JP6213693B2 - Core-sheath composite cross-section fiber with excellent hygroscopic and anti-mold properties - Google Patents

Description

  The present invention relates to a core-sheath composite cross-section fiber excellent in hygroscopicity and antifungal properties.

  Synthetic fibers made of thermoplastic resins such as polyamide and polyester are widely used for clothing and industrial applications because they are excellent in strength, chemical resistance, heat resistance and the like.

  In particular, polyamide fiber has excellent moisture absorption and release properties in addition to its unique softness, high tensile strength, coloring properties when dyeing, and high heat resistance, and is widely used for applications such as innerwear and sportswear. ing. However, polyamide fibers do not have sufficient moisture absorption and release performance compared to natural fibers such as cotton, and have problems such as stuffiness and stickiness, and are inferior to natural fibers in terms of wearing comfort. It has become.

  From such a background, synthetic fibers having excellent moisture absorption / release performance for preventing dullness and stickiness and having wearing comfort close to natural fibers have been demanded mainly for inner use and sports apparel use.

  Therefore, Patent Document 1 discloses a polyether block amide copolymer having a core-sheath composite cross-sectional fiber having a core part and a sheath part, the core part not exposed on the fiber surface, and a hard segment made of polycaproamide. A core-sheath composite cross-section fiber having a core / sheath area ratio of 3/1 to 1/5 in a fiber cross section is disclosed.

  Patent Document 2 discloses a core-sheath composite cross-section fiber having a thermoplastic polymer as a core and a fiber-forming polyamide as a sheath, and the main component of the thermoplastic polymer forming the core is a polyether ester. A core-sheath composite cross-section fiber excellent in moisture absorption / release characteristics is disclosed which is an amide copolymer and has a core portion ratio of 5 to 50% by weight of the total weight of the composite fiber.

  In Patent Document 3, a polyether block amide copolymer is used as a core part, and a fiber-forming polymer such as polyamide or polyester is used as a sheath part, and the core part is exposed in an exposure angle range of 5 ° to 90 °. A core-sheath composite cross-sectional fiber excellent in antistatic performance, water absorption performance, and contact cooling feeling is disclosed. The core-sheath composite cross-section fibers of Patent Documents 1 to 3 are increasingly used as woven or knitted fabrics for inner and sports applications.

International Publication No. 2014/10709 JP-A-6-136618 International Publication No. 2008/123586

  However, the core-sheath composite cross-section fibers of Patent Documents 1 to 3 are excellent in moisture absorption / release properties due to the high moisture absorption performance of the core component polymer, but have high shrinkage characteristics and are flexible polymers. The problem was that the material was easily deformed and easily wrinkled. The same phenomenon was likely to occur during washing. Furthermore, the core part deteriorated by repeated actual use, and a decrease in moisture absorption performance due to repeated use was also a problem.

  An object of the present invention is to overcome the problems of the prior art and to provide a core-sheath composite cross-sectional fiber excellent in moisture absorption / release performance and antifungal properties. It is another object of the present invention to provide a core-sheath composite cross-section fiber that maintains moisture absorption performance even after washing.

  In order to solve the above-described problems, the present invention has the following configuration.

(1) The core polymer is a polyether ester amide copolymer , the sheath polymer is a polyamide having a dicarboxylic acid unit whose main component is a sebacic acid unit, and the boiling water shrinkage is 6.0 to 12.0. %, A core-sheath composite cross-section fiber having a stress per unit fineness of 3% elongation in a fiber tensile test of 0.60 cN / dtex or more.

  (2) The core-sheath composite cross-section fiber according to (1), wherein the α crystal orientation parameter of the sheath part is 2.10 to 2.70.

  (3) The core-sheath composite according to (1) or (2), wherein the stress retention per unit fineness at 3% elongation in a tensile test of the fiber before and after boiling water treatment is 60% or more Cross-section fiber.

  (4) A fabric having at least a portion of the core-sheath composite cross-section fiber according to any one of (1) to (3).

  (5) A fiber product having at least a portion of the core-sheath composite cross-section fiber according to any one of (1) to (3).

  ADVANTAGE OF THE INVENTION According to this invention, the core-sheath composite cross-section fiber which is excellent in moisture absorption performance and antifungal property, and also maintains moisture absorption performance even if it wash | cleans can be provided.

  The core-sheath composite cross-section fiber of the present invention uses a polyamide having a dicarboxylic acid unit containing a sebacic acid unit as a main component in the sheath polymer, and a thermoplastic polymer having high moisture absorption performance as the core polymer.

  A polyamide having a dicarboxylic acid unit mainly composed of a sebacic acid unit in a sheath is a polymer composed of a high molecular weight substance in which a so-called hydrocarbon is connected to a main chain through an amide bond. Examples include pentamethylene sebacamide, polyhexamethylene sebacamide, and copolymers thereof, but from an economical aspect, relatively easy to produce yarn, dyeability, and excellent mechanical properties. Such a polyamide is preferably a polyamide mainly composed of polyhexamethylene sebacamide.

