JP3297581B2 - Rayon fiber containing tourmaline fine particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel rayon fiber containing tourmaline fine particles, and more particularly to a rayon fiber containing tourmaline fine particles which emits active electrons and has an activating effect on living cells.

[0002]

2. Description of the Related Art In recent years, it has been noted that active electrons activate living cells and have a favorable effect on living organisms. These active electrons can be used, for example, to regulate the autonomic nervous system and motor nervous system, sleep deeply and mentally. Researches on stabilization and promotion of recovery from fatigue have been actively made.

As a substance that emits such active electrons, naturally occurring tourmaline has been found. This tourmaline is a substance that has a permanent spontaneous electric polarization, and does not change its polarization vector due to an external electric field. In addition to the strongest permanent polarization characteristics among minerals, far-infrared radiation is also recognized.

[0004] The present inventors have conducted repeated studies to develop materials such as health apparel using tourmaline having such a function. First, the fine particles of tourmaline are contained in the fibers to form clothes and supporters. Was found to improve blood circulation in the body by wearing it, and proposed an electret fiber containing 3 to 4% by weight of tourmaline (Japanese Patent Publication No. 6-104926). On the other hand, rayon fiber is more suitable as a fiber material for health apparel because it is richer in hygroscopicity, more excellent in spinnability, better in dyeability and less expensive than synthetic fiber.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a tourmaline fine particle-containing fiber which further improves the above-mentioned electret fiber, largely releases active electrons, and has a good activating effect on living cells. It was done.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a tourmaline fine particle-containing fiber which emits much more active electrons than conventional electret fibers. When tourmaline fine particles are added and kneaded in the stock solution, the cellulose xanthate that is temporarily generated in the spinning stock solution is a kind of polymer electrolyte. The inventors have found that rayon exhibiting electret properties can be obtained, and have completed the present invention based on this finding.

That is, according to the present invention, fine particles of tourmaline having a particle size of 0.2 μm or less are uniformly prepared using cellulose xanthate.
Do not spin the monodispersed viscose rayon spinning solution.
And rayon fibers containing tourmaline fine particles characterized by containing tourmaline fine particles in the range of 0.05 to 1.0 % by weight.

In the present invention, the rayon fiber containing tourmaline fine particles, which has an electric conductivity of 2.2 μS / cm or more after 3 hours from the start of the test in the active electron generation test, is preferable.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The rayon fiber containing tourmaline fine particles of the present invention is a combination of rayon fiber and tourmaline. In general, when a fine powder of the second substance is mixed into a solution of a polymer material that is a fiber raw material, the fine powder is more likely to be agglomerated by its surface energy as the particles become finer. It will be difficult. Therefore, the dispersion of such fine particles is generally performed by adding an appropriate dispersant.
It is extremely difficult to uniformly mix fine particles having a particle size of less than about. On the other hand, tourmaline has a permanent spontaneous electric polarizability, and more active electrons can be emitted by making it into a fine powder.

When rayon fibers are produced, cellulose xanthate is formed temporarily in the spinning dope. When this cellulose xanthate is mixed with tourmaline fine particles, the tourmaline fine particles have a particle size of 0.3 μm. In the following cases, particles are usually aggregated,
Cellulose xanthate was found to be uniformly dispersed without aggregation. This is considered to be due to the ionic interaction of cellulose xanthate with the fine particles of tourmaline. Therefore, in the present invention, even without the addition of a dispersant, even tourmaline fine particles having a particle diameter of 0.2 μm or less can be extremely uniformly dispersed. Further, preparation of such tourmaline fine particles having a particle diameter of 0.2 μm or less is difficult by a dry pulverization method, and is usually performed by a water granulation method.

The tourmaline used in the tourmaline fine particle-containing rayon fiber of the present invention has a composition of MX ₃ B ₃ Al ₃ (AlSi ₂ O ₉ ) ₃ (O, OH, F) ₄ (where M is Na or Ca, X is Al, Fe, Li, M
g or Mn).

