DE2605084A1 - ACID DYES, PROCESS FOR THEIR PRODUCTION AND THEIR USE - Google Patents

Description

LAWYERS Ka / be

DR JUR-DIPL-CHEM-WALTERBEIT

Ä O Feb 9, 1976

DR. JUR. HaNS CHR. Ax

FRANKFURTAM AAAiN-HOCHSf

Our no. 20 276

Montedison SpA
Milan / Italy

Acid dyes, processes for their preparation and their use ^ -

The present invention relates to novel acidic dyes for dyeing striped nylon and methods of making the same.

In particular, the present invention relates to the use of such yellow or orange-yellow shaded ones. Dyes found in Are hardly soluble in water, are free of sulfonic acid groups and contain a carboxylic acid chain, for dyeing polyamide fibers.

As is known in the field of man-made and man-made fibers, One of the typical properties is good dyeability of manufactured articles. On the: field of polyamide fibers

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in particular, it is difficult to obtain completely uniform colors, because variations in the physical and chemical nature of the pasers have a significant impact on the parbing. Color flaws, resulting from this are commonly referred to as "stripes" or "streakiness".

In general, dyeing is required to have uniformity and good stability properties. These two requirements apart from lightfastness, are not always in the same dye, especially with regard to the polyamide fibers, before.

In this context it can even be said that, the more genuine a color, the less compensating or leveling there is and vice versa. For these fibers, and in particular for polyamides, generally dispersed and anionic dyes are used to achieve defined color tones appropriately selected is used.

The dispersed colors (e.g. Microsetile-ACNA) can suitably to achieve pale shades inasmuch as they have a high leveling ability in terms of covering Unfold fiber strips are used.

In addition to the practical impossibility of achieving very intense color tones in the production of medium and rich color tones Shades with these dyes show their poor fastness to wet treatments, which are not always appropriate for different ones Objects requirements are met, are taken into account.

The selected anionic dyes (e.g. 3. Nailammide-ACNA)

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_ ~ z. -.

have good opportunities for dark hues and bad opportunities for medium hues while they are generally unsuitable for providing pale shades because of their inadequate leveling ability are.

The use of auxiliaries of the anion active type (e.g. Dispergal FP, sold by Montecatini Edison), cation active type (e.g. Dispersol CWL, sold by Montecatini Edison) or of the nonionic type in dyeing leads to certain improvements for the achievement medium color shades, but with these dyes it is never possible to obtain pale color shades that are well equalized with certainty.

It has now been found that polyamide fiber fabrics, even if they are very streaky, in a boiling aqueous bath with a pH value between alkaline at the beginning to slightly acidic (even when working in the absence of auxiliaries) when using of easily soluble dyes that do not have any free sulfonic acid groups contain, but carry a carboxylic acid chain and the general formula

(I)

COOH

in which the radical R is a methyl or ethyl radical and R _{1 is} a hydrogen atom or a methyl radical and the carboxylic acid radical in relation to the azo group substitutes the hydrogen atoms in the meta or para position, all in yellow

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-I-

or yellow-orange hues.

These new dyes are produced in a manner known per se by reacting the aqueous hydrochloric acid solution of the diazonium salt the suitable aminobenzoic acid and Ν, Ν-diethyl-m-amino-acetooder-propionan.ilid manufactured.

The colorations obtained are always balanced, regardless of their intensity, and the authenticity is particularly good in the case of wet treatments excellent.

When comparing the dyes according to the invention with the known dyes which show the best results in terms of the leveling capacity, in particular with Yellow Nailamide ER, CI Acid Yellow 25, No. 18835, Orange Nailamide EPO, CI. Acid Orange 28, was' found that, surprisingly, that the dyes of the invention have a markedly superior Egalisierungsvermögen with respect to the strip, although they especially as regards the wet treatments show good general fastness properties.

When compared with dispersed dyes such as Yellow Microsetile 5R, CI. Disperse Yellow 7, No. 26090, Orange Microsetile GR, CI, Disperse Orange 3, No. 11005 for dyeing polyamide fibers, it was found that the dyes according to the invention the achievement of better stability with the same leveling ability to wet treatments, while the others generally maintain good stability properties will.

Another important property of the dyes according to the invention is the achievement of particularly intense color tones. Indeed, it can be observed that at the same concentration the intensity of the colors produced by such color

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substances is provided, the intensity that is known by ' dispersed dyes is provided exceeds. This intensity is of the same order of magnitude, too for rich color tones, such as the intensity created by the anionic dyes, with which only poor coverage of the stripes can be achieved is provided.

