JP2019143258A - Core-sheath-type polyester composite fiber, false-twist yarn of core-sheath-type polyester composite fiber, knitted fabric, and manufacturing method of core-sheath-type polyester composite fiber - Google Patents

Abstract

To provide a core-sheath-type polyester composite fiber excellent in deodorant property, antibacterial property, spinnability and processability.SOLUTION: There is provided a core-sheath-type polyester composite fiber having a core part constituted by polyester A and a sheath part constituted by 100 pts.mass of polyester B and 1.5 to 5.0 pts.mass of a polyester resin composition B containing deodorant fine particles, and satisfying following (1) to (3). (1) The deodorant fine particles mainly contain zinc oxide and silicon dioxide, and a mass ratio of the zinc oxide and the silicon dioxide is (zinc oxide):(silicon dioxide)=15:85 to 40:60. (2) Average particle diameter of the deodorant fine particles is 0.1 to 2.0 μm. (3) An oil agent is adhered to a surface of a single fiber and adhered amount of the oil agent is 0.5 to 3.0 mass% based on all mass of a constitutional fiber.SELECTED DRAWING: None

Description

  The present invention relates to a core-sheath type polyester composite fiber, a false twisted yarn of a core-sheath type polyester composite fiber, a woven or knitted fabric, and a method for producing a core-sheath type polyester composite fiber.

  Conventionally, in order to obtain a fiber having excellent deodorizing properties, it is known to fix the deodorizing fine particles to the fibers (for example, Patent Document 1).

JP 2000-301638 A

  However, Patent Document 1 has a problem that the deodorizing property is not sufficient because the deodorizing fine particles are easily removed. In some cases, antibacterial properties are not sufficient. Therefore, it is conceivable to contain deodorant fine particles in the fiber. In such a case, it is necessary to increase the content of the deodorant fine particles in order to improve the deodorant property. And there was a problem that it was inferior in workability. An object of the present invention is to solve the above-described problems of the prior art and to provide a polyester fiber excellent in any of deodorizing property, antibacterial property, spinnability, and processability. .

  As a result of intensive studies, the present inventors have found that polyester fibers containing specific deodorant fine particles only in the sheath portion of the core-sheath composite fiber and having a specific amount of oil attached to the fiber surface are deodorant and antibacterial. As a result, the present invention was completed.

That is, the gist of the present invention is the following (1) to (9).
(1) A core-sheath type in which a core part is composed of polyester A, and a sheath part is composed of 100 parts by mass of polyester B and 1.5 to 5.0 parts by mass of deodorant fine particles. A core-sheath type polyester composite fiber which is a polyester composite fiber and satisfies the following (i) to (iii).
(i) The deodorizing fine particles are mainly composed of zinc oxide and silicon dioxide, and the mass ratio of the zinc oxide to the silicon dioxide is (zinc oxide) :( silicon dioxide) = 15: 85 to 40:60. .
(ii) The deodorant fine particles have an average particle size of 0.1 to 2.0 μm.
(Iii) The oil agent is adhered to the surface of the single fiber, and the adhesion amount of the oil agent is 0.5 to 3.0% by mass with respect to the total mass of the constituent fibers.
(2) The core-sheath type polyester composite fiber according to (1), wherein the dynamic friction coefficient is in a range of 0.5 or less.
(3) The core-sheath polyester composite fiber according to (1) or (2), which has an antibacterial activity value of 2.2 or more and a deodorizing property to acetic acid of 60% or more.
(4) The total amount of ester-forming sulfonic acid metal salt compound and / or ester-forming sulfonic acid phosphonium salt compound is 1.0 to 5.0 mol% with respect to all the acid components constituting the polyester B. The core-sheath type polyester composite fiber according to any one of (1) to (3), which is polymerized.
(5) The core-sheath polyester composite fiber according to (4), which has a deodorizing property against ammonia of 70% or more.
(6) A false twisted yarn of a core-sheath type polyester composite fiber, wherein the core-sheath type polyester composite fiber of any one of (1) to (5) is false twisted.

(7) A method for producing the core-sheath polyester composite fiber according to any one of (1) to (5), comprising the following steps (a) to (e) in this order.
(A) A step of preparing polyester A and polyester B.
(B) A step of adding the deodorizing fine particles at a ratio of 1.5 to 5.0 parts by mass with respect to 100 parts by mass of the polyester B to obtain a polyester resin composition B.
(C) A step in which polyester A is arranged on the core side, polyester resin composition B is arranged on the sheath side, and melt spinning is performed using a die for a conventional core-sheath type composite fiber.
(D) A step of attaching an oil agent to the surface after melt spinning so that the adhesion amount is 0.5 to 3.0 mass% with respect to the total mass of the constituent fibers.
(E) A step of taking up at a take-up speed of 1000 to 6000 m / min using a take-up roller.
(8) A woven or knitted fabric comprising the core-sheath polyester composite fiber according to any one of (1) to (5).
(9) A woven or knitted fabric including the false twisted yarn of the core-sheath polyester composite fiber of (6).

