JP7117710B2 - Core-sheath type polyester composite fiber, false twist yarn of core-sheath type polyester composite fiber, woven and knitted fabric, and method for producing core-sheath type polyester composite fiber - Google Patents

Description

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

BACKGROUND ART Conventionally, in order to obtain fibers with excellent deodorizing properties, it has been known to fix deodorant fine particles to fibers (for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2000-301638

However, in Patent Document 1, the deodorizing fine particles tend to fall off, so there is a problem that the deodorizing properties are not sufficient. In addition, the antibacterial properties were not sufficient in some cases. Therefore, it is conceivable to include deodorant fine particles in the fiber, but in such a case, it is necessary to increase the content of deodorant fine particles in order to improve the deodorant property. And there was a problem that it was inferior to workability. The technical object of the present invention is to solve the problems of the prior art as described above and to provide a polyester fiber that is excellent in all of deodorizing properties, antibacterial properties, spinnability, and workability. .

As a result of intensive studies by the present inventors, it was found that a polyester fiber containing specific deodorizing fine particles only in the sheath of a core-sheath type composite fiber and having a specific amount of oil attached to the fiber surface has deodorizing and antibacterial properties. The present inventors have completed the present invention by discovering that it is excellent in all of properties, spinnability, and processability.

That is, the gist of the present invention is the following (1) to ( 5 ).
(1) A core-sheath type in which the core is composed of polyester A and the sheath is composed of 100 parts by mass of polyester B and 1.5 to 5.0 parts by mass of polyester resin composition B containing deodorant fine particles. A core-sheath type polyester conjugated fiber which is a polyester conjugated fiber and satisfies the following (i) to (iv).
(i) the deodorant fine particles contain zinc oxide and silicon dioxide in an amount of 80% by mass or more, and the mass ratio of the zinc oxide to the silicon dioxide is (zinc oxide):(silicon dioxide)=15:85 or more; It is 40:60.
(ii) The deodorizing fine particles have an average particle diameter of 0.1 to 2.0 μm.
(iii) Polyester B is obtained by copolymerizing 1.0 to 5.0 mol % of a metal salt compound of an ester-forming sulfonic acid with respect to the total acid component of the polyester B.
(iv) The mass ratio of the core to the sheath (core/sheath) is 85/15 to 60/40.
( 2 ) A false-twisted yarn of a core-sheath type polyester conjugate fiber obtained by false-twisting the core-sheath type polyester conjugate fiber according to ( 1 ).

( 3 ) A method for producing the core-sheath type polyester conjugate fiber described in ( 1 ), comprising the following steps (a) to (d) in this order.
(a) a step of preparing polyester A and polyester B;
(b) A step of adding 1.5 to 5.0 parts by mass of deodorizing fine particles to 100 parts by mass of polyester B to obtain a polyester resin composition B;
(c) A step of disposing the polyester A on the core side and the polyester resin composition B on the sheath side, and melt-spinning them using a conventional spinneret for core-sheath type composite fibers.
(d) Using a take-up roller, take-up at a take-up speed of 1000 to 6000 m/min.
( 4 ) A woven or knitted fabric containing the core-sheath type polyester composite fiber of ( 1 ).
( 5 ) A woven or knitted fabric comprising the false twisted yarn of the core-sheath type polyester composite fiber according to ( 2 ).

The core-sheath type polyester conjugate fiber of the present invention contains specific deodorizing fine particles only in the sheath of the core-sheath type conjugate fiber, and the polyester constituting the sheath contains a specific ester-forming sulfonate group-containing dicarboxylic acid. , the deodorizing property against acetic acid, the antibacterial property, and the deodorizing property against ammonia are all excellent.

The present invention will be described in detail below.
[Sheath-core polyester composite fiber]
The core-sheath type polyester conjugate fiber of the present invention is composed of polyester A in the core portion and polyester resin composition containing 100 parts by mass of polyester B and 1.5 to 5.0 parts by mass of deodorant fine particles in the sheath portion. 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 and 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 ester-forming sulfonic acid metal salt compound and/or the ester-forming sulfonic acid phosphonium salt compound is 1.0 to 5.0 mol% in total with respect to the total acid component of the polyester B. It is polymerized.

