JPS62100701A - Production of plastic optical parts having antireflection film - Google Patents

Abstract

PURPOSE:To improve the resistance to scuffing by irradiating an ion beam in the stage of forming at least either of a surface hardened layer and antireflection by vacuum deposition. CONSTITUTION:The ion beam is irradiated in the state of forming at least either of the surface hardened layer and antireflection layer by vacuum deposition in the stage of forming the antireflection layer consisting of the surface hardened layer 2 and the antireflection layer 3 by a vacuum deposition method on the plastic optical parts 1. The ion beam is irradiated only in the vapor deposition stage of the surface hardened layer, only in the vapor deposition stage of the antireflection layer and the vapor deposition stage of both the surface hardened layer and the antireflection layer. The ion beam may be irradiated in the vapor deposition stage of the respective layers or the vapor deposition stage of an optional layer if the surface hardened layer and antireflection layer consist respectively of the multiple layers. The perspiration resistance, resistance to scuffing and weatherability is thereby improved.

Description

[Detailed Description of the Invention] - No. 1! ilv The present invention is a plastic that has an antireflection coating on a plastic optical component that has excellent adhesion, sweat resistance, scratch resistance, weather resistance, and is durable.

The present invention relates to a method for manufacturing optical components manufactured by

In the past, optical parts such as camera lenses, eyeglass lenses, and displays were often made of glass, but plastic materials have the advantages of being lightweight, impact resistant, and easy to process. For this reason, it has come to be used in place of glass. Particularly recently, the market for plastic eyeglass lenses has been growing rapidly due to their lightness, safety, and fashionability.

However, plastic spectacle lenses have a problem in that they are inferior in scratch resistance compared to glass spectacle lenses.

In order to improve the scratch resistance of plastic eyeglass lenses, various methods have been proposed for modifying the surface of plastic eyeglass lenses. For example, as shown in FIG. 1, a plastic eyeglass lens base 1 is coated with a surface hardening layer 2 made of silicon dioxide or the like by vacuum evaporation, and then a surface reflection layer 2 is coated on the surface hardening layer 2 by vacuum evaporation. Anti-reflective layer 3 made of silicon dioxide, zircon dioxide, etc. that reduces
A method of coating is known. The surface hardening layer 2 is made of a substance containing silicon dioxide as a main component, and has an optical thickness of 1 to 10%.
(In.: design wavelength in the visible light range, the same applies hereafter). As shown in FIG. 2, the antireflection film 3 has an optical thickness in the order of medium refractive index layer 3-1, high refractive index layer 3-2, and low refractive index layer 3-3. /4-person /2-1 entry. /4 three-layer structure is widely used. In the medium refractive index layer of 3-1,
Silicon oxide, aluminum oxide, etc. are used for the high refractive index layer 3-2, zirconium oxide, titanium oxide, etc. are used for the low refractive index layer 3-3, and silicon dioxide, etc. are used for the low refractive index layer 3-3. In addition, recently, silicon oxide and aluminum oxide used for the medium refractive index layer are difficult to evaporate, so as shown in FIG.
A four-layer antireflection layer is provided, which is composed of two layers: 3-1-1 and a silicon dioxide layer (low refractive index layer) 3-1-2, and has a refractive index equivalent to that of the medium refractive index layer 3-1. A method is proposed.

Furthermore, as shown in FIG. 4, before applying the surface hardening layer 2, an organic hard coat layer 4 such as a silicone resin is coated on the plastic eyeglass lens base 1 by a dipping method, a spinner method, etc. Methods for further improving scratch resistance are also commonly used.

However, although plastic eyeglass lenses having an antireflection coating composed of a surface hardening layer and an antireflection layer obtained by these methods can improve scratch resistance to a certain extent, they are not as good as conventional glasses with an antireflection coating. It has the disadvantage of being inferior in scratch resistance compared to spectacle lenses.

The present invention solves the drawbacks of the prior art and includes a plastic optical component that is composed of a hardened surface layer and an antireflection layer that have excellent scratch resistance and durability. An object of the present invention is to provide a method for manufacturing a plastic optical component having an antireflection coating.

According to the present invention, there is provided a method for manufacturing a plastic optical component having an antireflection coating that satisfies the above objects.

That is, when forming an antireflection coating composed of a surface hardening layer and an antireflection layer on a plastic optical component by a vacuum evaporation method, the present invention provides that at least one layer of the surface hardening layer and the antireflection layer is formed on a plastic optical component by a vacuum evaporation method. The present invention relates to a method for manufacturing a plastic optical component having an antireflection coating, which is characterized by irradiating with an ion beam during vacuum deposition.

