US20040194234A1

US20040194234A1 - Dyed and/or printed non-woven fabric

Info

Publication number: US20040194234A1
Application number: US10/484,642
Authority: US
Inventors: Heike Bartl; Uwe Marg
Original assignee: Individual
Current assignee: Carl Freudenberg KG
Priority date: 2001-07-24
Filing date: 2002-06-28
Publication date: 2004-10-07
Also published as: DE50205529D1; EP1412578B1; DE10135940B4; EP1412578A1; CN1535342A; WO2003014464A1; DE10135940A1; CN1245552C

Abstract

The invention relates to a dyed and/or printed non-woven fabric consisting of non-split and/or at least partially split microfibres and/or microfilaments consisting of synthetic polymers containing at least one polyester constituent and at least one polyamide constituent and, optionally, at least one polyurethane constituent, said fabric having been dyed and/or printed by means of at least one azo dye which is produced on the non-woven fabric. The invention also relates to a method for dyeing and/or printing the inventive fabric.

Description

The present invention is directed to a dyed and/or printed nonwoven fabric which is made of unsplit and/or of at least partially split microfibers and/or microfilaments of synthetic polymers, including at least one polyester component and at least one polyamide component and, optionally, at least one polyurethane component, and which is dyed and/or printed using at least one azo dye produced on the nonwoven, as well as to a method for dyeing and/or printing of the same.

Often, less than satisfactory quality is achieved when using conventional textile dyeing or textile printing methods to dye or print textile materials manufactured from plastics. Difficulties arise in the dyeing or printing process, particularly when the textile material contains different plastic components, such as polyester and polyamide, since, typically, their dyeing characteristics vary considerably. This is described, for example, in BASF's “Manual-Dying and Finishing of Polyamide Fibres and Their Blends with Other Fibres” B358e /12.72, p. 149.

For example, if the polyester component of such a textile material is dyed using a disperse dyestuff, the polyamide component of the material is often stained bled into by this dyestuff, and/or the dyestuff migrates under the action of heat from the polyester component to the polyamide component. The result is inadequate color fastness and poor uniformity of the dyed textile material. This problem is also evident when working with other plastic components, such as polyurethane.

Even greater difficulties arise when dyeing textile materials composed of a blend of polyester and polyamide microfibers, as explained, for example, in “Färben von Polyester-, Polyester-/Polyamid- und Polyacrylnitril-Mikrofasem” [Dyeing of Polyester, Polyester/Polyamide and Polyacrylonitrile Microfibers]—Technical Information 00127.00.94, Sandoz Chemikalien AG [Sandoz Chemicals AG], Textile Division, 4132 Muttenz, pp. 24 to 40. For that reason, multistage dyeing and/or printing processes are generally used to dye and/or print textile materials containing various plastic components, in each stage of these processes, one of the plastic components being dyed and/or printed using a dyestuff class suitable for it. Often relatively costly cleaning steps are required in-between the various dyeing stages, in order to remove, inter alia, excess dye or dye that has bonded unstably to the material.

Especially problematic is the dyeing or printing of nonwovens composed of a blend of microfibers and/or microfilaments, such as polyester/polyamide split fibers, since the split fibers are unevenly distributed in the nonwoven, while, on the other hand, in comparable polyamide/polyester microfiber woven fabrics, typically only one component, generally the filling, is made of polyamide/polyester split fibers.

Furthermore, in nonwovens of this kind, the density of the fibers and/or filaments, i.e., the number of fibers and/or filaments per unit surface area, is greater than in comparable woven or knitted fabrics, so that greater dyestuff quantities are required to dye such nonwovens. This increased dyestuff use, on the one hand, and the uneven distribution of the fibers, on the other hand, result in generally poorer color fastness qualities for the nonwovens, which are produced from a plurality of plastic components and dyed or printed, and composed of microfibers and/or microfilaments, than for comparable woven fabrics made of the same synthetic polymers.

The object of the present invention is, therefore, to select a suitable dyestuff class which enables nonwovens made of different plastic components to be dyed and/or printed by using only one dyestuff class and, thus, to provide a dyed and/or printed nonwoven composed of unsplit and/or of at least partially split microfibers and/or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component, and optionally at least one polyurethane component, that is distinguished by good to excellent color fastness, in particular washfastness, perspiration fastness, water and light fastness, as well as by good rubbing fastness.

This objective is achieved by providing a dyed and/or printed nonwoven made of unsplit and/or of at least partially split microfibers and/or microfilaments of synthetic polymers containing at least one polyester component, at least one polyamide component, and optionally at least one polyurethane component, which has been dyed and/or printed using at least one azo dye, a so-called developer dyestuff, produced on the nonwoven.

The nonwoven used is a staple-fiber nonwoven or a spunbonded nonwoven, preferably a spunbonded nonwoven, made of unsplit and/or of at least partially split microfibers and/or microfilaments. 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 are preferably manufactured in accordance with methods as described in EP 0 814 188. The corresponding descriptions are incorporated herein by reference.

The basic weight (or mass per unit area) of the nonwoven to be colored may vary over a broad range. The basic weight of the nonwoven is preferably 15 to 400 g/m ², more preferably 50 to 350 g/m², and most preferably 80 to 200 g/m².