  The polyamide having a dicarboxylic acid unit whose main component is a sebacic acid unit in the sheath includes various additives such as matting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystal nucleating agents, A fluorescent whitening agent, an antistatic agent, a hygroscopic polymer, carbon, and the like may be copolymerized or mixed as necessary with a total additive content of 0.001 to 10% by weight.

  The thermoplastic polymer having high hygroscopic performance in the core portion refers to a polymer having ΔMR measured in a pellet shape of 10% or more, and examples thereof include polyether ester amide copolymers, polyvinyl alcohol, and cellulose-based thermoplastic polymers. Among them, polyether ester amide copolymers are preferable from the viewpoint of good thermal stability and compatibility with the polyamide in the sheath and excellent peel resistance.

  ΔMR here refers to weighing 1 to 2 g of a pellet in a weighing bottle, drying it at 110 ° C. for 2 hours, measuring the weight (W0), and then measuring the pellet at 24 ° C. and a relative humidity of 65%. The weight (W65) after holding for a time is measured. And the weight (W90) after hold | maintaining a pellet for 24 hours at 30 degreeC and 90% of relative humidity is measured. And it is calculated according to the following formula.

MR65 (%) = [(W65−W0) / W0] × 100
MR90 (%) = [(W90−W0) / W0] × 100
ΔMR (%) = MR90−MR65.

  The polyether ester amide copolymer is a block copolymer having an ether bond, an ester bond and an amide bond in the same molecular chain. More specifically, one or two or more polyamide components (A) selected from lactam, aminocarboxylic acid, diamine and dicarboxylic acid salt, and polyetherester component consisting of dicarboxylic acid and poly (alkylene oxide) glycol ( It is a block copolymer polymer obtained by subjecting B) to a polycondensation reaction.

  Examples of the polyamide component (A) include lactams such as ε-caprolactam, dodecanolactam and undecanolactam, ω-aminocarboxylic acids such as aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, polyhexamethylene azimuth There are nylon salts of diamine-dicarboxylic acid, which are precursors such as pamide, polyhexamethylene sebacamide, polyhexamethylene dodecanamide, and the preferred polyamide component is ε-caprolactam.

  The polyether ester component (B) is composed of a dicarboxylic acid having 4 to 20 carbon atoms and poly (alkylene oxide) glycol. Examples of the dicarboxylic acid having 4 to 20 carbon atoms include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and dodecanoic acid, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. An aromatic dicarboxylic acid such as an acid, an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, and the like can be mentioned, and one or a mixture of two or more can be used. Preferred dicarboxylic acids are adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid. Examples of the poly (alkylene oxide) glycol include polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, and the like. Polyethylene glycol having good moisture absorption performance is preferred.

  The number average molecular weight of the poly (alkylene oxide) glycol is preferably from 300 to 10,000, more preferably from 500 to 5,000. It is preferable for the molecular weight to be 300 or more because the fiber is less likely to splash out of the system during the polycondensation reaction and the moisture absorption performance is stable. Moreover, it is preferable that it is 10000 or less because a uniform block copolymer is obtained and the spinning property is stabilized.

  The constituent ratio of the polyetherester component (B) is preferably 20 to 80% in terms of mol ratio. When it is 20% or more, good hygroscopicity is obtained, which is preferable. Moreover, it is preferable that it is 80% or less because good dyeing fastness and washing durability can be obtained.

  As such a polyether ester amide copolymer, “MH1657”, “MV1074”, etc. manufactured by Arkema are commercially available.

  The core-sheath composite cross-section fiber of the present invention is required to have a boiling water shrinkage of 6.0 to 12.0%. When the boiling water shrinkage rate exceeds 12.0%, the fiber is likely to be deformed in the dyeing process, and easily wrinkled. Further, when the boiling water shrinkage rate is less than 6.0%, although the fouling resistance is excellent, the operability in the yarn making process may be deteriorated and the quality may be deteriorated. By setting the boiling water shrinkage in the above range, the anti-mold property is excellent. Preferably, it is 6.0 to 10.0%.

  The core-sheath composite cross-section fiber of the present invention needs to have a stress per unit fineness of 0.60 cN / dtex or more when stretched by 3% in a fiber tensile test. The stress at the time of 3% elongation in the tensile test of the fiber was determined by performing a tensile test on the sample under the constant speed elongation condition shown in JIS L1013 (chemical fiber filament yarn test method, 2010). Obtain from the strength at the point of 3% elongation. The strength divided by the fineness of the fiber is the stress per unit fineness at 3% elongation in the fiber tensile test.

