EP3031960B1 - Monofilament élastique - Google Patents

Monofilament élastique Download PDF

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Publication number
EP3031960B1
EP3031960B1 EP14834881.6A EP14834881A EP3031960B1 EP 3031960 B1 EP3031960 B1 EP 3031960B1 EP 14834881 A EP14834881 A EP 14834881A EP 3031960 B1 EP3031960 B1 EP 3031960B1
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Prior art keywords
monofilament
elastic
elastic monofilament
unit
ratio
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German (de)
English (en)
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EP3031960A4 (fr
EP3031960A1 (fr
Inventor
Nobuaki Tanaka
Hiroshi Tsuchikura
Kota NAKAMURA
Hidetoshi Sakai
Takuya RYOMOTO
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Toray Industries Inc
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Toray Industries Inc
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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 relates to an elastic monofilament which is excellent in fatigue resistance to repeated deformation in a bending direction, and is suitable for use in various industrial uses such as marine materials, construction materials, safety materials, clothing materials, civil engineering materials, agricultural materials, vehicle materials and sport materials, particularly, suitable for use in woven or knitted structures having elasticity.
  • a monofilament made of a thermoplastic elastomer is known to have excellent rubber elasticity. Since a woven or knitted fabric made from such a monofilament made of the thermoplastic elastomer has excellent elasticity, development for use in clothing materials such as stockings, medical materials such as supporters, sport materials such as trampolines, bedding materials such as beds, and sitting materials such as office chairs/car seats is being progressed.
  • Patent Documents 1 to 3 propose that a woven or knitted fabric made from the thermoplastic elastomer can be suitably used in application to office chairs and automobile chairs.
  • a monofilament made of a thermoplastic elastomer containing, as its main component, a polyester or a polyether is known.
  • a woven or knitted fabric made from the conventional monofilament made of the thermoplastic elastomer has a problem of reduction in elastic recovery after repeated deformation, that is, so-called permanent set in fatigue at the time of long-term use.
  • an elastic monofilament is proposed (see Patent Documents 2 and 3).
  • Patent Document 2 describes that an effect of reducing change in the knitted or woven structure after repeated deformation of a fabric and of excellent long-term durability is obtained by using an elastic composite monofilament in which a two-component polyester-based elastomer is used as a main raw material, the monofilament has a sheath (sheath of core-sheath structure)-core (core of core-sheath structure) shape having an area ratio of a core part in a fiber cross-sectional area of 50% or more, the melting point of a core part component is 150°C or higher and lower than 200°C, and the melting point of a sheath part component is lower than the melting point of the core part component by 20°C or more and less than 50°C, and partially melting or fusing a low melting point component used in a sheath side to form a fusion point at an intersection part of a knitted or woven texture, thereby improving a force of constraint.
  • a sheath sheath of core
  • Patent Document 3 a single component monofilament made of a polymer of particular components, and having a creep ratio at 80°C for 24 hours under a 15% extension stress at room temperature of 5% or less is proposed as a monofilament having reduced change in property due to repeated deformation.
  • the elastic monofilament is required to exhibit high rubber elasticity, and in both of the single component monofilament made of the thermoplastic elastomer (see Patent Document 3) and the core-sheath composite monofilament made of two polymers (see Patent Document 2), the monofilament (both of core and sheath in the case of core-sheath composite monofilament) is, as a premise, made of the thermoplastic elastomer, and exhibits rubber elasticity which is as high as possible.
  • Patent Document 1 Japanese Translation of PCT International Application Publication JP-T-1997-507782 ; Patent Document 2: 1999-152625 and Patent Document 3: 1999-172532 .
  • JP-A-2004-176228 concerns a core-sheath composite monofilament in which the sheath component is a polyester-based elastomer and the core component is a polytrimethylene terephthalate.
  • an object of the present invention is to provide an elastic monofilament excellent in resistance to permanent set in fatigue at practical use of an elastic seat.
