EP0045458B1 - Continuous or semi-continuous process for dyeing a voluminous woven fabric containing cellulosic fibres with azoic developing dyes - Google Patents

Description

The invention explained below relates to the uniform dyeing of voluminous fabrics, e.g. Cord, velvet, terry cloth or pile goods, made of cellulose fibers, especially cotton, with water-insoluble azo dyes produced on the fiber according to a continuous or semi-continuous method, the priming by pre-padding with a coupling component under alkaline conditions and the subsequent dye development wet-on-wet by padding with a diazo component in the presence of acid or acid-providing substances.

When dyeing cotton fabrics with azo developing dyes on the padder, the coupling component and the diazo component are generally applied from separate baths, with intermediate drying taking place between the two blocks. This process has been known for a long time and is carried out worldwide.

In this connection, many attempts have already been made to save the intermediate drying, which is expensive in terms of time and energy consumption, and to develop the dye on the fiber by wet-in-wet padding the diazonium compound onto the goods which are wet from the primer with the coupling component perform. However, such a project could only be implemented in exceptional cases. However, such a working principle has so far failed when applied to voluminous fabrics. There are two main reasons for this, which have caused these failures and which have not yet been remedied.

On the one hand, the penetration of the already wet goods in the second padding with the solution of the diazo component does not occur quickly enough, i.e. even during the eligible dive time. On the other hand, after squeezing after the second padding process, there is no longer enough development liquor in the goods with the diazonium compounds and alkali binders required for dye formation in order to ensure complete penetration of the fabric and thus complete coupling out of the coupling component to the dye.

However, there are limits to increasing the concentration of these two substances, if only because of the limited solubility of the diazonium compounds in the aqueous pad bath and especially because the alkali binder concentration (acetic acid) must not be increased arbitrarily, otherwise the alkaline primer first comes into contact with the developing liquor locally the pH is shifted by the high acid concentration so that the desired azo coupling is adversely affected. This results in uneven and non-colored goods.

The object of the present invention was therefore to remedy the shortcomings described above in relation to the two-bath dyeing of voluminous textile material with the components for forming water-insoluble azo dyes on the fiber. In order to carry out wet-on-wet dyeing, it was particularly important to achieve a sufficiently high additional liquor absorption of the moist primer at the second padding in order to enable a sufficient liquor exchange and to keep the concentration conditions in the padding liquor (development liquor) within normal limits hold.

This object is achieved according to the invention by adding 30 to 60 g / l of the polymeric or mixed polymer of acrylic acid amide in the form of a 2 to 8, preferably 4 to 5% by weight, aqueous setting and 2 to 20 g / l of an anionic or nonionic wetting agent is added.

• a) lineare oder verzweigte Polymerisate des Acrylsäureamids;
• b) Mischpolymerisate aus Acrylsäureamid und Halbestern der Maleinsäure mit Polyglykoläthern von natürlichen oder synthetischen Fettalkoholen mit (12 bis 18 C-Atomen) mit 5 bis 10 Mol Äthylenoxid je Mol Fettalkohol, im Gewichtsverhältnis von 1:0,05 bis 1:0,5 (bezogen auf das Acrylsäureamid);
• c) Mischpolymerisate aus Acrylsäureamid und Acrylamidopropansulfonsäure im Gewichtsverhältnis von 1:0,05 bis 1:0,5 (bezogen auf das Acrylsäureamid);
• d) Mischpolymerisate aus Acrylsäureamid und N-Vinyl-N-methylacetamid im Gewichtsverhältnis von 1:0,05 bis 1:0,5 (bezogen auf das Acrylsäureamid);
• e) Mischungen der vorstehend unter a) bis d) genannten Polymerisate untereinander und gegebenenfalls im Kombination mit c-Caprolactam im Gewichtsverhältnis von 1:0,5 bis 1:1 (bezogen auf die Polymerisate).

