EP3500697B1 - Verfahren zur herstellung von acryl- oder modacrylfasern mit desodorierender wirkung - Google Patents

Verfahren zur herstellung von acryl- oder modacrylfasern mit desodorierender wirkung Download PDF

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Publication number
EP3500697B1
EP3500697B1 EP17856929.9A EP17856929A EP3500697B1 EP 3500697 B1 EP3500697 B1 EP 3500697B1 EP 17856929 A EP17856929 A EP 17856929A EP 3500697 B1 EP3500697 B1 EP 3500697B1
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EP
European Patent Office
Prior art keywords
acrylic
fiber
tank
modacrylic fiber
modacrylic
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.)
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Application number
EP17856929.9A
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English (en)
French (fr)
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EP3500697A2 (de
Inventor
Ahmet Alper ONCUL
Orhan Caliskan
Emrah EREN
Caglar Yilmaz
Mehmet Aydost ARAS
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.)
Aksa Akrilik Kimya Sanayii AS
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Aksa Akrilik Kimya Sanayii AS
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Priority claimed from TR2017/01927A external-priority patent/TR201701927A2/tr
Application filed by Aksa Akrilik Kimya Sanayii AS filed Critical Aksa Akrilik Kimya Sanayii AS
Publication of EP3500697A2 publication Critical patent/EP3500697A2/de
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Publication of EP3500697B1 publication Critical patent/EP3500697B1/de
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Classifications