In the present invention, by forming a core-sheath type conjugate fiber, the spinnability is improved and the practical strength is excellent. In addition, the concentration of the deodorant fine particles on the fiber surface can be maintained at a level that allows sufficient deodorant and antibacterial properties to be exhibited, and the content of the deodorant fine particles in the entire fiber can be reduced, resulting in excellent cost benefits. It has the effect of

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

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

Although the intrinsic viscosity of polyester A is not particularly limited, it is preferably, for example, 0.45 to 0.80, more preferably 0.50 to 0.75. When the intrinsic viscosity of the polyester A 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.

(Polyester resin composition B)
The polyester resin composition B constituting the sheath 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, more preferably 2.5 to 4.0 parts by mass. If the amount of the deodorant fine particles is less than 1.5 parts by mass, there is a problem that the deodorant performance and antibacterial performance are inferior. , there is a problem that the spinning runnability is deteriorated.

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

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

By using the specific deodorant fine particles described above, both deodorant and antibacterial properties can be improved. Preferably, the antibacterial activity value is 2.2 or more and the deodorant property against acetic acid is 60% or more. More preferably, the antibacterial activity value is 2.5 or more, and the deodorant against acetic acid is 65% or more, and more preferably, the antibacterial activity value is 2.5 or more, and the deodorant against acetic acid 70% or more. The method for calculating the antibacterial activity value and the deodorizing property against acetic acid will be described later in Examples.

(Polyester B)
Polyester B is obtained by copolymerizing a total of 1.0 to 5.0 mol % of an ester-forming sulfonate group-containing dicarboxylic acid with respect to all the constituent acid components. With such a configuration, a synergistic effect with the use of the specific deodorant fine particles is exhibited, and the deodorant property against ammonia can be 70% or more, preferably 74% or more. more preferably 80% or more. A method for calculating the deodorant property against 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, and examples thereof include 5-sodium sulfoisophthalic acid and 5-potassium sulfoisophthalic acid. , 5-lithiumsulfoisophthalic acid, sodium sulfonaphthalenedicarboxylic acid, sodium sulfophenyldicarboxylic acid, 5-sodium sulfoterephthalic acid and other dicarboxylic acids, and ethylene glycol esters thereof.

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

Polyester B is obtained by copolymerizing an ester-forming sulfonate group-containing dicarboxylic acid in a total ratio of 1.0 to 5.0 mol% with respect to all the constituent acid components. .5 mol% copolymerization is preferable, 1.0 to 4.0 mol% copolymerization is more preferable, and 1.0 to 3.0 mol% copolymerization is more preferable. is more preferable. When the copolymerization amount is 1.0 mol % or more, the ammonia deodorant performance is excellent. On the other hand, when it is 5.0 mol % or less, the spinning operation is excellent. In other words, when the copolymerization ratio is within the above range, the ammonia deodorizing performance and the spinning runnability are well balanced.

Although the intrinsic viscosity of polyester B is not particularly limited, it is preferably 0.45 to 0.80, 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.

In the core-sheath type polyester composite fiber of the present invention, an oil agent (so-called spinning oil agent) may be attached to the surface of the constituent fibers. The amount of the oil applied is not particularly limited, but is preferably 0.3 to 3.0% by mass, more preferably 0.5 to 2.5% by mass, relative to the total mass of the constituent fibers. is more preferable, and 0.5 to 1.0% by mass is even more preferable.

The oil agent is not particularly limited, but generally includes a mixture containing a lubricant component and a surfactant component, which will be described later. Examples of lubricant components include ether-based compounds, ester-based compounds, mineral oils, and silicone-based oils. Surfactant components include anionic surfactants, nonionic surfactants, amphoteric surfactants, and the like. In addition, various modifiers may be contained in the oil agent depending on the intended use. Modifiers include dyeability improvers, antistatic agents, antioxidants, and the like.

