JP2003015092A - Spectacle lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spectacle lens which has good anti-fogging properties and cleanability with water and does not change the surface characteristics possessed by the lens. SOLUTION: This spectacle lens has a base material lens and an inorganic hydrophilic hard layer formed on the surface of the base material lens, in which the inorganic hydrophilic hard layer contains titanium oxide and a photocatalyst suppressing component against the photocatalyst effect possessed by the titanium oxide. This inorganic hydrophilic hard layer (lyophilic part) is deposited and formed by an LDP process or multicomponent vacuum vapor deposition process. As a result, the spectacle lens which hardly fogs even under the high-moisture environment can be provided. The stains of the lens surface can be removed by cleaning with water and since the lens surface is not worn by wiping cloth, wiping paper, etc., the lens surface can be maintained for a long period without being flawed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inorganic hydrophilic hard layer containing a surfactant (hereinafter, also referred to as “philic portion”,
In the present specification, "amphiphilic" refers to a property having an affinity for a solvent including water, and also includes "hydrophilicity")
Relates to a spectacle lens having a surface formed thereon. More specifically, the present invention has an inorganic hydrophilic hard layer impregnated with a surfactant as a lyophilic portion on the surface, so that fogging is less likely to occur on the surface, and stains can be easily removed by washing with water. The present invention relates to a spectacle lens which is capable of being formed and is less likely to be scratched on the surface.

[0002]

2. Description of the Related Art Conventionally, there has been a great demand for anti-fog spectacle lenses by a lens surface coating treatment, but such a lens surface coating treatment for the purpose of preventing fog has not reached a practical level. This is because the specifications of eyeglasses are very strict, and it is difficult to manufacture an eyeglass lens that satisfies these strict specifications.

By the way, WO96-29375 discloses an invention of an antifogging lens based on the photocatalytic effect of anatase type titanium oxide. This publication also discloses a method in which anatase-type titanium oxide and silica are fused to have photocatalytic activity to maintain hydrophilicity and reduce surface reflectance. However, both of them have problems in terms of hardness (mechanical strength) or reflectance when applied to eyeglass lenses, and application to eyeglass lenses is currently extremely difficult. Particularly in the case of the composite film, there is a problem that the hardness cannot be improved due to the limitation of the composition for exhibiting the optical function, and as a result, the reflectance is slightly increased, and it is difficult to match the specification conditions of the glasses.

[0004] Further, as a treatment expected to be anti-fogging, the application of a surfactant to the surface of the lens using a spray can be mentioned, but the application to a lens base material which is originally hydrophobic or water repellent is general. Therefore, there was a problem that it was poor in sustainability and transient. Furthermore, it is complicated because the spray must be carried with him at all times. By the way, at present, it is general to provide a plastic lens with a hard layer formed by coating a composite plastic such as silica or an organic material on the hard plastic surface substrate. Furthermore, what is called an antireflection film, which is multi-coated with a material having an appropriate refractive index on the surface of a plastic lens and has a film designed to reduce the reflectance, is also used. Also in coating, a hard film is used as the outermost layer.

A generally used hard layer is mainly composed of silica, and is formed so that its hardness can cope with dust and the like in the outside world. For this reason, the plastic lens having such a hard layer formed is much less likely to be scratched than ordinary plastic materials. However, since the spectacle lens is generally cleaned by adhering to the lens surface with a cloth or paper for wiping spectacles and wiping off dirt, if fine sand particles or the like are attached during the wiping, If the lens surface is rubbed with a wiping cloth, it will be damaged relatively easily. In this way, the scratches once attached to the lens cannot be repaired, resulting in significantly shortening the life of the lens.

The stains on the spectacle lens are wiped off with a cloth such as a cloth because the surface of the lens is hydrophobic and the lens surface repels water even after washing with water, so that the lens can be washed efficiently. Cannot do it, and
Since the lens surface is hydrophobic, the water on the lens surface may become water droplets and remain on the lens surface after cleaning.If water droplets are left in this way, water evaporates and new dirt in the form of water droplets is formed. For some reasons.

The inventors of the present invention have made extensive studies in view of such a situation. As a result, an inorganic hydrophilic hard layer containing specific components is formed on a substrate, and this is impregnated with a surfactant for a long period of time. By allowing the base material to remain stable over a period of time, the base material itself is provided with a lyophilic property, thereby facilitating the anti-fog effect and allowing the effect to be maintained for a long period of time. By cleaning the spectacle lens with the inorganic hydrophilic hard layer formed thereon, it is possible to easily remove stains adhering to the surface and to effectively prevent the generation of new stains due to residual water droplets. That is, the present invention has been completed.

[0008]

It is an object of the present invention to provide an eyeglass lens which is hard to be fogged by water vapor, and to provide an eyeglass lens suitable for cleaning the eyeglass lens whose surface has been conventionally cleaned by wiping with water. The purpose is to do.

More specifically, it is an object of the present invention to provide a spectacle lens which has good antifogging property and water washability but does not change the surface property of the lens.

[0010]

SUMMARY OF THE INVENTION An eyeglass lens of the present invention has a base lens and an inorganic hydrophilic hard layer formed on the surface of the base lens, and the inorganic hydrophilic hard layer contains titanium oxide. And a photocatalyst inhibiting component for the photocatalytic action of the titanium oxide.