  The stress per unit fineness at the time of 3% elongation in the tensile test of the fiber is a rising portion of the tensile strength-elongation curve and is a parameter indicating the rigidity of the fiber. The greater this value (the steeper the rise of the tensile strength-elongation curve), the stiffer the fiber. That is, by setting the stress per unit fineness at the time of 3% elongation in the fiber tensile test to be 0.60 cN / dtex or more, the deformation of the fiber in the dyeing process is suppressed, and the fiber has excellent antifungal properties. Can do. Preferably it is 0.70 cN / dtex or more.

  In the core-sheath composite cross-section fiber of the present invention, the α crystal orientation parameter of the polyamide in the sheath part is preferably 2.10 to 2.70, more preferably 2.20 to 2.60. It is generally known that an α crystal is a stable crystal form and is formed when a high stress is applied. By setting the α crystal orientation parameter of the polyamide in the sheath within such a range, the polyamide in the sheath is preferentially subjected to drawing during spinning and drawing between take-up rollers and drawing between take-off rollers, and α crystals that are stable crystal forms. Can be sufficiently present. As a result, the stretching force is concentrated on the polyamide in the sheath during melt spinning, the crystallization of the thermoplastic polymer having a high hygroscopic performance in the core is suppressed, and the hygroscopic performance of the core-sheath composite fiber can be further enhanced. At the same time, the rigidity of the sheath portion is increased, and the tensile stress of the core-sheath composite fiber can be further increased.

  When the α crystal orientation parameter of the polyamide of the sheath is 2.10 or more, the crystallization of the polyamide of the sheath advances, the tensile stress at 3% elongation as the core-sheath composite cross-section fiber becomes good, and the core Therefore, the crystallization of the thermoplastic polymer having high moisture absorption performance does not proceed and the moisture absorption / release performance is also improved. On the other hand, when the α crystal orientation parameter is 2.70 or less, the crystallization of the polyamide in the sheath portion does not proceed, and the occurrence of yarn breakage and fluff generation in the high-order processing step can be suppressed, so that productivity is improved.

  The core-sheath composite cross-section fiber of the present invention preferably has a stress retention per unit fineness of 60% or more at 3% elongation in a fiber tensile test before and after boiling water treatment. By setting it as such a range, there is little change in the fiber structure and crystal orientation in the dyeing process, the fiber shrinkage is suppressed, the fiber rigidity is easily maintained, and the fiber has excellent anti-mold properties. it can. When the fiber is treated with boiling water, the fiber structure changes mainly in the amorphous part, the hydrogen bond between the amide bonds in the amorphous part is cut, the mobility of the molecular chain is improved, and the degree of orientation is lowered. As a result, the fiber structure changes and the degree of orientation of the amorphous part change, so that the fiber shrinks and the stiffness of the fiber decreases. Therefore, by suppressing the shrinkage of the fiber as much as possible and maintaining the rigidity of the fiber as much as possible before and after boiling water, the deformation of the fiber in the dyeing process is suppressed, and the antifungal property is improved. Furthermore, deformation of the fiber is suppressed even during washing, and the anti-mold property is improved.

  The thermoplastic polymer having high hygroscopic performance of the core part constituting the core-sheath composite cross-section fiber of the present invention is a polymer having low crystallinity and poor rigidity. Therefore, it is also a polymer whose shrinkage characteristics are increased by boiling water treatment and flexibility is easily increased. Therefore, the core-sheath composite cross-section fiber of the present invention has a rigid sheath portion by selecting a polyamide made of polyhexamethylene sebacamide having a relatively high rigidity and low shrinkage among polyamides as the sheath portion polymer. Since it is made into a fiber under specific spinning conditions (heat set temperature, oiling position, etc.) as described later, the shrinkage characteristics are suppressed and the rigidity is improved, so that the fender resistance and moisture absorption performance are improved. is there. More preferably, it is 70% or more.

  The core-sheath composite cross-section fiber of the present invention preferably has a tensile strength of 3.0 cN / dtex or more, more preferably 3.5 to 5.0 cN / dtex. By setting it as such a range, it becomes possible to provide a product excellent in practical durability.

  The core-sheath composite cross-sectional fiber of the present invention preferably has an elongation of 35% or more, more preferably 40 to 65%. By setting it as such a range, the passage property in high-order processes, such as weaving, knitting, and false twisting, becomes good.

  The core-sheath composite cross-section fiber of the present invention needs to have a function of adjusting the humidity in the clothes in order to obtain good comfort when worn. As an index of humidity adjustment, the temperature in the clothes typified by 30 ° C. × 90% RH and the outside air temperature humidity typified by 20 ° C. × 65% RH when performing light to medium work or light to medium exercise ΔMR expressed by the difference in moisture absorption is used. A larger ΔMR corresponds to higher moisture absorption performance and better comfort when worn.

  The core-sheath composite cross-section fiber of the present invention preferably has a ΔMR of 5.0% or more. More preferably, it is 7.0% or more, More preferably, it is 10.0% or more. By setting it as this range, the stuffiness and stickiness at the time of wear can be suppressed, and the clothing excellent in comfort can be provided.

