DE1159899B - Process for dyeing or printing textile goods - Google Patents

Description

INTERNAT. KL. D 06 p

GERMAN

PATENT OFFICE

B 61129 IVc / 8m

REGISTRATION DATE: FEBRUARY 4, 1961

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: DECEMBER 27, 1963

It has been found that textiles, such as fibers, threads, flakes, woven and knitted fabrics, are washable can dye or print if you use the product in the presence of strongly alkaline agents Dyes that have one or more reactive, preferably bound via nitrogen, oxygen or sulfur Have hydrogen atoms or which are capable of one or more such hydrogen atoms to form during the dyeing or printing process, and with uncolored polyfunctional compounds, the at least three preferably bonded via carbon or to phosphorus and optionally bear ethyleneimine groups substituted by aliphatic radicals or which are capable to form three or more such groups during the dyeing or printing process, if necessary treated at elevated temperature.

The new method is preferably used for dyeing or printing textiles from native and / or regenerated cellulose. However, it can also be used on textile goods made of polyacrylonitrile or copolymers of acrylonitrile with other vinyl compounds or on textile material linear polyesters, ζ. B. from polyethylene glycol terephthalate or based on terephthalic acid and p-dimethylolcyclohexane, useful.

As strongly alkaline agents are preferably used inorganic agents such. B. in particular Alkali metal hydroxides or carbonates, such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate. But you can also those compounds that under the usual conditions of dyeing or printing pass into strongly alkaline agents, use, for example Alkali metal bicarbonates, such as sodium or potassium bicarbonate, as well as di- or ^ alkali metal phosphates, such as disodium phosphate or trisodium phosphate. Mixtures of two or more can also be used strongly alkaline agents can be used.

Not only azo dyes such as + 'j Mono-, dis- or polyazo dyes, metal complex dyes, anthraquinone dyes, azomethine dyes. Triphenylmethane dyes, oxazine dyes, dioxazine dyes or tetrazaporphin dyes, such as phthalocyanine dyes, but also so-called optical brighteners, e.g. B. fluorescent Compounds of the stilbene. Benzimidazole, benzoxazole or benzthiazole series mentioned. One can according to the invention also start from mixtures of two or more dyes.

The dyes of the type identified above carry one or more, preferably via nitrogen, Process for dyeing or printing textile goods

Applicant:

Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Gerhard Lützel, Dr. Werner Rohland

and Dr. Dieter Ludsteck, Ludwigshafen / Rhein, have been named as the inventor

Oxygen and / or sulfur-bound reactive hydrogen atoms, e.g. B. in the form of primary or secondary amino groups, sulfonic acid amide groups, sulfonic acid alkyl amide groups, such as those with low molecular weight alkyl radicals, sulfonic acid aryl amide groups, such as sulfonic acid anilide groups, carboxamide groups, carboxylic acid alkyl amide groups, such as those with low molecular weight alkyl groups, hydroxyl groups and / or sulfhydryl groups. Of particular technical interest are those dyes which contain one or more reactive hydrogen atoms in the form of sulfonic acid amide groups, HO-alkylene groups, HoN-alkylene groups and / or sulfonic acid alkylamide groups with preferably low molecular weight alkylene groups or alkyl groups, for example dyes with HoN - SO- Groups, HO · CH ₂ · CH ₂ groups, H ₂ N _{· CH 2} · CHo groups, HO · CH ₂ · CH ₂ · NH · SO ₂ groups and / or H ₃ C _{· NH · SO 2} groups . However, dyes which have one or more reactive hydrogen atoms bonded via carbon are also suitable for the process according to the invention, for example the dye of the formula

[Nickel phthalocyanine]

= C-CH ₃

obtainable under the procedure of Belgian patent 551 700. Dyes that are capable of

309 770/373

one or more reactive, preferably bonded via nitrogen, oxygen or sulfur Forming hydrogen atoms during the dyeing or printing process is, for example, dyes with methylene ether groups or methylene ester groups. These groups go during the Process in methylol groups over.

