JPH09225054A - Gas mask and storing device for gas mask - Google Patents

Abstract

PROBLEM TO BE SOLVED: To preserve the long-time defogging and visibility-securing performances of a gas mask to prevent condensed water and water drops stuck to lenses from clouding or dimming by providing the inner surface of the lens part of the gas mask with a photocatalyst and by making the surface hydrophilic according to photo-excitation. SOLUTION: A layer containing a photocatalyst like a crystalline titanium oxide, etc., is formed on the surface of a base material on the inner surface of the lens part of a gas mask. The surface of the lens, with the surface structure like this, is made highly hydrophilic according to the photo-excitation of the photocatalyst. Thus, when the moisture in the atmosphere condenses and sticks, it uniformly forms membranous water instead of growing into a state of water drops, therefore, the water condensed from moisture and/or water drops are prevented from clouding or dimming the lenses and visibility is secured. The photocatalyst used here is a substance which is capable of generating conduction electrons and electron holes in the excitation of the electrons in the valence band when irradiated with light having a larger energy than the energy gap between the conduction band and the valance band of the crystal of the photocatalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas mask and a storage device for the gas mask.

[0002]

2. Description of the Related Art Since a gas mask is used in close contact with the face, the lens part becomes cloudy due to breathing. As a result, there is a problem in that visibility is deteriorated during use.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a gas mask which does not cloud the lens portion during use and is excellent in ensuring visibility. Another object of the present invention is to provide a gas mask capable of maintaining antifog properties and visibility assurance for a long period of time. Another object of the present invention is to provide a gas mask capable of permanently maintaining antifog properties and visibility.

[0004]

SUMMARY OF THE INVENTION The present invention is based on the discovery that, in a member having a surface layer containing a photocatalyst formed thereon, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the following mechanism. That is, when the photocatalyst is irradiated with light having an energy larger than the energy gap between the valence band upper end and the conduction band lower end of the photocatalyst, the electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. The action of either or both of them probably imparts polarity to the surface and collects polar components such as water and hydroxyl groups. Then, one or both of conduction electrons and holes and the above-mentioned polar component cooperate with each other to cut off a chemical bond between the surface and the contaminant chemically adsorbed on the surface, and to cause a chemical adsorbed water on the surface. Is adsorbed, and a physically adsorbed water layer is formed thereon. Also, once the surface of the member has been made highly hydrophilic, the hydrophilicity of the surface will continue for some time even if the member is kept in a dark place.

The present invention provides a gas mask having a surface layer containing substantially transparent photocatalyst particles on at least the inner surface of the lens portion. By providing a surface layer containing photocatalyst particles on at least the inner surface of the lens portion, the photocatalyst exhibits a high degree of hydrophilicity in response to photoexcitation, whereby condensed water and / or water droplets of attached moisture are surfaced. It spreads evenly over the surface of the layer and is prevented from becoming clouded or overwhelmed by moisture condensed water and / or water drops, thus ensuring visibility.

In a preferred embodiment of the present invention, the surface layer further contains silica. By containing silica, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when held in a dark place is improved. The reason seems to be related to the ability of silica to store water in its structure.

In a preferred embodiment of the present invention, the surface layer further contains a solid acid. When the solid acid is contained, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when kept in a dark place is improved. The reason is that when a solid acid is contained in the surface layer, the polarity of the surface is large regardless of the presence or absence of light, so it is easier to selectively adsorb water molecules that are polar molecules than hydrophobic molecules. . Therefore, a stable physical adsorption water layer is easily formed, and even if it is kept in a dark place,
Surface hydrophilicity can be maintained at a high level for a fairly long time.