  The core-sheath composite cross-sectional fiber of the present invention preferably has a ΔMR retention of 90% or more and 100% or less after 20 washings. More preferably, it is 95% or more and 100% or less. By setting it as this range, since the washing durability which can endure actual use is obtained, the clothing which hold | maintained the outstanding comfort can be provided. Furthermore, providing △ MR of 5.0% or more and having a ΔMR retention rate of 90% or more after 20 washings provide clothes with durability and durability that can withstand actual use. Is possible.

  The core-sheath composite cross-section fiber of the present invention may be either a filament or a staple, and is selected depending on the application. Further, the total fineness, the number of filaments (for long fibers), and the length / crimp number (for short fibers) are not particularly limited, but considering the use as a long fiber material for clothing, the total fineness is 5 -235 dtex, and the number of filaments is preferably 1-144.

  The core-sheath composite cross-section fiber of the present invention can be obtained by melt spinning and composite spinning techniques. For example, polyamide (sheath part) and thermoplastic polymer (core part) with high moisture absorption performance are melted separately, measured and transported with a gear pump, formed into a composite flow as it is, and discharged from a melt spinneret. The yarn is cooled to room temperature by a yarn cooling device such as the above, and is fed and converged by the oil supply device, entangled by the first fluid entanglement nozzle device, and drawn according to the ratio of the peripheral speeds of the take-up roller and the drawing roller. Further, the yarn is heat-set by a drawing roller and wound by a winder (winding device).

  In order to obtain the core-sheath composite cross-section fiber of the present invention, it can be preferably controlled by selecting a polyamide having an appropriate molecular structure, a suitable take-up speed, a fueling position, and a heat set temperature after stretching. These will be described in detail below.

  As described above, the polyamide used in the core-sheath composite cross-section fiber of the present invention is a polyamide having a dicarboxylic acid unit whose main component is a sebacic acid unit in the sheath, a so-called hydrocarbon is connected to the main chain via an amide bond. It is preferable to use a polymer comprising a high molecular weight substance. By selecting a polyamide having a high ability to form hydrogen bonds between amide bonds in the sheath part, even during high-temperature dyeing and drying exceeding 100 ° C., the hydrogen bond between the amide bonds in the amorphous part is not easily broken. Thus, the core-sheath composite cross-section fiber excellent in the anti-mold property of the fabric during dyeing can be obtained. The ability to form hydrogen bonds between amide bonds here is determined by the degree of freedom of the polyamide molecular main chain, that is, the number of methylene groups per amide bond. Therefore, the core-sheath composite cross-section fiber excellent in the antifungal property of the fabric at the time of dyeing is obtained by selecting the polyamide of the range concerning a sheath part.

  The polyamide used for the core-sheath composite cross-section fiber of the present invention includes various additives such as matting agents, flame retardants, antioxidants, ultraviolet absorbers, infrared absorbers, crystal nucleating agents, fluorescent whitening agents, An antistatic agent, a hygroscopic polymer, carbon and the like may be copolymerized or mixed as necessary with a total additive content of 0.001 to 10% by weight.

  The sulfuric acid relative viscosity of the polyamide chip used for the core-sheath composite cross-section fiber of the present invention is preferably 2.30 to 3.30. By setting it as such a range, it becomes possible to add suitable extending | stretching to the polyamide of a sheath part. When the relative viscosity of sulfuric acid of the polyamide in the sheath is 2.30 or more, a practical fiber strength and elongation can be obtained. On the other hand, when the relative viscosity of sulfuric acid is 3.30 or less, the melt viscosity is suitable for spinning, so that the spinnability at the time of melt spinning is improved, and stable production without yarn breakage becomes possible. More preferably, it is 2.50-3.10.

  The ratio of the core part of the core-sheath composite cross-section fiber of the present invention is preferably 20 parts by weight to 80 parts by weight with respect to 100 parts by weight of the composite fiber. More preferably, it is 30 to 70 parts by weight. By setting it as such a range, it becomes possible to add suitable extending | stretching to the polyamide of a sheath part. In addition, good dyeing fastness and moisture absorption performance can be obtained.

  In the melting step, for the polyamide having a dicarboxylic acid unit composed mainly of a sebacic acid unit used in the sheath part, in the case of polyhexamethylene sebacamide chip, 250 to 290 ° C., a thermoplastic having high moisture absorption performance used in the core part In the case of “MH1657” manufactured by Arkema, the polymer is preferably 220 to 260 ° C.

