JPH04240205A - Synthetic fiber and product composed of the same - Google Patents

Abstract

PURPOSE:To obtain synthetic fiber, containing metallic copper or its compound and metallic germanium or its compound, excellent in antimicrobial action, having health, discoloration preventive, deodorant effects, etc., and useful as a material for hosiery, etc. CONSTITUTION:The objective fiber containing (A) at least one of metallic copper and its compound [preferably copper(I) iodide, etc.] and (B) at least one of metallic germanium and its compound (preferably germanium phosphite, etc.). The aforementioned fiber is preferably obtained by premixing the components (A) and (B) with a dispersion medium, adding the resultant components (A) and (B) to a fiber-forming polymer after polymerization and subsequently spinning the prepared polymer. In the process, the components (A) and (B) are preferably formed into fine particles having <=1mum particle size.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to synthetic fibers and products made therefrom. In particular, it relates to synthetic fibers and textile products that have antibacterial and health effects.

0002

BACKGROUND OF THE INVENTION A large number of synthetic drugs that are rapidly effective against diseases have been provided and are widely used, but drug toxicity has become a major problem. Therefore, preventive or therapeutic methods using slow-acting but highly safe natural herbal medicines and trace amounts of rare elements contained in hot springs, etc., have been reviewed in recent years and are now widely used. One such conventional technology focuses on the health and pharmacological effects of germanium, and uses germanium and its compounds for the treatment and prevention of skin diseases, internal organs diseases, eye diseases, cancer, etc., and for beauty effects, etc. It is proposed to use. In addition, textile products, especially those that come in direct contact with the skin, such as socks, underwear, and towels,
Secretions from the human body, bacteria, mold, etc. cause problems such as bad odors, skin inflammation due to infection, and yellowing of textile products, and these problems are harmless to the human body and last for a long time. There has been a demand for the development of textile products that do not cause

0003

[Contents of the Invention] From the above points, the present applicant has developed a textile product that can effectively utilize the health and pharmacological effects of germanium, as well as maintain its antibacterial and deodorizing effects for a long period of time, and that does not cause yellowing. We have been promoting development. As a result, we found that when germanium compounds are used in textile products that are indispensable in daily life, the health and pharmacological effects of germanium can be utilized on a daily basis and extremely easily. If germanium compounds are retained in the fibers rather than in the fibers, they will not fall off from the fibers and will be durable, will not impair the texture, texture, processability, etc. of the fibers, will be safe for the human body, and will have antibacterial properties. We have discovered that it is possible to provide synthetic fibers and textile products that have long-lasting effects, deodorizing effects, and anti-discoloration effects, and based on this discovery, we have developed synthetic fibers containing inorganic and/or organic germanium compounds. The application was filed earlier (Japanese Patent Application No. 1-192292).

[0004] The present inventors conducted further research on synthetic fibers containing germanium compounds and found that when metal copper and/or copper compounds coexist with germanium in synthetic fibers, their health effects, antibacterial effects,
It is possible to further improve the ability to prevent discoloration, especially the antibacterial effect, and also to reduce the amount of germanium used, which is expensive and difficult to obtain.Also, as germanium, in addition to germanium compounds, metal germanium can also be effectively used. They discovered this and completed the present invention. Therefore, the present invention is a synthetic fiber containing (A) at least one of metallic copper and a copper compound, and (B) at least one of metallic germanium and a germanium compound. Furthermore, the present invention also includes textile products obtained from the above synthetic fibers.

The synthetic fibers of the present invention include fiber-forming polyesters (eg, polyethylene terephthalate,
polybutylene terephthalate, etc.), polyamide-based (e.g. nylon-6, nylon-66, etc.), polyolefin-based (e.g. polyethylene, polypropylene), polyurethane-based, polyacrylonitrile-based, polyvinyl chloride-based,
Examples include, but are not limited to, synthetic fibers such as polyvinylidene chloride, polyvinyl alcohol (vinylon, etc.). Among the above-mentioned fibers, particularly polyester, polyamide, polyolefin, polyurethane, and polyacrylonitrile Synthetic fibers are desirable.Synthetic fibers may be in the form of short fibers, staples, or long fibers (filaments), and the length, thickness, etc. of the fibers may be appropriately selected depending on the purpose and manner of use.