  The core-sheath type polyester composite fiber of the present invention contains specific deodorant fine particles only in the sheath part of the core-sheath type composite fiber, and further has a specific amount of oil attached to the surface of the fiber. (Especially deodorant property to acetic acid), antibacterial properties, spinnability and processability are all excellent. Furthermore, when polyester which comprises a sheath part contains ester-forming sulfonate group containing dicarboxylic acid in a specific ratio, it will also be excellent in the deodorizing property with respect to ammonia.

Hereinafter, the present invention will be described in detail.
[Core-sheath polyester composite fiber]
The core-sheath type polyester composite fiber of the present invention is a polyester resin composition in which the core part is composed of polyester A, and the sheath part includes 100 parts by mass of polyester B and 1.5 to 5.0 parts by mass of deodorant fine particles. A core-sheath type polyester composite fiber composed of B, which satisfies the following (1) to (3).
(1) The deodorizing fine particles are mainly composed of zinc oxide and silicon dioxide, and the mass ratio of zinc oxide to silicon dioxide is (zinc oxide) :( silicon dioxide) = 15: 85 to 40:60.
(2) The average particle size of the deodorant fine particles is 0.1 to 2.0 μm.
(3) The oil agent is adhered to the surface of the single fiber, and the adhesion amount of the oil agent is 0.5 to 3.0 mass% with respect to the total mass of the constituent fibers.

  In the present invention, by using the core-sheath type composite fiber, the spinnability is improved and the practical strength is excellent. In addition, while maintaining the concentration of deodorant fine particles on the fiber surface at a level at which sufficient deodorant and antibacterial properties are expressed, the content of the deodorant fine particles with respect to the entire fiber can be lowered, which is excellent in cost merit. There is an effect.

  The mass ratio of the core portion and the sheath portion is not particularly limited, but from the viewpoint of achieving both spinnability, fiber strength, and cost merit, the core portion / sheath portion is 85/15 to 60/40. Is more preferable, and 80/20 to 65/35 is more preferable.

(Polyester A)
The polyester A constituting the core is not particularly limited, and examples thereof include a polyester composed of a terephthalic acid component and an ethylene glycol component, and 80 mol% or more of all structural units being ethylene terephthalate.

  Although the intrinsic viscosity of polyester A is not specifically limited, For example, it is preferable that it is 0.45-0.80, and it is more preferable that it is 0.50-0.75. When the intrinsic viscosity of the polyester A is 0.45 or more, the practical strength is further improved, and when the polyester A is 0.80 or less, the spinning operability is further improved.

(Polyester resin composition B)
The polyester resin composition B constituting the sheath part contains 100 parts by mass of polyester B and 1.5 to 5.0 parts by mass of deodorant fine particles. The content of the deodorant fine particles is preferably 2.0 to 4.5 parts by mass, and more preferably 2.5 to 4.0 parts by mass. If the amount of the deodorizing fine particles is less than 1.5 parts by mass, there is a problem that the deodorizing performance and antibacterial performance are inferior. On the other hand, if the amount exceeds 5.0 parts by mass, the polyester deteriorates due to the action of the deodorizing particles. There is a problem that the spinning operability deteriorates.

(Deodorant fine particles)
The deodorant fine particles are mainly composed of zinc oxide and silicon dioxide. Here, the main component means that the mixture of zinc oxide and silicon dioxide is 80% by mass or more.

  The mass ratio of zinc oxide and silicon dioxide in the deodorant fine particles is (zinc oxide) :( silicon dioxide) = 15: 85-40: 60, preferably 20: 80-35: 65, 25 : 75 to 30:70 is more preferable. If the proportion of zinc oxide is less than the above range, there is a problem that the antibacterial property is poor, and if the proportion of zinc oxide exceeds the above range, there is a problem that the deodorizing property is deteriorated. That is, in the present invention, in order to achieve both deodorant properties and antibacterial properties, the mass ratio of zinc oxide and silicon dioxide in the deodorant fine particles is set within a specific range.

  The average particle size of the deodorant fine particles is 0.1 to 2.0 μm, and preferably 0.4 to 1.7 μm. If it is less than 0.1 μm, secondary agglomeration tends to occur at the time of melt-kneading in the spinning step, and the resulting coarse particles clog the polymer filtration filter, which makes it impossible to continue the operation. On the other hand, if it exceeds 2.0 μm, there is a problem that some coarse particles are clogged in the polymer filtration filter, making it impossible to continue the operation.

  By using the above-mentioned specific deodorant fine particles, both deodorant and antibacterial properties can be improved. Preferably, the antibacterial activity value is 2.2 or more, and the deodorization property against acetic acid is 60% or more. More preferably, the antibacterial activity value can be 2.5 or more, and the deodorizing property against acetic acid can be 65% or more, and still more preferably, the antibacterial activity value is 2.5 or more and deodorizing against acetic acid. The property can be set to 70% or more. In addition, about the antibacterial activity value and the calculation method of deodorizing property with respect to acetic acid, it mentions later in an Example.

