DE2112694A1 - Process for dyeing textile material containing amino or amide groups - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. F. Assmann ^ "* *" r »λ /

R-Koenigsbei ^ er - Dipl.Phys.R. Holzbauer Z II ä O 9 4

Dr. F. Zamsiein jun.

Patent attorneys

8 Munich 2, Bräuhausstraße 4 / III

1-6994 *

CIBA-GEIGY A. G., CH-4002 Basel / Switzerland

Process for dyeing amino or amide groups

Textile material

With regard to the stricter regulations for the protection of water against pollution in many places the dyeing of textile materials by customary methods due to the disadvantage that large amounts of water are consumed and contaminated. It is therefore already proposed been used to dye textile materials in dyebaths from organic solvents.

The present invention now addresses this problem. The invention thus provides a process for dyeing amino- or amidgruppenhaltigern textile material, which is characterized in that, in a homogeneous solution of one or more, in each case at least one free sulfonic acid group and at least one fiber-reactive group-containing dyes in a preferably at least 70 ⁰ G boiling chlorinated aliphatic hydrocarbon in a mixture with up to 50% of a hydrophilic solvent, preferably at the boiling point of the organic solvent mixture, colors.

Dyes which can be used according to the invention are those into consideration, which contain both at least one sulfonic acid group and at least one fiber-reactive group. The dyes can belong to a wide variety of dye classes, such as the classes of mono-, dis- and polyazo dyes, anthraquinone, Perinone, quinophthalone, oxazine, nitro, phthalo

108842/1823

cyanine, stilbene and methine dyes, including the styryl, azamethine, polymethine and azostyryl dyes.

The following fiber-reactive groups capable of reacting with the substrate with the formation of a covalent bond are to be mentioned: the chloromaleiny! Amino groups, the propiol grouping, mono- and dichlorocrotonylamino groups, bromine or chloroacry! Amino groups, acrylic! Amino groups, vinylsulfone groups and in particular the groups containing a labile substituent which can easily be split off when the pair of bonding electrons is carried along, for example aliphatically bonded sulfuric acid or thiosulfuric acid ester groups and aliphatically bonded sulfonyl or sulfonyloxy groups or halogen atoms, in particular an aliphatically bonded chlorine atom. These labile substituents are expediently in the α- or ß-position of an aliphatic radical which is bonded to the dye molecule via an aminocarbonyl or aminosulfonyl group an acetyl radical or in a- and ß- position of a propionyl radical. Examples of such radicals are, for example, chlorine or α, β-dichloro or dibromopropionylamino groups or α-chloroacetylamino groups. However, the halogen atoms which can be split off are preferably located in a heterocyclic radical containing preferably 2 to 3 ring heteroatoms, in particular ring nitrogen atoms, such as, for example, in a phthalein, pyridazine, pyridazone, quinoxaline, quinazoline, oxazole, thiazole, above all but in a pyrimidine or, in particular, triazine ring, for example in a grouping of the formula "

-NH-C ' ^X CZ -NH

N N or N. -. "

Halogen.

wherein Z is a hydrogen atom, an optionally substituted one

10984 2/182 3

Amino group, an etherified oxy or mercapto group or a Halogen atom or an alkyl, aryl or aralkyl group, A is halogen or alkylsulfonyl and E is hydrogen or halogen. The halogen atoms are fluorine and bromine, preferably but chlorine atoms. Of particular interest is the use of dyes which form the grouping of the formula

-NH-C CZ ₁

I Il J-

NN

halogen

contain, where Z-. a chlorine atom, an NH ^ group or the d

The radical of an aliphatic or aromatic amine or alcohol means, and also those fiber-reactive groups, those which can be split off Substituent a quaternary ammonium or in particular bonded to a carbon atom of a heterocyclic radical Represents hydrazinium group, i.e. a group of the formula

? 2

C '

-NH-C CN (CH,) _O NH _O

-Cl

+ N (CH ₃ ) ₂ NH

^cl ci

where Z «is a hydrogen atom, an optionally substituted one Means amino group or an etherified oxy or mercapto group.