In a preferred embodiment of the present invention, the surface layer further contains silicone.
By containing silicone, by photoexcitation of the photocatalyst, at least a part of the organic group bonded to the silicon atom in the silicone is replaced with a hydroxyl group, and a physically adsorbed water layer is formed on the organic group, so that the surface is It exhibits a high degree of hydrophilicity close to a water wetting angle of 0 °, and improves the hydrophilicity maintaining ability when kept in a dark place.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A specific surface structure of the inner surface of the lens portion of the gas mask of the present invention will be described.
On the surface of the lens in the present invention, as shown in FIG. 1 or 2, a layer containing a photocatalyst such as crystalline titanium oxide is formed on the surface of the base material. By taking such a surface structure, the surface of the lens is highly hydrophilized in response to photoexcitation of the photocatalyst. As a result, even if the moisture in the atmosphere is condensed and adheres, it does not grow in the form of water droplets, and a uniform water film is formed, which prevents the moisture condensed water and / or water droplets from clouding or clinging. And the visibility is secured.

In FIG. 2, when the surface layer consists of photocatalyst particles only, the photocatalyst is preferably an oxide. Oxides are hydrophilic when no pollutants in the environment are adsorbed, so a uniform water film can be formed by removing the pollutants by photoexcitation and forming an adsorbed water layer. It is. In FIG. 3, M represents a metal element. Therefore, in the case of FIG. 3, the outermost surface is made of a general inorganic oxide. Also in this case, since the oxide shows hydrophilicity in the state where the pollutant in the environment is not adsorbed, the pollutant is excluded by the photoexcitation action of the photocatalyst mixed in the surface layer other than the above-mentioned inorganic oxide, and is adsorbed. A uniform water film can be formed by forming the water layer.

As the substrate of the lens portion of the gas mask of the present invention, a glass substrate such as laminated glass or a transparent plastic substrate such as polycarbonate can be preferably used.

A photocatalyst is a photocatalyst of an electron in the valence band when it is irradiated with light (excitation light) having an energy (that is, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. A substance that is excited (photoexcited) to generate conduction electrons and holes. For example, anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, dibismuth trioxide, tungsten trioxide, oxide trioxide. Diiron, strontium titanate and the like can be preferably used. Photocatalyst is anatase type titanium oxide, rutile type titanium oxide,
It is preferably one selected from zinc oxide, tin oxide and strontium titanate. Then, the photocatalyst is excited by ultraviolet rays and does not absorb light of wavelengths longer than that, so that coloring of the surface layer due to absorption of visible light hardly occurs.

Photoexcitation of the photocatalyst of the surface layer may be performed by indoor illumination or sunlight incident from the environment, but in order to more surely make the lens surface exhibit a high degree of hydrophilicity during use, It is desirable to provide a dedicated storage tool having a built-in light source capable of photoexciting the photocatalyst, and store the gas mask in the storage tool at least immediately before use. Here, the gas mask storage device preferably further includes a battery and a conductor circuit for connecting the light source and the battery. By allowing the light source to be turned on by the battery, the light source can be turned on even when there is no power supply.
Thereby, it is possible to more surely exhibit a high degree of hydrophilicity during use. In addition, the storage tool for the gas mask may further include a power supply connection terminal and a conductor circuit that connects the light source and the power supply connection terminal. As a result, the power source can be used in a situation where the power source is available, so that the life of the battery can be prolonged. Further, the storage tool for the gas mask may further be provided with an adapter connection terminal and a conductor circuit for connecting the light source and the battery. As a result, the light source can be charged even when there is a power source, so that the light source can be turned on even when there is no power source. Thereby, it is possible to more surely exhibit a high degree of hydrophilicity during use. Also,
An ON / OFF switch may be provided on the conductor circuit of the storage tool for the gas mask. Thereby, the light source can be turned on only immediately before use to make the surface of the lens highly hydrophilic, so that energy can be saved. Further, the closed circuit may be formed when the conducting wire circuit of the storage device for the gas mask is closed. Thereby, the light source is irradiated only when the lid is closed, and ultraviolet rays are often used for photoexcitation of the photocatalyst, which is safe. Further, since the light source is turned on only when the lid is closed, it is possible to save energy. Further, a mirror surface may be formed on the inner wall of the storage tool for the gas mask. As a result, the illuminance of the light source with which the lens surface is irradiated can be increased, so that the lens surface can be made hydrophilic faster.

As a light source used for photoexcitation of the photocatalyst, a metal halide lamp, a mercury lamp, a xenon lamp, a black light lamp, a germicidal lamp or the like can be preferably used. In order to make the surface of the base material highly hydrophilic by photoexcitation of the photocatalyst, the illuminance of the excitation light is 0.001 mW / cm.
^It may be ² or more, but is preferably 0.01 mW / cm ² or more, and more preferably 0.1 mW / cm ² or more.