Examples of such polymers or copolymers of acrylic acid amide are:

• a) linear or branched polymers of acrylic acid amide;
• b) copolymers of acrylic acid amide and half-esters of maleic acid with polyglycol ethers of natural or synthetic fatty alcohols with (12 to 18 carbon atoms) with 5 to 10 moles of ethylene oxide per mole of fatty alcohol, in a weight ratio of 1: 0.05 to 1: 0.5 ( based on the acrylic acid amide);
• c) copolymers of acrylic acid amide and acrylamidopropanesulfonic acid in a weight ratio of 1: 0.05 to 1: 0.5 (based on the acrylic acid amide);
• d) copolymers of acrylic acid amide and N-vinyl-N-methylacetamide in a weight ratio of 1: 0.05 to 1: 0.5 (based on the acrylic acid amide);
• e) Mixtures of the polymers mentioned above under a) to d) with one another and optionally in combination with c-caprolactam in a weight ratio of 1: 0.5 to 1: 1 (based on the polymers).

The polymers of acrylic acid amide used or their copolymers with the other monomers mentioned above under a) to e) have a molecular weight of 1.0 × 10 ⁶ to 2.5.10 ⁶ , preferably of 1.5.106 to 2.0.106.

The specific properties of the acrylic acid amide polymers mentioned surprisingly result in an increase in the liquor absorption at the same roller pressure (in bar / cm ² ). This effect is roughly proportional to the amount of products used, ie the higher the application concentration, the greater the increase in liquor intake within a technically justifiable range (in line with the recommended concentrations of the added polymers).

Through the participation of polymers or Copolymers of acrylic acid amide and a wetting agent in the context of the present invention succeed in increasing the liquor absorption by the material to be dyed when wet-on-wet bridging with the developing liquor and in promoting their penetration rate through the voluminous substrate in such a way that level, well-colored Textiles can be obtained.

Surprisingly, according to the new working principle, depending on the setting and performance of the foulard used, liquor absorption values of an additional 70 to 90% (based on the weight of the dry goods) are achieved on the textiles in addition to the fleet already lying on the textile web from the primer block, which is in the end makes up a total liquor intake of 140 to 170% by weight for both blocks. In this additional amount of liquor, the diazonium compound can be dissolved in the necessary amount and the alkali binder concentration is within the usual limits. In addition, the wetting agent ensures rapid distribution of the second padding liquor in the dyed material, so that there is even dye formation on the fiber.

However, if the diazo component of the auxiliaries according to the invention is omitted in the second block, then no additional liquor absorption is obtained - or a maximum of 20% by weight additional liquor absorption when the pad is set to the weakest pressure. In this small amount of liquor, however, a 4 to 5 times higher concentration of the diazonium compound and the alkali binder would have to be dissolved than under normal conditions (with intermediate drying).

Now, with continuous dyeing, the use of acrylic acid amide polymers or corresponding mixed polymers in the padding liquors is no longer new. Thus, use is made of this in the process according to DE-A-2815511, which, taking into account the fixing conditions, amounts to suppressing the migration of disperse dyes onto polyester / cellulose blended fabrics in the course of intermediate drying and thus the occurrence of gray haze during thermal insulation. In the case of DE-A1-2738497, the aid is also used to prevent migration during intermediate drying. In these known techniques, the action of the acrylic polymers is based on counteracting the migration of the liquor or of the dye or finishing agent contained therein during intermediate drying. However, this finding cannot be interpreted in the direction of the present invention idea, where the opposite behavior of the polymer additive is decisive for the compensation of the liquor distribution.

Suitable textile materials for the process according to the invention are voluminous fabrics, such as cord, velvet, terry cloth and pile fabric, made of cellulose fibers, in particular cotton, for which levelness is particularly important. The mentioned dyed material can even be used as a raw chair (advantageous for very full or covered shades).

For dyeing textiles according to the present invention, the chemical compounds which are customary for producing development dyes and are listed in the Color Index, 3rd edition 1971 as “Azoic Coupling Component” and “Azoic Diazo Component” (diazo component) are suitable.

