DE1768884B2 - Durable, concentrated aqueous true solutions of metal-free direct dyes - Google Patents

Description

<^^ - _N = N ^ J ^ NH - CO - HN - ^^> - N = 1

para position to the azo groups of the monoazo * dye residues, or the remainder of a Dmmide of carbonic acid, fumaric acid or cyanuric acid, each containing 1 part by weight of dye, 1 to 8 parts by weight of water and 0.5 to 5 parts by weight of urea.

2 Durable solutions according to claim I, in which F and F _{2 represent} residues of the same sulfonic acid group-containing monoazo dyes.

3. Durable solutions according to claim 1, containing 0.5 to 2 parts by weight of urea.

4. Durable solutions according to claim 1, containing the dye of the formula

OCH ₃

I SO ₃ H

or the dye of the formula SO ₃ H

OCH ₃ OCH ₃

SO, H

SO, H

-CO -

CH, CH ₃

SO ₃ H

or the dye of the formula SO ₃ H

OH OH

HO ₃ S HO ₃ S

or the dye of the formula

H ₂ N pH

NH- CO - HN

OCH ₃ OCH ₃

SO ₃ H
HO NH ₂

SO ₃ H

HO ₃ S SO ₃ H

or the dye of the formula

CH ₃ OH

HO ₃ S - ^ (~ \ - N = N-HO ₃ S HO ₃ S

OH

SU ₃ H

CH ₃

NH-CO-

SO ₃ H

SO ₃ H

5, Use of the stable solutions according to 60 direct dyes of the disazo series of the formula
h I Fb Pi

g g

Claim I for coloring paper.

t r «c

in which F, and F ₂ radicals which are the same or of one another

-—— ~ various sulfonic acid group-containing monoazo-

6s dyes and D the direct bond between two Phenyl radicals, this bond depending on the para position

The invention relates to durable, concentrated to the azo groups of the monoazo dyes, erte aqueous real solutions of metal-free or the remainder of a diamide of carbonic acid, the

Fumaric acid or cyanuric acid mean containing fe I part by weight of dye, 1 to 8 parts by weight of water and 0.5 to 5 parts by weight, preferably 0.5 to 2 parts by weight, urea,

The invention also relates to the use of these durable solutions for dyeing paper.

The substantive azo dyes preferably contain I to 4 water-solubilizing agents per azo group Groups.

These preparations are made by mixing and, if necessary, brief heating of the constituents mentioned produced and can also use other resources such. B. dyeing auxiliaries or paper finishing products for paper coloring, such as pH-stabilizing auxiliaries, e.g. B. amino acids, Phosphates and acetates. The urea itself can be used as a pH-stabilizing aid.

Plasticizers, water repellants, wet strength improvers can also be added to the preparations or dispersants are added.

From the French patent specification 1 420 403 are preparations, removing 1 part by weight of dye, 0.01 to 75 parts by weight of water and 2 to 100 parts of an acid amide are known.

These preparations are used exclusively for dyeing leather, with only leather dyes, in particular metal complex dyes can be used. In all of the examples mentioned French patent, metal complex dyes are used. Metal-free direct dyes are not known.

The new sprinkling has the advantage that significantly less acid amide is used; they are therefore more economical and the wastewater is less polluted.

The new preparations can be used as real solutions, optionally after dilution with water Coloring of paper can be used, whereby the paper in the bulk, by painting or through Dipping can color.

The preparations produced in this way have the advantage of being easier to use. The annoying dusting when weighing dye powder is omitted. They are also suitable for continuous dyeing processes.

The preparations can be stored for several months at room temperature. They are not turning frost this solution for coloring paper in bulk gives a lively, yellow coloration,

Example 2

68.4 parts of the sodium salt of the disazo dye of the formula

OCH ₃

C = O

sensitive and insensitive to fungal attack. In the following examples, parts are parts by weight and percentages are percentages by weight. ₅ o temperature are introduced as a 55% strength aqueous paste in 275 parts of water at 40 ° and stirred until homogeneous. When 100 parts of urea are added, the dye dissolves. After filtering off small amounts of insoluble impurities, 500 parts of a solution are obtained which can be kept for several months at room temperature. Vivid yellow colorations of paper are obtained with this solution.

