JP4945427B2 - Negative ion generating material and method for producing the same - Google Patents

Description

  The present invention relates to a negative ion generating material, more specifically, a novel fiber comprising a mixed fiber in which one of two different types of charged fibers is charged with a negative charge and brought into contact with each other to generate negative ions. The present invention relates to a negative ion generating material and a manufacturing method thereof.

  Negatively charged air ions, so-called negative ions, have played an important role in maintaining human health and have a healing effect. Many materials and methods for generating have been proposed. In particular, due to the rapid progress of therapeutic medicine using active electrons in recent years, the mechanism of action of negative ions on the human body has been elucidated. The interest in negative ions is increasing as a result of the effectiveness of certain electrons.

  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. Kneaded with alkali cellulose and spun to produce charged rayon fiber (see Patent Document 1), synthetic yarn mixed with tourmaline fine powder and silk yarn (see Patent Document 2), and generates negative ions A wool fiber product (see Patent Document 3) that generates negative ions obtained by heat treatment after contacting an aqueous solution in which inorganic fine particles and a keratinized wool-dissolving substance are dispersed with a wool fiber product, or polyamide synthetic fiber or wool or Minus for heat insulation supporter made of double structure knitted fabric with outer surface made of both blended fibers and lining made of polyvinyl chloride fiber ON-generated fabric (see Patent Document 4), two types of polyesters with different melt viscosities are eccentrically combined, and a medical patch base fabric (see Patent Document 5) made of polyester composite fiber having latent crimping ability, conductive A fiber product that generates negative ions made of a blended yarn of a core-sheath acrylic composite conductive fiber containing a conductive component such as a conductive powdered metal oxide in the core and other fibers (see Patent Document 6), bamboo A composite knitted fabric (see Patent Document 7) that generates negative ions composed of a side-by-side type or an eccentric core-sheath type composite fiber of a cellulose-based fiber and two or more polyester-based polymers is proposed.

  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. In addition, a special technique such as a combination of the above and the like is required, and when a raw material mixed with fine particles is spun, the spinning nozzle is easily damaged. In addition, when inorganic fine particles that generate negative ions are dispersed in a keratinized wool-dissolving substance, complicated treatment is required to keratinize the wool-dissolving substance, and this dispersion is attached to the surface of the wool fiber. However, even if the negative ion generation ability is given, the stability is low, and it is difficult to maintain the ability for a long time.

  Furthermore, a special knitting technique must be used to form a double structure knitted fabric with an outer fabric and a lining made of different fabrics, or to form a composite fiber that is eccentrically compounded. In addition, there are drawbacks in that a complicated operation using a special apparatus is required to manufacture a core-sheath acrylic composite conductive fiber containing conductive powder in the core.

  In addition, in the method of generating negative ions by rubbing a material containing 8% by mass or more of materials that are easily charged with negative static electricity with materials that are not easily charged with negative static electricity, polyvinylidene chloride may be used as a material that is easily charged with negative static electricity. Although known (see Patent Document 8), polyvinylidene chloride has a low moldability and a large triboelectric chargeability, so that it is formed into a fiber and mixed with other fibers to form a fabric. It was very difficult.

The present inventors have previously developed a novel that can generate negative ions by utilizing the characteristics of the material itself and can maintain this ability for a long period of time without mixing a piezoelectric substance such as tourmaline. As a suitable fiber material, a fiber cloth composed of natural protein fibers and polyvinylidene chloride fibers and capable of generating negative ions, in which the polyvinylidene chloride fibers are charged with a negative charge has been proposed (see Patent Document 9).
However, protein fibers, such as silk fibers, used for this fiber cloth lack the wear resistance and have the disadvantages that they are altered and yellowed by ultraviolet rays.

