JPH0813252A - Alginic acid-based fiber, its production and product therefrom - Google Patents

Abstract

PURPOSE:To obtain an alginic acid-based fiber being flexible when drying without causing gluing of fiber, excellent in mechanical characteristics such as dry strength, dry elongation, knot strength, knot elongation, etc., having excellent properties even when formed into nonwoven fabric, woven fabric or paper and especially suitable as a medical fiber. CONSTITUTION:A water-soluble alginic acid monovalent salt aqueous solution is spun in a hydrochloric acid bath to afford an alginic acid fiber. The alginic acid fiber is introduced into a divalent metal salt aqueous solution (preferably >=pH 7) to afford an alginic acid divalent metal salt fiber defined by the formula and having 60-90wt.% of the divalent metal salt ratio. The resultant alginic acid divalent metal salt fiber is dehydrated by a hydrophilic organic solvent and dried. This alginic acid-based fiber contains the divalent metal and has 60-90% divalent metal salt forming ratio, >=1.5h/d dry strength and >=8% dry elongation. A nonwoven fabric, woven fabric, paper, especially a material for applying to wounded face or hemostatic cotton as a medical fiber product is produced from the fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a water-insoluble alginate fiber and a method for producing the same. More particularly, the present invention relates to a water-insoluble alginate-based fiber itself which has no sticking to fibers, is suitable for nonwoven fabrics, woven fabrics and papermaking, has excellent mechanical properties such as strength and elongation, and a method for producing the same. The present invention also relates to an alginic acid-based fiber itself having antibacterial properties in addition to the properties of the water-insoluble alginate-based fiber, and a method for producing the same. Further, the present invention relates to nonwoven fabrics, woven fabrics and papermaking using these water-insoluble alginate fibers. The water-insoluble alginic acid-based fiber of the present invention is particularly useful as a fiber material for medical use such as a wound surface material and hemostatic cotton.

[0002]

The monovalent metal salt of alginic acid is water-soluble, and the monovalent metal salt of alginic acid is substantially dissolved by spinning the monovalent metal salt aqueous solution of alginic acid in a coagulating bath consisting of a hydrochloric acid solution or a divalent metal salt aqueous solution. Water-insoluble alginate fiber (hereinafter referred to as alginate fiber) that has been replaced with hydrogen selectively,
Alternatively, it has been conventionally known to obtain a water-insoluble alginate-based fiber in which a monovalent metal is substantially substituted with a divalent metal (hereinafter, referred to as a divalent metal alginate fiber).

[0003] For example, to extrude an aqueous solution of a monovalent metal salt of alginic acid while using an aqueous solution containing calcium ions as a coagulation bath to produce fibers of a bivalent metal alginate salt,
British Patent Nos. 5,676,641, 5,687,71, 5,571,657, 6,249,87 and 13,947
No. 41, No. 4,421,583, JP-A-61-1744.
No. 99, JP-A-5-209318.

[0004] Since divalent metal alginate fibers, particularly calcium alginate fibers, gel with 0.9% saline, when used on the wound surface, they absorb the exuding bodily fluid and gel to protect the wound surface. It is known to help regenerate the skin. Moreover, since the alginic acid divalent metal salt fiber has a high affinity with body fluids and is naturally absorbed in the body, it is not necessary to remove the gelation product on the wound surface in order to replace the wound surface material. Is known to be good. It is known that alginic acid bivalent metal salt fibers have a higher hemostatic effect than alginic acid fibers.

Utilizing such properties, the bivalent metal salt of alginic acid fiber is used as a fiber for a coating material or a raw material fiber for paper for medical use.

[0006]

However, alginic acid fibers such as alginic acid fibers and divalent metal alginate fibers produced by the above-mentioned conventional method have a certain degree of strength but lack flexibility. In particular, it was unsuitable for processing into a nonwoven or woven fabric.

Alginic acid fibers such as alginic acid fibers or alginic acid divalent metal salt fibers produced by the above-mentioned conventional method usually contain 200% or more of water after spinning, and a drying step of drying this water is carried out. In, the adjacent fibers are glued to each other to form a so-called glued fiber. If the fibers are stuck together, the alginate fibers become brittle and the mechanical properties are extremely low. Alginic acid-based fibers having such agglutination are unsuitable for use as raw materials for nonwoven fabrics and woven fabrics that require fibers in a defibrated state during the manufacturing process.

