ES2370492T3 - METHOD FOR PRELIMINARY TEXTILE TREATMENT CONTAINING CELLULOSE. - Google Patents

Abstract

Method for the preliminary treatment of cellulose-containing textile comprising the following steps: (a) treatment of cellulose-containing textile with a polymer or copolymer solution that can be obtained by (a1) Polymerization or copolymerization of N-vinyl amide of the general formula I, in which case N-vinyl amide comonomers of (meth) acrylates, N-vinyl pyrrolidone, N-vinylimidazole, ethylene, propylene, 1-butene and 1,3-butadiene are selected, R is selected from hydrogen and C1- alkyl C10, and (a2) optionally partial hydrolysis, (b) optional drying of the treated textile, and (c) optional saponification of at least a fraction of the amide groups, in which case at least one of the steps (a2) and (C).

Description

Method for preliminary treatment of textile containing cellulose

The present invention relates to a method for the preliminary treatment of textile with cellulose content comprising the following steps:

(a) Textile treatment containing cellulose with a polymer or copolymer solution that can be obtained by means of

(a1) Polymerization or copolymerization of N-vinyl amide of the general formula I,

In which case the N-vinyl amide comonomers are selected from (meth) acrylates, N-vinyl pyrrolidone, N-vinylimidazole, ethylene, propylene, 1-butene and 1,3-butadiene,

R is selected from hydrogen and C1-C10 alkyl, and

(a2) optionally partial hydrolysis,

(b)

 optional drying of treated textile, and

(C)

 optional saponification of at least a fraction of the amide groups,

15 In which case at least one of the steps (a2) and (c) is performed.

Textile dyeing containing cellulose can be done according to different methods. Nowadays, dyeings with reactive, Cuba or direct dyes are usual. In many cases it is observed, however, that the degree of exhaustion, that is to say the fraction of dye that can be obtained from the dye bath on the textile, as well as the level of solidity of the dyeing, leave much to be desired.

20 Mainly in reactive dyes, often only a degree of exhaustion is obtained which is distinctly below 80%. This is caused, for example, because in many cases it is not possible to achieve a complete reaction of the reactive group (anchor) with the OH groups of the cellulose. Residual dye is removed regularly through the treatment plant.

The level of solidity in many cases unsatisfactory of the dye is caused mainly because it is not fixed

25 all the dye sufficiently. It is observed when using the textile that the unbound dye is washed during the wash cycle performed by the end user. Even the apparently sufficient fixed reactive dye can be washed, if the chemical bond dissociates between the reactive dye and the fibers during the usual washing processes, which also results, in addition to the stain of adjacent tissues, a discoloration of washed textile.

30 To improve the level of solidity of the dyes mainly with reactive dyes today, cationic products are frequently used for subsequent treatment for dyed textile but which is linked with additional process steps in the dyeing or finishing process and consequently causes higher costs .

In addition, it was proposed to apply cationic agents to textile containing cellulose for further treatment and also polyethyleneamines before the dyeing process itself. This application produces a distinctly more tincture

35 intense (Bunt-Denim, TI / T 240 d, July 1993, BASF Aktiengesellschaft), although in many cases an unwanted ring coloration can be observed; that is to say, some, or all the fibers are not dyed in a homogeneous way by the transverse cut but only on the surface. In case of strong mechanical loading of dyed fibers of this type, dyeing is easily removed mechanically, and the fibers get an unwanted appearance within a shorter time.

Therefore, it was an object of the present invention to provide a method for the preliminary treatment of textile that prevents the disadvantages of the state of the art and provides dyeing textile in a mainly uniform manner.

In addition, it was an objective of the present invention to provide a method by which the textile can be dyed without producing high salt loads from the dye baths to be removed.

According to this, the method defined at the beginning was found.

Textiles or textiles containing cellulose should be understood in the context of the present invention textile fibers containing cellulose, finished and semi-finished textile products containing cellulose and manufactured goods prepared therefrom, which also include textiles for industry clothing, for example, also carpets and other textiles for domestic use and textile fabrics that are used for industrial purposes. To these also belong non-molded structures such as flocs, linear structures such as ropes, filaments, threads, yarns, cords, ropes, twisted threads and three-dimensional structures such as felts, fabrics, nonwovens and wadding. Textiles containing cellulose may be of natural origin, for example cotton or linen or mixed fabrics, for example with cotton / polyester, cotton / polyamide, in which case the size of the cellulose fraction is not critical.