European Patent 0 814 188 likewise describes manufacturing microfibers and/or microfilaments containing at least one polyester component and at least one polyamide component, and optionally at least one polyurethane component, the manufacturing preferably being carried out in accordance with this method. The corresponding description is incorporated herein by reference.

In one preferred embodiment of the present invention, the nonwoven to be colored is made of unsplit and/or at least partially split microfibers and/or microfilaments composed of at least one polyester component and of at least one polyamide component, these two components preferably being present in a proportion of 5 to 95% by weight of at least one polyester component and of 95 to 5% by weight of at least one polyamide component, more preferably of 15 to 85% by weight of at least one polyester component and 85 to 15% by weight of at least one polyamide component, and most preferably of 30 to 70% by weight of at least one polyester component and of 70 to 30% by weight of at least one polyamide component.

The titer of the microfibers and/or microfilaments present in the nonwoven is ≦1 dtex, preferably 0.02 to 0.95 dtex, more preferably 0.05 to 0.85 dtex, and most preferably 0.1 to 0.5 dtex.

The polyamide component of the nonwoven is preferably polyamide 6, polyamide 66 or polyamide 11.

The polyester component of the nonwoven preferably includes polyethylene terephthalate, polypropylene terephathalate, polybutylene terephthalate, polylactic acid, their blends or 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. Kulkami in “Colourage”, Aug. 21, 1986, pp. 30 to 33. The corresponding literature descriptions are incorporated herein by reference. If the polyester component is a lactic acid-based polyester, one can refer to EP 1 091 028 for a description of its manufacturing. The corresponding description is incorporated herein by reference.

The azo dye is produced on the nonwoven by coupling at least one dyestuff developer component with at least one fast color salt or at least one fast color base, subsequently to its diazotization, as described below.

Another subject of the present invention is a method for dyeing and/or printing the nonwoven described above, in that the nonwoven is treated with at least one dyestuff developer component at a temperature of ≧90° C. and at least one fast color salt or at least one fast color base, and the dyestuff developer component is coupled with the fast color salt or the fast color base, subsequently to its diazotization, on the nonwoven.

Such dyestuff developer components, fast color bases and fast color salts, suited for producing an azo dye in a coupling process on the nonwoven to be dyed, are known, per se, to one skilled in the art and are described, for example, in “Rath-Lehrbuch der Textilchemie” [Rath Textbook of Textile Chemistry], Springer Publishers, Berlin, Heidelberg, New York, 3rd edition 1972, pp. 422 to 432, pp. 548 to 556 and pp. 690 to 697 or in the corresponding color cards of the dyestuff manufacturer, e.g., “Naphtol® AS, Echtf{dot over (a)}rbebasen/Echtf{dot over (a)}rbesalze DF1007 D/E” [Naphtol® AS, color fast bases/color fast salts DF1007 D/E] of the firm DyStar Textilfarben [DyStar Textile Dyes], Frankfurt. The corresponding literature descriptions are incorporated herein by reference. Appropriate quantities of the components to be used in each instance, i.e., of the dyestuff developer components, fast color bases and fast color salts, may vary, for example in dependence upon the titer of the microfibers and/or microfilaments or of the polymer components employed. They may be determined in preliminary tests by one skilled in the art.

The dyestuff developer component and the fast color salt or the fast color base may be applied to the nonwoven either simultaneously or in succession. Preferably, these components are successively applied to the nonwoven.

If a fast color base is used for coupling with the dyestuff developer component, then it must be diazotized prior to the coupling, i.e., converted to its corresponding diazonium salt. This diazotization may take place in accordance with customary methods known to one skilled in the art. It is preferably carried out by reaction of the particular fast base with an inorganic nitrite, preferably sodium nitrite, in the presence of an organic or inorganic acid, preferably hydrochloric acid.

For that reason, the use of a fast color salt is especially preferred in the method of the present invention, since there is no need for a diazotization prior to the coupling.

The dyestuff developer component may preferably be selected from the group consisting of arylamides of aromatic hydroxycarboxylic acids, arylamides of keto acids and hydroxynaphthyl ketones.

Preferably used as arylamides of aromatic hydroxycarboxylic acids are amides of 2-hydroxy-3-naphthoic acid, particularly 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid o-toluidide, 2-hydroxy-3 naphthoic acid-4,6-dimethoxy-3-chloroanilide, 2-hydroxy-3-naphthoic acid a-naphthylamide, [bis-2-hydroxy-3-naphthoic acid]dianiside, amides of anthracene, particularly 2-hydroxy-3-anthracene-carboxylic acid o-toluidide, amides of carbazole, particularly 2-hydroxycarbazole-3-carboxylic acid 4′-choroanilide or amides of diphenylene oxide, particularly 3-hydroxydiphenylene oxide-2-carboxylic acid 2′,5′-dimethoxyanilide.

Preferably used as arylamide of a keto acid is diacetic acid o-toluidide or terephthaloyl-bis-acetic acid bis-[2-methoxy-4-chloro-5-methylanilide]. Preferred fast color bases may be selected from the group consisting of o-chloroaniline, o-nitroaniline, m-nitro-p-toluidine, 4-diethylsulfonamido-1-amino-1-methoxybenzene, 4-chloro-2-aminodiphenyl ether, α-aminoanthraquinone, 4-amino-3-methoxyazabenzene, 4-amino-1-benzoylamino-3-methoxy-6-methylbenzene, o-dianisidine, 4-amino-4′-methoxydiphenylamine, 3,5-bis-trifluoromethylaniline and 3-fluorosulfonyl aniline.

