JP5814576B2 - Processed layer formation method - Google Patents

Description

  The present invention relates to a treatment layer forming method for forming a treatment layer by applying a treatment liquid to a substrate surface of an optical article, and an optical article on which the treatment layer is formed.

  Conventionally, an immersion method has been used as a method for forming a treatment layer such as a hard coat layer on a lens. In this immersion method, a treatment layer is formed on the surface of the lens substrate by immersing the lens substrate in a treatment liquid. However, when the treatment liquid forming the treatment layer is composed of a plurality of compositions, the concentration distribution of these compositions is not uniform in the treatment liquid, and there is also a concentration deviation in the treatment layer formed on the lens surface. Occur. For example, when a hard coat layer is formed as a treatment layer, if the concentration of each composition as described above is uneven, the scratch resistance becomes non-uniform and the film thickness distribution is not uniform. It will occur and the appearance will be poor.

On the other hand, a method of forming a treatment layer by applying a treatment liquid to a lens by an ink jet method is known (for example, see Patent Document 1).
In the method of manufacturing a lens described in Patent Document 1, a processing liquid is finely formed into droplets on a lens, applied to the surface of the lens, and the surface of the processing layer is formed on a uniform surface by the leveling action of the processing liquid. Yes. Here, the leveling action is an action of forming a uniform coated surface by the fluidity of the processing liquid itself.
It has also been proposed to apply a treatment liquid to a lens by a spray method (see, for example, Patent Document 2).

JP 2003-200102 A Special table 2001-518202 gazette

By the way, even when the method as described in Patent Document 1 is used, when the processing liquid is constituted by a plurality of composition liquids, the processing liquid is stored in the ink tank in a state where the compositions are confused. For this reason, the concentration distribution of each composition constituting the processing liquid may not be uniform in the ink tank. In this case, the concentration distribution of each composition of the applied processing liquid is also biased. . In addition, in each droplet ejected by the ink jet method, the concentration distribution of each composition constituting the treatment liquid may be biased. Even in such a case, there is a problem that the concentration distribution of the applied processing liquid is biased.
The same applies to the case where the lens processing liquid is applied by the spray method as shown in Patent Document 2, and the concentration distribution of each composition constituting the processing liquid is uniform in the tank storing the processing liquid. If not, there is a bias in the concentration distribution of the applied treatment liquid.

  In view of the above-described problems, an object of the present invention is to provide a processing layer forming method capable of forming a processing layer having a uniform concentration distribution, and an optical article.

  The treatment layer forming method of the present invention is a treatment layer formation in which a treatment liquid formed by mixing n types of composition liquids (n is an integer of 2 or more) is coated on the surface of a substrate to form a treatment layer. A head part into which the composition liquid is introduced; a nozzle hole provided in the head part for ejecting the composition liquid; and the composition liquid introduced into the head part by outputting an ultrasonic wave. A spray coating method using a spray coating apparatus having an ultrasonic vibrator to be atomized, atomizing the composition liquid by ultrasonic waves output from the ultrasonic vibrator, and spraying the atomized composition liquid from a nozzle hole Then, a coating process in which the composition liquid is sequentially dropped onto the surface of the substrate, and a treatment layer that forms the treatment layer by firing the composition liquid dropped onto the surface of the substrate after the coating process. And forming the coating As long as the i-th composition liquid is the i (1 ≦ i ≦ n) -th dropped composition liquid, and the i-th application process is the step of dropping the i-th composition liquid, at least the first application is performed. It is characterized by comprising a leveling step of making the layer thickness of the dropped composition liquid uniform over the surface of the substrate after the step.

Here, the first coating step is a step in which the first composition liquid is dropped directly on the surface of the substrate, and the composition from the second coating step to the n-th coating step is dropped on the surface of the substrate. In this step, different types of composition liquids are dropped on the liquid layer.
In the present invention, in the first coating step, the composition liquid (primary composition liquid) is first dropped on the surface of the substrate by a spray coating method. At this time, in the spray coating method, the composition liquid is vibrated and atomized by the ultrasonic wave output from the ultrasonic vibrator, and the atomized composition liquid is sprayed from the nozzle hole of the head portion and applied to the lens. . At this time, since the amount of droplets of the composition liquid atomized by the frequency of the ultrasonic wave output from the ultrasonic vibrator is controlled to a substantially constant value, the amount applied to the lens is also constant, and the composition liquid is uniformly distributed. Can be applied. Further, in the leveling step after the first coating step, the leveling action of the dropped primary composition liquid can make the thickness of the primary composition liquid uniform over the surface of the substrate, A layer (initial layer) of the primary composition liquid can be formed.
Thereafter, each composition liquid (secondary to nth composition liquid) is sequentially dropped by a spray coating method in the second to nth application steps. At this time, since the spray coating method is used as described above, the dropping amount of each droplet becomes equal, and each composition liquid can be dropped uniformly within the surface of the substrate surface. Therefore, a layer of the treatment liquid in which the concentration distribution of the n kinds of composition liquids is uniform can be formed on the surface of the substrate. Accordingly, by firing the treatment liquid layer in the treatment layer forming step, a treatment layer having a uniform concentration distribution in the surface and having a uniform performance can be formed.

In the treatment layer forming method of the present invention, the spray coating apparatus includes an air injection unit that injects air from a nozzle hole toward the base material, and the coating step is performed by atomizing the sprayed from the nozzle hole. It is preferable that the composition liquid is sprayed onto the base material with air jetted from the air jet section.
In this invention, the application position of the atomized composition liquid ejected from the nozzle hole can be accurately controlled by adjusting the air ejection amount and the ejection speed ejected from the air ejection section. In addition, since the ejection position can be accurately controlled, the amount of the composition liquid dripped at the ejection position can be controlled more accurately, and as a result, a treatment liquid having a uniform concentration distribution is applied to the lens surface. Can do.

  In the treatment layer forming method of the present invention, it is preferable that in the coating step, the composition liquid is dropped by a spray coating method in descending order of surface tension.

In this invention, n kinds of composition liquids of the n-th composition liquid dropped by the n-th coating process are dropped from the first composition liquid dropped by the first coating process in descending order of the surface tension. Yes.
Here, for example, when a composition liquid having a small surface tension is dropped on the surface of the base material in the first application step, a uniform initial layer cannot be formed on the surface of the base material because the leveling action is not sufficient. As a result, interference fringes may occur on the surface of the substrate, resulting in poor appearance. On the other hand, in the present invention, an initial layer having a uniform thickness is formed on the surface of the substrate because a composition liquid having a large surface tension and a large leveling action is first dropped on the surface of the base material as a primary composition liquid. As a result, the thickness of the treatment layer is uniform and the appearance can be improved.
Similarly, even when it is necessary to use a composition liquid having a small surface tension in the second to n-th coating steps, the thickness of the treatment liquid can be changed by dropping the composition liquid having a large surface tension first. Therefore, a treatment layer having a uniform thickness can be formed.
In the leveling step after the first coating step, the surface tension of the primary composition liquid is 25 (mN / m) in order to form an initial layer having a uniform thickness by the leveling action of the primary composition liquid. ) It is preferably 40 (mN / m) or less, and the composition liquid under such conditions has sufficient leveling performance at room temperature and easily forms an initial layer of uniform thickness on the substrate surface. Can do.

  In the treatment layer forming method of the present invention, it is preferable that in the coating step, the leveling step is performed after each i-th coating step.

  In the present invention, the leveling step is also performed after each step from the second coating step to the n-th coating step. Thereby, the layer of the composition liquid dropped before each coating process and the composition liquid dropped in each coating process can be mixed with a uniform concentration distribution, and these composition liquids are confused by the leveling action. The thickness of the formed layer can be made uniform over the surface of the substrate. Therefore, a layer of processing liquid having a uniform thickness can be formed on the surface of the substrate, and by processing such a processing liquid in the processing layer forming step, the thickness is uniform and the appearance is good. A layer can be reliably formed.

  In the treatment layer forming method of the present invention, the treatment layer is formed in an inner treatment layer formed in a circular region at the center of the surface of the base material and in a radially outer region of the inner treatment layer on the surface of the base material. An inner treatment layer, and the inner treatment layer is formed of a treatment liquid configured by mixing a first composition liquid and a second composition liquid different from the first composition liquid, The outer treatment layer is a treatment liquid configured by mixing the first composition liquid and a third composition liquid having a smaller hardness than the second composition liquid and different from the first composition liquid. The coating step includes a first coating step and a second coating step, and the first coating step includes the first region over the circular region and the radially outer region of the surface of the substrate. One composition liquid is dropped, and the second coating step is performed in the circular region of the substrate. An inner coating step of dropping the composition solution, and an outer coating step of dropping said third composition liquid to the radially outer side region of the substrate is preferably provided with a.

  In the present invention, treatment layers (inner treatment layer, outer treatment layer) having different compositions can be formed on the surface of the base material in the central circular region and the outer diameter outer region. For example, when a hard coat layer is formed as a treatment layer on a substrate such as a lens, the second composition liquid having a high hardness is used in the circular region at the center of the substrate, so that It is possible to form a hard coat layer that can more reliably suppress scratches and the like. Further, when such a hard coating layer having a large hardness is formed on the entire surface of the substrate, cracks and the like are likely to occur when an external stress such as an impact is applied. On the other hand, by providing an outer treatment layer formed using a third composition liquid having a lower hardness than the second composition liquid in the outer diameter region, stress can be absorbed by the buffering action of the outer treatment layer. Damage such as cracks can be suppressed.

  At this time, in the treatment layer forming method of the present invention, after the inner coating process and before the outer coating process, the second composition liquid dropped onto the circular region is baked, and the second composition liquid is baked. It is preferable to provide a pre-baking step for fixing to the circular region.

  In this invention, after performing an inner side application process, before implementing an outer side application process, a temporary baking process is implemented. As a result, the leveling action of the second composition liquid applied in the circular region does not spread the applied region, and the inner treatment layer can be fixed in the desired circular region.

  Here, in the treatment layer forming method of the present invention, the circular region is an area of 55% or more and 75% or less of the entire surface of the base material, and the radially outer region is 25% of the entire surface of the base material. The area is preferably 45% or less.

  In the present invention, the area ratio between the circular region and the radially outer region is set to 55:45 to 75:25. By forming the inner treatment layer and the outer treatment layer with such an area ratio, the central part of the base material where it is desired to prevent scratches can be set to an appropriate hardness, and damage due to impact can be prevented well. Can do.

In the processing layer formation method of this invention, it is preferable that the said processing layer formed by baking the said processing liquid is a hard-coat layer.
The hard coat layer is a layer composed of a treatment liquid in which a plurality of composition liquids are mixed. By using the treatment layer forming method as described above, the composition ratio (concentration) of each composition liquid in the plane of the hard coat layer. Distribution) can be made uniform, uniform scratch resistance can be obtained, and a layer having a good appearance without interference fringes can be formed.

