JP5057433B2 - Fibers having metal adsorption characteristics, etc. and fiber products thereof - Google Patents

Description

The present invention relates to a fiber having a unique surface obtained by coating an alginate fiber with chitosan and having a metal adsorption characteristic and the like, and a fiber product using the fiber as a main material.

Conventionally, products using chitosan have been developed as antibacterial, deodorant and antifungal products.
However, regarding the pursuit of chemical fibers that are compatible with chitosan (providing a synergistic effect), although there are some techniques for attaching chitosan to chemical fibers, the current situation is that it has not been done much.
This invention is based on the research that chitosan can be attached to the surface of alginate fiber in a unique shape, and based on the results of research that chitosan brings about a very high synergistic effect by the attachment, the combination of alginate fiber and chitosan It is to try to make it.

Alginic acid is a polysaccharide contained in brown algae and the like, is a kind of dietary fiber, and is an organic substance also contained in corals of red algae.
Alginic acid is insoluble in water, but it is also extracted as a soluble salt such as sodium alginate (collectively referred to as algin) and is an organic substance used for food additives and other purposes.
Alginic acid is a compound having (R-COOH) as an acid component, and has two types of structures: Β-D-mannuronic acid (M) and α-L-guluronic acid (G) which is an optical isomer thereof. (1-4) -bonded linear polymers, each of which is a monosaccharide having a carboxyl group.

The fiber made of alginic acid is free from sticking and rich in flexibility. In particular, the fiber is excellent in flexibility even in a dry state, and has excellent spreadability. Therefore, it can be easily processed into a nonwoven fabric, woven fabric, and paper. Moreover, since it is excellent in dry strength, dry elongation, knot strength, and knot elongation, it is useful as a medical fiber product, in particular, a medical material such as a wound contact material and hemostatic cotton. Often used in the paper and textile industries.

Japanese Patent Laid-Open No. 08-013252 “Alginic acid fiber, production method and product thereof” is known technology relating to alginate fiber.
JP 08-013252

Alginic acid fibers have various excellent properties as described above, but in order to enhance their versatility while making good use of high-quality fibers, further improvements, addition of effects and development of applications are required. For example, when used in the medical field, there is a demand for medical materials having high antibacterial / deodorant and antifungal properties.

By the way, research on the use of chitosan and its starting material, chitin, which have remarkable antibacterial, deodorant and antifungal properties, has been progressing rapidly in various fields in recent years.
Chitin is a substance that is physically and chemically strong and difficult to dissolve because of its role in supporting and protecting the body. Chitin exists together with proteins and calcium carbonate in vivo, but chitosan is obtained by removing these with dilute acid or dilute alkali and further removing the acetyl group with strong alkali. Industrially, the C2-position acetamide group in the chitin skeleton is mainly deacetylated and converted to a free primary amino group.

Raw materials are crustacean exoskeletons such as crabs and shrimps. In short, chitosan is obtained by deacetylating chitin obtained from crustacean exoskeletons such as crabs and shrimps by boiling treatment in concentrated alkali.

Chitosan's antibacterial properties are thought to be due to the amino group attracting the negative charge on the cell wall of the bacterium, inhibiting the freedom of the bacterium and leading to death. It can be immobilized on the surface of cellulose or PET by chemical bonding, and is expected to improve dyeability, adsorb and sustained release of drugs, and antibacterial properties.

Moreover, since chitosan has a hemostatic effect, cotton-like fibers are used as a hemostatic agent. Chitin and chitosan derivatives are also added to cosmetics. In the agricultural field, it is said that it has an effect of improving germination rate and yield, and seed coating and spreading on soil are carried out. Chitosan has antibacterial activity and is applied to food and clothing.

Now, while researching such chitin, chitosan, and alginic acid, a heavy metal adsorption test was conducted on chitosan and alginic acid powder, and it was found that each had an action of adsorbing heavy metals. Next, these were made into fibers, and chitosan fibers and alginic acid fibers were adsorbed with heavy metals, respectively.Furthermore, an adsorption experiment was conducted with a mixture of chitosan fibers and alginic acid fibers, and further with alginate fibers coated with chitosan. As a result, the test results showed that the adsorption effect of heavy metals increased. That is, comparing the amount of heavy metal adsorption, chitin, chitosan, alginic acid powder, chitin, chitosan, alginic acid fiber, and alginic acid fiber coated with chitosan were improved in this order.

Considering the availability of chitosan in a wide range, chitosan can be used as a coating modification material for alginate fibers, and the effects of chitosan and the effects of alginate fibers can be synergized and amplified.
In the form of a special coating of alginate fiber with chitosan, the effects of both can be synergized, and new application development has become possible by the accumulation of the fiber.

