Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/653—Nitrogen-free carboxylic acids or their salts
  • D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8209—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing amide groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8219—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and amide groups

Definitions

• the present invention relates to a method for dyeing and / or printing textile material containing unsplit and / or at least partially split microfibers and / or microfilaments from at least one polyamide component and optionally at least one further polymer component, according to which the textile material is treated with formic acid and with at least a dye selected from the group comprising anionic acid dyes, metal complex dyes,
• Reactive dyes, direct dyes and cationic dyes are colored and / or printed.
• Textile materials which at least partially consist of polyamide, have found widespread use in a wide variety of applications, such as the clothing industry or the automotive industry, due to their diverse excellent properties.
• For optical Design of the textile materials are usually dyed, with anionic acid dyes, metal complex dyes, reactive dyes, direct dyes (noun dyes) or cationic dyes being used with satisfactory results for the dyeing of the polyamide component.
• the corresponding textile materials contain one or more polyamide components in the form of optionally split microfibers and / or microfilaments with a titer of ⁇ 1 dtex, on the other hand, these can often only be inadequate with the above-mentioned dyes, i.e. with insufficient depth of color and color equality between the different areas.
• These difficulties in the dyeing of polyamide microfibers and / or microfilaments are based, among other things, as described, for example, in K.
• the amount of dye required is greater, the smaller the titer and the higher the density of the microfibers and filaments, i.e. is the number of microfibers and filaments per unit area of the textile material.
• nonwovens which at least partially consist of split polyamide microfibers and / or microfilaments
• the dyeing or printing of nonwovens is therefore particularly problematic, since in these materials the density of the microfibers and / or filaments is significantly greater and the titer of the fibers is significantly lower than in corresponding ones Woven or knitted fabrics, in which usually only one component, usually the weft, is made of microfibers consists.
• the dyeing is made more difficult by the uneven distribution of the microfiber and / or microfilaments in the nonwoven.
• the object of the present invention was therefore to provide a method for dyeing and / or printing textile materials containing unsplit and / or at least partially split microfibers and / or microfilaments from at least one polyamide component and optionally at least one further polymer component, according to the the coloring of the polyamide microfiber and polyamide microfilament component is achieved with a very good depth of color.
• the resulting dyeing and / or printing should preferably also have sufficient color fastness and different batches of the dyed and / or printed textile material should preferably have a more uniform color dropout, ie a better color consistency.
• This object was achieved by the process according to the invention for dyeing and / or printing textile material containing unsplit and / or at least partially split microfibers and / or microfilaments from at least one polyamide component and optionally at least one further polymer component, according to which the textile material is treated with formic acid and with at least one dye selected from the group comprising acid dyes, metal complex dyes, reactive dyes, direct dyes and cationic dyes and / or printed.
• the textile material preferably contains unsplit and / or at least partially split microfibers and / or microfilaments which have at least one natural, semisynthetic or synthetic polymer component as a further polymer component. Cellulose and / or wool and / or silk are preferred as the natural polymer component.
• a semisynthetic polymer component is present as a further polymer component, this can preferably be selected from the group consisting of viscose, cellulose acetate, copper silk (Cupro) and Lyocell. If a synthetic polymer component is present as a further polymer component, this can preferably be selected from the group consisting of polyester, polyurethane, polyacrylonitrile, polypropylene and polyvinyl alcohol.
• the textile material to be dyed preferably consists of unsplit and / or at least partially split microfibers and / or microfilaments which consist of at least one polyamide component and at least one polyester component and optionally at least one polyurethane component, these preferably comprising 15 to 99% by weight of at least one Polyamide component and 85 to 1 wt .-% of at least one polyester component and / or at least one
• Polyurethane component and particularly preferably from 30 to 90 wt .-% of at least one polyamide component and 70 to 10 wt .-% of at least one polyester component and / or at least one polyurethane component.
• the unsplit and / or at least partially split microfibers and / or microfilaments contain at least one polyester component, this can preferably be selected from the group consisting of Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polylactic acid, their mixtures and copolyesters.
