JPH09113702A - Optical product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily form a hard coating layer which does not cause absorption while durability of the hard coating layer is maintained by forming a modified layer in which the refractive index is gradually changed and forming a hard coating layer having a const. refractive index to specified film thickness. SOLUTION: This product consists of a synthetic resin base body, a modified layer formed on the base body and a hard coating layer. The modified layer contains a Si and/or Ti compd. and is formed by CVD method, and its refractive index changes from the base body side to the thickness direction. The hard coating layer contains Si and O and is formed by CVD method to a film thickness between >0.4μm and <5μm. By forming the hard coating layer to <5μm thickness, the inner stress can be decreased, which improves adhesion property with the modified layer. By forming the film to >0.4μm thickness, durability of the film can be obtd. by its thickness. The modified layer is preferably formed to a thickness between >100nm and <900nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an article having a cured layer on its surface for improving scratch resistance, and particularly to an optical article such as a CRT display, an optical lens and a liquid crystal display device. It relates to a manufacturing method.

[0002]

2. Description of the Related Art There is known a technique of forming a coating called a hard coat on the surface in order to improve scratch resistance of optical articles such as spectacle plastic lenses. In order to form this coating, a dipping surface treatment (dipping) technique of dipping an object in a silane coupling agent has been conventionally used. It is known that this immersion surface treatment technique is a very effective technique from the viewpoint of heat resistance when the material of the object is a synthetic resin.

However, in the dipping surface treatment technique, the composition of the dipping agent is different when the material of the coating film is different. Therefore, for example, when forming a hard coat on a plastic lens, a new high-refractive index lens is being developed, and a dipping agent for forming a hard coat having a refractive index compatible with this is developed. Must. Therefore, the burden of development cost of the dipping agent is becoming heavy.

Further, in the case of a plastic lens, since the dipping agent used differs depending on the refractive index of the lens, it is necessary to install a plurality of equipment such as a device for dipping surface treatment for each refractive index. Therefore, the depreciation cost of equipment tends to increase every year.

Further, recently, there is a tendency to receive an order for a custom-made plastic lens. Especially for eyeglass lenses,
Orders are received for one pair (two sheets), and the process of directly flowing through the integrated manufacturing line of the manufacturing plant is being considered. in this case,
In order to be able to form a hard coat regardless of the refractive index of a custom-made product, it is necessary to always install a dipping surface treatment equipment line for all the refractive indexes, which is a drawback that production efficiency deteriorates. have.

When a hard coat is formed by a conventional dipping surface treatment method, surface activation treatment such as dipping in an alkaline solution is indispensable as the surface treatment before coating. However, recently, problems such as waste liquid treatment used for these have begun to occur due to environmental problems and the like.

Furthermore, a condensation curing step is indispensable in the conventional coating film manufacturing step, and this step requires several hours, which is a very important improvement problem in shortening the delivery time.

Further, in the case of an object in which a plurality of coatings need to be laminated, if all these coatings are formed by the dipping surface treatment method, many kinds of expensive dipping agents are required, which is not suitable for the manufacturing cost. There is also a problem.

Therefore, as a technique for forming a coating without using the dipping surface treatment method, a technique for producing a coating by plasma CVD is disclosed in Japanese Patent Laid-Open No. 140356/1993. This technology is used for transparent resin windows used in vehicles,
A silicon-containing film (SiOx film) is formed by plasma CVD in order to form a surface hardened film for improving adhesion and surface hardness.

Further, in order to form a multi-layer coating, in European Patent EP-203730, an organosilicon compound is formed on an optical component substrate by a dip surface treatment method, and an antireflection film is formed thereon. In addition, there is proposed a method in which an organic substance-curable substance (water repellent coat) is further formed thereon.

Further, Japanese Patent Application Laid-Open No. 62-247302 discloses a technique of forming a silazane compound on an antireflection coating film of an inorganic material to impart water repellency to modify the surface.

In the case of eyeglass plastic lenses, an organic silicone coating called a hard coat for protecting the plastic lenses is formed by a dipping surface treatment method (dipping method), and then an antireflection film is formed by a vacuum deposition method. There is also known a method of reducing the manufacturing cost by reducing the type of the dipping agent by using the method described above.

Further, in JP-A-7-56001 and JP-A-7-56002, the occurrence of interference fringes is suppressed by changing the refractive index of the hard coat layer of the plastic lens in the film thickness direction. Is disclosed. For this reason, the hard coat layer is formed of a material in which a high refractive index material and a low refractive index material are mixed, and the refractive index is changed by changing the mixing ratio in the film thickness direction.

[0014]

However, the coating film formed by the method described in the above-mentioned Japanese Patent Laid-Open No. 5-140356 has a low hot water resistance and requires a hot water resistance of plastic lenses for eyeglasses. It cannot be used for objects that are subject to Specifically, the film formed by this method has a thickness of 80
In a hot water immersion test at 10 ° C for 10 minutes, the film peels off.

In addition, like EP-203730,
The method of forming a coating film of a plurality of layers by combining the immersion surface treatment method and another vapor phase growth method requires a very long curing time for the coating film formed by the immersion surface treatment method. In addition, since the process moves to the next step of forming the antireflection film, it is inevitable that the film is once exposed to the atmosphere, and it is difficult to perform consistent steps continuously.

Further, as in JP-A-7-56001 and JP-A-7-56002, a hard coat layer is formed on the surface of a plastic substrate by a CVD method, and the refractive index of the hard coat layer is changed in the film thickness direction. I tried to let you. However, in this case, there is a problem that absorption occurs in the hard coat layer. Further, in forming the hard coat layer, it was difficult to form the film so that the refractive index of the hard coat layer was gradually changed. In other words, there is a problem that the refractive index of the hard coat layer becomes uneven, and the refractive index changes in an unstable state. Furthermore, this uneven part is inferior in durability,
I also found it to be brittle.

Recently, especially in the field of spectacle lenses, the demands of users for lenses have diversified, and the refractive index of the base material has also diversified, so that it is necessary to form a film suitable for each base material. Is coming. Therefore, unless the material, structure, film thickness, manufacturing method, etc. of the antireflection film that is adapted to the antireflection film formed on the problematic hard coat layer are examined, it is possible to adapt to the diversified user requirements. It's gone.

It is an object of the present invention to provide an optical article provided with a hard coat layer which retains durability of the hard coat layer, does not absorb, and can be easily formed.

[0019]

The inventor of the present invention forms a hard coat layer on the surface of a plastic substrate having various refractive indexes to gradually change the refractive index while improving the durability of the lens. I tried to overcome the difficulty.

As a result, it was decided to modify the film thickness of the hard coat layer having a constant refractive index by providing a modified layer having a gradually changing refractive index. That is, in order to maintain sufficient durability, the hard coat layer was conventionally formed to have a film thickness of 5 μm or more, but it was found that this film thickness was too thick to gradually change the refractive index. However, it has also been found that if the thickness of the hard coat layer is made too thin so that the refractive index can be gradually changed, the original durability is deteriorated.

The inventor of the present invention intends to easily form a hard coat layer that does not cause absorption while maintaining the durability of the hard coat layer to obtain a hard coat layer and a modified layer having an optimum film thickness. Intended.

In order to achieve the above object, according to the present invention, a synthetic resin substrate and at least one of a Si-based compound and / or a Ti-based compound formed on the substrate are included, and A modified layer formed by the CVD method, in which the refractive index changes in the thickness direction, and Si and O.
And a hard coat layer formed by the CVD method having the above, wherein the thickness of the hard coat layer is thicker than 0.4 μm and thinner than 5 μm.

The modified layer is thicker than 100 nm and is 900 n
It is desirable that the thickness is thinner than m.

In order to achieve the above object, according to the present invention, a transparent substrate is prepared and plasma is used by using at least one of an organic compound gas containing Si and / or an organic compound gas containing Ti. The first step of forming a modified layer whose refractive index changes from the base material side in the thickness direction on the base material by the chemical vapor deposition method described above; and an organic compound gas containing Si and an oxygen gas. A hard coat layer having a thickness of more than 0.4 μm, less than 5 μm, and a thickness greater than that of the modified layer is formed on the modified layer by a chemical vapor deposition method using plasma using a mixed gas. The manufacturing method of the optical article characterized by having a process.

The first film has a structure in which the refractive index changes in the film thickness direction by gradually increasing the energy supplied to the plasma or gradually increasing or decreasing the gas flow rate. can do.

In the first or second step, it is desirable to control the pressure of the mixed gas atmosphere to a pressure higher than 0.4 Pa and lower than 13 Pa.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described.

First, a transparent base material is prepared, the base material is placed in a vacuum container of a plasma CVD apparatus, a gas in which methyltriethoxysilane is vaporized is introduced, plasma is generated, and energy supplied to the plasma is supplied. Is gradually increased to form the modified layer. The modified layer thus formed has a refractive index gradually changing in the film thickness direction. The thickness of the modified layer is formed to be thicker than 100 nm and thinner than 900 nm.

Methyltriethoxysilane gas was continuously introduced to generate plasma, and the pressure in the vacuum vessel was adjusted to 0.
The hard coat layer is formed while controlling it to be larger than 4 Pa and smaller than 13 Pa. The thickness of the hard coat layer is
It is formed to be thicker than 0.4 μm and thinner than 5 μm.