Example 3

95.6 parts of the sodium salt of the disazo dye CI. Direct Yellow 50 (Color Index, 2nd Edition,

No. 29 025) are mixed homogeneously as a 40% strength aqueous paste in 160 parts of water and mixed with 200 parts Urea added. The dye goes into solution when heated to 70 to 80 '. After filtering with the addition of 5 parts of "Hyflo" filter earth and

Cooling gives 600 parts of a solution which can be kept for several months at room temperature. It lively reddish-yellow paper colors can be produced with it.

Example 4

101.6 parts of the sodium salt of the disazo dye CI. Direct Yellow 34 (Color Index, 2nd Edition, No. 29 060) are used as a 37% aqueous paste in

415 parts of water were stirred until homogeneous and after addition of 175 parts of urea heated to 85 to 90 °, the dye going into solution. 6 parts are added "Hyflo" filter earth to the solution and filtered. The 865 parts of dye solution obtained are at Raum several Can be kept for months. You get

The temperatures are given in degrees Celsius. thus lively golden yellow paper colors.

Example] B e i s ρ i e 1 5

62.4 parts of the sodium salt of the disazo dye 55 126.4 parts of the sodium salt of the disazo dye the formula of the formula

C = O

60

are in the form of a 50% aqueous paste in 275 parts of water were stirred until homogeneous and brought into solution by adding 100 parts of urea. The dye solution adjusted to SOO parts is at Can be kept at room temperature for several months. In case of

65 OH

HO ₃ S-ZV ^ N = N

HOiS

NH-

SO ₃ H

C = O

are as a 40% aqueous paste in a solution of Carry 250 parts of urea and 310 parts of water in a hurry * and dissolve it by heating to 60 to 70 ".

After adding 5 parts of Hyflo filter earth and Filtering gives 875 parts of a dye solution, which can be kept for several months at room temperature. With this dye solution, vivid make ichariacbrote paper colors,

Example 6

99.2 parts of the sodium salt of the disazo dye CJ. Direct Blue 15 (Color Index, 2, Edition, jo No. 24 4UO) are used as a 50% jge aqueous paste in one Solution of 152 parts of urea and 410 parts of water dissolved at room temperature and after addition filtered by 4 parts of "Hyflo" filter earth. You get 760 parts of a dye solution which can be kept for several months at room temperature. Leave it »Use it to produce lively blue dyeing of paper anyway.

20th

Example 7

99.2 parts of the sodium salt of disazo CI. Direct Blue I (Color Index, 2nd Edition, No. 24410) are mixed homogeneously as a 50% aqueous paste in 402 parts of water and thoroughly Addition of 200 parts of urea dissolved at room temperature. After using a clarifying filtration 800 parts are obtained from 5 parts of Hyflo filter earth a dye solution that can be kept for several months at room temperature. This gives lively ones blue paper dye.

Dyeing instruction A

100 parts of chemically bleached sulfite cellulose are ground in 2000 parts of water in a hollander.

0.3 part of the preparation according to Example 2 is added to this mass. After 15 minutes, sizing takes place and then the fixation. Paper made from this material has a yellow hue of medium intensity The waste water is colorless, and the fastness properties of the dye lind good.

Paper dyeings with similar nuances can be clouded by removing the dyes from the Examples 2, 4 and 25 used directly as such and in the the rest of the dyeing according to the instructions in the dyeing example A or B,

Dyeing instruction B

In a pulper 70 parts of chemically bleached Sulötcellulose from needle pin and 30 parts chemically bleached sulphate cellulose from birch wood in 2000 parts Whipped water.

