JPH09211203A - Optical article having antireflection film and method for manufacturing the same - Google Patents

Abstract

(57) An object of the present invention is to provide an optical component having a coating formed by sputtering, having high durability, and having a coating which can be manufactured by a manufacturing process by consistent bright layer growth. A refractive index modification layer and a hard coat layer are arranged between a synthetic resin substrate and an antireflection film. The refractive index modified layer contains at least one of a Si-based compound and a Ti-based compound, and the refractive index changes in the thickness direction. The hard coat layer has a larger film thickness than the modified layer, has a constant refractive index, and contains Si and O. The antireflection film is
It is formed by alternately stacking a TiO ₂ film and a SiO ₂ film by sputtering. The TiO ₂ film has a wavelength of 500
The refractive index for light having a wavelength of not less than nm and not more than 550 nm is 2.3.
It is 6 or more and 2.60 or less.

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.

Further, in the immersion surface treatment technique, if the material of the coating film is different, the composition of the dipping agent is also different. For this reason,
For example, when forming a hard coat on a plastic lens, every time a new high-refractive index lens is developed, a dipping agent must be developed to form a hard coat having a refractive index compatible with this. I won't. 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 article in which a plurality of coatings need to be laminated, if these coatings are all formed by the dipping surface treatment method, many kinds of expensive dipping agents are required, which is not suitable for the manufacturing cost. There are also problems.

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. Method is used. At this time, by using two to three types of hard coat equipment, functionally selecting a hard coat film corresponding to several types of plastic lenses, and forming the same hard coat film on a plurality of types of plastic lenses, Measures have been taken to reduce the manufacturing cost.

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.

Further, in JP-A-5-107402, when a TiO ₂ layer is used as an antireflection film, if the refractive index is made larger than 2.35, the packing density inside the thin film increases and the thin film It is described that the internal true stress, that is, the compressive stress becomes large, and film peeling may partially occur.

[0015]

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 warm water immersion test at 10 ° C. for 10 minutes, the film is bulged, which has the drawback that good appearance cannot be obtained.

Further, as in 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 time for curing 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, in the techniques described in JP-A-7-56001 and JP-A-7-56002, it is possible to suppress the generation of interference fringes by changing the refractive index of the hard coat layer. In order for this layer to actually act as a hard coat layer for protecting the plastic lens, it needs to be a hard film. Therefore, the hard coat layer is usually a thick film (usually 3 μm).
Above). However, in the above disclosed technique, in order to keep the space charge composed of positive and negative ions such as metal and oxygen generated in the plasma in an equilibrium state, it is necessary to control the positive and negative ions to stabilize. is there. However, in practice, performing this control for a long time tends to make the bias voltage generated on the substrate side unstable. Therefore, the plasma discharge
Due to the phenomenon of intermittent or interruption, the atomic composition ratio inside the formed thin film becomes non-uniform, the oxygen bond state in the hard coat layer is lost, and the formed oxide film contains a lower oxide. The hard coat layer itself absorbs and is colored.

Therefore, when the hard coat layer is actually formed by the techniques described in JP-A-7-56001 and JP-A-7-56002, the hard coat layer is colored, which causes a problem in practical use. This coloring becomes more remarkable as the film thickness is increased in order to improve the mechanical durability of the hard coat layer.

Therefore, transparent plastic lenses such as spectacles can be applied to Japanese Patent Laid-Open Nos. 7-56001 and 7-560.
It is actually very difficult to carry out the technique described in Japanese Patent Laid-Open No. 02-202.

The present inventor also tried to form a modified layer having a refractive index changing in the thickness direction between the substrate and the hard coat layer under various conditions. However, in the formed optical article, there are problems that the film is peeled off, a problem occurs in optical characteristics, and that it is weak against impact.

Further, when an organic silicone hard coat by conventional dipping (immersion treatment) is provided on a plastic lens, the lens is soaked in a dipping solution in the vertical direction, so that the film thickness distribution in the radial direction of the lens becomes uneven. I will end up. For example, even if the refractive index of the lens and the hard coat are made approximately the same, the difference in reflection at the interface between the two causes the interference fringes (ripple) to be emphasized, which impairs the aesthetic appearance. Absent. This means that the lens itself has a curved surface,
It turned out that it appears particularly noticeably.