  On the other hand, in order to overcome the drawbacks of silk fibers as described above, a method of processing an epoxy resin after treatment with an aqueous polyethylene glycol solution (see Patent Document 10), a mixture of an aqueous fibroin solution and a highly hydrophilic resin is applied to the fiber surface. The applied fabric is dried and wet-heat treated (see Patent Document 11). The silk fiber product is dipped in an aqueous solution such as polyethylene glycols and crown ethers, dried, treated with an epoxy resin, and further heat-treated. A method (see Patent Document 12) and the like have been proposed. However, when these treatments are carried out, the wear resistance and UV resistance are improved, but the ability to generate negative ions based on friction with polyvinylidene chloride fibers and hydrophilicity are improved. It is inevitable that the sex will decline.

JP-A-4-327207 (Claims and others) JP-A-10-331042 (Claims and others) JP 2001-355182 A (Claims and others) JP 2003-247151 A (Claims and others) JP 2004-43988 A (Claims and others) JP 2004-91984 (Claims and others) JP 2004-124348 A (Claims and others) JP 2002-95960 A (Claims and others) JP 2007-191834 A (Claims and others) JP-A-11-323735 (Claims and others) JP-A-5-71073 (Claims and others) JP-A-5-71072 (Claims and others)

  The present invention generates negative ions by utilizing the characteristics of the material without mixing foreign substances such as tourmaline, semiconductor materials, radioactive materials, etc., and has a higher negative ion generation capability than conventional ones, and has a long period of time. The purpose of the present invention is to provide a negative ion generating material that lasts without a decrease in its ability.

  In the negative ion generating material composed of a mixed fiber cloth containing silk fiber and polyvinylidene chloride fiber, the present inventors have the ability to generate negative ions and hydrophilicity if the silk fiber is coated with ultrahigh molecular weight poly-γ-glutamic acid. Thus, the present inventors have found that the friction resistance and ultraviolet resistance can be improved without deteriorating the preferable physical properties inherently possessed by silk fibers.

  That is, the present invention comprises a mixed fiber cloth comprising a silk fiber coated with an ultrahigh molecular weight poly-γ-glutamic acid having a mass average molecular weight of 600,000 to 3 million, and a polyvinylidene chloride fiber, and the polyvinylidene chloride After immersing silk fibers in a negative ion generating material characterized by negatively charged fibers and a poly-γ-glutamic acid aqueous solution, and drying, an aqueous suspension or compound of a compound having a carbodiimide group After immersing in an aqueous functional epoxy compound solution and crosslinking reaction, it is dried to form silk fibers coated with ultra-high molecular weight poly-γ-glutamic acid having a mass average molecular weight of 6 to 3 million, The present invention provides a method for producing a negative ion generating material characterized in that it is blended with polyvinylidene chloride fiber and formed into a cloth shape.

  The negative ion generating material of the present invention is composed of two types of fibers, that is, silk fibers coated with poly-γ-glutamic acid and polyvinylidene chloride fibers. In this way, negative ions are effectively generated by the combination of the hydrophilic silk fiber at the upper part of the charged column and the polyvinylidene chloride fiber at the lowest level of the charged column. In addition, poly-γ-glutamic acid has a water retention rate of 3000 mass times, which is the highest value in the polymer, and when this is coated on silk fibers in a thin film form, poly (γ-glutamic acid) can be obtained without impairing the excellent properties of silk. High negative ion generation ability by friction with vinylidene chloride fiber.

  As the silk fiber used in the present invention, raw silk for producing silkworms can be used, but silkworm silk produced by silkworm having a high fineness is preferable. As the fiber diameter of the silk fiber, a range of 20 to 40 μm is appropriate in view of a composite state with polyvinylidene chloride.

  The poly-γ-glutamic acid covering the silk fiber surface has a mass average molecular weight of 600,000 to 3,000,000 obtained by polymerizing glutamic acid using a bacterium belonging to the genus Bacillus separated from the viscous material of natto It is necessary to use an ultra-high molecular weight one. In order to apply a high-strength coating on the surface of silk, it is preferable to use one having a mass average molecular weight of 2 million or more.

