JPH09132869A - Antimicrobial fiber and fiber product using the fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial fiber having extremely low toxicity against a human body and useful as a medical hygiene material, etc., by compounding a fiber of a specific thermoplastic resin with a polylysine usually used as a food preservative, etc. SOLUTION: A polylysine such as ε-polylysine of the formula or its salt is compounded by kneading, etc., into a fiber of a thermoplastic resin having no functional group which has affinity for the polylysine or its salt. The abundance of the polylysine or its salt in the outer layer of the fiber is made to be larger than that in the inner layer by a method in which the polylysine or its salt is added only in the sheath component of a core-sheath conjugate fiber, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial fiber. More specifically, the present invention relates to an antibacterial fiber or an antibacterial fiber product suitable for medical hygiene materials, daily life related materials, general clothing materials, bedding materials, and filter materials.

[0002]

BACKGROUND ART Various bacteria and fungi are present in our living space. Especially in a hot and humid environment such as Japan, bacteria and fungi easily grow. As a result, the skin may be damaged, or the fiber may be deteriorated, discolored, deteriorated, or give off an offensive odor to give discomfort. In particular, since synthetic fibers hardly absorb sweat, when the fibers are put on the body, microorganisms propagate due to the adhesion of sweat, causing a spoilage phenomenon and producing an offensive odor. Further, it has been desired to develop comfortable and hygienic antibacterial fiber products, such as occurrence of food poisoning due to bacterial growth in food containers and water filtration materials, and rapid increase in MRSA infectious disease patients due to nosocomial infection.

[0003] From this point of view, organotin and organomercury compounds have been used to impart antibacterial properties to fibers, but at present, most of such compounds are used due to their toxicity. It is banned.

As an alternative, a method has been proposed in which a highly safe silicone quaternary ammonium salt is applied to a textile product such as carpet. However, the silicone quaternary ammonium salt has reactivity with cellulose fiber,
Although it has anti-washing and anti-bacterial properties, synthetic fibers have only a temporary anti-bacterial effect.

It has long been known that compounds such as silver, copper and zinc have antibacterial properties.
Many attempts to add antibacterial properties by adding zinc to a polymer have been proposed, for example, in JP-A-54-147220. An attempt to add zeolite-based solid particles ion-exchanged with silver ions and copper ions to a polymer has been proposed in, for example, JP-A-59-133235.

However, in these methods, the polymer discolors due to the metal compound. In addition, the fibers and fiber products obtained by these methods may pose a problem in hygiene to the human body, particularly to infants with weak skin, depending on the intended use.

In recent years, attempts have been made to apply chitin and chitosan derivatives having low toxicity to the human body and high safety to textiles as antibacterial agents. For example, Japanese Patent Application Laid-Open No. 5-5274 proposes an antibacterial short-fiber non-woven fabric to which a composite consisting of a deacetylated product of chitin and a cellulose fine powder is fixed. Although these fiber products have achieved high antibacterial properties and durability, only hydrophilic non-woven fabric can be obtained because cellulose exhibits hydrophilicity.

[0008]

The present invention has extremely low toxicity to the human body, has excellent antibacterial properties, and is suitable as a medical hygiene material, life-related material, general clothing material, bedding material, and filter material. It is intended to provide an antibacterial fiber that can be used, and an antibacterial fiber product.

The present inventors have conducted extensive studies in order to achieve the above object, and as a result, by incorporating polylysine or a salt thereof into the fiber as an antibacterial agent, the toxicity to the human body is extremely low and the antibacterial property is excellent. The present invention has been completed, knowing that it is possible to provide a fiber or a fiber product having the above.