The thickness of the surface layer containing the photocatalyst is 0.4
It is preferable that the thickness is less than or equal to μm. Then, white turbidity due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. More preferably, the thickness of the surface layer containing the photocatalyst is 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency.
Further, when the film thickness is reduced, the wear resistance of the surface layer is improved. The surface of the surface layer may be further provided with a wear-resistant or corrosion-resistant protective layer capable of being made hydrophilic and other functional films.

The surface layer preferably has a refractive index not so high as compared with the substrate. Preferably, the refractive index of the surface layer is 2 or less. Then, light reflection at the interface between the substrate and the surface layer and the interface between the surface layer and air can be suppressed. In order to reduce the refractive index of the surface layer to 2 or less, a substance having a refractive index of 2 or less is used for the photocatalyst, or if the photocatalyst has a refractive index of 2 or more, another substance having a refractive index of 2 or less is used for the surface layer. To be added. As a photocatalyst having a refractive index of 2 or less, tin oxide (refractive index: 1.9) or the like can be used. 2
Photocatalysts having the above refractive index include anatase type titanium oxide (refractive index 2.5) and rutile type titanium oxide (refractive index 2.7). In this case, other substances having a refractive index of 2 or less are used. , For example, calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), magnesium carbonate (refractive index 1.5), strontium carbonate (refractive index 1.5),
Dolomite (refractive index 1.7), calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), silica (refractive index 1.5), alumina (refractive index 1.6), silica Sand (refractive index 1.6), montmorillonite (refractive index 1.
5), kaolin (refractive index 1.6), sericite (refractive index 1.6), zeolite (refractive index 1.5), tin oxide (refractive index 1.9), etc. are added to the surface layer.

Metals such as Ag, Cu and Zn can be added to the second layer. The second layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.

The second layer includes pt, Pd, Ru and R.
A platinum group metal such as h, Ir, Os can be added. The second layer to which the metal is added can enhance the redox activity of the photocatalyst and improve the deodorizing purification action and the like. Further, when a solid acid other than the photocatalyst is added, the acidity of the solid superacid is improved by the addition of the platinum group metal, so that the hydrophilicity is also improved and the water film formation of the adhered water is further promoted, The hydrophilicity-maintaining property is also improved when the photocatalyst is not irradiated with the excitation light for a certain period of time.

When the substrate is a glass containing an alkali network modifying ion such as sodium (soda lime glass, parallel plate glass, etc.), an intermediate layer such as silica may be formed between the substrate and the surface layer. Good. Then, the diffusion of the alkali network modifying ions from the base material to the surface layer during the firing is prevented, and the photocatalytic function is more effectively exhibited.

The term "hydrophilic" refers to the property of being easily conformed when water is dropped on the surface, and generally refers to a state where the water wetting angle is less than 90 °. The term "highly hydrophilic" as used in the present invention refers to a property in which water is very easily blended when water is dropped on the surface, and more specifically, a state in which a water wetting angle is 10 ° or less, preferably 5 ° or less.

The solid acid used in the present invention includes Al carrying sulfuric acid.
₂ O ₃ , sulfuric acid supported TiO ₂ , sulfuric acid supported ZrO ₂ , sulfuric acid supported SnO ₂ , sulfuric acid supported Fe ₂ O ₃ , sulfuric acid supported SiO ₂ ,
Sulfuric acid supporting HfO ₂ , TiO ₂ / WO ₃ , WO ₃ / SnO
₂ , WO ₃ / ZrO ₂ , WO ₃ / Fe ₂ O ₃ , SiO _{2
· Al 2 O 3, TiO 2} / SiO 2, TiO 2 / Al 2
O ₃ TiO ₂ / ZrO _{2 and the} like can be preferably used.