  In the take-up step, the take-up speed is preferably 2500 to 3400 m / min. By setting it as such a range, the orientation crystallization of the core polymer is appropriately advanced, and the crystallization of the core polymer is moderately suppressed, so that the stress per unit fineness at the time of 3% elongation and the boiling water shrinkage rate are reduced. It can be controlled within a preferable range, and is excellent in moisture absorption performance and antifungal properties. Furthermore, moisture absorption performance can be maintained even after washing. When it exceeds 3400 m / min, the orientation crystallization of the polyamide in the sheath proceeds when it is stretched by spinning tension, but the α-crystal orientation parameter of the polyamide in the sheath decreases because the mechanical stretch ratio decreases, and the sheath The rigidity of the polymer is reduced and it tends to become wrinkles. If it is less than 2500 m / min, the mechanical stretch ratio is increased, but since the stretching by spinning tension is insufficient, the α crystal orientation parameter of the polyamide in the sheath is lowered, the rigidity of the sheath polymer is lowered, and It becomes a fiber that tends to become. In addition, the oriented crystallization of the core polymer proceeds and the moisture absorption performance decreases. More preferably, it is 2700-3200 m / min.

  In the refueling step, it is preferable that the refueling position from the lower surface of the base is 800 to 1500 mm. The polymer discharged from the die is blown with cooling air by a cooling device to solidify the yarn. From the solidification position to the oil supply position, the polymer is stretched by spinning tension accompanied by an accompanying flow, and then between the take-up roller and the drawing roller. Mechanical stretching. The core-sheath composite cross-section fiber of the present invention has a high mechanical stretch ratio in order to enhance the orientation crystallization of the sheath polymer and increase the rigidity, and to suppress the crystallization of the core polymer and enhance the moisture absorption performance. The point is to reduce the spinning tension. That is, by setting the refueling position in such a range, the stress per unit fineness at the time of 3% elongation in the fiber tensile test can be increased, and a fiber excellent in antifungal properties and moisture absorption performance can be obtained. When the oil supply position is less than 800 mm, the bend between the base and the oil supply position becomes large, and since the yarn is supplied with the yarn not solidified sufficiently, thread breakage frequently occurs and operability may be reduced. is there. In addition, when the oil supply position exceeds 1500 mm, the spinning tension increases, so that the oriented crystallization of the core polymer progresses and the moisture absorption performance decreases, and the mechanical stretch ratio decreases and the rigidity of the sheath polymer decreases. For this reason, the fiber may easily become wrinkles. More preferably, it is 1000-1300 mm.

  In the stretching step, the heat setting temperature after stretching is preferably 165 to 180 ° C. Due to the stretching between the rollers, the fibers having undergone oriented crystallization are further crystallized by the high-temperature heat setting treatment on the heating roller, and the fiber structure is stabilized. The boiling water shrinkage ratio depends on the shrinkage of the amorphous part of the fiber, that is, the ratio of the amorphous part. In addition, the heat setting temperature as used in the field of this invention shows the preset temperature of a heating roller.

  The polymer having high hygroscopic performance of the core part constituting the core-sheath composite cross-section fiber of the present invention has high amorphousness and high shrinkage, so that the boiling water shrinkage when fiberized with a single polymer is large. It is expected that. Therefore, the core-sheath composite cross-section fiber of the present invention uses a polyamide having a dicarboxylic acid unit mainly composed of a sebacic acid unit as a sheath polymer, which has relatively high rigidity and low shrinkage among polyamides. Stiffness is given to the sheath, the shrinkage of the core is suppressed, and the fiber structure is stabilized by heat setting after stretching at such a temperature range, and the boiling water shrinkage is controlled to 6.0 to 12.0%. And a fiber having excellent antifungal properties can be obtained. When the heat setting temperature is lower than 165 ° C., the crystallization of the polyamide in the sheath portion is insufficient, the fiber structure is not stable, and the fibers may be prone to wrinkles. Also, when the heat set temperature exceeds 180 ° C, fibers with excellent anti-mold properties can be obtained. However, contamination of the spinning oil decomposition products is promoted on the heating roller, resulting in frequent deterioration in quality and spun yarn breakage. In some cases, the passability of the high-order machining process deteriorates. More preferably, it is 170-175 degreeC.

  The core-sheath composite cross-section fiber of the present invention is preferably used for apparel because it has excellent moisture absorption performance, and the form of the cloth can be selected according to the purpose such as woven fabric, knitted fabric, and non-woven fabric. As described above, the larger the ΔMR, the higher the moisture absorption performance, and the better the comfort when worn. Therefore, the fabric having at least a part of the core-sheath composite fiber of the present invention can be used for clothing having excellent comfort by adjusting the mixing ratio of the composite fiber of the present invention so that ΔMR is 5.0% or more. Can be provided. As clothing, it can be set as various textile products, such as innerwear and sportswear.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the measuring method of the characteristic value in an Example, etc. are as follows.

(1) Sulfuric acid relative viscosity A polyamide chip sample was dissolved so as to be 1 g with respect to 100 ml of sulfuric acid having a concentration of 98% by weight, and the flow time (T1) at 25 ° C. was measured using an Ostwald viscometer. Subsequently, the flow-down time (T2) of only 98% by weight sulfuric acid was measured. The ratio of T1 to T2, that is, T1 / T2, was defined as sulfuric acid relative viscosity.

