WO2021014620A1 - Procédé de fabrication de fibres de poils d'animaux irrétrécissables - Google Patents

Procédé de fabrication de fibres de poils d'animaux irrétrécissables Download PDF

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WO2021014620A1
WO2021014620A1 PCT/JP2019/029069 JP2019029069W WO2021014620A1 WO 2021014620 A1 WO2021014620 A1 WO 2021014620A1 JP 2019029069 W JP2019029069 W JP 2019029069W WO 2021014620 A1 WO2021014620 A1 WO 2021014620A1
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Prior art keywords
animal hair
sliver
solvent
diamine
fiber
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PCT/JP2019/029069
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English (en)
Japanese (ja)
Inventor
亮 梅原
吉紀 水森
典雄 早川
秀行 藤井
俊次 後藤
大郎 藤田
好央 長田
俊文 大橋
秀行 中島
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株式会社トーア紡コーポレーション
株式会社ソトー
森保染色株式会社
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Priority to PCT/JP2019/029069 priority Critical patent/WO2021014620A1/fr
Priority to JP2021534491A priority patent/JP7283670B2/ja
Priority to CN201980096523.1A priority patent/CN113853461B/zh
Publication of WO2021014620A1 publication Critical patent/WO2021014620A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides

Definitions

  • the present invention is a method for producing shrink-proof animal hair fibers having excellent water-resistant washability, and in particular, environmentally friendly in which the discharge of adsorptive organic chlorine compounds from the production process and the residue of chlorine compounds in the fibers are minimized.
  • a method for producing shrink-proof animal hair fiber is provided.
  • liquid / liquid interfacial polymerization method composed of a non-aqueous system
  • fabric treatment of woven fabrics, knitted fabrics, and non-woven fabrics described in Patent Documents 5 and 6 described later examples of treatment on a sliver which is a continuum of animal hair fiber bundles. There is no.
  • the Split Pad Chlorinator method of Fleissner, Germany is based on research and development at CSIRO, in which wool is chlorinated and then Hercosett resin (Hercosett) is coated on the fibers, so-called chlorine. It was a chemical / resin treatment. These have spread widely mainly in China, are mass-produced, and are offered at low manufacturing costs. From these points, most of the shrink-proofing treatment of wool can be summarized as continuous shrink-proofing treatment using a wool top sliver and a chlorination treatment method.
  • Adsorbable organic chlorine compounds (AOX-Absorbable Organic Halogens) are discharged into rivers. It has been reported that when fish ingest it and humans ingest it through the food chain, it causes the development of "cancer". Furthermore, it has been confirmed that chlorine reacts with proteins in wool and remains as residual chlorine in wool fibers.
  • the shrink-proofing process for knitted fabrics and woven fabrics made of wool fibers is due to the treatment of an aqueous solution using an oxidizing agent such as a chlorine agent. Therefore, treatment spots are likely to occur, leading to dyeing spots and the like, and considerable production control is required. In that respect, in the sliver treatment, after the shrink-proof treatment, the treatment spots are corrected by a gil step, a combing step, or the like, so that the shrink-proof balance is maintained and a uniform wool shrink-proof spun yarn can be produced. In this sense, continuous shrink-proof processing using a wool sliver is currently the mainstay.
  • this method is a method in which the surface of wool is subjected to chlorine oxidation treatment to inhibit the water-repellent function, which is the original property of wool, and to impart only shrink resistance. Therefore, it is a major research and development task today to impart shrinkage resistance without impairing the water repellency of wool fibers.
  • a hydrophilic resin for example, a polyamide epichlorohydrin resin (Dick Hercules, Harcosett 57 Hercosett) for the first time by making the wool surface hydrophilic. ..
  • a hydrophobic wool For example, as shown in the central portion of FIG. 3, a "seagrass kelp" -like coating occurred on the surface of the wool fibers, or as shown on both sides of the central portion in FIG. 3, adhesion occurred between the fibers.
  • FIG. 4 shows the fiber surface when adhesion occurs between the fibers.
  • FIG. 3 is a photograph showing the treated wool fibers when the hydrophobic wool surface is to be coated with a water-soluble hercoset resin.
  • FIG. 4 is an electron micrograph showing the surface state of wool fibers when adhesion occurs between the fibers (magnification: 1000 times).
  • One of the features of the present invention is that the surface of wool fibers is coated with a hydrophobic synthetic polymer to impart shrinkage resistance and maintain the original hydrophobicity of wool without damaging the original properties of wool. ..
  • the basic technology that leads to this concept is a liquid-liquid interface polymerization method that utilizes an interface consisting of an aqueous phase and an organic phase.
  • Technological development for wool tops and woolen fabrics using this interfacial polymerization method (Patent Document 2) can be traced back to the 1963s, but the organic phase is harmful to health and the environment, such as perchlorethylene and toluene. Since a solvent composed of carbon tetrachloride or the like is used, it has not been industrially successful.
  • the woolen fabric is immersed in an aqueous phase containing diamine, squeezed, and immediately immersed in a toluene organic solvent in which dichloride dichloride is dissolved, and interfacial polymerization is performed using the liquid-liquid interface formed on the surface of the wool fiber.
  • a toluene organic solvent in which dichloride dichloride is dissolved
  • interfacial polymerization is performed using the liquid-liquid interface formed on the surface of the wool fiber.
  • the dibasic acid dichloride reacts with water to become a dicarboxylic acid, which results in slowing down the interfacial polymerization reaction. How to solve the hydrolysis of this dibasic acid dichloride has become a big issue, and the present situation is hindering its practical application.
