WO2002053825A1 - Fibre acrylique courte et procede de teinture de celle-ci - Google Patents

Fibre acrylique courte et procede de teinture de celle-ci Download PDF

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Publication number
WO2002053825A1
WO2002053825A1 PCT/JP2001/011604 JP0111604W WO02053825A1 WO 2002053825 A1 WO2002053825 A1 WO 2002053825A1 JP 0111604 W JP0111604 W JP 0111604W WO 02053825 A1 WO02053825 A1 WO 02053825A1
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WO
WIPO (PCT)
Prior art keywords
dry heat
acrylic
dyeing
short fibers
acrylic short
Prior art date
Application number
PCT/JP2001/011604
Other languages
English (en)
Japanese (ja)
Inventor
Kiyomiti Ninomiya
Original Assignee
Kanebo, Limited
Kanebo Gohsen Limited
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 Kanebo, Limited, Kanebo Gohsen Limited filed Critical Kanebo, Limited
Priority to JP2002554314A priority Critical patent/JPWO2002053825A1/ja
Publication of WO2002053825A1 publication Critical patent/WO2002053825A1/fr

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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

Definitions

  • the present invention relates to an acrylic short fiber and a method for dyeing an acrylic short fiber, which have a small decrease in dry heat shrinkage even by hot bath dyeing.
  • Acrylic fibers can be dyed by adsorbing a cationic dye in a boiling bath, or by immersing the dye in an aqueous cationic dye solution immediately after being extruded from a spinneret in a wet spinning method to physically knead the dye between the fibers. There is a so-called soaking process.
  • the method of adsorbing cationic dyes on fibers in this boiling bath is more suitable for dyeing small lots of various products than the dyeing method, but the fibers shrink when heated at a high temperature.
  • the dry heat shrinkage of acryl raw cotton hardly remains. This means that it cannot be used for purposely shrinking under dry heat conditions.
  • the dye is pushed into the inside of the fiber, so the dyeing speed is much higher, and it is suitable for mass production.
  • the heat drawing applied before cutting into short fibers causes distortion in the fiber structure, and the short fibers after cutting have the advantage of remaining dry heat shrinkage.However, the dye is drawn between spinning and hot drawing. Since a special process of passing through a solution is required, there is a drawback that it is unsuitable for dyeing small lots of various varieties.
  • An object of the present invention is to provide a high-quality dyeing method suitable for dyeing small lots of many varieties.
  • An object of the present invention is to obtain short fibers that maintain dry heat shrinkage. Disclosure of the invention
  • acrylic short fibers exhibiting dry heat shrinkage are dyed with a cationic dye in a warm bath at 80 ° C or lower, and acrylic short fibers and acryl short fibers exhibiting dry heat shrinkage are used.
  • the acrylic short fiber which satisfies the dry heat shrinkage of 20 to 50% at 120 to 150, and has a dry heat residual shrinkage of at least 14% at 120 to 130.
  • Acrylic staple fiber and acrylic staple fiber are dyed in a warm bath using a cationic dye.
  • the acrylic short fiber used in the present invention is not particularly limited as long as it exhibits a dry heat shrinkage of 20% to 50% at 120 to 150.
  • acryl short fibers having the following composition.
  • a polymer solution of the following (I) and (II) is mixed by any known method to obtain a spinning dope, and subjected to predetermined stretching as necessary, such as spinning stretching, primary stretching, and dry heat stretching. Can be obtained by shortening the fiber.
  • This fiber has a dry heat shrinkage of 20% or more.
  • polymer (II) contains the sulfonic acid-containing monomer in an amount of 0 to 10% by weight.
  • 25 to 70% by weight of vinyl chloride may be used instead of the above 25 to 70% by weight of methyl acrylate.
  • This fiber also has a dry heat shrinkage of 20% or more.
  • the content of the halogen-containing monomer in the polymer (I) is 20 to 54% by weight
  • the content of the sulfonic acid-containing monomer in the polymer is 0.5 to 6% by weight, 20 to 60% by weight of acrylonitrile, 35 to 78% by weight of (meth) acrylate ester instead of methyl acrylate, and 2 to 5% by weight of sulfonic acid-containing monomer Can also be used.
  • This fiber also has a dry heat shrinkage of 20% or more.
  • the polymer (I) is produced by a known method called aqueous emulsion polymerization or solution polymerization of 40% by weight or more of acrylonitrile and 20 to 60% by weight of halogen-containing monomer and 0.5 to 5% by weight of sulfonic acid-containing monomer. After removing the residual monomers, the process is usually dissolved in a spinning solvent or used as a spinning stock solution.However, the polymer polymerized in the following process has few voids generated during spinning, and the This is preferable because gloss is not lost.
  • the polymer (I) is composed of 20 to 60% by weight of a halogen-containing monomer composed of vinyl chloride, vinylidene chloride or vinyl bromide or a mixture thereof, acrylonitrile and a small amount of, for example, 0.5 to 5% by weight of arylsulfone.
  • Monomers such as sodium acrylate, sodium styrenesulfonate or sodium 2-acrylamido-2-methylpropanesulfonate are treated with azobisisopropane in an organic solvent such as dimethylformamide, dimethylsulfoxide or dimethylacetamide.
  • Polymerization is carried out using a polymerization initiator such as thyronitrile and azobisdimethylvaleronitrile.
  • a polymer having a composition of 5 to 40% by weight of sodium arylsulfonate, 10 to 85% by weight of acrylonitrile, and 10 to 50% by weight of a halogen-containing monomer is prepared by the above polymerization method in dimethylformamide.