As a result, the optical article of the present invention can be manufactured.

As the above-mentioned substrate, polycarbonate, polymethylmethacrylate and copolymers thereof, diethylene glycol bisallyl carbonate (Pittsburgh
CR-39) polymer produced by Plate Glass Co., Ltd., polyester, unsaturated polyester, acrylonitrile-styrene copolymer, vinyl chloride, polyurethane, epoxy resin, halogen (excluding fluorine) and mono- or di-containing hydroxyl group. It is possible to use a substrate made of a material arbitrarily selected from a polymer of a (meth) acrylate and an isocyanate compound or a copolymer thereof. Among the polyesters, polyethylene terephthalate is particularly preferably used.

Of these, particularly preferable are polymers of diethylene glycol bisallyl carbonate, polyurethane, and halogen (excluding fluorine).
Further, a substrate composed of a mono- or di- (meth) acrylate having a hydroxyl group, an isocyanate compound, a polymer or a copolymer thereof can be used.

Further, as a gas used for forming the modified layer or the hard coat layer, tetraethoxysilane is used.
Si (OC ₂ H ₅ ) ₄ , dimethoxydimethylsilane (CH ₃ )
₂ Si (OCH ₃ ) ₂ , methyltrimethoxysilane CH ₃ S
i (OCH ₃ ) ₃ , tetramethoxysilane Si (OC
H ₃ ) ₄ , ethyltrimethoxysilane C ₂ H ₅ Si (OCH
₃ ) ₃ , diethoxydimethylsilane (C ₂ H ₅ O) ₂ Si (C
H _{3) 2,} methyltriethoxysilane CH ₃ Si (OC ₂ H
₅ ) _{3 and the} like are preferably used.

When forming the modified layer, an organic compound gas containing Ti may be used. For example, tetramethoxy titanium Ti (OCH ₃ ) ₄ and tetraethoxy titanium
Ti (OC ₂ H ₅ ) ₄ , Tetra-i-propoxy titanium Ti
_{(O-i-C 3 H} 7) 4, tetra -n- propoxytitanium Ti (O
_{-n-C 3 H 7) 4} , tetra -n- butoxy Ti (O-n-C
₄ H ₉ ) ₄ , tetra-i-butoxytitanium Ti (O-i-C ₄ H ₉ ).
₄ , tetra-sec-butoxy titanium Ti (O-sec-C
₄ H ₉ ) ₄ , tetra-t-butoxytitanium Ti (O-t-C ₄ H ₉ ).
₄ , tetradiethylaminotitanium Ti (N (C ₂ H ₅ ) ₂ ) ₄
Etc. are preferably used. When forming the modified layer, of these organic compounds containing Si and organic compounds containing Ti, one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

Further, in the chemical vapor deposition (CVD) method using plasma used in the present invention, the raw material gas is discharged by applying thermal energy and electric energy, and in a non-thermal equilibrium state in the plasma atmosphere. A method of promoting a reaction and depositing a thin film on a substrate,
Commonly used types include a parallel plate electrode type, a capacitive coupling type and an inductive coupling type. Particularly in the present invention, plasma-enhanced C that applies an electric field and a magnetic field parallel to the main plane of the substrate
It is suitable to form by the VD (PECVD) method.

By applying a magnetic field parallel to the electric field, an electric field due to the magnetic field occurs between the opposing electrodes, and the ions in the plasma are accelerated toward the substrate holder. Further, the electric field due to this magnetic field makes the plasma density uniform, and it is possible to suppress ion damage to the substrate and temperature rise. Therefore, especially when forming a thin film on a transparent substrate material such as a plastic lens, or when using a substrate made of a material whose side chain group is easily broken by ion damage or a material with low heat resistance, damage to the substrate Because there are few
Plasma-enhanced CVD that applies a magnetic field is very effective.

In the present invention, the film thickness of the hard coat layer is 5 μm.
By making it thinner than m, the internal stress can be reduced and the adhesion with the modified layer can be enhanced. Also, 0.4μ
By making it thicker than m, the durability of the film can be secured depending on the thickness of the film. Moreover, since the refractive index of the hard coat layer is not changed in the film thickness direction, a hard coat layer having a large film thickness can be easily formed.

The modified layer improves the adhesion between the hard coat layer and the substrate, and absorbs the impact applied to the hard coat layer, thereby improving the environment resistance of the entire coating.

Further, since the modified layer changes the refractive index in the film thickness direction, it is possible to prevent the occurrence of interference fringes due to the difference in refractive index between the base material and the coating.

Further, the hard coat layer can be easily made transparent even if the film thickness is large by adjusting the amount of oxygen from the composition, so that a transparent hard coat can be formed. Further, since the modified layer is not a hard coat layer, it may be thin. Therefore, when the modified layer contains Ti,
It can be made transparent by making it thin. From these things, the coating film of the present invention can be made transparent, and the method of the present invention can be preferably used for forming the coating film for the plastic lens for spectacles.

Further, since both the modified layer and the hard coat layer can be formed by the vapor phase growth method, it is possible to form a coating film composed of a plurality of layers in a continuous process.

[0042]

An embodiment of the present invention will be described below.

First, as a first embodiment of the present invention, a plastic lens having a modified layer and a coating composed of first, second and third hard coat layers on the surface of the plastic lens of the base material is prepared. The manufacturing method will be described.

The plastic lens of the base material is composed of a polymer of diethylene glycol bisallyl carbonate (CR-39 manufactured by Pittsburgh Plate Glass Co., Ltd.).

On this substrate, Balzels
The above-mentioned film is formed using a PECVD apparatus manufactured by rs). This PECVD apparatus is equipped with an electromagnetic coil outside the vacuum chamber. The electromagnetic coil is arranged in the space between the pair of electrodes arranged in the vacuum chamber so as to apply a magnetic field in a direction parallel to the electric field. In the space between the electrodes, a carousel-type base material holder is arranged so as to hold the main plane of the base material parallel to the electric field.

First, as a preparatory step, the lens of the base material was cleaned by passing it through an ultrasonic cleaning machine and placed in a base material holder in a vacuum chamber of a PECVD apparatus. After that, 2.7 in the vacuum chamber.
It was evacuated to × 10 to ⁴ Pa.

Next, the step of forming the modified layer will be described.

Methyltriethoxysilane was vaporized by heating a container containing methyltriethoxysilane, which was connected to the vacuum chamber, and methyltriethoxylane gas was flown into the vacuum chamber at a flow rate of 100 SCCM. When the pressure in the vacuum chamber reaches 0.7 Pa, apply 5 to the electromagnet coil outside the vacuum chamber.
A current of A was applied to apply a magnetic field between the electrodes, and at the same time, a high frequency output of 2 KW was applied to the cathode for 3 minutes. As a result, plasma is generated between the electrodes. The magnetic field stabilizes the low pressure arc discharge. The flow rate of the methylethoxysilane gas during this period is 100 SCCM. After that, the high-frequency output of the cathode is gradually increased stepwise at a rate of 40 W / min, and is controlled to reach 2.5 KW in 12 minutes. The flow rate of the methylethoxysilane gas during this 12 minutes is kept constant at 180 SCCM.

In these 12 minutes, a modified layer having a stepwise change in refractive index is formed. The modified layer is formed while controlling the film thickness so that the film thickness is smaller than the combined thickness of the first, second, and third hard coat layers formed in the next step. In this embodiment, the film is formed to have a specific thickness that is in a range larger than 100 nm and smaller than 900 nm.

Next, the steps of forming the first, second and third hard coat layers will be described.

Continuing the step of forming the modified layer, 50 SCCM of oxygen gas was flown into the vacuum chamber and the pressure in the vacuum chamber was adjusted to 0.5.
Pa and flow rate of methylethoxysilane gas 180S
CCM, high frequency output 2.5KW, electromagnet coil 5A,
The first hard coat layer was formed for 20 minutes.

After that, the oxygen gas flow rate was increased to 100 SCCM, the vacuum chamber pressure was set to 0.8 Pa, the high frequency output of the cathode was changed to 3 KW, the methylethoxysilane gas flow rate was 180 SCCM, and the electromagnet coil 5A was used for another 20 times. A second hard coat layer was formed for a period of time.

Finally, the flow rate of oxygen gas was increased to 200 SCCM, the conductance of the exhaust system was adjusted by a variable orifice so that the vacuum chamber pressure was kept at 1.0 Pa, and the flow rate of methylethoxysilane gas was 1
A third hard coat layer was further formed with 80 SCCM, the electromagnet coil 5A, and the cathode high frequency output of 3 KW.

The thicknesses of the first, second and third hard coat layers were controlled so that the combined thickness of these layers would be thicker than the thickness of the modified layer. In this embodiment, 0.4 μ
The film thickness was controlled so that the thickness was in the range larger than m and smaller than 5 μm, and was larger than the film thickness of the modified layer.

Next, as the second to fifth embodiments of the present invention, a modified layer and first, second and third hard coat layers are formed on the surface of the plastic lens of the base material. A method for producing a coated plastic lens will be described.

