JP2024027385A - Fiber and fabric - Google Patents

Abstract

To provide fibers and a fabric which exhibit high antibacterial properties.SOLUTION: The present invention provides fibers covered with rare-earth ferrite composition containing rare-earth ferrite and a resin, and a fabric composed of the fibers.SELECTED DRAWING: None

Description

FIELD OF THE INVENTION This invention relates to fibers and fabrics. Specifically, it relates to fibers and fabrics that exhibit high antibacterial properties.

In recent years, from the viewpoint of hygiene, various antibacterial-treated products have become available. Antibacterial needs are increasing not only for items directly used by consumers, but also for interior materials of buildings, air conditioner filters, chair seats, etc.

As agents that exhibit antibacterial effects, compounds such as phenol, organotin, triazine, halogenated sulfonylpyridine, captan, organocopper, chlornaphthalene, and chlorophenylpyritazine are known (patented). (See Reference 1).

Furthermore, silver ions, copper ions, zinc ions, and the like are known as ions that exhibit antibacterial effects. For example, metal powders such as silver, copper, zinc, or their alloys or compounds are supported on a carrier, and a trace amount of these metal ions is eluted to utilize their toxicity. Patent Document 2 discloses a dispersion having deodorizing and antibacterial/antifungal properties, in which a carboxylic acid metal salt formed from a carboxyl group-containing polymer and a metal compound is dispersed.

Furthermore, in recent years, ferrite compounds have been proposed as algaecide agents that have low environmental pollution and are excellent in safety. For example, in Patent Documents 3 and 4, the main component is orthoferrite containing a rare earth element selected from lanthanum (La), praseodymium (Pr), neodymium (Nd), and yttrium (Y), iron, and oxygen. An anti-algae additive, an anti-algae paint using the same, and an anti-algae product in which the paint is applied to the surface of a substrate are disclosed.

Japanese Unexamined Patent Publication No. 63-17249 Japanese Patent Application Publication No. 2-288804 JP2005-272320A International Publication No. 2021/193644

However, the antibacterial agent in the drug form described in Patent Document 1 and the antibacterial agent that utilizes the toxicity of metal ions described in Patent Document 2 may have environmental pollution and safety issues. On the other hand, in Patent Documents 3 and 4, the antibacterial effect of orthoferrite is not studied.

It is an object of the present invention to provide fibers and fabrics that exhibit a high degree of antimicrobial properties.

The present invention is as follows.
<Aspect 1> A fiber coated with a rare earth ferrite composition containing a rare earth ferrite and a resin.
<<Aspect 2>> The fiber according to Aspect 1, wherein the fiber is subjected to a heat treatment after being coated with the rare earth ferrite composition.
<Aspect 3> The rare earth ferrite has the following formula (1):
Ln _2x Fe _{2 (1-x)} O ₃ (1)
(In formula (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium, and yttrium, and x is a number of 0.50 or more and less than 1.00.)
The fiber according to aspect 1, having a composition represented by:
<<Aspect 4>> The fiber according to Aspect 3, wherein x in the formula (1) is a number from 0.65 to 0.85.
<Aspect 5> The fiber according to aspect 1, wherein the rare earth ferrite is lanthanum ferrite.
<<Aspect 6>> The fiber according to Aspect 1, which is used for antibacterial, deodorizing, and antifungal purposes.
<Aspect 7> A fabric comprising the fiber according to any one of aspects 1 to 5.
<Aspect 8> The fabric according to aspect 7, which is used for antibacterial, deodorizing, and antifungal purposes.
[Aspect 9] Socks, tights, masks, air conditioner filters, curtains, bath mats, insoles, bedding, underwear, swimsuits, gloves, sports protectors, white coats, surgical clothes, work clothes, towels, dishcloths, gauze, bandages, or seating surfaces The fabric according to aspect 8.
<<Aspect 10>> A method for producing the fiber according to Aspect 1, comprising:
A method comprising: immersing a raw material fiber in a rare earth ferrite dye solution containing a rare earth ferrite and a resin; and subjecting the fiber after the immersion to a heat treatment.
<<Aspect 11>> The method according to Aspect 10, wherein the temperature of the heat treatment is 80°C or more and 180°C or less.
<<Aspect 12>> A method for manufacturing the dough according to Aspect 7, comprising:
A method comprising: immersing a raw material fabric in a rare earth ferrite dye solution containing a rare earth ferrite and a resin; and subjecting the fabric after the immersion to a heat treatment.
<<Aspect 13>> The method according to Aspect 12, wherein the temperature of the heat treatment is 80°C or more and 180°C or less.

