WO2020115928A1 - Antibacterial fiber, and method for manufacturing antibacterial fiber - Google Patents

Abstract

Provided is an antibacterial fiber in which the content of antibacterial glass in the core part is made to be less than the content of antibacterial glass in the sheath part, thereby making it possible for the added amount of antibacterial glass to be small, and further, for the fiber to exhibit superior antibacterial properties. Also provided is an efficient method for manufacturing such an antibacterial fiber. The antibacterial fiber includes a thermoplastic resin and antibacterial glass as added components, the average diameter of the antibacterial fiber is set to be a value within a range of 1-50 μm, and the antibacterial fiber comprises a core part and a sheath part. When the content of the antibacterial glass in the core part with respect to the total amount of the antibacterial fiber is defined as Q1 (weight %), and the content of the antibacterial glass in the sheath part with respect to the total amount of the antibacterial fiber is defined as Q2 (weight %), Q1 and Q2 satisfy relational expression (1): Q1<Q2.

Description

Antibacterial fiber and method for producing antibacterial fiber

The present invention relates to an antibacterial fiber and a method for producing the antibacterial fiber.
In particular, by having a core portion and a sheath portion, and the content of the antibacterial glass in the core portion is smaller than the content of the antibacterial glass in the sheath portion, the compounding amount of the antibacterial glass can be small, and thus The present invention relates to an antibacterial fiber exhibiting excellent antibacterial properties and a method for producing the antibacterial fiber.

Traditionally, antibacterial fiber products that have undergone antibacterial processing have become popular. As a method of producing such an antibacterial fiber, a method of fixing an antibacterial glass composition (glass particles) on the surface of a fiber substrate of synthetic fiber or natural fiber, and a method of dispersing the antibacterial glass composition in the fiber substrate There is a method (Patent Document 1).

As a method for fixing glass particles on the surface of the fiber substrate, (a) fixing the glass particles in an adhesive form via an adhesive polymer layer formed on the surface of the fiber substrate, and (b) fixing glass particles The surface side is further covered with an overcoat made of a polymer or the like, (c) the surface of the glass particles is previously covered with a fixing resin layer, and the fixing resin layer is softened by heating and adhered to the surface of the fiber substrate, It is disclosed that an antibacterial fiber can be obtained by, for example, fixing the composite particles by curing the resin layer.

Further, as a method for dispersing glass particles in a fiber substrate, glass particles may be blended in a spinning stock solution to be a fiber substrate, and the fibers may be spun to obtain an antibacterial fiber in a dispersed state. It is disclosed.

On the other hand, Patent Document 2 discloses a core-sheath type composite fiber in which the core portion contains an antibacterial agent, and the ratio of the sheath portion after alkali reduction processing is 2 to 20% by weight based on the fiber weight. Disclosed is an antibacterial polyester fiber having an antibacterial agent content of 0.1 to 10% by weight based on the weight of the fiber and a color difference (ΔE) before and after alkali reduction treatment of less than 2.0. ..

JP 2001-247333 A Japanese Patent Laid-Open No. 11-158730

However, the antibacterial fiber obtained by the method of fixing glass particles on the surface of the fiber substrate disclosed in Patent Document 1 is fixed with a binder or covered with an overcoat to fix the glass particles on the surface of the fiber. It was Therefore, there is a problem that not only it is troublesome to fix the glass particles, but also it is difficult to obtain sufficient antibacterial property, and the cost is increased, which is economically disadvantageous.

Further, in the antibacterial fiber obtained by the method of dispersing antibacterial glass particles in the fiber substrate disclosed in Patent Document 1, only the antibacterial glass particles fixed on the fiber surface exhibit the antibacterial effect. On the other hand, the central part of the fiber also contains glass particles. Therefore, there has been a problem that a large amount of expensive antibacterial glass particles containing silver or the like must be added.

On the other hand, in the antibacterial fiber disclosed in Patent Document 2, only the core portion is prevented in order to prevent the antibacterial property from being deteriorated due to oxidation of silver which is an antibacterial component due to alkali reduction processing and discoloration (coloring), and as a result. Contains an antibacterial agent. Therefore, since there is no antibacterial agent on the fiber surface, there is a problem that a sufficient antibacterial effect cannot be obtained.

Therefore, as a result of intensive studies, the inventors of the present invention have found that an antibacterial fiber containing a thermoplastic resin and an antibacterial glass as a blending component and having an average diameter of the antibacterial fiber in the range of 1 to 50 μm. The antibacterial fiber has a core portion and a sheath portion, and the content of the antibacterial glass in the core portion is Q1 (% by weight) with respect to the total amount of the antibacterial fiber. When the content of the antibacterial glass in the sheath portion is Q2 (% by weight) with respect to the total amount of the antibacterial fiber, Q1 and Q2 are antibacterial fibers satisfying a predetermined relational expression. The present invention has been completed by finding that excellent antibacterial properties are exhibited even when the amount of antibacterial glass is small.

That is, the present invention, by reducing the content of the antibacterial glass in the core portion, than the content of the antibacterial glass in the sheath portion, the compounding amount of the antibacterial glass can be a small amount, thereby exhibiting excellent antibacterial properties. It is an object of the present invention to provide an antibacterial fiber that can be manufactured, and an efficient method for producing such an antibacterial fiber.

According to the present invention, an antibacterial fiber containing a thermoplastic resin and an antibacterial glass as a compounding component, wherein the antibacterial fiber has an average diameter within a range of 1 to 50 μm, The core portion and the sheath portion are provided, and the content of the antibacterial glass in the core portion is Q1 (% by weight) with respect to the total amount of the antibacterial fiber, and the content of the antibacterial glass in the sheath portion is included. Provided is an antibacterial fiber characterized in that Q1 and Q2 satisfy the following relational expression (1) when the amount is Q2 (% by weight) based on the total amount of the antibacterial fiber. Can solve the problem.
Q1<Q2 (1)
That is, the content of the antibacterial glass in the core portion can be adjusted to be smaller than the content of the antibacterial glass in the sheath portion, and thus, a relatively small amount of the antibacterial glass is mixed with respect to the total amount of the antibacterial fiber. Even in the amount, excellent antibacterial properties can be exhibited from the initial stage to a long period of time.

In constructing the antibacterial fiber of the present invention, Q1 is preferably 0 or 0 to less than 1% by weight (excluding 0% by weight).
With this structure, the content of the antibacterial glass in the core portion, which is less likely to contribute to the development of the antibacterial effect, can be reduced.

In constructing the antibacterial fiber of the present invention, it is preferable to set Q2 to a value within the range of 1 to 10% by weight.
With this configuration, the antibacterial glass can be blended in a more suitable range with respect to the total amount of the antibacterial fiber.

In constructing the antibacterial fiber of the present invention, it is preferable to further include agglomerated silica particles as a blending component.
With such a structure, the silica particles having high hydrophilicity are attached to the periphery of the antibacterial glass, so that the dissolution rate of the antibacterial glass becomes uniform and the coloring property of the antibacterial fiber is excellent. It becomes a thing.

In constructing the antibacterial fiber of the present invention, it is preferable to set the volume average particle diameter of the antibacterial glass to a value within the range of 0.1 to 5 μm.
With this structure, not only the antibacterial glass can be more uniformly dispersed in the resin component, but also the antibacterial glass can be stably processed into the antibacterial fiber.

In constructing the antibacterial fiber of the present invention, it is preferable that the thermoplastic resin is any one or more of polyester resin, polyamide resin and polyolefin resin.
With such a configuration, the antibacterial glass can be more uniformly dispersed in the resin component, so that an excellent antibacterial effect can be obtained.

In constructing the antibacterial fiber of the present invention, the form of the antibacterial fiber is preferably any one of woven fabric, non-woven fabric and felt.
That is, if the antibacterial fiber of the present invention is an antibacterial fiber having a predetermined shape, even if the compounding amount of the antibacterial glass is reduced, a woven fabric, a nonwoven fabric and a felt exhibiting excellent antibacterial properties are obtained. be able to.

Another aspect of the present invention is a method for producing an antibacterial fiber, which comprises a core portion and a sheath portion, and contains a thermoplastic resin and an antibacterial glass as a compounding component, in the following step (1): (3) A method for producing an antibacterial fiber, which comprises:
(1) Step of preparing antibacterial glass (2) The content of antibacterial glass in the core part is set to Q1 (wt%) with respect to the total amount of antibacterial fiber, and the antibacterial glass in the sheath part When the content is Q2 (% by weight) based on the total amount of the antibacterial fiber, the obtained antibacterial glass is thermoplastic so that Q1 and Q2 satisfy the following relational expression (1). Step of preparing core spinning solution and sheath spinning solution by dispersing in resin Q1<Q2 (1)
(3) A step of composite spinning using a core-sheath composite spinneret with the core spinning solution as the core and the sheath spinning solution as the sheath to form an antibacterial fiber having an average diameter of 1 to 50 μm. By including (1) to (3), the content of the antibacterial glass in the core part can be made smaller than the content of the antibacterial glass in the sheath part.
Therefore, a relatively small amount of the antibacterial glass is required with respect to the total amount of the antibacterial fiber, and it is possible to exhibit excellent antibacterial properties.

FIG. 1 is an electron micrograph (SEM image, magnification 2000) of the antibacterial fiber according to the present embodiment.
FIG. 2 is a schematic view of an antibacterial fiber having a core portion and a sheath portion according to this embodiment.
FIG. 3 is an electron micrograph (SEM image, magnification 2000) of the antibacterial fiber according to Example 1.
4(a) to 4(c) are EDX mapping analysis results of the antibacterial fiber according to Example 1.
5(a) to 5(c) are EDX mapping analysis results of the antibacterial fiber according to Example 2.

[First Embodiment]
The first embodiment is an antibacterial fiber containing a thermoplastic resin and an antibacterial glass as a compounding component, wherein the antibacterial fiber has an average diameter within a range of 1 to 50 μm. Is provided with a core portion and a sheath portion, and the content of the antibacterial glass in the core portion is Q1 (% by weight) with respect to the total amount of the antibacterial fiber, and When the content is Q2 (% by weight) with respect to the total amount of the antibacterial fiber, Q1 and Q2 satisfy the following relational expression (1), and the antibacterial fiber is characterized.
Q1<Q2 (1)
Hereinafter, the antibacterial fiber as the first embodiment will be specifically described for each constituent requirement.