The material of the plastic lens used, the type of gas used, and the film thickness of each layer are the same as in the first embodiment. In the manufacturing process, the preparation process, the modified layer formation process, and the first and second hard coat layer formation processes are
The description is omitted because it is similar to the first embodiment.

The third hard coat layer was formed by changing the pressure in the vacuum chamber in each example. Specifically, the pressure of the vacuum chamber in the step of forming the third hard coat layer is 3.0 Pa in the second embodiment and 6.0 P in the third embodiment.
a, the fourth example was set to 9.0 Pa, and the fifth example was set to 12.0 Pa to form the third hard coat layer, respectively.

The other conditions of the step of forming the third hard coat layer, the flow rate of methylethoxysilane gas, the flow rate of oxygen gas, the high frequency output of the cathode, and the setting of the electromagnet are the same as those in the first embodiment.

Next, as a sixth embodiment of the present invention, a plastic in which a coating film consisting of a modified layer and first, second and third hard coat layers is formed on the surface of a plastic lens as a base material. A method of manufacturing the lens will be described.
The film thickness of each layer was the same as that of the first embodiment.

In this example, a lens made of a polyurethane polymer was used as the base material. The same PECVD equipment as in the first embodiment was used.

First, as a preparatory step, the base lens is cleaned by passing it through an ultrasonic cleaning machine, and it is installed on a carousel type substrate holder between the cathode electrode and the anode electrode in the vacuum chamber of the PECVD apparatus, and 2.7. It was evacuated to × 10 to ⁴ Pa.

Next, the step of forming the modified layer will be described.

Methyltriethoxylane was vaporized by heating a container containing methylethoxysilane connected to the vacuum chamber, and methyltriethoxylane gas was flown into the vacuum chamber at a flow rate of 35 SCCM. At the same time, by heating the container containing dimethoxydimethylsilane connected to the vacuum chamber, vaporize dimethoxydimethylsilane,
Dimethoxydimethylsilane gas was flowed into the vacuum chamber at a flow rate of 148 SCCM. When the pressure in the vacuum chamber reached 0.5 Pa, a current of 5 A was passed through the electromagnet coil outside the vacuum chamber while maintaining the gas flow rate to apply a magnetic field between the electrodes. Then, the flow rate of methyltriethoxysilane gas is gradually increased at a rate of 110 SCCM per minute, and at the same time,
While gradually reducing the flow rate of dimethoxydimethylsilane gas at a rate of 98.7 SCCM per minute, a high frequency output of 2 KW was applied to the cathode for 1.5 minutes to form a modified layer in 1.5 minutes.

The process of forming the first, second and third hard coat layers will be described.

Further, subsequently, the flow rate of methyltriethoxysilane is 200 SCCM and the flow rate of oxygen gas is 50 SC.
When the CM flowed and the pressure in the vacuum chamber became 1.0 Pa and the flow rate became stable, a current of 5 A was passed through the external electromagnet coil and, at the same time, a high frequency output of 2.5 KW was applied for 17 minutes to the first hard coat. Layers were formed.

Further, the flow rate of oxygen gas is set to 100 SCCM.
, The conductance of the exhaust system is adjusted by the variable orifice so that the pressure in the vacuum chamber becomes 2.0 Pa, the high frequency output of the cathode is increased to 3 KW, the flow rate of methyltriethoxysilane gas is 200 SCCM, and the external electromagnet coil 5A is increased. Then, the second hard coat layer was continuously formed for 17 minutes.

Finally, the flow rate of oxygen gas is set to 200 SCCM.
The pressure in the vacuum chamber is 2.0 Pa, the high frequency output of the cathode is 3 kW, and the flow rate of methyltriethoxysilane gas is 2
The third hard coat layer was formed with 00 SCCM and the external electromagnet coil 5A for 17 minutes.

Next, as seventh, eighth, and ninth embodiments, plastic lenses having a modified layer and a coating consisting of a first, a second, and a third hard coat layer formed on the surface are manufactured. The method for doing so will be described.

The material of the plastic lens of the substrate used, the type of gas used, the film thickness of each layer, the preparation step, the step of forming the modified layer, and the step of forming the first hard coat layer are the same as those in the sixth embodiment. The description is omitted because it is similar to the above.

The second and third hard coat layers were formed by changing the pressure in the vacuum chamber in each example. Specifically, the pressure in the vacuum chamber is 5.0 Pa as the seventh embodiment, 8.0 Pa as the eighth embodiment, and 1 Pa as the ninth embodiment.
The pressure was set to 2.0 Pa to form the second and third hard coat layers. The conditions other than the pressure in the vacuum chamber, the gas flow rate, the high frequency output of the cathode, and the setting of the electromagnet coil in the steps of forming the second and third hard coat layers are the same as those in the sixth embodiment.

Next, as a tenth to thirteenth embodiment of the present invention, a modified layer and a modified layer are formed on the base plastic lens.
A method of manufacturing a plastic lens including the first, second and third hard coat layers and the multilayer antireflection film in this order will be described. The modified layer and the first, second and third hard coat layers had the same thickness as in the first embodiment.

As a tenth embodiment, the plastic lens manufactured in the first embodiment is placed in another vacuum vapor deposition apparatus, the pressure in the vacuum chamber is evacuated to 1.3 × 10 to ³ Pa, and then 1 Al ₂ O ₃ layer, Zr by electron gun vapor deposition while controlling in a pressure range of 3 × 10 ^{3 to} 1.3 × 10 ² Pa
An O ₂ layer, a ZrO ₂ layer, and a SiO ₂ layer were sequentially stacked. As a result, an Al ₂ O ₃ layer, a ZrO ₂ layer, a ZrO ₂ layer, and a Si layer are formed on the third hard coat layer manufactured in the first embodiment.
A plastic lens having a multi-layered antireflection film including an O ₂ layer was manufactured.

In addition, as an eleventh embodiment, the plastic lens manufactured in the fifth embodiment is placed in another vacuum vapor deposition apparatus, and the pressure in the vacuum chamber is 1.3 × 10 ³ P.
After evacuating to ^{a, 1.3 × 10 ~ 3 ~1.3} × 10 ~ 2 P
Al ₂ O by electron gun evaporation while controlling in the pressure range of a
_Three layers, a ZrO ₂ layer, a ZrO ₂ layer, and a SiO ₂ layer were laminated in this order. As a result, an Al ₂ O ₃ layer, a ZrO ₂ layer, and a Zr layer were formed on the third hard coat layer manufactured in the fifth embodiment.
A plastic lens further including a multilayer antireflection film including an O ₂ layer and a SiO ₂ layer was manufactured.

As a twelfth embodiment, the plastic lens manufactured in the sixth embodiment is placed in another vacuum vapor deposition apparatus, the pressure in the vacuum chamber is evacuated to 1.3 × 10 to ³ Pa, and then 1 Al ₂ O ₃ layer, Zr by electron gun vapor deposition while controlling in a pressure range of 3 × 10 ^{3 to} 1.3 × 10 ² Pa
An O ₂ layer, a ZrO ₂ layer, and a SiO ₂ layer were sequentially stacked. As a result, the Al ₂ O ₃ layer, the ZrO ₂ layer, the ZrO ₂ layer, and the Si layer formed on the third hard coat layer manufactured in the sixth embodiment are formed.
A plastic lens having a multi-layered antireflection film including an O ₂ layer was manufactured.

As a thirteenth embodiment, the plastic lens manufactured in the ninth embodiment is placed in another vacuum vapor deposition apparatus, the pressure in the vacuum chamber is evacuated to 1.3 × 10 to ³ Pa, and then 1 Al ₂ O ₃ layer, Zr by electron gun vapor deposition while controlling in a pressure range of 3 × 10 ^{3 to} 1.3 × 10 ² Pa
An O ₂ layer, a ZrO ₂ layer, and a SiO ₂ layer were sequentially stacked. As a result, the Al ₂ O ₃ layer, the ZrO ₂ layer, the ZrO ₂ layer, and the SiO ₂ layer formed on the third hard coat layer manufactured in the ninth embodiment
A plastic lens having a multilayer antireflection film including _two layers was manufactured.

Next, as fourteenth to seventeenth embodiments of the present invention, a modified layer is formed on the plastic lens of the base material.
First, second and third hard coat layers, a multilayer antireflection film,
A method of manufacturing a plastic lens provided with the water-repellent thin films in order will be described. The film thicknesses of the modified layer and the first, second and third hard coat layers are the same as in the first embodiment.

The plastic lens of the fourteenth embodiment is
The product produced in the tenth example was further immersed in a dipping solution tank containing hexamethyldisilazane, and then heat-cured at 65 ° C. for 30 minutes to prevent reflection of the water-repellent thin film serving as a water stain prevention coat. It was manufactured by forming on a film.

The plastic lens of the fifteenth embodiment is
The film formed in the eleventh example was further immersed in a dipping solution tank containing hexamethyldisilazane, and then heat-cured at 65 ° C. for 30 minutes to prevent the water-repellent thin film serving as a water stain prevention coating from being antireflection. It was manufactured by forming on a film.