When the antireflection film is formed by the vacuum evaporation method, the antireflection film is formed on one lens surface, the lens surface is inverted again in the vacuum chamber, and then the other lens surface is reflected. Form a barrier film. Therefore, the film formed on the first lens surface and the film formed after reversing the film are heated in the vacuum chamber. Since the surfaces are only subjected to a heating history once, the stresses remaining inside the thin films differ from each other, which causes a problem in mechanical durability. In addition, the appearance problem of the antireflection film due to the adhesion of dust to the lens surface due to the operation of the double-sided reversing mechanism is also considered.

Furthermore, in the antireflection film formed by the vacuum evaporation method, the spectral characteristics are likely to change with time in reflectance and transmittance. That is, the refractive index of the film tends to change with time. Many of the possible causes are the presence of pores inside the film, and this is because water in the atmosphere is adsorbed by the pores.

The present invention solves the above problems, has an antireflection film formed by sputtering, has a large environment resistance, and is provided with a film that can be formed in a consistent process by a vapor phase growth method. It is intended to provide an optical article.

[0025]

In the present invention, an antireflection film is simultaneously formed on both surfaces of a substrate by a sputtering method. The antireflection film is composed of alternating TiO ₂ layers and SiO ₂ layers, and the TiO ₂ layers have an optical design wavelength λ of 5
In the range of 00 to 550 nm, the refractive index of the layer is 2.
36 to 2.60. The film peeling is solved by disposing the refractive index modification layer and the hard coat layer between the antireflection film and the base material by the plasma CVD method. Specifically, in order to achieve the above object, according to the present invention, a synthetic resin base material and at least one of a Si-based compound and a Ti-based compound formed on the base material are included in the thickness direction. Toward the modified layer and a hard coat layer formed on the modified layer, having a film thickness larger than that of the modified layer, having a constant refractive index, and containing Si and O. And on the hard coat layer,
The antireflection film is formed by alternately stacking TiO ₂ films and SiO ₂ films, and the TiO ₂ film has a refractive index of 2.36 or more and 2.3 or more for light having a wavelength of 500 nm or more and 550 nm or less. An optical article is provided which is 60 or less.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the refractive index of a TiO ₂ layer on an antireflection film formed by alternately laminating a TiO ₂ layer and a SiO ₂ layer formed of a sputtered film has a refractive index of 2.36 to 2.6.
The reason for setting to 0 will be described.

If the refractive index of the TiO ₂ layer is made larger than 2.61, the packing density inside the thin film increases,
The stress inside the thin film, that is, the compressive stress becomes large. Therefore, when the film does not have sufficient ductility, when the tension from the substrate side acts, the relative strength of the compressive stress of the thin film against this tension is large, so this tension acts on the breaking strength at the interface between the substrate and the thin film, It acts on the interface so as to release the elastic strain energy of the residual compressive stress of the thin film, and causes a so-called buckling phenomenon (protrusion of the film) that partially peels the thin film from the substrate. On the other hand, the TiO ₂ layer has a refractive index of 2.
It has been found that by setting the ratio to 36 to 2.60, it is possible to suppress the optical film from changing over time, and in particular, it has an advantage that the heat resistance becomes extremely high.

As a result of intensive studies on the above-mentioned drawbacks, the present inventors have found that the substrate, the TiO ₂ layer and the SiO ₂ layer are alternately laminated.
Between the antireflection film composed of the sputtered film and the base material,
It has been found that the above defects can be eliminated by forming a refractive index modification layer and a hard coat layer, which are formed of a mixture coating or a compound coating and are formed of a Si organic compound and / or a Ti organic compound, by a PECVD method. .

