JPH0980357A - Spectacles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress sticking of or to easily remove the soiling stuck to spectacles, by forming a surface layer comprising single material of photocatalyst particles or a surface layer containing photocatalyst particles on a part of spectacles to be in contact with a human body. SOLUTION: A surface layer comprising a single material of photocatalyst particles or a surface layer containing photocatalyst particles is formed on at least a part of the frame of spectacles which is to be in contact with a human body so as to make the frame surface hydrophilic. This surface layer may contain such particles that can not suppress the hydrophilic effect of the photocatalyst particles but suppresses the oxidation reduction effect of the particles. Namely, since the surface layer comprising a single material of photocatalyst particles or containing photocatalyst particles is formed on the part of spectacles such as the frame or nose pad which is to be in contact with human body, soilings due to secretion, dirt or cosmetics hardly stick to the frame or the like, and even when soiling stick, the stuck soilings are decomposed and removed. Further, since the surface is made hydrophilic, roilings stuck to the surface can be easily removed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to spectacles, especially those capable of keeping a frame, a nose pad and the like clean.

[0002]

2. Description of the Related Art Nose pads and temples for glasses (ear hooks)
The part of is the part that directly contacts the human skin. Therefore, in Japanese Utility Model Application Laid-Open No. 3-47513, the presence of antibacterial zeolite in at least parts of the spectacle frame that come into contact with the skin suppresses the growth of various bacteria originating from stains such as human body secretions. Proposals have been made.

[0003]

As described above, even if the growth of various bacteria can be suppressed by applying the antibacterial zeolite to the frame or the like as described above, the adhesion of dirt itself can be suppressed or the adhered dirt can be easily removed. It will not be dropped.

[0004]

The present inventors have found that photocatalyst particles such as titanium oxide have a function of decomposing dirt and malodorous components by a redox reaction and a function of hydrophilizing the surface of an article (superhydrophilization). The present invention has been made based on the finding that

The decomposition action of the substance by the photocatalyst particles is based on a conventionally known redox reaction. When the photocatalyst particles are irradiated with ultraviolet rays or the like, electron-hole pairs are generated by photoexcitation, of which electrons are on the surface. Oxygen is reduced to generate superoxide ions (O ₂ ⁻ ), and holes oxidize surface hydroxyl groups to generate hydroxyl radicals (· OH), and these extremely reactive active species (O ₂ ⁻ ) are generated. The substance attached to the surface is decomposed by the redox reaction of (.OH).

On the other hand, the hydrophilizing action of the photocatalyst particles has not been known until now, but has recently been newly found by experiments of the present inventors. Although the theoretical basis is not completely elucidated, the hydroxyl group (OH
^-) is chemically adsorbed onto the surface of the photocatalyst particles, or a hydroxyl group (OH ^-) is replaced with an organic group, further the hydroxyl (OH ^-)
The water molecules in the air are physically adsorbed on the surface, and the physical adsorption water increases to increase the hydrophilicity of the surface, and the contact angle with water is 0 °.
We believe that a super-hydrophilic surface close to the surface will be realized.

As a specific example, a case where the surface layer is made of a silicone resin having a Si—O bond will be described. As shown in FIG.
Since the alkyl group (R) is bonded to the atom, the surface layer shows hydrophobicity. However, when light having an energy higher than the band gap energy of the photocatalyst particles is irradiated, first, as shown in FIG. alkyl group (R) by the photocatalytic effects hydroxyl - is substituted (chemisorption), further the hydroxyl ^(OH) - exhibit hydrophilic water molecules in the air are physically adsorbed ^(OH).

Further, titanium oxide (Ti) is used as photocatalyst particles.
O ₂ ) will be described. The state shown in FIG. 2A before the light irradiation is changed to the state shown in FIG. 2A when the light is irradiated, as shown in FIG. 2B. hydroxyl group constituting the (OH ^-) is a Ti atom, a hydrogen atom (H ⁺⁾ is chemically adsorbed to the oxygen atom (O), further the hydroxyl - water molecules and in the air a hydrogen atom (H ^{+) (OH)} Exerts hydrophilicity by physical adsorption.

In the above description, it is clear that the decomposing action of the substance and the hydrophilizing action are completely different. However, in a specific example, even in the case of TiO ₂ , the anatase type TiO ₂ can be oxidized and reduced. However, rutile type TiO ₂ hardly exhibits a substance decomposing action based on a redox reaction. Also, among the photocatalysts, tin oxide does not show a decomposition effect of a substance based on a redox reaction. In these photocatalyst particles, the energy level of the conduction band is not sufficiently high, so that the reduction reaction does not proceed. As a result, the electrons excited by the photoexcitation in the conduction band become excessive, and the electron-hole pairs generated by the photoexcitation are oxidized and reduced. It is believed that they recombine without participating in the reaction. However, both rutile TiO ₂ and tin oxide exhibit a hydrophilizing action. Further, the photocatalytic layer needs to have a thickness of at least 100 nm or more in order to exhibit the decomposing action of the substance.
Above is possible. From these facts, it can be said that the decomposition action of the substance by the photocatalyst and the hydrophilization action are completely different.