The present invention provides an alginic acid fiber improved to have higher antibacterial, deodorant, antifungal, and heavy metal adsorption properties than the conventional single alginate fiber due to the effect of chitosan and a fiber product thereof. With the goal.
Materials with high safety such as antibacterial properties can be provided in the medical field and textile field.

Furthermore, it is providing the alginic acid fiber as a highly versatile raw material to each field | area.
And the point to the application to the environmental field | area which is one of the main subjects of this invention is mentioned.
A system that applies biochemical reactions with excellent characteristics to production of useful substances, decomposition of environmental pollutants, analysis, medical treatment, etc. is called a bioreactor, and the use of chitosan in a bioreactor is also an object of the present invention. Focusing on the high antibacterial properties and metal adsorption properties brought about by the synergistic effect of chitosan and alginate fiber, not only in the medical field and textile industry, but also in industrial waste treatment, wastewater treatment from industrial wastewater, ponds, lakes, The purpose is to apply to environmental fields such as sludge treatment of rivers, recovery and removal of metal ions.

In addition, it is also an object of the present invention to effectively utilize natural resources such as chitin and chitosan as one of the few huge unused biological resources (biomass) left on the earth while resource depletion is called out.

Incidentally, the present applicant is not aware of a known technique relating to a product made of alginic acid fibers and chitosan and other modified materials and alginic acid fibers.

In order to solve the above problems, the present invention uses chitosan (1) as a modifying material in order to modify the fiber surface of the alginate fiber (2). The means is based on a structure in which alginate fibers (2) are coated with chitosan (1).

For example, there is a method in which an aqueous solution of sodium alginate is extruded from a base (a base provided with a number of fine nozzles) in a solution called a coagulation bath to cause a chemical reaction, and then the solvent is removed to form a fiber. Coating can be performed by adding a chitosan aqueous solution to the coagulation bath. At this time, it is possible to form a chitosan coating that is uneven, irregular, and has a particularly large surface area by slowing down the extrusion speed within a predetermined range, or by applying vibration to the die and high-frequency vibration to the chitosan aqueous solution. It turned out to be. By this method, the cross section of the alginate fiber is formed into a noncircular deformed cross section.

An elastic vibration wave having a high frequency (in a narrow sense, an elastic vibration wave having a high frequency of 16 kHz or more) is applied during the coating operation to apply high-frequency vibration to the inside and the film. Then, when the alginate fiber is enlarged and viewed, the cross section is not a perfect circle, but is distorted, circular with a distorted surface area, and the fiber surface is irregularly uneven.
In accordance with the shape, chitosan adheres irregularly to irregularities, so that the surface area becomes even larger.

As described above, the fiber according to the present invention and the fiber product thereof are mainly composed of a fiber having a metal adsorption characteristic and the like, characterized in that the alginic acid fiber (2) is non-uniformly coated with chitosan (1). Providing textile products.
The spinning method of the alginic acid fiber (2) is called wet spinning, in which the sodium salt is replaced with a magnesium salt or a calcium salt to coagulate and precipitate.

The coating may be performed by attaching chitosan (1), covering with a thin film of chitosan (1), spraying chitosan (1) onto the fiber surface, or other application methods.
Even if these methods are used, the entire fiber surface may be coated with chitosan (1), or may be deposited with a certain spacing, or coated in a spiral with respect to the fiber direction. The fiber may be spun while passing through a sponge-like material (for example, sponge) rich in water absorption containing chitosan (1).
In the method in which alginic acid is formed into a fiber and extruded into a coagulation liquid containing chitosan to form fibers, the extrusion speed is reduced within a predetermined range, or vibration is applied to the die and high-frequency vibration is applied to the chitosan aqueous solution. It is possible to form a chitosan coating that is uniform, irregular and has a particularly large surface area.

Thus, by coating the alginic acid fiber unevenly with chitosan, it was possible to increase the surface area and increase the adsorptivity of heavy metals.
Furthermore, by shortening and opening the fibers and forming a nonwoven fabric randomly laminated with Weber, the porosity can be reduced, the surface area can be increased, and the heavy metal adsorption characteristics can be increased.

In this way, a textile product which is a fabric or non-woven fabric mainly composed of alginate fiber (3) coated with chitosan is prepared.
The antibacterial, deodorant, antifungal and heavy metal adsorption effects of chitosan (1) can be added while taking advantage of the heavy metal adsorption characteristics of the alginate fiber (3).

