US20040163189A1

US20040163189A1 - Method for dyeing and/or printing textile material

Info

Publication number: US20040163189A1
Application number: US10/484,397
Authority: US
Inventors: Heike Bartl; Robert Groten
Original assignee: Individual
Current assignee: Carl Freudenberg KG
Priority date: 2001-07-24
Filing date: 2002-07-11
Publication date: 2004-08-26
Also published as: CN1535341A; DE10135941A1; EP1409788A1; WO2003012194A1

Abstract

The invention relates to a method for dyeing and/or printing textile material containing non-split and/or at least partially split micro-fibres and/or micro-filaments, composed of at least one polyamide component and optionally at least one additional polymer component. According to said method, the textile material is treated with formic acid and is dyed and/or printed using at least one dye, selected from the group containing anionic acidic dyes, metal complex dyes, reactive dyes, direct dyes and cationic dyes.

Description

FIELD OF THE INVENTION

The present invention is directed to a method for dyeing and/or printing on a textile material containing unsplit and/or at least partially split microfibers and/or microfilaments composed of at least one polyamide component and optionally of at least one other polymer component, in accordance with which the textile material is treated with formic acid and is dyed and/or printed using at least one dyestuff selected from the group including anionic acid dyestuffs, metal complex, reactive, direct, and cationic dyestuffs.

BACKGROUND

Due to their multivarious exceptional properties, textile materials which are at least partially made of polyamide are widely used in many different application areas, such as in the clothing or automotive industry. For the most part, to produce their optical design, textile materials are dyed. Typically, satisfactory results are obtained when the polyamide component is dyed by using anionic acid dyestuffs, metal complex, reactive, direct (substantive) or cationic dyestuffs.

On the other hand, if the textile materials contain one or more polyamide components, optionally in the form of split microfibers and/or microfilaments having a titer of ≦1 dtex, then the above mentioned dyestuffs often do not suffice for dyeing these materials, i.e., they produce less than adequate color depth and color uniformity among the various lots. These difficulties encountered when dyeing polyamide microfibers and/or microfilaments are due, inter alia, to a surface area which is enlarged, as compared to textile materials composed of fibers and/or filaments having a titer of >1 dtex. Such enlarged surface areas require increased dyestuff quantities, as described, for example, by K. Parton in, “Dying Nylon Microfibre”, International Dyer, June 1996, pp. 14 to 21.

In this context, the smaller the titer is and the greater the density of the microfibers and microfilaments is, i.e., the greater the number of microfibers and microfilaments per unit area of the textile material, the greater the required dyestuff quantity is.

For that reason, it is especially problematic to dye or print nonwovens, which are at least partially composed of split polyamide microfibers and/or microfilaments, since, in these materials, the density of the microfibers and/or microfilaments is substantially greater, and the titer of the fibers is substantially smaller than in comparable woven or knitted fabrics, in which typically only one component, mostly the filling, is made of microfibers. In addition, the dyeing process is made more difficult by the uneven distribution of the microfibers and/or microfilaments in the nonwoven fabric.

It is for this reason that it is not possible to dye the polyamide component to a sufficient color depth when working with these nonwovens having the above-mentioned dyestuff classes.

SUMMARY OF THE INVENTION

It is, therefore, the object of the present invention to devise a method for dyeing and/or printing textile materials containing unsplit and/or at least partially split microfibers and/or microfilaments composed of at least one polyamide component and possibly of at least one further polymer component, in accordance with which the polyamide microfiber and polyamide microfilament component are dyed to an excellent color depth. Moreover, the dye and/or print result should also exhibit adequate color fastness, and different lots of the dyed and/or printed textile material should preferably show a more uniform final color quality, i.e., an improved color evenness. This objective is achieved by the method according to the present invention for dyeing and/or printing textile material containing unsplit and/or at least partially split microfibers and/or microfilaments composed of at least one polyamide component and optionally of at least one other polymer component, in accordance with which the textile material is treated with formic acid and is dyed and/or printed using at least one dyestuff selected from the group including acid, metal complex, reactive, direct, and cationic dyestuffs.

The textile material preferably contains unsplit and/or at least partially split microfibers and/or microfilaments, which, as a further polymer component, include at least one natural semisynthetic or synthetic polymer component. As a natural polymer component, cellulose and/or wool and/or silk preferably come under consideration. If a semisynthetic polymer component is provided as a further polymer component, it is preferably selected from the group including viscose, cellulose acetate, continuous-filament cuprammonium (cupro), and lyocell. If a synthetic polymer component is provided as a further polymer component, it is preferably selected from the group including polyester, polyurethane, polyacrylonitrile, polypropylene, and polyvinyl alcohol.

The textile material to be dyed is preferably made of unsplit and/or of at least partially split microfibers and/or microfilaments, which are composed of at least one polyamide component and of at least one polyester component and optionally of at least one polyurethane component, these preferably including 15 to 99% by weight of at least one polyamide component and 85 to 1% by weight of at least one polyester component and/or at least one polyurethane component and more preferably 30 to 90% by weight of at least one polyamide component and 70 to 10% by weight of at least one polyester component and/or of at least one polyurethane component.