The core-sheath type polyester conjugate fiber of the present invention preferably has a coefficient of dynamic friction on the surface of the fiber in the range of 0.5 or less, more preferably 0.45 or less, and even more preferably 0.40 or less. , 0.32 or less. When it is 0.5 or less, it is excellent in texture such as sleeve threadability when made into a fabric. In order to make the dynamic friction coefficient of the fiber surface within the above range, for example, specific deodorant fine particles are added to the sheath of the fiber in the spinning process, and the deodorant fine particles are exposed on the fiber surface, so that the fiber surface and the friction body A method of reducing the contact area with the surface of the fiber to reduce friction, a method of adjusting the amount of oil agent on the fiber surface to the above range, and a method of further making the mode of the deodorant fine particles more preferable (for example, zinc oxide and silicon dioxide A more preferable range of the mass ratio with, a more preferable range of the particle size, or a more preferable range of the content relative to the polyester B) can be adopted. In the present invention, the exposure of the deodorant fine particles on the fiber surface contributes to the reduction of the dynamic friction coefficient in addition to the development of deodorant and antibacterial properties. In addition, the lower the coefficient of dynamic friction, the better, and the lower limit thereof is not particularly limited, but is, for example, about 0.1. A method of calculating the coefficient of dynamic friction will be described later in Examples.

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

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

The core-sheath type polyester conjugate fiber of the present invention may optionally contain a micropore-forming agent, a cationic dye dyeing agent, an anti-coloring agent, a heat Additives such as stabilizers, optical brighteners, matting agents, colorants, hygroscopic agents, etc. may be included.

[False Twisted Yarn of Core-Sheath Type Polyester Composite Fiber]
By subjecting the core-sheath type polyester conjugate fiber of the present invention to a false twisting process, a false twisted yarn of the core-sheath type polyester conjugate fiber can be obtained. False-twisted yarn has the advantage of being more excellent in bulkiness.

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

[Manufacturing method of core-sheath type polyester composite fiber]
A method for producing a core-sheath type polyester conjugate fiber is not particularly limited, but includes, for example, the following steps (a) to (d) in this order.
(a) a step of preparing polyester A and polyester B;
(b) A step of adding 1.5 to 5.0 parts by mass of deodorizing fine particles to 100 parts by mass of polyester B to obtain a polyester resin composition B;
(c) A step of disposing the polyester A on the core side and the polyester resin composition B on the sheath side, and melt-spinning them using a conventional spinneret for core-sheath type composite fibers.
(d) Using a take-up roller, take-up at a take-up speed of 1000 to 6000 m/min.

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

In step (b), 100 parts by mass of polyester B is added with 1.5 to 5.0 parts by mass of deodorizing fine particles to obtain polyester resin composition B. As a method for adding the deodorant fine particles, a conventional method can be adopted and there is no particular limitation. One method is to use batches. Alternatively, a side feeder may be used to mix the deodorant fine particles and the polyester B before feeding into the extruder.

In the step (c), the polyester A is placed on the core side and the polyester resin composition B is placed on the sheath side, and melt-spun using a conventional spinneret for core-sheath type conjugate fibers. The spinning temperature for melt spinning is not particularly limited, but a technique of 270 to 300° C. can be mentioned.

After melt spinning, an oil may be applied to the surface of the fiber. As a method for attaching the oil agent, a conventional method can be adopted and there is no particular limitation, but examples include a roller lubrication method, a guide lubrication method using a metering pump, an immersion lubrication method, and a spray lubrication method. be done.

In step (d), a known take-up roller is used to take off at a take-up speed of 1000 to 6000 m/min. is more preferable. If the take-up speed is less than 1,000 m/min, there is a problem of poor productivity, and if it exceeds 6,000 m/min, a problem of deterioration in spinning operability occurs.

[Method for producing false twisted yarn of core-sheath type polyester composite fiber]
As a method for producing the false twisted yarn of the core-sheath type polyester conjugate fiber, there is a method of subjecting the core-sheath type polyester conjugate fiber of the present invention to a false twisting process according to a conventional method. False twisting conditions are not particularly limited. For example, when a spindle method is used, false twisting is preferably performed at a temperature of 160 to 220° C. and a false twist coefficient of 27,000 to 32,000.