Furthermore, in forming an antireflection coating composed of a surface hardening layer and an antireflection layer on a plastic optical component by a vacuum evaporation method, the present invention irradiates the optical component with an ion beam in advance, and then The present invention relates to a method for manufacturing a plastic optical component having an antireflection coating, which comprises irradiating with an ion beam during vacuum deposition of at least one of a surface hardening layer and an antireflection layer.

Materials for the plastic optical parts used in the present invention include, for example, polymethyl methacrylate, polystyrene, polycarbonate, diethylene glycol bisallyl carbonate (C:R-39), 1
A composition comprising as at least two essential components a compound having at least two unsaturated cycloacetal groups per molecule and a compound having at least two mercapto groups per molecule, at least two unsaturated cycloacetals per molecule. Examples include reaction products of a compound having a group and an unsaturated alcohol having a hydroxyl group and an acryloyl group or a methacryloyl group in one molecule.

To manufacture plastic optical parts, for example, casting method, molding method (injection method)
Alternatively, a press molding method or the like is used, and the material is molded into an arbitrary shape by these methods.

On such plastic optical components, it is common to provide a hard coat layer of organic material such as silicone resin by dipping or spraying to improve scratch resistance. The scratch resistance can also be improved by providing a single-layer or multi-layer surface hardening layer on the hard coat layer 1 by vacuum evaporation. As the surface hardening layer, a single layer film of silicon dioxide is widely used.

In the present invention, the term plastic optical components includes both plastic optical components without a Bartco-1 layer and plastic optical components with a hard coat layer.

The thickness of the surface hardening layer is 1 to 10λ. (0.5~5 lm)
That's about it.

In the present invention, the effect of the present invention can be fully exhibited even if the surface hardened layer is directly formed on the plastic optical component by vacuum evaporation method. If the surface of the plastic optical component is treated with an ion beam beforehand, the surface of the plastic optical component will be sputtered and cleaned, further improving the adhesion between the plastic optical component and the hardened surface layer. do.

The conditions for treating the surface of a plastic optical component with an ion beam cannot be determined unconditionally as they vary depending on the acceleration voltage and acceleration current of the ion beam used, but generally the acceleration voltage is 200 to 500V and the acceleration current is 20 to 20V. 50m
A. It is preferable that the irradiation time is within the range of 1 to 5 minutes. For example, when the accelerating voltage of the ion beam is 300 V and the accelerating current is 30 mA, approximately 1 minute of irradiation time is sufficient.

The plastic optical component having the surface-hardened layer thus obtained is further provided with a single-layer or multi-layer antireflection layer by a vacuum layer deposition method. This can prevent reflections at the interface with the atmosphere. Materials for vapor deposition include silicon oxide, silicon dioxide, aluminum dioxide, zirconium dioxide, titanium dioxide, yttrium oxide, tantalum oxide, hafnium oxide, ytterbium oxide,
Examples include cerium liquefaction and magnesium fluoride.

When forming an antireflection coating composed of a surface hardening layer and an antireflection layer on a plastic optical component by vacuum evaporation, it is necessary to apply a vacuum to at least one of the surface hardening layer and the antireflection layer. Ion beam is irradiated during vapor deposition. When an ion beam is irradiated during vapor deposition, the vapor deposited particles and the ion beam become one and reach the surface of the plastic optical component, heating the surface and giving energy to the vapor deposition particles, causing migration on the surface of the plastic optical component. It is considered that the effects of the present invention are enhanced and the effects of the present invention are realized.

The ion beam is irradiated only when depositing the surface hardening layer, only when depositing the antireflection layer, or when depositing both the surface hardening layer and the antireflection layer. When the surface hardening layer and the antireflection layer each consist of multiple layers, the ion beam may be irradiated during the deposition of each layer, or the ion beam may be irradiated during the deposition of any layer. In addition, the ion beam may be irradiated until the deposition material forms one layer, or it may be irradiated until a certain optical film thickness is reached, and then evaporated without ion beam irradiation to form one layer. It may be formed. In order to maximize the effects of the present invention, it is preferable to irradiate with an ion beam at least when forming the uppermost layer of the antireflection film.