According to the present invention, fibers and fabrics are provided that exhibit a high degree of antibacterial properties. The fibers and fabrics of the present invention not only have the effect of rapidly killing various bacteria, but also have excellent antiseptic properties, odor resistance, and mold resistance.

"fiber"
The fiber of the present invention is a fiber coated with a rare earth ferrite composition containing a rare earth ferrite and a resin.

<Raw fiber>
The portion of the fiber of the present invention from which the rare earth ferrite composition has been removed (hereinafter also referred to as "raw material fiber") may be a filament yarn or a spun yarn. The filament yarn may be monofilament or multifilament.

The constituent material of the raw material fiber in the present invention is arbitrary. The raw material fiber in the present invention may be a natural fiber or a chemical fiber. Natural fibers may be plant fibers or animal fibers. The chemical fiber may be a recycled fiber, a semi-synthetic fiber, or a synthetic fiber.

The vegetable fiber may be cotton, hemp, etc., or purified cellulose, etc. The animal fiber may be silk, wool, etc. The recycled fibers may be rayon, cupro, polynosic, etc. Semi-synthetic fibers may be acetate, triacetate, promix, etc. Synthetic fibers may be acrylic, polyester, nylon, polyurethane, etc.

The length and thickness (denier) of the raw material fibers in the present invention are arbitrary and may be appropriately selected depending on the intended use.

<Rare earth ferrite composition>
The rare earth ferrite composition in the fiber of the present invention includes a rare earth ferrite and a resin. The rare earth ferrite composition may contain a dispersant in addition to these.

(Rare earth ferrite)
Rare earth ferrite, for example, has the following formula (1):
Ln _2x Fe _{2 (1-x)} O ₃ (1)
(In formula (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium, and yttrium, and x is a number of 0.50 or more and less than 1.00.)
It may have a composition represented by:

The rare earth ferrite in the present invention may be in any form as long as x in the above formula (1) is a number of 0.50 or more and less than 1.00. For example, a solid solution with a uniform composition may be formed, a mixture of _three LnFeO phases and _three Ln ₂ O phases, or a solid solution with a uniform composition, _three LnFeO phases, and Ln ₂ O It may also be a mixture with _three phases. Moreover, it may contain phases other than these.

x in formula (1) may be 0.55 or more, 0.60 or more, 0.65 or more, 0.70 or more, or 0.75 or more, and 0.90 or less, 0.85 or less, It may be 0.80 or less, 0.75 or less, 0.70 or less, 0.65 or less, or 0.60 or less.

Typically, x in the above formula (1) may be, for example, a number of 0.50 or more and 0.95 or less, and further may be 0.60 or more and 0.90 or less, particularly , may be a number of 0.65 or more and 0.85 or less.

The rare earth (Ln) in formula (1) may particularly be lanthanum from the viewpoint of antibacterial properties and cost, and therefore the antibacterial agent of the present invention may be lanthanum ferrite.

It is desired that the rare earth ferrite in the present invention has a size comparable to that of bacteria from the viewpoint of effectively expressing antibacterial properties. From this point of view, rare earth ferrite is in the form of particles, and the 50% diameter (d50 particle size) in the volume integrated distribution of particle size distribution is 0.05 μm or more, 0.08 μm or more, 0.10 μm or more, 0.12 μm or more, 0. .15 μm or more, or 0.18 μm or more, and may be 0.50 μm or less, 0.45 μm or less, 0.40 μm or less, 0.35 μm or less, 0.30 μm or less, or 0.25 μm or less.

The rare earth ferrite in the present invention may be synthesized, for example, by applying an appropriate stress to a mixture containing a rare earth source and an iron source in a predetermined ratio, pulverizing and mixing the mixture, and then firing the mixture.

As the rare earth source, for example, oxides of desired rare earth elements may be used, as well as bastnaesite, monazite, xenotime, etc. As the rare earth element, it is preferable to use lanthanum from the viewpoint of antibacterial properties of the obtained rare earth ferrite particles and cost. Among them, if La ₂ O ₃ is used, it is possible to produce lanthanum ferrite particles that are highly effective and relatively inexpensive.