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

[Woven and Knitted]
The woven or knitted fabric of the present invention contains the core-sheath type polyester conjugate fiber of the present invention or the false twist yarn of the core-sheath type polyester conjugate fiber of the present invention, and is preferably contained at a mixing ratio of 25% by mass or more. It is more preferably contained at a mixture ratio of 80% by mass or more, more preferably at a mixture ratio of 80% by mass or more. Mixing methods include mixed filament, mixed spinning, mixed twist, mixed weaving, and mixed knitting. In the woven or knitted fabric of the present invention, the place where the core-sheath type polyester conjugate fiber of the present invention or the false twist yarn of the core-sheath type polyester conjugate fiber of the present invention is used is not particularly limited, and it can be used on either the front side or the back side. good too.

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

When the woven or knitted fabric of the present invention is a knitted fabric, specific examples of the texture are not particularly limited, and examples thereof include canoko, milled or smooth. The density of the knitted fabric is not particularly limited, and can be appropriately set according to the application.

Applications of the woven or knitted fabric of the present invention are not particularly limited, but clothing such as socks, underwear, sportswear, dress shirts, work clothes, shoe materials, and hats due to its excellent antibacterial and deodorant properties. Therefore, it can be preferably used for applications such as household materials such as curtains and sofas and sewing threads.

EXAMPLES Next, the present invention will be specifically described with reference to Examples. Various characteristic values and evaluations in the examples were performed as follows.

(1) Intrinsic Viscosity Measured by a conventional method at a temperature of 20° C. using an equal mass mixture of phenol and ethane tetrachloride as a solvent.

(2) Average particle size (median size) of deodorant fine particles
Polyester resin composition B was dissolved in hexafluoro-2-propyl alcohol (concentration: 5% by mass), and a laser diffraction/scattering particle size analyzer (manufactured by Shimadzu Corporation, "SALD-7100") was used. measured by

(3) Spinnability Evaluation was made according to the following criteria according to the number of yarn breakages during spinning during continuous operation for 24 hours.
○: 0 to 1 times of thread breakage △: 2 to 4 times of thread breakage ×: 5 or more times of thread breakage -: Thread cannot be collected

(4) False Twisting Workability Evaluated according to the following criteria according to the number of yarn breakages during spinning during continuous operation for 24 hours.
○: 0 to 1 times of thread breakage △: 2 to 4 times of thread breakage ×: 5 or more times of thread breakage

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

(6) Antibacterial activity value According to JIS L0217 103 method, unwashed fabric (size 0.40 g ± 0.05 g) (the false twist yarn of the core-sheath type polyester composite fiber of the present invention is mixed so that the mixing ratio is 50% by mass. A tubular knitted fabric obtained by using a tubular knitting machine manufactured by Eiko Sangyo Co., Ltd. (bottle diameter: 3.5 inches, number of needles: 260 N) is prepared by arranging polyester false twisted yarn (80 dtex 24 f), and described in JIS L1902. The antibacterial activity value of Moraxella was measured based on the bacterial liquid absorption method.

(7) Acetic acid deodorizing property Sample fabric (size 10 cm × 10 cm) (polyester false twisted textured yarn (80 dtex 24 f) so that the mixture rate of false twist yarn of the core-sheath type polyester composite fiber of the present invention is 50% by mass. For the tubular knitted fabric obtained using a tubular knitting machine manufactured by Eiko Sangyo Co., Ltd. (bottle diameter: 3.5 inches, number of needles: 260N), SEK deodorant processing specified by the Textile Evaluation Technology Council Measurement was performed using acetic acid as an odor component in accordance with the deodorant performance evaluation method in mark certification, and the results were shown as an odor reduction rate (unit: %).