The plastic lens of the sixteenth embodiment is
What was formed in the twelfth example was further immersed in a dipping solution tank containing hexamethyldisilazane, and then heat-cured at 65 ° C. for 30 minutes, whereby the water-repellent thin film serving as a water stain prevention coat was antireflection. It was manufactured by forming on a film.

The plastic lens of the seventeenth embodiment is
The water-repellent thin film to be used as the anti-water stain coat was subjected to antireflection by immersing the product formed in the thirteenth example in a dipping solution tank containing hexamethyldisilazane and then heat-curing at 65 ° C. for 30 minutes. It was manufactured by forming on a film.

Next explained is a plastic lens of the eighteenth embodiment of the invention. The plastic lens of the eighteenth embodiment is provided with a modified layer, first, second and third hard coat layers in this order on the surface of the plastic lens of the base material. This manufacturing method will be described. The film thickness of each layer is the same as that of the first embodiment.

First, as a preparatory step, after cleaning the polyurethane lens by passing through an ultrasonic cleaning machine, it was placed in a vacuum chamber of a PECVD apparatus manufactured by Balzers and 2.7 × 10 ⁴ P
Exhausted to a.

Then, a gas of dimethyldiethoxylane was flown into the vacuum chamber at a flow rate of 11 SCCM and a gas of tetraisopropoxytitanium was flowed at a flow rate of 9 SCCM. When the pressure in the vacuum chamber reached 0.5 Pa, a current of 2.6 A was passed through the electromagnet coil outside the vacuum chamber to apply a magnetic field between the electrodes, and at the same time, a high frequency output of 0.6 KW was applied to the cathode for 45 seconds. After that, the flow rate of tetraisopropoxy titanium gas was changed from 9 SCCM to 0 SCCM, and at the same time, the flow rate of dimethyldiethoxysilane gas was changed from 11 SCCM to 100 SCCM.
Was changed for 10 minutes to form a modified layer.

Subsequently, the flow rate of dimethyldiethoxysilane gas was 100 SCCM and the flow rate of oxygen gas was 35 S.
When the flow rate was stabilized by CCM and the pressure in the vacuum chamber became 1.0 Pa and the flow rate became stable, a current of 2.6 A was passed through the external electromagnet coil, and at the same time, a high frequency output of 0.8 KW was applied to the cathode for 25 minutes. 1 hard coat layer was formed.

Further, the flow rate of oxygen gas is increased to 70 SCCM, the conductance of the exhaust system is adjusted by the variable orifice so that the pressure in the vacuum chamber becomes 2.0 Pa, the high frequency output of the cathode is raised to 1 KW, and the dimethyl concentration is increased. A second hard coat layer was continuously formed for 25 minutes with a flow rate of diethoxysilane gas of 100 SCCM and an external electromagnet coil of 2.6A.

Finally, the flow rate of oxygen gas was set to 140 SCCM.
The third hard coat layer was formed for 25 minutes while maintaining other conditions.

As the 19th to 21st embodiments, the 18th embodiment
In the same steps as in the example of Example 1, the modified layer, the first, second, and third layers are formed.
Although a plastic lens having a hard coat layer of No. 2 was manufactured, the pressure in the vacuum chamber at the time of forming the second and third hard coat layers was set to 5.0 Pa in the nineteenth example.
0 is 8.0 Pa, and 21st is 1
It was set to 2 Pa.

The plastic lenses of the twenty-second to twenty-fifth embodiments are provided with a modified layer, first, second and third hard coat layers, and a multilayer antireflection film on the surface. The film thicknesses of the modified layer and the first, second and third hard coat layers are the same as in the first embodiment.

As a twenty-second embodiment, the one manufactured in the eighteenth embodiment is placed in another vacuum vapor deposition apparatus, the pressure in the vacuum chamber is evacuated to 1.3 × 10 to ³ Pa, and then 1 Al ₂ O ₃ layer, ZrO ₂ layer by electron gun vapor deposition while controlling in a pressure range of 3 × 10 ^{3 to} 1.3 × 10 ² Pa,
A ZrO ₂ layer and a SiO ₂ layer were sequentially stacked. This makes the first
A plastic lens having a multilayer antireflection film including an Al ₂ O ₃ layer, a ZrO ₂ layer, a ZrO ₂ layer, and a SiO ₂ layer is further manufactured on the third hard coat layer manufactured in the example 8 did.

As a twenty-third embodiment, the one manufactured in the nineteenth embodiment is put in another vacuum vapor deposition apparatus, and after the pressure in the vacuum chamber is evacuated to 1.3 × 10 to ³ Pa, Al ₂ O ₃ layer, ZrO ₂ layer by electron gun vapor deposition while controlling in a pressure range of 1.3 × 10 ^{3 to} 1.3 × 10 ² Pa,
A ZrO ₂ layer and a SiO ₂ layer were sequentially formed. This makes the first
A plastic lens having the third hard coat layer prepared in Example 9 and further including a multilayer antireflection film including an Al ₂ O ₃ layer, a ZrO ₂ layer, a ZrO ₂ layer and a SiO ₂ layer is manufactured. did.

As a twenty-fourth embodiment, the one manufactured in the twentieth embodiment is put into another vacuum vapor deposition apparatus, the pressure in the vacuum chamber is evacuated to 1.3 × 10 to ³ Pa, and then 1 Al ₂ O ₃ layer, ZrO ₂ layer by electron gun vapor deposition while controlling in a pressure range of 3 × 10 ^{3 to} 1.3 × 10 ² Pa,
The ZrO ₂ layer and the SiO ₂ layer were laminated in this order. This allows the second
A plastic lens having a multilayer antireflection film including an Al ₂ O ₃ layer, a ZrO ₂ layer, a ZrO ₂ layer, and a SiO ₂ layer on the third hard coat layer prepared in Example No. 0. did.

As a twenty-fifth embodiment, the one manufactured in the twenty-first embodiment is placed in another vacuum vapor deposition apparatus, the pressure in the vacuum chamber is evacuated to 1.3 × 10 to ³ Pa, and then 1 Al ₂ O ₃ layer, ZrO ₂ by electron gun evaporation while controlling in the pressure range of 3 × 10 ³ 〜1.3 × 10 ² Pa
_Two layers, a ZrO ₂ layer, and a SiO ₂ layer were sequentially stacked. As a result, an Al ₂ O ₃ layer, a ZrO ₂ layer, a ZrO ₂ layer, and a Si layer were formed on the third hard coat layer manufactured in the 21st Example.
A plastic lens having a multi-layered antireflection film including an O ₂ layer was manufactured.

The plastic lenses of the twenty-sixth to twenty-ninth embodiments are provided with a modified layer, first, second and third hard coat layers, a multilayer antireflection film and a water-repellent thin film on the surface. .

The plastic lens of the 26th embodiment is
The product manufactured in the 22nd Example was further dipped in a dipping solution tank containing hexamethyldisilazane, and then heat-cured at 65 ° C. for 30 minutes to form a water-repellent thin film as an anti-reflection film. Manufactured by forming on top.

The plastic lens of the 27th embodiment is
The product manufactured in the 23rd Example was further immersed in a dipping solution tank containing hexamethyldisilazane and then heat-cured at 65 ° C. for 30 minutes to form a water-repellent thin film serving as an anti-water stain coat on the antireflection film. Manufactured by forming on top.

The plastic lens of the 28th embodiment is
The product manufactured in the twenty-fourth embodiment was further immersed in a dipping solution tank containing hexamethyldisilazane, and then heat-cured at 65 ° C. for 30 minutes to form a water-repellent thin film as an anti-water stain coating on the antireflection film. Manufactured by forming on top.

The plastic lens of the 29th embodiment is
The product manufactured in the 25th Example was further dipped in a dipping solution tank containing hexamethyldisilazane, and then heat-cured at 65 ° C. for 30 minutes to form a water-repellent thin film serving as an anti-water stain coat as an antireflection film. Manufactured by forming on top.

Next, as comparative examples, the plastic lenses of the first to fourth comparative examples were manufactured.

In the plastic lenses of the first and second comparative examples, as in the plastic lens of the first embodiment, a modified layer, first, second and third hard coat layers are formed on the surface of the base lens. I have it.

The material of the base lens of the plastic lenses of the first and second comparative examples, the film thickness of each layer, and the manufacturing method are almost the same as those of the first to fifth embodiments. The pressure in the vacuum chamber in the step of forming the second and third hard coat layers is different from that in the first to fifth embodiments.

In the plastic lenses of the first to fifth examples, the pressure in the vacuum chamber at the time of forming the first, second and third hard coat layers is 0.5 to 12 Pa. In the plastic lens of the comparative example, the pressure in the vacuum chamber was set to 0.4 Pa during the formation of the first, second and third hard coat layers. The other conditions are the same as those in the first embodiment, and therefore the description is omitted.

In the plastic lens of the second comparative example, the pressure in the vacuum chamber was set to a value when the first hard coat layer was formed.
0.4 Pa, 0.8 when forming the second hard coat layer
Pa, 13 Pa when forming the third hard coat layer. The other conditions are the same as those in the first embodiment, and therefore the description is omitted.