[0008] As an example of using dried bivalent metal alginate fiber fibers as a product, there is a sheet-shaped wound dressing material.
This is hard when dry and the strength of the sheet is low, so it easily breaks apart and is not practical as a wound dressing material.

When the alginic acid-based fibers containing water are dried so that the fibers do not come into contact with each other in order to avoid the sticking of the fibers, the drying efficiency is poor, and the sticking of the alginic acid-based fibers cannot be completely prevented. Therefore, the alginic acid-based fiber is stored in a wet state without being dried, and the wet state is exclusively used for paper production. However, even when such alginate fibers in a wet state are wet-processed,
When it is dried thereafter, it is unavoidable that the fibers are adhered to each other, and it has a plate-like (sulfur-like) shape and poor flexibility.

As described above, alginic acid divalent metal salt fibers are used as medical fibers for coating materials or as raw material fibers for paper. However, a solution of the divalent metal salt is spun as a spinning bath and dried. The resulting divalent metal alginate fiber had high strength, but had the drawback of lacking flexibility and brittleness, and had extremely low dry elongation, knot elongation and knot strength. For this reason, such dried alginic acid divalent metal salt fibers lacked utility in the medical field such as wound dressing materials and hemostatic cotton.

Therefore, the present invention solves the above-mentioned problems, there is no sticking of fibers, it is flexible when dried, and it has excellent mechanical properties such as dry strength, dry elongation, knot strength and knot elongation, Further, it is an object of the present invention to provide an alginate-based fiber, a method for producing the same, and a product thereof, which have excellent properties even when this fiber is used as a nonwoven fabric, a woven fabric, or papermaking, and which is particularly suitable as a medical fiber. Another object of the present invention is to provide an alginic acid-based fiber having antibacterial properties, a method for producing the same, and a product thereof in addition to the above objects.

[0012]

The alginic acid fiber of the present invention contains a divalent metal, has a divalent metal salinization rate defined by the following formula (1) of 60 to 90%, and a dry strength of 1. 5 g
/ D or more and a dry elongation of 8% or more.

[0013]

[Equation 4] Another alginate-based fiber of the present invention is characterized by containing an antibacterial compound in addition to the above properties.

The production method of the present invention for producing an alginic acid-based fiber having the above-mentioned properties is (2) obtained by spinning (1) an aqueous solution of a water-soluble monovalent alginic acid salt into a hydrochloric acid bath to obtain an alginic acid fiber. By introducing the alginic acid fiber into the aqueous solution of the divalent metal salt, the metal is substituted to obtain the divalent metal chlorinated alginate fiber, and (3) the obtained divalent metal chlorinated alginate fiber is dehydrated with a hydrophilic organic solvent. Characterize.

The production method of the present invention for producing an alginic acid-based fiber having the above-mentioned properties is (1) spinning an aqueous solution of a water-soluble monovalent alginic acid salt into a hydrochloric acid bath to give an alginic acid fiber, and (2) obtaining The resulting alginic acid fiber is subjected to metal substitution by introducing it into an aqueous solution of a divalent metal salt adjusted to pH = 7 or above, and the divalent metal salinization ratio defined by the above formula (1) is 60 to 90%. A valent metal chlorinated alginate fiber is obtained, and (3) the obtained divalent metal chlorinated alginate fiber is dehydrated with a hydrophilic organic solvent.

The method for producing an alginic acid fiber containing an antibacterial compound according to the present invention comprises the steps of (1) adding an antibacterial compound to a water-soluble monovalent alginate aqueous solution and spinning the resulting mixture in a hydrochloric acid bath. (2) The obtained alginic acid fiber is introduced into an aqueous solution of a divalent metal salt adjusted to pH = 7 or more to replace the metal, and the above-mentioned formula (1) is obtained.
A divalent metal chlorinated alginic acid fiber having a divalent metal chlorination rate of 60 to 90% defined in (3) is obtained, and (3) the obtained divalent metal chlorinated alginic acid fiber is dehydrated with a hydrophilic organic solvent. .

The nonwoven fabric of the present invention is characterized by being manufactured using the alginate fiber of the present invention.

The woven fabric of the present invention is characterized by being manufactured using the alginic acid fiber of the present invention.

The papermaking machine of the present invention is characterized by being manufactured using the alginic acid fiber of the present invention.

The medical fiber product of the present invention is characterized by being manufactured using the alginate fiber of the present invention.