Iron sources include oxides such as FeO, Fe ₃ O ₄ and Fe ₂ O ₃ ; oxyoxides such as FeOOH, ferrihydrite and schubermannite; water such as Fe(OH) ₂ and Fe(OH) ₃ . oxide; etc. may be used. Among these, if FeOOH is used as an iron source, it has higher reactivity than Fe ₂ O ₃ etc., so it can be fired at a lower temperature, and the grain size is smaller compared to Fe ₂ O ₃ etc. Small rare earth ferrite particles can be produced.

The ratio of the rare earth source to the iron source may be determined as appropriate to match the value of x in equation (1) for the desired rare earth ferrite particles.

The pulverization and mixing may be dry pulverization or wet pulverization. The stress applied to the mixture of rare earth source and iron source in the first crushing may be, for example, friction force, shear force, shear stress, impact force, etc.

Examples of the method of applying the above-mentioned stress include a method of wet grinding in a ball mill. When the first pulverization is carried out by wet pulverization, water, alcohol, etc. may be used as the liquid medium. After the mixture of the rare earth source and the iron source is pulverized and mixed by wet pulverization, if necessary, the liquid medium may be removed by an appropriate method such as heating and drying, followed by firing.

The firing temperature and firing time are not particularly limited, and can be set as appropriate.

The firing temperature is, for example, 700°C or higher, 800°C or higher, 900°C or higher, or 1,000°C or higher, and, for example, 1,300°C or lower, 1,200°C or lower, 1,100°C or lower, or 1, It may be carried out at temperatures below 000°C.

The firing time is, for example, 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 6 hours or more, 8 hours or more, 12 hours or more, or 15 hours or more, and 72 hours or less, 48 hours or less, 36 hours or more. It may be carried out for less than 1 hour, 24 hours or less, 18 hours or less, or 15 hours or less.

The surrounding atmosphere during firing may be an oxidizing atmosphere, for example, firing may be performed in air.

After firing, the fired product may optionally be treated with water. It is thought that by this water treatment, part or all of the Ln ₂ O ₃ phase contained in the fired product is hydrolyzed into other phases, and the antibacterial activity is further improved. However, the present invention is not bound to any particular theory.

Rare earth ferrite can be obtained as described above. The obtained rare earth ferrite may be pulverized and classified as necessary, and then used.

The antibacterial agent in the present invention exhibits excellent antibacterial effects even when used alone, as verified in the Examples below. However, one of the preferred embodiments of the present invention is to use the antibacterial agent specified in the present invention in combination with another antibacterial agent. Other antibacterial agents used in combination here may be, for example, organic antibacterial agents. The organic antibacterial agent may be, for example, a thiazoline compound, a quaternary ammonium salt, a cationic polymer, a phenolic compound, or the like.

(resin)
The resin contained in the rare earth ferrite composition functions as a binder for coating the fibers and fixing the rare earth ferrite to the fibers.

The resin may be selected from, for example, acrylic resin, acrylic silicone resin, silicone resin, amino alkyd resin, epoxy resin, phenol resin, polyurethane resin, unsaturated polyester resin, vinyl chloride resin, fluororesin, and the like.

The proportion of the resin in the rare earth ferrite composition may be appropriately set depending on the balance between antibacterial properties and fixing properties of the rare earth ferrite in the fiber of the present invention. The proportion of the resin in the rare earth ferrite composition is 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or It may be 100% by mass or more, and 500% by mass or less, 300% by mass or less, 200% by mass or less, 180% by mass or less, 160% by mass or less, 140% by mass or less, or 120% by mass or less.

(dispersant)
The dispersant contained in the rare earth ferrite composition has the function of dispersing rare earth ferrite and suppressing agglomeration of rare earth ferrite.

Dispersants include, for example, polyacrylic acid, polyacrylic acid copolymers, sodium polyacrylate, ammonium polyacrylate, sodium salts of carboxylic acid copolymers, ammonium salts of carboxylic acid copolymers, and sulfonic acids. It may be selected from sodium salts of copolymers, sodium polycarboxylate, sodium sodium sulfonate, phosphonic acid amine salts, cationic polymers, and the like.

The proportion of the dispersant in the rare earth ferrite composition may be appropriately set depending on the balance between antibacterial properties and dispersibility of the rare earth ferrite in the fiber of the present invention. The proportion of the dispersant in the rare earth ferrite composition may be 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more, based on 100 parts by mass of rare earth ferrite. It may be 100% by weight or less, 80% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, or 35% by weight or less.