Alginate fiber (2) is coated unevenly with chitosan (1) and silver (7) is adhered, or alginate fiber (2) is coated unevenly with chitosan (1) and silver (7) at the same time The fiber which has the metal adsorption | suction characteristic characterized by these, and the fiber product which uses the fiber as a main material are also provided.
Metal adsorption by silver ions Antibacterial Deodorizing effect can be added.
By adopting this configuration, the metal adsorption property of silver (7) is combined with chitosan (1), and the adsorption effect is further enhanced.

Further, for example, there is a method in which an aqueous solution of sodium alginate is extruded from a base (a base provided with a number of fine nozzles) in a solution called a coagulation bath to cause a chemical reaction, and then the solvent is removed to form a fiber. In this coagulation bath, calcium nitrate and silver nitrate (6) are added to an aqueous chitosan solution, and the chitosan (1) and silver (7) are simultaneously and unevenly adhered to the alginate fiber (2) by silver (7) and chitosan ( 1) can be coated at the same time.
This fiber can be shortened to create an unemployed fabric.

Furthermore, the alginate fiber (3) with non-uniform coating of chitosan (1) is used as the short fiber (4), and the short fiber (11) is further immersed in silver nitrate (6) to which silver (7) is adhered. A non-woven fabric characterized by being made by adding reinforcing short fibers (5) to
By using a non-woven fabric, the fibers are randomly stacked, so that the surface area is increased and a material capable of adsorbing more heavy metals is obtained.

The short fibers (4) (11) and the reinforcing short fibers (5) are desirably in a ratio of 100% by weight; 0% to 5%; 95%. As the proportion of short fibers (4) (11) increases, the content of chitosan (1) naturally increases.
The purpose of the present invention is not only for products that come into direct contact with the human body, but also for the application to environmental fields such as industrial waste treatment, wastewater treatment from industrial wastewater, sludge treatment for ponds, lakes, rivers, etc. and recovery and removal of metal ions. Therefore, the weight ratio may be changed as appropriate according to the purpose.

The reinforcing short fibers (5) are made of polypropylene, but may be at least one mixed fiber selected from polyester fibers, polyamide fibers and polyolefin fibers.

By adopting the above configuration, the fiber and the fiber product of the present invention have the following effects.
Alginic acid fibers are free from sticking and rich in flexibility. In particular, since they are excellent in flexibility and openability, they can be easily processed into non-woven fabrics, woven fabrics, and paper fabrics.
Moreover, since it is excellent in dry strength, dry elongation, knot strength, and knot elongation, it is useful as a medical fiber product, in particular, a medical material such as a wound contact material and hemostatic cotton. Often used in the paper and textile industries.
It is an advantage of the present invention that antibacterial, antifungal and heavy metal adsorption properties of chitosan can be added to this high quality and heavy metal adsorption algin fiber.
Needless to say, as a synergistic effect of the two, the metal adsorption characteristics are large and strong as shown in the experimental results of the following “Embodiments of the Invention”.

Chitosan has antibacterial activity and is applied to food and clothing. Alginate fiber is also an excellent fiber as mentioned above, so its use extends to white coats, nursing clothes, urine pads, daily necessities, interiors, etc. It will also be a product for an aging society where high safety is required.

In the case of the nonwoven fabric according to the present invention, the short fibers (4) and the reinforcing short fibers (5) of the alginate fibers (2) and the chitosan (1) that are unevenly coated with chitosan (1) and silver nitrate (6) are unevenly distributed. The short fiber (4) and the reinforcing short fiber (5) of the alginate fiber (2) coated on the fiber, or the short fiber (11) and the reinforcing short fiber (5) immersed in the silver nitrate (6) are 100% by weight. Between 0% and 5%; 95%, the ratio can be arbitrarily changed according to the purpose of the product, and its versatility can be enhanced.

When a bioreactor is used as in the case of shells, the reaction can be performed under milder conditions than ordinary catalytic reactors, and there are advantages such as fewer by-products, fewer steps, and better yield. Many. Since the reaction proceeds at normal temperature and pressure, energy can be saved significantly. The metal adsorption properties brought about by the synergistic effect of chitosan (1) and silver (7) further accelerate the reaction of the bioreactor. Since silver ions exhibit extremely strong bactericidal power against bacteria and the like, synergistic effects are also expected in terms of enhancing antibacterial properties.

Now, chitin constitutes the shell of shrimp, crab and other crustaceans, dragonflies, cicada and other insect shells, or the cell walls of mushrooms and bacteria. Chitosan is obtained by alkaline hydrolysis. Chitin is presumed to be produced on earth after the cellulose, but most of it is discarded. In other words, since chitosan is produced from raw materials derived from biological resources, there is an advantage that the possibility of resource depletion is low. In other words, material selection is excellent in terms of effective use of natural resources.