  • the present inventors studied a cause for failure to obtain desired resistance to permanent set in fatigue in a woven or knitted fabric obtained from the conventional monofilament. Then, they searched for a configuration for improving fatigue resistance to repeated deformation in a bending direction of a monofilament based on an idea that fatigue resistance to repeated deformation in a tensile direction of the monofilament is improved in the conventional techniques for improving resistance to permanent set in fatigue of the woven or knitted fabric, but this is insufficient, and improvement in fatigue resistance to repeated deformation in a bending direction of the monofilament would be necessary. As a result, they found out that by adopting the following configuration, resistance to permanent set in fatigue of the woven or knitted fabric can be considerably improved as compared to before.
  • the elastic monofilament of the present invention is an elastic monofilament having a core-sheath composite structure, wherein a ratio of a core component is 2 to 40% by volume, the core component is a thermoplastic polyethylene terephthalate having, in the polymer, 95 to 100% by mass of a polyethylene terephthalate unit, and a sheath component is a copolymeric thermoplastic elastomer having a hard segment and a soft segment, and wherein the monofilament has a diameter of 0.1 to 1.0 mm, and a tensile strength of 0.3 to 3.0 cN/dtex.
  • the intrinsic viscosity (IV) of the thermoplastic polyethylene terephthalate used in the core component is 0.7 or higher.
  • the hard segment contains, as a main constituent unit, an aromatic polyester unit
  • the soft segment contains, as a main constituent unit, an aliphatic polyether unit and/or an aliphatic polyester 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.
  • a ratio of the hard segment to the soft segment is 35 : 65 to 75 : 25 (ratio by mass).
  • the elastic monofilament has a bending stiffness of 2.0 to 10 cN.
  • a rate of dimensional change is 0 to 5%.
  • the elastic monofilament excellent in fatigue resistance in a bending direction is obtained.
  • the elastic monofilament of the present invention has the core component containing a thermoplastic polyester having, in a polymer, 95 to 100% by mass of a thermoplastic polyester unit, namely a polyethylene terephthalate unit. Therefore, unlike the conventional elastic monofilament made only of the thermoplastic elastomer, the core component bears part of a stress which is applied to a filament when the monofilament is extended and/or bent. For this reason, in the elastic monofilament of the present invention, extension deformation and plastic deformation of the thermoplastic elastomer component are easily suppressed even when the monofilament is extended and/or bent.
  • the elastic monofilament of the present invention is difficult to be permanently set even when the monofilament undergoes extension and/or bending deformation, it also becomes possible to considerably improve resistance to permanent set in fatigue of a woven or knitted fabric typified by trampolines, supporters, beds, car seats, and office chairs, when the monofilament is used in the woven or knitted fabric.
  • Fig. 1 is a schematic side view for illustrating a method of measuring an amount of permanent set in fatigue in the present invention.
  • the elastic monofilament of the present invention is an elastic monofilament having a core-sheath composite structure, wherein a ratio of a core component is 2 to 40% by volume, the core component is a thermoplastic polyester, namely polyethylene terephthalate, having, in the polymer, 95 to 100% by mass of a polyethylene terephthalate unit, and a sheath component is a copolymeric thermoplastic elastomer having a hard segment and a soft segment, and wherein the monofilament has a diameter of 0.1 to 1.0 mm, and a tensile strength of 0.3 to 3.0 cN/dtex.
  • the core component is a thermoplastic polyester, namely polyethylene terephthalate, having, in the polymer, 95 to 100% by mass of a polyethylene terephthalate unit
  • a sheath component is a copolymeric thermoplastic elastomer having a hard segment and a soft segment
  • the elastic monofilament of the present invention improves fatigue resistance to repeated deformation in a bending direction by combining a thermoplastic elastomer having rubber elasticity with a thermoplastic polyester resin having no rubber elasticity, namely polyethylene terephthalate, in a particular constitution. It was found out that a remarkable effect regarding resistance to permanent set in fatigue is obtained while retaining elasticity in the bending direction by daringly reducing rubber elasticity in the tensile direction of the monofilament, which is not reduced as a premise in the conventional techniques.
  • an elastic woven fabric made from an elastic monofilament as a weft, and a polyethylene terephthalate monofilament as a warp is used in office chairs or car seats.
