DE2404854A1 - DYE PREPARATIONS FOR TRANSFER PRINTING - Google Patents

Description

BASF Aktiengesellschaft

Our reference: O. Z. 30 362 E / Wil 6700 Ludwigshafen, January 30, 197 *

Dye preparations for transfer printing

The invention relates to dye preparations suitable for transfer printing, the dyes of the formula I in addition to the usual constituents

R-HIT N ^ NH-R ^J

included in the
D the remainder of a diazo component,
R hydrogen or alkyl,
X denotes hydrogen, cyano or carbamoyl and R ¹ denotes hydrogen, acyl, alkylsulfonyl or optionally substituted alkyl, phenyl or cycloalkyl.

The radicals R ¹ can be identical or different. Acyl and alkylsulfonyl radicals R ¹ are, for. B. formyl, acetyl, propionyl, methylsulfonyl or ethylsulfonyl.

In particular, the invention relates to dye preparations suitable for transfer printing, the dyes of Formula Ia

27/74. . / 2

509834/0929

O.ζ.30

Yes

included in the

D is the remainder of a diazo component, R is hydrogen or alkyl with one to five carbon atoms, X is hydrogen, cyano or carbamoyl and

R ^{2 is} hydrogen or optionally duroh hydroxy, alkoxy with one to four carbon atoms or C-acyloxy with one to three carbon atoms, substituted alkyl with two to six carbon atoms, cycloalkyl with five to eight carbon atoms or phenyl

mean.

The radicals R can also be identical or different.

The radicals D are preferably from the benzene, azobenzene, thiazole, thiadiazole, thiophene, benzthiazole or benzisothiazole series

In the benzene series, the radicals D should have at least one S-substituent of the 2nd order, e.g. B. cyano, nitro, methylsulfonyl, Contain ethylsulfonyl, trifluoromethyl, carbomethoxy, carboethoxy or carboisobutoxy. Further suitable substituents are fluorine, chlorine, bromine, methyl, ethyl, methoxy or Kthoxy.

Substituents for the heterocyclic radicals D are, for example, cyano, nitro, chlorine, bromine, carbomethoxy, carbo-

509834/0929

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24G48S4

ethoxy, carboisobutoxy, methyl, methoxy, ethoxy or methyl mercapto.

R radicals are in addition to hydrogen z. B. ethyl, propyl, butyl and especially methyl.

Optionally substituted alkyl and cycloalkyl radicals R and R ² are, for example, methyl, ethyl, n- and i-propyl, n- and i-butyl, amyl, cyclohexyl, methylcyclohexyl, norboroyl, methoxy, ethoxy, propoxy and butoxypropyl, methoxy - And ethoxyethyl and hydroxyethyl and propyl. Hydroxyl groups

ι?
the radicals R and R can be esterified with formic acid, acetic acid or propionic acid to give the C-acyloxyalkyl groups.

The dyes of the formula I are known compounds. Dyes of this type and their production are z. B. in German Offenlegungsschrift 2,062,717.

The dye preparations according to the invention also contain the dyes of the formula I auxiliaries as they are for use are required and customary in the transfer printing process. Dye preparations for transfer printing are described in German Offenlegungsschrift 1,771,813, for example. The transfer printing process and carrier for it are ζ, Β. in German Offenlegungsschrift 1,769,757 and 1,771 explained.

Of the dyes of the formula I, those which have the formula Ib

5 0 9834/0929 / 4

- 4 - O.Z. 30th

^Ib

correspond in the

D ^{1 is} a radical of the benzene, thiazole, thiadiazole or thiophene

Row and
Br alkyl with 1 to 4 carbon atoms, alkoxyalkyl with a total of 3 to

β carbon atoms or hydroxyalkyl with 2 to 3 carbon atoms are.

Residues D of the benzene series are preferably represented by cyano, trifluoromethyl, carbomethoxy, carboethoxy, chlorine, bromine, Nitro, methyl or methoxy substituted.