In one preferred embodiment of the method of the present invention, the nonwoven to be colored is treated with at least one dyestuff developer component in accordance with the exhaust dyeing method, optionally by adding dyestuff carriers. In this connection, both the treatment temperature, as well as the treatment duration may vary over a broad range.

The treatment temperature is preferably 90 to 150° C., especially 100 to 130° C. The treatment duration is preferably 10 to 180 minutes, more preferably 20 to 120 minutes, and most preferably 25 to 60 minutes.

In another preferred embodiment of the method of the present invention, the nonwoven to be colored is treated with at least one dyestuff developer component in accordance with the pad dyeing method, optionally followed by an intermediate drying. Preferably, the duration of the intermediate drying is 30 seconds to 10 minutes, especially 2 to 5 minutes. The temperature during the intermediate drying process is preferably 80 to 180° C., especially 100 to 150° C. The intermediate drying may preferably be followed by a heat treatment, optionally in the presence of steam. The temperature and the duration of the heat treatment may vary over a broad range.

The temperature during the heat treatment in the presence of steam is preferably 100 to 130° C., especially 102 to 120° C. If the treatment is carried out without steam, the treatment temperature is preferably 150 to 240° C., especially 175 to 210° C.

The duration of the heat treatment is preferably 15 seconds to 60 minutes, more preferably 2 to 45 minutes, and most preferably 5 to 30 minutes.

The dyestuff developer components, fast color bases and fast color salts are preferably each used in the form of an aqueous solution. The subsequent coupling of these components to form an azo dye on the nonwoven is likewise preferably carried out in an aqueous solution.

To this end, it may be necessary to dissolve the components to form a solution, in accordance with customary methods known to one skilled in the art, as described, for example, for similar dyestuff developer components in “Rath-Lehrbuch der Textilchemie” [Rath Textbook of Textile Chemistry], Springer Publishers, Berlin, Heidelberg, New York, 3rd edition 1972, p. 549. The corresponding literature is incorporated herein by reference.

The treatment of the nonwoven using at least one fast color salt or at least fast color base, and the coupling of the dyestuff developer component with the fast color salt or the fast color base, subsequently to its diazotization, on the nonwoven may likewise be preferably carried out in accordance with the exhaust dyeing method or the pad dyeing method, optionally including intermediate drying and optionally a subsequent heat treatment, optionally in the presence of steam, in each case both the treatment duration as well as the treatment temperature being variable in dependence upon the particular method.

In the exhaust dyeing method, the temperature is preferably −10 to 130° C., more preferably 0 to 60° C., and most preferably 5 to 30° C. The treatment duration in the exhaust dyeing method is preferably 5 to 120 minutes, more preferably 10 to 60 minutes, and most preferably 15 to 45 minutes.

In the pad dyeing method, the temperature is preferably −10 to 60° C., especially 0 to 30° C. The treatment duration in the pad dyeing method is typically very short and is preferably not more than 10 seconds.

If an intermediate drying and/or a heat treatment follow, optionally in the presence of steam, they may be carried out, respectively, under the conditions indicated above.

If the nonwoven is printed using one or more of the developer dyestuffs mentioned above, this may be accomplished in accordance with customary printing methods known to one skilled in the art.

To this end, the dyestuff developer component is preferably initially applied to the nonwoven in accordance with the dyeing methods mentioned above, or imprinted on the nonwoven using a customary method known to one skilled in the art.

The particular fast color base or fast color salt is then imprinted on the nonwoven, optionally using a screen to produce a pattern on the nonwoven.

The nonwoven is preferably printed in accordance with a direct printing method, preferably in accordance with a film printing method, particularly in accordance with the rotary screen or flat screen printing method, or in accordance with the ink jet method.

The printing of the nonwoven may preferably be followed by an intermediate drying process, and optionally by a subsequent heat treatment, optionally in the presence of steam, which may preferably be carried out under the conditions indicated above.

If the described nonwoven is printed by using printing pastes, these pastes may be manufactured in accordance with customary methods known to one skilled in the art and, in addition to the particular dyestuff developer component and the fast color base or the fast color salt, respectively, also contain other customary auxiliary agents, which may preferably be selected from the group including thickening agents, cross-linking agents, softeners, defoamers, wetting agents, and moisture agents. In addition, from the fast color base, it is also possible to produce the appropriate diazonium salt in the printing paste by diazotization.

Besides the particular dyestuff developer component and the fast color base or the fast color salt, respectively, as a further constituent, the printing pastes preferably contain only one or a plurality of thickening agents, which may preferably be selected from the group of natural or synthetic thickening agents. Natural thickening agents may preferably be selected from the group including optionally partially degraded starch, plant gums, carob seed flour, etherified polysaccarides and alginates. Synthetic thickening agents may preferably be selected from the group of water-soluble carboxy group-containing polymers, which may preferably be composed of (meth)acrylic acid and/or maleic anhydride.