In accordance with the invention, the cellulose-containing textile is treated in a step (a) with a polymer or copolymer solution obtained by

(a1) Polymerization or copolymerization of N-vinyl amide of the general formula I,

in which case suitable comonomers are selected,

R is selected from C1-C10 alkyl, branched or preferably unbranched, such as methyl, ethyl, n-propyl, isopropyl, 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; Particularly preferred is unbranched C1-C4 alkyl such as methyl, ethyl, n-propyl, n-butyl; and mainly hydrogen and (a2) optionally partial hydrolysis.

In one embodiment the present invention is used copolymers that can be obtained by copolymerization of N-vinylamide of the general formula I with at least one suitable comonomer, in which case the copolymers can be random copolymers, block copolymers and especially copolymers of graft. Suitable comonomers are (meth) acrylates such as, for example, acrylic acid methyl ester, methyl methacrylate, ethyl acrylate, N-vinyl pyrrolidone, N-vinylimidazole, ethyl methacrylate, ethylene, propylene, 1-butene or 1,3-butadiene.

In one embodiment, the copolymers that can be obtained by copolymerization of N-vinyl amide of the general formula I with at least one suitable comonomer contain at least 20% by weight, preferably at least 30% by weight, relative to the copolymer, of N -vinylamide of the general formula I.

In one embodiment of the present invention a copolymer solution is used which can be obtained by copolymerization of 20 to 90% by weight of N-vinyl amide of the general formula I and 10 to 80% by weight of selected comonomer of N-vinylpyrrolidone and N-vinylimidazole, and then, optionally, partial hydrolysis, in which case the data in% by weight refer respectively to the copolymer used.

In one embodiment of the present invention a copolymer solution is used which can be obtained by copolymerization of 20 to 80% by weight of N-vinylamide of the general formula I, 10 to 70% by weight of Nvinylimidazole and 10 to 70% by weight of N-vinyl pyrrolidone and then, optionally, partial hydrolysis, in which case the data in% by weight refer respectively to the copolymer used.

In another embodiment of the present invention a copolymer solution of at least two different monomers of the general formula I is used, in which case the copolymers can be random copolymers, block copolymers and especially graft copolymers.

In a preferred embodiment of the present invention, a homopolymer solution of Nvinylformamide is used.

In an embodiment of the present invention, the polymers or copolymers used in step (a) have a molecular weight Mw in the range of 10,000 to 1,000,000 g / mol, preferably 30,000 to 400,000 g / mol, determined for example by gel permeation chromatography.

In an embodiment of the present invention in step (a) a polymer or copolymer is used such that it can be obtained by polymerization or copolymerization of N-vinyl amide of the general formula I and then partial hydrolysis of the amide groups, for example with dilute aqueous alkali metal hydroxide or dilute aqueous solution of alkali metal carbonate or dilute aqueous acid, such as phosphoric acid or sulfuric acid, in which case they can be hydrolyzed, for example, 60 mol% or 30 mol% or 10 mol% All amida groups.

In an embodiment of the present invention, an aqueous solution of the polymer or copolymer is used which can be obtained by polymerization or copolymerization of N-vinyl amide of the general formula I, in a concentration of 0.1 to 20% by weight, preferably 0, 5 to 5% by weight.

In an embodiment of the present invention, it is used in the range of 0.1 to 10% by weight, preferably 2 to 8% by weight, with respect to the cellulose-containing textile, polymer or copolymer optionally partially hydrolyzed, which can be obtained by polymerization or copolymerization of N-vinyl amide of the general formula I.

In the context of the present invention, step (a) may be performed once or several times. In such a case, various polymers or copolymers of which at least one can be obtained by polymerization or copolymerization of N-vinyl amide can be used. But it is also possible to use the same polymer or copolymer that can be obtained by polymerization or copolymerization of N-vinylamide and optionally partial hydrolysis.

The treatment in step (a) can be carried out, for example, according to an extraction method or a gluing method.

