DE10345797A1 - Pretreatment of cellulose-containing textiles before dyeing, e.g. for production of colored hard-wearing fabrics, involves treatment with a vinylamide polymer which is at least partly hydrolysed before and-or after drying - Google Patents

Abstract

A (co)polymer solution for the pretreatment of textiles which is obtained by (co)polymerisation of an N-vinylamide, is subjected to at least partial hydrolysis of the amide groups before and/or after drying the treated textile. A method (M1) for the pretreatment of cellulose- containing textiles involves (a) treatment with a solution of (co)polymer obtained by (a1) (co)polymerisation of N-vinylamides of formula H2C=CH-NHCOR (I) in which R : H or 1-10C alkyl and optionally (a2) partial hydrolysis, (b) optional drying of the treated textile and (c) optional hydrolysis (at least partial) of the amide groups. At least one of the stages (a2) and (c) must be carried out. Independent claims are also included for (1) cellulose-containing textiles pretreated by this method (2) a method (M2) for the production of colored cellulose-containing textiles by dyeing textiles pretreated by M1 with reactive, vat or direct dyes (3) colored textiles obtained by M2 .

Description

• (a) Behandlung von zellulosehaltigem Textil mit einer Lösung von Polymer oder Copolymer, das erhältlich ist durch (a1) Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel I,
  
  wobei R gewählt wird aus Wasserstoff und C₁-C₁₀-Alkyl, und (a2) gegebenenfalls partielle Hydrolyse,
• (b) optional Trocknung des behandelten Textils, und
• (c) Verseifung zumindest eines Anteils der Amidgruppen, wobei man mindestens einen der Schritte (a2) und (c) durchführt.

The present invention relates to a process for the pretreatment of cellulosic textile, comprising the following steps:

• (a) treatment of cellulosic textile with a solution of polymer or copolymer obtainable by (a1) polymerization or copolymerization of N-vinylamide of general formula I,
  
  wherein R is selected from hydrogen and C ₁ -C ₁₀ -alkyl, and (a2) optionally partial hydrolysis,
• (b) optionally drying the treated textile, and
• (C) saponification of at least a portion of the amide groups, wherein at least one of the steps (a2) and (c) is carried out.

The To dye of cellulosic textile can be done by various methods. Usual are today colorations with reactive, vat- or direct dyes. In many cases, however, one observes that degree of exhaustion, i. the proportion of dye coming from the dyeing liquor can be applied to the textile, as well as authenticity level of coloring to be desired.

Especially in reactive dyeings becomes common receive only a degree of exhaustion, which is well below 80%. This is caused for example by the fact that it is in many make does not succeed, a complete Reaction of the reactive anchor with the OH groups of the cellulose to achieve. The remaining dye is usually disposed of via the treatment plant.

The in many cases Unsatisfactory level of authenticity of the coloring is especially characterized that does not cause all Dye is sufficiently fixed. It is observed in use of textile that unfixed dye during by the end user conducted washings is washed out. Even apparently sufficiently fixed reactive dye can be washed out if the chemical bond between reactive dye and fiber during the usual Washing processes is split, which in addition to the bleeding of the accompanying tissues also results in bleaching of the washed textile.

Around the authenticity level of dyeings especially with reactive dyes to improve today often cationic aftertreatment agents used for dyed textile, what but with additional Process steps in the dyeing process or in the equipment is connected and therefore causes higher costs.

Farther has been proposed, cationic aftertreatment agents and also Polyethylene amines prior to the actual dyeing process on cellulosic Apply textile. This application causes a much more intense coloring (Bunt-Denim, TI / T 240d, July 1993, BASF Aktiengesellschaft), however you can in many cases an undesirable ring color observe, that is, some or all fibers are not uniform across the cross-section, but instead only on the surface colored. With strong mechanical stress of such dyed fibers becomes the coloring easily removed mechanically, and the fibers get within a short time Time an undesirable Appearance.

task Therefore, the present compound was a pretreatment process of textile to provide that the disadvantages of the prior art avoids and in particular evenly dyed textile available power.