[0010]

The present invention has the following arrangement to solve the above-mentioned problems. (1) Polylysine or a salt thereof is added to a fiber made of a thermoplastic resin having no functional group having an affinity for the polylysine or a salt thereof, and a value of 0.
An antibacterial fiber characterized in that the content of said polylysine or a salt thereof is larger in the outer layer portion than in the inner layer portion of said fiber in an amount of from 0 to 5% by weight. (2) The antibacterial fiber according to item (1), wherein the thermoplastic resin is a polyolefin resin and the fiber is a polyolefin fiber. (3) The antibacterial fiber according to item (2), wherein the polyolefin fiber is a composite fiber composed of at least two components. (4) The antibacterial fiber according to any one of (1) to (3) above, wherein the salt of polylysine is at least one inorganic acid selected from hydrochloric acid, sulfuric acid, phosphoric acid and hydrobromic acid. (5) The antibacterial fiber according to any one of (1) to (3) above, wherein the salt of polylysine is at least one organic acid selected from acetic acid, propionic acid, fumaric acid, malic acid and citric acid. . (6) A non-woven fabric using the antibacterial fiber according to any one of (1) to (5) above. (7) A knitted fabric using the antibacterial fiber according to any one of (1) to (5) above. (8) A fiber molding using the antibacterial fiber according to any one of (1) to (5) above.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the polylysine, for example, a medium of Streptomyces albus subsp. S. Lysinopolymeris, which is a polylysine-producing bacterium belonging to the Streptomyces family, which is the ε-L-polylysine-producing bacterium described in JP-A-59-20359, is used. It is obtained by culturing in a medium and separating and collecting ε-L-polylysine from the obtained culture. Lysine is 1
Polylysine, which is an amino acid having two amino groups in the molecule, is generally composed of α-polylysine in which an amino group at the α-position is condensed with a carboxyl group and ε in which an amino group at the ε-position is condensed with a carboxyl group. -There are two types, polylysine, but ε obtained by the above-mentioned production method
-It is preferable to use polylysine in terms of safety. Furthermore, ε-polylysine is a substance listed in the list of food additives other than chemical synthesis compiled by the Ministry of Health and Welfare, and is used as a food preservative and the like. ε-Polylysine is represented by the following general formula.

[0012]

Embedded image

In the present invention, polylysine can be used in a free form, but at least one inorganic acid selected from hydrochloric acid, sulfuric acid, phosphoric acid and hydrobromic acid, or acetic acid, propionic acid, It can also be used in the form of a salt of at least one organic acid selected from fumaric acid, malic acid and citric acid. Polylysine, whether in free or salt form, has essentially no difference in efficacy as an antimicrobial agent. The polylysine salt is produced by a conventional method. For example, the polylysine is dissolved in a water-containing methanol solution, and the acid is added thereto. Once the solution has passed the neutralization point, cold acetone is added to precipitate the salt and it is dried. When the method of kneading polylysine or its salt into the fiber is adopted, this is crushed and used in a mortar or a ball mill.

As the fiber material used for the antibacterial fiber of the present invention, a thermoplastic resin having no affinity with polylysine or its salt is used. For example, polypropylene,
Polyolefin resins such as linear low-density polyethylene, low-density polyethylene, and high-density polyethylene, especially high-density or highly crystalline polyolefin resins are preferred.

When the antibacterial fiber of the present invention is a composite fiber composed of two or more kinds of resins, a sheath-core type, a parallel type, an eccentric sheath-core type,
Fibers of a composite type such as a multi-layer type or a sea-island type can be exemplified, but a sheath-core type, an eccentric sheath-core type, and a sheath-rich parallel type are particularly preferable. Further, the effect of the present application is great when the sheath component to which polylysine or a salt thereof is added is a polyolefin resin, and in this case, the core component of the polyolefin fiber may be composed of polyester or polyamide. High density polyethylene / polypropylene, linear high density polyethylene / as combination of sheath / core of composite fiber
Polypropylene, low-density polyethylene / polypropylene, binary copolymer or terpolymer of propylene with other α-olefin / polypropylene, linear high-density polyethylene / high-density polyethylene, low-density polyethylene /
High density polyethylene, various polyethylene / thermoplastic polyester, polypropylene / thermoplastic polyester,
Polyolefin fibers such as various polyethylene / nylon 6, polypropylene / nylon 6, binary copolymers of propylene and other α-olefins or ternary copolymers / nylon 6 can be mentioned.