The alginic acid-based fiber of the present invention is free from sticking and is highly flexible, especially even in a dry state and has excellent openability, so that it can be easily processed into a non-woven fabric, a woven fabric and a papermaking machine.
Moreover, since it is excellent in dry strength, dry elongation, knot strength, and knot elongation, it is useful as a medical fiber product, particularly as a medical material such as a wound surface material and hemostatic cotton.

The alginic acid fiber of the present invention needs to have a divalent metal salinity of 60 to 90%. Water-insoluble alginate-based fibers substantially substituted with a divalent metal having a divalent metal salinity of more than 90% are embrittled, have low elongation, and are easily broken. 60%
This is because if it is less than the above range, the fibers start to stick to each other and lack in flexibility.

The divalent metal salt ratio of the alginate fiber is defined by the above formula (1). That is, the divalent metal salification ratio is defined as a value based on the theoretical value of a divalent metal obtained by substituting 100% of hydrogen of a carboxyl group of alginic acid.
This is the percentage of the divalent metal actually substituted. When the divalent metal salinization rate is less than 100%, the remaining carboxyl groups remain as they are, or are replaced with other monovalent cations such as ammonium ions. When the divalent metal salt ratio is low, the solubility in water increases, and especially when the concentration becomes high in alginic acid, the above-described problem occurs. The term “substantially substituted by a divalent metal” used in the description of the prior art in the present specification corresponds to a state where the divalent metal chloride ratio exceeds 90%.

In the alginic acid fiber of the present invention, the divalent metal salt forming site may be unevenly distributed in the surface layer of the fiber,
Further, it may be uniformly present inside the fiber, and in any case, if the divalent metal salinization ratio is 60 to 90%, the object of the present invention can be achieved. The method for producing the alginate fiber of the present invention will be described in more detail below.

First, a stock solution containing no antibacterial compound or one containing an antibacterial compound is prepared as a spinning dope. The spinning solution is spun into a hydrochloric acid bath as a coagulation bath to form alginic acid fibers. By introducing the obtained alginic acid fiber into a divalent metal salt exchange bath consisting of a divalent metal salt aqueous solution adjusted to pH = 7 or more, a divalent metal is introduced into a carboxyl group in the alginic acid fiber,
Metal substitution as a divalent metal salt of carboxylic acid. The metal salt ratio of the obtained alginate fiber must be such that the divalent metal salt ratio defined by the above formula (1) is 60 to 90%. The bivalent metal chloroalginate fiber is dehydrated with a hydrophilic organic solvent. Then, the dehydrated divalent metal chlorinated alginic acid fiber is dried to obtain the dried alginic acid fiber of the present invention.

According to the method for producing alginate-based fibers of the present invention, the divalent metal chloride ratio in the obtained alginate-based fibers can be 60 to 90%, and therefore, the fibers exhibit flexibility during drying and have a high dryness. Alginate fibers having a strength of 1.5 g / d or more and a dry elongation of 8% or more can be obtained.

Preparation of stock solution for spinning The monovalent metal alginate used in the production of the alginate fiber of the present invention can be obtained on a common market. Examples of the alginic acid monovalent salt include sodium as a monovalent cation,
Potassium, magnesium, ammonium and the like may be bonded to alginic acid to form a salt, and these monovalent alginic salts are water-soluble. This monovalent metal alginic acid salt is dissolved in ion-exchanged water to obtain a spinning solution (spinning solution). The concentration of the spinning solution is preferably 3 to 6% by weight of the polymer concentration.

On the other hand, for the purpose of producing alginic acid-based fibers imparted with antibacterial properties, it can be produced by adding an antibacterial agent to the spinning solution obtained by the above method. As the antibacterial agent added to the spinning dope, for example, a quaternary ammonium salt having 10 or more carbon atoms, copper zeolite, silver zeolite and the like are suitably used. Particularly preferred is an antibacterial agent soluble in the spinning solution, and among the quaternary ammonium salts, a benzalkonium chloride salt is suitably used. The benzalkonium chloride salt is preferably approved and used as an antibacterial agent according to the Japanese Pharmacopoeia.

When the antibacterial agent does not dissolve in the spinning dope, it is used in the form of a fine powder dispersed in the spinning dope. The addition amount of the antibacterial agent is preferably 0.1 to 5% by weight based on the alginate. A method for producing the alginate-based fiber of the present invention using a spinning stock solution to which an antibacterial agent is added,
It can be produced by the same method as the method for producing the alginic acid-based fiber of the present invention using a spinning dope containing no antibacterial agent.