[0006] In the present invention, moisture such as perspiration penetrates into the synthetic fiber, and (A) at least one of metallic copper and a copper compound contained in the synthetic fiber, and (B)
It is thought that at least one of metal germanium and germanium compounds is gradually eluted in very small amounts, and this exhibits antibacterial, health and anti-yellowing effects. Therefore, as metal copper, copper compounds, metal germanium, and germanium compounds, those that do not dissolve in water at all or those that have too high water solubility are not preferable.
It is desirable to have a substance that can be gradually dissolved into water in extremely small amounts over a long period of time. Copper compounds and germanium compounds can be used as organic compounds as long as they are harmless, do not lose their antibacterial and health effects through heating during textile manufacturing, and can maintain their antibacterial and health effects over a long period of time. Also, any of inorganic copper compounds and germanium compounds can be used. Therefore, it is desirable to use copper compounds and germanium compounds that do not undergo decomposition or alteration due to heating during fiber manufacturing and can maintain their original antibacterial and health effects. Copper compounds and germanium compounds can also be used, even if they are decomposed or denatured by oxidation, as long as the products after decomposition or denaturation are safe and exhibit antibacterial or health effects.

As metal copper and metal germanium,
High purity, spherical particles with a sharp particle size distribution are desirable because they can be mixed and dispersed uniformly into synthetic fibers. Metallic copper and metallic germanium release extremely small amounts of copper or germanium ions from their crystal structures, and these metal ions exhibit antibacterial and health effects. Further, as an example of a preferable copper compound, copper iodide (I
), but is not limited thereto, of course. Furthermore, examples of preferable germanium compounds include inorganic germanium compounds such as germanium phosphite and germanium dioxide, and (GeCH2CH2COOH)O
3. Organic germanium compounds such as poly(carboxylethyl germanium sesquioxide) can be mentioned, but are not limited to these, of course. Depending on the type of polymer constituting the synthetic fiber, the manufacturing conditions (especially temperature conditions) when manufacturing the synthetic fiber, and the use of the synthetic fiber and textile products, the amount of metal copper and copper compounds, and metal germanium and germanium compounds It is better to select the most suitable ones and use them in combination. Furthermore, even if only one type of metal copper and copper compounds and one or two or more types of metal germanium and germanium compounds are contained in the synthetic fiber, or two of metal copper and copper compounds may be contained in the synthetic fiber. One or more types of metal germanium and germanium compounds may be contained in the synthetic fiber in combination with one or more types of germanium compounds.

[0008] Metallic copper and/or copper compounds, and metallic germanium and/or germanium compounds can be uniformly dispersed and contained in synthetic fibers, and furthermore, their dispersion improves the processability during fiberization and the resulting synthetic fibers. The method of mixing metal germanium and germanium compounds into the fiber is not particularly limited as long as the properties are not significantly impaired. Generally, it is convenient to add at least one of metallic copper and a copper compound and at least one of metallic germanium and a germanium compound into the synthetic fiber polymer after polymerization to produce copper and germanium-containing fibers. It is. For this purpose, metal copper, copper compounds,
The particle size of germanium metal and germanium compounds is preferably reduced to fine particles of 10 μm or less, particularly 5 μm or less, and further 1 μm or less, so as not to interfere with fiberization by any means such as wet grinding or dry grinding. It is preferable to leave it there. When the particle size of metallic copper, copper compound, metallic germanium, and germanium compound becomes large, it is undesirable because it causes clogging of the spinneret hole, yarn breakage, etc. during fiberization. In addition, the smaller the particle size of metallic copper, copper compounds, metallic germanium, and germanium compounds, the more they can exert antibacterial and health effects when added to fibers in small amounts, and the more stable their effects are. Also, it is desirable that the particle size is small.

When containing at least one of metallic copper and copper compounds and at least one of metallic germanium and germanium compounds in synthetic fibers, it is important to note that their presence in the polymerization system may interfere with polymerization or damage the resulting polymer. Since problems such as coloration and deterioration may occur during coalescence, it is best to add the synthetic fiber polymer after polymerization to spinning as described above. Fibers may be produced or spun by adding them to previously produced or obtained polymers. Generally, fiber-forming polymers have a high viscosity, and it is often difficult to uniformly disperse metal copper, copper compounds, metal germanium, and germanium compounds, so in such cases, it is better to use a dispersion medium. When used in combination with a dispersion medium, metal copper and/or copper compounds and metal germanium and/or germanium compounds contained in synthetic fibers can be eluted in small amounts stably over a long period of time. It is thought that this is because the water seeps out little by little from the inside of the fiber to the fiber surface, thereby promoting the infiltration of moisture into the inside of the fiber. Moreover, the combined use of a dispersion medium is also preferable from the viewpoint that orientational crystallization of polymer molecules can be promoted when the polymer is made into fibers.