  • perchlorethylene has been used as a new pollution-free solvent-silicone solvent (Mitsubishi Heavy Industries, Ltd., Shin-Etsu Chemical Co., Ltd.-dia-silicone and green earth, etc. It is being replaced by a cleaning limited company (Green Earth Ltd. Co.-silicone dry).
  • Green Earth Co., Ltd. discloses cyclic silicon of octamethyl-cyclotetrasiloxane (tetramer), decamethyl-cyclopentasiloxane (pentamer) and dodecamethyl-cyclohexasiloxane (hexamar) in Patent Documents 3 and 4.
  • the silicone solvent manufactured by Mitsubishi Heavy Industries, Ltd. is commercially available as a linear decamethyltetrasiloxane.
  • the critical interfacial tension of wool fibers is said to be 45-50 dyn / cm for single fibers and 30 dyn / cm for fiber populations.
  • the critical interfacial tension of Green Earth's silicone solvent is 17.8 dyn / cm, and the silicone solvent can be easily extended to the surface of each single fiber in the wool fiber population, resulting in uniform interfacial polymerization. It means that it will be done in.
  • the critical interfacial tension of water is around 72-76 dyn / cm, and in order to "wet" the surface of wool fibers with water, even if a penetrant is added to the aqueous solution, it is completely "wet". It's difficult. Therefore, the aqueous solution treatment lacks the uniformity of the treatment as compared with the solvent treatment, and treating the hydrophobic polymer with the aqueous solution medium poses a problem in terms of uniformity.
  • Non-Patent Document 1 shows the laws and regulations for tetrachlorethylene
  • the silicone solvent is a solvent that has no odor, no chemical burns, and is easy to handle, and is a convenient solvent for performing an interfacial polymerization treatment (Non-Patent Document 1).
  • the silicone solvent used in the present invention is a solvent that meets these needs and is immiscible with water. For this reason, a liquid-liquid interface is formed between the aqueous phase and the solvent phase.
  • a 0.1 mol / l hexamethylenediamine aqueous solution is placed in a container at room temperature, and then a silicon solvent is formed at room temperature.
  • FIG. 5 shows an experiment underlying the invention of the present invention.
  • I indicates a liquid-liquid interface formed by water and a silicon solvent, and due to the relationship of specific gravity, water is indicated at the bottom and silicon solvent is indicated at the top, and II in FIG. 5 is a liquid-liquid interface. Shows the formation of nylon polymer (white).
  • Patent Documents 5 and 6 include dibasic acid chloride after immersing the woolen fabric in an aqueous diamine solution, squeezing it, and air-drying it to remove water on the fibers to form a solid surface.
  • a method of immersing in a silicon solvent solution to form a solid-liquid interface and performing interfacial polymerization has been proposed.
  • the diamine aqueous solution is used at room temperature (about 25 ° C.) without being heated in order to prevent hydrolysis of animal hair fibers.
  • An object of the present invention is to provide a shrink-proof animal hair fiber having sufficiently excellent water resistance and washability without impairing the texture and other characteristics while maintaining the original water repellency which is one of the characteristics of the animal hair fiber. It is intended to provide a method for efficiently manufacturing in the form of a sliver. An object of the present invention is further to provide a method for producing shrink-proof animal hair fiber, which does not cause the outflow of adsorptive organic chlorine compound (AOX) discharged from the treatment step and does not contain residual chlorine substance in the animal hair fiber. It is what we are trying to provide.
  • AOX adsorptive organic chlorine compound
  • a sliver which is a continuum of animal hair fibers, is immersed in an alkaline agent-containing diamine aqueous solution at 30 to 45 ° C., and in a state where diamine is attached, the sliver is immersed in a silicon solvent in which dibasic acid chloride is dissolved.
  • the present invention relates to a method for producing shrink-proof animal hair fiber, which comprises coating the surface of animal hair fiber with polyamide.
  • the animal hair fiber sliver is immersed in a heated alkaline agent-containing diamine aqueous solution and squeezed to prepare a solution in which dibasic acid chloride is dissolved in a silicon solvent that does not cause environmental destruction or deterioration of the working environment.
  • polyamide is formed on the fiber surface by interfacial polymerization at the liquid / liquid interface.
  • the silicon solvent adhering to the animal hair fiber sliver is not dried and evaporated to recover the solvent, but the sliver is immediately immersed in a formic acid aqueous solution to remove oligomers, neutralized and washed with water. dry.
  • the silicon solvent adhering to the animal hair fiber top sliver is recovered by a separation method based on the difference in specific gravity of the waste liquid after the washing treatment. Surface cleanliness is a very important factor when polymerizing animal hair fibers, but since top slivers in recent years are mass-produced and low-cost methods, washing raw hair of animal hair fibers has many problems and remains. Insufficient control of impurities such as fat content, fiber pH, and mud and sand. In the present invention, it is preferable to clean the fiber surface and coat it with a hydrophobic polymer.
  • the present invention excellent shrink resistance can be imparted by treating with a hydrophobic polymer without impairing the original water repellency of animal hair fibers.
  • the air is hydrophobic and the animal hair fibers treated according to the method of the present invention exhibit strong hydrophobicity, and as a result, the present invention retains heat in order to strongly retain the microair layer between the animal hair fibers. It is possible to provide animal hair fiber products having high water repellency and high water repellency.
  • the present invention also provides a method for continuously producing an environment-friendly shrink-proof animal hair fiber sliver that does not allow adsorbent organochlorine compounds to flow out during process treatment and does not contain residual chlorine compounds in the fibers.
  • the present invention is a method relating to a method for producing shrink-proof animal hair fiber, which was achieved as a result of diligent research by improving the interfacial polymerization method announced by the Western Regional Research Laboratory (WRRL) of the US Department of Agriculture and Industry in 1963.