Coagulation bath For the coagulation bath, an aqueous hydrochloric acid solution is used. Its concentration is 5-1
0 g / l is preferred. The coagulation bath may be a multi-stage bath, and a method of sequentially decreasing the concentration may be employed. The temperature of the coagulation bath is not particularly limited, and is applied at normal temperature.

Divalent metal salt exchange bath The divalent metal salt exchange bath used for producing the alginate fiber of the present invention uses an aqueous solution of a divalent metal salt containing ammonia. The divalent metal salt includes salts of calcium, barium, nickel, cobalt and the like. In particular, when a calcium salt is used, the obtained alginic acid-based fiber containing calcium gels the exuding body fluid to protect the wound surface and aids the regeneration of the skin, so it is suitable for medical purposes. To be done.

The ratio of the divalent metal salt concentration to the ammonia concentration in the divalent metal salt exchange bath is adjusted so that the divalent metal salt is at least equimolar to ammonia. More preferably, the ratio is adjusted to about 1.1 to 1.4 mol of the divalent metal salt with respect to 1 mol of ammonia. Specifically, ammonia 3 to 10 g /
An aqueous solution of 10 to 30 g / liter of calcium chloride is preferred.

The pH of the divalent metal salt exchange bath is preferably adjusted to the basic side. The pH is preferably adjusted to a basic side of pH = 7 or more, particularly to pH = 8.0 to 9.0. If the pH is shifted to the acidic side, the divalent metal salt conversion rate of the alginate fiber becomes low, while if the pH is higher than 9.0, the substitution amount of the divalent metal salt becomes large, and the alginate fiber becomes This is because even if the divalent metal salt ratio increases and the fiber strength increases, the fiber elongation is low and the flexibility is lacking. By this pH adjustment, 10 to 40% of the carboxyl groups of alginic acid are not replaced by the divalent metal salt and remain as carboxyl groups or in the form of being substituted by ammonium.

The adjustment of the divalent metal salinization rate can be performed by the following method in addition to the above-described method of adjusting the pH. That is, when the gel-like alginate fiber after spinning is brought into contact with an aqueous solution of a divalent metal salt, the contact can be performed by adjusting the contact time, or by adjusting the concentration of the divalent metal salt, or by combining these. it can. Usually, the metal is exchanged by continuously or batchwise passing through a plurality of divalent metal salt exchange baths, which are preferably arranged at a stepwise lower concentration.

The divalent metal salt exchange bath may be a single bath, but it is necessary to use a plurality of baths and carry out the metal salt exchange by gradually lowering the concentration. It is effective in reducing the number.

Hydrophilic Organic Solvent Bath A hydrophilic organic solvent bath contains a hydrophilic organic solvent such as alcohols such as methanol, ethanol, isopropanol and normal propanol, ketones such as acetone and MEK, and esters such as methyl acetate and ethyl formate. Can be used. Particularly, methanol is preferable from the viewpoint of easiness of removing the organic solvent. These hydrophilic organic solvents can be used alone or in a mixed system.

It is preferable to arrange the hydrophilic organic solvent bath in multiple stages and gradually increase the concentration to perform slow organic solvent / water substitution, from the viewpoint of reducing the residual water content in the alginate fiber. Usually, the concentration is sequentially increased from an aqueous solution having a concentration of 60%, so that the final bath has a concentration of 99%.

Alginic acid-based fiber production process The alginic acid-based fiber of the present invention is produced in the following manner using the spinning stock solution, the coagulation bath, the divalent metal salt exchange bath and the hydrophilic organic solvent described above. As a spinning method, a usual wet spinning method is applied. That is, the spinning solution is discharged into a coagulation bath aqueous hydrochloric acid solution through a nozzle. Although the temperature of the spinning dope is not particularly limited, it is usually from 25 to 35 ° C, and the coagulation bath temperature is usually from 25 to 35 ° C. The coagulation baths are arranged in multiple stages, and the concentration is gradually reduced to regenerate the alginic acid fibers.

The gel-like alginate fibers taken from the coagulation bath are immediately introduced into the divalent metal salt exchange bath without washing with water. The carboxyl group of the alginic acid fiber becomes a divalent metal salt by the divalent metal salt exchange bath. The gel-like divalent metal chlorinated alginate fiber that has exited the divalent metal salt exchange bath contains 200 to 300% of water, depending on the elongation in the previous step. If this moisture is removed by a dryer, the fibers will stick together and become brittle, so in the present invention, dehydration is performed with a hydrophilic organic solvent.

