DE2418283A1 - METHOD OF DYING NATURAL PROTEIN FIBERS - Google Patents

Description

DR. B i HQ DIP L. -IN G. STAPF ΟΛ1ΟΟΟΟ DIPL.-ΙΠΘ. εθΚν ^? ΑΒ ~ ΠΓ. OR. CANDMAIR ΔΗ IOZO

PATEN ΪΑ: ΓΛ'Λί..ϊ.ϊ Case 1-8736 / 1 + 2 ₈ MÖNCHEN 80 · MAUERKlflCHERSTRM «

Germany

Attorney file 24 895 April 16, 1974

Process for dyeing natural protein fibers

For dyeing protein fibers such as wool with reactive dyes, a rich range is more brilliant Tones have been developed. However, difficulties arose with the dyes for dark tones, especially with Shades of black. Such shades can be more fiber-reactive with metal complexes, especially chromium and cobalt complexes Dyes can be achieved. However, it was found that metal complexes, which are common for wool dyes, of aliphatic monocarboxylic acids with 2-4 carbon atoms derived reactive groups contain, often only unsatisfactory Staining result. Above all, these dyes do not build up too deep black tones and when dyeing using the exhaust process The degree of extraction and the level of fibers often leave a lot to be desired.

It has therefore been proposed in English Patent No. 1,298,851 to include the protein fibers To dye complex formation capable, reactive monoazo dyes and then the dye on the fiber

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CIBA-GEIGY AG

to be treated with metal-releasing agents. Another one, Process based on metal-free azo dyes. is in English Patent No. 1,299,277 described. This is followed by dyeing with such dyes in the presence of a metal donor.

However, both methods show compared with

coloring using a finished metal complex; a number of disadvantages:

- Post-treatment increases the duration of the coloration.

- The procedure according to the English patent specification No. 1 299 277 is tricky because the chronicle complex should only form on the fiber if possible, which e.g. requires careful, slow heating of the liquor.

- There are large excesses in relation to the dye used of chromium salts necessary, the removal of which from the dyeing waste water is desirable for ecological reasons, but. is very difficult.

- The final nuance only shows up at the end of the.

Dyeing process. Corrections thereof are therefore difficult.

It has now been found that a narrow range of reactive metal complexes, namely those of the below given formula (I) also as finished metal complexes and after the usual dyeing process for deep shades build good fastness properties at the same time.

The invention thus relates to a method for dyeing natural protein fibers with fiber-reactive fibers Dyes, which is characterized by the fact that one

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- 3 -
a metal complex from Forpiel

SO H

1\

(D

wherein R-. Hydrogen, an alkyl, aralkyl or aryl radical, R2 is an acrylic, acetyl or propionyl radical substituted by one or two halogen atoms, Me is a chromium (III) or cobalt (III) ion and X is hydrogen, nitro, chlorine, methyl, methoxy, acetylamino, chloroacetylamino or propionylamino, in the presence a leveling agent from aqueous liquor on protein fibers or from an auxiliary carrier by means of transfer printing Heat treatment transmits.

Suitable reactive groups are, for example, the following radicals: chloroacetyl,
ß-chloropropionyl,
ß-bromopropionyl,
α-chloroacryl,
β-chloroacryl,
α, β-dichloropropionyl,
β-bromoacryl and in particular
oc-bromoacryl and
α, ß-dibromopropionyl.

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For the preparation of the complexes that can be used according to the invention, azo dyes are used which are obtained, for example, from the following diazo and coupling components: Diazo components:
l-hydroxy - ^ - amino - ^ - nitrobenzene, l-hydroxy - ^ - amino ^ -nitrobenzene, Ί-hydroxy-2-amino-4 , 6-dinitrobenzene , l-hydroxy ^ -amino ^ -nitro-ö-acetylaminobenzene , l-Hydroxy ^ -amino - ^ - chloro ^ -nitrobenzene, 1-hydroxy-2-amino-4-methyl-5-nitrobenzene, l-hydroxy ^ -amino ^ -methoxy ^ -nitrobenzene, 1-hydroxy-2- amino-4-nitro-6-propionyl-aminobenzenes 1-hydroxy-2-amino-4-nitro-6-chloroacetylarninobenzene. Coupling components:

l-hydroxy-7-a-minonaphthalene-3-sulfonic acid j 1-hydroxy-7-N-methylaminonaphthalene-3-sulfonic acid _j l-hydroxy-7-N-benzylaminonaphthalene-3-sulfonic acid J l-hydroxy-7-N-phenylaminonaphthalene- 3-sulfonsäureJ l-hydroxy-6-N-methylaminonaphthalene-3-sulphonic acid, 1-hydroxy-6-aminonaphthaiin ~ 3-sulfonic _s 1-hydroxy-8-aminonaphthalene-4-sulfonic acid, 2-hydroxy-6-aminonaphthalene-4 sulfonic acids 1-hydroxy-7-aminonaphthalene-4-sulfonic acid, 1-hydroxy-5-aminonaphthalene-3-sulfonic acid.

Because of the easy accessibility and the neutral black tone available with it, the dyes, which differs from l-hydroxy-2-amino-4- or -5-nitrobenzene as a diazo component and from l-hydroxy-7- or -6-aminonaphthalene-

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Derive 3-sulfonic acid as a coupling component, be ^ cmdg?. £> Interesting.

The metal complexes are prepared by methods known per se by diazotization, coupling, and metallization and acylation. These reaction steps can be carried out in different order, since the acylation both on the coupling component as well as on the azo dye, i.e. after the coupling, or in particular on the finished metal complex, i.e. as the last step.

The acid anhydrides and, in particular, chlorides of the acid radicals mentioned above are used as acylating agents corresponding acids.

The conversion of the monoazo dyes into the 1: 2 chromium or cobalt complexes takes place with the usual metal donors Agents, where there must be at least one metal atom for 2 molecules of monoazo dye. The metallization is in one carried out in a weakly acidic to alkaline medium. That is why it is advantageous to use metal compounds that are below these p "conditions are stable and no sparingly soluble salts form, such as chromium complexes of aliphatic dicarboxylic acids or hydroxycarboxylic acids or aromatic hydroxycarboxylic acids (e.g. oxalic acid, lactic acid, glycolic acid, citric acid and especially tartaric acid or salicylic acid). The cobalt plating can with cobalt sulfate, cobalt acetate or freshly precipitated cobalt hydroxide be performed. It is expedient to metallize in an aqueous solution, optionally with the addition of organic solvents such as alcohols or dimethylformamide, or in purely organic solvents, e.g. in alcohols, glycols, glycols

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ethers or esters, glycerine or katenon.

According to a preferred embodiment, the Dyes applied by transfer printing in a wet contact process. For this purpose, an auxiliary carrier, generally paper, printed in the usual way with an ink containing a chromium complex dye of the formula (I). The textile material to be printed is brought into contact with the printed auxiliary carrier in a moist state and heated. Corresponding procedures are for example described in British Patent Nos. 1,227,271 and 1,284. It is expedient to also impregnate the textile an aqueous preparation containing a thickener and a weak acid.

Another preferred dyeing method relates to the Kaitiager process. Here, the textile is with a aqueous dye preparation impregnated and then in wet Condition stored. The dye preparation contains in addition to the common thickeners a leveling agent and a weak one Acid. Furthermore, the dyestuffs of the formula (I) can be successfully obtained by the exhaust process from acidic aqueous Color the bathroom. A good degree of exhaustion and level and deep colorations are achieved. The p "value should be between 4.5 and about 6.5, which is best achieved by adding ammonium sulfate and acetic acid. The coloration will be around 80 to 110 ° C carried out in the presence of suitable leveling agents. To achieve good wet fastness properties, neutralization takes place at the end the dyeing process with a base, preferably with ammonia, to remove any dye components that are not fixed to the fiber to remove. This happens at 80 C and a p "of 8.0

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to 8.5. Then the material to be dyed is rinsed and, if necessary, wrinkled acidified.

Both nonionic and ionic, i.e. anionic and cationic nitrogen-containing Compounds are used in 'the process according to the invention.

It is advantageous to use polyglycol ether derivatives of long-chain mono- or diamines, at least one Nitrogen atom with the hydrocarbon residue of a long chain Fatty acid is substituted; In addition, these adducts can also be quaternized on a nitrogen atom or on Be esterified with a polybasic acid at the end of a polyglycol chain, or both quaternized and be esterified.

