JPH0913225A - Sheath-core type deodorant and antimicrobial conjugate fiber - Google Patents

Abstract

PURPOSE: To obtain a sheath-core type deodorant and antimicrobial conjugate fiber excellent in a deodorizing property and an antimicrobial property, having high washing durability, and further excellent in heat resistance, abrasion resistance and dyeability. CONSTITUTION: The sheath-core type deodorant and antimicrobial conjugate fiber comprises a core component comprising an olefinic polymer containing a deodorant in an amount of >=3wt.% based on the whole amount of the conjugate fiber, and a sheath component comprising a thermoplastic polymer which contains an antimicrobial agent in an amount of >=0.1wt.% based on the whole amount of the conjugate fiber and inorganic fine particles in an amount of 0.75-10wt.% based on the polymer of the sheath component, and which has a melting point of >=200 deg.C. The core component is preferably a sheath-core type hollow conjugate fiber having a hollow part in the fiber axial direction.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has excellent deodorant and antibacterial effects, and is also excellent in washing resistance, heat resistance, abrasion resistance and dyeability, so that it can be deodorized and antibacterial as in clothing applications. The present invention relates to a core-sheath type deodorant antibacterial fiber suitable for use in fields requiring ironing resistance, abrasion resistance, and deep dyeing in addition to performance.

[0002]

2. Description of the Related Art Synthetic fibers, particularly polyester fibers and polyamide fibers, are indispensable as clothing, stuffing materials, industrial materials, etc. in view of their excellent dimensional stability, weather resistance, mechanical properties and durability. Has become.

It has been desired that these fibers have further special functions depending on the intended use. For example, in applications such as hospital futon, sheets, and carpets that dislike bad odors,
It has been desired to have the ability to reduce the offensive odor that causes as much as possible.

On the other hand, various bacteria and molds are present in our living environment, and they propagate through mediators by adhering to the human body and fibers for reproduction, causing skin disorders, and deterioration and deterioration of fibers. May cause odor or give off a bad smell and cause discomfort. In particular, synthetic fibers are less likely to absorb sweat,
When the fibers are worn on the skin, microorganisms propagate on the skin to which sweat is attached, clothes, fillings and the like to cause a rot phenomenon, resulting in a sweaty odor. Therefore, it has been desired to develop a comfortable and hygienic synthetic fiber product that is cleaner and does not give off a bad odor.

From this point of view, many methods have been proposed so far for imparting deodorant and antibacterial properties to synthetic fibers. Among them, a core component composed of a thermoplastic polymer (particularly, a thermoplastic polymer having a melting point of 200 ° C. or higher) described in JP-A-6-228823 and a deodorant (particularly zinc oxide and silicon dioxide) The core-sheath type deodorant antibacterial conjugate fiber composed of a sheath component made of an olefin-based polymer containing an intimate mixed particle) and an antibacterial agent (in particular, antibacterial fine particles containing silver ion as an active ingredient) is excellent. It has deodorant and antibacterial effects as well as excellent wash resistance.

[0006]

However, since the core-sheath type deodorant antibacterial conjugate fiber is composed of an olefin polymer as the sheath component, it has insufficient heat resistance and can withstand ironing. And inferior in wear resistance,
Further, it has been found that when dyeing, there is a problem that it is difficult to dye a dark color due to the phenomenon of white blurring, and it is unsuitable for use in clothing applications and the like.

Therefore, the present invention has excellent deodorant and antibacterial effects, and has excellent washing resistance, heat resistance, ironing resistance, and abrasion resistance. It is an object of the present invention to provide a deodorant antibacterial fiber which is excellent, does not cause white blur when dyed, can be dyed in a dark color, and can be sufficiently used for clothing applications.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the sheath component has a melting point of 2 or less.
The present invention has been completed by discovering that a thermoplastic polymer having a temperature of 00 ° C. or higher and a core component may be composed of an odorant-containing olefin polymer, and an antibacterial agent and inorganic fine particles may be added to a sheath component.