  • a load at the time of sitting is imparted to the elastic woven fabric from a substantially vertical direction.
  • the elastic monofilament movement of which due to a load on the elastic woven fabric in a vertical direction is suppressed by a warp, is greatly deformed in a bending direction.
  • microscopic attention is paid to a bent part of the elastic monofilament, the elastic monofilament is compressed inside the bent part, and the elastic monofilament is greatly extended outside the bent part.
  • the core component bears a prescribed stress.
  • extension and deformation of a thermoplastic elastomer component and plastic deformation outside a bent part are suppressed, and excellent stretch back property of the thermoplastic elastomer used in the sheath component is hardly deteriorated.
  • thermoplastic polyester such as polyethylene terephthalate
  • creep elongation when the monofilament is exposed to bending deformation for a long period of time is also suppressed.
  • a woven or knitted fabric made from the elastic monofilament of the present invention is hardly set permanently over a long term, and can continuously exhibit excellent elasticity.
  • a ratio of the core component is required to be within a range of 2 to 40% by volume.
  • the ratio of the core component is less than 2% by volume, excessive extension outside a bent part due to the core component described above cannot be suppressed.
  • the ratio of the core component exceeds 40% by volume, since an amount of the thermoplastic elastomer component is too small, objective elasticity is hardly exhibited.
  • the ratio of the core component is preferably within a range of 3 to 20% by volume, and more preferably within a range of 3 to 13% by volume.
  • the monofilament may have a modified cross-sectional shape such as elliptic, quadrilateral, polygonal and polyphyllous cross sections, in addition to a circular cross section.
  • the elastic monofilament of the present invention has a diameter of 1.0 mm or less, preferably 0.7 mm or less.
  • a diameter 1.0 mm or less, preferably 0.7 mm or less.
  • an absolute amount of extension outside a bent part at the time of bending deformation is increased to easily cause plastic deformation, and when the monofilament is made into a woven or knitted fabric, permanent set in fatigue is easily caused.
  • the diameter is 0.1 mm or more since it becomes difficult to maintain the shape of a core-sheath composite form when the diameter is too small.
  • Average diameters L1 and L2 of cross sections each represent a diameter of an area equivalent circle.
  • thermoplastic polyester examples include polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and aromatic polyesters. From the viewpoint of versatility, heat resistance and high stiffness, polyethylene terephthalate is selected in the present invention as the core component.
  • the intrinsic viscosity (IV) of the thermoplastic polyester used in the core component is preferably 0.7 or higher, and more preferably 1.0 or higher.
  • the intrinsic viscosity (IV) is too low, since a load per molecular chain when the core component bears a stress becomes great, the resulting elastic monofilament tends to be permanently set. From the viewpoint of improvement in creep property of the resulting elastic monofilament, improvement in mechanical properties of the monofilament, and deformation controllability when the monofilament is bent, the intrinsic viscosity originally has no upper limit. However, it is preferable that the intrinsic viscosity (IV) is 1.4 or lower from the viewpoint of melting processability.
  • the thermoplastic polyester used in the core component is a polymer in which the thermoplastic polyester unit accounts for 95 to 100% by mass.
  • the thermoplastic polyester unit refers to components having a polyester skeleton other than components corresponding to the thermoplastic elastomer described later.
  • a copolymer with a component copolymerizable with the thermoplastic polyester or other thermoplastic polymers that can be blended with the thermoplastic polyester can be used, as far as the amount thereof is less than 5% by mass.
  • thermoplastic polyester unit when the amount of the thermoplastic polyester unit is less than 95% by mass, since mechanical properties of the thermoplastic polyester are deteriorated due to copolymerization or blending, this consequently leads to an elastic monofilament which easily causes permanent set in fatigue when the monofilament is made into a woven or knitted fabric.
  • the copolymerizable component examples 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, polyfunctional compounds, 5-sulfoisophthalic acid metal salts, and phosphorus-containing compounds.
  • the thermoplastic polyester constituting the core component is a so-called homopolymer, which is composed of substantially 100% by mass of the thermoplastic polyester unit.