(2) Orthochlorophenol relative viscosity (OCP relative viscosity)
The polyether ester amide copolymer chip sample was dissolved to 1 g per 100 ml of orthochlorophenol, and the flow-down time (T1) at 25 ° C. was measured using an Ostwald viscometer. Subsequently, the flow-down time (T2) of only orthochlorophenol was measured. The ratio of T1 to T2, that is, T1 / T2, was defined as the orthochlorophenol relative viscosity.

(3) Fineness 1. Set a fiber sample on a 125 m / round measuring instrument, rotate it 200 times, create a looped skein, dry with a hot air dryer (105 ± 2 ° C. × 60 minutes), and weigh A fine weight was calculated from a value obtained by weighing with a balance and multiplying by the official moisture content.

(4) Strength and elongation The fiber sample is subjected to a constant-speed elongation condition indicated by “TENSILON” (registered trademark) manufactured by Orientec Co., Ltd., UCT-100, in JIS L1013 (chemical fiber filament yarn test method, 2010). It was measured. The elongation was determined from the elongation at the point showing the maximum strength in the tensile strength-elongation curve. Further, the strength was determined by dividing the maximum strength by the positive fineness. The measurement was performed 10 times, and the average values were taken as strength and elongation.

(5) Stress per unit fineness at 3% elongation (3% elongation stress)
The tensile test of the fiber sample was performed by the method described in the above item (4), and the strength at the point where the sample in the tensile strength-elongation curve showed an elongation of 3% was determined to obtain a stress at 3% elongation. The measurement was performed 10 times, and the average value was defined as the stress at 3% elongation.

(6) α crystal orientation parameter The fiber sample was measured by laser Raman spectroscopy, and the intensity ratio (parallel to I1120) of the Raman band derived from the α crystal of nylon observed near 1120 cm ⁻¹ , By taking a ratio of intensity ratio (I1120) perpendicular) in vertical polarization, it was set as a parameter for evaluating the degree of orientation. In addition, the scattering intensity of each polarization condition (parallel / vertical) was normalized based on the Raman band intensity of a CH bending band (near 1440 cm ⁻¹ ) having a small anisotropy with respect to orientation.

α crystal orientation parameter = (I1120 / I1440) parallel / (I1120 / I1440) vertical Note that the fiber sample for orientation measurement was sectioned by a microtome after resin embedding (bisphenol-based epoxy resin, cured for 24 hours). The section thickness was 2.0 μm. The section sample was cut by being slightly tilted from the fiber axis so that the cut surface was elliptical, and a portion where the thickness of the elliptical short axis was constant was selected and measured. The measurement is performed in the microscopic mode, and the laser spot diameter at the sample position is 1 μm. The orientation of the core and sheath layer center was analyzed, and the orientation was measured under polarization conditions. The degree of orientation was evaluated from the ratio of the Raman band intensities obtained when the polarization direction coincided with the fiber axis and the perpendicular condition when the direction was perpendicular. Each measurement point was measured three times, and the average value was used. Detailed conditions are shown below.

Laser Raman spectroscopy equipment: T-64000 (Jobin Yvon / Ehime Bussan)
Condition: Measurement mode; Microscopic Raman Objective lens: x100
Beam diameter: 1μm
Light source: Ar + laser / 514.5nm
Laser power: 50mW
Diffraction grating: Single 600gr / mm
Slit: 100 μm
Detector: CCD / Jobin Yvon 1024 × 256.

(7) Boiling water shrinkage rate Measured according to JIS L1013: 2010 8.18.1 (Method B).

(8) Fabric production The core-sheath composite cross-section fiber of the present invention is used for warp and weft, and the warp density is set to 188 yarns / 2.54 cm and the weft density is 155 yarns / 2.54 cm. Weaved with tissue.

  The obtained green ground was scoured with a solution containing 2 g of caustic soda (NaOH) per liter using an open soaper, dried at 120 ° C. in a cylinder dryer, and then preset at 170 ° C. Thereafter, the temperature was raised to 120 ° C. at a rate of 2.0 ° C./min with a pressure-resistant drum type dyeing machine, and dyeing was performed for 60 minutes at a set temperature of 120 ° C. After dyeing, the fabric was washed with running water for 20 minutes, dehydrated and dried to obtain a woven fabric having a warp density of 200 / 2.54 cm and a weft density of 160 / 2.54 cm.

(9) Wrinkle-proof evaluation The woven fabric obtained in (8) above is subjected to JIS L1059-2 (Fashion test method for textile products-Part 2: Appearance evaluation after wrinkling (wrinkle method), 2009) The method described in the item 9 was used, and grade 5 (the smoothest appearance) to grade 1 (the most wrinkled appearance) were determined. In the case of grade 3 or higher, it was judged that the anti-mold property was excellent.

