DE1254575B - Process for dyeing and / or printing textile goods - Google Patents

Description

B (UNDESJtEFUBLIK 'GERMANY

Int. CL:

D 06 ρ ^ -

GERMAN

PATENT OFFICE

EDITORIAL

German class: 8m- 1/01

Number: 1 254 575

File number: B 66298IV c / 8 m

Avoidance day: March 10, 1962

Opening day: November 23, 1967

From the Belgian patent 570 896 it is known that one ·, containing hydroxyl groups Material, for example textiles made of cellulose, can be colored if you use dyes that contain reactive amino groups, and treated with S a polyepoxide. As polyepoxides only diepoxides, in particular butadiene diepoxides, are mentioned for this process.

With this dyeing process, relatively large amounts of the above are used for the amount of dye used reactive additives are required, only an unsatisfactory degree of fixation is achieved, i.e. h., 'man According to this process, it receives colorations in which the difference in color strength is between a non-soapy one and a soaped sample is right, substantial.

In addition, the method of the Belgian patent 570 896 is because of the strong irritant effect, which the butadiene diepoxide exerts on the eyes is severely restricted in its applicability.

It has now been found that textile goods, such as fibers, threads, flakes, woven and knitted fabrics, Can be dyed and / or printed on washfast, if you prefer to use the item in the presence alkaline agents with dyes that contain at least one preferably above nitrogen, oxygen or sulfur-bonded, reactive hydrogen atom, and with heterocyclic Compounds of the general formula I

Il

C-CH ₂ -CH ₂ -OX

Υ —CN NC-CH ₂ -CH ₂ -OX 11 V Il ο ο

in which X an organic radical which contains an epoxy group or a 4 »group which can be converted into an epoxy group, and Y an X - O - CH ₂ - CH ₂ radical or the CH ₂ = CH radical or one which can be converted into this group The remainder means treated, if appropriate at an elevated temperature.

The new process is preferably used for dyeing and / or printing hydroxyl groups containing material; this is textile material made from native and / or regenerated cellulose or from polyvinyl alcohol. However, it is also suitable for use on textiles made of cellulose ester, polyacrylonitrile or Copolymers of acrylonitrile with other vinyl compounds or on linear textile material Method of dyeing

and / or printing of textile goods

Register

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Walter Grosch, Mannheim;

Dr. Gerhart Lützel,

Dr. Werner Rohland, Ludwigshafen / Rhine

Polyesters, ζ. B. from polyethylene glycol terephthalate or based on terephthalic acid and p-dimethylolcyclohexane, It is also suitable for use on textiles made from natural and / or synthetic substances containing carboxamide groups, such as wool, natural silk or linear Polyamides, useful.

Not only azo dyes such as 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 benzothiazole series. According to the invention, mixtures of two can also be used or more dyes run out.

The dyes of the type identified above carry one or more reactive hydrogen atoms, preferably bonded via nitrogen, oxygen and / or sulfur, e.g. B. in the form of primary or secondary amino groups, heterocyclically bonded - NH - 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, carboxylic acid amide groups, carboxylic acid alkyl amide groups, and those with low molecular weight alkylhydryl groups, such as those with low molecular weight alkyl radicals. Of particular technical interest are those dyes which contain one or more reactive hydrogen atoms in the form of HO-alkylene groups. H ₂ N-alkylene groups and / or sulfonic acid

709 68.9 / 442

I 254

alkylamidgruppcn example, dyes with H2N contain preferably having low molecular weight Alkylcngruppcn or alkyl groups, - SCvGruppen, HO · CH ₂ · CH ^ groups, H ₂ N ■ CH ₂ · CH ₂ -Gruppcn, HO · CH ₂ · CH ₂ · NH ■ SO ₂ groups and / or H3C ■ NH ■ SOa 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 -] - SO2 ■ N

CH ₃ CH ₂

V = C-CHi

that according to the procedure of the Belgian patent 551 700 is available. Dyes that are capable of one or more, preferably via nitrogen, Oxygen or sulfur bound, • reactive hydrogen atoms during the dyeing and or or to form printing processes are, for example, dyes with methylene ether groups or Methyl ester groups. These groups convert to methylol groups during the process.