1. Thermoplastic resin (1) Main component (1)-1 type A thermoplastic resin is used as the main component of the resin constituting the antibacterial fiber of the present embodiment.
The type of such a thermoplastic resin is not particularly limited, but polyester resin, polyamide resin, polyurethane resin, polyolefin resin (including polyacrylic resin), rayon resin, polyvinyl acetate resin, cellulose At least one of a resin, a polyvinyl chloride resin, and a polyacetal resin is preferable.
The reason is that if the polyester resin has high mechanical strength, durability, and high heat resistance, antibacterial fibers having excellent flexibility and processability can be obtained at a relatively low cost. ..
In addition, a polyamide resin has high mechanical strength, durability, and heat resistance, and on the other hand, hygroscopic antibacterial fibers can be obtained at a relatively low cost.
In addition, a polyurethane resin can provide an antibacterial fiber having excellent elasticity while having high durability.
Furthermore, if it is a polyolefin resin (including a polyacrylic resin), it is possible to inexpensively obtain an antibacterial fiber having good transparency and processability.

Among these thermoplastic resins, polyester resin or polyolefin resin is more preferable.
That is, as a suitable polyester resin, at least one of polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, polylactic acid resin, polybutylene succinate resin, polyglycolic acid resin and the like can be mentioned. Among them, polyethylene terephthalate resin is preferable.
Suitable polyolefin resins include polypropylene resin, polyethylene resin (high-density polyethylene resin, linear polyethylene resin, low-density polyethylene resin, etc.), polymethylpentene resin, vinyl acetate copolymer resin, propylene copolymer resin. And the like, and polypropylene resin is preferable among them.

That is, the reason why the polyethylene terephthalate resin is suitable is that the thermoplastic resin composition has low heat resistance as compared with polybutylene terephthalate resin and the like, and therefore, a thermoplastic resin composition is required to have excellent flexibility. This is because it can be stably processed into the same shape.
More specifically, polyethylene terephthalate resin is characterized in that it has a lower crystallization rate than polybutylene terephthalate resin and that crystallization does not proceed unless it is at a high temperature. This is because

In addition, a polyethylene terephthalate resin is economically advantageous because it has high transparency, excellent heat resistance, practical strength, and excellent recyclability.
More specifically, plastic products made of polyethylene terephthalate resin, such as PET bottles, are currently in large quantities and are very inexpensive compared to other resin materials.
Furthermore, since polyethylene terephthalate resin is easier to reuse as compared with other resin materials, as is clear from the current situation where recycling is actively carried out, this means that polyethylene terephthalate resin It is a cheaper resin material.
The polyethylene terephthalate resin may be a copolymerized polyester containing another copolymerization component.

Further, polypropylene resin is excellent in mechanical strength such as tensile strength, impact strength, and compression strength, and can be adjusted according to the application.
Furthermore, since it is excellent in abrasion resistance and chemical resistance, and also excellent in quick-drying property and heat retaining property, it is considered that it can be suitably used for antibacterial fibers.

Therefore, by using polyethylene terephthalate resin or polypropylene resin as a main component, the crystallization of the thermoplastic resin composition in the process of manufacturing and molding the antibacterial fiber is effectively suppressed, and the antibacterial fiber or the antibacterial film is obtained. Etc. can be processed stably.

(1)-2 Number average molecular weight When the thermoplastic resin as the main component is polyethylene terephthalate resin, polypropylene resin or the like, it is preferable to set the number average molecular weight to a value within the range of 5,000 to 80,000.
The reason for this is that by setting the number average molecular weight of polyethylene terephthalate resin, polypropylene resin or the like to a value within such a range, it is possible to improve the compatibility with the resin that is a sub-component of the thermoplastic resin described below, This is because it is possible to effectively suppress the hydrolysis of and to disperse the antibacterial glass more uniformly.
Therefore, the number average molecular weight of the thermoplastic resin is more preferably within the range of 10,000 to 60,000, and even more preferably within the range of 20,000 to 50,000.

(1)-3 Melting Point Further, it is preferable to set the melting point of the thermoplastic resin as the main component to a value within the range of 150 to 350°C.
The reason for this is that if the melting point is 150° C. or higher, mechanical properties such as tensile strength and tear strength in the thermoplastic resin composition can be sufficiently ensured, and a suitable viscosity will be obtained upon heating and melting, so that it is appropriate. This is because workability can be obtained.
On the other hand, if the melting point is 350° C. or lower, the thermoplastic resin composition has good moldability and is easily mixed with other resin components of the thermoplastic resin described later.
Therefore, the melting point of the thermoplastic resin as the main component is more preferably set to a value within the range of 200 to 300°C, and further preferably set to a value within the range of 230 to 270°C.
The melting point of the resin can be measured according to ISO 3146.
When no melting point is observed, the glass transition point is preferably set to a value within the range of 150 to 350°C.

(1)-4 Blending amount Further, when the blending amount of the polyethylene terephthalate resin or the polypropylene resin is 100 parts by weight of the total amount of the thermoplastic resin composition, a value within a range of 80 to 99.4 parts by weight. It is preferable that

The reason for this is that by setting the blending amount of the polyethylene terephthalate resin or the polypropylene resin to a value within this range, hydrolysis of the resin can be effectively suppressed, while the thermoplastic resin composition can be used as an antibacterial fiber. This is because it becomes easy to process into an antibacterial film.
Therefore, it is more preferable that the blending amount of the polyethylene terephthalate resin or the polypropylene resin be a value within the range of 85 to 99 parts by weight, when the total amount of the antibacterial resin composition is 100 parts by weight, and 90 to 90 parts by weight. More preferably, the value is within the range of 98 parts by weight.

(1)-5 Tensile Strength Further, when the tensile strength of the resin as the main component is measured according to JIS L 1015, it is preferable to set it to a value within the range of 20 to 100 MPa.
The reason for this is that if the resin has a tensile strength of less than 20 MPa, the fibers may be broken during stretching, or the product may be torn during washing of the product using the antibacterial fiber.
On the other hand, when the tensile strength of the resin exceeds 100 MPa, the flexibility of the antibacterial fiber is not sufficient, and the intended use may be excessively limited.
Therefore, the tensile strength of the resin is more preferably set to a value within the range of 25 to 95 MPa, further preferably set to a value within the range of 30 to 90 MPa.

(2) Mixed Resin (2)-1 Kind When the thermoplastic resin in the present embodiment contains a polyethylene terephthalate resin as a main component, it is preferable to use a mixed resin containing a polybutylene terephthalate resin as another resin component.
The reason for this is that, by containing a polybutylene terephthalate resin having excellent hydrolysis resistance as compared with a polyethylene terephthalate resin, when the thermoplastic resin is heated and melted in the production and molding of the antibacterial fiber, an antibacterial glass is produced. This is because it is possible to effectively suppress the hydrolysis of the polyethylene terephthalate resin due to the contained water.
More specifically, the polybutylene terephthalate resin has higher lipophilicity than the polyethylene terephthalate resin and the number of ester bonds contained per unit weight is small, so that it is considered that hydrolysis is unlikely to occur.

Therefore, by containing the polybutylene terephthalate resin, it is possible to effectively suppress the hydrolysis of the polyethylene terephthalate resin as the main component, excellent dispersibility of the antibacterial glass, and to obtain an inexpensive thermoplastic resin You can
That is, a predetermined amount of antibacterial glass is first mixed with a polybutylene terephthalate resin to form a masterbatch containing a relatively high concentration of antibacterial glass, and then a polyethylene terephthalate resin is mixed to add water to the polyethylene terephthalate resin. It is possible to finally obtain an antibacterial resin composition with a predetermined mixing ratio while suppressing decomposition.

In addition, the polybutylene terephthalate resin in the present embodiment basically comprises terephthalic acid as an acid component or an ester-forming derivative thereof and 1,4-butanediol as a glycol component or an ester-forming derivative thereof. A polymer obtained by a polycondensation reaction.
However, when the total amount of the acid component is 100 mol %, another acid component may be contained as long as the value is within the range of 20 mol% or less.

(2)-3 Compounding amount Further, the compounding amount of the polybutylene terephthalate resin is preferably set to a value within a range of 0.5 to 25 parts by weight with respect to 100 parts by weight of the polyethylene terephthalate resin.
The reason for this is that by setting the blending amount of the polybutylene terephthalate resin to a value within such a range, the main component is polyethylene terephthalate resin that can be processed into antibacterial fibers and antibacterial films, but it also has hydrolysis resistance. This is because it is possible to obtain a thermoplastic resin having excellent dispersibility of the antibacterial glass.
Therefore, more specifically, the compounding amount of the polybutylene terephthalate resin is more preferably set within the range of 2 to 15 parts by weight, and more preferably 3 to 10 parts by weight, based on 100 parts by weight of the polyethylene terephthalate resin. It is more preferable to set the value within the range.

(3) Different resin components Further, in the present invention, the core portion and the sheath portion may use the same kind of thermoplastic resin, or may use different kinds. If the core portion and the sheath portion use the same type of thermoplastic resin, the core portion and the sheath portion have good affinity, and the antibacterial fiber can be stably obtained.
On the other hand, when the type of thermoplastic resin used is different between the core part and the sheath part, by using a resin having higher mechanical strength for the core part, the tensile strength and tear strength of the obtained antibacterial fiber can be improved. It can enhance mechanical properties.

2. Antibacterial Glass The antibacterial fiber according to the present embodiment contains antibacterial glass, and the antibacterial glass preferably contains silver ions as an antibacterial active ingredient.
The reason for this is that such antibacterial glass is highly safe, has a long-lasting antibacterial effect, and has high heat resistance, and therefore has excellent suitability as an antibacterial agent to be contained in antibacterial fibers. Is.

(1) Composition It is preferable that the antibacterial glass is selected from phosphoric acid antibacterial glass and borosilicate glass.
The reason for this is that if the phosphoric acid type antibacterial glass or borosilicate type glass absorbs the surrounding moisture and releases the antibacterial active ingredient while absorbing the water, the antibacterial action is prevented while preventing the discoloration of the thermoplastic resin. This is because the elution amount of the antibacterial active ingredient such as silver ions in the functional fiber can be adjusted within a suitable range.

(1)-1 Glass composition 1
The glass composition of the phosphoric acid-based antibacterial glass contains Ag ₂ O, ZnO, CaO, B ₂ O ₃ and P ₂ O ₅ , and when the total amount is 100% by weight, Ag ₂ O The compounding amount is within a range of 0.2 to 5% by weight, the ZnO compounding amount is within a range of 2 to 60% by weight, the CaO compounding amount is within a range of 0.1 to 15% by weight, The content of B ₂ O ₃ is in the range of 0.1 to 15% by weight, the content of P ₂ O ₅ is in the range of 30 to 80% by weight, and the ZnO/CaO weight ratio is Is preferably set to a value within the range of 1.1 to 15.

