JP2008168282A - Layer forming method and layer formation apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a layer forming method and a layer forming apparatus hardly causing cracks on a lens base material even in the firing process after layer formation by a spin coating method. <P>SOLUTION: The layer forming apparatus 1 is provided with a liquid coating device 100 for coating the surface of a rotating lens base material 50 with a liquid by the spin coating method to form layers, a liquid removing device 200 for removing the liquid adhering to the outer circumferential part of the lens base material 50. By this layer forming apparatus 1, excess liquid adhering to the outer circumferential part of the base material can be removed by the liquid removing device 200 after the base material 50 is coated with a hardening liquid by the spin coating method. Even the lens base material 50 is fired thereafter, cracks are hardly generated on the lens base material 50. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a layer forming method and a layer forming apparatus for forming an antireflection layer or the like on a plastic lens substrate.

Conventionally, in a plastic lens for spectacles or the like, a hard coat layer alone or a hard coat layer via a primer layer is formed on the surface of a lens substrate, and reflection to prevent ghost and flickering on the surface of the hard coat layer. A prevention layer is formed.
Conventionally, this antireflection layer has been mainly formed as a multilayer film by a vacuum deposition method, but recently, an antireflection layer composition comprising a curable liquid having an antireflection function has been devised. As a coating method of the composition for antireflection layer, the composition for antireflection layer is applied to the lens substrate on which the hard coat layer is formed alone or through a primer layer, and then cured. Is common.

  As a coating method of the composition for an antireflection layer, an immersion method or a spin coating method is mainly used. Among them, the spin coating method in which the anti-reflection layer forming composition is formed by discharging the anti-reflection layer forming composition onto the surface of the lens base material on which the hard coat layer alone or the hard coat layer via the primer layer has been previously formed and rotating. In addition to obtaining a uniform and high-quality antireflection layer, the processing speed is high and the apparatus is compact (for example, Patent Document 1).

JP 2003-290704 A

By the way, after such an antireflection layer is formed by the spin coating method, the lens substrate is generally baked in order to cure the layer forming substance (reactive silane compound or the like). However, at that time, cracks are generated in the outer peripheral portion of the lens base material (the edge portion which is the outer peripheral side surface of the lens base material and the outer peripheral end portion in the vicinity of the outermost peripheral end), and further, the generated crack is It has been a problem in manufacturing plastic lenses.
Accordingly, an object of the present invention is to provide a layer forming method and a layer forming apparatus in which cracks are unlikely to occur in a lens substrate even in a baking step after layer formation by a spin coating method.

The present inventors have found that the layer thickness on the lens substrate by spin coating and the layer thickness after firing are non-uniform as shown in FIG. That is, the layer thickness formed at the outer peripheral edge of the lens substrate is extremely thicker than the layer thickness near the center of the lens substrate. This is presumably because the layer made of the uncured layer-forming substance formed by the spin coating method is thick and the layer is cured as it is in the baking step. This outer peripheral end means the vicinity of the outermost peripheral end of the lens base material, and is, for example, in the range of 0.2 to 0.7 mm on the inner side from the outermost peripheral end of the lens base material.
And since internal stress concentrates in the thick part with thick layer thickness, it is estimated that a crack tends to generate | occur | produce from a thick part in a baking process. Furthermore, the outer peripheral side surface (edge portion) of the lens base material does not have a uniform layer thickness, and the lens base material has both surfaces and is applied twice, so the layer thickness becomes more non-uniform. As a result, it is estimated that cracks are likely to occur from the edge portion in the firing step. Moreover, since the crack once generated propagates and expands to the inside of the lens base material, the yield of the spectacle lens as a product is greatly deteriorated.
The present invention has been completed based on the above findings.

  In the layer forming method of the present invention, a liquid is applied to a surface of a rotating substrate by applying a liquid by a spin coating method to form a layer, and after the liquid applying step, the layer is cured by baking. A layer forming method comprising: a firing step, wherein the liquid adhering to an outer peripheral end near the outermost peripheral end of the substrate and the outer peripheral side surface of the substrate is removed before the firing step. It is characterized by doing.

