EP0074414B1 - Procédé pour la préparation de filaments de polymère d'acrylonitrile teints dans la masse - Google Patents

Procédé pour la préparation de filaments de polymère d'acrylonitrile teints dans la masse Download PDF

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Publication number
EP0074414B1
EP0074414B1 EP19810107025 EP81107025A EP0074414B1 EP 0074414 B1 EP0074414 B1 EP 0074414B1 EP 19810107025 EP19810107025 EP 19810107025 EP 81107025 A EP81107025 A EP 81107025A EP 0074414 B1 EP0074414 B1 EP 0074414B1
Authority
EP
European Patent Office
Prior art keywords
solution
colorant
spinning solution
spinning
dyed
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
EP19810107025
Other languages
German (de)
English (en)
Other versions
EP0074414A1 (fr
Inventor
Atuyoshi Tamura
Tsukasa Kanki
Kyosuke Hirano
Yosinori Shibukawa
Taizo Yasumoto
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.)
Kanegafuchi Chemical Industry Co Ltd
Original Assignee
Kanegafuchi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kanegafuchi Chemical Industry Co Ltd filed Critical Kanegafuchi Chemical Industry Co Ltd
Priority to EP19810107025 priority Critical patent/EP0074414B1/fr
Priority to DE8181107025T priority patent/DE3176162D1/de
Publication of EP0074414A1 publication Critical patent/EP0074414A1/fr
Application granted granted Critical
Publication of EP0074414B1 publication Critical patent/EP0074414B1/fr
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes

Definitions

  • the present invention relates to an improved method for preparing spin-dyed acrylonitrile polymer filaments from a colorant containing spinning solution, more particularly to an improved spinning method which permits the production of solution-dyed filaments in small lots.
  • GB-A-1 504796 discloses a process for the spin dying of an acid-modified acrylonitrile homopolymer or copolymer.
  • a particular basic dyestuff may be incorporated in the spinning solution by mixing a solution of the dyestuff with a solution of the polymer or by dissolving the polymer in a solution of the dyestuff. The mixture can then be homogenized and spun in the usual way-for example, according to the wet spinning process-but preferably it is spun according to the dry spinning process.
  • FR-A-1 154 696 discloses a process for producing uniformly colored fibers from acrylonitrile polymers. Pigments are uniformly dispersed throughout solutions used in spinning fibers from said polymers. A water-dispersion of a pigment with a selected organic solvent (a color concentrate) is incorporated in solutions of acrylonitrile polymers, and fibres are prepared therefrom.
  • the conventional solution-dyeing spinning method has been advantageous in that a small number of mixers are required because the spinning solution and the colorant are mixed in a process, e.g., spinning tank, which precedes the spinning metering pump.
  • a process e.g., spinning tank
  • Complete cleaning requires the disassembly of piping, filter, spinning solution feed pump, and metering pump. Color change in daily operation is carried out without such complete cleaning, and mixing of the previous color and the new color can easily happen, making color matching more difficult. Stopping the spinning machine for a long time for complete cleaning is quite uneconomical in small-lot production and is feasible only in the case where colored fibers of the same color are produced in a large quantity.
  • the conventional method cannot meet economically the market requirements for filaments of different colors mixed together rather than filaments of a single color.
  • the present invention relates to a method for preparing spin-dyed acrylonitrile polymer filaments from a colorant-containing spinning solution which comprises injecting a colorant in a solvent which does not coagulate or precipitate the polymer, into a spinning solution in a nozzle holder in which a mixer and a spinneret are integrated by linking the two or arranging the mixer on the line just before the nozzle, whereby the colorant is uniformly mixed with the spinning solution and in a mixing ratio of spinning solution to colorant solution of 5:1 to 100:1 by volume.
  • the colorant solution is injected in a predetermined ratio into a passage between the spinning metering pump and the spinneret by the metering feed pump which interlocks with the spinning metering pump.
  • the colorant solution is mixed with the spinning solution in a nozzle holder in which a mixer and a spinneret are integrated by linking the two or arranging the mixer on the line just before the nozzle.
  • the nozzle holder is of a structure such that the spinning solution and colorant liquid are mixed and passed as a piston-like flow without hold-up and need not be replaced when a color change is required.
  • the method of the present invention permits one to obtain filaments of any desired color simply by changing the colorant to be injected.
  • the polymers to which the method of this invention is applied are acrylonitrile homopolymers and copolymers, preferably acrylonitrile polymers and modacrylic polymers having acid groups (such as carboxylic acid and sulfonic acid groups) in an amount of 10 to 100 mg equivalent/kg fiber.
  • acrylonitrile polymers may contain 0 to 10 wt% of methyl methacrylate, methyl acrylate, and/or vinyl acetate, or up to 60 wt%, preferably not less than 10 wt%, of vinyl chloride and/or vinylidene chloride.
  • the colorants which can be used in the method of this invention include common cationic dyes, disperse dyes, and acid dyes, and metal complex dyes soluble in organic solvents. These dyes are used in the form of solutions in ethylene glycol, acetic acid, water, etc. or dispersions having a particle size of less than 0.1 pm. Those dyes which have high affinity for polymers are preferable from the standpoint of spinning and color fastness. Cationic dyes should preferably be combined with acrylonitrile polymers or modacrylic polymers. Such a combination results in less dissolution of dyes in the spinning bath and provides colored filaments having good color development and color fastness.
  • the mixing ratio of spinning solution to colorant solution is 5:1 to 100:1 by volume. If the colorant solution is mixed in more than the upper limit of this ratio, the viscosity of the spinning solution decreases to such an extent that spinning is difficult to perform, and if the colorant solution is mixed in less than the lower limit of this ratio, the color density cannot be increased and color shading can easily happen.
  • the spinning solution should preferably have a viscosity from 0.5 to 50 Pas at 25°C for uniform mixing.
  • the method of this invention it is possible to minimize losses of colored spinning solution resulting from color change which has been a serious drawback in solution-dyeing spinning, and to improve greatly the operating rate of the spinning machine for the production of a variety of filaments of different colors in small quantities.
  • the method of the present invention can be applied to the known conventional spinning methods. From the standpoint of uniform coloring it is more suited to wet spinning which employs acetone, DMF, DMSO, ammonium thiocyanate, nitric acid, zinc chloride, etc. as a solvent for preparing the spinning solution.
  • the method of the present invention makes it easy to provide solution-dyed tows of different colors from individual spinnerets, instead of mixing filaments of different colors in order to obtain a deep colortone. This eliminates the blending offilaments and makes it possible to change color easily for each spinning and to provide desired color arrangements of deep tone.
  • a 7.5% coloring solution was prepared by diluting with acetone Cathilon@ Yellow RLH liquid, (aqueous solution of a cationic dye; made by Hodogaya Chemical Co., Ltd.).
  • the spinning solution was supplied by a gear pump at a rate of 200 ml/min, and the coloring solution was supplied by a constant rate pump at a rate of 20 ml/min.
  • the mixing of the spinning solution and coloring solution was accomplished in a mixing unit installed immediately before the nozzle holder.
  • the colored spinning solution was extruded from a spinneret having 6000 holes, each having a diameter of 0.08 mm, followed by coagulation in an acetone/water coagulating bath.
  • the colored, extruded filaments underwent drying, drawing, and heat treatment so that the final fineness of a single filament was 3 denier (0.33 tex) and the fineness of the tow was 18000 denier (2000 tex). Nonuniformity of coloring was not observed in the resulting colored tow, and the coloring concentration was 3% o.w.f..
  • Example 1 Three kinds of tows colored in yellow, red, and blue were prepared as in Example 1 by switching the colorants in the order of A, B, and C as shown in Table 1.
  • a 8.0% coloring solution was prepared by diluting Basacryl@ Red GL (liquid, made by BASF) with dimethylformamide.
  • the spinning solution was supplied by a gear pump at a rate of 200 ml/min, and the coloring solution was supplied at a rate of 15 ml/min.
  • the mixing of the spinning solution and coloring solution was accomplished in a mixing unit installed immediately before the nozzle holder.
  • the colored spinning_solution was extruded from a spinneret having 6000 holes, each having a diameter of 0.08 mm, followed by coagulation and 400% drawing in a dimethylformamide/water coagulating bath.
  • the colored filaments underwent drying and heat treatment so that the final fineness of single filament was 3 denier (0.33 tex) and the fineness of the tow was 18000 denier (2000 tex).
  • Nonuniformity of coloring was not observed in the resulting colored tow, and the coloring concentration was 2.5% o.w.f.. No contamination occurred in the spinning bath.
  • a spinning solution containing 22.5% polymer was prepared by dissolving in dimethylformamide a copolymer consisting of 95% acrylonitrile and 5% methyl acrylate.
  • a 5% coloring solution was prepared by diluting with dimethylformamide Spilon@ Blue GNH (made by Hodogaya Chemical Co., Ltd.). Colored tows were prepared from the spinning solution and coloring solution as in Example 3 using a dimethylformamide/water coagulating bath.
  • the resulting colored tows have a deep color tone which is characteristic for metal complex dyes and different from the bright color tone obtained by dyeing acrylic fibers with a cationic dye. Also, the resulting tows exhibited good lightfastness, class 6, which is one of the characteristics of metal complex dyes.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Claims (5)