The expression "dyes which should have one or more reactive hydrogen atoms" state that the dyes of the type indicated have one or more active hydrogen atoms carry, which enable these dyes to react in the manner of a so-called Michael addition.

The new process can be applied both to dyes which are free of water-solubilizing groups and to water-soluble dyes. The latter dyes usually have one or more sulfonic acid and / or carboxyl groups as water-solubilizing groups. Dyes which contain one or more sulfonic acid amide groups or sulfonic acid alkyl amide groups, such as sulfonic acid (β -hydroxyethyl) amide groups or sulfonic acid methyl amide groups, as water-solubilizing groups can advantageously be used for the process according to the invention. The dyes used can be nouns, but they can also be so-called reactive dyes, which are capable of entering into a chemical bond with the item to be dyed or printed. In the case of substantive dyestuffs, the new process improves the fastness properties of the dyeings and prints, and in the case of reactive dyestuffs, the new process increases the proportion of dyestuffs fixed on the dyed material and thus significantly improves the abundance of reactive dyestuffs.

As uncolored polyfunctional compounds, at least three preferably over carbon or ethyleneimine groups bonded to phosphorus and optionally substituted by aliphatic radicals carry, it is advantageous to use those compounds that have three or more groups of the general formula

Mean radicals and each of the radicals X and Y for a hydrogen atom or for a suitably low molecular weight Alkyl radical, such as a methyl or ethyl radical, can stand. Preferably one uses the process known from US Pat. No. 2,520,619 by the action of ethyleneimine Compound of the formula which is easily obtainable on cyanuric acid chloride

N-C

H ₂ C

CH ₂

ν /

C-N

Il \

N CH ₂

H ₂ C-

-CH ₂

for the method according to the invention.

Further uncolored polyfunctional compounds of the aforementioned type are, for example, those through Implementation of phosphorus halides, phosphorus oxyhalides or thiophosphorus halides with Ethyleneimine or propyleneimine obtainable compounds, such as those known from literature Connections of the formulas

and H> C
"H> C

N-

P = O

IHa

N -

J3

IHb

CH-X

- N

45

Carry CH-Y, where X and Y are the same or different Finally, here is also the effect of 3 moles of ethyleneimine on 1 mole of hexahydro-1,3,5-triacrylol-S-triazine (N, N ', N "-triacryloyl-trimethylene triamine), the preparation of which is described in the reports of German Chemical Society, Vol. 81 (1948), pp. 527 to 531, and in the Journal of the American Chemical Society, 70: 3079-3081 (1948), available compound of the formula

CO-CH ₂ -CH ₂ -N

CH ₂

CH ₂

Man

H ₂ C

H ₂ C

H ₂ C

CH ₂ CH ₂

N-CH ₂ -CH ₂ OC-N N-CO

\ _c / CH ₂ -CH ₂ -N

_c H ₂

CH ₂

specially mentioned.

Uncolored polyfunctional compounds which are capable of forming at least three ethyleneimine groups, preferably bonded via carbon or to phosphorus and optionally substituted by aliphatic radicals, during the dyeing and / or printing process include, for example, those compounds which contain at least three Cl · CH ₂ · CH ₂ · NH · SO ₂ groups.

The fixation of the dyes on the material to be dyed is already possible at ordinary temperature, ie at approximately 15 to 30 ^° C., according to the new process.

However, it is expedient to fix the dyes in the usual way, e.g. B. by steaming or by dry heating, at temperatures between 30 and 200 ⁰ C, preferably between 40 and 150 ⁰ C, provided that the material to be dyed and / or printed allows the use of these temperatures. The duration of the fixing process can vary within wide limits, since it depends on the nature of the dyes used, the uncolored polyfunctional compounds, the strongly alkaline agents and the material to be dyed, as well as the fixing temperature; however, it can easily be determined by experiment. The dyes are advantageously fixed on cellulose textile material by steaming or by dry heating at 70 to 150 ^° C. In this temperature range, the dyes are generally fixed within about 5 to 10 minutes.