  The optical article of the present invention includes a base material, an inner treatment layer provided in a circular region at the center of the surface of the base material, and an outer treatment provided in an outer diameter region of the inner treatment layer on the surface of the base material. A hardness of the inner treatment layer is greater than a hardness of the outer treatment layer.

  In this invention, the optical article comprises an inner treatment layer in the center circular area and an outer treatment layer in the outer diameter area of the outer periphery on the surface of the substrate, and the hardness of the inner treatment layer is higher than the hardness of the outer treatment layer. It is set large. In such an optical article, since the hardness of the center part of the base material is large, scratches and the like can be suppressed. Further, when a treatment layer having such hardness is formed on the entire surface of the substrate, cracks and the like are likely to occur when an external stress such as an impact is applied. On the other hand, in the present invention, the outer treatment layer having a lower hardness than the inner treatment layer is provided in the outer diameter region, so that the stress can be absorbed by the buffering action of the outer treatment layer, and damage such as cracks is suppressed. can do.

It is the schematic which shows the spray coat apparatus used in order to apply | coat a hard-coat layer to the surface of a lens base material in the process layer formation process of 1st embodiment to this invention. It is a flowchart which shows the formation procedure of the hard-coat layer of 1st embodiment. It is the schematic which shows the state of the lens surface in each process in the formation procedure of a hard-coat layer, FIG. 3 (A) is a figure which shows the state immediately after a 1st application | coating process, FIG. The figure which shows the state immediately after a primary leveling process, FIG.3 (C) is the schematic which shows the state immediately after a 2nd application | coating process. FIGS. 4A and 4B are schematic views showing the state of the lens surface in each step in the hard coat layer forming procedure, and FIGS. 4A and 4B are views showing the state immediately after the second leveling step, and FIG. These are figures which show the state after a baking process. It is a figure which shows schematic structure of the spray coat apparatus used at the application | coating process of 2nd embodiment. It is a flowchart which shows the formation procedure of the hard-coat layer of 2nd embodiment. It is the schematic which shows the state of the lens surface in each process in the formation procedure of the hard-coat layer of 2nd embodiment, FIG. 7 (A) is a figure which shows the state immediately after a 1st application | coating process, FIG. B) is a diagram showing a state immediately after the first leveling step, FIG. 7C is a schematic diagram showing a state immediately after the second application step, and FIG. 7D is a second leveling step. It is a figure which shows the state immediately after It is the schematic which shows the state of the lens surface in each process in the formation procedure of the hard-coat layer of 2nd embodiment, FIG. 8 (A) is the schematic which shows the state immediately after a 3rd application | coating process, FIG. (B) (C) is a figure which shows the state immediately after a 3rd leveling process, FIG.8 (D) is a figure which shows the state after a baking process. It is a top view which shows the outline of the lens of 3rd embodiment. It is a flowchart which shows the formation method of the hard-coat layer of 3rd embodiment. It is the schematic which shows the state of the lens surface in each process in the formation procedure of the hard-coat layer of 3rd embodiment, FIG. 11 (A) is the surface of the lens base material immediately after a 1st leveling process, FIG. FIG. 11B is a schematic diagram illustrating the surface of the lens substrate immediately after the inner coating process, and FIG. 11C is a schematic diagram illustrating the surface of the lens substrate immediately after the outer coating process.

[First embodiment]
Hereinafter, the processing layer formation method of 1st embodiment which concerns on this invention is demonstrated based on drawing.
FIG. 1 is a schematic view showing a spray coating apparatus for applying a hard coat layer on the surface of a lens substrate. FIG. 2 is a flowchart showing a procedure for forming a hard coat layer.

The treatment layer forming method of the first embodiment is a method of forming a hard coat layer as a treatment layer on a spectacle lens as an optical article (hereinafter referred to as a lens).
This hard coat layer is a layer formed by mixing and baking a plurality of kinds (two kinds in this embodiment) of composition liquids. In order to eliminate appearance defects such as interference fringes, such a hard coat layer is formed in a uniform thickness dimension on the surface of the lens substrate, and in order to make the scratch resistance uniform, It is necessary to form so that the composition ratios of a plurality of types of composition liquids to be formed are the same, that is, the concentration distribution of each composition in the plane is uniform. In the present invention, in order to form such a hard coat layer, each composition liquid is applied by a spray coat method using a spray coat apparatus 100 as shown in FIG. 1 according to a processing procedure as shown in FIG.

[Configuration of spray coating equipment]
First, the structure of the spray coat apparatus 100 used for application | coating of each composition liquid is demonstrated based on FIG. For example, as shown in FIG. 1, the spray coating apparatus 100 includes two ultrasonic spray units 110 (a first ultrasonic spray unit 110 </ b> A and a second ultrasonic spray unit 110 </ b> B) and a lens on which the lens substrate 1 is held. A holding unit 101 and a control unit 102 are provided.
The ultrasonic spray unit 110 includes an ultrasonic nozzle 111 (head unit), a tank 112 connected to the ultrasonic nozzle 111, an air injection unit 113 provided in the vicinity of the ultrasonic nozzle 111, and the ultrasonic nozzle 111. And a head moving unit 114 to be moved.

The ultrasonic nozzle 111 is connected to the tank 112 and the composition liquid stored in the tank 112 is introduced. Here, the primary composition liquid stored in the first tank 112A is introduced into the ultrasonic nozzle 111 of the first ultrasonic spray unit 110A, and the first ultrasonic composition 111 is stored in the ultrasonic nozzle 111 of the second ultrasonic spray unit 110B. The secondary composition liquid stored in the second tank 112B is introduced.
The ultrasonic nozzle 111 has an ultrasonic transducer 115 and a nozzle hole 116, respectively.
The ultrasonic vibrator 115 is configured by, for example, a piezoelectric element to which a pair of electrodes are connected, and when a voltage is applied between the pair of electrodes, the piezoelectric element vibrates and outputs ultrasonic waves. As a result, the composition liquid introduced into the ultrasonic nozzle 111 is vibrated by the ultrasonic wave output from the ultrasonic vibrator 115 to be atomized and ejected from the nozzle hole 116.

The tank 112 is a container in which the composition liquid is stored. The primary composition liquid is stored in the first tank 112A, and the secondary composition liquid is stored in the second tank 112B. In each of the first tank 112A and the second tank 112B, each composition liquid is stored alone, so that it does not mix and the concentration distribution is kept constant.
Here, the first composition liquid is a composition liquid that is first dropped on the surface of the lens substrate 1, and the second composition liquid is a composition liquid that is dropped after the first composition liquid is dropped. The primary composition liquid has a larger surface tension than the secondary composition liquid. The surface tension of the primary composition liquid is, for example, 25 (mN / m) or more in order to form a uniform primary composition liquid layer on the surface of the lens substrate 1 in the first leveling step described later. It is preferable to adjust to 40 (mN / m) or less, and in this embodiment, it is adjusted to 30 (mN / m).
Specifically, the first tank 112A stores a coating liquid in which a silicon-based hard coating agent whose surface tension is adjusted with a surfactant is dissolved in a butyl cellosolve solvent as a primary composition liquid. 112B stores a coating liquid in which an amine-based curing catalyst is dissolved in a methanol solvent as a secondary composition liquid.

  The air injection unit 113 is provided in the vicinity of the nozzle hole 116 of the ultrasonic nozzle 111. The air injection unit 113 introduces air toward the lens base 1 held by the lens holding unit 101, that is, blows air at a predetermined flow rate and a predetermined wind speed. Thereby, the air injection part 113 can spray and apply | coat the composition liquid ejected from the nozzle hole 116 of the ultrasonic nozzle 111 to the lens base material 1. FIG.

The head moving unit 114 is provided in the ultrasonic nozzle 111 and moves the ultrasonic nozzle 111 along the x-axis, y-axis, and z-axis that are orthogonal to each other under the control of the control unit 102. The head moving unit 114 is provided for the ultrasonic nozzle 111 of the first ultrasonic spray unit 110A and the ultrasonic nozzle 111 of the second ultrasonic spray unit 110B, respectively. The ultrasonic nozzle 111 of 110A and the ultrasonic nozzle 111 of the second ultrasonic spray unit 110B can be individually moved.
Any configuration may be used as such a head moving unit 114. For example, a rail provided along the y-axis, a pole erected along the z-axis on the rail, a drive shaft provided along the x-axis at the tip of the pole, and a drive shaft A holding unit that holds the ultrasonic nozzle 111 movably on the z-axis, a Y driving unit that moves the pole in the y-axis direction on the rail, and an X moving unit that moves the holding unit on the driving axis in the x-axis direction; A configuration including Z moving means for moving the ultrasonic nozzle 111 along the z axis can be exemplified.
Here, the head moving unit 114 that individually moves the ultrasonic nozzle 111 of the first ultrasonic spray unit 110A and the ultrasonic nozzle 111 of the second ultrasonic spray unit 110B is illustrated. The ultrasonic nozzle 111 of the ultrasonic spray unit 110A and the ultrasonic nozzle 111 of the second ultrasonic spray unit 110B are each held by one holding member, and this holding member is moved along the xyz axis by one head moving unit. It is good also as a structure to make. Furthermore, the configuration is not limited to the configuration in which the ultrasonic nozzle 111 is moved. For example, the configuration may be such that the lens holding unit 101 or a stage (not shown) provided with the lens holding unit 101 is moved along the xyz axis.

  The lens holding unit 101 holds the lens substrate 1 with the surface of the lens substrate 1 on which the hard coat layer is formed facing the ultrasonic nozzle 111. The lens holding unit 101 may include a posture adjusting mechanism that adjusts the holding angle of the held lens base material 1.

The control unit 102 controls the overall operation of the spray coating apparatus 100.
Specifically, the control unit 102 controls the head moving unit 114 to move the ultrasonic nozzle 111 to a predetermined position. Then, while moving the ultrasonic nozzle 111, a voltage is applied to the ultrasonic vibrator 115 of the ultrasonic nozzle 111 to atomize each composition liquid supplied from the tank 112, and the air injection unit 113 is driven. The atomized composition liquid is sprayed and applied to the surface of the lens substrate 1.
At this time, the control unit 102 controls the head moving unit 114 to move the ultrasonic nozzle 111 in a spiral shape so as to draw a circle from the center point of the lens substrate 1 toward the outer peripheral edge. Apply. Thereby, the composition liquid can be uniformly dropped onto the surface of the lens substrate 1.