In addition, it is also possible to add a resisting agent to one of the printing pastes to prevent coupling between the dyestuff developer component and the fast color base or the fast color salt, in order to form a pattern on the nonwoven to be printed.

The nonwoven may optionally undergo an aftertreatment following the coupling of the components to form the azo dye in that the nonwoven is heated or treated with steam, also at an elevated temperature. The steam treatment—the final steam treatment—is preferably carried out at a temperature of 100 to 130° C., preferably at 102 to 120° C., the heating (postsetting) at a temperature of 150 to 240° C., preferably at 175 to 210° C. The duration of the treatment may preferably be 10 seconds to 30 minutes, more preferably 30 seconds to 15 minutes, and most preferably 2 minutes to 10 minutes.

The dyeing and/or printing of the nonwoven may preferably be followed by a cleaning of the nonwoven, preferably by rinsing with water or an aqueous solution containing sodium hydrosulphide and sodium hydroxide, also at an elevated temperature, and/or optionally by a soaping of the nonwoven, it being necessary, of course, to select conditions which do not permit total destruction of the applied azo dye.

To intensify the color depth, subsequently to the dyeing and/or printing operation, the dyed and/or printed nonwoven may be treated with a bathochromic agent in the course of the finishing process. In this context, as bathochromic agents, all chemicals come into consideration which change the angle of refraction of light on the surface of the nonwoven, e.g., by forming a film, in such a way that the angle of refraction between the air and the nonwoven has a value greater than one. Suitable chemicals are, for example, polyacrylates, polyurethanes and polysiloxanes, which are commercially available, for example, under the designations Badena® Eco 282, Finistrol® KSE-D, Baypret® USV and Arristan® 64. If the film formed is composed of chemicals which also protect the dyes from external influences, such as Badena® Eco 282, for example, then the color fastness may also be improved at the same time.

The bathochromic agent may also be applied in accordance with customary methods known to one skilled in the art. The bathochromic agent may preferably be applied to the textile material using the pad dyeing method, at a pH of 2 to 12, preferably of 3 to 9, especially of 4 to 8, and be fixed at temperatures of 40 to 180° C., preferably of 100 to 160° C. for a duration of 1 second to 120 minutes, preferably from 5 seconds to 45 minutes, especially of 30 seconds to 2 minutes. The appropriate quantity of the bathochromic agent may vary in each instance and be determined by one skilled in the art in simple preliminary tests. For Badena® Eco 282, the appropriate quantity is preferably 10 to 100 g/L liquor, especially 20 to 50 g/L liquor.

The nonwoven dyed and/or printed in accordance with the present invention and composed of unsplit and/or of at least partially split microfibers and/or microfilaments of synthetic polymers including at least one polyester component and at least one polyamide component and, optionally, at least one polyurethane component is distinguished by good to excellent color fastness, even subsequently to a heat treatment, in particular by good to excellent washfastness, perspiration fastness, water and light fastness, as well as by good rubbing fastness.

The nonwoven dyed and/or printed in accordance with the method of the present invention is, therefore, particularly suited for manufacturing clothing, home textiles, lining materials, preferably for luggage, as well as for manufacturing textile products in the medical and/or hygienic sector.

Another subject matter of the present invention is, therefore, the use of at least one nonwoven dyed and/or printed in accordance with the present invention, for manufacturing clothing, as home textiles, as lining materials, preferably for luggage, such as for briefcases or suitcases, as well as for textile material in the medical and/or hygienic sector.

By using only one dyestuff class to simultaneously dye the various plastic components of the nonwoven to be colored, in comparison to known related-art methods, inter alia, cleaning steps may be eliminated, on the one hand, thereby reducing the amount of waste water that is produced and, on the other hand, enabling the nonwovens described here to be dyed and/or printed more quickly and, thus, more cost-effectively, as well.

The light fastness of the textile synthetic material dyed and/or printed in accordance with the present invention was determined in accordance with EN ISO 105 B02, the washfastness at 40° C., also following heat treatment, in accordance with EN ISO 105 C06 A2S, the resistance to water in accordance with EN ISO 104 E01, the resistance to perspiration in accordance with EN ISO 104 E04, and the resistance to mechanical rubbing in accordance with EN ISO 105 X12. The corresponding descriptions are incorporated herein by reference.

The present invention is elucidated in the following on the basis of examples. These explanations are merely exemplary and in no way restrict the general inventive idea.