Moreover, when manufacturing industrially, it is preferable to use as a raw material the waste produced in manufacturing processes, such as tofu, natto, and soy sauce manufactured using wheat, soybeans, etc. as a raw material.
In order to coat silk fiber with poly-γ-glutamic acid in a uniform and strong thin film, a compound having a carbodiimide group or a bifunctional epoxy compound is used as a crosslinking agent.
Examples of the compound having a carbodiimide group include a compound having two or more carbodiimide groups for causing an intermolecular crosslinking reaction, that is, a polyvalent carbodilite. This can be obtained, for example, by decarboxylating polyfunctional organic isocyanate.
Examples of the bifunctional epoxy compound include diglycidylbenzene, diglycidylcyclohexane, diglycidylurea and the like.

The amount of the compound having a carbodiimide group or the bifunctional epoxy compound is selected in the range of 0.001 to 0.1% by mass based on the mass of the silk fiber.
The ratio of the silk fiber and poly-γ-glutamic acid used is selected in the range of 0.001 to 0.5 parts by mass, preferably 0.003 to 0.1 parts by mass, per 100 parts by mass of the silk fiber.

In order to produce the negative ion generating material of the present invention, the silk 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 silk fiber, followed by centrifugation or Remove the water by filtration and dry.
Next, this poly-γ-glutamic acid adsorbed silk fiber is wound around, for example, a plastic pipe, immersed in a weakly acidified solution containing a crosslinking agent, kept at 20-50 ° C., and then raised to 80 ° C. Allow the crosslinking reaction to occur. This reaction time is usually about 0.5 to 3 hours. The liquidity at this time is adjusted by adjusting the pH to 5 to 6 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 silk fiber is taken out, washed with water, and dried at 80 to 100 ° C.
In this way, silk fibers coated with ultra-high molecular weight poly-γ-glutamic acid having a mass average molecular weight of 6 to 3 million are formed.

  In the above cross-linking reaction, in the case of a compound having a carbodiimide group, an alkyl ether bond of isourea is formed between the hydroxyl group of serine which is an active group in the silk fibroin molecule, and a carboxyl group of the active group of poly-γ-glutamic acid. An acylurea bond is formed with each group.

On the other hand, in the case of a bifunctional epoxy compound, a hydroxy ether bond is formed between the hydroxyl group of serine which is an active group in the silk fibroin molecule, and a β-hydroxy ester is formed between the carboxyl group of poly-γ-glutamic acid. A bond is formed.
The negative ion generating material of the present invention is produced by mixing the poly-γ-glutamic acid-coated silk fiber obtained as described above and polyvinylidene chloride fiber. When these fiber components are brought into contact with each other and mechanically subjected to friction, a negative charge is charged on the polyvinylidene chloride fiber in the mixed fiber, and negative ions are generated.
The mixing ratio of the poly-γ-glutamic acid-coated silk fiber and the polyvinylidene chloride fiber in the negative ion generating material of the present invention is in the range of 20:80 to 80:20 by mass ratio.

  In order to effectively generate negative ions in the material of the present invention, the degree of freedom of the fibers in the material can be adjusted so that the movement of the human body can be efficiently synchronized with the friction between the fibers due to the movement of the fibers during use. It is desirable to have a large structure. Material structure design is important for the generation of negative ions. For example, in a flat fiber structure, woven fabric, knitted fabric, nonwoven fabric with low needle punch density, nonwoven fabric with high needle punch density, and web fixing with water jet The degree of freedom of movement of the fibers decreases in the order of non-woven fabric, knitted fabric, and woven fabric, and the generation of negative ions also decreases.

Negative ions generated from the negative ion generating material of the present invention can be easily measured, for example, by using an air ion measuring device manufactured based on the principle of the Gel Diene method.
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)
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] = I / (e · F) (2)
In the above formula, I: 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 clones / second)

The value of I in 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.
I = (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 diene method air ion measuring apparatus. In this measurement, a sample to be measured for negative ions is dried at 40 ° C. for 2 hours and then stored in a desiccator for 12 hours.