The dispersion medium is preferably a substance that is compatible with the polymer and is liquid at room temperature. Examples of dispersion media include ester-based, phosphorus-based, polyester-based plasticizers and polyester polyols when the fiber-forming polymer is polyester, and hydroxyamides and sulfonamides when the fiber-forming polymer is polyamide. , oxybenzole esters, etc., and when the fiber-forming polymer is a polyolefin, cycloparaffins,
Naphthenic oil etc. can be used. In either case, it is suitable that the dispersion medium has a similar chemical structure to the polymer in which it is used, has similar solubility parameters, and is compatible with the polymer. When a dispersion medium is used in combination, at least one of metal copper and copper compounds, and at least one of metal germanium and germanium compounds are mixed with the dispersion medium, and this mixture is added to the fiber-forming polymer. It is desirable to adopt it. Using a metering pump, it is possible to add the mixture to the fiber-forming polymer in a precise quantitative ratio and also to add the mixture to the fiber-forming polymer in a precise proportion, and also to add the metal copper and/or copper compound and the metal germanium and/or germanium compound in the dispersion medium mixture. The concentration is 10-70% by weight, preferably 3
If it is set to about 0 to 60%, fluidity in the metering pump piping will be good.

Metallic copper and/or copper compounds in synthetic fibers,
The blending amount of metal germanium and/or germanium compound is based on the weight of the polymer for synthetic fibers, converted to copper and germanium elements, and is determined by the following formula 1.
~Equation 4;

[Equation 1] 0.0001% by weight≦Cu≦5.0% by weight

[Math. 2] 0.03% by weight ≦ Ge ≦ 5.0% by weight

[Math. 3] 0.03% by weight≦Cu+Ge≦10.0% by weight

It is desirable that the amount satisfies 0:100<Cu:Ge≦50:50. Among them, Cu is 0
．． 1% by weight or more and 5.0% by weight or less, Ge is 0.1% by weight
It is particularly desirable that the above is 5.0% by weight or less, Cu+Ge is 0.2% by weight or more and 7.0% by weight or less, and the ratio satisfies Equation 4 above.

In general, if the content of copper and germanium is lower than the lower limit values of formulas 1 to 3 above, it will be difficult to impart antibacterial and health effects to synthetic fibers, and if the content of copper and germanium is lower than the lower limit values of formulas 1 to 3, it will be difficult If it exceeds this value, it becomes difficult to form fibers, and the physical properties of the resulting synthetic fibers also deteriorate and the cost increases. In particular, if Cu+Ge is less than 0.03% by weight, the antibacterial effect and health effect of the synthetic fiber will be low;
．． If it exceeds 0% by weight, it will be difficult to form fibers, and the physical properties of the resulting synthetic fibers will deteriorate. The use of such large amounts of expensive copper and germanium, especially germanium, is also undesirable from an economic point of view. If you want synthetic fibers to have strong health effects, use Ge in formula 4 above.
It is better to increase the ratio of