(8) Ammonia deodorizing property Sample fabric (size 10 cm × 10 cm) (polyester false twisted textured yarn (80 dtex 24 f) is aligned so that the mixture rate of false twist yarn of the core-sheath type polyester composite fiber is 50% by mass, Regarding tubular knitted fabric obtained using a tubular knitting machine manufactured by Eiko Sangyo Co., Ltd. (bottle diameter: 3.5 inches, number of needles: 260N), SEK deodorant processing mark certification specified by the Textile Evaluation Technology Council Measurement was performed using ammonia as an odor component according to the deodorizing performance evaluation method, and the results were expressed as an odor reduction rate (unit: %).

(9) Crimp ratio A yarn to be measured was wound 5 times using a measuring machine with a frame circumference of 1.125 m, and the skein was left suspended on a stand for a whole day and night. Next, the skein was immersed in boiling water under a load of 0.000147 cN/dtex (load 1) and heat-treated for 30 minutes. Next, while the load 1 was applied, a light load of 0.00177 cN/dtex (load 2) was further applied, and the skein length a (cm) was measured. Next, only the load 2 was removed and a heavy load of 0.044 cN/dtex (load 3) was applied, and the length b (cm) of the skein was measured. Then, the crimp rate (%) after boiling water treatment was calculated according to the following formula. The measurement was performed on three pieces to be measured, and the average of the measurements was taken as the crimp ratio.
Crimp ratio after boiling water treatment (%) = [(ba)/b] × 100

Comparative example 1
Polyester A (polyethylene terephthalate) having an intrinsic viscosity of 0.70 was prepared. Then, with respect to 100 parts by mass of polyester B (polyethylene terephthalate) having an intrinsic viscosity of 0.70, zinc oxide and silicon dioxide are mixed at a ratio of (zinc oxide): (silicon dioxide) = 27:73 (mass ratio). A polyester resin composition B was prepared by adding 3.5 parts by mass of deodorizing fine particles (average particle size: 0.8 μm).
Polyester A and polyester resin composition B are put into a conventional melt spinning machine, and the melt is filtered using a metal filter with an opening of 30 μm, and then 24 fibers that can be spun into a core-sheath cross-sectional shape fiber. Spinning was carried out at a ratio of (polyester A (core)):(polyester resin composition B (sheath)) = 70:30 (mass ratio) from a spinneret having spinning holes.

The spun yarn is cooled by an air flow, passed through an oiling device (oil supply device) to adhere an oil (manufactured by Takemoto Yushi Co., Ltd., polyether oil), and taken up at a spinning speed of 3250 m / min. A core-sheath type polyester composite fiber was obtained (132 dtex 24 f).

Next, the obtained yarn (half-drawn yarn) is false-twisted and drawn with a conventional false-twisting machine at a false-twist coefficient of 30000 and a draw ratio of 1.65. A false twisted yarn of core-sheath type polyester composite fiber was obtained (80 dtex 24 f, crimp rate 55%). Furthermore, polyester false twisted yarn (80 dtex 24 f) was arranged so that the mixed ratio of false twisted yarn of the core-sheath type polyester composite fiber was 50% by mass, and a tubular knitting machine manufactured by Eiko Sangyo Co., Ltd. (bob diameter: 3.5 inches, The number of needles: 260N) was used to create a tubular knitted fabric. This knitted fabric was scoured by a conventional method and dyed at a temperature of 130° C. for 30 minutes according to the following recipe.
Dye UVITEX EBF: 1% omf
Auxiliary Nikka Sun Salt SN-130: 0.5 g / l
Acetic acid: 0.2ml/l

Comparative example 2
The procedure was carried out in the same manner as in Comparative Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide)=15:85.

Comparative example 3
The procedure was carried out in the same manner as in Comparative Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide)=40:60.

Comparative example 4
The procedure was carried out in the same manner as in Comparative Example 1, except that the average particle size of the deodorant fine particles was 0.1 μm.
Some filter clogging was observed in the polymer filtration process.

Comparative example 5
The procedure was carried out in the same manner as in Comparative Example 1, except that the average particle size of the deodorant fine particles was changed to 2.0 μm.
Some filter clogging was observed in the polymer filtration process.