Best results are achieved by a dyeing method according to which a first slightly alkaline stage is provided. For this purpose, systems that are buffered with borates and phosphates are suitably used, which allow dyeing to be started at pH values between pH 8.5 and 9 and the values successively by the gradual addition of organic acids according to usual techniques, can be lowered to slightly acidic pH values (5 _; ~ 5 »5).

For pale shades it is preferred to dye at pH to complete between pH 6 and 6.5. Working according to this procedure gives the best migration and leveling ability achieved without significant reduction in affinities.

The fabric is in the presence of before dyeing

1 g / l of Anionic UN 100 (a non-ionic detergent from Montedison) and

1-2 g / l trisodium phosphate washed, the treatment was started at 30 ⁰ C and the treatment was carried out for 40 minutes at 8O ⁰ C.

The following examples serve to illustrate the present invention, unless otherwise indicated, denote the

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Parts parts by weight.

example 1

2.85 parts by weight of p-aminobenzoic acid, in a concentration of 72.5 % _} corresponding to 2.06 parts by weight of pure p-aminobenzoic acid, were dissolved in 8 ml of HCl, d = 1.18, and 30 ml of water.

This solution was then by slowly adding a solution of 1.05 parts of sodium nitrite in 10 ml of water at a Temperature between 5 and 10 ° C diazotized.

The diazo solution turned into a solution at 5 to 10 C after clarification of 3.1 parts of Ν, Ν-diethyl-m-aminoacetaniiid in 15 ml of acetic acid, Poured 8 parts of sodium acetate in the form of crystals and 50 ml of water.

After stirring for about three hours at 5 to 10 ^° C., the mixture was filtered. The low temperature was washed with water and then dried. This procedure gave 3.15 parts of a dye of the formula

HOOC -

VL / -

NHCOCH

wherein R of the general formula (I) denotes the methyl radical, as yellow powder that transforms the streaky polyamide fibers into a real

yellow powder, the foiyamiaiasern in dispute in one uniform, bright orange hue.

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In an analogous manner, the dye in which R of the formula (I) means an ethyl radical. The same results were obtained with this dye.

Example 2

2.06 parts of pure m-aminobenzoic acid were diazotized according to the method described in Example 1 and 3> 1 parts of N, N-diethyl-m-aminoaeetanilide coupled.

According to this procedure, 3> 8 parts of the dye became the general Formula-

N = N

CH
COOH NHCOCH °

where the radical R of the general formula (I) is a methyl radical,. as a yellow powder that the polyamide fibers, too streaky, colored in a true, uniform, bright yellow shade.

In an analogous manner and with the same results, a dye was prepared in which the radical R is the general Formula (I) denotes an ethyl radical.

Example 3

3.0. Part 3 ~ ⁱ amino l-methyl-benzoic acid was dissolved in 8 ml of HCl, d = 1.18, and 30 ml of water. This solution was at 5 - 10 ° C

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by slowly adding a solution of 1.37 parts of sodium nitrite diazotized in 10 ml of water.

The diazo solution became - after clarification - a solution at 5 - 10 ° C of 4.1 parts of Ν, Ν-diethyl-m-amino-acetaniiid in 15 ml of acetic acid, 12 parts of sodium acetate in the form of crystals and 50 ml Poured water.

After stirring for about three hours at 5-10 ° C, the mixture became filtered and the precipitate washed with water and then dried.

This procedure gave 5 »^ parts of the dye of the general formula

COOH

as a yellow powder, which the polyamide fibers, also streaky, in a bright, solid and uniform yellow-orange hue colored, received.

example H

100 g of textured and particularly stripy nylon fabric, which was formed into a tubular stocking, after washing, in a dye bath that
0.3 g monosodium phosphate per liter,
1.7 g sodium phosphate contained per liter, brought and 20

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Treated minutes at 60 ° C.

Separately, 0.2 of the dye prepared in Example 2 was used the formula

: ooh

mixed with ammonia and then dissolved in water was added to the dyebath through a sieve, checking that the pH was between 8, ^ and 9.

This dyebath was then slowly brought to the boil and held at that temperature for twenty minutes.

Acetic acid then gradually became over the course of 50 minutes added until the pH drops to a value of 6 - 5 * 5 with the dyebath boiling for 30 minutes became. This was followed by extensive rinsing and washing.