If step (a) is desired in the manner of an extraction method then it is possible to pass the cellulose-containing textile, to be treated preliminary, by a preferably aqueous bath, which contains a polymer or copolymer solution that can be obtained by polymerization or copolymerization of N-vinylamide of the general formula I. The textile with cellulose content to be treated preliminary is then guided by roller and the excess solution is squeezed out.

If step (a) is desired in the manner of the gluing method, then ordinary machines can be used. Dyeing presses are preferred which contain two compressed rollers as an essential element, between which the cellulose conductive textile is conducted and which is to be treated preliminary. On top of the rollers is a liquid containing polymer or copolymer solution that can be obtained by polymerization or copolymerization of N-vinyl amide of the formula I, which is poured onto the textile and moisturizes it. The textile is squeezed by pressure and a constant recharge is guaranteed. In another embodiment of the sizing, one or more impregnation baths are operated through which the textile with cellulose content to be treated is conducted. Next, the textile runs through a dyeing machine and the excess solution is squeezed out.

In an embodiment of the present invention, preliminary treatment is carried out in step (a) in the presence of at least one fixing product. Suitable fixative products are, for example:

Urea-formaldehyde and melamine-formaldehyde addition products, optionally in combination with inorganic salts such as, for example, MgCl2 · 6 H2O or NH4Cl, mainly condensation products of ureaformaldehyde-glyoxal, whose hydroxyl groups may be partially or quantitatively etherified with methanol , for example,

Condensation products of N, N'-dimethylurea with glyoxal, isocyanates or their dimers or trimers, such as, for example, 4,4'-methylene (diphenyl isocyanate) MDI, hexamethylene diisocyanate HDI, isophorondiisocyanate, respectively free or blocked with, for example, 3, 5-dimethylpyrazole, acetonoxime or sec.-butanoxime, mainly trimeric hexamethylene diisocyanate and trimeric isophorondiisocyanate, respectively free or blocked. Examples are found in EP-B 0 206 059,

Di-, tri- and polyepoxides selected from, for example, diols, polyols, diamines, polyamines reacted with epichlorohydrin,

Oligomeric carbodiimines,

Di- and trialdehydes such as, for example, glutardialdehyde, glyoxal, dextranpolialdehydes, as well as starch aldehydes, prepared for example according to US 2001-0025102 A1;

Epoxysilanes, prepared for example according to DE 35 28 006 and DE 41 28 894, Poly-alkoxycarbonyl-amino derivatives As well as aziridine compounds such as trimethylolpropantris- (betaaziridino) -propionate. Very particularly preferred di-, tri- and polyepoxides are

in which case z is respectively an integer in the range of 0 to 10.

10 Following step (a), the textile treated according to step (a) can be dried (b). This drying (b) to be carried out optionally can be carried out in ordinary appliances, for example drying stoves or also in fresh air. Temperatures in the range of 30 ° C to 120 ° C are convenient, 70 to 110 ° C are preferred. The drying duration usually depends on the drying temperature and the desired residual moisture content and can be in the range of 30 seconds to 3 hours, although longer or shorter durations are possible.

15 If it is desired to perform step (a) several times, then it is possible to dry after each individual treatment step (a) or preferably only after the last treatment step (a).

In the optional step (c) of the method according to the invention at least a fraction of the amide groups is saponified. By these, the amide groups of the polymers or copolymers applied to the textile according to step (a), which can be obtained by polymerization or copolymerization of N-vinyl amide of the general formula, are to be understood.

In the context of the present invention at least one of the steps (a2) and (c) is performed; that is, the cellulose-containing textile can be treated with partially hydrolyzed N-vinylamide polymer or copolymer of the general formula I and dispense with step (c), or step (c) can be performed and without partial hydrolysis according to ( a2).

In an embodiment of the present invention, the cellulose-containing textile is treated with a polymer or copolymer solution that can be obtained by polymerization or copolymerization of N-vinylamide of the general formula I and that has been partially hydrolyzed according to step ( a2), optionally dried according to step (b) and then at least a fraction of the amide groups according to step (c) is saponified.