The plastic lenses of the third and fourth comparative examples are the same as the plastic lenses of the sixth to ninth examples, and the modification layer, the first, second and third hard layers are formed on the surface of the polyurethane lens. It has a coat layer. The film thicknesses of the modified layer and the first, second and third hard coat layers are the same as in the first embodiment.

The steps of manufacturing the plastic lenses of the third and fourth comparative examples are almost the same as the steps of manufacturing the sixth to ninth examples, but the steps of forming the modified layer, the first, second, and Third
In the step of forming each of the hard coat layers, the pressure in the vacuum chamber is different from that in the sixth to ninth examples.

In the plastic lenses of the sixth to ninth examples, the step of forming the modified layer and the first, second and third steps are performed.
In the step of forming the hard coat layer, the pressure of the vacuum chamber was set to 0.5 Pa or more and 12 Pa or less, but the plastic lens of the third comparative example is a step of forming the modified layer,
Also, in the step of forming the first, second, and third hard coat layers, the pressure in the vacuum chamber was set to 0.4 Pa, respectively. The other conditions are the same as those in the sixth to ninth embodiments, and thus the description thereof will be omitted.

In the plastic lens of the fourth comparative example, in the step of forming the modified layer and the step of forming the first hard coat layer, the pressure in the vacuum chamber was 0.4 Pa, the second and the third lenses were formed.
In the step of forming the hard coat layer, the pressure in the vacuum chamber was set to 13 Pa. The other conditions are the same as those in the sixth to ninth embodiments, and thus the description thereof will be omitted.

Next, the plastic lens samples for eyeglasses obtained in the above-mentioned first to twenty-ninth examples and the first to fourth comparative examples were evaluated. The evaluation items and their contents are as follows.

Evaluation items 1) Adhesion According to JIS D-202, cuts 1 mm apart are vertically and horizontally placed on the surface of the sample, and cellophane tape (product name: Nichiban brand cellophane tape) is pasted on the cuts. Peel off the tape with force to see if film peeling occurs.

2) Scratch resistance (a) Steel wool having a roughness of # 0000 is loaded under a load of 600 g.
The sample is pressed against the sample and reciprocated 30 times in 15 seconds, and then the sample surface is checked for scratches.

(B) Sand eraser (Lion product name
A sand eraser ER-502) is pressed against the sample with a load of 500 g, and reciprocates 30 times for 15 seconds, and then the sample surface is checked for scratches.

3) Hot water resistance After immersing in constant temperature water of 80 ° C. for 10 minutes, it is examined whether or not there is a change in the film on the surface of the sample.

4) Heat resistance After standing for 5 minutes in the air at 100 ° C. in an air oven, it is examined whether or not the film on the sample surface is changed.

5) Alkali resistance After immersing in an aqueous solution of sodium hydroxide (PH11) for 6 hours, it is examined whether or not the film on the surface of the sample is changed.

6) Acid resistance After dipping in an aqueous nitric acid solution (PH1) for 6 hours, it is examined whether or not the film on the sample surface is changed.

With respect to the above-mentioned evaluation items, Table 1 collectively shows the evaluation results of Examples and Comparative Examples.

[0116]

[Table 1]

As can be seen from Table 1, the above-mentioned Examples 1 to 1
All 29 samples are superior to the samples of Comparative Examples 1 to 4 in terms of adhesion and scratch resistance (steel wool). Moreover, all the samples of Examples 1 to 29 described above are superior in chemical resistance to acid to the samples of the second and fourth comparative examples. Also, hot water resistance, heat resistance,
In terms of alkali resistance, the durability is equivalent to that of the comparative example.

This is considered to be due to the following.

In the hard coat layers of Examples 1 to 29, the pressure of the mixed gas was 0.5 to 12 Pa by PECVD using a mixed gas of an alkoxysilane compound and oxygen gas.
The range is controlled. Thereby, Examples 1-29
The composition and structure of the hard coat layer are excellent in durability and composition. In addition to this, since the hard coat layer does not contain a high-refractive index material, it can be easily made transparent by adjusting the amount of oxygen, so that the film thickness can be increased, and this thickness further increases the mechanical durability. And chemical resistance are obtained. Therefore, the hard coat layer is
It has excellent mechanical durability and chemical resistance, and acts as a hard coat layer.

Further, the modified layers of Examples 1 to 29 are arranged between the hard coat layer and the base material and have good adhesion to both, so that the adhesion between the coating and the base material is improved. . Further, the modified layers of Examples 1 to 29 are considered to have the function of absorbing the impact applied to the hard coat layer, and enhance the mechanical durability of the coating.

From the above, it is considered that the coating films of Examples 1 to 29 are excellent in environmental resistance.

Further, since the hard coat layers of Examples 1 to 29 contain the oxide of silicon which is a low refractive index material, they can be easily made transparent even if they are thick. The modified layer is
In addition to the hard coat layer that acts as a hard coat layer, it is provided on the base material side of the hard coat layer,
Since the mechanical durability and chemical resistance of the modified layer itself are not required, the film thickness can be reduced. Therefore, the modified layers of Examples 1 to 29 contain an oxide of Ti, which is a high-refractive index material that is apt to lack oxygen, but have a small film thickness.
Can be easily made transparent.

Therefore, the modified layer, the hard coat layer and the like formed in each of the above Examples 1 to 29 are excellent in the environmental resistance,
Moreover, since it is transparent to visible light, it is suitable for use as a coating for plastic lenses for spectacles.

In each of Examples 1 to 29 described above, the refractive index of the modified layer is continuously changed in the film thickness direction by gradually changing the high frequency output or the gas flow rate when forming the modified layer. I am letting you. In the manufacturing methods of Examples 1 to 29, the high frequency output or the gas flow rate can be set such that the refractive index of the modified layer is continuous with the refractive index of the base material and the refractive index of the first hard coat layer. . By disposing such a modified layer between the base material and the first hard coat layer, it is possible to effectively prevent the occurrence of interference fringes when light is incident from the outside. Therefore, this Example 1
When used as a coating of a plastic lens for eyeglasses, the coating of No. 29 prevents generation of interference fringes and is optically excellent.

As a 30th embodiment of the present invention, a coating film comprising a modified layer, first, second and third hard coat layers and a multilayer antireflection film is formed on the surface of a plastic lens as a base material. A method of manufacturing the provided plastic lens will be described.

The plastic lens as the base material is composed of a polymer of diethylene glycol bisallyl carbonate (CR-39 manufactured by Pittsburgh Plate Glass Co., Ltd.).

On this base material, Balzels (Balze)
rs) PECVD equipment and vacuum evaporation equipment,
A coating film having the above-described structure is formed. The vacuum chamber of the PECVD apparatus and the vacuum chamber of the vacuum vapor deposition apparatus are connected by a load lock chamber. The load lock chamber is a space for moving the base material from the vacuum chamber of the PECVD apparatus to the vacuum chamber of the vacuum deposition chamber while maintaining a vacuum.

The vapor deposition apparatus is constructed so that the vapor deposition source is heated by the electron beam.

First, as a preparatory step, the lens of the base material is cleaned by passing it through an ultrasonic cleaning machine and placed in a base material holder in the vacuum chamber of the PECVD apparatus. After that, 2.7 in the vacuum chamber.
Exhaust to × 10 to ⁴ Pa.

Next, the step of forming the modified layer will be described.

By heating a container containing methyltriethoxysilane, which is connected to the vacuum chamber, methyltriethoxylane is vaporized, and methyltriethoxylane gas is flown into the vacuum chamber at a flow rate of 100 SCCM. When the pressure in the vacuum chamber reaches 0.7 Pa, apply 5 A to the electromagnet coil outside the vacuum chamber.
Current is applied to apply a magnetic field between the electrodes, and at the same time, a high frequency output of 2 KW is applied to the cathode for 3 minutes. This allows
Plasma is generated between the electrodes. The magnetic field stabilizes the low pressure arc discharge. The flow rate of methyltriethoxysilane gas during this period is 100 SCCM. After that, the high-frequency output of the cathode is gradually increased stepwise at a rate of 40 W / min, and is controlled to reach 2.5 KW in 12 minutes. The flow rate of the methyltriethoxysilane gas for 12 minutes is set to 180 SCCM and kept constant.

In this step, the modified layer is formed by controlling the film thickness to 500 nm. The refractive index of the modified layer gradually changes in the film thickness direction.

Next, the steps of forming the first, second and third hard coat layers will be described.

Continuously to the step of forming the modified layer, 50 SCCM of oxygen gas was supplied to the vacuum chamber, and the pressure of the vacuum chamber was set to 2.1.
Pa, flow rate of methyltriethoxysilane gas 18
0SCCM, high frequency output 2.5KW, electromagnet coil 5A
Then, the first hard coat layer is formed. The thickness of the first hard coat layer is 0.1 μm.

After that, the oxygen gas flow rate was increased to 100 SCCM, the vacuum chamber pressure was set to 2.5 Pa, the cathode high frequency output was changed to 3 KW, the methyltriethoxysilane gas flow rate was 180 SCCM, and the electromagnet coil 5A was used. 2 hard coat layer is formed. The thickness of the second hard coat layer is 0.2 μm.