You can carry out the method according to the invention by the to be colored and / or Goods to be printed with the strongly alkaline agents, the dyes and the uncolored polyfunctional ones Connections of the type identified above one after the other and in any order treated. Preferably, however, the material to be dyed is treated with dye baths or printing pastes which at the same time the strongly alkaline agents, the dyes and the uncolored polyfunctional ones Contain compounds of the type identified above. The material treated in this way is then in Usually spooled, soaped if necessary and finished. It can be of interest to Dyestuff preparations that contain, in addition to the dyes, the uncolored polyfunctional compounds of the type identified above, optionally together with dispersants and / or Contain dyeing or printing auxiliaries.

The uncolored polyfunctional compounds are expediently used together with dispersants used in finely divided form or as solutions in water-miscible solvents. as Water-miscible solvents are primarily used for dialkylcarboxamides, such as dimethylformamide or dimethylacetamide, lactams, such as N-methyl-2-pyrrolidone, Ethers, such as glycol ether or tetrahydrofuran, but also alcohols, such as methanol, Ethanol or isopropanol, ketones such as acetone, and / or organic acids such as formic acid or Acetic acid.

The dye baths and printing pastes of the type used in accordance with the invention can also be strongly alkaline agents, dyes and uncolored polyfunctional compounds are the usual dyeing auxiliaries or printing auxiliaries, provided that these funds do not match those required for the process Starting materials react in an undesirable manner. Such dyeing auxiliaries and printing auxiliaries are, for example, surface-active compounds, such as alkyl sulfonates, or compounds that prevent the migration of dyes, such as sodium acetate, or agents that increase solubility and improve the fixation of the dyes, such as urea, or thickeners, e.g. B. Oil-in-water emulsions, Tragacanth thickening, alginates or methyl cellulose.

As a rule, the dye baths and printing pastes are impregnated onto the goods to be treated applied by means of a padder or by printing. However, it is possible to use the new procedure also with the help of other common dyeing machines and devices, such as jiggers, tubs, Reel vat or dyeing machine. In the case of textile goods made of cellulose, it is also possible at the same time with the new dyeing and printing process, a so-called high-level refinement of the goods, e.g. Legs Anti-crease finishing.

The new process for dyeing or printing textiles is generally used per 100 parts one or more reactive reactants, preferably bound via nitrogen, oxygen or sulfur Hydrogen atom-containing dye approximately 10 to 200 parts of a strongly alkaline acting agent and about 20 to 400 parts of an uncolored polyfunctional compound, the at least three preferably bonded via carbon or to phosphorus and optionally through carries aliphatic radicals substituted Äthylenimineruppen or which is capable of two or more such Form groups during the dyeing and / or printing process.

The dyeings and prints obtainable according to the invention are generally distinguished excellent wet fastness properties. If you start from water-soluble dyes, it is recommended it is advisable to use dyes that have only a low affinity for the material to be dyed, because they do so the washing out of any unfixed dye components is facilitated. With water-insoluble The new process produces dyes and prints of remarkable dyes good rub and solvent fastness.

A major advantage of the method according to the invention over the known dyeing and printing processes with so-called reactive dyes consists in the fact that dyes are used for the new process without so-called "reactive" groups can use, in contrast to the known Reactive dyes can be stored for practically unlimited periods.