• Corresponding copolyesters can be obtained either by partially exchanging the acid component and / or the diol component during the preparation of the polyester, as for example in Büttner "Basically Modified Polyester Fibers” in “Die Angewandte Makromolekulare Chemie” 40/41, 1974, page 57 -70 (No. 593) or GG Kulkarni, Colorage, August 21, 1986, pages 30-33.
• the corresponding literature descriptions are hereby introduced as a reference and are considered part of the disclosure.
• the textile material made of microfibers and / or microfilaments used for coloring can likewise preferably have a polyester based on lactic acid as described in EP 1 091 028.
• the corresponding description is hereby introduced as a reference and is considered part of the disclosure.
• the polyamide component of the textile material made of microfibers and / or microfilaments can preferably be selected from the group consisting of polyamide 6, polyamide 66 and polyamide 11.
• the polyamide component can also preferably have groups which can be dyed with anionic or cationic dyes.
• the polyamide component can preferably have at least one amino group which is optionally at least simply substituted with an aliphatic radical and / or an optionally substituted aryl or heteroaryl radical.
• the polyamide component can preferably have at least one hydroxyl, carboxyl or sulfonate residue.
• Such groups can be introduced into the polyamide component by customary methods known to those skilled in the art.
• Correspondingly modified polyamide components are described, for example, in A. Anton, Textile Chemist and Colorist & American Dyestuff Reporter Vol. 32, No.3, March 2000, pages 26 to 32. The corresponding description is hereby introduced as a reference and is considered part of the disclosure.
• the titer of the microfibers and / or microfilaments that make up the material to be dyed is preferably 0.02 to 0.95 dtex, particularly preferably 0.05 to 0.8 dtex and very particularly preferably 0.1 to 0.5 dtex ,
• the weight per unit area of the textile material is preferably 15 to 400 g / m 2 , particularly preferably 40 to 300 g / m 2 and very particularly preferably 50 to 200 g / m 2 .
• the textile material to be dyed is preferably used in the form of a woven fabric, knitted fabric, knitted fabric, fleece or a nonwoven fabric.
• the textile material is particularly preferably in the form of a nonwoven fabric, which preferably consists of unsplit and / or at least partially split polyester / polyamide microfibers and / or polyester / polyamide microfilaments.
• a nonwoven fabric which preferably consists of unsplit and / or at least partially split polyester / polyamide microfibers and / or polyester / polyamide microfilaments.
• the nonwoven is preferably a staple fiber nonwoven or a spunbonded nonwoven, particularly preferably a spunbonded nonwoven.
• nonwovens can be produced by customary methods known to the person skilled in the art, as described, for example, in Dr. Helmut Jörder, "Nonwovens-based textiles", avr textbook, P. Keppler Verlag KG, Heusenstamm 1977, pages 13 to 20.
• Corresponding spunbonded nonwovens can preferably be produced by methods as described in EP 0 814 188. The corresponding descriptions are hereby introduced as a reference and are considered part of the disclosure.
• the treatment of the textile material with formic acid can be carried out both before and during the dyeing and / or printing with acid, metal complex, direct, reactive or cationic dyes.
• the textile material is preferably treated with formic acid before dyeing and / or printing.
• Both the treatment of the textile material and the dyeing can be carried out continuously, semi-continuously or batchwise.
• the treatment of the textile material is carried out discontinuously, this is preferably done according to the exhaust process, preferably on a jet dyeing machine, a reel runner or a jigger.
• the treatment of the textile material with formic acid can also preferably be carried out continuously, preferably according to the immersion, splash (coating), foam or spray process, as described, for example, in Dr. Helmut Jörder, "Non-woven textiles (nonwovens)", avr specialist book, P. Keppler Verlag KG, Heusenstamm 1977, pages 72 to 79 for applying binders are described.
• the corresponding literature is hereby introduced as a reference and is considered part of the disclosure.
• the continuous treatment of the textile material with formic acid is preferably carried out according to the block process, preferably according to the block heat-setting or block steaming process.
• this treatment of the textile material with formic acid is followed by intermediate drying and, if appropriate, heat treatment, if appropriate in the presence of steam.