Individual .Diazo components D NH ₂ are, for example: 2-amino-benzonitrile, 2-amino-5-chloro-benzonitrile, 2-amino-5-bromo-benzonitrile, 2-amino-3> 5-dichloro-benzonitrile, 2-amino -5-nitrobenzonitrile, 2-amino-3-chloro-5-nitro-benzonitrile, 2-amino-5-cyano-benzonitrile, 2-amino-1-trifluoromethylbenzene, 2-amino-5-chloro-1-trifluoromethylbenzene, 2 -Amino-1,4-dichlorobenzene, 2-amino-1,3,5-trichlorobenzene; 5-Nitroanthranilic acid methyl ester, ethyl ester, propyl ester, 2-amino-l-methylsulfonylbenzene, l-amino-2,4-dinitrobenzene, l-amino-4-nitrobenzene, l-amino-2-methyl-4-nitrobenzene, l-amino -2-methoxy-4-nitrobenzene, 1-amino-2-nitro-4-chlorobenzene; Anthranilic acid methyl ester, anthranilic acid isobutyl ester, anthranilic acid methoxyethyl ester, 5-chloro-anthranilic acid methyl ester, o- and p-aminoacetophenoii, 4-aminobenzaldehyde, l-amino-2,5-dicyanbenzene, l-amino-2,4-dicyan-3,5 -dimethylbenzene, 4-aminoazobenzene.

5098 3 4/0929 _{/ 5}

- 5 - O.Z. 30 3.62

2-Amino-5-nitrothiazole, 2-Amino-3-cyano-4-methyl-thiophene-5-carboxylic acids ^ ethyl ester, 2-amino-3-cyano-4-methyl-thiophene-5-carboxylic acid! sobutyl ester, 2-Amino-3-cyano-4-methyl-5-bromothiophene, 2-amino-3-cyano-4-methyl-5-chlorothiophene, 2-Amino-3-cyano-4-methyl-5 ■■■ nitro-thiophene, 2-amino-3 # 5-dinitro-thiophene, 2-amino-3 »5-dinitro-4-methyl-thiophene, 3-methylmercapto-5-amino-l, 2,4-thiadiazole, 3-methoxycarbonylethylmercapto-5-amino-l, 2,4-thiadiazole, 3-chloro-5-amino-l, 2,4-thiadiazole, 2-aminobenzothiazole, 2-amino-6-chlorobenzothiazole, 2-Atnino-6-methoxy-benzothiazole, 2-Amino-6-nitrobenzthiazole, 3-Amino-benzisothiazole, 4-Amino-benzisothiazole, 3-amino-5-nitrobenzisothiazole, 4-amino-7-nitro-benzisothiazole, 4-Amino-7-chlorobenzisothiazole, 4-Amino-5-chloro-7-nitro'-benzisothiazole

The parts and percentages given in the exemplary embodiments below relate to weight.

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example 1

29.5 parts of 2-aminobenzonitrile are in 800 parts of water and 80 parts of tree 30 # hydrochloric acid solved. Then 750 parts of ice are used and at 0 to 5 ° C 77 parts of a 23? 6 sodium nitrite solution closed at once. To Stirring for two hours at 0 to 5 C, the clear to cloudy

Diazonium salt solution mixed with the following suspension:

66.0 parts of 2,6-bis (β-methoxyethylamino) -3-oyan-4-methylpyridine are dissolved in 80 parts by volume of dimethylformamide with heating, then 12.5 parts of an intercalation product of about 23 moles of ethylene oxide to 1 mole of sperm alcohol and gives the Solution with stirring to a mixture of 30 parts by volume 30 / tiger Hydrochloric acid and 1000 parts by volume of water.