Moreover, since the amino group of chitosan forms a chelate with heavy metal ions, it can be applied to recovery of metal ions from plating waste liquid, removal of heavy metal ions from factory wastewater, and collection of uranium in seawater.
If attention is paid to this effect, the alginic acid fiber (3) according to the present invention is further devised to be densified and reduced in voids to treat industrial waste, industrial wastewater, etc., cars, air purifiers. A filter such as an air conditioner may be created.
When producing a sheet for industrial waste treatment, various modes of large and small thickness can be devised. In addition, a pond and a lake. It can also be used as a heavy metal adsorbing carrier such as river sludge and a heavy metal adsorbent containing radioactive substances.

By the way, the reason why the chitosan-coated alginic acid fiber (3) of the present invention is made non-woven fabric is because it aims at the following effects. That is, the nonwoven fabric has the merits of opening the fibers and laminating them randomly with Webber, so that the fibers can be uniformly distributed, there is little unevenness in density, and the porosity is small. As a result, the surface area becomes larger than when a solute dissolved, suspended, or dispersed in the solution is adsorbed, and the non-woven fabric can be adsorbed efficiently.
The alginic acid fiber itself has an irregular shape in cross-sectional view, adheres silver, and the coated chitosan also becomes uneven unevenly according to the surface, so the surface area is combined with the above-described nonwoven fabric configuration. There is an effect of further increasing.

As a method for obtaining the nonwoven fabric of the present invention, the fiber is cut into a few mm and wet nonwoven fabric by paper making method, spunlace nonwoven fabric by hydroentanglement method, needle punch nonwoven fabric in which fibers are entangled with a fiber locker, and Marifries type stitch bond nonwoven fabric Can obtain a non-woven fabric of 100% chitosan-coated alginate fiber.
Another method of using low melting point reinforced short fibers is to mix chitosan-coated alginate fiber (3) with reinforced short fibers to form a random web, and then (a) intersection of reinforced short fibers using hot air jet air It is possible to achieve the object of the present invention even in an air-through nonwoven fabric in which fibers are entangled by thermal bonding, and (b) a thermal bond nonwoven fabric in which the intersection points of reinforcing short fibers are point-bonded while crushing the entire web with a calender roll. is there.
Furthermore, an Arachne type stitch bond nonwoven fabric in which a web of chitosan-coated alginate fiber (3) is stitched with other fibers to form a nonwoven fabric can also be used. At this time, the type of fiber forming the stitch is not particularly concerned. Further, a chemical bond nonwoven fabric using a resin by spraying or the like to such an extent that the web of chitosan-coated alginate fiber (3) is lightly needle punched and does not cause deterioration in performance such as adsorption can also be used.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples, and various forms of the invention actually exist.

[Experiment details]
1, 10 w / v% chitosan aqueous solution (DAC70%, MW = 4.0 × 10 ⁴ ) from the nozzle of 50 holes (Φ0.1mm) to the first coagulation bath (satCaCl ₂ /50% MeOHaq.), Second coagulation bath (50 % MeOHaq.) And wound at a draw ratio of 1.2. After washing with methanol, it was immersed in a 1% NaOH / H ₂ O; MeOH = 1; 9 solution for 24 hours to remove Ca. Alginate fiber is solidified in a first coagulation bath (CaCl ₂ aq.) And a second coagulation bath (3% CaCl ₂ /50% MeOHaq.) From a 50 hole (Φ0.1 mm) nozzle with a 4% sodium alginate aqueous solution. The film was wound at a draw ratio of 1.2.

2. The alginate fiber coated with chitosan is a 4% sodium alginate aqueous solution from the nozzle of 50 holes (Φ0.1mm), the first coagulation bath (3% CaCl ₂ aq. Containing 0.1% chitosan acetic acid solution), the second The solution was solidified in a coagulation bath (3% CaCl ₂ /50% MeOHaq.) And wound up at a draw ratio of 1.2.

3. Experiment A of chitosan-coated alginate fiber adsorbed with silver; 4% sodium alginate aqueous solution from a 200-hole (Φ0.1mm) nozzle in a coagulation bath (5% HNO3aq containing 0.1% chitosan acetic acid solution and 0.1% silver nitrate) Solidified and wound up at a draw ratio of 1.2. Thereafter, for decalcification, the mixture was washed with stirring in water for 3 days, stirred in methanol for one day and air-dried to cut fibers.
Experiment _{B; (. 3% CaCl 2} aq containing 0.1% chitosan acetate solution) of a 4% sodium alginate aqueous solution through the nozzle of 50 holes (0.1 mm in diameter), the first coagulation bath, the second coagulation bath (3% CaCl ₂ / 50% MeOHaq.), Wound up at a draw ratio of 1.2, immersed in a 0.1% silver nitrate solution for 1 to 20 minutes, washed with pure water and air-dried to cut the fibers.

