DE2028218A1 - Process for dyeing or printing natural or synthetic polyamide or polyurethane fiber materials - Google Patents

Description

• - - File number - HOE 70 / F

Frankfurt (Main) -Hochst, June 5, 1970 Dr. MÖ / B

Process for dyeing or printing natural or synthetic polyamide or polyurethane fiber materials

In French patent specification 1,067,449, the suitability of sulfonic acids and carboxylic acid group-free 1: 2 chromium and 1: 2 cobalt complex monoazo dyes which form the group -SO _n -R, where R is a β-hydroxyethyl radical, an aliphatic radical with at least three carbon atoms or preferably means an aralkyl or aryl radical, contained in the diazo component, for dyeing nitrogen-containing natural or synthetic fiber materials, such as wool, silk, leather, polyamide or polyurethane fibers. In the French patent mentioned, however, no metal complexes monoazo dye with the group -SO ₂ -R, in which R represents the β-hydroxyethyl radical, is disclosed. Disclosed there are only those 1: 2 chromium and 1: 2 cobalt complex monoazo dyes which contain the group -SOp-R in the diazo component, where R is an aliphatic radical having at least 3 carbon atoms, an aryl or aralkyl radical.

It has now been found that 1: 2 chromium or 1 ^ -K complex monoazo dyes which are free of water-solubilizing groups, but at least once contain the hydrophilic group -SO ₂ -CH ₂ -CH ₂ -OH, on natural or synthetic nitrogen-containing fiber materials, such as wool, synthetic polyamide or polyurethane fibers, can produce dyes or prints more evenly than with the dyes disclosed in the cited French patent. Those obtainable with these dyes on the fiber material mentioned

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Dyes or prints of very good levelness also distinguish B ^ h characterized by good light and wet fastness properties.

The dyes used according to the method are both the symmetrical and the asymmetrical 1: 2 chromium or 1: 2 cobalt complex monoazo dyes, which contain, for example, 1 or 2 groups of the formula -SO ₂ -CH ₂ -CH ₂ - OH in the diazo or azo component of the underlying monoazo dyes, the metal complex dyes mentioned alone or in a mixture with one another, or in particular in a mixture with 1: 2 chromium or 1: 2 cobalt complex monoazo dyes, which are free from sulfonic acid, carboxylic acid and -SOg-CHo-CHo-OH groups can be used.

Since the dyes used according to the process with the -SOn-CHg-CHg-OH group more hydrophilic than that in the cited French patent disclosed dyes are, where this property is reinforced by the additional OH radical contained in the group mentioned, pull the dyes used according to the process from aqueous dye liquor or from the printing paste in comparison slower to the nitrogenous fiber materials, making them in the fiber remain more capable of migration and thus result in the more evenly colored dyeings and thus a more uniform image of the fiber dyeings.

Dyeing is done in an aqueous liquor in the pH range 4.0 - 3.0, preferably in the pH range 7.0 - 6.0, the pH value being adjusted to 7.0 at the beginning of the dyeing process, and during the dyeing process by adding organic and inorganic acids such as acetic acid, Formic acid or sulfuric acid, also acidic salts such as ammonium sulfate, monosodium phosphate, or mixtures of acids and acidic salts is reduced to 6.0. The dyes are absorbed and fixed at temperatures between about 70 ° and 130 ° C. (exhaust process).

A Färbevariante is that the dyes from aqueous solution or dispersion padded to the fiber material or applied with the aid of commonly used in printing processes thickeners and at about 90 ° - 220 ° C

1098S1 / 1785

Dry heat or steam can be fixed. ' ^: .'; Auxiliaries which can be added to the dyes or the dyeing preparations produced therewith are known: auxiliaries, such as, for example, anionic or nonionic dispersants and wetting agents.

The 1: 2 »chromium and 1: 2 cobalt complex monoazo dyes used ₍ which are free from water-solubilizing acidic groups, such as the -SO ₉ H and -COOH group, and at least one hydrophilic. -SOg-CHg-CHg -OH Gruppd carry, contain, per Hetallatom two ■ FärbstoffmolckUle complexed. the complex-forming monoazo dyes contained in o _y o ^f-position to the azo group capable of complexing two substituents, such as, -OH, -NH _2, -NH-alkyl, -NH-aryl, -COOH or one of these substituents and in the second o-position a group which can be converted into a complex-forming substituent during metallization, such as the -OCHg group -Hydroxy-o'-N-raethylarainoazo dyes, o-hydroxy-o'-N-phcnylaminoazo dyes, o-carboxy-o'-hydroxyazo dyes, o-carboxy-o'-aminoazo dyes, o-methoxy-o'-hydroxyazo dyes, o- Methoxy-o-aminoazo dyes and especially ο, ο ^f -dihydroxyazo dyes.

