JP4824125B1 - Negative ion generating polyester fiber and manufacturing method of negative ion generating product using the same - Google Patents

Abstract

[PROBLEMS] To generate negative ions by utilizing the properties of polyester fibers without mixing foreign materials such as tourmaline, semiconductor substances, radioactive substances, etc. into polyester fibers with high heat retention and high negative ion generation materials. Provided is a negative ion generating fiber which has a higher ability to generate negative ions than those of the ones and has a high heat retention property that lasts for a long period of time without decreasing its capacity.
It comprises a mixed fiber comprising an ultrafine polyester fiber coated with an ultrahigh molecular weight poly-γ-glutamic acid having a mass average molecular weight of 1,000,000 to 3,000,000 and an untreated ultrafine polyester fiber. A short fiber length and a collection of ultra-fine polyester fibers give high heat retention due to air with low thermal conductivity that is significantly hindered from moving in the infinite number of minute spaces formed, and untreated polyester The fiber is a polyester fiber that is negatively charged and generates many negative ions by contact or friction.
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Description

  The present invention relates to a negative ion generating polyester fiber and a method for producing a negative ion generating product using the same. More specifically, in addition to excellent heat retention, a novel polyester fiber that generates negative ions and the same are used. The present invention relates to a method for producing a negative ion generating product.

  Negative ions play a major role in maintaining human health and have a healing effect, which has attracted more attention than before, and many materials and methods for artificially generating this Has been proposed. In particular, as a result of the rapid progress of therapeutic medicine using electrons in recent years, the mechanism of action of negative ions on the human body has been elucidated. As a result, the electrons that are the source of negative ions are the active oxygen that causes health impairment. It has become clear that it inhibits the body's production, and interest in negative ions is increasing.

  As one of the methods of utilizing these negative ions, there is known a method for producing clothing and a futon cover with a fiber having a function of generating negative ions. There is a chargeable rayon fiber produced by kneading an alkali cellulose and spinning it (see Patent Document 1). However, in order to knead inorganic fine particles that generate negative ions such as tourmaline into a fiber raw material and spin it, it must be pulverized to a particle size of 0.8 μm or less, which includes dry pulverization and wet pulverization. Special techniques such as using with are required. In addition, when a raw material mixed with fine particles is spun, the spinning nozzle is easily damaged.

  Moreover, what uses a polyester fiber is also known (refer patent document 2). However, when using polyester fibers, a structure in which two types of polyester fibers having different melt viscosities are combined eccentrically or a structure in which the polyester fibers have pores with an average pore radius of about 20 nm must be adopted. , Extremely complex and costly.

  Furthermore, a composite knitted fabric that generates negative ions composed of cellulosic fibers and two or more polyester side-by-side type or core-sheath type composite fibers is also known (see Patent Document 3). However, this is also complicated in structure.

JP-A-4-327207 (Claims and others) JP 2005-68565 A (Claims and others) JP 2004-124348 A (Claims and others)

  Accordingly, the object of the present invention is to prevent foreign matters such as tourmaline, semiconductor materials, radioactive materials and the like from being mixed into the fiber, and has a higher ability to generate negative ions as compared with the prior art, without reducing its performance over a long period of time, and keeping heat An anion-generating polyester fiber rich in water is provided.

  In addition to the fact that the ultrafine polyester fiber having a short fiber length has a characteristic that is rich in heat retention and is used, the present inventors have a means for changing only the surface characteristics without changing the physical properties of the ultrafine polyester fiber. As a result of diligent research, ultra-high molecular weight poly-γ-glutamic acid ultra-thin film was coated and fixed on the surface of ultra-fine polyester fiber using a cross-linking agent, and this was mixed with uncoated ultra-fine polyester fiber and brought into contact with each other Alternatively, it was found that a large amount of negative ions is generated by rubbing, and the present invention has been made.