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 to dyes that are free from water-solubilizing groups, as well as water-soluble dyes. The latter dyes usually carry a or several sulfonic acid and / or carboxyl groups as water-solubilizing groups. Advantageous you can use dyes that contain one or more sulfonic acid alkylamide groups, such as sulfonic acid (/? - hydroxyethyl) amide groups or sulfonic acid methylamide groups, as water-solubilizing groups, use for the method according to the invention. The dyes used can be substantive be, but they can also be so-called reactive dyes, which are capable of being colored with the or to enter into a chemical bond with the goods to be printed. With nouns, dyes the new process improves the fastness properties of the dyeings and prints, and in the case of reactive dyes, the new process makes the proportion of on the dyed material washable Fixed dyes increased and thus the abundance of reactive dyes significantly improved.

Alkaline agents which do not contain any free amino groups are, for example, inorganic ones Compounds such as alkali hydroxide or alkali salts of weak acids such as sodium carbonate, Sodium hydrogen carbonate, sodium acetate, disodium phosphate or trisodium phosphate; but it is organic compounds such as pyridine or trimethylbenzylammonium hydroxide are also mentioned.

Examples of radicals which can be converted into an epoxy group are those radicals, the halohydrin groups the general formula

Groups which can be converted into the CH ₂ = CH - CO radical are, for example, / 9-chloropropionyl groups or quaternary groups of the formula

-CO-CH ₂ -CH ₂ -N-

Hal®

- C - C -
HO shark

65

contain.

cited.

Compounds of general formula I can for example after in the Belgian patent 595 149 described process by adding suitable alcohols to the double bonds of hexahydro-1,3,5-triacryloyl-s-triazine can be obtained.

Such suitable alcohols are, for example, glycerol-a-monochlorohydrin, glycerol-ß-monochlorohydrin, a-methylglycerol-a-monochlorohydrin, ß- methylglycerol-a-monochlorohydrin and 2,3-epoxypropanol.

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. Advantageously the dyes are fixed on the textile material made of cellulose by steaming or by dry heating at 70 to 150 ⁰ C. In this temperature range, the fixation of the dyes is usually complete 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 alkaline agents, the dyes and the reactive additives of the type identified above are dealt with one after the other and in any order. Preferably however, if the material to be dyed is treated with dyebaths or printing pastes, which are also alkaline effective agents, the dyes and the reactive additives of the type identified above contain, these reactive additives optionally also in the dye liquor or the printing paste can be prepared. The material treated in this way is then rinsed in the usual way, if necessary soaped and finished. It can be of interest to start from dye preparations, In addition to the dyes, the reactive additives of the type identified above, if appropriate together with dispersants and / or dyeing or printing auxiliaries.

The reactive additives of the type identified above are expediently in aqueous solution

used. But they can also be used together with dispersants in finely divided form or as Solutions in water-miscible solvents can be used. As a water-miscible solvent dialkylcarboxamides such as dimethylformamide or dimethylacetamide, lactams, such as N-methyl-2-pyrrolidone, ether, 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, into consideration.

The dye baths and printing pastes of the type according to the invention can, in addition to alkaline agents, Dyes and reactive additives of the type described are the usual dyeing auxiliaries or printing auxiliaries, provided these resources do not match those required for the process Starting materials react in an undesirable manner. Such dyeing auxiliaries and / or 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 dyes, such as urea or thickeners, ζ. Β. 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. It is also the case with textile goods made of cellulose possible, at the same time as the new dyeing and / or printing process, a so-called high-end finishing Good, e.g. B. a crease-proof finish.

For the new process for dyeing and / or printing textiles, one uses im generally per 100 parts of dye, about 10 to 200 parts of an alkaline agent and about 20 to 400 parts of a reactive additive of the type indicated above.

According to the process of this invention, using a relatively small amount of the reactive additive of the type described in the dye liquor strong and washfast dyeings and achieves dye yields that cannot be achieved by the process of Belgian patent 570 896 can be achieved although relatively large amounts of the reactive additive are used according to this process will.

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

In a mixture consisting of 17 parts of a commercially available mixture of α- and / 3-glycerol monochlorohydrin, 15 parts of benzene and 13 parts of hexahydro-lSS-triacryloyl-s-triazine, 6.7 parts of finely ground sodium hydroxide in small amounts are added with stirring at room temperature Proportions added. The mixture is then stirred for 1 hour at a temperature of about 40 ^° C. and is expediently separated from residues by filtration.

The benzene is removed from the solution by distillation under reduced pressure. Of the The residue is mixed with 250 parts of water and 350 parts of an alginate thickener that is 1000 parts Contains 40 parts dry matter, mixed.

