Laminate and method for manufacturing spectacle lens

Abstract

The present disclosure addresses the problem of providing a laminate that can easily undergo lens edging, and has excellent water repellency and oil repellency after a first temporary protective layer and a second temporary protective layer are removed. A laminate according to the present disclosure comprises a spectacle lens base material, a water-repellent and oil-repellent layer, a first temporary protective layer, and a second temporary protective layer in this order. The first temporary protective layer contains a metal fluoride or titanium oxide, and the second temporary protective layer is a metal layer.

Description

Laminate and method for manufacturing eyeglass lenses

[0001] The present disclosure relates to a laminate and a method for manufacturing an eyeglass lens.

[0002] Patent Document 1 discloses "a method for edging an oil-repellent coated eyeglass lens by edging an oil-repellent coated lens into various lens shapes using an edging machine, the method comprising the steps of: attaching adhesive tape, which has a thickness of 10 to 100 μm and has a Young's modulus of 1 GPa or more and has a silicone adhesive coated on the surface of the polymer film, to both sides of the lens to be processed; and then setting the lens in the edging machine."

[0003] Japanese Patent Application Laid-Open No. 2004-347660

[0004] The present disclosure relates to a laminate having, in this order, an eyeglass lens substrate, a water- and oil-repellent layer, a first temporary protective layer, and a second temporary protective layer, wherein the first temporary protective layer contains a metal fluoride or titanium oxide, and the second temporary protective layer is a metal layer.

[0005] 1 is a schematic cross-sectional view of a laminate;

[0006] The present disclosure will be described in detail below. The laminate of the present disclosure is easy to bead and has excellent water and oil repellency after removing the first temporary protective layer and the second temporary protective layer. The term "easy to bead" means that the axial and horizontal deviations from the design values ​​can be reduced during beading. Hereinafter, the first temporary protective layer and the second temporary protective layer will be collectively referred to simply as "temporary protective layer." The following description of the constituent elements may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment.

[0007] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0008] [Laminate] The laminate is preferably used to fix the laminate by pressing a fixing member against the second temporary protective layer in the laminate and then grinding. In other words, it is preferably used in step 1 of the eyeglass lens manufacturing method described below. FIG. 1 is a cross-sectional schematic diagram of a laminate 100. The laminate 100 has a water- and oil-repellent layer 4 on an eyeglass lens substrate 2, a first temporary protective layer 6 on the water- and oil-repellent layer 4, and a second temporary protective layer 8 on the first temporary protective layer 6. The laminate 100 may further have other layers such as an anti-reflection layer, a primer layer, and a hard coat layer, which will be described later. If the laminate 100 has the other layers, it is preferable that the other layers be disposed between the eyeglass lens substrate 2 and the water- and oil-repellent layer 4. The laminate 100 in Figure 1 is an embodiment having a water- and oil-repellent layer 4 on both sides of the eyeglass lens substrate 2, and a first temporary protective layer 6 and a second temporary protective layer 8 on only one side, but is not limited to this embodiment, and for example, the laminate may have a water- and oil-repellent layer, a first temporary protective layer, and a second temporary protective layer on both surfaces of the eyeglass lens substrate.

[0009] The luminous transmittance of the laminate is preferably less than 100%, more preferably 90% or less, and even more preferably 88% or less. The lower limit is preferably 0% or more, more preferably 10% or more, and even more preferably 20% or more. A method for adjusting the luminous transmittance includes, for example, adjusting the thickness of each layer (e.g., the first temporary protective layer and the second temporary protective layer) of the laminate. The luminous transmittance is the average value of the transmittance at wavelengths of 380 to 780 nm, and can be measured using a spectrometer.

[0010] <Eyeglass Lens Substrate> Examples of the eyeglass lens substrate include eyeglass lens substrates made of organic or inorganic materials, with eyeglass lens substrates made of organic materials (such as plastic lens substrates) being preferred. Examples of eyeglass lens substrates include finished lenses in which both the convex and concave surfaces are optically finished and molded to the desired dioptric power, semi-finished lenses in which only the convex surface is finished as an optical surface (e.g., spherical, rotationally symmetric aspherical, and progressive surfaces), and semi-finished lenses in which the concave surface is processed and polished to match the wearer's prescription. Examples of organic materials include acrylic resins, methacrylic resins, thiourethane resins, allyl resins, episulfide resins, polycarbonate resins, polyurethane resins, polyester resins, polystyrene resins, polyethersulfone resins, poly(4-methylpentene-1) resins, diethylene glycol bisallyl carbonate resins (CR-39), and polyvinyl chloride resins.

