JP3286307B1 - Deodorant using liquid composition - Google Patents

Abstract

Abstract: PROBLEM TO BE SOLVED: To constantly release negative ions that are beneficial to the human living environment. The negative ions deodorize and decompose ammonia gas and formaldehyde in particular, thereby improving living space and the natural environment, and reducing sick house disease. A deodorant using a liquid composition having an inhibitory action is proposed. SOLUTION: The deodorant using the liquid composition of the present invention comprises:
A binder liquid having conductive properties and / or a binder liquid in which a conductive substance is dispersed has a far-infrared radiation characteristic, and is made by finely pulverizing and mixing minerals that generate negative ions. By continuously releasing negative ions without applying a stimulus such as physical external force, ammonia and formaldehyde can be deodorized and decomposed in a short time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a far-infrared radiation characteristic which is useful for human living environment, and has a deodorizing effect of ammonia odor and formaldehyde by constantly emitting negative ions, thereby providing a natural environment. The present invention relates to a deodorant using a liquid composition for improving the deodorant.

[0002]

2. Description of the Related Art Conventionally, there have been disclosed proposals for a deodorizing method and a deodorizing material using tourmaline or a composite ceramic obtained by mixing serpentine, magnesia, amphibolite, silica, zeolite and the like with tourmaline. I have. Of these proposals, tourmaline is used alone or tourmaline, serpentine, magnesia,
The proposal to use composite ceramics mixed with amphibole, silica, zeolite, Otani stone, etc. proposes a method for producing synthetic fibers with heat retention and deodorizing properties by mixing these fine powders into the fibers in the spinning process. Have been.

[0003]

However, the proposal of impregnating and mixing the tourmaline alone or composite ceramics using serpentine, zeolite or other ores with the tourmaline in the fiber has been proposed to directly touch the skin, Alternatively, since external stimuli such as vibration and friction are required, there is a problem that the deodorizing effect in the air cannot be obtained because the clothing is mainly limited to wearable clothes (Japanese Patent Laid-Open No. 9-170110). Gazette, JP-A-9-256242). In other words, if only fine powder such as tourmaline is mixed, the release amount of negative ions is very small, and the release amount expands drastically only under certain conditions, and further stimulates frictional force and physical stress. Unless given, the anion could be released temporarily, but the anion could not be released constantly, so it was necessary to continuously stimulate. Therefore, the present inventors, after extensive research, have sufficient far-infrared radiation characteristics without directly contacting the skin and without giving any external stimulus, and constantly emit a large amount of negative ions. It is an object of the present invention to propose a deodorizing material that can produce a deodorizing effect in the air.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been proposed in view of the above, and it is an object of the present invention to maintain the surface resistivity of a material around a finely powdered mineral obtained by pulverizing a mineral that generates negative ions within a certain range. As a result, it has been found that a large amount of negative ions can be constantly released from the finely divided mineral. That is, according to the present invention, the resin binder liquid has a far-infrared radiation characteristic and oxidizes by mineral baking containing 99 to 1% by weight of garnet as a mineral that generates negative ions and zirconium, barium, lanthanum, cerium, and neodymium. 1 to 99% by weight of the excitable material
Generates negative ions in the state of the coating layer
10 ⁵ to 10 ⁸ Ωcm
The present invention relates to a deodorant using a liquid composition, which emits far-infrared rays and constantly releases negative ions in the state of a coating layer.

[0005]

Embodiments of the present invention will be described below. The resin binder liquid used in the present invention may be any one that can form a layer (film) by coating, and generates negative ions in the state of the coating layer.
The surface resistivity of the surrounding material of the generated mineral is 10 ⁵ to 10 ⁸ Ω
cm, for example, a so-called binder
Conductive polymers may be used, and various resins such as silver and copper
And other electrically conductive materials (hereinafter referred to as conductive materials)
Is mixed with the above range of electric conductivity (hereinafter referred to as conductive).
U). Further, any form such as a paint may be used. For example, all kinds of paints except negative ion-focusing paints, unusual green paints, and electrodeposition paints can be used, such as oil-based paints, water-based paints, alcoholic paints,
It can be exemplified in a wide range such as a cellulose paint and a synthetic resin paint. Among them, one of the emulsion polymerization paints, especially water-based paints
The seed acrylate copolymer emulsion paint can be used most effectively.