(Polyester B)
The polyester B may be the same as the polyester A as described above, for example. Alternatively, it is preferable that the polyester B is obtained by copolymerizing a total of 1.0 to 5.0 mol% of ester-forming sulfonic acid group-containing dicarboxylic acid with respect to the total acid components. With such a configuration, a synergistic effect with the use of the specific deodorant fine particles described above can be achieved, and the deodorizing property with respect to ammonia can be 70% or more, preferably 74% or more. More preferably 80% or more. A method for calculating the deodorizing property with respect to ammonia will be described later in Examples.

  The sulfonate group-containing dicarboxylic acid is not particularly limited as long as it is a monomer component having both a dicarboxyl group and a sulfonate group in the molecule. For example, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid , 5-lithium sulfoisophthalic acid, sodium sulfonaphthalenedicarboxylic acid, sodium sulfophenyl dicarboxylic acid, dicarboxylic acid such as 5-sodium sulfoterephthalic acid, and ethylene glycol esters thereof.

  Among these, 5-sodium sulfoisophthalic acid is particularly preferably used from the viewpoints of operability and cost during melt spinning.

  Polyester B is preferably one in which ester-forming sulfonic acid group-containing dicarboxylic acids are copolymerized at a ratio of 1.0 to 5.0 mol% in total with respect to all of the constituent acid components. More preferably, it is copolymerized in an amount of 0 to 4.5 mol%, more preferably 1.0 to 4.0 mol%, and more preferably 1.0 to 3.0 mol%. More preferably, it is a polymerized one. When the copolymerization amount is 1.0 mol% or more, the ammonia deodorizing performance is further improved. On the other hand, when the content is 5.0 mol% or less, the spinning operability is further improved. That is, when the copolymerization ratio is in the above range, the balance between ammonia deodorizing performance and spinning operability is further improved.

  The intrinsic viscosity of polyester B is not particularly limited, but is preferably 0.45 to 0.80, and more preferably 0.50 to 0.75. When the intrinsic viscosity of the polyester B is 0.45 or more, the practical strength is further improved, and when it is 0.80 or less, the spinning operability is further improved.

(Oil)
In the core-sheath type polyester composite fiber of the present invention, an oil agent (so-called spinning oil agent) is attached to the surface of the constituent fiber. The adhesion amount of the oil agent is 0.5 to 3.0% by mass, preferably 0.5 to 2.5% by mass, and 0.5 to 2.0% by mass with respect to the total mass of the constituent fibers. It is more preferable that

  The oil agent is used for the purpose of improving the convergence of the yarn in the spinning process and improving the process passability. For example, the oil agent is removed in the scouring process after producing the knitted fabric or woven fabric. In general, the adhesion amount (addition concentration) is reduced. However, in the present invention, when the amount of the oil agent is in the normal range (for example, about 0.3 to 0.4% by mass), the defect is that the single yarn falls off from the end face of the finished yarn in the spinning process. Will occur. Due to these drawbacks, the unraveling property of the wound yarn is remarkably deteriorated, resulting in a problem that leads to the generation of broken yarn in the yarn processing step. The present inventors have studied various causes of such defects. And, since deodorant fine particles containing a high concentration of silicon dioxide as described above and having a small average particle size are used, if the additive concentration of the oil is low, the deodorant particles are exposed on the fiber surface. Therefore, it was speculated that the contact area between the single yarns may be reduced, and the convergence of the multifilament may be significantly deteriorated. Furthermore, in such a case, in addition to the reduction in the contact area between the single yarns, in the present invention, the deodorant fine particles contain silicon dioxide at a high concentration, so that the convergence is significantly worsened. I guessed it would be.

  That is, in the present invention, in order to solve the above-described problems, the amount of the oil agent is increased in a specific range, unlike the conventional technique. By adopting such a technical idea, the present invention improves the convergence between constituent fibers even when the specific deodorant fine particles as described above are used in order to enhance the deodorant property and antibacterial property. And completed by improving the workability. That is, if the amount of oil attached is less than 0.5% by mass, there arises a problem that processing operability deteriorates. When it exceeds 3.0 mass%, the resistance at the time of oil agent application will become large, and the problem that spinning operability will deteriorate will occur.

  Long fibers used mainly for clothing are often added with texture and function by yarn processing. In the yarn processing process, it is necessary to unwind the yarn taken off in the spinning process. Therefore, the unwinding property of the yarn is one of the important quality items. In the present invention, the spinning oil is added at a high concentration within a range where the spinning operability is not impaired, and the spinning oil additive concentration is specified for the purpose of improving the processing operability by increasing the convergence of the single yarn. It is necessary to be in the range.

  Although it does not specifically limit as an oil agent, The mixture containing the lubricant component and surfactant component which are mentioned later is generally mentioned. Examples of the lubricant component include ether compounds, ester compounds, mineral oils, and silicone oils. Examples of the surfactant component include anionic surfactants, nonionic surfactants, and amphoteric surfactants. Moreover, various modifiers may be contained in the oil according to the intended use. Examples of the modifier include dyeability improvers, antistatic agents, and antioxidants.