If the unsplit and/or at least partially split microfibers and/or microfilaments contain at least one polyester component, it may preferably be selected from the group including polyethylene terephthalate, polypropylene terephathalate, polybutylene terephthalate, poly-lactic acid, their blends and copolyesters.

Suitable copolyesters are able to be obtained either by partially exchanging the acid component and/or the diol component when producing the polyester, as described, for example, by Büttner in “Basisch modifizierte Polyesterfasern” [Basic-Modified Polyester Fibers] in “Die Angewandte Makromolekulare Chemie” [Applied Macromolecular Chemistry] 40/41, 1974, pp. 57-70 (no. 593) or by G. G. Kulkarni in “Colourage”, August 21 ^st, 1986, pp. 30 to 33. The corresponding literature descriptions are incorporated herein by reference.

As a polyester component, the textile material composed of microfibers and/or microfilaments used for coloration may likewise preferably include a lactic acid-based polyester, as described in the EP 1 091 028. The corresponding description is incorporated herein by reference.

The polyamide component of the textile material of microfibers and/or microfilaments may preferably be selected from the group including polyamide 6, polyamide 66 and polyamide 11.

It is likewise preferable for the polyamide component to have groups which are dyeable using anionic or cationic dyestuffs.

As a group which is dyeable using anionic dyestuffs, the polyamide component may preferably have at least one amino group which is optionally at least monosubstituted with one aliphatic residue and/or with an optionally substituted aryl or heteroaryl residue.

As a group which is dyeable using cationic dyestuffs, the polyamide component may preferably have at least one hydroxyl, carboxyl or sulphonate residue.

Such groups may be introduced into the polyamide component in accordance with customary methods known to one skilled in the art. Polyamide components modified in this way are described, for example by A. Anton in “Textile Chemist and Colorist & American Dyestuff Reporter”, vol. 32, no. 3, March 2000, pp. 26 through 32. The corresponding description is incorporated herein by reference.

The titer of the microfibers and/or microfilaments which make up the material to be dyed is preferably 0.02 to 0.95 dtex, more preferably 0.05 to 0.8 dtex, and most preferably 0.1 to 0.5 dtex.

The mass per unit area of the textile material is preferably 15 to 400 g/m ², more preferably 40 to 300 g/m², and most preferably 50 to 200 g/m².

The textile material to be dyed is preferably used in the form of a woven fabric, knitted fabric, or a nonwoven fabric. It is especially preferable for the textile material to be provided as a nonwoven fabric, preferably made of unsplit and/or at least of partially split polyester/polyamide microfibers and/or of polyester/polyamide microfilaments. Surprisingly, it was ascertained that treating such nonwovens with formic acid yields a reduction in the pilling effect, as well as a smooth and more uniform nonwoven surface.

The nonwoven is preferably a staple-fiber nonwoven or more preferably a spunbonded nonwoven. Nonwovens of this kind may be manufactured in accordance with customary methods known to one skilled in the art, as described, for example, by Dr. Helmut Jörder in “Textilien auf Vliesbasis (Nonwovens)” [Nonwoven-Based Textiles], avr textbook, P. Keppler Publishers KG, Heusenstamm 1977, pp. 13 to 20. Such spunbonded nonwovens may preferably be manufactured in accordance with methods as described in EP 0 814 188. The corresponding descriptions are incorporated herein by reference.

The textile material may be treated with formic acid both prior to, as well as during the dyeing and/or printing operations employing acid dyestuffs, metal complex, direct, reactive or cationic dyestuffs. The textile material is preferably treated prior to the dyeing and/or printing with formic acid.

Both the treating, as well as the dyeing of the textile material may be carried out continuously, semicontinuously or discontinuously.

If the textile material is treated in a discontinuous operation, this is preferably carried out in accordance with the exhaust dyeing method, preferably on a jet dyeing apparatus, a winch back, or a jig.

The treatment of the textile material using formic acid may likewise be preferably carried out continuously, preferably in accordance with the immersion, slop-padding (coating), foam dyeing or spray methods, as described, for example, by Dr. Helmut Jörder in “Textilien auf Vliesbasis (Nonwovens)” [Nonwoven-Based Textiles], avr textbook, P. Keppler Publishers KG, Heusenstamm. 1977, pp. 72 to 79, for applying binding agents. The corresponding literature is incorporated herein by reference.

The continuous treatment of the textile material with formic acid is also preferably carried out in accordance with the pad dyeing method, preferably in accordance with the pad thermofixation or pad steaming method.

This treatment of the textile material with formic acid is optionally followed by an intermediate drying, and optionally by a heat treatment, in some instances accompanied by steam.

The temperatures and the treatment duration may vary, both during the intermediate drying, as well as during the heat treatment. Preferably, the duration of the intermediate drying is 1 to 10 minutes; the temperature is preferably 40 to 150° C.