Some of the polymerization products of acrylic acid amide used according to the invention are known (DE-A-2 542 051, Cassella Aktiengesellschaft), but they are used for a completely different purpose, namely to suppress the “frosting effect” when dyeing polyester fibers with disperse dyes.

• Die erste Klotzung zur Grundierung des Textilgutes erfolgt üblicherweise auf dem Foulard mit einer alkalischen Lösung einer Kupplungskomponente. Man erhält dabei in der Regel Flottenaufnahmewerte zwischen 70 und 80 Gew.-%. Nach einem Luftgang (kontinuierlich) oder einer zwischengeschobenen kurzen Verweilzeit (halbkontinuierlich) wird dann die so hergestellte Grundierung nass-in-nass in Gegenwart von Alkalibindemittel (Säure oder säureliefernden Substanzen) mit der eine kupplungsfähige Diazokomponente enthaltenden Entwicklungsflotte auf dem Foulard überklotzt, wobei man dieser zweiten Klotzflotte die erfindungsgemässe Kombination aus Acrylsäureamid-Polymerisat und Netzmittel in den angegebenen Mengen zusetzt.

The new procedure is carried out as follows:

• The first padding for priming the textile goods is usually carried out on the padder with an alkaline solution of a coupling component. Fleet absorption values of between 70 and 80% by weight are generally obtained. After an air passage (continuous) or an interposed short dwell time (semi-continuous), the primer thus produced is then wet-on-wet in the presence of alkali binders (acid or acid-providing substances) with the development liquor containing a coupling-capable diazo component on the padding, whereby this is padded second padding liquor adds the combination of acrylic acid polymer and wetting agent according to the invention in the amounts indicated.

The following examples are intended to explain the present invention, but not to restrict it in any way - also with regard to the wetting agents to be used. The percentages evident in the exemplary embodiments mean percentages by weight; in the case of wet treatment of textiles, such percentages relating to liquor absorption relate to the weight of the dry goods.

example 1

• 20 g/I Azoic Coupling Component 2 mit der C.I.-Nr. 37505,
• 20 cm³/1 Natronlauge 32,5%ig,
• 5 cm³/1 eines Schutzkolloids auf Basis eines Fettsäure-Eiweiss-Kondensationsproduktes, und 2 g/I eines Netzmittels auf Basis eines Alkylsulfonats.

A cotton cordware is first padded on the foulard at 70% liquor absorption with an aqueous solution containing the following substances:

• 20 g / I Azoic Coupling Component 2 with CI no. 37505,
• 20 cm ^3/1 sodium hydroxide solution of 32.5% strength,
• 5 ^cm3 / 1 of a protective colloid based on a fatty acid-albumen condensation product and 2 g / I of a wetting agent based on an alkyl sulfonate.

• 40 'g/1 einer 45%igen, flüssigen Zubereitung der Diazoniumverbindung von Azoic Diazo Component 9 mit der C.I.-Nr. 37040,
• 2,4 g/I Amidosulfonsäure,
• 30 g/I Natriumacetat krist.,
• 5 cm³/l Essigsäure 60%ig,
• 30 g/I einer 4,3%igen, wässrigen Einstellung eines linearen Polymerisats von Acrylsäureamid (Molekulargewicht 1,4.10⁶), und
• 5 gl/ eines Netzmittels auf Basis eines Natriumalkylsulfonats mit 10% des Additionsproduktes von 8 Mol Äthylenoxid an 1 Mol Isotridecanol.

After an air passage of 60 seconds, the primer thus prepared is icklurigsflöttevon on the padder wet-on-wet with an aqueous overpadded decision _W: "

• 40 'g / 1 of a 45% liquid preparation of the Diazonium compound of Azoic Diazo Component 9 with the CI no. 37040,
• 2.4 g / l amidosulfonic acid,
• 30 g / l sodium acetate crystal,
• 5 cm ³ / l acetic acid 60%,
• 30 g / l of a 4.3% aqueous setting of a linear polymer of acrylic acid amide (molecular weight 1.4.10 ⁶ ), and
• 5 g / of a wetting agent based on a sodium alkyl sulfonate with 10% of the addition product of 8 moles of ethylene oxide and 1 mole of isotridecanol.