Next, the organic solvent is preferably removed from the dehydrated fibers by natural drying or hot air drying. Contact drying with a roller or the like is desirably avoided to prevent the fibers from sticking to each other. The drying temperature is set so that the fiber temperature does not exceed 100 ° C. If the drying temperature exceeds 105 ° C., the alginic acid-based fibers become unfavorable because they become brittle. The drawing of the fiber during the alginate-based fiber production process is usually performed in a range of 1.2 times or less.

[0041]

【Example】

[Example 1] Sodium alginate (Grade 1-7F, 1% aqueous solution, manufactured by Kimitsu Chemical Industry Co., Ltd., viscosity at 20 ° C., 775 mPa · s) was added to ion-exchanged water, and sufficiently stirred to prepare a 4% by weight aqueous solution. . This was filtered with a 300 mesh filter and defoamed to obtain a spinning dope.

The above spinning dope was used to form 0.08 mm pores into 25
It was spun from a nozzle with 00 nozzles into a coagulation bath consisting of 15 g / l hydrochloric acid at 35 ° C. Subsequently, the mixture was passed through a divalent metal salt exchange bath consisting of an aqueous solution of 15 g / l calcium chloride at 35 ° C., which was adjusted to pH = 8.5 by supplying ammonia at 5 g / l to obtain divalent metal salt. Was replaced.

Further, 60%, 70%, 80%, 90%,
After sequentially passing through a hydrophilic organic solvent bath composed of a 95% aqueous methanol solution, the film was wound at a speed of 10 m / min.
Further, it was thoroughly washed with a 99% methanol solution, drained with a dehydrator, and then dried with hot air to obtain an alginic acid-based fiber of this Example 1. The performance of the obtained fiber is shown in Table 1 below.

Example 2 The winding speed was 15 m / min.
The alginic acid-based fiber of Example 2 was obtained by the same method as in Example 1 except that the ejection amount was changed to the same fineness as in Example 1. The performance of the obtained fiber is shown in Table 1 below.

Example 3 The winding speed was 20 m / min.
An alginic acid-based fiber of Example 3 was obtained by the same method as in Example 1 except that the discharge amount was changed to the same fineness as in Example 1. The performance of the obtained fiber is shown in Table 1 below.

Example 4 The composition of the divalent metal salt exchange bath was changed to a divalent metal salt exchange bath comprising 10 g / l of ammonia and 30 g / l of calcium chloride, and the winding speed was changed to 20 m / min. The alginic acid-based fiber of Example 4 was obtained in the same manner as in Example 1. The performance of the obtained fiber is shown in Table 1 below.

[0047]

[Table 1] Comparative Example 1 50 g of calcium chloride at 35 ° C.
The production was carried out in the same manner as in Example 1 except that the liter was used and the divalent metal salt exchange bath was omitted. The obtained fiber was used as the fiber of Comparative Example 1.

On the other hand, except that the divalent metal salt exchange bath was omitted, all were produced in the same manner as in Example 1 above. The obtained fiber was used as the fiber of Comparative Example 1. The fiber of Comparative Example 1 was replaced with 1
It was immersed in 0 times water for 10 minutes. Although the fiber after immersion maintained its shape as it was, the pH of water in the fiber was 2.8, which was considerably lower than that of body fluid, and thus could not be used as a wound dressing.

The performances of the fibers of Comparative Examples 1 and 2 are shown in Table 2 below.

[0050]

[Table 2] According to Table 2 above, the conventional alginic acid-based fiber substantially substituted with a divalent metal (that is, the divalent metal alginate fiber of Comparative Example 1) has the same strength and elongation as the alginic acid-based fiber of the present invention. It turns out that it is low compared with. On the other hand, it is understood that the conventional substantially hydrogen-substituted alginic acid fiber (that is, the alginic acid fiber of Comparative Example 1) has the same strength and elongation as the alginic acid fiber of the present invention. The fiber of Comparative Example 1 has a low pH when immersed in water as described above, and is therefore unsuitable for a wound dressing.

Comparative Example 2 A fiber of Comparative Example 2 was produced in the same manner as in Example 1 except that the hydrophilic organic solvent bath of Example 1 was changed to water. When the obtained fiber was dried, it was fixed in a squid-like shape and could not be opened.