• the temperatures and the duration of the treatment can vary both during intermediate drying and during heat treatment.
• the duration of the intermediate drying is preferably 1 to 10 minutes, the temperature is preferably 40 to 150 ° C.
• a heat treatment is carried out, its duration is preferably 1 second to 60 minutes and its temperature is preferably 100 to 240 ° C.
• the textile material can preferably also be treated with formic acid during printing with at least one of the dye classes mentioned above. If appropriate, an intermediate drying and, if appropriate, a heat treatment, optionally in the presence of water vapor, is preferably also carried out here under the conditions specified above.
• the printing can be carried out according to various methods known to the person skilled in the art.
• the printing of the textile material is preferably carried out according to a direct printing method, preferably according to a film printing process, particularly preferably according to the rotary film or flat film printing process, or according to the ink jet process.
• the formic acid used to treat the textile material is preferably used in the form of an aqueous treatment liquor.
• the pH of this liquor is preferably adjusted to 1 to 3, particularly preferably 1.5 to 2.5, the amount of formic acid required for pH adjustment being dependent on the initial pH of the water used.
• the duration of treatment of the textile material varies and is among others depending on the pH of the treatment liquor and / or the treatment temperature.
• the process according to the invention for treating the textile material is preferably carried out at elevated temperature, in order, for example, shorten the treatment time.
• the temperature is preferably 5 to 140 ° C., particularly preferably 10 to 130 ° C. and very particularly preferably 20 to 100 ° C.
• the duration of the treatment with formic acid in the exhaust process is preferably 5 minutes to 600 minutes, particularly preferably 10 minutes to 2 hours and very particularly preferably 15 minutes to 100 minutes.
• the treatment time is usually very short and is preferably not more than 10 seconds.
• the textile material is preferably rinsed with formic acid, preferably with water, and optionally neutralized and / or optionally dried.
• the dyeing and / or printing of the textile material with at least one dye selected from the group of acid, metal complex, direct, reactive or cationic dyes can be carried out by customary methods known to the person skilled in the art.
• the dyeing and / or printing is preferably carried out according to the methods given above for the treatment with formic acid, the treatment and the dyeing or printing, as explained above, not having to take place simultaneously.
• the acid, metal complex, direct, reactive or cationic dyes suitable for coloring the polyamide component are known per se to a person skilled in the art and are described, for example, in Rath, “Textbook of Textile Chemistry”, Chapter V “The Artificial Organic Dyes”, Chapter VI “The Use of dyes in dyeing ", Chapter VII” The use of dyes in the printing works ", pages 367 to 742, Springer-Verlag, 3rd edition 1972 or in the corresponding color cards of the dye manufacturers.
• the corresponding literature descriptions are hereby introduced as a reference and are considered part of the disclosure.
• the appropriate amounts of the dyes can vary, for example depending on the textile material or class of dyes used. They can be determined by a specialist through preliminary tests.
• the textile material is first pretreated with formic acid and then dyed with at least one reactive dye in the exhaust process, the dye initially in the presence of vinegar and / or Formic acid, preferably extracted at a pH of 1 to 6, particularly preferably from 1.5 to 2.5 and then in the neutral to alkaline pH range, preferably at pH 7 to 12, particularly preferably at pH 7.5 to 10 is reactively bound to the microfibers and / or microfilaments of the textile material.
• the unbound dye is then removed from the fiber by an alkaline wash, preferably at pH 9-10.
• the dyeing and / or printing of the textile material can preferably be followed by cleaning of the textile material, preferably by rinsing with water, even at elevated temperature and optionally soaping the nonwoven fabric.
• the textile materials treated with formic acid by the process according to the invention and dyed and / or printed with acid, direct, reactive or cationic dyes are distinguished by a very good depth of color, by excellent wet and / or light fastness and by a uniformity of color within a lot and between different lots in addition to good strength values.
• the method according to the invention surprisingly also improves the feel and reduces the pilling.