Experiment 1, metal adsorption, 1 g each of chitin / chitosan powder and three kinds of fibers was immersed in 100 ml of a metal mixed solution (each 10 ppm) for 24 hours, and then the metal concentration of the supernatant was quantified by ICP emission spectrometry.
Experiment 2, 70% non-woven fabric with 30% polypropylene coated with chitosan on alginate fiber
Each of the non-woven fabrics was immersed in 1 ml of a metal mixed solution (each 10 ppm) in 100 ml for 12 hours, and then the metal concentration of the supernatant was quantified by ICP emission analysis.

[results of the experiment]
The chitosan fiber spun in the calcium system was supple and water-insoluble chitosan fiber was obtained by decalcification / deacetate treatment. Moreover, it was confirmed that chitosan-coated alginate fiber was coated with chitosan on the fiber surface by ninhydrin dyeing.
Table 1 shows the results of each metal adsorption amount. As for the powder, chitosan obtained a higher adsorption amount than chitin except for Mg ²⁺ . In the fiber, the adsorption amount of chitosan-coated alginate fiber exceeded that of other fibers in most metal ions.
Table 2 Table 3 shows the results of each metal adsorption amount. The chitosan-coated alginate fiber nonwoven fabric obtained a higher adsorption amount for most metal ions than the chitosan-coated alginate fiber.
Table 1 shows a heavy metal adsorption test. Table 2 shows a chitosan-coated alginate fiber nonwoven fabric heavy metal adsorption test. Table 3 is a chitosan-coated alginate fiber nonwoven fabric heavy metal adsorption test (unit: ppm).

As is apparent from the experimental results, it was found that a large amount of heavy metal was adsorbed on the alginate fiber coated with chitosan.
As apparent from the experimental results in Tables 2 and 3, it was found that the heavy metal adsorbed more on the non-woven fabric of alginate fiber coated with chitosan than the fiber coated with chitosan.
It can be said that this is the result of the high metal adsorption characteristics of the combination of chitosan and alginic acid fibers and the fact that the fibers are randomly laminated by using a non-woven fabric, so that the surface area is increased and heavy metals are adsorbed.
Applications to environmental fields such as industrial waste treatment and recovery and removal of metal ions from industrial wastewater can be expected. The fiber (nonwoven fabric) according to the present invention may be used to make a filter such as a car, an air purifier, or an air conditioner. Further, a sheet made of the fibers (nonwoven fabric) according to the present invention can be laid under industrial waste and used as a heavy metal adsorbing carrier or a heavy metal adsorbing tool containing a radioactive substance. Moreover, it can be used not only for industrial purposes, but also as a filter used to purify water as a water purifier for a personal house.
The above is the result of the experiment, and an embodiment carried out based on this will be described next.

Example 1 is a fiber in which alginate fiber (2) is non-uniformly coated with chitosan (1).
Example 2 is a fiber in which chitosan is not coated with a fiber in which chitosan (1) is unevenly coated on alginate fiber (2).
Example 3 is a fiber in which alginate fibers (2) are non-uniformly coated with chitosan (1) and silver (7), and the alginate fibers with silver (7) adhered after decoating chitosan (1) Example 3 of 1), alginic acid fiber coated with chitosan (1) and silver (7) at the same time (Example 3-2) prepared by two methods are disclosed.
Example 4 is a nonwoven fabric made from the fibers of Example 1 or Example 2.
Example 5 is the nonwoven fabric produced in Example 3.
It is.

Next, Example 1 of a fiber obtained by unevenly coating chitosan (1) on an alginate fiber (2) and its fiber product will be described.
First, the coating method will be described. Chitosan (1) is used as a modifying material in order to modify the fiber surface of the alginate fiber (2). The means is based on a method of coating alginate fiber (2) with chitosan (1). For example, as shown in FIG. 1, a sodium alginate aqueous solution (8) is extruded in a solution called a first coagulation bath at a speed within a predetermined range from a die by a pressure within a predetermined range, and then the solvent is removed to remove the fiber. It is a method to make. Coating can be continuously performed by adding the chitosan aqueous solution (8) to the first coagulation bath.
The second coagulation bath is a 3% calcium chloride / 50% methanol (10) solution, which solidifies the fiber efficiently.