This process gave a completely equalized yellow color with the following fastness properties:

Fastness to natural light: 5 Fastness to washing at 60 ° C

(ÜNI = Ente Italiano Unificazione according to the A.A.T.C.C. US standards): 4-5M-5M-5,

where the first number is the change in hue, the second number

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the discoloration on nylon and the third number means the discoloration on wool.

Analogous results were obtained with the corresponding dye, which was derived from N, N-diethyl-m-amino-propioanilide.

Example 5

Following the procedure described in Example 4, the same material was made with the dye of the formula prepared in Example 1

HOOC- / O V-N = N-

colored. It became a completely equalized orange color with the following authenticity:

Fastness to natural light: 5 Fastness to washing at 60 ° C (UNI): 4 / 4-5 / 4,

where the numbers given have the same meaning as given in Example 4 _? own, receive.

Analogous results were obtained with a dye obtained by using from Ν, Ν-diethyl-m-amino-propionani'liä. obtained.

Example 6 (comparative example)

100 g of the same textured nylon fabric used in Example 4

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was used were immersed in a dye bath containing 0.3 g of monosodium phosphate per liter and
Contained 1.7 g disodium phosphate per liter.

Separately from this, iO.8 g of Yellow Nailamide ER (CI. Acid Yellow

\to the
25, No. 18p35) dissolved in water and added to the dyebath, the pH being adjusted to between pH 8.5 and 9 by optionally adding ammonia. The dye bath was then brought slowly to boiling ι · and held 20'Minuten at this temperature.

Acetic acid was then gradually added over a period of 1 ½ minutes until the pH was reduced to 6-5 »5, the dyebath being kept boiling for 30 minutes. This was followed by extensive rinsing and washing.

A yellow coloration with obvious streaks was obtained. which showed the limited leveling ability of the dye on the material to be dyed. This is done by comparison with the material colored according to example *} clearly expressed brought.

The fastness properties were as follows:

Fastness to natural light: 6 Fastness to washing at 6O ⁰ C: ^ -5 / ^ - 5 / ^ - 5.

Example ¹ J (comparative example)

According to the method described in Example 6, the same material was colored with Orange Nailamide EPO (CI. Acid Orange 28).

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According to this process, an orange coloration with clearly visible stripes was obtained, which has limited leveling power of the dye on the colored material. This is shown by comparison with the material Example 5 illustrates to a great extent.

The fastness properties were as follows:

Fastness to sunlight: 5

Fastness to washing at 60 ° C: 4-5 / 4-5 / 4-5.

Example 8 (comparative example)

100 g of the same textured nylon cloth that was mentioned in Example 4 was, after previous washing, in a dye bath containing 1 g of ELU (nonionic surfactant, sold by Montecatini Edison) emulson with a pH equal to by additive of acetic acid was _{adjusted to 5 S} 5 contained, brought.

Separately from this, 0.6 g of Microsetile 5R Yellow (CI. Disperse Yellow 7, No. 26090) and then added to the dye bath through a sieve. The bath was then slowly heated to boiling point and kept boiling for 60 minutes. The fabric was then rinsed extensively and carefully washed.

According to this procedure, a well-leveled coloration was obtained, which was comparable to that according to example 4 and was significantly better than that which was achieved according to example 6.

The fastness properties were as follows:

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Fastness to sunlight: 5/6

Fastness to washing at 60 ° C.: 4/2 / 4-5.

The fastness values compared to the wet treatments are significantly worse than those for the dyeings according to Example 4 and 6 were obtained.

Example 9 (comparative example)

According to the method described in Example 8, the same material was mixed with the dye Orange Microsetile GR (CI. Disperse Orange 3, No. 11005) colored.

According to this method, a well-leveled orange coloration which was comparable to the coloration obtained according to Example 5 and was significantly better than the coloration obtained for Example 7 was obtained. ·
The fastness properties were as follows:

Fastness to sunlight: 4

Fastness to washing at 60 ° C: 2-3 / 1-2 / 2-3.

It was observed that the fastness values to moisture the values obtained for the colorations according to Examples 5 and 7 are considerably inferior.

Example IO

100 g of a textured and particularly striped nylon fabric in the form of a tubular stocking were made according to the preceding Wash in a dye bath that

0.3 g of monosodium phosphate per liter and 1.7 g of disodium phosphate per liter, brought and 20 Mi-

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grooves treated at 60 ° C.