[Method of forming hard coat layer]
Next, a forming method for forming a hard coat layer on the surface of the lens substrate 1 will be described. In the formation of the hard coat layer, as shown in FIG. 2, the first coating step S1, the first leveling step S2, the second coating step S3, the second leveling step S4, and the baking step S5 (treatment layer formation). Step). Note that the first application step S1, the first leveling step S2, the second application step S3, and the second leveling step S4 are application steps of the present invention.
3 and 4 are schematic views showing the state of the lens surface in each step in the procedure for forming the hard coat layer as described above, and FIG. 3 (A) shows the state immediately after the first coating step S1. FIG. 3B is a diagram showing a state immediately after the first leveling step S2, FIG. 3C is a schematic diagram showing a state immediately after the second coating step S3, and FIG. FIGS. 4A and 4B are views showing a state immediately after the second leveling step S4, and FIG. 4C is a view showing a state after the firing step S5.

(First application process)
The first application step S1 is a step of applying (dropping) the first composition liquid supplied from the first tank 112A onto the surface of the lens substrate 1 using the spray coating apparatus 100 described above. In this primary coating step, as shown in FIG. 3A, the dropped primary composition liquid droplets 11 are dropped onto the surface of the lens substrate 1 in an adjacent state.

(First leveling process)
The first leveling step S2 is a step in which the primary composition liquid droplets 11 are left in a dropped state for a predetermined time after the first coating step S1. As described above, the primary composition liquid has a sufficient surface tension to form the uniform initial layer 12 by the leveling action. Therefore, by leaving the lens base material 1 to which the first composition liquid is dropped, the initial layer 12 that is a layer of the first composition liquid is formed.
Here, the standing time in the first leveling step S2 is preferably 5 seconds or more and less than 20 seconds, and more preferably 10 seconds. When the time of the primary leveling step is less than 5 seconds, the primary composition liquid is not sufficiently uniformed by the leveling action, and the initial layer 12 has a non-uniform thickness. In addition, when the time of the first leveling step S2 is 20 seconds or more, liquid sagging, dust adhesion, and the like occur, resulting in poor appearance. On the other hand, by setting the time as described above, it is possible to form the initial layer 12 having a uniform layer thickness, and it is possible to suppress liquid sagging and dust adhesion that cause poor appearance.

(Secondary coating process)
The second coating step S3 is an initial stage in which the secondary composition liquid supplied from the second tank 112B is formed on the surface of the lens substrate 1 by using the spray coating apparatus 100, as in the first coating step S1. This is a step of applying (dropping) on the layer 12. In this secondary coating step, as shown in FIG. 3C, the dropped secondary composition liquid droplets 13 are dropped onto the surface of the lens substrate 1 in an adjacent state.
Here, in FIG. 3C, in order to make each process easy to understand, there is a boundary between the droplet 13 of the secondary composition liquid and the initial layer 12, and it is displayed as separated. Actually, the initial layer 12 and the dropped droplets of the secondary composition liquid 13 are mixed simultaneously with the dropping of the secondary composition liquid. At this time, each droplet 13 of the secondary composition liquid that is dropped by the spray coating method has the atomization size of the composition liquid determined by the ultrasonic frequency of the ultrasonic vibrator 115. The amount can be made uniform, and it is dropped with a uniform dropping amount. For this reason, at each position on the surface of the lens substrate 1, the mixing ratio of the primary composition liquid of the initial layer 12 and the dropped secondary composition liquid is uniform in the plane.

(Secondary leveling process)
The second leveling step S4 is a step of leaving the second composition liquid droplets 13 dropped for a predetermined time after the second coating step S3, as in the first leveling step S2. Thus, a uniform mixed layer 14 is formed as shown in FIGS. 4A and 4B by the leveling action of the primary composition liquid and the secondary composition liquid. In FIG. 4A, the primary composition liquid layer and the secondary composition liquid are shown in order to show that the mixed layer 14 is composed of a mixed liquid of the primary composition liquid and the secondary composition liquid. However, in actuality, as shown in FIG. 4B, a mixed layer of processing liquid in which these primary composition liquid and secondary composition liquid are uniformly mixed is shown. 14 is formed.
Here, as in the first leveling step S2, the standing time in the second leveling step S4 is preferably 5 seconds or more and less than 20 seconds, and more preferably 10 seconds. This is the same reason as the first leveling step. That is, when the standing time is less than 5 seconds, the primary composition liquid is not sufficiently uniformized by the leveling action, and the layer thickness of the mixed layer 14 becomes nonuniform. In addition, when the time of the second leveling step S4 is 20 seconds or more, liquid sagging, dust adhesion, and the like occur, resulting in poor appearance. On the other hand, by setting the time as described above, it is possible to form the mixed layer 14 having a uniform layer thickness, and it is possible to suppress liquid sagging and dust adhesion that cause poor appearance.

(Baking process)
The firing step S5 is a step of firing the mixed layer 14 formed by the coating steps S1 to S4 at, for example, 80 ° C. for 2 hours to form the hard coat layer 15.

[Operational effects of the first embodiment]
In the method for forming a hard coat layer according to the first embodiment as described above, in the first coating step S1, a primary composition liquid that is one type of composition liquid that constitutes the processing liquid for forming the hard coat layer is used. It is dropped on the surface of the lens substrate 1 by a spray coating method using the spray coating apparatus 100. Then, in the first leveling step S2, the primary composition liquid layer (initial layer 12) having a uniform thickness is formed on the surface of the lens substrate 1 by the leveling action of the dropped primary composition liquid. Then, in the second coating step S3, the secondary composition liquid is dropped on the formed initial layer 12 by a spray coating method, and the formed mixed layer 14 is baked in the baking step, which is a treated layer. Form a layer.
In such a method of forming the hard coat layer, the primary composition liquid is dropped by the spray coating method, so that the dropping amount of each droplet 11 of the primary composition liquid dropped on the surface of the lens substrate 1 is equal. Each droplet 11 can be dropped at an equal interval. Therefore, in the primary leveling step, the initial layer 12 having a uniform thickness can be formed by the leveling action of the droplets 11 of the primary composition liquid. Similarly, a droplet 13 of the secondary composition liquid is dropped on the initial layer 12 by a spray coating method. For this reason, the mixing ratio of the primary composition liquid and the secondary composition liquid in the mixed layer 14 formed on the surface of the lens substrate 1 becomes uniform. Therefore, in the hard coat layer 15 formed by firing such a mixed layer 14, the composition ratio of each composition liquid is uniform in the plane, and the scratch resistance and the like of the hard coat layer 15 are also uniform. . Furthermore, since each composition liquid is dropped using the spray coat method and the film thickness is made uniform by the leveling action, the layer thickness of the mixed layer 14 becomes uniform and the layer thickness of the hard coat layer 15 becomes uniform. Therefore, it is possible to form the hard coat layer 15 having a good appearance without interference fringes and the like.

Here, when the composition liquid is dropped by the ink jet method, reaction and aggregation of the composition liquids may occur in the tank or the ink jet head, and a heavy molecular weight body may be formed. In addition, since it is necessary for the ink jet apparatus to make the nozzle hole a minute hole diameter in order to control the discharge amount, when the agglomerated composition liquid or the heavy molecular weight as described above is generated, the treatment liquid is discharged from the nozzle hole. It may be difficult to discharge the liquid, and the processing liquid may not be applied uniformly.
On the other hand, in this embodiment, each composition liquid is stored in a separate tank and applied by a spray coating method. In such a spray coating method, since the droplet size of the composition liquid is determined not by the hole diameter of the nozzle hole 116 but by the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115, the hole diameter of the nozzle hole 116 is determined by the inkjet apparatus. Thus, it is not necessary to form a small diameter. Therefore, the nozzle hole 116 can be formed in a relatively large hole diameter, and each composition liquid can be ejected from the nozzle hole 116 even when aggregation or the like occurs. Therefore, compared with the ink jet method, the range of ink properties that can be adapted is wide, and the degree of freedom in designing the liquid can be expanded.
Further, in the spray coating method, the spray discharge itself becomes a solvent removal process, and the concentrated liquid lands. For this reason, it is possible to increase the thickness of the treatment layer (hard coat layer) to be formed.

  In addition, since each of the composition liquids stored in the first tank 112A and the second tank 112B is stable as a single unit with respect to changes in chemical liquid characteristics over time, for example, a plurality of composition liquids are contained in the tank. Compared with the case where the processing liquid which mixed these is stored, the lifetime of each composition liquid can be extended and manufacturing cost can be reduced.

  Further, the spray coating apparatus 100 is provided with an air injection unit 113 in the vicinity of the nozzle hole 116 of the ultrasonic nozzle 111, and the composition liquid ejected from the nozzle hole 116 is sprayed onto the lens substrate 1 by air. Applied. For this reason, since the application position of the composition liquid is assisted by the air of the air injection unit, the application position can be easily controlled, and even a surface having a curved surface such as a lens is easily uniform. A treatment layer (hard coat layer) with a sufficient thickness can be formed.

Furthermore, when it is desired to change the composition ratio of each composition liquid constituting the hard-coat layer, the composition liquid to be atomized by changing the vibration frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 in the spray coat apparatus 100. The amount of droplets can be adjusted, and the composition ratio can be easily changed on the surface of the lens substrate 1. Therefore, even when a hard coat layer having different properties is formed, it is not necessary to separately purify the composition liquid, and the composition ratio of the composition liquid can be changed on the lens substrate 1 to cause the reaction. Can be improved.
In addition, it is not necessary to perform the first application process and the second application process in separate production lines, and these application processes can be completed in the spray coating apparatus 100. Therefore, a long production line is unnecessary and the number of processes can be reduced.

  The first composition liquid has a surface tension larger than that of the second composition liquid, and is first dropped on the surface of the lens substrate 1 in the first application step S1. For this reason, the initial layer 12 having a uniform layer thickness can be formed by the first leveling step S2. When such an initial layer 12 is formed, even when a secondary composition liquid having a low surface tension is dropped on the initial layer 12, the mixed layer of the primary composition liquid and the secondary composition liquid is easily uniformized. The hard coat layer 15 having a good appearance can be formed.

  In the present embodiment, the second leveling step S4 is performed after the second coating step S3. For this reason, the mixed layer 14 having a uniform layer thickness can be more reliably formed, the layer thickness of the hard coat layer 15 can be more reliably uniformed, and inconveniences such as poor appearance can be prevented. it can.

[Second Embodiment]
In the first embodiment, the example in which the hard coat layer is formed by using two kinds of composition liquids (the first composition liquid and the second composition liquid) is shown, but the composition is constituted by three or more kinds of composition liquids. A similar procedure can be used when the hard coat layer is formed from the treatment liquid.
In the second embodiment, a forming method for forming a hard coat layer with a processing liquid obtained by mixing three kinds of composition liquids will be described.