(Coating mode)
In the fiber of the present invention, the raw fiber is coated with a rare earth ferrite composition. Here, "coating" means that the composition adheres to part or all of the outer surface of the raw fiber to form a "layer", or that a part of the composition penetrates into the inside of the raw fiber. It is a concept that includes the state of being. Specifically, for example, at least a part of the resin in the rare earth ferrite composition penetrates into the inside of the raw material fiber, and the rare earth ferrite is fixed and fixed to the outer surface of the raw material fiber by this resin. be. However, the present invention is not bound to any particular theory.

The fiber of the present invention may be heat-treated after the raw fiber is coated with the rare earth ferrite composition. By this heat treatment, the rare earth ferrite is more firmly fixed to the raw material fiber. As a result, the fibers of the present invention have excellent washing resistance, and, for example, falling off of rare earth ferrite due to washing etc. is suppressed. The heat treatment may be performed, for example, at a temperature of 80° C. or higher and 180° C. or lower. The heat treatment will be described later in the description of the method for producing fibers and fabrics.

"material"
The fabric of the present invention may be composed of the fibers of the present invention as described above, or may be a nonwoven fabric coated with a rare earth ferrite composition.

When the fabric of the present invention is composed of the fibers of the present invention, the fabric may be composed only of the fibers of the present invention, or may be composed of the fibers of the present invention and other fibers. good.

The fabrics of the present invention can be used, for example, in socks, tights, masks, air conditioner filters, curtains, bath mats, insoles, bedding, underwear, swimwear, gloves, sports protectors, white coats, surgical clothes, work clothes, towels, dish towels, gauze, and bandages. , may be applied to the seat surface, etc.

《Fiber manufacturing method》
The fiber of the present invention is, for example,
The fibers may be produced by a method including dipping raw fibers in a rare earth ferrite dye solution containing rare earth ferrite and resin, and heat-treating the fibers after dipping.

The raw material fiber may be appropriately selected depending on the desired configuration of the fiber of the present invention.

A rare earth ferrite dye solution is a dispersion containing a rare earth ferrite and a resin, and optionally a dispersant, in the same proportions as the rare earth ferrite composition in the desired fiber, and diluted with a solvent. The solvent may be one or more selected from water and water-soluble organic solvents, and is typically water.

The solid content concentration of the rare earth ferrite dye solution may be, for example, 0.5% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, for example. , 50% by weight or less, 40% by weight or less, 30% by weight or less, or 25% by weight or less.

The entire fiber may be soaked, or only a portion of the fiber may be soaked.

The dipping time can be set to the time required for the entire portion of the raw fiber immersed in the rare earth ferrite dye solution to be uniformly wetted by the rare earth ferrite dye solution. The immersion time may be, for example, 1 second or more, 3 seconds or more, 5 seconds or more, or 10 seconds or more, and 30 minutes or less, 20 minutes or less, 10 minutes or less, 5 minutes or less, 3 minutes or less, 1 minute or less. , or 30 seconds or less.

The temperature of the rare earth ferrite dye solution during dipping may be lower than the heating temperature in the heat treatment described below. The temperature of the rare earth ferrite dye solution during dipping may be, for example, 0°C or higher, 5°C or higher, 10°C or higher, 15°C or higher, or 20°C or higher, and for example, lower than 80°C, 60°C or lower, or 50°C. The temperature may be below 40°C or below 30°C, typically at room temperature.

The temperature of the heat treatment for the fibers after soaking may be, for example, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher, and 180°C or lower, 170°C or lower, 160°C or lower, The temperature may be 150°C or lower, or 140°C or lower.

The heat treatment time may be, for example, 20 seconds or more, 30 seconds or more, 1 minute or more, 1 minute and 30 seconds or more, and for example, 10 minutes or less, 8 minutes or less, 6 minutes or less, 4 minutes or less, or 3 minutes or less. It may be less than 1 minute.

The surrounding atmosphere during the heat treatment may be any of an oxidizing atmosphere, an inert atmosphere, and a reducing atmosphere, and typically may be air.

《Dough manufacturing method》
The fabric of the present invention is, for example,
The fibers of the present invention produced by the above method, or the fibers of the present invention and other fibers, can be produced by weaving, knitting, thermocompression bonding, etc.
It may be manufactured by a method that includes immersing a raw material fabric in a rare earth ferrite dye solution containing a rare earth ferrite and a resin, and subjecting the fabric after dipping to a heat treatment.