Pure tourmaline is used as a gem, and a crystal can be artificially synthesized at present. In the present invention, such an artificially obtained tourmaline can also be used. This tourmaline is a substance that performs permanent spontaneous electric polarization, and does not change the polarization vector under the influence of an external electric field. It is also known that tourmaline has the strongest permanent polarization characteristics among minerals and emits far-infrared rays. In addition, a piezoelectric effect in which the ionic crystal causes dielectric polarization in response to a stress caused by an external force, and a pyroelectric effect in which electric charges appear on the surface when a part of the crystal is heated are also observed. Furthermore, from the fact that this tourmaline is contained in fibers in the form of fine particles, active electrons are released.
It has already been confirmed.

[0013] Since tourmaline has spontaneous permanent polarization, it is more effective to make it into fine particles. Therefore,
In the present invention, those having a particle diameter of 0.2 μm or less are used, and particularly those having a particle diameter of 0.2 μm or less and an average particle diameter of 0.1 μm or less are preferable because they emit more active electrons. . The content of tourmaline fine particles, the active electricity
The amount is selected from the range of 0.05 to 1.0 % by weight with respect to the rayon fiber in view of the balance of the amount of the released fibers and the economy . When the content is less than 0.05% by weight, the emission amount of active electrons is too small, and the effect of the present invention is not sufficiently exhibited. When the content exceeds 1.0 % by weight, the effect is not improved for the amount. not seen, that rather Do not economically disadvantageous.

The tourmaline fine particle-containing rayon fiber of the present invention may contain, in addition to tourmaline, other ceramics, if desired, usually in a proportion of 10% by weight or less based on the rayon fiber. As other ceramics,
For example, far-infrared radiation materials such as cordierite mainly composed of alumina and silicic acid, β-spodumene, zirconia, zircon, magnesia, and aluminum titanate are preferably exemplified. Further, a transition metal compound such as manganese dioxide, iron oxide, chromium oxide, cobalt oxide, or copper oxide, silicon nitride, silicon carbide, or the like may be contained.

Next, a preferred example of the method for producing the tourmaline fine particle-containing rayon fiber of the present invention will be described. First, the tourmaline is pulverized to a particle size of 0.2 μm or less.
Prepare tourmaline microparticles . As a method of pulverizing tourmaline, any of a wet method and a dry method can be used. In the present invention, a wet method using water is particularly advantageous in that operability and fine particles can be obtained. Next, for example, tourmaline fine particles prepared by a wet method and other ceramics used in some cases are added to a viscose rayon spinning stock solution, and further diluted with water as necessary, to obtain a spinning stock solution having an appropriate concentration and viscosity. Prepare. If necessary, an antibacterial agent, a fungicide, a deodorant, and the like may be appropriately added to the stock solution. Next, spinning is performed using a spinning method conventionally used in the production of rayon fibers to obtain rayon fibers containing tourmaline fine particles.

In the present invention, among the tourmaline-fine-particle-containing rayon fibers thus obtained, in particular, in an active electron generation test described later, the electric conductivity of water at the point of time when 3 hours have passed after the start of the test. Degree of 2.2 μS / cm
The above is preferable. There is a correlation between the electric conductivity of the water and the emission amount of the active electrons, and the higher the electric conductivity of the water, the larger the emission amount of the active electrons.

[0017]

The rayon fiber containing tourmaline fine particles of the present invention can activate a living cell in spite of a small tourmaline content, and can release a large amount of active electrons having an effect of promoting the activity of subcutaneous blood circulation. It is suitably used as a material for health clothing.

[0018]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Production of rayon fiber containing tourmaline fine particles According to a conventional method, 350 parts by weight of an aqueous solution of caustic soda having a concentration of 20% per 100 parts by weight of pulp are added and stirred at room temperature for 2 hours to prepare alkali cellulose. .
Next, 30 parts by weight of carbon disulfide is added to the alkali cellulose and stirred at room temperature for 3 hours to obtain a solution of sodium cellulose xanthogenate. Next, this was diluted with an aqueous solution of caustic soda to prepare a spinning dope (cellulose 8.7% by weight, total alkali content 6.0% by weight, total sulfur content 2.4% by weight), which was obtained by a water granulation method. The tourmaline fine particles having a particle size of 0.2 μm or less (average particle size of 0.15 μm) were added to the fiber at 0.05, 0.
1, 0.2, 0.3, 0.5, 1.0, 2.0, 3.
0, 5.0, and 7.0% by weight were uniformly mixed.