The fiber-reactive dyes containing sulfo groups which are used according to the present invention can furthermore have the following fiber-reactive groups: 2-methylthio-4-fluoropyriinidine-5-carbonyl-, 2,4-bis- (phenylsulfonyl) -triazinyl-6-, 2- (3'-Carboxyphenyl) -sulfonyl-4-chlorotriazinyL-6-, 2- (3'-sulfophenyl) -sulfonyl-4-chlorotriazinyl-6-, 2,4-bis- (3 ¹ -carboxyphenyl-sulfonyl- 1 ') - triazinyl-6-, 2-carboxymethylsulfonyl-pyriniidyl-4-, 2-methyl-1-sulfonyl-6-methyl-1-pyrimidinyl-4-, 2-phenylsulfonyl-6-ethyl-pyrimidinyl-4-, 2 , e-bisraethylsulfonyl-pyrimidinyl-ö-, 2,6-bis-methylsulfonyl-

109842/1823

5-chloro-pyrimidinyl-4-, 2,4-bis-methylsulfonyl-pyrimidinyl-5-sulfonyl-, 2-methylsulfonyl-pyrimidinyl-4-, 2-phenylsulfonylpyrimidinyl-4-, Z-Trichloromethylsulfonyl-o-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-ynethylpyrimidinyl-4-, 2-methylsulfonyl-S-bromo-o-methyl-pyrimidinyl-A-, 2-methylsulfonyl-5-chloro-o-ethyl-pyrimidinyl ^ -, 2-methylsulfonyl-5-chloro-6-chloromethyl-pyrimidinyl-4-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl-, 2-methylsulfonyl-5-nitro-6-methylpyrimidinyl-4-, 2,5, o-Tris-methylsulfonyl-pyrimidinyl ^ -, 2-methylsulfonyl-5, 6-dimethyl-pyrimidinyl-4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-chloropyrimidinyl-4-, 2, o-Bis-methylsulfonyl-S-chloro-pyrimidinyl ^ -, 2-methylsulfonyl-6-carboxy-pyrimidinyl-4-, 2-methylsulfonyl-5-sulfo-pyriraidinyl-4-, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl-4-, 2-methylsulfonyl-5-carboxy-pyrimidinyl-4-, 2-methylsulfonyl-5-cyano-6-methoxy-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-pyrimidinyl-4-, 2-sulfoethylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-broin-pyriInIdinyl-4-, 2-phenylsulfonyl-5-chloro-pyrimidinyl-4-, 2-carboxymethylsulfonyl-5-chloro-6-ynethylpyrimidinyl-4-, 2-methylsulfonyl-6-chloro-pyrimdin-4- and -5-carbonyl-, 2,6-bis (methylsulfonyl) -pyrimidine-4- or -5-carbonyl-, 2-ethylsulfonyl-ö-chloro-pyrimidine-S-carbonyl-, 2,4-bis (methylsulfonyl) pyrimidine-5-sulfonyl-, 2-methylsulfonyl 4-chloro-6-methylpyrimidine-5-sulfonyl or carbonyl, 2,4-dichloro-5-fluoro-pyrimidin-6-yl-, 2-chlorobenzthia2ol-5- or -6-carbonyl- or -5- or -6-sulfonyl-, 2-arylsulfonyl- or 2-alkylsulfonylbenzthiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl, such as 2-methylsulfonyl- or 2-ethy1sulfonylbenzthiazole-5- or -6-sulfonyl- or -carbonyl-, 2-phenylsulfonyl-benzthiazole-5- or -6-sulfonyl- or -carbonyl- and the corresponding derivatives of 2-sulfonylbenzthiazole-5- or -6-carbonyl- or -sulfonyl-, those on the fused-on benzene ring Contain sulfo groups, such as 2-chlorobenzothiazole-5- or -6-carbonyl- or -sulfonyl-, 2-chlorobenzimidazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-1-methylbenzimidazole-5- or