In an embodiment of the present invention, step (c) is carried out in such a way that the textile treated and dried optionally is treated with dilute aqueous solution of alkali metal hydroxide or dilute aqueous solution of alkali metal carbonate, preferably with hydroxide sodium, potassium hydroxide, sodium carbonate solution or potassium carbonate solution. As concentrations are suitable, for example 0.5 to 10% by weight, preferably 2 to 5% by weight.

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

The pressure conditions of the passage (c) are not critical, it can be operated, for example, at normal pressure but also pressures of 1.1 bar to 10 bar are conceivable, for example.

Step (c) can be carried out in the form of a continuous or discontinuous process.

In step (c) a fraction of the amide groups is usually saponified.

In an embodiment of the present invention at least one third of the amide groups of the polymer or copolymers of step (a) are saponified, preferably at least 90% molar and particularly preferably at least 95% molar.

In an embodiment of the present invention, the amide groups of the polymers or copolymers of step (a) are quantified saponified quantitatively.

Naturally, in the context of the present invention following step (c) neutralization steps can also be carried out, preferably with organic acids such as, for example, citric acid, tartaric acid, adipic acid or succinic acid. In the context of the present invention, following step (c), rinsing and drying steps can also be performed.

If the preliminary treatment according to the invention has been carried out in the presence of one or more fixing agents, then it is preferred after the preliminary treatment to associate, for example, a thermal fixing step (d). For example, it can be set at temperatures of 150 ° C to 190 ° C for a period of 30 seconds at 5 minutes. The fixing step (d) is suitable in all the fixing and drying equipment usual in the textile industry, for example in tension racks and drying stoves, for example with circulating air.

Another aspect of the present invention is cellulose-containing textile, preliminary treated according to the method of the invention. In particular it is suitable for the preparation of dyed textile. Another aspect of the present invention is, therefore, the use of the cellulose-containing textile, preliminary treated, in accordance with the invention for the production of dyed textile.

Another aspect of the present invention is a method for the production of dyed textile, hereinafter also referred to as the dyeing method according to the invention. The dyeing method according to the invention is based on the cellulose-containing textile preliminary treated according to the invention and comprises at least one dyeing step using at least one reactive dye, tub or direct, in which case the selection of the

or of the reactive, Cuba or direct dyes is not critical.

The dyeing method according to the invention can be carried out, for example, at normal pressure or pressures of 1.1 to 20 bar. It is preferred to perform the dyeing method according to the invention at normal pressure.

The dyeing method according to the invention can be carried out, for example at temperatures in the range of room temperature to 100 ° C; temperatures in the range of 50 to 90 ° C are preferred. If it is desired to carry out the dyeing method according to the invention at pressures of 1.1 to 20 bar, temperatures in the range of 100 to 130 ° C are conceivable.

The dyeing method according to the invention can be carried out in an aqueous dye bath, in which case the proportion between the bath liquid and the concentration of the reactive dye (s) or tank dyes can be found in the usual dimensions for dry cleaning. .

In an embodiment of the dyeing method according to the invention to the dye bath, usual amounts of inorganic salts can be added, for example alkali metal or alkaline earth metal salts such as halides, carbonates or sulfates, preferably NaCl or Na2SO4. Usual amounts of inorganic salts may be, for example, 60 to 80 g / l dye bath.

In a preferred embodiment of the present invention, the dye bath contains inorganic salts such as, for example, NaCl or Na2SO4 in the range of 0 to 20 g / l, mainly up to 15 g / l.

An improved depletion of the dye bath is observed. If cuts are made through the dyed textile according to the invention, a uniform dyeing is observed from side to side and virtually no ring-shaped coloration. Even after a long mechanical wear and several washes, the dyed textile according to the invention maintains a bright coloration. In addition, it is possible to dispense with the use of dye baths with high salt content and still obtain good dyeing results.

Naturally, in the context of the present invention, the usual step of dyeing can also follow usual post-treatment steps in the dry cleaners; for example, steps of soaping later, rinsing, drying and also steps to squeeze can be mentioned.

By executing the dyeing process according to the invention, textile with dyed cellulose content according to the invention is obtained, which is also an aspect of the present invention.

