JPH09211201A - Optical article with coating film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical article having a coating film which has high environmental resistance and can be formed in continuous processes by vapor phase growth method. SOLUTION: This product consists of a synthetic resin base body, a modified layer formed on the base body, and a hard coating layer formed on the modified layer. The modified layer contains at least one of Si and Ti compds. and has the refractive index changing in the thickness direction. The hard coating layer is thicker than the modified layer, has a const. refractive index and contains Si and O. The modified layer is formed in such a manner that at least the interface part in contact with the hard coating layer is in an amorphous state.

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. Then, it is proposed to further form an organic substance curable substance (water repellent coat) on it.

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.

[0014]

However, the coating film formed by the method described in JP-A-5-140356 described above has a low hot water resistance and, like a plastic lens for eyeglasses, a hot water resistance. Cannot be used for required objects. Specifically, the coating formed by this method,
In a hot water immersion test at 80 ° C. for 10 minutes, the film is bulged, which has a drawback that a good quality in appearance cannot be obtained.

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 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. However, in practice, performing this control for a long time tends to make the bias voltage generated on the substrate side unstable. Therefore, the discharge due to plasma is intermittently or interrupted, 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. Will contain a lower oxide, and the hard coat layer itself will absorb and color.

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

The present inventor has also tried to form a modified layer whose refractive index changes in the thickness direction between the base material 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 a vertical direction, so that unevenness in film thickness distribution occurs in the radial direction of the lens. 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.

The present invention solves the above problems and provides an optical article having a coating having a high environmental resistance, excellent optical characteristics and which can be formed in a consistent process by a vapor phase growth method. To aim.

[0022]

Means for Solving the Problems The present inventor has formed a modified layer whose refractive index changes in the thickness direction between a base material and a hard coat layer under various conditions. The problems under each condition such as the material of the modified layer, the film forming conditions, and the compatibility between the modified layer and the hard coat layer or the substrate were studied.
As a result, by making the refractive index modified layer at the interface with the hard coat layer an amorphous structure, the interface between the base material and the hard coat layer is not distinguished, and the refractive index modified layer and the hard code layer, and the base material It was found that the adhesion with the hard coat layer can be enhanced and reflection from the interface can be prevented.

Therefore, in order to achieve the above object, according to the present invention, a synthetic resin base material and a base material formed on the base material,
Containing at least one of Si-based and Ti-based compounds,
A modified layer having a refractive index changing in the thickness direction, and a film formed on the modified layer, having a thickness larger than that of the modified layer, having a constant refractive index, and containing Si and O. And a hard coat layer containing the hard coat layer, wherein the modified layer is amorphous at least at a portion of an interface in contact with the hard coat layer.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described.

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 vacuum vessel, each monomer gas is introduced in a plasma atmosphere, and the monomer is placed on the substrate. By forming a thin film of the compound formed by the plasma reaction while adjusting the flow rate ratio of each monomer, an organic or inorganic compound having good intermediate adhesion between the base material and the hard coat. A refractive index modified layer is formed.

An alkoxy group-containing organic and / or inorganic silicon compound thin film, which is the original hard coat layer, is formed thereon.

At this time, the modified layer is formed such that the vicinity of the interface with the hard coat layer has an amorphous structure. As a result, a strong adhesion strength between the plastic base material and the hard coat layer can be provided, and furthermore, interference fringes can be suppressed.

The amorphous structure in the present invention has an amorphous structure containing at least one of Si-based and Ti-based substances as a main component, but the present invention is based on at least one of the Si-based and Ti-based materials. A structure in which an organic compound is included in a part of the amorphous structure containing the substance as a main component is also included.

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.

Of these, particularly preferred are polymers of diethylene glycol bisallyl carbonate, polyurethane, and halogens (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.

The base material has a low refractive index of 1.70.
It is possible to use one having a high refractive index as described above.

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 production 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.

Further, in the chemical vapor deposition (CVD) method using plasma, which is used in 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.

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.