The parts and percentages mentioned in the examples are units of weight, unless stated otherwise. The parts of the volume relate to the parts by weight as under normal conditions measured liters to the kilogram.

example 1

A solution of 20 parts of the dye of the formula H ₃ C -CO-HN OH

O • CH ₂ • CH - CHo - N

CHo • CH ₂ • OH

CHo

OH

SO ₃ H

(obtainable by coupling diazotized 4-aminophenyl - [2 - hydroxy - 3 - (Ν, Ν - bis - 2 - hydroxyethyl) aminopropyl] ether with l-hydroxy-8-acetylaminonaphthalene-3,5-disulfonic acid) and 20 parts of potassium bicarbonate in 1,000 parts of water is mixed with 10 parts Triäthylenmelamin of formula Ha with gentle heating to about 50 ⁰ C. With the clear solution cotton fabric or rayon fabric is padded, dried and then steamed about 5 to 8 minutes at 100 ⁰ C. The goods are then rinsed and soaped as usual. Only a small amount of dye is washed out in the process. A bluish red dyeing with very good wet fastness properties is obtained.

Used instead of 10 parts of triethylene melamine 20 parts of triethylene melamine give even deeper colorations, which are also very good Wet fastness properties.

Use about 50 to 400 parts of triethylene melamine instead of 20 parts of triethylene melamine and if the rest of the procedure is as stated in the first paragraph, then in the case of tissue, one obtains from Cotton or rayon improves the wet and dry wrinkle angle.

Example 2

A mixture of 20 parts of the sodium salt of the dye of the formula IV described in Example 1, 100 parts of urea and 30 parts of sodium bicarbonate is mixed with a mixture of 430 parts by volume of water, in which 20 parts of triethylene melamine of the formula Ha have been dissolved, and 400 parts of sodium alginate thickener (the 40 parts of dry matter contains in 1000 parts). Cotton fabric is printed with the printing paste obtained in this way, dried and then ^{steamed at 100 °} C. for about 5 to 8 minutes. The printed material is then rinsed and soaped as usual. Bluish-tinged red prints with very good wet fastness properties are obtained.

Example 3

20 parts of a copper phthalocyanine dye obtainable by reacting copper phthalocyanine tetrasulfonic acid chloride with monoacetylethylenediamine and subsequent cleavage of the acetyl radicals, which contains about two to three HOgS groups and about two to one HgN · CHz · CH2 · NH ■ SOo groups, are divided into 1000 parts of an aqueous space Dissolved mixture containing 20 parts of sodium carbonate, 150 parts of a 10% solution of the compound of the formula Hb obtainable by reacting 1 mole of hexahydro-1,3,5-triacryloyl-S-triazine with 3 moles of ethyleneimine in dimethylformamide and 200 parts of urea . With this solution, cotton is impregnated, dried and then heat-set for 5 minutes at 150 ⁰ C (ie, dry heated at 150 ⁰ C). After the usual aftertreatment, a deep turquoise-blue dyeing with very good wet fastness properties is obtained.

Example 4

A solution of 20 parts of the dye given in Example 3 in 1000 parts by volume of water is mixed with 10 parts by volume of aqueous sodium hydroxide solution (38 ⁰ Be) and 20 parts of tris (l-aziridinyl) phosphine oxide of the formula HIa. This mixture is applied to cellulose tissue using a padder. Then, the fabric is dried and then steamed at 100 ⁰ C. After the usual finishing of the goods by rinsing and soaping, in which only a very small amount of dye is lost by washing out, a turquoise-blue dyeing with excellent wet fastness properties is obtained.

Example 5

A cotton fabric dyed in the usual way with the direct dye: o Cotonerol V extra (Color Index ·, 2nd edition, 1956, vol. 3, p. 3306, CI No. 35430) on a reel skid or on a jig 2% cotton fabric is mixed with a solution which contains 20 parts of sodium carbonate and 20 parts of tri ethylene melamine of the formula Ha in 1000 parts by volume, padded. The material is then dried and then steamed at 100 ° C. for about 5 to 8 minutes. The deep gray dyeing obtained in this way surpasses a dyeing carried out only as usual for direct dyes ία for comparison by better wet fastness properties.

