WO2015020163A1

WO2015020163A1 - Elastic monofilament

Info

Publication number: WO2015020163A1
Application number: PCT/JP2014/070923
Authority: WO
Inventors: 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
Priority date: 2013-08-09
Filing date: 2014-08-07
Publication date: 2015-02-12
Also published as: KR102168814B1; EP3031960A4; KR20160040292A; MX2016001715A; EP3031960A1; CN105765118B; JP6489773B2; CA2920777C; EP3031960B1; US20160194788A1; JP2015057522A; CA2920777A1; CN105765118A

Abstract

The present invention provides an elastic monofilament having exceptional fatigue resistance and elasticity especially in a bending direction and exceptional creep properties after high temperature is applied. This elastic monofilament has a sheath-core conjugated structure having a diameter of 0.1-1.0 mm and a core component ratio of 2-40 vol.%. In the elastic monofilament, the core component is a thermoplastic polyester having 95-100 mass% of thermoplastic polyester units in the polymer, the sheath component is a copolymerization system thermoplastic elastomer having a hard segment and a soft segment, and the tensile strength of the elastic monofilament is 0.3-3.0 cN/dtex.

Description

Elastic monofilament

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.

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. For example, 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.

As an example of a monofilament constituting a woven or knitted fabric applied to such a use, a 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. Against this issue, 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).

Specifically, 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., and 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. By partially melting or fusing the low melting point component arranged on the side, forming a fusion point at the intersection of the knitting / woven structure to improve the binding force, the change in the knitted fabric structure during repeated deformation of the fabric It is described that an effect that is small and excellent in long-term durability can be obtained.

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.

In these proposals, 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. 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. .

Japanese National Patent Publication No. 9-507782 JP-A-11-152625 JP-A-11-172532

However, in the proposals related to the improvement of the settling of the elastic sheet and the like disclosed in Patent Documents 2 and 3, the settling resistance at the time of actual use is still insufficient.
Accordingly, 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.

As a result of investigating the cause that the desired sag resistance cannot be obtained in the woven or knitted fabric obtained from the conventional monofilament, 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. When the structure which improves the fatigue resistance with respect to a deformation | 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.

Further, according to a preferred embodiment of the elastic monofilament of the present invention, the intrinsic viscosity (IV) of the thermoplastic polyester used for the core component is 0.7 or more.

According to a preferred aspect of the elastic monofilament of the present invention, the hard segment includes an aromatic polyester unit as a main structural unit, and 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, and the aliphatic polyether unit and / or the aliphatic polyester unit is a poly (tetramethylene oxide) glycol unit.

According to a preferred aspect of the elastic monofilament of the present invention, the ratio of the hard segment to the soft segment is 35:65 to 75:25 (mass ratio).

According to a preferred embodiment of the elastic monofilament of the present invention, 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%.

According to the present invention, an elastic monofilament having excellent fatigue resistance in the bending direction can be obtained. Thereby, it becomes possible to remarkably improve the settling resistance at the time of actual use of the woven or knitted fabric represented by the trampoline, the supporter, the bed, the car seat, and the office chair.

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. That is, since 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. 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 an elastic monofilament having a tensile strength of 0.3 to 3.0 cN / dtex. is there.

That is, 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 reason why such a remarkable effect was obtained is presumed as follows.

As a typical example of 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. In such a use mode, the load at the time of sitting is applied to the elastic fabric from a substantially vertical direction. At this time, paying attention to the deformation behavior of one elastic monofilament, 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. Further, when microscopically focusing on the bent portion of the elastic monofilament, the elastic monofilament is compressed inside the bent portion, and the elastic monofilament is greatly expanded outside the bent portion.

In such a field, in the elastic monofilament using only the conventional thermoplastic elastomer, by extending greatly on the outer side of the bending, a deformation beyond the elastically deformable elongation inherent in the thermoplastic elastomer occurs, causing plastic deformation, As a result, it is considered that the knitted and knitted fabrics are set.

On the other hand, in the same case, in the core-sheath type composite monofilament in which a thermoplastic polyester such as polyethylene terephthalate is used as the core component and a thermoplastic elastomer is arranged in a specific configuration as in the present invention, the core component is constant. By taking this stress, 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. Furthermore, by arranging a thermoplastic polyester such as polyethylene terephthalate as the core component, 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.