Next, a method for forming the surface layer will be described. First, the production method in the case where the surface layer is composed of only the photocatalyst will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. In this case, there are roughly three methods. One method is a sol coating and firing method, the other method is an organic titanate method, and the other method is an electron beam evaporation method. (1) Sol-coating and firing method Anatase-type titanium oxide sol is applied to the surface of a substrate by a method such as spray coating, dip coating, flow coating, spin coating, or roll coating, and then fired. (2) Organic titanate method Titanium alkoxide (tetraethoxy titanium, tetramethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, etc.), titanium acetate, titanium chelate, etc. are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.). , After diluting with a non-aqueous solvent such as alcohol (ethanol, propanol, butanol, etc.), while partially or completely proceeding the hydrolysis, the mixture is spray-coated, dip-coated, Apply by methods such as flow coating method, spin coating method, roll coating method,
dry. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Electron beam evaporation method An amorphous titanium oxide layer is formed on the surface of a substrate by irradiating a titanium oxide target with an electron beam. After that, firing at a temperature higher than the crystallization temperature of anatase,
Phase transition of amorphous titanium oxide to anatase titanium oxide.

Next, the case where the surface layer is composed of a photocatalyst and silica will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. In this case, for example, there are the following three methods. One method is the sol coating firing method, the other is the organic titanate method, the other is 4
This is a functional silane method. (1) Sol coating and baking method A mixture of anatase-type titanium oxide sol and silica sol is applied to the substrate surface by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, and a roll coating method, and then fired. I do. (2) Organic titanate method Titanium alkoxides (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, and other organic titanates are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) and silica sol. Add alcohol (ethanol,
After diluting with a non-aqueous solvent such as propanol, butanol, etc., and then allowing the hydrolysis to proceed partially or completely, the mixture is spray-coated, dip-coated, flow-coated,
It is applied by a method such as spin coating or roll coating and dried. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Tetrafunctional silane method A mixture of tetraalkoxysilane (tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane, etc.) and anatase type titanium oxide sol is spray-coated or dip-coated on the surface of a substrate. , A flow coating method, a spin coating method, a roll coating method, or the like, and if necessary, hydrolyzing to form silanol, and then silanol is subjected to dehydration condensation polymerization by a method such as heating.

Next, the case where the surface layer is composed of a photocatalyst and a solid acid will be described by taking as an example the case where the photocatalyst is anatase type titanium oxide and the solid acid is TiO ₂ / WO ₃ . In this case, the ammonia solution of tungstic acid and anatase type titanium oxide sol are mixed, and if necessary, a mixture diluted with a diluent (water, ethanol, etc.) is spray-coated or dip-coated on the surface of the substrate. Law,
It is applied by a method such as a flow coating method, a spin coating method, a roll coating method or the like, and baked. Other methods include electron beam evaporation and hydrolysis and dehydration polycondensation of organic titanates such as titanium alkoxide, titanium acetate, and titanium chelate to form an amorphous titanium oxide film, and then tungstic acid is applied, and then amorphous. Heat treatment is performed at a temperature at which titanium oxide is crystallized and a TiO ₂ / WO ₃ composite oxide is formed.

Next, the case where the surface layer is composed of a photocatalyst and silicone will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. The method in this case is to mix a coating composed of uncured or partially cured silicone or a precursor of silicone and anatase type titanium oxide sol, and hydrolyze the precursor of silicone as needed, and then mix the mixture. Spray coating method on the surface of the substrate,
It is applied by a method such as a dip coating method, a flow coating method, a spin coating method, a roll coating method, etc., and a hydrolyzate of a silicone precursor is subjected to dehydration polycondensation by a method such as heating to obtain anatase type titanium oxide particles. A surface layer made of silicone is formed. The formed surface layer, by photoexcitation of anatase type titanium oxide by irradiation with light including ultraviolet rays, at least a part of the organic group bonded to the silicon atom in the silicone molecule is substituted with a hydroxyl group, and further on it. A physically adsorbed water layer is formed,
It exhibits a high degree of hydrophilicity. Here, the precursor of silicone includes methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, and phenyl. Trimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane,
Phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyl Diethoxysilane, phenylmethyldibutoxysilane, phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, a hydrolyzate thereof, and a mixture thereof can be suitably used.

