JP5145864B2 - Method for manufacturing optical article - Google Patents

Description

  The present invention relates to an optical article made of a resin for optical materials and a method for producing the same.

Conventionally, an optical substrate is formed by injecting a resin material into a mold and polymerizing it by a method such as heating. An optical article in which hardness is improved, scratch resistance, antireflection function, and the like are provided on this optical base material and a method for producing the same are known.
Here, since the internal stress remains in the optical base material removed from the mold after polymerization, it is said to be weak against external forces such as physical impact.

When an optical base material in which such internal stress remains is stored for a long period of time, a phenomenon occurs in which the optical base material gradually deforms in a direction to release or relax the internal stress, and the shape of the optical base material and the optical article The frequency may not be maintained.
For this reason, an annealing treatment at a temperature exceeding the glass transition point (Tg) is often applied to the optical base material after the polymerization and before various functions are imparted. Thereby, the internal stress of the optical substrate can be relaxed, and the shape and frequency of the optical article can be stabilized.

  On the other hand, a polymerizable composition having a high refractive index having a refractive index (nd) of 1.7 or more has been proposed as a resin material for an optical substrate used in the optical article as described above. (For example, see Patent Documents 1, 2, and 3). According to the resin material having such a high refractive index, an optical article having excellent optical characteristics can be configured.

JP 2006-169190 A (pages 3 to 8) JP 2006-83313 A (pages 4 to 10) JP 2006-182908 A (pages 4 to 10)

However, since the resin materials described in Patent Documents 1 to 3 have thermoplastic properties, there is a possibility that the shape of the optical base material may change if annealing treatment is performed at a temperature exceeding Tg. When the optical substrate is deformed, there is a problem that the shape and frequency of the optical article as the final product are not maintained, and the quality is deteriorated.
Such a subject is not limited to the resin materials described in Patent Documents 1 to 3, but is common to resin materials having thermoplasticity.

  An object of the present invention is to provide an optical article that can hardly change the shape of the optical base material and can maintain the shape and power, and a method for manufacturing the same.

The optical article of the present invention comprises an optical base material and a coating layer provided on the surface of the optical base material, and uses a TMA (Thermomechanical Analyzer), a 50 g load, a 1 mm diameter needle probe, an initial temperature of 25 When the thermo-mechanical analysis of the optical base material is performed under the conditions of ℃ and a heating rate of 10 ° C./min, the amount of deformation of the optical base material at the measurement temperature of the glass transition point of the optical base material + 10 ° C. However, it is 10% or more of the thickness of the optical base material at the initial temperature, and the coating layer is formed of a material that cures at a temperature below the glass transition point of the optical base material.

  According to this invention, the optical substrate is made of a material having a large amount of deformation at the measurement temperature (Tg + 10 ° C.), that is, a material having thermoplasticity. And the coating layer formed from the material hardened | cured at the temperature below the glass transition point (Tg) of an optical base material is provided in the surface of an optical base material.

  Here, since the coating layer is formed of a material that cures at a temperature equal to or lower than the Tg of the optical substrate, the optical substrate is heated above its Tg when the coating layer material is cured on the surface of the optical substrate. It will not be done. Therefore, there is a low possibility that the optical substrate having thermoplasticity is deformed when the coating layer is formed.

And even if the hardened coating layer is heated more than Tg of an optical base material, the shape can be maintained, without softening.
That is, when the optical article of the present invention is annealed at a temperature equal to or higher than Tg of the optical substrate, the optical substrate is softened, but the coating layer provided on the surface of the optical substrate is not softened.
Since the coating layer prevents the deformation of the optical substrate softened by the annealing treatment, an optical article having the intended shape and frequency can be obtained.
In addition, according to annealing treatment, the internal stress of an optical base material can be relieved and the shape and frequency of an optical article can be stabilized.

  Therefore, the optical article of the present invention is an excellent optical article that can maintain the shape and the power without changing the shape of the optical base material even when the annealing treatment at a temperature equal to or higher than Tg of the optical base material is performed. .

In the present invention, “the coating layer is cured at a temperature lower than the glass transition point of the optical substrate” means that the temperature applied from the outside when the raw material composition forming the coating layer is cured is the optical substrate. It means that it is below Tg.
For example, when the raw material composition is cured by heat polymerization, the external heating needs to be Tg or less of the optical substrate.
In addition, for example, when the raw material composition is cured by irradiation with energy such as ultraviolet rays, it is necessary to adjust the temperature of the raw material composition during polymerization to be equal to or lower than the Tg of the optical substrate.

  In the optical article of the present invention, the optical substrate is preferably formed from a substrate composition containing a compound represented by the general formula (1).

In formula (1), M is a Sn atom, Si atom, Zr atom, Ti atom, or Ge atom. R ₁ is an alkylene group having 1 to 4 carbon atoms, X ₁ is an S atom or an O atom, and n is an integer of 0 to 4. Y is any of the following formula (1-1), formula (1-2), or formula (1-3).

The compound represented by the general formula (1) has a high refractive index and gives an optical base material excellent in optical properties, but has a problem that deformation is caused by annealing treatment because it has thermoplasticity.
On the other hand, in the present invention, the coating layer is cured at a temperature not higher than Tg of the optical substrate formed from the substrate composition containing the compound represented by the general formula (1), and is applied to the surface of the optical substrate. By being formed, the coating layer does not become soft even at a high temperature, and the coating layer does not deform, and as a result, the shape of the optical substrate is maintained.
For this reason, even if the optical substrate is heated at a temperature exceeding Tg by annealing treatment, the shape and power can be maintained, and an optical article having a high refractive index and excellent optical characteristics can be provided.

In the optical article of the present invention, it is preferable that the coating layer is a coating layer for preventing deformation of the optical substrate.
In this invention, since the coating layer for preventing deformation of the optical substrate is formed on the surface of the optical substrate, the coating layer prevents the optical substrate from changing its shape. An optical article that can maintain its shape and power can be provided.

In the optical article of the present invention, it is preferable that the coating layer also serves as at least one of a primer layer, a hard coat layer, and an antireflection layer.
In this invention, the coating layer can also serve as at least one of a primer layer, a hard coat layer, and an antireflection layer provided in a conventional optical article. Articles can be manufactured. For this reason, it is possible to provide an optical article that is not deformed even if annealing is performed without complicating the configuration.

  The method for producing an optical article of the present invention includes: a base material forming step for forming an optical base material; and a coating layer for preventing deformation of the optical base material on the surface of the optical base material after the base material forming step. After the coating layer forming step of forming at a temperature below the glass transition point of the optical substrate and the coating layer forming step, the coating layer and the optical substrate are heated at a temperature exceeding the glass transition point of the optical substrate. An optical process, and using a TMA (Thermomechanical Analyzer), a thermomechanical machine for the optical substrate under the conditions of a load of 50 g, a needle-in probe with a diameter of 1 mm, an initial temperature of 25 ° C., and a heating rate of 10 ° C./min. When the analysis is performed, the deformation amount of the thickness of the optical substrate at the measurement temperature of the glass transition point of the optical substrate + 10 ° C. is 10% of the thickness of the optical substrate at the initial temperature. It is the above.

According to this invention, the coating layer for preventing deformation is formed on the surface of the thermoplastic optical substrate formed in the substrate forming step at a temperature not higher than Tg of the optical substrate (coating layer forming step).
In this coating layer forming step, the optical substrate is not heated to a temperature equal to or higher than its Tg. Therefore, the possibility that the optical substrate having thermoplasticity is deformed is low.

In the annealing step subsequent to the coating layer forming step, the coating layer and the optical substrate are heated at a temperature exceeding the Tg of the optical substrate.
Thereby, the internal stress of the optical substrate can be relaxed, and the shape and frequency of the optical article can be stabilized.

