Spectacle lens and method of fabricating the same

Abstract

To provide a spectacle lens with sufficiently superior paint mark resistance (paint mark test result), and a method of fabricating the same.SOLUTION: A spectacle lens provided herein comprises a base material, a water-repellent layer formed on the base material, and a protective layer formed on the water-repellent layer, the protective layer containing 50 mass% or more of polysilazane.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a spectacle lens and a manufacturing method thereof, and in particular to a spectacle lens having sufficiently excellent paint mark resistance (paint mark test results) and a manufacturing method thereof. [Background technology]

[0002] Various coated spectacle lenses are used, and their surfaces are usually smooth. Ophthalmic lenses have been developed in which a hydrophobic / oleophobic coating is further applied to such a smooth surface (see, for example, Patent Document 1). However, it may be necessary to form paint marks on this hydrophobic / oleophobic coating. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2008-513815 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it is difficult to form a paint mark on this hydrophobic and oleophobic coating, and even if a paint mark could be formed, when the ophthalmic lens on which the paint mark was formed was placed into a bag, the paint mark would come into contact with the bag and disappear or become misaligned. In other words, the ophthalmic lens shown in Patent Document 1 has problems in that it is difficult to form a paint mark, and the paint mark would unintentionally disappear or become misaligned.

[0005] Under these circumstances, an object of one aspect of the present disclosure is to provide a spectacle lens having sufficiently excellent paint mark resistance (paint mark test results), and a method for manufacturing the same. [Means for solving the problem]

[0006] The present inventors have found that the above problems can be solved by providing a protective layer containing a predetermined amount of polysilazane on a water-repellent layer.

[0007] The present disclosure relates to the following [1] to [6]. [1] A spectacle lens comprising a substrate, a water-repellent layer formed on the substrate, and a protective layer formed on the water-repellent layer, wherein the protective layer contains 50% by mass or more of polysilazane. [2] The eyeglass lens according to [1] above, wherein the polysilazane has a number average molecular weight of 100 to 10,000, the number average molecular weight being the number average molecular weight in terms of polymethyl methacrylate, measured by gel permeation chromatography. [3] The eyeglass lens according to [1] or [2] above, wherein the polysilazane has a weight-average molecular weight of 100 to 10,000, the weight-average molecular weight being a weight-average molecular weight calculated as polymethyl methacrylate, measured by gel permeation chromatography. [4] The spectacle lens according to any one of the above [1] to [3], wherein the polysilazane has a molecular weight distribution of 1.0 to 3.5, the molecular weight distribution being calculated from the number average molecular weight and weight average molecular weight in terms of polymethyl methacrylate, measured by gel permeation chromatography. [5] The spectacle lens according to any one of the above [1] to [4], wherein the polysilazane has at least one selected from the group consisting of a structural unit represented by formula (1-1), a structural unit represented by formula (1-2), and a structural unit represented by formula (1-3). [ka] [ka] [ka] (In the formula (1-1), R is -(CH2) x (CF2) y CF3 (wherein x is an integer of 1 to 5 and y is an integer of 1 to 10) or a fluorine-containing group represented by the following structural formula (X1): [ka] ···(X1) (In formula (X1), n ​​represents an integer of 1 to 70.) [6] A method for manufacturing a spectacle lens, comprising: a water-repellent layer forming step of forming a water-repellent layer on a substrate; and a protective layer forming step of forming a protective layer on the water-repellent layer using a protective layer composition containing 50% by mass or more of polysilazane. [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a spectacle lens having sufficiently excellent paint mark resistance (paint mark test results) and a method for manufacturing the same. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view of a spectacle lens according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an example of an embodiment of the present disclosure will be described. However, the embodiment described below is an example for embodying the technical idea of ​​the present disclosure, and the present disclosure is not limited to the following description. Any selected or combined embodiment of the matters described in this specification is also included in the present disclosure. In this specification, preferred definitions can be selected arbitrarily, and combinations of preferred definitions can be considered more preferred. In this specification, the expression "XX to YY" means "XX or more and YY or less." In this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." In this specification, the amount of each component contained in a composition means the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component are present in the composition. In this specification, "room temperature" refers to the ambient temperature without temperature control such as heating or cooling, and is generally around 20°C, but is not limited to this temperature as it may vary depending on the weather and season. In this specification, the term "solid content" refers to non-volatile content excluding volatile substances such as solvents, and refers to components that remain without volatilizing when the composition is dried, and includes those that are liquid, syrup-like, or waxy at room temperature. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0011] In this specification, the term "a water-repellent layer formed on a substrate" includes not only "a case where a water-repellent layer is formed directly on a substrate" but also "a case where a hard coat layer, an anti-reflection layer, or the like is formed between the substrate and the water-repellent layer." In this specification, the expression "protective layer formed on a water-repellent layer" includes not only "the case where a protective layer is formed directly on a water-repellent layer" but also "the case where another layer is formed between the water-repellent layer and the protective layer." The protective layer is a layer that is removed when the lens is used as a final eyeglass lens, and as an example, by retaining the protective layer after the lens is completed until it is processed to fit into an eyeglass frame, it can contribute to preventing scratches on the eyeglass lens, improving the ease of printing paint marks, and preventing slippage on the lens surface during processing. In this specification, the term "main component" means that other components may be contained within the scope of the present disclosure, and preferably means a component that accounts for 50 to 100% by mass of the total, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass. In this specification, "vapor deposition" includes, for example, vacuum vapor deposition, ion plating, sputtering, etc. In the vacuum vapor deposition, an ion beam assisted method in which an ion beam is irradiated simultaneously during vapor deposition may be used.

[0012] The number average molecular weight, weight average molecular weight, and z average molecular weight in this embodiment are each based on the molecular weight in terms of polymethyl methacrylate measured by gel permeation chromatography, and refer to values ​​measured under the following sample preparation conditions and measurement conditions. Here, the z-average molecular weight means the average molecular weight defined by the following formula (X). z average molecular weight=ΣniMi 3 / ΣniMi 2 (X) (In formula (X), Mi represents the molecular weight of component i in the compound, and ni represents the molar fraction of component i.) <Sample preparation conditions> A predetermined volume of the measurement solvent is added to a predetermined mass of the residue sample dehydrated under a nitrogen stream and gently stirred at room temperature. After visually confirming that the sample has dissolved, the mixture is filtered through a 0.45 μm filter to prepare a sample. The measurement samples (polysilazanes (1-(1H,1H,2H,2H-perfluorooctyl)silazane represented by structural formula (X) described below, perhydrosilazane represented by structural formula (Y) described below, polysilazane X represented by structural formula (X) described below), compound X described below, and water-repellent compound 1 (perfluoropolyether group-containing silane compound) described below) are measured by gel permeation chromatography under the following measurement condition 1. Meanwhile, siloxane Z represented by structural formula (Z) described below is measured by gel permeation chromatography under the following conditions. <Measurement condition 1> Apparatus: Gel permeation chromatograph (GPC) Detector: Differential refractive index detector RI (RI-504 manufactured by Showa Denko K.K. (now Resonac Corporation), sensitivity 32) Column: TSKgel GMHHR-H(S) x 2 (φ4.6 mm x 15 cm, Tosoh Corporation) Solvent: hexafluoroisopropanol containing 5 mM sodium trifluoroacetate Flow rate: 0.3mL / min Column temperature: 40oC Injection volume: 0.020mL Standard sample: Monodisperse polymethyl methacrylate (PMMA) manufactured by Showa Denko K.K. (currently Resonac Corporation) <Measurement condition 2> Apparatus: Gel permeation chromatograph (GPC) Detector: Differential refractive index detector RI (RI-104 manufactured by Showa Denko K.K. (now Resonac Corporation), sensitivity -16) Column: 1 TSKgel Super HZM-N, 1 HZ2000 (6.0 mm x 15 cm, Tosoh Corporation) Solvent: Toluene Flow rate: 0.45mL / min Column temperature: 40oC Injection volume: 0.020mL Standard sample: Monodisperse polystyrene manufactured by Tosoh Corporation The molecular weight measured by gel permeation chromatography in this embodiment in terms of polymethyl methacrylate does not necessarily have to coincide with the molecular weight obtained by other calculation methods, which are not particularly limited and include, for example, matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS) and nuclear magnetic resonance (NMR) methods used in the examples described below.