  • WRRL Western Regional Research Laboratory
  • a synthetic polymer is synthesized on the surface of animal hair fibers (particularly wool fibers) using a silicon solvent without environmental regulations, and the entire surface of the animal hair fibers is reticulated (see FIG. 1) with the polymer. Cover each animal hair fiber one by one.
  • FIG. 1 is a photomicrograph of the surface of shrink-proof animal hair fibers produced by the production method of the present invention when observed with an optical microscope at a magnification of 400 times.
  • the animal hair fiber sliver is immersed in an alkaline agent-containing diamine aqueous solution at a predetermined temperature to attach diamine.
  • the animal hair fiber in the present invention means one or more kinds of natural keratinous fibers selected from the group consisting of wool, cashmere, mohair, angora, camel and the like.
  • a sliver is a bundle of fibers arranged in a straight line without twisting, and is usually a continuous fiber group having a length of several hundred meters or more.
  • the sliver may have been subjected to one or more treatments selected from so-called cleaning treatments, card treatments, gil treatments, and combing treatments.
  • the cleaning treatment is a treatment performed for the purpose of removing (or removing) oils and fats on the surface of animal hair fibers and impurities such as mud and sand.
  • the card treatment is a treatment performed for the purpose of loosening animal hair fibers into a continuous fiber bundle.
  • the gil treatment is a treatment performed for the purpose of aligning and making the fiber bundles uniform.
  • the combing treatment is a treatment performed for the purpose of removing short fibers and impurities in the fiber bundle and further aligning the fibers in parallel.
  • the sliver is preferably washed from the viewpoint of coating the fiber surface with polyamide.
  • the remaining amount of fat and oil of the sliver is not particularly limited, but from the viewpoint of coating the fiber surface with polyamide, for example, it is usually 0.8% owf or less (particularly 0.3 to 0.8% owf). Is preferable, and more preferably 0.3 to 0.5% owf.
  • Animal hair fiber sliver may be obtained by purchasing a so-called top sliver from the market.
  • the animal hair fiber sliver may be purchased from the market and washed before use.
  • the animal hair fiber top sliver is used with a back washer to reduce the remaining amount of fat and oil to 0.4 to 0.8% owf (1.3% owf before the washing treatment) and pH to be about 7.0. And completely remove mud, sand, etc., and use the top sliver after drying treatment.
  • the mass of animal hair fiber sliver per unit length is usually 10 to 40 g / m, particularly 20 to 30 g / m.
  • Animal hair fiber sliver may be used by mixing other fibers.
  • synthetic fibers such as polyester, acrylic, nylon, aramid and vinyl chloride and regenerated cellulose fibers such as silk, cotton, linen and rayon may be included.
  • the diamine aqueous solution has a temperature of 30 to 45 ° C. and contains an alkaline agent.
  • Animal hair fibers (particularly wool fibers) have different degrees of "scale” rise depending on the water temperature. For example, in “cold water”, there is no rise in “scale”. Further, for example, in warm water (40 ° C.), a rise is seen, and water permeates into the animal hair fiber. Further, for example, water vapor (100 ° C.) easily permeates and diffuses inside the animal hair fiber. Therefore, the absorption of amines depends on the treatment temperature.
  • the present invention by setting the temperature of the diamine aqueous solution to the above temperature, the "scale" of the animal hair fiber rises, the uptake of high-concentration diamine occurs, and a high-concentration diamine phase is formed in the epidermis layer. Therefore, in the next step, it was found that the dibasic acid chloride dissolved in the silicon solvent attacks the diamine phase and the interfacial polymerization reaction is established. It was also found that the animal hair fiber sliver can be continuously shrink-proofed. As a result, as shown in FIG. 1, it was possible to uniformly coat the animal hair single fibers with a nylon coating in a net-like manner.
  • the temperature of the diamine aqueous solution is too low, the permeation of the diamine aqueous solution into the animal hair fibers is suppressed, so that the amount of diamine adsorbed on the surface of the fibers is small and the interfacial polymerization reaction with the dibasic acid chloride is limited. .. As a result, the amount of polyamide coating produced is small, and the water resistance system washability is lowered. On the other hand, if the temperature of the diamine aqueous solution is raised too much in order to increase the amount of diamine absorbed, animal hair fibers (particularly wool fibers) are hydrolyzed.
  • Animal hair fiber is an amphoteric protein and is composed of acidic amino acids, basic amino acids, and neutral amino acids.
  • Diamine in an aqueous diamine solution is adsorbed on acidic amino acids and lipids having carboxyl residues in animal hair fibers. Further, the temperature of the diamine aqueous solution is raised to the above temperature, and an alkaline agent is added to the diamine aqueous solution as described later. As a result, the absorption of diamine into animal hair fibers and the extermination of hydrochloric acid by hydrolysis of dibasic acid chloride in the next step are promoted. Therefore, it is considered that the polyamide is uniformly coated on the surface of the animal hair fiber in the next step.
  • the temperature of the diamine aqueous solution is preferably 35 to 45 ° C., more preferably 36 to 44 ° C., still more preferably 38 to 42 ° C., most preferably, from the viewpoint of further improving shrinkage resistance, texture and water repellency. It is preferably 39 to 41 ° C.
  • the details of the phenomenon in which the shrinkage resistance, texture and water repellency are further improved when the diamine aqueous solution has a temperature in the above-mentioned preferable range are not clear, but it is considered to be based on the following mechanism.
  • the body temperature of an animal having animal hair fibers is usually about 39 to 40 ° C., and the closer to this temperature, the higher the rising effect of the above-mentioned "scale” on animal hair fibers.