Based on the above findings, the present invention has been made to solve the conventional problems, and the eyeglasses according to the present invention are
A surface layer consisting of photocatalyst particles alone or a surface layer containing photocatalyst particles was provided on at least a portion of the frame that comes into contact with the human body to make the surface hydrophilic.

The redox action of the photocatalyst particles decomposes dirt, but there is a risk that the frame may be corroded or discolored depending on the material of the frame. Therefore, the surface layer may contain particles that suppress the redox action of the photocatalyst particles without inhibiting the hydrophilization action of the photocatalyst particles. It is also possible to add antibacterial metals such as Ag, Cu and Zn in order to exert antibacterial properties.

For the same reason, a protective layer containing particles that suppress the redox action of the photocatalyst particles without suppressing the hydrophilization action of the photocatalyst particles is provided between the surface layer and the frame, or the photocatalyst particle surface is provided. You may make it provide the protective film containing the particle which suppresses the oxidation-reduction effect | action of a photocatalyst particle, without suppressing the hydrophilization effect | action of a photocatalyst particle. When the protective film is provided, it is preferable to remove the protective film on the surface of the portion of the photocatalyst particles exposed to the outside air in order to enhance the hydrophilic effect.

As the photocatalyst particles, titanium oxide is most preferable, but in addition, ZnO, SnO ₂ , SrTiO ₃ , WO
₃ , metal oxides such as Bi ₂ O ₃ and Fe ₂ O ₃ .
It is considered that, since a metal element and oxygen are present on the surface, a hydroxyl group (OH ⁻ ) is easily adsorbed on the surface, and therefore, it is easy to exhibit hydrophilicity.

Titania (titanium oxide) will be described as an example of a method of forming a hydrophilic surface layer containing photocatalyst particles. The formation of amorphous titania, the application of silica-containing titania, the application of tin oxide-containing titania, the application of titania-containing Application of a silicone paint and the like can be mentioned.

The formation of amorphous titania is a method in which a surface to be coated is first coated with amorphous titania, which is baked to change the phase to crystalline titania, and any of the following methods can be employed. . (1) Hydrolysis and dehydration condensation polymerization of an organic titanium compound An alkoxide of titanium, for example, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium, or a hydrochloride such as hydrochloric acid or ethylamine After adding a decomposition inhibitor and diluting with an alcohol such as ethanol or propanol, the mixture is applied after partially or completely promoting the hydrolysis, and then the mixture is applied, and the temperature is from room temperature to 200 ° C. And dry. By drying, the hydrolysis of the alkoxide of titanium is completed to form titanium hydroxide, and a layer of amorphous titania is formed by dehydration-condensation polymerization of titanium hydroxide. Instead of titanium alkoxide,
Other organic titanium compounds such as titanium chelates or titanium acetate may be used. (2) Formation of amorphous titania by inorganic titanium compound Inorganic titanium compound such as TiCl ₄ or Ti (S
Hydrolysis and dehydration polycondensation are performed by applying an acidic aqueous solution of O ₄ ) ₂ and drying at a temperature of 100 to 200 ° C.
Form a layer of amorphous titania. Or it may form a layer of amorphous titania on the surface to be coated by chemical vapor deposition of TiCl _4. (3) Formation of amorphous titania by sputtering A target of metal titanium is irradiated with an electron beam in an oxidizing atmosphere to form a layer of amorphous titania on the surface to be coated.