[0013] In this specification, the term "paint markability" refers to the degree to which ink of each main component is printed on the lens surface when marking is required on the lens surface during the spectacle lens manufacturing process.

[0014] [Eyeglass lenses] The eyeglass lens of the present embodiment comprises a substrate, a water-repellent layer formed on the substrate, and a protective layer formed on the water-repellent layer, and may further comprise a hard coat layer, an underlayer, a functional layer, and other layers as necessary.

[0015] The spectacle lens of this embodiment has sufficiently excellent paint mark resistance (paint mark test results). Although the reason for this effect is not clear, it is presumed that the paint mark resistance (paint mark test results) can be sufficiently improved by the protective layer containing 50 mass % or more of polysilazane. However, the mechanism is not limited to this.

[0016] 1 is a schematic cross-sectional view of a spectacle lens 1 of this embodiment. The spectacle lens 1 of this embodiment includes a lens substrate 11, a hard coat layer 21f provided on the object-side surface 11a of the lens substrate 11, a functional layer 31f provided on the object-side surface 21fa of the hard coat layer 21f, a water-repellent layer 41f provided on the object-side surface 31fa of the functional layer 31f, and a protective layer 51f provided on the object-side surface 41fa of the water-repellent layer 41f.

[0017] When the lens substrate 11 is a finished lens, the eyeglass lens 1 of this embodiment further comprises a hard coat layer 21b provided on the eyeball-side surface 11b of the lens substrate 11, a functional layer 31b provided on the eyeball-side surface 21bb of this hard coat layer 21b, a water-repellent layer 41b provided on the eyeball-side surface 31bb of this functional layer 31b, and a protective layer 51b provided on the eyeball-side surface 41bb of this water-repellent layer 41b.

[0018] Although not shown, an underlayer may be provided between the lens substrate 11 and the hard coat layer 21f, or between the lens substrate 11 and the hard coat layer 21b.

[0019] 1, the eyeglass lens 1 of this embodiment is provided with functional layers 31b, 31f on the eyeball-side surface 11b and the object-side surface 11a of the lens substrate 11, respectively, to impart characteristics such as reflective spectral characteristics to the eyeglass lens 1. The functional layers 31b, 31f are provided on the eyeball-side surface 11b and the object-side surface 11a of the lens substrate 11 directly or indirectly via another layer. Each layer in the eyeglass lens of this embodiment will be described below.

[0020] <Lens substrate> The lens substrate may be either a finished lens or a semi-finished lens. The surface shape of the lens substrate is not particularly limited and may be flat, convex, concave, etc. In typical lens substrates and spectacle lenses, the object-side surface is convex and the eyeball-side surface is concave. However, the present disclosure is not limited to this. The lens substrate may be used for any of a single-vision lens, a multifocal lens, a progressive-power lens, etc. For example, in a progressive-power lens, the near-vision region (near vision region) and the progressive-power region (intermediate region) are usually included in the lower region, and the distance-vision region (distance vision region) is included in the upper region. As the lens substrate, a colorless one is usually used, but a colored one can also be used as long as the transparency is not impaired.

[0021] The lens substrate is preferably a meniscus type. By incorporating a specific compound into the meniscus type lens substrate, astigmatism can be suppressed.

[0022] There are no particular restrictions on the optical center thickness of the lens substrate, but it is preferably 0.5 to 5.0 mm, more preferably 0.5 to 3.0 mm, and particularly preferably 0.5 to 2.0 mm. There are no particular restrictions on the diameter of the lens substrate, and it is usually about 50 to 100 mm.

[0023] The refractive index ne of the lens substrate is not particularly limited, but is preferably 1.49 or more. The upper limit of the refractive index ne of the lens substrate is not particularly limited, and may be, for example, 1.80 or less.

[0024] The resin for the lens substrate is not particularly limited, and examples thereof include urethane resins (e.g., polythiourethane resins, polyurethane resins), polysulfide resins, episulfide resins, polycarbonate resins, acrylic resins, styrene resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, polyether resins, and transparent resins obtained by curing a polymerizable composition containing a (thio)epoxy compound having one or more disulfide bonds in the molecule. These may be used alone or in combination of two or more. Among these, polythiourethane resins, polysulfide resins, and polyurethane resins are preferred, and polythiourethane resins and polysulfide resins are more preferred. Inorganic glass can also be used. The lens substrate may be either undyed (colorless lens) or dyed (dyed lens).

[0025] (Lens substrate manufacturing method) The lens substrate is not particularly limited, but can be obtained, for example, by a manufacturing method including a step of polymerizing and curing a polymerizable composition capable of preparing the above-mentioned resin, and a step of annealing the cured resin.

[0026] The polymerization is preferably a cast polymerization method, and the lens substrate can be obtained, for example, by injecting a polymerizable composition into a mold formed by combining a glass or metal mold with a tape or a gasket, and then polymerizing the composition.

[0027] The polymerization conditions can be appropriately set depending on the polymerizable composition. The polymerization initiation temperature is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 40°C. It is preferable to raise the temperature from the polymerization initiation temperature and then heat to harden and form the composition. The maximum temperature is, for example, usually 110 to 130°C.

[0028] After the polymerization is complete, the lens substrate may be released from the mold and then subjected to an annealing treatment. There are no particular restrictions on the temperature for the annealing treatment, but it is preferably 100 to 150°C.

[0029] <Water-repellent layer> The water-repellent layer is not particularly limited, and may be, for example, a condensate of a water-repellent layer composition containing a compound having a silyl group at least at one end of the molecular chain. The water-repellent layer may be formed directly on the substrate, on a hard coat layer, or on a functional layer, but is preferably formed on an antireflection layer.

[0030] <<Water-repellent layer composition>> The water-repellent layer composition is not particularly limited, and may contain a water-repellent compound having a silyl group at at least one end of the molecular chain, and may contain other components such as a solvent, if necessary. The water-repellent layer composition contains a water-repellent compound having a silyl group at least at one end of the molecular chain, thereby improving the water repellency of the water-repellent layer to be formed.

[0031] (water-repellent compound) The water-repellent compound may consist solely of a water-repellent compound having a silyl group at one end of the molecular chain, or may consist solely of a water-repellent compound having silyl groups at both ends of the molecular chain, or may contain both a water-repellent compound having a silyl group at one end of the molecular chain and a water-repellent compound having silyl groups at both ends of the molecular chain. The water-repellent compound has a silyl group at at least one end, which allows a condensation reaction to occur during vapor deposition to form a water-repellent layer. Examples of the silyl group include trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, tripropyloxysilyl, and trihexyloxysilyl. These may be used alone or in combination of two or more.