Finally, the flow rate of oxygen gas was increased to 200 SCCM, the conductance of the exhaust system was adjusted by a variable orifice so that the vacuum chamber pressure was kept at 2.5 Pa, the flow rate of methyltriethoxysilane gas was 180 SCCM, and the electromagnet was set. A third hard coat layer is further formed while the high frequency output of the coil 5A and the cathode is 3 KW. The thickness of the third hard coat layer is 0.2 μm
To

By this step, a hard coat layer having a total film thickness of 0.5 μm is formed.

Next, the substrate lens having the modified layer and the hard coat layer described above is moved to the load lock chamber together with the substrate holder, and one surface of the substrate lens is oriented toward the vapor deposition source of the vacuum vapor deposition apparatus. The substrate lens is turned so that the substrate lens faces to the vacuum chamber, and the substrate lens is sent to the vacuum deposition chamber.

Then, the vacuum chamber of the vacuum evaporation apparatus is set to 1.3 ×
After evacuating to 10 to ³ Pa, an antireflection film consisting of the following four layers was formed on the third hard coat layer on the surface of the substrate lens facing the vapor deposition source by the electron beam heating vapor deposition method under the following vapor deposition conditions. Formed by. However, as the vapor deposition source, TiO _x (0 <x <2) is used for the first layer and the third layer, and SiO ₂ is used for the second layer and the fourth layer.

Various conditions of vacuum vapor deposition (where A represents angstrom) First layer Titanium dioxide 114A (geometric film thickness) 0.049λ (optical film thickness) Pressure during vapor deposition 4 × 10 to ³ Pa (O ₂ atmosphere) second layer silicon dioxide 380A (geometrical film thickness) 0.1605λ (optical film thickness) deposition pressure 1 × 10 to ³ Pa third layer titanium dioxide 1167A (geometrical film thickness) 0.5λ (Optical film thickness) Pressure during vapor deposition 5 × 10 to ³ Pa (O ₂ atmosphere) Fourth layer Silicon dioxide 871A (Geometric film thickness) 0.244λ (Optical film thickness) Pressure during vapor deposition 1 × 10 to ³ However, the above-mentioned optical film thickness is defined by the product of the refractive index of the layer and the geometric film thickness. Also, the central wavelength λ = 525 nm
The refractive index of titanium dioxide in the first and third layers is 2.25, and the refractive index of silicon dioxide in the second and fourth layers is 1.47.

As a result, after the antireflection film is formed on one surface of the base lens, the other surface is turned toward the evaporation source by the base surface reversing mechanism attached to the lens substrate holder. Again, the antireflection film is formed under the same vapor deposition conditions as described above.

Through these steps, a plastic lens having a modified layer, first, second and third hard coat layers and a multilayer antireflection film on both sides of the base lens can be manufactured.

The plastic lens provided with the coating of the 31st embodiment of the present invention has the same structure as the plastic lens provided with the coating of the 31st embodiment, but the film thickness of the 31st hard coat layer is changed. The thickness of the second hard coat layer was 0.5 μm, the thickness of the third hard coat layer was 1.0 μm, and the total thickness of the hard coat layer was 2 μm. The rest of the configuration is the same as that of the thirtieth embodiment and the manufacturing process is also the same, so a description thereof will be omitted.

The plastic lens provided with the coating of the 32nd embodiment of the present invention has the same structure as the plastic lens provided with the coating of the 30th embodiment, but the film thickness of the first hard coat layer is changed. 1.2 μm, the thickness of the second hard coat layer is 1.4 μm, and the thickness of the third hard coat layer is 1.
4 μm, and the total film thickness of the hard coat layer was 4 μm. The rest of the configuration is the same as that of the thirtieth embodiment and the manufacturing process is also the same, so a description thereof will be omitted.

Next, as a 33rd embodiment of the present invention,
On the surface of the plastic lens of the base material, the modified layer, the first,
A method of manufacturing a plastic lens on which a coating film including the second and third hard coat layers and a multilayer antireflection film is formed will be described.

In this example, a lens made of a polyurethane polymer was used as the substrate. As the PECVD equipment, the same equipment as in the 30th embodiment was used.

First, as a preparatory step, the base lens is cleaned by passing it through an ultrasonic cleaning machine, and it is set on a carousel type substrate holder between the cathode electrode and the anode electrode in the vacuum chamber of the PECVD apparatus, and then 2.7. Exhaust to × 10 to ⁴ Pa.

Next, the step of forming the modified layer will be described.

By heating the container containing methyltriethoxysilane connected to the vacuum chamber, methyltriethoxylane is vaporized, and methyltriethoxylane gas is flown into the vacuum chamber at a flow rate of 35 SCCM. At the same time, by heating the container containing the dimethoxydimethylsilane connected to the vacuum chamber, the dimethoxydimethylsilane is vaporized, and the flow rate of the dimethoxydimethylsilane gas is 148SCC.
Flow into the vacuum chamber with M. When the pressure in the vacuum chamber reaches 2.0 Pa, a current of 5 A is applied to the electromagnet coil outside the vacuum chamber while maintaining the gas flow rate to apply a magnetic field between the electrodes. Then, while gradually increasing the flow rate of the methyltriethoxysilane gas at a rate of 110 SCCM per minute, and at the same time gradually decreasing the flow rate of the dimethoxydimethylsilane gas at a rate of 98.7 SCCM per minute,
A high frequency output of 2 KW is applied to the cathode to form a modified layer.

In this step, the modified layer is formed by controlling the film thickness to 500 nm.

The steps of forming the first, second and third hard coat layers will be described.

Further, subsequently, the flow rate of methyltriethoxysilane is 200 SCCM and the flow rate of oxygen gas is 50 SC.
When the CM flowed and the pressure in the vacuum chamber became 2.0 Pa and the flow rate became stable, a current of 5 A was passed through the external electromagnet coil and, at the same time, a high-frequency output of 2.5 KW was applied to the cathode to form the first hard coat layer. To form. The thickness of the first hard coat layer is 0.10 μm.

Further, the flow rate of oxygen gas is set to 100 SCCM.
, The conductance of the exhaust system is adjusted by the variable orifice so that the pressure in the vacuum chamber becomes 2.0 Pa, the high frequency output of the cathode is increased to 3 KW, the flow rate of methyltriethoxysilane gas is 200 SCCM, and the external electromagnet coil 5A is increased. To form a second hard coat layer. The thickness of the second hard coat layer is 0.2 μm.

Finally, the flow rate of oxygen gas was set to 200 SCCM.
The pressure of the vacuum chamber is 2.0 Pa, the high frequency output of the cathode is 3 KW, the flow rate of methyltriethoxysilane gas is 200 SCCM, and the external electromagnet coil 5A is used to form the third hard coat layer. The thickness of the third hard coat layer is 0.2 μm.

As a result, a hard coat layer having a total film thickness of 0.5 μm is formed.

Next, the base lens on which the modified layer and the hard coat layer are formed is moved to the load lock chamber together with the base holder, and one surface of the base lens is directed toward the vapor deposition source of the vacuum vapor deposition apparatus. The substrate lens is turned so that the substrate lens faces to the vacuum chamber, and the substrate lens is sent to the vacuum deposition chamber.

Then, the vacuum chamber of the vacuum vapor deposition apparatus is set to 1.3 ×
After evacuating to 10 to ³ Pa, an antireflection film consisting of the following four layers was formed on the third hard coat layer on the surface of the substrate lens facing the vapor deposition source by the electron beam heating vapor deposition method under the following vapor deposition conditions. Formed by. However, as the vapor deposition source, TiO _x (0 <x <2) is used for the first layer and the third layer, and SiO ₂ is used for the second layer and the fourth layer.

Various conditions of vacuum vapor deposition (where A represents angstrom) First layer Titanium dioxide 130A (geometric film thickness) 0.055λ (optical film thickness) Pressure during vapor deposition 4 × 10 ³ Pa (O ₂ atmosphere) second layer silicon dioxide 333A (geometrical film thickness) 0.0915λ (optical film thickness) deposition pressure 1 × 10 to ³ Pa third layer titanium dioxide 1189A (geometrical film thickness) 0.5λ (Optical film thickness) Pressure during vapor deposition 5 × 10 to ³ Pa (O ₂ atmosphere) Fourth layer Silicon dioxide 880A (Geometric film thickness) 0.242λ (Optical film thickness) Pressure during vapor deposition 1 × 10 to ³ However, the above-mentioned optical film thickness is defined by the product of the refractive index of the layer and the geometric film thickness. Also, the central wavelength λ = 525 nm
The refractive index of titanium dioxide in the first and third layers is 2.25, and the refractive index of silicon dioxide in the second and fourth layers is 1.47.

Thus, after the antireflection film is formed on one surface of the base lens, the other surface is turned toward the evaporation source by the base surface reversing mechanism attached to the lens substrate holder. Again, the antireflection film is formed under the same vapor deposition conditions as described above.

Through these steps, a plastic lens having a modified layer, first, second and third hard coat layers and a multilayer antireflection film on both sides of the base lens can be manufactured.