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■ · t -

• The starting materials used are uniform, higher molecular weight alkylamines or amine mixtures, such as those obtained when converting natural fatty acid mixtures, for example tallow fatty acid, into the corresponding amines. Amines with 16 to 22 carbon atoms to which at least 5 to 10 and not more than 60 to 70 mol of ethylene oxide are attached are suitable. The following amines may be mentioned in detail: hexadecylamine, octadecylamine, arachidylamine CH (CHg) ₁ -NH ₂ , behenylamine CH (CHg) ₂₁ -NH ₂ , octadecenylamine and N-alkylpropylenediamines with the corresponding hydrocarbon radicals.

Both the quaternization and the esterification of the nitrogen-containing 'polyglycol ether derivatives are advantageously carried out by known methods, no intermediate deposition being necessary.

For the quaternization, usual alkylation ^ or Aralkylating agents such as dimethyl sulfate, ethyl bromide or benzyl chloride can be used; however, chloroacetamide is preferred as the quaternizing agent, Ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin. or epibromohydrin.

As polybasic oxygen acids for education The acidic esters can be organic polycarboxylic acids such as maleic acid or polybasic inorganic oxygenates. acids such as phosphoric acid or sulfuric acid are used. Instead of the acids, their functional derivatives, such as

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4058

Acid anhydrides, acid halides, acid esters or acid amides can be used. According to a particularly preferred embodiment, the acidic sulfuric acid esters are prepared directly in the form of their ammonium salts by heating the starting materials with amidosulfonic acid in the presence of urea. Both the quaternization and the partial esterification conveniently be carried out by simply mixing the reactants with heating, conveniently to a temperature between 50 and 100 ⁰ C.

Particularly advantageous leveling agents that may be mentioned are: the adduct of oleylamine and 8 mol. Ethylene oxide and the mixture of

a) an adduct of 1 mole of tallow amine (consisting of 30 $ hexadecylamine, 25 ^ octadecylamine and 45 ^ octadecenylamine) and 7 moles of ethylene oxide, quaternized with chloroacetamide and

b) the ammonium salt of the acid sulfuric acid ester of the same, non-quaternary adduct,

and also the individual components a) and b) of the mixture mentioned.

The amount of leveling agent in the dye baths is about 0.5 to 2 $ of the fiber weight, depending on amount of dye used.

Other additives that the dye bath or the padding liquor may contain,

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are for example thickeners, salts and acids. The thickeners should be stable in an acidic environment and not be destroyed by the presence of a metal donor. Such thickeners are e.g. British gum or etherified carubic acids. Two salts are sodium sulphate and ammonium ". 'sulfate., sodium chloride or primary and secondary phosphates, and as acids, aliphatic mono- or dicarboxylic acids which are in the aliphatic chain except for the carboxy carbon atom have at most 4 · carbon atoms. However, only the aliphatic are of practical importance Monocarboxylic acids such as formic or acetic acid.

The amount of acid in the dyebath is 2 to 8 ^ of the fiber weight, depending on the amount and type of dye.

According to the present process, natural nitrogen-containing fibers can be dyed. These include silk and, above all, wool. The processing state of the fiber material can be selected as desired. However, particularly good results are achieved when dyeing unwoven wool, such as loose wool, sliver or yarn, but fabrics made from the fiber materials mentioned are also dyed with good results.

The present process mainly produces dark tones such as navy blue or black.

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

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CIBA-GEIGYAG example 1

In 4000 parts V / water of 50, 4 parts 8c acetic acid, 2 parts of the ammonium salt of the acidic sulfuric acid ester of the adduct of a fatty amine (consisting of ~ 50% hexadecylamine, 20% octadecylamine and
K ^% octadecenylamine) and 7 mol of ethylene oxide, and 4 parts of ammonium sulfate dissolved.

8 parts of the constitution dye prepared by known methods

BrCH ₀ CHCOEN-

² I.

