DE1126840B - Process for printing matted, regenerated cellulose material with reactive dyes - Google Patents

Description

INTERNAT.KL. D 06 q

GERMAN

PATENT OFFICE

G32106IVc / 8n

REGISTRATION DATE: APRIL 21, 1961

NOTICE THE REGISTRATION AND ISSUE OF EDITORIAL: 5. A P R I L 1962

The present invention relates to a method for producing deep and uniform color prints with reactive dyes on matted, regenerated cellulose material.

If matted, regenerated cellulose is printed with a printing paste containing reactive dyes, see above Depending on the dye, one obtains, to a greater or lesser extent, weaker and less uniform colors Prints than on cotton.

It has now been recommended to use printing paste for cotton printing for the purpose of producing stronger colors Print urea, thiourea and / or guanidine or its salts in amounts up to about 20%> based on the total weight of the printing paste. To now also on matted, regenerated cellulose The urea or thiourea or Guanidine content of the printing paste increased. This achieves a deeper color strength, but not always the required evenness of the prints.

It has now been found that deep and even color prints can be produced on matted, regenerated Cellulosic material can be produced if this is done before printing with reactive dyes with compounds of the general formula I.

X = C

(I)

NH,

puddles.

In formula I, X is the thio or imino group, but preferably the oxo group, R the primary amino group, a secondary or tertiary amino group, a lower alkoxy group, such as, for example, the methoxy or ethoxy group, or an aliphatic radical containing up to 4 carbon atoms, such as ζ. B. the methyl, ethyl, propyl or butyl or an acid amide radical _{, for example the -CH 2 CONH 2} radical, preferably the first-mentioned primary amino group.

If the compound of general formula I is guanidine, it can also be in the form of its salts, eg. B. as carbonate.

As is known, “reactive dyes” are those dyes which contain hydroxyl groups Textile materials enter into a chemical bond and for this purpose in the presence of acid-binding, alkaline-reacting agents, such as sodium or potassium carbonate, sodium or potassium hydroxide, Sodium or potassium bicarbonate, di- or tri-sodium phosphate, tetrasodium pyrophosphate Process for printing matted, regenerated cellulose material

with reactive dyes

Applicant: J. R. Geigy A. G., Basel (Switzerland)

Representative: Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Ch.em. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority: Switzerland of April 23, 1960 (No. 4627)

Dr. Hans Rafael, Weil / Rhine,

and Siegfried Bode, Grenzach (Bad.), have been named as inventors

or sodium metasilicate, and optionally fixed at an elevated temperature. The reactive dyes can belong to a wide variety of dye classes, for example the nitro, azo, anthraquinone, Phthalocyanine or formazyl series. They can also contain heavy metal bound in complexes. The reactive groups of these dyes can be any substituents which, at temperatures, as they are customary in dyeing and printing processes for reactive dyes, with alkalis with entrainment of the binding electron pair react. The reactive substituent can, for example, be the residue of a /? - halogen fatty acid or the residue of a cyclic carbimide halide adjacent to a tertiary ring nitrogen Ring carbon atom contains at least one halogen atom. In particular, it can consist of a Azine ring of aromatic character consist of at least two tertiary ring nitrogen atoms and an these adjacent ring carbon atoms at least one halogen, such as. B. contains chlorine or bromine, thus for example a mono-, di- or trihalodiazinyl or a mono- or dihalotriazinyl radical be.

For padding the regenerated cellulose material, it is expedient to use an aqueous approximately 10% strength Solution of compounds of formula I.

Printing the regenerated cellulose padded with compounds of the formula I according to the invention

209 558/401

Reactive dyes are expediently done in the presence acid-binding agents, such as. B. sodium carbonate, and optionally at a higher temperature.

The inventive method results in an improved uniformity of the prints on matt, regenerated cellulosic material. In addition, it has the advantage that it is due to the padding with compounds of the formula I improved dyeability of matted, regenerated cellulose material succeeds in using cotton and matted, regenerated cellulose material at the same time or one after the other one and the same reactive dyes containing printing paste in practically equally strong and uniform To print shades of color, while it was previously necessary, at every transition from cotton printing to print on matted, regenerated cellulose and vice versa, also to change the printing paste, what is naturally associated with loss of time and additional work.

In the examples below, parts are parts by weight.

In the structural formulas of the examples are dyes with di- and trichloro-pyrimidylamino groups as Represented containing 4,6-di- or 4,5,6-trichloro-2-pyrimidyl radicals. In reality it is Isomeric mixtures with predominantly 2,6-di- or 2,5,6-trichloropyrimidyl-4-groups and 4,6-di- or 4,5,6-trichloropyrimidyl-2-groups, and the given formulas are to be interpreted accordingly.

example 1

Matted viscose rayon is with an aqueous solution containing per 1000 parts of urea 100 parts, impregnated, squeezed to 100% weight gain, and dried at 80 to 100 ⁰ C. The pretreated fabric is then printed using one of the usual methods with the following printing ink:

40 parts of the dye of the formula., N - c;

HO NH

Cl

CC - Cl

Cl

100 parts urea,
200 parts of water,

10 parts of the sodium salt of 3-nitrobenzenesulfonic acid, 620 parts of sodium alginate (5% strength aqueous solution), 30 parts of sodium carbonate

1000 parts of printing ink.