In this way, a further liquor absorption of 70% is obtained on the textile material. After a second air passage of 60 seconds and a hot water passage at 80 ° C to the dye coupling, the result is a level and well-colored, bright red cotton cord. The aftertreatment of the dyeing is carried out as is customary with developing dyes.

Example 2

• 18 g/l Azoic Coupling Component 20 mit der C.I-Nr. 37530,
• 18 g/I Natronlauge 32,5%ig,
• 5 g/I eines Schutzkolloids auf Basis eines Fettsäure-Eiweiss-Kondensationsproduktes, und
• 2 g/I eines Netzmittels auf Basis eines Alkylsulfonats.

Cotton cord should be dyed continuously. To do this, block the textile material on the foulard with 80% liquor absorption using an aqueous solution of:

• 18 g / l Azoic Coupling Component 20 with CI no. 37530,
• 18 g / l caustic soda 32.5%,
• 5 g / l of a protective colloid based on a fatty acid-protein condensation product, and
• 2 g / l of a wetting agent based on an alkyl sulfonate.

• 56 g einer stabilisierten Diazoniumverbindung von Azoic Diazo Component 3 mit der C.L-Nr. 37010 (in handelsüblicher Einstellung),
• 2 g eines Dispergiermittels auf Basis von oxäthyliertem Stearylalkohol,
• 45 g einer 4%igen, wässrigen Einstellung des Mischpolymerisats aus Acrylsäureamid und Acrylamidopropansulfonsäure im Gewichtsverhältnis von 1:0,1, bezogen auf das Acrylsäureamid (Molekulargewicht des Mischpolymerisats 1,9·10⁶),
• 5 g eines Netzmittels aus einem Natriumalkylsulfonat und 10% des Additionsproduktes von 8 Mol Äthylenoxid an 1 Mol Isotridecanol.

After padding and a direct air passage, this primer is padded wet-on-wet with a developing liquor containing per liter of water:

• 56 g of a stabilized diazonium compound from Azoic Diazo Component 3 with the CL no. 37010 (in commercial setting),
• 2 g of a dispersant based on ethyl stearyl alcohol,
• 45 g of a 4% aqueous setting of the copolymer of acrylic acid amide and acrylamidopropanesulfonic acid in a weight ratio of 1: 0.1, based on the acrylic acid amide (molecular weight of the copolymer 1.9 × 10 ⁶ ),
• 5 g of a wetting agent from a sodium alkyl sulfonate and 10% of the addition product of 8 moles of ethylene oxide with 1 mole of isotridecanol.

When padding over, a renewed liquor absorption of the goods of 80%, totaling 160% liquor absorption, is obtained. An air passage of 40 seconds and a hot water passage at 80 ° C complete the dye coupling.

• 1. Seifbad von 60°C mit
• 1 g/I Oleylmethyltaurin und
• 5 g/I Soda kalz.
• 2. und 3. Seifbad kochend mit
• 0,5 g/I Oleylmethyltaurin und
• 2 g/I Soda kalz.

The dyeing thus produced is then soaped in an aqueous liquor with the addition of the following substances:

• 1. Soap bath at 60 ° C with
• 1 g / l oleyl methyl taurine and
• 5 g / l soda ash.
• 2nd and 3rd soap bath boiling with
• 0.5 g / l oleyl methyl taurine and
• 2 g / l soda ash.

Rinsing and drying end this continuous coloring. A strong red, well-colored cotton cord is achieved in this way.

Is allowed, however, in the above dyeing process in the padding liquor with the Azoic Diazo Component the copolymer and the surfactant away, then one (cm ² to 0.5 bar /) obtained even when recorded on weakest pressure Foulard just another liquor pick-up of the max. 20% and an uneven dyeing as well as an undyed cotton cord.