In the present invention, the inorganic hydrophilic hard layer preferably contains a simple oxide or a complex oxide of silicon, zirconium and titanium. Titanium oxide forming such an inorganic hydrophilic hard layer has a photocatalytic action, but the catalytic action of this titanium oxide is suppressed by a metal such as zirconium or its oxide. Then, the titanium oxide whose photocatalysis is suppressed is water and a solvent (for example, a surfactant).
In addition to exhibiting a very high affinity for both, the photocatalytic action of titanium oxide is suppressed even if a surfactant is present on the surface, so that the surfactant does not undergo photodecomposition, Can exist stably for a long period of time. Therefore, the spectacle lens of the present invention exhibits extremely high hydrophilicity and hydrophilicity.

Further, in the present invention, the atomic ratio of zirconium atom to titanium atom in the inorganic hydrophilic hard layer is in the range of 99.9: 0.1 to 70:30, and the ratio of titanium atom and zirconium atom to silicon atom is set. The atomic ratio is preferably in the range of 99.9: 0.1 to 40:60. Further, in the spectacle lens of the present invention, the inorganic hydrophilic hard layer may be formed in a layered form or may not be formed as a uniform layer, and such an inorganic hydrophilic hard layer is deposited in the amount thereof. When calculated from the above, the average value of the thickness is 10 ^{−3 to} 0.
It is preferably in the range of 5 μm.

In the present invention, the inorganic hydrophilic hard layer is preferably a layer formed by the LDP method or the vacuum deposition method. Further, in the present invention, the surfactant is alkyl ether sulfate ester salt, polyoxyethylene alkyl ether, fatty acid alkanolamide, fatty acid methylglucamide, α-olefin sulfonate, alkylamine oxide and linear alkylbenzene sulfonate. It is preferable to contain at least one kind of surfactant selected from the group consisting of:

Further, in the present invention, the surfactant is preferably contained in the inorganic hydrophilic hard layer in an amount of 50% by weight or less. In the eyeglass lens of the present invention,
The contact angle of the inorganic hydrophilic hard layer with water is preferably in the range of 0 to 50 degrees. Further, in the present invention, it is preferable that the component forming the inorganic hydrophilic hard layer is a component that does not easily elute even when contacted with water.

The Mohs hardness of the inorganic hydrophilic hard layer formed on such a spectacle lens is preferably in the range of 5-9.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The spectacle lens of the present invention will be specifically described below. When a spectacle lens encounters a high-humidity environment, fine water droplets are formed on the surface of the spectacle lens to cause light scattering and thus become cloudy. Therefore, it is a requirement for antifogging that the surface of the spectacle lens is made of a highly hydrophilic material. Further, in order for water droplets to adhere to the surface of the base material of the spectacle lens and spread as an ultra-thin film to give a transparent feeling, the contact angle of the base material itself to water is infinitely close to 0 °. is necessary. Such a state is only confirmed (superhydrophilic) on the surface of the photocatalytic titanium oxide (anatase type) film after ultraviolet irradiation, and is not found in general inorganic materials.

As described above, even if an attempt is made to apply a titanium oxide film having photocatalytic activity to the surface of spectacles, the refractive index is high and it becomes a mirror surface, and the hardness of the substance itself is low, which poses a practical problem. Further, there is also a problem that the function does not last long if the irradiation of ultraviolet rays is stopped, and there are many obstacles to its practical use. Further, as described above, even if the surface-active agent is applied to the hydrophobic or water-repellent substrate by spraying, the antifogging effect is not so large. This means that the water-friendly effect of the surfactant has not been effectively realized on the water-repellent substrate.

That is, in order for the lens to exhibit antifogging properties, the base material itself can adsorb the surfactant and remain stable for a long period of time, that is, the base material itself is not only hydrophilic but also has a hydrophilic property. It is necessary to have a medium property.
Furthermore, it is necessary that the photocatalytic activity of titanium oxide is moderately suppressed and the hydrophilicity of titanium oxide be good so that the surfactant on the surface is not decomposed by the photocatalytic action of titanium oxide. is there. In this way, the titanium oxide contained in the layer on the lens surface has a photocatalytic activity suppressed so that the photocatalytic activity is suppressed so that the surfactant is not photodegraded, and the titanium oxide having a photocatalytic activity is As a result, the surfactant on the surface can be retained on the surface for a long period of time without being subjected to photodegradation, and at the same time, the metal oxide having such characteristics and the surfactant on the surface work together. Therefore, it is considered that the glasses can exhibit good anti-fogging property.

From this point of view, when an inorganic hydrophilic hard layer made of a simple oxide or a complex oxide of silicon, titanium and zirconium is formed on the lens surface as a base material, the surface activity of the inorganic hydrophilic hard layer is increased. It has been found that when the agent is impregnated, the moisture does not become a water drop even when it encounters a high humidity environment, and it adheres as a thin film so that the lens does not easily fog and the effect lasts for a long time. That is, since an inhibitor is contained so that the photocatalytic activity of titanium oxide forming the inorganic hydrophilic hard layer is suppressed, the inorganic hydrophilic hard layer has excellent hydrophilicity and hydrophilicity (including hydrophilicity). Can be granted. In the present invention, the photocatalytic effect of titanium oxide is suppressed by the coexistence of an oxide of a metal such as zirconium, and thus the layer containing titanium oxide whose photocatalytic effect is suppressed is very hydrophilic. And lyophilic.

Furthermore, in the present invention, in addition to titanium oxide, silica for reducing the refractive index, and metal oxides such as zirconium, which is a component that suppresses the photocatalytic action of titanium oxide, form a trinity to form an appropriate ratio. By combining the above, it is possible to form an antifogging film that can withstand the specification conditions of the lens. In addition, the antifogging film having such a configuration is excellent in hydrophilicity and hydrophilicity, and can be well impregnated with, for example, a surfactant, and the surfactant on the surface is decomposed over a long period of time. Stable on the surface without being damaged.