Here, the base material is, for example, a disk-shaped plastic lens base material having a predetermined thickness. Hereinafter, the outer peripheral end portion and the outer peripheral side surface of the base material are collectively referred to as an outer peripheral portion.
ADVANTAGE OF THE INVENTION According to this invention, in the baking process after spin coating, while it becomes difficult to produce a crack in the surface layer of a base-material outer peripheral part, it can prevent a crack expanding to a base-material main body. In addition, as a method for removing the liquid, in addition to wiping, a non-contact method such as air blowing may be used.

In this invention, it is preferable that the removal method of the liquid adhering to the outer peripheral edge part and outer peripheral side surface of a base material is the wiping off of the said liquid. Further, it is preferable that the wiping means is performed on the base material while rotating at least one of the base material and the wiping means for wiping. As a material for wiping, a liquid absorbent article such as cloth or sponge is preferably used.
When wiping off, the liquid can be reliably removed from the surface of the outer peripheral portion of the substrate, and it is particularly effective to wipe off while rotating the substrate.

In the present invention, the substrate is preferably a spectacle lens substrate, the layer is an organic layer, and the liquid is an organic layer forming composition.
According to the present invention, after removing the coating liquid adhering to the outer peripheral side surface (edge portion) of the spectacle lens substrate, and also removing excess liquid remaining on the outer peripheral end of the substrate, In the firing step, cracks are unlikely to occur in the surface layer of the outer peripheral portion of the lens base material, and the cracks can be prevented from expanding into the lens base body. The degree of liquid removal is preferably controlled so that the layer thickness distribution at the outer peripheral edge of the substrate is uniform.
Here, examples of the organic layer include a primer layer, a hard coat layer, an antireflection layer, and an antifouling layer. In particular, the thickness of the antireflection layer needs to be precisely controlled, and since the spin coating method is often employed, it is important to take measures against cracking, and it is very preferable to apply the method of the present invention. .

  Moreover, the liquid can be removed more reliably by using a cloth for wiping off the liquid adhering to the outer peripheral portion of the base material and pressing the cloth against the outer peripheral side surface of the base material. For example, when the base material is a spectacle lens base material, not only the outer peripheral side surface (edge portion) in direct contact with the cloth but also the liquid adhering to the outer peripheral end portion of the lens base material can be absorbed. Although it does not specifically limit as this cloth, It is preferable that liquid absorbency, such as cotton, felt, or a nonwoven fabric, is high. In addition, as a material constituting such a cloth, it is desirable in terms of liquid absorbency that the surface tension is higher than that of the liquid to be spin-coated.

In the present invention, the wiping described above is preferably performed on the outer peripheral side surface and the outer peripheral end of the substrate.
According to the present invention, when the base material is, for example, a spectacle lens base material, not only the outer peripheral side surface (edge portion) of the base material but also the outer peripheral end portion of the base material wipes off the adhering liquid after spin coating. As for the outer peripheral end of the substrate, the excess portion of the coated liquid can be more reliably removed, and the generation and propagation of cracks on the substrate surface can be reliably prevented in the subsequent firing step. The wiping width of the outer peripheral edge is preferably 0.2 to 0.7 mm, more preferably 0.2 to 0.5 mm from the outer peripheral edge of the substrate toward the center.
Moreover, it is preferable that the above-mentioned cloth is impregnated with an organic solvent.
When the cloth is impregnated with such an organic solvent, excess liquid present on the surface of the substrate can be easily absorbed and removed. Here, the organic solvent to be impregnated into the cloth is preferably one having moderate volatility. For example, it may be an alcohol solvent such as ethanol, methanol, or isopropanol, a ketone solvent such as acetone or methyl ethyl ketone, or an ether solvent such as propylene glycol monomethyl ether (PGME) or glycerol diglycidyl ether. In particular, a liquid that is the same as the solvent that is the main component of the spin coating liquid is preferable because of high compatibility. It should be noted that the amount of the organic solvent to be impregnated is preferably such that it does not drip or fall off the cloth.

The layer forming apparatus of the present invention includes a liquid coating apparatus that forms a layer by applying a liquid to the surface of a rotating base material by a spin coating method, and a liquid that adheres to the outer peripheral side surface and the outer peripheral edge of the base material. And a liquid removing device for removing water.
According to such a layer forming apparatus of the present invention, after the liquid is applied to the base material by the spin coating method, the liquid attached to the outer peripheral portion of the base material can be removed by the liquid removing device. Therefore, when a layer is formed by applying a thermosetting liquid to the substrate with the layer forming apparatus of the present invention, cracks occur in the surface layer on the outer periphery of the substrate even if the substrate is fired thereafter. Hard to do.