That is, the present invention provides a mixed polyester fiber comprising a polyester fiber (A) coated with an ultrahigh molecular weight poly-γ-glutamic acid having a mass average molecular weight of 1,000,000 to 3,000,000 and an untreated polyester fiber (B), The present invention provides a negative ion generating polyester fiber characterized in that the uncoated polyester fiber is negatively charged.
In this invention, it is preferable that the outer diameter of the said polyester fiber (A) and the said polyester fiber (B) is 5 micrometers-14 micrometers, and length is 5 mm-10 mm. Moreover, it is preferable that the coating process of the said polyester fiber (A) is performed using the bifunctional epoxy compound as a crosslinking agent. Furthermore, it is preferable that the coating ratio of the ultrahigh molecular weight poly-γ-glutamic acid with respect to 100 parts by mass of the polyester fiber (A) is in the range of 0.001 to 0.3 parts by mass. Furthermore, the mixing ratio of the polyester fiber (A) and the polyester fiber (B) is preferably 80:20 to 10:90 by mass ratio.

  The present invention also provides a cold-proof outer garment in which the above-described negative ion-generating polyester fiber is filled in a finely woven fabric having air permeability, a resin-processed fabric having air permeability, or an aggregate bag structure subjected to three-dimensional quilting. The present invention provides a method for producing a negative ion generating product characterized by forming a bedding, a sleeping bag, and the like.

  According to the present invention, the amount of negative ions generated is significantly larger than that of a conventionally known negative ion generating material, for example, a fiber cloth made of viscose fiber kneaded with tourmaline. On top of that, it has the effect of lasting for a long time. Moreover, there exists an effect excellent also in heat retention.

It is explanatory drawing for demonstrating the principle of the measuring apparatus of the air ion based on the gel Diene method used in order to quantitate a negative ion. 2 is a graph showing the relationship between the voltage applied to the outer cylinder 1 and the current flowing through the inner cylinder 2 in FIG. 1. It is a side schematic solution figure showing the whole structure of a measuring device. It is a graph which shows the relationship between the processing coating fraction of poly-gamma-glutamic acid, and the generation amount of an anion. It is a graph which shows the relationship between the poly- (gamma) -glutamic acid covering ultrafine polyester fiber cotton fraction in mixed cotton, and the amount of negative ion generation. It is a graph which shows the relationship between a very fine polyester fiber diameter and the amount of negative ion generation.

Hereinafter, embodiments of the present invention will be specifically described.
The negative ion generating polyester fiber of the present invention is composed of two types of polyester fibers (A) and (B) having different surface characteristics. That is, one polyester fiber (A) coated with poly-γ-glutamic acid has a polyamide structure with a higher surface charged series and the other is an uncoated polyester fiber (B) with a lower charged series. Because of this combination, both fibers are blended and a large amount of negative charge is generated on the untreated polyester fiber (B) by contact or friction. Furthermore, the polyester fiber (A) coated with poly-γ-glutamic acid has an actual measurement value of 22 ° C. ± 2 ° C. and a relative humidity of 69% ± 2% in the case of a fiber having a fiber diameter of 10.4 microns. 12.4% of water is retained, and water effectively acts on the negative ions generated on the untreated polyester fiber (B), resulting in high negative ion generation ability.

  The polyester fiber that can be used in the present invention can be suitably produced by using a polyester polymer of a grade for ultra-fine polyester fiber and using a nozzle for fineness in an ordinary spinning machine. By increasing the surface area of the fiber, the area of contact or friction between the fibers increases, the negative ion generation capacity increases, and the amount of air constrained in movement between the fibers increases, thus maintaining a heat retention effect. Therefore, it is preferable that the fineness is as fine as possible, and a fiber size in the range of 5 to 14 microns is particularly suitable. As the ultra-fine polyester fiber, for example, 1.7 dTex × 51 mm (diameter 13 microns), 1.1 dTex × 38 mm (diameter 10.4 microns), 0.8 dTex × 35 mm (diameter 8.9 microns) used in the following examples. And 0.23 dTex × 35 mm (diameter 4.8 microns).

  When using the ultra-fine polyester fibers (A) and (B), the woven fabric of the form according to the application is filled with the air flow into the space obtained by quilting, and the fiber structure seems to have high heat retention. In addition, the fiber length is preferably 5 mm to 10 mm, more preferably 6 mm to 8 mm. In this way, for example, the above-described negative ion generating polyester fiber is filled in a finely woven fabric having air permeability, a resin processed fabric having air permeability, or a collective bag structure subjected to three-dimensional quilting. A winter jacket, bedding, a sleeping bag, etc. can be formed.