[0011] The thickness of the spectacle lens substrate is preferably 1 to 30 mm from the viewpoint of ease of handling. The spectacle lens substrate may be opaque or colored, as long as it has light-transmitting properties.

[0012] <Water- and Oil-Repellent Layer> The laminate has a water- and oil-repellent layer on an eyeglass lens substrate. The water- and oil-repellent layer preferably contains at least one selected from the group consisting of organosilicon compounds, their hydrolysates, and their hydrolyzed condensates. The hydrolyzate of an organosilicon compound refers to a compound produced by hydrolyzing the hydrolyzable groups in an organosilicon compound having hydrolyzable groups. The hydrolyzate of an organosilicon compound may be a complete hydrolyzate in which all of the hydrolyzable groups in the organosilicon compound are hydrolyzed, a partial hydrolyzate in which some of the hydrolyzable groups are decomposed, or a mixture thereof. The hydrolyzed condensate of an organosilicon compound refers to a compound produced by condensing the hydrolyzed organosilicon compound having hydrolyzable groups. The hydrolyzed condensate of an organosilicon compound may be a complete hydrolyzed condensate in which all of the hydrolyzed groups in the hydrolyzate are condensed, a partial hydrolyzed condensate in which only some of the hydrolyzed groups are condensed, or a mixture thereof.

[0013] Examples of the organosilicon compound include a silane compound, a silazane compound, a silanol compound, a siloxane compound, a silicate compound, and a silyl ester compound, with the silane compound being preferred.

[0014] Examples of the hydrolyzable group include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, and an isocyanate group.

[0015] The organosilicon compound preferably has a fluorine atom-containing group, such as a group having a perfluorocarbon structure or a group having a perfluoropolyether structure.

[0016] Examples of the organosilicon compound include those described in WO 2020 / 039795, U.S. Pat. No. 4,410,563, EP 0,203,730, EP 749,021, EP 844,265, and EP 933,377.

[0017] The thickness of the water- and oil-repellent layer is preferably 1 to 1000 nm. The water- and oil-repellent layer may be either a single layer or a multilayer.

[0018] <First temporary protective layer> The laminate has a first temporary protective layer on the water- and oil-repellent layer. The laminate preferably has the first temporary protective layer adjacent to the water- and oil-repellent layer. By having the first temporary protective layer in the laminate, the temporary protective layer can be easily removed from the water- and oil-repellent layer in step 2 described below, and the effect on the water- and oil-repellent properties of the water- and oil-repellent layer after removing the temporary protective layer is small.

[0019] The first temporary protective layer includes a metal fluoride or titanium oxide.

[0020] The metal fluoride is preferably magnesium fluoride, calcium fluoride, lanthanum fluoride, neodymium fluoride, or cerium fluoride, and more preferably magnesium fluoride. When the first temporary protective layer contains a metal fluoride, it is also preferable that the first temporary protective layer is a metal fluoride layer. The metal fluorides may be used alone or in combination of two or more. When the first temporary protective layer contains a metal fluoride, the content of the metal fluoride is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more, relative to the total mass of the first temporary protective layer. The upper limit is preferably 100% by mass or less. In particular, it is preferable that the content of magnesium fluoride satisfies the above-mentioned preferred range.

[0021] Titanium oxide is Ti ２ O ３ , TiO ２ , Ti ２ Although either O or TiO may be used, Ti is preferred in that it provides a more excellent effect of the present invention. ２ O ３ The titanium oxide may be either amorphous or crystalline, but is preferably crystalline. The crystal system is not particularly limited, but examples of titanium oxide include TiO ２ When containing TiO ２The crystal system of is preferably rutile. The first temporary protective layer is also preferably a titanium oxide layer. The form of titanium oxide can be adjusted by the method for forming the first temporary protective layer (for example, the target material, the atmosphere and temperature during film formation, etc.). When the first temporary protective layer contains titanium oxide, the content of titanium oxide is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more, relative to the total mass of the first temporary protective layer. The upper limit is preferably 100% by mass or less.