The thus obtained spinning dope containing tourmaline fine particles was treated with sulfuric acid 120 at a spinning speed of 60 m / min using a spinneret having a pore size of 0.08 mm and 50 holes.
g / L, 280 g / L of sodium sulfate, and 15 g / L of zinc sulfate in a spinning bath at a temperature of 50 ° C., and then drawn by a conventional two-bath tension spinning method to form a 15% fineness tourmaline-containing rayon fiber N.
o1 to No10 were obtained.

(2) Measurement of change in electric conductivity of water Using the various tourmaline-containing rayon fibers obtained in (1) above, active electrons are generated as described below, and the change in electric conductivity of water is measured. It was measured. FIG. 1 is a schematic diagram of an experimental device for examining the state of generation of active electrons. Each sample is mounted on a sample mounting portion 3 provided inside a sample activator 2 in the sample activation device. 100 m of clean air subjected to a treatment such as carbon dioxide removal from the blower pump 1 to the sample activator 2
Introduce at a rate of 1 / min. At this time, the sample in the sample mounting section 3 is made of a heating element 4 such as ceramics provided in the sample activator 2.
To maintain the temperature at 35 ° C. For this temperature control, the sample activator 2 is equipped with a thermometer 5 and a temperature sensor 6.

The air that has passed through the sample mounting section 3 is distilled water 10 (a constant temperature bath 8)
Maintained at 1 ° C., conductivity at 21 ° C. 1.7 μS
/ Cm) on the water surface. A platinum rod 11 is inserted into the distilled water 10, and the change in the electric conductivity is
It was measured with an electric conductivity meter 12 (Precision LCR meter 4285A, manufactured by Hewlett-Packard Company). In addition, 7 is a power supply. The relationship between the electric conductivity and the tourmaline content at 3 hours after the start of the measurement is shown in FIG. 2 as a graph curve A, and detailed numerical values are shown in Table 1.

COMPARATIVE EXAMPLE 1 (1) Production of Rayon Fiber Containing Tourmaline Fine Particles In Example 1 (1), instead of the tourmaline fine particles having a particle diameter of 0.2 μm or less, a particle diameter of 1.0 μm or less (average particle diameter of 0.8 μm) was used. Except for using the tourmaline fine particles described in (1), rayon fibers No. 12 to No. 21 containing tourmaline fine particles were prepared in the same manner as in Example 1 (1). In addition,
Sample No. 11 is rayon fiber containing no tourmaline fine particles.

(2) Measurement of change in electric conductivity of water Using the rayon fiber containing various tourmaline fine particles obtained in the above (1) and the rayon fiber not containing the tourmaline fine particles, in the same manner as in Example 1 (2), The change in electrical conductivity of water was measured. The relationship between the electric conductivity and the tourmaline content at the time when three hours have elapsed after the start of the measurement is shown in FIG. 2 as a graph curve B, and detailed numerical values are shown in Table 1.

[0025]

[Table 1]

As can be seen from Table 1 and FIG.
The electric conductivity (curve B) of the rayon fiber containing tourmaline fine particles having a particle size of 0 μm or less is a value of 2.08 to 2.17 μS / cm, which is higher than 1.84 μS / cm of the sample No11 containing no tourmaline. It shows that a large amount of active electrons are emitted, but the content is 0.05 to
There is almost no change even at 2.0% by weight.

On the other hand, the electric conductivity of the rayon fiber containing tourmaline fine particles having a particle diameter of 0.2 μm or less (curve A) is 2.
As the content decreases from 0% by weight, the electric conductivity increases, reaches a peak at 0.2 and 0.3% by weight, and decreases as the content further decreases. That is, the comparative example
As compared with Sample Nos. 12 to 21 of Example 1 , the electric conductivity shows a remarkably high value, indicating that an extremely large amount of active electrons are emitted.