EXAMPLE 1

A spunbonded nonwoven having a basic weight of 100 g/m[0055] ², composed of partially split microfibers of 70% by weight polyethylene terephthalate and of 30% by weight polyamide 66 having a titer of approximately 0.15 dtex was dyed in accordance with the exhaust dyeing method using an aqueous hydroxynaphthoic-acid derivative preparation containing C.I. Azoic Coupling Component 5, (trade name: Naphtol AS-G, DyStar), bottom-dyed, and subsequently coupled with a fast color salt preparation containing C.I. Azoic Diazo Component 33 (salt) (trade name: Echtrotsalz [Fast Red Salt] FRN, DyStar).
To this end, the naphthol was initially dissolved using a cold dissolving process, 1.4 g of the naphthol being made into a paste with 10 mL of a 10% by weight castor oil solution and 5 mL of a 10% by weight sodium hydroxide solution, over which was poured 20 mL of 60° C. water containing 0.0175 g of a trisodium nitrilotriacetate-based complexing agent. [0056]
The volume was subsequently adjusted with 135 mL of 20° C. water containing 0.0825 g of a trisodium nitrilotriacetate-based complexing agent and 30 mL of a 10% by weight sodium choride solution. The mixture was agitated for 5 min at 40° C. [0057]
Ten grams of the spunbonded nonwoven was subsequently bottom-dyed using the resulting solution, at a liquor ratio of 1:20. To this end, the solution, together with the nonwoven, was placed in a dye beaker and heated to 130° C. at 1.5° C./min. Following a residence time of 30 min at 130° C., cooling was carried out to 80° C. at 1.5° C./min, and rinsing for 10 min at a liquor ratio of 1:10 with 199.8 mL of 40° C. water containing 0.2 mL of a 32% by weight sodium hydroxide solution, 10 g sodium chloride and 0.1 g of a trisodium nitrilotriacetate-based complexing agent. [0058]
The development using the fast color salt preparation was likewise carried out in accordance with the exhaust dyeing method at a liquor ratio of 1:10, immediately following the bottom-dyeing process. For this purpose, 0.9144 g of the fast red salt was dissolved in 94 mL of 10° C. water containing 6 mL of a 0.15% by weight solution of a dispersing agent based on an ethoxylated higher alcohol and 1 g sodium acetate. The naphthol-bottomed nonwoven was treated with this solution in a dyeing apparatus at 20° C. for 30 min and subsequently soaped for 15 min at 70° C. with a solution containing 1 g/L of sodium carbonate and 0.5 g/L of a dispersing agent based on an ethoxylated higher alcohol. [0059]
The resulting light fastness of the dyed nonwoven, as well as the wash fastness at 40° C., the resistance to water, the resistance to perspiration, and the resistance to mechanical rubbing are indicated in Table 1. [0060]

EXAMPLE 2

A spunbonded nonwoven having a basic weight of 100 g/m[0061] ², composed of partially split microfibers of 70% by weight polyethylene terephthalate and of 30% by weight polyamide 66 having a titer of approximately 0.15 dtex was bottom-dyed and rinsed as in Example 1.
The development using the fast color salt preparation was carried out in accordance with the pad dyeing method, immediately following the bottom-dyeing process. For this purpose, 6.92 g of the fast red salt preparation was dissolved in 99 mL of 15° C. water containing 1 mL of a 7% by weight solution of a dispersing agent based on an ethoxylated higher alcohol and 1 g of sodium acetate. The pH was adjusted to 5 with 60% by weight acetic acid. The bottom-dyed, moist nonwoven was padded with this solution at 20° C. The liquor uptake was 100% by weight based on the weight of the nonwoven used. The nonwoven was subsequently treated with circulating air at 20° C. for 60 seconds and soaped, in the manner indicated in Example 1. [0062]
The resulting light fastness of the dyed nonwoven, as well as the wash fastness at 40° C., the resistance to water, the resistance to perspiration, and the resistance to mechanical rubbing are indicated in Table 1. [0063]

EXAMPLE 3

A spunbonded nonwoven having a basic weight of 100 g/m[0064] ², composed of partially split microfibers of 70% by weight polyethylene terephthalate and of 30% by weight polyamide 66 having a titer of approximately 0.15 dtex was bottom-dyed in accordance with the exhaust dyeing method using a liquid hydroxybenzocarbazole carboxylic acid preparation containing C.I. Azoic Coupling Component 13, (trade name: Naphtol AS-SG fl., DyStar), and subsequently coupled with a fast color salt preparation containing C.I. Azoic Diazo Component 33 (salt) (trade name: Echtrotsalz [Fast Red Salt] FRN, DyStar). The bottom-dyeing process was carried out in accordance with the exhaust dyeing method at a liquor ratio of 1:20. For this purpose, 196.5 mL of 40° C. water containing 2 g of sodium chloride and 0.1 g of a trisodium nitrilotriacetate-based complexing agent was poured over 3.5 g of the naphthol, and the mixture was then agitated for 5 min at 40° C. Ten grams of the spunbonded nonwoven was subsequently bottom-dyed using the resulting solution, at a liquor ratio of 1:20. To this end, the solution, together with the nonwoven, was placed in a dye beaker and heated to 130° C. at 1.5° C./min. Following a residence time of 30 min at 130° C., cooling was carried out to 80° C. at 1.5° C./min, and rinsing for 10 min at a liquor ratio of 1:20 with 199.8 mL of 40° C. water containing 0.2 mL of a 32% by weight sodium hydroxide solution, 4 g sodium chloride, and 0.1 g of a trisodium nitrilotriacetate-based complexing agent.
The development using the fast color salt preparation was likewise carried out in accordance with the exhaust dyeing method at a liquor ratio of 1:10, immediately following the bottom-dyeing process. For this purpose, 99.95 mL of 15° C. water containing 0.05 g of a dispersing agent based on an ethoxylated higher alcohol and 1 g sodium acetate was poured over 1.01 g of the fast red salt. The pH was adjusted to 4.5 with 60% by weight acetic acid. The naphthol-bottomed nonwoven was treated with this solution in a dyeing apparatus at 20° C. for 30 min and subsequently soaped for 15 min at 70° C. with a solution containing 1 g/L of sodium carbonate and 0.5 g/L of a dispersing agent based on an ethoxylated higher alcohol. [0065]
The resulting light fastness of the dyed nonwoven, as well as the wash fastness at 40° C., the resistance to water, the resistance to perspiration, and the resistance to mechanical rubbing are indicated in Table 1. [0066]