[0032] The water-repellent compound may have a siloxane chain structure. The siloxane chain is not particularly limited, and examples thereof include a polydimethylsiloxane group, a polydiethylsiloxane group, and a polydipropylsiloxane group. These may be used alone or in combination of two or more. When the water-repellent compound has a siloxane chain structure, adhesion to the functional layer described below tends to be improved.

[0033] The water-repellent compound may have a fluorinated alkyl group. By having the fluorinated alkyl group, the load-bearing capacity of the water-repellent layer can be improved. The fluorinated alkyl group is, for example, a perfluoroalkyl group. The number of carbon atoms in the fluorinated alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 3. It is preferable that the water-repellent compound has a fluorinated alkyl group at the molecular terminal.

[0034] The number average molecular weight of the water-repellent compound is not particularly limited, but from the viewpoint of further improving the load-bearing capacity of the water-repellent layer, it is preferably 100 to 10,000, more preferably 400 to 2,000, even more preferably 500 to 1,500, and particularly preferably 600 to 1,200.

[0035] The weight average molecular weight of the water-repellent compound is not particularly limited, but from the viewpoint of further improving the load-bearing capacity of the water-repellent layer, it is preferably 100 to 10,000, more preferably 400 to 2,000, even more preferably 500 to 1,500, and particularly preferably 600 to 1,200.

[0036] The z-average molecular weight (Mz) of the water-repellent compound is not particularly limited, but from the viewpoint of further improving the load-bearing capacity of the water-repellent layer, it is preferably 100 to 10,000, more preferably 400 to 2,000, even more preferably 500 to 1,500, and particularly preferably 600 to 1,200.

[0037] Furthermore, the molecular weight distribution (Mw / Mn) of the water-repellent compound is not particularly limited from the viewpoint of further improving the load-bearing capacity of the water-repellent layer, but is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0.

[0038] Furthermore, the ratio (Mz / Mw) of the z-average molecular weight (Mz) to the weight-average molecular weight (Mw) of the water-repellent compound is not particularly limited, but from the viewpoint of further improving the load-bearing capacity of the water-repellent layer, it is preferably 1.0 to 8.0, more preferably 1.0 to 5.0, and particularly preferably 1.0 to 3.5.

[0039] From the viewpoint of improving the load-bearing capacity of the water-repellent layer, the water-repellent compound preferably has a poly(fluorinated alkyleneoxy) fluorinated alkyl ether group, more preferably a group represented by the following formula (1a): The poly(fluorinated alkyleneoxy) fluorinated alkyl ether group may be linear or branched. However, when determining whether it is linear or branched, the terminal silyl group is not taken into consideration. -(CF2O) a (C2F4O) b (C3F6O) c (C4F8O) d - (1a) (In formula (1a), a is 0 to 100, b is 0 to 100, c is 0 to 100, d is 0 to 30, and a+b+c+d is 10 to 200.)

[0040] In the above formula (1a), the arrangement of repeating units, the numbers of which are represented by a, b, c, and d, is random or block. There are no particular restrictions on a as long as it is 0 to 100, but it is preferably 1 to 80, more preferably 3 to 70, and particularly preferably 5 to 60. There are no particular restrictions on b as long as it is 0 to 100, but it is preferably 1 to 80, more preferably 3 to 70, and particularly preferably 5 to 60. There are no particular limitations on c as long as it is 0 to 100, but it is preferably 0 to 50, more preferably 0 to 30, and particularly preferably 0 to 20. There are no particular restrictions on d as long as it is 0-30, but it is preferably 0-25, more preferably 0-20, and particularly preferably 0-10. There are no particular limitations on a+b+c+d as long as it is 10-200, but it is preferably 30-170, more preferably 50-150, and particularly preferably 70-130.

[0041] A method for introducing the group represented by formula (1a) into the water-repellent layer includes forming the water-repellent layer from a water-repellent layer composition containing a water-repellent compound.

[0042] The content of the water-repellent compound is not particularly limited, but from the viewpoint of improving water repellency, it is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass relative to the solid content of the water-repellent layer composition.

[0043] <Solvent> The water-repellent layer composition may or may not contain a solvent. The solvent is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents having 5 to 20 carbon atoms, such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, isooctane, and isododecane; aromatic hydrocarbon solvents having 6 to 10 carbon atoms, such as benzene, toluene, and xylene; ether solvents, such as diethyl ether, tetrahydrofuran, dioxane, and dipropylene glycol dimethyl ether; ester solvents, such as ethyl acetate and butyl acetate; acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone. aprotic polar solvents such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tris(trimethylsiloxy)methylsilane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and other silicone-based solvents; fluorine-based solvents such as hexafluorobenzene, trifluoromethylbenzene, hexafluorometaxylene, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecafluorohexyl methyl ether, and other fluorine-based solvents. These may be used alone or in combination of two or more. Among these, fluorine-based solvents are preferred from the viewpoint of solubility.

[0044] The thickness t of the water-repellent layer is not particularly limited, but is preferably 0.1 to 100 nm, more preferably 0.1 to 50 nm, and particularly preferably 0.1 to 20 nm.

[0045] <Protective layer> The protective layer is not particularly limited as long as it is formed on a substrate and contains 50 mass % or more of polysilazane. For example, it can be obtained by vapor deposition or coating of a protective layer composition. However, it is preferable to vapor-deposit the protective layer composition, as this allows the protective layer to be formed regardless of the composition of the water-repellent layer.

[0046] (Protective layer composition) The protective layer composition is not particularly limited as long as it contains polysilazane, and may or may not contain other components such as a solvent. When the protective layer composition contains polysilazane having multiple silazane structures (-Si-NH-) instead of siloxane structures (-Si-O-), the paint mark resistance (paint mark test results) of the protective layer can be improved.

[0047] The content of polysilazane relative to 100% by mass of the solid content of the protective layer composition is not particularly limited as long as it is 50% by mass or more, but from the viewpoint of paint mark resistance, it is preferably 50 to 100% by mass, more preferably 50 to 95% by mass, and particularly preferably 55 to 90% by mass.

[0048] <Polysilazane> The polysilazane is not particularly limited as long as it has a plurality of silazane structures (-Si-NH-), but from the viewpoint of paint marking properties, it preferably has at least one selected from the group consisting of a structural unit represented by formula (1-1), a structural unit represented by formula (1-2), and a structural unit represented by formula (1-3), more preferably has at least one selected from the group consisting of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2), and particularly preferably has a structural unit represented by formula (1-1). [ka] [ka] [ka] In formula (1-1), R is -(CH2) x (CF2) y It represents a fluorine-containing group represented by CF3 or the following structural formula (X1), where x represents an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 2. y represents an integer of 1 to 10, preferably an integer of 3 to 7, more preferably an integer of 4 to 6, and particularly preferably 5. [ka] ···(X1) In formula (X1), n ​​represents an integer of 1 to 70, preferably an integer of 1 to 55, and more preferably an integer of 3 to 40.

[0049] -(CH2) in polysilazane x (CF2) y The number of carbon atoms in the fluorine-containing group represented by CF3 is not particularly limited, but is preferably 20 or less, more preferably 3 to 15, and particularly preferably 6 to 10, from the viewpoint of paint marking properties.