In the present invention, each monomer of the alkoxy group-containing organotitanium compound and the alkoxy group-containing organosilicon compound is made into a gas state in a decompression container, each monomer gas is introduced into a plasma atmosphere, and those monomers are introduced onto the substrate. By depositing a thin film of a monomer and a forming compound generated by plasma reaction while adjusting the flow rate ratio of each monomer, an organic or inorganic material with good intermediate adhesion between the base material and the hard coat. A compound refractive index modified layer is formed. Here, the first purpose of forming this refractive index modified layer is to increase the adhesion strength at the interface by providing a pseudo amorphous amorphous structure at the interface with the plastic substrate. Also, by adjusting the flow rate ratio of the monomer, the refractive index in the crystal axis of the growing thin film is changed, that is, by providing optical inhomogeneity, the oxidation degree of the thin film is changed or the packing density is changed. The purpose is to change the true stress itself formed inside the thin film by changing it, and to cancel the true stress between the hard coat film formed thereon and the antireflection film formed by sputtering.

In the present invention, as the base material, polycarbonate, polymethyl methacrylate and its copolymer, a polymer of diethylene glycol bisallyl carbonate (CR-39 manufactured by Pittsburgh Plate Glass Co., Ltd.), polyester, unsaturated polyester, acrylonitrile-styrene copolymer are used. Arbitrarily selected from polymers, vinyl chloride, polyurethane, epoxy resins, halogens (excluding fluorine), polymers of mono- or di (meth) acrylates containing hydroxyl groups and isocyanate compounds, or copolymers thereof. A base material made of a material can be used. Among the polyesters, polyethylene terephthalate is particularly preferably used.

The base material has a low refractive index of 1.
A high refractive index of 70 or more can be 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.

When the refractive index modifying layer and the hard coat layer are formed on the transparent resin substrate, Ti and Ti are used as the forming materials thereof.
Introducing a monomer and / or oxygen gas composed of a system-based and / or Si-based alkoxy group-containing organic compound into a vacuum chamber,
The reaction is performed in a plasma atmosphere to deposit a thin film on the transparent resin substrate. In particular, when forming the refractive index modified layer, it is preferable to control the pressure of these monomers in the plasma atmosphere by adjusting the flow rate ratio of each monomer.

Further, in the chemical vapor deposition (CVD) method using plasma, which is used for forming the modified layer and the hard coat layer in the present invention, discharge is performed by applying heat energy and electric energy to the source gas. This is a method of accelerating the reaction in a non-thermal equilibrium state in the plasma atmosphere and depositing a thin film on the substrate. Commonly used methods include a parallel plate electrode type, a capacitive coupling type or an inductive coupling type. . Particularly in the present invention, plasma-enhanced CVD (PE) in which an electric field and a magnetic field are applied in parallel to the main plane of the substrate.
The CVD method is preferable.

In the present invention, the gas to be reacted with the organic compound gas containing Si and the organic compound gas containing Ti is not particularly limited, but oxygen and nitrogen are generally used.

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 production method of the present invention, as the Si-containing organic compound used in the first and second steps, tetraethoxysilane Si (OC ₂ H ₅ ) ₄ and dimethoxydimethylsilane (CH ₃ ) ₂ Si ( OCH _{3) 2,} methyltrimethoxysilane _{CH 3 Si (OCH 3) 3} , tetramethoxysilane Si (OCH _{3) 4,} ethyltrimethoxysilane _{C 2 H 5 Si (OCH 3} ) 3, diethoxy dimethyl silane (C _{2 H 5 O) 2 Si (CH} 3) 2, methyltriethoxysilane _{CH 3 Si (OC 2 H 5} ) 3 and the like are suitably used.

In the manufacturing method of the present invention, the organic compounds containing Ti used in the first step include tetramethoxy titanium Ti (OCH ₃ ) ₄ , tetraethoxy titanium Ti (OC ₂ H ₅ ) ₄ , tetra -i- propoxytitanium _{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-butoxytitanium Ti (O
_{-sec-C 4 H 9) 4} , tetra -t- butoxy Ti (O-t-
C ₄ H ₉ ) ₄ , tetradiethylaminotitanium Ti (N (C ₂
H ₅ ) ₂ ) _{4 and the} like are preferably used.