If there is a heat treatment, its duration is preferably one second to 60 minutes and its temperature preferably 100 to 240° C.

During the printing operation using at least one of the previously mentioned dyestuff classes, the textile material may also be preferably treated with formic acid. Here as well, this treatment is optionally followed by an intermediate drying, and optionally by a heat treatment, optionally accompanied by steam, preferably under the conditions indicated above.

In this context, the printing operation may be carried out in accordance with various methods known to one skilled in the art. The textile material is preferably printed in accordance with a direct printing method, preferably in accordance with a film printing method, more preferably in accordance with the rotary screen or flat screen printing method, or in accordance with the ink jet method.

The formic acid used for treating the textile material is preferably used in the form of an aqueous treatment liquor. The pH value of this liquor is preferably adjusted to 1 to 3, more preferably to 1.5 to 2.5, the amount of formic acid needed to adjust the pH value being dependent on the initial pH value of the water used.

The treatment duration of the textile material varies and is dependent, inter alia, on the pH value of the treatment liquor and/or on the treatment temperature.

The method according to the present invention for treating the textile material is preferably carried out at an elevated temperature in order to shorten the treatment duration, for example.

If the textile material is treated using formic acid in accordance with the exhaust dyeing method, the temperature is preferably 5 to 140° C., more preferably 10 to 130° C., and most preferably 20 to 100° C.

The duration of the treatment using formic acid in accordance with the exhaust dyeing method is preferably 5 minutes to 600 minutes, more preferably 10 minutes to two hours, and most preferably 15 minutes to 100 minutes.

If the textile material is treated using formic acid in accordance with the pad dyeing method, then the treatment duration is typically very short and is preferably not more than 10 seconds.

Following the treatment with formic acid, the textile material is preferably rinsed, preferably with water, and, if necessary, neutralized and/or dried.

The textile material is dyed and/or printed using at least one dyestuff selected from the group including acid dyestuffs, metal complex, direct, reactive or cationic dyestuffs in accordance with customary methods known to one skilled in the art. The dyeing and/or printing operations preferably take place in accordance with the methods indicated above for treating with formic acid, as explained above, there being no need for the treatment and the dyeing and/or printing to take place simultaneously. The acid dyestuffs, metal complex, direct, reactive or cationic dyesstuffs suited for dyeing the polyamide component are known per se to one skilled in the art and are described, for example, by Rath in, Lehrbuch der Textilchemie” [Textbook of Textile Chemistry], Chapter V, Die künstlichen organischen Farbstoffe”, [The Synthetic Organic Dyestuffs], Chapter VI, Die Anwendung der Farbstoffe in der Färberei” [The Application of Dyestuffs in the Dyeing Shop], Chapter VII, Die Anwendung der Farbstoffe in der Druckerei” [The Application of Dyestuffs in the Print Shop], pp. 367 to 742, Springer Publishers, 3rd edition 1972 or in the corresponding color cards of the dye manufacturers. The corresponding literature descriptions are incorporated herein by reference. The appropriate dyestuff quantities may vary each time, for example as a function of the textile material or of the dyestuff class used. They may be determined in preliminary tests by one skilled in the art.

In one especially preferred specific embodiment of the method according to the present invention, the textile material is first pretreated with formic acid and subsequently dyed using the exhaust dyeing method with at least one reactive dye, the dye initially being exhausted in the presence of acetic and/or formic acid, preferably at a pH value of 1 to 6, more preferably of 1.5 to 2.5, and subsequently reactively bonded in the neutral to alkaline pH range, preferably at pH 7 to 12, more preferably at pH 7.5 to 10, to the microfibers and/or microfilaments of the textile material. The unbonded dye component is subsequently removed from the fiber in a final alkaline washing process, preferably at pH 9 to 10.

The dyeing and/or printing of the textile material may preferably be followed by a cleaning of the textile material, preferably by rinsing with water, also at an elevated temperature and, if needed, by a soaping of the nonwoven.

To improve color fastness, following the dyeing operation using acid dyestuffs, metal complex, reactive, direct or cationic dyestuffs, an after treatment is possible using the customary fastness-improving auxiliary agents known to one skilled in the art, as described, for example, in “Der neue THK—Textilhilfsmittelkatalog 2000” [The New THK Catalog of Textile Auxiliary Agents 2000], Deutscher Fachverlag GmbH [German Textbook Publishers GmbH] 1999, Frankfurt am Main, pp. 98-109 and pp. 132-134. The corresponding literature is incorporated herein by reference.

The textile materials treated with formic acid in accordance with the method of the present invention and dyed and/or printed using acid dyestuffs, direct, reactive or cationic dyestuffs, are distinguished by outstanding depth of color, superior wet fastness and/or light fastness, as well as by evenness of color within one lot, and, additionally, by good stability values among various lots.

Surprisingly, the method of the present invention also improves the handle and reduces the pilling of spunbonded nonwovens made of unsplit and/or of at least partially split microfibers and/or microfilaments.