Example 3

• 20 g/I Azoic Coupling Component 24 mit der C.I-Nr. 37540 (gelöst nach der Kaltlösevorschrift),
• 20 cm³/1 Natronlauge 32,5%ig,
• 5 cm³/1 eines Schutzkolloids auf Basis eines Fettsäure-Eiweiss-Kondensationsprodukts,
• 3 cm³/1 eines Netzmittels auf Basis eines Alkylsulfonats, und
• 3 cm³/1 eines Sequestriermittels auf Basis von einem Äthylendiaminacetat.

A raw cotton cord should be dyed continuously with development dyes. To do this, block the textile material on the foulard at 70% liquor absorption with an aqueous liquor which contains the following substances:

• 20 g / I Azoic Coupling Component 24 with the CI no. 37540 (solved in accordance with the cold release regulations),
• 20 cm ^3/1 sodium hydroxide solution of 32.5% strength,
• 5 ^cm3 / 1 of a protective colloid based on a fatty acid-albumen condensation product,
• 3 ^cm3 / 1 of a wetting agent based on an alkyl sulfonate, and
• 3 ^cm3 / 1 of a sequestering agent based on a Äthylendiaminacetat.

• 56 g/I einer stabilisierten Diazoniumverbindung von Azoic Diazo Component 49 mit der C.I.-Nr. 37050 (in handelsüblicher Einstellung), 60 g/I einer 4%igen, wässrigen Einstellung des Mischpolymerisats aus Acrylsäureamid und dem Maleinsäurehalbester eines Polyglykoläthers aus dem Additionsprodukt von 8 Mol Äthylenoxid an 1 Mol Isotridecanol, im Gewichtsverhältnis von 1:0,075, bezogen auf das Acrylsäureamid, (Molekulargewicht des genannten Mischpolymerisats 1,47.10⁶), und
• 5 g/I eines Netzmittels auf Basis eines Alkylsulfonats und eines oxäthylierten Isotridecanols.

After padding, an air passage of 2 minutes is switched on and then this primer is padded wet-on-wet onto the foulard with an aqueous development liquor of:

• 56 g / l of a stabilized diazonium compound from Azoic Diazo Component 49 with the CI no. 37050 (in a commercially available setting), 60 g / l of a 4% strength, aqueous setting of the copolymer of acrylic acid amide and the maleic acid half ester of a polyglycol ether from the addition product of 8 mol of ethylene oxide with 1 mol of isotridecanol, in a weight ratio of 1: 0.075, based on the acrylic acid amide , (Molecular weight of said copolymer 1.47.10 ⁶ ), and
• 5 g / l of a wetting agent based on an alkyl sulfonate and an oxyethylated isotridecanol.

After padding, an air passage of 30 seconds and a hot water passage at 80 ° C follow to complete the dye formation by coupling. Then the dyed goods are soaped and dried as in Example 2. In this way you get a perfectly colored cord in a dull orange tone.

The liquor absorption of the textile material dyed as above when padding is again 90%, so that, according to the invention, a total liquor absorption of 160% is achieved. However, if the goods are colored without the Zu block of the copolymer and the wetting agent wet-on-wet padded over, then no further liquor absorption and an uneven, non-colored cord are obtained.

Example 4

• 20 g/I Azoic Coupling Component 8 mit der C.L-Nr. 37525 (nach der Kaltlösevorschrift gelöst), 20 cm³/l Natronlauge 32,5%ig,
• 100 cm³/1 Äthanol denat.,
• 2 cm³/1 eines Netzmittels,
• 5 cm³/1 eines Schutzkolloids auf Basis eines Fettsäure-Eiweiss-Kondensationsproduktes, und
• 2 cm³/1 eines Sequestriermittels.

For dyeing on the foulard, block a terry cloth with 80% liquor absorption with an aqueous solution of:

• 20 g / I Azoic Coupling Component 8 with CL no. 37525 (dissolved according to the cold dissolving instructions), 20 cm ³ / l sodium hydroxide solution 32.5%,
• 100 cm ^3/1 Ethanol denat.,
• 2 ^cm3 / 1 of a wetting agent,
• 5 ^cm3 / 1 of a protective colloid based on a fatty acid-albumen condensation product, and
• 2 ^cm3 / 1 of a sequestering agent.