Separately, 0.2 g of the dye according to Example 2 the formula

N = N-

COOH

mixed with ammonia, dissolved in water and added to the dyebath through a sieve, checking that the pH is between pH was 8.5 and 9. This mixture was then slowly brought to the boil and kept at this temperature for 20 minutes.

Acetic acid was then gradually added over the course of 40 minutes until the pH decreased to between 6 and 5-5 and the dyebath was boiled for 30 minutes. Afterward the dyed material was rinsed and washed extensively.

According to this procedure, a completely leveled yellow-orange color became achieved, which showed the following stability properties:

Fastness to natural light: 5 Fastness to washing at 60 ° C (ÜNI): 4 / 4-5 / 4-5,

where the first number is the change in tone, the second number is the discoloration of nylon and the third number is the discoloration of wool represents.

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Example 11 (comparative example)

100 g of the same textured nylon fabric named in the example was added to the dye bath that

0.3 g of monosodium phosphate per liter and 1.7 g of disodium phosphate per liter contained, brought.

0.8 g of Nailamide ER Yellow (CI. Acid Yellow 25, No. 18835) dissolved in water and added to the dye bath, it was checked that the pH was 8.5 to 9, ammonia being added if necessary. The mixture was then slowly heated to boiling and held at this temperature for 20 minutes.

Then acetic acid gradually became over 40 minutes added until the pH dropped to pH 6 to 5.5. The dyebath was boiled for 30 minutes. The dyed material was then rinsed and washed extensively.

A yellow coloration with obvious streaks was obtained, the streaks being the limited leveling power of the dye on the material to be colored. This is shown by comparison with that colored according to Example 10 Material clearly expressed.

The stability properties were as follows:

Fastness to natural light: 6 Fastness to washing. At 6O ⁰ C: 4-5 / 4-5 / ¹ IS.

Example 12 (comparative example)

Following the procedure described in Example 11, the

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the same material dyed with the dye Orange Nailamide EPO (CI. 'Acid Orange 28).

According to this method, an orange coloration was obtained which showed clearly visible streaks, which had the limited leveling power of the dye on the material to be colored made clear !. That is clear from a comparison with that according to Example 11 colored material can be seen.

The stability properties were as follows:

Fastness to natural light:. 5 Fastness to washing at 60 ° C: 4-5 / 4-5 / 4-5.

Example 13 (comparative example)

100 g of the same textured nylon fabric from Example 10 were, after previous washing, placed in a dye bath which contained (L g of emuls on ELU per liter with a pH of 5 ₉ 5 stabilized by the addition of acetic acid.

Separately from this, 0.6 g of the dye Yellow Microsetile 5R (CI. Disperse Yellow 7, No. '26090) was passed through a sieve into the' Dyebath dispersed. The dyebath was then slowly brought to the boil and kept at this temperature for 60 minutes. The material was then rinsed extensively and carefully washed.

A well-leveled yellow coloration was obtained which was comparable to that obtained in Example 10 and clearly better than that obtained in Example 11.

The stability properties were as follows:

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Fastness to natural light 5 to 6 fastness to scrubbers at 6O ⁰ C: 4/2 / 4-5.

The stabilities towards the dimensional treatment were those obtained for the dyeings according to Examples 10 and 11, superior.

Example 14 (comparative example)

Following the procedure described in Example 13, the same was followed Material dyed with the dye Orange Microsetile GR - (CI. Disperse Orange 3, No. 11005).

According to this procedure, a well-leveled orange coloration comparable to that obtained in Example 10 was obtained and was definitely better than that obtained in Example 12.

The stability properties were as follows:

Fastness to natural light: 4 Fastness to washing at 60 ° C: 2-3 / 1-2 / 2-3.

The stabilities to wet treatments are clearly inferior to those obtained for Examples 10 and 12.

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Claims (2)

Claims 1. Dyes of the general formula NH-CCMl. wherein R is a methyl radical or an ethyl radical and R is a hydrogen atom or denote a methyl radical and the carboxyl radical in relation to the azo group is hydrogen atoms in the meta or para position substituted. 2. Process for the preparation of the dyes according to claim 1, characterized in that the suitable diazonium salt of m- or p-amino-benzoic acid with the corresponding N, N-diethyl-m-amino-acylanilide sour coupling. 3 · Method for the balanced dyeing of irregular polyamide fibers in yellow and orange hues, characterized in that the dyes according to Claim 1 are used. For: Montedison S.p.A. Milan / I / fcalien Dr.H.J.WoIff Lawyer 609835/0919