For that reason, the textile materials dyed and/or printed in accordance with the method of the present invention are excellently suited for manufacturing clothing, as home textiles, as covering or upholstering fabrics, as lining materials, preferably for luggage, such as for briefcases or suitcases, as textiles for furnishing means of transportation, such as motor vehicles, railway vehicles, watercraft, or airplanes, preferably for the interior appointments of means of transportation, or as textile materials in the medical and/or hygienic sector.

For that reason, another subject matter of the present invention is the use of the textile material dyed and/or printed in accordance with the method of the present invention for manufacturing clothing, as home textiles, as covering or upholstering fabrics, as lining materials, preferably for luggage, such as for briefcases or suitcases, as textiles for furnishing means of transportation, preferably for the interior appointments of means of transportation, or as textile materials in the medical and/or hygienic sector.

The wash fastness of the textile material treated and dyed and/or printed in accordance with the method of the present invention at 40° C. and 60° C., respectively, was determined in accordance with EN ISO 105 C06 A2S and EN ISO 105 C06 C2S, respectively; the perspiration fastness in accordance with EN ISO 105 E04, the rubbing fastness in accordance with EN ISO 105 X12, and the tear resistance in accordance with DIN EN 29073, part 3. The reduction in the pilling was determined in accordance with the random pilling test as defined by DIN 53876. The corresponding descriptions are incorporated herein by reference.

As a measure for the color depth of the dyeing, the K/S value in the absorption maximum of the dyeing is used. This value may be calculated in accordance with the Kubelka-Munk formula from the reflectance values, as follows:

\frac{K}{S} (λ_{\max}) = \frac{{(1 - R)}^{2}}{2 R}

where

λ_maxis the wavelength in the absorption maximum

R is the reflectance value in the absorption maximum (λ _max).

The reflectance values R were measured using a color measuring instrument of the type Colorflash C22S of the firm Optronik. The greater the K/S ratio is, the deeper is the dyeing.

The present invention is elucidated in the following on the basis of examples. These explanations are merely exemplary and do not restrict the general inventive idea.

EXAMPLE 1

a) [0053]
A spunbonded nonwoven having a mass per unit area of 100 g/m[0054] ²composed of partially split microfilaments of 70% by weight polyethylene terephthalate and of 30% by weight of polyamide 66 having a titer of approximately 0.15 dtex was treated using the exhaust dyeing method with demineralized water (initial pH value=6.3), to which 25 ml/l 98-100% by weight formic acid (0.66 mol/l, density=1.22 g/mol) was added, after which the pH value was 2.0, given a liquor ratio of 1:10. To this end, after adding the formic acid at 20° C., heating was carried out at a rate of 2° C./min to 60° C., and treatment was carried out for 30 min at 60° C. The treated nonwoven was subsequently rinsed under cold running water until a neutral pH value was reached, and then dried at room temperature.
b) [0055]
The nonwoven treated in accordance with a) was dyed using 2% by weight (with respect to the weight of the nonwoven) of the reactive dye Dimaren® brilliant blue K-BL (Clariant, Germany), the liquor ratio being 1:10. The pH value was adjusted at 20° C. using 98-100% by weight of formic acid to pH 2; heating was then carried out at a rate of 2° C./min to 60° C., and the dye was exhausted for 30 min at 60° C. The pH value was subsequently adjusted by adding solid sodium carbonate to pH 9; heating was then carried out at a rate of 2° C./min to 90° C., and dyeing for 30 min at 90° C. The coloration was subsequently rinsed under running water and soaped two times for 15 min each at 60° C. using 4 g/l of a commercial light-duty detergent, the liquor ratio being 1:100. The pH value was adjusted in the process using solid sodium carbonate to pH 9. Finally, the coloration was rinsed with cold water. [0056]
Table 1 shows the enhanced color depth (K/S value), the color fastness and tear resistance values which resulted, in comparison to a reference dye manufactured without formic acid treatment, but otherwise comparably produced. [0057]

EXAMPLE 2

A spunbonded nonwoven treated with formic acid in accordance with Example 1a), having a mass per unit area of 100 g/m[0058] ², composed of partially split microfilaments of 70% by weight of polyethylene terephthalate and of 30% by weight of polyamide 66 having a titer of approximately 0.15 dtex was dyed using 2% by weight (with respect to the weight of the nonwoven) of the reactive dye Dimaren® red 8RB (Clariant, Germany), the liquor ratio being 1:10. The pH value was adjusted at 20° C. using 60% by weight of acetic acid to pH 2; heating was then carried out at a rate of 2° C./min to 60° C., and the dye was exhausted for 30 min at 60° C. The pH value was subsequently adjusted by adding solid sodium carbonate to pH 9; heating was then carried out at a rate of 2° C/min to 90° C., and dyeing for 30 min at 90° C. The coloration was subsequently rinsed under running water and soaped two times for 15 min each at 60° C., using 4 g/l of a commercial light-duty detergent, the liquor ratio being 1:100. The pH value was adjusted in the process using solid sodium carbonate to pH 9. Finally, the coloration was rinsed with cold water.
Table 2 shows the enhanced color depth (K/S value), the color fastness and tear resistance values which resulted, in comparison to a reference dye manufactured without formic acid treatment. [0059]