  The poly-γ-glutamic acid that covers the surface of the ultra-fine polyester fiber is a mass average molecular weight of 1,000,000 to 3,000,000 obtained by polymerizing glutamic acid with a bacterium belonging to the genus Bacillus separated from the viscous material of natto. It is necessary to use a high molecular weight one. In order to apply a high-strength coating to the surface of the ultra-fine polyester fiber, it is preferable to use one having a mass average molecular weight of 1.5 million or more.

  Moreover, when manufacturing industrially, it is preferable to use as a raw material the waste which arises in manufacturing processes, such as tofu, natto, and soy sauce which make wheat, soybeans, etc. as a raw material. In order to coat poly-γ-glutamic acid on the ultrafine polyester fiber in a uniform and strong thin film, it is preferable to use a bifunctional epoxy compound as a crosslinking agent. Examples of the bifunctional epoxy compound include ethylene glycol diglycidyl ether, diglycidyl benzene, diglycidyl cyclohexane, diglycidyl urea and the like.

  The amount of the bifunctional epoxy compound used is preferably in the range of 0.001 to 0.1% by mass with respect to the mass of the ultrafine polyester fiber. Further, the proportion of the ultrafine polyester fiber and poly-γ-glutamic acid used is preferably in the range of 0.001 to 0.3 parts by mass, more preferably 0.003 to 0.1 parts by mass, per 100 parts by mass of the ultrafine polyester fiber. Within.

In order to produce the negative ion generating fiber of the present invention, the ultrafine polyester fiber is immersed in an aqueous solution containing a predetermined amount of poly-γ-glutamic acid, and the poly-γ-glutamic acid is sufficiently adsorbed to the ultrafine polyester fiber, followed by filtration. To remove water.
Next, this ultra-fine polyester fiber adsorbed with poly-γ-glutamic acid is wound around, for example, a plastic pipe, immersed in a liquid adjusted to weak acidity containing a cross-linking agent, held at 40-60 ° C., and then 80 ° C. The crosslinking reaction is carried out by raising the temperature to 90 ° C., and the reaction is terminated. This reaction time is usually about 2 to 4 hours. The liquidity at this time is adjusted by adjusting the pH to 4 to 4.5 with an organic acid such as acetic acid or propionic acid, or an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid. After completion of the crosslinking reaction, the ultrafine polyester fiber is taken out, washed with water, and dried at 80 to 100 ° C.
In this way, ultrafine polyester fibers coated with ultrahigh molecular weight poly-γ-glutamic acid having a mass average molecular weight of 1,000,000 to 3,000,000 are formed.
In the crosslinking reaction, a β-hydroxyester bond is formed between the bifunctional epoxy compound and the carboxyl group of poly-γ-glutamic acid.

  The negative ion generating fiber of the present invention is produced by mixing the poly-γ-glutamic acid-coated ultrafine polyester fiber (A) obtained as described above and an untreated ultrafine polyester fiber (B). Then, when these fiber components are brought into contact with each other and mechanically friction is applied, the polyester fibers coated with poly-γ-glutamic acid by the negative charges generated by charging on the untreated ultrafine polyester fibers (B) in the mixed fibers. The water held by (A) acts and negative ions are generated.

  The mixing ratio of the poly-γ-glutamic acid-coated ultrafine polyester fiber (A) and the untreated ultrafine polyester fiber (B) in the negative ion generating fiber of the present invention is preferably 80:20 to 10:90, more preferably by mass ratio. Is in the range of 60:40 to 15:85.

The negative ions generated from the highly heat-retaining negative ion generating polyester fiber material of the present invention can be easily measured by using, for example, an air ion measuring device manufactured based on the Gerdien principle.
FIG. 1 is an explanatory view of this measuring apparatus, which is composed of an outer cylinder (applied voltage cylinder) 1 and an inner cylinder (collecting electrode cylinder) 2 which are electrically insulated. The outer cylinder 1 is connected to a DC power source 4 and the inner cylinder 2 is connected to an electrometer 3. When negative current is applied to the outer cylinder 1 while air containing air ions is passed through the gap between the outer cylinder 1 and the inner cylinder 2 at a constant flow rate in the axial direction, negative ions in the air passing between the cylinders are When the voltage applied to the outer cylinder 1 is increased and the voltage applied to the outer cylinder 1 is increased, the current flowing through the inner cylinder 2 gradually increases. Then, under an applied voltage at which all ions passing through the point P can be captured at the T point, all ions entering between the inner cylinders are captured by the inner cylinder 2 and flow to the inner cylinder 2 when the applied voltage exceeds this value. The current becomes a constant value.