That is, according to the present invention, (1) a core component made of an olefin polymer containing 3% by weight or more of a deodorant with respect to the entire conjugate fiber, and an antibacterial agent with respect to the entire conjugate fiber of 0.1. A core-sheath type deodorant antibacterial property, characterized in that the core-sheath type deodorant antibacterial property is characterized by comprising 1% by weight or more and 0.75 to 10% by weight of inorganic fine particles with respect to the sheath component, and a sheath component made of a thermoplastic polymer having a melting point of 200 ° C. or higher. The composite fiber, (2) the deodorant is intimately mixed fine particles composed of zinc oxide and silicon dioxide, the mixing ratio thereof is 1: 3 to 3: 1, the average primary particle diameter of the mixed particles is 5 to 30 nm, and the aggregate The core-sheath type deodorant antibacterial conjugate fiber according to (1) above, which has an average particle diameter of 3 μm or less.
(3) The antibacterial agent has a particle size of 3 containing silver ions as an active ingredient.
The core-sheath type deodorant antibacterial composite fiber according to (1) or (2) above, which is an antibacterial fine particle having a particle size of μm or less, and (4) an inorganic fine particle,
The core-sheath type deodorant antibacterial composite fiber according to any one of (1) to (3) above, which is an inert inorganic fine particle having an average particle size of 1 μm or less and a maximum particle size of 5 μm or less, and (5) a core component. The core-sheath type deodorant antibacterial composite fiber according to any one of (1) to (4) above, wherein the weight ratio of the sheath component is 30:70 to 70:30, and (6) the core component is in the fiber axis direction. The core-sheath type deodorant antibacterial composite fiber according to any one of (1) to (5) above, which has a hollow portion, and (7) the core-sheath type according to (6), wherein the hollow ratio is 5 to 35%. A deodorant antibacterial composite fiber is provided.

The thermoplastic polymer having a melting point of 200 ° C. or higher which constitutes the sheath component of the composite fiber of the present invention has heat resistance,
If abrasion resistance and dyeability are good and melt spinning is possible,
Although any one can be used, preferred examples thereof include polyester containing polyethylene terephthalate or polybutylene terephthalate as a main component, nylon 6, nylon 66 or polyamide containing metaxylenediamine nylon as a main component. it can.

On the other hand, as the polymer constituting the core component of the composite fiber of the present invention, the deodorant added does not cause any inconvenience such as decomposition and deterioration, and is excellent in odor permeability and does not cause hydrolysis. (Since deodorants easily absorb water, polymers that are easily hydrolyzed such as polyester are unsuitable.) Therefore, olefin polymers are used. For example, various polyethylenes such as low-density polyethylene and high-density polyethylene, Examples thereof include polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene / vinyl acetate copolymer and the like, with polypropylene being particularly preferable.

The thermoplastic polymer having a melting point of 200 ° C. or higher which constitutes the sheath component of the composite fiber of the present invention is 0.1% by weight or more, preferably 0.1 to 7% by weight based on the whole composite fiber.
% By weight, more preferably 1 to 3% by weight, and 0.75 to 10% by weight, preferably 2 to 8% by weight of the sheath component.
%, More preferably 4 to 6% by weight of inorganic fine particles.

When the content of the antibacterial agent is less than 0.1% by weight,
Sufficient antibacterial effect is not obtained, and further the effect of improving deodorant performance is not recognized. On the other hand, even if a large amount of antibacterial agent is added, the antibacterial property almost reaches the saturated state, there is no meaning to increase the content, the cost becomes high, and it is economically disadvantageous,
It is preferably 7% by weight or less. In addition, the inorganic fine particles disturb the molecular orientation of the thermoplastic polymer of the sheath component during melt spinning and drawing, and develop microvoids, thereby facilitating the adsorption of external odors and bacteria, and further permeating the odor in the sheath component. However, if the addition amount of the inorganic fine particles is less than 0.75% by weight with respect to the sheath component, microvoids are generated. It is not enough to make it manifest, and excellent deodorant and antibacterial properties cannot be obtained. On the other hand, if the amount of the inorganic fine particles added exceeds 10% by weight, the number of yarn breakages during spinning and drawing increases, which is not suitable.