In addition, it is preferable that a shutter that blocks liquid scattered from the base material during spin coating is disposed between the liquid applying apparatus and the liquid removing apparatus.
According to the layer forming apparatus having this configuration, the shutter for blocking the liquid scattered from the base material is disposed between the liquid applying apparatus and the liquid removing apparatus so that the liquid can be opened and closed. It is possible to prevent the removal device from being contaminated.

  Hereinafter, embodiments of the layer forming method and the layer forming apparatus of the present invention will be described in detail. In this embodiment, layer formation on a plastic lens base material for eyeglasses (hereinafter also referred to as “lens base material” or simply “base material”) is illustrated, but the present invention is not limited to this. And various optical lenses, recording media (CD, DVD), and substrates such as liquid crystal panels.

[Configuration of layer forming apparatus]
FIG. 1 is a schematic view of a layer forming apparatus 1 according to an embodiment of the present invention. The layer forming apparatus 1 removes the applied liquid from the liquid coating apparatus 100 that applies a liquid to the surface of the rotating lens substrate 50 by spin coating to form a layer, and the outer peripheral portion of the coating layer. And a liquid removing device 200.
In the liquid coating apparatus 100, a tank 11 in which a spin coating operation is performed on the base material 50 is formed, and a holder 20 that rotatably holds the base material 50 is disposed at the bottom of the tank 11, and the tank 11 is formed with a coating waste liquid discharge port 111. In addition, a discharge device 12 having a pressurized tank (not shown) and a nozzle 121 communicated with a tube is disposed above the tank 11, and moves between a standby position and above the holder 20. It has become.
In addition, the HEPA filter 13 is provided in the upper part of the layer forming apparatus 1, and the inside of the layer forming apparatus 1 has a local clean structure.

  The liquid application apparatus 100 in FIG. 1 is configured around a holder 20 as shown in an enlarged view in FIG. The holder 20 is attached to the holder 23, a cylindrical rotary shaft 21 that rotates using a motor 30 as a power source, a bearing 223, a housing 22, a holder 23 provided on one end side of the rotary shaft 21, and the holder 23. The suction pad 24 is configured to hold the base material 50 disposed on the suction pad 24.

The rotary shaft 21 is provided with a toothed pulley 211 at the end opposite to the holder 23 side, and a timing belt 302 wound around the pulley 211 and a toothed pulley 301 provided in the motor 30. The rotation of the motor 30 is transmitted to the rotating shaft 21.
In addition, a pipe 29 from a vacuum pump 40 is connected to the swivel joint 28 at the end of the rotating shaft 21 on the pulley 211 side, and is arranged on the suction pad 24 through the inside of the rotating shaft 21 by suction of the vacuum pump 40. The substrate 50 made is adsorbed.

The bearing 223 includes a housing 22 provided around the rotation shaft 21, holds a plurality of balls 221 that are rotatable with the rotation shaft 21 by a ball holding portion 222, and rotates the balls 221 to rotate the rotation shaft. 21 is smoothly rotated.
Note that the end portion of the rotating shaft 21 protrudes from the bearing 223 and is structured to be screwed after the holder 23 is inserted into the protruding portion.

  The holder 23 is a disk-shaped member made of Teflon (registered trademark), and has a structure in which the end of the rotary shaft 21 is inserted and fixed into a hole 231 formed in the center. Further, a protrusion 232 rising from the periphery of the hole 231 is formed, and the suction pad 24 is attached around the protrusion 232.

The suction pad 24 is an annular member in plan view formed of nitrile rubber, fluorine rubber, chloroprene rubber, silicone rubber or the like, and has a substantially U-shaped cross section, and one of the opposing portions in the U-shape is The other portion is supported by the holder 23 and serves as a holding portion 241 of the lens substrate 50.
In addition to such a rubber material, various elastic members that can follow and adhere to the shape of the substrate 50 can be used as the material of the suction pad 24.