Comparative example 6
The procedure was carried out in the same manner as in Comparative Example 1, except that the content of deodorant fine particles with respect to 100 parts by mass of polyester B was changed to 1.5 parts by mass.

Comparative example 7
The procedure was carried out in the same manner as in Comparative Example 1, except that the content of deodorant fine particles with respect to 100 parts by mass of polyester B was changed to 5.0 parts by mass. Spun yarn breakage occurred several times due to the increased content of deodorant fine particles.

Comparative example 8
The procedure was carried out in the same manner as in Comparative Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide)=5:95. Comparative Example 8 was inferior in antibacterial properties.

Comparative example 9
The procedure was carried out in the same manner as in Comparative Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide)=50:50. In Comparative Example 9, the deodorizing property against acetic acid was poor.

Comparative example 10
The procedure was carried out in the same manner as in Comparative Example 1, except that the average particle size of the deodorant fine particles was 0.05 μm. In Comparative Example 10, the filter was clogged with coarse particles generated by secondary agglomeration in the polymer filtration step, and the spinning operation could not be continued.

Comparative example 11
The procedure was carried out in the same manner as in Comparative Example 1, except that the average particle size of the deodorant fine particles was changed to 4.0 μm. In Comparative Example 11, due to the presence of coarse particles, clogging of the filter occurred in the polymer filtering step, making it impossible to continue the spinning operation.

Comparative example 12
The procedure was carried out in the same manner as in Comparative Example 1, except that the content of deodorant fine particles with respect to 100 parts by mass of polyester B was changed to 0.5 parts by mass. In Comparative Example 12, the antibacterial property and the deodorizing property against acetic acid were inferior, and the coefficient of dynamic friction was excessively large, resulting in poor texture.

Comparative example 13
The procedure was carried out in the same manner as in Comparative Example 1, except that the content of deodorant fine particles with respect to 100 parts by mass of polyester B was changed to 7.0 parts by mass. In Comparative Example 13, polyester B was degraded by the action of the deodorant fine particles, and yarn breakage occurred frequently during the spinning process, resulting in poor spinnability.

Comparative example 14
The procedure was carried out in the same manner as in Comparative Example 1, except that the sheath did not contain the deodorant fine particles. Comparative Example 14 was inferior in antibacterial properties and deodorant properties.

Example 1
In polyester B, the same procedure as in Comparative Example 1 was carried out, except that sulfoisophthalic acid was copolymerized at a rate of 1.5 mol % with respect to the total acid components constituting the polyester.

Example 2
The procedure of Example 1 was repeated except that the copolymerization amount of sulfoisophthalic acid was changed to 1.0 mol %.

Example 3
The procedure of Example 1 was repeated except that the copolymerization amount of sulfoisophthalic acid was changed to 5.0 mol %. Due to the increase in the amount of sulfoisophthalic acid copolymerized, yarn breakage occurred several times during the spinning process, but the level was not problematic in terms of operation, and it was sufficiently practical.

Example 4
The procedure was carried out in the same manner as in Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide)=15:85.

Example 5
The procedure was carried out in the same manner as in Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide=) 40:60.

Example 6
The procedure was carried out in the same manner as in Example 1, except that the average particle diameter of the deodorant fine particles was 0.1 μm.
Although some filter clogging was confirmed in the polymer filtration process, it was not a problem to the extent that the operation could not be continued, and it was sufficiently practical.

Example 7
The procedure was carried out in the same manner as in Example 1, except that the average particle size of the deodorant fine particles was changed to 2.0 μm.
Although some filter clogging was confirmed in the polymer filtration process, it was not a problem to the extent that the operation could not be continued, and it was sufficiently practical.

Example 8
The procedure was carried out in the same manner as in Example 1, except that the amount of deodorant fine particles added to 100 parts by mass of polyester B was changed to 1.5 parts by mass.

Example 9
The procedure was carried out in the same manner as in Example 1, except that the amount of deodorant fine particles added to 100 parts by mass of polyester B was changed to 5.0 parts by mass. Due to the increased content of the deodorant fine particles, the spun yarn was broken several times, but the level was not a problem, and the yarn was sufficiently durable for practical use.