Here, conventionally, when an annealing process is performed on an optical article including an optical base material having thermoplasticity, the optical base material is deformed, and the shape and frequency of the optical product that is the final product are not maintained, resulting in deterioration in quality. There was a problem of being.
On the other hand, in the present invention, in the coating layer forming step, a deformation preventing coating layer is formed on the surface of the optical substrate. Since the coating layer is not softened even in the annealing process, its shape can be maintained, and the shape of the optical substrate adjacent to the coating layer is also maintained.

  Therefore, according to the method for producing an optical article of the present invention, the shape of the optical substrate is hardly changed even when the annealing step at a temperature equal to or higher than Tg of the optical substrate is performed, and the shape and frequency can be maintained. Optical articles can be manufactured.

  In this invention, it is preferable to form the said optical base material from the base material composition containing the compound shown by General formula (1) at the said base material formation process.

In formula (1), M is a Sn atom, Si atom, Zr atom, Ti atom, or Ge atom. R ₁ is an alkylene group having 1 to 4 carbon atoms, X ₁ is an S atom or an O atom, and n is an integer of 0 to 4. Y is any of the following formula (1-1), formula (1-2), or formula (1-3).

The compound represented by the general formula (1) has a high refractive index and gives an optical base material excellent in optical properties, but has a problem that deformation is caused by annealing treatment because it has thermoplasticity.
On the other hand, in the present invention, the coating layer forming step is a process for forming an optical base material which is formed from a base material composition containing the compound represented by the general formula (1). An annealing process is performed at a temperature exceeding the Tg of the optical substrate formed from the substrate composition after making the shape of the optical substrate difficult to change by curing at a temperature below Tg and forming on the surface of the optical substrate. To relax the internal stress of the optical substrate. From this, the manufacturing method of the optical article which maintains a shape and frequency can be provided.

In the method for producing an optical article of the present invention, the coating layer forming step includes a primer layer forming step of forming a primer layer on the surface of the optical substrate, and a hard coat on the surface of the optical substrate or the surface of the primer layer. A structure that serves as at least one of a hard coat layer forming step for forming a layer and an antireflection layer forming step for forming an antireflection layer on the surface of the optical substrate, the surface of the hard coat layer, or the surface of the primer layer Is preferred.
In this invention, the coating layer forming step serves as at least one of the primer layer forming step, the hard coat layer forming step, and the antireflection layer forming step, thereby shortening the step after the annealing step. Thus, a simplified method for manufacturing an optical article can be provided.

  In the present invention, since a coating layer formed from a material that cures at a temperature of Tg or less of the optical substrate is provided on the surface of the optical substrate having thermoplasticity, annealing treatment at a temperature of Tg or more of the optical substrate is performed. Even in the case where the coating is applied, deformation of the optical substrate can be prevented by the presence of the coating layer, and an optical article having the intended shape and frequency can be obtained.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the optical article and the manufacturing method thereof according to the present invention are not limited to the following embodiments.
FIG. 1 is a cross-sectional view showing a schematic configuration of the optical article of the present embodiment.
FIGS. 2-5 is a flowchart figure which shows Embodiment 1-9 of the manufacturing method of an optical article, respectively.
6-8 is schematic which shows the manufacturing method of the optical article of this embodiment.

[Optical article]
FIG. 1 shows an optical article 1 of the present embodiment. Hereinafter, the optical article 1 will be described with reference to FIG. In the present embodiment, the optical article 1 is a spectacle lens.
In FIG. 1, an optical article 1 of the present embodiment includes an optical substrate 10 and a coating layer 2 formed on the surface of the optical substrate 10. The surface of the coating layer 2 may include a layer P indicated by a two-dot chain line.

When TMA was used for thermomechanical analysis of the optical substrate 10 under the conditions of a load of 50 g, a 1 mm diameter needle probe, an initial temperature of 25 ° C., and a heating rate of 10 ° C./min, Tg + 10 of the optical substrate 10 The deformation amount of the thickness of the optical substrate 10 at the measurement temperature of ° C. is 10% or more of the thickness of the optical substrate 10 at the initial temperature.
That is, the optical substrate 10 has thermoplasticity.

It is preferable that the optical base material 10 is formed from the resin material which has the high refractive index which consists of the base material composition 11 containing the compound shown by General formula (1).
In General formula (1), M is a Sn atom, Si atom, Zr atom, Ti atom, or Ge atom. R ₁ is an alkylene group having 1 to 4 carbon atoms, X ₁ is an S atom or an O atom, and n is an integer of 0 to 4. Y is one of the following formulas (1-1), (1-2), or (1-3).

Normally, in the optical article 1, a primer layer, a hard coat layer, and an antireflection layer are laminated on the surface of the optical base material 10 from the inside to the outside. However, depending on the article, the primer layer and the antireflection layer are laminated. May be omitted.
The coating layer 2 of this embodiment is at least one of a primer layer, a hard coat layer, and an antireflection layer.
That is, the coating layer 2 is drawn in a single layer structure in FIG. 1, but has a single layer structure or a multilayer structure composed of a plurality of layers.
The coating layer 2 is for preventing deformation of the optical substrate 10 and is formed by curing at a temperature equal to or lower than Tg of the optical substrate 10.

For this reason, the layer P shown with the coating layer 2 and a dashed-two dotted line has the structural example shown below.
(Configuration 1) The coating layer 2 has a two-layer configuration consisting of a primer layer and a hard coat layer. A layer P indicated by a two-dot chain line is an antireflection layer.
(Configuration 2) The coating layer 2 has a single layer configuration composed of a hard coat layer. A layer P indicated by a two-dot chain line is an antireflection layer.
(Configuration 3) The coating layer 2 has a three-layer configuration including a primer layer, a hard coat layer, and an antireflection layer. The layer P indicated by the two-dot chain line is not formed.
(Configuration 4) The coating layer 2 has a multilayer configuration including an antireflection layer in which a plurality of inorganic layers are laminated. The layer P indicated by the two-dot chain line is not formed.

The primer layer is made of urethane resin or the like. The hard coat layer is made of a silicone or acrylic material. The antireflection layer has a single layer structure or a multilayer structure composed of a plurality of layers. As an example of a multilayer structure, a layer made of SiO ₂ and a layer made of ZrO ₂ or TiO ₂ are alternately stacked.

[Method of manufacturing optical article]
2 to 5 are flowcharts showing an example of a method for manufacturing an optical article according to the present embodiment.
Hereinafter, the manufacturing method of the present embodiment will be described based on FIGS. 2 to 5 for the following four embodiments.

  In any manufacturing method of the optical article 1, a base material forming step of forming the optical base material 10 from the base material composition containing the compound represented by the general formula (1) is performed, and after this base material forming step, A coating layer forming step for forming a coating layer 2 for preventing deformation of the optical substrate 10 on the surface of the optical substrate 10, and an anion for heating the coating layer 2 and the optical substrate 10 at a temperature exceeding Tg of the optical substrate 10. A process.

[First Embodiment]
In FIG. 2, a first embodiment of a method for manufacturing an optical article 1 will be described. In the method of the first embodiment, as a base material forming step, first, a raw material preparation step (S101) for preparing a base material composition 11 that is a raw material of the optical base material 10 is carried out, followed by a glass mold injection step ( S102), a thermosetting step (S103), and a release step (S104) are performed, and then a coating layer forming step is performed. Specific procedures of the glass mold injection step (S102), the thermosetting step (S103), and the release step (S104) will be described later.
The coating layer forming step includes a primer layer forming step (S105) for forming a primer layer on the surface of the optical substrate 10, and a hard coat layer forming step (S106) for forming a hard coat layer on the surface of the primer layer. These steps are performed in order. Thereby, the coating layer 2 composed of the primer layer and the hard coat layer shown in the configuration 1 is formed on the surface of the optical substrate 10. In addition, the specific procedure of these processes is mentioned later.
An annealing step (S107) is performed after the coating layer forming step.
In this annealing step, the coating layer 2 including the primer layer and the hard coat layer and the optical substrate 10 are heated at a temperature exceeding the Tg of the optical substrate 10.
After the annealing step, an antireflection layer forming step (S108) is performed. Thereby, the optical article 1 is completed. Although the antireflection layer forming step is performed after the annealing step, the optical article 1 may be completed without performing the antireflection layer forming step. The specific procedure of the antireflection layer forming step (S108) will be described later.