As shown in FIG. 1, the liquid removal apparatus 200 that is a wiping means includes a rotatable support column 201 and an arm 202 that can move in the horizontal direction as the support column 201 rotates. As shown in FIG. 3, the tip of the arm 202 is a roll 202A, and a cotton cloth is wound around the roll 202A to form a liquid removing unit 202B. As shown in FIGS. 1 and 3, the liquid removing unit 202 </ b> B can come into contact with the edge portion 50 </ b> A of the lens base material 50 as the support column 201 rotates.
Further, if the liquid removing unit 202B is slightly abutted against the edge portion 50A, the surface of the cloth constituting the liquid removing unit 202B is deformed as shown in FIG. 4 so that the cloth also abuts on the outer peripheral end 50B of the lens substrate. become able to.
In the layer forming apparatus 1, a shutter 150 that blocks liquid scattered from the base material at the time of spin coating is disposed between the liquid applying apparatus 100 and the liquid removing apparatus 200 so as to be openable and closable. It is good also as a structure which can be rotated by.

[Configuration of lens after layer formation]
FIGS. 5A and 5B are cross-sectional views of the spectacle lens 500, and show a plurality of layers finally stacked on the lens substrate 50.
In FIG. 5A, a primer layer 501, a hard coat layer 502, an antireflection layer 503, and an antifouling layer 504 are respectively formed on the concave surface side and the convex surface side of the lens 500 in this order from the surface of the substrate 50. .
The primer layer 501 is formed of urethane resin or the like, and is formed when it is necessary to improve the adhesion between the base material 50 and the hard coat layer 502 or when it is necessary to improve the impact resistance. As in FIG. 5B, the hard coat layer 502 may be formed directly on the substrate 50 without forming the primer layer 501.

  The hard coat layer 502 is formed with a thickness of about 2 μm, for example, with a silicone or acrylic material in order to prevent the lens 500 from being damaged. When the hard coat layer 502 is formed directly on the base material 50, it is preferable to perform alkali treatment, acid treatment, polishing treatment with fine particles, plasma treatment, etc. on the surface of the base material 500 in advance. And the adhesion between the hard coat layer 502 and the hard coat layer 502 are improved.

Further, the antireflection layer 503 is formed as a lower refractive layer than the hard coat layer 502, the primer layer 501, and the base material 50, which are lower than the antireflection layer 503, in order to prevent surface reflection of the lens 500.
As will be described later, the antireflection layer 503 is applied to the processed surface 52 of the lens substrate 50 by the liquid applying apparatus 100 and can be formed not only as a single layer but also as a multilayer layer.
As the coating liquid LQ applied by the liquid applying apparatus 100, a fluorine compound, a silane compound, or the like can be used. For example, silica-based particles having an internal cavity, and a fluorine-containing silane compound represented by the general formula: X _m R ¹ _3-m Si—Y—SiR ¹ _3-m X _m (wherein R ¹ is carbon A composition comprising a monovalent hydrocarbon group of formulas 1 to 6, Y is a divalent organic group containing one or more fluorine atoms, X is a hydrolyzable group, and m is an integer of 1 to 3. It is.
In the present embodiment, the silane compound is diluted with an organic solvent, hydrolyzed by adding water or thin hydrochloric acid, acetic acid, etc. as necessary, and a sol in which silica-based fine particles are colloidally dispersed in the organic solvent. Then, a surfactant, a UV absorber, an antioxidant, etc. are added as necessary, and the mixture is sufficiently stirred and used as the coating liquid LQ.
The layer thickness of the antireflection layer 503 is controlled within a range of ± 10 nm with respect to a predetermined layer thickness of 100 nm, for example, in order to realize desired optical characteristics.
The antifouling layer 504 is formed by adding a fluorine-containing compound as an antifouling component, and is formed as the outermost layer of the spectacle lens 500.

(Layer formation method)
When each layer is formed on the surface of the base material 50 to manufacture the lens 500 described above, first, the lens base material 50 is formed by heating and / or irradiating light with respect to a liquid plastic raw material. 50, a primer layer 501 and a hard coat layer 502 are formed. The primer layer 501 and the hard coat layer 502 are formed by applying a coating solution by a dipping method, a spinner method, a roll coating method, a spray method, an ink jet method or a flow method, and then drying by heating. Then, the surface of the hard coat layer 502 is subjected to surface modification treatment by plasma, and then the antireflection layer 503 is applied by a spin coating method using the liquid coating apparatus 100.

