EP0057457B1 - Verfahren zum egalen Di- und Trichromiefärben von Polyacrylnitrilmaterialien - Google Patents

Verfahren zum egalen Di- und Trichromiefärben von Polyacrylnitrilmaterialien Download PDF

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Publication number
EP0057457B1
EP0057457B1 EP82100689A EP82100689A EP0057457B1 EP 0057457 B1 EP0057457 B1 EP 0057457B1 EP 82100689 A EP82100689 A EP 82100689A EP 82100689 A EP82100689 A EP 82100689A EP 0057457 B1 EP0057457 B1 EP 0057457B1
Authority
EP
European Patent Office
Prior art keywords
dye
dyeing
migrating
tone
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82100689A
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German (de)
English (en)
French (fr)
Other versions
EP0057457A1 (de
Inventor
Manfred Herrmann
Rico Jenny
Manfred Motter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
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Publication of EP0057457A1 publication Critical patent/EP0057457A1/de
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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
    • 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
    • D06P3/70—Material containing nitrile groups
    • D06P3/76—Material containing nitrile groups using basic dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/927—Polyacrylonitrile fiber

Definitions

  • the invention relates to a method for level dyeing and trichromatic dyeing of polyacrylonitrile materials with specific dye combinations, and the colored material and the dye combinations as such.
  • the cationic dyes specially developed for dyeing polyacrylonitrile fibers are generally notable for good drawing and building properties, a high level of fastness and a bright color.
  • their migration ability on most substrates made of polyacrylonitrile fiber material at cooking temperature is only low. The consequence of this is that there are irregularities which arise due to the high drawing speed of these dyes during the mounting process; these can only be remedied under conditions which run counter to the productivity of the dyeing operation or the quality maintenance of the textile structure, such as e.g. B. by extending the cooking phase or by a significant increase in the dyeing temperature.
  • the invention was based on the object of dyeing polyacrylonitrile material or blended fabric containing polyacrylonitrile quickly and correctly, regardless of the type of fiber or packaging, both irrespective of the type and also lightfast.
  • the solution to this problem consists in dyeing polyacrylonitrile material or blended fabrics containing polyacrylonitrile with an aqueous dye liquor which contains a combination of at least two dye mixtures, each consisting of at least one migrating cationic and at least one non-migrating cationic dye which migrate together tone-on-tone .
  • Non-migrating cationic dyes are understood to mean those dyes that migrate to a small extent, but whose migration ability is limited. If polyacrylonitrile materials are dyed with these dyes, any initial irregularities that may occur during the cooking phase are no longer leveled out.
  • the dye component a) can be either a single dye or a mixture of the migrating cationic dyes as defined. The same is the case with dye component b), where it is also a single dye or a mixture of cationic dyes.
  • aqueous dyeing liquor optionally contains other additives and / or retarders customary in dyeing.
  • An advantage of the method according to the invention is that it is acceptable to pull it on, since this is compensated for in the dyeing time (about 30 to 45 minutes at 102 to 104 ° C.). This results in further advantages, such as a shortened heating-up phase in particular (20 to 25 minutes and no longer 45 to 90 minutes are required to increase the bath temperature from 80 to 100 ° C).
  • a further advantage of the process according to the invention is that, despite everything, uneven colorations can be leveled out without difficulty by prolonged cooking.
  • the method according to the invention permits level tone-on-tone dyeing of all polyacrylonitrile materials in all possible colors.