[Second Embodiment]
2nd Embodiment of the manufacturing method of the optical article 1 is described based on FIG. In FIG. 3, in the second embodiment of the method for manufacturing the optical article 1, the primer layer forming step is not performed as the coating layer forming step as compared with the first embodiment, and the hard coat layer is formed on the surface of the optical substrate 10. It is characterized by performing the step (S205). Thereby, the coating layer 2 shown in the configuration 2 is formed on the surface of the optical substrate 10. The annealing step (S206) is performed after the coating layer forming step, similarly to the annealing step (S107) shown in FIG. This annealing step is performed by heating the coating layer 2 made of a hard coat layer and the optical substrate 10 at a temperature exceeding the Tg of the optical substrate 10.
After the annealing step, the antireflection layer forming step (S207) is performed in the same manner as the antireflection layer forming step (S108) shown in FIG. Thereby, the optical article 1 is completed.
Since the base material forming step is the same as the base material forming steps S101 to S104 shown in FIG.
In the method of the second embodiment, the hard coat forming step (S205), the annealing step (S206), and the antireflection layer forming step (S207) are the hard coat layer forming step (S106) and annealing step (S107) shown in FIG. And antireflection layer forming step (S108).

[Third Embodiment]
A third embodiment of the method for manufacturing the optical article 1 will be described with reference to FIG. In FIG. 2, the primer layer forming step (S105) and the hard coat layer forming step (S106) are performed as the coating layer forming step. In this embodiment, the primer layer forming step (S305) and the hard coat layer forming step are performed. Following the step (S306), the antireflection layer forming step (S307) is carried out to perform the coating layer forming step. Thereby, the coating layer 2 shown in the configuration 3 is formed on the surface of the optical substrate 10. The annealing step (S308) is performed after the coating layer forming step, similarly to the annealing step (S107) shown in FIG. Thereby, the optical article 1 is completed. This annealing step is performed by heating the coating layer 2 including the primer layer, the hard coat layer, and the antireflection layer, and the optical substrate 10 at a temperature exceeding the Tg of the optical substrate 10.
In addition, since a base material formation process is the same as that of the base material formation process shown in FIG. 2, the same code | symbol is provided. The primer layer forming step (S305), the hard coat layer forming step (S306), and the annealing step (S308) are the primer layer forming step (S105), the hard coat layer forming step (S106), and the annealing step (shown in FIG. 2). This is the same as S107).

[Fourth Embodiment]
4th Embodiment of the manufacturing method of the optical article 1 is described based on FIG. The manufacturing method of the optical article 1 shown in FIG. 5 is that the primer layer forming step (S105) and the hard coat layer forming step (S106) are performed as the coating layer forming step in FIG. The coating layer forming step is not performed, and the coating layer forming step is performed only from the antireflection layer forming step (S405). Thereby, the coating layer 2 shown in the configuration 4 is formed on the surface of the optical substrate 10. The annealing step (S406) is performed after the coating layer forming step, similarly to the annealing step (S107) shown in FIG. Thereby, the optical article 1 is completed. In the annealing step, the coating layer 2 made of an antireflection layer and the optical substrate 10 are heated at a temperature exceeding the Tg of the optical substrate 10.
In addition, since a base material formation process is the same as that of the base material formation process shown in FIG. 2, the same code | symbol is provided.

[Base material forming step]
FIG. 6 is a schematic diagram illustrating an example of the base material forming step. FIGS. 6A and 6B are schematic views showing a specific procedure of the glass mold injection step (S102) performed after the raw material preparation step (S101), and FIG. 6C is a specific example of the thermosetting step (S103). FIG. 6D is a schematic diagram showing a specific procedure of the mold release step (S104).

  As shown in FIG. 6A, the molding glass mold 20 is for molding the optical substrate 10. In the molding glass mold 20, a pair of glass molds 21 and 22 are arranged to face each other through a gap, and an adhesive tape 23 is wound around the outer peripheral surfaces of the pair of glass molds 21 and 22 to form a cavity 24. doing. The cavity 24 surrounded by the pair of glass molds 21 and 22 and the adhesive tape 23 is formed so as to form the optical substrate 10 having a frequency of about -3D.

In the glass mold injection step (S102), as shown in FIG. 6B, the base material composition 11 obtained in the raw material preparation step is injected into the cavity 24 using the injection nozzle 25. And a thermosetting process (S103) is performed after a glass mold injection process (S102).
In the thermosetting step (S103), as shown in FIG. 6C, the base material composition 11 is cured by heating or ultraviolet irradiation to form the optical base material 10. Furthermore, a mold release step (S104) is performed after the thermosetting step (S103).
In the mold release step (S104), as shown in FIG. 6D, the adhesive tape 23 is removed from the pair of glass molds 21 and 22 and the optical base material 10, and the pair of glass molds 21 and 22 is removed from the optical base material 10. The optical substrate 10 is taken out after being separated. Thereby, the optical base material 10 is formed.

[Coating layer forming process]
7 and 8 are schematic views illustrating an example of a coating layer forming step of the method for manufacturing the optical article 1.
FIG. 7 is a schematic perspective view showing a configuration of a dipping apparatus 30 used for forming the coating layer 2 by a dipping method as an example of a wet process in the coating layer forming step. Hereinafter, as an example of the coating layer forming step of each of the embodiments described above, the primer layer forming step (S105) by the dipping method will be described with reference to FIG.

The dipping device 30 includes a tank 34 and an elevating part 31. In the tank 34, a primer composition made of urethane resin or the like as the coating composition L is stored.
The elevating unit 31 includes a gripping tool 33 and a rod 32, and the gripping tool 33 is connected to the rod 32. The raising / lowering part 31 has a structure which raises / lowers in the direction of the arrow shown in FIG. The gripping tool 33 grips the outer peripheral surface portion of the optical base material 10 and the elevating part 31 descends, so that the optical base material 10 is immersed in the coating composition L in the tank 34. After dipping, the optical substrate 10 is pulled up from the tank 34 by raising the elevating unit 31, and the coating composition L is applied to the optical substrate 10. After coating, the coating composition L applied to the optical substrate 10 is subjected to a curing treatment by heating or ultraviolet irradiation, and the coating composition L is cured to obtain the optical substrate 10 on which the primer layer is formed. . Thereby, the optical article 1 in which the coating layer 2 made of the coating composition L is formed on the surface of the optical substrate 10 is obtained. Note that the pulling speed and curing treatment conditions can be determined as appropriate.
Further, in the hard coat layer forming step (S106) and the antireflection layer forming step (S108) using the dipping device 30, the method for forming the hard coat layer and the antireflection layer is substantially the same as described above. Whether it contains a hard coat composition made of silicone or acrylic material or an organic layer composition made of organic matter, and the pulling speed and curing treatment conditions are also different. It is. In addition, the same material as before is used for the hard coat composition and the organic layer composition for the antireflection layer.

FIG. 8 is a schematic cross-sectional view showing a configuration of a vacuum deposition apparatus 40 used for forming a coating layer by a vacuum deposition method as an example of a dry process in the coating layer forming step.
Hereinafter, the vacuum evaporation method used for an antireflection layer formation process (S405) as an example of the coating layer formation process of each above-mentioned embodiment is explained based on FIG.