EXAMPLE 3

A spunbonded nonwoven having a mass per unit area of 100 g/m[0060] ², composed of partially split microfilaments of 70% by weight of polyethylene terephthalate and of 30% by weight of polyamide 66 having a titer of approximately 0.15 dtex was dyed in accordance with the exhaust dyeing method using 2% by weight (with respect to the weight of the nonwoven) of the reactive dye Realan® red G (DyStar, Germany), the liquor ratio being 1:10. The pH value was adjusted at 20° C. using 25 ml/l 98-100% by weight of formic acid to pH 2; heating was then carried out at a rate of 2° C./min to 60° C., and the dye was exhausted for 30 min at 60° C. The pH value was subsequently adjusted by adding solid sodium carbonate to pH 9; heating was then carried out at a rate of 2 ° C./min to 90° C., and dyeing for 30 min at 90° C. The dye coloration resulting from dye treatment was subsequently rinsed under running water and, given a liquor ratio of 1:100, soaped two times for 15 min each at 60° C., using 4 g/l of a commercial light-duty detergent. The pH value was adjusted in the process using solid sodium carbonate to pH 9. Finally, the dye was rinsed with cold water.
Table 3 shows the enhanced color depth (K/S value), the color fastness and tear resistance values which were obtained for the dye produced in accordance with Example 3, in comparison to a reference dye manufactured at pH 4 using 60% by weight of acetic acid. [0061]

EXAMPLE 4

A spunbonded nonwoven treated in accordance with Example 1a), having a mass per unit area of 100 g/m[0062] ², composed of partially split microfilaments of 70% by weight of polyethylene terephthalate and of 30% by weight of polyamide 6 having a titer of approximately 0.15 dtex, was treated for purposes of anionically modifying the polyamide, using the exhaust dyeing method, the liquor ratio being 1:10, with a liquor composed of 10% by weight (with respect to the weight of the nonwoven) Sandozspace® S, with a sulphonated triazine derivative, (Clariant, Muttenz, Switzerland), with 30% by weight (with respect to the weight of the nonwoven) of sodium chloride and with 5% by weight (with respect to the weight of the nonwoven) of sodium carbonate. Starting out from 20° C., heating was carried out at a rate of 2° C./min to 130° C.; treatment for 60 min at 130° C.; and cooling at a rate of 2° C./min to 80° C. The nonwoven treated in this manner was rinsed under running water, dried, and dyed in accordance with the exhaust dyeing method, the liquor ratio being 1:10, using 3% by weight (with respect to the weight of the nonwoven) of the cationic dye Astrazon® red 5BL (DyStar, Germany) in the presence of 6 g/l of sodium sulphate (anhydrous). The pH value was adjusted using 60% by weight of acetic acid to 4.5.
Starting out from 20° C., heating was carried out at a rate of 2° C./min to 130° C.; dyeing for 60 min at 130° C.; and cooling at a rate of 2° C./min to 80° C. The coloration resulting from dye treatment was subsequently rinsed under running water and soaped using 1 g/l of a commercial light-duty detergent and 2 g/l of sodium carbonate at 40° C. for 15 min. [0063]
Table 4 shows the enhanced color depth (K/S value), the color fastness and tear resistance values which were obtained for the dye produced in accordance with Example 4, in comparison to a reference dye not pretreated with formic acid, but otherwise comparably manufactured. [0064]

EXAMPLE 5

A spunbonded nonwoven having a mass per unit area of 100 g/m[0065] ²composed of partially split microfilaments of 70% by weight of polyethylene terephthalate and of 30% by weight of polyamide 66 having a titer of approximately 0.15 dtex was treated on a jet dyeing apparatus (Soft-TRD, firm Thies, Coesfeld, Germany), the liquor ratio being 1:20, using an aqueous liquor containing 200 ml/l 98-100% by weight of formic acid (5.3 mol/l, density=1.22 g/mol), at pH 1.75. Starting out from 20° C., heating was carried out at 1.5° C./min to 60° and treatment for 45 min at 60° C. Dyeing was carried out following a rinsing two times of five minutes each with 20° C. warm water, the liquor ratio being 1:10, using 1% by weight (with respect to the weight of the nonwoven) of the levelling agent Levegal LPA (Bayer A G, Germany) and a mixture of the following acid dyestuffs and metal complex dyestuffs: 0.46% by weight (with respect to the weight of the nonwoven) of Isolan® red S-RL, 0.26% by weight of Supranol® yellow 4GL (with respect to the weight of the nonwoven) and 0.22% Supranol® red RO1 (with respect to the weight of the nonwoven) (all dyes from DyStar, Germany). The pH value was adjusted using 60% by weight of acetic acid to 4. Starting out from 20° C., heating was carried out at 2° C./min to 90° C.; dyeing for 90 min at 90° C.; and, subsequently, cooling to 60° C. Rinsing was subsequently carried out with 30° C. warm water, the liquor ratio being 1:40; and treatment, the liquor ratio being 1:20, using 4% by weight (with respect to the weight of the nonwoven) of the after treatment agent Solfix® E (Ciba, Spezialitätenchemie [Specialty Chemistry], Basel) at 40° C. for 10 min. 50% by weight of sodium hydroxide solution was then added to the treatment liquor at 40° C. in an amount of 1% by weight (with respect to the weight of the nonwoven), and treatment was carried out for a further 40 min at 40° C. Rinsing was subsequently carried out with cold water, the liquor ratio being 1:40, and acidification was carried out using 1 ml/l of 60% by weight of acetic acid.
Table 5 shows the enhanced color depth (K/S value), the color fastness values and the average color deviation within the lot, which were obtained for the dye produced in accordance with Example 5, in comparison to a reference dye not pretreated with formic acid, but otherwise comparably manufactured. The pilling values in accordance with DIN 53867 are indicated in Tables 6a and 6b. [0066]