That is, the inorganic hydrophilic hard layer containing the titanium oxide in which the photocatalytic activity of the titanium oxide is lost and further preferably impregnated with the surfactant is originally the substrate itself. In addition to having a high hydrophilicity that cannot be realized only by the characteristics, it becomes possible to express a very high hydrophilicity on the surface of the lens. The photocatalytic action of this titanium oxide is appropriately suppressed, and the surface-active agent is not decomposed by the photocatalytic action. That is, the layer containing titanium oxide in which the photocatalytic activity is suppressed exhibits high hydrophilicity and high hydrophilicity per se, and by impregnating this with a surfactant, the photocatalytic activity suppressed is suppressed. By virtue of the fact that the surfactant is not photodegraded and its properties are maintained for a long period of time, the highly hydrophilic property and the surfactant cooperate to realize an extremely excellent antifogging effect.

On the other hand, a method has been considered in which the entire surface of the base material is made porous so as to exhibit the same effect, but the surface of the base material is apt to be scratched and easily soiled, which is difficult to use. . Since the inorganic hydrophilic hard layer according to the present invention is firmly bonded to the spectacle lens, the antifogging effect thereof is usually lost even when used in the same manner as a normal spectacle lens for at least 2 years. There is no.

Further, in the present invention, when the inorganic hydrophilic hard layer impregnated with the above-mentioned surfactant is formed on the surface of the spectacle lens, the surface of the spectacle lens is washed by washing with water. It is possible to easily remove the attached dirt and effectively prevent the generation of new dirt due to the residue such as water drops. In the first place, the surface of the spectacle lens is poor in water wettability, and even if you try to wash the spectacle lens with water, the surface of the spectacle lens repels water, so water droplets are formed on the surface, and if you dry it, it will take time to completely dry. I will end up. Further, on the surface of the lens after drying, a trace (new stain) formed in the contact portion with the lens remains on the adhered water drop, and it is considerably difficult to wipe it off.

Generally, in the use environment of the spectacle lens, dirt is liable to be adhered, particularly oil dirt, dust, sand dust and the like. Also, if the surface is wiped off frequently, the surface is likely to be scratched due to abrasion due to sand grains. Generally, the hard layer is composed of Si ₂ since SiO ₂ is the main component.
When sand grains having a hardness of O ₂ or more are attached, the sand grains often scratch the spectacle lens when attempting to wipe off stains on the spectacle lens. Under such circumstances, if the surface of the spectacle lens can be made hydrophilic so as not to be newly stained by washing with water, the spectacle lens can be cleaned by washing with water. If the dirt can be removed by washing with water, the surface of the spectacle lens is much less likely to be scratched than the surface of the lens can be wiped with a cloth or paper.

By the way, since the spectacles are used for a long period of time, it is necessary that the hydrophilic portion formed on the spectacle lens has high durability. Therefore, as described above, in the present invention, the inorganic hydrophilic hard layer is formed on the spectacle lens so that the spectacle lens can be imparted with a stable hydrophilic property (philicity) for a long period of time, and a surfactant is added thereto. It is impregnated.

Since the spectacle lens of the present invention is formed with an inorganic hydrophilic hard layer having extremely excellent hydrophilicity (contact angle to water is as close to 0 degree as possible), the lens is immersed in water. Even if the water is pulled up, the water forms an extremely thin layer on the lens surface and spreads uniformly to be in a state of being attached, so that the lens can be dried in a relatively short time. As a result, it is possible to maintain a relatively clear lens surface without the generation of new dirt due to water droplets. Moreover, by washing the lens with water, it is possible to prevent the generation of scratches on the lens surface.

The spectacle lens base material of the present invention may be glass or plastic, but the plastic lens is softer and more easily damaged than the glass lens. Therefore, the effect of the present invention is applied to the plastic lens. It appears remarkably in some cases. A hard layer is preferably formed on the surface of such a spectacle lens, regardless of whether the material forming the spectacle lens is glass or plastic. Such a hard layer is usually formed of silicon oxide as described above.

In the spectacle lens of the present invention, a specific inorganic material described later is used as a material for forming the inorganic hydrophilic hard layer. Further, it is preferable to adjust the components of the inorganic hydrophilic hard layer so that the components forming the inorganic hydrophilic hard layer do not easily elute even when contacting with water. The surfactant to be impregnated in the inorganic hydrophilic hard layer is a cationic surfactant, an anionic surfactant,
It may be either an amphoteric surfactant or a nonionic surfactant, and specifically, sodium alkyl ether sulfate, polyoxyethylene alkyl ether, fatty acid alkanolamide, fatty acid methylglucamide, α
-Sodium olefin sulfonate, alkylamine oxide, linear alkylbenzene sulfonic acid and the like can be mentioned. It is desirable that such a surfactant is impregnated in the inorganic hydrophilic hard layer in an amount of 50% by weight or less, preferably 30% by weight or less, particularly preferably 20% by weight or less. . The coating amount is 10 ^{-2 to} 200 mg, preferably 10 ^-1 to 80 mm for a lens having a diameter of 80 mm.
50 mg is desirable.

This surface-active agent may be impregnated by mixing the surface-active agent in water when washing with water after forming the inorganic hydrophilic hard layer on the spectacle lens. It may be impregnated by applying it directly to the hard layer, wiping it off after application and spreading it thinly. The last remaining haze of the surfactant can be made transparent and uniform, for example, simply by blowing. This is due to the presence of the highly hydrophilic inorganic hydrophilic hard layer under the surface of the surfactant layer, which increases the water wettability.