[0050] The number average molecular weight of the polysilazane is not particularly limited, but is preferably 100 to 10,000, more preferably 200 to 5,000, and particularly preferably 250 to 2,500, from the viewpoint of paint mark properties.

[0051] The weight average molecular weight of the polysilazane is not particularly limited, but is preferably 100 to 10,000, more preferably 200 to 5,000, and particularly preferably 250 to 2,500, from the viewpoint of paint mark properties.

[0052] The z-average molecular weight (Mz) of the polysilazane is not particularly limited, but is preferably 100 to 10,000, more preferably 200 to 5,000, and particularly preferably 250 to 2,500, from the viewpoint of paint mark resistance.

[0053] The molecular weight distribution of polysilazane is not particularly limited, but from the viewpoint of paint mark resistance, it is preferably 1.0 to 3.5, more preferably 1.5 to 3.0, and particularly preferably 2.0 to 3.0.

[0054] The ratio (Mz / Mw) of the z-average molecular weight (Mz) to the weight-average molecular weight (Mw) of the polysilazane is not particularly limited, but from the viewpoint of paint mark resistance, it is preferably 1.0 to 8.0, more preferably 1.0 to 5.0, and particularly preferably 1.0 to 3.5.

[0055] <Solvent> The protective layer composition may or may not contain a solvent. The solvent is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as hexane and heptane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran (THF), and dioxane; halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride; alcohol solvents such as methanol, ethanol, and propanol; and water. These may be used alone or in combination of two or more. Among these, alcohol solvents are preferred from the viewpoint of solubility.

[0056] <Other ingredients> The other components are not particularly limited, and examples thereof include compound X (other perfluoropolyether group-containing silane compounds); etc. These may be used alone or in combination of two or more. Among these, compound X (other perfluoropolyether group-containing silane compounds) is preferred.

[0057] The content of other components relative to 100% by mass of the solid content of the protective layer composition is not particularly limited as long as it is less than 50% by mass, but from the viewpoint of paint mark resistance, it is preferably 0 to 48% by mass, more preferably 5 to 46% by mass, and particularly preferably 10 to 45% by mass.

[0058] The number average molecular weight of compound X (another perfluoropolyether group-containing silane compound) is not particularly limited, but from the viewpoint of paint marking properties, it is preferably 100 to 10,000, more preferably 300 to 5,000, and particularly preferably 500 to 2,000.

[0059] The weight average molecular weight of compound X (another perfluoropolyether group-containing silane compound) is not particularly limited, but from the viewpoint of paint mark properties, it is preferably 100 to 10,000, more preferably 300 to 5,000, and particularly preferably 500 to 2,000.

[0060] The z-average molecular weight (Mz) of compound X (another perfluoropolyether group-containing silane compound) is not particularly limited, but from the viewpoint of paint mark resistance, it is preferably 100 to 10,000, more preferably 300 to 5,000, and particularly preferably 500 to 2,000.

[0061] The molecular weight distribution of compound X (another perfluoropolyether group-containing silane compound) is not particularly limited, but from the viewpoint of paint marking properties, it is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0.

[0062] The ratio (Mz / Mw) of the z-average molecular weight (Mz) to the weight-average molecular weight (Mw) of the compound X (another perfluoropolyether group-containing silane compound) is not particularly limited, but from the viewpoint of paint marking properties, it is preferably 1.0 to 8.0, more preferably 1.0 to 5.0, and particularly preferably 1.0 to 3.5.

[0063] The thickness t of the protective layer is not particularly limited, but is preferably 0.1 to 100 nm, more preferably 0.1 to 50 nm, and particularly preferably 0.1 to 20 nm.

[0064] <Hard coat layer> By providing a hard coat layer, it is possible to impart scratch resistance (abrasion resistance) to the eyeglass lens and also to increase the durability (strength) of the eyeglass lens. For details about the hard coat layer, see, for example, paragraphs 0025 to 0028 and 0030 of JP2012-128135A. The hard coat layer is, for example, a cured film made of a curable composition containing an inorganic oxide and a silicon compound. The curable composition preferably further contains a polyfunctional epoxy compound.

[0065] The inorganic oxide is not particularly limited, and examples thereof include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tungsten oxide, zinc oxide, tin oxide, beryllium oxide, and antimony oxide. These may be used alone or in combination of two or more. Among these, silicon oxide is preferred. Colloidal silica may also be used as the inorganic oxide.

[0066] The content of the inorganic oxide is not particularly limited, but is preferably 10 to 80 mass %, more preferably 20 to 70 mass %, and particularly preferably 25 to 50 mass %, of the solid content of the curable composition.

[0067] The silicon compound is, for example, a silicon compound having a hydrolyzable group such as an alkoxy group.The silicon compound is preferably a silane coupling agent having an organic group bonded to a silicon atom and a hydrolyzable group.The organic group bonded to a silicon atom is preferably an organic group having a functional group such as an epoxy group such as a glycidoxy group, a vinyl group, a methacryloxy group, an acryloxy group, a mercapto group, an amino group, or a phenyl group, and more preferably an organic group having an epoxy group.In addition, the silicon compound may have an alkyl group bonded to silicon.

[0068] The commercially available silane coupling agent is not particularly limited, and examples thereof include the trade names KBM-303, KBM-402, KBM-403, KBE402, KBE403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd. These may be used alone or in combination of two or more.

[0069] The content of the silicon compound is not particularly limited, but is preferably 20 to 90 mass %, more preferably 30 to 80 mass %, and particularly preferably 50 to 75 mass %, of the solid content of the curable composition.

[0070] The polyfunctional epoxy compound is a polyfunctional epoxy compound containing two or more epoxy groups in one molecule, preferably a polyfunctional epoxy compound containing two or three epoxy groups in one molecule. Commercially available polyfunctional epoxy compounds are not particularly limited, and examples include EX-201, EX-211, EX-212, EX-252, EX-313, EX-314, EX-321, EX-411, EX-421, EX-512, EX-521, EX-611, EX-612, EX-614, and EX-614B from the "Denacol" series manufactured by Nagase ChemteX Corporation. These compounds may be used alone or in combination of two or more.

[0071] The content of the polyfunctional epoxy compound is not particularly limited, but is preferably 0 to 50 mass %, more preferably 10 to 40 mass %, and particularly preferably 15 to 30 mass %, of the solid content of the curable composition.

[0072] The above-mentioned curable composition can be prepared by mixing optional components such as an organic solvent, a leveling agent, and a curing catalyst, in addition to the components described above, as needed. The hard coat layer can be formed by applying a curable composition to a substrate and then subjecting it to a curing treatment (thermal curing, photocuring, etc.). There are no particular limitations on the means for applying the curable composition, and commonly used methods such as dipping, spin coating, and spraying can be used. For curable compositions containing a polyfunctional epoxy compound, the curing treatment is usually carried out by heating. The heat curing treatment can be carried out, for example, by placing the lens coated with the curable composition in an environment with an ambient temperature of 50 to 150°C for about 30 minutes to 3 hours.

[0073] <Underlayer> A primer layer may be formed between the lens substrate and the hard coat layer to improve adhesion. For details about the primer layer, see, for example, paragraphs 0029 to 0030 of JP-A No. 2012-128135. The underlayer can be formed from, for example, an aqueous resin composition containing at least one type of resin particles selected from the group consisting of polyurethane resin, acrylic resin, and epoxy resin.

