JPH06228823A - Core-sheath type deodorant antibacterial composite fiber - Google Patents

Abstract

(57) [Summary] [Objective] To provide a fiber having excellent deodorant properties, antibacterial properties, and high washing durability. [Structure] A core component made of a thermoplastic polymer, and a thermoplastic polymer containing a deodorant in an amount of 3% by weight or more based on the entire conjugate fiber and an antibacterial agent in an amount of 0.1% by weight or more based on the entire conjugate fiber. A core-sheath type deodorant antibacterial composite fiber having a sheath component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent deodorant and antibacterial effects and its durability, and is used in the field of filling materials, interior fields such as curtains and carpets, various papermaking fields, and industrial material fields such as various filters, which are averse to bad odors. The present invention relates to a core-sheath type deodorant antibacterial fiber suitable for use in.

[0002]

2. Description of the Related Art Synthetic fibers, especially polyester fibers and polyamide fibers, are indispensable as clothing, stuffing materials and industrial materials because of their excellent dimensional stability, weather resistance, mechanical properties and durability. Has become. However, it has been desired to add a special function depending on the intended use. For example, in applications such as hospital futons, sheets, and carpets that dislike bad odors, there has been a demand for a textile product that has the ability to reduce the bad odor that causes the odor as much as possible.

Conventionally, as a fiber having a deodorant property,
It is known that a natural coniferous tree, an extract from a broad-leaved tree, an extract from a green tea or the like is attached to the surface of a textile product by a post-processing method or the like (Japanese Patent Laid-Open No. 62-153).
No. 88, JP-A No. 62-250283) have the drawback of insufficient durability. In particular, there has been a problem that the deodorant performance is extremely deteriorated when repeated washing or the like is performed, or when the textile is dyed.

It has also been proposed to incorporate a deodorant in the resin for the purpose of improving durability, and a polyester resin containing a divalent iron ion compound and L-ascorbic acid (special JP-A-60-66753, JP-A-62-215010) and the like are known, but the heat resistance is insufficient, or the discoloration occurs after deodorizing a malodorous substance from a textile product, so that a specific There was a problem that it could only be used for its intended purpose.

Further, in Japanese Patent Laid-Open No. 2-99606,
A method of kneading zinc silicate having an amorphous structure composed of zinc oxide and silicon dioxide into polyester or polyamide has been proposed, but polyester or polyamide cannot be expected to have a sufficient deodorizing effect because of its low odor permeability. Especially when the deodorant is mixed into the entire yarn cross section,
There is a problem that the deodorant in the central portion of the yarn cannot fully exert the deodorizing effect as compared with the surface portion.

On the other hand, in our living environment, various bacteria and molds exist, and they adhere to the human body and fibers through mediators and propagate to cause skin disorders, and deterioration and deterioration of fibers. May cause odor or give off a bad smell and cause discomfort. In particular, synthetic fibers absorb less sweat, so
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, there has been a time when a method of applying an organic tin or organic mercury compound to the fiber was used to impart antibacterial property to the fiber, but the toxicity of these compounds has been regarded as a problem, and at present. Almost all of them have been discontinued.

As a particularly safe antibacterial and antifungal agent to be applied to fibers by a post-processing method, silicone 4 has been conventionally used.
Grade ammonium salts are used. For example, Japanese Unexamined Patent Publication No. 57-51874 discloses a carpet in which an organosilicone quaternary ammonium salt is adsorbed and a method for producing the carpet. However, since the silicone-based quaternary ammonium salt has reactivity to cellulosic fibers and thus exhibits an antibacterial effect with washing durability, it has only a temporary antibacterial effect to synthetic fibers. Has not been done.