Comparative example 15
The procedure of Example 1 was repeated except that the amount of sulfoisophthalic acid copolymerized in polyester B was changed to 0.5 mol %. Compared with Example 1, the ammonia deodorizing property was inferior.

Comparative example 16
The procedure was carried out in the same manner as in Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide)=5:95. Comparative Example 16 was inferior in antibacterial properties.

Comparative example 17
The procedure was carried out in the same manner as in Example 1, except that the mass ratio of zinc oxide and silicon dioxide contained in the deodorant fine particles was set to (zinc oxide):(silicon dioxide)=50:50. In Comparative Example 17, the deodorizing property against acetic acid was poor.

Comparative Example 18
The procedure was carried out in the same manner as in Example 1, except that the average particle size of the deodorant fine particles was 0.05 μm. In Comparative Example 18, the filter was clogged with coarse particles generated by secondary agglomeration in the polymer filtration step, and the spinning operation could not be continued.

Comparative example 19
The procedure was carried out in the same manner as in Example 1, except that the average particle size of the deodorant fine particles was 4.0 μm. In Comparative Example 19, the filter was clogged with coarse particles in the polymer filtration process, and the spinning operation could not be continued.

Comparative example 20
The procedure was carried out in the same manner as in Example 1, except that the amount of deodorant fine particles added to 100 parts by mass of polyester B was changed to 0.5 parts by mass. In Comparative Example 20, the antibacterial properties and deodorizing properties against acetic acid were poor, and the coefficient of dynamic friction was high and the texture was poor.

Comparative example 21
The procedure was carried out in the same manner as in Example 1, except that the amount of deodorant fine particles added to 100 parts by mass of polyester B was changed to 7.0 parts by mass. In Comparative Example 21, the spinnability was poor due to the deterioration of the polyester B due to the action of the deodorant fine particles.

Comparative example 22
The procedure was carried out in the same manner as in Example 1, except that the sheath did not contain the deodorant fine particles. Comparative Example 22 was inferior in antibacterial properties and deodorant properties.

Tables 1 and 2 show the evaluation results in Examples and Comparative Examples.

Claims (5)

A core-sheath type polyester composite fiber having a core composed of polyester A and a sheath composed of 100 parts by mass of polyester B and 1.5 to 5.0 parts by mass of polyester resin composition B containing deodorizing fine particles. A core-sheath type polyester composite fiber which satisfies the following (1) to (4).
(1) The deodorant fine particles contain zinc oxide and silicon dioxide in an amount of 80% by mass or more, and the mass ratio of zinc oxide to silicon dioxide is (zinc oxide):(silicon dioxide)=15:85 to 40. :60.
(2) The deodorizing fine particles have an average particle size of 0.1 to 2.0 μm.
(3) The polyester B is copolymerized with 1.0 to 5.0 mol % of a metal salt compound of an ester-forming sulfonic acid with respect to the total acid components constituting the polyester.
(4) The mass ratio of the core to the sheath (core/sheath) is 85/15 to 60/40. A false-twisted yarn of a core-sheath type polyester conjugate fiber, which is obtained by false-twisting the core-sheath type polyester conjugate fiber according to claim 1 . A method for producing the core-sheath type polyester composite fiber according to claim 1 , comprising the following steps (a) to (d) in this order.
(a) a step of preparing polyester A and polyester B;
(b) A step of adding 1.5 to 5.0 parts by mass of deodorizing fine particles to 100 parts by mass of polyester B to obtain a polyester resin composition B;
(c) A step of disposing the polyester A on the core side and the polyester resin composition B on the sheath side, and melt-spinning them using a conventional spinneret for core-sheath type composite fibers.
(d) Using a take-up roller, take-up at a take-up speed of 1000 to 6000 m/min. A woven or knitted fabric comprising the core-sheath type polyester conjugate fiber according to claim 1 . A woven or knitted fabric comprising the false twist yarn of the core-sheath type polyester composite fiber according to claim 2 .