  The vacuum vapor deposition device 40 includes a vacuum container 41, an exhaust device 42, a gas supply device 43, and a pressure gauge 44. The vacuum deposition apparatus 40 is a so-called electron beam vacuum deposition apparatus.

The vacuum vessel 41 includes evaporation sources 46 and 47 in which a deposition material is set in the vacuum vessel 41, a filament 48 that heats and dissolves the evaporation materials of the evaporation sources 46 and 47, and a substrate on which the optical substrate 10 is placed. A support base 45, a substrate heating heater 49 for heating the optical substrate 10, and the like are provided. Further, a cold trap for removing moisture remaining in the vacuum vessel 41 as needed, a device for introducing a gas such as oxygen, ionizing and accelerating the introduced gas and irradiating the optical substrate 10, a film A device for managing the thickness is provided. Examples of the vapor deposition material include inorganic materials such as SiO ₂ , ZrO ₂ , and TiO ₂ .

  The evaporation sources 46 and 47 are crucibles in which a vapor deposition material is set, and are arranged at the lower part in the vacuum vessel 41. The thermoelectrons generated when the filament 48 generates heat are accelerated and deflected by an electron gun, and are irradiated to the vapor deposition material set in the evaporation sources 46 and 47 to evaporate. So-called electron beam evaporation is performed. The current value of the electron beam is not particularly limited, but the current value has a close relationship with the deposition rate, and can be adjusted according to the required deposition rate. In addition, other methods for evaporating the vapor deposition material include a method in which a resistor such as tungsten is energized to melt and vaporize the vapor deposition material, so-called resistance heating vapor deposition, and a method in which a material to be vaporized with high energy laser light is irradiated. There is.

  The base material support base 45 is a support base on which a predetermined number of optical base materials 10 are placed, and is disposed in the upper part of the vacuum container 41 facing the evaporation sources 46 and 47. The substrate support 45 preferably has a rotation mechanism in order to ensure the uniformity of the coating layer 2 formed on the optical substrate 10 and to improve mass productivity.

  The substrate heating heater 49 is made of, for example, an infrared lamp, and is disposed on the substrate support 45. The substrate heating heater 49 heats the optical substrate 10 to perform outgassing or moisture removal from the optical substrate 10 to ensure adhesion of the layer formed on the surface of the optical substrate 10. In addition to the infrared lamp, a resistance heater or the like can be used. However, when the material of the optical substrate 10 is plastic or resin, it is preferable to use an infrared lamp.

The exhaust device 42 is a device that exhausts the inside of the vacuum vessel 41 to a high vacuum, and includes a turbo molecular pump and a pressure control valve that keeps the pressure inside the vacuum vessel 41 constant.
The gas supply device 43 includes a gas cylinder containing a gas such as Ar, N ₂ , and O ₂ and a flow rate control device that controls the flow rate of the gas. The gas built in the gas cylinder is introduced into the vacuum vessel 41 via the flow rate control device.
The pressure gauge 44 detects the pressure in the vacuum vessel 41. Based on the pressure value detected by the pressure gauge 44, the pressure control valve of the exhaust device 42 is controlled by a control signal from a control unit (not shown), and the pressure in the vacuum vessel 41 is maintained at a predetermined pressure value. Be drunk. There are two methods for adjusting the pressure, such as a method of changing the conductance of the exhaust port and a method of changing the introduction amount by introducing gas. Therefore, the pressure in the vacuum container 41 can be controlled by a method of controlling a flow rate control device that controls the flow rate of the gas supplied from the gas cylinder of the gas supply device 43. Further, when the pressure is adjusted with the residual pressure after exhausting without particular adjustment, the refractive index may change, so the film thickness needs to be adjusted. In particular, when pressure control is not performed, the pressure may change greatly during vapor deposition.

  Examples 1 to 9 of this embodiment will be described below.

[Example 1]
In Example 1, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG.

The flowchart which shows the manufacturing method of the optical article 1 which concerns on Example 1 is FIG. 2 which shows 1st Embodiment mentioned above.
First, as a base material formation process, a raw material preparation process (S101), a glass mold injection process (S102), a thermosetting process (S103), and a mold release process (S104) are performed in order. Hereinafter, a base material formation process is demonstrated with reference to FIG. 2 and FIG.
In the raw material preparation step (S101), the base material composition 11 containing the compound represented by the general formula (1) is formed as the composition of the optical base material 10 that forms the optical article 1.
30 g of tetrakis (2,3-epithiopropylthio) tin (hereinafter referred to as “Sn-1”) is added as a raw material of the optical base material 10 and 0.3 g of SEESORB701 (manufactured by Sipro Kasei Kogyo) is added as an ultraviolet absorber. Mix well with sufficient agitation. After stirring and mixing, 0.1 g of N, N dimethylcyclohexylamine as a polymerization catalyst was added and mixed, and then deaerated for 15 minutes while stirring under reduced pressure to 1.5 kPa or less, whereby the general formula (1) The base material composition 11 containing the compound shown by is obtained. The Tg of the resin obtained by polymerizing the base composition 11 made of Sn-1 is 110 ° C.

  A glass mold injection step (S102) is performed after the raw material preparation step (S101). In the glass mold injection step (S102), the base material composition 11 is injected into the molding glass mold 20 shown in FIG. 6A as shown in FIG. 6B.

  After the glass mold injection step (S102), a thermosetting step (S103) is performed. In the thermosetting step (S103), as shown in FIG. 6C, the molding glass mold 20 and the base material composition 11 injected into the molding glass mold 20 are heated from 30 ° C. to 120 ° C. over 20 hours. The optical substrate 10 is formed by raising the temperature and polymerizing and curing the substrate composition 11.

  A mold release process (S104) is performed after a thermosetting process (S103). Thereby, as shown in FIG.6 (D), the optical base material 10 is obtained. Here, it was confirmed that the optical substrate 10 has a frequency of about -3D. Further, a plastic plate having a thickness of 2 mm was formed using two mirror-finished glass flat plates, and the optical substrate 10 was cut out with a diamond cutter. Using a Abbe refractometer, the refractive index of the D-line of 589.3 nm was measured for the refractive index of the cut optical substrate 10 using an Abbe refractometer, and it was confirmed that nd = 1.794.

After the release step (S104), a primer layer forming step (S105) and a hard coat layer forming step (S106) are performed in order as a coating layer forming step. First, the primer layer forming step (S105) will be described with reference to FIG.
Into a stainless steel tank 34, 220 g of methyl alcohol and 91.8 g of water are charged and mixed with sufficient stirring. After stirring and mixing, composite fine particle sol mainly composed of titanium oxide, tin oxide and silicon oxide (rutile type crystal structure, methanol dispersion, total solid concentration 20% by weight, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIQUE 1120Z ”, Hereinafter referred to as“ Optlake 1120Z ”), and mixed by stirring. After stirring and mixing, 77 g of aqueous polyester (manufactured by Ito Optical Co., Ltd.) is added and mixed by stirring. 0.1 g of a silicone-based surfactant (trade name “L-7604” manufactured by Nihon Unicar Co., Ltd.) is added and mixed by stirring for 2 hours. Thereby, a primer composition is obtained as the coating composition L for forming the primer layer. The optical base material 10 after the mold release step (S104) is immersed in the primer composition using an immersion apparatus 30 shown in FIG. Thereby, the primer composition is applied to the surface of the optical substrate 10. The pulling speed is 200 mm / min. The optical base material 10 coated with the primer composition is subjected to a heat treatment at 80 ° C. for 30 minutes. As a result, a primer layer formed on the surface of the optical substrate 10 is obtained.