The inorganic hydrophilic hard layer formed on such a spectacle lens has a suppressed photocatalytic action of titanium oxide, and exhibits an extremely high affinity for water particularly when a surfactant is applied. When the contact angle between this inorganic hydrophilic hard layer and water is measured, the contact angle shows a value as close as possible to 0 degree. However, such an inorganic hydrophilic hard layer is relatively rare to form a uniform layer on the surface of the spectacle lens, and is formed as a discontinuous precipitation mark, or the inorganic hydrophilic hard layer is a spectacle lens. It often exists by forming islands on the surface of. When such an inorganic hydrophilic hard layer is formed in at least 5 to 40% of the area of the spectacle lens surface, the contact angle between the spectacle lens and water is significantly reduced. Even when the inorganic hydrophilic hard layer is discontinuously formed, when the contact angle between the spectacle lens surface (with the inorganic hydrophilic hard layer) and water is measured, it is usually 0 to
It shows a value within the range of 50 degrees, preferably 0 to 30 degrees. The contact angle between the inorganic hydrophilic hard layer and water is usually 0-5.
It is desirable that the range is 0 degrees, preferably 0 to 30 degrees, and more preferably infinitely close to 0 degrees. By forming an inorganic hydrophilic hard layer whose components are adjusted so as to have such a contact angle on a spectacle lens, when water is contacted with the spectacle lens or when the lens is washed, droplets of water are generated. A thin water film forms and spreads over the entire surface and does not exist on the spectacle lens surface in the form of water droplets. Therefore, after washing with water, moisture on the surface of the glasses is removed in a short time,
Since water does not remain in the form of water drops and remains on the lens surface, it is possible to effectively prevent new stains from adhering to the cleaned water.

Such an inorganic hydrophilic hard layer, that is, the hydrophilic part contains at least one metal selected from the group consisting of Si, Ti and Zr, and contains F, N, B, H and
It preferably contains at least one atom selected from the group consisting of O. Particularly, in the present invention, Si: Zr: Ti in the inorganic hydrophilic hard layer is usually 2% in atomic ratio.
0: 1: 10 to 2000: 10: 1, preferably 20
It is desirable to set the amount within the range of 0: 1: 10 to 200: 10: 1.

In particular, by containing a small amount of Ti and Zr, an inorganic hydrophilic hard layer containing Si and a spectacle lens,
In particular, the bonding strength to the hard layer formed on the surface of the spectacle lens becomes high (in the present specification, the "inorganic hydrophilic hard layer" means the hydrophilic portion and the hydrophilic portion formed on the spectacle lens of the present invention. The "hard layer" refers to the layer with high scratch resistance on the lens surface where the lens surface is coated with a composite material plastic such as silica or organic material.) In contrast, the content of Ti or Zr is When it is large relative to Si, it causes an increase in the refractive index of the inorganic hydrophilic hard layer, and particularly
If Ti is too much, the scratch resistance of the inorganic hydrophilic hard layer is significantly reduced. Therefore, the content ratio of Ti or Zr to Si is
There may be limitations when applying this lens to eyeglasses. Especially, the atomic ratio of Ti and Zr (Ti / Zr) is usually 9
9.9 / 0.1-70 / 30, preferably 99 / 1-8
By setting it within the range of 5/15, an inorganic hydrophilic hard layer having higher strength can be formed. In addition, the atomic ratio of Si to (Ti + Zr) (Si
/ (Ti + Zr)) is usually 99.9 / 0.1-40 /
60, preferably 99/1 to 50/50, and particularly preferably 95/5 to 45/55, to form an inorganic hydrophilic hard layer having remarkably high strength and remarkably excellent hydrophilicity. You can Thus a small amount of Ti and
Zr forms a strong bond (for example, chemical bond, physicochemical bond, physical bond, etc.) with an oxygen atom in the hard layer under the inorganic hydrophilic hard layer in some form. Presumed. Since the bonding force between Ti and Zr and the oxygen atom is significantly higher than the bonding force between Si and the oxygen atom,
The presence of a small amount of Ti and Zr in the inorganic hydrophilic hard layer significantly improves the bonding strength to the lower layer of the inorganic hydrophilic hard layer, and the hydrophilicity of the inorganic hydrophilic hard layer containing Ti and Zr. Is higher than the inorganic hydrophilic hard layer containing only Si, and has excellent hydrophilicity and neoplasticity. That is, in general, anatase-type titanium oxide has a photocatalytic action, but the photocatalytic action of this titanium oxide is suppressed by the coexistence of a photocatalytic suppressing component composed of a metal oxide such as zirconium. In this way, titanium oxide whose photocatalytic action is appropriately suppressed exhibits extremely high hydrophilicity and hydrophilicity.

Such an inorganic hydrophilic hard layer rarely forms a uniform layer as described above, and usually has a structure in which a plurality of types of compounds are partially precipitated, so that the average Although it is not always easy to determine the thickness, the average thickness of the inorganic hydrophilic hard layer calculated from the deposited compound and the deposition area of this compound is usually 10Å to 0.
It is desirable to be in the range of 5 μm, preferably 500 Å to 0.3 μm. By forming the inorganic hydrophilic hard layer with such a thickness, it is possible to form the inorganic hydrophilic hard layer exhibiting good hydrophilicity and neoplasticity without adversely affecting the transparency of the spectacle lens. . In addition, the inorganic hydrophilic hard layer having an average thickness within the above range is also excellent in durability, and normally, even if the eyeglass lens is repeatedly cleaned by washing with water for at least 2 years, its hydrophilic property is not increased. There is no loss of sex. That is, as a result of the experiment, in the usual case, this inorganic hydrophilic hard layer can be maintained in the same state as the initial state for at least 2 years.