109842/1823

-6-earbonyl- or -sulfonyl-, 2-chloro-4-methylthiazole- (l, 3) -5-earbonyl- or -4- or -5-sulfonyl radicals and the N-oxide des Chlorine or 4-nitroquinoline-5-carbonyl radicals. Also mentioned are the 2,2,3, S-tetrafluorocyclobutanecarbonyl-1- or -sulfonyl-1-, 2-fluoro-2-chloro-3,3-difluorocyclobutane-1-carbonyl- and β- (2,2,3,3-tetrafluoro-cyclobutyl-1) -acryloyl-, a- or ß-bromoacryloyl and α- or ß-alkyl or -arylsulfonylacryloyl residues.

According to the definition to be used according to the invention A large number of dyes are known. They can be produced by conventional methods, e.g. by Acylation of primary or secondary amino group-containing dyes of the classes mentioned above, in particular the Anthraquinone, phthalocyanine or azo series with acylating agents which have one or more reactive groups contain. Examples of such acylating agents are the anhydrides or chlorides of the aliphatic acylamino radicals listed above corresponding acids, e.g. acrylic acid, propiolic acid, chloromaleic acid, chloroacrylic acid, α, ß-dibromopropionic acid, ß-chloropropionic acid etc., but especially the heterocyclic ones Reactive radicals corresponding halides, called.

Those dyes which contain reactive heterocyclic groups with at least two heteroatoms are particularly preferred have, such as in particular halogen-s-triazinyl radicals, the phenoxy, alkoxy, alkoxyalkoxy and arylamino radicals carry heterocyclic radicals, the sulfonyl leaving groups carry, heterocyclic radicals that represent fluorine-containing heterocycles »such as, in particular, fluorine-containing pyrimidyl radicals, as well those dyes containing halogenated C 1, C, fatty acids as the reactive group exhibit.

As examples of such dyes according to the invention can be used, the following are listed:

109842/1823

/ N H-C 'C-Cl

IN THE

N N

Cl

O NH

O NH

NH-C C-NH

Cl

SO ₃ H

N = N

-GT C-NH

Γ CH ₃ NN

Cl

9 8 4 2/1823

HO ₃ S-

HO ₃ S.

Q

Il

N -

¹ C

Cu '

C = N 'N-C

NH-C C-Cl j. π

N N

NH ₂

as

SO ₃ H

-NH-C C-Cl

Il

N N

Cl

SO ₃ H HO NH-R '

/ ~ V_ N = N- ^

wherein R 'is a group of the formulas ^N Y ^C1 -er

Y ^

Cl

N ^ SO ₂ CH ₃

L

or

Cl

Cl-C

^s CO- means.

1098A2 / 1823

Furthermore, dyes according to the definition can also be used which contain heavy metals in complex bonds.

The heavy metals are manganese, iron, preferably ' Chromium, cobalt, nickel and especially copper in question.

Such dye complexes are preferably derived from those azo dyes that have a group of the formula

X Y

contain, in which X and Y are each hydroxyl groups, carboxyl groups, amino groups or alkylsulfonylamino groups. There come but also dyes of the phthalocyanine series in question.

Examples of suitable fiber-reactive, sulfonic acid group-containing Metal complexes are the following examples:. .

HO ₃ S OH HO Cl

CH ₂ = CH-CO-MH Yl

1: 2 chromium complex

H HO O ₂ N PH

C ₂ H ₄ -SO ₂ O-SO ₃ H

-N = N

H, -SO,

1: 2 cobalt mixed complex

SO ₃ H

109842/1823

HO,

CM! I

^N o

NH

SO ₃ H

Il

- Cu-Q

N = N

HO ₃ S HO ₃ S

—NH-CO

Cl

HO ₃ S OH

N = N

HO NH-CO-C ₂ H ₄ -N /> - Cl

Cl

HO,

O Cl

SO ₃ H

1: 1 chromium complex HO ₃ S 0 - Cu

ί I NH

N = N

Cl O

SO ₃ H

O - ~ Cu-O
f

Vn =]