  • Decisive for the success of the dyeing process according to the invention is the mixing ratio of the dye components a) and b) used in each case in the dye mixtures. It can vary within wide limits, for example, that 2 to 98% of the dye component a) and 98 to 2% of the dye component b) are present.
  • dye component a) It is preferred to use 20 to 80% of dye component a) and 80 to 20% of dye component b). However, particular preference is given to those dye mixtures which contain component b) d. H. contain the non-migrating dye in excess. The mixing ratio is essentially determined by the migration ability of the individual dyes.
  • Migrating cationic dyes are those with a more or less delocalized positive charge, the cation weight of which is less than 310, in particular less than 275, the parachor of which is less than 750, in particular less than 680 and the log P of which is less than 3.6, in particular less than 2, 8 is.
  • the parachor is calculated according to the article by O. R. Quayle Chem. Rev. 53, 439 (1953) and log P means the relative lipophilicity, the calculation of which by C. Hansch et al. J. Med. Chem. 16, 1207 (1973). The influence of the charge of the dye cations was not taken into account, which results in log P values which are approximately 6 log units higher.
  • the cationic migrating and non-migrating dyes can belong to different classes of dyes.
  • they are salts, for example chlorides, sulfates, methosulfates, acetates or metal halides, for example zinc chloride salts of azo dyes, such as monoazo dyes or hydrazone dyes, diphenylmethane, methine or azomethine dyes, ketone imine, cyanine, azine, oxazine or thiazine dyes.
  • the dye mixtures according to the invention provide a balanced di- and trichrome of cationic dyes with very good migratory properties and excellent lightfastness, which enable simple and safe dyeing.
  • R 5 is an unsubstituted alkyl group having 7 to 17 carbon atoms
  • R 6 and R 7 are each an unsubstituted lower alkyl group
  • n is 2 or 3.
  • cationic organic ammonium compounds of the general formula III which have at least one higher alkyl radical in which R s is an optionally interrupted by oxygen atoms, not further substituted alkyl chain with 8 to 18, preferably 8 to 12 carbon atoms, Rg hydrogen, the methyl or ethyl group and X ⁇ has the meaning given, or compounds of the general formula IV in which one of R 10 , R 11 and R 12 is an R an unsubstituted alkyl group having 7 to 18 carbon atoms and the other two R are hydrogen or a lower alkyl radical which may be substituted by hydroxyl groups, n the numbers 2 or 3 and X () has the meaning given , or compounds of the general formula V in which R 13 is an unsubstituted alkyl group having 8 to 18 carbon atoms, R 14 is hydrogen, an unsubstituted alkyl group having up to 18 carbon atoms or the unsubstituted phenyl radical, R 15 is an unsubstituted lower alkyl
  • R 5 is an unsubstituted alkyl group having 7 to 17 carbon atoms
  • Q S.NR 20 or O R 16 , R 17 , R 18 , R 19 and R 20 independently of one another, each hydrogen, a lower one optionally substituted by hydroxyl or lower alkoxy groups
  • X e is the anion of an organic or inorganic acid and n is 1 or 2.
  • Those retarders of the formula VII are particularly suitable with a cation weight of 228, a parachor of 665 and a log P of 6.68, those of the formula VIII with a cation weight of 258, a parachor of 744 and a log P of 5.65, and those of the formula IX with a cation weight of 248, a parachor of 693 and a log P of 6.32, where X e is the anion of an organic or inorganic acid.
  • the addition of a retarder has the effect that the dyeing speed of the cationic dyes is reduced.
  • the use of the dye mixture of a) and b) and retarder which can be used according to the invention makes it possible to save about 50 to 100% of the amount of retarder compared to previously customary processes.
  • the amounts in which the dye combinations and optionally retarders which can be used according to the invention are used in the dyebaths can vary within wide limits depending on the desired depth of color; in general there have been amounts of dye of a total of 0.01 to 5, preferably 0.01 to 2, and retarder additives of 0.01 to 3, preferably 0.1 to 1.0 percent by weight of one or more of the retarders mentioned, based on the weight of the Polyacrylonitrile material, proven to be advantageous.