The single yarn fineness of the antibacterial fiber of the present invention is not particularly limited, but in order to make the surface area of the fiber as large as possible and position the antibacterial agent on the surface layer of the fiber, it is desirable that the fineness is as small as possible. Be done. When used for medical protective materials, etc., excellent flexibility is required, so that it is preferably 5 denier or less, particularly 2 denier or less.

The cross-sectional shape of the antibacterial fiber can be circular or irregular. In the case of the irregular cross section, for example, a flat shape, a polygon such as a triangle to an octagon, a T-shape, a multilobe shape, an elliptical shape, a hollow cross-section, and the like can be used, and the shape is not particularly limited. . Further, in the antibacterial fiber of the present invention, additives such as a surfactant, a stabilizer, a flame retardant, and a coloring agent which are usually used for fibers can be used as necessary within a range not hindering the effects of the present invention. it can.

As an example of the method of producing the antibacterial fiber of the present invention, a method of attaching polylysine or its salt to the fiber surface will be described. First, a long fiber made of the above resin is spun out and drawn by using an ordinary melt spinning machine. At the time of spinning, the take-up speed is preferably about 100-1500 m / min. The stretching may be performed in multiple stages if necessary, and the stretching ratio is usually about 1.5 to 7.0 times. Further, the obtained tow is crimped if necessary, and then cut into a predetermined length to obtain short fibers. Although an example of the manufacturing process of short fibers is disclosed above, it is formed into a non-woven fabric, a spun yarn, a knitted woven fabric, a fiber molded product, or the like through a higher-order processing process if necessary.

In this step, after spinning the fiber, an aqueous solution or alcohol solution of polylysine or its salt is attached to the fiber. The polylysine concentration of this aqueous solution or alcohol solution is preferably 0.1 to 25% by weight in terms of pure content, and is adjusted appropriately before use. As a method of adhesion, a roller method, a dipping method, a spraying method, a pad drying method, or the like can be used. The adhesion may be carried out in any of the spinning process, the drawing process and the crimping process, but it is possible to achieve uniform adhesion when mixed and used in various fiber oil agents used in the usual spinning process and drawing process, and It is simple and preferable. The amount of polylysine attached to the fiber is 0.01 to 5% by weight in terms of pure content based on the weight of the fiber. If it is less than 0.01% by weight, the antibacterial effect is weak, and if it exceeds 5% by weight, the antibacterial property almost reaches a saturated state, and it is meaningless to increase the content, and it is not economically preferable. Similarly, when the long fibers are used as they are, the antibacterial fibers may be similarly attached with an aqueous solution or alcohol solution of polylysine or a salt thereof in the spinning step and the drawing step. Further, regardless of whether it is a short fiber or a long fiber, a process other than the spinning process, the drawing process, and the crimping process, for example, the primary or secondary fiber product (nonwoven fabric, spun yarn, filament yarn, knitted woven fabric, or fiber molded product) is formed, and then the above-mentioned adhesion method Can also be attached.

A polymer whose fiber material does not have a functional group having affinity with polylysine or a salt thereof, such as a polyolefin-based material, may be, for example, kneading a surfactant or forming a void on the fiber surface. By modifying, it is possible to greatly improve the adhesive force when polylysine or a salt thereof is attached to the surface.

Next, as a most preferable method for obtaining the antibacterial fiber of the present invention, a method of kneading polylysine or a salt thereof into the fiber will be described. 0.01-5% by weight, preferably 0.1-3, in terms of pure content, based on the total fiber weight
% Of polylysine or its salt is mixed and added to the polyolefin resin. When the content of polylysine is less than 0.01% by weight, it is difficult to obtain a sufficient antibacterial effect.
On the other hand, if it exceeds 5% by weight, the antibacterial property almost reaches the saturated state, there is no meaning to increase the content, the cost becomes high, and the spinning stability becomes disadvantageous, which is not preferable.