Hereinafter, the coating process of the antireflection layer 503 will be described with reference to FIGS.
In the coating process of the antireflection layer 503, the substrate 50 is held as follows and spin coating is performed.
First, as shown in FIG. 6, the lens base material 50 is supplied to the suction pad 24 of the holder 20 and suction chucked by the vacuum pump 40. When the lens base material 50 is set on the holder 20, the motor 30 is operated to rotate the lens base material 50 via the rotating shaft 21 of the holder 20, while the coating liquid is applied from the nozzle 121 to the processing surface 52 of the base material 50. LQ is discharged.
Then, the coating liquid LQ is spread from the inside to the outside of the processed surface 52 of the base material 50 by centrifugal force. At this time, the coating liquid LQ is scattered radially from the surface of the lens base material by the rotation of the base material 50. However, since the shutter 150 is disposed, there is no possibility that the cloth of the liquid removing unit 202B is contaminated by the coating liquid LQ. .

After completion of the spin coating, the shutter 150 is opened, the support column 201 of the liquid removing apparatus 200 is rotated, and the liquid removing unit 202B is brought into contact with the edge portion 50A of the rotating substrate 50. And the uncured liquid adhering to the outer peripheral part 500A (the edge part 50A and the outer peripheral end part 50B of the processed surface 52) of the lens base material 50 is wiped off while adjusting the rotation speed of the base material 50 to about 500 to 1000 rpm. The wiping time is preferably about 1 to 5 seconds. The wiping width of the outer peripheral end portion 50B is preferably 0.2 to 0.7 mm, more preferably 0.2 to 0.5 mm from the outer peripheral edge of the substrate 50 toward the center.
In addition, since hardening of the apply | coated liquid becomes a problem, it is preferable to complete wiping within 5 minutes immediately after the end of the speed coat.

After the outer peripheral portion 500 </ b> A is wiped off, the base material 50 is dried and fired. Since the coating liquid LQ is applied to the surface of the substrate 50 with a uniform thickness, the cured antireflection layer 503 also has a uniform thickness. Such an operation is performed on both surfaces of the substrate 50.
By forming the antifouling layer 504 as the outermost layer of the base material 50 on the antireflection layer 503, the spectacle lens 500 is completed.

According to this embodiment described above, the following effects can be obtained.
(1) The layer forming apparatus 1 includes a liquid coating apparatus 100 that forms a layer by applying a liquid to the surface of a rotating lens base material 50 by a spin coating method, and an outer peripheral portion 500A (edge portion) of the lens base material 50. 50A, and the liquid removing device 200 that removes the liquid adhering to the outer peripheral end portion 50B). After applying the liquid to the lens substrate 50 by the spin coat method, the liquid removing device 200 removes the substrate. The excess liquid adhering to the outer peripheral portion 500A can be reliably removed. Therefore, there is no thick portion on the surface of the outer peripheral portion 500 </ b> A, and even if the base material 50 is baked and cured, cracks are unlikely to occur in the base material 50.

(2) Since the liquid removing unit 202B of the liquid removing apparatus 200 can be brought into contact with the edge part 50A of the base material 50, the liquid adhering to the edge part 50A can be reliably absorbed and removed, and the thick part is eliminated. Can do. Furthermore, since the liquid removing unit 202B can absorb the coating liquid also from the outer peripheral end 50B, the thick portion of the surface layer of the outer peripheral end 50B can be quickly removed.

(3) Furthermore, since the liquid removing unit 202B is made of cloth, the excess coating liquid adhering to the edge portion 50A and the outer peripheral end portion 50B can be absorbed quickly. In particular, when the cloth constituting the liquid removing portion 202B is in direct contact with the outer peripheral end portion 50B, the coating liquid can be reliably absorbed from the portion.
(4) When the wiping width of the outer peripheral end portion is in the range of about 0.2 to 0.7 mm from the outer peripheral edge of the substrate toward the center, crack generation from the outer peripheral end portion can be effectively suppressed. , No problem when processing the target.
(5) Since the shutter 150 is disposed between the liquid application apparatus 100 and the liquid removal apparatus 200 in the layer forming apparatus 1, the liquid scattered from the base material during spin coating can be blocked. Contamination of the liquid removing unit 202B can be prevented.

