WO2015020163A1 - Monofilament élastique - Google Patents

Monofilament élastique Download PDF

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Publication number
WO2015020163A1
WO2015020163A1 PCT/JP2014/070923 JP2014070923W WO2015020163A1 WO 2015020163 A1 WO2015020163 A1 WO 2015020163A1 JP 2014070923 W JP2014070923 W JP 2014070923W WO 2015020163 A1 WO2015020163 A1 WO 2015020163A1
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Prior art keywords
elastic monofilament
monofilament
elastic
unit
component
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PCT/JP2014/070923
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English (en)
Japanese (ja)
Inventor
田中　伸明
弘至 土倉
中村　浩太
秀敏 坂井
卓也 良本
Original Assignee
東レ株式会社
東レ・モノフィラメント株式会社
東レ・デュポン株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=52461491&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2015020163(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 東レ株式会社, 東レ・モノフィラメント株式会社, 東レ・デュポン株式会社 filed Critical 東レ株式会社
Priority to EP14834881.6A priority Critical patent/EP3031960B1/fr
Priority to MX2016001715A priority patent/MX2016001715A/es
Priority to US14/910,895 priority patent/US20160194788A1/en
Priority to CN201480055594.4A priority patent/CN105765118B/zh
Priority to CA2920777A priority patent/CA2920777C/fr
Priority to KR1020167006010A priority patent/KR102168814B1/ko
Publication of WO2015020163A1 publication Critical patent/WO2015020163A1/fr

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    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent

Definitions

  • the present invention is excellent in fatigue resistance against repeated deformation in the bending direction, and has various industrial uses such as marine materials, building materials, safety materials, clothing materials, civil engineering materials, agricultural materials, vehicle materials, and sports materials, particularly elasticity.
  • the present invention relates to an elastic monofilament suitable for use in a woven / knitted structure.
  • thermoplastic elastomers Monofilaments using thermoplastic elastomers are known to have excellent rubber elasticity, and woven and knitted fabrics using such monofilaments made of thermoplastic elastomer have excellent elasticity.
  • Development of medical materials such as supporters, sports materials such as trampolines, bedding materials such as beds, and seating materials such as office chairs / car seats is underway.
  • Patent Documents 1 to 3 propose that a woven or knitted fabric using a thermoplastic elastomer can be suitably used for an office chair or an automobile chair.
  • thermoplastic elastomer monofilament whose main component is polyester or polyether is known, but a monofilament composed of a conventional thermoplastic elastomer.
  • the knitted and knitted fabrics using the knitted fabric have a problem of lowering the elastic recovery rate at the time of repeated deformation, that is, the settling at the time of long-term use.
  • the woven and knitted fabric has excellent mechanical properties and elastic recovery properties at the time of repeated deformation.
  • Elastic monofilaments have been proposed for the purpose of obtaining (see Patent Documents 2 and 3).
  • Patent Document 2 discloses a sheath (core-sheath structure) / core (core-sheath structure) in which the core material occupies 50% or more of the area ratio of the core portion of the fiber cross-sectional area, using a two-component polyester elastomer as a main raw material.
  • the core component has a melting point of 150 ° C. or more and less than 200 ° C.
  • the sheath component has a melting point lower than the melting point of the core component by 20 ° C. or more and less than 50 ° C.
  • Patent Document 3 discloses that a single-component monofilament using a polymer composed of a specific component and having a creep rate of 5% or less at 80 ° C. for 24 hours under a 15% elongation stress at room temperature is caused by repeated deformation. Proposed as a monofilament with little change in properties.
  • the elastic monofilament it is considered necessary for the elastic monofilament to exhibit high rubber elasticity, and a single component monofilament made of a thermoplastic elastomer (see Patent Document 3) and a core-sheath composite monofilament made of two kinds of polymers.
  • a single component monofilament made of a thermoplastic elastomer see Patent Document 3
  • a core-sheath composite monofilament made of two kinds of polymers in any of (see Patent Document 2), it is assumed that the monofilament (both the core and the sheath in the case of the core-sheath composite monofilament) is made of a thermoplastic elastomer and exhibits as high rubber elasticity as possible. .