The plastic lens provided with the coating of the thirty-fourth embodiment of the present invention has the same structure as the plastic lens provided with the coating of the thirty-third embodiment, but the thickness of the first hard coat layer is changed. 0.5 μm, the thickness of the second hard coat layer is 0.5 μm, and the thickness of the third hard coat layer is 1.
The total film thickness of the hard coat layer was 2 μm. The rest of the configuration is the same as that of the 33rd embodiment, and the manufacturing process is also the same, so description thereof will be omitted.

The plastic lens provided with the coating of the thirty-fifth embodiment of the present invention has the same constitution as the plastic lens provided with the coating of the thirty-third embodiment, but the thickness of the first hard coat layer is changed. 1.2 μm, the thickness of the second hard coat layer is 1.4 μm, and the thickness of the third hard coat layer is 1.
The total thickness of the hard coat layer was 4 μm. The rest of the configuration is the same as that of the 33rd embodiment, and the manufacturing process is also the same, so description thereof will be omitted.

The plastic lens of the 36th embodiment is
On the surface of the plastic lens of the base material, a coating film comprising a modified layer, first, second and third hard coat layers and a multilayer antireflection film is provided in order. This manufacturing method will be described.

First, as a preparatory step, the polyurethane lens was cleaned by passing it through an ultrasonic cleaner, and then installed in a vacuum chamber of a PECVD apparatus manufactured by Balzers Co., Ltd., and 2.7 × 10 ⁴ P was used.
Exhaust to a.

Next, the step of forming the modified layer is performed.

Flow rate of dimethyldiethoxylane gas is 11
A gas of tetraisopropoxytitanium was caused to flow into the vacuum chamber by SCCM at a flow rate of 9 SCCM. The pressure in the vacuum chamber is 2.9.
When Pa is reached, a current of 2.6 A is applied to the electromagnet coil outside the vacuum chamber to apply a magnetic field between the electrodes, and at the same time, a high frequency output of 0.6 KW is applied to the cathode for 45 seconds. afterwards,
The flow rate of tetraisopropoxytitanium gas is changed from 9 SCCM to 0 SCCM, and at the same time, the flow rate of dimethyldiethoxysilane gas is changed from 11 SCCM to 100 SCCM in 10 minutes.

By this step, the modified layer is formed by controlling the film thickness to 500 nm.

Then, the flow rate of dimethyldiethoxysilane gas is 100 SCCM and the flow rate of oxygen gas is 35 S.
When the flow rate was stabilized by CCM and the pressure in the vacuum chamber became 2.9 Pa and the flow rate became stable, a current of 2.6 A was passed through the external electromagnet coil and, at the same time, a high frequency output of 0.8 KW was applied to the cathode, A hard coat layer is formed. The thickness of the first hard coat layer is 0.10 μm.

Further, the flow rate of oxygen gas was increased to 70 SCCM, the conductance of the exhaust system was adjusted by the variable orifice so that the pressure in the vacuum chamber became 2.9 Pa, and the high frequency output of the cathode was raised to 1 KW, and the dimethyl concentration was increased. The second hard coat layer is formed with a flow rate of diethoxysilane gas of 100 SCCM and an external electromagnet coil of 2.6A. The thickness of the second hard coat layer is 0.2 μm.

Finally, the flow rate of oxygen gas was changed to 140 SCCM.
The third hard coat layer is formed while maintaining other conditions. The thickness of the third hard coat layer is
0.2 μm.

As a result, a hard coat layer having a total film thickness of 0.5 μm is formed.

Next, the substrate lens having the above-mentioned coating formed thereon is moved together with the substrate holder into the load lock chamber so that one surface of the substrate lens faces the deposition source of the vacuum deposition apparatus. The orientation of the base lens is changed and the base lens is sent to the vacuum deposition chamber.

Then, the vacuum chamber of the vacuum vapor deposition apparatus is set to 1.3 ×
After evacuating to 10 to ³ Pa, an antireflection film consisting of the following four layers was formed on the third hard coat layer on the surface of the substrate lens facing the vapor deposition source by the electron beam heating vapor deposition method under the following vapor deposition conditions. Formed by. However, as the vapor deposition source, TiO _x (0 <x <2) is used for the first layer and the third layer, and SiO ₂ is used for the second layer and the fourth layer.

Various conditions of vacuum vapor deposition (where A represents angstrom) First layer Titanium dioxide 130A (geometric film thickness) 0.055λ (optical film thickness) Pressure during vapor deposition 4 × 10 ³ Pa (O ₂ atmosphere) second layer silicon dioxide 333A (geometrical film thickness) 0.0915λ (optical film thickness) deposition pressure 1 × 10 to ³ Pa third layer titanium dioxide 1189A (geometrical film thickness) 0.5λ (Optical film thickness) Pressure during vapor deposition 5 × 10 to ³ Pa (O ₂ atmosphere) Fourth layer Silicon dioxide 880A (Geometric film thickness) 0.242λ (Optical film thickness) Pressure during vapor deposition 1 × 10 to ³ However, the above-mentioned optical film thickness is defined by the product of the refractive index of the layer and the geometric film thickness. Also, the central wavelength λ = 525 nm
The refractive index of titanium dioxide in the first and third layers is 2.25, and the refractive index of silicon dioxide in the second and fourth layers is 1.47.

As a result, after the antireflection film is formed on one surface of the base lens, the other surface is turned toward the evaporation source by the base surface reversing mechanism attached to the lens substrate holder. Again, the antireflection film is formed under the same vapor deposition conditions as described above.

Through these steps, a plastic lens having a modified layer, first, second and third hard coat layers and a multilayer antireflection film on both sides of the base lens can be manufactured.

The plastic lens provided with the coating of the thirty-seventh embodiment of the present invention has the same structure as the plastic lens provided with the coating of the thirty-sixth embodiment, but the thickness of the first hard coat layer is changed. 0.5 μm, the thickness of the second hard coat layer is 0.5 μm, and the thickness of the third hard coat layer is 1.
The total film thickness of the hard coat layer was 2 μm. The rest of the configuration is the same as that of the 33rd embodiment, and the manufacturing process is also the same, so description thereof will be omitted.

The plastic lens provided with the coating of the 38th embodiment of the present invention has the same structure as the plastic lens provided with the coating of the 36th embodiment, but the thickness of the first hard coat layer is 1.2 μm, the thickness of the second hard coat layer is 1.4 μm, and the thickness of the third hard coat layer is 1.
The total thickness of the hard coat layer was 4 μm. The rest of the configuration is the same as that of the 33rd embodiment, and the manufacturing process is also the same, so description thereof will be omitted.

Next, as a fifth comparative example, a modified layer was formed on the surface of the plastic lens of the base material, and the first, second and third layers were formed.
A method for producing a plastic lens provided with a coating composed of the hard coat layer and the multilayer antireflection film will be described.

The plastic lens provided with the coating of this comparative example is almost the same as that of the 30th embodiment in the material of the base material, the modified layer, and the manufacturing steps of the first, second and third hard coat layers. , The thickness of the first hard coat layer is 0.10 μm,
The thickness of the hard coat layer is 0.15 μm, the thickness of the third hard coat layer is 0.15 μm, and the total thickness of the hard coat layer is 0.4 μm. Since the other structure is the same as that of the thirtieth embodiment, the description thereof will be omitted.

In the plastic lens of the sixth comparative example, the film thickness of the first hard coat layer is 2.0 μm, the film thickness of the second hard coat layer is 1.5 μm, and the film thickness of the third hard coat layer. Is 1.5 μm, and the total thickness of the hard coat layer is 5
μm. The rest of the configuration and manufacturing process are the same as in the thirtieth embodiment, so description will be omitted.

Next, as a seventh comparative example, a modified layer was formed on the surface of the plastic lens of the substrate, and the first, second and third layers were formed.
A method for producing a plastic lens provided with a coating composed of the hard coat layer and the multilayer antireflection film will be described.

The plastic lens provided with the coating of this comparative example is the same as that of the 33rd embodiment in the material of the base material, the modified layer, and the manufacturing steps of the first, second and third hard coat layers.
The thickness of the first hard coat layer is 0.10 μm, the thickness of the second hard coat layer is 0.15 μm, the thickness of the third hard coat layer is 0.15 μm, and the total thickness of the hard coat layer is Is 0.4 μm. Since the other structure is the same as that of the 33rd embodiment, description thereof will be omitted.

In the plastic lens of the eighth comparative example, the film thickness of the first hard coat layer was 2.0 μm, the film thickness of the second hard coat layer was 1.5 μm, and the film thickness of the third hard coat layer. Is 1.5 μm, and the total thickness of the hard coat layer is 5
μm. The rest of the configuration and manufacturing process are the same as in the 33rd embodiment, so description will be omitted.

Next, the mechanical durability of the samples of the plastic lens for spectacles obtained in the above Examples 30 to 38 and Comparative Examples 5 to 8 was evaluated. As the evaluation items, the items of the samples of Examples 1 to 29 were evaluated, and the impact resistance and interference fringes were evaluated. The evaluation contents of impact resistance and interference fringes are
It is as follows.

Impact resistance In each of the above-described Examples and Comparative Examples, a sample using a lens having a center thickness of 1.2 mm as a base lens is used as a sample. And 127 cm based on US FDA standards
A steel ball weighing 16.4 g was dropped from the height to the center of the sample lens, and one that did not crack was passed.