Ion beam irradiation conditions vary depending on the accelerating voltage and accelerating current of the ion beam used, so they cannot be determined unconditionally, but usually the accelerating voltage is 500 to 800 V and the accelerating current is 50 to 80 trrA to achieve the desired film thickness. It is irradiated until

The basic principle of the ion gun is that ionized substances (e.g. Ar,
02, N2 gas, etc.) is introduced into an ion generation chamber, ionized, and only the ions are extracted as an ion beam. Various ion guns are manufactured depending on the ionization generation method. In the present invention, the type of ion gun is not particularly limited.

As shown in FIG. 5, the ion gun (10) is installed facing a dome 7 (a lens dome in the case of eyeglass lenses) in which a brass optical component 6 is arranged in a vacuum base chamber 5. The operation of the ion gun 10 can be freely controlled from outside the chamber 5, and the ion beam can be irradiated at any time and with any output. The dome 7 rotates and the ion beam uniformly irradiates the plastic optical component 6.

The ion beam is Ar,0 which is ionized and maintains its power.
2, N2, etc., and when irradiated onto a plastic surface, the plastic surface is spattered as described above, making it possible to clean the surface. Also,
When ion beams are irradiated simultaneously during vapor deposition, the vapor deposited particles and the ion beam reach the surface as a harmonious body, which heats the surface and gives energy to the vapor deposited particles, increasing the migration effect on the surface.

As a result, the antireflection coating formed becomes dense and hard, and has improved scratch resistance. Optically, it has a higher refractive index than an antireflection coating produced by simple vacuum deposition.

Conventionally, plasma surface cleaning activated vapor deposition methods and ion blating methods using a plasma atmosphere have been widely practiced for similar purposes, but ion beam irradiation is superior in the following points.

■To create a plasma atmosphere, use L O-4 Torr.
The ion beam requires a gas pressure of 10
It can be used in high vacuums below Torr, and there is little entrainment of gas molecules into the coating.

■Since the plasma atmosphere spreads throughout the chamber, it is easy for impurities sputtered from the walls to be incorporated into the film, but since the ion beam is directional and can only irradiate the target object, there is no risk of this happening.

■Ion beams have greater power (energy) than plasma, and can be easily controlled in a variable and stable manner.

■From the above three points, the performance of the coating by ion beam irradiation is
The reproducibility is better than the plasma atmosphere method.

In the present invention, an ion gun having the above-mentioned excellent functions was installed in a vacuum evaporation apparatus, and was applied to the production of surface hardening layers and antireflection layers of plastic optical components.

As a result, it has become possible to create an antireflection coating composed of a surface hardening layer and an antireflection layer that has excellent scratch resistance and N4 outstanding durability.

Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

In addition, the characteristics of the eyeglass lenses obtained in each piece were measured according to the following method. The results are shown in Table 1.

1) Adhesion crosshatch test 2) #Na1l lOg, NH4Cl34g in 1u of sweat water
, Na2) IPO4 @ 12820 (2.5 g) were mixed in an aqueous solution for 24 hours at 25° C. for testing.

3) Apply a load of 200g with #abrasion-resistant steel wool (Ryo 000),
The surface was rubbed 50 times and the degree of scratches was observed with the naked eye.

4) The surface condition was examined after being exposed to a weather-resistant weatherometer for 240 hours.

Example 1 In the dome 7 in the vacuum deposition chamber 5 shown in FIG.
A spectacle lens made of diethylene glycol bisallyl carbonate resin was placed, and before a surface hardening layer was attached to the surface of the lens, an Ar ion beam was irradiated with an acceleration voltage of 300 V and an acceleration current of 30 III A for 1 minute to perform surface cleaning. The ion gun used was of the thermionic impact type. Next, the ion beam irradiation was temporarily stopped, and at the same time as the deposition of silicon dioxide (S102) for the surface hardening layer was started, an Ar ion beam was irradiated at an accelerating voltage of 500 V and an accelerating current of 50 mA to obtain the optical film thickness. Irradiation was continued until the temperature reached /2.

after that.

The Ar ion beam irradiation was stopped, and the total optical film thickness was 2 people. It continued until. As shown in FIG. 6, the surface hardened layer A consists of a 0/2 layer 11 that was irradiated with the first Ar ion beam and three layers that were not irradiated with the Ar ion beam. /2 layers 12.