Example 6

A solution of 20 parts of the copper phthalocyanine dye available as described in the third paragraph in 1000 parts by volume of water is mixed with 10 parts by volume of aqueous sodium hydroxide solution (38 ^: Be) and 150 parts of a 10% solution of the triacryloyl- s-tri-

azine mixed with 3 mol of ethyleneimine available compound of formula Hb in dimethylformamide. With this mixture cotton fabric is padded, steamed for 5 minutes at 100 ⁰ C, rinsed and soaped off thereafter. A very deep turquoise-blue dyeing with excellent wet fastness properties is obtained.

One prepared with the same dye in the usual way for reactive dyes for comparison turquoise-blue coloring is considerably weaker in color than the coloring obtained in accordance with paragraph 1.

The copper phthalocyanine dye used above can be prepared as follows: To an aqueous paste of 250 parts of ice, 250 parts of water and 50 parts of copper phthalocyanine-4,4 ', 4 ", 4 "'- tetrasulfonic acid chloride stirs a solution of 30 parts of the hydrochloride of 1-amino-4-chlorobutyn- (2) in 150 parts of water and the mixture is made by adding 10% aqueous Sodium carbonate solution has a ρκ value of about 7. The mixture is stirred for several hours Room temperature and gives if the pH value does not change even without adding sodium carbonate solution changed more, so much dilute hydrochloric acid that a pH value of 2 to 3 is reached, filtered the deposited dye and dried it under reduced pressure at low temperature.

Instead of the dye identified above, the dyeing process explained in the first paragraph can be used also Diazomarineblau R (Color Index,

6 .. 2nd edition, 1956, vol. 3, p. 3301, C.I. No. 35080), Sirius light red violet RL (Color Index, 2nd edition. 1956, Vol. 3, p. 3203, C.I. No. 25410) and by the reaction of copper phthalocyanine trisulfonic acid chloride A dye obtainable with ammonia, which has one HC ^ S group and two HaN · SCV groups use as dyes.

Other dyes that are suitable for the dyeing process specified in the first paragraph,

can by uniting diazotized! 1-aminobenzene-2-sulfonic acid (ß-aminoethyl) amide, of diazotized l-aminobenzene-4-sulfonic acid amide, of diazotized 1-aminobenzene-4-sulfonic acid - (ß- hydroxyethyl) amide or of diazotized 1-aminobenzene 4-sulfonic acid bis (/ 3-hydroxyethyl) amide can be obtained with the following couplable compounds:

10

Example 8

8 parts of the dye of the formula obtained by the process of German patent 742,939

H ₃ C

H ₂ N

Coupling connection hue l- (2-chloro-5-sulfophenyl) -3-methyl-
pyrazolone- (5) yellow l-hydroxynaphthalene-S ^ -disulfone-
acid Red 1-hydroxynaphthalene-4-sulfonic acid Red 1-hydroxynaphthalene-5-sulfonic acid Red 1 -Benzoylamino-8-hydroxy-
naphthalene-4,6-disulfonic acid Bluish red 1 -Benzoylamino-8-hydroxy-
naphthalene-3,6-disulfonic acid Bluish red

H ₃ CC

C-CH ₃

SO ₂ NH ₂

CH ₃

These monoazo dyes give colorations in the table next to the coupling components specified tones.

are undNaphthalin-sulfonic acid 2-along with 12 parts of the condensation product of formaldehyde and 10 parts Triäthylenmelamin of the formula Ha in 1000 parts of water dissolved with gentle heating to about 50 ⁰ C. 8 parts of 50% strength potassium hydroxide solution are then added to the mixture. This solution is applied to cotton using a padder. The material to be dyed is then dried, ^{steamed for 8 minutes at 100 °} C. and rinsed and soaped as usual. Red dyeings with very good wet fastness properties are obtained.