FIG. 5 is a diagram showing a schematic configuration of a spray coating apparatus used in the coating process of the second embodiment. FIG. 6 is a flowchart showing a procedure for forming a hard coat layer according to the second embodiment. 7 and 8 are schematic views showing the state of the lens surface in each step in the procedure for forming the hard coat layer as described above, and FIG. 7A shows the state immediately after the first coating step S1. FIG. 7B is a diagram showing a state immediately after the first leveling step S2, FIG. 7C is a schematic diagram showing a state immediately after the second coating step S3, and FIG. D) is a diagram showing a state immediately after the second leveling step S4, FIG. 8A is a schematic diagram showing a state immediately after the third coating step S6, and FIGS. 8B and 8C are The figure which shows the state immediately after 3rd leveling process S7, FIG.8 (D) is a figure which shows the state after baking process S5.
In the following description of the embodiment, the same reference numerals are given to the same configurations and processes as those in the first embodiment, and the description thereof is omitted or simplified.

Since the treatment liquid for forming the hard coat layer of the second embodiment uses three kinds of composition liquids (first composition liquid, second composition liquid, and third composition liquid), these treatment liquids are used. As shown in FIG. 5, the spray coating apparatus 100 for applying the composition liquid to the surface of the lens substrate 1 includes three ultrasonic spray units 110 (110A, 110B, 110C), and 3 corresponding to each. Two tanks (112A, 112B, 112C) are provided.
In this embodiment, in order to show an example in which a hard coat layer is formed by a processing liquid obtained by mixing three kinds of composition liquids (a first composition liquid, a second composition liquid, and a third composition liquid), these However, in the case where a treatment layer such as a hard coat layer is formed with four or more composition liquids, the number of tanks corresponding to the number of the composition liquids is provided. Is provided.
Here, the first composition liquid is stored in the first tank 112A, the second composition liquid is stored in the second tank 112B, and the third composition liquid is stored in the third tank 112C. The surface tension of each composition liquid has a relationship of (surface tension of primary composition liquid)> (surface tension of secondary composition liquid)> (surface tension of tertiary composition liquid).
As an example of such a composition liquid, for example, as a primary composition liquid, a coating liquid of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane in a butyl cellosolve solvent (surface tension: about 30 (mN / m)), As the secondary composition liquid, a coating liquid (surface tension: about 20 (mN / m)) in which metal oxide fine particles mainly composed of titanium oxide and silicon oxide are dispersed in methanol, and as the third composition liquid, aluminum (III). A coating solution (surface tension: about 15 (mN / m)) in which acetylacetonate is dissolved in a methanol solvent can be used.

  And in formation of the hard-coat layer of 2nd embodiment, as shown in FIG. 6, 1st coating process S1, 1st leveling process S2, 2nd coating process S3, 2nd leveling process S4, 1st A tertiary coating step S6, a third leveling step S7, and a firing step S5 (treatment layer forming step) are performed. In the present embodiment, the first coating step S1, the first leveling step S2, the second coating step S3, the second leveling step S4, the third coating step S6, and the third leveling step S7 are performed. This is the coating process of the present invention.

The formation method of such a hard-coat layer of 2nd embodiment is 1st application | coating process S1-2nd leveling process S4 (FIG.7 (A)-(D)) by the procedure similar to said 1st embodiment. ).
And after 2nd leveling process S4, 3rd application | coating process S6 is implemented and a 3rd composition liquid is dripped on the mixed layer 14. As shown in FIG. This third coating step S6 is supplied from the third tank 112C as shown in FIG. 8A using the spray coater 100, as in the first coating step S1 and the second coating step S3. A droplet 16 of the third composition liquid is dropped on the mixed layer 14 formed on the surface of the lens substrate 1.
Here, in FIG. 8A, there is a boundary between the liquid droplet 16 of the tertiary composition liquid and the mixed layer 14 and they are displayed as separated from each other. Simultaneously with the dropping of the composition liquid, the mixed layer 14 and the dropped liquid droplet 16 of the third composition liquid are mixed.

In the third leveling step S7, as in the first leveling step S2 and the second leveling step S4, the third composition liquid droplet 16 is dropped for a predetermined time after the third coating step S6. This is a step of leaving it in a state where it is applied. Thus, a uniform mixed layer 17 is formed as shown in FIGS. 8B and 8C by the leveling action of the primary composition liquid, the secondary composition liquid, and the tertiary composition liquid. In FIG. 8B, the initial layer 12 and the third composition liquid layer are separated to show that the mixed layer 17 is constituted by mixing the initial layer 12 and the third composition liquid. Actually, as shown in FIG. 8C, a mixed layer 17 of processing liquid in which the primary composition liquid, the secondary composition liquid, and the tertiary composition liquid are uniformly mixed is shown. It is formed.
Here, also in the standing time in the third leveling step S7, like the first leveling step S2 and the second leveling step S4, it is preferably 5 seconds or more and less than 20 seconds, more preferably 10 seconds. .
Thereafter, as shown in FIG. 8D, a firing step S5 is performed, and the mixed layer 17 is fired to form the hard coat layer 15A.

[Effects of Second Embodiment]
In the second embodiment as described above, the following operational effects can be obtained in addition to the operational effects of the first embodiment.

  That is, a coating liquid in which metal oxide fine particles are dispersed in methanol is used as the second composition liquid, and a coating liquid in which aluminum (III) acetylacetonate is dissolved in a methanol solvent is used as the third composition liquid. The scratch resistance can be improved.

  Furthermore, leveling performance is difficult only with the secondary composition liquid (surface tension: 20 (mN / m)) and the tertiary composition liquid (surface tension: 15 (mN / m)). In the first application step and the first leveling step, the initial layer 12 made of the first composition liquid having a large surface tension is formed, so that the low leveling performance can be compensated. Therefore, no interference fringes are formed on the formed hard coat layer, and the appearance can be improved.

  In addition, when a processing liquid in which three kinds of composition liquids are mixed or a processing liquid in which two of the three kinds are mixed is used, heavy molecular weight formation or molecular aggregate formation occurs due to reaction in the processing liquid, As the particle diameter increases, it may be difficult to eject the processing liquid from the nozzle holes. On the other hand, in this embodiment, since the three kinds of composition liquids are stored in separate tanks and sequentially applied by the spray coating method, inconvenience at the time of discharging the composition liquid due to clogging of nozzle holes or the like is avoided. It is possible to react and form compounds such as heavy molecular weights on the surface of the lens.

[Third embodiment]
Next, the optical article and the processing layer forming method of the third embodiment of the present invention will be described.
That is, in the first embodiment and the second embodiment described above, a lens in which one hard coat layer formed of a treatment liquid obtained by mixing a plurality of types of composition liquids is provided on the surface of the lens base 1 is exemplified. In contrast, in the third embodiment, a lens in which two types of hard coat layers having different hardnesses are formed in different regions and a method for forming the hard coat layer will be described.

[Lens configuration]
FIG. 9 is a plan view schematically showing the lens 200 of the third embodiment.
As shown in FIG. 9, the lens 200 of the third embodiment includes an inner hard coat layer 201 as an inner treatment layer formed in a circular area Ar <b> 1 in the center of the surface of the lens substrate 1, and the surface of the lens substrate 1. And an outer hard coat layer 202 as an outer treatment layer formed in the outer diameter area Ar2 of the circular area Ar1. The inner hard coat layer 201 has a higher hardness than the outer hard coat layer 202.

  Here, the area ratio between the circular region Ar1 where the inner hard coat layer 201 is provided and the radially outer region Ar2 where the outer hard coat layer 202 is provided is preferably 55:45 to 75:25. This is because, when the area of the inner hard coat layer 201 is less than 55% of the entire surface of the lens substrate 1 and when the area of the inner hard coat layer 201 occupies an area greater than 75%, the impact resistance of the hard coat layers 201 and 202 decreases. Because it will end up. In the present embodiment, the area ratio between the inner hard coat layer 201 and the outer hard coat layer 202 is set to 60:40.

[Method of forming hard coat layer]
FIG. 10 is a flowchart showing a method for forming a hard coat layer in the third embodiment. FIG. 11 schematically shows the surface of the lens substrate 1 immediately after the first leveling step S2, the surface of the lens substrate 1 immediately after the inner coating step S31, and the surface of the lens substrate 1 immediately after the outer coating step S33. FIG.
The formation method of the hard coat layer of the third embodiment is an application example of the first embodiment and the second embodiment, and two substantially similar hard coat layer formation methods are used on the surface of the lens substrate 1. A hard coat layer is formed.
That is, the inner hard coat layer 201 and the outer hard coat layer 202 are treatment layers formed by a treatment liquid composed of a primary composition liquid and a secondary composition liquid, respectively. Here, in the inner hard coat layer 201 and the outer hard coat layer 202, the same composition liquid (first composition liquid) was used as the first composition liquid, and the surface tension was adjusted with a surfactant in, for example, a butyl cellosolve solvent. A coating solution in which a silicon hard coat agent is dissolved is used. On the other hand, as the secondary composition liquid, different types of composition liquids are used for the inner hard coat layer 201 and the outer hard coat layer 202. That is, as the secondary composition liquid of the inner hard coat layer 201, a coating liquid (second composition liquid) in which iron (III) acetylacetonate is dissolved in a methanol solvent is used, and the secondary composition of the outer hard coat layer 202 is used. As the liquid, a coating liquid (third composition liquid) in which manganese (III) acetylacetonate is dissolved in a methanol solvent is used.

  And as shown in FIG. 10, the hard-coat layers 201 and 202 of 3rd embodiment are 1st coating process S1, 1st leveling process S2, inner side coating process S31, temporary baking process S32, outer side coating process S33. , And the procedure of baking step S5. Here, the inner coating step S31, the pre-baking step S32, and the outer coating step S33 are steps in which the secondary composition liquid is dropped onto the initial layer 12 formed from the primary composition liquid. It corresponds to a process. Therefore, the first application step S1, the first leveling step S2, the inner side application step S31, the temporary baking step S32, and the outer side application step S33 are the application steps of the present invention.

  Further, in forming the hard coat layers 201 and 202, each composition liquid is used by using a spray coat apparatus 100 having at least three first tanks 112A, second tanks 112B and third tanks 112C as shown in FIG. Is applied. Here, the first composition liquid (first composition liquid) is stored in the first tank 112A, and the second composition liquid constituting the processing liquid for forming the inner hard coat layer 201 is stored in the second tank 112B. Is stored, and the third tank 112C stores a third composition liquid that is a secondary composition liquid that constitutes the processing liquid for forming the outer hard coat layer 202.