Here, Ag ₂ O is an essential component as an antibacterial ion-releasing substance in the glass composition 1, and by containing such Ag ₂ O, when the glass component is dissolved, silver ions are gradually added at a predetermined rate. It can be eluted, and excellent antibacterial properties can be exhibited for a long period of time.

Further, it is preferable to set the content of Ag ₂ O within the range of 0.2 to 5% by weight.
The reason for this is that if the content of Ag ₂ O is 0.2% by weight or more, sufficient antibacterial properties can be exhibited.
On the other hand, if the blending amount of Ag ₂ O is 5% by weight or less, the antibacterial glass is less likely to discolor, and the cost can be suppressed, which is economically advantageous.
Therefore, the content of Ag ₂ O is more preferably 0.5 to 4% by weight, and further preferably 0.8 to 3.5% by weight.

Further, P ₂ O ₅ is an essential constituent component in the glass composition 1, and basically functions as a network-forming oxide. In addition, in the present invention, in addition to the transparency improving function of the antibacterial glass and the silver ion. Is also involved in the uniform release of

The content of P ₂ O ₅ is preferably in the range of 30 to 80% by weight.
The reason for this is that if the content of P ₂ O ₅ is 30% by weight or more, the transparency of the antibacterial glass is unlikely to decrease, and it is easy to ensure uniform release of silver ions and physical strength. is there.
On the other hand, if the compounding amount of P ₂ O ₅ is 80% by weight or less, the antibacterial glass is less likely to yellow, and the curability is good, so that the physical strength is easily secured.
Therefore, the compounding amount of P ₂ O ₅ is more preferably in the range of 35 to 75% by weight, and further preferably in the range of 40 to 70% by weight.

Moreover, ZnO is an essential constituent component of the glass composition 1, has a function as a network-modifying oxide in antibacterial glass, prevents yellowing, and has a function of improving antibacterial property.

The content of ZnO is preferably in the range of 2 to 60% by weight based on the total amount.
The reason for this is that if the content of ZnO is 2% by weight or more, the effect of preventing yellowing and the effect of improving antibacterial properties are easily exhibited, while the content of ZnO is 60% by weight. This is because when the value is the following, the transparency of the antibacterial glass is unlikely to decrease and the mechanical strength is easily secured.
Therefore, the content of ZnO is more preferably in the range of 5 to 50% by weight, and further preferably in the range of 10 to 40% by weight.

Further, it is preferable to determine the compounding amount of ZnO in consideration of the compounding amount of CaO described later.
Specifically, the weight ratio represented by ZnO/CaO is preferably set to a value within the range of 1.1 to 15.
The reason is that if the weight ratio is 1.1 or more, the yellowing of the antibacterial glass can be efficiently prevented, while if the weight ratio is 15 or less, the antibacterial glass is antibacterial. This is because the volatile glass is unlikely to become cloudy or yellow.
Therefore, the weight ratio represented by ZnO/CaO is more preferably set to a value within the range of 2.0 to 12, and further preferably set to a value within the range of 3.0 to 10.

CaO is an essential constituent component in the glass composition 1, and basically functions as a network-modifying oxide, and also lowers the heating temperature when producing an antibacterial glass and, together with ZnO, prevents yellowing. Can be demonstrated.

The content of CaO is preferably in the range of 0.1 to 15% by weight based on the total amount.
The reason for this is that if the content of CaO is 0.1% by weight or more, the function of preventing yellowing and the effect of lowering the melting temperature are likely to be exhibited, while the content of CaO is 15% or less.
This is because if it is at most% by weight, it is easy to suppress the decrease in the transparency of the antibacterial glass.
Therefore, the content of CaO is preferably in the range of 1.0 to 12% by weight, and more preferably in the range of 3.0 to 10% by weight.

B ₂ O ₃ is an essential constituent component in the glass composition 1 and basically functions as a network-forming oxide. In addition, in the present invention, in addition to the transparency improving function of the antibacterial glass and the silver ion. It is a component that is also involved in the uniform release property of.

The content of B ₂ O ₃ is preferably in the range of 0.1 to 15% by weight based on the total amount.
The reason for this is that if the content of B ₂ O ₃ is 0.1% by weight or more, the transparency of the antibacterial glass can be sufficiently ensured, and the uniform release of silver ions and mechanical strength can be ensured. This is because it is easy.
On the other hand, if the compounding amount of B ₂ O ₃ is 15% by weight or less, yellowing of the antibacterial glass is easily suppressed, and the curability is good, and the mechanical strength is easily secured.
Therefore, the content of B ₂ O ₃ is preferably in the range of 1.0 to 12% by weight, and more preferably in the range of 3.0 to 10% by weight.

It should be noted that CeO ₂ , MgO, Na ₂ O, Al ₂ O ₃ , K ₂ O, SiO ₂ , BaO and the like may be added in predetermined amounts as optional constituents of the glass composition 1 within the scope of the present invention. preferable.

(1)-2 Glass composition 2
Further, as the glass composition of the phosphoric acid-based antibacterial glass, instead of substantially not containing ZnO, Ag ₂ O, CaO, B ₂ O ₃ and P ₂ O ₅ were contained, and the total amount was 100% by weight. Sometimes, the content of Ag ₂ O is in the range of 0.2 to 5% by weight, the content of CaO is in the range of 15 to 50% by weight, and the content of B ₂ O ₃ is 0.1. Value within the range of up to 15% by weight, P ₂ O ₅ content within the range of 30 to 80% by weight, and CaO/Ag ₂ O weight ratio within the range of 5 to 15 It is preferable that

Here, the content of Ag ₂ O can be the same as that of the glass composition 1.
Therefore, the content of Ag ₂ O is preferably in the range of 0.2 to 5% by weight, and more preferably in the range of 0.5 to 4.0% by weight, based on the total amount. More preferably, it is more preferably in the range of 0.8 to 3.5% by weight.

Also, by using CaO as the antibacterial glass, it basically functions as a network-modifying oxide, and at the same time, lowers the heating temperature when producing the antibacterial glass and exerts a yellowing prevention function. can do.

That is, it is preferable to set the content of CaO within the range of 15 to 50% by weight based on the total amount.
The reason for this is that if the content of CaO is 15% by weight or more, the yellowing prevention function and the melting temperature lowering effect are exhibited even if ZnO is not substantially contained. This is because if the content of CaO is 50% by weight or less, the transparency of the antibacterial glass can be sufficiently ensured.
Therefore, the amount of CaO blended is more preferably in the range of 20 to 45% by weight, and further preferably in the range of 25 to 40% by weight.

The CaO content is preferably determined in consideration of the Ag ₂ O content. Specifically, the weight ratio represented by CaO/Ag ₂ O is set to a value within the range of 5 to 15. Preferably.
More specifically, the weight ratio represented by CaO/Ag ₂ O is more preferably in the range of 6 to 13, and further preferably in the range of 8 to 11.

In addition, B ₂ O ₃ and P ₂ O ₅ can have the same contents as the glass composition 1.
Further, components such as CeO ₂ , MgO, Na ₂ O, Al ₂ O ₃ , K ₂ O, SiO ₂ and BaO are optional components within the scope of the present invention, as in the case of the glass composition 1. It is also preferable to add a fixed amount.

(1)-3 Glass composition 3
Further, the glass composition of borosilicate glass contains B ₂ O ₃ , SiO ₂ , Ag ₂ O, and an alkali metal oxide, and when the total amount is 100% by weight, the blending amount of B ₂ O ₃ is In the range of 30 to 60% by weight, the content of SiO ₂ in the range of 30 to 60% by weight, the content of Ag ₂ O in the range of 0.2 to 5% by weight, alkali When the content of the metal oxide is within the range of 5 to 20% by weight, the content of Al ₂ O ₃ is within the range of 0.1 to 2% by weight, and the total amount is less than 100% by weight. It is preferable that other glass components (alkaline earth metal oxide, CeO ₂ , CoO, etc.) be contained as a residual component in a value within the range of 0.1 to 33% by weight.

Here, in the composition of the alkaline antibacterial glass, B ₂ O ₃ basically functions as a network-forming oxide, but is also involved in the transparency improving function and the uniform release of silver ions. To do.
Further, SiO ₂ has a function as a network-forming oxide in the antibacterial glass and a function of preventing yellowing.
Furthermore, Ag ₂ O is an essential constituent component in the antibacterial glass, and by dissolving the glass component and eluting silver ions, excellent antibacterial properties can be exhibited for a long period of time.

Alkali metal oxides, such as Na ₂ O and K ₂ O, basically function as network-modifying oxides, while also exerting a function of adjusting the dissolution characteristics of antibacterial glass, thereby improving the water resistance of antibacterial glass. By reducing the amount, the amount of silver ions eluted from the antibacterial glass can be adjusted.

As the alkaline earth metal oxide, for example, by adding MgO or CaO, it is possible to perform the function as a network modification oxide, while, like the alkali metal oxide, the transparency improving function of the antibacterial glass and melting. It can exert the function of adjusting the temperature.
In addition, by separately adding CeO ₂ , Al ₂ O ₃ , or the like, it is possible to improve the discoloration property to an electron beam, the transparency, or the mechanical strength.

(2) Elution rate Further, the elution rate of the antibacterial ions from the antibacterial glass is preferably set to a value within the range of 1×10 ² to 1×10 ⁵ mg/Kg/24Hr.
The reason for this is that when the elution rate of such antibacterial ions is less than 1×10 ² mg/Kg/24 Hr, the antibacterial property may be significantly reduced, while the elution rate of such antibacterial ions is 1×10 2. ^This is because if it exceeds ⁵ mg/Kg/24 Hr, it may be difficult to exert the antibacterial effect for a long time, or the transparency of the obtained antibacterial fiber may decrease. Therefore, from the viewpoint of more preferable balance between such antibacterial properties and transparency, the elution rate of antibacterial ions from the antibacterial glass is set to a value within the range of 1×10 ³ to 5×10 ⁴ mg/Kg/24Hr. Is more preferable, and a value within the range of 3×10 ³ to 1×10 ⁴ mg/Kg/24Hr is further preferable. The elution rate of such antibacterial ions can be measured under the following measurement conditions.
(Measurement condition)
100 g of antibacterial glass is immersed in 500 ml of distilled water (20° C.) and shaken for 24 hours using a shaker. Then, after the Ag ion eluate is separated using a centrifuge, it is further filtered through a filter paper (5C) to obtain a measurement sample. Then, Ag ions in the measurement sample are measured by ICP emission spectroscopy, and the amount of Ag ion elution (mg/Kg/24Hr) is calculated.