. , Example 9

Example 7

20 parts of the under the name C. I. Direct

20 parts of a dye preparation containing 10 parts of Violet 48 (Color Index, 2nd edition, 1956, Vol. 3, of the _{disazo dyes known by the method of German patent 35} p. 3249, CI No. 29125),

742,939 available dye of the formula

H ₂ NO ₂ S

H ₃ CC

C-CH ₃

NO ₂

contains, are stirred into 1000 parts of water and mixed with 15 parts Aziridinylphosphinoxyd of formula IIIa under heating at 40 to 50 ⁰ C. 20 parts of potassium carbonate are then added to the solution, which has cooled to room temperature. Cotton fabric is impregnated with this dye bath using a padder. The material to be dyed is then dried, ^{steamed for 5 to 8 minutes at 100 °} C. and then finished as usual. A yellow, very good wetfast dyeing is obtained.

Instead of the cobalt complex dye indicated above, 20 parts of the corresponding dye are used Chromium complex dye, orange dyeings are obtained which also have very good wet fastness properties.

15 parts of the compound of the formula Hb obtainable by reacting 1 mole of hexahydro-1,3,5-triacryloyl-s-triazine with 3 moles of ethyleneimine and 5 parts of the sodium salt of a copolymer of molar amounts of styrene and maleic acid are converted into 1000 parts with gentle heating Dissolved in water. This solution is mixed with 20 parts of trisodium phosphate and then applied to cotton fabric. After intermediate drying, the material to be dyed is ^{steamed for 5 minutes at 100 °} C. and finished as usual. Violet dyeings with very good wet fastness properties are obtained.

If 30 parts of disodium phosphate are used

Instead of 20 parts of trisodium phosphate, similarly good colorations are obtained.

Example 10

20 parts of the under the name AnthralanblauFR (Color Index, 2nd edition, 1956, Vol. 3,

S. 3505, CI No. 62150) known anthraquinone dye and 10 parts of triethylene melamine of the formula Ha are dissolved together in 1000 parts of water and mixed with 20 parts of trisodium phosphate. Cotton fabric is impregnated with this dye bath. The material to be dyed is then dried, ^{steamed for 8 minutes at 100 °} C. and then rinsed and soaped as usual. A blue dyeing with very good wet fastness properties is obtained.

Example 11

Instead of the dyes or dye preparations given in Examples 1, 2, 3, 4, 6, 7, 8, 9 and 10, 20 parts each are used

309 770/373

12th

the dyes identified in Tables I and II and proceed as in the rest of the mentioned examples, so you get wet-fast on fabrics made of cotton or rayon Dyeings in the shades given in Tables I and II.

Table I.

Dye Color Index, 2nd Edition, 1956,

Vol. 3, page number

Color Index,
Vol. 3,
serial number hue 62510 Gray 15715 Gray 62500 Blue-gray 11210 Red 17770 orange 14006 yellow 16265 Bordo 19065 yellow 17065 Bordo 17060 Red-violet 17055 blue 45186 violet 44510 blue

Alizarmuranol BB -

Silky gray BB

Cellitone blue-green B Cellitone red GG ...

Supraminorange R

Palatine light yellow 3 GN. Palatine eight bordo BN .. Palatine eight yellow 5 GN.

Anthralan bordo B

Supraminbordo B

Supramine blue R

Fast Acid Violet B

Wool blue FBL ....

3506 3076 3505 3017 3100 3051 3085 3115 3093 3093 3092 3385 3379

Table II

Serial
No.

dye

hue

ClH ₂ C

CO-NH

(obtainable according to the procedure of Belgian patent 594 263)

N = N -Τ V-SO ₂ NH ₂

(obtainable according to the procedure of the German patent 742 939)

yellow

violet

13th

continuation

14th

Serial
No.

dye

hue

= N -YN- SO ₂ NH ₂
Λ /

H ₂ N · O ₂ S

(obtainable according to the procedure of the German patent 742 939)

OH

ClH ₂ C

CO · NH

V-N = N

HO ₃ S

(obtainable according to the procedure of Belgian patent 594 263) Γ

NO

(obtainable according to the procedure of the German patent 1 040 720)