  The core-sheath type polyester composite fiber of the present invention preferably has a dynamic friction coefficient on the fiber surface in the range of 0.5 or less, more preferably 0.45 or less, and further preferably 0.40 or less. 0.32 or less is more preferable. When it is 0.5 or less, it is excellent in texture such as sleeve-stretching properties when made into a fabric. In order to set the dynamic friction coefficient of the fiber surface within the above range, for example, by adding specific deodorant fine particles to the fiber sheath in the spinning process and exposing the deodorant fine particles to the fiber surface, the fiber surface and the friction body A method for reducing the contact area and the friction, or a method for setting the amount of oil on the fiber surface within the above range, and a method for making the deodorant fine particles more preferable (for example, zinc oxide and silicon dioxide). In which the mass ratio is set to a more preferable range, the particle size is set to a more preferable range, or the content relative to the polyester B is set to a more preferable range. In the present invention, the above-described deodorant fine particles are exposed on the fiber surface, so that in addition to expressing deodorant properties and antibacterial properties, it also contributes to reducing the dynamic friction coefficient. The lower the dynamic friction coefficient, the better. The lower limit is not particularly limited, but is about 0.1, for example. A method for calculating the dynamic friction coefficient will be described later in Examples.

  The total fineness of the core-sheath polyester composite fiber of the present invention is not particularly limited, but is mainly intended for use in clothing fibers and is preferably 20 to 200 dtex from the viewpoint of fabric texture. More preferably, it is 20-180 dtex.

  The number of filaments of the core-sheath polyester composite fiber of the present invention is not particularly limited, but is preferably 12 to 96, and preferably 18 to 72 from the viewpoint of spinning operability and fabric texture. Is more preferable.

  In the core-sheath type polyester composite fiber of the present invention, a fine pore forming agent, a cationic dye dyeing agent, a coloring preventing agent, a heat, as necessary, in the core part or the sheath part as long as the effects of the present invention are not impaired. Additives such as stabilizers, optical brighteners, matting agents, colorants, hygroscopic agents may be included.

[False twisted yarn of core-sheath type polyester composite fiber]
By performing false twisting on the core-sheath polyester composite fiber of the present invention, a false twist yarn of the core-sheath polyester composite fiber can be obtained. By using false twisted yarn, there is an advantage that it is more excellent in bulkiness.

  The crimp rate of the false twisted yarn of the core-sheath type polyester composite fiber of the present invention is not particularly limited, but is preferably 5 to 70%, and more preferably 10 to 65%. A method for obtaining the crimp rate will be described later in the embodiment.

[Method for producing core-sheath type polyester composite fiber]
The method for producing the core-sheath type polyester composite fiber is not particularly limited, and includes, for example, the following steps (A) to (E) in this order.
(A) A step of preparing polyester A and polyester B.
(B) A step of adding the deodorizing fine particles at a ratio of 1.5 to 5.0 parts by mass with respect to 100 parts by mass of the polyester B to obtain a polyester resin composition B.
(C) A step in which polyester A is arranged on the core side, polyester resin composition B is arranged on the sheath side, and melt spinning is performed using a die for a conventional core-sheath type composite fiber.
(D) A step of attaching an oil agent to the surface after melt spinning so that the adhesion amount is 0.5 to 3.0 mass% with respect to the total mass of the constituent fibers.
(E) A step of taking up at a take-up speed of 1000 to 6000 m / min using a take-up roller.

  In step (A), polyester A and polyester B as described above are prepared.

  In the step (b), deodorant fine particles are added at a ratio of 1.5 to 5.0 parts by mass with respect to 100 parts by mass of polyester B to obtain polyester resin composition B. The method for adding the deodorant fine particles can be a conventional method and is not particularly limited. For example, a master obtained by melting and kneading deodorant fine particles and polyester B in a melt extruder into a chip. A technique using a batch can be mentioned. Moreover, the method of mixing a deodorant microparticles | fine-particles and polyester B before throwing into an extruder using a side feeder is also mentioned.

  In the step (c), polyester A is disposed on the core side, polyester resin composition B is disposed on the sheath side, and melt spinning is performed using a base for a core-sheath type composite fiber. The spinning temperature of melt spinning is not particularly limited, but a method of 270 to 300 ° C. can be mentioned.

  In the step (d), after melt spinning, an oil agent is adhered to the fiber surface so that the adhesion amount is 0.5 to 3.0 mass% with respect to the total mass of the constituent fibers. As a method for attaching the oil agent, a conventional method can be adopted and is not particularly limited, but examples thereof include a roller oil supply method, a guide oil supply method using a metering pump, an immersion oil supply method, and a spray oil supply method. It is done.

  In the step (e), a known take-up roller is used and the take-up speed in the step (e) is preferably 1000 to 6000 m / min, and the take-up speed in the step (e) is preferably 2500 to 4000 m / min. It is more preferable that When the take-up speed is less than 1000 m / min, there is a problem that the productivity is inferior, and when it exceeds 6000 m / min, a problem that the spinning operability deteriorates occurs.

[Method for producing false twisted yarn of core-sheath polyester composite fiber]
Examples of the method for producing the false twisted yarn of the core-sheath type polyester composite fiber include a method of subjecting the core-sheath type polyester composite fiber of the present invention to false twist processing according to a conventional method. The false twisting conditions are not particularly limited. For example, when a spindle method is used, false twisting is preferably performed under conditions of a temperature of 160 to 220 ° C. and a false twist coefficient of 27000 to 32000.

