JP2002122820A - Ophthalmic lens having hard coating layer and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ophthalmic lens having antireflection films improved in scratching resistance without degrading their adhesion property and heat resistance. SOLUTION: The antireflection films consisting of the laminated films of, successively from a hard coating layer side, a SiO2 layer as ground surface layer, an intermediate-refractive index layer consisting, of equivalent films of an SiO2 layer, ZrO2 layer a high-refractive index layer consisting of a ZrO2 layer, and a low-refractive index layer consisting of an SiO2 layer, are increased in the film thickness of the SiO2 layer of the ground layer from 0.25λ to 0.5λ and are set in the physical film thicknesses ratio of the SiO2 layer and the ZrO2 layer so as to satisfy the relation 2.0:1<=SiO2 layer:ZrO2 layer<=3.0:1, thereby, the improvement in the scratching resistance and the maintenance of the adhesion property and the heat resistance are realized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectacle lens having an antireflection film.

[0002]

2. Description of the Related Art Since a lens having a higher refractive index has a higher light reflectivity on the surface, an antireflection film formed by laminating thin films having different refractive indices and utilizing the interference effect of light has the same effect as a spectacle lens. It is very effective for optical parts intended for transmission, and is widely used for lenses of cameras.

[0003] A material often used for an antireflection film is a metal oxide. As a method of forming the antireflection film, there are many dry processes such as a vacuum evaporation method and a sputtering method. In particular, antireflection films having a wide band are often used by alternately stacking low refractive index layers and high refractive index layers while adjusting the film thickness. On the other hand, in spectacle lenses that often use a synthetic resin, the antireflection film composed of a metal oxide also plays an important role in increasing the strength of the lens together with the hard coat layer. Above all, it is known that the underlayer formed on the surface of the hard coat layer affects the properties of the antireflection film and also has a great influence on the hardness of the antireflection film. However, the adhesion of the film is affected by the thickness of each material layer constituting the anti-reflection film, the thickness ratio of the SiO ₂ layer and the ZrO ₂ layer and the balance of stress in the present invention. It is not easy to increase the strength by changing the film thickness ratio.

[0004]

Recently, there has been an increasing demand for lenses having high scratch resistance, especially for spectacle lenses. One of the methods for improving the scratch resistance of a lens is to increase the hardness of the antireflection film on the outermost surface of the lens. In an antireflection film mainly using a metal oxide, the underlayer has the greatest effect on hardness and has little effect on antireflection characteristics. However, by increasing the thickness of the underlayer, the hardness of the antireflection film can be increased. On the other hand, the change in the film configuration causes the stress balance between the materials of each layer to be lost, causing a decrease in adhesion and the like. In many cases, sufficient durability cannot be obtained. An object of the present invention is to provide a spectacle lens with an antireflection film having sufficient hardness and abrasion resistance in consideration of the balance of stress in the antireflection film and also having durability. .

[0005]

Means for Solving the Problems The present invention has been made to achieve the above object, and the invention described in claim 1 is to provide a SiO ₂ layer as an underlayer in order from the surface of the hard coat layer. A medium refractive index layer composed of an equivalent film composed of a ZrO ₂ layer and a SiO ₂ layer, a high refractive index layer composed of a ZrO ₂ layer, and an antireflection film composed of a low refractive index layer composed of a SiO ₂ layer. In a spectacle lens, the thickness of the underlayer is 0.25λ to 0.5λ in terms of optical distance when the design wavelength is 500 nm to 550 nm.

According to a second aspect of the present invention, in the first aspect of the present invention, before laminating the antireflection film on the hard coat layer, the surface is cleaned by an oxygen ion beam using oxygen plasma. The feature is that the adhesion of the film is further enhanced.

According to the third aspect of the invention, it is possible to satisfy both hardness and adhesion by limiting the total physical thickness ratio of the SiO ₂ layer and the ZrO ₂ layer.

According to a fourth aspect of the present invention, there is provided a hard coat layer coated and cured on a synthetic resin substrate,
The present invention relates to a hard coat composition most useful for realizing the present invention.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The conditions satisfying the object of the present invention are as follows. First, the thickness of the underlayer can be increased to improve the hardness of the antireflection film. And the third is that the reflectance and interference color of the anti-reflection characteristics can be the same as those of the current configuration. .