Further, in the conjugate fiber of the present invention, the thermoplastic polyolefin-based polymer constituting the core component is 3% by weight or more, preferably 3 to 10% with respect to the entire conjugate fiber.
%, More preferably 5 to 8% by weight of deodorant.

When the content of the deodorant is less than 3% by weight, it becomes difficult to obtain a sufficient deodorizing effect. In addition, even if a large amount of deodorant is added, improvement in deodorant performance commensurate with the content cannot be expected, and the cost is rather high.
Since it leads to deterioration of fiber performance and spinning productivity, it is desirable to set it to 10% by weight or less.

The above-mentioned deodorant, antibacterial agent and inorganic fine particles used in the present invention are not particularly limited, and deodorant, antibacterial agent and inorganic fine particles conventionally used by being mixed with fibers can be used. .

Among them, as the deodorant, the weight ratio of zinc oxide and silicon dioxide is 1: 3 to 3: 1, preferably 1 :.
Intimately mixed particles of 2 to 2: 1 are preferably used. According to a transmission electron microscope observation, the intimately mixed fine particles are
The average primary particle size is 5 to 30 nm, preferably 10 to 20
nm, the average particle size of aggregation is 3 μm or less, preferably 1 μm
It is as follows. If the average agglomeration particle size exceeds 3 μm, the pack pressure increases during melt spinning and the yarn breaks, which is not preferable.

As the antibacterial agent, antibacterial fine particles containing silver ions as an active ingredient and having a particle size of 3 μm or less, preferably 1 μm or less are preferably used.

The antibacterial fine particles are obtained by supporting silver ions on solid particles, and contain ions of copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, thallium, etc. in addition to the silver ions. You may have. Further, as the solid particles, zirconium phosphate [NaZr ₂ (PO
₄ ) ₃ ] such as zirconium, A-type zeolite,
X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcyme, clinoprolite, iabasite,
Examples include inorganic ion exchangers such as zeolites such as lionite and apatites such as hydroxyapatite [Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ]. Among them, zirconium phosphate is preferable from the viewpoints of antibacterial properties, resistance to discoloration, resistance to washing, and elution of silver ions. The particle diameter of the antibacterial microparticles is 3 μm or less, preferably 1 μm or less, and if it exceeds 3 μm, it is not preferable because it causes an increase in pack pressure during melt spinning and yarn breakage.

Further, examples of the inorganic fine particles include titanium dioxide, silicon dioxide, zinc oxide, barium sulfate, zirconium oxide, aluminum oxide, magnesium oxide, calcium carbonate and the like. Among them, titanium dioxide, silicon dioxide, zinc oxide, Barium sulfate is preferred, and titanium dioxide and silicon dioxide are particularly preferred. From the viewpoint of dispersibility, the average particle size of the inorganic fine particles is preferably 1 μm or less, and more preferably 0.7 μm. In addition, the maximum particle size is 5 from the viewpoint of silk-forming property.
It is preferably not more than μm, particularly preferably not more than 3 μm. The proportion of coarse particles contained in the inorganic fine particles is preferably 1% or less, particularly 0.5% or less.

With respect to the composition ratio of the core component and the sheath component, the core component / the sheath component (weight ratio) is preferably 30/70 to 70/30, and particularly 45/55 to 55/45. Is preferred. When it exceeds 70/30, the original fiber performance of the sheath component polymer is deteriorated, moreover, the sheath component polymer is liable to be broken, and the spinning productivity tends to be deteriorated. On the other hand, if it is less than 30/70, the deodorizing performance is likely to deteriorate.

In the core-sheath type composite fiber of the present invention, the core component preferably has a hollow portion in the fiber axis direction. By having the hollow portion, the odor permeability of the core component is increased, and the deodorizing effect is further improved. In this case, the hollow rate is preferably 5 to 35%. If the hollow ratio exceeds 35%, breakage of the hollow portion may occur, and the spinnability may be deteriorated.