  • an object of the present invention is to provide an elastic monofilament that is excellent in anti-sagging resistance during actual use of an elastic sheet or the like.
  • the present inventors have repeated the monofilament tension direction in order to improve the sag resistance of the woven or knitted fabric.
  • the fatigue resistance against deformation has been improved, but this alone is not sufficient, and it is necessary to improve the fatigue resistance against repeated deformation in the monofilament bending direction.
  • transformation was examined, it discovered that the settling resistance of a woven or knitted fabric could be improved significantly by adopting the following structure.
  • the elastic monofilament of the present invention has a core-sheath composite structure having a diameter of 0.1 to 1.0 mm and a core component ratio of 2 to 40% by volume, and the core component is thermoplastic in the polymer. It is a thermoplastic polyester having a polyester unit of 95 to 100% by mass, a sheath component is a copolymer thermoplastic elastomer having a hard segment and a soft segment, and has a tensile strength of 0.3 to 3.0 cN / dtex. It is a characteristic elastic monofilament.
  • the intrinsic viscosity (IV) of the thermoplastic polyester used for the core component is 0.7 or more.
  • the hard segment includes an aromatic polyester unit as a main structural unit
  • the soft segment includes an aliphatic polyether unit and / or an aliphatic polyester unit as a main structural unit.
  • the aromatic polyester unit is a polybutylene terephthalate unit
  • the aliphatic polyether unit and / or the aliphatic polyester unit is a poly (tetramethylene oxide) glycol unit.
  • the ratio of the hard segment to the soft segment is 35:65 to 75:25 (mass ratio).
  • the bending hardness of the elastic monofilament of the present invention is 2.0 to 10 cN, and after heat treatment at 160 ° C. under a constant length for 3 minutes, 0.1 cN
  • the dimensional change rate when held for 12 hours under the / dtex tension is 0 to 5%.
  • an elastic monofilament having excellent fatigue resistance in the bending direction can be obtained.
  • the elastic monofilament of the present invention is different from the conventional elastic monofilament using only a thermoplastic elastomer because the thermoplastic polyester unit of 95 to 100% by mass of the thermoplastic polyester unit in the polymer is arranged in the core component.
  • the core component bears a part of the stress that the filament receives when the monofilament is stretched and / or bent. For this reason, even when the elastic monofilament of the present invention is stretched and / or bent, the deformation and plastic deformation of the thermoplastic elastomer component are easily suppressed.
  • the elastic monofilament of the present invention is difficult to recover even when subjected to elongation and / or bending deformation, it has been used for woven and knitted fabrics represented by trampolines, supporters, beds, car seats, office chairs and the like. However, the set resistance of the woven or knitted fabric can be remarkably improved.
  • FIG. 1 is a schematic side view for explaining a method for measuring the amount of settling in the present invention.
  • the elastic monofilament of the present invention has a core-sheath composite structure having a diameter of 0.1 to 1.0 mm and a core component ratio of 2 to 40% by volume, and the core component is thermoplastic in the polymer.
  • the elastic monofilament of the present invention combines a thermoplastic elastomer having rubber elasticity and a thermoplastic polyester resin such as a specific polyethylene terephthalate that does not have rubber elasticity in a specific configuration, thereby being resistant to repeated deformation in the bending direction.
  • the fatigue resistance is improved, and the elasticity of the monofilament tensile direction, which was assumed not to be reduced by the prior art, is reduced. Is found to be obtained.
  • the usage mode of the elastic monofilament of the present invention a case where an elastic fabric using an elastic monofilament as a weft and a polyethylene terephthalate monofilament as a warp is used for an office chair or a car seat will be described as an example.
  • the load at the time of sitting is applied to the elastic fabric from a substantially vertical direction.
  • the elastic monofilament whose movement is suppressed by the warp with respect to the load from the vertical direction to the elastic fabric is greatly deformed in the bending direction.
  • the elastic monofilament is compressed inside the bent portion, and the elastic monofilament is greatly expanded outside the bent portion.
  • the core component is constant.