  • the surface of animal hair fibers is coated in a finer mesh and more uniformly. As a result, shrinkage resistance, texture and water repellency are further improved.
  • the diamine in the diamine aqueous solution used in the present invention is usually a water-soluble diamine.
  • the water-soluble diamine include aliphatic diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and octamethylenediamine; and paraphenylenediamine, metaphenylenediamine, paraxylenediamine, and metaxylenediamine.
  • Aromatic diamines can be mentioned.
  • the diamine is not particularly limited to these, and two or more of these diamines may be used in combination.
  • Preferred diamines are aliphatic diamines, especially hexamethylenediamine.
  • the concentration of diamine in the diamine aqueous solution is not particularly limited, and is usually 0.01 to 0.7 mol / L, preferably 0.02 to 0.15 mol from the viewpoint of further improving shrinkage resistance, texture and water repellency. / L, more preferably 0.03 to 0.08 mol / L.
  • the concentration of diamine in the diamine aqueous solution is the concentration with respect to the total amount of the diamine aqueous solution.
  • the diamine aqueous solution contains an alkaline agent and may further contain an additive such as a penetrant.
  • the alkaline agent is used to exterminate (that is, remove) hydrochloric acid produced by the reaction of diamine and dibasic acid chloride.
  • hydrochloric acid is not exterminated, so that the formation of polyamide is inhibited, and as a result, the shrinkage resistance is lowered.
  • the alkaline agent is not particularly limited as long as it is a substance capable of neutralizing hydrochloric acid. Specific examples of the alkaline agent include sodium hydroxide, sodium carbonate, sodium silicate, potassium hydroxide and the like.
  • the concentration of the alkaline agent in the diamine aqueous solution is not particularly limited, and is usually 0.01 to 0.7 mol / L, preferably 0.02 to 0 from the viewpoint of further improving shrinkage resistance, texture and water repellency. It is .15 mol / L, more preferably 0.03 to 0.08 mol / L.
  • the concentration of the alkaline agent should be as low as possible in consideration of yellowing of animal hair fibers and the like.
  • Penetrants are used to promote the penetration of diamines into animal hair fibers.
  • specific examples of the penetrant include nonionic surfactants such as polyoxyalkylene alkyl ethers and the like.
  • a nonionic surfactant is available as, for example, commercially available SSK630 (polyoxyalkylene alkyl ether) manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.
  • the concentration of the penetrant in the diamine aqueous solution is not particularly limited, and is usually 0.1 to 2.0% soln. From the viewpoint of further improving shrinkage resistance, texture and water repellency, it is preferably 0.5 to 2.0%. It is 1.5% soln., More preferably 0.8 to 1.2% soln. "% Soln.” Is a unit based on the volume ratio.
  • the contact time between the sliver and the diamine aqueous solution is not particularly limited as long as the polyamide is formed on the surface of the animal hair fiber in the next step, and is usually 1 second to 10 minutes, further improving the shrinkage resistance, texture and water repellency. From the viewpoint of the balance with the production efficiency, it is preferably 2 seconds to 5 minutes, more preferably 5 seconds to 3 minutes, further preferably 10 seconds to 3 minutes, particularly preferably 20 seconds to 3 minutes, sufficiently preferably. 30 seconds to 3 minutes, most preferably 1.5 minutes to 3 minutes.
  • the contact time between the sliver and the diamine aqueous solution can be controlled by adjusting the operating speed described later.
  • the drawing treatment method is not particularly limited as long as it can squeeze out the excess liquid contained in the sliver, and examples thereof include a method using a mangle.
  • the aperture ratio is not particularly limited, and is usually 50 to 90%, preferably 60 to 90%, and more preferably 70 to 90%.
  • the drawing ratio is a value represented by ⁇ x / (x + y) ⁇ ⁇ 100 (%), where x is the mass of the liquid adhering to the sliver and y is the mass of the sliver. The same applies to the drawing ratio in the following steps.
  • the solvent used in this process must be an environmentally friendly solvent that is not subject to legal restrictions (that is, a solvent that is not subject to legal regulations for environmental protection).
  • the solvent used in this step needs to be a solvent that is immiscible with water, thereby forming a liquid-liquid interface.
  • the solvent used in this step needs to be inert as a third condition.
  • a silicon solvent particularly a silicone solvent is used.
  • Specific examples of the silicon solvent include linear silicon (particularly linear silicone) manufactured by Mitsubishi Heavy Industries Industrial Equipment Co., Ltd., that is, decamethyltetrasiloxane, and cyclic silicon manufactured by Green Earth Co., Ltd. (particularly cyclic).
  • the preferred solvent is a silicone solvent (particularly a siloxane solvent), and examples thereof include linear or cyclic silicones (particularly linear or cyclic siloxane). More preferred solvents are linear or cyclic siloxanes. Particularly preferred is diamond silicone manufactured by Mitsubishi Heavy Industries Industrial Equipment Co., Ltd.
  • dibasic acid chloride used in the present invention examples include aliphatic dicarboxylic acid chlorides such as succinic acid chloride, adipic acid chloride, pimelic acid chloride, suberic acid chloride, azelaic acid chloride, sebatic acid chloride, and cyclohexanedicarboxylic acid chloride; terephthalic acid.
  • Aromatic dicarboxylic acid chlorides such as chloride, isophthalic acid chloride, orthophthalic acid chloride; and bischloroformates such as hexanediol bischloroformate and decandiol bischloroformate.
  • the dibasic acid chloride is not particularly limited to these, and two or more of these dibasic acid chlorides may be used in combination.