Organic compounds containing these Si and Ti
As the organic compound containing, one kind may be used alone, or two or more kinds may be used in combination.

Next, the case of forming an antireflection film will be described. Formed in said transparent resin substrate by PECVD, refractive index-modifying layer, in the present invention on the hard coat layer, double-sided simultaneous or one side to the antireflection film and the TiO ₂ layer and the SiO ₂ layer by sputtering Forming an antireflection film composed of a sputtered film of alternating layers. At this time, when the optical design wavelength λ of the TiO ₂ layer is in the range of 500 to 550 nm, the refractive index of the layer is set to have a value of 2.36 to 2.60, whereby a plastic substrate and a hard coat are formed. Improves adhesion to layers and anti-reflective film, improves hot water resistance, heat resistance, chemical resistance, anti-fog properties, prevents dust adhesion and scratches, and prevents interference fringes due to aesthetic appearance. Can be improved.

Next, a specific manufacturing method according to the present invention will be described. The monomer container containing the Ti-alkoxy group-containing organic compound heats the connector to the vacuum chamber from the outside to vaporize it and introduce it into the vacuum chamber, and at the same time introduce oxygen gas. The flow rate of each gas at that time may be appropriately selected according to each purpose, but preferably S
In the case of i-type alkoxy group-containing organic compound gas,
200 SCCM, 30 to 200 SCCM in the case of a Ti-based alkoxy group-containing organic compound gas, and 50 to 200 SCCM of oxygen gas are used individually or in combination and flow into the vacuum chamber. In addition, the pressure in the vacuum chamber at that time is 0.
Stabilizes in the range of 5 to 12 Pa, high frequency 2 on the cathode side
Apply ~ 3.5 KW. At the same time, a current is applied to an electromagnet coil installed outside the vacuum chamber to stabilize the low pressure arc discharge by applying a magnetic field to the plasma atmosphere.

By applying such a magnetic field, an electric field is generated between the electrodes facing each other, and the ions in the plasma are accelerated toward the substrate holder. In addition, this electric field makes the plasma density uniform and suppresses ion damage to the substrate and temperature rise. Therefore, when a thin film is formed on a base material such as a plastic lens, a very effective thin film can be formed when a material whose side chain group is easily broken by ion damage or a material having low heat resistance is used. . As described above, the hard coat layer and / or the refractive index modification layer formed of the Ti-based and / or Si-based alkoxy group-containing organic compound thin film can be directly formed on the plastic lens by such a method.

Then, after forming the refractive index modifying layer and the hard coat layer on the transparent resin substrate, the carousel type substrate holder is divided into twelve divided substrate holding holders which are respectively sent to the sputtering chamber. An antireflection film is formed on both surfaces simultaneously by sputtering.

Further, in the present invention, if necessary,
An anti-water stain coating may be provided on the antireflection film. As the organic silazane compound used in the water scorching preventing coating shown by the following unit formula _{C p F 2p + 1 CH 2} CH 2 Si (NH) 1.5 ( however, P is a positive integer) are those preferably used.

As the method for forming the water stain prevention coat, a wet method such as an immersion method or a dry method such as vacuum deposition, sputtering, or CVD can be used.

If a shock absorbing layer made of urethane, polyvinyl acetal or the like is provided on the base material, an optical article having further improved adhesion and shock resistance can be obtained.

[0047]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The following examples are examples of forming a coating on a plastic lens for eyeglasses.

Example 1 In this example, a refractive index modified layer was formed on a lens substrate by using a PECVD apparatus manufactured by Balzers and a sputtering apparatus.
A hard coat layer having a three-layer structure and an antireflection film are formed. The sputtering apparatus has two sputtering chambers, and a film can be formed in each chamber. The vacuum chamber of the PECVD apparatus and the vacuum chamber of the sputtering 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.