  • the stretch deformation and plastic deformation of the thermoplastic elastomer component on the outer side of the bend are suppressed, and the excellent stretch-back property of the thermoplastic elastomer disposed on the sheath component is unlikely to be impaired.
  • a thermoplastic polyester such as polyethylene terephthalate
  • creep elongation when exposed to bending deformation for a long time is also suppressed. For this reason, it is thought that the woven or knitted fabric using the elastic monofilament of the present invention is difficult to stick over a long period of time and can continue to exhibit excellent elasticity.
  • the ratio of the core component is in the range of 2 to 40% by volume from the viewpoint of achieving both improved heat-resistant creep characteristics and elasticity in the bending direction.
  • the ratio of the core component is less than 2% by volume, it is not possible to suppress over-extension on the outside of the bend due to the above-described core component, and when the core component exceeds 40% by volume, the thermoplastic elastomer component Therefore, the target elasticity is hardly exhibited.
  • the core component is preferably in the range of 3 to 20% by volume, more preferably in the range of 3 to 13% by volume.
  • an irregular cross-sectional shape such as an ellipse, a square, a polygon, and a multi-leaf cross-section can be taken in addition to the round cross-section.
  • the diameter of the elastic monofilament of the present invention is 1.0 mm or less, preferably 0.7 mm or less. If the diameter is too large, the absolute amount of elongation outside the bending at the time of bending deformation increases and plastic deformation is likely to occur, and it becomes easy to cause settling when a woven or knitted fabric is formed. In order for the elastic monofilament to exhibit its function, there is essentially no lower limit of the diameter. However, if the diameter is too small, the core-sheath composite form becomes difficult, so the diameter is 0.1 mm or more.
  • the average diameter of the cross section of the elastic monofilament is L1
  • the average diameter of the cross section of the core component is L2
  • the sheath component along an arbitrary line segment t drawn from the center of gravity of the cross section of the core component to the outer periphery of the elastic monofilament is Lt
  • Lt corresponding to an arbitrary line segment t over the entire outer periphery of the elastic monofilament satisfies the following relationship. ⁇ 15 (%) ⁇ (Lt ⁇ LT) ⁇ 100 / LT ⁇ 15 (%)
  • LT (L1 ⁇ L2) / 2.
  • the average diameters L1 and L2 of the cross section represent the diameter of the area equivalent circle. If the above relationship is satisfied, the thickness of the sheath component maintains a constant thickness over the entire circumference of the elastic monofilament, so that there is no region where the amount of the sheath component is small, or there is no extremely large portion. Therefore, problems such as excessive elongation during bending deformation and tearing of the sheath component and non-uniform elastic recovery are unlikely to occur.
  • thermoplastic polyester examples include polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and aromatic polyester. From the viewpoint of versatility, heat resistance, and high rigidity. Polyethylene terephthalate is preferably used.
  • the intrinsic viscosity (IV) of the thermoplastic polyester used for the core component is preferably 0.7 or more, more preferably 1.0 or more. If the intrinsic viscosity (IV) is too low, the load per molecular chain when the core component is subjected to stress increases, and the resulting elastic monofilament tends to become loose. From the viewpoints of improving the creep properties, mechanical properties, and deformation control properties of the resulting elastic monofilament, the intrinsic viscosity has no inherent upper limit, but the intrinsic viscosity (IV) is 1.4 or less from the viewpoint of melt processability. It is preferable that
  • the thermoplastic polyester used for the core component is a polymer having a thermoplastic polyester unit of 95 to 100% by mass.
  • the thermoplastic polyester unit means a component other than a component having a polyester skeleton and corresponding to a thermoplastic elastomer described later.
  • a copolymer of a component copolymerizable with the thermoplastic polyester or another thermoplastic polymer that can be blended can be used as long as it is less than 5% by mass.
  • thermoplastic polyester unit when the thermoplastic polyester unit is less than 95% by mass, the mechanical properties of the thermoplastic polyester are impaired by copolymerization or blending, and as a result, an elastic monofilament that is prone to settling when formed into a woven or knitted fabric.