[0074] As the aqueous resin composition, commercially available aqueous polyurethanes can be used as they are, or diluted with an aqueous solvent as needed. Commercially available aqueous polyurethanes are not particularly limited, and examples include the "Evaphanol" series (trade name) manufactured by Nicca Chemical Co., Ltd., the "Superflex" series (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., the "Adeka Bontiter" series (trade name) manufactured by ADEKA Corporation, the "Olestar" series (trade name) manufactured by Mitsui Chemicals, Inc., the "Bondic" series and the "Hydran" series (trade name) manufactured by Dainippon Ink and Chemicals, Inc., the "Impranil" series (trade name) manufactured by Bayer, the "Sofranate" series (trade name) manufactured by Nippon Soflan Co., Ltd., the "Poise" series (trade name) manufactured by Kao Corporation, the "Sunprene" series (trade name) manufactured by Sanyo Chemical Industries, Ltd., the "Izelax" series (trade name) manufactured by Hodogaya Chemical Co., Ltd., and the "Neoletz" series (trade name) manufactured by Zeneka Corporation. These polyurethanes may be used alone or in combination of two or more.

[0075] The underlayer can be formed, for example, by applying the above-mentioned aqueous resin composition to the surface of the substrate and drying it.

[0076] <Functional layer> The functional layer for imparting the above-mentioned reflection spectral characteristics may be provided directly on the surface of the lens substrate, or may be provided indirectly via another layer. Examples of the functional layer include an antireflection layer, an ultraviolet absorbing layer, an infrared absorbing layer, a photochromic layer, an antistatic layer, and an antifogging layer. These may be used alone or in combination of two or more. Known techniques related to spectacle lenses can be applied to these functional layers. Among these, it is preferable to have an antireflection layer.

[0077] Furthermore, it is possible to form an additional layer on the functional layer. Examples of such layers include an antifouling layer, an antifogging layer, a polarizing layer, a light control layer, etc. Known techniques can be applied to any of these functional layers without any restrictions.

[0078] (Anti-reflection layer) There are no particular limitations on the antireflection layer, as long as it can impart reflective spectral characteristics to the spectacle lens surface having the antireflection layer. The antireflection layer has low refractive index layers and high refractive index layers alternately arranged (formed by sequential lamination) by, for example, a vacuum deposition method. The number of layers in the antireflection layer is not particularly limited, but is preferably 4 to 11 layers, more preferably 5 to 8 layers. More specifically, the antireflection layer can be formed by determining the film thickness of each layer through optical simulation using a known method based on the refractive index of the film materials for forming the high-refractive index layer and the wavelength of light to be reflected or the wavelength of light to be reduced in reflection, and sequentially stacking the high-refractive index layer and the low-refractive index layer under film formation conditions determined to achieve the determined film thickness. The film formation material may be an inorganic material, an organic material, or an organic-inorganic composite material, with inorganic materials being preferred from the standpoints of film formation and ease of availability. By adjusting the type of film formation material, film thickness, stacking order, etc., the reflection spectral characteristics for each of blue light, ultraviolet light, green light, and red light can be controlled.

[0079] The refractive index of the low refractive index layer is not particularly limited, but is preferably 1.35 to 1.80, more preferably 1.45 to 1.50 at a wavelength of 500 to 550 nm. The low refractive index layer may be made of one or a mixture of two or more inorganic oxides or fluorides selected from the group consisting of silicon oxide (also known as silica; for example, SiO2), magnesium fluoride (for example, MgF2), and barium fluoride (for example, BaF2), and is preferably made of silicon oxide. In the above examples, for convenience, oxides and fluorides are shown in terms of stoichiometric composition, but those in which oxygen or fluorine is deficient or in excess of the stoichiometric composition can also be used as high refractive index or low refractive index materials.

[0080] The refractive index of the high refractive index layer is not particularly limited, but is preferably 1.90 to 2.60, and more preferably 2.00 to 2.40, at a wavelength of 500 to 550 nm. The high refractive index layer is made of, for example, an inorganic oxide. The inorganic oxide used in the high refractive index layer is preferably at least one selected from the group consisting of zirconium oxide (also called zirconia; for example, ZrO2), tantalum oxide (Ta2O5), yttrium oxide (for example, YO3), titanium oxide (for example, TiO2), niobium oxide (for example, Nb2O5), hafnium oxide (for example, HfO2), and aluminum oxide (Al2O3), and more preferably at least one selected from the group consisting of zirconium oxide and tantalum oxide.

[0081] The thickness of each layer included in the antireflection layer can be determined by optical simulation as described above. The layer structure of the antireflection layer can be, for example, as follows, from the lens substrate side to the outermost surface side of the lens: A structure in which the layers are stacked in the following order: first layer (low refractive index layer), second layer (high refractive index layer), third layer (low refractive index layer), fourth layer (high refractive index layer), fifth layer (low refractive index layer), sixth layer (high refractive index layer), and seventh layer (low refractive index layer); Examples of such a structure include a first layer (high refractive index layer), a second layer (low refractive index layer), a third layer (high refractive index layer), a fourth layer (low refractive index layer), a fifth layer (high refractive index layer), and a sixth layer (low refractive index layer) stacked in this order. Examples of preferred combinations of low refractive index layers and high refractive index layers include a combination of a coating primarily made of silicon oxide and a coating primarily made of zirconium oxide, and a combination of a coating primarily made of silicon oxide and a coating primarily made of niobium oxide.Preferred examples of antireflection layers include an antireflection layer that includes at least one laminate structure in which these two coating layers are adjacent to each other.

[0082] Preferably, each of the above layers is a coating containing the aforementioned high refractive index material or low refractive index material as a main component. Such a coating can be formed by depositing a film using a film-forming material (e.g., a vapor deposition source) containing the above material as a main component. The main components of the film-forming material are the same as those described above. The coating and film-forming material may contain trace amounts of impurities that are inevitably mixed in, and may also contain other components, such as other inorganic substances or known additive components that play a role in assisting film formation, to the extent that the function performed by the main component is not impaired. The film can be formed by a known film-forming method, and from the viewpoint of ease of film formation, it is preferably formed by vapor deposition.

[0083] In addition to the high-refractive-index layer and the low-refractive-index layer described above, the antireflection layer may also include, at any position on the antireflection layer, a coating containing a conductive oxide as its main component, preferably one or more conductive oxide layers formed by vapor deposition using a vapor deposition source containing a conductive oxide as its main component. The inclusion of the conductive oxide layer can prevent the eyeglass lens from becoming electrically charged and attracting dust and dirt. The conductive oxide is not particularly limited, but from the viewpoint of the transparency of the spectacle lens, preferred examples include indium oxide, tin oxide, zinc oxide, titanium oxide, composite oxides thereof, etc. These may be used alone or in combination of two or more. Among these, tin oxide and indium tin oxide (ITO) are more preferable from the viewpoints of transparency and conductivity.

[0084] [Method of manufacturing eyeglass lenses] The method for manufacturing a spectacle lens according to this embodiment includes a water-repellent layer forming step of forming a water-repellent layer on a substrate, and a protective layer forming step of forming a protective layer on the water-repellent layer using a protective layer composition, and may further include other steps as necessary.

[0085] <Water-repellent layer formation process> The water-repellent layer can be obtained by, for example, vapor deposition or coating of a water-repellent layer composition, but is preferably obtained by vapor deposition.