FIG. 3 is a schematic side view showing the overall 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 aspirator 9 is operated. A constant amount of air is passed through the apparatus and passed 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.

  In the present invention, the amount of negative ions calculated in this way is significantly larger than the amount of negative ions generated in a fiber cloth made of viscose fibers kneaded with conventionally known negative ion generating materials such as tourmaline. In addition, it has the advantage of lasting for a long time.

  Next, the best mode for carrying out the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Reference example 1
An aqueous solution 1 containing 100 g of Chinese sak silk thread (fineness of 21 denier or more) and 0.0034% by mass of poly-γ-glutamic acid (manufactured by Fukuoka Brewing Cooperative Association) having a mass average molecular weight of 3 million based on the weight of the sak silk thread After immersing in 5 liters at 40 ° C. for 1 hour to adsorb poly-γ-glutamic acid to the cocoon silk thread, it was centrifuged to remove moisture, and then air-dried.
The sachet yarn adsorbed with poly-γ-glutamic acid thus obtained is wound around a plastic pipe having an outer diameter of 10 mm. Subsequently, a polymer compound having a carbodiimide group (made by Nisshinbo Co., Ltd.) having a carbodiimide equivalent of 355 to 380 (molecular weight of polymer / number of carbodiimide groups in the polymer) obtained by decarboxylation condensation of organic diisocyanate is 40% by weight of water. A suspension was prepared to prepare 3 liters of a pH 5.5, 0.2% by weight aqueous solution, and a plastic pipe around which the above sample was wound was immersed therein, and the temperature was kept at 80 ° C. and reacted for 1 hour. Thereafter, it was taken out, washed with water, dried at 90 ° C., cut into 51 mm, and uniformly coated with 0.0034% by mass of poly-γ-glutamic acid to produce crimped silk fibers.
Next, by changing the amount of poly-γ-glutamic acid relative to the cocoon silk thread and treating in the same manner, it was coated with 0.03% by mass, 0.06% by mass and 0.09% by mass of poly-γ-glutamic acid, respectively. Silk fiber samples were produced.

Reference example 2
100 g of the same Chinese sak silk thread as in Reference Example 1 was immersed in 1.5 liter of an aqueous solution containing 0.0034% by mass based on the mass of this sak silk thread at 40 ° C. for 1 hour. γ-glutamic acid was adsorbed and air-dried. In this way, a cocoon yarn coated with poly-γ-glutamic acid is wound on a plastic pipe having an outer diameter of 10 mm, and ethylene glycol diglycidyl ether (special grade reagent manufactured by Tokyo Chemical Industry Co., Ltd.) adjusted to pH 4.5 with acetic acid is used. After being immersed in 3 liters of a 1% by weight aqueous solution and heated to 40 ° C. for 1 hour, the temperature was raised to 80 ° C. and reacted for 2 hours. Next, the treated silk fiber was taken out, washed with water, dried, cut into 51 mm, and a crimped silk fiber sample uniformly coated with 0.0034% by mass of poly-γ-glutamic acid was produced.
Next, by changing the amount of poly-γ-glutamic acid relative to the cocoon silk thread and treating in the same manner, it was coated with 0.03% by mass, 0.06% by mass and 0.09% by mass of poly-γ-glutamic acid, respectively. Silk fiber samples were produced.