Now the textile material is dried and then steamed for 7 to 10 minutes or during 4 to 6 minutes of dry heat treatment at 150 Subject to up to 180 ° C. The goods treated in this way are first rinsed cold, then hot and then during Soaped for 30 minutes with a solution of 2 parts of curd soap in 1000 parts of water. You get one deep, even red pressure.

Under otherwise identical conditions, but without pre-treatment of the textile material with urea, weaker and uneven prints are obtained.

A similar result is obtained if the tissue is mixed with thiourea instead of urea, Pretreated guanidine carbonate, acetamide or methyl urea.

If all other things being equal are used, one of those listed in the table below is used Dyes, this also gives deep, even prints.

40

Tabel

No. SO ₃ H SO ₃ H OH dye ₃ Η , Ν - [-C _x "Λ O- K Ν - Cl c ^X Cl Hue on
Cellulose fibers i NH-CO- < Λ ^ ^V C - / ^ v-N = N- Ί ι NH- N = \ 1 Ί HO ₃ S- - \ - ' \ -SO ₃ H Brilliant red SO ₃ H \ / SC / Cl C-, ' NH-CO-CH ₃ OH
ι c ^{/ N} -CH / -. NH
! \ ( ^) - N = N- ^Y \ 2 HO ₃ S- Red \

Dye shade on cellulose fiber !!

.N

OH NH C

Cl

CH

Cl

HO ₃ S- _x

—SO ₃ H

SO ₃ H

> _ N = N ■
HO ₃ S

SO _a H

OH NH - CO - CH = C - CH ₃

J ί

S \ ei

SO ₃ H

> CO NH- /> SO ₃ H _OH

N ^/ ι

N = N / Y SO ₃ HI _x I.

NH-C

SO ₃ H

/ N / \ Kf-N /

ι ι i ^ - J- ^ ¹ \

CH ₃

SO ₃ H

Cl

^ N-CC

NH-C _x / CH

^ N = C (

HO ₃ S-

\ _N == N - CH - C HOOC-C = N , Cl

NH

-SO ₃ H

Cl

SO ₃ H

Cl

C-N

NH-CO-CH = C-CH ₃

C-NH

Q ₌

NH.

> -SO ₃ H QH

N = N-

SO,

-SO ₃ H brilliant red

Brilliant red

Red

Reddish yellow

Reddish yellow

Scarlet fever

Dye hue on cellulose fibers

^X C -N
HCC; J) C-NH- <

"ν = Ν ^κ

-SO ₃ H OH SO ₃ H

SO ₃ H

SO ₃ HH ₂ N SO ₃ H

Cl

: c

ci-c;

c-NH

SO ₃ H

Cl-CH ₂ -CH ₂ -CO-NH-Y ^X , SO ₃ HC

CH ₃

N - CH-C '

^CI

C -N _:.

JC-NH- / V-SO ₃ HC =

HN '

SO, H

HO ₁ S- / NN = N- / ^X -N = NN = N-CH-C
Ί
O

Scarlet fever

orange

HO ₃ S

SO ₃ H

Yellow

HO ₃ S

V /

I.
Cl

Yellow

NH-CO-CH ₂ -CHo-Cl

SO.H

, N—

HO ₃ S - <

VN = N- /

V-N = N-,

SO _S H CH ₃

NH ₈

Brown

Orange brown

Example 2

Spun rayon is at 20 ° C with a 10% aqueous Thiourea solution padded to 100% weight

10

increased and then squeezed at 80 to 100 ° C dried. The pretreated goods are printed with the following printing ink:

30 parts of the dye of the formula

HO, S

SO ₈ -CH,

100 parts urea,
200 parts of water,

10 parts of the sodium salt of 3-nitrobenzenesulfonic acid, 630 parts of sodium alginate (5% 18 ^e aqueous solution), 30 parts of potassium carbonate

Parts of printing ink.

The printed fabric is steamed or dried for 7 to 10 minutes while subjected to 4 minutes to a dry heat treatment at 150 to 18O ⁰ C. It is then rinsed cold and hot and soaped for 30 minutes with a solution of 2 parts of curd soap in 1000 parts of water at boiling temperature. A deep, even violet print is obtained.

If all other working conditions are the same without pretreatment of the textile material, the result is a significantly weaker and uneven pressure.
An equally deep and even pressure is achieved if the tissue is pretreated with urea, guanidine carbonate, acetamide or methylurea instead of thiourea.

Deep, even prints can also be obtained if, under otherwise identical conditions, the above Example used one of the dyes listed in the following table.