So ₃ H

SO ₃ H

109842/1 823

HO ₃ S 0 ~ Cu-O

SO ₃ H

XM

N = N - ^ jM ' ^ \ / ~ ^0H ^ O ₃ H

ί ~ \ - NH-CO

HO ₃ S

COCH ^

HO ₃ SO-CH ₂ -CH ₂ -SO ₂ N

0-Cu-0

N = N

° 3 ^H

CH,

Cl Cl

/ - \ SO H

W ^x > -NH 0-Cu - 0 \ 3

-N

JH,

SO ₃ H

SO ₃ H

.0-Cu-O

Cl

N- /

NH

Cl

H ₂ N SO ₃ H

HO ₃ S

109842/1823

0-Cu-O

X) -Cu-O. HoC- C \

Cl-C ₉ H ^ -NH-SO ₉

C ₂ H ₄ Cl

The organic solvent mixture used consists of a chlorinated aliphatic hydrocarbon and a hydrophilic solvent.

Chlorinated aliphatic hydrocarbons are used for use: carbon tetrachloride, chloroform, methylene chloride, trichloroethane, tetrachloroethane, dibromoethylene and above all Trichlorethylene and perchlorethylene.

As hydrophilic solvents which are miscible with water, for example, aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethers and acetals such as diisopropyl ether, diphenylene oxide, dioxane, tetrahydrofuran, glycerol formal f and glycol formal, as well as acetonitrile and pyridine, diacetone alcohol, and also higher-boiling glycol derivatives such as ethylene glycol monomethyl, ethyl and butyl ether and diethylene glycol monomethyl or ethyl ether and diethylene glycol monomethyl or ethyl ether, thiodiglycol and in particular the group of butethylene carbonate 7, 120 ^Q C boiling, water-miscible, aprotic, hydrophilic solvents, such as N, N-dimethylformamide, Ν, Ν-dimethylacetamide, N-hexamethylphosphoric acid triamide, N-methylpyrrolidone, 1,5-dimethylpyrrolidone, N, N-dimethyl-methoxyacetamide, Ν, Ν, Ν ', N ¹ -Tetra-

1098 A 2/1823

methyl urea, tetramethylene urea, tetramethylene sulfone (Sulfolane), 3-methylsulfolane and dimethyl sulfoxide.

Preferred mixtures of these solvents contain.

98 to 60, preferably 97 to 70, percent by weight of the halogen

alLpnatic
nated hydrocarbon and 2 to 40, preferably 3 to 30, percent by weight of the hydrophilic component.

In preferred solvent mixtures is used as

chlorinated aliphatic hydrocarbons trichlorethylene and in particular perchlorethylene mixed with a hydrophilic solvent, or the amide or lactam of a lower fatty acid, in particular Ν, Ν-dimethylacetamide or N, N-dimethylformamide or phosphorus-containing solvents such as N-hexamethylphosphoric triamide in a mixture with a chlorinated aliphatic hydrocarbon. Particularly good solvent mixtures consist of: perchlorethylene / NjN-dimethylformamide, Trichlorethylene / N, N-dimethy! Formamide, perchlorethylene / N, N-dimethy! Acetamide, or perchlorethylene / N-hexamethylene / phosphoric acid triamide.

The present dyeing process is suitable for dyeing textile material containing amino and amide groups, such as certain Modacrylic fibers, e.g. polypropylenes modified with amines, modified polyester fibers containing amino groups and preferably synthetic polyamide material, especially poly (hexamethylene adipic acid amide) or nylon 6,6, (poly (cJ.-caprolactam) or nylon 6, poly (hexamethylene sebacic acid amide) or nylon 6,10 or poly (11-amino-undecanoic acid) or nylon 11, as well natural polyamide material, such as wool.