The first application step S1 and the first leveling step S2 are the same steps as those in the first embodiment and the second embodiment, and as shown in FIG. Then, the primary composition liquid is applied to form the initial layer 12 having a uniform thickness.
In the inner coating step S31, as shown in FIG. 11B, the second composition liquid supplied from the second tank 112B is applied to the circular region Ar1 of the initial layer 12 using the spray coater 100. Dripping. In the inner coating step S31, the dropped second composition liquid is mixed with the primary composition liquid of the initial layer 12, and the mixing ratio of the primary composition liquid and the second composition liquid in the circular region Ar1 is An inner mixed layer 18 that is uniform in the plane is formed.
And temporary baking process S32 is implemented immediately after inner side application | coating process S31. In this temporary baking step S32, for example, baking is performed at 80 ° C. for 30 minutes to fix the second composition liquid applied to the circular region Ar1, and the spread to the radially outer region Ar2 is prevented.
Thereafter, an outer coating step S33 is performed. In the outer coating step S33, as shown in FIG. 11C, the third composition liquid supplied from the third tank 112C is applied to the radially outer region Ar2 in the initial layer 12 using the spray coater 100. And dripping. Thereby, the dropped third composition liquid is mixed with the first composition liquid of the initial layer 12, and the mixing ratio of the first composition liquid and the third composition liquid in the outer diameter area Ar2 is in-plane. A uniform outer mixed layer 19 is formed.
Finally, the firing step S5 is performed, and the formed mixed layer is fired to form hard coat layers 201 and 202 as shown in FIG.

[Operational effects of the third embodiment]
The third embodiment can exhibit the following operational effects in addition to the operational effects of the first embodiment.
That is, the lens 200 of the third embodiment is formed in the inner hard coat layer 201 formed in the center circular region Ar1 and the outer diameter outer region Ar2 outside the circular region Ar1 on the surface of the lens substrate 1. The outer hard coat layer 202, and the inner hard coat layer 201 is formed with a hardness greater than that of the outer hard coat layer 202.
Therefore, the inner hard coat layer 201 can prevent scratches at the center of the lens 200, and the lens 200 having excellent scratch resistance can be provided. Further, when a hard coat layer having a high hardness is formed on the entire surface of the lens 200, it is vulnerable to impact, and for example, cracks or the like are likely to enter the hard coat layer. On the other hand, since the outer hard coat layer 202 having a smaller hardness than the inner hard coat layer 201 is provided in the radially outer region Ar2, when an impact is applied, the buffer action of the outer hard coat layer 202 Damage to the inner hard coat layer 201 can be suppressed, and the lens 200 having a hard coat layer resistant to impact can be provided.
Here, when the area of the inner hard coat layer 201 is less than 55% or more than 75% of the surface of the lens substrate 1, the impact resistance is lowered. In contrast, in the present embodiment, the area of the inner surface of the lens substrate 1 occupied by the inner hard coat layer 201 is 60%, and the area of the outer hard coat layer 202 is 40%. Therefore, good impact resistance can be obtained.

  In addition, when two kinds of different hard coat layers are formed, it is difficult to manufacture by a conventionally used dipping method or spin coat method. On the other hand, when the composition liquid is applied by the spray coating method, the composition liquid can be accurately applied to a desired position of the lens substrate, and the two different hard coat layers described above are in-plane. It is possible to easily form a lens formed in another area.

In the lens 200 as described above, as in the first embodiment and the second embodiment, each composition liquid is dropped on the lens base material 1 in order by a spray coating method, and After the next coating process, a first leveling process is performed. For this reason, in the hard coat layers 201 and 202, the composition ratio of the composition liquids in the surface is uniform, so that the hard coat layers 201 and 202 having uniform scratch resistance can be formed, and the uniform Since it can be formed in a layer thickness, there is no defect such as interference fringes and the appearance can be improved.
Such a lens having excellent impact resistance can prevent the lens surface from being damaged in a special environment accompanied by intense exercise such as behavior during a disaster or lifesaving. Further, the present invention can be applied to an optical lens such as a camera lens or a telescope lens in which the central portion is exposed and protrudes and the outer peripheral portion is held by a casing.

  Furthermore, after the inner coating step S31, the temporary baking step S32 is performed, and then the outer coating step S33 is performed. The hard coat layers 201 and 202 can be formed in desired regions without protruding into the region Ar2.

[Modification]
It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
For example, in each of the above embodiments, the optical article has been described as a spectacle lens, but the present invention is not limited thereto, and may be a lens incorporated in another optical device such as a camera lens or a telescope lens. Further, the present invention is not limited to lenses as optical articles, but also applies to various optical components used for light transmission, reflection, spectroscopy, etc., and cover glasses used for watches, for example, prisms and reflection mirrors. be able to.

  Moreover, in each said embodiment, although the hard-coat layer was illustrated as a process layer formed with a process liquid, it is not limited to this. The treatment layer can be applied to any layer formed of a treatment liquid obtained by mixing a plurality of composition liquids. For example, the present invention can be applied as a method for forming a primer or the like.

  Moreover, it is preferable to apply | coat to the surface of a base material in order with the large surface tension of a composition liquid in an application | coating process. However, for example, each composition liquid has a surface tension of, for example, 25 (mN / m) or more and 40 (mN / m) or less and has a sufficient leveling action. Since an initial layer having a uniform layer thickness can be formed over the lens, even if the application order of the composition liquid is changed, for example, a lens provided with a hard coat layer having a better appearance and scratch resistance than the lens of the current product Can be formed.

  Furthermore, although 2nd leveling process S4 was implemented in 1st embodiment and the 2nd leveling process S4 and 3rd leveling process S7 were implemented in 2nd embodiment, for example, 3rd embodiment was shown. Thus, it is good also as a formation method which does not implement the leveling process after a 2nd application | coating process. That is, in the second and subsequent coating steps, a layer (liquid) of the composition liquid previously applied is formed on the surface of the base material. Therefore, it is not necessary to provide a standing time by dropping the composition liquid on this layer. The composition liquids immediately mix with each other and act to form a mixed layer having a uniform thickness. Therefore, even when the leveling step is not performed after the second coating step, it is possible to form a treatment layer having a uniform thickness dimension. However, depending on the type of composition liquid to be applied, for example, when the surface tension is extremely small, it may be difficult to form a mixed layer of uniform thickness immediately after dropping of the composition liquid. As in the first and second embodiments, it is preferable to perform the i-th leveling step after each i-th coating step.

  In the third embodiment, the lens 200 provided with the inner hard coat layer 201 and the outer hard coat layer 202 is illustrated, but a configuration in which a plurality of outer hard coat layers are further provided may be employed. For example, the outer hard coat layer may include a first hard coat layer adjacent to the inner hard coat layer and a second hard coat layer provided adjacent to the outer diameter of the first hard coat layer.

  Further, the inner hard coat layer and the outer hard coat layer may each be formed of a processing liquid composed of three or more kinds of composition liquids. In this case, the inner coating process, the temporary baking process, and the outer coating process may be performed after the third coating process as in the second coating process.

Moreover, in each said embodiment, it is good also as a structure with which the spray coat apparatus 100 is equipped with an attitude | position adjustment part. In this case, by changing the holding posture of the lens base material, even when the lens base material is formed in a convex shape, for example, the distance between the ultrasonic nozzle 111 and the lens base material is kept constant, and the lens base material The composition liquid can be sprayed from the normal direction of the surface of 1.
Moreover, although the example which applies the composition liquid by moving the ultrasonic nozzle 111 spirally toward the outer periphery from the center of the lens base material 1 was shown as a coating method of the composition liquid, it is not limited to this. For example, the composition liquid may be applied by moving the ultrasonic nozzle 111 in one direction as in the ink jet method.
In addition, each ultrasonic spray unit 110 of the spray coating apparatus 100 includes the air injection unit 113 and is configured to spray the atomized composition liquid ejected from the nozzle hole 116 with air. It is good also as a structure which is not provided with the air injection part 113. FIG. In this case, for example, the nozzle hole 116 may be brought close to the lens substrate 1 and the composition liquid droplets ejected from the nozzle hole 116 may be directly applied to the lens substrate 1.

  In addition, the specific structure and procedure for carrying out the present invention can be appropriately changed to other structures and the like within a range in which the object of the present invention can be achieved.

In the following, embodiments of the present invention will be described in more detail.
[Example 1]
(Lens base material)
As a lens substrate, a plastic lens for spectacles made of diethylene glycol bisallyl carbonate (trade name: CR-39) was used.

(Adjustment of composition liquid)
A primary composition solution obtained by dissolving a silicon hard coat agent (trade name: NSC-2705, manufactured by Nippon Seika Co., Ltd.) in a butyl cellosolve solvent, and filtering the solution whose surface tension is adjusted with a surfactant through a 2 μm filter. (A) was adjusted.
In addition, a 2 μm filter was prepared by dissolving a solution of 1,8-diazabicyclo [5,4,0] undecene-7 (manufactured by San Apro Co., Ltd.), which is a curing catalyst for the primary composition liquid (A), in methanol and a butyl cellosolve solvent. The secondary composition liquid (B) was adjusted by filtration.

(Application of composition liquid)
The formation method (S1-S5) of the hard-coat layer of said 1st embodiment was implemented.
(1. First application process)
Using the spray coating apparatus 100 as shown in FIG. 1 described in the first embodiment, only the first composition liquid (A) was applied (dropped) on the surface of the lens substrate by a spray coating method. At this time, in the first ultrasonic spray unit 110A, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, the liquid transport amount of the first composition liquid from the first tank 112A is 3 ml / min, and the lens base material. The gap between the nozzle hole 116 and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Moreover, the lens base material was mounted horizontally and the air introduction angle of the air injection part 113 was made into the perpendicular direction.
(2. First leveling process)
By allowing the first composition liquid (A) to stand for 10 seconds after dropping, adjacent liquid droplets are mixed by the leveling action of the first composition liquid (A), and a uniform film having a thickness of 22 μm is formed. It was.
(3. Secondary application process)
Next, using the spray coating apparatus 100 used in the primary coating step, the secondary composition liquid (B) was dropped onto the surface of the uniform film of the primary composition liquid (A). At this time, in the second ultrasonic spray unit 110B, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, the liquid transport amount of the secondary composition liquid from the second tank 112B is 3 ml / min, and the lens base material. The gap between the nozzle hole 116 and the nozzle hole 116 was 100 mm, and the average droplet diameter was 24 μm. Moreover, the lens base material was mounted horizontally and the air introduction angle of the air injection part 113 was made into the perpendicular direction.
(4. Second leveling process)
The secondary composition liquid was left for 10 seconds to impregnate the uniform film of the primary composition liquid.
(5. Firing step)
After the second leveling step, it was quickly baked and dried at 80 ° C. for 2 hours to obtain a lens substrate on which a hard coat layer having a uniform film thickness of 20 μm was formed.

[Comparative Example 1-1]
A treatment liquid (C) in which the primary composition liquid (A) and the secondary composition liquid (B) were mixed in advance was generated. In the first application step of Example 1, the treatment liquid (C) was applied to the surface of the lens substrate instead of the first composition liquid (A). Thereafter, the first leveling process of Example 1 was performed, and then the firing process of Example 1 was performed to obtain a lens substrate on which a hard coat layer was formed.