Further, it has long been known that compounds such as silver, copper and zinc, which elute silver ions, copper ions and zinc ions, have antibacterial properties. For example, the water solubility of silver nitrate is
It has been widely used as a disinfectant and germicide. However, the solution form is inconvenient in terms of handling and has a drawback that it is limited in terms of application. Therefore, if ions or salts of silver, copper, zinc or the like are retained in the polymer body, such drawbacks can be overcome and it can be expected to be used in a wide range of fields. For example, a method in which a metal compound such as silver, copper or zinc is mixed with a polymer to form a fiber has been proposed in JP-A-54-147220. Also, a method of adding and mixing zeolite-based solid particles ion-exchanged with silver ions and copper ions to an organic polymer has been proposed in JP-A-59-133235.

However, in these methods, the metal compound has a great influence on the properties of the polymer, and the usable range is remarkably limited, and the productivity in the fiberizing process, especially the single yarn breakage during spinning, A problem occurs that the pack life is shortened due to clogging of the pack filter. Further, if the metal ion is simply contained in the polymer, the action of the metal ion on the external bacterium becomes insufficient, so that the level of antibacterial effect is low and a sufficient effect cannot be expected.

In order to solve the problems of the prior art, the present inventors use a polyolefin-based polymer containing zinc oxide and silicon dioxide as a sheath and a thermoplastic polymer having a melting point of 200 ° C. or higher as a core. An application was previously filed for a deodorant conjugate fiber in which the surface of a core-sheath type conjugate fiber is coated with N-polyoxyalkylene-N, N, N-trialkylammonium salt and a melanin resin (Japanese Patent Application No. 4- 199
No. 46).

[0012]

However, although the above deodorant composite fiber is excellent in deodorant property and antibacterial property,
It has been found that there is a problem that the ammonium salt applied to the surface of the fiber is removed during repeated washing, and the antibacterial effect is reduced.

Therefore, the object of the present invention is to show more excellent deodorizing and antibacterial effects, and to eliminate deodorizing even after repeated washing.
It is to provide a deodorant antibacterial fiber having excellent anti-washing properties and having no deterioration in antibacterial performance.

[0014]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors have considered that the surface of a fiber is not coated with an antibacterial agent but kneaded into the fiber together with a deodorant, and various investigations have been made. In the process of layering, it was found that when a deodorant and an antibacterial agent are mixed and kneaded into the fiber, not only washing resistance but also deodorant property is significantly improved, and the present invention has been completed. .

That is, in the present invention, a core component made of a thermoplastic polymer, a deodorant, and an antibacterial agent are mixed in an amount of 3% by weight or more and 0.1% by weight or more with respect to the entire conjugate fiber. Core-sheath type deodorant antibacterial conjugate fiber, which has a sheath component made of a thermoplastic polymer.

As the thermoplastic polymer constituting the core component of the composite fiber of the present invention, any polymer can be used as long as it can be melt-spun, but various fiber applications including mechanical properties and heat resistance can be used. A thermoplastic polymer having a melting point of 200 ° C. or higher is preferably used in order to satisfy the properties required for the above. Preferable examples thereof include polyester containing polyethylene terephthalate or polybutylene terephthalate as a main component, nylon 6, nylon 66 or polyamide containing metaxylene diamine nylon as a main component.

On the other hand, as the thermoplastic polymer constituting the sheath component of the composite fiber of the present invention, any thermoplastic polymer may be used as long as it does not cause inconveniences such as decomposition and deterioration due to the added deodorant and antibacterial agent. However, a polyolefin polymer is particularly preferably used. Examples of such polyolefin-based polymers include low-density polyethylene,
Various polyethylene such as high density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-
1, ethylene / vinyl acetate copolymer and the like,
Polypropylene is particularly preferable.

In the thermoplastic polymer constituting the sheath component, the deodorant and antibacterial agent contained therein microscopically inhibit the molecular orientation during stretching, disturb the internal structure of the sheath, and Odor and bacteria are easily adsorbed, deodorants and antibacterial agents are more likely to act, and overall excellent deodorant and antibacterial performance is exhibited. It becomes remarkable.