The application of the silica-containing titania is to form a layer made of a mixture of titania and silica on the surface to be coated. The ratio of silica to the total of titania and silica is 5 to 90 mol%, preferably 10 to 70 mol%, more preferably 10 to 50 mol%. The following method can be employed for forming the surface layer made of silica-containing titania. (1) A suspension containing particles of anatase type or rutile type titania and particles of silica is applied to a surface to be coated, and fired at a temperature equal to or lower than the softening point of the substrate (object to be coated). (2) Based on a mixture of a precursor of amorphous silica (for example, tetraalkoxysilane such as tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium, etc.) and crystalline titania sol After applying to the surface of the material and hydrolyzing it as necessary to form silanol, heating at a temperature of about 100 ° C. or more and subjecting the silanol to dehydration polycondensation, the titania is bound with amorphous silica. Obtained surface layer (photocatalytic coating). In particular, if the dehydration condensation polymerization of silanol is performed at a temperature of about 200 ° C. or higher, the degree of polymerization of silanol can be increased, and the alkali resistance performance of the photocatalytic coating can be improved. (3) Dispersing silica particles in a solution of amorphous titania precursor (organic titanium compound such as alkoxide, chelate or acetate of titanium, or inorganic titanium compound such as TiCl ₄ or Ti (SO ₄ ) ₂ ) Is applied to the surface of the base material, and the titanium compound is cooled to room temperature for 20 minutes.
By subjecting it to hydrolysis and dehydration polycondensation at a temperature of 0 ° C.,
A thin film of amorphous titania in which silica particles are dispersed is formed. Next, the amorphous titania is changed into crystalline titania by heating to a temperature higher than the crystallization temperature of titania and lower than the softening point of the substrate. (4) Amorphous titania precursor (organic titanium compound such as alkoxide, chelate or acetate of titanium, or inorganic titanium compound such as TiCl ₄ or Ti (SO ₄ ) ₂ ) in a solution of amorphous titania precursor (For example, tetraalkoxysilanes such as tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium, etc., silanols which are hydrolysates thereof, or polysiloxanes having an average molecular weight of 3000 or less) And apply to the surface of the substrate. Then, these precursors are subjected to hydrolysis and dehydration polycondensation to form a thin film composed of a mixture of amorphous titania and amorphous silica. Next, the amorphous titania is changed into crystalline titania by heating to a temperature higher than the crystallization temperature of titania and lower than the softening point of the substrate.

The application of the tin oxide-containing titania is to form a layer made of a mixture of titania and tin oxide on the surface to be coated. The ratio of tin oxide to the total of titania and tin oxide is 1 to 95 mol%, preferably 1 to 50 mol%. The following method can be adopted as a method for forming a surface layer made of titania mixed with tin oxide. (1) A suspension containing particles of anatase type or rutile type titania and particles of tin oxide is applied to a surface to be coated, and fired at a temperature equal to or lower than the softening point of the substrate (object to be coated). (2) Dispersion of tin oxide particles in a solution of a precursor of amorphous titania (organic titanium compound such as titanium alkoxide, chelate or acetate, or inorganic titanium compound such as TiCl ₄ or Ti (SO ₄ ) ₂ ) The resulting suspension is applied to the surface of the substrate, and the titanium compound is heated to room temperature for 20 minutes.
By subjecting it to hydrolysis and dehydration polycondensation at a temperature of 0 ° C.,
A thin film of amorphous titania in which tin oxide particles are dispersed is formed. Next, the amorphous titania is changed into crystalline titania by heating to a temperature higher than the crystallization temperature of titania and lower than the softening point of the substrate.

The titania-containing silicone paint is applied by using a paint in which titania (photocatalyst particles) is dispersed in a film-forming element made of uncured or partially cured silicone (organopolysiloxane) or a precursor of silicone. . Specifically, after the above coating material is applied to the surface of the base material, and after the film-forming element is cured, when the photocatalyst is photoexcited, the organic group bonded to the silicon atom of the silicone molecule is replaced with a hydroxyl group by the action of the photocatalyst. Then, the contact angle of the surface with water becomes close to 0 °, and the surface becomes hydrophilic (super-hydrophilic). This method can cure the film forming element at a relatively low temperature, and can be applied as many times as necessary,
In addition, there is an advantage that it can be easily made hydrophilic even by sunlight. The following resins can be used as the resin. Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltriisopropoxysilane, ethyltri-t-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-
Propyltri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltrit-butoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-
Decyltriisopropoxysilane, n-decyltri-t-
Butoxysilane, n-octadecyltrichlorosilane,
n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n
-Octadecyltri-t-butoxysilane, phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, tetrachlorosilane, tetrabromosilane, tetramethoxy Silane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane,
Dimethyldibromosilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, triethoxyhydrosilane , Tribromohydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane, Trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane , Trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycid Xypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldi Ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-
Methacryloxypropyltri-t-butoxysilane, γ
-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxysilane , Γ-
Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltrit-
Butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and their partial hydrolysates or mixtures thereof can be used. .

In order to ensure good hardness and smoothness of the silicone resin film, it is preferable to contain 10 mol% or more of the three-dimensionally crosslinked siloxane. In order to provide sufficient flexibility of the resin film while securing good hardness and smoothness, it is preferable to contain 60 mol% or less of the two-dimensional crosslinked siloxane. In order to increase the rate at which the organic group bonded to the silicon atom of the silicone molecule is replaced with a hydroxyl group by photoexcitation, use is made of a silicone in which the organic group bonded to the silicon atom of the silicone molecule is an n-propyl group or a phenyl group. Is preferred. An organopolysilazane compound having a silazane bond can be used instead of the silicone having a siloxane bond.