[0022] The thickness of the first temporary protective layer is preferably 3 nm to 400 nm, more preferably 5 nm to 300 nm, and even more preferably greater than 10 nm and less than 100 nm. In particular, when the first temporary protective layer contains a metal fluoride, the thickness of the first temporary protective layer is preferably 10 to 100 nm, more preferably greater than 10 nm and less than 100 nm. Furthermore, when the first temporary protective layer contains titanium oxide, the thickness of the first temporary protective layer is preferably greater than 20 nm and less than 80 nm, more preferably 25 to 75 nm. The thickness of the first temporary protective layer can be measured, for example, using a quartz crystal film thickness meter.

[0023] <Second temporary protective layer> The laminate has a second temporary protective layer on the first temporary protective layer. The laminate preferably has a second temporary protective layer adjacent to the first temporary protective layer. By having the second temporary protective layer on the laminate, adhesion between the fixing member and the laminate in step 1 described below is excellent, axial deviation when grinding the laminate can be suppressed, and beading processing can be easily performed.

[0024] The second temporary protective layer is a metal layer. The metal in the metal layer is not particularly limited, but preferably contains at least one selected from the group consisting of aluminum, zinc, copper, and nickel (hereinafter also referred to as "specific metal"), and more preferably contains aluminum. The metal may be either a pure metal or an alloy, with pure metal being preferred. When the second temporary protective layer contains the specific metal, it may further contain other metals. Examples of other metals include known metals.

[0025] The content of the specific metal is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more, based on the total mass of the second temporary protective layer. The upper limit is preferably 100% by mass or less. In particular, it is preferable that the content of aluminum satisfies the above-mentioned preferred range.

[0026] When the first temporary protective layer contains a metal fluoride, the thickness of the second temporary protective layer is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably more than 10 nm. The upper limit is preferably 150 nm or less, more preferably 100 nm or less, and even more preferably 80 nm or less. When the first temporary protective layer contains titanium oxide, the thickness of the second temporary protective layer is preferably 5 nm or more, and more preferably more than 5 nm. The upper limit is preferably less than 150 nm, and even more preferably 100 nm or less.

[0027] When the first temporary protective layer contains a metal fluoride, the total thickness of the first temporary protective layer and the second temporary protective layer is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more. When the first temporary protective layer contains a metal fluoride, the upper limit of the total thickness of the first temporary protective layer and the second temporary protective layer is not particularly limited, but is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Furthermore, when the first temporary protective layer contains titanium oxide, the total thickness of the first temporary protective layer and the second temporary protective layer is preferably 40 nm or more and 70 nm or less. The ratio of the thickness of the first temporary protective layer to the thickness of the second temporary protective layer is preferably 40 or less, more preferably 20 or less. Furthermore, the ratio of the thickness of the first temporary protective layer to the thickness of the second temporary protective layer is preferably 0.05 or more, more preferably 0.1 or more.

[0028] <Other Layers> The laminate may have other layers in addition to the above layers. Examples of other layers include a primer layer, a hard coat layer, an anti-reflection layer, and an intermediate layer. When the laminate has an intermediate layer, it is preferable that the laminate has the intermediate layer on the side of the water- and oil-repellent layer opposite to the first temporary protective layer and the second temporary protective layer. When the laminate has other layers, it is preferable that the laminate further has a primer layer, a hard coat layer, and an anti-reflection layer in this order from the eyeglass lens substrate side between the eyeglass lens substrate and the water- and oil-repellent layer.

[0029] The primer layer is a layer that improves the adhesion of the hard coat layer to the eyeglass lens substrate. The primer layer preferably contains a resin, more preferably a urethane resin, an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, or a polyolefin resin. The thickness of the primer layer is preferably 0.3 to 2 μm.

[0030] The hard coat layer is a layer disposed on a spectacle lens substrate and provides scratch resistance to the spectacle lens substrate. Examples of hard coat layers include organic hard coat layers, inorganic hard coat layers, and organic-inorganic hybrid hard coat layers. The thickness of the hard coat layer is preferably 1.0 to 20.0 μm, and more preferably 1.5 to 15.0 μm.

[0031] The composition for forming a hard coat layer preferably contains at least one selected from the group consisting of an inorganic compound, a polymerization initiator, and an organic solvent. Examples of the inorganic compound include inorganic oxides and silsesquioxanes.