When polylysine or its salt is kneaded into a polymer whose fiber material does not have a functional group having an affinity with polylysine or its salt, such as a polyolefin type, the kneaded polylysine or its salt is bleeding. It is easy to get out, and the concentration of polylysine or its salt is higher in the outer layer portion than in the inner layer portion, so that an antibacterial fiber having an excellent antibacterial effect can be obtained. Furthermore, among olefin resins, high density and high crystallinity resins such as high density polyethylene and high crystallinity polypropylene are used, or they are stretched at least 4 times to be highly oriented, and polylysine or its salt is kneaded. The bleed-out of polylysine or a salt thereof to the outer layer of the fiber can be further promoted by placing the incorporated antibacterial fiber under high temperature and high humidity.
Fibers obtained by kneading polylysine or a salt thereof into polyolefin fibers have excellent washability,
It has a particularly preferable effect that the antibacterial effect is highly durable.

The polylysine or its salt used in the present invention preferably has an average particle size of 5 μm or less. Particle size is 5 μm
If it exceeds the range, filter clogging or yarn breakage is likely to occur during melt spinning, which makes it difficult to use. Particularly when considering application to medical hygiene materials, yarns having a single fiber denier of about 2 deniers are required, and if the particle diameter is large, yarn breakage and pack pressure are undesirably increased. Therefore, the average particle size of polylysine used in the present invention is 5 μm or less, more preferably 2 μm.
m or less is desirable.

In the present invention, the antibacterial agent kneaded into the fiber is
Either polylysine or a salt thereof may be used, but a polylysine salt is preferable in view of thermal stability during melt spinning. Even when a polylysine salt is used, it is desirable to set the addition step and the spinning temperature to 260 ° C or lower.
This is because when the temperature exceeds 260 ° C, the antibacterial effect is maintained, but coloring gradually occurs.

Further, when polylysine or a salt thereof is kneaded, the fiber should be a sheath-core type composite fiber, and the polylysine should be contained only in the polyolefin resin of the sheath component in view of mechanical properties, spinning stability and cost. To more desirable. When the types of polymers of the core component and the sheath component are different, the composite ratio is 20/80 to 8 for the core component / the sheath component (weight ratio).
It is preferably 0/20, particularly 40/60 to 60
It is more preferably / 40. When it exceeds 80/20, the sheath component is likely to be broken and the productivity is lowered. On the other hand, if it is less than 20/80, the original fiber performance of the core component is deteriorated.

Further, by using the same polymer for both the sheath and the core and kneading and adding polylysine or a salt thereof only to the sheath portion, there is no boundary between the sheath component and the core component, antibacterial property, mechanical properties and spinning stability. It is possible to obtain an antibacterial fiber made of a homopolymer which is desirable in terms of properties and cost.

As a method for producing a nonwoven fabric made of the antibacterial fiber of the present invention, for example, a short-weight fiber of the antibacterial fiber is used to prepare a web having a required basis weight by a carding method or an air laid method. Alternatively, the web may be directly formed by a melt blow method, a spun bond method, or the like. The web produced by the above method can be processed by a known method such as a needle punch method, a suction dryer method, a high pressure water flow method, a hot air drying device, an ultrasonic fusing device, or a hot roll method to obtain a nonwoven fabric. The basis weight of this non-woven fabric is not particularly limited, but is preferably 10 g / m ² or more and 200 g / m ² or less. When the basis weight is less than 10 g / m ² , not only is the basis weight too low to make it difficult to produce a uniform nonwoven fabric, but the utility value as a nonwoven fabric is poor. On the other hand, when the fabric weight exceeds 200 g / m ² , the fabric weight is too high, and the nonwoven fabric becomes thick and hard, which is not preferable especially as a material for medical hygiene nonwoven fabric.