(3) Volume average particle diameter Further, the volume average particle diameter (volume average primary particle diameter, D50) of the antibacterial glass is preferably set to a value within the range of 0.1 to 5.0 μm.
The reason for this is that by setting the volume average particle diameter of the antibacterial glass to a value within such a range, the antibacterial glass can be more uniformly dispersed, and the thermoplastic resin containing the antibacterial glass is This is because it can be more stably processed into an antibacterial fiber or an antibacterial film.

That is, when the volume average particle diameter of the antibacterial glass is 0.1 μm or more, mixing/dispersion in the resin component is easy, light scattering is suppressed, or transparency is easily secured.
On the other hand, if the volume average particle diameter of the antibacterial glass is 5.0 μm or less, the antibacterial fiber is easily dispersed in the resin component, and the mechanical strength of the antibacterial fiber is easily secured.
Therefore, more specifically, the volume average particle diameter of the antibacterial glass is more preferably set to a value within the range of 0.5 to 4.0 μm, and is set to a value within the range of 1.0 to 3.0 μm. It is more preferable that the volume average particle diameter (D50) of the antibacterial glass is the particle size distribution obtained by using a laser type particle counter (based on JIS Z 8852-1) or a sedimentation type particle size distribution meter, or It can be calculated from the particle size distribution obtained by performing image processing based on an electron micrograph of antibacterial glass.

(4) Specific Surface Area The specific surface area of the antibacterial glass is preferably set to a value within the range of 10,000 to 300,000 cm ² /cm ³ .
The reason for this is that if the specific surface area is a value of 10000 cm ² /cm ³ or more, it is easy to mix and disperse it in the resin component and handle it, and when producing antibacterial fiber, surface smoothness and mechanical This is because it is easy to secure strength.
On the other hand, when the specific surface area is 300,000 cm ² /cm ³ or less, mixing/dispersion in the resin component becomes easy, light scattering hardly occurs, and deterioration of transparency can be suppressed.
More specifically, the specific surface area of the antibacterial glass is more preferably in the range of 15,000 to 200,000 cm ² /cm ³ , and even more preferably in the range of 18,000 to 150,000 cm ² /cm ^3. ..
The specific surface area (cm ² /cm ³ ) of the antibacterial glass can be obtained from the results of particle size distribution measurement. Assuming that the antibacterial glass is spherical, the measured data of the particle size distribution is used to measure the unit volume (cm ³ ) Surface area (cm ² ).

(5) Shape The shape of the antibacterial glass is a polyhedron, that is, a plurality of corners and faces, and for example, a polyhedron having 6 to 20 faces is preferable.
The reason for this is that the shape of the antibacterial glass is a polyhedron as described above, and unlike the antibacterial glass having a spherical shape or the like, it is easy for light to proceed in a certain direction in a plane. This is because it is possible to effectively prevent the resulting light scattering, and thus it is possible to improve the transparency of the antibacterial glass.
Further, by making the antibacterial glass into a polyhedron in this way, not only the mixing and dispersion in the resin component is facilitated, but especially when the antibacterial fiber is produced by using a spinning device, etc. Is characterized by being easily oriented in a certain direction.
Therefore, the antibacterial glass can be easily dispersed uniformly in the resin component, and light scattering by the antibacterial glass in the resin component can be effectively prevented, and excellent transparency can be exhibited.
Furthermore, if the shape of the antibacterial glass is a polyhedron in this way, the external additive to be described later is likely to adhere, and it is difficult to re-aggregate during production or use, so that the average particles during the production of the antibacterial glass. It is easy to control the diameter and variations.

(6) Surface Treatment The surface of the antibacterial glass is preferably treated with a polyorganosiloxane/silicone resin, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like.
Thereby, the adhesive force between the antibacterial glass and the thermoplastic resin can be adjusted.

(7) External Additive It is also preferable to externally add agglomerated silica particles (dry silica, wet silica) to the antibacterial glass.
As long as they contain agglomerated silica particles as a main component, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium carbonate, shirasu balloon, quartz particles, glass balloons and the like may be used alone or in combination of two or more.
Of these, agglomerated silica particles (dry silica, wet silica) or colloidal silica, which is an aqueous dispersion thereof, is particularly preferable because the number average primary particle size is small and the dispersibility in antibacterial glass is extremely excellent. It is an external additive.
That is, since such agglomerated silica particles are dispersed while loosening the agglomerated state, the antibacterial glass can be uniformly dispersed even if it adheres to the periphery of the antibacterial glass and is in the resin component. Is. Thereby, the antibacterial glass can be uniformly dispersed in the antibacterial fiber without unevenness.

Further, the number average secondary particle diameter of the agglomerated silica as an external additive is preferably set to a value within the range of 1 to 15 μm.
The reason for this is that if the number average secondary particle diameter of the external additive is a value of 1 μm or more, the dispersibility of the antibacterial glass 10 becomes good, light scattering is suppressed, and transparency can be secured.
On the other hand, if the number average secondary particle size of the external additive is 15 μm or less, it is easy to mix/disperse and handle in the resin component, and when producing an antibacterial fiber or an antibacterial film, This is because it is easy to secure surface smoothness, transparency, and mechanical strength.
Therefore, the number average secondary particle diameter of the external additive is more preferably within the range of 5 to 12 μm, and even more preferably within the range of 6 to 10 μm.
The number average secondary particle diameter of the external additive can be measured using a laser particle counter (based on JIS Z885-2) or a sedimentation particle size distribution meter.
The number average secondary particle size of the external additive can also be calculated by performing image processing from these electron micrographs.

When the external additive is basically agglomerated, it is preferable to set the number average primary particle diameter in a loosened state to a value within the range of 0.005 to 0.5 μm.
The reason is that when the number average primary particle diameter of the external additive is 0.005 μm or more, the effect of improving the dispersibility of the antibacterial glass is easily obtained, light scattering is suppressed, and the transparency is lowered. This is because it is possible to suppress
On the other hand, when the number average primary particle diameter of the external additive is 0.5 μm or less, the effect of improving the dispersibility of the antibacterial glass is likely to be obtained, and when the antibacterial fiber or the antibacterial film is produced, This is because mixing/dispersion in the resin component and handling are similarly easy, and surface smoothness, transparency, and mechanical strength can be sufficiently secured.
Therefore, the number average primary particle diameter of the external additive is more preferably set to a value within the range of 0.01 to 0.2 μm, and further preferably set to a value within the range of 0.02 to 0.1 μm.
The number average primary particle diameter of the external additive can be measured by the same method as the number average secondary particle diameter.

Further, it is preferable that the addition amount of the aggregated silica as an external additive is set to a value within the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the antibacterial glass.
The reason for this is that the dispersibility of the antibacterial glass becomes good when the amount of the external additive added is a value of 0.1 parts by weight or more.
On the other hand, when the addition amount of the external additive is 50 parts by weight or less, it is easy to uniformly mix with the antibacterial glass, and the transparency of the obtained antibacterial resin composition does not easily decrease.

Therefore, the amount of the external additive added is more preferably 0.5 to 30 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the antibacterial glass. More preferably.

(8) Water Content Even when the antibacterial glass contains water, the water content is 1×10 ⁻⁴ to 5 parts by weight based on 100 parts by weight of the solid component of the antibacterial glass. It is preferable that the value is within the range.
The reason for this is that by setting the water content to a value within such a range, even when the step of drying the antibacterial glass is omitted during the production of the thermoplastic resin composition, the thermoplastic resin is hydrolyzed. This is because decomposition can be effectively suppressed and the antibacterial glass can be uniformly dispersed.
That is, if the water content is a value of 1×10 ⁻⁴ parts by weight or more, it is not necessary to use an excessively large antibacterial glass drying facility, and the time required for the drying step is excessively long. This is because it is less likely to occur and the economy is not significantly impaired.
On the other hand, if the water content is 5 parts by weight or less, the above-mentioned hydrolysis of the thermoplastic resin can be stably suppressed.

Therefore, it is more preferable to set the water content of the antibacterial glass to a value within the range of 1×10 ⁻³ to 1 part by weight based on 100 parts by weight of the solid component of the antibacterial glass, and preferably 1×10 ^−2. It is more preferable to set the value within the range of 1×10 ⁻¹ wt %.
The water content in the antibacterial glass can be measured, for example, by an electronic moisture meter by the heating weight loss method at 105°C, or by using the Karl Fischer method.

(9) Compounding amount Further, the compounding amount of the antibacterial glass is set to Q1 (wt%) with respect to the total amount of the antibacterial fiber, and the antibacterial property in the sheath part is set. When the glass content is Q2 (% by weight) based on the total amount of antibacterial fiber, Q1 is 0 or less than 0 to 1% by weight (however, 0% by weight is excluded), and Q2 is A value within the range of 1 to 10% by weight is preferable.
The reason for this is that by setting the compounding amount of the antibacterial glass to a value within such a range, the hydrolysis of the thermoplastic resin is effectively suppressed, and the antibacterial glass is uniformly dispersed in the resin component, resulting in excellent antibacterial properties. This is because the effect can be obtained.
Further, with such a configuration, the content of the antibacterial glass in the core portion can be adjusted to be smaller than the content of the antibacterial glass in the sheath portion, and by extension, a small amount relative to the total amount of the antibacterial fiber. This is because excellent antibacterial properties can be exhibited even with the compounding amount.

That is, when Q1 is a value of 0 or less than 1% by weight, the central portion of the antibacterial fiber does not contain excessive antibacterial glass, and the absolute amount is sufficient, so that the antibacterial fiber has a sufficient amount. This is because it is possible to impart antibacterial properties.
On the other hand, when Q2 is a value within the range of 1 to 10% by weight, the amount of water contained in the antibacterial glass increases with the compounding amount of the antibacterial glass, but the hydrolysis of the thermoplastic resin is sufficient. It is because it can be suppressed to. Further, it is easy to process into an antibacterial fiber or an antibacterial film.
Therefore, more specifically, it is more preferable to set Q1 to 0 or less than 0.5% by weight, and it is more preferable to set Q2 to a value within the range of 1.5 to 9% by weight. Further, Q1 is more preferably 0 or less than 0.1% by weight, and Q2 is more preferably a value within the range of 2 to 8% by weight.