[0086] The deposition is carried out, for example, by vacuum deposition. The heating temperature during vacuum deposition is not particularly limited, but is preferably 400 to 1000°C, more preferably 550 to 1000°C, still more preferably 600 to 1000°C, and particularly preferably 650 to 1000°C. The heating temperature for vapor deposition refers to the temperature at which pellets or the like impregnated with the water-repellent layer composition are heated during vapor deposition. -2 It is preferable to carry out the deposition in a deposition space controlled to a vacuum of 0.1 Pa or less.

[0087] Heating during vapor deposition can be performed using, for example, a halogen heater, resistance heating, or an electron gun, but among these, using an electron gun for heating and vapor deposition allows for the formation of a highly accurate thin film. The power of the electron gun varies depending on the material used, the vapor deposition device, the degree of vacuum, and the irradiation area, but the preferred conditions are an acceleration voltage of about 6 kV and an applied current of about 5 to 40 mA.

[0088] The deposition time is not particularly limited, but is preferably within 1000 seconds, more preferably within 800 seconds, and particularly preferably within 600 seconds. By depositing within such a time, even if a water-repellent material containing multiple components with slightly different deposition start temperatures is used, the components can be deposited almost simultaneously, and a uniform film can be obtained.

[0089] The deposition is preferably carried out using a porous material impregnated with the water-repellent layer composition. As the porous material, it is preferable to use a sintered filter made by sintering a fused silica porous body or a metal powder with high thermal conductivity such as copper or stainless steel. From the viewpoint of obtaining an appropriate deposition rate, the mesh size of the sintered filter is suitably set to 40 to 200 μm, preferably 80 to 120 μm. Alternatively, a pellet in which steel wool is filled in a copper container can also be suitably used. The water-repellent layer composition may be used as it is or in the form of a solution by impregnating the porous material.

[0090] To form a water-repellent layer on a spectacle lens by coating, a method can be employed in which a water-repellent layer composition is dissolved in an organic solvent and applied to the surface of the spectacle lens. The coating method is not particularly limited, and examples thereof include dipping, spin coating, spraying, flow coating, doctor blade coating, roll coating, gravure coating, curtain flow coating, etc. These may be used alone or in combination of two or more.

[0091] After the formation of the water-repellent layer, a heating step may be performed. In the heating step, a reaction between the water-repellent layer composition and the spectacle lens surface is promoted. By carrying out this heat treatment, it is possible to suppress a decrease in water repellency due to physical and chemical stresses in daily use, such as wiping the spectacle lens surface or the adhesion of detergent, and thereby improve durability.

[0092] The temperature for the heat treatment is not particularly limited, but is preferably 40 to 90°C, more preferably 50 to 80°C, and particularly preferably 55 to 70°C. The time for the heat treatment is not particularly limited, but is preferably 0.1 to 10 hours.

[0093] <Protective layer formation process> The protective layer can be obtained, for example, by vapor deposition or coating of a protective layer composition, but is preferably obtained by vapor deposition.

[0094] The deposition is carried out, for example, by vacuum deposition. The heating temperature during vacuum deposition is not particularly limited, but is preferably 400 to 1000°C, more preferably 550 to 1000°C, still more preferably 600 to 1000°C, and particularly preferably 650 to 1000°C. The heating temperature for vapor deposition refers to the temperature at which pellets or the like impregnated with the protective layer composition are heated during vapor deposition. -2 It is preferable to carry out the deposition in a deposition space controlled to a vacuum of 0.1 Pa or less.

[0095] Heating during vapor deposition can be performed using, for example, a halogen heater, resistance heating, or an electron gun, but among these, using an electron gun for heating and vapor deposition allows for the formation of a highly accurate thin film. The power of the electron gun varies depending on the material used, the vapor deposition device, the degree of vacuum, and the irradiation area, but the preferred conditions are an acceleration voltage of about 6 kV and an applied current of about 5 to 40 mA.

[0096] The deposition time is not particularly limited, but is preferably within 1000 seconds, more preferably within 800 seconds, and particularly preferably within 600 seconds. By depositing within such a time, even if multiple protective layer materials with slightly different deposition start temperatures are used, they can be deposited almost simultaneously, and a uniform film can be obtained.

[0097] The deposition is preferably carried out using a porous material impregnated with the protective layer composition. As the porous material, it is preferable to use a sintered filter made by sintering a fused silica porous body or a metal powder with high thermal conductivity such as copper or stainless steel. From the viewpoint of obtaining an appropriate deposition rate, the mesh size of the sintered filter is suitably set to 40 to 200 μm, preferably 80 to 120 μm. Alternatively, a pellet in which steel wool is filled in a copper container can also be suitably used. The protective layer composition may be used as it is or in the form of a solution by impregnating the porous material.

[0098] To form a protective layer on a spectacle lens by coating, a method can be employed in which a protective layer composition is dissolved in an organic solvent and then coated on the surface of the spectacle lens. The coating method is not particularly limited, and examples thereof include dipping, spin coating, spraying, flow coating, doctor blade coating, roll coating, gravure coating, curtain flow coating, etc. These may be used alone or in combination of two or more.

[0099] After forming the protective layer, a heating step may be performed. In the heating step, a reaction between the protective layer composition and the spectacle lens surface is promoted. By carrying out this heat treatment, it is possible to suppress a decrease in protective performance due to physical and chemical stresses in daily use, such as wiping the spectacle lens surface or the adhesion of detergent, thereby improving durability.

[0100] The temperature for the heat treatment is not particularly limited, but is preferably 40 to 90°C, more preferably 50 to 80°C, and particularly preferably 55 to 70°C. The time for the heat treatment is not particularly limited, but is preferably 0.5 to 10 hours.

[0101] As described above, the present disclosure provides a spectacle lens with sufficiently excellent paint mark resistance (paint mark test results) and a method for manufacturing the same. [Example]

[0102] The present embodiment will be described in more detail below using examples and comparative examples, but the present disclosure is not limited to the following examples.

[0103] [Gel permeation chromatography (Mn, Mw, Mz)] 5 mL of the measurement solvent described below (or 4 mL of the measurement solvent described below) was added to 3 mg of sample, and the mixture was gently stirred at room temperature. The sample was visually confirmed to have dissolved in the measurement solvent. The mixture was then filtered using a 0.45 μm filter to prepare a measurement sample. The measurement samples (polysilazanes (1-(1H,1H,2H,2H-perfluorooctyl)silazane represented by structural formula (X) described below, perhydrosilazane represented by structural formula (Y) described below, polysilazane X represented by structural formula (X) described below), compound X described below, and water-repellent compound 1 (perfluoropolyether group-containing silane compound) described below) were subjected to gel permeation chromatography under the following measurement condition 1. Siloxane Z represented by structural formula (Z) described below was also subjected to gel permeation chromatography under the following conditions. <Measurement condition 1> Apparatus: Gel permeation chromatograph (GPC) Detector: Differential refractive index detector RI (RI-504 manufactured by Showa Denko K.K. (now Resonac Corporation), sensitivity 32) Column: TSKgel GMHHR-H(S) 2 pieces (φ4.6 mm x 15 cm, Tosoh Corporation) Solvent: hexafluoroisopropanol containing 5 mM sodium trifluoroacetate Flow rate: 0.3mL / min Column temperature: 40oC Injection volume: 0.020mL Standard sample: Monodisperse polymethyl methacrylate (PMMA) manufactured by Showa Denko K.K. (currently Resonac Corporation) <Measurement condition 2> Apparatus: Gel permeation chromatograph (GPC) Detector: Differential refractive index detector RI (RI-104 manufactured by Showa Denko K.K. (now Resonac Corporation), sensitivity -16) Column: 1 TSKgel Super HZM-N, 1 HZ2000 (6.0 mm x 15 cm, Tosoh Corporation) Solvent: Toluene Flow rate: 0.45mL / min Column temperature: 40oC Injection volume: 0.020mL Standard sample: Monodisperse polystyrene manufactured by Tosoh Corporation

[0104] [Preparation of Water-Repellent Layer Composition] A 20% by mass solution of a composition containing 100% by mass of water-repellent compound 1 (a perfluoropolyether group-containing silane compound) was prepared and impregnated into a metal pellet containing steel wool in a copper container so that the solid content after solvent evaporation would be 15 mg. After impregnation with the 20% by mass solution, the pellet was heated in an oven set at 80°C for 20 minutes to evaporate the solvent and leave a solid content of 15 mg.