About 500 to 1000 parts of ice and then about 65 parts of 50% sodium hydroxide solution are added to the coupling until the pH of the mixture is 2.5-3.2. After the coupling has ended, the mixture is ^{heated to 70 °} C., filtered off and washed with hot water. After drying, about 97 to 9 parts of a yellow powder of the formula are obtained

^cir

H, C CN
⁵

IH-CH ₂ -CH ₂ -O-CH, because in dimethylformamide it has a yellow color

509834/0929

"T-O.Z. J5o

6 parts of this powder are dispersed in 94 parts of a mixture consisting of 5 parts of ethylcellulose, 70 parts of ethyl alcohol, 20 parts of ethyl acetate and 5 parts of ethyl glycol, and the dye paste obtained is printed on transfer paper and dried. Hun contacting the paper bit of the "face on a fabric of polyester» acetate or polyamide and heated 50 seconds at 190 ⁰ C to 200 ⁰ C. Is obtained in this way gives a strong yellow coloration of the fabric "it very good light and lS barrel fastness.

Example 2

78 parts of 1-amino-2-trifluoromethyl-4-chloro-benaol are dissolved at 0 to 20 ⁰ C in 400 parts of 96 £ sulfuric acid. The mixture is cooled to 0-4 ° C., 110 parts of 45 nitrosylsulfuric acid are added and the mixture is stirred for 3 hours at 0 to 5 ° C. The mixture is then poured onto 1200 parts of ice with drilling, razed for 50 minutes and filtered. The diaaonium solution with 117 parts of the coupling component of the formula is used to destroy excess nitrous acid

H, C CH

KH-CH ₂ -CH ₂ -OH

509834/0929

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added and the pH of the coupling is raised to 2 to 3 by adding sodium hydroxide solution at 0 to 5 ^{0 C.} After the coupling has ended, the dyestuff of the formula which has precipitated out is sucked off

CH,

riff Hz C CN

Vn = N-

NH-CH ₂ -CH ₂ -OH, washed with water and dried.

A dye ink consisting of 100 parts of this dye, 400 parts of gum ether, 200 parts of starch ether and 300 parts Water is applied to transfer paper and dried. Now a fabric made of polyethylene terephthalate or polyamide is made pressed onto the printed side of the paper and heated the paper to 190 to 200 ° C for 30 seconds.

This gives the synthetic fiber a strong, golden yellow color. The coloration is very light and wet fast.

The following tables can be used in an analogous manner 1 to 4 by specifying the substituents and the hue of the dye produce and on dyes apply the goods to be colored (Examples 3 to 114).

509834/0929

Table 1

- 0.Z.30 362.

IH-Ä

B ep.
Mr. S ¹ Β ² B. E * E ⁵ Hue of
Fbg. on poly-
ithylenet «r -
phthalate 3 CE ₂ CE ₂ OCE ₃ (0B ₂ ) ₂ O0 _B , ° 3 ^H 7 CH E. right) A. H V ν · Η jfc J Ί Vvfl ^ CH, M. W. H VJl Il - H H Cl M. 6th η O ₂ B ₅ Il Il E. M. 7th η CB ₃ N Il Ml Il 8th η (CEg) ₃ O0E (CE ₃ ) ₂ N ■ W. N 9 • A ' (CBg) ₂ OCB ₃ Il « Μ Μ 10 CBgCEgOE N N Il Μ Il 11 η M. N ^Of 3 Il Il

-10-

509834/0929

o.Z. 30 362

E.g. E ¹ R ² Ci ₃ CF, e5 hue 12th CE ₂ CE ₂ OE (CE ₂ ) ₂ 0CE ₅ R. CI Cl right) 13th O ₂ H ₅ C ₂ E ₅ R. ο, E. R. 14th R. H R. R. E. R. 15th R. R. R. CI Cl R. 16 R. CE ₂ CE ₂ OE R. R. E. R. 17th H (CH ₂ ) ₃ OH R. R. R. 18th It R. R. R. Cl R. 19th CE ₂ CE ₂ OCE ₅ OH ₂ CH ₂ OCH ₃ R. H E. R. 20th ^C 6 ^S 5 E. R. R. R. It 21 R. CE ₂ CE ₂ OCE ₅ R. COOCE R. R. 22nd CE
2 5 v, R. R. R.
3 R. 23 R. CE ₂ CE ₂ OCE ₅ R. R.