• the textile materials dyed and / or printed by the process according to the invention are therefore outstandingly suitable for the production of clothing, as home textiles, as upholstery fabrics, as lining materials, preferably for luggage, such as e.g. Bags or suitcases, as textiles for equipping means of transport, e.g. Motor vehicles, rail vehicles, water vehicles or aircraft, preferably for the interior of means of transport or as textile materials in the medical and / or hygienic field.
• Another object of the present invention is therefore the use of the textile material dyed and / or printed by the process according to the invention for the production of clothing, as home textiles, as upholstery fabrics, as lining materials, preferably for luggage, particularly preferably for bags and / or suitcases Textiles for furnishing means of transport, preferably for the interior of means of transport, or as textile materials in the medical and / or hygienic field.
• the fastness to washing of the textile material treated and dyed and / or printed by the process according to the invention at 40 ° C. or 60 ° C. was determined according to EN ISO 105 C06 A2S or EN ISO 105 C06 C2S, the sweat fastness according to EN ISO 105 E04 Fastness to rubbing in accordance with EN ISO 105 X12 and tear resistance in accordance with DIN EN 29073, Part 3.
• the reduction in pilling was determined in accordance with DIN 53876 in the random pilling test certainly.
• the corresponding descriptions are hereby introduced as a reference and are considered part of the disclosure.
• the K / S value in the absorption maximum of the dyeings is used as a measure of the color depth of the dyeings. This can be calculated using the Kubelka-Munk formula from the remission values as follows:
• the reflectance values R were measured using a Colorflash C22S color measuring device from Optronik. The higher the K / S ratio, the deeper the color.
• Example 1 In the following the invention will be explained with the aid of examples. These explanations are only examples and do not limit the general idea of the invention.
• Example 1 Example 1 :
• the mixture was heated at 60 ° C. at 20 ° C. and min.
• the treated nonwoven fabric was then rinsed under cold, flowing water until the pH was neutral and dried at room temperature.
• the a) treated in accordance with non-woven fabric was washed with 2 wt .-% (based on the weight of the nonwoven fabric) of the reactive dye Dimaren ® Brilliant Blue K-BL (Clariant, Germany) at a liquor ratio of 1: colored 10th
• the pH was adjusted at 20 ° C. with 98-100% by weight formic acid to pH 2, then the mixture was heated to 60 ° C. at 2 ° C./min and the dye was removed at 60 ° C. for 30 minutes.
• the pH was then adjusted to 9 by adding solid sodium carbonate, then the mixture was heated to 90 ° C. at 2 ° C./min and stained at 90 ° C. for 30 minutes.
• the dyeing was then rinsed under running water and at a liquor ratio of 1: 100 with 4 g / l of a commercially available mild detergent twice for 15 min at 60 ° C. soaped.
• the pH was adjusted to 9 with solid sodium carbonate.
• the color was rinsed with cold water.
• a spunbonded nonwoven fabric treated with formic acid according to Example 1 a) and having a basis weight of 100 g / m 2 consisting of partially split microfilaments of 70% by weight polyethylene terephthalate and 30% by weight polyamide 66 with a titer of approx. 0.15 dtex was mixed with 2 wt .-% (based on the weight of the nonwoven fabric) of the reactive dye Dimaren ® Red 8RB (Clariant, Germany) at a liquor ratio of 1: colored 10th
• the pH was adjusted to pH 2 at 20 ° C. using 60% by weight acetic acid, then the mixture was heated to 60 ° C. at 2 ° C./min and the dye was removed at 60 ° C. for 30 minutes.
• the pH was then adjusted to 9 by adding solid sodium carbonate, then the mixture was heated to 90 ° C. at 2 ° C./min and stained at 90 ° C. for 30 minutes.
• the dyeing was then rinsed under running water and soaped twice at a liquor ratio of 1: 100 with 4 g / l of a commercially available mild detergent for 15 min at 60 ° C.
• the pH was adjusted to 9 with solid sodium carbonate. Finally, the color was rinsed with cold water.