When the synthetic fiber of the present invention is used for clothing such as underwear, socks, stockings, gloves, etc. that come into direct contact with the human body, bath towels, etc., its antibacterial effect prevents the growth of fungi and mold, deodorizes, and causes skin irritation. It has effects such as preventing yellowing and yellowing, and also has beauty effects and effects such as making blood alkaline due to its health effects. The synthetic fibers of the present invention can also be used as fabrics and base fabrics for various treatments, and as materials for preventing spoilage and preserving the freshness of foods. Therefore, the present invention encompasses not only synthetic fibers but also all textile products formed from the synthetic fibers, such as filaments, fabrics such as knitted fabrics and non-woven fabrics, clothing, etc., are all included in the present invention. . Among them, the socks and stockings according to the present invention are suitable for manufacturing particularly good properties as described later. Even if socks and stockings are knitted from yarns made only of the synthetic fibers of the present invention, they can be knitted from yarns made of only the synthetic fibers of the present invention, blended yarns with other fibers, blended yarns,
It may also be knitted from twisted yarns or the like. Furthermore, when knitting socks and stockings, threads made of fibers containing copper and germanium can be used on the entire top and bottom, on the bottom half, or only on the toes and heels. The effects of the present invention can also be fully exhibited. In the socks and stockings of the present invention obtained by knitting synthetic fibers containing copper and germanium, extremely small amounts of copper and germanium contained in the fibers are eluted by moisture or water vapor sweated from the feet during wear. It has a good antibacterial effect against fungi and molds present in secretions from toes, etc., and can prevent fungal infections, skin inflammation, other diseases, and the occurrence of bad odors caused by foot stuffiness. , provides a comfortable fit.

The synthetic fibers of the present invention are particularly produced by Trichophyton mentagrophyti, which belongs to Trichophyton.
hophyton mentagrophytee,
IFO 5466), Trichophyton labrum
(Trichophyton rubrum, IFO
5467), Aspergillus flavus (As
pergillus flavus, IFO 63
43), Aspergillus niger
illus niger, IFO 6341), Penicilliu
m citrium, IFO 6352), Fusarium lini,
IFO 4468), Rhizophus nigricans (R
hizopus nigricans, IFO 5
781), Cladosporium reginii (Cla.
IFO
8588), Pseudomona
s) It shows a strong antibacterial effect against bacteria such as Staphylococcus aureus and Escherichia coli, but it also shows an antibacterial effect against other fungi.

[0015]

[Example] <Example 1> 6 kg of metallic copper particles (manufactured by Mitsui Kinzoku Mining Co., Ltd.: MNFT1040), 1 kg of germanium dioxide (manufactured by Japan Electronics Metals Co., Ltd.), and polyester plasticizer (manufactured by Adeka Argus Co., Ltd.: product name PN-350) 7kg
After rough mixing, wet pulverization was performed using a vibration mill (MB-1 type vibration mill manufactured by Chuo Kakoki Co., Ltd.) to obtain an average particle size of 1.2 μm.
The mixture was made into fine particles, dried at 120° C., cooled, and defoamed under vacuum to produce a finely divided mixture of metallic copper, germanium dioxide, and a plasticizer. The fine particulate mixture produced above was mixed with polyethylene terephthalate ([η] = 0.65 dl/g
:Intrinsic viscosity measured in a constant temperature bath at 30℃ using a mixed solvent of equal amounts of phenol and tetrachloroethane),
3.0% by weight of metallic copper, based on the weight of the polyester
(3.0% by weight in terms of Cu element) and 0.5% by weight of germanium dioxide (0.35% by weight in terms of Ge element). After spinning using
d. A polyester staple fiber with a fiber length of 51 mm was produced, and socks were made from this fiber by a conventional method.

<Example 2> In place of metallic copper, cuprous iodide was added in an amount of 1.0% by weight (based on the weight of polyester).
(0.33% by weight calculated as Cu element), and instead of germanium dioxide (GeCH2CH
2COOH)2O3 to 1 based on the weight of the polyester
．． Socks were made in the same manner as in Example 1, except that the amount was 0% by weight (0.43% by weight in terms of Ge element). <Example 3> Hydroxyamide was used as a dispersion medium, the polymer was changed from polyester to nylon 6 (manufactured by Ube Industries), and the content of metallic copper was 3.0% by weight (Cu element) based on the weight of nylon 6. (3.0% by weight)
and germanium dioxide content 0.5% by weight (Ge
0.35% by weight in terms of elements), and the rest is as in Example 1.
I made socks in the same way. <Comparative Example> Socks were made in the same manner as in Example 1, except that metallic copper and germanium dioxide were not used, and the polyester plasticizer was used in the same amount as in Example 1.