  In the false twisting process described above, for example, simultaneous stretching may be performed at 1.4 to 1.8 times.

[Weaving and knitting]
The woven or knitted fabric of the present invention contains the core-sheath type polyester composite fiber of the present invention or the false twisted yarn of the core-sheath type polyester composite fiber of the present invention, and preferably contains a mixed ratio of 25% by mass or more. More preferably, it is contained at a mixing ratio of not less than mass%, more preferably at a mixing ratio of not less than 80 mass%. Examples of the mixing method include mixed fiber, mixed spinning, knitting, knitting, and knitting. In the woven or knitted fabric of the present invention, the location where the core-sheath polyester composite fiber of the present invention or the false-twisted yarn of the core-sheath polyester composite fiber of the present invention is not particularly limited, and is used for either the front surface or the back surface. Also good.

  When the woven or knitted fabric of the present invention is a woven fabric, specific examples of the structure are not particularly limited, and examples thereof include plain weave, twill weave, satin weave, and entangled weave. The fabric density is not particularly limited, and can be appropriately set depending on the application.

  In the case where the woven or knitted fabric of the present invention is a knitted fabric, specific examples of the structure thereof are not particularly limited, and examples thereof include canopy, milling, smooth, and the like. The knitted fabric density is not particularly limited, and can be appropriately set depending on the use.

  The use of the woven or knitted fabric of the present invention is not particularly limited, but because of its excellent antibacterial and deodorant properties, apparel such as socks, underwear, sportswear, dress shirts, work clothes, shoe materials, and hats Therefore, it can be preferably used for daily life materials such as curtains and sofas, and sewing threads.

  Next, the present invention will be specifically described with reference to examples. In addition, the various characteristic values and evaluation in an Example were performed as follows.

(1) Intrinsic Viscosity It was measured based on a conventional method under the condition of a temperature of 20 ° C. using a mixture of equal mass of phenol and ethane tetrachloride as a solvent.

(2) Average particle diameter (median diameter) of deodorant fine particles
A laser diffraction / scattering particle size analyzer (“SALD-7100”, manufactured by Shimadzu Corporation) is used for a solution (concentration: 5 mass%) in which the polyester resin composition B is dissolved in hexafluoro-2-propyl alcohol. Measured.

(3) Adhering amount of spinning oil The adhering amount of spinning oil was measured by the following procedure using a rapid residual oil extractor (R-II type) manufactured by Tokai Keiki Co., Ltd.
About 2 g of the sample was sampled and the mass was accurately measured. The measured value here was set to A. The oil was extracted from this sample using ethanol. The mass of the oil was obtained by completely evaporating the ethanol in the extract and measuring the mass of the remaining liquid. The measured value of the oil content was B. The adhesion concentration of the spinning oil was calculated using the following formula.
Adhering amount of spinning oil (mass%) = (B / A) × 100

(4) Spinnability Evaluation was made according to the following criteria according to the number of yarn breakage during spinning when operated continuously for 24 hours.
○: Number of times of thread breakage is 0 to 1 △: Number of times of thread breakage is 2 to 4 times ×: Number of times of thread breakage is 5 times or more −: Thread cannot be collected

(5) False twist processability The following criteria were evaluated according to the number of yarn breaks during spinning when the operation was continued for 24 hours.
○: Number of times of thread breakage 0 to 1 △: Number of times of thread breakage 2 to 4 times ×: Number of times of thread breakage 5 times or more

(6) Coefficient of dynamic friction The coefficient of dynamic friction was measured using a Yarn Sangyo Co., Ltd. yarn running friction coefficient measuring device (ME-P01).
The test piece (friction body) is a mirror-polished stainless steel material with an outer diameter of 16 mm and a length of 100 mm. The friction angle is 180 °, the yarn speed is 100 m / min, and the tension of the automatic tension controller is 10 g. Threaded. The tensions T1 and T2 before and after the test piece were measured, and the dynamic friction coefficient (μd) was calculated using the following equation.
μd = {(1 / (friction angle × π / 180)} × ln (T2 / T1)

(7) Antibacterial activity value According to JIS L0217 103 method, unwashed fabric (size 0.40 g ± 0.05 g) (so that the mixture ratio of the false twisted yarn of the core-sheath polyester composite fiber of the present invention is 50% by mass) Prepare polyester false twisted yarn (80dtex24f) and prepare a cylindrical knitting machine (cylinder diameter: 3.5 inches, number of needles: 260N) manufactured by Eikoh Industries, Ltd., as described in JIS L1902. The antibacterial activity value of Moraxella was measured based on the bacterial solution absorption method.

(8) Acetic acid deodorant cloth (size 10 cm × 10 cm) as a sample (polyester false twisted yarn (80 dtex 24 f) so that the mixture ratio of false twisted yarn of the core-sheath type polyester composite fiber of the present invention is 50% by mass) SEK deodorization processing designated by the Council for Textile Evaluation Technology for the tube knitting machine (bottle diameter: 3.5 inches, number of needles: 260N) manufactured by Eikoh Industries, Ltd. In accordance with the deodorant performance evaluation method in the mark certification, measurement was performed using acetic acid as an odor component, and the result was expressed as an odor reduction rate (unit:%).