The advantage and technical progress, brought about by the application This dye is achieved, is a significantly improved ability to compensate for material-related differences in affinity nitrogen-containing fibers compared to structurally comparable dyes, but which do not contain -SO ^ -CHg-CHg-OH groups.

The following examples serve to illustrate the dyeing process. example 1

! fan prepares a dye liquor from 300 nl water at 30 ° C and 100 mg of the 1: 2 cobalt complex of the Konoazo dye oU (2 ^l -oxy-5'-nitrobenzene-1 ^f -azo) -acetoacetic acid- (3-ß-oxyethylsulfonyD) -anllid, 300 mg disodium phosphate and 300 mg ammonium sulfate.

After adding 10 g of a fabric made of polyamide fibers Heated to boiling temperature within 30 to 60 PfLnuts etc.

10M61 / 17 «■ ·

I hour at boiling temperature · dyed * Then it was * rinsed 'and dried. A level yellow coloration is obtained that is very old; -. good light and wet fastness *.- V. . -. '* - - " ^v ν

Nan can achieve the same result if nan at temperatures between 70 ° and 100 ° C or under HT conditions
colors at temperatures between 101 ° and 130 ° C.

Also can be used in place of the mixture of disodium phosphate and
. Ammonium sulfate by adding organic or inorganic
Acids or their salts, or by means of buffer mixtures in a pH range of 4 to 3, can be used. The colorations obtained are identical to one another.

i ■ ■ ■

The dyes listed in the table below can be colored according to the same procedure. I.fa »also receives
strong colorations with very good levelness and with good light and lightness
Wet fastness properties.

109851/1785

Example Kr .

dye

Color shade on polyamide fibers

l ^ -Cobalt mixed complex of dyes

4- (2 ^f -Oxy-5 * -nitrobenzene-l'-azo) -. L- (2 ^M , 5 ^H -dichlorophenyl) -3-methyl-pyrazol - ^ - 5-one, and l- (2 '-0xy-5'-oxyethylsulfonylbenzene-1'-azo) -2-naphthol 1: 2 ~ Chromium mixed complex of dyes

1- (2 ^f- oxy-5 ^f -ntrobenzene-l ^l -azo) ~ 2-naphthol and 1- (2'-oxy-5'-ß-oxyethylsulfonyl-benzene l'-azo) -2-naphthol ■■ ■■ '.

1: 2 cobalt mixed coraplex of

1- (2'-Oxy-5 * -chlorobenzene-l'-azo) -2-naphthol and 1- (2 ^f -> 0xy-5 ^f -β-oxyethylsulfonylbenzene "-l ^f azo) -2-naphthol

1: 2 chrouconplex of the dyes

4- (2 ^t -0xy-5 ^t -nitrobenzene-l ^t -azo) -l-phenyl-3-methyl-pyrazole-5-όη and

4- (2 ^l -0xy-5 ^l -ß-oxyethylsulfonylbenzene-1 ^f azo> -l-phenyl-3-methyl-pyrazol * 5-one

I ^ -Chrommlschkomplcx der dyes

4- (2 · -0xy * -4'-nitrobenzene-1'-azo) -1-pheny 1-3-methyl-pyrazol-5-one and

4- (2 ^t -0ky-4 ^l -ß-oxyethylsulfonylbenzene-l ^l ~ aZo) -l-phenyl-3-methyl-pyrazol-5-one red-brown

corinth

bordo

orange

O IXJ 00

Example no.

Dye shade on polyamide fibers

1: 2 cobalt nischkoinplex of dyes

4 ~ (2'-Oxybenzol-l ^t -azo) -l-phenyl-3-methylpyrazol -5-one and

i - ^ '- Oxy-S'-ß-oxyethylsulfonylbenzene-l'-azo) -l-phenyl ~ 3-methyl-pyrazol-5-one