In the conjugate fiber of the present invention, the thermoplastic polymer constituting the sheath component is contained in an amount of 3% by weight or more, preferably 3 to 10% by weight, more preferably 5 to 8% by weight, based on the entire conjugate fiber. Deodorant and composite fiber as a whole to 0.
1% by weight or more, preferably 0.1 to 7% by weight, and more preferably 1 to 3% by weight of an antibacterial agent are mixed and added.

When the content of the deodorant is less than 3% by weight, it is 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.

Further, if the content of the antibacterial agent is less than 0.1% by weight, a sufficient antibacterial effect cannot be obtained, and further the effect of improving the deodorizing performance cannot be 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 point in increasing the content, the cost becomes high, and it is economically disadvantageous. desirable.

The deodorant and antibacterial agent used in the present invention are not particularly limited, and deodorant and antibacterial agents 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 the following. If the aggregated average particle size exceeds 3 μm, the pack pressure during melt spinning and the yarn breakage are unfavorable.

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 those in which silver ions are supported on solid particles, and in addition to the silver ions, ions such as copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium and thallium are contained. You may have. As solid particles, zirconium phosphate [NaZr2 (PO4
) 3] such as zirconium, A-type zeolite,
X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcime, clinoprolyte, earbasite,
Examples thereof include zeolites such as lionite, and inorganic ion exchangers such as apatites such as hydroxyapatite [Ca10 (PO4) 6 (OH) 2]. Of these, zirconium phosphate is preferable from the viewpoints of antibacterial properties, discoloration resistance, washing resistance, silver ion elution properties, and the like. 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.

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. If it exceeds 70/30, the sheath constituent polymer is apt to break, and the spinning productivity is reduced.
On the other hand, if it is less than 30/70, the original fiber performance of the core component polymer is deteriorated.

The composite fiber of the present invention is obtained by melt-spinning the core-sheath type composite fiber using the above-mentioned core component and sheath component by a commonly used core-sheath type composite spinning device, and then stretching and heat-treating by a conventional method. It can be manufactured.

The core-sheath type deodorizing and antibacterial composite fiber of the present invention is a deodorizing and antibacterial property as a woven or knitted product in the form of long fibers, spun yarns, etc. Can be used in the fields where

Particularly, in the core-sheath type composite fiber of the present invention,
When the core component is composed of a thermoplastic polymer having a melting point of 200 ° C or higher and the sheath component is composed of a polyolefin-based polymer having a lower melting point than this, heating is performed at a temperature higher than the sheath melting point and lower than the core component melting point. By doing so, it is possible to fuse the fibers without mixing the binder fibers,
It is extremely useful for papermaking and filter applications.

[0030]

The core-sheath type deodorant antibacterial conjugate fiber of the present invention has a thermoplastic polymer for maintaining the fiber performance, which is disposed in the core component,
The sheath component is composed of a thermoplastic polymer containing a deodorant and an antibacterial agent. Therefore, since the deodorant and the antibacterial agent are concentrated on the surface layer of the composite fiber, the external odor and bacteria are
Deodorant and antibacterial effects are effectively exhibited.

In the thermoplastic polymer (particularly polyolefin type polymer) of the sheath component, when the melt-spun yarn is stretched to enhance the molecular orientation and to improve the strength, the deodorant and the antibacterial agent, especially the deodorant, are contained. Deodorant fine particles and antibacterial fine particles microscopically inhibit the molecular orientation of the polymer,
By disturbing the internal polymer structure of the surface layer, external odors and bacteria are easily adsorbed, deodorants and antibacterial agents are easily acted, and the deodorant function and antibacterial function are more easily exhibited.

Further, in the deodorant antibacterial composite fiber of the present invention,
Since both the deodorant and the antibacterial agent are kneaded in the thermoplastic polymer of the sheath component, they do not fall off by washing and have excellent wash resistance.

Although the reason why the deodorant effect is remarkably improved by mixing and containing the deodorant and the antibacterial agent has not been clarified yet, the addition of the antibacterial agent causes the molecular orientation of the thermoplastic polymer of the sheath component to be improved. Is further inhibited, the internal structure becomes more disordered, the deodorizing function is further enhanced, and the antibacterial action of the antibacterial agent suppresses the growth of bacteria causing odor.