  • the thermoplastic polyester used in the core component can contain additives such as matting agents such as titanium oxide, calcium carbonate, kaolin and clay, pigments, dyes, lubricants, antioxidants, heat-resistant agents, steaming-resistant agents, light-resistant agents, ultraviolet absorbing agents, antistatic agents and flame retardants, as far as the amount thereof is within a range in which the effect of the present invention is not impaired, specifically, the amount is 5% by mass or less.
  • the amount of titanium oxide is 0.01 to 1% by mass.
  • thermoplastic elastomer constituting the sheath component of the elastic monofilament of the present invention is required to be a copolymeric thermoplastic elastomer having a hard segment and a soft segment, such as styrene-based elastomers, polyester-based elastomers, polyurethane-based elastomers, and polyamide-based elastomers.
  • the reason therefor is that in the case of a blend-type thermoplastic elastomer typified by olefin-based elastomers, heat resistance is deficient, and there are concerns about interface peeling of a sea-island component and recycle property.
  • the thermoplastic elastomer used in the present invention preferably has a melting point of 150°C or higher, particularly 180°C or higher.
  • a preferable aspect of the polyester-based elastomer used in the present invention is that a hard segment has, as a main constituent unit, an aromatic polyester unit mainly formed of an aromatic dicarboxylic acid or an ester forming derivative thereof, and a diol or an ester forming derivative thereof.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate.
  • the above aromatic dicarboxylic acid is mainly used. If necessary, part of this aromatic dicarboxylic acid can be replaced with an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid and 4,4'-dicyclohexyldicarboxylic acid, or an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Furthermore, an ester forming derivative of a dicarboxylic acid, for example, lower alkyl esters, aryl esters, carbonic acid esters and acid halides can be of course used equally.
  • an ester forming derivative of a dicarboxylic acid for example, lower alkyl esters, aryl esters, carbonic acid esters and acid halides can be of course used equally.
  • diols having a molecular weight of 400 or less for example, aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol, alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, and tricyclodecanedimethanol, and aromatic diols such as 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]cyclohexane, 4,4
  • a preferable 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.
  • the soft segment of the polyester-based elastomer used in the present invention has, as a main constituent unit, an aliphatic polyether unit and/or an aliphatic polyester unit.
  • the aliphatic polyether include poly(ethylene oxide)glycol, poly(propylene oxide)glycol, poly(tetramethylene oxide)glycol, poly(hexamethylene oxide)glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of poly(propylene oxide)glycol, and a copolymer glycol of ethylene oxide and tetrahydrofuran.
  • Examples of the aliphatic polyester include poly( ⁇ -caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
  • poly(tetramethylene oxide)glycol an ethylene oxide adduct of poly(propylene oxide)glycol, a copolymer glycol of ethylene oxide and tetrahydrofuran, poly( ⁇ -caprolactone), polybutylene adipate, and polyethylene adipate.
  • poly(tetramethylene oxide)glycol is a preferable constituent unit. It is preferable that the number average molecular weight of these soft segments is around 300 to 6000 in the copolymerized state.
  • the ratio of the hard segment to the soft segment is within a range of 35 : 65 to 75 : 25 (ratio by mass).
  • a third component can be provided outside the sheath component composed of the thermoplastic elastomer, or further inside the core component composed of the thermoplastic polyester, as far as the effect of the present invention is not impaired.
  • the thermoplastic elastomer constituting the sheath component preferably has a Shore D hardness within a range of 30 to 65. By setting the Shore D hardness within the above range, it becomes possible to suppress excessive extension at the time of bending deformation while controlling the amount of the hard segment which is easily deformed plastically.
  • the thermoplastic elastomer used in the sheath component can contain matting agents such as titanium oxide, calcium carbonate, kaolin, and clay, pigments, dyes, lubricants, antioxidants, heat-resistant agents, steaming-resistant agents, light-resistant agents, ultraviolet absorbing agents, antistatic agents and flame retardants, as far as the amount thereof is within a range in which the effect of the present invention is not impaired, specifically, the amount is 5% by mass or less.