[0032] The inorganic oxide is preferably a metal oxide particle. Examples of the metal oxide particle include oxide particles of at least one metal selected from the group consisting of Ti, Zr, Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, and In, and composite metal oxide particles thereof. Composite metal oxide particles are oxide particles containing two or more metals (metal atoms). The inorganic oxide particle is preferably a SiO ２ (silicon oxide), Al ２ O３ (aluminum oxide), SnO ２ (tin oxide), ZrO ２ (zirconium oxide) and TiO ２ (titanium oxide), and SiO ２ and ZrO ２ It is more preferable that the composition contains at least one selected from the group consisting of:

[0033] Silsesquioxane is a silane compound obtained by hydrolysis of a trifunctional silane compound such as alkoxysilane, chlorosilane, or silanol.

[0034] The antireflection layer may have either a single-layer structure or a multilayer structure. The antireflection layer is preferably an inorganic antireflection layer. The inorganic antireflection layer refers to an antireflection layer composed of an inorganic compound. The multilayer antireflection layer may have a structure in which high-refractive-index layers and low-refractive-index layers are alternately laminated. The high-refractive-index layers preferably contain titanium, zirconium, aluminum, niobium, tantalum, or lanthanum oxide. The low-refractive-index layers preferably contain a silica compound. The thickness of the antireflection layer is preferably 0.2 to 3.0 μm, more preferably 0.3 to 2.0 μm.

[0035] [Method for manufacturing laminate] Examples of the method for manufacturing the laminate include known manufacturing methods. As the method for manufacturing the laminate, a method for manufacturing a laminate including the steps of forming a water- and oil-repellent layer on a spectacle lens substrate, forming a first temporary protective layer on the water- and oil-repellent layer, and forming a second temporary protective layer on the first temporary protective layer is preferred.

[0036] The step of forming the water- and oil-repellent layer is preferably a step of applying a water- and oil-repellent layer-forming composition to a spectacle lens substrate and curing it. Examples of methods for applying the water- and oil-repellent layer-forming composition include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating. Examples of curing methods include drying, which may or may not involve heating during drying. The water- and oil-repellent layer-forming composition is a composition containing various components and / or precursors thereof that may be contained in the water- and oil-repellent layer described above, and preferably further contains an organic solvent.

[0037] Examples of processes for forming the first temporary protective layer include dry film-forming methods such as physical vapor deposition and chemical vapor deposition, and wet film-forming methods such as coating, with physical vapor deposition being preferred. Physical vapor deposition methods include evaporation methods such as thermal evaporation and electron beam evaporation, and sputtering, with thermal evaporation or sputtering being preferred. When forming a first temporary protective layer containing titanium oxide, it is preferable to perform evaporation or sputtering in an inert gas using titanium oxide as a target. In this case, performing evaporation or sputtering without supplying oxygen gas makes it easier to remove the titanium oxide film, and it is easier to obtain a titanium oxide film with the desired properties that can maintain water and oil repellency after removing the first temporary protective layer.

[0038] The substrate temperature during the film formation is preferably 27 to 75° C., more preferably 27 to 50° C. The dry film formation method and the wet film formation method may be carried out under normal pressure, reduced pressure, or high pressure, and are preferably carried out under reduced pressure. In the dry film formation method, the pressure at the start of film formation is 4.0×10 －３ Pa or less is preferable, and 3.5 × 10 －３ Pa or less is more preferable.

[0039] Examples of the process for forming the second temporary protective layer include dry film-forming methods such as physical vapor deposition and chemical vapor deposition, and wet film-forming methods such as coating, with physical vapor deposition being preferred. Examples of the physical vapor deposition methods include the methods described above, with thermal evaporation being preferred. The dry film-forming and wet film-forming methods may be performed under normal pressure, reduced pressure, or high pressure, with reduced pressure being preferred.

[0040] The method for producing the laminate also preferably includes the steps of forming a primer layer on the eyeglass lens substrate, forming a hard coat layer on the primer layer, forming an anti-reflection layer on the hard coat layer, forming a water- and oil-repellent layer on the anti-reflection layer, forming a first temporary protective layer on the water- and oil-repellent layer, and forming a second temporary protective layer on the first temporary protective layer. The steps of forming the water- and oil-repellent layer, the first temporary protective layer, and the second temporary protective layer are as described above.

[0041] The step of forming the primer layer is preferably a method of applying a primer layer-forming composition onto a spectacle lens substrate. The step of forming the primer layer may include a drying step. Heating may or may not be performed during drying.