After cleaning the CR-39 lens substrate by passing it through an ultrasonic cleaner, it was placed in a vacuum chamber of a PECVD apparatus manufactured by Balzers and evacuated to 2.7 × 10 ⁻⁴ Pa, and then methyltriethoxysilane was added. A gas is supplied at a flow rate of 100 SCCM and introduced until the pressure in the vacuum chamber reaches 0.7 Pa, a current of 5 A is supplied to the external electromagnet coil, and at the same time, a high frequency output of 2 KW is applied to the cathode for 3 minutes. 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 monomer gas during these 12 minutes is 180S.
The CCM was kept constant, and in this step, a refractive index modified layer was formed on both surfaces of the lens substrate.

Further, subsequently, the oxygen gas flow rate is set to 5 in the vacuum chamber.
After flowing 0 SCCM and setting the vacuum chamber pressure to 0.5 Pa to form a hard coat layer for 20 minutes, the oxygen gas flow rate is set to 100
Increase to SCCM, flow to the vacuum chamber and vacuum chamber pressure 0.8
At the same time as setting the pressure to Pa, the high frequency output of the cathode was changed to 3 kW, and the hard coat layer was formed for another 20 minutes. Then, finally, the oxygen gas flow rate was increased to 200 SCCM and flowed, and the vacuum chamber pressure was 1.0 Pa as it was. The conductance of the exhaust system was adjusted by a variable orifice so that the hard coat layer was formed while the high frequency output of the cathode was kept at 3 KW.

Next, the substrate holders divided into 12 pieces from the carousel type substrate holders were individually removed by the holding holder removing mechanism and once moved to the load lock chamber, and then vertically installed in the sputtering chamber. While continuously flowing along with the substrate holding holder along the two guide rails, oxygen gas and argon gas were introduced into the sputtering chamber at a ratio of 9: 1, and the pressure was adjusted to 2 to 3 Pa. Electric power of 40 KW was supplied to the Ti targets placed on both sides to deposit a TiO ₂ film on the lens substrate at 115 Å.

Next, the holder for holding the substrate was moved to the other sputter chamber, and oxygen gas and argon gas were introduced into the sputter chamber at a ratio of 9: 1 to 2 to 3 Pa, where T
As with i, 30 on the Si target installed on both sides
A power of KW was supplied to deposit a _second SiO ₂ film in a thickness of 360 Å. Similarly, while the sputtering chamber and the substrate holding holder were alternately moved, a total of 6 layers of antireflection film were formed by depositing another 4 layers including the TiO ₂ film and the SiO ₂ film on the lens substrate. .

At that time, the film thicknesses of the third layer, the fourth layer, the fifth layer and the sixth layer were set to 420 angstroms, 150 angstroms, 350 angstroms and 915 angstroms, respectively. At that time, the respective refractive indexes of the TiO ₂ film and the SiO ₂ film at the design wavelength of 550 nm were 2.36 and 1.52.

Example 2 A polyurethane lens was passed through an ultrasonic cleaner to clean it, and then PECV manufactured by Balzers.
It was installed in the vacuum chamber of the equipment D and evacuated to 2.7 × 10 ^-4 Pa, then the gas of methyltriethoxysilane was flowed at 35 S.
Flow rate of CCM and dimethoxydimethylsilane gas 14
8 SCCM flow, introduced until the pressure in the vacuum chamber reaches 0.5 Pa, 5 A current is passed through the external electromagnet coil, and at the same time a high frequency output of 2 KW is applied to the cathode for 1.5 minutes Each flow rate of dimethoxydimethylsilane is 110 SCC per minute
The refractive index modification layer was formed in 1.5 minutes while gradually increasing and decreasing at a rate of M, 98.7 SCCM.

Further, subsequently, the flow rate of methyltriethoxysilane is 200 SCCM and the flow rate of oxygen gas is 50 SC.
When a flow of CM is applied and the pressure in the vacuum chamber becomes 1.0 Pa and the flow rate is stable, a current of 5 A is applied to the external electromagnet coil, and at the same time, a high frequency output of 2.5 KW is applied for 17 minutes to form a hard coat layer. Further, the flow rate of oxygen gas is increased to 100 SCCM, and the pressure in the vacuum chamber is increased to 2.
The conductance of the exhaust system was adjusted by the variable orifice so that it became 0 Pa, and the high frequency output of the cathode was 3
The temperature was raised to KW, followed by forming a hard coat layer for 17 minutes, and finally, the flow rate of oxygen gas was increased to 200 SCCM to form a hard coat layer for another 17 minutes.