For the latter method, the raw material dough may be selected as appropriate depending on the desired configuration of the dough of the present invention. Regarding the rare earth ferrite dyeing solution, dipping method, and heat treatment, reference can be made to the description of the fiber manufacturing method.

《Synthesis of lanthanum ferrite》
0.35 mol parts of La ₂ O ₃ and 0.30 mol parts of FeOOH (La:Fe = 70:30 (molar ratio)) and water were placed in a ball mill using 10 mmΦ alumina spheres as grinding media. , and pulverized and mixed for 5 hours. The obtained pulverized product was dried at 300° C. for 15 hours and then crushed using a rotary crusher. The obtained crushed material was fired at 700° C. for 15 hours, and then crushed with a hammer mill to obtain a crushed material.

Next, the crushed material was treated with water. In this water treatment, the obtained crushed material is put into a washing tank, purified water is added and stirred, the treated water is removed by filtration, and then new purified water is added and stirring and filtration are repeated. It was carried out by the method. The end point of the water treatment was defined as the point in time when the treated water and the purified water had the same conductivity.

The crushed material after the water treatment was dried at 130° C. for 15 hours and then crushed again in a hammer mill to obtain lanthanum ferrite.

《Example 1》
(1) Preparation of lanthanum ferrite dye solution In a paint can with a capacity of 0.3 L, add 67.1 g of water as a solvent and DISPER BYK-154 (manufactured by BYK, ammonium polyacrylate dispersant, solid content 42 Mass %, written as "BYK-154" in the table) 7.7 g (solid content 3.23 g) was added and stirred, then 12.9 g of lanthanum ferrite obtained above and 150 g of 0.3 mmΦ zirconia beads were added. added. The paint can was attached to a paint shaker, and dispersion was performed for 12 hours at a vibration frequency of 50 rpm. Thereafter, 12.3 g (solid content) of VONCOAT HY-364 (water-based acrylic urethane emulsion manufactured by DIC Corporation, solid content 60% by mass, written as "HY-364" in the table) was placed in a paint can. 7.38 g) was added little by little. The paint can was again placed in the paint shaker and dispersed for 2 hours at a vibration frequency of 50 rpm. Then, the zirconia beads were removed from the contents of the paint can using a filter to obtain a lanthanum ferrite dyeing solution (undiluted solution).

(2) Fabric Dyeing 100 mL of the lanthanum ferrite dye solution (undiluted solution) obtained above was placed in a stainless steel vat. A polyester fabric of A5 size was immersed as a raw material in this dye solution, and after the dye solution was uniformly soaked into the fabric, the fabric was pulled up. After dripping from the fabric had stopped, the fabric was tumble dried at 60°C for 3 minutes. Next, the antibacterial fabric of Example 1 was obtained by heat-treating the fabric for 3 minutes at 130° C. in a dryer.

(3) Measurement of the amount of lanthanum ferrite adhered The mass of the obtained antibacterial fabric and the polyester fabric before dyeing was measured, and the difference was determined to determine the lanthanum ferrite composition (lanthanum ferrite, resin, and dispersant) adhered to the fabric. The amount of lanthanum ferrite attached to the antibacterial fabric (mass proportion to the polyester fabric before dyeing) was determined by multiplying this value by the proportion of lanthanum ferrite in the composition.

(4) Evaluation of antibacterial properties Four antibacterial fabric samples cut into 2.5 cm x 2.5 cm were placed in a sample tube with a capacity of 30 mL. 500 μL of milk was dropped onto the sample, and the sample tube was tightly stoppered. This sample tube was left for 24 hours in a constant temperature and humidity chamber at a temperature of 40° C. and a humidity of 90% RH. After 24 hours, the sample tube was removed from the constant temperature and humidity chamber, 1,500 μL of pure water was added into the sample tube, and the sample was shaken for 10 minutes at 60 rpm using a shaker to wash out bacteria. .

Collect 100 μL of the washing solution, make it emit light using the ATP measurement kit "Lucifer AT100" manufactured by Kikkoman Biochemifa Co., Ltd., and measure the amount of ATP luminescence using the company's luminometer "Lumitester C-110". (RLU) was measured.

On the other hand, instead of the antibacterial fabric, a similar polyester fabric that had not been dyed with the lanthanum ferrite dye solution was used, and the ATP luminescence amount (RLU) was measured in the same manner, and this was used as a blank value.