    • 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
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • the invention relates to a method intended for the production of acrylic and modacrylic fiber having anti-odor feature.
  • textile products that are being produced in recent years have created positive effect in terms of human health as well as facilitating the human life.
  • One of the studies performed on textile products is to obtain textile product raw materials that are suppressing and/or preventing the odor and having anti-odor feature.
  • Acrylic fiber is the synthetic fiber type that is the most similar to wool, and it is a textile raw material used either by itself and/or as mixed with synthetic fiber types.
  • Acrylic fiber that has features such as easy washing and preserving its shape, resistant against moth, oil and chemicals and being able to be dyed in bright colors of perfect fastness, is a textile raw material which is extensively used.
  • Sweat that is a very suitable environment for the bacterial growth, is structurally odorless.
  • the source of bad sweat smells spreading from the human body is various bacteria and microorganisms growing at different parts of the body.
  • biocides are chemical materials that are generated by the mixture of one or more active materials, and have controlling or destroying effect on microorganisms covering bacteria, fungus, tang, mold or yeast.
  • the anti-odor feature is provided through coating on the surface of fiber / fabric.
  • chemical materials are added at the chemical finishing step of the fiber production process and anti-odor feature is provided.
  • the coating is abraded following specific number of washes, and the anti-odor feature of the fiber / fabric is lost.
  • ZnO zinc oxide
  • a layer of which 99% is consisting of pure silver adheres on the surface of synthetic raw materials such as polyester or on the surface of natural thread raw materials.
  • the silver layer adheres on the polymer, and it becomes a physical part of the textile's texture.
  • the invention is the preparation and production method of nanofiber food packaging films by the electro-spinning method of referred hybrid polymer solution by ensuring aloe vera -which is a natural polymer- and zinc oxide addition to the copolymer -which is formed by using polyvinyl alcohol biodegradable polymer material whose short name is PVA, and which is formed by mixing each and some of the polymers such as polyethylene glycol whose short name is PEG, polyvinyl pyrrolidone whose short name is PVP and polylactic acid whose short name is PLA with a slight amount of PVA biodegradable polymer when required- for it to ensure anti-microbial effect when required.
  • acrylic/modacrylic fibers comprising zinc oxide or zinc pyrithione are known also from US2010/029156A1 , JP3349028B2 , US3061398A , and US2014/272152A1 .
  • the present invention makes it necessary to remove the above-mentioned problems and to make technical innovation in the relevant field.
  • the main object of the invention is to reveal the structure of a method that will enable the production of acrylic / modacrylic fiber having anti-odor effect.
  • Another object of the invention is to reveal the production method of acrylic / modacrylic fiber having anti-odor effect by using zinc oxide (ZnO) that has anti-bacterial feature.
  • ZnO zinc oxide
  • Another object of the invention is to ensure the obtainment of acrylic / modacrylic fiber having anti-odor effect by the addition of zinc oxide (ZnO) at the preparation step of polymer solution (dope) in the fiber production process.
  • ZnO zinc oxide
  • Another object of the invention is to enable the confinement of zinc oxide powders in acrylic / modacrylic fiber.
  • Another object of the invention is to ensure an acrylic / modacrylic fiber structure whose anti-odor feature isn't easily lost after washing.
  • Another object of the invention is to reveal an acrylic / modacrylic fiber structure allowing the absorption of ultraviolet lights due to the anti-UV feature of zinc oxide.
  • the invention relates to a method that will enable the production of acrylic / modacrylic fiber (1) having anti-odor effect.
  • the acrylic / modacrylic fiber (1) which is the subject of invention and produced as having anti-odor feature is comprising the elements of polyacrylonitrile (PAN) (2), solvent (3), polymer solution (Dope) (4), dilute polymer solution (5), zinc oxide (ZnO) (6) or zinc pyrithione (6.a), tank 1 (7), tank 2 (8), heat exchanger (9), dynamic mixer (10) and fiber spinning machine (11).
  • PAN polyacrylonitrile
  • Dope polymer solution
  • Polyacrylonitrile (PAN) (2) is an acrylic material, and it is a material having polymer structure which is frequently used in clothing, textile fields. The crystal elongation and crystallization ratio of acrylic fiber -which was previously produced as homopolymer through 100% polymerization of acrylonitrile- is very high. For this reason, its features such as being dyed and absorption of humidity are negative, and dying it is very hard. In order to improve these features and to provide the capacity of being dyed, it has been transformed to copolymer by the addition of a second monomer, and its features have been made suitable for use in textile. Polyacrylonitrile (PAN) (2) is a type of thermoset polymer.
  • Co-polyacrylonitrile (co-PAN) (2) includes comonomer at a rate of 4-12%. This comonomer is generally vinyl acetate or methyl acrylate. The molecular weight of co-polyacrylonitrile (co-PAN) (2) is in between 90,000 - 200,000.
  • the solvent (3) which is used as dissolver, is DMAc, DMF, DMSO and similar solutions which are polar aprotic solvents.
  • the polymer solution (4) is a viscous solution called "Dope" where polyacrylonitrile (PAN) (2) dissolves in the solvent (3).
  • PAN polyacrylonitrile
  • the dilute polymer solution (5) is a polymer solution which is prepared as more dilute than the polymer solution (Dope) (4).
  • Tank 1 (7) is the location where the solvent (3) and polyacrylonitrile (PAN) (2) are mixed, and polymer solution (Dope) (4) is obtained.
  • Tank 2 (8) is the location where the dilute polymer solution (5) is prepared, and the zinc oxide (ZnO) (6) or zinc pyrithione (6.a) is added into this dilute polymer solution (5).
  • the heat exchanger (9) is enabling the complete dissolution of solutions at a temperature of 70-100°C.
  • Dynamic mixer (10) is used for mixing and homogenizing the dilute polymer solution (5) in which the prepared polymer solution (Dope) (4) and zinc oxide (ZnO) (6) or zinc pyrithione (6.a) are added.
  • Acrylic / modacrylic fiber (1) which is the subject of the invention is a new fiber produced by adding zinc oxide (ZnO) (6) and used in the fields of clothing, home textile and technical textile having anti-odor feature.
  • ZnO zinc oxide
  • the acrylic / modacrylic fiber (1) which is the subject of the invention is a new fiber produced by adding zinc pyrithione (C 10 H 8 N 2 O 2 S 2 Zn) (6.a), and used in the fields of clothing, home textile and technical textile having anti-odor feature.
  • the solvent (3) doesn't have sufficient temperature for dissolution.
  • the polyacrylonitrile (PAN) (2) in the solvent (3) is passed through the heat exchanger (9) which is heated up with vapor for the its dissolution, and after completion of dissolution, the polymer solution (4) called dope is obtained.
  • the obtained dope (4) is sensitive to heat so it is slightly cooled as being passed from water cooled exchanger (9) without being kept at high temperature.
  • the polymer solution (dope) (4) in tank 1 (7), and the dilute polymer solution (5) in tank 2 (8) in which zinc oxide (ZnO) (6) is added are transferred to fiber spinning machine (11).
  • the dilute polymer solution (5) in which zinc oxide (ZnO) (6) is added is delivered to fiber spinning machine (11) through the high power system called dynamic mixer (10).
  • dynamic mixer (10) the high power system
  • An acrylic / modacrylic fiber (1) having anti-odor effect is obtained by the wet spinning method from the final mixture obtained.
  • powder zinc pyrithione (6.a) with a grain size of 0,1-5,0 micrometers is added in the dilute polymer solution (5) prepared in tank 2 (8).
  • the polymer solution (dope) (4) in tank 1 (7), and the dilute polymer solution (5) in tank 2 (8) in which zinc pyrithione (6.a) is added are transferred to fiber spinning machine (11).
  • An acrylic / modacrylic fiber (1) having anti-odor effect is obtained by the wet spinning method from the final mixture obtained.
  • the referred acrylic / modacrylic fiber (1) includes zinc pyrithione (6.a) at a rate of 0.3-5% in weight.
  • Zinc pyrithione (6.a) is confined in fiber (1).
  • the representative form of the referred preparation method is shown in Figure 4 , and its diagram is shown in Figure 5 .
  • the prepared polymer solution (4) is fed to a bath consisting of water - solvent mixture after having the required injections, filtering and pressurizing are made.
  • the feeding is made over a perforated plate called spinneret bearing holes in between 10,000-100,000 microns.
  • the zinc oxide (ZnO) (6) -that is initially in the solution in solid form without dissolving-, or the zinc pyrithione (6.a) in the other embodiment becomes contained in the fibers at this phase. This operation is called coagulation, and the bath in which fibers form is called coagulation bath.
  • the solvent amount on it is required to be below 0.5%. For this reason, washing operation is realized.
  • basic dyes are used in dying of fibers.
  • the acidic groups at the ends of polymer chain make a chemical bond with the basic dyes, and the dyeing of the fiber is ensured.
  • the dyeing operation is realized as the absorption of dye by the fiber that passes through the dye bath and of which solvent is removed.
  • a fiber drawing operation which is applied by heating it in two separate baths is realized. This operation is called as wet stretching.
  • the length of the fiber increases by six times.
  • chemical finish is a lubricant material covering the surface of fiber, and it is a mixture of organic substances used in order to provide the operation and required softness of fiber in textile operations, and adjusting the friction of fiber with each other and on the metal surfaces.
  • the fiber coming out of the chemical finish bath is dried by getting passed through a serial drying roll heated up by vapor.
  • the water vapor leaving the surface of fiber is removed by being carried by the air in an aspiration system.
  • the fibers are required to be curly, not straight, to hold each other.
  • the curling operation providing wool feature and appearance to the fiber is performed while passing in between two rolls inside a crimping box of the tow band. Another importance of the crimping operation is enabling the penetration of vapor to each point of the fiber bands during the annealing phase.
  • acrylic / modacrylic fiber (1) having anti-odor effect is obtained.
  • the anti-odor and anti-bacterial effect of zinc on textile products activates when the skin spreads moisture, and an active variability is formed in between the fibers and the skin.
  • Zinc oxide (ZnO) (6) having positive zeta potential easily holds on the cell membrane of negative bacteria, and Zn +2 ions are released. The released zinc ions interact with the bacteria. Vital ions such as sodium etc. inside the bacteria change place with the zinc ions. Due to this displacement, the metabolism of bacteria starts to collapse, and bacterial cell deaths becomes realized. By the death of bacteria which is the cause of bad odors, the sweat smell becomes prevented.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (7)