Test for antibacterial activity The antibacterial activity was tested using the socks prepared in Examples 1 to 3 and comparative examples above, and pharmacopoeial gauze for reference (control example), by the methods (1) and (2) below. The test was conducted. (1) Antibacterial effect test example 1 by inoculation with bacteria-containing liquid
A plurality of test pieces each weighing 0.2 g/piece were cut out from the toe portions of the socks prepared in Example 3 and Comparative Example and from the pharmaceutical gauze. (a) Staphylococcus aureus [Staphylococcus aureus] in sterile liquid broth
ATCC 6538P (IFO 12732)]
A bacterial solution was prepared in which Staphylococcus aureus was suspended at approximately 340,000 Staphylococcus aureus cells per 0.2 ml of solution. (b) Klebsiella pneumoniae [Kleb.
siella pneumoniae ATCC
4352 (IFO 13277)] in 0.2 ml of liquid
A bacterial suspension containing approximately 300,000 Klebsiella pneumoniae bacteria was prepared. The above bacterial solution (
0.2 ml/test piece (0.2 ml/test piece) of each of a) and bacterial solution (b)
．． After culturing at a temperature of 37° C. for 18 hours, the cells were taken out and the ratio of increase/decrease in the number of bacteria, the value of increase/decrease in the number of bacteria, and the difference in the value of increase/decrease in the number of bacteria were measured. Here, bacterial count increase/decrease ratio = {number of viable bacteria on the test piece after 18 hours of culture} ÷
{Number of viable bacteria just before culturing (number of planted bacteria)}, increase/decrease in the number of bacteria = l
og10 [increase/decrease ratio in bacterial count], and difference in bacterial count increase/decrease value = [increase/decrease value in bacterial count of the test piece of the comparative example that does not contain copper or germanium] - [increase/decrease value in the bacterial count of the test piece of each example]. The antibacterial test results against Staphylococcus aureus are shown in Table 1, and the antibacterial test results against Klebsiella pneumoniae are shown in Table 2.

The results were as shown in Tables 1 and 2.

[Table 1]

[0019]

[Table 2]

From the results in Tables 1 and 2, Examples 1 to 3
It can be seen that the socks of the present invention have extremely superior antibacterial activity compared to the socks of the comparative example and the pharmacopoeial gauze of the control example. (2) Clinical test A test was conducted in which 10 patients with sweaty foamy tinea wore the socks prepared in Example 1 for 8 hours a day, washed them after each day, and wore them for 2 weeks. As a result, significant effects were observed in 6 patients, including the disappearance of wetness and odor in the feet, cessation of itching, and reduction in epithelial peeling of the skin.

[0021]

[Effects of the Invention] Due to their antibacterial properties, the synthetic fibers and textile products of the present invention cause problems such as the generation of bad odors due to secretions from the human body, bacteria, mold, etc., skin inflammation due to infection, and yellowing of textile products. It is effective in promoting health, as it can prevent and eliminate problems, and its health effects can also achieve beauty effects and alkalinization of the blood. In the present invention, metallic copper and/or copper compounds, and metallic germanium and/or germanium compounds, which have antibacterial and health effects, are not simply attached to the surface of the fibers, but are contained and retained inside the synthetic fibers. Because of this, they do not fall off from the fibers and are durable, and can exert their antibacterial and health effects over a long period of time without impairing the texture, texture, processability, etc. of the fibers. The synthetic fiber of the present invention further contains metallic copper and/or a copper compound together with metallic germanium or a germanium compound, so that it has a particularly superior antibacterial effect compared to the case of germanium alone. It is economical because it can reduce the amount of water used. Among the textile products of the present invention, socks and stockings in particular have excellent antibacterial and deodorizing effects, prevent feet from getting stuffy, prevent bad odors emitted from toes, etc., and protect feet that tend to become unclean. Can be kept hygienic at all times.

Claims (4)

[Claims] 1. A synthetic fiber containing (A) at least one of metallic copper and a copper compound, and (B) at least one of metallic germanium and a germanium compound. [Claim 2] At least one of metallic copper and a copper compound.
The seeds and at least one of metal germanium and germanium compounds are expressed in the following formulas 1 to 4 in terms of copper element and germanium element; Equation 2: 0.03 wt%≦Ge≦5.0 wt% [Equation 3] 0.03 wt%≦Cu+Ge≦10.0 wt% [Equation 4] Satisfies 0:100<Cu:Ge≦50:50 2. The synthetic fiber of claim 1, containing the synthetic fiber in an amount of 3. A product formed from the synthetic fiber of claim 1 or claim 2. 4. The product according to claim 3, which is a sock.