Example 5 The spinning dope of Example 1 was
The alginic acid-based fiber of Example 5 was obtained by the same method as in Example 1 except that benzalkonium chloride was added and mixed so as to be 1.0% by weight with respect to alginic acid.
The performance of the obtained fiber is shown in Table 3 below. [Example 6] To the spinning dope of Example 1 above, an antibacterial agent Novalon (trade name: manufactured by Toagosei Co., Ltd.) prepared by adhering silver to zeolite was added so as to be 1.0% by weight with respect to alginic acid. An alginic acid-based fiber of Example 6 was obtained by the same method as in Example 1 except that the fibers were mixed. The performance of the obtained fiber is shown in Table 3 below.

[0053]

[Table 3] Example 7 The alginic acid-based fibers of Examples 1 to 6 and the fiber of Comparative Example 1 were each weighed at 50 g / card by a carding machine.
After forming the m ² web, a nonwoven fabric was manufactured by a needle punching machine. The fibers of Examples 1 to 6 were less likely to be cut and scattered during processing, and each of the obtained nonwoven fabrics had a very soft feel.

On the other hand, the fibers of Comparative Example 1 had a large amount of scattered substances during processing and were difficult to be made into a non-woven fabric. The produced non-woven fabrics were the same as the non-woven fabrics obtained from the fibers of Examples 1 to 6 above. The touch was relatively hard.

Example 8 A fiber sanitary processing effect test was performed on each of the nonwoven fabrics of Example 7 manufactured using commercially available absorbent cotton and alginate-based fibers obtained from Examples 5 and 6. The antibacterial performance was evaluated based on the method (test method determined by the Textile Sanitation Processing Council). The obtained evaluation is shown in Table 4 below.

[0056]

[Table 4] According to Table 4 above, the non-woven fabric of Example 7 produced by using the alginic acid-based fiber of Example 6 is completely sterilized with respect to each test bacterium, but the local absorbent cotton has almost no antibacterial effect. I understand.

Example 9 Each nonwoven fabric produced by the method of manufacturing a nonwoven fabric of Example 7 using each fiber of Examples 1 to 6 and Comparative Example 1 was placed in physiological saline (0.9%). It gelled gradually when immersed. On the other hand, when immersed in a 5% saline solution, it rapidly gelled and dispersed.

These characteristics of the nonwoven fabric using the alginate-based fiber of the present invention are such that, when this nonwoven fabric is used as a material for a wound surface, the gel formed upon contact with body fluid will protect the wound surface softly. And that the patient can replace the wound dressing without pain. Like the antibacterial nonwoven fabric of Example 8, the wound dressing may be provided with antibacterial properties.

Example 10 The alginic acid fiber of Example 10 was obtained in the same manner as in Example 1 except that the organic solvent in the hydrophilic organic solvent bath was changed to ethyl alcohol. The performance of the obtained fiber is shown in Table 5 below.

Example 11 An alginic acid fiber of Example 11 was obtained by the same method as in Example 1 except that the organic solvent in the hydrophilic organic solvent bath was changed to isopropyl alcohol. The performance of the obtained fiber is shown in Table 5 below.

Example 12 The alginic acid fiber of Example 12 was produced in the same manner as in Example 1 except that the divalent metal salt of the divalent metal salt exchange bath was changed to barium chloride. The performance of the obtained fiber is shown in Table 5 below.

[0062]

[Table 5]

[0063]

The alginic acid-based fiber of the present invention is free from sticking and is flexible in a dry state, and has excellent mechanical properties such as dry strength, dry elongation, knot strength and knot elongation. The equilibrium water content of this alginic acid-based fiber is 13 to 16% in the standard state of 60% RH and 25 ° C. The alginate-based fiber of the present invention has the above-mentioned properties, so that a non-woven fabric such as a woven fabric and a needle punch can be manufactured in a dry state.Moreover, the obtained woven fabric and the non-woven fabric are flexible, and medical fiber products, It is suitable as a wound dressing using this fiber.

When the alginate-based fiber of the present invention is used as a wound dressing or a hemostatic cotton, it is soft and can wrap the wound softly, so that the pain of the patient can be relieved.
Moreover, the wound surface is absorbed by absorbing exudate bodily fluids and gelling.
Protects against external stimuli and aids in wound surface recovery.
Since the alginic acid fiber of the present invention has a high affinity with body fluids and is naturally absorbed in the body, it can be replaced while the gel part of the wound surface material is left on the wound surface even when the wound surface material is replaced. The scratches are regenerated quickly.