3. Antibacterial Fiber (1) Form As shown in the electron micrograph (SEM image) of FIG. 1 and the schematic view of FIG. 2, the antibacterial fiber 1 according to the present embodiment includes a core portion 20 and a sheath portion 30. The content of the antibacterial glass 10 in the core portion 20 is smaller than the content of the antibacterial glass 10 in the sheath portion 30.
The average diameter of the antibacterial fiber is preferably set to a value within the range of 1 to 50 μm.
The reason is that if the average diameter of the antibacterial fiber is 1 μm or more, it is easy to secure the mechanical strength of the antibacterial fiber and the antibacterial fiber can be stably manufactured.
On the other hand, if the average diameter of the antibacterial fiber is 50 μm or less, the flexibility of the antibacterial fiber can be ensured and the antibacterial fiber can be applied to a wide range of applications.
Therefore, the average diameter of the antibacterial fiber is more preferably within the range of 2 to 49 μm, further preferably within the range of 3 to 48 μm.
The average diameter of the antibacterial fiber can be obtained by measuring the diameter at several points (for example, 5 points) with an electron microscope, a micrometer, or a caliper, and taking the average value. It can also be obtained as the equivalent circle diameter.

(2) Core Part (2)-1 Kind of Thermoplastic Resin As the kind of the thermoplastic resin used for the core part, the above-mentioned thermoplastic resins can be used. Further, the number average molecular weight and the melting point of the thermoplastic resin are also preferably set to values within the ranges described above.

(2)-2 Average Diameter Further, the average diameter Φ of the core portion of the antibacterial fiber 1 according to the present embodiment is preferably set to a value within the range of 0.3 to 40 μm.
The reason for this is that by setting the average diameter of the core portion to a value within this range, it is possible to sufficiently secure mechanical properties such as tensile strength and tear strength.
Therefore, the average diameter of the core portion is more preferably set to a value within the range of 0.5 to 35 μm, and further preferably set to a value within the range of 0.7 to 30 μm.
The average diameter of the core portion can be obtained by actually measuring the diameter at several points with an electron microscope or a micrometer (for example, 5 points) and taking the average value.

(3) Sheath part (3)-1 Kind of thermoplastic resin As the kind of thermoplastic resin used for the sheath part, the above-mentioned thermoplastic resins can be used. Further, the number average molecular weight and the melting point of the thermoplastic resin are also preferably set to values within the ranges described above.

(3)-2 Thickness of Sheath Portion The thickness t of the sheath portion of the antibacterial fiber 1 according to this embodiment is preferably set to a value within the range of 0.7 to 49.7 μm.
The reason for this is that by setting the thickness of the sheath portion to a value within this range, sufficient antibacterial properties can be maintained from the initial stage to a long period.
Therefore, the thickness of the sheath portion is more preferably set to a value within the range of 1 to 45 μm, further preferably set to a value within the range of 5 to 40 μm.
The thickness of the sheath portion can be obtained by actually measuring several points t (for example, 5 points) with an electron microscope or a micrometer and taking the average value thereof.

(4) Relational expression Q1<Q2
In the antibacterial fiber according to the present embodiment, the content of the antibacterial glass in the core portion is set to Q1 (% by weight) with respect to the total amount of the antibacterial fiber, and the content of the antibacterial glass in the sheath portion is set to , Q1 and Q2 satisfy the following relational expression (1), where Q2 (% by weight) is based on the total amount of the antibacterial fiber.
Q1<Q2 (1)
As a result, the content of the antibacterial glass in the core portion can be made smaller than the content of the antibacterial glass in the sheath portion, so that the concentration distribution of the antibacterial glass in the antibacterial fiber can be provided, and thus the excellent antibacterial property can be obtained. Can be demonstrated.

Further, it is more preferable that Q1 and Q2 satisfy the following relational expression (2).
0<Q2-Q1≦10 (2)
This is because the concentration distribution of the antibacterial glass in the antibacterial fiber can be set in the optimum range.

Therefore, as Q1 and Q2 satisfying such a relational expression, it is preferable that Q1 is 0 or less than 1% by weight (excluding 0% by weight), and Q2 is within the range of 1 to 10% by weight. A value is preferable. Further, Q1 is more preferably 0 or less than 0.5% by weight, and Q2 is more preferably set to a value within the range of 1.5 to 9% by weight. Further, Q1 is more preferably 0 or less than 0.1% by weight, and Q2 is more preferably a value within the range of 2 to 8% by weight.
This is because if the value of Q1 is within this range, the antibacterial effect of the antibacterial glass can be effectively obtained even when the average diameter of the antibacterial fiber is small. On the other hand, if Q2 has a value within this range, the content of the antibacterial glass with respect to the entire antibacterial fiber can be set within an appropriate range.

(5) Tensile Strength Further, as the antibacterial fiber according to the present embodiment, from the viewpoint of imparting sufficient strength to the product when processed into a woven fabric or the like, the tensile strength measured according to JIS L 1015 It is preferable to set (cN/dtex) to a value within the range of 3 to 50 cN/dtex.
The reason for this is that if the tensile strength (cN/dtex) of the antibacterial fiber is less than 3 cN/dtex, the fiber may be broken during stretching, or the product may be torn when laundering the product using the antibacterial fiber. This is because there may be cases where
On the other hand, if the tensile strength (cN/dtex) of the antibacterial fiber exceeds 50 cN/dtex, the flexibility of the antibacterial fiber may not be sufficient, and the intended use may be excessively limited.
Therefore, the tensile strength (cN/dtex) of the antibacterial fiber is more preferably in the range of 3.5 to 30 cN/dtex, and more preferably in the range of 4.5 to 20 cN/dtex. More preferable.

(6) Others The apparent weaving degree and the number of crimps of the antibacterial fiber are not particularly limited, and can be appropriately adjusted according to the application of the antibacterial fiber.
The apparent weaving degree of the antibacterial fiber can be appropriately adjusted according to the application, but it is preferably a value within the range of 0.1 to 50 dtex, for example, a value within the range of 0.5 to 30 dtex. Is more preferable, and a value within the range of 1 to 10 dtex is further preferable.
Further, the number of crimps of the antibacterial fiber can be adjusted according to the application from the viewpoint of imparting elastic force, texture, etc., and the greater the number of crimps, the greater the elastic force.
Generally, the number of crimps of the antibacterial fiber is preferably 5 to 90 per 25 mm of fiber, and is preferably 50 to 90 for applications requiring elasticity.

4. Dispersion aid Further, the antibacterial fiber in the present embodiment preferably contains a dispersion aid of antibacterial glass.
The reason for this is that the antibacterial glass can be dispersed more uniformly by including the dispersion aid.

(1) Type The type of dispersion aid is not particularly limited, and examples thereof include an aliphatic amide-based dispersion aid, a hydrocarbon-based dispersion aid, a fatty acid-based dispersion aid, a higher alcohol-based dispersion aid, Although metal soap-based dispersion aids, ester-based dispersion aids, and the like can be used, aliphatic amide-based dispersion aids are particularly preferable.

Further, the aliphatic amide-based dispersion aid is roughly classified into fatty acid amides such as stearic acid amide, oleic acid amide, and erucic acid amide, and alkylene fatty acid amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide. However, it is more preferable to use alkylene fatty acid amide.
The reason is that the alkylene fatty acid amide can improve the dispersibility of the antibacterial glass without lowering the thermal stability of the antibacterial resin composition, as compared with the fatty acid amide.
In addition, since the melting point is 141.5 to 146.5° C. and the stability of the antibacterial fiber during molding is excellent, it is particularly preferable to use ethylenebisstearic acid amide among alkylene fatty acid amides.

(2) Blending amount The blending amount of the dispersion aid is preferably a value within the range of 1 to 20 parts by weight when the antibacterial glass is 100 parts by weight.
The reason for this is that the dispersibility of the antibacterial glass in the antibacterial fiber can be sufficiently improved if the compounding amount of the dispersion aid is 1 part by weight or more.
On the other hand, when the amount of the dispersion aid compounded is 20 parts by weight or less, mechanical properties such as tensile strength and tear strength in the antibacterial resin composition can be sufficiently ensured, and the dispersion aid can be bleeded from the antibacterial resin composition. This is because it is difficult to get out.
Therefore, the blending amount of the dispersion aid is more preferably within the range of 3 to 12 parts by weight, and more preferably within the range of 5 to 8 parts by weight, based on 100 parts by weight of the antibacterial glass. Is more preferable.

5. Other compounding ingredients In the antibacterial fiber of the present embodiment, a stabilizer, a release agent, a nucleating agent, a filler, a dye, a pigment, an antistatic agent, if necessary, within a range that does not impair the original purpose. Additives such as oils, lubricants, plasticizers, sizing agents, ultraviolet absorbers, antifungal agents, antiviral agents, flame retardants, flame retardant aids, other resins, elastomers and the like are preferably added as optional components.
The method of adding these optional components to the antibacterial fiber is not particularly limited, and for example, it is also preferable to carry out melt kneading with the thermoplastic resin together with the antibacterial glass.

6. Form The antibacterial fiber according to the present embodiment is preferably processed into a cotton-like or sheet-like molded product such as a woven fabric, a non-woven fabric, a woven fabric, a felt, and a web.
Further, when the antibacterial fiber of the present embodiment is processed into cotton, woven fabric, non-woven fabric, knit, felt, web, etc., it may be processed using only the antibacterial fiber of the present embodiment, but other types It is also preferable that the fibers of (1) and the antibacterial fibers of the present embodiment are mixed and spun to be processed as a plied yarn, a covering yarn, or a braid.
Other types of fibers include synthetic fibers such as nylon, polyester and polyurethane, natural fibers such as cotton and silk, carbon fibers and glass fibers.
Even when mixed with other types of fibers, mixed-spun, and processed into a twisted yarn, a covering yarn, or a braid, it has the same antibacterial properties as the antibacterial fibers of the present embodiment, and antibacterial properties even after repeated washing. It has the excellent feature of lasting sex.

Further, in the processed products such as cotton, woven fabric, and knitted fabric, which are obtained by processing the antibacterial fiber or the antibacterial fiber of the present embodiment according to the use, further dyeing and various finishing processes (anti-wrinkle, anti-staining) , Flame-retardant, insect-proof, mildew-proof, deodorant, moisture-absorbing, waterproof, glazing, anti-pill, etc.) are also preferable.
Thereby, a function other than the antibacterial property can be imparted.