  • the dibasic acid chloride usually requires that at least one hydroxyl group out of two hydroxyl groups derived from two carboxyl groups is substituted with a chlorine atom, but preferably two hydroxyl groups are substituted with a chlorine atom.
  • Preferred dibasic acid chlorides are aliphatic dicarboxylic acid chlorides, especially sebatic acid dichloride.
  • the concentration of dibasic acid chloride in the silicon solvent is not particularly limited, and is usually 0.01 to 0.7 mol / L, from the viewpoint of further improving shrinkage resistance, texture and water repellency. Therefore, it is preferably 0.02 to 0.15 mol / L, and more preferably 0.03 to 0.08 mol / L.
  • the concentration of dibasic acid chloride in the silicon solvent is the concentration with respect to the total amount of the silicon solvent and the dibasic acid chloride (that is, the total amount of the dibasic acid chloride solution).
  • the silicon solvent (that is, the dibasic acid chloride solution) may further contain an additive such as a water absorbent (for example, Molecular Sieve 4A1 / 8 (Molecular Sieve)).
  • a water absorbent for example, Molecular Sieve 4A1 / 8 (Molecular Sieve)
  • the temperature of the silicon solvent (that is, the dibasic acid chloride solution) is not particularly limited, and is preferably room temperature (for example, 15 to 25 ° C.) from the viewpoint of further improving the shrinkage resistance, texture and water repellency and the balance between production efficiency. is there.
  • the contact time between the sliver and the silicon solvent (that is, the dibasic acid chloride solution) is not particularly limited as long as polyamide is formed on the surface of the animal hair fiber in this step, and is usually 1 second to 1 minute, and is shrink-proof. From the viewpoint of further improving the texture and water repellency and the balance between the production efficiency, it is preferably 1 to 30 seconds, and more preferably 5 to 20 seconds.
  • the contact time between the sliver and the silicon solvent (that is, the dibasic acid chloride solution) can be controlled by adjusting the operating speed described later.
  • the drawing treatment method the same method as the drawing treatment method in the diamine aqueous solution dipping step is used, and for example, a method using a mangle is used.
  • the aperture ratio is not particularly limited, and is usually 50 to 90%, preferably 60 to 90%, and more preferably 70 to 90%.
  • the drying step is usually carried out without particular limitation.
  • a water washing step, an acid washing step, and a softening treatment step may be performed before the drying step.
  • the first water washing step, the acid washing step, the second water washing step, the softening treatment step and the drying step are sequentially performed.
  • the excess polyamide can be removed.
  • the diamine component, the dibasic acid chloride component and the alkaline agent component on the fiber surface are removed by immersing the sliver in water.
  • the oligomer formed in the step of dipping in the dibasic acid chloride solution may also be exterminated.
  • the temperature of water in the first washing step is not particularly limited, and is preferably room temperature (for example, 15 to 25 ° C.) from the viewpoint of further improving shrinkage resistance, texture and water repellency and balancing production efficiency.
  • the contact time between the sliver and water in the first washing step is not particularly limited as long as the above-mentioned extermination is achieved, and is usually 1 second to 1 minute, further improving shrinkage resistance, texture and water repellency, and manufacturing efficiency. From the viewpoint of the balance with the above, it is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.
  • the contact time between the sliver and water can be controlled by adjusting the operating speed described later.
  • the first washing step after immersing the sliver in water, it is usually subjected to squeezing treatment.
  • the drawing treatment method the same method as the drawing treatment method in the diamine aqueous solution dipping step is used, and for example, a method using a mangle is used.
  • the aperture ratio is not particularly limited, and is usually 50 to 90%, preferably 60 to 90%, and more preferably 70 to 90%.
  • a silicon solvent that is, a dibasic acid chloride solution
  • the silicon solvent adhering to the sliver is mixed with the water in this step, and such a silicon solvent can be separated and recovered by utilizing the difference in specific gravity with water.
  • the silicon solvent is positioned higher based on the difference in specific gravity with water, while the water is positioned lower. Therefore, the silicon solvent can be separated and recovered from the upper part in the tank.
  • the oligomer formed during the formation of polyamide on the fiber surface is removed by immersing the sliver in an aqueous acid solution.
  • the residual diamine component and the polyamide excessively formed in the dipping step in the dibasic acid chloride solution may be removed.
  • the acid in the aqueous acid solution is not particularly limited, and examples thereof include aliphatic monocarboxylic acids such as formic acid.
  • the acid used in this step is not particularly limited to these, and two or more of these acids may be used in combination.
  • Preferred acids are aliphatic monocarboxylic acids, especially formic acid.
  • the concentration of the acid in the aqueous acid solution is not particularly limited, and is usually 0.01 to 10%, preferably 0.1 to 10% from the viewpoint of further improvement of shrinkage resistance, texture and water repellency and a balance between production efficiency. It is 5%, more preferably 0.5 to 2%.
  • the unit of concentration "%" is the volume ratio to the total amount.
  • the temperature of the acid aqueous solution in the acid cleaning step is not particularly limited, and is preferably room temperature (for example, 15 to 25 ° C.) from the viewpoint of further improving shrinkage resistance, texture and water repellency, and balancing production efficiency.
  • the contact time between the sliver and the aqueous acid solution is not particularly limited as long as the above-mentioned extermination is achieved, and is usually 1 second to 1 minute, which is a balance between further improvement of shrinkage resistance, texture and water repellency and production efficiency. From the viewpoint, it is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.
  • the contact time between the sliver and the acid aqueous solution can be controlled by adjusting the operating speed described later.
  • the acid cleaning step after immersing the sliver in the acid aqueous solution, it is usually subjected to drawing treatment.
  • drawing treatment method the same method as the drawing treatment method in the diamine aqueous solution dipping step is used, and for example, a method using a mangle is used.