  • a dimethylformamide solution containing the polymer 20 to 60% by weight of a halogen-containing monomer and acrylonitrile and, if necessary, sodium arylsulfonate are present in the presence of other additives such as a coloring inhibitor. Polymerize underneath.
  • the unreacted monomer in the obtained polymerization dope is removed at a temperature as low as possible using a low evaporator or a rotary thin film evaporator, and then the polymer concentration is adjusted to 20 to 30% by weight. Then, additives are added to obtain a spinning solution of the polymer (I).
  • the polymer (II) a polymer of 30 to 75% by weight of acrylonitrile, 70 to 25% by weight of methyl acrylate and 0 to 10% by weight of a sulfonic acid-containing monomer was prepared in dimethylformamide. Polymerization is performed by a polymerization method, and the unreacted monomer in the obtained polymerization dope is removed. Thereafter, the concentration of the polymer (II) is adjusted to 20 to 30% by weight.
  • a spinning dope is obtained.
  • the spinning dope is spun from a normal spinneret into a coagulation bath.
  • Coagulation The solid bath is preferably an aqueous solution of the same organic solvent as the organic solvent of the spinning dope to reduce the cost of solvent recovery and simplify the recovery process.
  • the organic solvent concentration is 40 to 70% by weight, preferably 50%.
  • the temperature is 15 to 35 ° C, preferably 18 to 28 ° C.
  • the undiluted spinning solution is spun into a coagulation bath, and the coagulated filament is usually subjected to spinning through a spinning bath of a numerical value with a gradually decreasing solvent concentration.
  • the spinning draw ratio is usually 3 times or more, preferably 4 to 10 times, and more preferably 5 to 8 times.
  • wash in a water bath at 50 ° C or more apply oil before drying, and dry and bake with a hot roller type or a dryer used in combination with a hot air dryer. In this drying step, it is preferable to perform a slight shrinkage of about 10% as compared with the constant-length tension drying in terms of drying, baking effect, prevention of mechanical overload, and the like.
  • the primary stretching is performed with a wet heat of 60 to L0 ° C, preferably 80 to L0 ° C, and the primary stretching magnification is the amount of the halogen-containing monomer in the polymer (I) and the polymer in the fiber. Although it depends on the content of (II), it is better to carry out at the draw ratio immediately before entering the overdrawing region from the viewpoint of fiber performance such as shrinkage performance, strength, gloss and dyeability, operability, and productivity.
  • the shrinkage ratio increases with the increase in the draw ratio where the draw ratio is low, but the shrinkage ratio increases when the draw ratio exceeds a certain ratio. Reaches saturation, or conversely, the draw ratio decreases.
  • the stretch ratio or more is called an overstretched region. In this overdrawing region, not only saturation and reduction of the shrinkage rate, but also drawbacks such as a decrease in the strength and elongation of the fiber, a decrease in the dyeability, and a break in single yarn occur.
  • One large continuous shrinkage after dry baking and before primary stretching e.g. 20-5 A step of performing 0% shrinkage and then performing primary stretching may be employed.
  • the fiber after the primary drawing is subjected to post-oil adhesion and mechanical crimping
  • the fibers are shortened by cutting to an appropriate fiber length by a conventional method.
  • a wet heat shrinkage / dry heat drawing step is applied after the primary drawing and before the crimping.
  • the fibers are subsequently contracted by moist heat.
  • the temperature is from 80 ° C to 130 ° C, preferably from 90 ° C to 115 ° C.
  • Shrinking at low temperatures does not provide the desired shrinkage.
  • shrinkage between fibers is so severe that shrinkage at high temperatures has a serious effect on fiber properties and operability.
  • the shrinkage ratio varies depending on the amount of the halogen-containing monomer in the polymer (I) and the content of the polymer (II) in the fiber. However, considering the shrinkage performance, fiber performance, operability, productivity, etc. It is preferably about 0.95 times.
  • the stretching temperature is from 80 to 140 ° (preferably from 90 to 110 ° C. If the stretching temperature is too low, the stretching ratio is not sufficient, and the fiber is whitened at a low ratio. Conversely, if the drawing temperature is too high, sticking between the single fibers, yellowing due to heat, etc. are observed, and the dry heat shrinkage is adversely affected.
  • an acrylic material exhibiting a dry heat shrinkage of 20% to 50% at 120 to 150 which is suitably used as a yarn for dyeing in the present invention.
  • Short fibers can be produced.
  • the cationic dye used in the present invention has a positive charge and is adsorbed on a fiber having a negative charge such as a sulfonate group or a carboxylic acid group.
  • a fiber having a negative charge such as a sulfonate group or a carboxylic acid group.
  • a maker name Nichilon dye etc. is mentioned. Among them, dyes that can be quickly adsorbed on fibers even when dyed at a low temperature are preferable.
  • those having an index / mixture (Imix.) Of C or more are preferable, and those of B or more are particularly preferable.
  • concentration of the dye is not particularly limited, for example, 5% by weight or less per fiber weight is suitably used.
  • the dyeing temperature is at most 80 ° C, preferably at most 75 ° C, particularly preferably at most 70 ° C. By dyeing at a low temperature of 80 or less, it is possible to maintain high residual shrinkage after dyeing.
  • the dyeing time is preferably 30 to 50% longer than generally used, for example, about 30 to 60 minutes, but is not limited thereto.
  • a dyeing agent such as an ether cyanide compound.