Accordingly, became Found the initially defined method.

Cellulose-containing textile or textiles in the context of the present invention are cellulose-containing Textile fibers, cellulose-containing textile semi-finished and finished goods and finished products derived therefrom, which include textiles for the clothing industry, for example, carpets and other home textiles as well as technical purposes serving textile structures. These include unshaped structures such as flakes, linear structures such as twine, threads, yarns, linen, cords, ropes, threads and body structures such as felts, fabrics, nonwovens and wadding. Cellulosic textiles may be of natural origin, for example cotton, wool or flax, or blended fabrics, for example cotton / polyester, cotton / polyamide, the size of the cellulose content being uncritical.

wobei
R gewählt wird aus C₁-C₁₀-Alkyl, verzweigt oder bevorzugt unverzweigt, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt unverzweigtes C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl;
und insbesondere Wasserstoff
und (a2) gegebenenfalls partielle Hydrolyse.According to the invention, cellulose-containing textile is treated in step (a) with a solution of polymer or copolymer obtainable by
(a1) polymerization or copolymerization of N-vinylamide of the general formula I,

in which
R is selected from C ₁ -C ₁₀ -alkyl, branched or preferably unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- Pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably unbranched C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, n-butyl;
and especially hydrogen
and (a2) optionally partial hydrolysis.

In an embodiment The present invention uses copolymers obtained by copolymerization of N-vinylamide of the general formula I with at least one suitable Comonomer are available, where copolymers are random copolymers, block copolymers and especially graft copolymers. Suitable comonomers are, for example, (meth) acrylates such as, for example, methyl acrylate, Methyl methacrylate, ethyl acrylate, N-vinyl pyrrolidone, N-vinyl imidazole, Ethyl methacrylate, ethylene, propylene, 1-butene or 1,3-butadiene.

In an embodiment contain copolymers obtained by copolymerization of N-vinylamide of the general Formula I are available with at least one suitable comonomer, at least 30 wt .-%, preferably at least 50 wt .-%, based on Copolymer, to N-vinylamide of the general formula I.

In an embodiment In the present invention, copolymers of at least two are used various monomers of the general formula I, wherein it is in copolymers to random copolymers, block copolymers and especially graft copolymers can act.

In a preferred embodiment The present invention uses homopolymers of N-vinylformamide one.

In one embodiment of the present invention, the polymers or copolymers used in step (a) have a molecular weight M _w in the range of 10,000 to 1,000,000 g / mol, preferably 30,000 to 400,000 g / mol.

In an embodiment In the present invention, in step (a), such a polymer is used or copolymer available is by polymerization or copolymerization of N-vinylamide of general formula I and subsequent partial hydrolysis of Amide groups, for example with dilute aqueous alkali or dilute aqueous alkali carbonate or more dilute aqueous Acid like for example, phosphoric acid or sulfuric acid, wherein, for example, 60 mol% or 30 mol% or 10 mol% of all Amide groups can be hydrolyzed.

In an embodiment the present invention provides aqueous solution of the polymer or copolymer, available by polymerization or copolymerization of N-vinylamide of general formula I, in a concentration of 0.1 to 20 wt .-%, preferably 0.5 to 5 wt .-% used.

In one embodiment of the present invention, in the range from 0.1 to 10% by weight, preferably 2 to 8 wt .-%, based on cellulosic textile, of optionally partially hydrolyzed polymer or copolymer, obtainable by polymerization or copolymerization of N-vinyl amide of the general formula I.

in the In the context of the present invention, one can use step (a) perform several times. It can various polymers or copolymers are used, of which at least one by polymerization or copolymerization of N-vinyl amide is available. But you can also use the same polymer or copolymer, by polymerization or copolymerization of N-vinylamide and optionally partial hydrolysis is available.

The Treatment in step (a) may, for example, according to a Pulling out or a padding process done.