In addition, the film coated with the above coating may be attached to the surface of the substrate with a transparent adhesive such as soapy water. Here, a plastic film such as polyethylene terephthalate, polyester, or polyethylene can be preferably used as the film base material.

[0027]

【Example】

Embodiment 1 FIG. (+ Amorphous silica) 0.69 g of tetraethoxysilane (Wako Pure Chemical Industries), 1.07 g of anatase type titanium oxide sol (TA-15, average particle size 10 nm), and 29.88 g of ethanol,
0.36 g of pure water was mixed to prepare a coating liquid.
This coating solution was applied by flow coating to 1
It was applied on a 0 cm square glass substrate. By holding this glass plate at a temperature of about 150 ° C. for about 20 minutes, tetraethoxysilane is subjected to hydrolysis and dehydration polycondensation, and a coating in which anatase-type titanium oxide particles are bound with amorphous silica is applied to the glass plate. Formed on the surface. The weight ratio of titanium oxide and silica in this coating was 1.
After leaving this glass plate in the dark for several days, an ultraviolet light source (Sankyo Denki, black light blue (BLB) fluorescent lamp)
Was used to irradiate the surface of the sample with ultraviolet light having an ultraviolet illuminance of 0.5 mW / cm ² for about 1 hour to obtain a # 1 sample. For comparison, a 10 cm square glass plate was left in the dark for several days # 2
Samples were also prepared. First, a water drop was dropped on the # 1 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) based on the contact angle with water 30 seconds after dropping. As a result, when a water drop was dropped from the micro syringe onto the sample surface, it was observed that the water droplet spread uniformly on the sample surface in a water film shape. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water droplet adapted to the surface but did not reach a uniform water film state.
The contact angle with water after 30 seconds was 30 °. next,
The # 1 sample and the # 2 sample were blown to examine whether or not clouding occurred. As a result, while the # 2 sample was clouded,
No haze occurred in one sample. In addition, the # 1 sample
After that, the sample was left in the dark for 2 days to obtain a sample # 3. And #
Similarly, the contact angle of the three samples with water was measured by a contact angle measuring device. As a result, when a water drop was dropped on the sample surface from the microsyringe on the # 3 sample, it was observed that the water droplet spread uniformly on the sample surface like a # 1 sample. The contact angle with water was maintained at about 3 °. Next, the presence or absence of fogging after spraying was observed for the # 3 sample. As a result, no fogging was observed.

Embodiment 2 FIG. (+ TiO ₂ / WO ₃ ) An amorphous titanium oxide film is deposited on the surface of a 10 cm square soda lime glass plate by an electron beam evaporation method, and then 50
By firing at a temperature of 0 ° C., the amorphous titanium oxide was crystallized to produce anatase type titanium oxide. The film thickness of the anatase type titanium oxide film was 100 nm. Furthermore, tungstic acid dissolved in 25% aqueous ammonia was added thereto and converted to a tungstic acid weight of 0.1%.
After applying 6 μg / cm ² , it was baked at a temperature of 500 ° C.
After leaving this glass plate in the dark for several days, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm ² for about 1 hour using a BLB fluorescent lamp to obtain a # 4 sample. For comparison, the # 2 sample used in Example 1 in which a 10 cm square glass plate was left in the dark for several days was also prepared. First, # 4 sample and #
Drops of water were dropped on the two samples, and the state after the drop was observed and the contact angle with water was measured. As a result, it was observed that when water droplets were dropped from the microsyringe on the sample surface of the # 4 sample, the water droplets spread uniformly on the sample surface in the form of a water film. 3
The contact angle with water after 0 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water droplet adapted to the surface but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °. Next, the # 4 sample and the # 2 sample were blown to examine whether or not fogging occurred. As a result, the # 2 sample generated haze, whereas the # 4 sample did not. Further, the # 4 sample was left in a dark place for two days thereafter to obtain a # 5 sample. Then, for the # 5 sample, the contact angle with water was similarly measured by a contact angle measuring device. As a result, when a water droplet was dropped on the sample surface from the microsyringe on the # 5 sample, it was observed that the water droplet spread uniformly over the sample surface in the form of a water film, similarly to the # 4 sample. The contact angle with water was maintained at about 1 °.
Next, with respect to the # 5 sample, it was observed whether or not clouding occurred after the breathing. As a result, no fogging was observed.