(9) Ammonia deodorant fabric (size 10 cm × 10 cm) (a polyester false twisted yarn (80 dtex24f) was prepared so that the mixture ratio of the false twisted yarn of the core-sheath polyester composite fiber was 50% by mass, In the SEK deodorization processing mark certification designated by the Council for Textile Evaluation Technology for Eiko Sangyo Co., Ltd.'s cylinder knitting machine (cylinder knitted fabric obtained using a hook diameter: 3.5 inches, the number of needles: 260 N) According to the deodorant performance evaluation method, measurement was performed using ammonia as an odor component, and the result was expressed as an odor reduction rate (unit:%).

(10) Crimp rate The yarn to be measured was used as a casserole with a winding number of 5 using a measuring machine having a frame circumference of 1.125 m, and left for a day and night with the casserole suspended from a stand. Next, the casserole was placed in boiling water under a load of 0.000147 cN / dtex (load 1) and subjected to thermal heat treatment for 30 minutes, and then lightly removed with filter paper and left to air-dry for 30 minutes. Next, with the load 1 applied, a light load (load 2) of 0.00177 cN / dtex was further applied, and the casket length a (cm) was measured. Next, only the load 2 was removed, a heavy load of 0.044 cN / dtex (load 3) was applied, and the length b (cm) of the cassette was measured. And the crimp rate (%) after boiling water treatment was computed according to the following formula. In addition, it performed about 3 used as a measuring object, and each average was made into the crimp rate.
Crimp rate (%) after boiling water treatment = [(ba) / b] × 100

Example 1
Polyester A (polyethylene terephthalate) having an intrinsic viscosity of 0.70 was prepared. And with respect to 100 mass parts of polyester B (polyethylene terephthalate) whose intrinsic viscosity is 0.70, zinc oxide and silicon dioxide are mixed in a ratio of (zinc oxide) :( silicon dioxide) = 27: 73 (mass ratio). The polyester resin composition B was prepared by adding 3.5 parts by mass of the deodorant fine particles (average particle size 0.8 μm).
The polyester A and the polyester resin composition B were put into a conventional melt spinning machine, and after the melt was filtered using a metal filter having an opening of 30 μm, the core-sheath cross-sectional shape fibers could be spun. Spinning was performed from a die having a spinning hole formed at (polyester A (core part)) :( polyester resin composition B (sheath part)) = 70:30 (mass ratio).

  The spun yarn is cooled by an air flow, passed through an oiling device (oil supply device), and an oil agent (manufactured by Takemoto Yushi Co., Ltd., polyether-based oil agent) is attached so that the adhesion amount is 1.0 mass%. The core-sheath polyester composite fiber of the present invention was obtained (132 dtex 24f).

Next, the obtained yarn (semi-drawn yarn) was drawn with a conventional false twisting machine at a false twisting factor of 30000 and a draw ratio of 1.65 times, and further heat-treated with a heater plate at 175 ° C. As a result, a false twisted yarn of the core-sheath type polyester composite fiber of the present invention was obtained (80 dtex 24f, crimp rate 55%). Furthermore, the polyester false twisted yarn (80 dtex 24f) is aligned so that the mixture ratio of the false twisted yarn of the core-sheath polyester composite fiber is 50% by mass, and the Yoko Sangyo cylinder knitting machine (bottle diameter: 3.5 inches, The number of needles: 260 N) was used to create a tubular knitted fabric. This knitted fabric was refined by a conventional method and dyed at a temperature of 130 ° C. for 30 minutes according to the following formulation.
Dye UVITEX EBF: 1% omf
Auxiliary Nikka Sun Salt SN-130: 0.5 g / l
Acetic acid: 0.2 ml / l

Example 2
The same procedure as in Example 1 was conducted except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide) = 15: 85.

Example 3
The same procedure as in Example 1 was conducted except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide) = 40: 60.

Example 4
The same operation as in Example 1 was performed except that the average particle size of the deodorant fine particles was 0.1 μm.
Although some filter clogging in the polymer filtration step was confirmed, this was not a problem that prevented the operation from being continued, and was sufficiently practical.

Example 5
This was carried out in the same manner as in Example 1 except that the average particle size of the deodorant fine particles was 2.0 μm.
Although some filter clogging in the polymer filtration step was confirmed, this was not a problem that prevented the operation from being continued, and was sufficiently practical.

Example 6
The same operation as in Example 1 was performed except that the content of the deodorant fine particles with respect to 100 parts by mass of polyester B was 1.5 parts by mass.

Example 7
The same operation as in Example 1 was performed except that the content of the deodorant fine particles with respect to 100 parts by mass of polyester B was 5.0 parts by mass. As the content of the deodorant fine particles increased, spun yarn was generated several times. However, it was at a level that does not cause any problem in operation, and was sufficiently durable for practical use.

Example 8
The same procedure as in Example 1 was performed except that the amount of the spinning oil applied was 0.5% by mass. Due to the small amount of oil added, the convergence of the single yarn is slightly lower than in Example 1, and several times of broken yarns due to unwinding failure occurred in the false twisting process, but there is no problem in operation. It was sufficient to withstand practical use.