Although not shown, when releasing the alginate fiber (2) into the first coagulation bath, it is possible to slow down the extrusion speed within a predetermined range, or to vibrate the base, or the first coagulation bath (chitosan aqueous solution). High-frequency vibration is applied to the alginate fibers to form a chitosan coating that is uneven, irregular, and has a particularly large surface area.

FIG. 2A is a perspective view showing a fiber state of Example 1 in which alginate fiber (2) is coated with chitosan (1) by a method in which a chitosan aqueous solution is added to a coagulation bath, and FIG. It is sectional drawing of the fiber of.
When the alginate fiber (3) according to the present invention spun in this way is enlarged, it is not a clean cylindrical shape, and the fiber surface is distorted and uneven.
Since chitosan also adheres unevenly in accordance with its shape, the surface area becomes even larger as shown in FIGS. 2A and 3A. It is characterized by an uneven coating.
Along with this, it is considered that the metal adsorption property is enhanced in combination with the synergistic effect of chitosan (1) and alginate fiber (2).

FIG. 4A is an enlarged perspective view showing a fiber state of Example 2 in which chitosan (1) is adhered to the surface of alginate fiber (2) at a certain interval, and FIG. 5A is a diagram of FIG. 4A in Example 2. It is sectional drawing of the fiber of a figure.
The coating may be performed by attaching chitosan (1), covering with a thin film of chitosan (1), spraying chitosan (1) onto the fiber surface, or other application methods. Even if these methods are used, the entire fiber surface may be coated with chitosan (1), or may be deposited with a certain spacing, or coated in a spiral with respect to the fiber direction. The fiber may be spun while passing through a sponge-like material (for example, sponge) rich in water absorption containing chitosan (1).
In any of the coating methods, chitosan is coated so that non-circular alginic acid fibers have unevenly uncoated portions.
Since these fibers are coated with chitosan extracted from natural products, it is highly safe and biocompatible.

As Example 3, the alginate fiber (2) is coated with chitosan (1) unevenly and further silver (7) is adhered (1 of Example 3), or chitosan (1) and silver (7) are not mixed simultaneously. The fiber (2 in Example 3) coated and adhered uniformly will be described.
The third embodiment is shown in FIGS. 1B and 2B. FIG. 3B and FIG. 4B. As shown in FIG. 5B, silver (7) is adhered.
First, after the chitosan (1) is unevenly coated on the alginate fiber (2), silver (7) may be further adhered in a separate step.
When coating chitosan (1) and silver (7) at the same time, add calcium nitrate and silver nitrate (6) to the chitosan aqueous solution in the coagulation bath, so that chitosan (1) and silver (7) are simultaneously and unevenly alginate. Silver and chitosan (1) can be coated simultaneously by attaching to the fiber (2).

Examples of the fiber product made from the alginate fiber (3) coated with chitosan of the present invention include a fabric and a nonwoven fabric (20).
The nonwoven fabrics of Example 4 and Example 5 will be described.
FIG. 6A is a manufacturing process diagram of a nonwoven fabric comprising a step of decoating alginate fiber (2) with chitosan (1) and a step of attaching silver (7) to the coated alginate fiber.
FIG. 6B is a manufacturing process diagram of a nonwoven fabric in which alginate fiber (2) is mixed with chitosan (1) and silver nitrate (6) simultaneously and coated.

The alginate fiber (3) coated with chitosan (1) was used as the short fiber (4), and the non-woven fabric (20) was prepared using only the short fiber (4). A non-woven fabric (20) may be prepared by adding reinforced short fibers (5) thereto.
Specifically, it is solidified in an aqueous solution of sodium alginate fiber (8)), solidified in a coagulation bath (13), wound at a draw ratio of 1.2, then decalcified, washed with water for 3 days, stirred in water for one day, and air-dried. The cut fibers were cut, and the reinforcing short fibers (5) were added to prepare a nonwoven fabric (20).