0.2 part of the preparation obtained according to Example 4 is added to this mass. After 20 minutes paper is made from this mass.

The absorbent paper produced in this way has a golden yellow shade of medium intensity.

Dyeing instruction C

100 parts of chemically bleached sulfite cellulose are ground in 2000 parts of water in a hollander.

To this mass, n-in gives 0.9 parts of the preparation according to Example 2. After 15 minutes, the sizing and then the fixation takes place. Paper that made This substance is produced, possesses.1 a shade of yellow. The waste water is colorless and the fastness properties of the dye are good.

Dyeing instruction D

In a pulper, VO parts are chemically bleached sulfite cellulose from softwood and 30 parts are chemically Bleached sulphate cellulose from birch wood whipped in 2000 parts of water.

1.2 parts of the preparation obtained according to Example 4 are added to this mass. After 20 minutes paper is made from this mass.

The absorbent paper produced in this way has a golden yellow shade.

Preparations of similar quality can be produced according to Examples 1 to 7 if dyes of the Table 1 below of the formula

C-N = N-D-NH-X-HN-E-N- = N-F

uses, where the symbols C, D, E, F and X have the meanings listed in the columns.

C = remainder of D = remainder of Table 1 F = remainder of X = Resl from Shade on papic example
No. 1-aminobenzene 1 -amino- E = remainder of 2-aminonaph- Phosgene yellow 8th 3-sulfonic acid 2-methoxy 1-amino thalin-4,8-di- benzene 3-methyl- sulfonic acid 2-aminonaph- 1 -amino- benzene like C the same yellow 9 thalin-5,7-di- 3-methylbenzene like D sulfonic acid 2-aminonaph- the same like C the same yellow 10 thalin * 6.8 * di like D sulfonic acid the same the same like C Fumaric acid yellow 11th 1-amino * 3 * methyl- 1-amino 2'AmirtO- benzene like C Phosgene orange 12th 2-methylene benzene 5-hydroxy like D 4 _s 6-disulfone * naphthalene* acid 7-slilffiiisäire

continuation

example
Nf. C = Resl of D = Resl from F. = Resl from F = remainder of X = remainder of Color on paper 13th 1-amino 2-amino like D like C Phosgene yellowish 2-methylbenzene 5-hydroxy Scarlet fever 4-sulfonic acid naphthalene- 7 -: Sulphonic acid 14th 1-amino the same like D like C the same yellowish 4-methylbenzene Scarlet fever 3-sulfone drinks 15th 1-amino the same like D like C the same Scarlet fever 4-methoxy » benzene- 3-sulfonic acid 16 1-amino 2-amino Like D like C Phosgene Scarlet fever 4-methoxy 5-hydroxy benzene- naphthalene- 2-sulfonic acid 7-sulfonic acid 17th 1-amino the same like D like C the same Scarlet fever 2-methoxy benzene- 4-sulfonic acid 18th 2-amino the same like D like C the same Scarlet fever naphthalene- 4.8-disulfone acid 19th 2-amino the same like D like C the same Scarlet fever naphthalene- 6.8-disulfonic acid 20th 2-amino the same like D 2-amino the same Scarlet fever naphthalene- naphthalene- 4.8-disulfonic acid 6-sulfonic acid 21 3-acetylamino the same like D like C the same Scarlet fever 1 -aminobenzene- 6-sulfonic acid 22nd 2-amino the same like D like C 2-amino Scarlet fever naphthalene- 4,6-dichloro 4.8-disulfonic acid 1,3,5-iriazine 23 the same the same like D like C 2-phenyl- Scarlet fever amino 4,6-dichloro 1,3,5-triazine 24 2-amino the same like D like C 2-phenyl- Scarlet fever jjaphthafin- atSBfio * 5,7-disafibic acid 4,6-dkhlOT ' 3'-solfon- acid 25th 2-amino the same like D like C Phosgene Scarlet fever naphthalmic 6-sulfonic acid 26th 1-amino 2-area like D like C Phosgene Red naphthalene- 5-hydroxy 4,6-disulfonic acid naphthalene- 7-sulfonic acid 27 I-amino the same like D likeC the same Red naphthalene- 5-sulfonic acid

Preparations of similar quality can be produced according to Examples I to 7. if dyes of the following Table 2 of the formula (TI) are used, the symbols K ₁ . K ₂ and B those in the column »arafge-

have given meanings.