Do you wish Step (a) to perform in the manner of an exhaust method, so can be the vorzubehandelnde cellulosic textile by a preferably aqueous Fleet pull, which is a solution of polymer or copolymer, available by polymerization or copolymerization of N-vinylamide of the general Formula I, contains. Subsequently pulling the cellulosic textile to be treated by rolling and squeeze off excess solution.

Do you wish Step (a) to perform in the manner of a padding method, so you can do common Use machines. Preferred are foulards that are essential Element containing two superimposed rollers through which the pretreated cellulosic textile is performed. Above the rollers is liquid, containing solution of polymer or copolymer, available by polymerization or copolymerization of N-vinylamide of the general Formula I, filled and wets the textile. The pressure squeezes the textile and ensures a constant order. In another embodiment the padding is done with one or more impregnating baths the cellulosic textile to be treated is drawn. Afterwards is that going? Textile through a foulard, and excess solution becomes squeezed off.

in the Following step (a), textile treated according to step (a) can be obtained dry (b). This optional drying (b) can be carried out in common Equipment, such as drying cabinets, or in the fresh Perform air. Temperatures in the range of 30 ° C up to 120 ° C are useful, preferably 70 to 110 ° C. Drying time is usually dependent from the drying temperature and the desired residual moisture content and may be in the range of 30 seconds to 3 hours, however also longer or shorter ones Time periods possible.

Do you wish To perform step (a) several times, so you can after each treatment step (a) dry or preferably only after the last treatment step (a).

in the optional step (c) of the process according to the invention is saponified at least a proportion of the amide groups. Among them are the amide groups the one or more according to step (a) to understand polymers or copolymers applied to the textile, by polymerization or copolymerization of N-vinylamide of the general Formula I available are.

you leads in the Within the scope of the present invention, at least one of the steps (a2) and (c) by, i. You can partially cellulosic textile with hydrolyzed polymer or copolymer of N-vinylamide of the general Treat formula I and skip step (c) or you can Perform step (c) and refrain from partial hydrolysis according to (a2).

In an embodiment In the present invention, a cellulosic textile is treated with a solution of polymer or copolymer obtainable by polymerization or copolymer of N-vinylamide of the general formula I and the one according to step (a2) has partially hydrolyzed, optionally after step (b) dries and saponify afterwards at least a portion of the amide groups according to step (c).

In an embodiment of the present invention Step (c) is done by treating and if necessary dried textile with diluted aqueous alkali or dilute aqueous alkali carbonate treated, preferably with sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or potassium carbonate solution. When Concentrations are for example 0.5 to 10 wt .-%, preferably 2 to 5 wt .-% suitable.

In an embodiment is the temperature at which step (c) is carried out in the range of room temperature to 90 ° C, preferably in the range of 70 to 90 ° C.

The Pressure conditions of step (c) are not critical, for example operate at atmospheric pressure, but pressures of, for example, 1.1 Bar up to 10 bar are also conceivable.

step (c) can be in the form of a continuous or discontinuous Execute method.

In Step (c) usually becomes at least a portion of the amide groups saponified.

In an embodiment The present invention saponifies at least one third of the Amide groups of the polymer or copolymers from step (a), preferably at least 90 mol% and more preferably at least 95 mol%.

In an embodiment The present invention saponifies the amide groups of or the polymers or copolymers from step (a) quantitatively.

Of course you can in the context of the present invention, following step (c) neutralization steps, preferably with organic acids such as for example citric acid, Tartaric acid, Adipic acid or Succinic acid, carry out. Also, one can in the context of the present invention in connection at step (c) flushing and dry steps.

One Another aspect of the present invention is cellulosic Textile, pretreated by the process according to the invention. It is suitable in a special way for the production of dyed textile. Another Aspect of the present invention is therefore the use of pretreated according to the invention cellulose-containing textile for the production of dyed textile.

One Another aspect of the present invention is a method for Production of dyed Textile, also referred to below according to the invention dyeing process. The dyeing process according to the invention is from pretreated according to the invention cellulosic textile and comprises at least one dyeing step using at least one reactive, vat or Direct dye, wherein the choice of or the reactive, or vat Direct dye is not critical.