7. Uses Among the above-mentioned forms, the use of the sheet-shaped molded article is not particularly limited, and examples thereof include clothing, bedding, interior fittings, absorbent cloths, packaging materials, miscellaneous goods, and filtration media.
Examples of clothing include underwear, shirts, sportswear, aprons, socks, insoles, stockings, tights, socks, kimono, ties, handkerchiefs, scarves, mufflers, hats, gloves, household or medical masks, etc. Is mentioned.
Examples of bedding include duvet covers, quilt batting, pillowcases, pillow batting, towelettes, sheets, and mattress liners. In particular, it is suitable for use in bedding that is difficult to wash, such as duvets and down pillows.

Examples of interior fittings include curtains, mats, carpets, rugs, cushions, cushions, wall hangings, wall coverings, tablecloths, moquettes, and the like.
Examples of absorbent cloths include towels, towels, handkerchiefs, mops, diapers, tampons, sanitary napkins, adult incontinence products and the like.
Examples of the packaging material include furoshiki, wrapping paper, and food packaging.

Examples of miscellaneous goods include various brushes such as toothbrushes, scrubbing brushes, brushes, handbags, lunch mats, pen cases, wallets, eyeglass cases, eyeglass wipes, curtains, coasters, mouse pads, stuffed toys, and pet beds. ..
Examples of the filtration medium include filters for air conditioners, ventilation fans, air inlets and air purifiers, filters for water purification, and the like, and can be applied to household, industrial, automobile, and other filters.
Other uses include artificial hair, tents, light-shielding sheets such as grass sheets, soundproofing materials, sound absorbing materials, and cushioning materials.

[Second Embodiment]
The second embodiment is the method for producing an antibacterial fiber according to the first embodiment, which includes a core portion and a sheath portion, and a thermoplastic resin, an antibacterial glass, and a combination component. A method for producing an antibacterial fiber comprising the following steps (1) to (3):
(1) Step of preparing antibacterial glass (2) The content of antibacterial glass in the core part is set to Q1 (% by weight) with respect to the total amount of antibacterial fibers, and
When the content of antibacterial glass in the sheath part is Q2 (% by weight) based on the total amount of antibacterial fibers,
A step of dispersing the obtained antibacterial glass in a thermoplastic resin so that Q1 and Q2 satisfy the following relational expression (1) to prepare a spinning solution for core and a spinning solution for sheath Q1< Q2 (1)
(3) A step of composite spinning using a core-sheath composite spinneret with a core stock spinning solution as a core and a sheath spinning solution as a sheath to obtain an antibacterial fiber having an average diameter of 10 to 30 μm. The method for producing an antibacterial fiber as the second embodiment will be specifically described with a focus on the points different from the first embodiment.
The antibacterial fiber according to the present embodiment can be manufactured by the manufacturing method including at least the steps (1) to (3) described above, and if necessary the following steps (4) to (6) are added. Good.

1. Step (1): To the extent that antibacterial glass is prepared Step (1) is a step of producing antibacterial glass from a glass raw material containing an antibacterial active ingredient.
That is, the antibacterial glass can be produced by a conventionally known method, and for example, it is preferable to produce it by the method (1)-1 to 3 below.

(1)-1 Melting Step In the melting step, it is preferable that the glass raw materials are accurately weighed and uniformly mixed, and then melted using, for example, a glass melting furnace to prepare a glass melt.
When mixing glass raw materials, it is preferable to use a mixing machine (mixer) such as a universal stirrer (planetary mixer), an alumina porcelain crusher, a ball mill, a propeller mixer. For example, when a universal stirrer is used, Is 100 rpm, the rotation number is 250 rpm, and the glass raw materials are preferably stirred and mixed under the conditions of 10 minutes to 3 hours.

As the glass melting conditions, for example, it is preferable to set the melting temperature to a value in the range of 1100 to 1500° C. and the melting time to a value in the range of 1 to 8 hours.
The reason for this is that under such melting conditions, the production efficiency of the glass melt can be increased and the yellowing of the antibacterial glass at the time of production can be reduced as much as possible.
In addition, after obtaining such a glass melt, it is preferable to inject it into flowing water and cool it to obtain a glass body also for water pulverization.

(1)-2 Crushing Step Next, the glass body obtained in the crushing step is preferably crushed to obtain an antibacterial glass which is a polyhedron and has a predetermined volume average particle diameter.
Specifically, it is preferable to perform coarse pulverization, medium pulverization, and fine pulverization as described below.
By carrying out in this way, the antibacterial glass having a uniform volume average particle diameter can be efficiently obtained.
However, depending on the application, in order to control the volume average particle size more finely, it is also preferable to further classify after crushing and perform sieving treatment or the like.

In the coarse pulverization, it is preferable to pulverize the glass body so that the volume average particle diameter becomes about 10 mm.
More specifically, when the glass melt in the molten state is water granulated, or by crushing the amorphous glass body with a bare hand or a hammer, a predetermined volume average particle diameter and Preferably.
It is confirmed from an electron micrograph that the antibacterial glass after coarse crushing is usually a lump without corners.

In the medium pulverization, it is preferable to pulverize the antibacterial glass after the coarse pulverization so that the volume average particle diameter becomes about 1 mm.
More specifically, for example, using a ball mill, the antibacterial glass having a volume average particle size of about 10 mm is changed to an antibacterial glass having a volume average particle size of about 5 mm, and then a rotary mill or a rotary roll (roll crusher) is used. It is preferable that the antibacterial glass has a volume average particle diameter of about 1 mm.
The reason for this is that, by carrying out the multi-stage medium pulverization in this manner, it is possible to effectively obtain an antibacterial glass having a predetermined particle size without producing an antibacterial glass having an excessively small particle size. ..
It has been confirmed from electron micrographs that the antibacterial glass after medium pulverization is a polygon having corners.

In fine pulverization, antibacterial properties after medium pulverization were carried out in the state where agglomerated silica particles as an external additive having a volume average particle diameter of 1 to 15 μm were added so that the volume average particle diameter becomes 1.0 to 5.0 μm. It is preferred to crush the glass.
More specifically, for example, a rotary usher, a rotary roll (roll crusher), a vibration mill,
It is preferable to grind the antibacterial glass using a vertical mill, a dry ball mill, a planetary mill, a sand mill, or a jet mill.
Among these dry mills, it is more preferable to use a vertical mill, a dry ball mill, a planetary mill and a jet mill.
The reason for this is that by using a vertical mill or planetary mill, it is possible to impart an appropriate shearing force, and without causing antibacterial glass with an excessively small particle size, the antibacterial properties of a polyhedron having a predetermined particle size can be obtained. This is because glass can be effectively obtained.

When fine grinding is performed using a vertical mill, dry ball mill, planetary mill, etc., zirconia balls or alumina balls are used as grinding media, the container is rotated at 30 to 100 rpm, and the antibacterial glass after medium grinding is used for 5 to 50 hours. During the period, it is preferable to perform a pulverization process.
When a jet mill is used, it is preferable that the antibacterial glasses after medium crushing are made to collide with each other by accelerating in a container and applying a pressure of 0.61 to 1.22 MPa (6 to 12 Kgf/cm ² ).
The antibacterial glass after finely pulverized with a dry ball mill or jet mill is a polyhedron having more corners than the antibacterial glass after medium pulverization, and has a volume average particle diameter (D50) and a specific surface area. It has been confirmed by an electron micrograph and particle size distribution measurement that it is easy to adjust the value to a predetermined range.

Further, when finely pulverizing using a planetary mill or the like, it is preferable to perform it in a substantially dry state (for example, relative humidity is 20% Rh or less).
The reason for this is that a classifier such as a cyclone can be attached to a planetary mill or the like to circulate the antibacterial glass without aggregating it.
Therefore, by controlling the number of circulations, the volume average particle size and particle size distribution of the antibacterial glass can be easily adjusted to a desired range, and the drying step after pulverization can be omitted.

On the other hand, the antibacterial glass having a specific range or less can be easily removed by using a bag filter in a dry state.
Therefore, it becomes easier and easier to adjust the volume average particle size and particle size distribution of the antibacterial glass.

(1)-3 Drying Step Next, in the drying step, it is preferable to dry the antibacterial glass obtained in the crushing step.
The reason for this is that by drying the antibacterial glass, it is possible to reduce the possibility that the thermoplastic resin will cause hydrolysis when the antibacterial glass and the thermoplastic resin are mixed in the following steps. is there.
In addition, as the drying step, it is preferable to also perform the drying treatment after performing the solid-liquid separation treatment, and the equipment used for these treatments is not particularly limited, but for solid-liquid separation, a centrifuge or the like is used for drying. Can use a dryer or an oven.
Further, after the step of drying the antibacterial glass, a part of the antibacterial glass agglomerates, and therefore it is preferable to disintegrate the agglomerated antibacterial glass with a disintegrator.

2. Step (2): Step of preparing a spinning dope The step (2) is a step of producing a spinning dope using the antibacterial glass obtained in the step (1).
In the step (2), it is preferable to produce the spinning dope by melt-kneading the antibacterial glass or the masterbatch in which the antibacterial glass is dispersed in the thermoplastic resin with the resin pellets or the recycled resin flakes.
Further, in the step (2), it is preferable to further add an additive such as a coloring masterbatch, an antioxidant, an internal lubricant and a crystallization agent.
Then, in the step (2), the content of the antibacterial glass in the core portion is set to Q1 (% by weight) with respect to the total amount of the antibacterial fiber, and the content of the antibacterial glass in the sheath portion is set to be antibacterial. When Q2 (% by weight) is set to the total amount of the functional fibers, the obtained antibacterial properties are mixed and dispersed in the glass so that Q1 and Q2 satisfy the following relational expression (1). Prepare the spinning dope for the sheath and the spinning dope for the sheath.
Q1<Q2 (1)
Here, it is preferable that Q1 is 0 or less than 1% by weight (excluding 0% by weight), and Q2 is a value within the range of 1 to 10% by weight.
When polyethylene terephthalate resin is used as the main component as the thermoplastic resin, it is preferable to mix and disperse the polybutylene terephthalate resin.
This is because hydrolysis of the polyethylene terephthalate resin, which is the main component, can be effectively suppressed, and a spinning stock solution in which the final concentration of antibacterial glass is uniformly dispersed can be obtained.