When the refractive index modifying layer and the hard coat layer are formed on the transparent resin substrate, Ti is used as a forming material for them.
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 the refractive index modification layer and the hard coat layer on the transparent resin substrate. In particular, when forming the refractive index modified layer, by forming so that the vicinity of the interface between the refractive index modified layer and the hard coat layer on it has a pseudo amorphous amorphous structure, a strong adhesion strength is obtained, Furthermore, interference fringes can be suppressed.
If necessary, an antireflection film may be formed thereon, and if necessary, a water-repellent thin film made of a fluorine-based and / or silicon-based organic compound may be formed on the antireflection film.

In the present invention, the method for forming the antireflection film is not particularly limited. That is, the chemical vapor deposition method (C
VD) and physical vapor deposition methods can be appropriately used. A specific forming method may be appropriately selected from a vacuum vapor deposition method, a sputtering method, an ion plating method, a plasma CVD method and the like.

Further, in the present invention, a water stain prevention coat may be provided on the antireflection film, if necessary. 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 ( Here, 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.

Further, if a shock absorbing layer made of urethane type, polyvinyl acetal or the like is provided on the base material, the adhesiveness is further improved.
An optical article with improved impact resistance can be obtained.

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.

The pressure in the vacuum chamber at that time is 0.5 to 12 P.
Stabilized in the range of a, high frequency 2 to 3.5K on the cathode side
Apply W. 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. Due to such a method of applying a magnetic field, an electric field is generated between opposing electrodes, and ions in plasma are accelerated toward the substrate holder side. 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 substrate material such as a plastic lens, or when a material whose side chain group is easily broken by ion damage or a material having low heat resistance is used, a very effective thin film can be formed.

By such a method, it is possible to directly form the refractive index modifying layer and / or the hardening layer made of the Ti-based and / or Si-based alkoxy group-containing organic compound thin film on the plastic lens.

Particularly, in the vicinity of the interface between the refractive index modified layer and the hardened layer, the gas flow rate of the Si-based alkoxy group-containing organic compound is gradually increased, and at the same time, the gas flow rate of the Ti-based alkoxy group-containing organic compound is gradually increased. Reduce to. At this time, the ratio of the change amount of the gas flow rate of the Si-based alkoxy group-containing organic compound to the change amount of the gas flow rate of the Ti-based alkoxy group-containing organic compound is included in each change amount.
When converted to the ratio of the number of atoms and the number of Ti atoms, it is 1:
Accurately increase and decrease the flow rate so as to be (3 or less). As a result, the refractive index change layer has an amorphous structure near the interface with the hard coat layer. If the atomic ratio is out of this range, a crystalline structure is exhibited, and the adhesion strength at the interface tends to decrease.

[0046]

[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 modifying layer and a hard coat having a three-layer structure were formed on a polyurethane lens substrate using a PECVD apparatus manufactured by Balzers and a vacuum vapor deposition apparatus. A layer and an antireflection film are 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 PECVD apparatus has 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 direction of the electric field.

First, the polyurethane lens was cleaned by passing it through an ultrasonic cleaning machine, placed in a vacuum chamber of a PECVD apparatus manufactured by Balzers, evacuated to 2.7 × 10 ⁻⁴ Pa, and then dimethyldiethoxylane gas was discharged. Flow rate 11 SCCM
And tetraisopropoxy titanium gas flow 9SCC
Flow M and introduce until the pressure in the vacuum chamber reaches 2.9 Pa. At the same time as applying a current of 2.6 A to the external electromagnet coil, a high frequency output of 0.6 KW was applied to the cathode for 45 seconds, during which tetraisopropoxy titanium gas was gradually reduced at a rate of 3 SCCM per minute, and at the same time. Dimethyldiethoxysilane gas 5 SC / min
A refractive index modified layer having a thickness of 260 nm was formed on both surfaces of the base material while increasing the ratio of CM.

The number of Si atoms contained in 5 SCCM, which is the increase in the flow rate of dimethyldiethoxysilane gas,
Decrease in flow rate of tetraisopropoxy titanium gas 3SC
The ratio with the number of Ti atoms contained in CM is 1: 1.2.