Then, the value obtained from the ATP luminescence amount of the antibacterial fabric of Example 1 and the blank value using the following formula was defined as antibacterial property (ATP reduction rate (%)).
ATP reduction rate (%) = {(Blank value - ATP luminescence amount of antibacterial fabric)/Blank value} x 100

(5) Evaluation of fixation ability of lanthanum ferrite The washout obtained from the bacteria washing operation in "(4) Antibacterial evaluation" above was visually observed. If the washing solution is colorless and transparent, the lanthanum ferrite does not fall off from the antibacterial fabric, and the fixation of the lanthanum ferrite is "good." On the other hand, if the washing solution is colored brown, the antibacterial The lanthanum ferrite fell off from the fabric, and the fixation of the lanthanum ferrite was evaluated as "poor."

The results are shown in Table 1.

《Example 2 and 3》
In "(2) Performing fabric dyeing", instead of the lanthanum ferrite dyeing solution (undiluted solution) obtained in the same manner as in Example 1, use 100 mL of a diluted solution obtained by using this undiluted solution as shown in Table 1. An antibacterial fabric was prepared and evaluated in the same manner as in Example 1, except that it was used.

The results are shown in Table 1.

《Examples 4 to 8》
In "(1) Preparation of lanthanum ferrite dyeing solution", VONCOAT S-5 (water-based acrylic emulsion manufactured by DIC Corporation, solid content 60% by mass, solid content 60% by mass, the table shows "S- A lanthanum ferrite dye solution (undiluted solution) was prepared in the same manner as in Example 1, except that the amounts of each component were as shown in Table 1.

In "(2) Fabric dyeing", antibacterial fabrics were prepared and evaluated in the same manner as in Example 1, except that the following dye solutions were used.
Examples 4 and 7: 100 mL of stock solution obtained above
Examples 5 to 6 and 8: 100 mL of a diluted solution obtained from the stock solution obtained above as shown in Table 1

In Example 7, no heat treatment was performed after dyeing the fabric.

The results are shown in Table 1.

《Comparative example 1》
Comparative Example 1 concerns a polyester fabric that was not dyed with a lanthanum ferrite dye solution, and the amount of ATP issued in the antibacterial evaluation of Comparative Example 1 was used as a blank value for Examples 1 to 8 above.

《Examples 9 to 14, and 16 and 18》
In "(2) Fabric dyeing", A5 size cotton fabric was used instead of A5 size polyester fabric, and the same type of undyed cotton fabric was used as a blank value in "(4) Antibacterial evaluation". The investigation was conducted in the same manner as Examples 1 to 6, Example 8, and Example 7, except that the ATP luminescence amount of the fabric was used.

The results are shown in Table 1.

《Example 15》
In "(1) Preparation of lanthanum ferrite dye solution", BYNIBLAN 701 (vinyl chloride resin emulsion manufactured by Shin-Etsu Chemical Co., Ltd., solid content 30% by mass, written as "BYNIBLAN" in the table) was used as the resin, The amount of each ingredient is as listed in Table 1,
In "(2) Fabric dyeing", an antibacterial fabric was prepared in the same manner as in Example 9, except that 10 g of the stock solution obtained above and 100 mL of a diluted solution with 90 g of water were used as the dye solution. It was evaluated.

The results are shown in Table 1.

《Example 17》
In "(2) Fabric dyeing", antibacterial fabric was prepared and evaluated in the same manner as in Example 9, except that 100 mL of a diluted solution obtained by adding 98 g of water to 2 g of the obtained stock solution was used as the dye solution. did.

The results are shown in Table 1.

《Comparative example 2》
Comparative Example 2 concerns a cotton fabric that was not dyed with a lanthanum ferrite dye solution, and the amount of ATP issued in the antibacterial evaluation of Comparative Example 2 was used as a blank value for Examples 9 to 18 above.

From the results in Table 1, the effectiveness of the antibacterial fabric of the present invention was confirmed.

《Antibacterial properties against Enterobacteriaceae, Staphylococcus aureus, Trichophyton and Sporeform bacteria》
Using the antibacterial fabrics obtained in Examples 1 to 7, 9 to 14, and 18, the antibacterial properties against Escherichia coli, Staphylococcus aureus, Trichophyton, and Sporeform bacteria were examined.

Escherichia coli, Staphylococcus aureus, Trichophyton, and Sporeform bacteria were used as test bacteria, and bacterial solutions were prepared so that the initial ATP luminescence amount was 50,000 RLU, and these were used as test bacterial solutions.