EXAMPLE 4

A spunbonded nonwoven having a basic weight of 100 g/m2, composed of partially split microfibers of 70% by weight polyethylene terephthalate and of 30% by weight polyamide 66 having a titer of approximately 0.15 dtex, was bottom-dyed in accordance with the exhaust dyeing method using a liquid hydroxybenzocarbazole carboxylic acid preparation containing C.I. Azoic Coupling Component 13, (trade name: Naphtol AS-SG fl., DyStar), and subsequently coupled with a fast color salt preparation containing C.I. Azoic Diazo Component 33 (salt) (trade name: Echtrotsalz [Fast Red Salt] FRN, DyStar). For this purpose, 3 g of the naphthol was stirred into a 90° C. solution containing, in addition to 65 mL of water, 0.05 g of a trisodium nitrilotriacetate-based complexing agent and 0.5 mL of a dispersing agent based on a naphthalenesulfonic acid-formaldehyde condensate. The volume was subsequently adjusted to 100 mL with boiling water. Ten grams of the nonwoven was padded with this solution at 90-95° C. The liquor uptake was 100% by weight based on the weight of the nonwoven used. Intermediate drying was then carried out for 90 seconds at 140° C. [0067]
To produce the developing liquor, which was applied to the bottom-dyed nonwoven using the pad dyeing method, initially 3.9 g of the fast color base was dissolved with 58.5 mL of 15° C. water and 1 mL of a 3% by weight solution of a dispersing agent based on an ethoxylated higher alcohol, over which was poured 40.5 mL of 15° C. water containing 0.1 mL of a dispersing agent based on an ethoxylated higher alcohol and 1 g sodium acetate. The pH was adjusted to 5.5 with 60% by weight acetic acid. [0068]
The bottom-dyed fabric was padded with this solution at 20° C. The liquor uptake was 100% by weight based on the nonwoven used. The material was then treated with circulating air at 20° C. for 60 seconds, post-set at 200° C. for 180 seconds, and soaped, as indicated in Example 1. [0069]
The resulting light fastness of the dyed nonwoven, as well as the wash fastness at 40° C., the resistance to water, the resistance to perspiration, and the resistance to mechanical rubbing are indicated in Table 1. [0070]

EXAMPLE 5

A spunbonded nonwoven having a basic weight of 100 g/m[0071] ², composed of partially split microfibers of 70% by weight polyethylene terephthalate and of 30% by weight polyamide 66 having a titer of approximately 0.15 dtex was initially padded with Naphtol AS (Dystar), an aqueous hydroxynaphthoic acid preparation containing C.I. Azoic Coupling Component 2 as dyestuff developer component. The nonwoven was subsequently dried at 140° C. for 90 seconds.
A stock paste A of 500 g Diagum A8 (BF Goodrich, Diamalt, Barcelona, Spain), a thickening agent based on carob flour, 491 g water and 9 g of sodium nitrite and a stock paste B of 500 g Diagum A8, 440 g water and 60 g phosphoric acid were then prepared. To prepare a printing paste, 30 g of the fast base, fast red B (Dystar), C.I. Azoic Diazo Component 5, diluted with 70 g water, was then stirred into 600 g of stock paste A, and 300 g of stock paste B was added thereto. The resulting paste was subsequently post-stirred for five minutes to bring about a diazotization of the fast base. Then, using a screen in accordance with screen-printing method, the paste thus obtained was then applied to the nonwoven, which had previously been padded with the dyestuff developer component. To remove the non-coupled fast base, the nonwoven was then treated for 30 minutes at a temperature of 90° C. with sodium hydrosulphide in aqueous sodium hydroxide solution and subsequently soaped with Calgon T and sodium carbonate. [0072]

EXAMPLE 6

A spunbonded nonwoven having a basic weight of 100 g/m2, composed of partially split microfibers of 70% by weight polyethylene terephthalate and of 30% by weight polyamide 66 having a titer of approximately 0.15 dtex was initially padded with an aqueous solution of Naphtol AS (Dystar), an hydroxynaphthoic acid preparation containing C.I. Azoic Coupling Component 2 as dyestuff developer component. The nonwoven was subsequently dried at 140° C. for 90 seconds. The nonwoven, pretreated in this manner, was then dried using a screen, printed with a paste of 200 g of aluminum sulfate monohydrate, 200 g of water and 600 g of cellulose ether, and then dried for three minutes at a temperature of 120° C. [0073]
The material was then padded with a solution containing 24 g/L of Variamin blue salt BN (Dystar, C.I. Azoic Diazo Component 35), dissolved with the aid of 1 g/L of a dispersing agent Dispersogen ASN based on an ethoxylated higher alcohol (Clariant). No coupling occurred at the spots on the nonwoven where the aluminum sulfate had previously been applied, so that the resulting nonwoven showed a white pattern. The air-drying lasted 60 seconds. [0074]
The nonwoven was subsequently reductively cleaned using sodium hydrosulphide and sodium hydroxide solution, rinsed with hot running water, and then soaped at boil with a solution containing 1 g/L each of Naphtopon E (Bayer AG, Germany), Calgon T (Benkieser) and sodium carbonate. [0075]

