Spectacle lens and method for manufacturing same

Abstract

A spectacle lens comprising: 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.

Description

Eyeglass lenses and their manufacturing method

[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.

[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). It is sometimes necessary to form paint marks on this hydrophobic / oleophobic coating.

[0003] Special Publication No. 2008-513815

[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. That is, 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.

[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 items [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, the protective layer containing 50% by mass or more of polysilazane. [2] The spectacle lens according to item [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 spectacle lens according to item [1] or [2] above, wherein the polysilazane has a weight-average molecular weight of 100 to 10,000, the weight-average molecular weight being the weight-average molecular weight in terms of polymethyl methacrylate, measured by gel permeation chromatography. [4] The spectacle lens according to any one of [1] to [3] above, 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 [1] to [4] above, 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). (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): ...(X1) (wherein, 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.

[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.

[0009] FIG. 1 is a schematic cross-sectional view of a spectacle lens according to the present embodiment.

[0010] The following describes an example of an embodiment of the present disclosure. However, the embodiments described below are merely examples for embodying the technical concept of the present disclosure, and the present disclosure is not limited to the following description. The present disclosure also includes any embodiment or combination of any of the features described herein. In this specification, preferred specifications may be selected arbitrarily, and combinations of preferred specifications are considered more preferable. In this specification, the term "XX to YY" means "XX or greater and YY or less." In this specification, for preferred numerical ranges (e.g., ranges of content, etc.), lower and upper limits described in stages can be independently combined. For example, a description of "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 obtain "10 to 60." In this specification, when multiple substances corresponding to each component are present in the composition, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. As used herein, "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. As used herein, "solid content" refers to non-volatile content excluding volatile substances such as solvents, and indicates components that remain without volatilization when the composition is dried, and includes liquid, starch syrup-like, and wax-like substances at room temperature. As used herein, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

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

[0012] The number average molecular weight, weight average molecular weight, and z-average molecular weight in this embodiment are 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 refers to 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 measurement solvent is added to a predetermined mass of a residue sample that has been dehydrated under a nitrogen stream, and the mixture is gently stirred at room temperature. After visually confirming that the sample has dissolved, the mixture is filtered using 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, and 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 measurement condition 1 below. 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, sensitivity 32, manufactured by Showa Denko K.K. (now Resonac Corporation)) Column: Two TSKgel GMHHR-H(S) (φ4.6 mm × 15 cm, manufactured by Tosoh Corporation) Solvent: hexafluoroisopropanol with 5 mM sodium trifluoroacetate Flow rate: 0.3 mL / min Column temperature: 40°C Injection amount: 0.020 mL Standard sample: Monodisperse polymethyl methacrylate (PMMA) manufactured by Showa Denko K.K. (now Resonac Corporation) <Measurement condition 2> Apparatus: Gel permeation chromatograph GPC Detector: Differential refractive index detector RI (RI-104, sensitivity -16, manufactured by Showa Denko K.K. (now Resonac Corporation)) Column: TSKgel One Super HZM-N, one HZ2000 (6.0 mm × 15 cm, manufactured by Tosoh Corporation) Solvent: toluene Flow rate: 0.45 mL / min Column temperature: 40°C Injection amount: 0.020 mL Standard sample: monodisperse polystyrene manufactured by Tosoh Corporation Note that 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.Other calculation methods are not particularly limited, and examples thereof include calculation methods using matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS) and nuclear magnetic resonance spectrometry (NMR), which are 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 Lens] 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 has functional layers 31b, 31f provided 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 directly or indirectly via another layer on the eyeball-side surface 11b and the object-side surface 11a of the lens substrate 11. Each layer in the eyeglass lens of this embodiment will now be described.

[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, or the like. In ordinary 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 thereto. The lens substrate may be used for any of a single-vision lens, a multifocal lens, a progressive-power lens, and the like. 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. A colorless lens substrate is usually used, but a colored lens may also be used as long as it does not impair transparency.

[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] The optical center thickness of the lens substrate is not particularly limited, but 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. The diameter of the lens substrate is not particularly limited, but 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. There is no particular upper limit to the refractive index ne of the lens substrate, and it may be, for example, 1.80 or less.