  • the concentration of the propellant is not particularly limited, but, for example, 10% by weight or less per fiber weight is suitably used. Further, when the content is 5% by weight or less, a decrease in residual shrinkage can be suppressed, and therefore, it is particularly preferable.
  • the packing density of the acrylic short fibers is preferably such that shrinkage of the short fibers can be physically suppressed, for example, preferably 0.20 gZcm 3 or more, more preferably 0.30 gZcm. It is 3 or more, more preferably 0.35 g / cm 3 or more. However, from the viewpoint of exerting the effect of physically restricting shrinkage, it is preferably 0.37 gZ cm 3 or more, particularly preferably 0.45 g / cm 3 or more.
  • the soaping after dyeing is such that shrinkage of the acrylic short fibers can be suppressed as much as possible.
  • the heating time is preferably 65 ° C or more and 20 minutes or more. Drying after soaping is preferably performed at 90 ° C. or less from the viewpoint of preventing shrinkage of the acrylic short fiber. More preferably, it is 80 or less.
  • the acrylic short fiber used in the present invention can be dyed after being blended with another fiber, and can also be blended with another fiber after dyeing and used for commercialization.
  • the acryl-based short fibers obtained by the present invention maintain high dry heat shrinkage even at low temperatures.
  • those having a dry heat residual shrinkage of 120 to 130 ° (: 14% or more) are suitable for high pile products.
  • the polymer solutions of the following (I) and ( ⁇ ) are mixed by any known method to obtain a stock solution for spinning, and the yarn spun with the stock solution for spinning is spin-drawn by a usual method and then dried.
  • the fiber after oil adhesion is subjected to dry heat drawing after primary heat drawing and shrinkage, and is shortened by a conventional method. An acrylic short fiber exhibiting 7% dry heat shrinkage was obtained.
  • the acryl-based short fibers were packed in an Obermeier dyeing machine at a density of 0.37 g / cm 3 and dyed at a maximum temperature of 72 ° C. for 60 minutes.
  • a black dye of I mix a black dye of I mix.
  • B Niichilon Black manufactured by Nissei Kasei Co., Ltd.
  • Carrier Gin K manufactured by Nissei Chemicals, Inc. was used in an amount of 3.0% by weight per fiber weight.
  • the acrylic short fibers exhibiting a dry heat shrinkage of 37% under dry heat conditions of 150 ° C. for 5 minutes used in Example 1 were applied to an O.O. Maya single dyeing machine at 0.37 gZcm 3. And dyed at a maximum temperature of 70 ° C for 30 minutes.
  • As the dye a yellow dye of I mix.
  • a to B (a blend of Nichilon OrangeGL, Nichilon RedGL and Nichilon BlueGL manufactured by Nissei Kasei Co., Ltd.) was used in an amount of 0.915% by weight per fiber weight Used at concentrations.
  • the acrylic short fibers exhibiting a dry heat shrinkage of 37% under dry heat conditions of 150 ° C. for 5 minutes used in Example 1 were applied to an O.O. Maya single dyeing machine at 0.37 gZcm 3. At a maximum temperature of 7 Ot for 60 minutes.
  • a blue dye a blend of Nichilon OrangeGL, Nichilon RedGL and Nichiion BlueGL, manufactured by Nissei Kasei Co., Ltd.
  • Example 1 7.1 2 6.0 5 5 5 5 3 4 ⁇
  • Example 2 2.2 3 0.0 5 5 5 4-5 4 ⁇
  • Example 3 4.9 2 8.5 5 4 4 2-3 4 ⁇
  • the acrylic short fibers of Examples 1 to 3 can obtain the target hue and have a sufficient dry heat residual shrinkage, and are suitable as shrinkable cotton for high pile and pore products.
  • Table 1 the acrylic short fibers of Examples 1 to 3 can obtain the target hue and have a sufficient dry heat residual shrinkage, and are suitable as shrinkable cotton for high pile and pore products.
  • the high pile and pore products manufactured using the acrylic short fibers of Examples 1 to 3 had a very favorable texture because the acrylic short fibers sufficiently shrunk.
  • Table 3 shows the results of evaluation of the residual shrinkage and the like.
  • the acrylic short fibers dyed by the method of the present invention have a sufficient dry heat shrinkage even after dyeing, and in particular, a dryness of 14% or more suitable for high pile products.
  • a dryness of 14% or more suitable for high pile products One having heat residual shrinkage was also obtained.
  • Table 411 and Table 412 show the results of evaluation of the fastness after dyeing for the case without soaping and the case with soaping, respectively.
  • Table 5 shows the results of treating the acrylic short fibers obtained in Example 4 with a warm bath at 85 ° C and 90 ° C.
  • the acrylic short fiber of the present invention has a target hue and fastness irrespective of dark color or light color, and has a high residual shrinkage. As a result, it can be used for shrinking under dry heat conditions.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne une fibre acrylique courte capable de conserver une contractilité à une chaleur sèche élevée; un procédé de fabrication de cette fibre mettant en oeuvre un procédé de teinture conçu pour la teinture d'une production de petit lot d'une vaste gamme de produits. Cette fibre développant une contractilité à une chaleur sèche comprise entre 20 et 50 % entre 120 et 150 °C est caractérisée en ce qu'elle est teinte au moyen d'un colorant cationique dans un bain chaud à une température égale ou inférieure à 80 °C, par conséquent, étant donné que la fibre acrylique courte comprend une teinte cible de couleur, une rapidité indépendante de la densité de la couleur et une contractilité résiduelle élevée, la fibre courte peut également être utilisée dans une application dans laquelle elle est soumise à une contraction dans des conditions de chaleur sèche.
PCT/JP2001/011604 2000-12-28 2001-12-27 Fibre acrylique courte et procede de teinture de celle-ci WO2002053825A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002554314A JPWO2002053825A1 (ja) 2000-12-28 2001-12-27 アクリル系短繊維及びアクリル系短繊維の染色方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000400803 2000-12-28
JP2000-400803 2000-12-28