Furthermore, in the core-sheath type composite fiber of the present invention,
When polyester is used as a thermoplastic polymer having a melting point of 200 ° C or higher, which constitutes the sheath component, the alkali weight reduction processing further promotes the formation of microvoids in the sheath component, further improving the odor and the ability to adsorb bacteria. In addition, the odor permeability of the sheath component is further increased, the deodorant and antibacterial functions are further improved, and the effect of microvoids has the effect of improving the sharpness of dyeing. In addition,
It is also possible to obtain a refreshing texture like hemp.

The thermoplastic polymer having a melting point of 200 ° C. or higher constituting the sheath component of the core-sheath type composite fiber of the present invention and / or the olefin polymer constituting the core component may optionally contain a flame retardant or insect repellent. Additives such as agents, hydrophilizing agents and antistatic agents can be added.

The conjugate fiber of the present invention is a core-sheath type composite fiber or a core-sheath type hollow conjugate fiber, which is prepared by using a core-sheath type composite spinning device or a core-sheath type hollow composite spinning device, which is usually used, using the above core component and sheath component. Can be melt-spun, and then stretched and heat treated by a conventional method.

The core-sheath type deodorant / antibacterial composite fiber of the present invention is a deodorant / antibacterial property as a woven or knitted product in the form of long fibers, spun yarn or the like, or as a nonwoven fabric, stuffed cotton, paper or the like in the form of short fibers. It can be used for fields requiring washing resistance, heat resistance, abrasion resistance and dyeability, especially for clothing and interior applications.

[0027]

The core-sheath type deodorant antibacterial composite fiber of the present invention is an olefin-based deodorant containing a deodorant containing a thermoplastic polymer containing an antibacterial agent and inorganic fine particles and having a melting point of 200 ° C. or higher. The polymer constitutes the core component. In this way, since the olefin-based polymer having poor heat resistance, abrasion resistance and dyeability is coated with a thermoplastic polymer such as polyester and polyamide, which has good heat resistance, abrasion resistance and dyeability, The heat resistance, abrasion resistance and dyeability of the conjugate fiber of the present invention are significantly improved as compared with the conventional conjugate fiber having an olefin polymer as a sheath component. Also,
Since the antibacterial agent is concentrated on the surface layer, the antibacterial effect is effectively exhibited against external bacteria.

In the thermoplastic polymer having a melting point of the sheath component of 200 ° C. or higher, an antibacterial agent contained in the thermoplastic polymer when melt spinning or drawing is performed to enhance the molecular orientation and improve the strength.
Inorganic fine particles disturb the molecular orientation of the thermoplastic polymer of the sheath component and develop microvoids, thereby facilitating the adsorption of external odors and bacteria, and further increasing the permeability of the odor in the sheath component, included in the core component. Makes it easy for odors to reach deodorants. This effect is particularly remarkable when the composite fiber is subjected to alkali reduction processing, because the formation of microvoids is promoted.

On the other hand, in the olefin polymer as the core component, the deodorant contained therein, particularly the deodorant fine particles, microscopically inhibits the molecular orientation of the polymer during melt spinning and stretching, and the inside of the polymer is Disturbing the structure makes it easier to absorb the odor that has permeated the sheath component. Especially, the core component
When the hollow portion is provided in the fiber axis direction, the odor enters the hollow portion and the chance of contact with the deodorant contained in the core component increases, so that the deodorizing effect is further improved.

The functions of the sheath component and the core component are combined to enhance the antibacterial and deodorant functions.

In the composite fiber of the present invention, the sheath component is
Since it is composed of a thermoplastic polymer such as polyester or polyamide instead of a non-staining olefin-based polymer, it shows good dyeability by itself. Since the molecular orientation of the plastic polymer is disturbed and the microvoids are expressed, the structure has a structure in which the dye is more likely to enter, and the dyeability is further improved. In particular, when the composite fiber is subjected to alkali reduction processing, the formation of microvoids is promoted, so that the dyeing property is further improved and the dyeing sharpness becomes good.

Further, in the deodorant antibacterial composite fiber of the present invention,
Since the antibacterial agent is kneaded into the thermoplastic polymer of the sheath component and the deodorant is kneaded into the olefin polymer of the core component,
It does not fall off by washing and has excellent wash resistance.