Such an inorganic hydrophilic hard layer can be formed by depositing silicon oxide, titanium oxide, and zirconium oxide using, for example, an aqueous solution depositing method (LDP method). Specifically, this LDP method comprises a compound containing Si and a compound containing Ti in an aqueous medium,
After dissolving a compound capable of forming an oxide of a metal such as Zr that can be a photocatalyst inhibiting component, immerse the spectacle lens to be treated in this aqueous solution and deposit the compound containing the metal on the spectacle lens surface It is a method of forming by.

The aqueous medium used here is usually water, but an organic solvent such as alcohol may be mixed within a range that does not impair the characteristics of the aqueous medium. In addition, examples of the compound containing the above metal include hexafluorometal acid salt, and it is particularly preferable to use ammonium salt of hexafluorometal. Specifically, ammonium hexafluorosilicate _{((NH 4) 2 SiF 6} : 6 silicon fluoride ammonium), ammonium hexafluorotitanate _{((NH 4) 2 TiF 6} : 6 titanium fluoride ammonium) and hexafluoro Ammonium zirconate ((NH ₄ ) ₂ ZrF ₆ : zirconium ammonium fluoride)
Can be mentioned. These can be used alone or in combination. When an alkali metal is used as the photocatalyst suppressing component, the hexafluorometal acid salt is dissolved in a solvent such as lithium chloride, potassium chloride, sodium chloride, etc. By depositing titanium and silicon oxide, an alkali metal can be contained in the inorganic hydrophilic hard layer. In the present invention, it is preferable to use the ammonium salt of hexafluorometal as described above, but ammonium hexafluorostannate ((NH ₄ ) ₂ SnF ₆ ) is added to the ammonium salt of hexafluorometal. Ammonium hexafluoroferrate ((NH ₄ ) ₂ FeF ₆ ), ammonium hexafluorozincate ((NH ₄ ) ₂ ZnF ₆ ), ammonium hexafluorostrontate ((NH ₄ ) ₂ SrF ₆ ), hexafluorotungstic acid Ammonium ((NH ₄ ) ₂ WF ₆ ) and other hexafluorometal acid salts such as ammonium hexafluorobismuthate ((NH ₄ ) ₂ BiF ₆ ) may be contained. These can be used alone or in combination.

The above-exemplified compounds are examples of ammonium salts, but may be alkali metal salts such as Li, K and Na, alkaline earth metal salts and the like. By using such an alkali metal salt, a small amount of alkali metal can be contained in the inorganic hydrophilic hard layer as a photocatalyst inhibitor. Particularly in the present invention, ammonium hexafluorosilicate ((NH ₄ ) ₂ SiF ₆ ), ammonium hexafluorozirconate ((NH ₄ ) ₂ ZrF ₆ ) and ammonium hexafluorotitanate ((NH ₄ ) ₂ TiF ₆ ) are used. Preference is given to using. When the silicon-containing compound and the titanium-containing compound are used in combination as described above, as described above, Si: Z in the inorganic hydrophilic hard layer (philic portion) is used.
The ratio of r: Ti to atomic% is usually 20: 1: 10 to 20
00: 10: 1, preferably 200: 1: 10-20
It is desirable to use the above compounds in an amount within the range of 0: 10: 1.

More specifically, as shown in FIGS. 2 and 3, the metal contained in the hexafluorometal salt is ammonium hexafluorosilicate, ammonium hexafluorozirconate, and ammonium hexafluorotitanate. In terms of atomic ratio, silicon atom and titanium atom are usually in the range of 99.9: 0.1 to 60:40, preferably 99: 1 to 80:20, and titanium atom and zirconium atom are usually 99. .9: 0.1-90: 1
0, preferably 99: 1 to 95: 5, particularly preferably 9
In the range of 9: 1 to 97: 3, silicon and zirconium are usually contained in a ratio of 99.9: 0.1 to 90:10, preferably 9.
It is desirable to use it in such an amount that it falls within the range of 9: 1 to 95: 5. FIG. 2 shows a preferable range of the amount of ammonium hexafluorometalate used when the above ammonium hexafluorometalate is used. Further, the preferable ratio of this silicon, zirconium and titanium is shown in FIG. The shaded area in FIGS. 2 and 3 is the preferred range. Although the above description has centered on zirconium as a photocatalyst inhibitor that moderately suppresses the photocatalytic action of titanium oxide, other metals such as hafnium and tin can also be used as equivalent photocatalyst inhibitors.

The photocatalytic action of titanium oxide is
It is suppressed by containing an oxide of zirconium as described above, in addition to this zirconium, lithium,
It can also be suppressed by containing an alkali metal such as potassium or sodium. When such an alkali metal is used, the content of the alkali metal in the inorganic hydrophilic hard layer is usually 10 ⁻³ to 10 ⁻⁴ % by weight.

Generally, when a fluorine scavenger such as boron oxide is added to an aqueous solution in which a hexafluorometallate compound is dissolved, boron is bound to fluorine in the hexafluorometallate compound to form stable boron fluoride. Since the ions are formed, the metal forming the hexafluorometal salt compound is deposited on the surface of the base material (lens) in an active state.