  • copolymerizable components include aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and azelaic acid, diol compounds such as diethylene glycol and 1,4-butanediol, Examples thereof include polyfunctional compounds, 5-sulfoisophthalic acid metal salts, and phosphorus-containing compounds.
  • the thermoplastic polyester constituting the core component is so-called 100% by mass consisting of thermoplastic polyester units. A homopolymer is preferred.
  • thermoplastic polyester used in the core component is a matting agent or pigment such as titanium oxide, calcium carbonate, kaolin, clay, etc., as long as the effects of the present invention are not impaired, specifically, 5% by mass or less.
  • Additives such as dyes, lubricants, antioxidants, heat resistance agents, heat resistance agents, light resistance agents, ultraviolet absorbers, antistatic agents and flame retardants can be included.
  • titanium oxide is contained in an amount of 0.01 to 1% by mass from the viewpoint of improving the durability of the elastic monofilament, although the glossiness of the resulting elastic monofilament is suppressed and a high-class feeling is produced and the detailed mechanism is unknown. It is preferable to do.
  • the thermoplastic elastomer constituting the sheath component of the elastic monofilament of the present invention is a copolymer thermoplastic elastomer having a hard segment and a soft segment such as a styrene elastomer, a polyester elastomer, a polyurethane elastomer, and a polyamide elastomer. is required.
  • the reason is that blend-type thermoplastic elastomers represented by olefin elastomers are insufficient in heat resistance, and have concerns about interfacial peeling of sea-island components, recyclability, and the like.
  • the thermoplastic elastomer used in the present invention has a melting point of 150 ° C. or higher, particularly preferably 180 ° C. or higher, from the viewpoints of heat resistance and mechanical properties.
  • the hard segment is mainly composed of aromatic dicarboxylic acid or an ester-forming derivative thereof and an aromatic polyester unit formed from a diol or an ester-forming derivative thereof. Is a preferred embodiment.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4′- Examples thereof include dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate.
  • the aromatic dicarboxylic acid is mainly used. If necessary, a part of the aromatic dicarboxylic acid may be used as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4′-dicyclohexyldicarboxylic acid. It can also be substituted with an alicyclic dicarboxylic acid such as an acid, or an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Furthermore, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonates and acid halides can of course be used equally.
  • diols having a molecular weight of 400 or less such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.
  • Aliphatic diols such as 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecane dimethanol and the like, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p -Hydroxy) diphenylpropane, 2,2'-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2- Hydroxyethoxy) phenyl
  • Aromatic diols such as cyclohexane, 4,4′-dihydroxy-p-terphenyl, and 4,4′-dihydroxy-p-quarterphenyl are preferably used, such diols being ester-forming derivatives such as acetyl It can also be used in the form of body or alkali metal salt.
  • dicarboxylic acids can be used in combination of two or more.
  • a preferred example of such a hard segment is a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol.
  • a hard segment composed of a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and a polybutylene isophthalate unit derived from isophthalic acid and / or dimethyl isophthalate and 1,4-butanediol is also preferably used. It is done.
  • the soft segment of the polyester elastomer used in the present invention is mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit.
  • Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide) Examples thereof include ethylene oxide addition polymers of glycol, and copolymer glycols of ethylene oxide and tetrahydrofuran.
  • polyesters examples include poly ( ⁇ -caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
  • the elastic properties of the resulting polyester elastomers indicate that poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adducts, ethylene oxide and tetrahydrofuran
  • copolymer glycol, poly ( ⁇ -caprolactone), polybutylene adipate, polyethylene adipate and the like is preferred, and among these, poly (tetramethylene oxide) glycol is a preferred embodiment.
  • the number average molecular weight of these soft segments is preferably about 300 to 6000 in the copolymerized state.
  • the elastic monofilament of the present invention preferably has a ratio of the hard segment to the soft segment, that is, a copolymerization ratio in the range of 35:65 to 75:25 (mass ratio).
  • the third component is used outside the sheath component made of thermoplastic elastomer or thermoplastic for the purpose of imparting thermal adhesiveness, etc., as long as the effects of the present invention are not impaired. It can arrange
  • the thermoplastic elastomer constituting the sheath component preferably has a Shore D hardness of 30 to 65.