Next, the substrate holding holder divided into 12 pieces from the carousel type substrate holder was removed by the holding holder removing mechanism, moved once to the load lock chamber, and then installed vertically in the sputtering chamber. While continuously flowing along with the substrate holding holder along the two guide rails, oxygen gas and argon gas were introduced into the sputtering chamber at a ratio of 9: 1, and the pressure was adjusted to 2 to 3 Pa. Electric power of 45 KW was supplied to the Ti targets placed on both sides, and a TiO ₂ film was deposited on the lens base material in a thickness of 115 Å.

Next, the substrate holding holder was moved to the other sputter chamber, and oxygen gas and argon gas were added at 9: 1.
Introduced into the sputtering chamber at a rate of 2 to 3 Pa
As with Ti, 3 on the Si target installed on both sides
A power of 0 KW was supplied to deposit a _second SiO ₂ film in a thickness of 360 Å. Similarly, while moving both the sputtering chambers together with the substrate holding holder alternately, another 4 layers including the TiO ₂ film and the SiO ₂ film were deposited on the lens substrate to form a total of 6 antireflection films. .

At that time, the film thicknesses of the third, fourth, fifth and sixth layers were 420 Å, 150 Å, 350 Å and 915 Å, respectively. At that time, the respective refractive indexes of the TiO ₂ film and the SiO ₂ film at the design wavelength of 550 nm were 2.45 and 1.52.

Example 3 A polyurethane lens was passed through an ultrasonic washing machine to be washed, and then PECV manufactured by Balzers Co., Ltd.
Was placed in a vacuum chamber of the D device was evacuated to 2.7 × 10 ^over 4 Pa, the flow rate of dimethyl diethoxy-run gas 11SC
CM and tetraisopropoxy titanium gas flow rate 9S
CCM is flown and introduced until the pressure in the vacuum chamber reaches 2.9 Pa, and a current of 2.6 A is flown to the external electromagnet coil, and at the same time, a high frequency output of 0.6 KW is applied to the cathode for 45 seconds while tetraisopropoxy titanium Gas and dimethyldiethoxysilane flow rates of 9 SCC per minute
The refractive index modification layer was formed for 45 seconds while gradually increasing and decreasing at a ratio of M and 11 SCCM.

Subsequently, the flow rate of dimethyldiethoxysilane gas is 100 SCCM and the flow rate of oxygen gas is 35 SC.
When the CM flowed 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 by 25
It is applied for a minute to form a hard coat layer, 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 2.9 Pa, and the high frequency of the cathode is increased. The output was increased to 1 KW, the hard coat layer was continuously formed for 25 minutes, and finally the flow rate of oxygen gas was increased to 140 SCCM, and the hard coat layer was formed for another 25 minutes.

Next, the substrate holding holder divided into 12 pieces from the Carousel type substrate holder is removed by the holding holder removing mechanism, moved once to the load lock chamber, and then installed vertically in the sputter chamber. Along with the two guide rails, oxygen gas and argon gas were made 9: 1 while continuously flowing together with the substrate holding holder.
Was introduced into the sputtering chamber at a rate of 2 to 3 Pa. Power of 50 KW was supplied to the Ti targets placed on both sides to deposit a TiO ₂ film on the lens substrate at 115 Å.

Next, the substrate holding holder is moved to the other sputter chamber, and oxygen gas and argon gas are mixed with 9: 1.
Introduced into the sputtering chamber at a rate of 2 to 3 Pa
As with Ti, 3 on the Si target installed on both sides
A power of 0 KW was supplied to deposit a _second SiO ₂ film in a thickness of 360 Å. Similarly, the TiO ₂ film and the SiO ₂ film, together with the substrate holding holder, are alternately moved in both sputtering chambers to deposit another 4 layers on the lens substrate to form a total of 6 layers of antireflection film. did.