The textile with dyed cellulose content according to the invention is very suitable for the production of substrates capable of wear, dyed brightly, for example for pants that also have a bright coloration after mechanical loading and repeated washing.

The invention is explained by working examples.

Examples 1 to 16 and comparative example V1

I. Substances used

I.1. Production of poly-N-vinylformamide (homopolymers)

The preparation of poly-N-vinylformamide was carried out by free radical polymerization, see "Kinetics and modeling of free radical polymerization of N-vinylformamide", L. Gu, S. Zhu, A.N. Hrymak, R.H. Pelton, Polymer 2001, 42, 3077.

The partial hydrolysis is then carried out at 80 ° C with 25% by weight sodium hydroxide.

The molecular weight was determined using gel permeation chromatography (GPC) with polystyrene as standard. The degree of hydrolysis was determined by titulometry.

Table 1: Summary of poly-N-vinylformamides used by way of example in step (a) of the preliminary treatment method according to the invention

Polyvinylformamide

Hydrolyzed amide groups according to step (a2) [molar%] Mw [g / mol]

P1

0 30,000

P2

10 400,000

(continuation)

Polyvinylformamide

Hydrolyzed amide groups according to step (a2) [molar%] Mw [g / mol]

P3

30 400,000

P4

60 400,000

P5

0 400,000

I.2. Preparation of N-vinylformamide copolymers

5 Preparation P7

550 g of distilled water and 34 g of N-vinylimidazole were charged to a 2-liter flask and heated to 75 ° C. A mixture of 138.8 g of Nvinylformamide and 170 g of N-vinyl pyrrolidone was added dropwise, stirring for a period of 2 hours. At the same time, a solution of 1.7 g of azo-bis-isobutyronitrile in 100 g of distilled water began to be added dropwise. After 3 hours the solution addition was completed

Azobisisobutyronitrile aqueous as well as the mixture of N-vinylformamide and N-vinyl pyrrolidone. It was stirred for another two hours at 75 ° C and a viscous, clear, colorless solution was obtained. Mw (GPC): 620,000 g / mol, solids content: 20.1% by weight.

For the preparation of P6, P8 and P9, we proceeded respectively as described above, in which case the total amount of comonomers was 342.8 g and N-vinylimidazole was constantly charged and the comonomers were added.

15 N-vinylformamide or N-vinyl pyrrolidone. The molecular weights are found in table 1 a.

They are respectively random copolymers.

Table 1 a: Summary of poly-N-vinylformamide copolymers used by way of example in step (a) of the preliminary treatment method according to the invention

Polyvinylformamide Copolymer

Comonomers [% by weight] Mw [g / mol]

VFA

NVP NIV

P6

80 - twenty 580,000

P7

40 fifty 10 620,000

P8

90 - 10 590,000

P9

twenty 40 40 610,000

Abbreviations: NVFA: N-vinylformamide, NVP: N-vinyl pyrrolidone, NVI: N-vinylimidazole, data in% by weight respectively refer to the total mass of copolymer of poly-N-vinylformamide P8 was used as an aqueous solution with a content of solid of 19.7% by weight, P9 as aqueous solution with solid content of 25.1% by weight.

20 I.3. Dyes used: Coloring 1: hexasodium salt of the dye illustrated below:

Coloring mixture 2: from 33.3% by weight Color Index Reaktiv Yellow 208 Color Index Reaktiv Red 268

5 Color Index Reaktiv blue 263 Color mixture 3: from to 33.3% by weight Color Index Reaktiv orange 84 Color Index Reaktiv red 141 Color Index Reaktiv blue 160

10 Color 4: Color Index Reaktiv blue 71 Color 5: Octosodium salt

15 Coloring 6: pentasodium salt of

I.4. Used fixing agents

Fixing agent F1: Trimeric hexamethylene diisocyanate modified with methylpolyethylene glycol, prepared according to EP B 0 206 059, examples 1 and 2, as a 70% solution by weight in propylene carbonate. The quantities used always refer to the entire solution.