  • the aperture ratio is not particularly limited, and is usually 50 to 90%, preferably 60 to 90%, and more preferably 70 to 90%.
  • the diamine component, the dibasic acid chloride component and the alkaline agent component on the fiber surface are more sufficiently removed by immersing the sliver in water.
  • the temperature of water in the second washing step is not particularly limited, and is preferably room temperature (for example, 15 to 25 ° C.) from the viewpoint of further improving shrinkage resistance, texture and water repellency and balancing production efficiency.
  • the contact time between the sliver and water in the second washing step is not particularly limited as long as the above-mentioned extermination is achieved, and is usually 1 second to 1 minute, further improving shrinkage resistance, texture and water repellency, and manufacturing. From the viewpoint of balance with efficiency, it is preferably 5 to 40 seconds, and more preferably 10 to 30 seconds.
  • the contact time between the sliver and water can be controlled by adjusting the operating speed described later.
  • the drawing treatment method the same method as the drawing treatment method in the diamine aqueous solution dipping step is used, and for example, a method using a mangle is used.
  • the aperture ratio is not particularly limited, and is usually 50 to 90%, preferably 60 to 90%, and more preferably 70 to 90%.
  • the sliver is immersed in an aqueous solution of a softener to impart flexibility to the fibers.
  • the softener in the aqueous softener solution is not particularly limited as long as it is a drug known as a drug capable of imparting flexibility in the field of fibers (particularly animal hair fiber or wool fiber), and examples thereof include paraffin compounds.
  • the paraffinic compound is available as a commercially available Bryan LC-35 (nonionic, solid paraffin softener) manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
  • the concentration of the softener in the aqueous softener solution is not particularly limited, and is usually 0.01 to 10%, and is preferably 0. From the viewpoint of further improvement of shrinkage resistance, texture and water repellency and a balance between production efficiency. It is 1 to 5%, more preferably 0.5 to 2%.
  • the unit of concentration "%" is the volume ratio to the total amount.
  • the temperature of the aqueous softener solution in the softening treatment step is not particularly limited, and is preferably 20 to 50 ° C., more preferably 30 to 30 to 50 ° C. from the viewpoint of further improving shrinkage resistance, texture and water repellency and balancing production efficiency. It is 50 ° C.
  • the contact time between the sliver and the aqueous softener solution is not particularly limited as long as the fibers are provided with flexibility, and is usually 1 second to 1 minute, which further improves shrinkage resistance, texture and water repellency, and improves production efficiency. From the viewpoint of balance, it is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.
  • the contact time between the sliver and the aqueous softener solution can be controlled by adjusting the operating speed described later.
  • the softening process after immersing the sliver in the softener aqueous solution, it is usually subjected to drawing treatment.
  • drawing treatment method the same method as the drawing treatment method in the diamine aqueous solution dipping step is used, and for example, a method using a mangle is used.
  • the aperture ratio is not particularly limited, and is usually 50 to 90%, preferably 60 to 90%, and more preferably 70 to 90%.
  • the drying step the sliver wet in the previous steps is dried.
  • any drying method known in the field of fibers can be used.
  • Specific examples of the drying method include a suction drying method in which drying is performed while sucking, a suction drum dryer manufactured by Milling Sner, and the like.
  • the drying temperature in the drying step is not particularly limited as long as it can achieve drying without damaging the fibers (particularly animal hair fiber or wool fiber), and further improvement of shrinkage resistance, texture and water repellency and production efficiency. From the viewpoint of the balance with the above, the temperature is preferably 50 to 100 ° C, more preferably 70 to 90 ° C.
  • the operating speed is not particularly limited as long as the above-mentioned contact time is secured, and is preferably 0.1 to 10 m / min, more preferably 0.1 to 10 m / min, from the viewpoint of further improving shrinkage resistance, texture and water repellency, and balancing manufacturing efficiency. Is 0.5 to 3 m / min, more preferably 1.5 to 3 m / min.
  • one or more post-treatments selected from gil treatment and combing treatment may be performed on the sliver that has completed the drying step.
  • the gil treatment and the combing treatment are the same treatments as the gil treatment and the combing treatment mentioned in the description of the diamine aqueous solution immersion step, respectively.
  • the sliver is immersed in an aqueous diamine solution and then in a silicon solvent in which dibasic acid chloride is dissolved to coat the surface of the animal hair fiber with the polyamide, which is an adsorptive organochlorine compound discharged. (AOX) and the organochlorine compounds remaining in the fiber are controlled to a minimum.
  • the content of the adsorptive organochlorine compound (AOX) in the total effluent when squeezed in the dipping step in the dibasic acid chloride solution is less than 1 mg / kg.
  • the value measured by the activated carbon adsorption-combustion method specifically, the value measured based on ISO9652 (2004) is used.
  • the chloride ion concentration contained in the obtained sliver (animal hair fiber) is 2.0 mg / L or less, particularly 1.2 mg / L or less.
  • the chloride ion concentration (a value measured by a boiling extraction method based on a liquid chromatograph method, specifically, a value measured based on the JIS K 0127 general rule chloride ion concentration is used.
  • the water resistance was evaluated according to the Woolmark test method TM 31 based on ISO 6330.
  • the top sliver obtained in each of the Examples / Comparative Examples was spun to 2/28 Nm, the number of twists was set to 370 times / m for single yarn Z and 213 times / m for twin yarn, and after spinning, flat knitted fabric was knitted. Then, the knitting density was adjusted so as to have a cover factor of 0.41, and the obtained knitted fabric was subjected to a shrinkage resistance evaluation test.