A filament having a denier of 7 denier obtained by melt-spinning a polyvinylidene chloride fiber (made by Asahi Kasei Co., Ltd., softening point 150 to 165 ° C.) made of an equimolar copolymer of vinylidene chloride and vinyl chloride was cut to a length of 51 mm. A mixture of 2.1 kg of staple fibers and 0.9 kg of silk fibers coated with poly-γ-glutamic acid obtained in Reference Example 1 was scattered and defibrated in the air by a defibrating machine, and the cotton was mixed in a uniform state. A product was formed. Next, after collecting the cotton-like material on a moving wire mesh belt conveyor to form a layered body, it is inserted into a card machine with a sawtooth wire on a rotating cylinder, combed in the moving direction, and has a basis weight of 300 g / m ^2. The web was formed. Subsequently, needle punching was given to this and the nonwoven fabric was manufactured.
About the nonwoven fabric obtained in this way, the triboelectric charge between fibers was generated by a measurement air flow, and the number density of negative ions was measured as follows.
A 15 cm × 15 cm square piece is cut from the nonwoven fabric, dried at 40 ° C. for 2 hours, and stored in a desiccator for 12 hours.
Next, the sample is put into a sample tube of a gel diene method measuring apparatus, and air of 2.01 liter / min is flowed from the outside to the sample. 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 (1), (2 ) To obtain the negative ion number density [-D].
The measured value is measured at a time zone where the temperature and humidity are close to the same day on a standard sample obtained at 25 ° C. and 30% relative humidity of flowing air, and correction is made based on this value.
The results thus obtained are shown in Table 1.

  In addition, FIG. 4 shows a graph plotting the relationship between the ratio [P] of poly-γ-glutamic acid to the crushed silk thread and the negative ion number density [−D].

2.1 kg of the same polyvinylidene chloride fiber as used in Example 1 and 0.9 kg of the silk fiber coated with poly-γ-glutamic acid obtained in Reference Example 2 were mixed and scattered in the air by a defibrator. The fiber was defibrated to form a uniform mixture. Next, after collecting the cotton-like material on a moving wire mesh belt conveyor to form a layered body, it is inserted into a card machine with a sawtooth wire on a rotating cylinder, combed in the moving direction, and has a basis weight of 300 g / m ^2. The web was formed. Subsequently, needle punching was given to this and the nonwoven fabric was manufactured.
About the nonwoven fabric obtained in this way, the triboelectric charge between fibers was generated by an air flow for measurement, and the number density of negative ions was measured by the same method as in Example 1. The results are shown in Table 2.
In Table 2, for comparison, Sample No. which is not coated with poly-γ-glutamic acid is shown. The measurement results of 5 are also shown.

  In addition, FIG. 4 shows a graph plotting the relationship between the ratio [P] of poly-γ-glutamic acid to the crushed silk thread and the negative ion number density [−D].

  As can be seen from Table 1 and Table 2, fibers coated with silk using poly-γ-glutamic acid with ultra-high molecular weight as a cross-linking agent or a polymer having carbodiimide group or ethylene glycol diglycidyl ether and polychlorinated A non-woven fabric made of a mixed fiber with vinylidene fiber generates significantly more negative ions than a non-woven fabric made of a mixed fiber of silk fiber and polyvinylidene chloride fiber that does not use poly-γ-glutamic acid at all. This effect is manifested in a very small amount of poly-γ-glutamic acid processed into silk of 0.0034 to 0.03, because the thin film of poly-γ-glutamic acid covers the silk surface. This is considered to be due to the increase in the triboelectric charging property with the polyvinylidene chloride fiber from the increase in the affinity of water for water and the change in the charge series.

Examples 3-7
Sac silk yarn coated with 0.06% by mass of poly-γ-glutamic acid and the same polyvinylidene chloride fiber as used in Example 1 were in a mass ratio of 20:80 (Example 3), 30:70 (implementation) Example 4), 40:60 (Example 5), 60:40 (Example 6), 80:20 (Example 7) were used in the same manner as in Example 1 using mixed fibers, and the basis weight was 300 g / A web of m ² was formed and subjected to a rotating cylinder punching process to produce a nonwoven fabric.
The negative ion number density of these nonwoven fabrics was measured in the same manner as in Example 1, and the results are shown in Table 3.
For comparison, a poly-γ-glutamic acid-coated sac silk thread alone (Comparative Example 1), a polyvinylidene chloride fiber alone (Comparative Example 2), and a viscose fiber alone (Comparative Example 3) kneaded with a commercially available powdered tourmaline. The measurement results were also shown.