  1. Die Erfindung betrifft die Herstellungsmethode für eine Art acrylic / modacrylic Faser (1), dadurch gekennzeichnet;
    a) Zusatz von Lösungsmittel (3) in einem tank 1 (7)
    b) Zusatz von polyacrylonitrile (PAN) (2) in einem tank 1 (7)
    c) Durchführen von polyacrylonitrile (PAN) (2) von einem Wärmetauscher (9) damit es vollständig gelöst wird,
    d) Bildung in dem Tank 1 (7) eines noch dünneren polymer Lösungsmittel (5) von einem polymer Lösungsmittel (4) sog. Dope, in dem Tank 2 (8),
    e) Zusatz von Zink Oxyd (6) oder Zink Pyrithione (6a.) in dem Tank 2 (8),
    f) Mischung von Lösungsmitteln die in dem Tank 1 (7) und Tank 2 (8) vorbereitet worden sind mit Hilfe eines dynamischen Mixer (10) und Zusatz in einer Faserspinnmaschine (11),
    g) Gewinnung von der endgültigen Mischung acrylic / modacrylic Faser (1) entsprechend der Nassspinnmethode.
  2. Die Erfindung ist die acrylic / modacrylic Faser (1) Herstellungsmethode entsprechend Anspruch 1, dadurch gekennzeichnet; dass Zink pyritione (6a.) in Pulver form ist mit Größe von 0,1 - 0,5 Mikrometer.
  3. Die Erfindung ist die acrylic / modacrylic Faser (1) Herstellungsmethode entsprechend Anspruch 1, dadurch gekennzeichnet; dass Zink Oxyd (6a.) in Pulver form ist, mit Größe von 0,1 - 0,5 Mikrometer.
  4. Die Erfindung ist acrylic / modacrylic Faser (1) dass es mit der Herstellungsmethode entsprechend eines der vorherigen Ansprüche von acrylic / modacrylic Faser (1) hergestellt wurde.
  5. Acrylic / modacrylic Faser (1) entsprechend Anspruch 4, dadurch gekennzeichnet das es in rate % 0,3 - 5 Gew., Zink pyrithione (6.a) umfasst.
  6. Acrylic / modacrylic Faser (1) entsprechend Anspruch 4, dadurch gekennzeichnet das es in rate % 0,1 - 10 Gew., Zink Oxyd (6) umfasst.
  7. Acrylic / modacrylic Faser (1) entsprechend Anspruch 4 - 6, dadurch gekennzeichnet, das es Zink Oxyd (6) oder Zink pyrithione (6.a) umfasst, die mit Faser (1) begrenzt sind.
EP17856929.9A 2016-08-18 2017-07-12 Verfahren zur herstellung von acryl- oder modacrylfasern mit desodorierender wirkung Active EP3500697B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
TR201611640 2016-08-18
TR2017/01927A TR201701927A2 (tr) 2017-02-08 2017-02-08 Anti-odor Etkili Akrilik/Modakrilik Elyaf
PCT/TR2017/050314 WO2018063116A2 (en) 2016-08-18 2017-07-12 Acrylic/modacrylic fiber having anti-odor effect