EXAMPLE 6

A spunbonded nonwoven having a mass per unit area of 100 g/m[0067] ²composed of partially split microfilaments of 70% by weight of polyethylene terephthalate and of 30% by weight of polyamide 66 having a titer of approximately 0.15 dtex was impregnated in accordance with the pad dyeing method, with an aqueous liquor containing 280 ml/l (7.4 mol/l) of a 98-100% by weight formic acid and having a pH value of 1. The liquor uptake was 100% by weight with respect to the nonwoven used. The treated nonwoven was then dried for 90 seconds at 120° C. and subsequently set at 220° C. for 90 seconds. Washing was subsequently carried out with water and dyeing using the exhaust dyeing method in accordance with Example 4.

Tables 6a and 6b indicate the pilling values as defined by DIN 53867, in comparison to a reference dye not produced using formic acid.

TABLE 1


				Tear
				resistance
				[N]
Color	Washfastness	Perspiration	Rubbing	as defined
intensification	60° C.	fastness EN	fastness	by
K/S value	EN ISO 105	ISO 105 E04	EN ISO	DIN EN

	λmax = 620 nm	C06-C2S	acidic	alkaline	105 X12	29073 part 3

Dye	0.75	4-5S/4-5C	4-	4-5S/4-	4-5 dry/	256
manufactured in			5S/4-	5C	4-5 wet
accordance with			5C
Example 1
Reference	0.60	4-5S/4-5C	4-	4-5S/3-	4-5 dry/	266
produced without			5S/4-	4C	4-5 wet
formic acid			5C
treatment

TABLE 2


				Tear
				resistance
				[N]
Color	Washfastness	Perspiration	Rubbing	as defined
intensification	60° C.	fastness EN	fastness	by
K/S value	EN ISO 105	ISO 105 E04	EN ISO	DIN EN

	λmax = 560 nm	C06-C2S	acidic	alkaline	105 X12	29073 part 3

Dye	0.75	4-5S/3-4C	4-	4-5S/4-	4-5 dry/	271
manufactured in			5S/4-	5C	4-5 wet
accordance with			5C
Example 2
Reference	0.55	4-5S/3-4C	4-	4-5S/4-	4-5 dry/	278
produced without			5S/4-	5C	4-5 wet
formic acid			5C
treatment

TABLE 3


				Tear
				resistance
				[N]
Color	Washfastness	Perspiration	Rubbing	as defined
intensification	60° C.	fastness EN	fastness	by
K/S value	EN ISO 105	ISO 105 E04	EN ISO	DIN EN

	λmax = 525 nm	C06-C2S	acidic	alkaline	105 X12	29073 part 3

Dye	0.80	4-5S/4C	4-	4-5S/4-	4-5 dry/	280
manufactured in			5S/4-	5C	4-5 wet
accordance with			5C
Example 3
Reference	0.55	4-5S/4C	4-	4-5S/4-	4-5 dry/	256
produced without			5S/4-	5C	4-5 wet
formic acid			5C
treatment

TABLE 4


				Tear
				resistance
Color	Washfastness	Perspiration	Rubbing	[N]
intensification	40° C.	fastness	fastness	as defined by
K/S value	EN ISO 105	EN ISO 105 E04	EN ISO	DIN EN

	λmax = 515 nm	C06-A2S	acidic	alkaline	105 X12	29073 part 3

Dye	4.40	3S/3C	3-	3-	4-5 dry/	262
manufactured in			4S/4C	4S/4C	4 wet
accordance with
Example 4
Reference	3.00	3S/3C	3-	3-	4-5 dry/	267
produced without			4S/4C	4S/4C	4 wet
formic acid
treatment

TABLE 5


			Average color
Color	Washfastness	Perspiration	deviation
intensification	40° C.	fastness	DE (mean)
K/S value	EN ISO 105 C06-	EN ISO 105 E04	within

