JPH03113011A - Synthetic yarn and production thereof - Google Patents

Abstract

PURPOSE:To obtain synthetic yarn suitable for underwears, etc., having antimicrobial properties and healthy action by adding a copper compound) and a germanium (compound) to a polymer in a period from immediate after polymerization completion of polymer to just before spinning, kneading and spinning. CONSTITUTION:In a period from immediate after polymerization completion of polymer (e.g. polyethylene terephthalate or nylon 6) to just before spinning, the polymer is kneaded with copper (compound) (preferably metal copper or inorganic compound thereof) having <=10mum average particle diameter and germanium (compound) having <=10mum average particle diameter in the weight ratio of (1/99)-(50/50) dispersed into a dispersion medium (e.g. ester-based plasticizer or hydroxylamide) having compatibility with the polymer and then spun to give the objective yarn.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to copper compounds (in the present invention, copper may also be referred to as copper compounds) and germanium compounds (
The present invention relates to a synthetic fiber having antibacterial and health effects containing germanium (also referred to as a germanium compound).

<Prior Art> Many rapidly-acting synthetic drugs have been provided for treating diseases, but the toxicity of these drugs has also become a major problem.

Therefore, in recent years, Japanese and Chinese herbal medicine that uses slow-acting but safe natural compounds and hot spring therapy that contains trace amounts of rare elements have been reconsidered and are becoming popular in response to such problems.

In particular, the health effects of germanium have been recognized in recent years; for example, "Germanium Hymn" by Hiko Asai
Publications such as ``Germanium and I'' specifically describe the health effects of germanium, as well as publications such as
No. 13684, No. 63-28070, No. 63
-32358 publication, 63-32359 publication, 63-32359 publication
Proposals regarding the utilization of the pharmacological action of organic germanium have been made in JP-A No. 3-62492 and JP-A No. 63-62493.

Regarding inorganic germanium, Special Publication No. 63-2561
This is proposed in Publication No. 8'.

According to these proposals, specific examples of the health or pharmacological effects of germanium include cosmetic effects on skin diseases, cancer, internal organs diseases, and eye diseases.

On the other hand, in order to utilize the antibacterial effects of metal ions,
For example, Japanese Patent Laid-Open No. 147220/1983 proposes a method of mixing metal compounds such as silver, copper, zinc, etc. into a polymer to form fibers. Furthermore, a method of adding and mixing zeolite solid particles exchanged with silver ions and copper ions to an organic polymer is proposed in JP-A-59-133235. However, with these methods, the metal compound has a large effect on the polymer, severely limiting the usable range, and the life of the pack is short due to processability in the fiberization process, especially single fiber breakage during spinning, and back filter clogging. Otherwise, problems such as frequent fluffing during stretching may occur.

In addition, a method for attaching a composite of a copper, silver or zinc compound and casein to the fiber surface in a water-insolubilized state is disclosed in JP-A-56
-123474. By making the composite insoluble in water, this fiber can prevent the composite from falling off when washed with water, etc. However, in order to insolubilize the casein, formalin must be used, and after making it into a woven or knitted fabric,
There is a concern that formalin may be liberated during use.

<Problems to be Solved by the Invention> The present invention further improves the health effects and antibacterial properties of germanium compounds by using a germanium compound and a copper compound together and incorporating them into fibers, and also solves the above problems. The purpose of this invention is to provide synthetic fibers that are free from the above problems.

Means for Solving the Problems> That is, the present invention provides copper or its compound having an average particle size of 10 μm or less (aluminum and germanium or its compound fBl having an average particle size of 10 μm or less in a total of 0.1% by weight). It is a synthetic fiber characterized by containing 10% by weight or less, particularly preferably the weight ratio of (A) and (B) + A
+ / (It is a synthetic fiber whose Bl is 1/99 to 50150. Such a synthetic fiber is, for example.

Immediately after the polymerization of the fiber-forming polymer is completed and immediately before spinning, copper or its compound (N and its average particle size of 10 μm or less) having an average particle size of 10 μm or less dispersed in a dispersion medium that is compatible with the polymer is added. It can be produced by adding the following germanium or its compound (Bl) to the polymer, kneading it, and then spinning.

In the present invention, copper or its compound (A) and germanium or its compound (Bl) are dispersed in the polymer in the form of fine particles, so unlike coating on the fiber surface, a high degree of durability can be obtained. .