The above-mentioned non-woven fabric can be produced by mixing the antibacterial fiber of the present invention with other fibers, if necessary, within a range that does not impair the effects of the present invention. Other fibers include synthetic fibers such as polyamide, polyester, polyolefin, and acrylic, natural fibers such as cotton, wool, and hemp,
Examples include regenerated fibers such as rayon, cupra, and acetate, and semi-synthetic fibers.

The antibacterial non-woven fabric obtained by the present invention may be used alone, or may be used in the state of being laminated or integrated with other non-woven fabrics, knitted fabrics or mesh-like materials, films, molded articles and the like. You may. The non-woven fabric may be made of short fibers or long fibers. In the case of long fibers, the non-woven fabric may be directly made into a non-woven fabric by a melt blow method, a spun bond method or the like. In addition to the antibacterial non-woven fabric, the antibacterial fiber of the present invention and other fibers are mixed by a method such as cotton, mixed spinning, mixed fiber, mixed twisting, mixed knitting, and mixed fiber, and primary fibers such as knitted fabrics and fiber molded articles. Can be a product. Further, if necessary, these non-woven fabrics are subjected to secondary processing, and clothing fields such as underwear, shirts, blouses, socks, socks, and pantyhose, padding, futon side cloth, sheets, bed covers, pillow covers, cushions, etc. Medical equipment such as bedding, surgical masks, surgical clothes, caps, medical examination clothes, gauze, bed sheets, bandages, eye patches, sanitary materials such as diapers, incontinence pads, carpets, curtains, furniture Buffer,
Furniture and interior fields such as wallpaper, shoe linings, insoles,
Fields such as footwear materials, fruit protection materials, agricultural and horticultural materials such as food damage prevention materials, confectionery packaging materials, food packaging materials, furoshiki, towels, hand towels, scrubbing brushes, table cloths, aprons, kitchen wipes, kitchen gloves, makeup puffs It can be used in a wide range of fields, such as daily life related materials such as tea bags and wiping cloths, and industrial materials such as filter materials.

[0030]

The antibacterial fiber of the present invention exhibits antibacterial properties due to the attached or kneaded polylysine and its salt. Regarding the antibacterial action of polylysine, mold growth inhibitory action, Escherichia coil, Staphylococcus aur
eus), Pseudomonas aeru
ginosa), Bacillus subt
ilis) and other gram-positive and gram-negative bacteria. Although the details of these antibacterial actions are unknown, anionic constituents in the cell wall of the bacterium are adsorbed by the cationic amino group at the α-position of polylysine, resulting in inhibition of cell wall biosynthesis or substances inside or outside the wall. It is presumed that the antibacterial action is expressed because the active transport of erythrocyte is blocked. The antibacterial fiber of the present invention exhibits an excellent antibacterial effect. Furthermore, many molds and bacteria that exist around us are
Proliferates with sweat adsorbed on underwear and causes odor, but the antibacterial fiber of the present invention suppresses the growth of these molds and bacteria,
It is possible to suppress the generation of odors, and it also has odor and mold resistance.

[0031]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the performance evaluation in the examples was according to the following method.

Antibacterial property test (measurement of difference in increase / decrease in antibacterial number) Measured by the following method in accordance with "manufacturing effect evaluation test manual for antibacterial / deodorant processed product / bacteria number measuring method" (Textile Products Hygiene Processing Association, 1988) . Klebsiella Newmonani [K. pneumoni
ae (IF013277)] is a test piece
(0.2 g) is inoculated with 0.2 ml (the number of bacteria is about 6 × 10 ⁵ cells / ml), and cultured at a temperature of 37 ° C. for 18 hours. After the cultivation, the bacteria on the test piece were extracted with a phosphate buffer, the bacteria produced on the test piece were measured by the standard agar medium method, and the difference in the number of bacteria was calculated by the following formula. Unprocessed sample [A] Number of viable bacteria immediately after inoculation [B] Number of viable bacteria after 18-hour culture Antibacterial processed sample [C] Number of viable bacteria after 18-hour culture Increase / decrease in number of bacteria = log ₁₀ (B / A) −log ₁₀ (C / A) The difference in the increase / decrease in the number of bacteria obtained by the above formula is 1.6
If it is above, it will function enough as antibacterial performance. on the other hand,
When the difference in the number of bacteria increases or decreases less than 1.6, the antibacterial performance becomes insufficient and microorganisms propagate.