[0024] The resin for the lens substrate is not particularly limited, and examples thereof include urethane-based 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, with polythiourethane resins and polysulfide resins being more preferred. Inorganic glass can also be used. The lens substrate may be undyed (colorless lenses) or dyed (dyed lenses).

[0025] (Method for producing lens substrate) The lens substrate is not particularly limited, but can be obtained, for example, by a production 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. The annealing temperature is not particularly limited, but 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 at least one end of a 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, as necessary. By containing a water-repellent compound having a silyl group at at least one end of the molecular chain, the water-repellent layer composition can improve the water repellency of the water-repellent layer that is formed.

[0031] (Water-Repellent Compound) The water-repellent compound may be a water-repellent compound having only a silyl group at one end of the molecular chain, or may be a water-repellent compound having silyl groups at both ends of the molecular chain, or may include 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. By having a silyl group at at least one end of the water-repellent compound, a condensation reaction proceeds during vapor deposition to form a water-repellent layer. Examples of silyl groups 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. An example of the fluorinated alkyl group is 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 property 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 property 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 property 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, and more preferably has 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. -(CF ２ O) ａ (C ２ F ４ O) ｂ (C ３ F ６ O) ｃ (C ４ F ８ O) 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 number of units represented by a, b, c, and d, is random or block. There is no particular limitation 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 is no particular limitation 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 is no particular limitation 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 is no particular limitation on d, as long as it is 0 to 30, but it is preferably 0 to 25, more preferably 0 to 20, and particularly preferably 0 to 10. There is no particular limitation on a+b+c+d, as long as it is 10 to 200, but it is preferably 30 to 170, more preferably 50 to 150, and particularly preferably 70 to 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. Examples of suitable solvents include aprotic polar solvents such as methylsiloxane, silicone solvents such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tris(trimethylsiloxy)methylsilane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane, and fluorine-based solvents such as hexafluorobenzene, trifluoromethylbenzene, hexafluorometaxylene, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, and tridecafluorohexyl methyl ether. 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% by mass or more of polysilazane. For example, the protective layer can be obtained by vapor deposition or coating of a protective layer composition. However, from the viewpoint that a protective layer can be formed regardless of the composition of the water-repellent layer, it is preferable to vapor-deposit the protective layer composition.

[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 a plurality of silazane structures (-Si-NH-) instead of a siloxane structure (-Si-O-), the paint mark resistance of the protective layer (paint mark test results) can be improved.

[0047] The content of polysilazane relative to 100% by mass of the solids 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 properties, 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 markability, 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). In formula (1-1), R is —(CH ２ ) ｘ (CF ２ ) ｙ CF ３ or the following structural formula (X1): where x is 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 is 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. 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] -(CH ２ ) ｘ(CF ２ ) ｙ CF ３ The number of carbon atoms of the fluorine-containing group represented by the formula (I) 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 marking 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 marking 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 marking properties.

[0053] There are no particular restrictions on the molecular weight distribution of the polysilazane, 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 contain a solvent, 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 Components> 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 solids 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 mark 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 properties, 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 compound X (another perfluoropolyether group-containing silane compound) is not particularly limited, but from the viewpoint of paint mark 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, scratch resistance (abrasion resistance) can be imparted to the eyeglass lens, and the durability (strength) of the eyeglass lens can also be increased. For details of the hard coat layer, see, for example, paragraphs 0025 to 0028 and 0030 of JP 2012-128135 A. 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, KBE-9007, etc., 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. There are no particular limitations on commercially available polyfunctional epoxy compounds, and examples thereof 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, EX-614B, etc., of the trade name "Denacol" series manufactured by Nagase ChemteX Corporation. These 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 curable composition can be prepared by mixing optional components such as an organic solvent, a leveling agent, and a curing catalyst, as needed, in addition to the components described above. The hard coat layer can be formed by applying the curable composition to a substrate and then subjecting it to a curing treatment (thermal curing, photocuring, etc.). The method for applying the curable composition is not particularly limited, 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 performed by heating. The heat curing treatment can be performed, for example, by placing a lens coated with the curable composition in an environment with an ambient temperature of 50 to 150°C for approximately 30 minutes to 3 hours.