After the primer layer forming step (S105), a hard coat layer forming step (S106) is performed. Hereinafter, the hard coat forming step (S106) will be described with reference to FIG.
Into a stainless steel tank 34, 62.5 g of butyl cellosolve and 67.1 g of γ-glycidoxypropyltrimethoxysilane are charged and mixed with sufficient stirring. Thereafter, 30.7 g of 0.1 mol / liter hydrochloric acid is dropped into the tank 34 while stirring, and further stirred for 4 hours. Thereafter, the silane hydrolyzate is obtained by aging all day and night. To this silane hydrolyzate, 325 g of Optolake 1120Z and 12.5 g of glycerol diglycidyl ether (manufactured by Nagase Kasei Co., Ltd., trade name “Denacol EX-313”) are added. Thereafter, 1.36 g of iron (III) acetylacetonate and 0.15 g of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7001”, hereinafter referred to as “L-7001”), phenolic oxidation Add 0.26 g of an inhibitor (trade name “ANTAGE CRYSTAL” manufactured by Kawaguchi Chemical Co., Ltd.) and stir for 4 hours. Thereafter, the coating composition for forming a hard coat α layer is obtained as the coating composition L by aging all day and night.
The optical base material 10 on which the primer layer has been formed in the primer layer forming step is immersed in the hard coat α layer forming coating composition using an immersion apparatus 30 shown in FIG. Thereby, the coating composition for hard coat α layer formation is applied to the surface of the primer layer formed on the surface of the optical substrate 10. The pulling speed is 200 mm / min. The optical base material 10 to which the hard coat α layer forming coating composition is applied is subjected to a heat treatment at 80 ° C. for 30 minutes. Thereby, a hard coat α layer formed on the surface of the primer layer is obtained. In this way, the coating layer 2 shown in the configuration 1 is formed on the surface of the optical substrate 10.

  After the hard coat layer forming step (S106), an annealing step (S107) is performed. In the annealing step (S107), the primer layer and the optical substrate 10 on which the hard coat α layer is formed on the surface of the primer layer are subjected to an annealing process at 125 ° C. for 3 hours. Thereby, the optical article 1 is completed.

  After the annealing step (S107), the antireflection layer forming step (S108) is performed using the immersion apparatus 30 shown in FIG. An antireflection layer is formed as a layer P indicated by a two-dot chain line on the surface of the primer layer formed on the surface of the optical substrate 10 that has been subjected to the annealing treatment, and on the surface of the hard coat α layer formed on the surface of the primer layer. To do. Thereby, the optical article 1 is completed.

[Example 2]
Below, Example 2 of the present invention is described based on a drawing.
In Example 2, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG.

The flowchart figure which shows the manufacturing method of the optical article 1 which concerns on Example 2 is FIG. 3 which shows 2nd Embodiment mentioned above.
As shown in FIG. 3, the optical article manufacturing method of Example 2 is characterized in that only the hard coat layer forming step (S205) is performed as the coating layer forming step. In addition, since a base material formation process is the same as the base material formation process shown in FIG. 2, the same code | symbol is provided and description is abbreviate | omitted.

After the release step (S104), the hard coat layer forming step (S205) of Example 2 is performed as a coating layer forming step. Hereinafter, the hard coat layer forming step (S205) will be described with reference to FIG.
As the coating composition L, the optical base material 10 after the release step (S104) is immersed in the above-described coating composition for forming the hard coat α layer using the immersion apparatus 30 shown in FIG. Thereby, the coating composition for forming the hard coat α layer is applied to the surface of the optical substrate 10. The pulling speed is set to 200 mm / min as in the first embodiment. In the same manner as in Example 1, heat treatment at 80 ° C. for 30 minutes is performed on the optical substrate 10 to which the hard coat α-layer forming coating composition has been applied. As a result, a hard coat α layer is obtained on the surface of the optical substrate 10. In this way, the coating layer 2 shown in the configuration 2 is formed on the surface of the optical substrate 10.

  After the hard coat layer forming step (S205), the annealing step (S206) is performed in the same manner as the annealing step (S107) shown in the first embodiment. After the annealing step (S206), the antireflection layer forming step (S207) is performed in the same manner as the antireflection layer forming step (S108) shown in Example 1. An antireflection layer is formed as a layer P indicated by a two-dot chain line on the surface of the hard coat α layer formed on the surface of the optical substrate 10 subjected to the annealing treatment. Thereby, the optical article 1 is completed.

[Example 3]
Hereinafter, Example 3 of the present invention will be described with reference to the drawings.
In Example 3, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG.

The flowchart showing the method for manufacturing the optical article 1 according to Example 3 is FIG. 3 showing the second embodiment described above as in Example 2.
The manufacturing method of the optical article of Example 3 is characterized in that the hard coat β layer is formed in the hard coat layer forming step (S205) shown in FIG. 3 as the coating layer forming step. In addition, since a base material formation process is the same as the base material formation process shown in FIG. 2, the same code | symbol is provided and description is abbreviate | omitted.

Hereinafter, the hard coat layer forming step (S205) of Example 3 will be described with reference to FIG.
Put 1000 parts by weight of butyl cellosolve into a stainless steel tank 34, add 1200 parts by weight of γ-glycidoxypropyltrimethoxysilane, stir well, and then add 300 parts by weight of 0.1 mol / liter hydrochloric acid for a whole day and night. Stirring is continued to obtain a silane hydrolyzate. 30 parts by weight of L-7001 was added to the silane hydrolyzate and stirred for 1 hour, and then 7300 parts by weight of a composite fine particle sol (Optlake 1120Z) mainly composed of titanium oxide was added and stirred for 2 hours. Next, 250 parts by weight of an epoxy resin (manufactured by Nagase Kasei Co., Ltd., trade name Denacol EX-313) was added and stirred for 2 hours, and then 20 parts by weight of iron (III) acetylacetonate was added and stirred for 1 hour. By performing filtration with a filter, a coating composition for forming a hard coat β layer is obtained as the coating composition L.
In the coating composition for forming a hard coat β layer, the optical substrate 10 after the releasing step is immersed using an immersion apparatus 30 shown in FIG. Thereby, the coating composition for forming the hard coat β layer is applied to the surface of the optical substrate 10. The pulling speed is set to 200 mm / min as in the first embodiment. In the same manner as in Example 1, heat treatment at 80 ° C. for 30 minutes is performed on the optical substrate 10 on which the hard coat β-layer forming coating composition has been applied. Thereby, a hard coat β layer is obtained on the surface of the optical substrate 10. In this way, the coating layer 2 shown in the configuration 2 is formed on the surface of the optical substrate 10.

  After the hard coat layer forming step (S205), the annealing step (S206) is performed in the same manner as the annealing step (S107) shown in the first embodiment. After the annealing step (S206), the antireflection layer forming step (S207) is performed in the same manner as the antireflection layer forming step (S108) shown in Example 1. An antireflection layer is formed as a layer P indicated by a two-dot chain line on the surface of the hard coat β layer formed on the surface of the optical substrate 10 subjected to the annealing treatment. Thereby, the optical article 1 is completed.

[Example 4]
Embodiment 4 of the present invention will be described below with reference to the drawings.
In Example 4, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG.

The flowchart figure which shows the manufacturing method of the optical article 1 which concerns on Example 4 is FIG. 4 which shows 3rd Embodiment mentioned above.
As shown in FIG. 4, in the method for manufacturing an optical article of Example 4, the primer layer forming step (S305) and the hard coat layer forming step (S306) are performed as the coating layer forming step, followed by the antireflection layer forming step. There is a feature in performing (S307). Note that the primer layer forming step (S305) and the hard coat forming step (S306) are the same as those in the first embodiment, and thus the description thereof is omitted. Moreover, since the base material formation process is the same as the base material formation process shown in FIG. 2, the same code | symbol is provided and description is abbreviate | omitted.