Further, subsequently, the flow rate of dimethyldiethoxysilane gas is 100 SCCM and the flow rate of oxygen gas is 35 S.
When the CCM 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.
A hard coat layer was formed on the refractive index modified layer by applying for 5 minutes. Furthermore, the flow rate of oxygen gas is 70S.
The conductance of the exhaust system is adjusted by the variable orifice so that the pressure in the vacuum chamber becomes 2.9 Pa by increasing to CCM, and the high frequency output of the cathode is raised to 1 KW.
Subsequently, the hard coat layer was 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 lens base material holder is moved to the load lock chamber, and the lens base material holder is inverted by 90 °, so that one surface of the lens base material is directed toward the vapor deposition source and vacuum vapor deposition is performed. After being sent to a chamber and evacuated to 1.3 × 10 ⁻³ Pa, each layer of the antireflection film was formed on each hard coat layer by the electron beam heating vapor deposition method under the following vapor deposition conditions.

Various Conditions of Vacuum Deposition A: First Layer of Angstrom Titanium Oxide 420A (Geometric Film Thickness) Pressure during Deposition 4 × 10 ⁻³ Pa (O ₂ Atmosphere) Second Layer of Silicon Dioxide 420A (Geometric Film Thickness) Evaporation pressure 1 × 10 ⁻³ Pa Third layer Titanium oxide 2160A (geometric film thickness) Evaporation pressure 5 × 10 ⁻³ Pa (O ₂ atmosphere) Fourth layer Silicon dioxide 1200A (geometric film thickness) Evaporation After forming an anti-reflection film on one surface of the lens with an hourly pressure of 1 × 10 ⁻³ Pa or more, this time the other surface is turned toward the evaporation source by the double-sided inversion mechanism attached to the lens substrate holder. Flip it over,
Again, an antireflection film was formed under the same vapor deposition conditions as above. (Example 2) In the second example, as in the first example, a refractive index modification layer, a hard coat layer, and an antireflection film are formed, but dimethyldiethoxy when forming the refractive index modification layer. The amount of increase in the flow rate of silane gas is 8 SCCM, and the amount of decrease in the flow rate of tetraisopropoxy titanium gas is 6 SCC.
M.

The number of Si atoms contained in 8 SCCM, which is the increase in the flow rate of dimethyldiethoxysilane gas,
Reduction amount of tetraisopropoxy titanium gas 6SC
The ratio with the number of Ti atoms contained in CM is 1: 1.8.

Since the other manufacturing steps are the same as those in the first embodiment, the description thereof will be omitted.

(Embodiment 3) In the third embodiment, the refractive index modifying layer, the hard coat layer and the antireflection film are formed in the same manner as in the first embodiment, but when the refractive index modifying layer is formed. Increase the flow rate of dimethyldiethoxysilane gas by 11 SCC
M, and the amount of decrease in the flow rate of tetraisopropoxy titanium gas was 9 SCCM.

The number of Si atoms contained in 11 SCCM, which is the increase in the flow rate of dimethyldiethoxysilane gas, and the decrease in the flow rate of tetraisopropoxytitanium gas, 9
The ratio with the number of Ti atoms contained in SCCM is 1: 2.
6.

(Embodiment 4) In the fourth embodiment, the base lens having the antireflection film formed according to the first embodiment is returned to the load lock chamber again, and the lens base holder is inverted by 90 °. , Send it again to the vacuum chamber of PECVD equipment 1.3
After evacuation to × 10 ⁻³ Pa, a mixed gas of hexamethyldisilazane and oxygen was added at 10 SCCM and 50 respectively.
It is introduced into the vacuum chamber at a flow rate of SCCM, the pressure in the vacuum chamber at that time is controlled to 8 Pa, a current of 2.6 A is passed through the external electromagnet coil, and at the same time, a high frequency output of 0.6 kW is applied to the cathode, and a film thickness of 50 A water-repellent thin film, which is a water stain resistant coating, was formed to have a thickness of about 100 Å.