Example 9
The same procedure as in Example 1 was performed except that the amount of the spinning oil applied was 3.0% by mass. Due to the large amount of oil agent added, the resistance at the time of oil agent application was slightly higher than in Example 1, and several broken yarns were generated in the spinning process, but it is at a level that does not cause any problems in operation, and can sufficiently withstand practical use. It was a thing.

Comparative Example 1
The same procedure as in Example 1 was carried out except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide) = 5: 95. In Comparative Example 1, the antibacterial property was poor.

Comparative Example 2
The same procedure as in Example 1 was performed except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide) = 50: 50. In Comparative Example 2, the deodorizing property against acetic acid was poor.

Comparative Example 3
The same procedure as in Example 1 was performed except that the average particle size of the deodorant fine particles was 0.05 μm. In Comparative Example 3, the spinning operation cannot be continued because the filter due to coarse particles generated by secondary aggregation in the polymer filtration step is clogged.

Comparative Example 4
The same procedure as in Example 1 was performed except that the average particle size of the deodorant fine particles was 4.0 μm. In Comparative Example 4, due to the presence of coarse particles, filter clogging occurred in the polymer filtration step, making it impossible to continue the spinning operation.

Comparative Example 5
The same procedure as in Example 1 was performed except that the content of the deodorant fine particles with respect to 100 parts by mass of polyester B was changed to 0.5 parts by mass. In Comparative Example 5, the antibacterial property and the deodorizing property against acetic acid were inferior, the dynamic friction coefficient was excessive, and the texture was poor.

Comparative Example 6
The same procedure as in Example 1 was performed except that the content of the deodorant fine particles with respect to 100 parts by mass of polyester B was 7.0 parts by mass. In Comparative Example 6, the polyester B was deteriorated by the action of the deodorant fine particles, the spinning process cut yarns were frequently generated, and the spinnability was poor.

Comparative Example 7
The same procedure as in Example 1 was conducted except that the amount of the spinning oil applied was 0.3% by mass. In Comparative Example 7, the convergence property of the multifilament was low, the unraveling property was deteriorated, the yarns resulting from the unraveling failure occurred frequently in the false twisting process, and the false twisting workability was poor.

Comparative Example 8
The same procedure as in Example 1 was performed except that the amount of the spinning oil applied was 4.0% by mass. In Comparative Example 8, since the resistance of the oil film was excessively exhibited, the spinnability was poor.
Comparative Example 9
This was carried out in the same manner as in Example 1 except that no deodorant fine particles were contained in the sheath. In Comparative Example 9, the antibacterial and deodorant properties were poor.

Example 10
For polyester B, the same procedure as in Example 1 was carried out except that sulfoisophthalic acid was copolymerized at a ratio of 1.5 mol% with respect to all acid components constituting the polyester.

Example 11
The same procedure as in Example 10 was performed except that the copolymerization amount of sulfoisophthalic acid was 1.0 mol%.

Example 12
The same procedure as in Example 10 was conducted except that the amount of sulfoisophthalic acid copolymerized was 5.0 mol%. Although the amount of sulfoisophthalic acid copolymerization was increased, several yarn breaks were generated in the spinning process. However, the level of operation was not a problem and it was sufficiently practical.

Example 13
The same procedure as in Example 10 was performed except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide) = 15: 85.

Example 14
The same procedure as in Example 10 was performed except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide =) 40:60.

Example 15
The same operation as in Example 10 was performed except that the average particle size of the deodorant fine particles was 0.1 μm.
Although some filter clogging in the polymer filtration step was confirmed, this was not a problem that prevented the operation from being continued, and was sufficiently practical.

Example 16
The same operation as in Example 10 was performed except that the average particle size of the deodorant fine particles was 2.0 μm.
Although some filter clogging in the polymer filtration step was confirmed, this was not a problem that prevented the operation from being continued, and was sufficiently practical.

Example 17
The same procedure as in Example 10 was performed except that the amount of deodorant fine particles added to 100 parts by mass of polyester B was 1.5 parts by mass.

Example 18
The same procedure as in Example 10 was performed except that the amount of deodorant fine particles added to 100 parts by mass of polyester B was 5.0 parts by mass. As the content of the deodorant fine particles increased, spun yarn was generated several times. However, the spun yarn was at a problem-free level and was sufficiently practical.

Example 19
The same procedure as in Example 10 was performed except that the amount of the spinning oil applied was 0.5% by mass.
Due to the small amount of oil added, the convergence of the single yarn is slightly lower than in Example 10, and several yarns due to unwinding failure occurred several times in the false twisting process, but there is no problem in operation. It was sufficient to withstand practical use.

Example 20
The same operation as in Example 10 was performed except that the amount of the spinning oil added was 3.0% by mass.
Due to the large amount of oil agent added, the resistance at the time of oil agent application was slightly higher than in Example 10, and several broken yarns were generated in the spinning process, but there was no problem in terms of operation, and it could withstand practical use sufficiently. It was a thing.