HO ₃ S- 0 Cu No
j O / O \ Tabel -NH- H 2 C. -CH ₂ - -CH ₂ -Cl Hue on
Cellulose fibers No. ₃ s - I.
\ / dye , a SO -N = - cf.
\ C. -Cl HO
3 H. \ ^X C1 ruby 1 HO ₃ S- ' O" Cu \ , s-l ί -CO \ -N = N - HO NH violet 2 / N = \ / C. 5O ₃

209 558/401

C.
i
HO ₈ S- ⁷
\ N NO ₂ ( C. 11 Cu ^N N I. dye "^ O SO ₃ H
M. 12th - Cr Hue on
Cellulose fibers No. \ Cl-C
V
C. I. NO ₂ \ _N = N— ("
I.
/ \ C-Cl Ψ
SO ₃ H 2 C. C. Y ) - / ^x .
JH -N _x
/ C-HN-
/ ) NH ₂
s λ
V ^ ₁ -SO ₃ H Reddish blue 3 HO ₃ S- / \ 1 I.
SO ₃ H , N-C ^ Cl _x
> -
Cl-C _x ^ HO ₃ S- ^X Cf ^ he \ Co > HO ₃ S-T '' 2 Y-N = N-I _x ) ( Cu _/; N -Cf Λ-Ν-Ν- ^C \ "' Reddish blue 4th Y
SO ₃ H / HO ₃ S-; Y- N = N- ' _x - ) ( V ^X -NH- i ; c-ci Greenish
black 5 i
3
Y ■ "Cl , Cl \ ^A v_NH- / Y ; n Reddish
black ) ^V NH ₂ 6th , Cl

Example 3 padded, squeezed off to 100% weight increase

and dried at 80 to 100 ⁰ C. The pre-treated

Copper rayon is made with an aqueous solution, then fabric is made according to one of the usual which contains 100 parts of guanidine carbonate per 1000 parts, printed 65 methods with the following printing ink.

30 parts of the dye obtained by condensation of 1 mol of copper phthalocyanine disulf onic acid disulfonyl chloride with 2 moles of 4,4'-diamino-diphenyl-2,2'-disulfonic acid and then with 2 mol / 9-chlorocrotonic acid chloride,

100 parts urea,
200 parts of water,

10 parts of sodium salt of 3-nitrobenzene sulfonic acid, 630 parts of sodium alginate (5% aqueous solution of ^e), 30 parts of sodium carbonate,

Parts of printing ink.

The printed material is steamed for 7 to 10 minutes or dry heat treatment at 150 to 180 ⁰ C for 4 to 6 minutes.

threw. The textile material is first rinsed cold, then hot and then for 30 minutes with a Solution of 2 parts of curd soap in 1000 parts of water soaped at the boil. You get a deep, even turquoise blue print.

Under otherwise identical conditions, but without pretreating the textile material with guanidine carbonate, you get weaker and uneven prints.

A similar result can be obtained if ίο the tissue is used instead of guanidine carbonate with urea, Pretreated thiourea, acetamide or methylurea.

If one of the dyes listed in the following table is used under otherwise identical conditions, this also gives deep, even prints.

Table 3

No. dye O NH ₂ Hue on
Cellulose fibers 1 Condensation product of 1 mol of copper phthalocyanine sulfonic acid trisulfochloride
with 2 moles of ammonia, 1 mole of m-phenylene-diaminesulfonic acid and the condensate
cation product of 1 mole of cyanuric chloride and 1 mole of 2-aminobenzene-1-sulfonic acid Turquoise blue 2 Condensation product from 1 mole of copper phthalocyanine-disulfonic acid-disulfochlo-
rid with 1 mole of ammonia, 1 mole of 2,4-diaminobenzene-1-sulfonic acid and 1 mole
2,4,5,6-tetrachloropyrimidine / γ ^x - SO ₃ H Turquoise blue O NH ₂
• i O NH - <> - SO ₃ H Cl 3 \ ^/! \ ^{/ l} \ ^y ^ NH- / \ blue O ί VfH- / Y-SO ₃ H Cl NH-C ^ / C-Cl SO ₃ H 4th blue

No. HO ₃ SJ- 0 NH ₂
I. dye -C, , N-C / Hue on
Cellulose fibers I. ^V N = C ) C-Cl 5 ⁷ Y ■ 'v SO ₃ H ^X C1 blue 0 NH- V \ _NH- SO ₃ H

Claims (2)

PATENT CLAIMS: 1. A process for printing matted, regenerated cellulose material with reactive dyes, characterized in that this is done with compounds of the general formula I. (I) ^25th ΝΗ, wherein X is the oxo, thio or imino group and R is a primary, secondary or tertiary amino group, denotes an ether group or an aliphatic radical containing up to 4 carbon atoms, and then printed in the usual way with reactive dyes. 2. The method according to claim 1, characterized in that that one uses urea as the compound of formula I. © 20 »558/401 3.62