(Comparative Example 1) A polyurethane lens was passed through an ultrasonic cleaner to clean it, and then PECV manufactured by Balzers.
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, 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, during which tetraisopropoxytitanium is applied. Gas is gradually reduced at a rate of 11 SCCM per minute, and at the same time, dimethyldiethoxysilane gas is reduced to 13 per minute.
A refractive index modified layer having a thickness of 260 nm was formed on both surfaces of the substrate while increasing the ratio of SCCM.

The number of Si atoms contained in 13 SCCM, which is the increase in the flow rate of dimethyldiethoxysilane gas, and the decrease in the flow rate of tetraisopropoxytitanium gas, 1
The ratio with the number of Ti atoms contained in 3SCCM is 1:
3.2.

On each of the refractive index modified layers formed as described above, a flow rate of dimethyldiethoxysilane of 100 SCCM and a flow rate of oxygen gas of 35 SCCM were further passed, and the pressure in the vacuum chamber became 2.9 Pa. When the flow rate was stable, a current of 2.6 A was applied to 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 to form a hardened layer. Furthermore, the flow rate of oxygen gas is set to 7
Increase to 0SCCM, adjust the conductance of the exhaust system with a variable orifice so that the pressure in the vacuum chamber becomes 2.9 Pa, raise the high frequency output of the cathode to 1 KW, and subsequently form a hardened layer for 25 minutes, and finally Increase the flow rate of oxygen gas to 140 SCCM, and
A cured layer was formed for a minute.

Next, the lens base material holder is moved to the load lock chamber, the lens base material holder is inverted by 90 °, and one surface of the lens base material is turned toward the vapor deposition source.
After being sent to a vacuum evaporation chamber and evacuated to 1.3 × 10 ⁻³ Pa, each layer of the antireflection film was formed on each cured layer under the following evaporation conditions by an electron beam heating evaporation method.

Various Conditions of Vacuum Deposition A: First Layer of Angstrom Titanium Oxide 420A (Geometric Film Thickness) Pressure during Deposition 4 × 10 ⁻³ Pa (O ₂ Atmosphere) Second Layer Silicon Dioxide 420A (Geometric Film Thickness) Evaporation pressure 1 × 10 ⁻³ Pa Third layer Titanium oxide 2160A (geometric film thickness) Evaporation pressure 5 × 10 ⁻³ Pa (O ₂ atmosphere) Fourth layer Silicon dioxide 1200A (geometric film thickness) Evaporation Pressure per hour 1 × 10 ⁻³ Pa (Comparative Example 2) In the second comparative example, the refractive index modifying layer, the hard coat layer and the antireflection film are formed as in the first comparative example, but the refractive index modifying layer is formed. When forming the gas, the amount of increase in the flow rate of dimethyldiethoxysilane gas is set to 15 SCCM, and the amount of decrease in the flow rate of tetraisopropoxy titanium gas is set to 13S.
It was CCM.

The number of Si atoms contained in 15 SCCM, which is the increase in the flow rate of dimethyldiethoxysilane gas, and the decrease in the flow rate of tetraisopropoxytitanium gas, 1
The ratio with the number of Ti atoms contained in 3SCCM is 1:
4.0.

Comparative Example 3 In the third comparative example, the refractive index modifying layer, the hard coat layer and the antireflection film are formed as in the first comparative example, but when the refractive index modifying layer is formed. Increase the flow rate of dimethyldiethoxysilane gas by 22SCC
M, and the decrease amount of the flow rate of tetraisopropoxy titanium gas was 20 SCCM.

The number of Si atoms contained in 22SCCM, which is the increase in the flow rate of dimethyldiethoxysilane gas, and the decrease in the flow rate of tetraisopropoxytitanium gas, 2
The ratio with the number of Ti atoms contained in 0 SCCM is 1:
6.0.

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 soaking in 80 ° C. city water in a constant temperature bath for 10 minutes, it is examined whether there is any change in the film on the sample surface.

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 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.