[0042] The step of forming a hard coat layer is preferably a method of applying a hard coat layer-forming composition onto a primer layer and curing it. Examples of methods for applying the hard coat layer-forming composition include the above-mentioned methods for applying the water- and oil-repellent layer-forming composition. For example, when using a dip coating method, a spectacle lens substrate having a primer layer is immersed in a hard coat layer-forming composition, and then the spectacle lens substrate having the primer layer is pulled up and dried, thereby forming a coating film derived from the hard coat layer-forming composition on the primer layer of the spectacle lens substrate.

[0043] Examples of the curing method include heat treatment and exposure treatment. The conditions for the heat treatment and the light irradiation treatment can be appropriately adjusted depending on the various components contained in the composition for forming a hard coat layer. Examples of the type of light used for light irradiation include ultraviolet light and visible light. Examples of the light source include a high-pressure mercury lamp. The integrated light amount used for light irradiation is 100 to 10,000 mJ / cm from the viewpoints of productivity and curability of the coating film. ２ is preferred, and 100 to 5000 mJ / cm ２ is more preferred.

[0044] The anti-reflection layer can be formed by a dry method such as vacuum deposition, sputtering, ion plating, ion beam assisted deposition, or CVD.

[0045] [Method for manufacturing eyeglass lenses] The method for manufacturing eyeglass lenses of the present disclosure includes step 1 of pressing a fixing member against the second temporary protective layer of the above-mentioned laminate to fix the laminate and grinding the periphery of the laminate, and step 2 of removing the first temporary protective layer and the second temporary protective layer of the ground laminate.

[0046] <Step 1> Step 1 is a step of grinding the periphery of the laminate to process the laminate into a predetermined shape, which is a so-called beading process. Grinding can be performed using a known grinding device. FIG. 2 is a schematic diagram of the grinding device 300 used in step 1, and step 1 will be described in detail with reference to FIG. 2. First, the laminate 200 is placed between the fixing member 60 and the lens processing shaft 52 so that the fixing member 60 contacts the second temporary protective layer 40 of the laminate 200, and the fixing member 60 is pressed against the fixing member 60 to fix the laminate 200. In other words, the laminate 200 is pressed and fixed between the fixing member 60 and the lens processing shaft 52. 2, the fixing member 60 has a lens processing shaft 51, a lens lock cap 30 fixed to the tip of the lens processing shaft 51, and an adhesive tape 20 attached to the surface of the lens lock cap 30, and the surface of the adhesive tape 20 opposite the surface of the lens lock cap 30 is in contact with the second temporary protective layer 40 of the laminate 200, but this is not limited to such an embodiment. Also, in FIG. 2, the adhesive tape 20 has a three-layer structure with adhesive layers on both sides of a substrate, but this is not limited to such an embodiment.

[0047] An example of the grinding device 300 is LE-9000X (manufactured by Nidek Co., Ltd.), and an example of the adhesive tape 20 is LEAPIII (manufactured by 3M Co., Ltd.).

[0048] Next, the laminate 200 is rotated by rotating the fixing member 60 and the lens processing shaft 52, and the laminate 200 is ground into a predetermined shape by pressing a rotating grindstone against the periphery of the laminate 200. Examples of the grinding method in step 1 include the edging processes described in JP-A-2007-156226, JP-A-2003-141607, and JP-A-2007-505937.

[0049] <Step 2> Step 2 is a step of removing the temporary protective layers (first and second temporary protective layers) from the ground laminate. Methods for removing the temporary protective layers include, for example, tape peeling, using a release agent, dry wiping, and a combination thereof. The tape peeling or the use of a release agent is preferred because they allow for efficient removal of the temporary protective layers. The first and second temporary protective layers may be removed simultaneously or sequentially through the removal operation, with simultaneous removal being preferred. When the temporary protective layers are removed sequentially, a combination of different removal methods may be used. Dry wiping, for example, involves rubbing the temporary protective layer with a wipe. Tape peeling, for example, involves peeling the temporary protective layer using a known tape. Examples of release agents include organic solvents such as alcoholic solvents, water, and mixtures thereof, with alcoholic solvents being preferred. The release agent may contain an anionic surfactant, a cationic surfactant, and / or an amphoteric surfactant. The stripping agent may be acidic, neutral or alkaline.

[0050] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples in any way.