Br

Br

are dissolved in 100 parts of hot water and the above
Dyebath added. Then 100 parts of pre-wetted woolen knitting yarn are entered and the temperature of the bath is increased from 50 ° to 80 ° in the course of 30 minutes. To
20 minutes dyeing at 80 ° is heated to the boil and
then colored at the boil for 90 minutes. The dye goes almost entirely ^o f ^the substrate. After cooling the bath to 80, the ρ value of about 4.5 is increased by adding

Xl

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increased from ammonia solution to a permanent 8.5 and the dyed goods treated for 20 minutes at this temperature, a small amount of unfixed dye is removed. After thorough rinsing with hot and cold water, acidification with 1 part 80% formic acid, Centrifugation and drying gives a deep blue-black-dyed woolen yarn of very good wet and rub fastness as well as excellent lightfastness.

If, instead of the dye mentioned, 8 parts are given as Example 3 in the table below If the dye is used with otherwise the same procedure, the result is a uniform, full black coloration of very good fastness properties.

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CIBA-GEIGY AG Example 2

In a printing dyeing machine, a dye bath is prepared from 1000 parts of water at 50 °, 3 parts of So ^ iger Acetic acid, 1 part of the adduct of tallow fatty amine and 7 mol of ethylene oxide (quaternized with chloroacetamide and with Amidosulfonic acid / urea to the ammonium salt of the acidic Sulfuric acid ester of the quaternized adduct esterified), and 6 parts of the accessible by conventional methods Dye of the following constitution

NHCOC = CH.

Br

NO,

After charging 100 parts of wool fabric, the apparatus is pressure-tightly closed, the temperature was raised within 30 minutes from 50 to 1θβ and left for a further 60 minutes at 106 °. After cooling to 80 °, the pressure is released, the dyebath with ammonia solution on the pjW

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Set 8.5 and held at 80 ° for 20 minutes. The coloring is then completed as in Example 1. The wool fabric is an even, greenish black with very good general fastness properties colored.

The following table contains in column I. Diazotization components, in column II coupling components, in column III acylating agent, in column IV complexed metals. The combination of these elements leads to dyes of the same constitution as the dye of example 1 or 2; the after the same Shades obtainable by dyeing processes are given in column V of the table.

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co 00

cn

co

U] (P

ta ΰ

No. 1 -Hyd r oxy -2 -am in ο -
4-nitrobenzene i υ III IV V 1 " dd 1-hydroxy-7-amino-
naphthalene \ 3 ~ ^s ulfon · "
acid Chloroacetic acid
chloride chrome black 2 dd It α, ß-dibromopropion
acid chloride cobalt Dark brown 3 1-hydroxy-2-amino
5-nitrobenzene Il ti chrome black I. 1-hydroxy-2-amino
4-nitro-6-acetyl-
aminobenzene ti a-chloroacrylic acid
chloride chrome Blue black LT \
H
I. 5 1-hydroxy-2-amino
4-nitrobenzene ti a-bromooryl acid
chloride chrome violet
black 6th 1 -Hy dr oxy -2 -am in ο -
4-chloro-5-nitro-
benzene 1-hydroxy-6-amino
naphthalene-3-sulfone
acid α, β-dibromopropion
acid chloride chrome violet
black 7th 1-hydroxy-2-amino
4,6-dinitrobenzene ti It cobalt Navy blue 8th 2-hydroxy-6-amino
naphthalene-4-sulfone
acid a, ß-dichloropropion
acid chloride chrome black

N)

OO N) OO CJ

No. I. II - ■ III IV V ι- • 9 1-hydroxy-2-amino
4,6-dinitrobenzene 1-hydroxy-5-amino
naphthalene-3-sulfOn-
acid α, β-dichloropropionic
acid chloride chrome violet
black 10 1-hydroxy-2-amino
4-nitrobenzene 1-hydroxy-7-amino
naphthalene -4 -sulfone-
acid α, ß-dibromopropion
acid chloride chrome Black-
violet
·. , · -. ·.-'-- V · - ■■ - .. «. ■ .. ,,. 11 ^ ₁
ti It It cobalt Dark brown * 860V 12th 1-hydroxy-2-amino
5-nitrobenzene l-hydroxy-8-amino-
naphthalene-5-sulfone
acid ti chrome Gray-blue cn ^H
*> »Ι
ο 13th 1-hydroxy-2-amino
4-chloro-5-nitrobenzene It Il cobalt Dark blue CO
ο 14th 1-hydroxy-2-amino
4-nitrobenzene 1-hydroxy-7-methyl-
aminonaphthalene-3-
sulfonic acid Chloroacetic acid
chloride chrome black 2418283 15th ν
1-hydroxy-2-amino
4-nitro-6-chloro
acetylaminobenzene ti Il chrome violet
black 16 Il. 1-hydroxy-6-methyl-
aminonaphthalene-3-
sulfonic acid α, ß-dibromopropion
acid chloride chrome Dark-
violet -