H ₂ N

NH ₂

NH ₂

SO ₃ H

(obtainable according to the procedure of Belgian patent 591 121)

[Copper phthalocyanine]

-SO ₂ -NH-N

SO ₂

(obtainable from l-amino-l-aza-4-thiacyclohexane-4,4-dioxide by the method of

French patent 930 447)

O NH ₂

SO ₃ H

OCH ₃

H ₃ CO

(obtainable by reacting l-amino-4-bromoanthraquinone-2-sulfonic acid with l-amino-2,5-dimethoxyaniline)

Brown

Red

green

violet

Turquoise blue

blue

15th

continuation

16

dye

hue

H ₂ NO ₂ S

Blue-gray

(obtainable by coupling diazotized 1 _: hydroxy-2-amino-5-nitrobenzene with 1-hydroxynaphthalene-o-sulfonic acid amide and converting the monoazo dye

in the 1: 1 chromium complex)

Haha

C - C

SO ₂ - NH • CH ₂ -CH ₂ -N SO ₂

C - C

I.

H ₂ H ₂

[Copper phthalocyanine] -

(available from! - (ß-AminoäthylH-aza- ^ thiacyclohexane-M-dioxide according to the Procedure of French patent 930 447)

[Nickel phthalocyanine] - SO ₂ - N - ^

CH ₃ N = C-CH ₃

(obtainable according to the procedure of Belgian patent 551 700)

[Copper phthalocyanine] - (SO ₂ · NH · CH ₂ · CH ₂ OH) ₄ (obtainable according to the method of German patent 696 591)

[Copper phthalocyanine] -

CH ₃

SO ₂ -N

CH ₂ ■ CH ₂ OH, (obtainable according to the process of German patent 696 591)

[Copper phthalocyanine] -

CH ₂ • CH ₂ OH

SO ₂ -N

CH ₂ -CH ₂ OH,

(obtainable according to the procedure of the German patent 696 591)

Turquoise blue

Blue green

blue

blue

blue

17th

continuation

18th

Serial No.

dye

hue

[Copper phthalocyanine] -

SO ₃ H

OH

SO ₂ · NH

-N
N

CH ₃

C ^ 3

N = N - ^ - X / N =

^ V-N> - Cl

SO ₃ H ₀ Cl
(obtainable according to the process of German patent application B 57649 IVb / 22a)

green

NH

: N-

Q NH ₂

SO ₃ H

SO ₃ H

0 NH ^ V-NH

NH-NH ₂
(obtainable according to the procedure of the German patent application B 56640 IVb / 22b)

blue

H ₂ N OH

HO ₃ S

HOH ₂ CN N-CH ₂ OH

_{N == N} _ / ^ _ c c- ^ A

SO ₃ H

HOH ₂ CN N-CH ₂ OH

violet

il ο

(obtainable according to the process of the German patent application B 53565 IVb / 22a)

HO ₃ S

/ XN Cl

= C-CH ₃

OH ^ CH CH

1 I.

HO-H ₂ CN N-CH ₂ OH

/ ^c \

-N N-CH ₂ OH

yellow

Il ο

(obtainable according to the process of the German patent application B 53565 IVb / 22a)

309 770/373

19th

continuation

20th

Serial No.

dye

hue

OCHN OH

HO ₃ S

N = N- / V- N N -CH ₂ OH

SO ₃ H Il JII

Red

CH

HO-H ₂ CN

CH

N - CH ₂ OH

(obtainable according to the process of the German patent application B 53565 IVb / 22a)

OH

= N-Ii

N-CH ₂ OH

SO ₃ H

CH CH

HO-H ₂ CN N -CH ₂ OH

O NH

(obtainable according to the process of German patent application B 53565 IVb / 22a)