It has excellent antibacterial and health effects due to the synergistic action of the amphoteric compound, and is further characterized in that these effects are sustained over a long period of time.

In addition, it does not impair the feel or texture of the fiber itself.
It does not impair the processability of spinning, knitting, weaving, dyeing, sewing, etc. into final fiber products.

The fiber-forming polymer used in the present invention is not particularly limited as long as it can be spun by a conventionally known spinning method, and examples thereof include polyethylene L/7fL/phthalate, polybutylene terephthalate, and the like as main components. Examples include polyester polymers, polyamide thread polymers such as nylon 6 and nylon 66, and polyolefin thread polymers such as polyethylene and polypropylene.

The fibers of the present invention made of these polymers can be processed by high-order processing such as false twisting and crimp processing.

Shapes similar to pentagons and hexagons can be formed, and multi-lobed shapes such as trilobal, T-shaped, quadrilobal, pentagonal, hexalobular, heptalobal, and octalobular shapes can be formed due to the irregular cross-section nozzle used during spinning. It can take various shapes and cross-sectional shapes, and its effects are fully expressed. Also Zara,
It is also possible to use composite fibers with a so-called core-sheath structure or dorsal-ventral structure, and even in this case, the part of the polymer to which the mixture of a copper compound and a germanium compound is added accounts for 20% or more of the cross-sectional area of the fiber, and is desirable. It is desirable that a portion of the polymer be present at least partially on the surface of the fiber.

The copper compound (A) and germanium compound (Bl) used in the present invention both have an average particle size of 10 μm.
It is necessary that the following is true. The particle size is small (on the other hand, it can exhibit antibacterial and health effects with a smaller amount,
Moreover, the effect is also stable.

On the other hand, if the particle size becomes large, yarn breakage is likely to occur, which may deteriorate spinnability. Therefore, it is desirable to use particles having an average particle diameter of preferably 5 μm or less, particularly preferably 1 μm or less. The particles can be pulverized using a conventionally known wet or dry pulverizer.

Note that the average particle diameter in the present invention is the median diameter (particle diameter corresponding to 5096 on the integrated distribution curve), and is determined by the light transmission method, which is determined by measuring the light transmittance of a diluted dispersion of pulverized fine particles. For example, Micron Photosizer 3KC-20 manufactured by Seishin Enterprise Co., Ltd.
It is possible to measure using 0O3.

The synthetic fiber of the present invention must contain a total of 1% by weight or more and 10% by weight or less of a copper compound (Al and germanium compound (B)) having an average particle diameter of 10 μm or less as described above, In particular, the weight ratio fA)/fB) of the copper compound fAl and the germanium compound fB) is 1
/99 to 50150 is desirable. If the total weight is too low, the antibacterial and health effects will not be fully expressed, and if the total weight is too high, it will actually become difficult to form fibers.

This results in undesirable results such as deterioration of fiber physical properties and formation of stiffness. Therefore, preferably 0.2% by weight or more
．． A total weight of 0% by weight or less is desired. In addition, the weight ratio of copper compounds (Al) and germanium compounds (Bl) can be freely controlled to the desired performance, such as by increasing the amount of germanium compounds if you want to have strong health effects. As in, +Al
/(BI is desired to be l/99 to 50150.

In addition, in the expression of antibacterial and health effects, various copper compounds (Al and germanium compounds (Bl) are thought to play an important role, for example, by ionizing the copper and germanium elements,
It is more convenient to understand the content of each compound in the fiber as the content converted to the element. When considered in this way, 1. The synthetic fiber of the present invention contains copper and germanium in a total amount of 0.03% by weight or more and 10% by weight or less, preferably 0.2% by weight or more and 10% by weight or less in terms of elements. It is desirable to blend a specific amount of a copper compound (tAl) and a germanium compound (fB) with an average particle diameter of 10 μm or less into the powder.

Looking at each individual item, copper has an elemental conversion of 0.00
It is desired that the content be 0.01% by weight or more, preferably 0.05% by weight or more, particularly preferably 0.1% by weight or more and 5% by weight or less. On the other hand, germanium is 0.03% by weight or more, preferably 0.1% by weight in terms of element.
It is desirable that the content be 5% by weight or less.