[Comparative Example 1-2]
In the primary application step of Example 1, the secondary composition liquid (B) was applied instead of the primary composition liquid (A). Moreover, in the secondary application step, the primary composition liquid (A) was applied instead of the secondary composition liquid (B). Other than that performed the same process as Example 1, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 1-3]
In the purification of the primary composition liquid (A), a solution in which the surface tension was not adjusted without adding a surfactant was prepared. That is, a solution in which a silicon hard coat agent (manufactured by Nippon Seika Co., Ltd., trade name: NSC-2705) was dissolved in a butyl cellosolve solvent was filtered through a 2 μm filter to prepare a primary composition liquid (D). .
In Example 1, the primary composition liquid (D) was used instead of the primary composition liquid (A). Otherwise, the same process as in Example 1 was performed to obtain a lens substrate on which a hard coat layer was formed.

[Comparative Example 1-4]
In the primary application step of Example 1, the secondary composition liquid (B) was dropped instead of the primary composition liquid (A). In the second coating step, the primary composition liquid (D) prepared in Comparative Example 1-3 was dropped instead of the secondary composition liquid (B). Other than that performed the same process as Example 1, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 1-5]
In the first application step of Example 1, the first ultrasonic spray unit 110A and the second ultrasonic spray unit 110B are simultaneously controlled to provide the first composition liquid (A) and the second composition liquid (B). Were simultaneously applied (dropped). Thereafter, after performing the first leveling step, the firing step of Example 1 was performed to obtain a lens substrate on which a hard coat layer was formed.

[Comparative Example 1-6]
The standing time in the first leveling step and the second leveling step of Example 1 was set to 5 seconds. Other than that performed the same process as Example 1, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 1-7]
The standing time in the first leveling step and the second leveling step of Example 1 was 20 seconds. Other than that performed the same process as Example 1, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 1-8]
The standing time in the first leveling step and the second leveling step of Example 1 was 30 seconds. Other than that performed the same process as Example 1, and obtained the lens base material in which the hard-coat layer was formed.

[Evaluation method]
The appearance evaluation and scratch resistance evaluation of the lens base materials obtained in Example 1 and Comparative Examples 1-1 to 1-8 were performed.
(Appearance evaluation)
In the dark box, the interference fringes of the plastic lens were observed under a three-wavelength type fluorescent lamp (manufactured by Matsushita Electric Industrial Co., Ltd., trade name: National Palook) and evaluated in the following steps. Here, it was evaluated as ○ when the lens was better than the lens of the current product, Δ when it was similar to the lens of the current product, and × when it was worse than the current product.
(Abrasion resistance evaluation)
With bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), 10 reciprocating surfaces were rubbed under a load of 9.8 N (1 kgf), and the extent of damage within the range of 1 cm × 3 cm was visually observed. The evaluation was divided into stages. Here, when the number of scratches was 0 or more and less than 10, it was evaluated as ◯ when it was 10 or more and less than 50 (equivalent to the current product), and when it was 50 or more, it was evaluated as ×.
Table 1 below shows the results of appearance evaluation and scratch resistance evaluation.

As shown in Table 1, in Comparative Example 1-1, since the concentration distribution of the primary composition liquid (A) and the secondary composition liquid (B) is generated in the mixed processing liquid, the lens base material is used. Even in the layer of the treatment liquid applied, the concentration distribution was not uniform in the plane, and an appearance defect with interference fringes was observed.
In Comparative Example 1-2, as a result of first applying the secondary composition liquid having a small surface tension, in the first leveling step, the formation of a uniform film due to the leveling action becomes insufficient, and the appearance and scratch resistance are the current products. It became about.

In Comparative Example 1-3, the surface tension of the primary composition liquid (D) is small, and in the primary leveling step, it is impossible to form a film having a uniform thickness over the surface of the lens substrate. As a result, unevenness occurred in the concentration distribution of the primary composition liquid (A) and the secondary composition liquid (B) in the plane. For this reason, the appearance was worse than the current product, and the scratch resistance was also lowered.
In Comparative Example 1-4, since the surface tension of the secondary composition liquid (B) is larger than the surface tension of the primary composition liquid (D), compared with Comparative Example 1-4, in the primary leveling step. Although a uniform film could be formed, a film with a uniform thickness could hardly be formed, and both the appearance and scratch resistance were worse than the current product.

In Comparative Example 1-5, the surface tension of the composition liquids (A) and (B) was different when the liquid droplets landed, and thus unevenness occurred in the leveling action. For this reason, although the scratch resistance equivalent to the current product was obtained, interference fringes were confirmed and the appearance was poor.
In Comparative Example 1-6, the formation of a uniform film due to the leveling action in the first leveling process was not in time, and although scratch resistance equivalent to that of the current product was obtained, interference fringes were confirmed and the appearance was poor.
In Comparative Example 1-7 and Comparative Example 1-8, the standing time in the first leveling process was too long, and thus liquid sagging and dust adhesion were observed. Therefore, although the scratch resistance equivalent to that of the current product was obtained, interference fringes were confirmed and the appearance was poor.
On the other hand, in Example 1, no interference fringes were observed in the formed hard coat layer, and the scratch resistance was good.

[Example 2]
(Lens base material)
A plastic lens for spectacles made of thiourethane resin (trade name: Seiko Super Sovereign, refractive index 1.67) was used.

(Adjustment of composition liquid)
The primary composition was obtained by filtering a hydrolyzate of γ-glycidoxypropyltrimethoxysilane (made by Momentive Performance Materials) dissolved in butyl cellosolve solvent with a 2 μm filter after adjusting the surface tension with a surfactant. Liquid (E) was prepared.
Metal oxide fine particles mainly composed of titanium oxide and silicon oxide (trade name: OPTRAIQUE, manufactured by Catalytic Chemical Co., Ltd.) are dispersed in methanol, and a solution whose surface tension is adjusted with a surfactant is filtered through a 2 μm filter. A secondary composition liquid (F) was prepared.
Aluminum (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in a methanol solvent, and a solution whose surface tension is adjusted with a surfactant is filtered through a 2 μm filter to prepare a third composition solution (G). did.
The leveling performance (surface tension) of these composition liquids (E), (F), and (G) is 30 (mN / N) for the first composition liquid (E) and 20 for the second composition liquid (F). (MN / N) and the third composition liquid (G) was 15 (mN / N).

(Application of composition liquid)
The formation method (S1-S7) of the hard-coat layer of said 2nd embodiment was implemented.
(1. First application process)
Using the spray coating apparatus 100 as shown in FIG. 5 described in the second embodiment, only the first composition liquid (E) was applied (dropped) on the surface of the lens substrate by a spray coating method. At this time, in the first ultrasonic spray unit 110A, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, the liquid transport amount of the first composition liquid (E) from the first tank 112A is 3 ml / min, The gap between the lens substrate and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Moreover, the lens base material was mounted horizontally and the air introduction angle of the air injection part 113 was made into the perpendicular direction.
(2. First leveling process)
By allowing the first composition liquid (E) to stand for 10 seconds after dropping, the adjacent liquid droplets are mixed by the leveling action of the first composition liquid (E), and a uniform film having a layer thickness of 23 μm is formed. It was.
(3. Secondary application process)
Next, using the spray coating apparatus 100 used in the primary coating step, the secondary composition liquid (F) was dropped onto the surface of the uniform film of the primary composition liquid (E). At this time, in the second ultrasonic spray unit 110B, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, the liquid transport amount of the secondary composition liquid (F) from the second tank 112B is 3 ml / min, The gap between the lens substrate and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Moreover, the lens base material was mounted horizontally and the air introduction angle of the air injection part 113 was made into the perpendicular direction.
(4. Second leveling process)
In order to impregnate the second composition liquid (F) into the uniform film of the first composition liquid (E), the second composition liquid (F) is left for 10 seconds, and the first composition liquid (E) and the second composition liquid (F) are separated. A mixed layer (H) of a mixed uniform film was formed.
(5. Third application process)
Next, the third composition liquid (G) was dropped onto the surface of the mixed layer (H) using the spray coater 100 used in the first and second application steps. At this time, in the third ultrasonic spray unit 110C, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, the liquid transportation amount of the third composition liquid (G) from the third tank 112C is 3 ml / min, The gap between the lens substrate and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Moreover, the lens base material was mounted horizontally and the air introduction angle of the air injection part 113 was made into the perpendicular direction.
(6. Third leveling process)
The third composition liquid (G) was left for 10 seconds to impregnate the mixed layer (H).
(7. Firing step)
Thereafter, it was quickly baked and dried at 80 ° C. for 2 hours to obtain a lens substrate on which a hard coat layer having a uniform film thickness of 12 μm was formed.

[Comparative Example 2-1]
A treatment liquid (I) was produced by previously mixing the first composition liquid (E), the second composition liquid (F), and the third composition liquid (G). Then, in the first application step of Example 2, the treatment liquid (I) was applied to the surface of the lens substrate instead of the first composition liquid (E). Thereafter, after performing the first leveling step of Example 2, the firing step of Example 2 was performed to obtain a lens substrate on which a hard coat layer was formed.

[Comparative Example 2-2]
In the first application step of Example 2, the secondary composition liquid (F) was dropped instead of the primary composition liquid (E). In the second coating step, the third composition liquid (G) was dropped instead of the second composition liquid (F). Moreover, in the 3rd application | coating process, the 1st composition liquid (E) was dripped instead of the 3rd composition liquid (G). Other than that performed the same process as Example 2, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 2-3]
In the first application step of Example 2, the secondary composition liquid (F) was dropped instead of the primary composition liquid (E). In the second coating step, the primary composition liquid (E) was dropped instead of the secondary composition liquid (F). Other than that performed the same process as Example 2, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 2-4]
In the first application step of Example 2, the third composition liquid (G) was dropped instead of the first composition liquid (E). In the second coating step, the primary composition liquid (E) was dropped instead of the secondary composition liquid (F). In the third coating step, the second composition liquid (F) was dropped instead of the third composition liquid (G). Other than that performed the same process as Example 2, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 2-5]
In the first application step of Example 2, the third composition liquid (G) was dropped instead of the first composition liquid (E). Moreover, in the 3rd application | coating process, the 1st composition liquid (E) was dripped instead of the 3rd composition liquid (G). Other than that performed the same process as Example 2, and obtained the lens base material in which the hard-coat layer was formed.

[Comparative Example 2-6]
In the second coating step of Example 2, the third composition liquid (G) was dropped instead of the second composition liquid (F). In the third coating step, the second composition liquid (F) was dropped instead of the third composition liquid (G). Other than that performed the same process as Example 2, and obtained the lens base material in which the hard-coat layer was formed.