[0006] The conductive substance used to bring a certain range of conductivity to the binder liquid includes silver fine powder, copper fine powder, other conductive metal fine powder, carbon fiber fine powder, titanic acid, and the like. Examples thereof include whiskers of potassium, and one or more of these compositions can be selected and used.

The amount of the conductive substance to be added to the binder liquid varies depending on the type of the conductive substance, but 5 to 20 parts by weight of the conductive substance is effective for 100 parts by weight of the binder liquid. When the conductive substance is added to the binder liquid, the surface resistivity in the case of forming a coating layer or a coating film is in the range of 10 ⁵ to 10 ⁸ Ωcm, and a suitable conductivity can be obtained. A large amount of negative ions can be constantly generated from the negative ion generating mineral added therein.

[0008] As the minerals that generates negative ions, minerals 99 of oxide by mineral <br/> was calcined containing garnet 99-1 wt% zirconium, barium, lanthanum, cerium, all neodymium It is considered that a remarkable negative ion releasing effect is obtained when used in combination with% by weight, and the latter mineral acts as an exciting material for exciting the negative ion generating action of the former garnet.

Optimally, the amount of the mineral that generates the negative ions is 1 to 30 parts by weight of the mineral with respect to 100 parts by weight of the binder liquid (solid content: 33%).
Further, as a particle size for pulverizing the mineral, an average particle size of 300 μm or less is desirable, but the average particle size is 5 mm.
It is possible to use even less.

When a coating layer is formed from the liquid composition having the above-described structure, the negative ion generating mineral is a spontaneously polarized polar crystal, and a positive electrode and a negative electrode are spontaneously generated at both ends of the crystal to generate a potential. Since it is stored forever, a weak current always flows from the positive pole to the negative pole. When the surface resistivity of the surrounding material of the finely powdered mineral is large and the conductivity is low, the chargeability is increased and the current value of the weak current is reduced, so that the emission of negative ions is suppressed. Further, when the surface resistivity of the peripheral material of the finely powdered mineral is small and the conductivity is high, the potential between adjacent finely powdered minerals is neutralized, and the emission of negative ions is suppressed. Therefore, in the coating layer or coating state,
The surface resistivity of the surrounding material of the finely powdered mineral is 10 ⁵ to 10 ⁸
When the resistivity is within the range of Ωcm, the conductive layer has an appropriate conductivity, so that it is possible to maintain a high level of emission of negative ions on the surface of the coating layer.

Incidentally, the present inventors have obtained important knowledge on the generation of negative ions and the accompanying mechanism. That is,
For example the fine powder of garnet may have a very weak electric energy was known, was brought into contact with water into a fine powder of the garnet, as shown in FIG. 1,2 ¹⁷ O-NMR ( Nuclear magnetic resonance) The value of the signal half width is 78.3, which is clearly smaller than that of raw water 117.5 (Hz).
Hz. This means that by contacting raw water containing molecular groups called clusters with garnet fine powder, the clusters become smaller molecular groups, and furthermore, single molecular water is generated from these small molecular groups. Means According to another experiment, when water is passed through a column filled with garnet fine powder, water having a pH of 6.7 to 6.9 can be converted to a pH in a short time of 1 minute to several minutes.
It has been confirmed to be 8.8 to 10.0. It should be noted that there was a very small amount of eluted ions from the garnet fine powder, but this was not a change in pH due to these effects. From these, the water molecule shows an equilibrium state of H ₂ O⇔H ⁺ + OH ⁻ , and the concentration of hydrogen plus ion [H ⁺ ] is 10 ⁻⁷ mol / L (pH 7) in a neutral region.
This equilibrium state is broken when water molecules come into contact with the garnet fine powder, and a part of the hydrogen plus ions (H ⁺ ) becomes hydrogen gas (H ₂ ) and leaves the water. As a result, the concentration [OH ⁻ ] of the hydroxyl group negative ion increases, and the reformed water becomes alkaline. Then, the hydroxyl group negative ion (OH ⁻ ) combines with the surrounding water molecule (H ₂ O), becomes a hydroxyl negative ion (H ₃ O ₂ ⁻ ), is accumulated in water, and is relatively stabilized. In short, garnet fine powder has polar crystals, exhibits a reforming and purifying action to reduce water clusters in a short time, and has the electrical property of increasing the negative ions of water molecules to make water alkaline. I got a new finding.