When the divalent metal contained in the alginate-based fiber of the present invention is calcium, the fiber has an excellent hemostatic effect. Therefore, when this fiber is used as a wound dressing material, it is effective for an initial wound surface. It is.

In addition to the above-mentioned effects of the present invention, another alginic acid-based fiber of the present invention containing an antibacterial agent also has an effect of preventing various bacteria from invading the wound surface.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location D04H 1/42 P D21H 13/32 (72) Inventor Hiroshi Uejima 2-3, Hananomiyacho, Takamatsu City, Kagawa Prefecture No. 3 Inside Shikoku Institute of Industrial Technology (72) Inventor Satoshi Fukuoka 2-3-3 Hananomiyacho, Takamatsu City, Kagawa Prefecture Inside Shikoku Institute of Industrial Technology (72) Inventor Hideki Kobiga Takamatsu, Kagawa Prefecture 2-33-3 Hananomiyacho, Ichi, Japan Shikoku Institute of Industrial Technology, Institute of Industrial Technology (72) Inventor Ichiro Takeuchi, 8th floor, Kawakami, Takashima, Kitajima-cho, Itano-gun, Tokushima Toho Rayon Co., Ltd. (72) Invention Toshi Rayon Co., Ltd. Tohoku Rayon Co., Ltd. Tokushima Plant

Claims (12)

[Claims] 1. A compound containing a divalent metal and defined by the following formula:
Valency metal salinization rate is 60-90% and dry strength is 1.5
An alginic acid-based fiber having a g / d or more and a dry elongation of 8% or more. [Equation 1] 2. The alginate fiber according to claim 1, which contains an antibacterial compound. 3. The alginic acid-based fiber according to claim 1, wherein the divalent metal is at least one selected from calcium, barium, nickel, and cobalt. 4. A water-soluble alginic acid monovalent salt aqueous solution is spun in a hydrochloric acid bath to form alginic acid fibers, and (2) the obtained alginic acid fibers are introduced into an aqueous divalent metal salt solution for metal substitution. A divalent metal chlorinated alginic acid fiber is obtained by (3), and the obtained divalent metal chlorinated alginic acid fiber is dehydrated with a hydrophilic organic solvent. 5. (1) A water-soluble alginic acid monovalent salt aqueous solution is spun in a hydrochloric acid bath to form alginic acid fibers, and (2) the obtained alginic acid fibers are in a divalent metal salt aqueous solution adjusted to pH = 7 or more. By substituting it with a metal to give a divalent metal salification rate defined by the following formula of 60 to 90
% Divalent metal chloroalginate fiber is obtained, (3) A method for producing an alginic acid-based fiber, which comprises dehydrating the obtained divalent metal chlorinated alginic acid fiber with a hydrophilic organic solvent. 6. (1) A water-soluble alginic acid monovalent salt aqueous solution to which an antibacterial compound is added is spun in a hydrochloric acid bath to form alginic acid fibers, and (2) the obtained alginic acid fibers are adjusted to pH = 7 or more. The resulting divalent metal salt aqueous solution is subjected to metal substitution so that the divalent metal salification rate defined by the following formula is 60 to 90.
% Divalent metal chloroalginate fiber was obtained, (3) A method for producing an alginic acid-based fiber, which comprises dehydrating the obtained divalent metal chlorinated alginic acid fiber with a hydrophilic organic solvent. 7. The method for producing an alginic acid-based fiber according to claim 4, 5 or 6, wherein the divalent metal salt aqueous solution is arranged in a plurality of stages and the concentration is set to be gradually lower. 8. The divalent metal salt aqueous solution is an aqueous solution containing one kind selected from a calcium salt, a barium salt, a nickel salt and a cobalt salt, or an aqueous solution containing two or more kinds. A method for producing the alginic acid-based fiber described. 9. A non-woven fabric produced using the alginic acid-based fiber according to claim 1, 2, or 3. 10. A woven fabric produced by using the alginic acid-based fiber according to claim 1, 2 or 3. 11. A papermaking produced by using the alginic acid-based fiber according to claim 1, 2 or 3. 12. A medical fiber product produced by using the alginic acid-based fiber according to claim 1, 2, or 3.