No. I. II III IV V 17th 1-hydroxy-2-amino ~
^ - methoxy-S-nitro-
benzene l-hydroxy-6-methyl-
aminonaphthalene-3-
sulfonic acid Chloroacetic acid
chloride chrome Dark blue
Gray 18th It It dd cobalt Purple gray

Wool flannel is soaked on a padder with the dye preparation described below and on a Liquid absorption would be squeezed out by 1007o:

50 parts of .Dye No. 3 in the table 300 parts urea 320 parts Solvitose OFA 4% (thickener)

10 parts of a mixture of anionic fatty alcohol ether sulfate with nonionic wetting agents

10 parts of the leveling agent used in Example 2, 10 parts of sodium metabisulphite
10 parts acetic acid a 80%
280 parts of water

1000 parts padding liquor.

The impregnated fabric is then stored rolled up and packaged airtight for 48 hours at room temperature. After rinsing with cold water, the material is treated in a fresh bath with enough ammonia a 24% that a p _u of 8.5 is reached and at 80 ° for 15 minutes

ti

is adhered to. After rinsing in warm water, it is finally acidified with 80% acetic acid and dried. The wool fabric is colored in a slightly reddish, full black shade with excellent fastness properties.

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Example 4

A woolen fabric is soaked with the preparation described below and squeezed off on the padder to a moisture absorption of 250%:

4 parts Diaprint REG (acid-resistant thickener) 1 part sulfamic acid
0.2 parts thymol
0.2 parts emulsifier
94.6 parts of water

100 parts.

The impregnated material is then in a

heatable press for 3 minutes at 100 to 105 under one

Pressure of approx. 0.5 kg / cm compressed with a transfer paper, which bears a print pattern applied in the usual way from dye no. 3 of the table. After rinsing and When the woolen fabric is dried, it has a corresponding, deep black print pattern with very good fastness properties.

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Claims (7)

Claims 1, method of coloring or printing natural Protein fibers with fiber-reactive dyes in deep black, brown and navy blue tones, characterized in that one Protein fibers with a metal complex of the formula wherein R, hydrogen, an alkyl, aralkyl or aryl radical, R ^ an acrylic substituted by one or two halogen atoms. Acetyl or propionyl radical, Me a chromium III or Cobalt-III-ion and X hydrogen, nitro, chlorine, methyl, methoxy, Is acetylamino, chloroacetylamino or propionylamino, in the presence a leveling agent dyes from aqueous liquor or transfers the dye from an auxiliary carrier by transfer printing. 2. The method according to claim 1, characterized in that that you can get a dye of the formula 409845/0970 CIBA-GEiGY AG NH-R χ ^H S used, in which Me and X have the meaning given and R is an α-bromoacrylic or dibromopropionylresfist. 3 »Process according to claims 1 and 2, characterized in that that you can get dyes of the formula (in) —NH-R used. 409845/0970 4. Process according to Claims 1 to 3, characterized in that that after the transfer printing process, the dyes of the formula (I), (II) or (III) by heat treatment in the presence transfers of moisture from an auxiliary carrier to the textile material. 5. Process according to Claims 1 to 3, characterized in that the dyes of the formula (I), (II) or (III) by padding the textile material with an aqueous, applied a leveling agent containing, weakly acidic liquor and subsequent storage. 6. The method according to claims 1 to 3, characterized in that that one protein fibers with dyes of the formula (I), (II) or (III) by the exhaust process from aqueous Flotte.in The presence of a leveling agent colors. 7. The colored material obtained according to claims 1 to 6. 409845/0970