Also, for example, minerals 1 to 9 consisting of 99 to 1% by weight of the garnet and oxides obtained by firing minerals such as zirconium, barium, lanthanum, cerium, neodymium and the like.
The principle of generating negative ions in the air when used in combination with 9% by weight is that the moisture in the air comes into contact with the coating surface of a binder liquid mixed with mineral fine powder that excites the electrical properties of the garnet fine powder. As a result, air containing water molecules containing small clusters is immediately formed, and hydroxyl minus ions (H
₃ O ₂ ⁻ ), and found that a larger amount of negative ions were generated in the air than garnet fine powder alone.

On the basis of the above findings, the present inventors applied the liquid composition having the above-mentioned composition to a wool cement board, tatami, wallpaper, wall material,
By forming a coating layer on ceiling materials, cotton, acrylic fiber cloth, etc., deodorization is achieved by emitting far-infrared rays and generating negative ions in the dwelling space, which often becomes a semi-closed space. A deodorizing experiment showing the effect and air cleaning effect was carried out using ammonia gas and formaldehyde, and it was confirmed that a far-infrared radiation characteristic and a synergistic effect of generating negative ions have a significant deodorizing effect.

For example, a negative ion-generating Japanese paper (deodorant) having a coating layer formed on a Japanese paper using the liquid composition having the above-mentioned structure has a surface area of 0.3 square meters in a stationary state, and at least 600 particles per cubic centimeter of air. It was confirmed by measurement that emission of negative ions was continuously generated, and a patent application (Japanese Patent Application No. 2000-259840) was already filed. Therefore, the concentration of ammonia gas in the deodorization and decomposition reaction vessel of the negative ion generating Japanese paper having a coating layer formed on the Japanese paper using the liquid composition having the above-mentioned composition is 500 ppm,
It becomes 50 to 70 ppm or less in several hours, and the ammonia deodorization decomposition rate is 99% by further controlling the humidity.
The above values were obtained. Similarly, formaldehyde (HCH
O) The concentration of 500 ppm was reduced to 10 ppm or less in 2 to 3 hours, and a value at which the deodorizing decomposition rate was 98% or more was obtained. Also, as a result of analyzing the components contained in the negative ion generating Japanese paper after deodorizing and decomposing the ammonia (NH ₃ ) gas, a large amount of nitrate nitrogen (NO, NO
₂ , NO ₃ ) was confirmed to be contained.

The present inventors consider that the deodorizing action of the negative ions, which is constantly generated from the negative ion generating Japanese paper (the deodorizing material of the present invention), is changed by the following reaction.

As to the principle of generating negative ions from the above-mentioned negative ion generating Japanese paper (the deodorant of the present invention), as described above, moisture, which is moisture in the air, comes into contact with the coating surface of the deodorant of the present invention. As a result, the air immediately becomes air containing water molecules containing small clusters, and eventually becomes hydroxyl negative ions (H ₃ O ₂ ⁻ ) electrically charged to negative ions. That is, it is as shown in equations (1) and (2). ^{_{H 2 O⇔H + + OH - ···}} (1) H 2 O + OH - → H 3 O 2 - ··· (2)

The process of deodorizing and decomposing ammonia (NH ₃ ) gas, formaldehyde (HCHO) and the like by negative ions generated from the deodorant of the present invention is not complicated and simple, but is performed as described below. I believe. Ammonia (NH ₃ ) and formaldehyde (HCH
O) is a kind of reducing agent, and when oxidized, ammonia (N
H ₃ ) becomes nitric acid (HNO ₃ ), and eventually becomes ammonium nitrate (ammonium nitrate) and is stabilized. On the other hand, formaldehyde (HCHO) is oxidized to formic acid (HCOOH), which is further oxidized to carbon dioxide (CO ₂ ) and water (H ₂ O).
become. These ammonia (NH ₃ ) and formaldehyde (HCHO) take an extremely long time to be naturally oxidized in the air, but when hydroxyl negative ion (H ₃ O ₂ ⁻ ) comes into contact, the oxidizing action becomes active, It is oxidatively decomposed in a short time.