Fixing agent F2: Trimethylolpropantris- (betaaziridino) -propionate

II. General instructions for the preliminary treatment of tissues, with cellulose content, in accordance with the invention with poly-N-vinylformamide and for dyeing

II.1. General instruction for preventive treatment according to the invention of cellulose-containing fabrics with poly-N-vinylformamide

X g of poly-N-vinylformamide according to Tables 1 and 2 were dissolved in 100 ml of water. Then, by means of a dye press (producer: Mathis company, type No. HVF12085), a textile containing cellulose (100% cotton fabric, weight per unit area 160 g / m2, bleached, ready to dye) is impregnated. with the polymer solution obtained in this way. The liquid absorption was between 50 and 85% by weight, with respect to the weight of the article. The tissue was then dried at 80 ° C for 5 minutes.

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

To perform the comparative example, the procedure was described as described above, although poly-Nvinylformamide was omitted.

II.2 General instruction for dyeing tissue containing preliminary treated cellulose from II.1

An aqueous dye bath was prepared from 1 g / l of reactive dye, 1 g / l of 1-hydroxymethylidenebisphosphonic acid, 1 g / l of sodium salt of para-nitrobenzenesulfonic acid and 60 g / l of common salt as well as water. 100 ml of dyeing bath liquid was combined with 10 g of the textile pretreated according to the invention and transferred to a dyeing pump. The dyeing pump was sealed and applied to a dyeing apparatus (Ahiba Labomat) that had been preheated to 50 ° C. It was then heated for 15 min at 82 ° C and stained at 82 ° C for an additional 30 minutes. Then the dyeing pump was removed from the dyeing bath, opened and 1.5 g of Na2CO3, dissolved in 10 ml of water, were added to the dyeing liquid and homogenized. Then the dyeing pump was sealed, applied to the dyeing apparatus and to fix the dye was maintained for an additional 60 min at 82 ° C. Then it was cooled for about 30 minutes to about 30 ° C, the dyeing pump was opened and the dyed textile according to the invention was removed, which was then rinsed for 5 minutes at 60 to 70 ° C under running water. After rinsing the dyed textile according to the invention in a bath liquid ratio of 1:10 it was saponified with a solution of 2 g / l Na salt of poly (acrylic acid) (Mw 70,000 g / mol) to a pH value of 8.5 for a duration of 15 min at 98 ° C. It was then rinsed once more 5 minutes at 60 to 70 ° C and then for 5 min at 20 to 3 5 ° C under running water and then dried at 80 ° C in the drying oven with recirculation air for 20 minutes .

A dyed textile according to the invention was obtained according to examples 1 to 16 (table 2) and a comparison textile according to example V1. The textiles according to the invention according to examples 1 to 16 showed a bright coloration. The cuts showed that the fibers - differently than in the comparison textile according to comparative example V1 - were dyed uniformly and did not show ring-shaped coloration.

Table 2: Results of the preliminary treatment method according to the invention, the dyeing method according to the invention and the comparative experiments (V1) with dye 1

Example No.

V1 one 2 3 4

Poly-N-vinylformamide

- P1 P1 P1 P1

Amount used X [g]

- 0.625 1.25 2.5 5.0

Absorption of dyeing liquid [% by weight]

- 80 80 80 80

Washing fastness (ISO 105 C03)

4-5 5 5 5 5

Color Depth (V1 = 100%)

100 n.d. n.d. n.d. 135.1

10 Table 2 (continued)

Example No.

5 6 7 8

Poly-N-vinylformamide

 P2 P2 P2 P2

Amount used X [g]

0.625 1.25 2.5 5.0

Absorption of dyeing liquid [% by weight]

80 80 80 80

Washing fastness (ISO 105 C03)

Four. Five Four. Five 5 5

Color Depth (V1 = 100%)

n.d. n.d. n.d. 137.2

Table 2 (continued)

Example No.

9 10 eleven 12

Poly-N-vinylformamide

 P3 P3 P3 P3

Amount used X [g]

0.625 1.25 2.5 5.0

Absorption of dyeing liquid [% by weight]

80 80 80 80

Washing fastness (ISO 105 C03)

5 Four. Five 5 5

Color Depth (V1 = 100%)

n.d. n.d. n.d. 139.0

Table 2 (continued)

Example No.

13 14 fifteen 16

Poly-N-vinylformamide

 P4 P4 P4 P4

Amount used X [g]

0.625 1.25 2.5 5.0

Absorption of dyeing liquid [% by weight]

80 80 80 80

Washing fastness (ISO 105 C03)

Four. Five Four. Five 5 5

Color Depth (V1 = 100%)

n.d. n.d. n.d. 135.6

n.d .: not determined

Example No.

17 18 19 twenty twenty-one

Poly-N-vinylformamide

 P5 P5 P5 P5 P5

Amount used X [g]

5.0 5.0 5.0 5.0 5.0

Dye / Mix No.

2 3 4 5 6

Amount used dye / mixture [% by weight]

6 6 2 2 2

Washing fastness (ISO 105 C03)

Four. Five 5 5 4-5 5

Absorption of dyeing liquid [% by weight]

80 80 80 80 80

Washing fastness (ISO 105 C03)

Four. Five 5 5 Four. Five Four. Five

Color depth [%]

108 112 108 106 107

5 The color depth of a dyed sample, preliminary treated without polymer, is referred to as 100% respectively

The color depth of a textile sample preliminary treated without polymer, dyed, is referred to as 100%.

III. General instructions for the preliminary treatment of cellulose-containing textile according to the invention using poly-N-vinylformamide copolymer

III.1. Preliminary treatment according to the invention without fixing agent

50 g of poly-N-vinylformamide copolymer or 50 g of aqueous solution of poly-N-vinylformamide copolymer according to Table 1 a are charged with water to 1000 ml of dye bath liquid. Then, by means of a dyeing press (manufacturer Mathis, type No. HVF12085), a textile with cellulose content was impregnated (100%

15 cotton fabric, weight per unit area 160 g / m2, was bleached, prepared for dyeing) with the dyeing bath obtained in this way. The absorption of dyeing liquid was between 50 and 85% by weight, based on the weight of the article. The pre-treated textile was then dried at 80 ° C for 5 minutes.

III.2 Preliminary treatment according to the invention with fixing agent

50 g of poly-N-vinylformamide copolymer or 50 g is aqueous solution of poly-N-vinylformamide copolymer

20 according to table 1 a and 1.5 g of fixing agent according to table 3 were charged with water to 1000 ml of dyeing liquid. Then, by means of a dyeing press (manufacturer Mathis, type No. HVF12085), a textile with cellulose content (100% cotton fabric, weight per unit area 160 g / m2, impregnated, bleached, prepared for dye) with the dye bath obtained in this way. The absorption of the bath was 80% by weight, based on the weight of the article. The pre-treated textile was then dried at 160 ° C for 3 minutes and thus heat set.

5 III.3 Dyeing of textile treated previously according to II.1 or II.2

An aqueous dye bath was produced from 2 g / l of dye No. 4, 1 g / l of 1-hydroxymethylidenebisphosphonic acid, 1 g / l of sodium salt of para-nitrobenzenesulfonic acid, common salt according to Table 3 and water. 100 ml of the dyeing liquid was combined with 10 g of the textile previously treated according to the invention and transferred to a dyeing pump. The dyeing pump was sealed and applied to a dyeing apparatus (Ahiba 10 Labomat) which had been preheated to 50 ° C. It was then heated for 15 minutes at 82 ° C and stained for an additional 30 minutes at 82 ° C. The dyeing pump was then removed from the dyeing bath, opened and 1.5 g of Na2CO3, dissolved in 10 ml of water, were added to the dyeing liquid and homogenized. The dyeing pump was then sealed, applied to the dyeing apparatus and held for an additional 60 minutes at 82 ° C to fix the dye. Then it was cooled for 5 minutes to about 30 ° C, the dyeing pump was opened and the dyed textile was removed according to the

The invention was then rinsed for 5 minutes at 60 to 70 ° C under running water.

After rinsing, the dyed textile according to the invention was lathered in a proportion of dyeing liquid of 1:10 with a solution of 2 g / l of sodium salt of poly (acrylic acid) (Mw 70,000 g / mol) to a pH value of 8.5 for a duration of 15 min at 98 ° C. After this, it was washed once 5 min at 60 to 70 ° C and then 5 min at 20 to 35 ° C under running water and then dried in the drying oven with circulating air for 80 ° C

20 for 20 minutes.