[0034]

The present invention will be described in more detail with reference to the following examples. The performance evaluations in the examples are measured according to the following methods.

(1) Measurement of antibacterial property The test sample was placed on an agar medium seeded with Staphylococcus aureus and cultured at 37 ° C. for 24 hours to determine whether Staphylococcus aureus grew around the sample. The antibacterial effect was judged. (Judgment) ◯: No halo is generated because no bacterial growth is observed around the sample. Δ: Growth of some bacteria was observed around the sample,
Halo occurs partially. X: Bacterial growth was observed around the sample and no halo was generated.

(2) Determination of deodorant 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 deodorizing rate was defined as the rate of decrease in ammonia concentration.

In the case of hydrogen sulfide, a predetermined amount of sodium sulfide, distilled water, and high-concentration hydrochloric acid are 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.

When the above antibacterial and deodorant properties were measured on the sample after washing, the washing was carried out by the following method. That is, using an electric washing machine for home use, after washing for 5 minutes in an aqueous solution containing 40 g of neutral detergent new beads (trade name, manufactured by Kao Co., Ltd.) at 40 ° C., washing with running water for 2 minutes and dehydration Then, it was washed with running water for 2 minutes, dehydrated and dried. The repeated washing was performed by repeating the above operation.

[0039]

Examples 1 to 7 and Comparative Examples 1 and 2 Intimately mixed fine particles [S] in which the mixing ratio of zinc oxide and silicon dioxide is 2: 1 by weight.
Z-100; Suzuki Sogyo Co., Ltd., average primary particle size 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.] to prepare a master chip of SZ-100.

Similarly, a silver-based inorganic antibacterial agent in which silver ions and an inorganic ion exchanger (zirconium phosphate) are bonded [Novalon AG-300; manufactured by Toagosei Chemical Industry Co., Ltd.,
Average particle diameter 1 μm]
It was kneaded with G-810 to prepare a master chip of Novalon AG-300.

Both of these master chips were mixed with polypropylene polymer TG-810 so that the deodorant and the antibacterial agent had the contents shown in Table 1 to obtain a sheath component constituent polymer.

On the other hand, polyethylene terephthalate having an intrinsic viscosity of 0.64 was used as the core constituent polymer.
Along with the sheath component constituent polymer, a spinning temperature (core / sheath = 300 ° C./250° C.) and a discharge amount of 400 g from a core / sheath type composite spinning die having a nozzle hole diameter of 0.5 mm and a number of holes of 450 at a ratio shown in Table 1. / Min, and the take-off speed was 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 evaluation of the deodorant properties and antibacterial properties of the obtained fibers.

[0044]

[Table 1]

[0045]

[Table 2]

As is clear from the results shown in Table 2, the core-sheath type composite fibers of the present invention (Examples 1 to 5) have good deodorant properties and antibacterial properties, and also have excellent wash resistance. When the content of the deodorant is small (Comparative Example 1), the deodorant performance is insufficient, and also when the antibacterial agent is not included (Comparative Example 2), the deodorant property is not improved and the antibacterial property is not improved. There is no.

The weight ratio of the core component and the sheath component (core component:
When the (sheath component) is less than 30:70 (Example 6), the fiber performance is slightly inferior, and the number of yarn breakage during spinning is slightly increased.
When it exceeds 30 (Example 7), the number of yarn breakage during spinning is slightly increased.

[0048]

[Comparative Example 3] Polypropylene polymer TG of the sheath component
Polyethylene terephthalate having an intrinsic viscosity of 0.64 without using 810, 6% by weight of SZ-100, Novalon A
Add 1% by weight of G-300 and mix, nozzle hole diameter 0.5m
m, spinneret with 450 holes, spinning temperature 300 ° C,
Melt spinning was performed at a discharge rate of 400 g / min and a take-up speed of 900 m / min.