Example 21
The same procedure as in Example 10 was conducted except that the amount of sulfoisophthalic acid copolymerized in polyester B was 0.5 mol%. As compared with Example 10, the ammonia deodorant property was inferior, but the antibacterial property and the deodorant property against acetic acid were excellent.

Comparative Example 10
The same procedure as in Example 10 was conducted except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide) = 5: 95. In Comparative Example 11, the antibacterial property was inferior.

Comparative Example 11
The same procedure as in Example 10 was performed except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was (zinc oxide) :( silicon dioxide) = 50: 50. In Comparative Example 11, the deodorizing property against acetic acid was poor.

Comparative Example 12
The same operation as in Example 10 was performed except that the average particle size of the deodorant fine particles was 0.05 μm. In Comparative Example 12, the spinning operation cannot be continued because the filter with coarse particles generated by secondary aggregation in the polymer filtration step is clogged.

Comparative Example 13
The same procedure as in Example 10 was performed except that the average particle size of the deodorant fine particles was 4.0 μm. In Comparative Example 13, the spinning operation could not be continued because the filter with coarse particles was clogged in the polymer filtration step.

Comparative Example 14
The same procedure as in Example 10 was performed except that the amount of deodorant fine particles added to 100 parts by mass of polyester B was 0.5 parts by mass. In Comparative Example 14, the antibacterial property and the deodorizing property against acetic acid were inferior, the dynamic friction coefficient was high, and the texture was poor.

Comparative Example 15
The same procedure as in Example 10 was performed except that the amount of the deodorant fine particles added to 100 parts by mass of polyester B was 7.0 parts by mass. In Comparative Example 15, since the polyester B was deteriorated by the action of the deodorant fine particles, the spinnability was poor.

Comparative Example 16
The same procedure as in Example 10 was performed except that the amount of the spinning oil applied was 0.3% by mass. In Comparative Example 16, the convergence property of the multifilament was deteriorated, and the unwinding property was deteriorated due to the occurrence of the defect of the single yarn falling off, and the false twisting property was inferior.

Comparative Example 17
The same procedure as in Example 10 was performed except that the amount of the spinning oil applied was 4.0% by mass. In Comparative Example 17, since the resistance of the oil film was excessively exhibited, the spinnability was poor.

Comparative Example 18
The same procedure as in Example 10 was performed except that the deodorizing fine particles were not contained in the sheath. In Comparative Example 18, the antibacterial and deodorant properties were poor.

The evaluation results in Examples and Comparative Examples are shown in Table 1 and Table 2.

Claims (9)

A core-sheath type polyester composite fiber having a core part made of polyester A and a sheath part made of polyester resin composition B containing 100 parts by weight of polyester B and 1.5 to 5.0 parts by weight of deodorant fine particles. A core-sheath type polyester composite fiber satisfying the following (1) to (3).
(1) The deodorant fine particles are mainly composed of zinc oxide and silicon dioxide, and the mass ratio of the zinc oxide to the silicon dioxide is (zinc oxide) :( silicon dioxide) = 15: 85 to 40:60. .
(2) The average particle size of the deodorant fine particles is 0.1 to 2.0 μm.
(3) The oil agent is adhered to the surface of the single fiber, and the adhesion amount of the oil agent is 0.5 to 3.0 mass% with respect to the total mass of the constituent fibers.   The dynamic friction coefficient is in the range of 0.5 or less. The core-sheath type polyester composite fiber according to claim 1.   The core-sheath polyester composite fiber according to claim 1 or 2, wherein the antibacterial activity value is 2.2 or more and the deodorizing property against acetic acid is 60% or more.   The polyester B was copolymerized with a total of 1.0 to 5.0 mol% of the ester-forming sulfonic acid metal salt compound and / or the ester-forming sulfonic acid phosphonium salt compound with respect to the total acid component. The core-sheath-type polyester composite fiber according to any one of claims 1 to 3, wherein the core-sheath polyester composite fiber is used.   The core-sheath type polyester composite fiber according to claim 4, wherein the deodorizing property against ammonia is 70% or more.   A false twisted yarn of a core-sheath type polyester composite fiber, wherein the core-sheath type polyester composite fiber according to any one of claims 1 to 5 is false twisted. It is a method of manufacturing the core-sheath-type polyester composite fiber of any one of Claims 1-5, Comprising: The manufacturing method which contains the following processes (I)-(e) in this order.
(A) A step of preparing polyester A and polyester B.
(B) A step of adding the deodorizing fine particles at a ratio of 1.5 to 5.0 parts by mass with respect to 100 parts by mass of the polyester B to obtain a polyester resin composition B.
(C) A step in which polyester A is arranged on the core side, polyester resin composition B is arranged on the sheath side, and melt spinning is performed using a die for a conventional core-sheath type composite fiber.
(D) A step of attaching an oil agent to the surface after melt spinning so that the adhesion amount is 0.5 to 3.0 mass% with respect to the total mass of the constituent fibers.
(E) A step of taking up at a take-up speed of 1000 to 6000 m / min using a take-up roller.   A woven or knitted fabric comprising the core-sheath polyester conjugate fiber according to any one of claims 1 to 5. A woven or knitted fabric comprising the false-twisted yarn of the core-sheath polyester composite fiber according to claim 6.