1: 2 chromium mixed complex of dyes

l -. (2 ^l -Oxy-4 * -nitrobenzene-l ^t -azo) -2-naphthol and l - ^ '- Oxy-S'-ß-oxyethylsulfonylbenzene-l'-azo-) 2-naphthol

l: 2 ~ cobalt mixed complex of dyes

l- (2'-oxy-5 ^t -aniinosulfonylbenzene-l ^f -azo) -2-naphthol and

1_ (2 · -Oxy-5'-ß-oxyäthy1-sulfony1-benzene ~ I ¹ -azo) -2-naphthol

1: 2 chromodonic complex of dyes

l- (2 ^l -0xy-4'-nitiro-5'-chlorobenzene-l'-azo) -2-naphthol and l- (2 ^f- oxy-5'-ß-oxyäthy1-sulfonylbenzene-1 ^l «azo) -2 ~ naphthol

the dyes

4-i (2 '-OXy-5 ' -nitrpbenZol ^ l 'WaZo) -I- C4 "-ß-oxyäthy 1-

sulfonylphenyl) -3-methylpyrazol-5-one and 4 * (2 'rOxybenzol-1' -azo) _T l-pheny! -3-methylpyrazol-5-one reddish yellow

navy blue

navy blue orange

Kr. Dye shade on polyamide fibers

1: 2 chromic complex of the dyes

l- (2'-Oxy ~ 4 ^f -nitro-5'-chlorobenzene ~ l ^t -azo) -2-naphthol blue ♦ and l- (2'-Oxy-4 ^f -ß-oxyethylsulfonyl-benzene-l'- azo) ~ 2-naphthol

■ ' ₉ ■' ·! ■■■ ■ 'Vr --'-' · ΑΙ82 # 0 ^ ·

Example 13. «■; ''r / -' ¹ ·. ■ "■ -Γ-

A dye liquor is prepared from 300 ml of water at 30 ° C. and 100 mg of the 1: 2 mixed cobalt complex of the dyes ... . 4- (2'-Oxy-5'-nitrobenzene-l ^t -azo) -l- (2 '^ 5 ^t ' -dichlorophenyl) ~ 3-methyl-pyrazol-5-one and l- (2 ^f- oxy -5 ^l -ß-oxyäthylsulfonylbenzol-l ^f azo) -2-naphthol, Ig Duisburg sodium sulfate and 500 mg ammonium sulfate.

After adding 10 g of a woolen fabric, Λ heated to boiling temperature and colored at boiling temperature for 1 hour. This is followed by rinsing warm and drying. You get a level red-brown dyeing with very good light and needle fastness properties.

The same result is obtained if you move between * 70 ° and 100 ° C

or under HT conditions between 101 and 107 ° C

is working.

It can also be used instead of ammonium sulfate by adding organic

or inorganic acids or salts, or by , Buffer mixtures in a pH range of 4 to 8 can be used.

The colorations obtained are identical to one another.

The dyes listed in the table according to Example 1 can also be dyed on wool according to the procedure of Example 2. You obtain level k colorations having good light and wet fastness properties even with these products.

Example 14

A padding liquor is prepared from 1 l of water at 30 ° C. and 50 g of the 1: 2 chromium mixed complex of the dyes 1- (2'-oxy-5'-nitrobenzene-1'-azo) -2-naphthol and 1- (2 '-Oxy-5'-ß-oxyethylsulfonylbenzene-l ^t -azo) -2-naphthol:

With this padding liquor is polyamide fiber material on one

Impregnated padding, dried and then heat-set at 190 ° - 220 ° C. This is followed by warm rinsing and drying. You get a deep one

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^? original

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Corinth coloring with good levelness and with very good light and wet fastness properties.

The dyes from the table according to Example 1 can also be used to produce good, level dyeings with good light and wet fastness properties by hot air fixation.

Example 15 . .

A padding liquor is prepared from 1 liter of water at 30 ° C. and 50 g of the 1: 2 cobaltraisch complex of l ~ (2 ^l -0xy-5'-chlorobenzene-l * azo) -2-naphthol and l- (2 ' -Oxy ~ 5'-oxyethylsulfonylbenzene-1 ^r -azo) -

2-naphthol.

With this padding liquor, Polyaiaxdfaserinmaterial becomes on one Impregnated foulard and steam fixation without intermediate drying from 100 ° - 1O2 ° C.

After washing out, a level Bordo dyeing is obtained with good light and wet fastness properties.

The same good result is achieved if before steaming ι is intermediate drying, or at steam temperatures between 100 and 140 ° C is worked.

With the dyes listed in the table according to Example 1 good, level Produce dyeings with good wet and light fastness properties.