(10) ΔMR
The woven fabric obtained in (8) above is weighed in a weighing bottle of about 1 to 2 g, dried at 110 ° C. for 2 hours and weighed (W0), then the target substance is kept at 20 ° C. and relative humidity 65%. After holding for 24 hours, the weight is measured (W65). And this is hold | maintained at 30 degreeC and relative humidity 90% for 24 hours, Then, a weight is measured (W90). And it calculated according to the following formula.

MR65 = [(W65−W0) / W0] × 100% (1)
MR90 = [(W90−W0) / W0] × 100% (2)
ΔMR = MR90−MR65 (3)

(11) ΔMR after washing
The fabric obtained in the above (8) was repeatedly washed 20 times by the method described in No. 103 described in Appendix 1 of JIS L0217 (1995), and then the ΔMR described in the above (10) was measured and calculated. .

  When ΔMR was 5.0% or more, it was judged that good comfort was obtained when worn.

(12) ΔMR retention after washing As a change index of ΔMR before and after washing, ΔMR retention after washing was calculated by the following formula.

(ΔMR after washing process−ΔMR before washing process) / ΔMR before washing process × 100
When the ΔMR retention rate was 90% or more, it was judged that there was washing durability.

(13) High-order processing step passability When weaving a plain woven fabric with a core-sheath composite cross-section fiber of the present invention with a water jet loom at a weaving speed of 750 rpm and a weft length of 1620 mm at 10 mm (1000 m / cm) The number of stoppages due to yarn breakage of the loom was evaluated, and when the yarn breakage was 2 times or less, it was determined that the process was good.

Example 1
Polyether ester amide copolymer (manufactured by Arkema, MH1657 (chip ΔMR: 18.9)) having a relative viscosity of orthochlorophenol of 1.69, and nylon 610 having a relative viscosity of sulfuric acid of 2.72 as a core. Each was melted at 270 ° C., and spun from the concentric core-sheath composite base so that the core / sheath ratio (part by weight) = 50/50.

  At this time, the rotation speed of the gear pump was selected so that the total fineness of the obtained core-sheath composite yarn was 56 dtex, and the discharge amount was 22 g / min. Then, the yarn is cooled and solidified by the yarn cooling device, and the non-hydrous oil agent is supplied at the oil supply position 1000 mm from the lower surface of the base by the oil supply device. The roller is stretched at a peripheral speed of 2800 m / min, the stretching ratio between the take-off roller and the stretching roller is 1.50 times, the setting temperature of the stretching roller is 170 ° C., heat setting is performed, and the winding speed is 4000 m / min. The core-sheath composite cross-section fiber of 56 dtex24 filament was obtained.

  About the obtained core-sheath composite cross-section fiber, the fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, stress per unit fineness at 3% elongation before and after boiling water treatment The retention rate and the α crystal orientation parameter were measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

(Example 2)
A 56 dtex 24 filament core-sheath composite cross-section fiber was obtained in the same manner as in Example 1 except that the heat setting temperature of the heating roller was 180 ° C.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

(Example 3)
A 56 dtex 24 filament core-sheath composite cross-section fiber was obtained in the same manner as in Example 1 except that the heat setting temperature of the heating roller was 165 ° C.

  About the obtained core-sheath composite cross-section fiber yarn, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α The crystal orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

Example 4
A 56 dtex 24 filament core-sheath composite cross-section fiber was obtained in the same manner as in Example 1 except that the oil supply position was 1500 mm from the lower surface of the die and the winding speed was 3900 m / min.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

(Example 5)
A 56 dtex 24 filament core-sheath composite cross-section fiber was obtained in the same manner as in Example 1 except that the oil supply position was 800 mm from the lower surface of the die.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

(Example 6)
The core sheath of 56 dtex 24 filament was obtained in the same manner as in Example 1 except that the oiling position was 1500 mm from the bottom of the base, the draw ratio between the take-up roller and the draw roller was 1.45 times, and the take-up speed was 3900 m / min. A composite cross-section fiber was obtained.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

(Example 7)
The core sheath of 56 dtex 24 filament was obtained in the same manner as in Example 1 except that the oiling position was 800 mm from the bottom of the base, the draw ratio between the take-up roller and the draw roller was 1.55, and the take-up speed was 4100 m / min. A composite cross-section fiber was obtained.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

(Example 8)
Example 1 except that the winding speed of the take-up roller as the first roll was 2500 m / min, the draw ratio between the take-up roller and the drawing roller was 1.65 times, and the take-up speed was 3900 m / min. The core-sheath composite cross-section fiber of 56 dtex24 filament was obtained by the method.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

Example 9
Example 1 except that the winding speed of the take-up roller as the first roll was 3400 m / min, the draw ratio between the take-up roller and the drawing roller was 1.20 times, and the take-up speed was 3900 m / min. The core-sheath composite cross-section fiber of 56 dtex24 filament was obtained by the method.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 1.