[0073] <Underlayer> A underlayer (primer layer) may be formed between the lens substrate and the hard coat layer to improve adhesion. For details about the underlayer (primer layer), see, for example, paragraphs 0029 to 0030 of JP 2012-128135 A. The underlayer can be formed, for example, from an aqueous resin composition containing at least one type of resin particles selected from the group consisting of polyurethane resins, acrylic resins, and epoxy resins.

[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 thereof 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 "Eizelax" series (trade name) manufactured by Hodogaya Chemical Co., Ltd., and the "Neoletz" series (trade name) manufactured by Zeneka Corporation. These 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 reflective 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 additional layers on the functional layer. Examples of such layers include various functional layers such as an antifouling layer, an antifogging layer, a polarizing layer, and a light control layer. For these functional layers, known techniques can be applied without any restrictions.

[0078] (Anti-Reflection Layer) The anti-reflection layer is not particularly limited as long as it can impart reflection spectral characteristics to the spectacle lens surface having the anti-reflection layer. The anti-reflection layer has, for example, low-refractive index layers and high-refractive index layers alternately arranged (formed by sequential lamination) by vacuum deposition. The number of layers in the anti-reflection layer is not particularly limited, but is preferably 4 to 11 layers, more preferably 5 to 8 layers. More specifically, the film thickness of each layer is determined by optical simulation using a known method based on the refractive index of the film materials for forming the high-refractive index layers and the wavelength of light to be reflected or light whose reflection should be reduced, and the high-refractive index layers and low-refractive index layers are sequentially laminated under film-forming conditions determined to achieve the determined film thickness, thereby forming the anti-reflection layer. The film-forming material may be inorganic, organic, or organic-inorganic composite material, but inorganic materials are preferred from the standpoints of film formation and ease of availability. The reflection spectral characteristics for blue light, ultraviolet light, green light, and red light can be controlled by adjusting the type of film-forming material, film thickness, and lamination order.

[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 is made of silicon oxide (also called silica; for example, SiO ２ ), magnesium fluoride (e.g., MgF ２ ), and barium fluoride (e.g., BaF ２ The material may be one or a mixture of two or more inorganic oxides or fluorides selected from the group consisting of silicon oxide. In the above examples, the oxides and fluorides are shown in terms of stoichiometric composition for convenience, but oxides and fluorides in a state where oxygen or fluorine is deficient or excessive from the stoichiometric composition can also be used as high refractive index materials 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, 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 zirconium oxide (also called zirconia; for example, ZrO ２ ), tantalum oxide (Ta ２ O ５ ), yttrium oxide (e.g., Y ２ O ３ ), titanium oxide (e.g., TiO ２ ), niobium oxide (e.g., Nb ２ O ５ ), hafnium oxide (e.g., HfO ２ ) and aluminum oxide (Al ２ O ３ ), 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. Examples of the layer configuration of the antireflection layer include a configuration in which layers are stacked in the following order from the lens substrate side to the outermost lens surface side: 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); a configuration in which layers are stacked in the following order: first layer (high refractive index layer), second layer (low refractive index layer), third layer (high refractive index layer), fourth layer (low refractive index layer), fifth layer (high refractive index layer), and sixth layer (low refractive index layer). Examples of preferred combinations of low refractive index layers and high refractive index layers include a combination of a coating mainly composed of silicon oxide and a coating mainly composed of zirconium oxide, and a combination of a coating mainly composed of silicon oxide and a coating mainly composed 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 primarily composed of the high-refractive index material or low-refractive index material described above. Such a coating can be formed by depositing a film using a film-forming material (e.g., a vapor deposition source) primarily composed of the above material. 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 additives that assist film formation, to the extent that the function of the main component is not impaired. Film formation can be performed by known film-forming methods, and vapor deposition is preferred from the perspective of ease of film formation.

[0083] In addition to the high-refractive index layer and low-refractive index layer described above, the antireflection layer may also include, at any position on the antireflection layer, a coating primarily composed of a conductive oxide, preferably one or more conductive oxide layers formed by vapor deposition using a vapor deposition source primarily composed of a conductive oxide. The inclusion of a 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 eyeglass lens, preferred examples include indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof. These may be used alone or in combination of two or more. Among these, tin oxide and indium-tin oxide (ITO) are more preferred from the viewpoints of transparency and conductivity.