Example 16

50 g desl ^ -Chrommischkoaplexes the dyes 4- (2'-Oxy-5'-nitrobenzene-1'-azo) -l-phenyl ~ 3 ~

and 4- (2 ^t -.0xy-5 ^l -ß-oxyäthylsulfonylbenzol-l ^l ~ a2o) -l-piienyl-3-methyl-pyrazol-5-one are dissolved in 250 cm of water at 30 ° C and in 500 g Thickening, consisting of 3 parts by weight of water and 1 part by weight of crystal rubber, stirred in. Then it is adjusted to 1000 g with thickening or water,

That with this printing paste is then bedruckte.Polyamidfaser- or WoIlmaterial 20 with Hi s, at 100 ° - 102 ⁰ C damped. Then it is washed out and finished,

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# 028218

! {an receives a © on both wool and polyamide fiber orange-colored print with good lightness and plaidness. Equally good results are obtained when at steam temperatures between 100 ° and 140 ° C is worked.

The dyes from the table according to Example 1 are also used obtain level prints with good light and wet fastness properties under the specified conditions »

Example 17

50 g of the 1: 2 chromium mixed complex of the dyes 4 ~ (2 ^l -0xy-5 ^l -nitrobenzene-l ^t -azo) -l-phenyl-3-methyl-pyrazol-5-one and 4- (2'-oxy -5 ^? -Ss-oxyäthylsuIfonylbenzol-l ^l -azo) -l-phenyl-3-methyl-pyrazol-5-one are dissolved in 250 cm of water at 30 ° C and thickened in 500 g, consisting! stirred in from 3 parts by weight of water and 1 part by weight of crystal _{gourami r.} Then it is adjusted to 1000 g with thickening or water.

The Polyaraidfaserinmaterial printed with this printing paste is then a dry heat treatment at 190 ° - 220 ° C exposed. It is then rinsed and dried. You get an orange print shows good light and wet fastness properties.

Example 18

A dye liquor is prepared from 3ΌΟ ml of water at 30 ° C. with 200 rag of the l ^ -Chromralsch complex of the dyes 4- (2 ^t -oxy-4 ^t -nit "robenzol-i * -az; o) -lp: henyl-3 -inethyl-pyrazol-5-one and 4- (2 '«Oxy-4'-ß-oxyäthyIsulfonylbenzol-i'-azo) - l-phenyl-S-meth] rlpyrazol" 5-one and 1 sil formic acid 80% ig.

After adding 10 g of a knitted fabric made of polyurethane fiber heated in 30 - 80 minutes on cooked egg tartar and 1 hour at

Colored cooking temperature.

This is followed by rinsing warm and drying.

lf * n receives an equal örangefärbuag: with good lightfastness and hatefulnessa. The same results can be achieved if aaa instead of acidic acid use other organic or inorganic acid, or at temperatures of 70 ° - 140 ° C

colors.

Also the dyes listed in the table according to Example 1 can be dyed on polyurethane fibers with equally good results. "

109851/1786

Claims (6)

- 12 PATENT CLAIMS 1) Method stubbornly producing level and true dyeings on natural or synthetic nitrogen-containing fiber materials, characterized in that the said fiber materials are mixed with 1: 2 chroma or 1: 2 cobalt complex monoazo dyes which are free of acidic, water-solubilizing groups, but at least once contain the group -SO ₂ -CHg-CH ₂ -OH, in the pH range of 4 to 8 treated. 2) The method according to claim 1, characterized in that mixtures of 1: 2 chromium ~ and 1: 2 cobalt complex: imonoazo dyes that are free of acidic, water-solubilizing groups urid at least once the group -SO ₂ -CH ₂ -CH ₂ -OH, and 1; 2-chromium and 1: 2-cobalt complex monoazo dyes, which are free from acidic, water-solubilizing groups and the group -SO ₂ -CH ₂ -CH ₂ -OH, are used. 3) Method according to claim 1 or 2, characterized in that dyeing is carried out in the pH range 7-6, the pH value at the beginning of the Dyeing process is lowered to 7.0 and during the dyeing process to 6.0. 4) Method according to claim 1 to 3, characterized in that dyeing between about 70 ° and 130 ° C according to the exhaust process. 5) Method according to claim 1 or 2, characterized in that that you apply the dyes to the fiber using the padding method applies and at about 90 ° to 220 ° C by "dry heat or in fixed in a steam atmosphere. ■ 6) Method according to claim 1 or 2, characterized in that the dyes are applied to the fiber by a printing process and fixed at about 90 ° to 220 ° C by steaming or a dry heat treatment. BATH 109861/1786