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 the above-described embodiment, the roll 202A is merely a shaft for winding a cloth. However, if the roll 202A is a free roll, the lens base 50 rotates with the liquid removing unit 202B in contact with the lens base 50. Then, the liquid removing unit 202B can be rotated in the direction opposite to the base material 50. Then, the surface of the cloth can be used effectively. In this case, a brake mechanism or a drive mechanism may be provided on the free roll to control the rotation of the liquid removing unit 202B. Furthermore, if the column 201 can be moved in the vertical direction, the surface of the liquid removing unit 202B can be used more effectively.
Although the cloth is used as the material of the liquid removing unit 202B, the cloth is not limited to a narrowly defined cloth as long as it is soft and liquid absorbent to the extent that the substrate 50 is not damaged. For example, it may be felt, non-woven fabric, or sponge.

The cloth of the liquid removing unit 202B does not need to be used in a dry state, and may be used by impregnating a low boiling point organic solvent such as ethanol or acetone, or the diluted solvent itself of the coating liquid LQ. For example, FIG. 8 shows an example in which an organic solvent tank 250 is installed inside the layer forming apparatus 1. The organic solvent layer 250 has a lid 251 that can be opened and closed at the top. Moreover, the support | pillar 201 is a structure which can be moved up and down simultaneously with rotation.
Then, the arm 202 is moved by the rotation of the support column 201 to move the liquid removal unit 202B directly above the organic solvent tank 250, and after the lid 251 is opened, the support column 201 is moved up and down to apply organic to the cloth of the liquid removal unit 202B. Impregnate with solvent. The amount of the organic solvent impregnated into the cloth is limited to such an extent that the solvent does not drip or fall off the cloth. Furthermore, the amount of the organic solvent impregnated in the cloth when the cloth of the liquid removing section 202B is pressed against the edge part 50A of the base material 50 may be adjusted so as not to overflow and overflow to the surface of the base material 50. In addition, when immersing the liquid removing unit 202B in the organic solvent tank 250 during spin coating, it is preferable to perform the immersing operation with the shutter 150 closed in order to prevent contamination of the cloth.
Note that the inside of the support column 201 and the arm 202 may have a piping structure, and an appropriate amount of organic solvent may be supplied to the cloth of the liquid removing unit 202B from the organic solvent tank 250 through the inside of the piping.
When the cloth of the liquid removing unit 202B is impregnated with the organic solvent in this way, excess liquid existing on the surface of the edge portion 50A and the outer peripheral end portion 50B of the lens base 50 can be more easily absorbed and removed. become.
In this embodiment, the shutter 150 is used for the layer forming apparatus 1. However, the shutter 150 is not necessary if the holder 20 of the liquid coating apparatus 100 has a structure that moves up and down inside the tank 11.
As described above, the present invention is mainly illustrated and described mainly with respect to specific embodiments, but departs from the technical idea and object of the present invention with respect to the above-described embodiments. Without limitation, various modifications can be made by those skilled in the art in terms of shape, material, quantity, and other detailed configurations.

Next, examples of the present invention will be described. It should be noted that the numerical values and the like in the following description are merely examples for implementing the present invention. In addition, the same code | symbol was used for the location which is common in embodiment.
[Example 1]
As the lens substrate 50, a plastic lens substrate having a refractive index of 1.67 (manufactured by Seiko Epson Corporation, trade name “Seiko Super Sovereign (SSV)”) was used. A spectacle lens 500 was manufactured by forming a primer layer 501, a hard coat layer 502, an antireflection layer 403, and an antifouling layer 504 on the lens substrate 50 as follows, and the appearance was evaluated.

(Formation of primer layer 501)
77 g of commercially available aqueous polyester “A-160P” (manufactured by Takamatsu Yushi Co., Ltd., solid concentration 25%), 220 g of methanol, 31.5 g of propylene glycol monomethyl ether (PGME), 91.8 g of water, methanol-dispersed titanium dioxide-dioxide Zirconium-silicon dioxide composite fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20% by weight)) 78.8 g, and silicone surfactant (manufactured by Nihon Unicar Co., Ltd., trade name “L-7604”) 0.1 g was mixed and stirred for 2 hours. Application to the lens substrate 50 was carried out using an immersion method (pickup speed 20 cm / min), and the lens substrate 50 after application was heat-cured at 80 ° C. for 20 minutes. The primer layer 501 thus formed had a thickness of 0.5 μm and a refractive index of 1.67.