  • the dye liquor also contains electrolytes, such as sodium salts, for example sodium chloride, sodium sulfate and sodium nitrate: ammonium salts, such as ammonium chloride and ammonium sulfate; Potassium salts such as potassium chloride and potassium sulfate and / or tetramethylammonium salts, such as. B. tetramethylammonium chloride.
  • electrolytes such as sodium salts, for example sodium chloride, sodium sulfate and sodium nitrate: ammonium salts, such as ammonium chloride and ammonium sulfate; Potassium salts such as potassium chloride and potassium sulfate and / or tetramethylammonium salts, such as. B. tetramethylammonium chloride.
  • electrolytes such as sodium salts, for example sodium chloride, sodium sulfate and sodium nitrate: ammonium salts, such as ammonium chloride and ammonium
  • additives common in dyeing such as. B. formic acid, acetic acid, sulfuric acid, and compounds required for stabilizing a certain pH, such as sodium, potassium or ammonium acetate, citrate or phosphate, may be present in the dye liquor.
  • the process according to the invention which has the great advantage that it does not have to be adapted to a particular type of polyacrylonitrile fiber, but rather can be applied to all types of cationic dyeable material, is preferably carried out using the exhaust method. Due to the very good migration of the dye combinations, as highlighted, a certain degree of levelness when mounting the dyes is entirely permissible. B. by a greatly shortened heating phase. The unevenness that occurs may only be so great that it can be leveled out at the dyeing temperature (95 to 120 ° C) and with a normal cooking time (45 to 60 minutes).
  • the procedure according to the invention is such that the polyacrylonitrile material to be dyed is introduced at a temperature of about 80 ° C. into the dyebath loaded with the necessary additives, and this is heated to 100 ° to 104 ° C. in the course of 15 to 30 minutes, while about 30 to Leave at this temperature for 45 minutes and then cool.
  • the process according to the invention can be applied to all cationically dyeable fiber types of polyacrylonitrile and also to fast-pulling, normal-pulling or slow-pulling polyacrylonitrile fibers.
  • the polyacrylonitrile fibers consist mainly of approx. 85% acrylic and approx. 15% copolymer.
  • Mixed fibers containing polyacrylonitrile and z. B. cellulose, polyester or polyamide can be dyed according to the invention.
  • polyacrylonitrile fiber materials can be very diverse; For example, the following are considered: loose material, sliver, cable, yarn as a strand, cross-wound bobbins, warp beams, muffs, bobbins, woven and knitted fabrics, carpets and, above all, cross-wound and piece dyeing for the decoration sector.
  • the liquor ratio (ratio of kg of goods to liters of liquor) depends on the equipment, the substrate and the form of packaging, as well as the packing density. It varies widely, but is mostly between 1: 5 to 1 40.
  • the process according to the invention thus enables the production of level and lightfast mixed tone dyeings under HT conditions (102 to 105 ° C.) when using specific selected dye mixtures of cationic dyes. It represents a simple dyeing process that is independent of the type of polyacrylonitrile fiber to be dyed, whereby shorter heating times are possible than when using non-migrating cationic dyes and nevertheless completely level dyeings are obtained. This requires no or only small amounts of a cationic retarder which is adapted to the dye mixtures used according to the invention in terms of drawing and migration behavior. It enables simple repairs despite all the dyeings that have occurred unevenly, and in particular allows the shade to be re-adjusted at cooking temperature.
  • the colorations obtained are furthermore distinguished by good overall fastness properties, such as, in particular, wet fastness properties, such as fastness to washing, water, sweat, decaturation and steam.