O NH ₂

N-CH ₂ OH

CH CH

I I

HO-H ₂ CN N -CH ₂ OH

Il ο

(obtainable according to the process of German patent application B 53565 IVb / 22a)

N (CH ₂ O-CHa) ₂

N-L

^ VVZZ-SO ₃ H ^N < ^CH - ° -
(obtainable according to the process of the German patent application B 54864 IVb / 22a)

(SO ₂ - NHiO ₂

Γ Y

j cobalt phthalocyanine

(SO ₃ H) ₂
(obtainable according to the process of German patent specification 696 591)

Red

blue

Red

blue

21

continuation

22nd

dye

hue

P ^ '- Diaza copper phthalocyanine] - (SO ₂ • NH • C ₂ H ₄ • OH) ₂
(obtainable according to the process of German patent specification 696 591)

Γ Y

Diphenyl copper phthalocyanine 1

(SO ₂ · NH ₂ I ₂

SO ₃ H
(obtainable according to the process of German patent specification 696 591)

(SO ₂ • NH • C ₂ H ₄ • OH) ₃
Monophenyl copper phthalocyanine 1

SO ₃ H
(obtainable according to the process of German patent specification 696 591)

(SO ₂ · HN ₂ ) S
I tetraphenyl copper phthalocyanine i

(SO ₃ H) ₃
(obtainable according to the process of German patent specification 696 591)

VSO ₂ • NH • CH ₂ • CH - CH ₃ J ₂
Tetraphenyl copper phthalocyanine ί

(SO ₃ H) ₂
(obtainable according to the process of German patent specification 696 591)

NH • CH ₂ • CH - CH ₂ • OHi ₂
r υ

Copper phthalocyanine I.

SO ₃ H
(obtainable according to the process of German patent specification 696 591)

(SO ₂ · NH · CH ₂ · CH ₂ · OH) ₂
Copper phthalocyanine I.

SO ₃ H
(obtainable according to the process of German patent specification 696 591)

NH ₂

j copper phthalocyanine

SO ₂ NH

SO ₃ H

/ 2

SO ₃ H

(obtainable according to the method of French patent specification 1 194 460)

SO ₃ H

SO ₂ · NH

Nickel phthalocyanine 1

SO ₃ H

/ 3

(obtainable according to the method of French patent specification 1 194 460)

Reddish blue

Blue green

Green Blue

green

green

blue

blue

Turquoise blue

Turquoise blue

Continued 24

Serial
No.

Dye hue

OH

H ₂ N - SO ₂

SO ₃ H: 2-chromium complex

: 2-cobalt complex

: 2-chromium complex

H ₂ N-SO ₂

HOOC

OCH ₃ HO

H ₂ N-SO ₂ - ^) ^ N = N- <II Y = / ^ -N

CH ₃ CH ₃

HO ₃ S OH HO

CH ₃

: 1-chromium complex

H ₂ N-SO ₂

: 2-chromium complex

SO ₂ - NH ₂ : 2 cobalt complex
: 2-chromium complex

: 2-chromium complex

H ₂ N-SO ₂

Claims (1)

PATENT CLAIM: SO ₃ H SO ₃ H reddish orange Yellow-brown Scarlet fever Red Red Bordo
violet Blue violet 55 Process for dyeing or printing textile goods, characterized in that the material is mixed in the presence of strongly alkaline agents with dyes which have one or more reactive hydrogen atoms, preferably bonded via nitrogen, oxygen or sulfur, or which are capable of using one or more such hydrogen atoms during of the dyeing or printing process, and with uncolored polyfunctional compounds which carry at least three ethyleneimine groups, preferably bonded via carbon or phosphorus and optionally substituted by aliphatic radicals, or which are capable of three or more such groups during the dyeing or printing process to form, if necessary at elevated temperature, treated. Considered publications:
German Auslegeschriften No. 1058 016,1059 398, 059 399, 1 091 980. When the registration was announced, 10 staining tables were laid out. © 309 770/373 12.63