FIG. 2 is a graph showing the relationship between the voltage applied to the outer cylinder 1 and the current flowing through the inner cylinder 2. In FIG. 2, the current (ohmic current) flowing through the inner cylinder 2 that increases with the applied voltage is saturated even if the applied voltage is increased at a certain point in time and becomes saturated (saturated current).
Further, assuming that the mobility of ions in which all negative ions are trapped, that is, the critical mobility is kc, this kc is expressed by the following equation (1).
kc = [F / (4π · aV)] (1)
Where F: air flow rate (cm ³ / sec)
V: Applied voltage (volt)
a: Device constant

Further, the negative ion number density [D] is given by the following equation (2) from the average current flowing for a certain time in the saturation current.
[D] = Is / (e · F) (2)
In the above formula, Is: average current (ampere / second) flowing in a certain time in the saturation current amount region
[D]: Negative ion number density (pieces / cm ³ )
However, e: charge amount of one electron (1.6 × 10 ⁻¹⁷ coulomb / second)

The value of Is in the equation (2) can be obtained according to the following equation (3) from the charge amount Q (coulomb) accumulated in the inner cylinder 2 for a fixed time t seconds.
Is = (Q / t) (3)

  And the negative ion number density can be calculated | required based on said Formula by substituting the measured value obtained from a Gel Dien method air ion measuring apparatus to Formula (2). In this measurement, a sample whose negative ions are to be measured is dried in advance at 40 ° C. for 2 hours and then stored in a desiccator for 12 hours.

FIG. 3 is a schematic side view showing the entire structure of the negative ion measuring apparatus. When negative ions are measured using this apparatus, the sample is loaded into the sample tube 6 and the suction device 9 is operated. And let a certain amount of air flow through the apparatus and pass over the sample. The air that has passed over the sample passes between the outer cylinder 1 and the inner cylinder 2 and is discharged from the exhaust port 10. When the air amount reaches a steady state, a voltage is applied to the outer cylinder 1 in the following cycle for t seconds. Reference numeral 5 denotes an insulating plate, 7 denotes an air inlet, and 8 denotes a flow meter. 3 is an electrometer, and 4 is a DC power source.
0 → 40V → 0 → 60V → 0 → 80V → 0 → 100V → 0 → 120V → 0 → 140V → 0 → 160V

In this way, a voltage is repeatedly applied, and the charge amount Q (coulomb) accumulated for t seconds is measured.
Then, the current I flowing through the inner cylinder 2 is calculated by the equation (3), the saturation current value Is is obtained from the relationship graph between the current I and the applied voltage prepared in advance, and the negative ion number density [ D] is calculated.

  EXAMPLES Next, although an Example demonstrates this invention, this invention is not limited at all by these examples.

Reference Example: Ultra-fine polyester fiber 1.1 dTex × 38 mm (outer diameter 10.4 micron) 100 g, poly-γ-glutamic acid (manufactured by Fukuoka Brewing Co., Ltd.) having a mass average molecular weight of 3 million was 0.03 based on the mass of the ultra-fine polyester fiber. It was immersed for 1 hour at 40 ° C. in 1.5 liter of an aqueous solution containing a mass% ratio to adsorb poly-γ-glutamic acid to the ultrafine polyester fiber, and then air-dried. In this way, an ultrafine polyester fiber coated with poly-γ-glutamic acid was wound around a plastic pipe having an outer diameter of 10 mm. Next, this was immersed in 3 liters of a 1% by weight aqueous solution of ethylene glycol diglycidyl ether (special grade reagent manufactured by Tokyo Chemical Industry Co., Ltd.) adjusted to pH 4.5 with acetic acid, heated to 40 ° C. for 1 hour, and then 80 The temperature was raised to ° C. and reacted for 2 hours. Next, the treated polyester fiber is taken out, washed with water, dried, cut to a length of about 5 to 10 mm, and a sample of ultrafine polyester fiber uniformly coated with 0.01% by mass of poly-γ-glutamic acid is produced. did.
Next, the amount of poly-γ-glutamic acid with respect to the ultrafine polyester fiber 1.1dTex × 38 mm was changed and processed in the same manner to thereby obtain 0.03% by mass, 0.06% by mass, and 0.09% by mass, respectively. Samples of extra fine polyester fibers coated with poly-γ-glutamic acid were prepared.