To make the comparative examples, it was based on textile not previously treated respectively.

Dyed textile according to the invention was obtained according to examples 17 to 24 (Table 3) and comparison textiles according to comparative examples V2 to V6 (Table 4). The textiles according to the invention according to examples 17 to 24 showed a bright coloration. The cuts showed that the fibers, differently than in the case of textile

Comparison according to comparative examples V2 to V6, they were completely stained in a homogeneous manner and there was no ring-shaped coloration.

The values for L, A, B and Delta E were determined according to CIELAB.

Table 3: Dyeing of the preliminary treated textile

Example No.

17 18 19 twenty

Polyvinylformamide Copolymer

P6 P7 P8 P9

Common salt [g / l]

twenty twenty twenty twenty

Fixing agent

- - - -

L

56.48 56.85 57 55.51

TO

-28.08 -28.26 -27.53 -27.23

B

-34.26 -34.42 -32.87 -33

Delta E

0.93 / 5 1.27 / 5 0.8 / 3 1.34 / 3

Polyvinylformamide Copolymer

P8 P9 P8 P9

Common salt [g / l]

twenty twenty 0 twenty

Fixing agent

F1 F1 F2 F2

(continuation)

Example No.

17 18 19 twenty

L

55.56 54.3 56 52.99

TO

-27.33 -26.11 -27.22 -26.22

B

-34.16 -33.5 -34.29 -35.79

Delta E

1.36 / 3 1.32 / 4 1.21 / 3 1.97 / 4

Table 4: Comparative examples: Textile dyeing not previously treated

Example No.

V2 V3 V4 V5 V6

Polyvinylformamide Copolymer

- - - - -

Common salt [g / l]

- twenty 40 80 70

Fixing agent

- - - - -

L

64.07 60.54 56.59 53.94 55.75

TO

-27.79 -28.54 -27.88 -27.09 -28.43

B

-29.23 -31.39 -33.46 -34.3 -33.8

Delta E

- - - - -

Claims (11)

1. Method for the preliminary treatment of textile containing cellulose comprising the following steps: (a) treatment of textile containing cellulose with a solution of polymer or copolymer that can be obtained by (a1) Polymerization or copolymerization of N-vinyl amide of the general formula I, in which case N-vinyl amide comonomers of (meth) acrylates, N-vinyl pyrrolidone, N-vinylimidazole, ethylene, propylene, 1-butene and 1,3-butadiene are selected, R is selected from hydrogen and C1-C10 alkyl, and (a2) optionally partial hydrolysis,

(b)

 optional drying of treated textile, and

(C)

 Optional saponification of at least a fraction of the amide groups, in which case at least one of steps (a2) and (c) is performed.

2.

 Method according to claim 1, characterized in that an aqueous polymer or copolymer solution is used.

3.

 Method according to claim 1 or 2, characterized in that in the general formula I R represents hydrogen.

Four.

 Method according to one of claims 1 to 3, characterized in that the polymer or copolymer that can be obtained by polymerization or copolymerization of N-vinylamide of the general formula I, have an Mw in the range of 10,000 to 1,000,000 g / mol.

5.

 Method according to one of claims 1 bis 4, characterized in that the copolymer can be obtained by (a1) copolymerization of N-vinyl amide of the general formula I with at least one other comonomer selected from Nvinylpyrrolidone and N-vinylimidazole.

6.

 Method according to one of claims 1 bis 5, characterized in that the polymer or copolymer that can be obtained by using

(a1) Polymerization or copolymerization of N-vinyl amide of the general formula I and (a2) subsequent partial hydrolysis.

7.

 Textile containing cellulose that has been preliminary treated according to a method according to one of claims 1 to 6.

8.

 Use of preliminary treated textile according to a method according to at least one of claims 1 to 6, to produce dyed textile.

9.

 Method for the production of dyed textile containing cellulose, characterized in that textile dyeing containing pre-treated cellulose according to claim 7 with reactive dye, tub or direct dye.

10.

 Method according to claim 9, characterized in that the dyeing liquid contains one or more inorganic salts in the range of 0 to 20 g / l.

eleven.

 Textile containing cellulose, dyed, which can be obtained according to a method according to claim 9

or 10.