[0084] [Method for manufacturing eyeglass lenses] The method for manufacturing eyeglass lenses 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 Forming Step> The water-repellent layer can be obtained, for example, by vapor deposition or coating of a water-repellent layer composition, but is preferably obtained by vapor deposition.

[0086] The deposition is carried out by, for example, vacuum deposition. The heating temperature during the deposition in vacuum deposition is not particularly limited, but is preferably 400 to 1000°C, more preferably 550 to 1000°C, even more preferably 600 to 1000°C, and particularly preferably 650 to 1000°C. The heating temperature for the deposition refers to the temperature at which the pellets or the like impregnated with the water-repellent layer composition are heated during the deposition. The vacuum deposition is carried out at a temperature of 3.0 x 10 －２ It is preferable to carry out the deposition in a deposition space controlled to a vacuum of 100 Pa or less.

[0087] Heating during vapor deposition can be performed using, for example, a halogen heater, resistance heating, an electron gun, etc. Among these, using an electron gun for heating and vapor deposition allows for the deposition of a thin film with high precision. 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] Vapor 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 fused silica porous body or a sintered filter made by sintering a metal powder with high thermal conductivity, such as copper or stainless steel. From the viewpoint of obtaining an appropriate vapor deposition rate, the mesh size of the sintered filter is suitably 40 to 200 μm, preferably 80 to 120 μm. Alternatively, pellets in which steel wool is filled in a copper container are also suitably used. The water-repellent layer composition may be used as 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 adopted in which a water-repellent layer composition is dissolved in an organic solvent and 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.

[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 Forming Step> The protective layer can be obtained by, for example, vapor deposition or coating of a protective layer composition, but is preferably obtained by vapor deposition.

[0094] The deposition is carried out by, for example, vacuum deposition. The heating temperature during the deposition in 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 the deposition refers to the temperature at which the pellets or the like impregnated with the protective layer composition are heated during the deposition. The vacuum deposition is carried out at a temperature of 3.0 x 10 －２ It is preferable to carry out the deposition in a deposition space controlled to a vacuum of 100 Pa or less.

[0095] Heating during vapor deposition can be performed using, for example, a halogen heater, resistance heating, an electron gun, etc. Among these, using an electron gun for heating and vapor deposition allows for the deposition of a thin film with high precision. 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 a protective layer 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.

[0097] Vapor 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 fused silica porous body or a sintered filter made by sintering a metal powder with high thermal conductivity, such as copper or stainless steel. From the viewpoint of obtaining an appropriate vapor deposition rate, the mesh size of the sintered filter is suitably 40 to 200 μm, preferably 80 to 120 μm. Alternatively, pellets in which steel wool is filled in a copper container are also suitably used. The protective layer composition may be used as is or in the form of a solution, which is then impregnated into the porous material.

[0098] To form a protective layer on a spectacle lens by coating, a method can be adopted in which a protective layer composition is dissolved in an organic solvent and 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.

[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 was added to 3 mg of sample (or 4 mL of the measurement solvent described below to 4 mg of sample), and the mixture was gently stirred at room temperature. Dissolution of the sample in the measurement solvent was visually confirmed. 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 later, perhydrosilazane represented by structural formula (Y) described later, polysilazane (X) represented by structural formula (X) described later, compound X described later, and water-repellent compound 1 (perfluoropolyether group-containing silane compound) described later) were subjected to gel permeation chromatography under the following measurement conditions 1. Furthermore, siloxane Z represented by structural formula (Z) described later was 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: Two TSKgel GMHHR-H(S) (φ4.6 mm×15 cm, manufactured by Tosoh Corporation) Solvent <Measurement condition 2> Apparatus: Hexafluoroisopropanol with 5 mM sodium trifluoroacetate added Flow rate: 0.3 mL / min Column temperature: 40°C Injection volume: 0.020 mL Standard sample: Monodisperse polymethyl methacrylate (PMMA) manufactured by Showa Denko K.K. (now Resonaq Corporation) <Measurement condition 2> Apparatus: Gel permeation chromatograph GPC Detector: Differential refractive index detector RI (RI-104 manufactured by Showa Denko K.K. (now Resonaq Corporation), sensitivity -16) Column: TSKgel Super HZM-N 1 column, HZ2000 1 column (6.0 mm x 15 cm, manufactured by Tosoh Corporation) Solvent: Toluene Flow rate: 0.45 mL / min Column temperature: 40°C Injection volume: 0.020 mL Standard sample: Monodisperse polystyrene manufactured by Tosoh Corporation