  • matting agents such as titanium oxide, calcium carbonate, kaolin, and clay, pigments, dyes, lubricants, antioxidants, heat-resistant agents, steaming-resistant agents, light-resistant agents, ultraviolet absorbing agents, antistatic agents and flame retardants, as far as the amount thereof is within a range in which the effect of the present invention is not impaired, specifically, the amount is 5% by mass or less.
  • the tensile strength is within a range of 0.3 to 3.0 cN/dtex, preferably 0.3 to 2.94 cN/dtex, and further preferably 0.5 to 2.5 cN/dtex.
  • a higher-order processing step such as a weaving or knitting step, deterioration of the capability of passing through processes due to yarn breakage is hardly caused, and an elastic monofilament retaining sufficient elasticity is obtained.
  • the elastic monofilament of the present invention preferably has a bending stiffness of 2.0 to 10.0 cN.
  • a more preferable range of the bending stiffness 2.5 to 8.0 cN can be mentioned.
  • the bending stiffness is preferably within the above range in order to obtain a monofilament excellent in durability and excellent also in elasticity.
  • the rate of dimensional change when the monofilament is heat-treated for 3 minutes in a temperature condition of 160°C under fixed length, and then retained for 12 hours under a tension of 0.1 cN/dtex is preferably 0 to 5%.
  • heat treatment for 3 minutes at a temperature of 160°C assumes that the elastic monofilament is made into a woven or knitted fabric, and the fabric is subjected to heat setting.
  • the rate of dimensional change when the monofilament is heat-treated for 3 minutes at a temperature of 160°C under fixed length, and then retained for 12 hours under a tension of 0.1 cN/dtex is within the above range, even after the monofilament is made into an article such as a woven or knitted fabric, and the article is heat-set, it is not excessively extended, and can have excellent creep property.
  • a more preferable range of the rate of dimensional change when the monofilament is heat-treated for 3 minutes in a temperature condition of 160°C under fixed length, and then retained for 12 hours under a tension of 0.1 cN/dtex 0 to 3% can be mentioned.
  • the elastic monofilament of the present invention preferably has a boiling water shrinkage rate of 3 to 10%.
  • the elastic monofilament of the present invention can be of course used alone. Moreover, 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 other materials can be used as a composite yarn.
  • the elastic monofilament of the present invention can be manufactured by a core-sheath composite spinning method using a previously known coextrusion facility, it is possible to produce the elastic monofilament at high productivity and low cost.
  • thermoplastic polyester polymer constituting a core component and a thermoplastic elastomer constituting a sheath component of a core-sheath composite monofilament are melted in separate extruders, weighed with a gear pump and made to flow into a composite pack, respectively.
  • Two kinds of polymers of the core component and the sheath component which have been made to flow into the composite pack are filtered with a metal non-woven fabric filter or a metal mesh in the pack, introduced into a composite spinneret, and spun out in a form where the core component is surrounded with the sheath component.
  • a light-resistant agent is added to the thermoplastic elastomer resin for the purpose of reducing deterioration due to ultraviolet rays at the time of practical use.
  • a preferable light-resistant agent-added master chip for imparting the light-resistant agent to the elastic monofilament of the present invention include "Hytrel” (registered trademark) 21UV manufactured by Du Pont-Toray Co., Ltd.
  • the molten monofilament which has been spun out from a composite spinneret is passed through a heating cylinder and/or a heat-insulating cylinder arranged beneath the composite spinneret.
  • the length of the heating cylinder and/or the heat-insulating cylinder is preferably within a range of 10 to 150 mm, from the viewpoint of reduction in unevenness of fineness in a longitudinal direction of the resulting elastic monofilament.
  • the molten monofilament which has passed through the heating cylinder and/or the heat-insulating cylinder is cooled in a cooling bath containing water or polyethylene glycol as a solvent, and is taken up with a take-up roll which rotates at a desired surface speed.
  • the temperature of the cooling bath the temperature can be changed in consideration of circularity and unevenness of fineness of the resulting elastic monofilament.
  • the cooling temperature for obtaining the elastic monofilament of the present invention include a range of 20 to 80°C.