-11-

509834/0929

o.ζ. 30 362

E.g. R ¹ ■ ι (CH) ₅ ÖCH (CH ₃ ) ₂ ' R ² ■ R. R *. , «■ hue 24 I. CH ₂ GH ₂ OCH ₃ OH ₅ COOCH η yellow 25th H Il • Ι ClJ H η; 26th it . (C _B2 ) ₅ OCH (CH ₅ , ₂ η CF ₃ η H ' 27 ". ' ■■'' CH ₂ CH ₂ OH η η Cl η 28 C ₂ H ₅ OH ₅ CN N η 29 It • C ₅ H ₇ It H η 30th η « It CF η η 31 CH ₂ CH ₂ OCH '■' OK ₂ OH ₂ OCH ₅ OH ₅ η η η 32 It H η CH η 33 M. • CQOCB H η 34 E. η CK Ξ κ 35 η It

50 9 «3A / Ό 929

Table 2

O.Z. 50 362

240 ^ 854

H, C Ci

R ⁵ SHE *

E.g. R ¹ E ² Β * »Ο _{2 Β} 5 hue 36 Ξ V ₅ H n H golden yellow 37 It (CH ₂ ) j0CHj M. H N a 38 M. VW Πι 4 ± J> m Vr V ^ l \ WBi ■ / _Α R. M. Ν a 39 η (CH ₂ ) j0CHj OH, η N orange 40 η OCHj n Η Red orange 41 • A C ₂ H ₅ η N Il ■ charlach 42 η M. H n Il orange 43 η M. CI N a Red 44 η CjH _? (n) η η a

509834/0929

O.Z. 30 362

E.g. R ¹ C ₅ H ₇ W R. R * 1 Cl hue 45 C ₂ H ₅ C ₂ H ₅ R. ΐο ₂ R. Red 46 R. H R. R. R. R. 47 Cocoon, R. Eq R. H R. 48 η R. R. R. R. Red 49 η R. R. R. η fel & etiekig
Red 50 H (CV ₅ OCH ₃ BO ₂ R. R. orange 51 η R. η R. H R. 52 R. R. CH η R. Red 53 V ₅ R. R. R. Br Red 54 O ₂ H ₅ C ₂ H ₅ CH η H η 55 CH ₂ CH ₂ OCOCH ₅ CH ₂ CH ₂ OCOCH H .R yellow 56 • Λ H et

509834/0929

Table 3

X IH-S

O.T. 30 362

E.g. Diazo component R. R ¹ V X colored SO ₂ CH ₅ R. 57 H ° 2 ^E 5 ^C 2 ^E 5 H blaustieaie
Red 58 R. R. O ₄ H ₉ W R. R. 59 R. CH ₂ OH ₂ OCH ₃ H * R. 60 R. (OH _? ), O0 _Hj R. R. R. 61 R. R. = 2 = 5 R. R. 62 R. R. R. COlH ₂ R. 63 R. R. C, R. 64 H H H 65 O ₂ E ₅ C ₂ H ₅ Cl Red

- 15 -

509834/0928

O.Z. 30 362

E.g. Diazo component η CN H C CN
0 n E ¹ 2
ΈΓ Z IUt. 66 ΰΈ
Cl η O ₂ N- ^ n-KH ₂ H H 1 "embarrassing
Red 67 η η B. V ₃ 91 Μ 68 η η η ft. ^ ^ l fejg> l ^ Ο ^ »Π M. Il 69 B. IS / λ · πγ N nfiTt
\ ^Cä 2'3 3 * a 70 89 - " a - COIH ₂ κ 71 η H M. sot 72 R. V, Il 73 η (0H ₂ ) _; 0CH ₅ It Il 74 N M. GOIH ₂ H 75 η C ₂ E ₅ CI M. 76 M. N Il

-16-

5 0983A / 0929

Ββρ.