[0051] [Preparation of Substrate] A thiourethane-based synthetic resin substrate with a refractive index of 1.60 was prepared as the spectacle lens substrate. A polyurethane primer layer (thickness: 1 μm) with a refractive index of 1.67 and a silicone-based hard coat layer (thickness: 3 μm) with a refractive index of 1.67 were formed in this order on the surface of the spectacle lens substrate. The primer layer and hard coat layer were formed on both sides of the spectacle lens substrate. The hard coat layer was composed of an organosilicon compound having an epoxy group (including its hydrolysate and its hydrolyzed condensate) and TiO ２ The spectacle lens substrate on which the primer layer and hard coat layer were formed was placed in a rotating dome in the vacuum chamber of a vacuum deposition apparatus ("MC-1200DLX2" manufactured by Satislaw). The vacuum deposition apparatus was equipped with an ion source (Mark II+ manufactured by Veeco), and the ion source was equipped with a neutralizer capable of irradiating electrons in the same direction as the irradiation direction of the ion beam. After placing the spectacle lens substrate on which the primer layer and hard coat layer were formed, the vacuum was reduced to 3.5 x 10 －３ The chamber was evacuated to a vacuum until the pressure reached 100 Pa. After evacuation, the surface of the eyeglass lens substrate was cleaned by irradiating the substrate with an argon ion beam from the ion source. The cleaning conditions were an acceleration voltage of 90 V, an ion beam current density of 40 μA / cm ２ The cleaning was carried out for 60 seconds. After the cleaning, the first to sixth high-refractive index layers and the low-refractive index layers were formed so as to have the layer thicknesses shown in Table 1 below. The high-refractive index layers were formed using zirconium oxide (ZrO ２ ), and silicon oxide (SiO ２ After the sixth layer (low refractive index layer) was formed, a current density of 40 μA / cm was applied from an ion source to the low refractive index layer. ２The argon ion beam was irradiated. The acceleration voltage of the ion source was 72 V, and the ion beam irradiation time was 75 seconds. After the argon ion beam irradiation, the seventh layer (high refractive index layer) was formed, and after the seventh layer was formed, the eighth layer (SnO ２ Layers (layers) were formed to the thicknesses shown in Table 1. After forming Layer 8, Layer 9 (low refractive index layer) was formed. The formation method was the same as for Layers 1 to 6 described above. This resulted in an antireflection layer consisting of Layers 1 to 9. Next, Layer 10 (water- and oil-repellent layer) with a thickness of 20 nm was formed on the surface of Layer 9 using a water- and oil-repellent material X-12-5263HP (manufactured by Shin-Etsu Chemical Co., Ltd.), and Layer 11 (water- and oil-repellent layer) with a thickness of 20 nm was formed on the surface of Layer 10 using a water- and oil-repellent material DSX (manufactured by Daikin Industries, Ltd.). The formation method for each layer was the same as for Layers 1 to 9 described above. A multilayer film was formed on one side of the eyeglass lens substrate using the above procedure. After forming the multilayer film on one side of the eyeglass lens substrate, the eyeglass lens substrate was turned over and placed in a vacuum deposition apparatus, and a multilayer film was formed on the other side using the same procedure. This resulted in a laminated substrate having a water- and oil-repellent layer, an anti-reflection layer, a hard coat layer, a primer layer, a spectacle lens substrate, a primer layer, a hard coat layer, an anti-reflection layer, and a water- and oil-repellent layer in this order.

[0052] In Table 1, H1 to H4 are materials for forming high refractive index layers, and L1 to L4 are materials for forming low refractive index layers. In Table 1, the thickness of each layer is a physical thickness, which was measured using a quartz crystal film thickness meter.

[0053]

[0054] Examples 1 to 9 The laminates of Examples 1 to 9 were produced by the following procedure. A first temporary protective layer was formed on one side of the laminate base material formed by the method described above by the following method. A magnesium fluoride layer was formed on the water- and oil-repellent layer of the eyeglass lens 1 by thermal evaporation using a physical vapor deposition apparatus (BC-P: manufactured by Shincron, or 1200-DLX2: manufactured by Satisloh) while adjusting the thickness of the magnesium fluoride layer to the film thickness shown in the table below. When forming the magnesium fluoride layer, a thermal evaporation method using electron beam heating was used, and the magnesium fluoride layer was formed under reduced pressure (1 × 10 －３ ~1 x 10 －２ The experiment was carried out at 1000 kJ / min.