Embodiment 3 FIG. (+ TiO ₂ / amorphous silica,
Film sticking) First, 10 cm square polyethylene terephthalate (PE
T) After corona discharge treatment of the film, a primer (Shin-Etsu Chemical, PC-7A) is applied by a flow coating method,
A primer layer was formed by heat treatment at 120 ° C. for 5 minutes. Next, after the corona discharge treatment of the primer layer, a silicone hard coating solution was applied by a flow coating method and heat-treated at 120 ° C. for 10 minutes to form a hard coat layer. Next, after the corona discharge treatment of the hard coat layer, a photocatalyst coating liquid (titanium oxide 13
Parts by weight and 7 parts by weight of tetraethoxysilane in a mixed solvent of water and alcohol were applied by a flow coating method and dried at room temperature for 10 minutes to obtain a photocatalytic film. Soap water was applied to the back side of this film and attached to the surface of a 10 cm square glass substrate. After leaving this glass plate in the dark for several days, the surface of the sample was irradiated with ultraviolet rays for about 1 hour using a BLB fluorescent lamp at an ultraviolet illuminance of 0.5 mW / cm ² to obtain a # 6 sample. 10 for comparison
A # 2 sample used in Example 1 in which a cm square glass plate was left in the dark for several days was also prepared. First, water drops were dropped on the # 6 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) based on the contact angle with water 30 seconds after dropping. As a result, when the # 6 sample was dropped from the microsyringe onto the sample surface, it was observed that the water droplet spreads uniformly on the sample surface in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water droplet adapted to the surface but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °.
Next, the # 6 sample and the # 2 sample were blown to examine whether or not fogging occurred. As a result, the # 2 sample generated haze, whereas the # 6 sample did not. Further, the # 6 sample was left in a dark place for 2 days to obtain a # 7 sample. Then, for the # 7 sample, the contact angle with water was similarly measured by a contact angle measuring device. As a result, when a water droplet was dropped on the sample surface from the microsyringe on the # 7 sample, it was observed that the water droplet spread uniformly on the sample surface in the form of a water film similarly to the # 6 sample. The contact angle with water was maintained at about 3 °.
Next, with respect to the # 7 sample, it was observed whether or not clouding had occurred after breathing. As a result, no fogging was observed.

Embodiment 4 FIG. First, a primer coating (Shin-Etsu Silicone, PC-7A) was applied on the surface of a 10 cm square PMMA plate by a flow coating method, and then dried at 90 ° C. for 3 hours to form a primer layer. Next, a silicone hard coating agent (Shin-Etsu Silicone, KP-85) was applied thereon by a flow coating method and then dried at 90 ° C. for 3 hours to form a hard coat layer. Further, a wire electrode was used as an electrode on the surface by a corona discharge treatment device (Kasuga Denki), and the gap between the electrode tip and the sample surface was 2 mm and the voltage was 2 mm.
Corona discharge treatment was performed under the conditions of 6 kV, frequency of 39 kHz, and sample feeding speed of 4.2 m / min. On top of that, photocatalyst coating paint (anatase type titanium oxide sol (Nissan Chemical,
TA-15, solid content 15% by weight) 56 parts by weight, silica sol (Nippon Synthetic Rubber, Glasca A liquid, solid content 20% by weight)
After applying 33 parts by weight and 11 parts by weight of trimethylmethoxysilane (Nippon Synthetic Rubber, Glasca B solution) and diluting with ethanol) by the flow coating method, 9
It dried at 0 degreeC for 3 hours, and formed the photocatalyst containing layer. After leaving this PMMA plate in a dark place for several days, the surface of the sample was irradiated with ultraviolet rays for about 1 hour using a BLB fluorescent lamp at an ultraviolet illuminance of 0.5 mW / cm ² to obtain a # 8 sample. For comparison, a 10 cm square PMMA plate was left in the dark for several days #
Nine samples were also prepared. First, water drops were dropped on the # 8 sample and the # 9 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) based on the contact angle with water 30 seconds after dropping. As a result, when the # 8 sample was dropped from the microsyringe on the sample surface, it was observed that the water droplet spreads uniformly on the sample surface in the form of a water film. Also 30
The contact angle with water after 2 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 9 sample, when a water droplet was dropped from the microsyringe on the surface of the sample, the water droplet slightly adapted to the surface, but did not reach a uniform water film shape. The contact angle with water after 30 seconds was 60 °. Next, the # 8 sample and the # 9 sample were blown to examine whether or not clouding occurred. As a result, the # 9 sample was fogged, whereas the # 8 sample was not fogged. Further, the # 8 sample was left in the dark for 2 days thereafter to obtain a # 10 sample.
Then, with respect to the # 10 sample, the contact angle with water was similarly measured by the contact angle measuring device. As a result, when water droplets were dropped on the sample surface from the # 10 sample from the microsyringe, # 8
Similar to the sample, it was observed that the water droplets spread uniformly on the sample surface in the form of a water film. The contact angle with water was maintained at about 3 °. Next, with respect to the # 10 sample, it was observed whether or not clouding occurred after the breathing. As a result, no fogging was observed.