[0033]

The present invention will be described in more detail with reference to the following examples. The performance evaluation in the examples was measured according to the following method.

(1) Measurement of antibacterial property The measurement sample is placed on an agar medium in which Staphylococcus aureus is inoculated, and the bacteria are cultured at 37 ° C. for 24 hours, and the antibacterial property is determined by the presence or absence of growth of Staphylococcus aureus around the sample. The effect was judged.

(Judgment) ◯: Growth of bacteria is not recognized around the sample, and halo occurs.

Δ: Growth of some bacteria is recognized around the sample, and halo is partially generated.

X: Bacterial growth was observed around the sample and no halo was generated.

(2) Measurement of deodorizing property In the case of ammonia, the deodorizing rate was obtained by measuring the ammonia concentration using the apparatus shown in FIG. That is,
Ammonia sensor 1 [AE-235; Toa Denpa Co., Ltd.
Made] and ion meter 3 [IM-IE; Toa Denpa Co., Ltd.
Manufactured] and the recorder 4 are connected, the ammonia sensor 1 is attached to the closed container 5, and ammonia gas is injected into the container 5 with a syringe so as to be 500 ppm, and then the measurement sample 2 is set in the container 5. After standing for 2 hours, the ammonia concentration in the container 5 was measured. The rate of decrease in the ammonia concentration was defined as the deodorization rate.

In the case of hydrogen sulfide, a predetermined amount of sodium sulfide, distilled water, and high-concentration hydrochloric acid is added to a predetermined container to generate a fixed amount of hydrogen sulfide gas, and the measurement sample is suspended in the container.
After leaving it at 24 ° C. for 24 hours, the hydrogen sulfide gas concentration in the container was measured using a Kitagawa gas detector tube. The deodorizing rate was defined as the rate of decrease in hydrogen sulfide gas concentration.

The above-mentioned antibacterial property and deodorant property were measured by the following method for washing the sample after washing.

That is, using an electric washing machine for home use, after washing for 5 minutes in a 40 ° C. aqueous solution containing 2 g / l of neutral detergent New beads (trade name, manufactured by Kao Corporation), washing with running water for 2 minutes. It was then dehydrated and washed with running water for 2 minutes, dehydrated and dried. The repeated washing was performed by repeating the above operation.

(3) Measurement of abrasion resistance The following fabric was woven from the obtained composite fiber and had a diameter of 3.
Four 8 cm test pieces were collected.

Thread count: Warp 55 tex × 2 (2 / 36.11) Weft 74 tex × 2 (2 / 27.0) Density: Warp 19 / cm Weft 12 / cm Twist: Warp S470 ± 20 / Z490 ± 20 / m Weft S410 ± 20 / Z550 ± 20 / m Average fiber diameter: 31 ± 2 μm Mass per unit area in standard state: 185 g / m ² Then, the sample piece was attached to a Martindale friction tester and a pressing load of 9 was applied. 0.0 ± 0.2 kpa was added, and rubbing was performed in multiple directions, and the number of times of rubbing until fluff and fibrils were generated was measured. As the standard friction cloth, the cloth made of polyethylene terephthalate fiber (4 de × 51 mm) having the above-mentioned constitution was used, and the average value of the measured values of the four sample pieces was obtained, and the abrasion resistance was judged according to the following criteria.

(Judgment) ◯: Rubbing number of 500 times or more Δ: Rubbing number of 499 to 201 times ×: Rubbing number of 200 times or less (4) Measurement of heat resistance A sample of about 20 cm ² from the fabric woven in the above (3) A piece was sampled, an iron heated to 170 ± 5 ° C. was placed on this sample piece for 5 minutes, and the presence or absence of sticking of fibers was examined, and the heat resistance was judged according to the following criteria.

(Judgment) O: No adhesion of fibers.

X: There is sticking of fibers.