Publications (2)

Publication Number Publication Date
EP3500697A2 EP3500697A2 (de) 2019-06-26
EP3500697B1 true EP3500697B1 (de) 2020-12-16

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EP (1) EP3500697B1 (de)
CN (1) CN109689949A (de)
ES (1) ES2861580T3 (de)
PT (1) PT3500697T (de)
WO (1) WO2018063116A2 (de)

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CN111411513B (zh) * 2020-04-11 2023-04-28 浙江润峰健康科技有限公司 一种抗菌无纺布

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JPH1025663A (ja) 1996-07-11 1998-01-27 Asahi Chem Ind Co Ltd 消臭繊維製品
JPH10280277A (ja) * 1997-04-01 1998-10-20 Mitsubishi Rayon Co Ltd 抗菌性アクリル繊維及びその製造方法
CN1442518A (zh) * 2002-03-06 2003-09-17 青岛大学 一种含纳米粒子抗菌纤维的制造方法
CN100365178C (zh) * 2005-08-03 2008-01-30 厦门大学 聚丙烯腈基碳芯的制备方法
TR200603916A2 (tr) 2006-07-26 2007-11-21 Seyi̇t İpli̇k Teksti̇l Sağlik Ürünleri̇ İthalat İhracat Sanayi̇ Ve Ti̇caret Li̇mi̇ted Şi̇rketi̇ Gümüş içeren antibakteriyel iplik ve üretim metodu@
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Also Published As

Publication number Publication date
WO2018063116A3 (en) 2018-06-28
WO2018063116A2 (en) 2018-04-05
PT3500697T (pt) 2021-03-18
CN109689949A (zh) 2019-04-26
ES2861580T3 (es) 2021-10-06
EP3500697A2 (de) 2019-06-26
WO2018063116A4 (en) 2018-08-30

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