	λmax = 525 nm	A2S	acidic	alkaline	the lot

Dye manufactured in	0.75	4-5S/4-5C	4-5S/4-	4-	0.56
accordance with			5C	5S/4C
Example 5
Reference produced	0.55	4-5S/4-5C	4-5S/4-	4-	1.04
without			5C	5S/4C
formic acid treatment

In the preceding Tables 1 through 5, the ratings signify, respectively: [0073]
1 very poor [0074]
5 excellent [0075]
The average color deviation DE* (mean) was measured colorimetrically in accordance with CIELAB guidelines using a color measuring instrument of the type Colorflash C22S of the firm Optronik. For this purpose, 24 samples were taken at 10 m spaced intervals from the middle of the fabric web and measured against a master sample. The sample having the greatest color depth was defined as the master sample (sample having the highest K/S value) of the particular lot. By generating the mean value of the 24 individual color deviations dE, the average color deviation DE* (mean) was determined. The smaller the average color deviation DE* (mean) is, the better is the color constancy within the lot. [0076]
DE* is calculated from the brightness and color shade values of the dye in accordance with CIELAB guidelines, as follows: [0077]
DE*=root of DL* ² +DA* ² +Db* ²
DL*=difference of the brightness values [0078]
a*=difference of the red/green values [0079]
b*=difference of the yellow/blue values [0080]
of the master used for comparative dyeing. [0081]
Tables 6a and 6b: [0082]
The pilling values were determined in the random tumble pilling test as defined by DIN 53867. three [0083]

6a) Assessing the surface change in accordance with Table 2.1.1 of DIN 53867. The values indicated are average values from three measurements.



	Testing period

	1 min	2 min	5 min	10 min	20 min	30 min	40 min	50 min	60 min

Dye manufactured	8-9	8	7-8	7	5-6	4-5	4	4	3-4
in accordance
with Example 5
Reference 5	8-9	8	7	6	5	4	3-4	3-4	3
produced
without
formic acid
treatment
Dye manufactured	8	8	7-8	6-7	5	4-5	4	4	3-4
in accordance
with Example 6
Reference 6	8	7-8	7	6	4-5	3-4	3	3	2-3
produced
without
formic acid
treatment

6b) Description of the surface change in accordance with Table 2.1.2 of DIN 53867. The values indicated are average values from three measurements.



	Testing period

	1 min	2 min	5 min	10 min	20 min	30 min	40 min	50 min	60 min

Dye manufactured	1-2	2	2	2-3	2-3	2-3	2-3	3	3-4
in accordance
with Example 5
Reference 5	2	2-3	2-3	3	3-4	3-4	3-4	4	4
produced
without
formic acid
treatment
Dye manufactured	1-2	2	2	2	2	2-3	2-3	2-3	3
in accordance
with Example 6
Reference 6	1-2	2	3	3	3-4	4	4	4	4
produced
without
formic acid
treatment

Claims

What is claimed is:

1. A method for dyeing and/or printing textile material containing microfibers and/or microfilaments composed of at least one polyamide component and optionally of at least one further polymer component,

wherein the textile material is treated with formic acid and is dyed and/or printed using at least one dyestuff selected from the group including including acid dyestuffs, metal complex, reactive, direct, and cationic dyestuffs.

2. The method as recited in claim 1,

wherein, as a further polymer component, the microfibers and/or microfilaments have at least one natural polymer component, preferably cellulose and/or wool and/or silk.

3. The method as recited in claim 1 or 2,

wherein, as a further polymer component, the microfibers and/or microfilaments have at least one semisynthetic polymer component, which is preferably selected from the group including viscose, cellulose acetate, continuous-filament cuprammonium, and lyocell.

4. The method as recited in one of claims 1 through 3,

wherein, as a further polymer component, the microfibers and/or microfilaments have at least one synthetic polymer component which is preferably selected from the group including polyester, polyurethane, polyacrylonitrile, polypropylene, and polyvinyl alcohol.

5. The method as recited in claim 4,

wherein the microfibers and/or microfilaments are composed of at least one polyamide component and of at least one polyester component and optionally of at least one polyurethane component.

6. The method as recited in claim 5,

wherein the microfibers and/or microfilaments are composed of 15 to 99% by weight of at least one polyamide component and of 85 to 1% by weight of at least one polyester component and/or of at least one polyurethane component, preferably of 30 to 90% by weight of at least one polyamide component and of 70 to 10% by weight of at least one polyester component and/or of at least one polyurethane component.

7. The method as recited in one of claims 4 through 6,

wherein the polyester component is selected from the group including polyethylene terephthalate, polypropylene terephathalate, polybutylene terephthalate, poly-lactic acid, their blends and copolyester.

8. The method as recited in one of claims 1 through 7,

wherein the polyamide component is selected from the group including polyamide 6, polyamide 66 and polyamide 11.

9. The method as recited in one of claims 1 through 8,

wherein the polyamide component has at least one group which is dyeable using anionic dyestuffs.

10. The method as recited in claim 9,

wherein, as a group which is dyeable using anionic dyestuffs, at least one amino group is provided which is optionally at least monosubstituted with one organic residue, preferably one aliphatic residue and/or with an optionally substituted aryl or heteroaryl group.