Next, the type of copper compound fAl to be used is not particularly limited, but in addition to metallic copper, copper iodide, cuprous oxide, cupric oxide, cuprous oxide, copper thiocyanide, copper nitrate, cyanide, etc. It is possible to use at least one kind of copper, copper inorganic compounds such as copper arsenite, copper sulfate, copper borate, organic copper compounds, and the like. These copper compounds do not necessarily have to be blended into the fibers while maintaining their molecular structure (and thermal decomposition during blending does not pose a major problem. Preferably, metallic copper or its inorganic compound is used. Ru.

Germanium compounds (Bl includes germanium alone, germanium phosphite, inorganic germanium compounds such as germanium dioxide, (GeCH2CHtCOOH)
, Os, and at least one organic germanium compound such as poly(carboxylethylgermanium sesquioxide) described in Example 2 of Japanese Patent Publication No. 53-7960.

Note that the germanium compound (B) is also the same as the copper compound (A
), even if the compound molecules differ due to thermal decomposition before and after blending, there is no problem as the antibacterial and health effects are maintained to some extent, but organic germanium compounds in particular are easily thermally decomposed. The compounds exemplified above have heat resistance up to about 270°C and have excellent antibacterial properties.

This suitable compound can be sufficiently applied to fibers having a relatively high melting point such as polyester fibers.

The synthetic fiber of the present invention is obtained by blending the above-mentioned copper compound fA) and germanium compound (B) with a fiber-forming polymer and spinning it, and there is no particular restriction on the method of blending these compounds. However, thermoplastic polymers (hereinafter simply referred to as polymers) that can form one synthetic fiber, for example, usually have a high viscosity, and it is difficult to easily disperse and blend these compounds. For example, in the case of polyester, a germanium compound is sometimes used as a catalyst for the polycondensation agent, but the amount of germanium compound added in the present invention far exceeds the catalyst amount, so it is not added during the polymerization reaction. It is inconvenient to add. Additionally, as will be described later, an additive composition consisting of a dispersion medium and a copper compound (A + # and germanium compound iB) is added in the polymerization process of polymers such as polyester, polyamide, polyolefin, etc., accompanied by thermal history, This is not preferable because it tends to cause coloring of the resulting polymer and decomposition and volatilization of the dispersion medium. Therefore, when using such a polymer, it is preferable to add it at the stage immediately before spinning after polymerization is completed. Specifically, immediately after polymerization is completed, it is added to the polymerization tank in a dissolved state and mixed. A method of dispersing and blending, a method of adding and mixing and dispersing when manufacturing polymer pellets, a method of adding dissolved polymer to the pipe that sends the liquid to the spinning nozzle and dispersing and blending by dynamic or static mixing, pellets Examples include a method of adding the compound to an extruder for melting and extruding and mixing and dispersing it.

In the present invention, the copper compound (A) and the germanium compound fBl are easily dispersed and blended into the polymer, and at the same time, when the polymer is made into fibers, the polymer molecules are oriented and crystallized to stabilize the elution of the blended compounds. It is preferable to use a dispersion medium for the purpose of making the connection.

The dispersion medium is preferably a substance that is compatible with the fiber-forming polymer used and is liquid at room temperature.

By dispersing the copper compound (N) and germanium compound (B) in advance in such a dispersion medium, these compounds can be efficiently wet-pulverized, and even when added to a polymer, they can be extremely stable. In addition, after fiber formation, the dispersion medium transfers very little from the inside of the dense polymer structure to the fiber surface, thereby promoting the infiltration of water into the fibers, and dispersing the copper compound fA) and germanium compound fB. ) is thought to also promote the elution of

As the dispersion medium used in the present invention, for example, when the polymer is polyester, ester yarn, phosphorus, a plasticizer for polyester yarn, polyester polyol, etc. can be used, and when the polymer is polyamide, hydroxyamide, sulfonamide, oxyamide, etc. can be used. Penzole ester etc. are used.

When the polymer is a polyolefin, it is possible to use cycloparaffin, naphthene thread oil, etc., which have a similar structure to the polymer, or have similar solubility parameters, i.e. polarity Things that are similar are better.

Further, it is desirable that the viscosity of one dispersion medium be 10 voids or more at 25°C. 7. The antibacterial level after hot water washing may decrease slightly.

In the present invention, an additive composition consisting of a mixture of a fine particulate copper compound + A + and a germanium compound (Bl and the above-mentioned dispersion medium) is added to the polymer in an accurate quantitative ratio.
Moreover, in order to stably add and disperse the ingredients, it is preferable to use an addition method using a metering pump. For this purpose, good fluidity in the process piping is essential.
It is desirable to adjust the dispersion medium so that the concentration of the germanium compound in the additive composition is kept to the minimum necessary.