  As can be seen from this table, the nonwoven fabric composed of mixed fibers of poly-γ-glutamic acid-coated sachet yarn and polyvinylidene chloride fiber generates more negative ions than the nonwoven fabric composed of each fiber alone and commercially available products. In addition, the mixture ratio of poly-γ-glutamic acid-coated sachet yarn and polyvinylidene chloride fiber has the characteristic of generating an equal and high negative ion over a wide range (20:80 to 80:20). . This is advantageous for designing the final product such as lightness, heat retention and elasticity.

  Moreover, it shows in FIG. 5 as a graph which plotted the relationship between the ratio of the processed silk thread and the polyvinylidene chloride fiber in this case, and negative ion number density [-D].

  The present invention provides a negative ion generating material comprising a polyvinylidene chloride fiber having improved durability by coating the surface of a sak silk thread with an ultra-high molecular weight poly-γ-glutamic acid, which is important for human health. Fibers that generate a larger amount of negative ions that work than conventional blended yarns of sac silk yarn and polyvinylidene chloride fiber can be obtained, and can be widely used as clothing, bedding, and innerwear useful for health.

Explanatory drawing for demonstrating the principle of the measuring apparatus of the air ion based on the Keldieen method used in order to quantitate a negative ion. The graph which shows the relationship between the applied voltage to the outer cylinder 1 in FIG. 1, and the electric current which flows into the inner cylinder 2. FIG. Side surface schematic solution figure which shows the whole structure of a measuring apparatus. The graph which shows the relationship between the ratio of poly- (gamma) -glutamic acid of the nonwoven fabric obtained by the blend with the sac silk thread and the polyvinylidene chloride fiber which changed the ratio of poly- (gamma) -glutamic acid, and the generation amount of anion. The graph which shows the relationship between the blend ratio of both fibers and the generation amount of negative ions in a blend nonwoven fabric of poly-γ-glutamic acid-coated sachet yarn and polyvinylidene chloride fiber.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Outer cylinder 2 Inner cylinder 3 Electrometer 4 DC power supply 5 Insulation board 6 Sample cylinder 7 Air inlet 8 Flowmeter 9 Suction machine 10 Air exhaust port

Claims (6)

  It consists of a mixed fiber cloth containing a silk fiber coated with ultra high molecular weight poly-γ-glutamic acid having a mass average molecular weight of 600,000 to 3 million and a polyvinylidene chloride fiber, and the polyvinylidene chloride fiber is negatively charged. An anion generating material characterized by being made.   The negative ion generating material according to claim 1, wherein the coating treatment of the silk fiber with the ultrahigh molecular weight poly-γ-glutamic acid is carried out using a compound having a carbodiimide group or a bifunctional epoxy compound as a crosslinking agent.   The negative ion generating material according to claim 1 or 2, wherein a content ratio of the ultrahigh molecular weight poly-γ-glutamic acid coating to 100 parts by mass of silk fibers is in the range of 0.001 to 0.5 parts by mass.   The negative ion generating material according to claim 1, 2 or 3, wherein the ratio of the silk fiber to the polyvinylidene chloride fiber in the mixed fiber is in the range of 80:20 to 20:80 by mass ratio.   After immersing silk fiber in poly-γ-glutamic acid aqueous solution, after drying, immerse in aqueous suspension of compound having carbodiimide group or bifunctional epoxy compound aqueous solution, crosslink reaction, dry and mass Minus characterized by forming silk fibers coated with ultra-high molecular weight poly-γ-glutamic acid having an average molecular weight of 6 to 3 million, and then blending the silk fibers and polyvinylidene chloride fibers to form a cloth. A method for producing an ion generating material.   6. The method for producing a negative ion generating material according to claim 5, wherein the negative ion generating material is formed in a woven, knitted or non-woven shape.

Images