11. The method as recited in one of claims 1 through 8,

wherein the polyamide component has at least one group which is dyeable using cationic dyestuffs.

12. The method as recited in claim 11,

wherein the polyamide component has at least one hydroxyl, carboxyl or sulphonate group.

13. The method as recited in one of claims 1 through 12,

wherein the titer of the microfibers and/or microfilaments is preferably 0.02 to 0.95 dtex, preferably 0.05 to 0.8 dtex, and more preferably 0.1 to 0.5 dtex.

14. The method as recited in one of claims 1 through 13,

wherein the mass per unit area of the textile material is 15 to 400 g/m², preferably 40 to 300 g/m², and more preferably 50 to 200 g/m².

15. The method as recited in one of claims 1 through 14,

wherein the textile material is used in the form of a woven fabric, knitted fabric, or a nonwoven fabric, preferably in the form of a nonwoven fabric.

16. The method as recited in claim 15,

wherein the nonwoven fabric is at least partially made of split polyester/polyamide microfibers and/or of polyester/polyamide microfilaments.

17. The method as recited in claim 15 or 16,

wherein the nonwoven is a staple-fiber nonwoven.

18. The method as recited in claim 15 or 16,

wherein the nonwoven is a spunbonded nonwoven.

19. The method as recited in one of claims 1 through 18,

wherein the treatment is carried out using formic acid in aqueous liquor.

20. The method as recited in claim 19,

wherein the pH value of the aqueous liquor is adjusted using formic acid to 1 to 3, more preferably to 1.5 to 2.5.

21. The method as recited in one of claims 1 through 20,

wherein the textile material is treated prior to the dyeing and/or printing with formic acid.

22. The method as recited in one of claims 1 through 21,

wherein the textile material is treated with formic acid in a discontinuous operation, preferably in accordance with the exhaust dyeing method, preferably on a jet dyeing apparatus, a winch back, or a jig.

23. The method as recited in claim 22,

wherein the duration of the treatment using formic acid in accordance with the exhaust dyeing method is preferably 5 to 600 minutes, preferably 10 minutes to two hours, and more preferably 15 to 100 minutes.

24. The method as recited in claim 22 or 23,

wherein the temperature during the treatment using formic acid in accordance with the exhaust dyeing method is 5 to 140° C., preferably 10 to 130° C., and more preferably 20 to 100° C.

25. The method as recited in one of claims 1 through 21,

wherein the treatment of the textile material using formic acid is carried out in accordance with a continuous method, preferably in accordance with the pad dyeing, immersion, slop-padding (coating), foam dyeing or spray methods, more preferably in accordance with the pad thermofixation or pad steaming method, optionally with a subsequent intermediate drying and/or optionally with a subsequent heat treatment, optionally in the presence of steam.

26. The method as recited in claim 25,

wherein the duration of the treatment using formic acid in accordance with the pad dyeing method is not more than 10 seconds.

27. The method as recited in one of claims 1 through 20,

wherein the textile material is treated during the printing operation with formic acid, optionally followed by an intermediate drying and/or a heat treatment, optionally in the presence of steam.

28. The method as recited in claim 27,

wherein the textile material is printed in accordance with a direct printing method, preferably in accordance with a film printing method, more preferably in accordance with the rotary screen or flat screen printing method, or in accordance with the ink jet method.

29. The method as recited in claims 25 through 28,

wherein an intermediate drying of a duration of 1 to 10 minutes is subsequently carried out.

30. The method as recited in claim 29,

wherein the temperature during the intermediate drying is 40 to 150° C.

31. The method as recited in one of claims 25 through 30,

wherein a heat treatment of a duration of one second to 60 minutes is subsequently carried out.

32. The method as recited in claim 31,

wherein the temperature during the heat treatment is 100 to 240° C.

33. The method as recited in one of claims 1 through 32,

wherein, following the treatment with formic acid, the textile material is preferably rinsed with water and optionally neutralized and/or optionally dried.

34. The method as recited in one of claims 1 through 33,

wherein the dyeing and/or printing is carried out using at least one dyestuff from the group including reactive, acid, and metal complex dyestuffs, preferably using at least one reactive dyestuff.

35. A use of a textile material dyed and/or printed in accordance with a method as recited in claims 1 through 34 for manufacturing clothing.

36. A use of a textile material dyed and/or printed in accordance with a method as recited in claims 1 through 34 as home textiles.

37. A use of a textile material dyed and/or printed in accordance with a method as recited in claims 1 through 34 as covering fabrics.

38. A use of a textile material dyed and/or printed in accordance with a method as recited in claims 1 through 34 as lining materials, preferably as lining materials for luggage.

39. A use of a textile material dyed and/or printed in accordance with a method as recited in claims 1 through 34 as furnishing means of transportation, preferably for the interior appointments of means of transportation.

40. A use of a textile material dyed and/or printed in accordance with a method as recited in claims 1 through 34 as textile material in the medical and/or hygienic sector.