Hereinafter, the antireflection layer forming step (S307) performed after the hard coat layer forming step will be described with reference to FIG.
Into a stainless steel tank 34, 48.6 g of propylene glycol monomethyl ether and 14.1 g of γ-glycidoxypropyltrimethoxysilane are charged and mixed with sufficient stirring. Thereafter, 4 g of 0.1 mol / liter hydrochloric acid is dropped into the tank 34 while stirring, and the mixture is further stirred for 5 hours. Thereafter, 33.3 g of isopropanol-dispersed hollow silica gel (average particle size 91 nm, solid concentration 30% by weight, manufactured by Catalyst Kasei Kogyo Co., Ltd.) is added and mixed with sufficient stirring. Then, 0.03 g of L-7001 is added, sufficiently stirred, and dissolved to obtain a coating stock solution having a solid content concentration of 20%. To this coating stock solution having a solid content concentration of 20%, 114.7 g of a propylene glycol monoether solution containing a silicone-based surfactant (trade name “L-7604” manufactured by Nihon Unicar Co., Ltd.) with a concentration of 300 ppm was sufficiently added. And a coating liquid having a solid content concentration of about 4.7%, which is an organic layer composition for an antireflection layer, is obtained as the coating composition L.
The optical base material 10 after the hard coat layer forming step (S306) is immersed in the coating liquid having a solid content concentration of about 4.7% using the immersion apparatus 30 shown in FIG. Thereby, the coating liquid having a solid content concentration of about 4.7% is applied to the surface of the hard coat α layer formed in the order of the primer layer and the hard coat α layer from the surface of the optical substrate 10. The pulling speed is set to 100 mm / min as in the first embodiment. In the same manner as in Example 1, the optical base material 10 to which the coating liquid having a solid content concentration of about 4.7% is subjected to a heat treatment at 80 ° C. for 30 minutes to obtain an organic layer for an antireflection layer. Thereby, the organic layer for antireflection layers formed on the surface of the hard coat α layer is obtained. In this way, the coating layer 2 shown in the configuration 3 is formed on the surface of the optical substrate 10.

  After the antireflection layer forming step (S307), the annealing step (S308) is performed in the same manner as the annealing step (S107) shown in the first embodiment. Thereby, the optical article 1 is completed.

[Example 5]
Embodiment 5 of the present invention will be described below with reference to the drawings.
In Example 5, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG.

The flowchart which shows the manufacturing method of the optical article 1 which concerns on Example 5 is FIG. 5 which shows 4th Embodiment mentioned above.
As shown in FIG. 5, the optical article manufacturing method of Example 5 is characterized in that only the antireflection layer forming step (S405) is performed as the coating layer forming step. In addition, since a base material formation process is the same as that of the base material formation process shown in FIG. 2 of Example 1, the same code | symbol is provided and description is abbreviate | omitted.

After the release step (S104), an antireflection layer forming step (S405) is performed as a coating layer forming step. Hereinafter, the antireflection layer forming step (S405) will be described with reference to FIG.
Plasma processing is performed on the optical substrate 10 after the release step (S104). The plasma treatment condition is argon plasma 400 W for 60 seconds. In order from the surface of the plasma-treated optical substrate 10, SiO ₂ as the first layer, ZrO ₂ as the second layer, SiO ₂ as the third layer, ZrO ₂ as the fourth layer, and as the fifth layer SiO ₂ is formed by a vacuum deposition method using a vacuum deposition apparatus 40 shown in FIG. The vacuum evaporation apparatus 40 uses the device name “BMC-1000” manufactured by Vacuum Instrument Industry Co., Ltd. Thereby, the antireflection multilayer film which consists of the 1st layer which is an inorganic layer, the 2nd layer, the 3rd layer, the 4th layer, and the 5th layer as the coating layer 2 is obtained. In this way, the coating layer 2 shown in the configuration 4 is formed on the surface of the optical substrate 10.
The optical film thicknesses of the first to fifth layers constituting the antireflection multilayer film are as follows. The optical film thickness of SiO ₂ as the first layer is 0.083λ, the optical film thickness of ZrO ₂ as the second layer is 0.17λ, and the optical film thickness of SiO ₂ as the third layer is 0.075λ. The optical film thickness of ZrO ₂ as the fourth layer is 0.195λ, and the optical film thickness of SiO ₂ as the fifth layer is 0.025λ. The optical thicknesses of the first layer, the second layer, the third layer, the fourth layer, and the fifth layer are each λ / 4. The wavelength λ of the antireflection multilayer film is set to a design value of 520 nm.

  After the antireflection layer forming step, the annealing step (S406) is performed in the same manner as the annealing step (S107) shown in the first embodiment. Thereby, the optical article 1 is completed.

[Example 6]
The sixth embodiment of the present invention will be described below with reference to the drawings.
In Example 6, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG.

The flowchart showing the method for manufacturing the optical article 1 according to Example 6 is FIG. 5 showing the fourth embodiment described above, as in Example 5.
The optical article manufacturing method of Example 6 is characterized in that, as the coating layer forming step, in the antireflection layer forming step (S405) shown in FIG. 5, seven antireflection layers made of SiO ₂ and TiO ₂ are formed. There is. In addition, since a base material formation process is the same as that of the base material formation process shown in FIG. 2 of Example 1, the same code | symbol is provided and description is abbreviate | omitted.

After the release step (S104), an antireflection layer forming step (S405) is performed as a coating layer forming step. Hereinafter, the antireflection layer forming step (S405) of Example 6 will be described with reference to FIG.
Plasma processing is performed on the optical substrate 10 after the release step (S104). The plasma treatment condition is argon plasma 400 W for 60 seconds. In order from the surface of the optically treated optical substrate 10, SiO ₂ as the first layer, TiO ₂ as the second layer, SiO ₂ as the third layer, TiO ₂ as the fourth layer, and as the fifth layer SiO _2, TiO ₂ as the sixth layer, the SiO ₂ as the seventh layer, using a vacuum vapor deposition apparatus 40 shown in FIG. 8, formed by vacuum deposition. Thereby, the antireflection multilayer film which consists of the 1st layer, the 2nd layer, the 3rd layer, the 4th layer, the 5th layer, the 6th layer, and the 7th layer which are inorganic layers as the coating layer 2 is obtained. In this way, the coating layer 2 shown in the configuration 4 is formed on the surface of the optical substrate 10.
The optical film thicknesses of the first to seventh layers constituting the antireflection multilayer film are as follows. The optical film thickness of SiO ₂ as the first layer is 0.083λ, the optical film thickness of TiO ₂ as the second layer is 0.070λ, and the optical film thickness of SiO ₂ as the third layer is 0.10λ. The optical film thickness of TiO ₂ as the fourth layer is 0.18λ, the optical film thickness of SiO ₂ as the fifth layer is 0.065λ, and the optical film thickness of TiO ₂ as the sixth layer is 0.14λ. The optical film thickness of SiO ₂ as the seventh layer is 0.26λ. The optical film thicknesses of the first layer, the second layer, the third layer, the fourth layer, the fifth layer, the sixth layer, and the seventh layer are each λ / 4. The wavelength λ of the antireflection multilayer film is set to a design value of 520 nm.

  After the antireflection layer forming step (S405), the annealing step (S406) is performed in the same manner as the annealing step (S107) shown in the first embodiment. Thereby, the optical article 1 is completed.

[Example 7]
The seventh embodiment of the present invention will be described below with reference to the drawings.
In Example 7, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG. 1 has a two-layer configuration shown in Configuration 1 as in Example 1.

The flowchart showing the method for manufacturing the optical article 1 according to Example 7 is FIG. 2 showing the first embodiment described above in the same manner as Example 1.
The optical article manufacturing method of Example 7 is represented by the general formula (1) in which the optical base material 10 is formed using Sn-1 as the raw material of the optical base material 10 in the raw material preparation step (S101) shown in FIG. The feature is that tetrakis (3-oxetanylthio) tin (hereinafter referred to as “Sn-2”) is used as a raw material of the optical substrate 10 to form the substrate composition 11 containing the compound to be formed. Have.