  • Water resistance was evaluated according to IWS TM 31 based on ISO 6330. As an evaluation rule "Elongation”: Indicates an increase in length or width dimension caused by washing, expressed as a positive (+) dimensional change.
  • “Shrinkage” Indicates a decrease in length or width dimension caused by washing, expressed as a negative (-) dimensional change. Evaluated by the ISO 6330 5A and 7A wash cycle programs, both programs are carried out with a load of 1 kg, and the wash cycle and number of washes are determined by the product. As a calculation formula, the relaxation dimensional change rate in the width (WS) and length (LS) directions, the felt dimensional change rate, and the total dimensional change rate are calculated by the following formulas.
  • Area dimensional change rate (%) WS + LS ⁇ (WS x LS) / 100 ⁇ ⁇ : Area dimensional change rate ⁇ 3.0 (best); ⁇ : 3.0 ⁇ absolute value of area dimensional change rate ⁇ 5.0 (excellent); ⁇ : 5.0 ⁇ absolute value of area dimensional change rate ⁇ 8.0 (good); ⁇ : 8.0 ⁇ Absolute value of area dimensional change rate ⁇ 10.0 (possible (no problem in practical use)) X: 10.0 ⁇ absolute value of area dimensional change rate (there is a problem in practical use).
  • the pre-test knitted fabric (sample) produced by the shrinkage resistance evaluation was compared with the untreated knitted fabric as a control, and the texture was evaluated according to the following criteria.
  • the untreated knitted fabric as a control was produced by the same method as the knitted fabric production method in the shrinkage resistance evaluation except that an untreated sliver was used.
  • the texture is a feel based on the roughness and hardness of the knitted fabric.
  • ⁇ The knitted fabric (sample) showed a better texture than the untreated knitted fabric (excellent); ⁇ : The knitted fabric (sample) showed the same texture as the untreated knitted fabric (good); ⁇ : The knitted fabric (sample) was slightly coarser and harder than the untreated knitted fabric, but was within a practically acceptable range; X: The knitted fabric (sample) was clearly coarser and harder than the untreated knitted fabric (there was a problem in practical use).
  • the water repellency of the knitted fabric surface was tested according to the spray test of JIS L 1092-1992 and the evaluation criteria described, and evaluated based on the criteria in Table 3.
  • the knitted fabric to be evaluated is the knitted fabric (sample) before the test manufactured by the shrinkage resistance evaluation. 2 or more was a range where there was no problem in practical use, 3 was "good”, 4 was “excellent”, and 5 was "best”.
  • the chloride ion concentration contained in the wool fiber obtained in Example 1 was measured according to the following method. According to JIS K 0127 chloride ion concentration, the wool sample was boiled in distilled water, and the extracted chlorine ion was measured by ion chromatography. The measurement was requested to the Environmental Materials Office of the Industrial Technology Center of the "Aichi Industrial Science and Technology Center".
  • Example 1 shrink-proof animal hair fibers were continuously produced according to the following method.
  • Second step Next, the sliver that has undergone the first step is subjected to the second bath in the second tank (a silicon solvent in which sebatate dichloride is dissolved at 0.2 mol / L (specifically, decamethyl-cyclopentasiloxane (pentamer)). )), Soaked in a solvent containing molecular sheave 4A 1/8 "pellets, temperature 25 ° C.) for 10 seconds, and squeezed to 80% with a mangle.
  • a silicon solvent in which sebatate dichloride is dissolved at 0.2 mol / L specifically, decamethyl-cyclopentasiloxane (pentamer)
  • Third step The sliver that had undergone the second step was washed with water by immersing it in water in the third tank (at a temperature of 25 ° C. for 20 seconds, and squeezed to 80% with a mangle. In this step, water was used. Sodium oxide was exterminated, low molecular weight nylon resin was exterminated, and sebatic acid, which is a white precipitate produced, was exterminated.
  • the sliver that had undergone the third step was immersed in a 1% formic acid aqueous solution (temperature 25 ° C.) in the fourth tank for 20 seconds, and squeezed to 80% with a mangle. In this step, if excess polyamide is formed between the fibers, the excess polyamide is removed.
  • the sliver that had undergone the fourth step was washed with water by immersing it in water (temperature 25 ° C.) in the fifth tank for 20 seconds, and squeezed to 80% with a mangle.
  • the sliver that has undergone the 5th step is immersed in a softener aqueous solution (softener; 1% solution of Bryan LC35 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., temperature 40 ° C.) in the 6th tank for 20 seconds. After washing with water, the temperature was reduced to 80% with a mangle.
  • softener 1% solution of Bryan LC35 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd., temperature 40 ° C.
  • the sliver that had undergone the 6th step was dried at 85 ° C. with a suction drum dryer to obtain shrink-proof animal hair fibers.
  • Example 2 The concentration of hexamethylenediamine in the first bath was changed to 0.1 mol / L, the concentration of sodium hydroxide in the first bath was changed to 0.1 mol / L, and the concentration of dichloride sebatate in the second bath was 0.1 mol.
  • the shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 1 except that it was changed to / L.
  • Example 3 The concentration of hexamethylenediamine in the first bath was changed to 0.05 mol / L, the concentration of sodium hydroxide in the first bath was changed to 0.05 mol / L, and the concentration of dichloride sebatate in the second bath was changed to 0.05 mol.
  • the shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 1 except that it was changed to / L.
  • Example 4 The shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 1 except that the operating speed was changed to 4 m / min.
  • the processing time (contact time) of each step in this example was 1/2 of the processing time of each corresponding step in Example 1.