(Formation of hard coat layer 502)
The hard coat layer 502 was formed by applying the following coating solution on the primer layer 501. First, 62.5 g of butyl cellosolve and 67.1 g of γ-glycidoxypropyltrimethoxysilane were mixed. To this mixed solution, 30.7 g of 0.1 N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and then aged overnight. In this liquid, 325 g of methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20% by weight), glycerol diglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “ After adding 12.5 g of Denacol EX-313 "), 1.36 g of iron (III) acetylacetonate, 0.15 g of silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name" L-7001 "), phenol 0.63 g of a system antioxidant (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name “ANTAGE CRYSTAL”) was added, and the mixture was stirred for 4 hours and then aged overnight. The application was performed by a dipping method (pulling speed of 35 cm / min), followed by a heat curing treatment at 80 ° C. for 30 minutes and then a heat curing treatment at 125 ° C. for 180 minutes. The hard coat layer thus formed had a thickness of 2.0 μm and a refractive index of 1.67.

(Formation of antireflection layer 503)
The antireflection layer 503 was formed on the hard coat layer 502 using the layer forming apparatus 1 in the embodiment.
First, 48.6 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) and 14.1 g of γ-glycidoxypropyltrimethoxysilane were mixed, and 4.0 g of 0.1 N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was stirred for 5 hours. did. To this liquid, 33.3 g of isopropanol-dispersed hollow silica sol (average particle size 91 nm, solid content concentration 30 wt%) was added and mixed well, and then 0.06 g of Al (C5H7O2) 3 as a curing catalyst, a silicone surfactant ( A coating stock solution having a solid content concentration of 20% was obtained by adding 0.03 g of Nippon Unicar Co., Ltd. (L7604) and stirring and dissolving. In order to dilute the coating stock solution, a PGME solution containing a 300 ppm silicone surfactant (manufactured by Nippon Unicar Co., Ltd., L7604) was prepared, 35.3 g of the coating stock solution, and PGME containing the surfactant for dilution. 114.7 g of the solution was mixed and sufficiently stirred to prepare a coating solution (coating solution) having a solid content concentration of about 4.7%.
The application was performed by spin coating using the layer forming apparatus 1. Further, during the spin coating, the shutter 150 is closed as shown in FIG. 6, and the coating liquid that radiates from the lens substrate 50 contaminates the surface of the liquid removal unit 202 </ b> B of the liquid removal apparatus 200. Prevented. The liquid removing unit 202B is configured by winding a cotton cloth around a roll 202A.
Immediately after the application by spin coating, the shutter 150 was opened, the column 201 of the liquid removing apparatus 200 was rotated, and the arm 202 was moved horizontally toward the base material 50. And while rotating the base material 50 at 500 rpm, the liquid removal part 202B was contacted with the edge part 50A of the base material 50 for 3 seconds, and the coating liquid adhering to the edge part was wiped off. In that case, the coating liquid which comprised the thick layer in the outer peripheral edge part 50B (the vicinity of the outer periphery of the base material 50, the range of about 0.2-0.7 mm from an outer periphery) of the base material 50 Absorbed by the cloth of the liquid removing unit 202B.
After wiping the edge portion 50A, annealing was performed at 100 ° C. for 10 minutes. The antireflection layer 503 thus formed had a thickness of about 91 nm and a refractive index of about 1.42. Then, the base material 50 was inverted and the antireflection layer 503 was formed on the opposite side of the base material 50 by the same method. After coating on both sides, annealing was performed at 125 ° C. for 90 minutes.

