iinu

32

It'ispil'l

l) ia / (ikompoiu'iik ' Κ | ΐρρΙΐΜΜ' Λιιΐηρΐ1ΙΗΊΙΙι '

Mill 1'iily

CN

Nil, > N (C ¹ Hj) ₂

Bordo

NO ₁

OCH,

23 the same

<■ '> - N (CH.,) 2

violet

24 the same.

<f V- - N

25 the same.

26 the same

127 the same.

cw , cn 2CI C.
/ -2H ₅ r ^y \
CH., H ₂ C H ₂ C <f VN (C ₂
> = / H ₅ I ₂ /
NHCOCH, OCH,
/ <f ~ VN (C ₂ .H.O2 /
NHCOCH,

bluish border ο

Rolvioleil

violet

Blue violet

F, C

> -NH ₂ N (C ₂ H ₅ ),

reddish

129 the same.

Cl CH,

C ₂ H ₅

CH ₁ CH ₁ Cl

reddish

130

- N (C ₄ H,),

rotstichiiies

131

Cl

the same CAU

reddish

CH ₁

33

rditscl / iinu Ik'ispicl

138

139

140

141

Diazo component

Cl

132 i;, C ■

Cl

(T,

134 the same.

135 desul.

Nile,

136 desül.

137 the same.

Cl

V-NH,

CF., the like.

Br

CF,

the same

NIICOCIUCI

N (C (UI,

CH.,

NH-COCH, OCH,

CH,

ν- N (C ₂ H ₅ ),

OCH, N (C ₂ H ₅ ),

NHCOCH ₃

CH ₃

N (C ₂ H ₅ ) ₂

N (C ₂ H ₅ ),

NHCOCH ₃

C ₂ H ₅

CTUCH ₁ C

CH, - \

C ₂ H ₅

() r; i

riilslichiiies yellow

Oran lie

O πι η nc

Red

Red

yellowish orange

Orange reddish yellow reddish yellow

35

OllsCl / Ullj!

Hi'ispk'l

Diazo component

K up | il'iiij.; SkiiinpinK'nlr

· .Ml polyester

142 «-lusgl.

Br

, 43 / V NH ₂

/ CF,

yellowish orange

red-tinged (JeIb

144 F ₃ CW N'b

145 the same.

146 the same

147

148 the same.

149 the same.

Cl

CF,

150 the same.

151

152 the same.

Br

- NH ₁

;, N (C ₂ IIO ₂

^K y ~ N (CH ₂ CH ₂ Cl) ₂

C ₂ H ₅

- N

CH ₂ CH ₂ OCH ₃

N (C ₂ H ₅ J ₂

N (C ₂ Hj) ₂

NHCHO

C, H

;: ^rl 5

-N

C H, C H, Cl

- N (C ₂ H ₅ I ₂

yellow
yellow

reddish yellow

yellowish brick red

Brick red

Red-brown

Brick red

yellowish brick red

Brick red

ck

rorlsi'l / iiim

lit'ispii'l

154 the same.

37

(T ₁

• NII ₂ (T,

(Wed,

C 1

38

Just ^1. ml

() ranuc

O rai iue

155 the same

CIl,

CH ₁ (H,

reddish orange

156 H ₁ CO ₂ S <

157 dcsul.

158 dcsul.

159 the same

Nile

CF.,

160 H ₅ CO ₁ S-

161 dcsul.

NH,

CF,

162 dcsul.

CH,

N (C ₂ H ₅ ),

N (C ₂ H ₅ ),

C ₂ H ₅

CH,

Vh ₂ CH ₂ CC ₂ H ₅

V-N

CH,

> - N (C ₂ H ₅ ),

N (C ₂ H ₅ ),

CH,

' ^ν · Ν

CH ₅

CH,

reddish yellow

rotstichiucs (iclb

reddish yellow

red tinged yellow

rotstichiucs yellow

Orange

Oranuc

39

continuation

Example! Diazo component

163 H ₅ C ₂ O ₂ S

CF,

CF., CF,

164 H ₅ C ₂ O ₂ SK '> -NH ₂

CF,

165 the same.

166 the same

Coupling component

CII ₁ CH ₁ Cl

V N

CH,

- N (CH ₃ ) ₂

N (C ₄ H.,):

40

Nuance on

orange

orange

Orange orange

Claims (2)

Patent claims: I. Process / to print hydrophobic Fiber material according to the Tpmsl'eidruckprin / ip. ti a d u r c h g e k c η η / e i c h η e I that one sublimable, sulfogra, pen-free mono-olars the general formula X, ' A N N used, in which X ₁ and X _{1 are} hydrogen, optionally _{C 1} -C ₄ -alkyl or C ₅ -C ₇ -cycloalkyls _{which are substituted by C 1} - or C ₂ -alkoxy, F, Cl, Br or phenyl, and η is the number 1 , 2 or 3, and the ring A by NO ₁ , CN, F, Cl, Br, SO ₂ CH. ,, SO ₂ C ₁ H ₅ , QC, -alkyl or QC ₄ -alkoxy and the ring B by C ₁ -C ₄ -AlkVl, C, -C ₄ -alkoxy, CF ₃ , F, Cl, Br. Benzyloxy, phenoxy, optionally substituted by F, Cl or Br-substituted QQ-alkylcarbonylamino or formylamino. 2. The method according to claim 1, characterized in that that one dyes of the general formula ν CF ₃ R ₃ " yo Y ₁ used, in which Y, H, NO ₁ , CN, CF, or CH ,, Y, Y ₁ , Cl or Br, Y ₃ H or Cl, R ₁ 'and R ₁ H, C ₁ -C ₄ -alkyl, phenyl -C, -C, -alkyl, cyclopeiity !, cyclohexyl, methylcyclohexyl, QQ-chloroalkyl or C ₁ - or C ₂ -alkoxy-C _r C ₄ -alkyl, R ₃ H, C ₁ -C ₄ -alkyl, C , -C ₄ alkoxy, phenoxy, benzyloxy and R ₄ H, CH ₃ , CF ₃ , C ₇ H ₅ , Cl, Br or NHCOR ₅ , where R _{5 is} H, C _r C ₄ alkyl, QQ-chloroalkyl, C, -C ₄ -Bromalkyl or methoxy-C ₂ -C ₄ alkyl. Alkyl or C ₁ -C ₁ -AIkOW and d-τ Ring B third C, - (. '., - Alkyl, C ₁ -C ₁ -AIkOXy, Cl- ^1. ,, F, Cl, Br, Benzyl oxy. Phenoxy, optionally substituted by I ', Cl oiler B (', -C-alkylethylamino or l-'oi mylamino can be substituted. Before / ugl / u using Faibslolfc correspond! the general formula Cl- K. »