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

[0105] [Preparation of Protective Layer Composition 1] A 20% by mass solution of a composition containing 90% by mass of "1-(1H,1H,2H,2H-perfluorooctyl)silane" and 10% by mass of Compound X (another perfluoropolyether group-containing silane compound) was prepared, and this solution was 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 to 80°C for 20 minutes to evaporate the solvent, resulting in a solid content of 15 mg.

[0106] [Preparation of Protective Layer Composition 2] A 20% by mass solution was prepared by mixing 90% by mass of "perhydrosilazane" and 10% by mass of Compound X (another perfluoropolyether group-containing silane compound), and the solution was impregnated into a metal pellet containing steel wool in a copper container so that the solid content after solvent evaporation was 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, resulting in a solid content of 15 mg.

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

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

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

[0111] [Hard Coat Layer Film Thickness Measurement] The hard coat layer film thickness was measured by the following method. <Hard Coat Layer Film Thickness Measurement> The reflectance spectrum of a lens substrate on which one hard coat layer was formed 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, in order 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 0.5 N hydrochloric acid, 20 parts by weight of acetic acid, and 90 parts by weight of water, and 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 hydrolyzed 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, and the mixture was 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, trade 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 pull-up 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 deposition of the antireflection layer, ion gun treatment was performed to activate the surface. The ion gun treatment was performed under the following conditions: acceleration voltage: 500 V, acceleration current: 230 mA, introduced gas: oxygen (20 sccm), ion irradiation time: 30 seconds

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

[0114] Thereafter, the spectacle 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 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, except that protective layer compositions 2 to 6 shown in Table 1 were used instead of protective layer composition 1 in Example 1. The eyeglass lenses were then evaluated as follows. The results are shown in Table 1.

[0116] [Comparative Example 3] 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, except that no protective layer was formed, and this spectacle lens was subjected to the following evaluations. The results are shown in Table 1.

[0117] [Axis Misalignment Test] The axis misalignment test was performed using the following method and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1. An evaluation result of A can be said to be a good result. <Axis Misalignment Test Method> The axis misalignment state 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, product name Phoenix) was shaped into a predetermined shape. <Evaluation Criteria for Axis Misalignment Test> A: In three axis misalignment tests, no axis misalignment of 1 degree or more occurred. B: In 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 A or B 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 afterwards was judged visually. <Evaluation Criteria for Paint Mark Test> A: No change in the appearance of the paint mark B: The appearance of the paint mark is slightly faded C: Part of the paint mark has peeled off D: More than half of the paint mark has peeled off, and the original state is no longer recognizable

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

[0120]

[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 ...(X) (wherein, in structural formula (X), n represents 1 to 10, and R represents -CH ２ CH ２ (CF ２ ) ５ CF ３(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 (Y) (wherein, in 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 (X) (wherein, in structural formula (X), n represents 1 to 10, and R represents the following structural formula (X1)) (X1) (wherein, in 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 (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] From Table 1, it can be seen 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.

[0124] REFERENCE SIGNS LIST 1 eyeglass lens 11 eyeglass lens substrate 11a, 21fa, 31fa, 41fa object side surface 11b, 21bb, 31bb, 41bb eyeball side surface 21f, 21b hard coat layer 31f, 31b functional layer 41f, 41b water-repellent layer 51f, 51b protective layer

Claims

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 claim 1, wherein the polysilazane has a number average molecular weight of 100 to 10,000, and the number average molecular weight is the number average molecular weight in terms of polymethyl methacrylate, measured by gel permeation chromatography.

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

4. The spectacle lens according to claim 1 or 2, 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 eyeglass 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). (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): ...(X1) (wherein, 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.

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