  • the take-up speed should be a speed by which cooling solidification of the molten monofilament in a cooling bath is completed.
  • a range of 5 to 50 m/min is preferable.
  • the unstretched monofilament which has been taken up with a take-up roll is subjected to a stretching step after it is wound up once, or without being wound up.
  • a stretching step a multi-stage stretching method of two or more stages is preferably adopted for obtaining the elastic monofilament of the present invention.
  • the heating medium at the time of stretching warm water, a PEG bath, steam and a dry heat stretching machine can be used.
  • the second stage stretching temperature is set within a range of the melting point of the thermoplastic elastomer used in the sheath component under 50°C of the melting point to under 10°C of the melting point.
  • the elastic monofilament after stretching is then subjected to relaxation heat treatment.
  • the relaxation ratio is preferably within a range of 0.99 to 0.85.
  • the relaxation heat treatment temperature is preferably set within a range of the melting point of the thermoplastic elastomer used in the sheath component under 50°C of the melting point to under 10°C of the melting point, and examples of a more preferable range include the melting point of the thermoplastic elastomer under 40°C of the melting point to under 10°C of the melting point.
  • the relaxation heat treatment temperature within the above range, it becomes possible to obtain a monofilament having excellent elasticity even when deformed in a bending direction, by relaxing excessive orientation generated in the sheath component in a stretching step while suppressing heat fusion between elastic monofilaments in a heat treatment step.
  • the total stretching ratio obtained by multiplying the stretching ratio by the relaxation ratio is preferably set at less than 4.0-fold.
  • Examples of a more preferable range include less than 3.8-fold.
  • the elastic monofilament after relaxation treatment is wound up with a winding machine.
  • the winding tension is within a range of 0.10 cN/dtex or less.
  • the lower limit of 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 resistance to permanent set in fatigue in a bending direction, elasticity, and creep property after subjected to a high temperature, it can be suitably utilized of course in various industrial uses such as marine materials, construction materials, safety materials, clothing materials, civil engineering materials, agricultural materials, vehicle materials, and sport materials, and particularly, in elastic woven or knitted structure uses such as car seats and office chairs, which easily undergoes deformation in a bending direction at the time of practical use.
  • the external diameter of the elastic monofilament was measured at 10 points in a length direction, using a laser external diameter measuring apparatus manufactured by Anritsu Corporation, and the mean value of the resulting external diameters was defined as the diameter.
  • the fineness was measured in accordance with JIS L1013:2010 8.3.1 B Method.
  • a cross section obtained by cutting the elastic monofilament in a direction vertical to a fiber axis was observed with a digital microscope VHX-100F manufactured by Keyence Corporation.
  • the diameter of the core component was measured using a length measuring tool of the digital microscope, and the ratio (% by volume) of the core component was obtained from the cross-sectional area of the elastic monofilament and the cross-sectional area of the core component which had been obtained using an area measuring tool.
  • a temperature giving an extreme value of a melting endothermic curve obtained by measuring 10 mg of a sample at a heating rate of 10°C/min using a differential scanning calorimeter model DSC-7 manufactured by Perkin Elmer was defined as the melting point.
  • the elastic monofilament which had been cut into a length of about 4 cm was set below two stainless bars having a diameter of 2 mm, which were mounted at an interval of 10 mm in a horizontal direction, and a J-shaped hook made of stainless steel having a diameter of 1 mm was hooked on the elastic monofilament at the central position of two stainless bars.
  • the hook made of stainless steel was pulled up at a speed of 50 mm/min using a model TCM-200 universal tensile testing/compression testing machine manufactured by Minebea Co., Ltd., and the maximum stress generated then was defined as the bending stiffness.
  • the boiling water shrinkage rate was measured in accordance with JIS L1013:2010 8.18.1 (B Method).
  • a raw yarn sample (elastic monofilament) which had been wound around an iron plate having a length of 30 cm ten times so that there was neither raw yarn slack nor a gap between raw yarns was heat-treated for 3 minutes in a dry heat oven at a temperature of 160°C, taken out from the dry heat oven, and naturally cooled. Then, the raw yarn sample after heat treatment was mounted in a Tensilon model UTM-4-100 tensile testing machine manufactured by Orientec Co., Ltd.