Hereinafter, the raw material preparation step (S101) will be described.
In the raw material preparation step (S101), the base material composition 11 containing the compound represented by the general formula (1) that forms the optical base material 10 is formed.
30 g of Sn-2 as a raw material for the optical substrate 10, 0.3 g of SEESORB 701 (manufactured by Sipro Kasei Kogyo) as an ultraviolet absorber, and 0.3 g of trifluoromethanesulfonic acid as a polymerization catalyst are added and mixed with sufficient stirring. After stirring and mixing, 0.1 g of N, N dimethylcyclohexylamine as a polymerization catalyst was added and mixed, and then deaerated for 15 minutes while stirring under reduced pressure to 1.5 kPa or less, whereby the general formula (1) The base material composition 11 containing the compound shown by is obtained. The Tg of the resin obtained by polymerizing the base material composition 11 containing Sn-2 is 110 ° C.

  After the raw material preparation step (S101), the glass mold injection step (S102), the thermosetting step (S103), and the release step (S104) are performed in the same manner as in Example 1. Thereby, the optical substrate 10 is obtained. Here, it was confirmed that the optical substrate 10 has a frequency of about -3D. Further, a plastic plate having a thickness of 2 mm was formed using two mirror-finished glass flat plates, and the optical substrate 10 was cut out with a diamond cutter. Using a Abbe refractometer, the refractive index (nd) of the 589.3 nm D-line is measured with an Abbe refractometer, and it is confirmed that nd = 1.754. did. Note that the glass mold injection step (S102), the thermosetting step (S103), and the mold release step (S104) are the same as those in the first embodiment, and thus description thereof is omitted.

  After the mold release step (S104), the primer layer forming step (S105) and the hard coat layer forming step (S106) are performed in order as the coating layer forming step as in the first embodiment. In this way, the coating layer 2 shown in the configuration 1 is formed on the surface of the optical substrate 10. After the coating layer forming step, an annealing step (S107) and an antireflection layer forming step (S108) are performed in order. Thereby, the optical article 1 is completed.

[Example 8]
Hereinafter, an eighth embodiment of the present invention will be described with reference to the drawings.
In Example 8, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG. 1 has the two-layer configuration shown in Configuration 1 as in Example 1.

The flowchart showing the method for manufacturing the optical article 1 according to Example 8 is FIG. 2 showing the first embodiment described above, as in Example 1. FIG.
The manufacturing method of the optical article of Example 8 is shown by the general formula (1) in which the optical base material 10 is formed using Sn-1 as the raw material of the optical base material 10 in the raw material preparation step (S101) shown in FIG. As a raw material for the optical base material 10, tetrakis (2,3-epoxy-1-propylthio) tin (hereinafter referred to as “Sn-3”) is used to form the base material composition 11 containing the compound. It is characterized by its use.

Hereinafter, the raw material preparation step (S101) will be described.
In the raw material preparation step, the base material composition 11 containing the compound represented by the general formula (1) that forms the optical base material 10 is formed.
30 g of Sn-3 as a raw material for the optical substrate 10, 0.3 g of SESORB 701 (manufactured by Sipro Kasei Kogyo) as an ultraviolet absorber, and 0.015 g of trifluoromethanesulfonic acid as a polymerization catalyst are added and mixed with sufficient stirring. After stirring and mixing, 0.1 g of N, N dimethylcyclohexylamine as a polymerization catalyst was added and mixed, and then deaerated for 15 minutes while stirring under reduced pressure to 1.5 kPa or less, whereby the general formula (1) The base material composition 11 containing the compound shown by is obtained. The Tg of the resin obtained by polymerizing the base material composition 11 containing Sn-3 is 110 ° C.

  After the raw material preparation step, the optical substrate 10 is obtained by performing the glass mold injection step (S102), the thermosetting step (S103), and the mold release step (S104) in the same manner as in Example 1. Here, it was confirmed that the optical substrate 10 has a frequency of about -3D. Further, a plastic plate having a thickness of 2 mm was formed using two mirror-finished glass flat plates, and the optical substrate 10 was cut out with a diamond cutter. Using a Abbe refractometer, the refractive index (nd) of the 589.3 nm D-line is measured with an Abbe refractometer, and it is confirmed that nd = 1.758. did. Note that the glass mold injection step (S102), the thermosetting step (S103), and the mold release step (S104) are the same as those in the first embodiment, and thus description thereof is omitted.

  After the mold release step (S104), the primer layer forming step (S105) and the hard coat layer forming step (S106) are performed in order as the coating layer forming step as in the first embodiment. In this way, the coating layer 2 shown in the configuration 1 is formed on the surface of the optical substrate 10. After the coating layer forming step, an annealing step (S107) and an antireflection layer forming step (S108) are performed in order. Thereby, the optical article 1 is completed.

[Example 9]
The ninth embodiment of the present invention will be described below with reference to the drawings.
In Example 9, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG. 1 has a two-layer configuration shown in Configuration 1 as in Example 1.

The flowchart showing the method for manufacturing the optical article 1 according to Example 9 is FIG. 2 showing the first embodiment described above, as in Example 1. FIG.
In the manufacturing method of the optical article of Example 9, the concave side of the optical substrate 10 on which the primer layer and the hard coat α layer formed on the surface of the primer layer were formed in the annealing step (S107) shown in FIG. As shown in FIG. 9, it is arranged on the base opposite to the concave side or on the ring-shaped jig formed in the same shape as the peripheral edge of the optical substrate 10 and annealed. In addition, the concave surface side of the optical base material 10 is placed on the convex surface shape of the glass mold 26 having a convex shape so as to follow the shape of the concave surface side of the optical base material 10, and annealing treatment is performed. Features. The annealing treatment is performed at 125 ° C. for 3 hours as in the first embodiment. Thereby, the optical article 1 is completed. Since the manufacturing method other than the annealing step (S107) of Example 9 is the same as the manufacturing method of Example 1, description thereof is omitted.

[Example 10]
Optical article 1 was manufactured in the same manner as in Example 1 except that in the base material forming step, commercially available PMMA (polymethyl methacrylate) pellets were processed into a lens shape by an injection molding method to obtain optical base material 10.
When a flat plate was prepared from PMMA pellets and Tg was measured using TMA, it was 110 ° C.
[Example 11]
Optical article 1 was manufactured in the same manner as in Example 1 except that in the base material forming step, commercially available Pst (polystyrene) pellets were processed into a lens shape by an injection molding method to obtain optical base material 10.
A flat plate was prepared from Pst pellets, and Tg was measured using TMA.

  In Examples 1 to 11 described above, the Tg of the resin (that is, the optical substrate) obtained by polymerizing the substrate composition 11 constituting the optical substrate 10 is 110 ° C. or 95 ° C. Therefore, the temperature of the heat treatment for forming the coating layer 2 on the optical base material 10 is formed by curing at 80 ° C. which is equal to or lower than the Tg of the resin obtained by polymerizing the base material composition 11. Moreover, the temperature of the annealing process performed on the optical base material 10 on which the coating layer 2 is formed is 125 ° C. exceeding the Tg of the optical base material 10.

[Comparative Example 1]
In Comparative Example 1, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG. 1 has a non-layered structure that is not formed.

  The optical article manufacturing method of Comparative Example 1 is the same as the optical article 1 manufacturing method according to Example 1, but after the release step (S104), the primer layer forming step (S105) and the hard coat layer forming are performed as the coating layer forming step. The fact that the step (S106) is performed and then the annealing step (S107) is performed is characterized in that the annealing step is performed after the release step (S104).

  After the release step (S104), the optical substrate 10 is subjected to an annealing step in the same manner as the annealing step (S107) shown in the first embodiment. If necessary, a coating layer forming step may be performed after the annealing step.

[Comparative Example 2]
In Comparative Example 2, the coating layer 2 drawn on one layer of the optical article 1 shown in FIG. 1 has a two-layer configuration shown in Configuration 1 as in Example 1.