  • Shore D hardness By setting the Shore D hardness in the above range, it is possible to suppress excessive elongation during bending deformation while controlling the amount of hard segments that are easily plastically deformed.
  • thermoplastic elastomer used for the sheath component is a matting agent or pigment such as titanium oxide, calcium carbonate, kaolin, or clay as long as the effect of the present invention is not impaired, specifically, 5% by mass or less.
  • Dyes, lubricants, antioxidants, heat resistance agents, heat resistance agents, light resistance agents, ultraviolet absorbers, antistatic agents and flame retardants are examples of matting agent or pigment such as titanium oxide, calcium carbonate, kaolin, or clay as long as the effect of the present invention is not impaired, specifically, 5% by mass or less.
  • Dyes lubricants, antioxidants, heat resistance agents, heat resistance agents, light resistance agents, ultraviolet absorbers, antistatic agents and flame retardants.
  • the elastic monofilament of the present invention has a tensile strength in the range of 0.3 to 3.0 cN / dtex, preferably 0.3 to 2.94 cN / dtex, more preferably 0.5 to 2.5 cN / dtex. dtex.
  • a tensile strength in the range of 0.3 to 3.0 cN / dtex, preferably 0.3 to 2.94 cN / dtex, more preferably 0.5 to 2.5 cN / dtex. dtex.
  • the elastic monofilament of the present invention preferably has a bending hardness of 2.0 to 10.0 cN, and a more preferable range is 2.5 to 8.0 cN. If the bending hardness is too low, there is a concern that the elastic monofilament will extend excessively on the outside of the bending at the time of bending. On the other hand, if the bending hardness is too large, it is difficult to bend and deform and the target elasticity may not be exhibited. Occurs. From this point of view, the bending hardness is preferably in the above range in order to obtain a monofilament having excellent durability and elasticity.
  • the elastic monofilament of the present invention has a dimensional change rate of 0 to 5% when heat-treated for 3 minutes at 160 ° C. under a constant length and then held for 12 hours under a tension of 0.1 cN / dtex. preferable.
  • the heat treatment for 3 minutes at a temperature of 160 ° C. assumes that the elastic monofilament is woven or knitted and is subjected to heat setting or the like. After heat treatment at a constant length of 160 ° C.
  • the elastic monofilament of the present invention preferably has a boiling water shrinkage of 3 to 10%.
  • the elastic monofilament of the present invention can be used alone, or a plurality of the elastic monofilaments of the present invention can be used, or the elastic monofilament of the present invention and a filament of another material can be used together.
  • the elastic monofilament of the present invention can be produced by a core-sheath composite spinning method using a conventionally known co-extrusion equipment, it can be produced with high productivity and at low cost.
  • thermoplastic polyester polymer constituting the core component of the core-sheath composite monofilament and the thermoplastic elastomer constituting the sheath component are melted by separate extruders, each is measured with a gear pump and allowed to flow into the composite pack.
  • Two types of polymer, core component and sheath component, flowed into the composite pack are filtered through a metal non-woven filter or metal mesh in the pack and then introduced into the composite base, and the core component is surrounded by the sheath component. It is spun at.
  • the polymer used for spinning is previously set to a moisture content of less than 200 ppm using a vacuum dryer or the like. Is a preferred embodiment.
  • the moisture content satisfies the above range, not only is the composite abnormality difficult to occur, but an elastic monofilament having excellent durability can be easily obtained.
  • a master chip containing a large amount of desired pigments, light resistance agents, antibacterial agents, etc. is prepared, and thermoplasticity is obtained.
  • a polyester resin and / or a thermoplastic elastomer resin can be blended in a necessary amount to be spun.
  • thermoplastic elastomer resin for the purpose of reducing deterioration due to ultraviolet rays during actual use.
  • a light-resistant additive-added master chip for imparting a light-resistant agent to the elastic monofilament of the present invention “Hytrel” (registered trademark) 21UV manufactured by Toray DuPont can be exemplified.