Next, in order from the surface hardening layer toward the atmosphere, zil dioxide
17 (ZrO) layer 13. Silicon dioxide (S+02) layer 14
was deposited without ion beam irradiation. The total optical thickness of the zircon dioxide layer 13 and the silicon dioxide layer 14 is λ. /4. Subsequently, a zirconium dioxide layer 15, which is a high refractive index layer, is formed to have an optical thickness on top of the zirconium dioxide layer 15 without ion beam irradiation. I held court until I reached 2. Finally, while irradiating the silicon dioxide layer 16, which is a low refractive index layer, with an Ar ion beam at an accelerating voltage of 500 V and an accelerating current of 50 mA, the optical film thickness is increased. An antireflection layer was formed by irradiating the film to a temperature of /4.

Example 2 Reflection was carried out in the same manner as in Example 1, except that when depositing the zirconium dioxide layer 15, which is a high refractive index layer, Ar ion beam was irradiated with an accelerating voltage of 500 V and an accelerating current of 50 mA. A diethylene glycol bisallyl carbonate resin eyeglass lens with a protective coating was produced.

Example 3 Diethylene glycol bisallyl having an antireflection coating was prepared in the same manner as in Example 1, except that the silicon dioxide layer 16, which is the uppermost low refractive index layer, was deposited without Ar ion beam irradiation. A carbonate resin lens was manufactured.

Example 4 The surface of a diethylene glycol bisallyl carbonate resin eyeglass lens was irradiated with an Ar ion beam to perform surface cleaning in the same manner as in the example. Then,
Simultaneously with the start of vapor deposition of silicon dioxide for the surface hardening layer, a t-Ar ion beam was irradiated with an accelerating voltage of 500 V and an accelerating current of 5001 A, resulting in an optical film thickness of 2 mm.

The Ar ion beam was irradiated until . Next, a zircon dioxide layer and a silicon dioxide layer were sequentially deposited from the hardened surface layer toward the atmosphere without irradiating with an Ar ion beam. Enter the total optical thickness of the zircon dioxide layer and silicon dioxide layer. /4. Subsequently, a zirconium dioxide layer, which is a high refractive index layer, was deposited on top of the zirconium dioxide layer at an accelerating voltage of 500 V and an accelerating current of 50 mA while irradiating the ion beam until the optical film thickness became 0./2. While irradiating the silicon dioxide layer, which is a low refractive index layer, with an Ar ion beam at an accelerating voltage of 500 V and an accelerating current of 50 mA, the antireflection layer was formed by irradiating the silicon dioxide layer until the optical thickness became 11/4.

Example 5 Eyeglasses made of diethylene glycol bisallyl carbonate resin having an antireflection coating were produced in the same manner as in Example 4, except that the zircon dioxide layer, which is a high refractive index layer, was formed without Ar ion beam irradiation. A lens was created.

Example 6 The same procedure as in Example 4 was carried out, except that the zircon dioxide layer, which is a high refractive index layer, and the silicon dioxide layer, which is a low refractive index layer (top layer), were formed without Ar ion beam irradiation. A diethylene glycol bisallyl carbonate resin eyeglass lens having an antireflection coating was prepared by this method.

Comparative Example 1 Ar ion beam treatment (acceleration voltage 300
(2) Accelerating current: 30 mA, 1 minute) After that, an antireflection coating having the same film structure as in Example 1 was applied to this without ion beam irradiation.

Comparative Example 2 After the surface of a diethylene glycol bisallyl carbonate resin eyeglass lens was subjected to RF plasma treatment (500 W, 4 minutes), an antireflection coating having the same film structure as in Example 1 was applied thereto without Ar ion beam irradiation.

Example 7 In Example 1, instead of the diethylene glycol bisallyl carbonate resin eyeglass lens.

Antireflection was made in the same manner as in Example 1, except that a 5 gm silicone resin hard coat layer was used on the surface of a diethylene glycol bisallyl carbonate resin eyeglass lens, and with the same film structure as in Example 1. A coating was applied. The film structure of the obtained lens is shown in FIG.

Comparative Example 3 After the surface of a diethylene glycol bisallyl carbonate resin eyeglass lens having a silicone resin hard coat layer on its surface was subjected to Ar ion beam treatment (acceleration voltage 300 V, acceleration current 30 mA, 1 minute), the surface was not irradiated with an ion beam. An antireflection coating having the same coating structure as in Example 1 was applied.

Example 8 Antireflection was performed in the same manner as in Example 1, except that the surface of the diethylene glycol bisallyl carbonate resin eyeglass lens was not previously treated with an Ar ion beam, and with the same film structure as in Example 1. A coating was applied.

Comparative Example 4 In Example 1, the surface of a spectacle lens made of diethylene glycol bisallyl carbonate resin was not subjected to Ar ion beam treatment in advance, and an antireflection coating having the same film structure as in Example 1 was applied without irradiation with an ion beam.