[0010] Among them, the stress balance in the film occupies an important point. Looking at the physical film thickness ratio between the SiO ₂ layer and the ZrO ₂ layer, 2.0: 1 ≦ SiO ₂ layer: Zr
If the O ₂ layer ≦ 3.0: 1, the hardness, durability and reflection characteristics of the antireflection film were good, but 3.5: 1 ≦ SiO
_Two layers: The hardness of the antireflection film was improved when the ZrO ₂ layer was used, but a problem occurred in durability.

From these results, there is no limit to increasing the thickness of the underlayer.
2.0: 1 ≦ SiO _TwoLayer: ZrO_TwoLayer ≤
An effective film configuration was examined within the range of 3.0: 1.

On the other hand, there is a possibility that the adhesion may be reduced by increasing the thickness of the underlayer. Therefore, it is possible to further increase the adhesion between the hard coat layer and the antireflection film at the stage of surface treatment before vapor deposition. I thought it would be effective to introduce Therefore, it was studied to perform a surface treatment method of irradiating an oxygen ion beam using oxygen plasma before vapor deposition.

The component (A) used in the present invention has a particle diameter of 1 to 100 millimicrons of Si, Al, Sn, Sb, and T.
a, Ce, La, Fe, Zn, W, Zr, In, Ti, fine particles comprising at least one metal oxide selected from Ti, and / or Si, Al, Sn, Sb, Ta, Ce, La,
Specific examples of the composite fine particles composed of two or more metal oxides selected from Fe, Zn, W, Zr, In, and Ti include SiO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , T
a ₂ O ₅ , CeO ₂ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, W
It is obtained by dispersing inorganic oxide fine particles of O ₃ , ZrO ₂ , In ₂ O ₃ , and TiO _{2 in} a colloidal form in a dispersion medium such as water, an alcohol or other organic solvent. Or
Composite fine particles composed of two or more of these inorganic oxides are colloidally dispersed in water, alcohol, or another organic solvent. Further, it is also possible to use those obtained by treating the surface of these fine particles with an organosilicon compound or an amine compound in order to enhance the dispersion stability in the coating liquid. As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like.
In the treatment, the hydrolyzable group may be untreated or hydrolyzed. Further, after the treatment, a state in which the hydrolyzable group has reacted with the -OH group of the fine particles is preferable,
There is no problem in stability even when a part remains. Examples of the amine compound include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine. There is. It is necessary to add the organosilicon compound and the amine compound within the range of about 1 to 15% based on the weight of the fine particles. In all cases, the particle size is about 1 to 3
00 mμ is preferred.

The component (B) is a silane compound having a polymerizable reactive group such as a vinyl group, an allyl group, an acryl group, a methacryl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, and an amino group. Specific examples thereof include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, and methacryloxypropyl. Dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane N-beta is (aminoethyl)-.gamma.-aminopropyl methyl dialkoxysilane, and the like.

The component (B) may be used as a mixture of two or more kinds. In addition, it is more effective to use either method after hydrolysis or use of an acid treatment on the cured film.

Hereinafter, embodiments of the present invention will be shown and described in detail. The physical properties of the spectacle lens having the antireflection film formed in the examples were evaluated by the following test methods. (A) Scratch resistance test The surface was coated with a steel wool of # 0000 and a load of 1.00 ±
The abrasion resistance was evaluated by the method of scratching when the sample was reciprocated 10 times with an amplitude of 30 mm at 0.05 kg. (B) Adhesion test According to the JIS K5400 crosscut method and crosscut tape method, a 10 x 10 crosscut is made with a cutter knife, and the number of crosscuts remaining in the peeling test with a cellophane adhesive tape is counted to determine the adhesion. evaluated. (C) Heat resistance test After forming the antireflection film, the film was heated in an oven for 30 minutes, and then the presence or absence of cracks was evaluated. The heating temperature was increased by 5 ° C. starting from 40 ° C.