Example 1
200 g of a woven fiber obtained by cutting ultrafine polyester fiber 1.1 dTex × 38 mm into a length of about 10 mm and 10 mm of 1.1 dTex × 38 mm ultrafine polyester fiber coated with poly-γ-glutamic acid obtained in Reference Example 86 g of wrinkled fibers cut into front and rear lengths were mixed with air in a polyethylene bag. Next, about 286 g of this wrinkled mixture, about 10 g of the mixed mixture was packed in an independent box-shaped bag (box) by quilting using a cloth woven with ultra-fine polyester fibers, and the inlet was quilted. Sealed with The two types of fibers moved freely in an independent box-shaped bag (box), and favorable conditions were established for generating negative ions by contact or friction.

  One box thus obtained was dried and stored by a conventional method, and then placed in a sample tube of an air ion measuring apparatus by the gel diene method, and air was flowed from the outside to the sample at 2.01 liter / min. When this air passes between the double cylinders of the measuring device, the current value (I) flowing through the inner cylinder corresponding to the applied voltage (V) to the outer cylinder is obtained, and from the saturation current value (Is) ( 2) Negative ion number density-[D] was obtained using the formula.

In addition, the measured value measured the standard sample calculated | required at 25 degreeC of the air which flows through, and 30% of relative humidity in the time zone with the same temperature and humidity of the same day, and correct | amended from this value.
The results thus obtained are shown in Table 1 below.

  Moreover, the graph shown in FIG. 4 is obtained by plotting the relationship between the coating ratio (processed coating fraction) [P] and the negative ion number density- [D] of poly-γ-glutamic acid to the ultrafine polyester fiber at this time. It was.

  As can be seen from Table 1, the ultra-high molecular weight poly-γ-glutamic acid was used as a cross-linking agent, ethylene glycol diglycidyl ether was used, and the fibers were coated and fixed on ultrafine polyester fibers (1.1 dTex × 38 mm) and untreated The aggregate structure composed of mixed fibers with the same ultrafine polyester fiber produced significantly more negative ions than a single fiber aggregate of a single ultrafine polyester fiber that does not use any poly-γ-glutamic acid. . And even if the amount of poly-γ-glutamic acid coated on the ultrafine polyester fiber is as small as 0.01 to 0.03% by mass, this effect is exhibited because the poly-γ-glutamic acid thin film is an ultrafine polyester fiber. By covering the surface of the fiber, it is considered that there was a large change in the direction of increasing the triboelectric chargeability with the ultrafine polyester fiber from the increase in the affinity of the ultrafine polyester fiber to water and the change in the upper charging series. .

Examples 2-6
A cotton (1.1 dTex × 38 mm) of an ultrafine polyester fiber coated with 0.03% by mass of poly-γ-glutamic acid obtained in Reference Example and an uncoated ultrafine polyester fiber cotton of the same type were mixed. , Mass ratio 20:80 (Example 2), 30:70 (Example 3), 40:60 (Example 4), 60:40 (Example 5), 80:20 (Example 6) Using each mixed cotton, a fiber assembly was prepared in the same manner as in Example 1 by filling 10 g of the mixed into a box quilting bag of a plain woven fabric of extra fine polyester fibers. This was dried and stored by a conventional method, and then the negative ion number density was measured by the gel diene method in the same manner as in Example 1. The results are shown in Table 2 below.

  For comparison, a fiber aggregate of a poly-γ-glutamic acid 0.03% coated ultrafine polyester fiber cotton (Comparative Example 1), an uncoated ultrafine polyester fiber cotton fiber aggregate (Comparative Example 2), and a commercially available powder The same measurement results for viscose fiber alone (Comparative Example 3) kneaded with tourmaline are also shown.

  Based on Table 2, a graph plotting the relationship between the negative ion number density of mixed cotton- [D] and the mixing ratio (mass ratio) of poly-γ-glutamic acid-coated cotton and uncoated cotton is shown in FIG.