At that time, the film thicknesses of the third, fourth, fifth and sixth layers were 420 Å, 150 Å, 350 Å and 915 Å, respectively. At that time, the respective refractive indexes of the TiO ₂ film and the SiO ₂ film at the design wavelength of 550 nm were 2.58 and 1.52.

Comparative Example 1 The first comparative example has substantially the same manufacturing process as that of the first embodiment, but the film forming conditions in the manufacturing process of the antireflection film are the same as those of the first embodiment. The department is different. First
In the comparative example described above, the pressure in the sputtering chamber of the TiO ₂ film-based politics of the antireflection film was set to 4 to 8 Pa. Design wavelength 5 at this time
The refractive index of the TiO ₂ film at 50 nm was 2.20.

Comparative Example 2 The second comparative example has substantially the same manufacturing process as that of the second embodiment, but the film forming conditions of the manufacturing process of the antireflection film are the same as those of the second embodiment. The department is different. Second
In the comparative example described above, the pressure in the sputtering chamber of the TiO ₂ film-based politics of the antireflection film was set to 4 to 8 Pa. Design wavelength 5 at this time
The refractive index of the TiO ₂ film at 50 nm was 2.28.

(Comparative Example 3) The third comparative example has substantially the same manufacturing process as that of the third embodiment, but the film forming conditions in the manufacturing process of the antireflection film are the same as those of the third embodiment. The department is different. Third
In the comparative example described above, the pressure in the sputtering chamber of the TiO ₂ film-based politics of the antireflection film was set to 4 to 8 Pa. Design wavelength 5 at this time
The refractive index of the TiO ₂ film at 50 nm was 2.35.

Next, the mechanical durability of the plastic lens samples for eyeglasses obtained in the above Examples and Comparative Examples was evaluated. The evaluation details are shown below.

Evaluation items 1) Adhesion According to JIS D-202, cuts with a 1 mm interval are vertically and horizontally placed on the surface of the sample, and cellophane tape (cellophane tape manufactured by Nichiban Co., Ltd.) is stuck on the cuts and 4 kg 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 the film on the surface of the sample is changed.

4) Heat resistance After being left in an air oven at 100 ° C. for 5 minutes, 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 sample surface 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 surface of the sample is changed.

7) Interference fringes When natural light is radiated, those in which interference fringes are hardly visible are regarded as good, and those in which interference fringes are visible are regarded as defective.

8) Antistatic Property (Prevention of Dust Adhesion) After being left overnight under the condition of 20 ° C. and 65%, the film is rubbed with deer skin and judged by the degree of ash adhesion.

A: Ash is not attached B: Ash is attached 9) Anti-fog property After leaving the lens in a room at 23 ° C. and 50% RH for one day and night, expose the lens to the condition of 30 ° C. and 100% RH. Measure the time until cloudy weather occurs.

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

[0079]

[Table 1]

As can be seen from Table 1, all the samples of the above-mentioned examples have the following scratch resistance (steel wool and sand eraser), heat resistance, chemical resistance (acid), antistatic property and antifogging property. It is superior to all the samples of the comparative examples. Also,
The sample of this example is equivalent to the sample of the comparative example in terms of adhesion, hot water resistance, chemical resistance (alkali), and interference fringes.

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

In the present invention, a modified layer is provided between the hard coat layer and the base material. This modified layer has an amorphous structure at the interface with the substrate, thereby increasing the adhesion strength at the interface. In addition, by changing the flow rate ratio of the monomer gas at the time of forming the modified layer, the refractive index in the crystal axis of the growing thin film is changed, that is, the modified layer is provided with optical inhomogeneity. It is possible to change the degree of oxidation and the packing density. Thereby, the true stress itself formed inside the thin film can be changed, and the true stress with the hard coat layer formed on the modified layer and the antireflection film formed by the sputtering method can be offset.