Three sheets of antibacterial fabric cut into 2.5 cm x 2.5 cm were stacked and placed on two sterilized petri dishes. 500 μL of the test bacterial solution was inoculated into the center of the antibacterial fabric at the top of each Petri dish, and left to stand at a temperature of 35±2° C. under atmospheric conditions.

Immediately after inoculation (1 minute later), the antibacterial fabric in one Petri dish was taken out and placed in a stomacher for microbial testing, and 900 μL of physiological saline was added and thoroughly rubbed to wash out the test bacteria. Collect 100 μL of the washing solution, make it emit light using the ATP measurement kit "Lucifer AT100" manufactured by Kikkoman Biochemifa Co., Ltd., and measure the amount of ATP luminescence using the company's luminometer "Lumitester C-110". was measured.

Then, using the initial ATP luminescence amount (50,000 RLU) of the test bacterial solution as a blank value, the following formula:
ATP reduction rate (%) = {(Blank value - ATP luminescence amount of collected liquid)/Blank value} x 100
The ATP reduction rate (%) immediately after inoculation (1 minute later) was calculated.

24 hours after inoculation, the remaining antibacterial fabric in the petri dish was taken out and operated in the same manner to calculate the ATP reduction rate (%) 24 hours after inoculation.

The results are shown in Table 2.

From the results in Table 2, it was verified that the antibacterial fabric of the present invention exhibits high antibacterial properties against various bacteria. In addition, there was a tendency for samples with higher lanthanum ferrite fixation to the fabric to develop antibacterial properties more quickly immediately after inoculation with bacteria.

《Odor resistance》
Using the sample of Comparative Example 1 as a reference example, the deodorizing properties of the antibacterial fabric obtained in Example 4 were investigated by sensory evaluation and GC analysis.

(1) Sensory evaluation The antibacterial fabric of Example 4 cut into 2.0 cm x 2.0 cm and the sample of Comparative Example 1 (undyed polyester fabric) were placed in sample tubes with a capacity of 30 mL. . 100 μL of milk was dropped onto the sample, and the sample tube was tightly stoppered. This sample tube was left standing in a constant temperature and humidity chamber at a temperature of 40° C. and a humidity of 90% RH for 2 days (48 hours). Two days later, the sample tube was removed from the constant temperature and humidity chamber and the inside of the tube was smelled.The sample of Comparative Example 1 had a very strong odor of rotting milk, whereas the antibacterial fabric of Example 4 had a very strong odor of rotting milk. There was only a slight smell of milk.

(2) GC Evaluation The antibacterial fabric of Example 4 and the sample of Comparative Example 1 (undyed polyester fabric) cut into 2.0 cm x 2.0 cm were each placed in a vial. 100 μL of milk was dropped onto the sample, and the vial was tightly stoppered. This vial was left standing in a constant temperature and humidity chamber at a temperature of 40° C. and a humidity of 90% RH for 2 days (48 hours). Two days later, the vial was taken out from the constant temperature and humidity chamber, and GC analysis was performed using "GC-2010plus" manufactured by Shimadzu Corporation. When the peak areas of butyric acid were compared, it was found that the sample of Comparative Example 1 had a "7. ,643'', while the antibacterial fabric of Example 4 had a value of 4,599. In addition, butyric acid is considered to be one of the odor components when milk goes bad.

The above results are summarized in Table 3 below.

From the results in Table 3, it was verified that the antibacterial agent (lanthanum ferrite) contained in the antibacterial fabric of the present invention exhibits excellent deodorizing properties (resistance to putrid odor).

《Antibacterial properties against other bacteria》
The antibacterial fabric of the present invention exhibits excellent antibacterial properties against bacteria other than those tested above. The fact that the antibacterial agent (lanthanum ferrite) contained in the antibacterial fabric of the present invention exhibits excellent antibacterial properties against various bacteria will be verified by the following references.

《Reference example 1》
Using Salmonella enteridtidis as the test bacteria, a bacterial solution was prepared so that the initial ATP luminescence amount was 50,000 RLU, and this was used as the test bacterial solution. 0.1 g of lanthanum ferrite obtained by the same method as above was added to 9.9 g of this test bacterial solution, and the mixture was shaken for 2 hours using a tube rotator "MX-RL-E" manufactured by As One Co., Ltd. At this time, 1 mL of the liquid was collected 30 minutes, 1 hour, and 24 hours after the start of shaking, and the ATP reduction rate (%) of the collected liquid was measured.