[Evaluation method]
The appearance evaluation and the scratch resistance evaluation of the lens base materials obtained in Example 2 and Comparative Examples 2-1 to 2-6 were performed.
(Appearance evaluation)
In the dark box, the interference fringes of the plastic lens were observed under a three-wavelength type fluorescent lamp (manufactured by Matsushita Electric Industrial Co., Ltd., trade name: National Palook) and evaluated in the following steps. Here, it was evaluated as ○ when the lens was better than the lens of the current product, Δ when it was similar to the lens of the current product, and × when it was worse than the current product.
(Abrasion resistance evaluation)
With bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), 10 reciprocating surfaces were rubbed under a load of 9.8 N (1 kgf), and the extent of damage within the range of 1 cm × 3 cm was visually observed. The evaluation was divided into stages. Here, when the number of scratches was 0 or more and less than 10, it was evaluated as ◯ when it was 10 or more and less than 50 (equivalent to the current product), and when it was 50 or more, it was evaluated as ×.
Table 2 below shows the results of the appearance evaluation and scratch resistance evaluation.

As shown in Table 2, in Comparative Example 2-1, the concentrations of the primary composition liquid (E), the secondary composition liquid (F), and the tertiary composition liquid (G) in the mixed processing liquid. Since the distribution occurs, the concentration distribution is not uniform in the surface even in the layer of the treatment liquid applied with the lens substrate, and an appearance defect with interference fringes is observed.
Further, in Comparative Examples 2-2 to 2-5, in the first leveling process, formation of a uniform film by the leveling action is insufficient, interference fringes are observed, and scratch resistance is about the same as the current product. It was.
In Comparative Example 2-6, the first composition liquid (E) having a large surface tension was first applied. For this reason, an initial layer having a uniform film thickness can be formed by the leveling action of the primary composition liquid (E), and the third composition liquid (G) and the secondary composition liquid (F) dropped later. The low leveling performance was able to compensate, and the appearance was good, but only scratch resistance equivalent to the current product was obtained.
On the other hand, in Example 2, no interference fringes were observed in the formed hard coat layer, and the scratch resistance was good.

[Example 3-1]
(Lens base material)
A plastic lens for spectacles made of diethylene glycol bisallyl carbonate (trade name: CR-39) was used. As the plastic lens for eyeglasses used here, a plus lens having a curved surface on one side and a substantially central portion protruding in a convex shape was used.

(Adjustment of primer composition liquid)
Mix the polyester resin (trade name: Besresin, manufactured by Takamatsu Yushi Co., Ltd.) with methanol and propylene glycol monomethyl ether solvent, and filter the solution whose surface tension is adjusted with a surfactant through a 2 μm filter to prepare a primer composition solution. did.

(Adjustment of hard coat composition)
A first hard coat composition is prepared by dissolving a silicon hard coat agent (trade name: NSC-2705, manufactured by Nippon Seika Co., Ltd.) in a butyl cellosolve solvent, and filtering the solution with the surface tension adjusted by a surfactant through a 2 μm filter. The liquid (H) was adjusted.
A solution in which iron (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in a methanol solvent was filtered through a 2 μm filter to prepare a second hard coat composition liquid (I).
A solution in which manganese (III) acetylacetonate (manufactured by Nacalai Tesque, trade name: 21205-22) was dissolved in a methanol solvent was filtered through a 2 μm filter to prepare a third hard coat composition liquid (J).

(Application of composition liquid)
The formation method of the hard-coat layer of the said 3rd embodiment was implemented.
(1. Primer layer forming step)
Using a spray coating apparatus as shown in FIG. 5, the primer composition liquid was applied (dropped) on the surface of the lens substrate by a spray coating method. At this time, in the ultrasonic spray section, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator is 120 kHz, the liquid transport amount of the primer composition liquid from the tank is 3 ml / min, and the gap between the lens substrate and the nozzle hole is 100 mm. The average diameter of the droplets was 30 μm. In addition, the lens substrate was placed horizontally such that the convex surface faces the ultrasonic spray unit, and the air introduction angle of the air injection unit was set to the vertical direction. And at the time of application | coating to the surface layer of a convex surface, the distance of a lens base material and a nozzle hole was kept at 100 mm by controlling the movement of an ultrasonic nozzle to a z-axis direction suitably by a head moving part.
Then, it was baked and dried at 80 ° C. for 45 minutes to obtain a lens substrate on which a primer layer having a uniform film thickness was formed.
(2. First application process)
Using the spray coat apparatus 100 as shown in FIG. 5, only the first hard coat composition liquid (H) was applied (dropped) on the surface of the lens substrate by the spray coat method. At this time, in the first ultrasonic spray section 110A, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, and the liquid transport amount of the first hard coat composition liquid (H) from the first tank 112A is 3 ml / min. The gap between the lens substrate and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Further, the lens substrate was placed horizontally such that the convex surface faces the ultrasonic spray unit 110, and the air introduction angle of the air injection unit 113 was set to the vertical direction. Then, at the time of application to the convex surface layer, the distance between the lens substrate and the nozzle hole 116 was kept at 100 mm by appropriately controlling the movement of the ultrasonic nozzle 111 in the z-axis direction by the head moving unit 114.
(2. First leveling process)
By dropping the first hard coat composition liquid (H) for 10 seconds, adjacent liquid droplets are mixed by the leveling action of the first hard coat composition liquid (H), and a uniform film having a layer thickness of 23 μm is formed. Been formed.
(3. Secondary application process)
(3-1. Inner coating process)
Next, using the spray coat apparatus 100 used in the first coating step, the second hard coat composition liquid (I) was dropped onto the circular region at the center of the surface of the uniform film of the first hard coat composition liquid (H). . Here, the circular region was a concentric circle with the circular lens, and was a region having an area of 60% with respect to the entire surface of the lens substrate. At this time, in the second ultrasonic spray section 110B, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, and the liquid transport amount of the second hard coat composition liquid (I) from the second tank 112B is 3 ml / min. The gap between the lens substrate and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Further, the lens substrate was placed horizontally such that the convex surface faces the ultrasonic spray unit 110, and the air introduction angle of the air injection unit 113 was set to the vertical direction. Then, at the time of application to the convex surface layer, the distance between the lens substrate and the nozzle hole 116 was kept at 100 mm by appropriately controlling the movement of the ultrasonic nozzle 111 in the z-axis direction by the head moving unit 114.
(3-2. Second leveling step)
The second hard coat composition liquid (I) was left for 10 seconds to impregnate the uniform film of the first hard coat composition liquid (H).
(3-3. Temporary firing step)
After the second leveling step, the second composition solution was fixed by calcining at 80 ° C. for 30 minutes.
(3-4. Outside coating process)
Thereafter, using the spray coat apparatus 100 used in the first coating step, the third hard coat composition liquid (J) is converted into the second hard coat composition on the surface of the uniform film of the first hard coat composition liquid (H). It was dripped at the diameter outside area | region (outer periphery area | region used as an area of 40% with respect to the whole surface) of the circular area | region which apply | coated liquid (I). At this time, in the third ultrasonic spray unit 110C, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, and the liquid transport amount of the third hard coat composition liquid (J) from the third tank 112C is 3 ml / min. The gap between the lens substrate and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Further, the lens substrate was placed horizontally such that the convex surface faces the ultrasonic spray unit 110, and the air introduction angle of the air injection unit 113 was set to the vertical direction. Then, at the time of application to the convex surface layer, the distance between the lens substrate and the nozzle hole 116 was kept at 100 mm by appropriately controlling the movement of the ultrasonic nozzle 111 in the z-axis direction by the head moving unit 114.
(4. Firing step)
Thereafter, the lens base material is quickly baked and dried at 80 ° C. for 2 hours to promote fixing of the third composition liquid and the entire effect of the applied processing liquid, and a hard coat layer having a uniform film thickness of 14 μm is formed. Got.

[Example 3-2 to Example 3-4]
In Example 3-1, the area of the circular area where the second hard coat composition liquid (I) is applied in the inner application process, and the area of the outer diameter area where the third hard coat composition liquid (J) is applied in the outer application process. Changes were made as shown in Table 3 below. Other than that was carried out similarly to Example 3, and obtained the lens base material in which the hard-coat layer was formed.
That is, in Example 3-2, the area of the circular area where the second hard coat composition liquid (I) is applied in the inner application process and the outer diameter area where the third hard coat composition liquid (J) is applied in the outer application process. The area ratio to the area was 55:45.
In Example 3-3, the area of the circular area where the second hard coat composition liquid (I) is applied in the inner application process and the area of the outer diameter area where the third hard coat composition liquid (J) is applied in the outer application process. The area ratio was 65:35.
In Example 3-4, the area of the circular area where the second hard coat composition liquid (I) is applied in the inner application process and the area of the outer diameter area where the third hard coat composition liquid (J) is applied in the outer application process. The area ratio was 75:25.

[Comparative Example 3-1]
A treatment liquid (K) was prepared by previously mixing the first hard coat composition liquid (H) and the second hard coat composition liquid (I). And the layer of a process liquid is formed by the immersion method which immerses a lens base material in a process liquid (K), and the baking process of Example 3-1 is implemented, The lens base material in which the hard-coat layer was formed is obtained. It was.

[Comparative Example 3-2]
The treatment liquid (K) was applied to the lens substrate by spin coating. Then, the baking process of Example 3-1 was implemented and the lens base material with which the hard-coat layer was formed was obtained.

[Comparative Examples 3-3 to 3-7]
In Example 3-1, the area of the circular area where the second hard coat composition liquid (I) is applied in the inner application process, and the area of the outer diameter area where the third hard coat composition liquid (J) is applied in the outer application process. Changes were made as shown in Table 3. Other than that was carried out similarly to Example 3-1, and obtained the lens base material in which the hard-coat layer was formed.

[Evaluation method]
The lens substrates obtained in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-7 were evaluated for appearance, scratch resistance, and impact resistance.
(Appearance evaluation)
In the dark box, the interference fringes of the plastic lens were observed under a three-wavelength type fluorescent lamp (manufactured by Matsushita Electric Industrial Co., Ltd., trade name: National Palook) and evaluated in the following steps. Here, it was evaluated as ○ when the lens was better than the lens of the current product, Δ when it was similar to the lens of the current product, and × when it was worse than the current product.
(Abrasion resistance evaluation)
With bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), 10 reciprocating surfaces were rubbed under a load of 9.8 N (1 kgf), and the extent of damage within the range of 1 cm × 3 cm was visually observed. The evaluation was divided into stages. Here, the case of 0 or more and less than 10 was evaluated as ◯, the case of 10 or more and less than 50 (equivalent to the current product) was evaluated as Δ, and the case of 50 or more was evaluated as ×.
(Impact resistance evaluation)
A falling ball test corresponding to the FDA standard was conducted. With the convex surface of the lens on which the hard coat layer was formed facing upward, a steel ball having a mass of 16.3 g was dropped freely from a height of 67 cm in the vertical direction, and the height at the time of breaking was measured. If not broken, the height at which the steel ball was dropped was raised every 20 cm and tested again.
Table 4 below shows the results of appearance evaluation, scratch resistance evaluation, and impact resistance evaluation.