Then, the fibers were stretched, heat-treated and cut under the same conditions as in Example 2 to obtain fibers in which SZ-100 and Novalon AG-300 were kneaded into the whole fiber and which did not have a core-sheath structure. The results are shown in Table 3, and the deodorizing property was particularly poor.

[0050]

Comparative Example 4 In Example 2, 6% by weight of SZ-100 was used without using polyethylene terephthalate as a core component.
Polypropylene polymer TG-810 containing 1% by weight of Novalon AG-300 was used, nozzle hole diameter 0.5 mm,
From a spinneret having 450 holes, melt spinning was performed at a spinning temperature of 250 ° C., a discharge rate of 400 g / min, and a take-up speed of 900 m / min.

Then, the fibers were stretched, heat-treated and cut under the same conditions as in Example 2 to obtain fibers in which SZ-100 and Novalon AG-300 were kneaded into the whole fiber and which did not have a core-sheath structure. The results are as shown in Table 3, and both the deodorant property and the antibacterial property were poor, and the fiber performance was inferior.

[0052]

Example 8 In Example 2, S having an average particle diameter of 1 μm is used.
Z-100 and Novalon AG-300 were replaced with those having an average particle diameter of 4 μm, and other conditions were the same as in Example 2 to obtain a core-sheath type composite fiber.

The results are shown in Table 3, and the deodorizing property and the antibacterial property were good, and the washing resistance was excellent, but the number of yarn breakages during spinning was slightly large.

[0054]

Example 9 The core-sheath type composite fiber obtained in Example 2 was cut into a length of 5 mm, and 70 parts of this raw cotton was mixed with rubber latex [Unipol LX204 (trade name); Nippon Zeon Co., Ltd.]. )] As a solid component, and wood pulp [NBSP; Sanyo Kokusaku Pulp Co., Ltd.] as a papermaking auxiliary.
Manufactured] was mixed in water at a ratio of 15 parts. To this mixed slurry, aluminum sulfate 0.5 was added as a latex fixing agent.
After adding 1 part to adjust the pH to 4.5, the mixture was sent to a square paper machine and a paper having a basis weight of 25 g / m @ 2 was obtained by a usual method. The evaluation results of the obtained paper are as shown in Table 3, and the deodorant property,
It had excellent antibacterial properties.

[0055]

[Example 10] The core-sheath type composite short fibers obtained in Example 2 were put on a roller card to prepare a web having a basis weight of 200 g / m 2 by a conventional method, and heat-treated at 170 ° C for 20 minutes by a hot air dryer to fuse them. A binder-processed filter was obtained.
The evaluation results of the obtained filters are as shown in Table 3,
It had excellent deodorant and antibacterial properties.

[0056]

[Table 3]

[0057]

The core-sheath type deodorant fiber of the present invention has excellent deodorant and antibacterial properties and has high washing durability.

[Brief description of drawings]

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

[Explanation of symbols]

 1 sensor 2 measurement sample 3 ion meter 4 recorder 5 container

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location D01D 5/34 7199-3B D01F 1/10 7199-3B 6/04 B 7199-3B 8/06 7199-3B D06M 23/08

Claims (5)

[Claims] 1. A thermoplastic polymer containing a core component made of a thermoplastic polymer, a deodorant in an amount of 3% by weight or more based on the entire conjugate fiber, and an antibacterial agent in an amount of 0.1% by weight or more based on the entire conjugate fiber. A core-sheath type deodorant antibacterial composite fiber, comprising: 2. A thermoplastic polymer as a core component has a melting point of 200 ° C.
The core-sheath type deodorant antibacterial conjugate fiber according to claim 1, which is the above-mentioned thermoplastic polymer and the thermoplastic polymer of the sheath component is a polyolefin-based polymer. 3. 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 or 2, 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. 4. The core-sheath type deodorant antibacterial conjugate fiber according to claim 1, 2 or 3, wherein the antibacterial agent is antibacterial fine particles containing silver ions as an active ingredient and having a particle size of 3 μm or less. 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.