(5) Measurement of dyeability A measurement sample and a standard sample (polyethylene terephthalate fiber, 4 de × 51 mm) were used in the same bath at a bath ratio of 1:50 with 0.02% by weight of a disperse dye (Eastman Blue). Boiled for a minute and then made by Nippon Denshoku Industries Co., Ltd. photoelectric color difference meter (S
Z-Σ80), L, a, b of the obtained composite fiber
The values and the L ₀ , a ₀ , and b ₀ values of the standard sample dyed in the same bath were measured, and the color difference (ΔE) was calculated from the following formula. In addition, when the obtained conjugate fiber is dyed darker than the standard sample, it is indicated by "+", and when it is dyed in a light color, it is indicated by "-".

[0048]

(Equation 1)

The larger the value of the color difference (ΔE), the better the dyeability, and the judgment was made according to the following criteria.

⊚: + 2 ≦ ΔE ○: 0 <ΔE <+2 Δ: −2 <ΔE ≦ 0 ×: ΔE ≦ −2

[Examples 1 to 10 and Comparative Examples 1 to 4] Intimately mixed fine particle deodorant [SZ-100; manufactured by Suzuki Sogyo Co., Ltd.] in which the weight ratio of zinc oxide and silicon dioxide is 2: 1.
Average primary particle diameter 15 nm, aggregation average particle diameter 1 μm]
A twin-screw extruder manufactured by Nippon Steel Works Co., Ltd. was used to knead with polypropylene-based polymer [TG-810; Showa Denko KK, melt index 30, melting point 150 ° C.], and SZ-1
00 master chip was prepared.

Polypropylene polymer TG-was added to this master chip so that the content of the deodorant was as shown in Table 1.
It was mixed with 810 to obtain a core component constituent polymer.

On the other hand, a silver-based inorganic antibacterial agent [Novalon AG-300; manufactured by Toagosei Kagaku Co., Ltd., average particle size 1 μm] in which silver ions and an inorganic ion exchanger (zirconium phosphate) are bound to each other has an intrinsic viscosity. Kneaded with polyethylene terephthalate having a melting point of 0.63 and a melting point of 260 ° C. to obtain Novalon AG-30.
Zero master chips were made.

Similarly, as the inert inorganic fine particles, barium sulfate [manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.7 μm]
m, maximum particle diameter of 3 μm or less] was kneaded with the above polyethylene terephthalate to prepare a barium sulfate fine particle master chip.

The intrinsic viscosities of both of these master chips were adjusted so that the antibacterial agent and the inorganic fine particles had the contents shown in Table 1.
It was mixed with 63 of polyethylene terephthalate to obtain a sheath component constituent polymer.

The core component-constituting polymer and the sheath component-constituting polymer thus prepared were mixed at the ratios shown in Table 1 from a core-sheath type composite spinning die having a nozzle hole diameter of 0.5 mm and 450 holes, at a spinning temperature (core). / Sheath = 250 ° C./300° C.), discharge amount 400 g / min, and take-up speed 900 m / min.

The undrawn yarn thus obtained was drawn 2.5 times in warm water at 70 ° C., heat treated at 125 ° C. for about 20 minutes, and then cut into a length of 51 mm to obtain a denier of about 4 denier. A core-sheath type deodorant antibacterial composite short fiber was obtained.

Table 2 shows the results of evaluating the antibacterial properties, deodorizing properties, abrasion resistance, heat resistance and dyeing properties of the obtained fibers.

[0059]

[Table 1]

[0060]

[Table 2]

As is clear from the results of Table 2, the core-sheath type composite fibers of the present invention (Examples 1 to 10) have good deodorant and antibacterial properties, and excellent wash resistance. When the content of the deodorant is small (Comparative Example 1), the deodorant performance is insufficient, and when the antibacterial agent is not contained (Comparative Example 2),
There is no antibacterial property. Furthermore, when the content of the inorganic fine particles is small (Comparative Example 3), the deodorizing property is poor, and the antibacterial property and the dyeing property are somewhat poor. Further, when the content of the inorganic fine particles is large (Comparative Example 4), both the deodorant property and the antibacterial property are good, and the dyeability is remarkably improved, but the yarn breakage during spinning and drawing increases.

The weight ratio of the core component and the sheath component (core component:
When the sheath component) is less than 30:70 (Example 9), the deodorant performance is slightly lowered, and when it exceeds 70:30 (Example 1).
In 0), the fiber performance and abrasion resistance are slightly inferior, and the number of broken yarns during spinning is slightly increased.