  As shown in FIG. 5, when the ratio of the poly-γ-glutamic acid-uncoated ultrafine fiber in the mixed fiber cotton is between 20% by mass and 80% by mass, the generation of high negative ions is observed and occurs on the uncoated polyester fiber. A negative charge indicates a smooth conversion to negative ions. The rapid decrease in the generation of negative ions that occurs when the proportion of ultrafine polyester fiber is 20% by mass or less is a shortage of supply of water acting on the negative charge generated on the uncoated polyester fiber, and conversely the coated polyester. When the fiber cotton is 80% by mass or more, it is shown that the antistatic function works by the coated cotton, and the production of negative ions is reduced.

Examples 7-9
In order to determine the effect of the diameter of the ultra fine polyester fiber in the mixed fiber cotton on the generation of negative ions, 1.7 dTex × 51 mm (diameter 13 microns), 1.1 dTex × 38 mm (diameter 10.4 microns), 0.8 dTex × 35 mm With respect to four types of fibers (diameter 8.9 microns) and 0.23 dTex × 35 mm (diameter 4.8 microns), 0.03% by mass poly- with respect to each ultrafine polyester fiber by the method shown in the reference example. A cotton cut with 10 mm was produced by coating with γ-glutamic acid. Next, uncoated polyester fibers corresponding to the fineness of each coated cotton fiber were cut into 10 mm by the same method as in Example 1, mixed with each other, and filled with about 10 g in a quilting box, and four kinds of samples. And the number density of negative ions generated by the gel diene method was measured. The contents of Examples 7 to 9 are shown in Table 3 below, and the negative ion number density obtained for Examples 7 to 9 are shown in Table 4 below.

  Based on Table 3 and Table 4, the influence which the fiber diameter of mixed polyester fiber cotton has on negative ion generation is shown in FIG.

  As shown in FIG. 6, when the diameter of the ultra-fine polyester fiber is around 10 microns, the amount of negative ions rapidly decreases as the diameter becomes larger. This decrease is due to a decrease in fiber contact and friction due to a decrease in fiber surface area in a certain amount of fiber assembly.

  In the present invention, a part of ultrafine polyester fiber is used, and the surface of this fiber is coated with ultra-high molecular weight poly-γ-glutamic acid in an ultrathin film form, then insolubilized, and then cut into short pieces to form a wrinkle. Similarly, the fiber is cut short, and after wrinkling, the two are mixed to provide a fiber that has high heat retention and generates a large amount of negative ions. By filling this fiber into a textile fabric having a box-shaped bag formed by three-dimensional quilting, it can be used as a winter clothing, bedding, sleeping bag, etc. to protect humans from the cold and to maintain health. Therefore, it is expected to be widely used. Ultra-fine polyester fiber as a raw material is consumed in large quantities as a new high-value-added product, and is expected to make a significant contribution to the fiber and polymer industries.

1 Outer cylinder 2 Inner cylinder 3 Electrometer 4 DC power supply 5 Insulating plate 6 Sample cylinder 7 Air inlet 8 Flow meter 9 Suction machine 10 Air outlet

Claims (6)

  An uncoated treatment comprising a mixed polyester fiber comprising a polyester fiber (A) coated with an ultrahigh molecular weight poly-γ-glutamic acid having a mass average molecular weight of 1,000,000 to 3,000,000 and an untreated polyester fiber (B). A negative ion-generating polyester fiber, wherein the polyester fiber is negatively charged.   The anion-generating polyester fiber according to claim 1, wherein the polyester fiber (A) and the polyester fiber (B) have an outer diameter of 5 to 14 µm and a length of 5 to 10 mm.   The negative ion generating polyester fiber according to claim 1 or 2, wherein the polyester fiber (A) is coated using a bifunctional epoxy compound as a crosslinking agent.   The negative ion according to any one of claims 1 to 3, wherein a coating ratio of the ultrahigh molecular weight poly-γ-glutamic acid to 100 parts by mass of the polyester fiber (A) is in a range of 0.001 to 0.3 parts by mass. Generating polyester fiber.   The negative ion generating polyester fiber according to any one of claims 1 to 4, wherein a mixing ratio of the polyester fiber (A) and the polyester fiber (B) is 80:20 to 10:90 by mass ratio.   The negative ion generating polyester fiber according to any one of claims 1 to 5, wherein the woven fine air-permeable fabric, the resin-treated fabric having air permeability, or the assembly bag structure subjected to the three-dimensional quilting process. A negative ion generating product manufacturing method characterized by forming a cold protection outer garment, a bedding, a sleeping bag and the like.

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