The method of forming a metal compound thin film on a substrate by such a method is generally called the LPD method as described above. By this method, a simple film such as a silica film, a titanium oxide film or a zirconia film has been conventionally formed (however, these may be a continuous film, and a precipitation compound that does not lead to a continuous film form) Sometimes). However, in order to apply these to the spectacle lens surface, there is a problem in the application to the spectacle lens such that the refractive index is too high and the hardness is too low if these simple films are directly used. The present inventor has studied the deposition of such a metal film (metal oxide film), and as a result, from an aqueous solution in which a plurality of fluorometal compounds are dissolved, by incorporating a fluorine scavenger into the aqueous solution, a plurality of metal compounds can be simultaneously treated. Composite metal oxide film suitable for the purpose of precipitating (However, these may be a uniform film-like, it may be a discontinuous composite metal oxide precipitate, these are collectively referred to in this specification. Then, it was found that an “inorganic hydrophilic hard layer (or hydrophilic portion)” can be prepared.

That is, for example, (NH ₄ ) ₂ SiF ₆ , (NH ₄ ) ₂ Zr
F ₆ and (NH ₄ ) ₂ TiF ₆ are each in an appropriate amount (for example, 2000: 1: 10 to 2).
(Mole ratio 000: 10: 1) and mixed with boron oxide as a fluorine scavenger. SiO ₂ , ZrO ₂ , and TiO ₂ components were simultaneously deposited to form a composite film (inorganic hydrophilic hard layer). can do. This composite film (inorganic hydrophilic hard layer) acts so that zirconium oxide suppresses the photocatalytic action of titanium oxide, and in this inorganic hydrophilic hard layer, the photocatalytic action due to titanium oxide is appropriately suppressed. . Therefore, the inorganic hydrophilic hard layer of the present invention was rich in hydrophilicity and had a proper scratch resistance when applied to a spectacle lens. It is considered that this scratch resistance is expressed due to the addition of a small amount of ZrO ₂ component to the SiO ₂ -TiO ₂ composite film. With respect to the inorganic hydrophilic hard layer thus obtained, in the scratch resistance test performed by using a sem skin, SiO ₂ -T
The scratch resistance of the iO ₂ composite film is about 5 to 10 times higher than that of the iO ₂ composite film, and the strength is particularly suitable as a lens for glasses.

Generally, in the ternary starting material, (NH
₄ ) The adhesion strength of the composite film (inorganic hydrophilic hard layer) formed by depositing a small amount of ₂ ZrF ₆ and (NH ₄ ) ₂ TiF ₆ to the substrate largely depends on the mixing ratio. That is, from the viewpoint that it can be used as a spectacle lens, a limitation is imposed on the mixing ratio of these starting materials. For example, (N
_{H 4) 2 SiF 6, (} NH 4) 2 ZrF 6, (NH 4) 2 TiF 6 = 1: 1: 1
It has been confirmed that when the silica component is lowered to around (molar ratio), the adhesive strength of the film is significantly lowered.

By thus stirring the treatment aqueous solution containing the boric acid compound, it is completely dissolved and a transparent solution is formed. After that, when the transparent solution is left to stand, the whole solution becomes cloudy. Therefore, at this stage, the spectacle lens to be treated is immersed in this cloudy solution for usually 3 to 50 hours, preferably 5 to 30 hours. As a result, a deposit is deposited on the surface of the spectacle lens.

The above is an example of a method for forming an inorganic hydrophilic hard layer by precipitating it from an aqueous solution, and the present invention is not limited to these. Next, the spectacle lens having the deposit on the surface is pulled out from the solution, washed with water and dried. Since such a spectacle lens does not necessarily have a uniform surface state of the precipitate, if necessary, an inorganic hydrophilic hard formed on the surface using a soft polishing tool or polishing cloth. Polish so that the layers are uniform. Then, at this time, the average thickness of the inorganic hydrophilic hard layer can be adjusted.

The above method is an example of forming the inorganic hydrophilic hard layer by the LDP method, but such an inorganic hydrophilic hard layer (or hydrophilic portion) can also be formed by the multi-component vacuum vapor deposition method. It is possible. In the LDP method, generally, the film thickness can be controlled by the composition of the processing solution, the temperature of the processing solution, and the processing time. However, the LDP method is based on a precipitation phenomenon based on a chemical reaction, so that the film thickness can be controlled. High-precision control cannot be said to be easy, and it is difficult to specify the film thickness and control the uniform film thickness over a wide area.

On the other hand, the vacuum vapor deposition technique has an advantage that these can be controlled relatively easily. On the other hand, in the vacuum vapor deposition technique, in order to form a composite film made of a simple oxide or a complex oxide of silicon, titanium and zirconia, the cost of the device, the maintenance of the device, etc. becomes large. However, this method is highly useful as a method for producing the above-mentioned oxide composite thin film, considering the control of the formed film.

In the present invention, at least one kind of film made of a simple oxide or a complex oxide of silicon, titanium and zirconia is thus formed on the surface of the spectacle lens substrate by using any one of the above techniques. Can be formed. FIG. 1 shows a spectacle lens (coated lens) used while forming an inorganic hydrophilic hard layer on the surface and cleaning by washing with water in this manner, and wiping without an inorganic hydrophilic hard layer as in the conventional case. The relationship with the number of scratches generated per unit area over time in a spectacle lens (uncoated lens) used while cleaning is shown.

As is apparent from the graph shown in FIG. 1, many scratches occur in a short period of time in the uncoated lens, whereas in the coated lens of the present invention, even if used for at least 24 months, the surface of the uncoated lens remains on the surface. He was unable to detect any visible damage. Although the spectacle lens of the present invention was worn during these tests, it was possible to maintain a clear spectacle lens surface to the extent that no discomfort was felt by repeating the same maintenance method during the test period.