A mixture is poured into the thickened portion prepared in this way, while stirring of 30 parts of a commercially available sample of the method of the German patent 1 154 211 prepared dye of the formula

H ₂ NO ₂ S

H3CO

OCH3

SO ₂ NH ₂

100 parts of urea and 200 parts of warm water was obtained.

The printing paste produced in this way is used to print cotton fabric as usual. The printed material is dried and then steamed for about 4 to 8 minutes at 102 ⁰ C, or about 3 to 5 minutes at about 130 ⁰ C. After the usual washing process, a strong gray print with excellent fastness properties is obtained.

Similar gray prints are obtained if the printed fabric is not steamed for 4 to 8 minutes, but instead is heated to a dry temperature of about 140 to 160 ° C for 5 to 10 minutes for heat setting or if it is heated to a temperature of about 190 for about 30 seconds to 3 minutes ⁰ C, but otherwise proceed as described.

Example 2

If instead of 17 parts of glycerol monochlorohydrin, 12 parts of this compound are used and instead of 6.7 parts of ground sodium hydroxide 5 parts of this substance and proceed in otherwise, as described in Example 1, a similar gray print with excellent results is obtained Authenticity properties.

Example 3

20 parts of the under the name Acid Violet 9 (Color Index, 2nd edition, 1956, Vol. 3, p. 3385, C.I. No. 45 190) known dye of the formula

CH ₃

COONa

are used with 20 parts of the Belgian

7, 8th

See Patent 59-5149. Obtains a compound of the formula

O = C-CH ₂ -CH ₂ -O-CH ₂ -CH-CH ₂

H ₂ C-HC-H ₂ COH ₂ CH ₂ CCN NC-CH ₂ -CH ₂ -O-CH ₂ -CH-CH ₂

dissolved in so much water that 1000 parts by volume of solution are obtained. This solution will be equal in three Parts shared. With aqueous soda solution or with dilute hydrochloric acid, the pH value of these three Solutions adjusted to different values, namely to pH 11, pH 7 and pH 5.

The dye liquors obtained in this way are used to make fabric made of cotton or rayon on a padder impregnated. The colored materials thus obtained are dried and then dried for 5 to 8 minutes muffled. Violet dyeings with good fastness properties are obtained, of which those in the subsequent washing process show only a low washout loss, which is the case with the alkaline and the neutral dye liquor.

Similarly violet dyeings are obtained when the dyed textile material in place of the 5- to 8minütigcn steaming 5 to 10 minutes to dry 140 to 150 ⁰ C is heated and is moved as described above in the other.

The textile material impregnated with a neutral dye liquor of the type described is then used with an aqueous solution of an alkaline agent, e.g. B. with a solution containing 20 g of sodium carbonate contains water in 1000 parts by volume, impregnated and then as described above treated further, a violet dyeing with good fastness properties is obtained.

Example 4

A mixture consisting of 25 parts of hexahydro-1,3,5-triacryloyl-s-triazine, 34 parts of glycerol monochlorohydrin and 50 parts of water are 14 parts within 45 minutes with stirring

to powdered sodium hydroxide added in small portions. The mixture is then stirred at a temperature of 35 to 40 ^{° C. for about 1 hour.}

The mixture obtained in this way is mixed with a solution

the 20 parts of the dye of formula

HOOC

N- Jl

CH3

CH ₃

SO ₃ H

10 parts of sodium carbonate, 100 parts of urea and Contains 397 parts of water, and with 350 parts of a neutral alginate thickening that increases to 1000 parts Contains 40 parts of dry matter, stirred to a paste.

The printing paste produced in this way is used to print white cotton fabric. The printed fabric is dried and ^{steamed at 102 °} C. for 5 to 8 minutes. After the usual work-up, a yellow print on a white background is obtained which has very good fastness properties.

If the yellow dye given in this example is used instead of the one in the following The dyestuffs given in the table and the procedure otherwise as described, prints are obtained with similar fastness properties in the specified nuances.