In the elastic monofilament of the present invention, it is necessary that 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. When 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. From such a viewpoint, 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.

Further, as the cross-sectional shape of the elastic monofilament of the present invention, 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.

Here, 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, and 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 When the thickness of the elastic monofilament is Lt, it is preferable that 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 (%)
Here, 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.

Examples of the thermoplastic polyester that can be used for the core component 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

In the present invention, the thermoplastic polyester used for the core component is a polymer having a thermoplastic polyester unit of 95 to 100% by mass. Here, the thermoplastic polyester unit means a component other than a component having a polyester skeleton and corresponding to a thermoplastic elastomer described later. As a component having a structure other than the thermoplastic polyester unit, 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.

On the other hand, 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. Examples of the 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. In the present invention, the thermoplastic polyester constituting the core component is so-called 100% by mass consisting of thermoplastic polyester units. A homopolymer is preferred.

Further, the 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. Among them, 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.

As the polyester-based elastomer used in the present invention, 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.

Specific examples of the aromatic dicarboxylic acid 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.

In the present invention, 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.

Next, specific examples of the diol include 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.

These dicarboxylic acids, their derivatives, diol components and their derivatives 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. Further, 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.

Examples of the aliphatic polyester include poly (ε-caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. Among these aliphatic polyethers and / or aliphatic polyesters, 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 The use of copolymer glycol, poly (ε-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). By setting the ratio of the hard segment to the soft segment within the above range, not only can the thermal properties be difficult to pyrolyze during composite spinning, but also the sheath component has moderate elasticity, so it is an elastic monofilament with excellent stretch-back properties Can be obtained.

In addition, in the elastic monofilament of the present invention, 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 | position inside the core component which consists of polyester further.

In the elastic monofilament of the present invention, the thermoplastic elastomer constituting the sheath component preferably has a Shore D hardness of 30 to 65. 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.

The 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.

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. When the tensile strength satisfies the above range, an elastic monofilament that hardly causes deterioration of process passability due to yarn breakage or the like in a high-order processing step such as a weaving and knitting step and sufficiently retains elasticity. In particular, when the tensile strength exceeds 3.0 cN / dtex, the rigidity of the core-sheath composite monofilament is too high and the elasticity in the bending direction is impaired.

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. Here, 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. for 3 minutes, When the rate of dimensional change when held under a tension of 0.1 cN / dtex for 12 hours satisfies the above range, it does not stretch excessively even after being heat set as a product such as a woven or knitted fabric, and is excellent. Can have creep properties. As a more preferable range of the dimensional change rate after being heat-treated for 3 minutes under a temperature condition of 160 ° C. under a constant length and held under a tension of 0.1 cN / dtex for 12 hours, 0 to 3% is exemplified. Can do.

The elastic monofilament of the present invention preferably has a boiling water shrinkage of 3 to 10%. By setting the boiling water shrinkage in the above range, it is possible to obtain a product that is excellent in dimensional stability at the time of heat application and that is more difficult to wrinkle even when made into a woven or knitted fabric.

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.

Next, the method for producing the elastic monofilament of the present invention will be described in detail, but the method for producing the elastic monofilament is not limited to this.

Since 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.

That is, after the 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.

At this time, for the purpose of suppressing hydrolysis in the spinning machine of the thermoplastic elastomer and the thermoplastic polyester used for spinning, 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. When 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.

In addition, when imparting functions such as original deposition, light resistance and antibacterial properties to an elastic monofilament, 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.

Particularly, in the elastic monofilament of the present invention, it is preferable to add a light-proofing agent to the thermoplastic elastomer resin for the purpose of reducing deterioration due to ultraviolet rays during actual use. As a preferred 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.

In a preferred embodiment, 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.

If necessary, 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. Further, 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. In order to obtain the elastic monofilament of the present invention, the number of drawing steps in the drawing step is preferably a multistage drawing method having two or more steps. Moreover, also about the heat medium at the time of extending | stretching, warm water, a PEG bath, a vapor | steam, and a dry heat drawing machine can be used.

Regarding the stretching temperature, in order to obtain the elastic monofilament of the present invention, 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. By setting 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. By setting 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.