3. Step (3): Step of producing antibacterial fiber The antibacterial fiber according to the present invention can be produced by a method similar to the method applied to a commonly known composite fiber. Spinning includes melt spinning and solution spinning, and the method is selected depending on the resin used.
In the step (3), using a core-sheath composite spinneret, the molten spinning solution for core part is introduced into the core part, the spinning solution for sheath part is introduced into the sheath part, discharged from the spinneret, and then hot-stretched. It is preferable to fiberize.
Here, the spinning solution for core part and the spinning solution for sheath part refer to a molten resin obtained by melting a resin by heat in the case of melt spinning, and in the case of solution spinning, a stock solution in which a resin is dissolved in a solvent. Point to.
The yarn discharged from the spinneret is usually cooled, but the cooling method is not particularly limited, and a method of applying cold air to the spun yarn can be preferably exemplified.
It is also preferable that the spinning is carried out by a two-step system such as once winding or collecting in a can, if necessary, before carrying out the stretching treatment.
As a device used for spinning, a conventionally known device can be used.
For example, it is preferable to use a pressure melter type spinning machine or a uniaxial or biaxial extruder type spinning machine.
The reason for this is that antibacterial fibers having excellent surface smoothness can be efficiently obtained by using such a device.
The spinning shape is not particularly limited, but may be circular, flat, or polygonal such as hexagonal or star-shaped.
The spinning temperature is, for example, preferably 240° C. or higher and 320° C. or lower, and the winding speed is preferably 100 m/min or higher and 6000 m/min or lower.

Next, the fiber obtained by spinning is drawn.
The stretching step can be performed using a conventionally known method and apparatus, and for example, it is preferable to employ a direct spinning stretching method or a roller stretching method. When spinning and drawing are performed separately, it is preferable to use a hot water bath. ..
The direct spinning/drawing method is carried out by cooling the fiber once below the glass transition point after spinning, and then running it in a tube-type heating device in the temperature range of the glass transition temperature or higher and the melting point or lower to wind it.
In the roller drawing method, the spun yarn is wound and taken up by a take-up roller rotating at a predetermined speed, and the taken-up yarn is wound in one step or two steps or more depending on a group of rollers set to a temperature not lower than the glass transition temperature and not higher than the melting point of the thermoplastic resin. It is carried out by stretching in multiple stages.
The hot water bath is performed by immersing the fiber in hot water at 60°C to 90°C, preferably 80°C.
The stretching ratio is preferably 1.2 times or more from the viewpoint of increasing mechanical strength.
The upper limit of the draw ratio is not particularly limited, but it is preferably 7 times or less from the viewpoint of preventing the yarn from breaking due to excessive drawing.

4. Step (4): Crimp step Although the crimp step of step (4) is an optional step, the drawn yarn obtained in step (3) is guided to a crimp-applying device, and the yarn is false twisted to be bulky. Is a step of imparting elasticity and elasticity.
In the crimping step, conventionally known methods and devices can be used. For example, it is preferable to use a heating fluid crimping device that performs false twisting on the yarn by bringing the yarn into contact with the heating fluid.
The heating fluid crimp imparting device is a device for injecting a heating fluid such as steam onto a yarn to push the yarn together with the heating fluid into a compression adjusting section to impart crimp.
Here, the temperature of the heating fluid is preferably a value within the range of 100 to 150°C.
The reason for this is that if the temperature is within the above range, it is possible to avoid fusion of the fibers while obtaining a sufficient crimp.
Therefore, more specifically, the temperature of the heating fluid is more preferably set to a value within the range of 110 to 145°C, and further preferably set to a value within the range of 115 to 140°C.

5. Step (5): Post-treatment step Although the post-treatment step of step (5) is also an optional step, an oil agent is applied to the crimped yarn obtained in step (4), and the crimped yarn is dried by a dryer and then guided to a thermoset roller, In this step, the elongation is adjusted by the heating temperature.
The temperature of the thermoset roller is preferably set to a temperature within the range of 130 to 160° C. from the viewpoint of preventing troubles between the winding rolls such as fiber processing and winding rolls and defective shrinkage. ..
More specifically, the temperature of the thermoset roller is more preferably set to a value within the range of 135 to 155°C, and further preferably set to a value within the range of 140 to 150°C.

6. Step (6): Dyeing step The dyeing step, which is the step (6), is also an optional step, but after stretching, the antibacterial fibers crimped and/or thermoset as necessary are dyed under alkaline or acidic conditions. It is a process to do.
In the dyeing step, conventionally known methods and apparatuses can be used, and for example, handicraft dyeing, package dyeing, jet dyeing, rotary back dyeing, overmeier dyeing, cheese dyeing and the like are preferably used.
It is also preferable that the dyeing liquid contains, in addition to the dye, a leveling agent, a dyeing assistant, a dyeing assistant such as a sequestering agent, a dye fastness enhancer, and a fluorescent whitening agent, if necessary.
When dyeing under alkaline conditions, the pH can be adjusted to 7.5 to 10.5, and it is preferable to use a carbonate such as calcium carbonate or sodium hydroxide for adjusting the pH.
When dyeing under acidic conditions, the pH can be adjusted to 3.5 to 6.5. To adjust the pH, organic acids such as acetic acid, citric acid, malic acid, fumaric acid, succinic acid and salts thereof can be used. Preference is given to using.
After dyeing, it is preferable to carry out batch washing, and it is also preferable to carry out reduction washing or soaping.
The washing conditions may be the same as those used for conventional polyester fibers. In the case of reducing washing, a reducing agent, alkali, and sodium hydrosulfite can be used at 0.5 to 3 g/L, respectively. Treatment at -80°C for 10-30 minutes is preferred.

Hereinafter, the present invention will be described more specifically with reference to examples.
However, the present invention is not limited to the description of the following examples without any particular reason.

[Example 1]
1. Preparation of Antibacterial Glass (1) Melting Step When the total amount of antibacterial glass is 100% by weight, the composition ratio of P ₂ O ₅ is 50% by weight, the composition ratio of CaO is 5% by weight, and the composition ratio of Na ₂ O is 5% by weight. The composition ratio is 1.5% by weight, the composition ratio of B ₂ O ₃ is 10% by weight, the composition ratio of Ag ₂ O is 3% by weight, the composition ratio of CeO ₂ is 0.5% by weight, and the composition ratio of ZnO is 30% by weight. The respective glass raw materials were agitated by a universal mixer at a rotation speed of 250 rpm for 30 minutes until they were uniformly mixed so as to have a weight percentage.
Then, the glass raw material was heated using a melting furnace under the conditions of 1280° C. for 3 hours and 30 minutes to prepare a glass melt.

(2) Coarse crushing step The glass melt taken out from the glass melting furnace was poured into still water at 25° C. to granulate it to obtain coarsely crushed glass having a volume average particle diameter of about 10 mm.
As a result of observing the coarsely crushed glass at this stage with an optical microscope, it was confirmed that the roughly crushed glass was lumpy and had no corners or surfaces.

(3) Medium crushing step Next, using a pair of rotating rolls made of alumina (Tokyo Atomizer Co., Ltd., roll crusher), the coarsely crushed glass was used from the hopper under its own weight under the conditions of a gap of 1 mm and a rotation speed of 150 rpm. Was pulverized (volume average particle diameter of about 1000 μm) during the primary supply.
Further, using a rotary rotator made of alumina (Premax, manufactured by Chuo Kakoki Co., Ltd.), the coarsely crushed glass crushed in the primary was crushed in the secondary under the conditions of a gap of 400 μm and a rotation speed of 700 rpm to obtain volume average particles. The medium crushed glass had a diameter of about 400 μm.
As a result of observing the medium crushed glass with an electron microscope, it was confirmed that at least 50% by weight or more was a polyhedron with corners and faces.

(4) Fine pulverization step Then, 210 kg of alumina spheres having a diameter of 10 mm and 20 kg of medium pulverized glass pulverized secondarily were used as media in a vibrating ball mill (produced by Chuo Kakoki Co., Ltd.) having an internal volume of 105 liters. And 14 kg of isopropanol and 0.2 kg of a silane coupling agent A-1230 (manufactured by Nippon Unicar Co., Ltd.), respectively, and then finely pulverized for 7 hours under the conditions of a rotation speed of 1000 rpm and a vibration width of 9 mm. Then, finely pulverized glass was obtained.
As a result of observing this finely pulverized glass with an electron microscope, it was confirmed that at least 70% by weight or more was a polyhedron with corners and faces.

(5) Solid-Liquid Separation and Drying Steps The finely pulverized glass obtained in the previous step and isopropanol were subjected to solid-liquid separation under the conditions of a rotation speed of 3000 rpm for 3 minutes using a centrifuge (manufactured by Kokusan Co., Ltd.). went.
Then, using an oven, the finely pulverized glass was dried at 105° C. for 3 hours.

(6) Crushing step The finely crushed glass that has been dried and partially agglomerated is crushed using a gear type crusher (manufactured by Chuo Kakoki Shoji Co., Ltd.) to obtain a volume average particle diameter of 1.0 μm. Antibacterial glass (polyhedral glass) was used.
As a result of observing the antibacterial glass at this stage with an electron microscope, it was confirmed that at least 90% by weight or more was a polyhedron with corners and faces.

2. Production of antibacterial fiber (1) Spinning step (1)-1 Preparation of spinning solution for core part 100 parts by weight of polyethylene terephthalate resin having a number average molecular weight of 34,000 is used at a cylinder temperature using a BMC (bulk molding compound) injection molding machine. A core spinning solution was prepared by mixing and dispersing at 250° C. and a screw rotation speed of 30 rpm.

(1)-2 Preparation of spinning solution for sheath part 7 parts by weight of antibacterial glass, 95 parts by weight of polyethylene terephthalate resin having a number average molecular weight of 34,000, and 5 parts by weight of polybutylene terephthalate resin having a number average molecular weight of 26000 were added to BMC (bulk molding). Compound) Using an injection molding device, the mixture was mixed and dispersed at a cylinder temperature of 250° C. and a screw rotation speed of 30 rpm to prepare a spinning solution for a sheath portion.
Incidentally, a predetermined amount of antibacterial glass is mixed with polybutylene terephthalate resin, and after master batching, by mixing with polyethylene terephthalate resin, while suppressing the hydrolysis of polyethylene terephthalate resin, finally the above mixing ratio. The antibacterial resin composition of was obtained.