EXAMPLE 7

A spunbonded nonwoven having a basic weight of 100 g/m[0076] ², composed of partially split microfibers of 70% by weight polyethylene terephthalate and of 30% by weight polyamide 66 having a titer of approximately 0.15 dtex was initially padded with an aqueous solution of Naphtol AS (Dystar), an hydroxynaphthoic acid preparation containing C.I. Azoic Coupling Component 2 as dyestuff developer component. The nonwoven was subsequently dried at 140° C. for 90 seconds. The material pretreated in this manner was then printed with a paste of 60 g of fast orange salt GGD, 3 g of the dispersing agent Dispersogen ASN, 317 g of water, 70 g of aluminum sulfate monohydrate and 550 g of Tylose H 300, and then dried for three minutes at a temperature of 120° C.
The material was subsequently padded with a solution containing 24 g/L of Variamin blue salt BN, dissolved with the aid of 1 g/L of a dispersing agent Dispersogen ASN. No coupling occurred with the Variamin blue salt at the spots on the nonwoven where the aluminum sulfate had previously been applied. However, coupling did occur with the fast orange salt GGD, so that the resulting nonwoven showed a pattern. The air-drying lasted 60 seconds. [0077]

The nonwoven was subsequently reductively cleaned using sodium hydrosulphide and sodium hydroxide solution, rinsed with hot running water, and then soaped at boil with a solution containing 1 g/L each of Naphtopon E (Bayer AG), Calgon T (Benkieser) and sodium carbonate.

TABLE 1


Example 1:	Example 2:	Example 3:	Example 4:
Dyestuff	Dyestuff color:	Dyestuff color:	Dyestuff color:
color: yellow	yellow	grey-brown	grey-brown

wash 40° C.	4S/4C	4S/4C	4S/4C	4S/4C
EN ISO 105 C06 A2S
wash 40° C.	4S/4C	4S/4C	4S/4C	4S/4C
EN ISO 105 C06 A2S
following heat
treatment 1 min 150° C.
wash 40° C.	4S/4C	4S/4C	4S/4C	4S/4C
EN ISO 105 C06 A2S
following heat
treatment 1 min 180° C.
water	4-5S/4-5C	4-5S/4-5C	4-5S/4-5C	4-5S/4-5C
EN ISO 104 E01
perspiration acidic	4-5S/4-5C	4-5S/4-5C	4-5S/4-5C	4-5S/4-5C
EN ISO 104 E04
perspiration alkaline	4-5S/4-5C	4-5S/4-5C	4-5S/4-5C	4-5S/4-5C
EN ISO 104 E04
rubbing fastness	4 dry/	4 dry/	4 dry/	3-4 dry/
EN ISO 105 X12	3-4 wet	3-4 wet	3 wet	3 wet
light fastness	—	—	5	5
EN ISO 105 B02

Claims

1-39. (canceled)

40. A dyed and/or printed nonwoven, comprising:

at least one of microfibers and microfilaments of synthetic polymers, the synthetic polymers including at least one polyester component and at least one polyamide component; and

at least one azo dye disposed on the nonwoven.

41. The nonwoven as recited in claim 40, wherein the synthetic polymers include at least one polyurethane component.

42. The nonwoven as recited in claim 40, wherein the microfibers and/or microfilaments are unsplit.

43. The nonwoven as recited in claim 40, wherein the microfibers and/or microfilaments are at least partially split.

44. The nonwoven as recited in claim 40, wherein the at least one polyester component is 5 to 95% by weight of the synthetic polymer and the at least one polyamide component is 95 to 5% by weight of synthetic polymer.

45. The nonwoven as recited in claim 40, wherein the polyamide component is selected from the group consisting of polyamide 6, polyamide 66 and polyamide 11.

46. The nonwoven as recited in claim 40, wherein the polyester component includes at least one of polyethylene terephthalate, polypropylene terephathalate, polybutylene terephthalate, polylactic acid, and a copolyester.

47. The nonwoven as recited in claim 40, wherein a titer of the microfibers and/or microfilaments is ≦1 dtex.

48. The nonwoven as recited in claim 40, wherein the nonwoven is a staple-fiber nonwoven.

49. The nonwoven as recited in claim 40, wherein the nonwoven is a spunbonded nonwoven.

50. The nonwoven as recited in claim 40, wherein the nonwoven has a basic weight of 15 to 400 g/m².

51. A method for dyeing and/or printing a nonwoven with at least one azo dye, the nonwoven including at least one of microfibers and microfilaments of synthetic polymers, the synthetic polymers including at least one polyester component and at least one polyamide component, the method comprising:

treating the nonwoven with at least one dyestuff developer component at a treatment temperature of ≧90° C. and at least one of a fast color salt and a fast color base;

where the treating includes treating the nonwoven with a fast color base, diazotizing the diestuff developer component with the fast color base; and

coupling the dyestuff developer component and the fast color salt and/or the fast color base on the nonwoven.