Spinnability: The spinnability during melt spinning was evaluated by the following three grades based on the occurrence rate of yarn breakage. ：: No breakage of yarn occurred and operability was good. Δ: Thread breakage occurred twice per hour. ×: Thread breakage occurs three times or more per hour, which is a problem in operation.

Stretchability: Stretchability was evaluated according to the following three grades based on the occurrence rates of yarn breakage and single yarn breakage. ◯: No yarn breakage or single yarn breakage occurs, and operability is good. Δ: Thread breakage or single thread breakage occurred twice per hour. ×: Thread breakage occurs three times or more per hour, which is a problem in operation.

Distribution of polylysine: Ninhydrin was dropped on the cross section of the fiber and reacted with polylysine or its salt to develop a color, and then the surface layer and the inside were evaluated according to the following three grades. ◯: When a large difference was observed in coloration between the outer layer portion and the inner layer portion. Δ: When a color difference between the outer layer portion and the inner layer portion was observed. X: When there is no difference in coloration between the outer layer portion and the inner layer portion.

Washing test: Evaluation was performed according to JIS L0217-103. Use a household electric washing machine and use a neutral detergent 2
After washing for 5 minutes in a 40 ° C. aqueous solution containing g / l, running water was performed for 2 minutes for dehydration, and further running water was washed for 2 minutes for dehydration and drying. This was repeated 3 times, and the antibacterial property was evaluated by the above antibacterial property test.

Examples 1 to 6 Polypropylene (MFR: 16 g / 10 minutes, 230 ° C.)
High-density polyethylene (MFR: 16g /
10 minutes, 190 ° C.) as a sheath component, pore diameter 0.6 mm,
A sheath-core type composite fiber having a sheath-core ratio of 50/50 and a single yarn denier of about 7.5 d / f was spun using a sheath-core type spinneret having 350 holes. In the take-up step, a fiber oil containing ε-poly-L-lysine was attached by a touch roll. The obtained undrawn yarn was drawn 4.3 times at 110 ° C., mechanically crimped, heat-treated at 100 ° C. to suppress shrinkage, and then cut into a predetermined length to obtain a short fiber. These short fibers have about 15 crimps / 25 mm inch and a cut length of 51 m.
m, the single yarn fineness was about 2.0 denier. The obtained short fibers were made into a web by a card machine and heat-treated at 140 ° C. using a suction band dryer to obtain a nonwoven fabric having a basis weight of about 30 g / m ² .

Comparative Example 1 A nonwoven fabric was obtained by the same steps as in Examples 1 to 6 except that ε-poly-L-lysine was not added to the fiber oil agent and only the fiber oil agent was attached to the touch roll.

[0039] The amount of ε-poly-L-lysine attached to the fiber weight of the short fibers obtained in Examples 1 to 6 and Comparative Example 1, the difference in the bacterial count increase / decrease value of the non-woven fabric, the distribution of ε-poly-L-lysine,
The results of the washing test are shown in Table 1.

[0040]

[Table 1]

As is clear from Table 1, the fibers of Examples 1 to 6 of the present invention to which ε-poly-L-lysine is adhered in a certain amount or more have excellent antibacterial properties. However, ε
-Because poly-L-lysine is only attached to the surface of the fiber made of a resin having no affinity, it has an antibacterial effect after the washing test, as compared with the below-mentioned fiber in which the polylysine is kneaded into the fiber. Is hard to last.