As shown in Table 4, in Comparative Example 3-1 in which a hard coat layer was formed using a conventional dipping method and in Comparative Example 3-2 in which a hard coat layer was formed using a spin coat method, the treatment liquid (K) Therefore, even in the treatment liquid layer coated with the lens substrate, the concentration distribution was not uniform in the surface, and an appearance defect with interference fringes was observed. Further, in these dipping methods and spin coating methods, it is difficult to apply different hard coat composition liquids at the central portion and the outer peripheral portion of the lens substrate.
On the other hand, in Example 3-1 to Example 3-4 and Comparative Example 3-3 to Comparative Example 3-7, no interference fringes were observed in the formed hard coat layer, and scratch resistance was obtained. Was also good.
Further, in comparison with Example 3-1 to Example 3-4 and Comparative Example 3-3 to Comparative Example 3-7, in terms of impact resistance, in particular, the area of the circular region in the central portion is 55 to 75%. In this range, it was confirmed that strong impact resistance was obtained.

[Example 4]
(Lens base material)
As a lens substrate, a plastic lens for spectacles made of diethylene glycol bisallyl carbonate (trade name: CR-39) was used.

(Adjustment of composition liquid)
After dissolving propylene glycol monomethyl ether in a methanol solvent, the resin component (trade name: Besresin, manufactured by Takamatsu Yushi Co., Ltd.) is dissolved, and the solution whose surface tension is adjusted with a silicon surfactant is filtered through a 2 μm filter. The first composition liquid (L) was adjusted.
Further, a secondary composition is prepared by filtering a solution obtained by dissolving a composite fine particle sol containing titanium oxide and tin oxide having a crosslinking action necessary for the construction of the film of the primary composition liquid (L) in a methanol solvent with a 2 μm filter. The liquid (M) was adjusted.

(Application of composition liquid)
The composition liquid for forming a primer layer was apply | coated by the method similar to the formation method (S1-S5) of the hard-coat layer of said 1st embodiment.
(1. First application process)
Using the spray coating apparatus 100 as shown in FIG. 1 described in the first embodiment, only the first composition liquid (L) was applied (dropped) on the surface of the lens substrate by a spray coating method. At this time, in the first ultrasonic spray unit 110A, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, the liquid transport amount of the first composition liquid from the first tank 112A is 3 ml / min, and the lens base material. The gap between the nozzle hole 116 and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Moreover, the lens base material was mounted horizontally and the air introduction angle of the air injection part 113 was made into the perpendicular direction.
(2. First leveling process)
By allowing the first composition liquid (L) to stand for 10 seconds after dropping, the adjacent liquid droplets are mixed by the leveling action of the first composition liquid (L), and a uniform film having a thickness of 12 μm is formed. It was.
(3. Secondary application process)
Next, using the spray coating apparatus 100 used in the primary coating step, the secondary composition liquid (M) was dropped onto the surface of the uniform film of the primary composition liquid (L). At this time, in the second ultrasonic spray unit 110B, the frequency of the ultrasonic wave oscillated from the ultrasonic vibrator 115 is 120 kHz, the liquid transport amount of the secondary composition liquid from the second tank 112B is 3 ml / min, and the lens base material. The gap between the nozzle hole 116 and the nozzle hole 116 was 100 mm, and the average diameter of the droplets was 30 μm. Moreover, the lens base material was mounted horizontally and the air introduction angle of the air injection part 113 was made into the perpendicular direction.
(4. Second leveling process)
The secondary composition liquid (M) was left for 10 seconds to impregnate the uniform film of the primary composition liquid (L).
(5. Firing step)
After the second leveling step, the lens substrate was quickly baked and dried at 80 ° C. for 45 minutes to obtain a lens substrate on which a primer layer having a uniform film thickness of 18 μm was formed.

[Comparative Example 4-1]
The process liquid (N) which mixed the primary composition liquid (L) and the secondary composition liquid (M) previously was produced | generated. Then, in the first application step of Example 4, the treatment liquid (N) was applied to the surface of the lens substrate instead of the first composition liquid (L). Thereafter, the first leveling step of Example 4 was performed, and then the firing step of Example 4 was performed to obtain a lens substrate on which a primer layer was formed.

[Comparative Example 4-2]
In the primary application step of Example 4 above, the secondary composition liquid (M) was applied instead of the primary composition liquid (L). Moreover, in the secondary application step, the primary composition liquid (L) was applied instead of the secondary composition liquid (M). Other than that performed the same process as Example 4, and obtained the lens base material in which the primer layer was formed.

[Comparative Example 4-3]
In the purification of the primary composition liquid (L), a solution in which the surface tension was not adjusted without adding a surfactant was prepared. That is, a solution in which propylene glycol monomethyl ether was dissolved in a methanol solvent was filtered through a 2 μm filter to prepare a primary composition liquid (O).
In Example 1, the primary composition liquid (O) was used instead of the primary composition liquid (L). Other than that performed the same process as the said Example 4, and obtained the lens base material in which the primer layer was formed.

[Comparative Example 4-4]
In the first application step of Example 1, the first ultrasonic spray part 110A and the second ultrasonic spray part 110B are simultaneously controlled, and the first composition liquid (L) and the second composition liquid (N). Were simultaneously applied (dropped). Thereafter, after performing the first leveling step, the firing step of Example 4 was performed to obtain a lens substrate on which the primer layer was formed.

[Evaluation method]
The appearance evaluation and the scratch resistance evaluation of the lens base materials obtained in Example 4 and Comparative Examples 4-1 to 4-4 were performed.
(Appearance evaluation)
In the dark box, the interference fringes of the plastic lens were observed under a three-wavelength type fluorescent lamp (manufactured by Matsushita Electric Industrial Co., Ltd., trade name: National Palook) and evaluated in the following steps. Here, it was evaluated as ○ when the lens was better than the lens of the current product, Δ when it was similar to the lens of the current product, and × when it was worse than the current product.
(Impact resistance evaluation)
A falling ball test corresponding to the FDA standard was conducted. With the convex surface of the lens on which the hard coat layer was formed facing upward, a steel ball having a mass of 16.3 g was dropped freely from a height of 67 cm in the vertical direction, and the height at the time of breaking was measured. If not broken, the height at which the steel ball was dropped was raised every 20 cm and tested again.
Table 5 below shows the results of appearance evaluation and scratch resistance evaluation.

As shown in Table 5, in Comparative Example 4-1, since the concentration distribution of the primary composition liquid (L) and the secondary composition liquid (N) occurs in the mixed processing liquid, the lens base material Even in the layer of the treatment liquid applied, the concentration distribution was not uniform in the plane, and an appearance defect with interference fringes was observed.
In Comparative Example 4-2, as a result of first applying the secondary composition liquid (M) having a low surface tension, in the first leveling step, the formation of a uniform film due to the leveling action becomes insufficient, and an appearance defect is observed. It was.

  In Comparative Example 4-3, the surface tension of the primary composition liquid (O) is small, and in the primary leveling step, it is impossible to form a film having a uniform thickness over the surface of the lens substrate. As a result, unevenness occurred in the concentration distribution of the primary composition liquid (O) and the secondary composition liquid (N) in the plane. For this reason, the appearance was worse than the current product.

In Comparative Example 4-4, mixing unevenness occurred at the time of droplet collision in the air flow, and formation of a uniform film was difficult. For this reason, although the impact resistance is equivalent to the current product, interference fringes were observed, resulting in a poorer appearance than the current product.
On the other hand, in Example 4, no interference fringes were observed in the formed primer layer, and the impact resistance was good.

  The treatment layer forming method of the present invention can be suitably applied to the case where a treatment layer is formed with a treatment liquid obtained by mixing a plurality of composition liquids with respect to an optical article. Examples of the optical article include various lenses such as a spectacle lens, a camera lens, a telescope lens, and a condenser for a stepper, a cover glass for a prism, a watch, a protective glass for a display, and the like. Moreover, as a process layer formed with a process liquid, a hard-coat layer and a primer layer can be mentioned, for example.

  DESCRIPTION OF SYMBOLS 1 ... Lens base material (base material) 11 ... Droplet of primary composition liquid, 12 ... Initial layer of primary composition liquid, 13 ... Droplet of secondary composition liquid, 15, 15A ... Hard coat layer (Treatment layer), 16 ... Liquid droplets of the third composition liquid, 200 ... Lens (optical article), 201 ... Inner hard coat layer (inner treatment layer), 202 ... Outer hard coat layer (outer treatment layer).

Claims (4)

A treatment layer forming method of forming a treatment layer by sequentially applying n kinds (n is an integer of 2 or more) of a composition liquid to the surface of a substrate.
A head part into which the composition liquid is introduced, a nozzle hole provided in the head part for ejecting the composition liquid, and an ultrasonic wave that outputs ultrasonic waves and atomizes the composition liquid introduced into the head part The composition liquid is spray-coated using a spray coating apparatus having a vibrator, atomizing the composition liquid by ultrasonic waves output from the ultrasonic vibrator, and spraying the atomized composition liquid from a nozzle hole. Coating step of sequentially dropping onto the surface of the substrate,
After the coating step, a treatment layer forming step of firing the composition liquid dropped on the surface of the substrate to form the treatment layer;
With
The application step is at least first when the i (1 ≦ i ≦ n) -th dropped composition liquid is the i-th composition liquid and the i-th composition liquid drop is the i-th application step. A leveling step of making the layer thickness of the dropped composition liquid uniform across the surface of the substrate after the next coating step ;
The treatment layer comprises an inner treatment layer formed in a circular region at the center of the surface of the substrate, and an outer treatment layer formed in a radially outer region of the inner treatment layer on the surface of the substrate,
The inner treatment layer is formed of a treatment liquid configured by mixing a first composition liquid and a second composition liquid different from the first composition liquid,
The outer treatment layer is formed by mixing the first composition liquid and a third composition liquid having a hardness smaller than that of the second composition liquid and different from the first composition liquid. Formed by liquid,
The application step includes a first application step and a second application step,
In the first application step, the first composition liquid is dropped over the circular region and the radially outer region of the surface of the base material,
The second coating step includes an inner coating step of dropping the second composition liquid onto the circular region of the base material, and an outer coating step of dropping the third composition liquid onto the radially outer region of the base material. The process layer formation method characterized by including these. In the processing layer formation method of Claim 1 ,
After the inner coating process and before the outer coating process, the second composition liquid dropped onto the circular area is baked, and the provisional baking process for fixing the second composition liquid to the circular area is provided. A method for forming a treated layer. In the processing layer formation method of Claim 1 or Claim 2 ,
The circular region is an area of 55% or more and 75% or less of the entire surface of the base material,
The diameter outside region has an area of 25% or more and 45% or less of the entire surface of the base material. In the processing layer formation method in any one of Claims 1-3 ,
The treatment layer forming method, wherein the treatment layer formed by firing the composition liquid is a hard coat layer.

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