[Comparative Example 5] The deodorant (S
Z-100) master chip and antibacterial agent (Novalon A)
G-300) master chip so that the deodorant is 6.0% by weight and the antibacterial agent is 2.0% by weight with respect to the whole conjugate fiber.
It was mixed with G-810 to obtain a sheath component constituent polymer.

On the other hand, polyethylene terephthalate having an intrinsic viscosity of 0.63 is used as the core constituent polymer,
Spinning temperature (core / sheath = 300 ° C./250° C.), discharge rate 400 from a spinneret having a nozzle hole diameter of 0.5 mm and 450 holes at a weight ratio of 50:50 with the sheath component constituent polymer.
Melt spinning was performed at g / min and a take-up speed of 900 m / min.

Then, the core-sheath type composite short fibers in which SZ-100 and Novalon AG-300 were kneaded in a propylene-based polymer as a sheath component were drawn, heat-treated and cut under the same conditions as in Example 2. .

The results are shown in Table 2 and were excellent in deodorizing property and antibacterial property but poor in heat resistance, abrasion resistance and dyeability.

[Examples 11 to 20, Comparative Examples 6 to 9] In Examples 1 to 10 and Comparative Examples 1 to 4, core-sheath type hollow composite spinning spinnerets were used, and the core component was a hollow part in the fiber axis direction ( A core-sheath type hollow composite staple fiber having a hollow ratio of 20% was prepared (composite fiber constitution is as shown in Table 3).

The results are shown in Table 4.
The same tendency as in the case of 10 and Comparative Examples 1 to 4 was recognized, and in particular, by using the core-sheath hollow composite fiber, the deodorizing effect was further improved.

[0069]

[Table 3]

[0070]

[Table 4]

[Examples 21 to 26] In Example 12, the hollow ratio was variously changed as shown in Table 5 to prepare core-sheath type hollow composite staple fibers. The results are as shown in Table 5, and it was recognized that as the hollow ratio increases, the deodorizing effect also increases, but the fracture of the hollow portion also increases.

[Examples 27 and 28] The core-sheath type composite short fibers obtained in Example 2 and the core-sheath type hollow composite fibers obtained in Example 12 were treated with 1% NaOH at 95 ° C for 20 minutes. Alkali weight loss processing was applied. The results are shown in Table 5, in which the formation of microvoids in the sheath component was promoted, the deodorizing performance and the dyeability were further improved, and especially the dye vividness was remarkably improved.

[0073]

[Table 5]

Example 29 Intimately mixed fine particle deodorant having a mixing ratio of zinc oxide and silicon dioxide of 2: 1 by weight [SZ-100; manufactured by Suzuki Seigyo Co., Ltd., average primary particle diameter 15n
m, agglomeration average particle diameter 1 μm] with a twin-screw extruder manufactured by Japan Steel Works, Ltd. to produce polypropylene-based polymer [TG-8
10; Showa Denko KK, melt index 30, melting point 150 ° C.] and kneaded to prepare a master chip of SZ-100.

This master chip was mixed with polypropylene-based polymer TG-810 so that the content of the deodorant was 6.0% by weight based on the whole composite fiber, to obtain a core constituent polymer.

On the other hand, a silver-based inorganic antibacterial agent [Novalon AG-300; manufactured by Toagosei Kagaku Kogyo Co., Ltd., average particle diameter 1 μm] in which silver ions and an inorganic ion exchanger (zirconium phosphate) are bonded together has an intrinsic viscosity. Nylon 6 having a melting point of 235 ° C and a melting point of 1.34 was kneaded to prepare a master chip of Novalon AG-300.

Similarly, as the inert inorganic fine particles, barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.7 μm) was used.
m] was kneaded with the above nylon 6 to prepare barium sulfate fine particle master chips.

In both of these master chips, the content of the antibacterial agent was 2.0% by weight with respect to the whole conjugate fiber, and the content of the inorganic fine particles was 10% by weight with respect to the whole conjugate fiber.
It was mixed with nylon 6 having an intrinsic viscosity of 1.34 to obtain a sheath component constituent polymer.