[0055] Next, a second temporary protective layer was formed on the first temporary protective layer by the following method. An aluminum layer with a purity of 99% by mass or more was formed on the first temporary protective layer of the eyeglass lens 1 by thermal evaporation using a physical vapor deposition apparatus (BC-P: manufactured by Synchron, or 1200-DLX2: manufactured by Satisloh) while adjusting the thickness to the film thickness shown in the table below. When forming the aluminum layer, a thermal evaporation method using electron beam heating was used, and the aluminum layer was formed under reduced pressure (1 × 10 －３ ~1 x 10 －２ The experiment was carried out at 1000 kJ / min.

[0056] Example 10 A first temporary protective layer was formed on one side of the laminated substrate formed by the method described above by the following method. A titanium oxide layer was formed on the water- and oil-repellent layer of the eyeglass lens 1 by thermal evaporation using a physical vapor deposition apparatus (BC-P: manufactured by Shincron, or 1200-DLX2: manufactured by Satisloh) while adjusting the thickness thereof so as to achieve the film thickness shown in the table below. When forming the titanium oxide layer, a thermal evaporation method using electron beam heating was used under reduced pressure (1 × 10 －３ ~1 x 10 －２ The experiment was carried out at 1000 kJ / min.

[0057] Next, a second temporary protective layer was formed on the first temporary protective layer in the same manner as in Examples 1 to 9 described above.

[0058] [Comparative Examples 1 to 3] For the laminate of Comparative Example 1, the laminate base material formed by the above-mentioned method was used as is for the evaluation described below. For the laminate of Comparative Example 2, the first temporary protective layer was formed according to the method of Examples 1 to 9, and then the second temporary protective layer was not formed, and the laminate of Comparative Example 3 was produced by forming the second temporary protective layer according to the method of Examples 1 to 9 without forming the first temporary protective layer described above.

[0059] Comparative Example 4 A first temporary protective layer was formed on one side of the laminated substrate formed by the method described above by the following method: A physical vapor deposition apparatus (BC-P: manufactured by Shincron, or 1200-DLX2: manufactured by Satisloh) was used to deposit a SiO 2 film on the water- and oil-repellent layer of the eyeglass lens 1 by thermal vapor deposition to the thickness shown in the table below. ２The thickness of the layer was adjusted during formation. ２ When forming the layer, a thermal evaporation method using electron beam heating was used under reduced pressure (1 × 10 －３ ~1 x 10 －２ The experiment was carried out at 1000 kJ / min.

[0060] Next, a second temporary protective layer was formed in accordance with the method of Examples 1 to 9 to prepare a laminate.

[0061] [Comparative Example 5] The laminate of Comparative Example 5 was prepared by forming a first temporary protective layer on one side of the laminated base material formed by the above-described method in accordance with the method of Examples 1 to 9, and then depositing the SiO 3 film of Example 4 on the first temporary protective layer. ２ The second temporary protective layer was formed in accordance with the method for forming the first temporary protective layer.

[0062] [Evaluation] <Ease of bedding> Step 1 (bedding) was performed by the following method, and the axial deviation and horizontal deviation after grinding were measured to evaluate the ease of bedding. The optical center of the laminate was identified using a lens meter (LM-1200, manufactured by Nidek Co., Ltd.), and a total of three points, including the optical center, were marked on any line passing through the optical center so that they were equidistant from each other on the second temporary protective layer of the laminate (if no second temporary protective layer was present, on the first temporary protective layer or the laminate substrate). Next, using a lens blocker (CE-1, manufactured by Nidek Co., Ltd.), the laminate was attached with double-sided tape (LEAP III, manufactured by 3M Co., Ltd.) centered on a point shifted by the amount of eccentricity from the optical center (a point on a line passing through the above three points and shifted 5 mm from the optical center), and a lens lock cap was further attached thereon. The lens lock cap with the laminate attached was fitted onto one of the lens processing shafts of the edging machine, and then the laminate was sandwiched and fixed between the lens lock cap and the other processing shaft, and the edging process was performed with the eccentricity set to zero on the edging machine side. The equipment and tools used for the edging process are listed below. The eyeglass lenses were also edged using the same procedure as for the laminate.

[0063] Lens grinding machine: LE-9000X (manufactured by Nidek), chuck pressure: 50 kg. Lens shape: Nikon Classico, product number 9018 (approximately octagonal shape, 48 mm wide, 30 mm high and 30 mm long). Lens lock cap: minimum size cap (manufactured by Nidek).