In exhaust dyeing, the textile material to be dyed can be in the form of loose material, fleece, yarn or as a knitted fabric or Tissue are present. It is in loose form or in the form applied to a mechanical device in a stationary bath, in particular in suitable jiggers, reel runners, cross reel dyeing machines or similar dyeing machines, depending on the nature of the goods to be dyed, dyed.

10 9 8 4 2/1823

Dyeing can take place in dyeing machines or vessels that are in contact with the outside atmosphere (if necessary through a reflux condenser) or in closed vessels, such as pressure vessels, with or without pressure.

The dyeing is carried out at a temperature of about 40 to 130 ^° C., preferably at a temperature at which the textile material is not damaged, for example polyamide at 105 ^° C., for about 30 to 50 minutes.

After reaching the desired depth of color, the dyed goods are taken out of the dye bath and conveniently with a commercial cleaning booster, dissolved in, for example, perchlorethylene, post-treated. To remove the still adhering Solvent, the material is then treated either with steam or with a stream of hot air.

Another advantage of the dyeing process according to the invention is the shortening of the dyeing time compared to conventional dyeing processes.

In the following examples, unless otherwise stated, parts are parts by weight, percentages are percentages by weight, and temperatures are given in degrees Celsius.

109842/1823

example 1

0.3 parts of the dye of the formula

NH,

NC ₆ H ₅

are dissolved in 16 parts of Ν, Ν-dimethylformamide and diluted with 145 parts of perchlorethylene. Be in this fleet 5 parts of polyamide knitted fabric are dyed for 40 minutes at 105 °, then the knitted fabric is removed from the dye bath. 1 to 2 parts of a commercially available cleaning booster, as used in dry cleaning, come in 160 parts Perchlorethylene dissolved, and the dyed knitted fabric aftertreated for 10 minutes at 50 ° in this bath. Then it will Material dried in a stream of warm air. The result is a level red dyeing with excellent fastness properties.

Example 2

0.8 parts of the dye of the formula

Ο - ΛΛ - Ο

= N - C - C - CH _0-

I Il -J

HO-C N

are dissolved in 19 parts of Ν, Ν-dimethylformamide and 288 Parts of trichlorethylene diluted. In this liquor 10 parts of a polyamide-6,6 knitted fabric for 45 minutes at approx.

and
Dyed at 85 ° / then removed from the dye bath.

1 to 2 parts of a commercially available cleaning booster, such as

109842/1 823

it is used in dry cleaning, are dissolved in 320 parts of perchlorethylene and the dyed knitted fabric Post-treated 10 minutes at 50 ° ία this bath. Afterward the material is dried in a stream of warm air. It results a level yellow dyeing with good fastness properties.

Example 3

0.2 parts of a dye of the formula

Cl

CH ₃ OCH ₂ CH ₂ O -I * _N -i -'-NH

are dissolved in 19 parts of Ν, Ν-dimethylacetamide and diluted with 288 parts of perchlorethylene. In this liquor, 10 parts of a polyamide-6,6 knitted fabric are dyed for 45 minutes at 105 ° and then removed from the dyebath. 1 to 2 parts of a commercially available cleaning booster, as used in chemical cleaning, are dissolved in 320 parts of perchlorethylene and the dyed knitted fabric is aftertreated at 50 ° for 10 minutes. The dyed knitted fabric is then dried in a stream of warm air. λ The result is a level, scarlet dyeing with good fastness properties.

Example 4

0.2 parts of a dye of the formula

0 NH ₀

10 9842/18 23

are dissolved in 19 parts of Ν, Ν-dimethylformamide and 288 Share diluted perchlorethylene. In this fleet 10 Parts of a woolen fabric dyed at 90 ° for 45 minutes .. The dyed fabric is then removed from the dyebath. 1 to 2 parts of a commercially available cleaning booster, as used in dry cleaning, are dissolved in 320 parts of perchlorethylene and the dyed fabric is aftertreated for 10 minutes at 50 ° in this bath. Afterward the material is dried in a stream of warm air. The result is a level blue dyeing with good fastness properties.