The deodorizing decomposition of ammonia (NH ₃ ) gas will be described in more detail. First, when a hydroxyl negative ion (H ₃ O ₂ ⁻ ) encounters a reducing substance such as ammonia (NH ₃ ), it immediately decomposes to generate oxygen (O ₂ ) as shown in Equation (3). 2H ₃ O ₂ ⁻ → 3H ₂ O + 1 / 2O ₂ (3)

On the other hand, ammonia (NH ₃ ), together with moisture (H ₂ O) in the atmosphere, has ammonium ions (NH ₄ O).
H). The ammonium of the ammonium ion is oxidized by oxygen (O ₂ ) generated by the decomposition of the hydroxyl negative ion (H ₃ O ₂ ⁻ ) (formula (3)), and is reacted by the reactions shown in formulas (4) to (6). Transition to. That is, it becomes NO (nitrogen monoxide), NO ₂ (nitrogen oxide), and further changes to HNO ₃ (nitric acid). 2NH ₃ + 5 / 2O ₂ → 2NO + 3H ₂ O (4) 2NO + O ₂ → 2NO ₂ (5) 2NO ₂ + 1 / 2O ₂ + H ₂ O → 2HNO ₃ (6) (4) + ( 5) + (6) NH ₃ + 2O ₂ → HNO ₃ + H ₂ O (7)

The reaction formula of ammonium ion (NH ₄ OH) and hydroxyl negative ion (H ₃ O ₂ ⁻ ) is as shown in formula (8) from formulas (3) and (7). NH ₄ OH + 8H ₃ O ₂ ⁻ → HNO ₃ + 14H ₂ O (8)

Finally, the ammonia odor and the nitric acid are neutralized, and as shown in formula (9), ammonium nitrate (ammonium nitrate)
It becomes stable. NH ₄ OH + HNO ₃ → (NH ₄ ) NO ₃ (ammonium) + H ₂ O (9)

The deodorizing effect of ammonia can be generally considered to be due to the synergistic effect of far-infrared radiation effect and adsorption effect in addition to the hydroxyl negative ion.

Next, the deodorizing decomposition of formaldehyde (HCHO) will be described in more detail. The basic reaction for deodorizing formaldehyde in air is represented by the formulas (10) and (11).
It changes as shown in. That is, it becomes formic acid (HCOOH), and further becomes carbon dioxide gas (CO ₂ ) and water (H ₂ O). HCHO + 1 / 2O ₂ → HCOOH (10) HCOOH + 1 / 2O ₂ → CO ₂ + H ₂ O (11)

The hydroxyl negative ions (H ₃ O ₂ ^-)
Upon contact with reducing formaldehyde (HCHO), immediately decomposes as shown in formula (12) to form oxygen (O
₂ ) Generate. ^{_{4H 3 O 2 - → 6H 2}} O + O 2 ··· (12)

On the other hand, formaldehyde (HCHO) undergoes an oxidation reaction by oxygen (HCOOH) generated by the decomposition of hydroxyl anion (HCOOH), and changes according to the reactions shown in formulas (13) and (14). That is, it is changed to formic acid (HCOOH), and carbon dioxide (CO ₂ )
And water (H ₂ O) to deodorize. HCHO + 1 / 2O ₂ → HCOOH (13) HCOOH + 1 / 2O ₂ → CO ₂ + H ₂ O (14)

The reaction formula of formaldehyde (HCHO) and hydroxyl anion (H ₃ O ₂ ⁻ ) is as shown in formula (15) from the formulas (12) to (14). ^{_{HCHO + 4H 3 O 2 - →}} CO 2 + 7H 2 O ··· (1
5) It is considered that formaldehyde is deodorized and decomposed by hydroxyl negative ions, which are negative ions, through the above steps.