[0064] The positions of the three marked points on the laminate after grinding were evaluated using a profile projector V-16E (manufactured by Nikon Corporation), and the axial deviation (amount of rotational axis deviation) and horizontal deviation (amount of parallel axis deviation) from the design values ​​were measured and evaluated according to the following evaluation criteria.

[0065] - Evaluation criteria for axial deviation - "A": Absolute value of axial deviation is 1.000° or less "B": Absolute value of axial deviation is more than 1.000°

[0066] - Evaluation criteria for horizontal deviation - "A": Absolute value of horizontal deviation is 0.500 mm or less "B": Absolute value of horizontal deviation is more than 0.500 mm

[0067] The lens lock cap could not be attached to the laminate of Comparative Example 1, and the above-mentioned edging process could not be carried out.

[0068] <Water and oil repellency after peeling of temporary protective layer> The first and second temporary protective layers of the laminate ground in the evaluation of the axial deviation and horizontal deviation were removed by tape peeling. Tape peeling was performed by attaching Nichiban 405 cellophane tape (width 18 mm, length 10 mm) to the second temporary protective layer and peeling the tape. In all examples and comparative examples except Comparative Example 4 and Comparative Example 5, the first and second temporary protective layers were simultaneously removed by tape peeling. After removing the first and second temporary protective layers, a line was drawn on the removed surface using magic marker No. 500 black (for fine writing) (Teranishi Chemical Industry Co., Ltd.), and the water and oil repellency after removal of the temporary protective layer was evaluated according to the following criteria.

[0069] "A": The ink is a dotted line and the length of the dots is 2 mm or less. "B": The ink is a solid line or a dotted line and the length of the dots is more than 2 mm.

[0070] In the laminates of Comparative Examples 4 and 5, the temporary protective layer could not be peeled off by tape peeling.

[0071] [Results] The table below shows the materials and film thicknesses of the first and second temporary protective layers, as well as the evaluation results. In the table, the thickness of each layer was measured using a quartz crystal film thickness meter. In the table, the values ​​for axial deviation and horizontal deviation indicate the absolute value of the amount of deviation. A "-" in the evaluation column means that the evaluation could not be performed.

[0072]

[0073]

[0074]

[0075] The evaluation results confirmed that the laminate of the present disclosure is easy to bead and has excellent water and oil repellency after peeling off the first temporary protective layer and the second temporary protective layer. A comparison of Examples 1 to 9 confirmed that beading is easier when the thickness of the first temporary protective layer is more than 10 nm and less than 100 nm.

[0076] 2: Spectacle lens substrate 4: Water- and oil-repellent layer 6: First temporary protective layer 8: Second temporary protective layer 20: Adhesive tape 30: Lens lock cap 40: Second temporary protective layer 51, 52: Lens processing shaft 60: Fixing member 100, 200: Laminate 300: Grinding device

Claims

1. A laminate having a spectacle lens substrate, a water- and oil-repellent layer, a first temporary protective layer, and a second temporary protective layer in this order, wherein the first temporary protective layer contains a metal fluoride or titanium oxide, and the second temporary protective layer is a metal layer.

2. The laminate according to claim 1, wherein the metal layer contains at least one selected from the group consisting of aluminum, copper, zinc, and nickel.

3. The laminate according to claim 1 or 2, wherein the first temporary protective layer contains the metal fluoride, the thickness of the second temporary protective layer is more than 10 nm, and the total thickness of the first temporary protective layer and the second temporary protective layer is 20 nm or more.

4. The laminate according to any one of claims 1 to 3, wherein the metal fluoride is magnesium fluoride.

5. The laminate according to claim 1 or 2, wherein the first temporary protective layer contains the titanium oxide, and the thickness of the first temporary protective layer is more than 20 nm and less than 80 nm.

6. The laminate according to any one of claims 1 to 4, wherein the thickness of the first temporary protective layer is more than 10 nm and less than 100 nm.

7. A method for manufacturing a spectacle lens using the laminate according to any one of claims 1 to 6, comprising: step 1 of fixing the laminate by pressing a fixing member against the second temporary protective layer and grinding the periphery of the laminate; and step 2 of removing the first temporary protective layer and the second temporary protective layer in the ground laminate.

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