  • cross sections of fibers dyed with the dye combinations by the process according to the invention show a good coloration, a fact which speaks for the level failure of the dyeing.
  • dye combinations also represent a solid or liquid commercial form that can be stored for several months at temperatures from minus 20 ° C to plus 50 ° C without hesitation.
  • the dye combination can also contain the additives customary in commercial forms, such as electrolytes (for example sodium sulfate) and, if appropriate, dust binders medium, water, organic acids such as B. acetic acid and optionally other solvents.
  • dye combinations can be combined by z. B.
  • the yellow mixture with the red mixture, the yellow mixture with the blue mixture, the red mixture with the blue mixture or the yellow, red and blue mixture can be processed to any desired mixing tone.
  • These dye combinations are prepared in a known manner by mixing the individual components together.
  • Temperatures are given in degrees Celsius and percentages mean percentages by weight, based on the weight of the fiber material.
  • the specified amounts of dye refer to uncoupled goods, the retarder amounts to commercially available, i.e. H. coupé goods.
  • This green yarn, dyed in accordance with Example 1 is calcined together with the same amount of an undyed same yarn for 60 minutes at about 104 ° C. in a fresh bath containing 2% acetic acid (80%) and 10% Glauber's salt. treated, whereby a good tone-on-tone migration between the dyed and undyed yarn is achieved. This high leveling ability together with the good light fastness is not obtained when using only non-migrating or migrating cationic dyes.
  • Dralon® weaving yarn on cross-wound bobbins are crystallized in a Krantz-cross winder containing an aqueous dye liquor (approx. 5001 t) with 0.5% of an aqueous solution of dodecyldimethylbenzylammonium chloride, 2% acetic acid (80%), 1% sodium acetate, 10 % Glauber's salt calc. and a dye combination of 0.35% dye mixture I according to Example 1 and 0.13% of dye mixture II according to Example 1 and 0.1% dye mixture III in a liquor ratio of about 110 at 80 ° and for 5 minutes with a liquor circulation treated from the inside out.
  • the mixture is then heated to 104 ° within 25 minutes and dyed at this temperature for 30 minutes.
  • the mixture is then cooled, rinsed, centrifuged and dried. You get a completely brown brown dralon yarn.
  • the mixture is then heated to 104 ° C. in the course of 25 minutes and dyed at this temperature for 45 minutes.
  • the liquor is then cooled to 60 ° C; removes the dyed yarn from the dyeing machine, which is rinsed, centrifuged and then dried.
  • polyacrylonitrile yarn is dyed as described in Example 8 with the dye mixtures I to 111, but used in the concentrations given in Table 3 below, a beige or blue-gray coloration is obtained, the lightfastness of which is indicated in the last column of the table.
  • polyacrylonitrile yarn is also dyed here for comparison with the migrating dyes of the formulas (1) to (3) in the corresponding beige or blue-gray shade, dyeings are obtained whose lightfastness is indicated in the last column of Table 4 below.
  • 106 kg of polyacrylonitrile fabric are calcined on a Thies R-Jet dyeing machine containing an aqueous dye liquor (approx. 2100 l) with 2% acetic acid (80%), 10% Glauber's salt, 0.2% of an aqueous solution of dodecyldimethylbenzylammonium chloride and 0, 7% dye mixture V and 0.1% dye mixture VI in a liquor ratio of approx. 1 20 at 80 ° C. and kept at this temperature for 5 minutes. The temperature is then increased at a heating rate of 1 ° C / min to 105 ° C and dyed at this temperature for 45 minutes.
  • the liquor is then cooled from 2 ° C./min to 60 ° C., the dyed fabric is removed from the dyeing machine, rinsed, dewatered and dried. A completely level, well-dyed light olive polyacrylonitrile fabric with good lightfastness and perfect resistance to steaming is obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
EP82100689A 1981-02-04 1982-02-01 Verfahren zum egalen Di- und Trichromiefärben von Polyacrylnitrilmaterialien Expired EP0057457B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH742/81 1981-02-04
CH74281 1981-02-04