• a spunbonded nonwoven with a basis weight of 100 g / m 2 consisting of partially split microfilaments made of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 with a titer of approx. 0.15 dtex was extracted with 2% by weight. % (based on the weight of the nonwoven fabric) at a liquor ratio of 1 of the reactive dye Realan ® Red G (DyStar, Germany): dyed 10th
• the pH was adjusted to pH 2 at 20 ° C. with 25 ml / l of 98-100% by weight formic acid, then the mixture was heated to 60 ° C. at 2 ° C./min and the dye was removed at 60 ° C.
• the mixture was heated to 130 ° C at 2 ° C / min, treated at 130 ° C for 60 min and cooled to 80 ° C at 2 ° C / min.
• the thus treated nonwoven fabric was rinsed under running water, dried and the exhaust dyeing at a liquor ratio of 1: 10 to 3 wt .-% (based on the weight of the nonwoven fabric) of the cationic dye Astrazon ® Red 5BL (DyStar, Germany) in the presence of 6 g / l sodium sulfate (anhydrous) colored.
• the pH was adjusted to 4.5 with 60% by weight acetic acid.
• the mixture was heated to 130 ° C at 2 ° C / min, dyed at 130 ° C for 60 min and cooled to 80 ° C at 2 ° C / min. Afterwards the coloring was rinsed with running water and. soaped with 1 g / l of a commercially available mild detergent and 2 g / l sodium carbonate at 40 ° C for 15 min.
• the leveling agent Levegal LPA Levegal LPA (Bayer AG, Germany) and a mixture of the following acid were used at a liquor ratio of 1:10 with 1% by weight (based on the weight of the nonwoven) - or metal complex dyes: 0.46% by weight (based on the weight of the nonwoven) Isolan ® Red S-RL, 0.26% by weight Supranol ® Yellow 4GL (based on the weight of the nonwoven) and 0.22% Supranol ® Red R01 (based on the weight of the nonwoven) (all dyes from DyStar, Germany).
• the pH was adjusted to 4 with 60% by weight acetic acid.
• the mixture was heated to 90 ° C at 2 ° C / min, dyed at 90 ° C for 90 min and then cooled to 60 ° C. Rinsed 40 and at a liquor ratio of 1::. Thereafter, warm with 30 ° C water at a liquor ratio of 1 20 to 4% by weight (based on the weight of the nonwoven fabric) of the curing agent Solfix ® E (Ciba Specialty Chemicals, Basel) at 40 ° C treated 10 min. Sodium hydroxide solution 50% by weight was then added to the treatment liquor at 40 ° C. (based on the weight of the nonwoven) and treatment was continued at 40 ° C. for 40 minutes. It was then rinsed with cold water at a liquor ratio of 1:40 and acidified with 1 ml / l of 60% by weight acetic acid.
• Solfix ® E Ciba Specialty Chemicals, Basel
• a spunbonded nonwoven with a basis weight of 100 g / m 2 consisting of partially split microfilaments made of 70% by weight of polyethylene terephthalate and 30% by weight of polyamide 66 with a titer of approx. 0.15 dtex was padded with an aqueous liquor, which contained 280 ml / l (7.4 mol / l) of 98-100% by weight formic acid and whose pH was 1, impregnated. The liquor absorption was 100% by weight, based on the nonwoven used.
• the treated nonwoven fabric was then dried at 120 ° C. for 90 seconds and then fixed at 220 ° C. for 90 seconds. It was then washed with water and dyed in accordance with Example 4 using the exhaust method.
• Tables 1 to 5 mean the grades:
• the mean color deviation DE * (medium) was determined colorimetrically using a color measuring device type Colorflash C22S from Optronik according to the CIE-Lab. For this purpose, 24 samples were taken at a distance of 10 m from the center of the web were measured against a template. The color-deepest pattern (pattern with the highest K / S value) of the respective lot was defined as the template. The mean color deviation DE * (medium) was determined by averaging the 24 individual color deviations dE. The color constancy within the lot is the better, the smaller the mean color deviation DE * (medium).
• the pilling values were determined in accordance with DIN 53867 in the random tumble pilling test.
• the values given are mean values from 3 measurements.

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  • 2002-07-11 CN CNA028147235A patent/CN1535341A/zh active Pending
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