[0031]

According to the present invention, by providing a surface layer containing substantially transparent photocatalytic titanium oxide particles on at least the inner surface of the lens portion of the gas mask, the surface layer of the photocatalyst can be formed in response to photoexcitation of the photocatalyst. The surface exhibits hydrophilicity. Therefore, even if condensed water or water droplets of moisture adhere to the surface of the lens, the condensed water or water droplets that have adhered will spread evenly on the surface of the surface layer, so that clouding or crawling does not occur and the field of view is reduced. Reserved.

[Brief description of drawings]

FIG. 1 is a diagram showing a surface structure of a lens portion of a gas mask according to the present invention.

FIG. 2 is a diagram showing another surface structure of the lens portion of the gas mask according to the present invention.

Claims (16)

[Claims] 1. A surface layer containing substantially transparent photocatalyst particles is provided on at least the inner surface of the lens portion of the gas mask, and the photocatalyst renders the surface of the layer hydrophilic in response to photoexcitation. Condensed water and / or water droplets of the attached moisture are spread evenly on the surface of the layer, so that the lens is prevented from being clouded or covered by the water and / or water droplets of moisture. gas mask. 2. The surface layer containing the photocatalyst particles comprises:
The gas mask according to claim 1, further comprising silica. 3. The surface layer containing the photocatalyst particles,
The gas mask according to claim 1, further comprising a solid acid. 4. The surface layer containing the photocatalyst particles comprises:
The gas mask according to claim 1, further comprising silicone. 5. The gas mask according to claim 1, wherein the hydrophilicity of the surface of the layer in response to photoexcitation of the photocatalyst is 10 ° or less in terms of contact angle with water. 6. The gas mask according to claim 1, wherein the surface layer has a thickness of 0.4 μm or less. 7. The gas mask according to claim 1, wherein the surface layer has a thickness of 0.2 μm or less. 8. A hydrophilic protective layer is further provided on the surface of the surface layer.
The gas mask according to 5. 9. The gas mask according to claim 1, wherein the surface layer has a refractive index of 2 or less. 10. The storage device for a gas mask according to claim 1, further comprising a light source capable of optically exciting the photocatalyst. 11. The storage tool for gas mask according to claim 10, wherein the storage tool for gas mask further includes a battery and a lead wire circuit connecting the light source and the battery. . 12. The storage tool for the gas mask further includes a power supply connection terminal and a lead wire circuit connecting the light source and the power supply connection terminal.
Storage tool for gas mask according to 0 or 11. 13. The storage tool for gas mask according to claim 10, further comprising an adapter connection terminal and a lead wire circuit connecting the light source and the adapter connection terminal. Storage tool for gas mask. 14. An ON / OFF switch is provided on the conductor circuit, according to claim 11.
Storage tool for gas mask according to 3. 15. The conductor circuit forms a closed circuit when the storage device is closed.
Storage device for gas mask described in. 16. The storage device for a gas mask according to claim 10, wherein a mirror surface is formed on the inner wall of the storage device.