• 62 g/I einer stabilisierten Diazoniumverbindung von Azoic Diazo Component 2 mit der C.L-Nr. 37005,
• 30 g/I einer 4,5%igen, wässrigen Einstellung eines linearen Polymerisats von Acrylsäureamid (Molekulargewicht 1.4·10⁶),
• 5 g/I eines Netzmittels aus 80% eines Natriumalkylsulfonats und 20% des Additionsproduktes von 8 Mol Äthylenoxid an 1 Mol Isotridecanol, 16 cm₃/l Essigsäure 60%ig, und
• 2 cm³/1 eines Dispergiermittels auf Basis von oxäthyliertem Stearylalkohol.

The primer prepared in this way is then left to roll for 1 hour. Then the goods are padded on the wet-in-wet foulard with an aqueous development liquor which contains:

• 62 g / l of a stabilized diazonium compound from Azoic Diazo Component 2 with the CL no. 37005,
• 30 g / l of a 4.5% aqueous formulation of a linear polymer of acrylic acid amide (molecular weight 1.4 · 10 ⁶ ),
• 5 g / l of a wetting agent composed of 80% of a sodium alkyl sulfonate and 20% of the addition product of 8 moles of ethylene oxide with 1 mole of isotridecanol, 16 cm ₃ / l of 60% acetic acid, and
• 2 ^cm3 / 1 of a dispersant based on oxäthyliertem stearyl alcohol.

An additional 80% liquor absorption is obtained on the textile goods. After an air passage of 1 minute and a hot water passage at 80 ° C to the dye coupling and after the usual soaps (see example 2) and drying, a strong orange color results, which is well colored.

Claims (8)

1. A process for the even dyeing of a voluminous woven fabric consisting of or containing cellulose fibers, with water-insoluble azo dyestuffs produced on the fiber according to a continuous or semicontinuous method, in which the impregnation is performed by pre-padding the fabric web with a coupling component under alkaline conditions, and subsequently the development of the dyestuff is effected, wet-in-wet, by slop-padding the textile goods with a diazo component in the presence of an acid and/or an acid-forming substance, which comprises adding to the acidic developing liquor containing the diazo component capable of being coupled an auxiliaries' combination of polymers or copolymers of acrylic acid amide, said polymeric component being incorporated in an amount of from 30 to 60 g/I in the form of a 2 to 8% (by weight) preferably 4 to 5% (by weight), aqueous formulation, and of from 2 to 20 g/I of an anionic or nonionic wetting agent.

2. A process as claimed in claim 1, wherein as polymeric component linear or branched homopolymers of acrylic acid amide are added.

3. A process as claimed in claim 1, wherein as polymeric component copolymers of acrylic acid amide and semiesters of maleic acid with polyglycol ethers of natural or synthetic fatty alcohols (of from 12 to 18 carbon atoms) with from 5 to 10 mols of ethylene oxide per mol of fatty alcohol, in a weight ratio of from 1:0.05 to 1:0.5 (calculated on the acrylic acid amide) are added.

4. A process as claimed in claim 1, wherein as polymeric component copolymers of acrylic acid amide and acrylamido-propane-sulfonic acid in a weight ratio of from 1:0.05 to 1:0.5 (calculated on the acrylic acid amide) are added.

5. A process as claimed in claim 1, wherein as polymeric component copolymers of acrylic acid amide and N-vinyl-N-methylacetamide in a weight ratio of from 1:0.05 to 1:0.5 (calculated on the acrylic acid amide) are added.

6. A process as claimed in claims 2 to 5, wherein mixtures of the specified polymeric components one with another are added.

7. A process as claimed in claims 2 to 6, wherein to the specified polymeric components s-caprolactam is further added in a weight ratio of from 1:0.5 to 1:1 (calculated on the weight of the polymeric component).

8. A process as claimed in claims 1 to 7, wherein the applied polymers of acrylic acid amide or the copolymers thereof have a molecular weight of from 1.0x106 to 2.5 x 106.