  • the molten monofilament spun from the composite die is allowed to pass through a heating cylinder and / or a heat insulating cylinder arranged immediately below the composite die from the viewpoint of removing the distortion of the molecular structure generated in the die hole. is there.
  • the length of the heating tube and / or the heat insulating tube is preferably in the range of 10 to 150 mm from the viewpoint of reducing fineness unevenness in the longitudinal direction of the obtained elastic monofilament.
  • the molten monofilament that has passed through the heating tube and / or the heat insulating tube is cooled in a cooling bath using water or polyethylene glycol as a solvent, and then taken up by a take-up roll that rotates at a desired surface speed.
  • the temperature of the cooling bath can be changed while confirming the roundness and fineness unevenness of the obtained elastic monofilament, but the cooling temperature for obtaining the elastic monofilament of the present invention is exemplified by the range of 20 to 80 ° C. can do.
  • the take-up speed may be a speed at which the cooling and solidification of the molten monofilament is completed in the cooling bath, and in order to set the fiber structure of the undrawn yarn within a suitable range for obtaining the elastic monofilament of the present invention.
  • a range of 5 to 50 m / min is preferable.
  • the unstretched monofilament that has been taken up by the take-up roll is once taken up or is used for the drawing step without being taken up once.
  • the number of drawing steps in the drawing step is preferably a multistage drawing method having two or more steps.
  • steam, and a dry heat drawing machine can be used.
  • the stretching temperature of the second stage may be set to the melting point ⁇ 50 ° C. to the melting point ⁇ 10 ° C. of the thermoplastic elastomer disposed in the sheath component. This is a preferred embodiment.
  • the stretching temperature of the second stage in the above range where the molecular mobility of the thermoplastic elastomer is extremely high, excessive orientation of the thermoplastic elastomer in the stretching process is suppressed, and excellent elasticity is obtained even when deformed in the bending direction. It is possible to obtain an elastic monofilament having the same.
  • the stretched elastic monofilament is then subjected to relaxation heat treatment.
  • the relaxation magnification is preferably in the range of 0.99 to 0.85 from the viewpoint of suppressing yarn swaying and ensuring elastic recovery when subjected to repeated bending deformation.
  • the relaxation heat treatment temperature is preferably set to the melting point of the thermoplastic elastomer arranged in the sheath component from ⁇ 50 ° C. to the melting point of ⁇ 10 ° C., and more preferably, the melting point of the thermoplastic elastomer from ⁇ 40 ° C. to the melting point of ⁇ 10 ° C. Can be illustrated.
  • the relaxation heat treatment temperature within the above range, the thermal fusion between the elastic monofilaments is suppressed in the heat treatment process, and the excessive orientation generated in the sheath component is relaxed in the stretching process, thereby deforming in the bending direction. In this case, a monofilament having excellent elasticity can be obtained.
  • the total draw ratio obtained by multiplying the draw ratio by the relaxation ratio is set to less than 4.0 times.
  • less than 3.8 times can be exemplified.
  • the elastic monofilament after the relaxation treatment is wound by a winder, and at this time, the winding tension is preferably in the range of 0.10 cN / dtex or less.
  • the winding tension is preferably 0.02 cN / dtex or more.
  • the elastic monofilament of the present invention can be obtained.
  • the elastic monofilament of the present invention is particularly excellent in bending direction settling resistance, elasticity and creep properties after application of high temperature, so it is a marine product, building material, safety material, clothing material, civil engineering material, agricultural material, vehicle material.
  • it can be suitably used for elastic woven knitted structures such as car seats and office chairs that are easily deformed in the bending direction during actual use.
  • the melting point was defined as the temperature at which the extreme value of the melting endotherm curve obtained by measuring 10 mg of a sample at a heating rate of 10 ° C./min using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer.
  • E 0 the elongation when a load of 0.1 cN / dtex was applied
  • E 12 elongation when left for 12 hours in a state where a load of 0.1 cN / dtex was applied
  • E 12 -E 0 was defined as a dimensional change rate after heat treatment.
  • the number of measurements n was set to 5, and the average value thereof was adopted.