Publications (2)

Publication Number Publication Date
EP0057457A1 EP0057457A1 (de) 1982-08-11
EP0057457B1 true EP0057457B1 (de) 1985-08-21

Family

ID=4194147

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82100689A Expired EP0057457B1 (de) 1981-02-04 1982-02-01 Verfahren zum egalen Di- und Trichromiefärben von Polyacrylnitrilmaterialien

Country Status (7)

Country Link
US (1) US4410332A (enrdf_load_stackoverflow)
EP (1) EP0057457B1 (enrdf_load_stackoverflow)
JP (1) JPS57149573A (enrdf_load_stackoverflow)
DE (1) DE3265494D1 (enrdf_load_stackoverflow)
ES (1) ES509286A0 (enrdf_load_stackoverflow)
MX (1) MX157121A (enrdf_load_stackoverflow)
ZA (1) ZA82706B (enrdf_load_stackoverflow)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4462805A (en) * 1982-05-17 1984-07-31 Ciba-Geigy Corporation Mixture of cationic compounds for dyeing and printing textiles, leather and paper

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH9356A (de) * 1894-10-22 1895-05-31 Siemens Ag Anlaßvorrichtung bei Wechselstrommotoren mit Kurzschlußankern
US3107968A (en) * 1961-02-17 1963-10-22 Du Pont Dyeing of acid-modified acrylic and polyester fibers
CH1595464A4 (de) * 1964-12-10 1966-07-15 J R Geigey Ag Verfahren zum Färben, Klotzen oder Bedrucken von Textilmaterial aus polymerem und copolymeren Acrylnitril mit basischen Farbstoffen
BE757923A (fr) * 1969-10-25 1971-04-23 Geigy Ag J R Teinture de fibres textiles
US3945793A (en) * 1969-10-25 1976-03-23 Ciba-Geigy Ag Process for the colouration of acid-modified synthetic textile fibers and acrylic fibers
CH529257A (de) * 1970-09-05 1972-10-15 Sandoz Ag Hilfsmittel zum Färben oder Bedrucken
US4097233A (en) * 1972-12-16 1978-06-27 Nippon Kayaku Co., Ltd. Basic dye composition
JPS572747B2 (enrdf_load_stackoverflow) * 1972-12-16 1982-01-18
DE2317132C3 (de) * 1973-04-05 1982-03-11 Bayer Ag, 5090 Leverkusen Verfahren zum kontinuierlichen Färben von trockengesponnenem Fasergut aus Acrylnitrilpolymerisaten
CH592198B5 (enrdf_load_stackoverflow) * 1974-10-29 1977-10-14 Ciba Geigy Ag
US4181499A (en) * 1974-10-29 1980-01-01 Ciba-Geigy Corporation Process for the level dyeing of polyacrylonitrile materials of slow, normal and rapid absorptive capacity
CH618061B (de) * 1975-07-14 Ciba Geigy Ag Verfahren zum egalen faerben von langsam-, normal- und schnellziehenden polyacrylnitrilmaterialien.
US4116622A (en) * 1975-07-17 1978-09-26 Ciba-Geigy Corporation Dyeing preparations and process for dyeing polyacrylonitrile material in strong, neutral, clear blue shades
US4123222A (en) * 1976-03-23 1978-10-31 Ciba-Geigy Corporation Process for the dyeing or printing of polyacrylonitrile material
DE2731319B2 (de) * 1977-07-12 1981-02-19 Bayer Ag, 5090 Leverkusen Farbstoffmischungen und Verfahren zum Färben und Bedrucken von Polyacrylnitrilmaterialien
DE2822913C2 (de) * 1978-05-26 1982-08-19 Hoechst Ag, 6000 Frankfurt Verfahren zum Spinnfärben von Polymeren oder Mischpolymeren des Acrylnitrils

Also Published As

Publication number Publication date
US4410332A (en) 1983-10-18
JPS57149573A (en) 1982-09-16
DE3265494D1 (en) 1985-09-26
MX157121A (es) 1988-10-28
ZA82706B (en) 1983-01-26
ES8302143A1 (es) 1982-12-16
EP0057457A1 (de) 1982-08-11
JPH0329912B2 (enrdf_load_stackoverflow) 1991-04-25
ES509286A0 (es) 1982-12-16

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