The Dyeing process according to the invention can be carried out, for example, at atmospheric pressure or at pressures of 1.1 to 20 bar. It is preferred to carry out the dyeing process according to the invention at atmospheric pressure.

The Dyeing process according to the invention For example, at temperatures in the range of room temperature up to 100 ° C carried out are preferred, temperatures in the range of 50 to 90 ° C. Do you wish the dyeing process according to the invention when pressed from 1.1 to 20 bar, Temperatures in the range of 100 to 130 ° C are conceivable.

The Dyeing process according to the invention you can in watery dyeing liquor carry out, being liquor ratio and concentration of the reactive, vat or direct dyes in dyeing-usual orders of magnitude can lie.

you observed an improved leaching of the dyeing liquor. Leading Sections of dyed textile according to the invention by, it is observed a uniform coloration and virtually no ring dyeing. Also after a long time mechanical stress and multiple washes according to the invention retains dyed textile a brilliant coloring.

Of course you can one in the context of the present invention to the actual dyeing step still dyeing-usual post-treatment steps connect; Examples are Nachseifschritte, rinsing steps, drying steps and also equipment steps called.

By exercise the dyeing process of the invention receives according to the invention colored cellulose-containing Textile, which is also an aspect of the present invention.

Dyed cellulosic textile according to the invention is very well suited for the production of brilliantly colored, hard-wearing substrates, for example for trousers, which also have mechanical properties and repeated wash have a brilliant color.

The Invention will be explained by working examples.

Examples 1 to 16 and Comparative Example C1

I. Preparation of polyvinylamide

The Production of polyvinylformamide took place by free-radical polymerization, see. "Kinetics and modelling free radical polymerization of N-vinylformamide ", L.Gu, S. Zhu, AT. Hrymak, R.H. Pelton, Polymer 2001, 42, 3077.

The Determination of the molecular weight was carried out by gel permeation chromatography (GPC) with polystyrene as standard. The determination of the degree of hydrolysis was carried out by titration.

Verwendete Farbstoffe: Farbstoff 1: Hexanatriumsalz des unten abgebildeten Farbstoffs:

The hydrolysis or partial hydrolysis is then carried out at 80 ° C with 25 wt .-% sodium hydroxide solution. Table 1: Overview of the polyvinylformamides used by way of example in step (a) of the pretreatment process according to the invention

Dyes used: Dye 1: Hexasodium salt of the dye shown below:

Dye mixture 2: each 33.3% by weight

• Cibacron Yellow LS-R = Color Index Reactive Yellow 208 Cibacron Red LS-G = Color Index Reactive Red 268 Cibacron Blue LS-3R = Color Index Reactive Blue 263

Dye mixture 3: each 33.3% by weight

• Procion Orange H-ER = Color Index Reactive Orange 84 Procion Red 7EB = Color Index Reactive Red 141 Procion Blue H-ERD = Color Index Reactive Blue 160

Dye 4:

• Procion turquoise H-EXL = Color Index Reactive Blue 71

Dye 5: Procion carmine H-EXL, octa sodium salt of

Dye 6: Procion emerald H-EXL, pentasodium salt of

II. General rule for pretreatment according to the invention of the cellulose-containing tissue

X g polymer according to the tables 1 and 2 was dissolved in 100 ml of water. Subsequently was by means of a foulard (manufacturer Fa. Mathis, type no. HVF12085) a cellulosic textile (100% cotton woven fabric, bleached, to-dye) with the polymer solution thus obtained soaked. The liquor pickup was between 50 and 85 wt .-%, based on the weight of the goods. Subsequently The tissue was at 80 ° C Dried for 5 minutes.