Interference fringes When natural light is irradiated, interference fringes that are hardly visible are regarded as good, and interference fringes that are visible are regarded as defective.

Regarding the above-mentioned evaluation items, Examples 30 to 3 are used.
8 and Comparative Examples 5 to 8 are collectively shown in Table 2.

[0189]

[Table 2]

As can be seen from Table 2, Example 30 described above
All the samples of Nos. 38 to 38 are superior in durability, scratch resistance (steel wool), and impact resistance to all the samples of Comparative Examples 5 to 8. Further, in the heat resistance, the samples of Examples 30 to 38 are superior to the samples of Comparative Examples 3 and 4, and are equivalent to the samples of Comparative Examples 1 and 2. Further, regarding the scratch resistance (sand eraser) and the chemical resistance, the same durability as the comparative example is shown.

Regarding interference fringes, the present Example 30-
All 38 samples are superior to all samples of Comparative Examples 5-8.

It is considered that this is due to the following reasons.

The hard coat layers of Examples 30 to 38 were
By PECVD using a mixed gas of an alkoxysilane compound and oxygen gas, the pressure of the mixed gas is 0.5 to 12 P.
It is controlled within the range of a. As a result, the hard coat layer of this example has a composition and structure that are excellent in durability. In addition to this, since the thickness of this hard coat layer is made thicker than 0.4 μm, mechanical durability and chemical resistance are obtained by this thickness.
Moreover, since the hard coat layer is thinner than 5 μm, the internal stress is small, which increases the adhesion between the coating and the substrate. Therefore, the hard coat layer has mechanical durability,
Since it has excellent chemical resistance and high adhesion, it acts as a hard coat layer. Further, since the hard coat layer has a constant refractive index in the film thickness direction, it can be easily formed even if the film thickness is large.

Further, the modified layers of Examples 30 to 38 are arranged between the hard coat layer and the base material and have good adhesion to both, so that the adhesion between the coating and the base material is improved. There is.
Furthermore, it is considered that the modified layers of Examples 30 to 38 have a function of absorbing the impact applied to the hard coat layer and enhancing the adhesiveness by making the thickness greater than 100 nm and thinner than 900 nm, and the mechanical properties of the coating film. Increased durability.

Also, from an optical viewpoint, the present Examples 30 to 3 were used.
In No. 8, by setting the total film thickness of the first, second, and third hard coat layers to more than 0.4 μm and less than 5 μm, interference fringes are suppressed as shown in Table 2. Has been done.

The modified layer can suppress the generation of interference fringes due to the difference in the refractive index between the base material and the coating film by changing the refractive index in the film thickness direction. Moreover, since the modified layer has a small thickness, the refractive index can be easily changed.

In the coatings of the plastic lenses of Examples 30 to 38 described above, the optical thickness of each layer of the antireflection film was 0. 05 × λ or more and 0.15 × λ or less, the optical thickness of the third layer is 0.36 × λ or more and 0.49 × λ or less, and the optical thickness of the fourth layer is Since it is set to be not less than 0.15 × λ and not more than 0.35 × λ, it is possible to effectively suppress the generation of interference fringes due to the difference in refractive index between the antireflection film and air.

Further, the modified layer, the hard coat layer, the antireflection film and the like formed in each of the above Examples 30 to 38 are transparent to visible light.

Therefore, the plastic lenses for spectacles provided with the coatings of Examples 30 to 38 are transparent and have excellent aesthetic appearance.

Further, in the method for manufacturing the plastic lens of Examples 1 to 38, the modified layer, the first, second and third hard coat layers and the antireflection film are continuously formed by only the dry process. You can This manufacturing method has very simple steps, and unlike the conventional wet process, waste liquid treatment, surface activation treatment, condensation curing step, etc. are not required, so the manufacturing cost can be reduced. . Also,
It can also solve environmental pollution problems. Further, in the manufacturing method of the present embodiment, only by changing the film forming conditions such as the type of gas and the pressure in the vacuum container, a single PECVD apparatus can be used to manufacture a film in which the film properties such as the refractive index are changed. be able to. Therefore, unlike a wet process, it is not necessary to prepare a solution in advance, and a custom-made lens such as a lens of two lenses in one lot can be manufactured in a short delivery time.

In the above-mentioned Examples 1 to 38, the PECVD apparatus for increasing the plasma density by the magnetic field was used, but it is of course possible to use the plasma CVD apparatus which does not use the magnetic field.

In Examples 30 to 38 described above, the composition of the first layer, the second layer, the third layer and the fourth layer of the antireflection film was TiO ₂ ,
An antireflection film having a high visible light transmittance was formed by using SiO ₂ , TiO ₂ , or SiO ₂ , but when the visible light transmittance of the antireflection film may be low, for example, the base material is colored. In the case of a lens or when the structure of the present embodiment is used as a coating of a base material on which infrared light is incident, TiO _x ,
It is also possible to use SiO _y , TiO _x , or SiO _y . However, 0 <x <2 and 0 <y <2.

Further, a water-repellent thin film made of fluorine or a silicon compound can be formed on the antireflection film formed in each of Examples 1 to 38 by vapor phase growth method such as vacuum deposition. Further, the anti-water stain coating can be formed on the antireflection film by a wet process by a dipping surface treatment method called dipping. For example, an organic silazane compound represented by the following unit formula can be preferably used as the dipping solution.

[0204] Further, in the above-mentioned Examples 1 to 38, the flow rate of the gas when the modified layer or the hard coat layer is formed by the PECVD apparatus may be appropriately selected according to the purpose, but is preferably Si. 80 to 200 SCCM in the case of an organic compound gas containing OH and an alkoxy group, and 30 to 20 in the case of an organic compound gas containing Ti and an alkoxy group.
0 SCCM, and oxygen gas is set to 50 to 200 SCCM, and these are used alone or in combination and flow into the vacuum chamber.

The pressure in the vacuum chamber at this time is 0.5.
It is desirable to stabilize in the range of ~ 12Pa. By setting this pressure range, a modified layer or a hard coat layer having excellent durability can be formed for the above-mentioned evaluation items.

Further, as the energy applied to the electrodes, it is desirable to apply a high frequency of 2 to 3.5 KW.

Further, when forming the modified layer, it is possible to continuously change the refractive index in the same thin film by continuously changing the flow rate or the high frequency output (RF power) at the time of introducing gas. Become. Thereby, the refractive index of the modified layer can be made close to the refractive index of the base material on the side of the base material and close to the refractive index of the hard coat layer on the side of the hard coat layer.

[0208]

As described above, according to the present invention, a film having high environment resistance and capable of being transparent is manufactured on an optical article in a continuous process by a vapor phase growth method. be able to.

When the thickness of the modified layer and the hard coat layer is the same as that of the present invention, the optical properties are excellent in adhesion, scratch resistance, warm water resistance, heat resistance, chemical resistance and the like. An article is obtained.

Claims (10)

[Claims] 1. A synthetic resin base material, and at least one of a Si-based compound and / or a Ti-based compound formed on the base material, wherein the refractive index changes from the base material side in the thickness direction. A modified layer formed by a CVD method and a hard coat layer formed by a CVD method containing Si and O, wherein the hard coat layer has a thickness of more than 0.4 μm.
An optical article characterized by being thinner than μm. 2. The film thickness of the modified layer according to claim 1,
An article with a coating, characterized in that it is thicker than 100 nm and thinner than 900 nm. 3. An optical article according to claim 1 or 2, further comprising a single-layer or multi-layer antireflection film formed by a vacuum deposition method, the antireflection film being formed on the hard coat layer. 4. A transparent substrate is prepared, and at least one of an organic compound gas containing Si and / or an organic compound gas containing Ti is used, and the above-mentioned substrate is formed on the substrate by a chemical vapor deposition method using plasma. First step of forming a modified layer in which the refractive index changes from the substrate side in the thickness direction, and a chemical vapor deposition method using plasma using a mixed gas of an organic compound gas containing Si and oxygen gas And a second step of forming on the modified layer a hard coat layer thicker than 0.4 μm and thinner than 5 μm and thicker than the modified layer. . 5. The method for producing an optical article according to the first step and / or the second step of claim 4, wherein the film is formed while gradually increasing or decreasing the energy supplied to the plasma. 6. The method of manufacturing an optical article according to claim 1, wherein the film is formed while gradually increasing or decreasing the flow rate of the gas. 7. The pressure according to claim 4, 5 or 6, wherein the gas atmosphere in the first step and / or the gas atmosphere of the mixed gas in the second step is greater than 0.4 Pa.
A method for producing an optical article, which comprises controlling the pressure to be lower than Pa. 8. The method for manufacturing an optical article according to claim 4, 5 or 6 or 7, wherein the organic compound gas containing Si has an alkoxy group. 9. The organic compound gas according to claim 4, 5 or 6 or 7, wherein the organic compound gas containing Si contains at least one of methyltriethoxysilane, dimethoxydimethylsilane and dimethyldimethoxysilane. A method for manufacturing an optical article. 10. A method of manufacturing an optical article according to claim 4, 5 or 6 or 7 or 8 or 9, wherein the Ti-containing organic compound gas contains tetraisopropoxy titanium.