Examples 7 to 11 and Comparative Examples 2 and 3 High density polyethylene (MFR: 16 g / 10 min, 190
(° C), the amount of ε-poly-L-lysine hydrochloride powder shown in Table 2 was added, and the mixture was kneaded at 200 ° C using a single-screw vent extruder manufactured by Yamaguchi Seisakusho to give pellets. Polypropylene (MFR: 16 g / 10 min, 230 ° C.) was used as a core component, and high-density polyethylene in which the hydrochloride of ε-poly-L-lysine was kneaded was used as a sheath component. Using a sheath-core type spinneret of 350, a sheath-core type composite fiber having a sheath-core ratio of 50/50 and a single yarn denier of about 7.5 d / f was spun. The unstretched yarn obtained was 4.3 at 110 ° C.
10 times to reduce the shrinkage
After heat treatment at 0 ° C., it was cut into a predetermined length to obtain short fibers. These short fibers were short fibers having a crimp number of about 15/25 mm, a cut length of 51 mm, and a single yarn fineness of about 2.0 denier. The obtained short fibers are made into a web with a card machine,
It was heat-treated at 140 ° C. using a suction band dryer to obtain a nonwoven fabric having a basis weight of about 30 g / m ² . The amount of ε-poly-L-lysine added to the short fiber weight of the fibers obtained in Examples 7 to 11 and Comparative Examples 2 and 3, spinnability, stretchability, difference in the number of bacteria increase / decrease, ε-poly-L- Distribution of lysine hydrochloride,
The results of the washing test are shown in Table 2.

[0043]

[Table 2]

As is clear from Table 2, in Examples 7 to 11 of the present invention, the short fibers containing a certain amount of ε-poly-L-lysine have excellent anti-bacterial properties, spinnability and drawability. You can see that However, in Comparative Example 2, the content of ε-poly-L-lysine hydrochloride is low and the antibacterial property is low. In addition, Comparative Example 3 exhibits excellent antibacterial properties, but since the kneading amount is large, the spinnability and stretchability are poor, and there are problems in terms of productivity and cost. In addition, since ε-poly-L-lysine hydrochloride was kneaded into the fiber, the antibacterial property after the washing test showed good results as compared with Examples 1 to 6.

Example 12 Polypropylene (MFR: 16 g / 10 minutes, 230 ° C.)
High-density polyethylene (MFR: 16g /
10 minutes, 190 ° C.) as a sheath component, pore diameter 0.6 mm,
A sheath-core type composite fiber having a sheath-core ratio of 50/50 and a single yarn denier of about 7.5 d / f was spun using a sheath-core type spinneret having 350 holes. In the take-up step, a fiber oil agent added with ε-poly-L-lysine hydrochloride was attached by a touch roll. The obtained undrawn yarn was drawn 4.3 times at 110 ° C,
After mechanical crimping and heat treatment at 140 ° C. to suppress shrinkage, short fibers were cut into a predetermined length. These short fibers have about 15 crimps / inch and a cut length of 51 m.
m, the single yarn fineness was about 2.0 denier. The obtained short fibers were made into a web by a card machine and heat-treated at 100 ° C. using a suction band dryer to obtain a nonwoven fabric having a basis weight of about 30 g / m ² . As described above, Examples 7 to 1
The polylysine hydrochloride mentioned in 2 is a typical example of an inorganic acid, and the same effects of the present invention can be obtained even if other sulfate, phosphate or hydrobromide is used.

Example 13 ε-Poly-L instead of ε-Poly-L-lysine hydrochloride
A non-woven fabric was obtained by the same steps as in Example 12 except that the lysine propionate was added to the fiber oil agent. The polylysine propionate described in Example 13 is a typical example of organic acid, and the same effect of the present invention can be obtained by using other acetic acid, fumaric acid, malic acid or citric acid.