[0105] [Preparation of Protective Layer Composition 1] A 20% by weight solution of a composition containing 90% by weight of "1-(1H,1H,2H,2H-perfluorooctyl)silane" and 10% by weight of Compound X (another perfluoropolyether group-containing silane compound) was prepared and impregnated into a metal pellet in a copper container filled with steel wool so that the solid content after solvent evaporation would be 15 mg. After impregnation with the 20% by weight solution, the solvent was evaporated by heating in an oven set to 80°C for 20 minutes, resulting in a solid content of 15 mg.

[0106] [Preparation of Protective Layer Composition 2] A 20% by weight solution of a composition containing 90% by weight of "perhydrosilazane" and 10% by weight of Compound X (another perfluoropolyether group-containing silane compound) was prepared and impregnated into a metal pellet in a copper container filled with steel wool so that the solid content after solvent evaporation would be 15 mg. After impregnation with the 20% by weight solution, the pellet was heated in an oven set to 80°C for 20 minutes to evaporate the solvent and leave a solid content of 15 mg.

[0107] [Preparation of Protective Layer Composition 3] A 20% by weight solution of a composition containing 55% by weight of "perhydrosilazane" and 45% by weight of Compound X (another perfluoropolyether group-containing silane compound) was prepared and impregnated into a metal pellet in a copper container filled with steel wool so that the solid content after solvent evaporation would be 15 mg. After impregnation with the 20% by weight solution, the pellet was heated in an oven set to 80°C for 20 minutes to evaporate the solvent and leave a solid content of 15 mg.

[0108] [Preparation of Protective Layer Composition 4] A 20% by mass solution of a composition containing 90% by mass of "polysilazane X" and 10% by mass of compound X (another perfluoropolyether group-containing silane compound) was prepared and impregnated into a metal pellet in a copper container filled with steel wool so that the solid content after solvent evaporation would be 15 mg. After impregnation with the 20% by mass solution, the pellet was heated in an oven set at 80°C for 20 minutes to evaporate the solvent and leave a solid content of 15 mg.

[0109] [Preparation of Protective Layer Composition 5] A 20% by weight solution of a composition containing 100% by weight of "Siloxane Z" was prepared and impregnated into a metal pellet containing steel wool in a copper container so that the solid content after solvent evaporation would be 15 mg. After impregnation with the 20% by weight solution, the pellet was heated in an oven set to 80°C for 20 minutes to evaporate the solvent and leave a solid content of 15 mg.

[0110] [Preparation of Protective Layer Composition 6] A 20% by weight solution of a composition containing 100% by weight of compound X (another perfluoropolyether group-containing silane compound) was prepared and impregnated into a metal pellet containing steel wool in a copper container so that the solid content after solvent evaporation would be 15 mg. After impregnation with the 20% by weight solution, the pellet was heated in an oven set at 80°C for 20 minutes to evaporate the solvent and leave a solid content of 15 mg.

[0111] [Hard coat layer thickness measurement] The thickness of the hard coat layer was measured by the following method. <Hard coat layer thickness measurement> The reflectance spectrum of a lens substrate with one hard coat layer formed thereon was measured using a spectrophotometer (Olympus USPM-RU), and the film thickness of the hard coat film was calculated from the measured reflectance spectrum and the refractive index of the hard coat film. Here, to confirm the film thickness distribution, the film thickness was measured at three points: the top, center, and bottom of the lens substrate during the pulling process. The top of the lens substrate was located 30 mm above the center of the lens, and the bottom of the lens was located 30 mm below the center of the lens.

[0112] [Example 1] A glass container was charged with 90 parts by weight of colloidal silica (Snowtex-40, Nissan Chemical Industries, Ltd.), 81.6 parts by weight of the organosilicon compound methyltrimethoxysilane, 176 parts by weight of γ-glycidoxypropyltrimethoxysilane, 2.0 parts by weight of 0.5N hydrochloric acid, 20 parts by weight of acetic acid, and 90 parts by weight of water. The resulting mixture was stirred at room temperature for 8 hours and then allowed to stand at room temperature for 16 hours to obtain a hydrolysis solution. To this solution, 120 parts by weight of isopropyl alcohol, 120 parts by weight of n-butyl alcohol, 16 parts by weight of aluminum acetylacetone, 0.2 parts by weight of a silicone surfactant, and 0.1 parts by weight of an ultraviolet absorber were added, stirred at room temperature for 8 hours, and then aged at room temperature for 24 hours to obtain a coating solution. A plastic lens substrate (manufactured by HOYA Corporation, product name EYAS, prescription S 0.00, C 0.00, refractive index 1.60, colorless lens) pretreated with an alkaline aqueous solution was immersed in the above-mentioned coating solution. After immersion, the lens substrate was pulled up at a rate of 20 cm / min and heated at 120°C for 2 hours to form a cured film, forming a hard coat layer 3±1 μm thick. Next, a 600 nm thick antireflection layer was formed on the hard coat layer by vacuum deposition, consisting of nine alternating layers of silica and zirconia. After the deposition of the anti-reflection layer, an ion gun treatment was carried out to activate the surface under the following conditions. Accelerating voltage: 500V Accelerating current: 230mA Inlet gas: oxygen (20sccm) Ion irradiation time: 30 seconds

[0113] The dome containing the lens substrate was then moved to a chamber where the water-repellent layer composition was deposited. A pellet impregnated with the water-repellent layer composition was placed on a halogen heater heating table in the chamber. The pellet was heated with the halogen heater, and the water-repellent layer composition in the pellet was deposited. The temperature reached during heating was approximately 600°C. The pellet impregnated with the protective layer composition 1 was placed on a halogen heater heating table. The protective layer composition in the pellet was vapor-deposited by heating with the halogen heater. The temperature reached during heating was approximately 600°C. The thickness of the water-repellent layer was about 10 nm, and the thickness of the protective layer was about 8 nm.

[0114] Thereafter, the eyeglass lenses having the hard coat layer, anti-reflection layer, water-repellent layer, and protective layer formed on both surfaces of the lens substrate were subjected to the following evaluations. The results are shown in Table 1.