52. The method as recited in claim 51, wherein the dyestuff developer component is selected from the group consisting of arylamides of aromatic hydroxycarboxylic acids, arylamides of keto acids and hydroxynaphthyl ketones.

53. The method as recited in claim 52, wherein the dyestuff developer component is an arylamide of an aromatic hydroxycarboxylic acid and includes at least one of an amide of the 2-hydroxy-3-naphthoic acid, an amide of anthracene, an amide of carbazole, and an amide of diphenylene oxide.

54. The method as recited in claim 53, wherein the dyestuff developer component includes one of a 2-hydroxy-3-naphthoic acid anilide, a 2-hydroxy-3-naphthoic acid o-toluidide, a 2-hydroxy-3 naphthoic acid-4, a 6-dimethoxy-3-chloroanilide, a 2-hydroxy-3-naphthoic acid α-naphthylamide and a [bis-2-hydroxy-3-naphthoic acid]dianiside.

55. The method as recited in claim 54 wherein the dyestuff developer component includes 2-hydroxy-3-anthracene-carboxylic acid o-toluidide as an amide of anthracene.

56. The method as recited in claim 53, wherein the dyestuff developer component includes 2-hydroxycarbazole-3-carboxylic acid 4′-choroanilide as an amide of carbazole.

57. The method as recited in claim 53, wherein the dyestuff developer component includes 3-hydroxydiphenylene oxide-2-carboxylic acid 2′,5′-dimethoxyanilide as an amide of diphenylene oxide.

58. The method as recited in claim 52, wherein the dyestuff developer component includes diacetic acid o-toluidide or terephthaloyl-bis-acetic acid bis-[2-methoxy-4-chloro-5-methylanilide] as arylamide of a keto acid.

59. The method as recited in claim 52, wherein the fast color base including at least one of o-chloroaniline, o-nitroaniline, m-nitro-p-toluidine, 4-diethylsulfonamido-1-amino-1-methoxybenzene, 4-chloro-2-aminodiphenyl ether, α-aminoanthraquinone, 4-amino-3-methoxyazobenzene, 4-amino-1-benzoylamino-3-methoxy-6-methylbenzene, o-dianisidine, 4-amino-4′-methoxydiphenylamine, 3,5-bis-trifluoromethylaniline, and 3-fluorosulfonyl aniline.

60. The method as recited in claim 51, wherein the treating of the nonwoven with the dyestuff developer component is performed using an exhaust dyeing method.

61. The method as recited in claim 51, wherein the treating is performed at a temperature of 90 to 150° C.

62. The method as recited in claim 51, wherein the treating of the nonwoven with the dyestuff developer component is performed for a duration of 10 to 180 minutes.

63. The method as recited in claim 60, wherein the exhaust dyeing method includes intermediate drying and a subsequent heat treatment.

64. The method as recited in claim 63, wherein the subsequent heat treatment is performed using steam.

65. The method as recited in claim 63, wherein the intermediate drying process is performed at a temperature of 80 to 180° C.

66. The method as recited in claim 63, wherein the intermediate drying process is performed for a duration of 30 seconds to 10 minutes.

67. The method as recited in claim 64, wherein the subsequent heat treatment is performed at a temperature of 100 to 130° C.

68. The method as recited in claim 64, wherein the subsequent heat treatment is performed for a duration is 15 seconds to 60 minutes.

69. The method as recited in claim 51, wherein at least one of the treating step and the coupling step is performed using an exhaust dyeing method.

70. The method as recited in claim 69, wherein the treating is performed at a temperature of −10 to 130° C.

71. The method as recited in claim 69, wherein treating is performed for a duration of 5 to 120 minutes.

72. The method as recited in claim 51, wherein at least one of the treating step and the coupling step is performed using a pad dyeing method.

73. The method as recited in claim 72, wherein the pad dyeing method includes a subsequent drying and a subsequent heat treatment.

74. The method as recited in claim 72, wherein the treatment temperature during the pad dyeing method is −10 to 60° C.

75. The method as recited in claim 72, wherein the treatment is performed for a duration of not longer than 10 seconds.

76. The method as recited in claim 73, wherein the subsequent drying is performed at 80 to 180° C.

77. The method as recited in claim 73, wherein the subsequent drying is performed for 30 seconds to 10 minutes.

78. The method as recited in claim 73, wherein the subsequent heat treatment is performed using steam and at a temperature of 100 to 130° C.

79. The method as recited in claim 51, wherein the dyestuff developer component and/or the fast color base or the fast color salt is imprinted on the nonwoven.

80. The method as recited in claim 79, wherein the printing is performed using a direct printing method.

81. The method as recited in claim 80, wherein the direct printing method includes at least one of a rotary screen, a flat screen printing and an ink jet method.

82. The method as recited in claim 51, wherein at least one of the dyestuff developer component, the fast color base and the fast color salt are present in aqueous solution.

83. The method as recited in claim 51, wherein the coupling step is performed in an aqueous solution.

84. The method as recited in claim 51, further comprising employing the nonwoven in at least one of a clothing piece, a home textile, a lining material, a medical device, and a hygienic device.