Table 1 0υ ■...Excellent O...ExcellentΔ...Good×...Poor Next, the eyeglass lenses obtained in Example 1 were Table 2 shows a comparison with plastic eyeglass lenses with anti-reflection coatings already on the market.

Table 2 It can be seen that the products of the examples of the present invention have no abnormalities in sweat resistance, scratch resistance, and weather resistance, and are excellent as plastic eyeglass lenses coated with an antireflection coating.

2 As detailed above, a plastic optical component having an anti-reflection coating obtained by irradiating an ion beam during vacuum deposition of at least one of the hardened surface layer and the anti-reflection layer is comparable to glass. It has excellent adhesion between the antireflection coating and plastic optical components, and has excellent sweat resistance, scratch resistance, and weather resistance, and the antireflection coating is dense and hard. Therefore, the method of the present invention can be applied not only to plastic eyeglass lenses but also to all plastic optical parts that require an antireflection coating.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the film structure of a plastic eyeglass lens having a conventional antireflection coating. 1...Plastic eyeglass lens base 2...
. . . Surface hardening layer 3 . . . Antireflection layer FIG. 2 is a diagram showing the film structure of a plastic eyeglass lens having a conventional antireflection coating. ■・・・Plastic eyeglass lens base 2...
... Surface hardening layer 3 ... Antireflection layer 3-1 ... Medium refractive index layer 3-2 ... High refractive index layer 3-3 ... -Low refractive index layer FIG. 3 is a diagram showing the film structure of a plastic eyeglass lens having a conventional antireflection coating. I...Plastic eyeglass lens base? ...
...Surface hardened layer 3-1...Medium refractive index layer 3-1-1...High refractive index layer 3-1-2...Low refractive index layer 3 -2...High refractive index layer 3-3...Low refractive index layer Figure 4 shows the film structure of a conventional plastic eyeglass lens having a hard coat layer and an antireflection coating. FIG. 1...Plastic eyeglass lens base 2...
. . . Surface hardening layer 3 . . . Antireflection layer 4 . . . Hard coat layer FIG. 5 is a schematic diagram of an apparatus for carrying out the vapor deposition method according to the present invention. 5...Chamber 6...Plastic optical component 7...
Dome 8... Vapor deposition agent 9... Electron gun 10... Ion gun Figure 6 shows the via configuration of the diethylene glycol bisallyl carbonate resin eyeglass lens in Example 1. It is a diagram. L... Spectacle lens base A... Surface hardened layer 11... Layer 12 on which silicon dioxide is deposited while irradiating with an ion beam... Layer B on which silicon dioxide was deposited without irradiation...Antireflection layer 13...Layer 14 on which zircon dioxide was deposited without ion beam irradiation...Ion Layer 15 on which silicon dioxide was deposited without irradiating the beam...Layer 16 on which zircon dioxide was deposited without irradiating the ion beam...Silicon dioxide was deposited while irradiating the ion beam FIG. 7 is a diagram showing the film structure of a diethylene glycol bisallyl carbonate resin eyeglass lens in Example 7. 1... Spectacle lens base 4... Hard coat layer A made of silicone resin... Surface hardening layer 17... Silicon dioxide while irradiating with an ion beam Layer 18 on which silicon dioxide was vapor-deposited... Layer B on which silicon dioxide was vapor-deposited without ion beam irradiation... Anti-reflection layer 19... Zircon dioxide was vapor-deposited without ion beam irradiation. Vapor deposited layer 20... Layer 21 where silicon dioxide was vapor deposited without ion beam irradiation... Layer 22 where zircon dioxide was vapor deposited without ion beam irradiation...・A layer in which silicon dioxide is deposited while being irradiated with an ion beam.

Claims (2)

[Claims] (1) When forming an antireflection coating composed of a surface hardening layer and an antireflection layer on a plastic optical component by a vacuum evaporation method, vacuum is applied to at least one of the surface hardening layer and the antireflection layer. A method for manufacturing a plastic optical component having an antireflection coating, which comprises irradiating an ion beam during vapor deposition. (2) When forming an antireflection coating composed of a surface hardening layer and an antireflection layer on a plastic optical component by vacuum evaporation, the optical component is irradiated with an ion beam in advance, and then the surface hardening layer is formed. and a method for manufacturing a plastic optical component having an antireflection coating, which comprises irradiating with an ion beam during vacuum deposition of at least one of the antireflection layers.