(Formation of antifouling layer 504)
The composition for forming the antifouling layer 504 includes a fluorine silane compound A having a molecular weight of 2500 (trade name “KY-130” manufactured by Shin-Etsu Chemical Co., Ltd.) and a fluorine silane compound B having a molecular weight of 497.5 (Shin-Etsu). Chemical Industry Co., Ltd., trade name “KP-801”) and diluted with a fluorine-based solvent (Sumitomo 3M Co., Ltd., trade name “Novec HFE-7200”) as a solid content concentration 3 mass% solution Prepared. A porous ceramic pellet impregnated with 1 g of the above composition and dried was set in a chamber as a deposition source. After the pellets are dried, the pellets are set in a vacuum vapor deposition machine and evacuated until the ultimate pressure is in the range of 1.0 to 4.0 × 10 ⁻² Pa. After the above-described antireflection layer 503 is formed in the vacuum vapor deposition machine. The lens substrate 50 was introduced, and the pellets were heated from 400 ° C. to 500 ° C. to evaporate the silane compound, and an antifouling layer 504 was formed on the surface of the antireflection layer 503. After vapor deposition was completed, the inside of the vapor deposition machine was gradually returned to atmospheric pressure, and the spectacle lens 500 was taken out. Then, it hold | maintained for 2 hours in the constant temperature and humidity layer set to 90 degreeC90% RH.
The antifouling layer 504 may be formed not only by the dry method described above but also by a wet method such as an immersion method. In the case of the wet type, the lens base material 50 is immersed in a solution having a solid content concentration of 0.3% by mass, held for 1 minute, then pulled up at 15 cm / min, and then placed in a constant temperature and humidity chamber set at 90 ° C. and 90% RH. It is preferable to charge and hold for 1.5 hours.

[Comparative Example 1]
A spectacle lens 500 ′ was manufactured in the same manner as in Example 1 except that the edge portion 50A was not wiped in the formation of the antireflection layer 503 in Example 1.

[Evaluation methods and results]
In a dark box, the background was black, and the number of cracks occurring in the spectacle lenses 500 and 500 ′ obtained in Examples and Comparative Examples was observed with the naked eye using the transmitted light of a fluorescent lamp.
As a result, no crack was generated in the spectacle lens 500 of Example 1, but innumerable cracks were generated in the spectacle lens 500 ′ of Comparative Example 1. Therefore, it can be understood that the layer forming method and the layer forming apparatus 1 of the present invention are excellent.

  The present invention can be used for eyeglass lenses and other lenses in general.

Schematic of the layer formation apparatus concerning embodiment of this invention. The enlarged view of the holder in the said embodiment. The figure which shows the liquid removal method in the said embodiment. The figure which shows the other aspect of the liquid removal method in the said embodiment. Sectional drawing of the lens (base material) in the said embodiment. The figure which shows the liquid application apparatus and liquid removal apparatus in the said embodiment. The figure which shows the layer thickness of the lens base-material outer periphery end after the conventional spin coat. The figure which shows the liquid application apparatus and liquid removal apparatus in other embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Layer formation apparatus, 50 ... Lens base material, 50A ... Edge part (outer peripheral side surface), 50B ... Outer peripheral edge part, 100 ... Liquid application apparatus, 200 ... Liquid removal apparatus, 500, 500 '... Eyeglass lens, 500A ... Outer periphery Part

Claims (8)

A layer forming method comprising: a liquid applying step of forming a layer by applying a liquid to a surface of a rotating substrate by a spin coating method; and a baking step of hardening the layer by baking after the liquid applying step Because
Before the baking step, the liquid forming method is characterized in that the liquid adhering to the outer peripheral end near the outermost peripheral end of the base material and the outer peripheral side surface of the base material is removed. In the layer formation method according to claim 1,
The layer forming method, wherein the substrate is a substrate of an eyeglass lens, the layer is an organic layer, and the liquid is an organic layer forming composition. In the layer forming method according to claim 1 or 2,
A method of forming a layer, wherein the method of removing the liquid adhering to the outer peripheral edge and the outer peripheral side surface of the substrate is wiping off the liquid. In the layer forming method according to claim 3,
The layer forming method, wherein the wiping is performed on the base material while rotating at least one of the base material and the wiping means for wiping. In the layer forming method according to claim 3 or 4,
A layer forming method comprising using a cloth for wiping, and pressing the cloth against an outer peripheral side surface of a substrate. In the layer formation method according to claim 5,
The wiping is performed on the outer peripheral side surface and the outer peripheral end of the substrate. In the layer forming method according to claim 5 or 6,
A method of forming a layer, wherein the cloth is impregnated with an organic solvent.   A liquid application device that forms a layer by applying a liquid to the surface of a rotating substrate by a spin coating method, and a liquid removal device that removes the liquid attached to the outer peripheral side surface and the outer peripheral edge of the substrate. A layer forming apparatus comprising:

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