Example-1 (1) Preparation of Hard Coat Solution 1360 g of propylene glycol monomethyl ether,
Methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (trade name "Optreak 1120Z (S-7A8), solid content concentration 20% by weight", manufactured by Catalyst Chemical Industry Co., Ltd.) 6450 g and γ-glycidoxy 1700 g of propyltrimethoxysilane was mixed in. 500 g of a 0.05N hydrochloric acid aqueous solution was added dropwise to this mixed solution with stirring, and the mixture was stirred for 4 hours, aged for 24 hours, and then Fe (II).
I) 10 g of acetylacetonate, silicone surfactant (trade name "L-7001" manufactured by Nippon Unicar Co., Ltd.)
After adding 3 g and stirring for 4 hours, the mixture was aged for 24 hours to obtain a coating solution. (2) Coating and curing The coating liquid thus obtained is subjected to alkali treatment with a refractive index of 1.67 spectacle lens (Seiko Epson Corporation)
Co., Ltd., Seiko Super Sovereign Lens Fabric). The lifting speed was 20 cm / min. After air-drying at 80 ° C for 20 minutes after application,
Baking was performed for 20 minutes. (3) Formation of anti-reflection film On the surface of the hard coat layer obtained in (2), an underlayer (refractive index: 1.46) composed of an SiO ₂ layer having an optical thickness of 0.43λ (λ = 500 nm) ) Formed. Next, a 0.10λ-thick ZrO ₂ layer (refractive index: 1.99) and a 0.
A middle refractive index layer (refractive index: 1.80) composed of a 06λ SiO ₂ layer (refractive index: 1.46) was formed. Subsequently, a high refractive index layer made of a ZrO ₂ layer (refractive index: 1.99) having a thickness of 0.23λ was formed. Finally, a 0.24λ thick SiO
_An antireflection film was constructed by forming a low-refractive-index layer consisting of _two layers (refractive index: 1.46). From the base layer to the low-refractive-index layer, they were formed by a vacuum deposition method (degree of vacuum: 2.0 × 10 ⁻⁵ Torr). FIG. 1 shows the result of computer simulation of the reflection characteristics of the antireflection film having this configuration. Physical film thickness ratio of the SiO ₂ layer and the ZrO ₂ layer at this time is the SiO ₂ layer: ZrO ₂ layer = 3.0: 1. Table 1 shows the evaluation results of the spectacle lens having the obtained antireflection film.

Example-2 (1) Preparation of Hard Coat Solution 1700 g of 2-butoxyethanol, sol of titanium dioxide-tin dioxide composite fine particles dispersed in methanol (trade name "Optreak 1120Z (8Ru.
A8) ", solid content concentration 20% by weight) 5900 g and γ
-Glycidoxypropyltrimethoxysilane 1830 g
Was mixed. The mixture was added to a 0.05N hydrochloric acid aqueous solution 550.
g, stirred for 4 hours, aged all day and night, then 10 g of Al (III) acetylacetonate, silicon surfactant (trade name “L” manufactured by Nippon Unicar Co., Ltd.)
−7001 ”), and the mixture was stirred for 4 hours and then aged for 24 hours to obtain a coating solution. (2) Coating and curing The coating liquid thus obtained is subjected to alkali treatment with a refractive index of 1.67 spectacle lens (Seiko Epson Corporation)
Co., Ltd., Seiko Super Sovereign Lens Fabric). The lifting speed was 20 cm / min. After air-drying at 80 ° C for 20 minutes after application,
Baking was performed for 20 minutes. (3) Formation of anti-reflection film The optical film thickness is 0.25λ (λ = 5) on the surface of the hard coat layer.
An underlayer (refractive index: 1.46) composed of a 20 nm) SiO ₂ layer was formed. Next, a ZrO ₂ film having a thickness of 0.11λ is formed.
A medium refractive index layer (refractive index: 1.74) composed of an equivalent film made of a layer and an SiO ₂ layer having a thickness of 0.08λ was formed. Subsequently, a high refractive index layer (refractive index: 1.99) composed of a ZrO ₂ layer having a thickness of 0.29λ was formed. Finally, S with a film thickness of 0.26λ
An antireflection film was constructed by forming a low refractive index layer composed of an iO ₂ layer. Example 1 from the underlayer to the low refractive index layer
It was formed by a vacuum deposition method in the same manner as described above. FIG. 2 shows the result of a computer simulating the reflection characteristics of the antireflection film having this configuration. At this time, the physical film thickness ratio between the SiO ₂ layer and the ZrO ₂ layer is as follows: SiO ₂ layer: ZrO ₂ layer =
2.0: 1. Table 1 shows the evaluation results of the spectacle lens having the obtained antireflection film.