-N = NB - N = N- K ₂

(H)

Tabel

10

example
No. K | = Remainder of K ₂ = remainder of B = remainder of Tint on paper 28 I -amino-8-hydroxy- 1 -amino-8-hydroxy- 4.4 '"diamino reddish blue naphthalene- naphthalene- 1,! '- diphenyl 3,6-disulfonic acid 3,6-disulfonic acid 29 the same the same 4,4'-diamino blue 3,3'-dimethyl 1,1'-diphenyl 30th 1,8-dihydroxy the same 4,4'-diamino blue naphthalene- 3,3-dimethoxy 3 \ 6-disulfonic acid 1,1'-diphenyl 31 the same 1,8-dihydroxy the same blue naphthalene- 3,6-disulfonic acid 32 the same the same 4,4'-diamino blue 3,3'-dimethyl 1,1'-diphenyl 33 1 -amino-8-hydroxy- like K ₁ 4,4'-dietino blue naphthalene- 3,3'-dimethoxy 2,4-disulfuric acid 1,1'-diphenyl

Further compositions of preparations according to the invention are shown in Table 3 below listed, with the parts in the individual columns

of dye, the dye from the examples of Tables 1 and 2 mentioned above, the parts urea and the parts of water are given.

Tabel

example Parts Dye off Parts Parts No. example urea water 34 1.0 No. 2 0.5 8.0 35 1.0 No. 4 0.5 8.0 36 1.0 No. 6 0.5 8.0 37 1.0 number 1 5.0 6.0 38 1.0 No. 2 5.0 6.0 39 1.0 No. 9 5.0 6.0 40 1.0 No. 2 2.5 3.5 41 1.0 No. 4 1.0 6.0 42 1.0 No. 11 3.0 6.0 43 1.0 No. 25 2.0 7.0 44 1.0 No. 16 5.0 8.0 45 1.0 No. 24 5.0 8.0 46 1.0 No. 8 5.0 8.0 47 1.0 No. 29 5.0 8.0 4g 1.0 No. 2 2.0 6.0 49 1.0 No. 4 2.0 6.0

The dyes of the formula (I) can be prepared according to the information in German patents 122904, 132 511 and 216 666.

Dyes of the formula (I) in which A z. B. stands for the remainder of a cyanuric acid, can after German patent specification 436179.

The dyes of form! (II) can after the Information from German patent specification 74 593 can be obtained.

The dye of Example 25 can be prepared as follows: a) 2 moles are coupled using known methods diazotized 2-naphthylamm-6-sulfonic acid

1 mole 5,5'-dihydroxy-7,7'-disulfo-2,2'-di naphthylurea, or

b) diazotized 2-naphthylamm-6-sulfonic acid is coupled according to known methods on 2-Ammo 5-hydroxynaphthaBn-7-sulfonsätire and setzl

2 mol of the compound thus obtained with Phosgeti um, or

c) diazotized 2-naphthylamine-6-sulfonic acid is coupled modified to 2-acylamino-S-hydroxy-aphthalmic-sirifonic acid by known methods the acylamino by known methods and sets the Verbirtdxmg mn thus obtained Phosgene around.

Claims (1)

Claims; \, Stable, concentrated aqueous true solutions of MetaH-free direct dyes of the Dtsazo series of the formula F ₁ -DF ₂ (D wherein Fi and F ₂ radicals of the same or different sulfonic acid group-containing monoazo dyes and D the direct bond between two phenyl radicals, this bond each in OCH,