  The method for producing an optical article of Comparative Example 2 is characterized in that iron (III) acetylacetonate is used in the hard coat forming step of Example 1 and that iron (III) acetylacetonate is not included. And

  After the mold release step (S104), the primer layer forming step (S105) and the hard coat layer forming step (S106) are performed in order as the coating layer forming step as in the first embodiment. Then, after the hard coat layer forming step (S106), an annealing step is performed on the optical substrate 10 on which the primer layer and the hard coat layer are formed in the same manner as the annealing step (S107) shown in the first embodiment.

Here, the above-described Examples 1 to 11 and the optical substrates of Comparative Examples 1 and 2 and optical articles using the same were evaluated by the following evaluation methods. The evaluation items were the degree of curing of the coating layer 2 for preventing deformation, and the degree of deformation of the optical substrate 10 and the optical article 1 using the same.
Hereinafter, an evaluation method for each evaluation item will be described.

(I) Curing condition evaluation method.
The degree of curing was observed by touching the optical base material after the coating layer forming step for preventing deformation. The degree of curing was evaluated in the following three stages.
○: The coating layer for preventing deformation does not stick or collapse.
X: The coating layer for preventing deformation is sticky, or at least part of the coating layer for preventing deformation is easily removed from the optical substrate.
-: Since the coating layer for preventing deformation is not formed, evaluation is impossible.

(II) Deformation evaluation method.
The deformation of the optical substrate after the annealing step or the optical article using the optical substrate was visually observed. Deformation was evaluated in the following three stages.
A: The optical substrate or the optical article using the same is not deformed.
○: The optical substrate or the optical article using the same is hardly deformed.
X: The optical substrate or the optical article using the same is significantly deformed.

The above evaluation results are shown in Table 1.
Comparative Example 1 in which a coating layer for preventing deformation of the optical substrate is not formed on the surface of the optical substrate, and a primer layer and iron (III) acetylacetate as a coating layer for preventing deformation of the optical substrate on the surface of the optical substrate Examples 1 to 11 in which a coating layer for preventing deformation of the optical base material was formed on the surface of the optical base material, compared with Comparative Example 2 in which a hard coat layer not containing a natto was formed, It can be confirmed that the curing condition is excellent, and that the optical base material and the optical article using the same are excellent in preventing deformation.

  Therefore, according to each above-mentioned embodiment, coating layer 2 is hardened at the temperature below Tg of resin obtained by polymerizing substrate composition 11 containing the compound shown by general formula (1), and optical. Since the coating layer 2 maintains the shape of the optical substrate by being formed on the surface of the substrate 10, the optical article 1 capable of maintaining the shape and the frequency can be provided.

  In each of the above-described embodiments, the deformation preventing coating layer 2 of the optical substrate 10 is formed on the surface of the optical substrate 10, so that the deformation preventing coating layer 2 is formed on the optical substrate 10. Since the shape change is prevented, the optical article 1 capable of maintaining the shape and the frequency can be provided.

  In each of the above-described embodiments, the coating layer 2 can also serve as at least one of a primer layer, a hard coat layer, and an antireflection layer provided in a conventional optical article, and thus can be manufactured without increasing the manufacturing process. . For this reason, an optical article without deformation can be provided without complicating the configuration.

  In each of the above-described embodiments, the coating layer forming step is obtained by polymerizing the coating layer 2 for preventing deformation of the optical substrate 10 and the substrate composition 11 containing the compound represented by the general formula (1). The resin is cured at a temperature equal to or lower than the Tg of the resin and formed on the surface of the optical substrate 10, thereby making the optical substrate 10 difficult to change and then performing an annealing process at a temperature exceeding the Tg of the optical substrate 10. The internal stress of the substrate 10 is relaxed. From this, the manufacturing method of the optical article 1 which maintains a shape and frequency can be provided.

  In each of the above-described embodiments, the coating layer forming process serves as at least one of the primer layer forming process, the hard coat layer forming process, and the antireflection layer forming process, thereby shortening the process after the annealing process. . From this, the manufacturing method of the optical article 1 simplified can be provided.

Note that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a scope in which the object of the present invention can be achieved are included in the present invention.
For example, in each of the above-described embodiments, the optical substrate 10 has a shape having a concave surface and a convex surface. However, in the present invention, the optical base material 10 may have a shape having two flat surfaces, and a combination of a flat surface, a concave surface, and a convex surface. The shape may have two concave or convex surfaces, or may have a concave and flat surface and a convex and flat surface. Moreover, although the shape of the optical substrate is circular, in the present invention, it may be a polyhedron or a sphere.

  The present invention can be used for plastic eyeglass lenses, as well as dustproof glass, dustproof crystal, condenser lens, prism, microlens array, optical disk antireflection, display antireflection, solar cell antireflection, optical isolator, etc. can do.

Sectional drawing which shows schematic structure of the optical article concerning embodiment of this invention. The flowchart figure which shows the manufacturing method of the optical article which concerns on Example 1, 7-9 of the manufacturing method of the optical article concerning this embodiment. The flowchart figure which shows the manufacturing method of the optical article which concerns on Example 2, 3 of the manufacturing method of the optical article concerning embodiment of this invention. The flowchart figure which shows the manufacturing method of the optical article which concerns on Example 4 of the manufacturing method of the optical article concerning embodiment of this invention. The flowchart figure which shows the manufacturing method of the optical article which concerns on Example 5, 6 of the manufacturing method of the optical article concerning embodiment of this invention. Schematic which shows the base material formation process of the manufacturing method of the optical article concerning this embodiment. Schematic which shows an example of the coating layer formation process of the manufacturing method of the optical article concerning this embodiment. Schematic which shows an example of the coating layer formation process of the manufacturing method of the optical article concerning this embodiment. The schematic sectional drawing which shows the annealing process which concerns on Example 9 of the manufacturing method of the optical article concerning this embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Optical article, 2 ... Coating layer, 10 ... Optical base material, 11 ... Base material composition, 20 ... Molding glass mold, 21, 22 ... Glass mold, 23 ... Adhesive tape, 24 ... Cavity, 25 ... Injection nozzle , 26 ... Glass mold, 30 ... Dipping device, 31 ... Lifting unit, 32 ... Rod, 33 ... Grip, 34 ... Tank, 40 ... Vacuum deposition device, 41 ... Vacuum container, 42 ... Exhaust device, 43 ... Gas supply device , 44 ... Pressure gauge, 45 ... Base material support, 46, 47 ... Evaporation source, 48 ... Filament, 49 ... Heater for base material heating, L ... Coating composition, P ... Layer

Claims (3)

And forming an optical substrate having a thermoplastic,
And said the surface of the optical substrate to form a coating layer for preventing deformation of the optical substrate at a temperature below the glass transition point of the optical substrate,
And heating the optical substrate, wherein the coating layer is formed at a temperature above the glass transition point of the optical substrate,
Including
A method for manufacturing an optical article. In the manufacturing method of the optical article according to claim 1,
The optical substrate is formed from a substrate composition containing a compound represented by the general formula (1) .
A method for manufacturing an optical article.

(In Formula (1), M is a Sn atom, Si atom, Zr atom, Ti atom, or Ge atom. R1 is a C1-C4 alkylene group, X1 is a S atom or O atom. And n represents an integer of 0 to 4. Y is any of the following formula (1-1), formula (1-2), or formula (1-3).
In the manufacturing method of the optical article according to claim 1 or 2,
Forming the coating layer comprises:
Forming a primer layer on the surface of the optical substrate,
And said optical substrate or to form a hard coat layer on the surface of the primer layer,
And said optical substrate, the hard coat layer, or forming an anti-reflection layer on the surface of the primer layer,
Of at least one of the
A method for manufacturing an optical article.