In the core-sheath resin structure of the present invention, in order to satisfy the above-described range of the tensile strength of the present invention, it is preferable to set the total draw ratio obtained by multiplying the draw ratio by the relaxation ratio to less than 4.0 times. As a more preferable range, 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. By setting the winding tension within the above range, the load applied to the elastic monofilament during winding is reduced, and as a result, an elastic monofilament having excellent durability can be obtained. In order to obtain a winding package applicable to actual use, the lower limit of the winding tension is preferably 0.02 cN / dtex or more.

Thus, 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. In addition to various industrial uses such as sports materials and the like, 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.

Next, the elastic monofilament of the present invention will be described in more detail by way of examples. The definition and measuring method of the characteristics used in the examples are as follows. The number of measurements n was 1 unless otherwise specified.

[diameter]
Using an Anritsu laser outer diameter measuring instrument, the outer diameter of the elastic monofilament was measured at 10 points in the length direction, and the average value of the obtained outer diameters was taken as the diameter.

[Fineness]
Measured according to JIS L1013: 2010 8.3.1 B method.

[Strength, elongation and tensile strength]
Using a Tensilon UTM-4-100 type tensile tester manufactured by Orientec Co., Ltd., the strength of the monofilament was measured at three points with a constant-speed tension-type gripping interval of 25 cm in accordance with JIS L1013: 2010 8.5.1. The average strength and average elongation of 3 times were obtained. The strength was determined by dividing the average strength by the fineness.

[Ratio of core component diameter to core component]
The cut surface obtained by cutting the elastic monofilament in a direction perpendicular to the fiber axis is observed with a digital microscope VHX-100F manufactured by Keyence, and the diameter of the core component is measured using the length measurement tool of the digital microscope. The ratio (volume%) of the core component was determined from the cross-sectional area of the elastic monofilament and the cross-sectional area of the core component obtained using the area measurement tool.

[Melting point]
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.

[Bending hardness]
An elastic monofilament cut into a length of about 4 cm is set under a 2 mm diameter stainless steel rod installed at intervals of 10 mm in the horizontal direction, and a diameter of 1 mm is placed on the elastic monofilament at the center of the two stainless steel rods. A stainless steel hook was pulled up at a speed of 50 mm / min using a T-200 type universal tensile / compression tester manufactured by Menebea Co., Ltd., and the maximum stress generated at this time was defined as bending hardness. .

[Boiling water shrinkage (boiling yield)]
It measured according to JIS L1013: 2010 8.18.1 (B method).

[Intrinsic viscosity]
Into the flask, 8 g of a sample pulverized with a Willet pulverizer (filter hole diameter: 1 mm) is added to 100 mL of orthochlorophenol, and heat-treated at a temperature of 160 ° C. for 10 minutes. After the heat-treated flask was cooled with running water for 15 minutes, the relative viscosity η of the obtained solution was measured at a temperature of 25 ° C. using an Ostwald viscometer, and the approximate viscosity of intrinsic viscosity = (K1 × η) + K2. The intrinsic viscosity was determined by The constant K1 is 0.0242 and the constant K2 is 0.2634.

[Dimensional change after heat treatment]
A raw yarn sample (elastic monofilament) wound 10 times on an iron plate having a length of 30 cm so that there is no slack in the raw yarn and no gap between the raw yarns was heat treated in a dry heat oven at a temperature of 160 ° C. for 3 minutes, Removed from dry heat oven and allowed to cool naturally. Next, after the heat-treated raw yarn sample was attached to a Tensilon UTM-4-100 type tensile tester manufactured by Orientec Co., Ltd. with a yarn length of 25 cm, the elongation when a load of 0.1 cN / dtex was applied (E ₀ )% and elongation (E ₁₂ )% when left for 12 hours in a state where a load of 0.1 cN / dtex was applied, and 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.

[Elasticity evaluation]
An elastic monofilament was stretched with a 0.1 cN / dtex load on a commercially available badminton racket. After tensioning the elastic monofilament, the subject was subjected to 5 repeated load-dewetting motions with the palm from the direction perpendicular to the ball striking face, and then scored according to the following criteria. The number of subjects was 10, and the average value of the scores of 10 people was used as a result. Three to five points were accepted.
5 points: excellent rubber elasticity,
4 points: halfway between 3 and 5 points
3 points: rubber elasticity
2 points: halfway between 3 points and 1 point,
1 point: Hard.