(Comparative Example 1)
A core-sheath composite cross-section yarn of 56 dtex 24 filament was obtained in the same manner as in Example 1 except that the heat setting temperature of the heating roller was 190 ° C.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 2.

  At this level, where the heat setting temperature of the heating roller is high, the moisture absorption performance and anti-mold properties are excellent, and furthermore, the moisture absorption performance is maintained even after washing, but stains such as decomposition products of spinning oil on the heating roller. Was promoted, yarn breakage frequently occurred in the high-order processing step, and the process passability was poor.

(Comparative Example 2)
A core-sheath composite cross-section fiber of 56 dtex 24 filament was obtained in the same manner as in Example 1 except that the set temperature of the drawing roller was 150 ° C.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 2.

  At this level where the heat setting temperature of the heating roller is low, the balance between the shrinkage characteristics of the sheath nylon 610 and the core polyetheresteramide copolymer is lost, and the boiling water shrinkage is as high as 15.0%. It became a certain fabric.

(Comparative Example 3)
The core sheath of 56 dtex 24 filament was obtained in the same manner as in Example 1 except that the oiling position was 1800 mm from the bottom of the base, the draw ratio between the take-up roller and the draw roller was 1.30 times, and the take-up speed was 3500 m / min. A composite cross-section fiber was obtained.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 2.

  At this level, where the distance from the lower surface of the base to the oiling position is long, the rigidity of the sheath nylon 610 is lowered, the balance with the shrinkage characteristics of the core polyetheresteramide copolymer is lost, and the unit at 3% elongation The stress per fineness was as low as 0.58 cN / dtex, resulting in a woven fabric with creases.

(Comparative Example 4)
Example 1 except that the winding speed of the take-up roller as the first roll was 2200 m / min, the draw ratio between the take-up roller and the drawing roller was 1.80 times, and the take-up speed was 3800 m / min. The core-sheath composite cross-section fiber of 56 dtex24 filament was obtained by the method.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 2.

  At this level where the take-up speed is slow, the rigidity of the sheath nylon 610 is lowered, the balance with the shrinkage characteristics of the core polyetheresteramide copolymer is lost, and the boiling water shrinkage is 12.3%. It became the textile with.

(Comparative Example 5)
Example 1 except that the winding speed of the take-up roller as the first roll was 3700 m / min, the draw ratio between the take-up roller and the drawing roller was 1.05 times, and the take-up speed was 3700 m / min. The core-sheath composite cross-section fiber of 56 dtex24 filament was obtained by the method.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 2.

  At this level where the take-up speed is high, the rigidity of the sheath nylon 610 decreases, the balance with the shrinkage characteristics of the core polyether ester amide copolymer is lost, and the stress per unit fineness at 3% elongation is 0. The result was a low 54 cN / dtex and a woven fabric with creases, frequent thread breaks in the high-order processing step, and poor process passability.

(Comparative Example 6)
A core-sheath composite cross-section fiber of 56 dtex24 filaments was collected in the same manner as in Example 1 except that nylon 6 having a relative viscosity of sulfuric acid of 2.40 was used as the sheath and the heat setting temperature of the heating roller was 150 ° C.

  About the obtained core-sheath composite cross-sectional fiber, fineness, strength, elongation, stress per unit fineness at 3% elongation, boiling water shrinkage, retention rate of stress at 3% elongation before and after boiling water treatment, α crystal The orientation parameter was measured. Further, the obtained woven fabric was evaluated for anti-mold property, ΔMR, ΔMR after washing, and ΔMR retention after washing. These results are shown in Table 2.

  At this level, where the sheath polyamide is nylon 6, the rigidity of the sheath nylon 6 is low, the balance with the shrinkage characteristics of the core polyetheresteramide copolymer is lost, and the stress per unit fineness at 3% elongation Was as low as 0.53 cN / dtex.

Claims (5)

The core polymer is a polyether ester amide copolymer , the sheath polymer is a polyamide having a dicarboxylic acid unit whose main component is a sebacic acid unit, the boiling water shrinkage is 6.0 to 12.0%, and the fiber A core-sheath composite cross-section fiber having a stress per unit fineness of 3% elongation in a tensile test of 0.60 cN / dtex or more.   The core-sheath composite cross-section fiber according to claim 1, wherein the α crystal orientation parameter of the sheath is 2.10 to 2.70.   The core-sheath composite cross-section fiber according to claim 1 or 2, wherein a stress retention per unit fineness at 3% elongation in a tensile test of the fiber before and after boiling water treatment is 60% or more.   A fabric having at least a portion of the core-sheath composite cross-section fiber according to any one of claims 1 to 3.   A fiber product having at least a part of the core-sheath composite cross-section fiber according to any one of claims 1 to 3.