[0115] [Examples 2 to 4 and Comparative Examples 1 and 2] Except for using protective layer compositions 2 to 6 shown in Table 1 instead of protective layer composition 1 in Example 1, eyeglass lenses having a hard coat layer, an antireflection layer, a water-repellent layer, and a protective layer formed on both surfaces of a lens substrate were manufactured in the same manner as in Example 1, and the eyeglass lenses were subjected to the following evaluations. The results are shown in Table 1.

[0116] Comparative Example 3 Except for not forming a protective layer in Example 1, a spectacle lens having a hard coat layer, an antireflection layer, and a water-repellent layer formed on both surfaces of a lens substrate was manufactured in the same manner as in Example 1, and the spectacle lens was subjected to the following evaluations. The results are shown in Table 1.

[0117] [Axis misalignment test] The axial misalignment test was carried out by the following method and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1. An evaluation result of ◯ can be said to be a good result. <Axis misalignment test method> The state of axis misalignment was judged based on the angle of deviation from the reference line after an S-7.50 lens made of a lens substrate with a refractive index of 1.53 (manufactured by HOYA Corporation, trade name Phoenix) was shaped into a predetermined shape. <Evaluation criteria for misalignment test> ○: In three axis misalignment tests, no axis misalignment of 1 degree or more occurred. ×: Out of three axis misalignment tests, axis misalignment of 1 degree or more occurred at least once.

[0118] [Paint mark test] The paint mark test was carried out by the following method and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1. An evaluation result of ⊚ or ◯ can be said to be a good result. <Paint mark test method> A specified mark was printed as a paint mark on the protective layer, and the lens surface was rubbed 10 times with lens cleaning paper (Dusper K-3 (trade name), manufactured by Ozu Sangyo Co., Ltd., sometimes called "Silbon paper") at a load of 20 g, and the condition was then visually judged. <Evaluation criteria for paint mark test> ◎: No change in the appearance of the paint mark ○: The appearance of the paint mark is slightly faded △: Part of the paint mark has peeled off ×: More than half of the paint mark has peeled off and the original state is unrecognizable

[0119] [Dynamic friction coefficient measurement] The dynamic friction coefficient was measured by the following method. <Method for measuring the coefficient of dynamic friction> The dynamic friction coefficient was measured once under the following conditions using HM-3 (trade name) manufactured by Toyo Seiki Seisakusho, Ltd. The obtained results (dynamic friction coefficient) are shown in Table 1. <Condition> Test method: The convex surface of the eyeglass lens was placed on lens cleaning paper (Dasper K-3 (trade name), also known as "Silbon paper," manufactured by Ozu Sangyo Co., Ltd.) and the eyeglass lens and wire were fixed in place with Kapton tape. Load: 20g Measurement speed: 1500mm / min Measurement distance: 100 mm

[0120] [Table 1]

[0121] The meanings of the various abbreviations in Table 1 are as follows: (1) Protective layer: 1-(1H,1H,2H,2H-perfluorooctyl)silazane: structural formula (X) below: number average molecular weight: Mn = 1000, weight average molecular weight: Mw = 1100, z-average molecular weight: Mz = 1250, molecular weight distribution: Mw / Mn = 1.1, Mz / Mw = 1.1 [ka] (X) (In the structural formula (X), n represents 1 to 10, and R represents —CH2CH2(CF2)5CF3.) (2) Protective layer: Compound X (another perfluoropolyether group-containing silane compound): number average molecular weight: Mn = 770, weight average molecular weight: Mw = 890, z-average molecular weight: Mz = 1060, molecular weight distribution: Mw / Mn = 1.2, Mz / Mw = 1.2 (3) Protective layer: Perhydrosilazane: structural formula (Y) below: number average molecular weight: Mn = 150, weight average molecular weight: Mw = 170, z average molecular weight: Mz = 200, molecular weight distribution: Mw / Mn = 1.1, Mz / Mw = 1.2 [ka] (Y) (In the structural formula (Y), n represents an integer of 2 to 30.) (4) Protective layer: Polysilazane X: structural formula (X) below: number average molecular weight: Mn = 300, weight average molecular weight: Mw = 360, z average molecular weight: Mz = 470, molecular weight distribution: Mw / Mn = 1.2, Mz / Mw = 1.3 [ka] (X) (In the structural formula (X), n represents 1 to 10, and R represents the following structural formula (X1).) [ka] ··(X1) (In the structural formula (X1), n ​​represents 1 to 70.) (5) Protective layer: Siloxane Z: structural formula (Z) below: number average molecular weight: Mn = 3200, weight average molecular weight: Mw = 1100, z average molecular weight: Mz = 5250, molecular weight distribution: Mw / Mn = 1.27, Mz / Mw = 1.29 [ka] (Z) (In the structural formula (Z), n represents an integer of 10 to 60.) (6) Water-repellent layer: Water-repellent compound 1 (perfluoropolyether group-containing silane compound): number average molecular weight: Mn = 700, weight average molecular weight: Mw = 760, z-average molecular weight: Mz = 820, molecular weight distribution: Mw / Mn = 1.1, Mz / Mw = 1.1

[0122] Table 1 shows that Examples 1 to 4, in which a protective layer containing 50% by mass or more of polysilazane was provided on a water-repellent layer, had significantly better paint mark resistance (paint mark test results) of the protective layer than Comparative Examples 1 to 3.

[0123] From the results of the Examples and Comparative Examples described above, it can be seen that this embodiment provides a spectacle lens with sufficiently excellent paint mark resistance (paint mark test results) and a method for manufacturing the same. [Explanation of symbols]

[0124] 1. Eyeglass lenses 11. Eyeglass lens substrates 11a, 21fa, 31fa, 41fa Object side surface 11b, 21bb, 31bb, 41bb Eye side 21f, 21b Hard coat layer 31f,31b Functional layer 41f, 41b Water-repellent layer 51f,51b Protective layer

Claims

1. A substrate, a water-repellent layer formed on the substrate, and a protective layer formed on the water-repellent layer, The protective layer of the eyeglass lens contains 50% by mass or more of polysilazane.

2. The polysilazane has a number average molecular weight of 100 to 10,000, 2. The eyeglass lens according to claim 1, wherein the number average molecular weight is a number average molecular weight calculated as polymethyl methacrylate, measured by gel permeation chromatography.

3. The polysilazane has a weight average molecular weight of 100 to 10,000, 3. The eyeglass lens according to claim 1, wherein the weight average molecular weight is a weight average molecular weight calculated as polymethyl methacrylate, measured by gel permeation chromatography.

4. The polysilazane has a molecular weight distribution of 1.0 to 3.5, 3. The spectacle lens according to claim 1, wherein the molecular weight distribution is calculated from the number average molecular weight and weight average molecular weight in terms of polymethyl methacrylate, measured by gel permeation chromatography.

5. The spectacle lens according to claim 1 or 2, wherein the polysilazane has at least one selected from the group consisting of a structural unit represented by formula (1-1), a structural unit represented by formula (1-2), and a structural unit represented by formula (1-3). 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 (In the formula (1-1), R is -(CH ２ ) ｘ (CF ２ ) ｙ CF ３ (wherein x is an integer of 1 to 5, and y is an integer of 1 to 10) or a fluorine-containing group represented by the following structural formula (X1): 【Chemistry 4】 ... (X1) (In formula (X1), n ​​represents an integer of 1 to 70.)

6. a water-repellent layer forming step of forming a water-repellent layer on a substrate; and a protective layer forming step of forming a protective layer on the water-repellent layer using a protective layer composition containing 50% by mass or more of polysilazane.

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