The amount of ε-poly-L-lysine salt attached to the fibers in the nonwoven fabrics obtained in Examples 12 and 13, the difference in the increase / decrease value of the number of bacteria, the distribution of ε-poly-L-lysine salt, and the washing test The results are shown in Table 3.

[0048]

[Table 3]

As is clear from Table 3, the short fibers of Examples 12 and 13 of the present invention containing a certain amount of the salt of ε-poly-L-lysine have excellent antibacterial properties. However, since the ε-poly-L-lysine salt was only attached to the surface of the fiber made of a resin having no affinity, the antibacterial effect after washing showed a smaller value than in Examples 7 to 14.

Example 14 The antibacterial nonwoven fabric prepared in Example 8 was heated at 90 ° C. and RH 80%.
It was left under high temperature and high humidity for 1 hour. Table 2 shows the results of the difference in the bacterial count increase / decrease values of this antibacterial nonwoven fabric and the distribution of ε-poly-L-lysine hydrochloride. As is clear from Table 2, the bleeding out to the outer layer portion was promoted by placing it under high temperature and high humidity, and the antibacterial property was improved as compared with Example 8.

[0051]

The antibacterial fiber of the present invention has excellent antibacterial properties. Moreover, since polylysine or its salt used as a preservative for food is used as an antibacterial agent, it has very little effect on the human body during use and is very safe. For this reason, it can be used in various wide fields as an antibacterial fiber product.

[Procedure amendment]

[Submission date] November 12, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction contents]

Example 12 Polypropylene (MFR: 16 g / 10 minutes, 230 ° C.)
High-density polyethylene (MFR: 16g /
10 minutes, 190 ° C.) as a sheath component, pore diameter 0.6 mm,
A sheath-core type composite fiber having a sheath-core ratio of 50/50 and a single yarn denier of about 7.5 d / f was spun using a sheath-core type spinneret having 350 holes. In the take-up step, a fiber oil agent added with ε-poly-L-lysine hydrochloride was attached by a touch roll. The obtained undrawn yarn was drawn 4.3 times at 110 ° C,
After mechanical crimping and heat treatment at 100 ° C. to suppress shrinkage, short fibers were cut into a predetermined length. These short fibers have about 15 crimps / inch and a cut length of 51 m.
m, the single yarn fineness was about 2.0 denier. The obtained short fibers were made into a web by a card machine and heat-treated at 140 ° C. using a suction band dryer to obtain a nonwoven fabric having a basis weight of about 30 g / m ² . As described above, Examples 7 to 1
The polylysine hydrochloride listed in 2 is a typical example of an inorganic salt, and the same effects of the present invention can be obtained even when other sulfate, phosphate or hydrobromide is used.

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Claims (8)

[Claims] 1. A fiber comprising a thermoplastic resin in which polylysine or a salt thereof does not have a functional group having an affinity with the polylysine or a salt thereof, and 0.01 to 5 in terms of a pure content based on the weight of the fiber. An antibacterial fiber, which is contained by weight%, wherein the amount of the polylysine or its salt present in the fiber is higher in the outer layer than in the inner layer. 2. The antibacterial fiber according to claim 1, wherein the thermoplastic resin is a polyolefin resin and the fiber is a polyolefin fiber. 3. The antibacterial fiber according to claim 2, wherein the polyolefin fiber is a composite fiber composed of at least two components. 4. The antibacterial fiber according to claim 1, wherein the salt of polylysine is at least one inorganic acid selected from hydrochloric acid, sulfuric acid, phosphoric acid and hydrobromic acid. 5. A salt of polylysine is acetic acid, propionic acid,
The antibacterial fiber according to any one of claims 1 to 3, which is at least one organic acid selected from fumaric acid, malic acid, and citric acid. 6. A non-woven fabric using the antibacterial fiber according to claim 1. 7. A knitted fabric using the antibacterial fiber according to any one of claims 1 to 5. 8. A fiber molding using the antibacterial fiber according to any one of claims 1 to 5.