At this time, the total concentration of the copper compound (Al and germanium compound (B)) in the additive composition may be adjusted as appropriate depending on the desired content of fine particles in the fiber and the addition rate of the additive composition, but is preferably is 10 to 70%, more preferably 30 to 60%.

In this way, the fiber-forming polymer to which the copper compound (Al) and germanium compound (B) have been added is made into fibers by a conventionally known spinning and drawing method.

The dispersed copper compound (A) and germanium compound fBl are placed inside the polymer structure with a dense structure, and the dispersion medium used in combination slightly spreads these compounds and the amount of polymer lead, preventing moisture from entering. It is thought that the compound dissolves and oozes out due to the moisture that enters, exerting antibacterial and health effects.

The synthetic fibers of the present invention thus obtained can be used in underwear, socks, and stockings that come into direct contact with the skin.

When used for clothing such as gloves, bath towels, bedding, etc., it can effectively utilize its beauty effects and health effects such as making the blood alkaline. It can also be applied to cloths and base fabrics for various treatments. .

<Examples> Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto (Production method 1 of additive composition) Metallic copper (Mitsui Kinzoku Mining Co., Ltd.) Manufacturer: MFP powder)
3 kg of germanium dioxide for catalyst (manufactured by Japan Electronics Metals Co., Ltd.) and 500 g of polyester plasticizer (manufactured by Argus Co., Ltd.: trade name PN-35034 kg) were roughly mixed and mixed in a vibrating mill (MB-1, manufactured by Chuo Kakoki Co., Ltd.). The mixture was wet-pulverized to an average particle size of 1.2 μm using a vibrating mill (type vibrating mill), dried completely at 120°C, cooled, transferred to a preparation tank, and subjected to vacuum defoaming to obtain an additive composition (additional composition 1). .

(Production method of additive composition 2) 100 yytl of first grade acrylic acid reagent was dissolved in a solution of 80 y of first grade germanium phosphate (Ge HPOs) reagent dissolved in 600 mg of first grade concentrated hydrochloric acid reagent for 30 minutes while stirring. After stirring for 2 and 3 hours at room temperature, a mixture of 800 ml of first grade acetone reagent and 200 ml of distilled water was added and stirred for 24 hours to precipitate fine crystals.

The formed crystals were separated from each other and washed with acetone solvent.

After washing and purifying until there were no free 0g ions, 759 crystals were obtained by vacuum drying. The obtained crystals were dissolved in water at room temperature, and the Ge content was 425%. Ta.

In addition, the differential thermal analysis value has two endothermic peaks, the first being 148°C at the beginning of the peak, 173°C at the peak peak, and 2nd at the end of the peak.
08℃, second peak start 236℃, peak apex 280℃
A germanium compound with excellent heat resistance, which had a peak end point of 307°C and did not decompose below 325°C, was obtained.

Organic germanium compound 500 thus obtained
g and cuprous iodide (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 50 (1 g and polyester plasticizer (manufactured by Argus Co., Ltd.: product name PN-)
350) 1.5Kg was roughly mixed and wet-pulverized using a vibration mill (MB-1 type vibration mill manufactured by Chuo Kakoki Co., Ltd.) to obtain an average particle size of 0.7μm.After drying at 120℃, it was cooled and prepared. The mixture was transferred to a tank and degassed through the back window to obtain an additive composition (Additional Composition 2).

Example-1 [ηJ = 0.6 s dtl/g (intrinsic viscosity measured in a constant temperature bath at 30°C using an equal mixed solvent of phenol and tetrachloroethane), TiOx was 0.4 times dtl/g.
96-containing polyethylene terephthalate (PET)
(hereinafter referred to as Ge) was melted and extruded using a 50φ extruder, and the above additive composition 1 was added to the inlet of a static mixer installed in the molten PET pipe so that the germanium compound in PET was 0.5 times 1t96 (Ge). Element conversion 0.3
After continuously injecting, kneading and dispersing copper so that the copper content is 3.0% by weight, the number of holes is 31 using a known method.
Spinning and drawing were performed using a nozzle with a round cross section of 0.0 mm to obtain a polyester stable fiber having a fineness of 3 denier and a fiber length of 38 mm.