  • the treated sample (elastic monofilament) was removed from the bending wear characteristic tester and immediately suspended in a state where a load 2 of 6 g / mm 2 was applied as shown in FIG.
  • the distance A (mm) of the perpendicular drawn from the line a connecting the markings toward the maximum deformation point was determined, and the average value of the five measurements was used as the amount of stickiness.
  • copolymer thermoplastic elastomer (A-1) 51.9 parts by mass of terephthalic acid, 39.7 parts by mass of 1,4-butanediol and 47.6 parts by mass of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.04 parts by mass of titanium tetrabutoxide and mono -0.02 part by mass of n-butyl-monohydroxytin oxide was charged in a reaction vessel equipped with a helical ribbon type stirring blade, gradually heated from a temperature of 190 ° C and heated to a temperature of 225 ° C in 3 hours, The esterification reaction was carried out while allowing the reaction water to flow out of the system.
  • copolymer thermoplastic elastomer (A-2) 32.9 parts by mass of terephthalic acid, 9.6 parts by mass of isophthalic acid, 40.3 parts by mass of 1,4-butanediol and 46.7 parts by mass of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400 were added to titanium tetra Both 0.04 parts by weight of butoxide and 0.02 parts by weight of mono-n-butyl-monohydroxytin oxide were charged into a reaction vessel equipped with a helical ribbon type stirring blade and heated gradually from a temperature of 190 ° C. in 3 hours. The esterification reaction was carried out while heating to a temperature of 225 ° C.
  • Examples 1 to 6, Comparative Example 2, Comparative Example 4 As a polymer for the core component, a polyethylene terephthalate polymer (T manufactured by Toray Industries, Inc.) having a melting point of 257 ° C. dried to a moisture content of less than 100 ppm, an intrinsic viscosity of 1.21, and containing 0.1% by mass of titanium oxide. -701T) and a copolymer thermoplastic elastomer (A-1) dried to a moisture content of less than 100 ppm as the sheath component polymer, and a setting temperature of ⁇ 30 mm extruder of 295 ° C.
  • T polyethylene terephthalate polymer
  • A-1 copolymer thermoplastic elastomer
  • each molten polymer was filtered through a 200-mesh wire mesh, and then discharged from a core-sheath composite die having a hole diameter of 1.5 mm and 10 holes.
  • the discharged filament is passed through a heat insulating cylinder having a length of 30 mm attached immediately below the base, and then passed through a cooling water bath having a temperature of 25 ° C.
  • the obtained unstretched monofilament was stretched in the first stage at a stretch ratio described in Table 1 using a hot water tank adjusted to a temperature of 90 ° C. without being wound up, and then listed in Table 1. Using a dry heat stretching tank adjusted to the temperature, the second stage stretching was performed at the magnification described in Table 1.
  • the monofilament after drawing is subjected to relaxation heat treatment at a magnification shown in Table 1 using a dry heat bath adjusted to the temperature shown in Table 1, and the wound elastic monofilament is taken up with the winding tension shown in Table 1. Obtained.
  • the properties of the obtained monofilament were as shown in Tables 1 and 2.
  • Comparative Example 2 since the ratio of the core component was small, it was not possible to suppress overextension on the outer side of the bend, and the amount of settling was large.
  • the tensile strength exceeded 3.05 cN / dtex, and the elasticity in the bending direction was impaired.
  • Example 7 The same procedure as in Example 1 was performed except that 97% by mass of the copolymer-based thermoplastic elastomer (A-1) and 3% by mass of “Hytrel” (registered trademark) 21UV were used as the polymer for the sheath component. .
  • the properties of the obtained monofilament were as shown in Table 1.
  • Example 8 Comparative Example 3, Comparative Example 5
  • Example 1 except that a polyethylene terephthalate polymer (T-301T manufactured by Toray Industries, Inc.) containing a melting point of 257 ° C., an intrinsic viscosity of 0.71, and 0.1% by mass of titanium oxide was used as the core component polymer. It was done in the same way. The properties of the obtained monofilament were as shown in Tables 1 and 2. In Comparative Example 3 and Comparative Example 5, the tensile strength exceeded 3.05 cN / dtex, and the elasticity in the bending direction was impaired.