  • E 12 - E 0 was defined as the rate of dimensional change after heat treatment. Letting the measurement number n to be 5, the mean value of them was adopted.
  • the elastic monofilament was put up in a commercially available badminton racket under a load of 0.1 cN/dtex in both of warp and weft directions. After the elastic monofilament was put up, subjects were made to perform a repeated loading-unloading motion five times with a palm from a direction vertical to a ball shooting face, and the elasticity was scored based on the following criteria. The number of subjects was 10, and the mean value of the scores of 10 subjects was used as the result. Score 3 to score 5 were defined as acceptance.
  • the elastic monofilament was set in the testing machine in the state where a load of 2.5 kg/mm 2 was imparted to a yarn end opposite to the grasped yarn end of the monofilament, and the friction block was reciprocally contacted with the elastic monofilament 250 times at a reciprocating stroke of 25 mm and a speed of 120 reciprocations/min. This was retained for 24 hours in the state where the load was kept imparted.
  • the sample (elastic monofilament) after treatment was removed from the bending abrasion property testing machine, and immediately suspended in a perpendicular direction in the state where a load 2 of 6 g/mm 2 was imparted, as shown in Fig. 1 .
  • a distance A (mm) of a perpendicular line which was drawn from a line a connecting between marks towards a deformation maximum point was obtained, and the mean value of five times of measurement was defined as the amount of permanent set in fatigue.
  • a reactor equipped with a helical ribbon-type impeller was charged with 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 together with 0.04 part by mass of titanium tetrabutoxide and 0.02 part by mass of mono-n-butyl-monohydroxytin oxide.
  • the mixture was gradually heated from a temperature of 190°C to a temperature of 225°C over 3 hours to perform an esterification reaction while flowing reaction water to the outside of the system.
  • a reactor equipped with a helical ribbon-type impeller was charged with 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 together with 0.04 part by mass of titanium tetrabutoxide and 0.02 part by mass of mono-n-butyl-monohydroxytin oxide.
  • the mixture was gradually heated for 3 hours from a temperature of 190°C to a temperature of 225°C over 3 hours to perform an esterification reaction while flowing reaction water to the outside of the system.
  • respective molten polymers were filtered with a 200-mesh wire mesh, and discharged from a core-sheath composite spinneret having a pore diameter of 1.5 mm and a number of pores of 10.
  • the discharged filament was passed through a heat-insulating cylinder having a length of 30 mm, which had been mounted beneath the spinneret, passed through a cooling water bath at a temperature of 25°C, which had been mounted so as to have an air gap of 30 mm, and was taken up as an unstretched monofilament with a take-up roll rotating at a surface speed of 20 m/min.
  • the resulting unstretched monofilament was subjected to first stage stretching at a stretching ratio described in Table 1, without being wound once, using a warm water bath controlled to a temperature of 90°C, and subjected to second stage stretching at a ratio described in Table 1 using a dry heat stretching bath controlled to a temperature described in Table 1.
  • the monofilament after stretching was subsequently subjected to relaxation heat treatment at a ratio described in Table 1 using a dry heat bath controlled to a temperature described in Table 1, and wound at a winding tension described in Table 1 to obtain an elastic monofilament. Properties of the resulting monofilament were as shown in Table 1 and Table 2.
  • Comparative Example 2 since the ratio of the core component was small, excessive extension outside a bent part was not suppressed, and the amount of permanent set in fatigue was large. In Comparative Example 4, the tensile strength exceeded 3.05 cN/dtex, and elasticity in the bending direction was deteriorated.
  • Example 1 In the same manner as that of Example 1 except that, as the polymer for the sheath component, 97% by mass of the copolymeric thermoplastic elastomer (A-1) and 3% by mass of "Hytrel” (registered trademark) 21UV were used, the procedure was performed. Properties of the resulting monofilament were as shown in Table 1.