[Steel amount]
JIS L1095: 2008 9.10. Using a bending wear characteristic testing machine according to (Method B), grip one end of the frictional element (hard steel wire SWP-A) with a fixed diameter of 0.6 mm, and reciprocate the frictional element in advance. Gripping the elastic monofilament with markings of 200 mm on the outside of the stroke width under two free rollers provided so that the elastic monofilament bends at an angle of 55 ° to the left and right of the friction element. Set on the testing machine with a load of 2.5 kg / mm ² applied to the yarn end opposite to the yarn end, and contact the elastic element with the elastic monofilament 250 times with a reciprocating stroke of 25 mm and a speed of 120 reciprocations per minute. Then, the load was applied for 24 hours.

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. For the suspended sample (elastic monofilament 1), 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.

[Production of 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. After adding 0.2 parts by mass of tetra-n-butyl titanate to the reaction mixture and adding 0.05 parts by mass of “Irganox” (registered trademark) 1098 (hindered phenol antioxidant manufactured by Ciba Geigy), The temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was carried out for 1 hour and 50 minutes under the conditions. The obtained polymer was discharged into water in the form of a strand, and pellets of a copolymerized thermoplastic elastomer (A-1) having a hard / soft ratio of 48/52 (mass ratio) were obtained by cutting. The obtained pellet had a melting point of 200 ° C. and a Shore hardness D of 47.

[Production of 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. and allowing reaction water to flow out of the system. After adding 0.15 parts by mass of tetra-n-butyl titanate to the reaction mixture and adding 0.05 parts by mass of “Irganox” (registered trademark) 1098 (hindered phenol antioxidant manufactured by Ciba Geigy), The temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was carried out for 1 hour and 50 minutes under the conditions. The obtained polymer was discharged into water in the form of a strand, and cut into pellets of a copolymer thermoplastic elastomer (A-2) having a hard / soft ratio of 49/51 (mass ratio). The obtained pellet had a melting point of 160 ° C. and a Shore hardness D of 40.

(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 Φ30 mm extruder of 295 ° C. After melting with a φ40mm extruder with a temperature of 245 ° C, weighed the outer diameter (diameter) and core component ratios listed in Table 1 using gear pumps kept at temperatures of 245 ° C and 295 ° C, respectively. And introduced into a composite spin pack kept at a temperature of 290 ° C. In the composite spinning pack, 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. installed with an air gap of 30 mm, and a surface speed of 20 m / min. It was taken up as an unstretched monofilament with a take-up roller that was rotated at the same time. 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.
In 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. In Comparative Example 4, 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.

(Comparative Example 1)
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 φ30 mm extruder having a set temperature of 250 ° C. and a φ40 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.

As shown in Tables 1 and 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.

1. 1. Elastic monofilament after bending abrasion characteristic test Load a. Line connecting the markings A. The distance of the perpendicular line drawn from the line a connecting the markings toward the maximum deformation point (sag amount)

Claims

It 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 95 to 100% by mass of the thermoplastic polyester unit in the polymer. An elastic monofilament, wherein the sheath component is a copolymer thermoplastic elastomer having a hard segment and a soft segment as a sheath component, and has a tensile strength of 0.3 to 3.0 cN / dtex.
2. The elastic monofilament according to claim 1, wherein the thermoplastic polyester used for the core component has an intrinsic viscosity (IV) of 0.7 or more.
3. The elastic monofilament according to claim 2, wherein the hard segment has an aromatic polyester unit as a main constituent unit, and the soft segment has an aliphatic polyether unit and / or an aliphatic polyester unit as a main constituent unit.
4. The elastic monofilament according to claim 3, wherein the aromatic polyester unit is a polybutylene terephthalate unit, and the aliphatic polyether unit and / or the aliphatic polyester unit is a poly (tetramethylene oxide) glycol unit.
The elastic monofilament according to any one of claims 1 to 4, wherein the ratio of the hard segment to the soft segment is 35:65 to 75:25 (mass ratio).
The elastic monofilament according to any one of claims 1 to 5, wherein the bending hardness is 2.0 to 10 cN.
7. The dimensional change rate is 0 to 5% when heat-treated for 3 minutes under a temperature condition of 160 ° C. under constant length and then held for 12 hours under a tension of 0.1 cN / dtex. The elastic monofilament as described.