COMPARATIVE EXAMPLE 1 Comparative Example 1 will be described as a comparison of the above embodiment. The thickness of the underlayer is set to 0.08λ (λ = 520n) which is out of the range of the present invention.
m). Subsequent to the underlayer, a 0.13λ-thick ZrO
₂ layer and the intermediate refractive index layer made of SiO ₂ layer having a thickness of 0.06λ (refractive index 1.80) was formed, then the film thickness 0.26Ramuda Z
An antireflection film is formed by forming a high refractive index layer (refractive index 1.99) composed of an rO ₂ layer and finally a low refractive index layer composed of a SiO ₂ layer (refractive index 1.46) having a thickness of 0.255λ. I got a spectacle lens. At this time, the physical thickness ratio between the SiO ₂ layer and the ZrO ₂ layer was SiO ₂ layer: ZrO ₂ layer = 1.4: 1. Table 1 shows the evaluation results of the spectacle lens having the obtained antireflection film.
Shown in

Comparative Example 2 A comparative example 2 will be described as a comparison of the above examples. In this example, the focus was on the comparison of the film stress balance, and the antireflection characteristics were not particularly considered. The thickness of the underlayer was set to 0.65λ (λ = 520 nm), which is outside the range of the present invention. Subsequent to the underlayer, a ZrO ₂ layer having a thickness of 0.13λ and a thickness of 0.06λ
Of a medium refractive index layer (refractive index: 1.80) made of a SiO ₂ layer, and then a ZrO ₂ layer having a thickness of 0.28λ (refractive index: 1.80).
99) to form a high refractive index layer,
A low refractive index layer composed of a 7λ SiO ₂ layer was formed to obtain a spectacle lens having an antireflection film. At this time, the physical film thickness ratio between the SiO ₂ layer and the ZrO ₂ layer is as follows: SiO ₂ layer: ZrO ₂ layer =
3.5: 1. Table 1 shows the evaluation results.

[0021]

[Table 1]

[0022]

According to the spectacle lens having the antireflection film of the present invention, scratch resistance can be improved without impairing other characteristics.

[Brief description of the drawings]

FIG. 1 is a simulation result of antireflection characteristics according to Example 1 of the present invention.

FIG. 2 is a simulation result of antireflection characteristics according to a second embodiment of the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyuki Seki 3-3-5 Yamato, Suwa-shi, Nagano F-term in Seiko Epson Corporation (reference) 2H006 BA03 BA04 2K009 AA06 AA15 CC03 CC09 CC42 DD02 DD03 DD17 EE00 4J038 DL031 DL051 DL081 DL091 DL111 GA01 GA02 GA07 GA09 GA13 HA216 HA446 KA08 KA12 KA20 NA11 NA17 PB08 PC08

Claims (4)

[Claims] 1. A medium refractive index comprising a hard coat layer on a synthetic resin substrate, an SiO ₂ layer as an underlayer, and an equivalent film composed of a ZrO ₂ layer and an SiO ₂ layer in order from the surface of the underlayer. A spectacle lens having an antireflection film formed by laminating a high refractive index layer composed of a ZrO ₂ layer and a low refractive index layer composed of a SiO ₂ layer, the thickness of the underlayer is 0.1 mm in optical distance.
A spectacle lens characterized by having a wavelength of 25λ to 0.5λ (λ = 520 nm). 2. The method according to claim 1, wherein the surface treatment is performed by irradiating a beam of oxygen ions generated from oxygen plasma as a surface treatment of the hard coat layer before depositing the underlayer. The spectacle lens described. 3. The physical constitution of the underlayer, the medium refractive index layer, the high refractive index layer and the low refractive index layer, wherein the physical thickness ratio of the SiO ₂ layer and the ZrO ₂ layer is 2.0: 1 ≦ SiO ₂ layer. : ZrO ₂ layer ≦
3. The method according to claim 1, wherein the ratio is 3.0: 1.
The spectacle lens described. 4. The spectacle lens according to claim 2, wherein the hard coat layer contains at least the following components (A) and (B) as main components. (A). Particle size 1-100
Millimicron Si, Al, Sn, Sb, Ta, Ce,
Fine particles comprising at least one metal oxide selected from La, Fe, Zn, W, Zr, In, Ti and / or S
i, Al, Sn, Sb, Ta, Ce, La, Fe, Z
Composite fine particles (B) composed of two or more metal oxides selected from n, W, Zr, In, and Ti. Silane compounds having at least one or more polymerizable reactive groups