As the particles for suppressing the redox action of the photocatalyst particles, alkali metals (Na etc.), alkaline earth metals, alumina, silica, zirconia, antimony oxide, amorphous titanium oxide, aluminum, manganese etc. are used. Can be mentioned.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 A surface layer composed of anatase type titanium oxide particles, silica and a silicone resin is formed on the right nose pad and the right temple of the commercially available eyeglass frame shown in FIG. 3, and the left nose pad and the left temple are I left it as it was. Then, the illuminance on this spectacle frame is 0.5 mW / cm
UV light was irradiated for 1 week using the BLB lamp of No. ² .

(Example 2) A surface layer was formed of anatase type titanium oxide particles, silica, a silicone resin and Ag particles, and eyeglasses similar to Example 1 were prepared under other conditions.

Example 3 Eyeglasses having a surface layer formed by the same method as in Example 1 after spraying an aqueous sodium nitrate solution on the surface were prepared.

(Evaluation 1) The lenses were attached to the eyeglass frames of Examples 1, 2 and 3 and worn for one month as usual, and then washed with water. As a result, stains attached to the right nose pad and temple could be easily removed, but stains remained on the left nose pad and temple. In addition, when examining Example 3, no deterioration of the spectacle frame was observed.

(Evaluation 2) The surface condition of the left and right nose pads and the temples after washing with water in Evaluation 1 were compared, and the right nose pad and temple were the same before and after washing with water.
The left nose pad and temple were white and deteriorated.

[0026]

As described above, according to the present invention, since the surface layer composed of the photocatalyst particles alone or the surface layer containing the photocatalyst particles is provided at least in the portion of the eyeglass frame, the nose pad or the like that comes into contact with the human body, Due to the redox action of the photocatalyst particles, dirt originating from secretions, dirt, and cosmetics does not easily adhere to the frame, etc., and the dirt that has adhered is decomposed and removed, and the surface becomes hydrophilic, so the dirt that has adhered can be easily removed. You can

Further, the surface layer may contain particles which do not suppress the hydrophilizing action of the photocatalyst particles but suppress the redox action of the photocatalyst particles, or suppress the hydrophilizing action of the photocatalyst particles between the surface layer and the frame. Without providing a protective layer containing particles that suppress the redox action of the photocatalyst particles, or containing particles that suppress the redox action of the photocatalyst particles without suppressing the hydrophilization action of the photocatalyst particles on the surface of the photocatalyst particles Since the protective film is provided, the deterioration of the spectacle frame due to the redox action of the photocatalyst particles can be prevented, the hydrophilicity can be secured, and the dirt can be easily removed.

Furthermore, by adding an antibacterial metal such as Ag or Cu in addition to the photocatalyst particles, it is possible to suppress the growth of microorganisms using the attached dirt component as a nutrient source and prevent the deterioration by microorganisms.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a process of imparting hydrophilicity to the surface of a silicone resin containing photocatalyst particles.

FIG. 2 is a diagram illustrating a process of imparting hydrophilicity to a surface layer made of photocatalytic particles.

FIG. 3 is a perspective view of eyeglasses according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Makoto Senkoku 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu, Fukuoka Prefecture Totoki Kikai Co., Ltd. (72) Toshiya Watanabe Nakajima, Kokurakita-ku, Kitakyushu, Fukuoka 2-1, 1-1 Totoki Co., Ltd. (72) Inventor Shin Hayakawa 2-11-1, Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka (72) Inventor Atsushi Kitamura Kitakyushu, Fukuoka 2-1, 1-1 Nakajima, Kokurakita-ku Totoki Equipment Co., Ltd.

Claims (5)

[Claims] 1. Eyeglasses, characterized in that a surface layer comprising photocatalyst particles alone or a surface layer containing photocatalyst particles is provided on at least a portion of a frame or the like in contact with a human body. 2. The spectacles according to claim 1, wherein the surface layer contains particles that do not suppress the hydrophilizing action of the photocatalyst particles but suppress the redox action of the photocatalyst particles. 3. The spectacles according to claim 1, wherein between the surface layer and the frame, a protective layer containing particles that do not suppress the hydrophilization action of the photocatalyst particles and inhibit the redox action of the photocatalyst particles is provided. Eyeglasses characterized by being provided. 4. The spectacles according to claim 1, wherein the surface of the photocatalyst particles forming the surface layer contains particles that do not inhibit the hydrophilization action of the photocatalyst particles and inhibit the redox action of the photocatalyst particles. Eyeglasses characterized by being provided with a membrane. 5. The spectacles according to claim 4, wherein the protective film on the surface of the portion of the photocatalyst particles exposed to the outside air is removed.