Publications (1)

Publication Number Publication Date
WO2002053825A1 true WO2002053825A1 (fr) 2002-07-11

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006299473A (ja) * 2005-04-22 2006-11-02 Japan Exlan Co Ltd 低温可染収縮性アクリル繊維
JP2007239149A (ja) * 2006-03-09 2007-09-20 Kaneka Corp 低温可染型アクリル系繊維の染色方法及び該方法にて染色された低温可染型アクリル系繊維
US7612000B2 (en) 2004-07-16 2009-11-03 Kaneka Corporation Modacrylic shrinkable fiber and method for manufacturing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4428273B1 (fr) * 1967-08-31 1969-11-21
JPS4912178A (fr) * 1972-05-17 1974-02-02
JPS49110981A (fr) * 1973-03-02 1974-10-22

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4428273B1 (fr) * 1967-08-31 1969-11-21
JPS4912178A (fr) * 1972-05-17 1974-02-02
JPS49110981A (fr) * 1973-03-02 1974-10-22

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7612000B2 (en) 2004-07-16 2009-11-03 Kaneka Corporation Modacrylic shrinkable fiber and method for manufacturing the same
JP2006299473A (ja) * 2005-04-22 2006-11-02 Japan Exlan Co Ltd 低温可染収縮性アクリル繊維
JP2007239149A (ja) * 2006-03-09 2007-09-20 Kaneka Corp 低温可染型アクリル系繊維の染色方法及び該方法にて染色された低温可染型アクリル系繊維

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