If you use Ν, Ν-dimethylformamide instead of the 19 parts a 15 parts of N-hexamethylphosphoric triamide and proceeds in otherwise, as indicated in Example 4, dyed material is obtained just as well.

Example 5

0.2 parts of a dye of the formula

HO. S.

are dissolved in 19 parts of Ν, Ν-dimethylformamide and with 288 parts perchlorethylene diluted. In this dye liquor 10 parts of a polyamide 6,6 or wool knitting yarn are used during Stained at 121 ° for 45 minutes. Then it is rinsed in a new bath in pure Perchlpräthylen for 10 minutes at 50 °. The colored material is then dried in a stream of warm air. The result is a level blue dyeing with excellent fastness properties.

109842/1823

Claims (19)

Claims .1. Process for dyeing amino or amide groups Textile material, characterized in that one or more, in each case at least one, in a homogeneous solution free sulfonic acid group and at least one fiber-reactive group containing dyes in a chlorinated aliphatic Colors hydrocarbons mixed with up to 50% of a hydrophilic solvent. 2. The method according to claim 1, characterized in that one colored at the boiling point of the organic solvent mixture. 3. The method according to claim 1, characterized in that the solvent mixture is 98 to 60, preferably 97 to 70, Percent by weight of the halogenated aliphatic hydrocarbon and 2 to 40, preferably 3 to 30, percent by weight contains the hydrophilic component. 4. The method according to claim 1, characterized in that the solvent mixture used is trichlorethylene mixed with a hydrophilic solvent. 5. The method according to claim 1, characterized in that there is a mixture of perchlorethylene as a solvent mixture a hydrophilic solvent is used. 6. The method according to claim 1, characterized in that the amide or lactam is used as a solvent mixture lower fatty acid, in particular Ν, Ν-dimethylacetamide or Ν, Ν-Dimethylformamide, mixed with a chlorinated aliphatic Used hydrocarbon. 109842/1823 7. The method according to claim 1, characterized in that a phosphorus-containing solvent is used as the solvent mixture, in particular N-hexamethylphosphoric triamide, used in admixture with a chlorinated aliphatic hydrocarbon. 8. The method according to claim 1, characterized in that the solvent mixture is perchlorethylene / NjN-dimethylformamide or trichlorethylene / N, N-dimethylformamide or perchlorethylene / N, N-dimethylacetamide or perchlorethylene / N-hexamethylphosphoric triamide used. 9. The method according to claims 1 to 8, characterized in that that fiber-reactive dyes containing sulfonic acid groups are used which, as fiber-reactive groups, contain heterocyclic groups exhibit. 10. The method according to claim 9, characterized in that the fiber-reactive heterocyclic group has at least two heteroatoms, such as in particular the halogen-s-triazinyl radical, the phenoxy, alkoxy, alkoxyalkoxy and arylamino radicals. 11. The method according to claim 10, characterized in that the heterocyclic group is an s-triazine residue. 12. The method according to claims 1 to 8, characterized in that that fiber-reactive dyes containing sulfonic acid groups used which is a residue of a halogenated fiber-reactive group C,, fatty acid contain. 13. The method according to claim 9, characterized in that fiber-reactive dyes containing sulfonic acid groups are used, which contain a fluorine-containing pyrimidyl radical as a fiber-reactive group. 109842/1 823 14. Process according to Claims 1 to 13, characterized in that metal-free acidic reactive dyes are used. 15. Process according to Claims 1 to 13, characterized in that metal-containing acidic reactive dyes are used used. 16. The method according to claims 1 to 15, characterized in that natural and synthetic polyamide material is colored. 17. The method according to claim 16, characterized in that " to dye wool. 18. The method according to claim 16, characterized in that synthetic polyamide material is dyed. 19. The textile material dyed according to claims 1 to 15. 109842/1823