Further, since the spectacle lens of the present invention has hydrophilicity and hydrophilicity on its surface, it can adsorb a surfactant and the surfactant is not easily photodecomposed. Furthermore, due to the hydrophilicity of this spectacle lens and the lyophilic property of containing a surfactant on the surface, the spectacle lens becomes cloudy even if it is exposed to rainwater or in a high humidity environment such as when taking a bath. It has the advantage of being difficult. Conventionally, in such an environment, a method of forming a coating film on a spectacle lens by an anti-fog spray has been adopted. On the other hand, since the surface of the spectacle lens of the present invention has excellent hydrophilicity and lyophilicity, it has a good contact angle with water and a surfactant which is extremely difficult to elute due to the lyophilicity. Can be stably held for a long period of time. Therefore, even in a high humidity environment, the spectacle lens is less likely to fog,
Moreover, this antifogging effect is maintained for a long period of time.

The surface hardness of the spectacle lens formed with the inorganic hydrophilic hard layer of the present invention is usually in the range of 5 to 9,
Preferably, it has a Mohs hardness in the range of 6 to 8, and has a scratch resistance equivalent to that of a conventional spectacle lens having a hard layer. The details of the compound forming the inorganic hydrophilic hard layer thus obtained are not necessarily clear, but by containing an oxide of zircodium in titanium oxide, the photocatalytic activity of titanium oxide is appropriately suppressed, and Even if a surfactant is present, this surfactant is not photodecomposed by titanium oxide, and titanium oxide with such moderately suppressed photocatalytic activity also has good hydrophilicity. It will be because.

[0051]

According to the spectacle lens of the present invention, the inorganic hydrophilic hard layer (philic component) made of an inorganic material containing titanium oxide on the surface and a photocatalyst suppressing component for suppressing the photocatalytic action of the titanium oxide. ) Is formed,
This inorganic hydrophilic hard layer has not only good hydrophilicity but also excellent hydrophilicity. The inorganic hydrophilic hard layer has excellent hydrophilicity because the photocatalytic action of titanium oxide is appropriately suppressed, and the surface-active agent is not photodegraded by titanium oxide. It can be stably present in the inorganic hydrophilic hard layer for a long period of time. Therefore, since the spectacle lens of the present invention is stably impregnated with the surfactant, the cleaning water does not become water droplets on the lens surface and spreads uniformly over the entire lens, so that the high-humidity environment is maintained. Even under the lens, the lens is not easily fogged, and dirt attached to the lens can be easily washed off with water. Furthermore, the spectacle lens of the present invention can be kept clean by washing with water, and since this spectacle lens can be removed by washing with water, stains on the surface of the spectacle lens can be removed with a cloth, for example. Since it is not necessary to remove it by a conventional method, even when used for a long period of time, a clear effect is recognized in that the occurrence of scratches can be prevented as compared with a conventional spectacle lens.

[0052]

The present invention will now be described in more detail with reference to examples of the present invention, but the present invention should not be construed as limited thereto.

[0053]

Example 1 Ammonium hexafluorosilicate (ammonium hexafluorosilicate: (NH ₄ ) ₂ SiF ₆ ): 15
g, ammonium hexafluorotitanate (titanium ammonium hexafluoride: (NH ₄ ) ₂ TiF ₆ ): 0.75 g,
And ammonium hexafluorozirconate (zirconium ammonium hexafluoride: (NH ₄ ) ₂ Zr
F ₆ ): 0.1 g was weighed and added to 400 ml of pure water heated to 30 to 45 ° C. and mixed with stirring.

Boron oxide 1 was added to the treatment liquid thus prepared.
0 g was added. The whole treatment liquid was vigorously stirred to completely dissolve boron oxide in the treatment liquid. After a while after the dissolution, the whole liquid began to turn cloudy, so a plastic lens substrate provided with a hard layer prepared in advance was immersed. Treat the solution with 40
Immersion was terminated when the temperature was maintained at 24 ° C. for 24 hours, and the plastic lens was pulled up. Then, the plastic lens was taken out, lightly washed with water, and then dried.

The surface of the treated lens prepared as described above was polished with a polisher made of leather while using a small amount of neutral detergent to make the lens surface smooth. The inorganic hydrophilic hard layer thus formed has an average thickness of about 100.
0Å, and Si, Ti, Zr, and F atoms may be present in the inorganic hydrophilic hard layer thus formed (X-ray fluorescence analyzer (XRD), manufactured by JEOL Ltd.) Could be confirmed by. Further, the Si: Zr: Ti atomic ratio in the mixed reagent was 200: 1: 10, the Ti: Zr atomic% ratio in the deposited layer was 32: 2, and the Si: (Zr + Ti) atomic% ratio was Is 6
It was 3:37.

The photocatalytic activity of titanium oxide in the inorganic hydrophilic hard layer thus obtained was remarkably reduced. When this surface-treated lens is attached to spectacles and it becomes dirty while being used, cleaning is performed by rinsing with water,
It was carried out continuously for a year. After such use, the surface condition was compared with that of a normal lens which was also not used at all (see FIG. 1).

As a result, it was found that the lens that had been cleaned by washing with water was not significantly scratched. The spectacle lens in which this surfactant was interposed was placed in a high temperature and humidity container in which the temperature difference between the spectacle lens and the spectacle lens was set to 20 ° C. and the humidity difference to 70%, but the spectacle lens did not fog.