  • Example 5 The operating speed was changed to 4 m / min, the concentration of hexamethylenediamine in the first bath was changed to 0.1 mol / L, the concentration of sodium hydroxide in the first bath was changed to 0.1 mol / L, and the second bath.
  • the shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 1 except that the concentration of sebacate dichloride was changed to 0.1 mol / L.
  • the processing time (contact time) of each step in this example was 1/2 of the processing time of each corresponding step in Example 1.
  • Example 6 The operating speed was changed to 4 m / min, the concentration of hexamethylenediamine in the first bath was changed to 0.05 mol / L, the concentration of sodium hydroxide in the first bath was changed to 0.05 mol / L, and the second bath.
  • the shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 1 except that the concentration of sebacate dichloride was changed to 0.05 mol / L.
  • the processing time (contact time) of each step in this example was 1/2 of the processing time of each corresponding step in Example 1.
  • Example 7 The shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 3 except that the temperature of the first bath was changed to 37 ° C.
  • Example 8 The shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 3 except that the temperature of the first bath was changed to 35 ° C.
  • Example 1 The shrink-proof animal hair fiber was produced and evaluated by the same method as in Example 1 except that the temperature of the first bath was changed to 25 ° C.
  • Example 3 The evaluation was carried out by the same method as in Example 1 except that the wool top sliver was used as it was for evaluation without carrying out the first to seventh steps.
  • Example 2 Based on Example 1, hexamethylenediamine was subjected to interfacial polymerization treatment at 0.2 mol / L, sodium hydroxide, 0.2 mol / L, and a liquid temperature of 40 ° C. As a result, the amount of nylon polymer formed on the fibers of the wool top sliver increased within the permissible range, and the result of the washing test by TM31 was an area dimensional change rate of -9.0%.
  • Example 2 the amount of nylon polymer formed on the fibers was considerably small in the interfacial polymerization treatment of hexamethylenediamine 0.1 mol / L sodium hydroxide, 0.1 mol / L, liquid temperature 40 ° C. became. In the TM31 test, it showed -7.5%, and wool yarn with improved shrinkage resistance was produced.
  • Example 3 Under the conditions of Example 3, hexamethylenediamine was treated at 0.05 mol / L, sodium hydroxide at 0.05 mol / L, and a liquid temperature of 40 ° C. As a result, the nylon polymer formed on the fiber uniformly coats the wool surface as shown in FIG. 1, and therefore should be fully satisfied with the TM 31 test of -2.7%. I got the result. This was the optimum condition for eliminating the anisotropy (DFE) of the surface friction coefficient, which is the cause of felting of wool fibers, by coating the surface of wool fibers with nylon polymer uniformly and in a mesh pattern. .. When this condition is exceeded, the nylon polymer gums up, the adhesion between wool fibers increases, and the shrinkage resistance decreases.
  • DFE anisotropy
  • Example 4 the operating speed of the machine was changed to 4 m / min, and the solution treatment reaction times of the hexamethylenediamine bath, the sebatic acid dichloride bath and the formic acid treatment bath were changed to evaluate the shrinkage resistance.
  • the contact time of each drug was halved, a decrease in shrink resistance was observed.
  • sodium hydroxide plays a role of neutralizing "hydrochloric acid” generated in the interfacial polymerization reaction of hexadiamine and sebacate dichloride and catalytically accelerating the polymerization reaction. By increasing the salt concentration, the interfacial polymerization of this case is promoted.
  • hydrochloric acid is generated by the reaction between sebatic acid dichloride and water, and the neutralizing action of sodium hydroxide further contributes to the polymerization reaction.
  • Carbon tetrachloride, benzene, toluene, trichlorethylene, chloroform, Socal 25, Stoddard Solvent, perchloroethylene, etc. which are disclosed for liquid-liquid interfacial polymerization, are substances regulated from the standpoint of preserving the global environment. The production process using this is very restrictive. As a means to solve this problem, there is a silicon solvent. The present invention has clarified that an interfacial polymerization reaction is possible even when a silicon solvent is used.
  • the processing of animal hair fibers using a solvent has been avoided due to problems such as air pollution, water pollution, occupational hygiene, working environment, waste treatment, soil pollution, etc., but the inorganic silicon solvent implemented in the present invention has been avoided.
  • the present invention is the first in the wool industry to control the adsorptive organic chlorine compound AOX (Absorbable Organic Halogens) discharged from the treatment process and the "residual chlorine compound" in the animal hair fiber at the same time to the minimum. It provides a method for continuously producing a novel shrink-proof animal hair fiber sliver.
  • AOX Absorbable Organic Halogens

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention fournit un procédé pour fabriquer de manière efficace et sous forme de ruban d'excellentes fibres de poils d'animaux irrétrécissables qui tout en préservant sa résistance à l'eau naturelle constituant l'une des caractéristiques des fibres de poils d'animaux, présente une résistance suffisante au lavage à l'eau, sans endommagement de sa texture ni de ses autres caractéristiques. Plus précisément, l'invention concerne un procédé de fabrication de fibres de poils d'animaux irrétrécissables qui est caractéristique en ce que dans un état d'adhésion d'un diamine par immersion du ruban constituant un corps continu des fibres de poils d'animaux, dans une solution aqueuse de diamine comprenant un agent alcalin de 30 à 45°C, un polyamide revêt la surface des fibres de poils d'animaux par immersion dans un solvant au silicium obtenu par dissolution d'un chlorure d'acide dibasique.
PCT/JP2019/029069 2019-07-24 2019-07-24 Procédé de fabrication de fibres de poils d'animaux irrétrécissables WO2021014620A1 (fr)

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JP2021534491A JP7283670B2 (ja) 2019-07-24 2019-07-24 防縮性獣毛繊維の製造方法
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