Example-2 Additive composition 2 manufactured by additive composition manufacturing method 2 was used as PET
The germanium compound in it is 1.0% by weight (Ge element equivalent: 0.43 weight 11kg6), the copper compound is 1.0% by weight (
The fineness was 3 denier and the fiber length was 3 under the same conditions as in Example-1 except that the λ was 0.33% by weight in terms of Cu element.
An 8 mm polyester stable fiber was obtained.

Example 3 Additive composition manufacturing method Using hydroxyamide instead of the polyester plasticizer (PN-350, manufactured by Adeka Argus) in 1, the polymer of Example 1 was changed from polyethylene terephthalate to nylon 6 (manufactured by Ube Industries, Ltd.). A fineness 3 material containing 0.5% by weight of water-soluble germanium dioxide and 3% by weight of metallic copper was prepared in the same manner as in Example-1, except that K was changed.
A nylon 6 filament fiber of d was obtained.

Comparative Example-1 Only the polyester plasticizer (manufactured by Adeka Argus Co., Ltd., trade name PN-35(]) L, which was the dispersion medium used in producing the additive compositions used in Examples-1 and 2, was used as an example. - Added to 3.0% by weight/i% polyester polymer, which has the same content as 1 and 2, was dispersed and blended, and then made into fibers to form a copper compound tA) and a germanium compound tBj with a fineness of 3 denier and a fiber length of 38 mm. A polyester staple fiber containing no polyester staple fiber was obtained.

The various synthetic fibers obtained in Examples 1 to 3 and Comparative Example 1 were evaluated for antibacterial properties and milk preservability as described above.

■ Evaluation of antibacterial properties (measurement of sterilization rate) Suspend the following bacteria in sterilized liquid broth and inoculate 0.2 ml of this liquid onto 0.2 g of sample fiber.The number of Staphylococcus aureus bacteria is approximately 34. (about 300,000 Klebsiella pneumoniae)
After culturing at a temperature of 37° C. for 18 hours, the cells were taken out.

The number of viable bacteria on the sample before and after culturing was measured, and the ratio of increase/decrease in the number of bacteria, the value of increase/decrease, and the difference in the value of increase/decrease were calculated using the following formula. Table 1 shows the antibacterial properties against Staphylococcus aureus.
Table 2 shows the antibacterial properties against Klebsiella pneumoniae.

Test bacteria = (a) Staphylococcus aureus (Staph
ylococcusaureus ATCC6538P
(IFO12732) fbl Klebsiella pneumoniae (Kleb
siella pneumoniae ATCC4352
LIFO13277)) Sample size: i: 0.2Q Culture temperature/time = 37°C x] 8h Difference in bacterial count increase/decrease = Bacterial count increase/decrease value in blank test - Bacterial count increase/decrease value in processed sample Table (a) Yellow Staphylococcus Table 1 (bl) Klebsiella pneumoniae As is clear from Tables 1 and 2, when the synthetic fiber of the present invention was used, the proliferation of bacteria was significantly suppressed.

■ Evaluating the shelf life of milk: 5g of stable fibers are aligned using a hand card and stacked on top of each other.
After placing the dish in a petri dish with an inner diameter of 10 holes, 50 ml of commercially available milk in a bag was poured into the dish, and the dish was kept at a constant temperature of 2°C for 30 hours to observe the state of decomposition. The results are shown in Table 3.

As is clear from Table 3 below, the milk soaked with the synthetic fibers of the present invention had an extremely excellent preservability.

<Effects of the Invention> The synthetic fiber of the present invention has excellent antibacterial properties due to the synergistic effect of the copper compound and the GeI lemanium compound.

It exhibits health effects, and underwear made of the synthetic fiber of the present invention is effective because it leads to health improvement just by wearing it once.

Claims (3)

[Claims] (1) Copper or its compounds with an average particle size of 10 μm or less (
A) and germanium or its compound (B) with an average particle size of 10 μm or less in total of 0.1% by weight or more and 10% by weight
A synthetic fiber characterized by containing the following: (2) The weight ratio (A)/(B) of (A) and (B) is 1
The synthetic fiber according to claim 1, which has a ratio of /99 to 50/50. (3) Immediately after the polymerization of the fiber-forming polymer is completed and immediately before spinning, copper or its compound (A) having an average particle diameter of 10 μm or less dispersed in a dispersion medium that is compatible with the polymer and the average The method for producing synthetic fibers according to claim 1, wherein germanium or its compound (B) having a particle size of 10 μm or less is added to the polymer, kneaded, and then spun.