[0058]

Example 2 In Example 1, ammonium hexafluorosilicate (ammonium hexafluorosilicate: (N
H ₄ ) ₂ SiF ₆ ): 20 g, ammonium hexafluorozirconate (zirconium ammonium hexafluoride:
((NH ₄ ) ₂ ZrF ₆ )): 0.05 g and ammonium hexafluorotitanate (titanium ammonium hexafluoride:
(NH ₄ ) ₂ TiF ₆ ): 0.1 g was weighed, and this was mixed and dissolved in pure water at 35 to 40 ° C. to prepare 600 ml of the treatment liquid, and an inorganic hydrophilic hard layer was formed in the same manner.

That is, the processing liquid 400 m prepared in this way
10 g of boron oxide was added to 1 and strongly stirred similarly to dissolve. After a while after the dissolution, the whole liquid became transparent, so a plastic lens substrate having a pre-prepared surface coated with an antireflection multi-coat film coated with a silica film was immersed.

Approximately 2 with the treatment liquid kept at 30 to 40.degree.
Immersion was completed after continuing for 4 hours. Then, the plastic substrate was taken out, washed and dried. While smoothing the surface of the inorganic hydrophilic hard layer formed on the lens surface while polishing the surface of the treated lens prepared as described above with a neutral detergent using a leather polisher, a lens base material is obtained. The surface treatment was completed.

The average thickness of the inorganic hydrophilic hard layer thus formed was measured and found to be about 1000Å. Also, confirm that the atoms of Si, Ti, Zr, and F are present in the inorganic hydrophilic hard layer thus formed (X-ray fluorescence analyzer (XRD), manufactured by JEOL Ltd.). I was able to. The Si: Zr: Ti atomic% ratio in this layer is 2000: 4: 8, the Ti: Zr atomic% ratio in the deposited layer is 15: 1, and the Si: (Zr + Ti) atomic ratio is The% ratio was 84:16.

The photocatalytic activity of titanium oxide in the inorganic hydrophilic hard layer thus obtained was remarkably reduced. The lens surface thus treated was periodically washed with water to clean the lens surface which had been soiled by actual use. As a result, water dried without forming water drops on the lens surface (in a wet state on the surface), so that cleaning could be performed without leaving traces of water drops on the surface.

Further, the change in reflectance due to the hydrophilic portion coated on the surface of the antireflection film could be greatly suppressed by setting the film thickness to the minimum. The temperature difference between the spectacle lens and the spectacle lens interposing the surfactant is 20
Although it was placed in a high temperature and high humidity container in which the temperature difference and humidity difference were set to 70%, the spectacle lens did not fog.

[Brief description of drawings]

FIG. 1 is a spectacle lens (coated lens) of the present invention used while forming a hydrophilic part on the surface and cleaning by washing with water, and a spectacle lens of the present invention which is used without washing with a hydrophilic part as before. 7 is a graph showing the relationship with the number of scratches generated per unit area over time in the spectacle lens (uncoated lens) used.

FIG. 2 is a composition diagram showing an example of a suitable usage amount of a hexafluorometal salt used in producing the lens of the present invention.

FIG. 3 is a composition diagram showing an example of a composition of a metal compound in a hydrophilic part formed in the lens of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2K009 AA15 BB11 CC03 CC47 DD02                       DD03 DD06 DD12 DD16 EE02                 4F100 AA20B AA21B AA27B AA33B                       AG00A AH02B AH02H AH03B                       AH03H AH04B AH04H AK01A                       AR00B AT00A BA02 CA18B                       EH66B GB90 JA20B JB05B                       JK12B JK14 JL07 JL08B                       YY00B                 4G059 AA01 AC21 EA01 EA04 EA05                       EB03 EB05

Claims (11)

[Claims] 1. A photocatalyst having a base lens and an inorganic hydrophilic hard layer formed on the surface of the base lens, wherein the inorganic hydrophilic hard layer contains titanium oxide and the titanium oxide has the photocatalyst. An eyeglass lens comprising a photocatalyst inhibiting component for action. 2. The spectacle lens according to claim 1, wherein the inorganic hydrophilic hard layer contains a simple oxide or a complex oxide of silicon, zirconium and titanium. 3. The atomic ratio of zirconium atoms to titanium atoms in the inorganic hydrophilic hard layer is 99.9: 0.
It is in the range of 1 to 70:30, and the atomic ratio of titanium atom and zirconium atom to silicon atom is 99.9:
The spectacle lens according to claim 2, wherein the spectacle lens is in the range of 0.1 to 40:60. 4. The inorganic hydrophilic hard layer has a thickness of 10 ⁻³ to.
The first range of the present invention is in the range of 0.5 μm.
A spectacle lens according to item 2 or item 3. 5. The spectacle lens according to claim 1, wherein the inorganic hydrophilic hard layer is a layer formed by an LDP method or a vacuum deposition method. 6. The spectacle lens according to claim 1, wherein the inorganic hydrophilic hard layer containing titanium oxide is impregnated with a surfactant. 7. The surfactant is alkyl ether sulfate ester salt, polyoxyethylene alkyl ether,
Fatty acid alkanolamide, fatty acid methylglucamide,
The spectacle lens according to claim 6, further comprising at least one kind of surfactant selected from the group consisting of α-olefin sulfonate, alkylamine oxide and linear alkylbenzene sulfonate. 8. The spectacle lens according to claim 6, wherein the surfactant is contained in the inorganic hydrophilic hard layer in an amount of 50% by weight or less. 9. The contact angle of the inorganic hydrophilic hard layer with water is in the range of 0 to 50 degrees.
The spectacle lens according to the item. 10. The spectacle lens according to claim 1, wherein the component forming the inorganic hydrophilic hard layer does not easily elute even when contacted with water. 11. The spectacle lens according to claim 1, wherein the Mohs hardness of the inorganic hydrophilic hard layer is in the range of 5 to 9.