1. Un procédé pour la préparation de filaments de polymère d'acrylonitrile teints dans la masse à partir d'une solution de filage contenant une matières colorante qui comprend l'injection d'un colorant dans un solvant, qui ne coagule ni ne précipité le polymère, dans une solution de filage dans un porte-buse dans lequel un mélangeur et une filière sont intégrés par réunion de ces deux derniers ou par disposition du mélangeur sur le trajet juste avant la buse, si bien que la matière colorante est mélangée uniformément à la solution de filage et dans un rapport de mélange de la solution de filage à la solution de matière colorante de 5/1 à 100/1 en volume.
2. Un procédé comme revendiqué dans la revendication 1 dans lequel au moins deux filières sont utilisées pour la même solution de filage et des matières colorantes différentes sont injectées pour les filières respectives, si bien que l'on obtient à partir de la même solution de filage des câbles contenant des filaments teints de couleurs différentes.
3. Un procédé comme revendiqué dans la revendication 1 ou 2 dans lequel la matière colorante est un colorant.
4. Un procédé comme revendiqué dans la revendication 1 ou 2 dans lequel la matière colorante est un colorant cationique.
5. Un procédé comme revendiqué dans la revendication 1 ou 2 dans lequel le polymère est un polymère ou un copolymère d'acrylonitrile ayant des groupes acides.
EP19810107025 1981-09-07 1981-09-07 Procédé pour la préparation de filaments de polymère d'acrylonitrile teints dans la masse Expired EP0074414B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19810107025 EP0074414B1 (fr) 1981-09-07 1981-09-07 Procédé pour la préparation de filaments de polymère d'acrylonitrile teints dans la masse
DE8181107025T DE3176162D1 (en) 1981-09-07 1981-09-07 Method for preparing spin-dyed acrylonitrile polymer filaments

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19810107025 EP0074414B1 (fr) 1981-09-07 1981-09-07 Procédé pour la préparation de filaments de polymère d'acrylonitrile teints dans la masse

Publications (2)

Publication Number Publication Date
EP0074414A1 EP0074414A1 (fr) 1983-03-23
EP0074414B1 true EP0074414B1 (fr) 1987-05-06

Family

ID=8187897

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810107025 Expired EP0074414B1 (fr) 1981-09-07 1981-09-07 Procédé pour la préparation de filaments de polymère d'acrylonitrile teints dans la masse

Country Status (2)

Country Link
EP (1) EP0074414B1 (fr)
DE (1) DE3176162D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007120A1 (fr) * 1990-10-15 1992-04-30 E.I. Du Pont De Nemours And Company Procede de melange de solutions d'additifs dans des courants de solutions de filage de para-aramide
JP3795255B2 (ja) * 1999-05-21 2006-07-12 旭貿易株式会社 紡糸原料着色装置
BG67199B1 (bg) * 2017-01-27 2020-12-15 "Е.Миролио" Еад Метод и инсталация за производство на вискозна изкуствена коприна директно обагрена в маса в два цвята едновременно
BG67252B1 (bg) * 2017-06-27 2021-02-15 Е.Миролио ЕАД Метод за получаване на вискозна изкуствена коприна с променяща се дебелина, продукт, получен по този метод и инсталация за реализиране на метода

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2039708A (en) * 1932-10-22 1936-05-05 Eastman Kodak Co Coloring of cellulosic solutions
NL207711A (fr) * 1955-06-08
US2972546A (en) * 1957-03-08 1961-02-21 Eastman Kodak Co Method and apparatus for manufacturing colored sheeting
GB1383317A (en) * 1971-07-20 1974-02-12 Ici Ltd Melt spinning of coloured polymers

Also Published As

Publication number Publication date
DE3176162D1 (en) 1987-06-11
EP0074414A1 (fr) 1983-03-23

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