On the other hand, the tourmaline 0.1 obtained in Example 1 was used.
Rayon fibers containing 2% by weight and 5.0% by weight,
When observed with a high-resolution transmission electron microscope (TEM, JEM-200CX manufactured by JEOL Ltd.) at an accelerating voltage of 160 keV, those having a tourmaline content of 0.2% by weight had a tourmaline particle size of 0.2% by weight. 02-0.2 μm
And most are 0.1 μm or less, and are uniformly dispersed. On the other hand, when the tourmaline content is 5.0% by weight, the fine particles of tourmaline having a size of 0.1 μm or less are aggregated, and the size of the aggregate is 0.2 to 1.8 μm. Account for the majority.
That is, when the tourmaline content is small, the dispersion is extremely uniform, but when the tourmaline content is too large, aggregation is likely to occur. This is consistent with the fact that, as shown in Table 1 and FIG. 2, the electric conductivity is significantly increased when the tourmaline content is in the range of 0.05 to 2.0% by weight.

Application Example 1 Measurement of Skin Temperature by Thermography In thermography, skin temperature is detected by an ultra-sensitive infrared camera, and the temperature distribution (thermogram) is displayed in 10 colors. In a constant-temperature shielded room, the particle size of the sample No. 3 obtained in Example 1 was 0.2 μm.
mat A prepared using rayon fibers containing 0.2% by weight of tourmaline of 0.2 m or less (electrical conductivity of water of this fiber material after 3 hours of 2.42 μS / cm) and Comparative Example 1
Mat B using rayon fiber containing 0.2% by weight of tourmaline having a particle diameter of 1.0 μm or less obtained in (1).
μS / cm) and mat C made using rayon fibers containing no tourmaline of Sample No. 11 (electric conductivity of water of this fiber material after 3 hours, 1.84 μS / cm)
Each of the healthy adults was placed in a supine position, and the thermogram (skin temperature distribution) was measured. As a result, in tourmaline-containing mat A having a particle diameter of 0.2 μm or less,
In and after supine, skin temperature of both feet is 1.1 ° C
It can be seen that the blood pressure has risen and the subcutaneous blood circulation has become active. Next, tourmaline-containing mat B having a particle diameter of 1.0 μm or less
Then, the skin temperature of both feet increased by 0.6 ° C. And, in the mat C containing no tourmaline, there was almost no change in the skin temperature during and after supine.

Based on this finding, it has been found that the rayon fiber containing tourmaline fine particles increases the skin temperature and promotes subcutaneous blood circulation, and at the same time, increases the skin temperature corresponding to the particle size of the tourmaline fine particles and increases the electrical conductivity. It was found to correspond to the degree measurement. From this, by measuring the electrical conductivity of water, we know the amount of active electrons emitted,
Further, it was found that the activation effect on living cells, that is, the degree of subcutaneous blood circulation activity can be estimated.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an experimental apparatus for examining the generation state of active electrons.

FIG. 2 is a graph showing an example of a relationship between tourmaline content and water electrical conductivity in tourmaline fine particle-containing rayon fibers.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 blower pump 2 sample activator 3 sample mounting part 4 heating element 8 constant temperature bath 9 beaker 10 distilled water 12 electric conductivity meter

Continuation of front page (56) References JP-A-6-228808 (JP, A) JP-A-6-184808 (JP, A) JP-A-4-327207 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) D01F 1/00-2/30

Claims (2)

(57) [Claims] [Claim 1] A particle size of 0.1 with cellulose xanthate .
Biscoe in which tourmaline fine particles of 2 μm or less are uniformly dispersed
A rayon fiber containing tourmaline fine particles , which is prepared by spinning a stock solution for spinning slayon and contains fine tourmaline particles in a range of 0.05 to 1.0 % by weight. 2. A test for generating active electrons is started.
After 3 hours, the electric conductivity of the water is 2.2 μm.
2. The tourmaline fine particles according to claim 1, which is at least S / cm.
Rayon fiber .