Example 5 is a nonwoven fabric made from the fibers of Example 3.
As described above, the alginate fiber (3) coated with chitosan (1) and then coated with silver (7), that is, the alginate fiber (3) coated with chitosan (1) is made into short fibers (4) and further immersed in silver nitrate (6) In addition to chitosan aqueous solution in addition to the coagulation bath of sodium alginate aqueous solution, short fiber (11) added with silver (11 of Example 3), calcium nitrate and silver nitrate (6) are added to obtain chitosan (1) and silver At the same time, the fiber (2 in Example 3) in which (7) is non-uniformly adhered to the alginate fiber (2) is cut or shortened by the same method to produce a fiber in which silver (7) and chitosan (1) are adhered. Made unemployed cloth (20) as the main material.
As confirmed in Experiment B, a 4% sodium alginate aqueous solution was fed from a 50 hole (Φ0.1 mm) nozzle into the first coagulation bath (3% CaCl ₂ aq. Containing 0.1% chitosan acetic acid solution), the second coagulation bath. (3% CaCl ₂ /50% MeOHaq.) Solidified, wound up at a draw ratio of 1.2, immersed in 0.1% silver nitrate solution for 1 to 20 minutes, washed with pure water, air dried, and fiber The nonwoven fabric was made by adding cut reinforcing fibers (5).

The reinforcing short fiber (5) is at least one mixed synthetic fiber selected from polyester, polyester fiber, and polyolefin fiber, including polypropylene.

FIG. 7 is an explanatory diagram of the nonwoven fabric (20).
Fig. A shows non-woven fabric Example 4, using short fibers (4) of Example 1 or Example 2 (short fibers cut with non-uniform coating of alginate fiber (2) with chitosan (1)) And it is the nonwoven fabric (20) which consists of this and a reinforced short fiber (5).
Fig. B shows Example 5 of nonwoven fabric, which uses Example 3 (short fiber cut with alginate fiber (2) coated with chitosan (1) and silver (7)). This shows a nonwoven fabric (20) comprising this and reinforcing short fibers (5).

In Example 4 and Example 5, the non-woven fabric (20) increases the surface area because the fibers are randomly stacked. In addition, the surface of the fiber (3) coated with chitosan (1) is uneven and the surface area of the fiber itself is large.
Thus, by the combined effect of the structural form of the nonwoven fabric (20) and the surface shape of the fibers used, it can be densified and reduced in voids, and more heavy metals can be adsorbed. The adsorption rate becomes much higher.

The nonwoven fabric (20) using the short fiber (11) immersed in silver nitrate (6) and adhering silver (7) has remarkable metal adsorption properties, antibacterial properties and deodorant properties.
The following are the antibacterial test results of the nonwoven fabric (20) of Example 5 in which silver was added to chitosan-coated alginate fiber.
"test"
Test bacteria: Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa Legionella test method: After uniformly spreading a fixed amount (10 8 cells / mL) of bacterial solution on an agar plate (Muller-Hinto agar) with a sterile swab, 1 cm Incubate for 20 hours with 2 pieces of non-woven fabric on each side. As shown in FIG. 8, a non-woven fabric made of fibers having silver (7) with a 0.001% weight ratio attached to the right petri dish. Nonwoven fabric made of fibers with 1 (0.1) weight ratio of silver (7) of Example 3 attached to the left petri dish, and 0.2 (1) weight ratio of silver (7) of Example 3 to the lower dish. Nonwoven fabrics made with attached fibers were compared for comparison. The blocking zone formed in the left and lower petri dishes was confirmed with the naked eye. FIG. 8 shows photographs of the formation of blocking bands when different non-woven fabrics are placed on the three petri dishes. Because it is a drawing substitute photo, it is slightly blurred, so if you explain it, a non-woven fabric of the right petri dish is blocked by a circular band with a roughly equal width around the non-woven fabric of the left petri dish and the lower petri dish The belt was small.
As a result, the coating of chitosan (1) and silver (7) can be antibacterial both when treated over time or simultaneously as in Example 3 or Example 3-2. It turned out to be strong.
Tester: Kitasato Institute Basic Research Institute Infection Control Room

The present invention is expected to be usable in a wide range of fields, and the antibacterial fiber product of the present invention includes, as a fabric, a towel, a wet tissue, a toilet cloth, a kitchen cloth, a dust cloth, a drug bag of a dehumidifying agent and a fragrance, In addition, it can be used as a cleaning cloth.

Chitosan (1) -coated alginate fiber (3) with silver (7) added, or chitosan (1) aqueous solution with silver nitrate (6) added and mixed (12) to mix chitosan (1) and silver ( 7) Alginate fibers (2) with short fibers (fiber products) are examples of products such as air conditioners, air purifiers, car filters, waste disposal sheets, and various industrial products. A filter can be considered. It can be applied to the environmental field using high metal adsorption characteristics.

Examples of the use of the nonwoven fabric (20) according to the present invention that can be used in general households include a futon cover, a pillow cover, a table cloth, a costume cover, clothes, an insole for shoes, and the like. For medical purposes. A mask, a hat, clothes, etc. can be considered.
In addition, the ratio of the short fibers (4) (11) and the reinforcing short fibers (5) in the product that directly touches the human body is preferably 10%; 90% to 50%; 50%. The weight ratio of the whole nonwoven fabric (20) and the chitosan component is about 1 to 5%.