No. Diazo component Coupling component colour I.
2
3 2-aminonaphthalene-4,8-disulfonic acid
2-Hydroxy-l-aminobenzene-5-sulfonic acid
amide
2,5-dimethyl-1-amino-benzene 2-phenylindole-5-sulfonic acid
3-methylpyrazolone- (5) (1: 2-chromium-
complex)
3-methylpyrazolone- (5) (1: 2-cobalt-
complex) yellow
Red orange
Brown

Example 5

To a mixture consisting of 25 parts of hydroxahydro-1,3,5-triacryloyl-s-triazine, 34 parts of glycerol monochlorohydrin and 50 parts of water, 14 parts of powdered sodium hydroxide are added in small portions over a period of 45 minutes with stirring. The mixture is then stirred at a temperature of 35 to 40 ^{° C. for about 1 hour.} To the solution obtained, 20 parts of the dye described in more detail in Example 3, 10 parts of 32% sodium hydroxide solution, 50 parts of sodium sulfate and enough water are added to give 1000 parts by volume of liquor. Cotton fabric is impregnated with this dye liquor. The impregnated textile material is kept moist for several hours (preferably 12 to 24 hours) and then washed as usual. A violet dyeing with good fastness properties is obtained. ". ■ λ e-

^ Examples

If the dyes or dye preparations given in Examples 1, 2, 3, 4 and 5 are used instead 20 parts each of the dyes identified in Tables I and II and proceed otherwise, as explained in the examples mentioned, one obtains on fabrics made of cotton or Spun rayon wet fast dyeings in the shades given in Tables I and II. -

Table I.

10

Dye hame Color Index,

2nd edition, 1956,

3rd volume, page number

Color Index,

3rd volume, serial number

hue

AUzarimzranol BB Silky gray BB C. eltiton blue-green B Cellitonech red GG Supraminorange R Palatmecht yellow 3 GN Palatine right bordo BN Palatine light yellow 5 GN Anthralan bordo B Supraminbordo B Supramine blue R Fast Acid Violet B WoBechtbbu FBL Flavophosphines CI Basic Orange 21 CI Fluorescent Brightening Agent 1

Flavanones

CI Solvent Black 5 CI Acid Blade 2 Phenylene blue CI Direct Blue 107

Vixen

Methylene blue

3506 3076 3505 3017 3100 3051 3085 3115 3093 3093 3092 3385 3379 3397 3402 3341 3400 3420 3420 3407 3431 3355 3434

510

715 500 210 770 14006

265 065

065 17060 055 45186 510 46050

035 630 025 50415 50420

400 51 315 510 015

Table Π Gray

Gray

Blue-gray

Red

orange

yellow

Bordo

yellow

Bordo

Red-violet

blue

violet

blue

orange

orange

White

yellow

black

black

Bluish green

blue

violet

blue

dye hue

ClH ₂ C

CO NH

HO ₃ S (obtainable by the process of Belgian patent 594 263)

N = N - f \ - SO ₂ NH ₂

yellow

violet

(obtainable according to the method of the German patent 7.42 939)

799CMM42

11

ί 254 575

continuation

12th

dye

hue

H ₂ N · O ₂ S

SO ₂ NH ₂

C-CH ₃

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

OH

-ClH ₂ C

CO NH

(obtainable according to the procedure of Belgian patent S94 263)

NO

Fe

H ₃ CNO ₂ S (obtainable according to the process of German patent 1 040 720)

N-L N

NH ₂

H ₂ N- | j ' ^Nv jpNH ₂
NN

HN

SO ₃ H

/ ₂

Brown

Red

green

violet

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

[Copper phthalocyanine ^ 4-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)

Turquoise blue

O NH ₂

SO ₃ H

blue

OCH ₃

O NH

H ₃ CO

(obtainable by reacting l-amino-4-bromoanthraquinone-2-sulfonic acid with 1-amino-2,5-dimethoxyaniline)

13th

Serial No.

Continuation dye 14th

H ₂ NO ₂ S

NO ₂

(obtainable by coupling diazotized! l-hydroxy-2-amino-5-nitrobenzene with 2-Hydroxynaphthalene-6-sulfonic acid amide and conversion of the monoazo dye in the 1: l chromium complex)

H ₂ H ₂

[Copper Phthalocyanine H-SCfe - NH • CH ₂ • CH ₂ - N <^ SO ₂

^X C - Q ^/

I I

H ₂ H ₂

(obtainable from l - (/ 9-aminoethyl) -l-aza-4-thiacyclohexane-4,4-dioxide according to the method of French patent 930 447)

[Nickel phthalocyanine -

-SO ₂ -N

CH ₃ (obtainable according to the procedure of the Belgian patent SSl 700)

[Copper phthalocyanine ] ^ SO ₂ • NH • CH ₂ • CH ₂ OH) ₄

(obtainable according to the method of the German patent 6% 591)

[Copper phthalocyanine ^:

SO ₂ -N

^ CH ₃

CH ₂ OH

(obtainable according to the method of the German patent 6% 591)

, CH ₂ CH ₂ OH \

[Copper phthalocyanine -

SO ₂ -N

CH ₂ • CH ₂ OH J ₄

(obtainable according to the method of German patent 696 591) / OH

[Copper phthalocyanine J /

LSO ₂ NH

N N

"SO ₃ H

CH ₃

(obtainable according to the method of the German patent 1 130 096)

Cl

Cl

hue

Blue-gray

Turquoise blue

Blue green

blue

blue

blue

green

15th

continuation

16

Serial No.

dye

hue

O NH ₂

O NH

NH-NH ₂

H ₂ N OH

HO ₃ S

HOH ₂ CN N-CH ₂ OH

HOH ₂ C-N

SO ₃ H

\ r /

N-CH ₂ OH

(obtainable according to the method of the German patent 1 1S3 839) HO ₃ SO

N CH ₂ OH

(obtainable according to the procedure of the German patent 1 153 839)

O ^. * - OC · HN OH

HO ₃ S

N - CH ₂ OH

(obtainable according to the method of the German patent 1 133 839)

OH Il

YV N = Nj | S-N N-CH ₂ OH

^^ CH CH

I · I

SO ₃ H

HO H ₂ CN

N - CH ₂ OH

blue

violet

yellow

Red

Red

O (obtainable according to the procedure of the German patent 1 153 839)

17th

continuation

dye hue

O NH ₂

N - CH ₂ OH

(obtainable according to the procedure of the German patent 1 153 839)

N (CH ₂ · O · CHs) ₂

^ N-L HO NH <f N

N (CH ₂ O CHa) ₂ ^ SO ₃ H NH ₂ J ₂ (SO ₃ H) ₂ (obtainable by the process of German patent specification 696 591)

[Cobalt phthalocyanine

[3,3'-Diaza copper phthalocyanine-3— (SO ₂ · NH · C ₂ H ₄ · OH) ₂ (obtainable by the process of German Patent 696 591)

/ (SO ₂ · NHz) ₂ [Diphenyl copper phthalocyanine C

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

^ (SO ₂ · NH · C ₂ H ₄ · OH) ₃ [monophenyl copper phthalocyanine § ^ (obtainable according to the process of German patent specification 696 591)

.- (SO ₂ · NHa) ₃ [tetraphenyl copper phthalocyanine $ T

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

[Tetraphenyl copper phthalocyanine

OH

SO ₂ -NH- CH ₂ · CH - CH ₃ - (SO ₃ H) ₂ (obtainable by the process of German Patent 696 591) blue

Red

blue

Reddish blue

Teal green blue green

green

70 »689/442

continuation

Serial
No.

dye hue

[Copper phthalocyanine ■

OH

-SQ ₂ NH CH ₂ -CH-CH ₂ OH -SO ₃ H blue

(obtainable according to the process of the German patent specification 696 S91)

<(SO2 ■ NH - CH ₂ · CH ₂ · OH) ₂ SO ₃ H (obtainable according to the process of German patent specification 696 S91) blue

[Copper phthalocyanine

NH ₂

SO ₂ NH SO ₃ H

SO ₃ H

/ 2

Turquoise blue

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

SO ₃ H

[Nickel phthalocyanine} ^ ~>

-SO ₂ NH SO ₃ H

NH ₂

/ ₃

Turquoise blue

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

(SO ₂ - NH - CH ₂ - CH ₂ - NH ₂ J ₂

[Copper phthalocyanine

(obtainable by the process of German patent specification 1 198 471)

Turquoise blue

Claims (1)

Claim: Process for washfast dyeing and / or printing of textile goods, thereby characterized in that the material is preferably more alkaline in the presence Agents with dyes which contain at least one reactive hydrogen atom, preferably bonded via nitrogen, oxygen or sulfur, and with heterocyclic compounds of the general formula Il c CH ₂ -CH ₂ -OX Υ —CN NC-CH ₂ -CH ₂ -OX Il V Il ο ο in which X is an organic radical which contains an epoxy group or a group which can be converted into an epoxy group, and Y an X - O - CH ₂ - CH ₂ radical or the CH ₂ = CH radical or a group which can be converted into this group Remainder means treated, if appropriate at elevated temperature. Documents considered: French Patent No. 1 218 093. When the application was announced, two coloring tables with explanations were laid out. 709 689/442 11.67 O Bundesdruckerei Berlin