7) Impact resistance In each of the above-mentioned 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.

8) Interference fringes When natural light is irradiated, the ones in which the interference fringes are hardly visible are regarded as good, and the ones in which the interference fringes are visible are regarded as bad.

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 are in all of the comparative examples in terms of adhesion, scratch resistance (steel wool), chemical resistance (acid), impact resistance and interference fringes. Better than the sample. Further, in the heat resistance, the sample of this example is superior to the sample of Comparative Example 3 and is equivalent to the samples of Comparative Examples 1 and 2. Further, with respect to scratch resistance (sand eraser), warm water resistance, and chemical resistance (alkali), the same durability as that of the comparative example is shown, which is considered to be due to the following.

In this embodiment, the modified layer is arranged between the hard coat layer and the base material. The modified layer has an amorphous structure near the interface with the hard coat layer. As a result, the adhesion between the refraction-modified layer and the cured layer becomes good, and the effects of improving scratch resistance, impact resistance, and preventing interference fringes can be obtained. Further, since the modified layer is thicker than 100 nm and thinner than 900 nm, the adhesiveness is further enhanced.

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. Therefore, the hard coat layer has excellent mechanical durability and chemical resistance and acts as a hard coat layer.

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

Yes.

Further, since the hard coat layer of this embodiment contains the oxide of silicon which is a low refractive index material, it can be easily made transparent even if it is thick.

Further, the modified layer is a film provided separately from the hard coat layer which is a hard coat layer, and is disposed on the base material side of the hard coat layer. Durability and chemical resistance are not required.
Therefore, the modified layer of this example can be made thin. The modified layer contains an oxide of Ti, which is a high-refractive-index material that is deficient in oxygen and easily colored in order to change the refractive index, but in this embodiment, since the film thickness can be made thin, Can be transparent.

Also, the antireflection film can be made transparent because each layer is thin.

As described above, in this embodiment, since the hard coat layer, the modified layer, and the antireflection film can be made transparent while maintaining the durability of the entire film, a transparent film can be obtained, which is suitable for eyeglasses. Suitable for use as a coating for plastic lenses.

In the method of manufacturing the plastic lens of this embodiment, the modified layer, the first, second and third hard coat layers and the antireflection film can be continuously formed only by the dry process. 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. . Moreover, the problem of environmental pollution can be solved. Furthermore, the manufacturing method of the present embodiment is
By only 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 produce a film in which the film properties such as the refractive index are changed. 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.

Although the PECVD apparatus for increasing the plasma density by the magnetic field is used in the above embodiment, it is of course possible to use the plasma CVD apparatus which does not use the magnetic field.

[0091]

As described above, according to the present invention, there is provided an optical article having a coating having a large environment resistance, excellent optical characteristics and which can be formed in a consistent process by a vapor phase growth method. Can be provided.

The optical article produced by the production method of the present invention is excellent in scratch resistance, impact resistance, hot water resistance, heat resistance, chemical resistance, mechanical strength and transparency, and further, interference fringes are generated. An optical article that does not exist is obtained. In particular, the optical article of the present invention has a modified layer formed by the vapor phase growth method on the substrate, and the interface between the modified layer and the hard coat layer is made amorphous so that the adhesion is further improved. .

Claims (3)

[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 film thickness thicker than that of the modified layer, having a substantially constant refractive index, and containing Si and O; An optical article characterized in that an interface portion in contact with the coat layer is amorphous. 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. , Gradually increasing the supply amount of the organic compound gas containing Si supplied in the first step with time, and at the same time gradually decreasing the supply amount of the organic compound gas containing Ti with time. The manufacturing method of the optical article provided with the coating characterized by the above. 3. The ratio of the amount of increase in the organic compound gas containing Si per unit time to the amount of decrease of the organic compound gas containing Ti per unit time in the ratio of the increase amount of the gas according to claim 2. When converted into the number of Si atoms contained therein and the number of Ti atoms contained in the reduced amount of the gas,
A method for producing an optical article provided with a coating, which is controlled to 1: (3 or less).