The ATP reduction rate (%) of each collected solution was determined in the same manner as in Example 1, except that "Lucifer 250 Plus" manufactured by Kikkoman Biochemifa Co., Ltd. was used as the ATP measurement kit.

The results obtained are shown in Table 4.

《Reference examples 2 to 7》
A test bacteria solution was prepared in the same manner as in Reference Example 1, except that the bacteria listed in Table 4 were used as the test bacteria, and the antibacterial properties of lanthanum ferrite were investigated. The results obtained are shown in Table 4.

From the results in Table 4, it was verified that the antibacterial agent (lanthanum ferrite) contained in the antibacterial fabric of the present invention is effective against many types of bacteria.

《Moldproof》
The antibacterial fabric of the present invention also has excellent antifungal properties. It is verified by the following reference that the antibacterial agent (lanthanum ferrite) contained in the antibacterial fabric of the present invention exhibits not only antibacterial properties but also excellent antifungal properties.

《Reference example 8》
Lanthanum ferrite obtained by the same method as above is added to VONCOAT HY-364 (aqueous acrylic urethane emulsion manufactured by DIC Corporation, solid content 45% by mass) as a resin and mixed. A dispersion was prepared.

Using bar coater #10, the obtained lanthanum ferrite dispersion was coated on a paper base material and allowed to stand at room temperature for 1 day (24 hours) to dry to form a coating film with a thickness of 6 μm. By doing so, a sample for mold resistance evaluation was prepared.

To 1,000 mL of purified water, 10 g of high quality agar for culture medium (manufactured by Ina Shokuhin Kogyo Co., Ltd., product name "BA-70") and 30 g of granulated sugar were added and dissolved by heating to obtain a solution. The obtained solution was poured into a sterilized Petri dish and allowed to stand at room temperature to solidify, thereby preparing an agar medium.

The sample for mold resistance evaluation obtained above was cut into 5 cm square pieces and placed on an agar medium in a sterilized petri dish with the coating surface facing upward. 200 μL of the mold suspension was dropped onto the coated surface of the sample and spread evenly over and around the sample.

The petri dish was covered and allowed to stand at room temperature, and after 45 days, the area of mold that had grown was measured, and the ratio of the area of mold growth to the sample surface (5 cm x 5 cm = 25 cm ² ) was calculated. The area ratio of mold that developed on the sample for evaluating antifungal property of Reference Example 1 was only 6%.

From this, it was verified that the antibacterial agent (lanthanum ferrite) contained in the antibacterial fabric of the present invention exhibits not only antibacterial properties but also excellent antifungal properties.

Claims (13)

A fiber coated with a rare earth ferrite composition including a rare earth ferrite and a resin. The fiber according to claim 1, wherein the fiber is subjected to a heat treatment after being coated with the rare earth ferrite composition. The rare earth ferrite has the following formula (1):
Ln _2x Fe _{2 (1-x)} O ₃ (1)
(In formula (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium, and yttrium, and x is a number of 0.50 or more and less than 1.00.)
The fiber according to claim 1, having a composition represented by: The fiber according to claim 3, wherein x in the formula (1) is a number of 0.65 or more and 0.85 or less. The fiber of claim 1, wherein the rare earth ferrite is lanthanum ferrite. The fiber according to claim 1, which is used for antibacterial, deodorant, and antifungal purposes. A fabric composed of the fiber according to any one of claims 1 to 5. The fabric according to claim 7, which is used for antibacterial, anti-odor, and anti-mold purposes. Claims for socks, tights, masks, air conditioner filters, curtains, bath mats, insoles, bedding, underwear, swimwear, gloves, sports protectors, white coats, surgical gowns, work clothes, towels, cloths, gauze, bandages, or seating surfaces. The fabric according to item 8. A method for producing the fiber according to claim 1, comprising:
A method comprising: immersing a raw material fiber in a rare earth ferrite dye solution containing a rare earth ferrite and a resin; and subjecting the fiber after the immersion to a heat treatment. The method according to claim 10, wherein the temperature of the heat treatment is 80°C or more and 180°C or less. The method for manufacturing the dough according to claim 7,
A method comprising: immersing a raw material fabric in a rare earth ferrite dye solution containing a rare earth ferrite and a resin; and subjecting the fabric after the immersion to a heat treatment. The method according to claim 12, wherein the temperature of the heat treatment is 80°C or more and 180°C or less.