[0027]

Embodiments of the present invention will be described below. [Example 1] Powdered carbon fiber (Toray Co., Ltd. Tosca) as a conductive material was added to an aqueous coating material (Faircoat FX manufactured by New Year's Futech Co., Ltd.) containing a copolymerized emulsion of acrylic acid as a main component. 10 parts by weight with respect to parts by weight, and 10% by weight of a mixed fine powder (average particle size of 5 μm) composed of 5% by weight of garnet and 95% by weight of an excitable material to be an oxide obtained by firing minerals such as zirconium, barium, lanthanum, cerium, and neodymium Using a liquid composition prepared by adding parts by weight and sufficiently stirring and mixing, a coating layer was formed on Japanese paper in an amount of 220 g / m ² of the liquid composition. The surface resistivity of the coating layer after drying is 2.
It was 3 × 10 ⁶ Ωcm, and the amount of generated negative ions was 600 to 800 per cubic centimeter of air with a surface area of 0.3 square meters in a stationary state. In the ammonia gas deodorization experiment, 1.8 square meters of Japanese paper (0.1 mx 0.3 mx 60 sheets) on which a coating layer of the negative ion generating paint was formed was added to a 100-liter tetra-pack with air adjusted to 50% humidity. One liter was added, and ammonia (NH ₃ ) was added to a concentration of 500 ppm. One hour after the addition, the ammonia gas concentration becomes 50
ppm and 10 ppm or less in 3 hours. After the generation of the negative ions used in the ammonia deodorization experiment, the nitrate nitrogen contained in the Japanese paper was analyzed. The Japanese paper was immersed in purified water and analyzed for nitrate nitrogen and ammonia nitrogen in the immersion water, and as a result, nitrate nitrogen (NO, NO
₂ , NO ₃ ) was confirmed to be contained. As a result, as a nitrogen oxide generated by oxidizing ammonia in the anion-generating Japanese paper after the ammonia deodorization decomposition,
It was measured that nitrate nitrogen (NO, NO ₂ , NO ₃ ) was contained. It was measured that the amount of negative ions generated by the anion-decomposing washi after the ammonia deodorization decomposition was not changed at all from the amount generated before use, and that the negative ions were continuously generated constantly. Measurement of negative ion generation amount
The measurement was carried out using an ion measuring instrument SC-50 manufactured by Sigma-Tex Corporation and an ion measuring instrument IC-1000 manufactured by Universal Planning Co., Ltd. The measurement of the far-infrared radiation characteristics was performed at the Tokushima Prefectural Industrial Technology Center. The measurement results of the far-infrared radiation characteristics are shown in FIGS.

[0028]

As described above, the deodorant using the liquid composition of the present invention can provide far-infrared radiation which is beneficial to human living environment without giving any stimulus such as continuous external stress. By having characteristics and constantly releasing negative ions, it is possible to easily exert the deodorizing effect of formaldehyde, which is one of the causes of ammonia deodorization and sick house disease.

[Brief description of the drawings]

FIG. 1 ¹⁷ O-NMR (nuclear magnetic resonance) signal half width (H) of reformed water obtained by contacting garnet with purified water (raw water)
It is a graph which shows z).

FIG. 2 ¹⁷ O-NMR (nuclear magnetic resonance) of purified water (raw water)
It is a graph which shows a signal half value width (Hz).

FIG. 3 is a graph showing a far-infrared emissivity curve of a coating layer. At a measurement temperature of 39.9 ° C., a wavelength of 8 to 12 (μ
m) exhibits an emissivity of 93%.

FIG. 4 Far-infrared radiance (radiation amount) of the coating layer
It is a graph which shows a curve. Wavelength at a temperature of 39.9 ° C
8 to 10 (μm) radiant energy amount 1.00 w / cm
^Twothat's all.

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hideo Tamanoi 6177-3 Omaezaki, Omaezaki-cho, Haibara-gun, Shizuoka Pref. 56) References JP-A-11-165167 (JP, A) JP-A-6-268282 (JP, A) JP-A-2000-294 (JP, A) JP-A-11-155960 (JP, A) 10-270146 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) A61L 9/01-9/22

Claims (1)

(57) [Claims] 1. Oxidation by calcination of a mineral containing 99-1% by weight of garnet as a mineral having a far-infrared radiation characteristic in a resin binder liquid and generating negative ions, and all of zirconium, barium, lanthanum, cerium and neodymium. 1 to 99% by weight of the excitable material, which generates negative ions in the state of the coating layer
The surface resistivity of the surrounding material of the generated mineral is 10 ⁵ to 10 ⁸ Ω
cm , and emits far-infrared rays in the state of a coating layer and constantly emits negative ions.