(1)-3 Composite spinning Using a core stock spinning solution for the core and a sheath spinning solution for the sheath, there are 24 circular composite spinning holes with a core-sheath weight ratio of 50/50 and a nozzle diameter of 0.3 mm. Using the core-sheath composite spinneret, the antibacterial fiber was spun from the spinneret at a spinning temperature of 285° C. and a winding speed of 3000 m/min.

(2) Stretching Step Then, the mixture was passed through a tube type heating device and stretched while being heated to 90° C. and stretched 3 times to obtain an antibacterial fiber having an average diameter of 40 μm. The average diameter of the core was 30 μm.

3. Evaluation of Antibacterial Fiber (1) Electron Microscope Observation When the obtained antibacterial fiber was observed with a scanning electron microscope (JSM-6610LA, manufactured by JEOL Ltd.), the antibacterial glass showed white spots and the sheath portion of the antibacterial fiber. It was confirmed that it was dispersed only in. The black dots are bubbles. Results are shown in FIG.
The presence or absence of metal ions can also be determined by scanning electron microscope images and elemental mapping. That is, EDX measurement was performed (JED-2300 manufactured by JEOL Ltd.), and the distribution state of the constituent elements was qualitatively determined by mapping analysis. The results are shown in FIGS. 4(a) to (c).
Here, FIGS. 4A to 4C show the K line of the P (phosphorus) element (FIG. 4A), the K line of the C (carbon) element (FIG. 4B), and O (oxygen). 4) shows an EDX mapping image using the characteristic X-ray of the K-line of the element (FIG. 4(c)).

From FIG. 4(a), the antibacterial glass according to the antibacterial fiber of the present invention shows that the antibacterial glass is uniformly distributed in the entire antibacterial fiber from the EDX mapping image using the characteristic X-ray of the K ray of P element. It can be seen that there are a plurality of regions locally distributed with high concentration in the sheath portion. Further, from FIG. 4(b), it can be seen that the C element is not distributed at the location where the antibacterial fiber is distributed. Further, it can be seen from FIG. 4C that the O element is uniformly distributed.

(2) Chemical fiber staple test The tensile strength of the antibacterial fiber obtained in Example 1 was measured according to JIS L 1015 and evaluated according to the following criteria.
The initial load when measuring the tensile strength was 5.88 mN/1tex, the tensile speed was 20 mm/min, and the gripping interval was 10 mm. The results obtained are shown in Table 1.
⊚: Tensile strength of 3 cN/dtex or more and less than 8 cN/dtex ◯: Tensile strength of 2 cN/dtex or more and less than 10 cN/dtex (excluding the range of 3 cN/dtex or more and less than 8 cN/dtex)
Δ: Tensile strength of 1 cN/dtex or more and less than 12 cN/dtex (excluding the range of 2 cN/dtex or more and 10 cN/dtex or less)
X: Tensile strength is less than 1 cN/dtex and 12 cN/dtex or more

(3) Antibacterial evaluation 1-2
10 g of antibacterial fiber was used as a test piece for antibacterial evaluation. On the other hand, the test bacteria were cultivated on Trypticase Soy Agar (BBL) agar plate medium at 35° C. for 24 hours, and the growing colonies were suspended in 1/500-concentration normal broth medium (Eiken Chemical Co., Ltd.). , About 1×10 ⁶ CFU/ml.
Then, 0.5 ml of a suspension of Staphylococcus aureus (Stafylococcus aureus IFO#12732) and 0.5 ml of a suspension of Escherichia coli ATCC #8739 were uniformly contacted with the antibacterial fiber as a test piece, Furthermore, a polyethylene film (sterilized) was placed on each of the samples to make a measurement sample by the film cover method.
Next, the measurement sample is placed in a thermostatic chamber under conditions of humidity 95%, temperature 35° C., and 24 hours, and the number of bacteria before the test (growth colony) and the number of bacteria after the test (growth colony) are measured, respectively. Then, antibacterial properties 1 (Staphylococcus aureus) and antibacterial properties 2 (Escherichia coli) were evaluated according to the following criteria.
The number of bacteria (growth colony) before the test was 2.6×10 ⁵ (individual/test piece) for both Staphylococcus aureus and E. coli. The results obtained are shown in Table 1.
⊚: The number of bacteria after the test is less than 1/10000 of the number of bacteria before the test.
◯: The number of bacteria after the test is 1/10000 or more and less than 1/1000 of the number of bacteria before the test.
B: The number of bacteria after the test is 1/1000 or more and less than 1/100 of the number of bacteria before the test.
X: The number of bacteria after the test is 1/100 or more of the number of bacteria before the test.

[Example 2]
In Example 2, an antibacterial fiber was prepared in the same manner as in Example 1 except that the antibacterial glass in the sheath portion was 10 parts by weight and the thermoplastic resin was 100 parts by weight of a polypropylene resin having a number average molecular weight of 60000. Fabrication was performed and fiber evaluation and antibacterial property evaluation were performed in the same manner as in Example 1. The results obtained are shown in Table 1.
When the antibacterial fiber obtained in Example 2 was observed with a scanning electron microscope, the antibacterial glass dispersed only in the sheath portion of the antibacterial fiber was confirmed as in Example 1. The results are shown in Figure 1.
In addition, EDX measurement was performed by the same method as in Example 1, and the distribution state of the constituent elements was qualitatively determined by mapping analysis. The results are shown in FIGS. 5(a) to (c).
Here, FIGS. 5A to 5C show the K line of the P (phosphorus) element (FIG. 5A), the K line of the C (carbon) element (FIG. 5B), and O (oxygen). ) Shows an EDX mapping image using a characteristic X-ray of an element K-line (FIG. 5C).

From Fig. 5(a), it can be seen that the antibacterial glass is not distributed over the entire antibacterial fiber, but there are a plurality of regions locally distributed in high concentration in the sheath portion. Also, from FIG. 5(b), it can be seen that the sheath portion is brighter and the C element is more distributed. Further, from FIG. 5(c), the core is brighter because of the O element of polyethylene terephthalate or polybutylene terephthalate contained in the core.

[Example 3]
In Example 3, except that the sheath spinning solution was composed of 3 parts by weight of antibacterial glass, 95 parts by weight of polyethylene terephthalate resin having a number average molecular weight of 34000, and 5 parts by weight of polybutylene terephthalate resin having a number average molecular weight of 26000. In the same manner as in Example 1, an antibacterial fiber was produced, and fiber evaluation and antibacterial property evaluation were performed in the same manner as in Example 1. The results obtained are shown in Table 1.
When the antibacterial fiber obtained in Example 3 was observed with a scanning electron microscope, the antibacterial glass dispersed only in the sheath portion of the antibacterial fiber could be confirmed as in Example 1.

[Example 4]
In Example 4, the spinning solution for core part was composed of 0.5 part by weight of antibacterial glass, 95 parts by weight of polyethylene terephthalate resin having a number average molecular weight of 34,000, and 5 parts by weight of polybutylene terephthalate resin having a number average molecular weight of 26000. Other than the above, an antibacterial fiber was produced in the same manner as in Example 1, and fiber evaluation and antibacterial evaluation were performed in the same manner as in Example 1. The results obtained are shown in Table 1.
When the antibacterial fiber obtained in Example 4 was observed with a scanning electron microscope, it was confirmed that the antibacterial glass was more dispersed in the sheath portion of the antibacterial fiber.

[Comparative Example 1]
In Comparative Example 1, the same procedure as in Example 1 was performed except that the spinning solution for the sheath was the same as the spinning solution for the core, that is, the antibacterial glass was not mixed in the core and the sheath. The antibacterial fiber was produced by performing the fiber evaluation and the antibacterial evaluation in the same manner as in Example 1. The results obtained are shown in Table 1.

As described above, according to the present invention, the content of the antibacterial glass in the core portion is set to be smaller than the content of the antibacterial glass in the sheath portion, so that the compounding amount of the antibacterial glass can be small, and eventually It has become possible to obtain an antibacterial fiber capable of exhibiting excellent antibacterial properties, and an efficient method for producing such an antibacterial fiber.
Therefore, the present invention is expected to remarkably contribute to the improvement of the quality of antibacterial articles molded using the antibacterial fibers, particularly woven fabrics and nonwoven fabrics.

Claims (8)

1. An antibacterial fiber containing a thermoplastic resin and an antibacterial glass as a compounding component, wherein the antibacterial fiber has an average diameter within a range of 1 to 50 μm, and the antibacterial fiber is a core part. A sheath portion, wherein the content of the antibacterial glass in the core portion is Q1 (% by weight) based on the total amount of the antibacterial fiber, and the content of the antibacterial glass in the sheath portion is When the content is Q2 (% by weight) with respect to the total amount of the antibacterial fiber, the Q1 and Q2 satisfy the following relational expression (1).
   Q1<Q2 (1)
2. The antibacterial fiber according to claim 1, wherein the Q1 is 0 or less than 1% by weight (excluding 0% by weight).
3. The antibacterial fiber according to claim 1 or 2, wherein the Q2 has a value within a range of 1 to 10% by weight.
4. The antibacterial fiber according to any one of claims 1 to 3, further comprising agglomerated silica particles as a compounding ingredient.
5. The antibacterial fiber according to any one of claims 1 to 4, wherein the volume average particle diameter of the antibacterial glass is set to a value within a range of 0.1 to 5 µm.
6. The antibacterial fiber according to any one of claims 1 to 5, wherein the thermoplastic resin is one or more of a polyester resin, a polyamide resin and a polyolefin resin.
7. The antibacterial fiber according to any one of claims 1 to 6, wherein the form of the antibacterial fiber is one of a woven fabric, a non-woven fabric and a felt.
8. A method for producing an antibacterial fiber comprising a core part and a sheath part, and containing a thermoplastic resin and an antibacterial glass as compounding ingredients, characterized by including the following steps (1) to (3): A method for producing an antibacterial fiber.
   (1) Step of preparing antibacterial glass (2) The content of the antibacterial glass in the core portion is set to Q1 (% by weight) with respect to the total amount of the antibacterial fiber, and
   When the content of the antibacterial glass in the sheath portion is Q2 (% by weight) based on the total amount of the antibacterial fiber,
   A step of dispersing the obtained antibacterial glass in a thermoplastic resin so that Q1 and Q2 satisfy the following relational expression (1) to prepare a spinning solution for core and a spinning solution for sheath. Q1<Q2 (1)
   (3) A step of composite spinning using a core-sheath composite spinneret with the core spinning solution as a core and the sheath spinning solution as a sheath to obtain an antibacterial fiber having an average diameter of 1 to 50 μm.

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