  • Example 2 In the same manner as that of Example 1 except that, as the polymer for the core component, a polyethylene terephthalate polymer (T-301T manufactured by Toray Industries, Inc.) having a melting point of 257°C and an intrinsic viscosity of 0.71, and containing 0.1% by mass of titanium oxide was used, the procedure was performed. Properties of the resulting monofilament were as shown in Table 1 and Table 2. In Comparative Example 3 and Comparative Example 5, the tensile strength exceeded 3.05 cN/dtex, and elasticity in the bending direction was deteriorated.
  • T-301T manufactured by Toray Industries, Inc.
  • Example 2 In the same manner as that of Example 1 except that, the copolymeric thermoplastic elastomer (A-1) which had been dried until the moisture content became less than 150 ppm, as the polymer for the core component, and the copolymeric thermoplastic elastomer (A-2) which had been dried until the moisture content became less than 150 ppm, as the polymer for the sheath component, were melted in a ⁇ 30 mm extruder set at a temperature of 250°C, and a ⁇ 40 mm extruder set at a temperature of 215°C, respectably, and thereafter, introduced into a composite spinning pack retained at a temperature of 250°C using gear pumps retained at a temperature of 245°C and 250°C, respectably, the procedure was performed.
  • the elastic monofilament of the present invention was excellent in resistance to permanent set in fatigue in the bending direction, elasticity, and creep property after subjected to a 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)

Claims (7)

  1. Monofilament élastique comprenant une structure composite cœur-gaine, dans lequel la proportion du composant cœur est de 2 à 40 % en volume, le composant cœur est un poly(téréphtalate d'éthylène) thermoplastique ayant, dans le polymère, 95 à 100 % en masse d'un motif poly(téréphtalate d'éthylène), et le composant gaine est un élastomère thermoplastique copolymère ayant un segment dur et un segment mou, et dans lequel le monofilament a un diamètre de 0,1 à 1,0 mm, et une résistance à la traction de 0,3 à 3,0 cN/dtex.
  2. Monofilament élastique selon la revendication 1, dans lequel la viscosité intrinsèque (IV) du poly(téréphtalate d'éthylène) utilisé dans le composant cœur est de 0,7 ou plus, mesurée dans de l'orthochlorophénol par utilisation d'un viscosimètre d'Ostwald comme décrit ici.
  3. Monofilament élastique selon la revendication 2, dans lequel le segment dur contient, en tant que motif constitutif principal, un motif polyester aromatique, et le segment mou contient, en tant que motif constitutif principal, un motif polyéther aliphatique et/ou un motif polyester aliphatique.
  4. Monofilament élastique selon la revendication 3, dans lequel le motif polyester aromatique est un motif poly(téréphtalate de butylène), et le motif polyéther aliphatique et/ou le motif polyester aliphatique est un motif poly(oxytétraméthylène)glycol.
  5. Monofilament élastique selon l'une quelconque des revendications 1 à 4, dans lequel le rapport du segment dur au segment mou est de 35/65 à 75/25 (rapport en masse).
  6. Monofilament élastique selon l'une quelconque des revendications 1 à 5, ayant une rigidité en flexion de 2,0 à 10 cN, mesurée comme décrit ici.
  7. Monofilament élastique selon l'une quelconque des revendications 1 à 6, dans lequel le taux de changement dimensionnel quand le monofilament est traité à la chaleur pendant 3 minutes dans une condition de température de 160°C avec une longueur fixe, puis maintenu pendant 12 heures sous une tension de 0,1 cN/dtex comme décrit ici, est de 0 à 5 %.
EP14834881.6A 2013-08-09 2014-08-07 Monofilament élastique Active EP3031960B1 (fr)

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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
JP6745211B2 (ja) * 2016-12-28 2020-08-26 株式会社ジェイエスピー シート芯材
WO2018181699A1 (fr) * 2017-03-31 2018-10-04 東レ株式会社 Monofilament élastique et articles tricotés tissés
CN111527243A (zh) * 2017-10-18 2020-08-11 佛罗里达中心大学研究基金会有限公司 具有导电芯和变色涂层的纤维
KR20220112792A (ko) * 2019-12-23 2022-08-11 도레이 카부시키가이샤 분리막 및 그 제조 방법

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

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