As described above, the alginic acid fiber (3) and the nonwoven fabric (20) coated with chitosan according to the present invention are not limited to the medical field, but are used for industrial waste treatment. Industrial wastewater treatment, sludge treatment of ponds, lakes, rivers, etc. and recovery and removal of metal ions are also possible for environmental applications. The high antibacterial, antifungal, and heavy metal adsorption properties provided by chitosan and alginic acid fibers are used in various fields such as heavy metal adsorption sheets in landfills, filters, laying sheets at waste disposal sites, and waste drainage partial sheets Is possible.

FIG. A is an explanatory view showing a state in which a fiber having a metal adsorption property or the like is spun by coating alginate fiber (2) with chitosan (1). FIG. B is an explanatory view showing a state in which silver nitrate (6) is mixed with an alginate fiber and chitosan aqueous solution (9) and coated to spin a fiber having metal adsorption characteristics and the like. FIG. A is a perspective view showing a fiber state of Example 1 in which chitosan (1) is coated on alginate fiber (2) by a method in which an aqueous chitosan solution is added to a coagulation bath. FIG. B is a perspective view showing a fiber state of Example 1 in which silver nitrate (6) is mixed and coated with an aqueous chitosan solution (9). It is sectional drawing of the fiber of FIG. 2-A figure in FIG. FIG. A is a perspective view showing a fiber state of Example 2 in which chitosan (1) is adhered to the alginate fiber (2) surface at a predetermined interval. FIG. B is a perspective view showing a fiber state of Example 3 in which chitosan (1) and silver nitrate are adhered to the alginate fiber (2) surface at a predetermined interval. FIG. A is a cross-sectional view of the fiber of FIG. FIG. B is a cross-sectional view of the fiber of FIG. FIG. A is a production process diagram of a nonwoven fabric (20) in which silver is attached to chitosan (1). FIG. B is a production process diagram of a non-woven fabric (20) in which silver nitrate (6) is mixed with a chitosan aqueous solution (9) in an alginate fiber (2). FIG. A is an explanatory diagram of a nonwoven fabric (20) composed of the short fibers (4) and the reinforcing short fibers (5) of Example 1 or Example 2, showing Example 4 showing the nonwoven fabric. FIG. B is Example 5 showing a nonwoven fabric, and is an explanatory view of the nonwoven fabric (20) comprising the short fibers (4) and the reinforcing short fibers (5) in Example 3. 6 is a drawing-substituting photograph showing the antibacterial test results of the nonwoven fabric (20) of Example 5. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Chitosan 2 ... Alginate fiber 3 ... Fiber 4 coated with chitosan (1) ... Short fiber 5 ... Reinforced short fiber 6 ... Silver nitrate 7 ... ··· Silver 8 ··· Sodium alginate aqueous solution 9 ··· Chitosan aqueous solution (first coagulation bath)
10 ... 3% calcium chloride / 50% methanol (second coagulation bath)
DESCRIPTION OF SYMBOLS 11 ... Short fiber immersed in silver nitrate (6) 12 ... Mixing silver nitrate (6) with chitosan aqueous solution (9) 13 ... Fiber 20 which coated alginate fiber with chitosan (1) and silver nitrate (6) ... Nonwoven fabric

Claims (5)

A fiber having metal adsorption characteristics and the like, characterized in that the alginate fiber (2) is non-uniformly coated with chitosan (1) . The alginate fiber (2) is coated with chitosan (1) non-uniformly and further silver (7) is adhered, or the alginate fiber (2) is coated non-uniformly with chitosan (1) and silver (7) simultaneously. A fiber having characteristic metal adsorption characteristics. The alginic acid fiber (2) is non-uniformly coated with chitosan (1) and silver nitrate (6), the alginate fiber (2) is a short fiber (4), or chitosan (1) is non-uniformly coated with alginate fiber ( Alginic acid characterized in that 3) is a short fiber (4), and further is a short fiber (11) dipped in silver nitrate (6) to which silver (7) is adhered, and a reinforcing short fiber (5) is added thereto. Non-woven fabric mainly composed of fibers. The nonwoven fabric according to claim 3, wherein the reinforcing short fibers (5) are composed of one or more of polyester fibers, polyamide fibers and polyolefin fibers. The fiber having metal adsorption characteristics according to any one of claims 1 to 2, wherein a cross section of the alginate fiber (3) is formed into a non-circular deformed cross section.

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