Diazo component

E ¹

O.Z. 30 362

Fartte »

^C 2 ^H 5

(CHg) ₂ OCH ₅

2 ^H 5

(CHg) ₂ OCH ₅

2 ^H 5

CV

■ eharlaoh

oraaf

grttnetichif embarrassing

COIH ₂

CI

Red

tlaxiBtichif Red

(CHg) ₂ OCH ₅

(CHg) ₂ OCH ₅

509834 / 092S

O.Z. 50

E.g. Diazo component M. E ¹ R ² Z η N Parbtom 88 H ₅ C CH H _x CS
VH H (CHg) ₅ OCH (C. Il ■ felawfciehif
Red 89 η C ₂ H ₅ Ν It Tiolet 90 η ° 2 ^Η 5 Il ora & f 91 η R. (CHg) ₂ OCH ₅ H N 92 η M. V, Il 95 C ₅ H ₇ W C ₅ H ₇ (H) Il 94 (CHg) ₂ OCH ₅ C ₄ H ₉ (n) N

- 18 -

50983 4/0929

Table 4

H ₅ C CH DHK - (V / V NHfi HH-E

O.Z. 30 362

24CK854

E.g. D. CH H ClT CH the one E the other E hue N Br- ^ M- O ₂ HH ^ - 95 It H η ° 2 ^H 5 COCH ₅ yellow 96 η O ₃ H ₇ Cn) η W. 97 η (OHj) ₃ OOE ₃ M. H 98 SO ₂ CH ₅ H 99 It H H 100 N eocH ₅ * 101 η η yellowish
Red 102 N SO ₂ CH ₅ N 103 (CHg) ₅ OCH ₅ H It 104 (CHg) ₂ OCH ₅ COCH ₅ M.

-19-

50983 4/0929

O.Z. 30 362

«I.

one H the other H

hue

Cl

Cl

Cl

ei - // ν

Cl

(CE ₂ )

C ₄ H ₈ (n)

C ₂ H ₅ COCH.

SO ₂ CH ₅ COCH,

Red

golden yellow

yellow

509834/0 9 -20-

Claims (5)

Claims O.Z. 30 362 1. Containing dye preparations for transfer printing in addition to the usual ingredients, dyes of the formula 1 Tff 1 '
R-HN ^N NH-R in the D the remainder of a diazo component, R hydrogen or alkyl, X is hydrogen, cyano or carbamoyl and R is hydrogen, acyl, alkylsulfonyl or optionally mean substituted alkyl, phenyl or cycloalkyl. 2. Dye preparations according to Claim 1, the dyes the formula 2 JLJ 2 included in the D is the remainder of a diazo component, R is hydrogen or alkyl with 1 to 5 carbon atoms, X is hydrogen, cyano or carbamoyl and R is hydrogen or optionally by hydroxy, alkoxy with 1 to 4 carbon atoms or C-acyloxy with 1 to J carbon atoms substituted alkyl with 2 to 6 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or phenyl mean. 509834/0929 -21- O.Z. 30 362 3. Dye preparations according to Claim 2, characterized in that
D for the remainder of a diazo component of the benzene, thiazole, Thiadiazole or thiophene series, R for methyl
X for cyan and
R for alkyl with 1 to 4 carbon atoms, alkoxyalkyl with a total of 3 to 6 carbon atoms or hydroxyalkyl with 2 to 3 carbon atoms stand. . Dye preparations according to Claim 3 *, characterized in that D stands for the remainder of a diazo component of the benzene series which is substituted by cyano, trifluoromethyl, carbo methoxy, carboethoxy, chlorine, bromine, nitro, methyl or methoxy. 5. dye preparations according to claim 1 containing the Dye of the formula CN / Vn = N. CH ₅ -O-CH ₂ -CH ₂ -HN NH-CH ₂ -CH ₂ -O-CH ₃ BASF Aktiengesellschaft 50 9834/0929