The core component-constituting polymer and the sheath component-constituting polymer thus prepared were mixed at a weight ratio of 50:50 from a core-sheath type composite spinning die having a nozzle hole diameter of 0.5 mm and 450 holes, and a spinning temperature ( Melt composite spinning was performed at a core / sheath = 250 ° C./280° C.), a discharge rate of 400 g / min, and a take-up speed of 900 m / min.

The undrawn yarn thus obtained was drawn 2.5 times at 55 ° C., then heat-treated at 120 ° C. for about 15 minutes, and then,
It was cut into a length of 51 mm to obtain a core-sheath type deodorant antibacterial composite short fiber of about 4 denier.

The deodorizing property of the obtained composite fiber against ammonia gas was 99% or more in the initial stage and 97 after washing 10 times.
%, Deodorizing property against hydrogen sulfide was 94% in the initial stage and 92% after washing 10 times, and antibacterial property was in the initial stage after washing 5 times.
After 50 washes, the result was ◯. The heat resistance, abrasion resistance and dyeability were all good.

Example 30 In Example 29, a core-sheath hollow composite staple fiber having a hollow portion having a hollow ratio of 20% as a core component in the fiber axis direction was prepared by using a core-sheath type hollow composite spinning die. .

The deodorizing property of the obtained composite fiber against ammonia gas was 99% or more in the initial stage after washing 10 times, and the deodorizing property against hydrogen sulfide was 97% in the initial stage and 95% after washing 10 times. The antibacterial properties were good at the initial stage, after washing 5 times and after washing 50 times. The heat resistance, abrasion resistance and dyeability were all good.

[0084]

The core-sheath type deodorant antibacterial conjugate fiber of the present invention is
It has excellent deodorant and antibacterial properties as well as high washing durability, and also has excellent heat resistance, abrasion resistance, and dyeability, and in addition to deodorant and antibacterial properties, such as for clothing applications. hand,
It is suitable for use in fields where ironing resistance, abrasion resistance and deep dyeing are required.

[Brief description of the drawings]

FIG. 1 is a schematic side view showing a deodorizing performance measuring device used for evaluating the fiber of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Sensor 2 Measurement sample 3 Ion meter 4 Recorder 5 Container

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location D01D 5/34 D01D 5/34 D01F 1/10 D01F 1/10 8/14 8/14 Z

Claims (7)

[Claims] 1. The deodorant is 3% by weight with respect to the whole composite fiber.
A core component made of the above-mentioned olefin polymer,
A sheath component made of a thermoplastic polymer containing 0.1% by weight or more of an antibacterial agent with respect to the whole conjugate fiber and 0.75 to 10% by weight of inorganic fine particles with respect to the sheath component and having a melting point of 200 ° C. or higher. A core-sheath type deodorant antibacterial composite fiber characterized by: 2. The deodorant is intimately mixed fine particles composed of zinc oxide and silicon dioxide, and the mixing ratio thereof is 1: 3 to.
The core-sheath type deodorant antibacterial conjugate fiber according to claim 1, wherein the mixed primary particles have an average primary particle diameter of 5 to 30 nm and an aggregate average particle diameter of 3 µm or less. 3. The antibacterial agent is antibacterial microparticles containing silver ions as an active ingredient and having a particle size of 3 μm or less.
The core-sheath type deodorant antibacterial composite fiber described. 4. The core-sheath type deodorant antibacterial composite according to any one of claims 1 to 3, wherein the inorganic fine particles are inert inorganic fine particles having an average particle diameter of 1 μm or less and a maximum particle diameter of 5 μm or less. fiber. 5. The weight ratio of the core component and the sheath component is 30:70 to.
The core-sheath type deodorant antibacterial conjugate fiber according to any one of claims 1 to 4, which is 70:30. 6. The core-sheath type deodorant antibacterial conjugate fiber according to any one of claims 1 to 5, wherein the core component has a hollow portion in the fiber axial direction. 7. The core-sheath type deodorant antibacterial composite fiber according to claim 6, which has a hollowness of 5 to 35%.