  • T-301T manufactured by Toray Industries, Inc.
  • Copolymer thermoplastic elastomer (A-1) dried to a moisture content of less than 150 ppm as the core component polymer, and copolymer thermoplastic to the moisture content of less than 150 ppm as the sheath component polymer
  • the elastomer (A-2) was melted with a ⁇ 30 mm extruder having a set temperature of 250 ° C. and a ⁇ 40 mm extruder having a set temperature of 215 ° C., respectively, and then heated to 250 ° C. using a gear pump kept at a temperature of 245 ° C. and 250 ° C., respectively.
  • the same procedure as in Example 1 was carried out except that it was introduced into a composite spinning pack kept at a temperature.
  • the properties of the obtained elastic monofilament were as shown in Table 2.
  • the elastic monofilament of the present invention was excellent in the bending-direction set resistance, elasticity, and creep properties after application of high temperature.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Multicomponent Fibers (AREA)
  • Woven Fabrics (AREA)

Abstract

L'invention concerne un monofilament élastique présentant une résistance à la fatigue et une élasticité exceptionnelles, notamment dans une direction de courbure, et des propriétés de fluage exceptionnelles après qu'une température élevée est appliquée. La monofilament élastique a une structure conjuguée cœur-gaine ayant un diamètre de 0,1 à 1,0 mm et un rapport de composant de cœur de 2 à 40 % en volume.Dans le monofilament élastique, le composant de cœur est un polyester thermoplastique ayant 95 à 100 % en masse d'unités de polyester thermoplastique dans le polymère, le composant de gaine étant un élastomère thermoplastique de système de copolymérisation ayant un segment dur et un segment souple, et la résistance à la traction du monofilament élastique étant de 0,3 à 3,0 cN/dtex.
PCT/JP2014/070923 2013-08-09 2014-08-07 Monofilament élastique WO2015020163A1 (fr)

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EP14834881.6A EP3031960B1 (fr) 2013-08-09 2014-08-07 Monofilament élastique
MX2016001715A MX2016001715A (es) 2013-08-09 2014-08-07 Monofilamento elastico.
US14/910,895 US20160194788A1 (en) 2013-08-09 2014-08-07 Elastic monofilament
CN201480055594.4A CN105765118B (zh) 2013-08-09 2014-08-07 弹性单丝
CA2920777A CA2920777C (fr) 2013-08-09 2014-08-07 Monofilament elastique
KR1020167006010A KR102168814B1 (ko) 2013-08-09 2014-08-07 탄성 모노필라멘트

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WO2018181699A1 (fr) * 2017-03-31 2018-10-04 東レ株式会社 Monofilament élastique et articles tricotés tissés

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JP6745211B2 (ja) * 2016-12-28 2020-08-26 株式会社ジェイエスピー シート芯材
EP3697949A4 (fr) * 2017-10-18 2021-07-14 University of Central Florida Research Foundation, Inc. Fibres ayant un noyau électriquement conducteur et un revêtement changeant de couleur
KR20220112792A (ko) * 2019-12-23 2022-08-11 도레이 카부시키가이샤 분리막 및 그 제조 방법

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CN105220254A (zh) * 2015-10-20 2016-01-06 江苏金麟户外用品有限公司 一种改性跳布的制备方法
WO2018181699A1 (fr) * 2017-03-31 2018-10-04 東レ株式会社 Monofilament élastique et articles tricotés tissés

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JP2015057522A (ja) 2015-03-26
US20160194788A1 (en) 2016-07-07
JP6489773B2 (ja) 2019-03-27
EP3031960A4 (fr) 2017-03-22
CN105765118A (zh) 2016-07-13
EP3031960A1 (fr) 2016-06-15
CA2920777C (fr) 2021-08-17
KR20160040292A (ko) 2016-04-12
CN105765118B (zh) 2021-03-26
KR102168814B1 (ko) 2020-10-22
CA2920777A1 (fr) 2015-02-12
EP3031960B1 (fr) 2020-06-10
MX2016001715A (es) 2016-07-26

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