The textile pretreated according to the invention was then treated with 3 g / l sodium hydroxide in a liquor ratio of 1:20 at 70 ° C., then rinsed twice with water (25 ° C.) and then with an aqueous solution containing 1.5 g / l citric acid contained, neutralized (each liquor ratio 1:20, treatment duration 10 min at 30 ° C). The textile pretreated according to the invention was dried at 95 ° C. in a circulating air drying cabinet.

to execution of the comparative example was proceeded as described above, however polymer omitted.

III. General rule for coloring of the cellulose-containing tissue

An aqueous dyeing liquor was prepared from 1 g / l of reactive dye, 1 g / l of 1-hydroxymethylidenebisphosphonic acid, 1 g / l of para-nitrobenzenesulfonic acid sodium salt and 60 g / l of common salt. 100 ml of aqueous dyeing liquor were mixed with 10 g of fabric pretreated according to the invention and transferred to a staining bomb. The staining bomb was sealed and placed in a staining apparatus (Ahiba Labomat) preheated to 50 ° C. The mixture was then heated to 82 ° C. in the course of 15 minutes and dyed at 82 ° C. for a further 30 minutes. Then the staining bomb was removed from the dyebath, opened and the dye liquor 1.5 g Na ₂ CO ₃ , dissolved in 10 ml of water, added and homogenized. The staining bomb was then sealed, placed in the dyeing apparatus and held at 82 ° C for a further 60 min to fix the dye. The mixture was then cooled within 5 minutes to about 30 ° C, opened the dyeing bomb and removed the dyed textile according to the invention, which was then rinsed for 5 min at 60 to 70 ° C under running water.

After rinsing, the dyed textile according to the invention was in a liquor ratio of 1:10 with a solution of 2 g / l polyacrylic acid Na salt (M _w 70,000 g / mol) at a pH of 8.5 over a period of 15 soaped at 98 ° C min. It was then rinsed once for 5 min at 60 to 70 ° C and then for 5 min at 20 to 35 ° C under running water and then dried at 80 ° C in a convection oven for 20 minutes.

Tabelle 2 (Fortsetzung)

Tabelle 2 (Fortsetzung)

Tabelle 2 (Fortsetzung)

Tabelle 3 Tabelle 2 (Fortsetzung)

According to the invention, dyed textile according to Examples 1 to 16 (Table 2) and a comparison textile according to Comparative Example C1 were obtained. The textiles of the invention according to Example 1 to 16 showed a brilliant color. Sections showed that the fibers were dyed uniformly and had no ring dyeing, unlike the comparison textile according to Comparative Example C1. Table 2: Results of the pretreatment process according to the invention, the dyeing process according to the invention and of comparative experiments (V1) with dye 1

Table 2 (continued)

Table 2 (continued)

Table 2 (continued)

Table 3 Table 2 (continued)

Claims (9)

A process for pretreating cellulosic textile comprising the steps of: (a) treating cellulosic textile with a solution of polymer or copolymer obtainable by (a1) polymerizing or copolymerizing N-vinyl amide of general formula I,

wherein R is selected from hydrogen and C ₁ -C ₁₀ alkyl, and (a2) optionally partial hydrolysis, (b) optionally drying the treated textile, and (c) optionally saponifying at least a portion of the amide groups, using at least one of the steps (a2) and (c). Method according to claim 1, characterized in that that one is watery solution of polymer or copolymer. Method according to claim 1 or 2, characterized that in the general formula I R is hydrogen. Method according to one of claims 1 to 3, characterized in that the polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of the general formula I, an M _w in the range of 10,000 to 1,000,000 g / mol. Method according to one of claims 1 to 4, characterized that one uses polymer or copolymer, which is available by (a1) Polymerization or copolymerization of N-vinylamide the general formula I and (a2) subsequent partial hydrolysis. Cellulose-containing textile, pretreated after one Method according to one of the claims 1 to 5. Use of cellulosic textile, pretreated according to a method according to at least one of claims 1 to 5, for the production of colored Textile. Process for the production of dyed cellulosic textile, characterized in that pretreated cellulosic Textile according to claim 6 dyed with reactive, vat or direct dye. dyed cellulosic textile, available according to a method according to claim 8.