Further, the hard coat layer of this embodiment is made of PE.
The mixed gas pressure when forming by CVD is 0.5 to 1
It is controlled within the range of 2 Pa. As a result, the composition and structure of the hard coat layer of this example are excellent in durability. In addition, in addition to this, the hard coat layer of the present embodiment does not contain a high refractive index material, so that it can be easily made transparent by adjusting the amount of oxygen, so that it can be formed in a large film thickness. Furthermore, mechanical durability and chemical resistance can be obtained.

Due to the effects of the modified layer and the hard coat layer, the plastic lens provided with the coating of the present embodiment has high environmental resistance.

As described above, according to the present invention, a Ti-based and / or Si-based alkoxy group-containing organic compound is used to form a refractive index modifying layer and / or a hard coat layer on an eyeglass plastic lens by plasma CVD. Is formed and an antireflection film is formed thereon, TiO ₂
An antireflection film composed of a sputtered film composed of alternating layers of SiO ₂ layers and SiO ₂ layers is formed, and when the optical design wavelength λ of the TiO ₂ layer is in the range of 500 to 550 nm, the refractive index of the layer is By having 2.36 to 2.60, the adhesion between the plastic substrate, the hard coat layer and the antireflection film is improved, and the hot water resistance, heat resistance, chemical resistance, antifogging property, and dust adhesion prevention are provided. In addition, it has an effect of improving scratch resistance and preventing interference fringes and the like due to aesthetic appearance.

Further, since the antireflection film is formed by the sputtering method, it is possible to form the antireflection film on both surfaces of the base material at the same time, and it is possible to suppress the temporal change of the spectral reflectance characteristics and the like. In addition, since it can be formed on both sides at once, there is no need to invert the base material, and a consistent manufacturing process is established.

Furthermore, the surface activation treatment and the like, which are indispensable in the conventional wet hard coat, are no longer required, and the waste liquid treatment is eliminated, so that the problem of environmental pollution can be solved.

Further, as compared with the conventional hard coat by dipping, the condensation curing step is eliminated and the delivery time can be shortened.

[0089]

As described above, according to the present invention,
It is possible to provide an optical component having a coating, which has an antireflection film formed by sputtering, has high durability, and can be manufactured by a manufacturing process by consistent bright layer growth.

The optical article produced by the production method of the present invention has good adhesion of each layer and is difficult to be peeled off. Further, it is possible to obtain an optical article which is excellent in scratch resistance, impact resistance, hot water resistance, heat resistance, and chemical resistance, and further does not cause interference fringes. Then, by forming the antireflection film by sputtering, the temporal change of the spectral characteristics is further smaller than that of the optical article having the antireflection film formed by vapor deposition, and has high durability, and
An optical article having the above effects can be obtained.

[0091]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G02B 1/12 G02B 1/12

Claims (2)

[Claims] 1. A synthetic resin substrate, a modified layer formed on the substrate, containing at least one of a Si-based compound and a Ti-based compound, and having a refractive index changing in the thickness direction, A hard coat layer formed on the modified layer, having a thickness larger than that of the modified layer and having a constant refractive index, and containing Si and O; and a TiO ₂ film and a SiO on the hard coat layer. _An antireflection film formed by alternately stacking _two films, and the TiO ₂ film has a refractive index of 2.36 or more and 2.60 or less for light having a wavelength of 500 nm or more and 550 nm or less. An optical article characterized by: 2. A method of manufacturing an optical article having a coating film on a substrate, wherein an organic compound gas containing Si and Ti are provided on the substrate.
A first step of forming a modified layer whose refractive index changes in the thickness direction on the base material by a chemical vapor deposition method using plasma using at least one of organic compound gases containing A second step of forming a hard coat layer on the modified layer by a chemical vapor deposition method using plasma using a mixed gas of an organic compound gas containing Si and an oxygen gas; On the coat layer, by the sputtering method,
A third step of forming an antireflection film by alternately stacking a TiO ₂ film having a refractive index of 2.36 or more and 2.60 or less for light having a wavelength of 500 nm or more and 550 nm or less and an SiO ₂ film A method of manufacturing an optical article, comprising: