Polythiourethane film, eyeglass lens material, eyeglass lens, and method for manufacturing eyeglass lens

Abstract

A polythiourethane film containing a polythiourethane that is the reaction product of a thiol compound having two functional groups, a thiol compound having three or more functional groups, and an isocyanate compound.

Description

[Technical Field]

[0001] The present disclosure relates to a polythiourethane film, a material for an eyeglass lens, an eyeglass lens, and a method for manufacturing an eyeglass lens. [Background technology]

[0002] Plastic lenses are lighter and less likely to break than inorganic lenses, and are therefore rapidly becoming popular as optical elements for eyeglass lenses, camera lenses, etc. In recent years, functional lenses with various functions have been investigated. An example of a functional lens is a photochromic lens having photochromic properties. Functional lenses often include dyes, such as dyes, pigments, visible light absorbing dyes, photochromic dyes, or ultraviolet light absorbers.

[0003] Patent Document 1 describes a film that is made of a resin having a thiourethane bond, and that is characterized in that the molar ratio of sulfur to nitrogen (S / N) contained in the resin is 0.8 or more and less than 3.

[0004] For example, Patent Document 2 discloses an optical element comprising a lens substrate, an adhesive layer disposed on the lens substrate, and a functional film disposed on the adhesive layer, in which the adhesive layer contains ester polyurethane, the adhesive layer has an elongation of 1050 to 1400%, and the adhesive layer has a Young's modulus of 400 N / mm 2 Below, an optical element is described.

[0005] For example, Patent Document 3 describes a method for manufacturing a resin lens, in which a substrate lens is used as a first mold, a second mold is placed on one or both sides of the first mold with a substantially constant predetermined gap therebetween, the peripheral gap between the first and second molds is sealed with taping or a gasket to form a cavity, and a liquid resin raw material containing a functionality-imparting agent is injected into the cavity to cast-mold a functional resin layer, thereby integrating the substrate lens and the functional resin layer, characterized in that the first mold is a substrate lens having a thermoplastic elastomer adhesive layer formed on the side on which the functional resin layer is formed.

[0006] Patent Document 1: International Publication No. 2011 / 058754 Patent Document 2: Japanese Patent Application Laid-Open No. 2014-202904 Patent Document 3: International Publication No. 2014 / 125738 Summary of the Invention [Problem to be solved by the invention]

[0007] Functional lenses include laminated lenses, which have a film inserted inside the lens substrate, and lenses with a pigment kneaded into the substrate. Film materials used in laminated lenses include polyethylene terephthalate film, acrylic film, and polyvinyl alcohol film. However, when these films are heated and bonded to a lens substrate to obtain a functional lens, there is a problem in that streaks appear on the film during bonding. In light of this background, thiourethane films have been studied as films other than polyethylene terephthalate films, acrylic films, and the like (see, for example, Patent Document 1).

[0008] Furthermore, functional lenses require films to conform to the shape of the lens substrate. Lens substrates come in a variety of shapes, but it has been particularly difficult to make films conform to highly curved lens substrates. Furthermore, the functional lens having the above-mentioned structure is also required to have solvent resistance. In the case of a functional lens having the above-described structure, it is conceivable to laminate a layer such as a hard coat layer on a film. In this case, treatment with an organic solvent, an alkaline aqueous solution, or the like is often carried out, and the film is often damaged by the solvent.

[0009] The problem to be solved by the first embodiment of the present disclosure is to provide a polythiourethane film having excellent conformability and solvent resistance, a material for eyeglass lenses including the polythiourethane film, an eyeglass lens, and a method for manufacturing an eyeglass lens. [Means for solving the problem]

[0010] The means for solving the above problems include the following embodiments. <1> A polythiourethane film comprising a polythiourethane, the polythiourethane being a reaction product of a difunctional thiol compound, a tri- or higher functional thiol compound, and an isocyanate compound. <2> The bifunctional thiol compound has a thiol equivalent of 20% to 95% relative to 100% of the total thiol equivalent of the bifunctional thiol compound and the trifunctional or higher thiol compound. <1> The polythiourethane film according to claim 1. <3> The thickness is 100 μm to 600 μm <1> or <2> The polythiourethane film according to claim 1. <4> The minimum storage modulus is between 30°C and 160°C, and the minimum storage modulus is 3.00 x 10 6 Pa~1.40×10 7 Pa <1> ~ <3> The polythiourethane film according to any one of the above. <5> The polythiourethane has a molecular weight between crosslinking points of 950 to 3000. <1> ~ <4> The polythiourethane film according to any one of the above. <6> Furthermore, functional dyes <1> ~ <5> The polythiourethane film according to any one of the above. <7> The functional dye is a specific wavelength-cutting dye or a photochromic dye. <6> The polythiourethane film according to claim 1. <8> <1> ~ <7> and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film. <9> The polyurethane adhesive layer comprises a polycarbonate-based polyurethane containing anionic functional groups. <8> 1. A material for eyeglass lenses according to claim 1. <10> Furthermore, a hard coat layer is included as the outermost layer. <8> or <9> 1. A material for eyeglass lenses according to claim 1. <11> <8> ~ <10> a material for eyeglass lenses according to any one of the above items; and a spectacle lens substrate adhered to the polyurethane adhesive layer of the spectacle lens material. <12> The spectacle lens substrate has a convex surface or a concave surface bonded to the polyurethane adhesive layer of the spectacle lens material. <11> The eyeglass lens according to claim 1. <13> The eyeglass lens substrate has a radius of curvature of 62.5 mm to 125.0 mm. <11> or <12> The eyeglass lens according to claim 1. <14> Contains two or more of the above eyeglass lens materials <11> ~ <13> 10. The eyeglass lens according to claim 9, wherein the lens is a lens having a diameter of 10 mm or less. <15> The eyeglass lens substrate contains at least one selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane. <10> ~ <14> 10. The eyeglass lens according to claim 9, wherein the lens is a lens having a diameter of 10 mm or less. <16> <8> ~ <10> 10. A method for producing a spectacle lens, comprising the step of attaching the spectacle lens material according to any one of claims 1 to 9 to a spectacle lens substrate to obtain a spectacle lens. <17> The method includes a step of attaching the eyeglass lens material to an eyeglass lens substrate using a vacuum / compressed air molding machine to obtain an eyeglass lens. <16> A method for manufacturing eyeglass lenses according to claim 1. [Effects of the Invention]

[0011] The first embodiment of the present disclosure can provide a polythiourethane film having excellent conformability and solvent resistance, a material for an eyeglass lens including the polythiourethane film, an eyeglass lens, and a method for manufacturing an eyeglass lens. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 10 is a diagram for explaining attachment using a vacuum / compressed air forming machine. [Figure 2] 1 is a graph showing the transmittance of a lens with a film in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0013] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, 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. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component contained in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In this disclosure, when a material contains multiple substances corresponding to each component, the amount of each component in the material means the total amount of the multiple substances present in the material unless otherwise specified. In this disclosure, "poly(thio)urethane" means polyurethane or polythiourethane. In the present disclosure, "polycarbonate-based polyurethane" refers to a polyurethane containing structural units derived from an active hydrogen compound having a polycarbonate structure. In the present disclosure, the term "polycarbonate polyurethane having an anionic functional group" refers to a polycarbonate polyurethane containing a structural unit derived from an active hydrogen compound having an anionic functional group. Examples of the anionic functional group include a carboxyl group, a sulfonic acid group, a phosphate group, and a betaine structure-containing group such as sulfobetaine.

[0014] The present disclosure includes the following first and second embodiments. The first and second embodiments will be described in detail below.

[0015] (First embodiment) <Polythiourethane film> The polythiourethane film of the first embodiment (also simply referred to as the film in the first embodiment) contains polythiourethane, which is a reaction product of a difunctional thiol compound, a tri- or higher functional thiol compound, and an isocyanate compound. The polythiourethane film of the first embodiment has the above-described structure and is therefore excellent in conformability and solvent resistance.

[0016] Functional lenses include laminated lenses, which have a film inserted inside the lens substrate, and lenses with a pigment kneaded into the substrate. Film materials used in laminated lenses include polyethylene terephthalate film, acrylic film, and polyvinyl alcohol film. All of these are thermoplastic resin films. However, when these thermoplastic resin films are heated and laminated to a lens substrate to obtain a functional lens, problems arise, such as the occurrence of streaks in the film during lamination and insufficient adhesion to the hard coat layer. When adhesion to the hard coat layer is insufficient, it is necessary to place a primer layer between the film and the hard coat layer. The inventors anticipated that adhesion to the hard coat layer could be achieved by providing the surface with a material similar to the lens substrate, and focused on thiourethane film to investigate ways of attaching the film to the lens. Thermosetting resins undergo polymerization when heated, forming a polymer network structure, which hardens and cannot be restored to its original state. Therefore, there has been no previous research into heating and stretching a thermosetting resin film and bonding it to a lens substrate. However, the present inventors have focused on the above points and developed a thiourethane film that can be vacuum-formed or pressure-formed.

[0017] The polythiourethane film of the first embodiment preferably contains polythiourethane having a molecular weight between crosslinks of 950 to 3,000.

[0018] In functional lenses in which a film containing a photochromic compound is attached to a lens substrate, methods of imparting softness to the film have been considered to improve the conformability of the film. However, the more the film's softness improves, the more its solvent resistance tends to decrease. In other words, the conformability and solvent resistance of the film are in a trade-off relationship, and it has been difficult to achieve both. As a result of extensive research, the present inventors have found that by selecting polythiourethane as the material for the film and limiting the molecular weight between crosslinking points of the polythiourethane to a specific range, it is possible to achieve both good conformability and solvent resistance of the film. According to the investigations of the present inventors, when the molecular weight between crosslinking points of polythiourethane is large, the crosslinking density decreases and the film becomes softer, improving conformability but decreasing solvent resistance. On the other hand, when the molecular weight between crosslink points of the polythiourethane is small, the crosslink density increases and the film becomes hard, resulting in a decrease in conformability and an improvement in solvent resistance. After further investigation, the inventors discovered that when the molecular weight between crosslinking points of the polythiourethane is within a specific range, the film can achieve both good conformability and solvent resistance, and thus obtained the polythiourethane film of the first embodiment.

[0019] <Polythiourethane> The polythiourethane film of the first embodiment preferably contains polythiourethane having a molecular weight between crosslinks of 950 to 3,000.

[0020] (Molecular weight between crosslinking points) The polythiourethane in the first embodiment has a molecular weight between crosslinks of 950 to 3,000. The molecular weight between crosslinks means the molecular weight between crosslinks. The smaller the molecular weight between crosslinks, the harder the film and the higher the crosslink density. The higher the molecular weight between crosslinks, the softer the film and the lower the crosslink density.

[0021] The polythiourethane in the first embodiment preferably has an inter-crosslink molecular weight of 1,000 or more, more preferably 1,050 or more, from the viewpoint of the conformability of the film. From the viewpoint of the solvent resistance of the film, the polythiourethane in the first embodiment preferably has an inter-crosslinking molecular weight of 2800 or less, more preferably 2500 or less, and even more preferably 2000 or less.

[0022] The molecular weight between crosslinking points can be adjusted, for example, by adjusting the content ratio of a bifunctional thiol compound and a tri- or higher functional thiol compound that may be used as raw materials for polythiourethane.

[0023] (Method for measuring molecular weight between crosslinks) The molecular weight between crosslinks is calculated by the following formula. Molecular weight between crosslinking points Mc=2(1+μ)ρRT / E μ: Poisson's ratio (Poisson's ratio is assumed to be 0.5) ρ: density of polythiourethane (g / m 3 ) R: Gas constant (i.e., 8.314 J / K / mol) E: Storage modulus of polythiourethane (Pa) T: Absolute temperature (K) Here, the temperature T is 150°C (that is, 423.15K), and the elastic modulus E is the elastic modulus at 150°C. Note that 0°C is 273.15K, and an increase or decrease of 1°C is equivalent to an increase or decrease of 1K.

[0024] (Measurement of softening temperature and storage modulus) The viscoelasticity of the polythiourethane is measured using a dynamic viscoelasticity measuring device (for example, DMA8000 manufactured by PerkinElmer). A polythiourethane specimen measuring 30 mm x 5 mm and 2.5 mm thick is prepared. The measurement system is a single cantilever rectangle, and the temperature is raised from 30°C to 160°C at a rate of 3°C / min, and measurements are performed at a frequency of 1.0 Hz. The temperature at which tan δ obtained by measurement is maximized is taken as the softening temperature. During the temperature rise, the storage modulus is measured every minute.

[0025] The polythiourethane film of the first embodiment has a minimum storage modulus at 30°C to 160°C, and the minimum storage modulus is 3.00 × 10 6 Pa~1.40×10 7 Pa is preferred. "Having a minimum storage modulus between 30°C and 160°C" means that the temperature at which the storage modulus shows its minimum value is within the range of 30°C to 160°C. "Minimum storage modulus" means the storage modulus at the temperature at which the storage modulus shows its minimum value.

[0026] The minimum storage modulus is 4.00 x 10 6 Pa or more is more preferable, and 6.00 × 10 6 It is more preferable that the viscosity is 100 Pa or more. The minimum storage modulus is 1.30 x 10 7 Pa or less is more preferable, and 1.25 × 10 7 It is more preferable that the viscosity is 0.05 Pa or less. The method for measuring the minimum storage modulus is as described above.

[0027] The polythiourethane can be used without any particular limitation. Polythiourethane is a reaction product of a difunctional thiol compound, a trifunctional or higher functional thiol compound, and an isocyanate compound.

[0028] (Isocyanate compounds) The isocyanate compound may be a chain isocyanate compound or a cyclic isocyanate compound. Examples of the isocyanate compound include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, and aromatic aliphatic isocyanate compounds, and these compounds may be used alone or in combination. These isocyanate compounds may include dimers, trimers, prepolymers, etc. Examples of the isocyanate compound include the compounds exemplified in WO 2011 / 055540.

[0029] The isocyanate compound preferably includes a chain isocyanate compound and a cyclic isocyanate compound, and more preferably includes an aliphatic isocyanate compound and an aromatic isocyanate compound. This makes it easy to adjust, for example, the glass transition temperature Tg and the refractive index to within the desired range.

[0030] Among the above, the aliphatic isocyanate compound is preferably at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane.

[0031] Among the above, the aromatic isocyanate compound is preferably at least one selected from the group consisting of xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0032] (Thiol compounds) Examples of the thiol compound include a polythiol compound having two or more mercapto groups, a hydroxythiol compound having one or more mercapto groups and one or more hydroxyl groups, and the like, and these compounds are used alone or in combination. Examples of these thiol compounds include the compounds exemplified in WO 2016 / 125736.

[0033] (Bifunctional thiol compounds) Examples of bifunctional thiol compounds include methanedithiol, ethanedithiol, 1,3-propanedithiol, 1,2-ethanedithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl)ether, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptomethyl)sulfide, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters of thioglycolic acid and mercaptopropionic acid;

[0034] Bis(2-mercaptoethyl) sulfide, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl aliphatic polythiol compounds such as ethyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), and 4,6-bis(mercaptomethylthio)-1,3-dithiane;

[0035] aromatic polythiol compounds such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol;

[0036] Heterocyclic polythiol compounds such as 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane; and the like.

[0037] Among the above, the bifunctional thiol compound more preferably includes at least one selected from bis(mercaptoethyl) sulfide, 1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0038] (Trifunctional or higher thiol compounds) Examples of trifunctional or higher functional thiol compounds include 1,2,3-propane trithiol, tetrakis(mercaptomethyl)methane, trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptomethylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl) sulfide, and their thioglycolic acid esters and mercaptopropionic acid esters;

[0039] Aliphatic polythiol compounds such as 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane;

[0040] Aromatic polythiol compounds such as 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, and 1,3,5-tris(mercaptoethyleneoxy)benzene;

[0041] Heterocyclic polythiol compounds such as 2,4,6-trimercapto-s-triazine, 2,4,6-trimercapto-1,3,5-triazine, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane; and the like.

[0042] The tri- or higher functional thiol compound preferably includes at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.

[0043] As described above, the molecular weight between crosslink points can be adjusted, for example, by adjusting the content ratio of a bifunctional thiol compound and a tri- or higher functional thiol compound that may be used as raw materials for polythiourethane. In the first embodiment, the larger the thiol equivalent of the difunctional thiol compound in the polythiourethane, the larger the molecular weight between crosslinks. On the other hand, the larger the thiol equivalent of the trifunctional or higher functional thiol compound in the polythiourethane, the smaller the molecular weight between crosslinks.

[0044] For example, when a bifunctional thiol compound and a trifunctional or higher functional thiol compound are used as raw materials for polythiourethane, the bifunctional thiol compound preferably has a thiol equivalent of 20% to 95% relative to 100% of the total thiol equivalent of the bifunctional thiol compound and the trifunctional or higher functional thiol compound.

[0045] The bifunctional thiol compound has a thiol equivalent of 20% or more, relative to the total thiol equivalent of the bifunctional thiol compound and the trifunctional or higher thiol compound (100%), which allows for a larger molecular weight between crosslinking points. As a result, the film becomes moderately soft and has excellent conformability. From the above viewpoint, the bifunctional thiol compound preferably has a thiol equivalent of 30% or more, and even more preferably 35% or more, relative to 100% of the total thiol equivalent of the bifunctional thiol compound and the trifunctional or higher thiol compound.

[0046] The bifunctional thiol compound has a thiol equivalent of 95% or less, relative to the total thiol equivalent of the bifunctional thiol compound and the trifunctional or higher thiol compound (100%), thereby enabling the molecular weight between crosslinking points to be reduced. As a result, the film becomes moderately hard and has excellent solvent resistance. From the above viewpoint, the bifunctional thiol compound preferably has a thiol equivalent of 80% or less, and even more preferably 70% or less, relative to 100% of the total thiol equivalent of the bifunctional thiol compound and the trifunctional or higher thiol compound.

[0047] When the equivalent weight of all thiol compounds that polymerize with the isocyanate compound is taken as 1, the thiol equivalent weight of each thiol compound is calculated by multiplying the number of moles and the number of functional groups.

[0048] The equivalent ratio of the thiol group in the thiol compound to the isocyanato group in the isocyanate compound (thiol group / isocyanato group) is preferably 0.8 to 1.2, more preferably 0.85 to 1.15, and even more preferably 0.9 to 1.1. Within the above range, a polythiourethane suitable for use as an optical material, particularly as a plastic lens material for spectacles, can be obtained.

[0049] <Functional dyes> The polythiourethane film of the first embodiment preferably further contains a functional dye. Examples of functional dyes include dyes that cut off specific wavelengths (e.g., ultraviolet light, visible light, near-infrared light, infrared light, etc.), photochromic dyes (e.g., tetraazaporphyrin compounds, naphthopyran compounds, etc.), and infrared absorbing dyes.

[0050] (ultraviolet absorber) Specific examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, diphenylacrylate-based ultraviolet absorbers, phenol-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and oxanilide-based ultraviolet absorbers. More preferred embodiments of the ultraviolet absorber include malonic acid ester-based ultraviolet absorbers and oxanilide-based ultraviolet absorbers.

[0051] Specific examples of malonic acid ester-based ultraviolet absorbers include p-phenylenebis(methylenemalonic acid) tetraethyl ester, dimethyl p-methoxybenzylidenemalonate, and the like.

[0052] Examples of commercially available malonic acid ester-based ultraviolet absorbers include Hostavin PR-25 and Hostavin B-CAP (both manufactured by Clariant Chemicals).

[0053] Specific examples of oxanilide-based ultraviolet absorbers include 2-ethyl-2'-ethoxy-oxanilide and 2-isododecyl-2'-ethoxyoxanilide.

[0054] Examples of commercially available oxanilide-based ultraviolet absorbers include Hostavin VSU and Hostavin 3206 (both manufactured by Clariant Chemicals), and Tinuvin 312 (both manufactured by BASF).

[0055] (visible light absorbing pigment) The visible light absorbing dye may be a commercially available product, and is preferably an organic dye compound. Specific examples include porphyrin compounds and tetraazaporphyrin compounds. A more specific example is PD-311S (manufactured by Yamamoto Chemical Industry Co., Ltd.).

[0056] (near infrared absorbing dye) Examples of near-infrared absorbing dyes include cyanine compounds, phthalocyanine compounds, naphthoquinone compounds, azo compounds, and silver nanoplates.

[0057] (polarizing dye) Examples of polarizing dyes include anthraquinone-based dichroic dyes and azo-based dichroic dyes.

[0058] (photochromic dye) The photochromic dye is not particularly limited, and any one can be appropriately selected from conventionally known compounds capable of exhibiting photochromic properties. For example, one or more of pyran compounds, oxazine compounds, fulgide compounds, fulgimide compounds, bisimidazole compounds, etc. can be used depending on the desired photochromic properties and coloring.

[0059] The photochromic dye is preferably at least one compound selected from tetraazaporphyrin compounds, naphthopyran compounds, spiropyran compounds, spirooxazine compounds, fulgide compounds, and bisimidazole compounds.

[0060] Among photochromic dyes, compounds having at least one polymer chain selected from a polyalkyl group, a polyether group, a polyalkyleneoxy group, a polysiloxane group, a polycaprolactone group, a polycarbonate group, a polyester group, a poly(meth)acrylate group, a poly(thio)urethane group, and a polyepoxy group are preferred.

[0061] Photochromic dyes having polymer chains can be obtained by the methods described in, for example, WO 2009 / 146509, WO 2010 / 20770, WO 2012 / 149599, or WO 2012 / 162725.

[0062] Examples of photochromic dyes having polymer chains include the Reversacol series from Vivimed, and these can be used alone or in combination of two or more. As the photochromic dye having a polymer chain, it is preferable to use at least one selected from Reversacol Trent Blue, Reversacol Heath Green, Reversacol Chilli Red, Reversacol Wembley Grey, Reversacol Cayenne Red, Reversacol Peacock Blue, Reversacol Jalapeno Red, Reversacol Adriatic Blue, Reversacol Mendip Green, and Reversacol Marine Blue.

[0063] As the functional dye, commercially available products may be used, for example, specific wavelength cut dyes such as PD-311S (manufactured by Yamamoto Chemical Co., Ltd.); Plast Blue 8514 (anthraquinone dye, manufactured by Arimoto Chemical Industry Co., Ltd.), Plast Red 8320 (anthraquinone dye, manufactured by Arimoto Chemical Industry Co., Ltd.), Plast Yellow 8070 (methine dye, manufactured by Arimoto Chemical Industry Co., Ltd.), and the like.

[0064] The polythiourethane film of the first embodiment preferably has a thickness of 100 μm to 600 μm, more preferably 130 μm to 400 μm, even more preferably 150 μm to 300 μm, and particularly preferably 170 μm to 250 μm.

[0065] [Application] The polythiourethane film of the first embodiment can be used as eyeglass lenses, lamp covers, window films, and the like. Among the above, the polythiourethane film of the first embodiment is preferably used for eyeglass lenses.

[0066] <Manufacturing method of polythiourethane film> The polythiourethane film of the first embodiment can be produced by a conventional method. For example, the polythiourethane film of the first embodiment can be obtained using a polymerizable composition containing the above-mentioned components by a casting method (thin film coating-polymerization curing), a spin coating-polymerization curing method, a cast polymerization method, or the like.

[0067] The casting method and spin coating-polymerization and curing method are methods in which a viscosity-adjusted polymerizable composition is extruded through a die and cast onto a substrate, or a substrate carrying the polymerizable composition is rotated at high speed to form a thin film, and then polymerized and cured to obtain a film. The viscosity of the polymerizable composition when cast (coated) is appropriately selected depending on the coating method and its application. Casting polymerization is a method in which a polymerizable composition is injected between a pair of inorganic glass, metal, or resin plates sealed on all four sides and spaced 200 μm or less apart, and polymerized to obtain a film. The viscosity of the polymerizable composition during injection is appropriately selected depending on the injection method, curing process, etc. In the first embodiment, the obtained film may be annealed. Furthermore, the film may be formed by mixing fine particles such as metal oxides, fillers, etc. into the polymerizable composition.

[0068] <Eyeglass lens materials> The eyeglass lens material of the first embodiment includes the polythiourethane film of the first embodiment and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film.

[0069] <Polyurethane adhesive layer> The polyurethane adhesive layer is an adhesive layer containing polyurethane. The polyurethane adhesive layer preferably comprises a polycarbonate-based polyurethane containing anionic functional groups. The polyurethane can be used without any particular limitation. As the polyurethane, commercially available products may be used, or it may be produced from raw materials such as isocyanate and polyol. Specific examples of polyurethane that can be used include Takelac WS-5100 (manufactured by Mitsui Chemicals, Inc.) and Superflex 470 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0070] The eyeglass lens material preferably further includes a hard coat layer as the outermost layer. The eyeglass lens material may include, for example, a hard coat layer, the polythiourethane film of the first embodiment, and a polyurethane adhesive layer in this order, For example, it may include a hard coat layer, a polyurethane adhesive layer, the polythiourethane film of the first embodiment, and a polyurethane adhesive layer in this order.

[0071] The components of the hard coat layer can be selected appropriately. Examples of components of the hard coat layer include resins (e.g., urethane resins, thiourethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), hard coat agents (e.g., silane compounds), visible light absorbers, and infrared absorbers.

[0072] <Eyeglass lenses> The eyeglass lens of the first embodiment includes the eyeglass lens material of the first embodiment and an eyeglass lens substrate adhered to the polyurethane adhesive layer of the eyeglass lens material. The eyeglass lens of the first embodiment comprises the polythiourethane film of the first embodiment, a polyurethane adhesive layer adhered to at least one side of the polythiourethane film, and an eyeglass lens substrate adhered to the polyurethane adhesive layer.

[0073] <Eyeglass lens substrate> The eyeglass lens substrate is not particularly limited. The eyeglass lens substrate preferably contains at least one selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane, More preferably, the polymer contains at least one selected from the group consisting of polyepisulfide, polyurethane, and polythiourethane, It is more preferable that the material contains at least one selected from the group consisting of polyurethane and polythiourethane.

[0074] The polyepisulfide preferably comprises a constituent unit derived from an episulfide compound, or comprises a constituent unit derived from an episulfide compound and a constituent unit derived from a thiol compound. The polyurethane preferably comprises a structural unit derived from an isocyanate compound and a structural unit derived from a polyol compound. The polythiourethane preferably comprises a structural unit derived from an isocyanate compound and a structural unit derived from a thiol compound.

[0075] The method for producing the polyepisulfide may include a method using an episulfide compound alone or a method using an episulfide compound and a thiol compound. As a method for producing polyurethane, a method using an isocyanate compound and a polyol compound can be mentioned. As a method for producing polythiourethane, a method using the above-mentioned polyisocyanate compound and polythiol compound can be mentioned.

[0076] (episulfide compounds) Examples of the episulfide compound include epithioethylthio compounds, chain aliphatic 2,3-epithiopropylthio compounds, cyclic aliphatic 2,3-epithiopropylthio compounds, aromatic 2,3-epithiopropylthio compounds, chain aliphatic 2,3-epithiopropyloxy compounds, cyclic aliphatic 2,3-epithiopropyloxy compounds, and aromatic 2,3-epithiopropyloxy compounds, and these may be used alone or in combination of two or more. Examples of the episulfide compound include the compounds exemplified in WO2015 / 137401.

[0077] From the viewpoint of improving the solubility of the functional dye in the resin, the episulfide compound is preferably at least one selected from the group consisting of bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropyl) disulfide, bis(1,2-epithioethyl) sulfide, bis(1,2-epithioethyl) disulfide, and bis(2,3-epithiopropylthio)methane, and more preferably bis(2,3-epithiopropyl) disulfide.

[0078] (Thiol compounds) Specific examples, preferred specific examples, preferred aspects, etc. of the thiol compound are the same as the specific examples, preferred specific examples, preferred aspects, etc. described in the above section (Thiol compound).

[0079] (Isocyanate compounds) Specific examples, preferred specific examples, preferred aspects, etc. of the isocyanate compound are the same as the specific examples, preferred specific examples, preferred aspects, etc. described above in the section (Isocyanate compound).

[0080] (Polyol compound) The alcohol compound is one or more aliphatic or alicyclic alcohols. Specific examples include linear or branched aliphatic alcohols, alicyclic alcohols, and alcohols obtained by adding ethylene oxide, propylene oxide, or ε-caprolactone to these alcohols. Specific examples of the compounds that can be used include the compounds exemplified in WO2016 / 125736.

[0081] The polyol compound is preferably at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol.

[0082] In the eyeglass lens of the first embodiment, the convex or concave surface of the eyeglass lens substrate is preferably adhered to the polyurethane adhesive layer of the eyeglass lens material. The polythiourethane film of the first embodiment can be adhered to an eyeglass lens substrate via a polyurethane adhesive layer. Generally, the smaller the radius of curvature of the convex or concave curve, the sharper the lens curve, making it more difficult to adhere the polythiourethane film to the eyeglass lens substrate. The polythiourethane film of the first embodiment exhibits good adhesion even when applied to eyeglass lens substrates with a small radius of curvature. In the eyeglass lens of the first embodiment, the eyeglass lens substrate may have a small radius of curvature on the convex or concave surface.

[0083] For example, the radius of curvature of the spectacle lens substrate is preferably 62.5 mm to 125.0 mm, more preferably 70.0 mm to 100.0 mm, and even more preferably 75.0 mm to 90.0 mm. The polythiourethane film of the first embodiment can exhibit good curved surface conformability and adhesion even when applied to eyeglass lens substrates having a radius of curvature within the above range.

[0084] The eyeglass lens of the first embodiment may include two or more eyeglass lens materials.

[0085] <Coating layer> The spectacle lens of the first embodiment may include a coating layer. Specific examples of the coating layer include a hard coat layer, an anti-reflection layer, an anti-fogging coat layer, an anti-fouling layer, and a water-repellent layer. These coating layers can be used alone or in combination. When coating layers are applied to both sides, the same coating layer or different coating layers can be applied to each side.

[0086] In carrying out the coating treatment, a treatment using a solvent may be carried out before applying the coating composition to the film. Examples of such treatments include wiping the surface of the lens to be coated with the coating composition with an organic solvent, etching the surface with an alkaline aqueous solution, and immersing the lens in a coating solution containing a solvent. In this case, if the film has poor solvent resistance, the film will be damaged by the solvent, making it impossible to properly laminate the coating layer. The polythiourethane film of the first embodiment has excellent solvent resistance, and therefore, even when treated with a solvent such as an organic solvent or an alkaline aqueous solution, a coating layer can be laminated satisfactorily. As a result, in the eyeglass lens of the first embodiment, a coating layer can be laminated directly onto the polythiourethane film of the first embodiment without any other layer therebetween.

[0087] (Hard coat layer) The eyeglass lens of the first embodiment preferably includes a hard coat layer. The hard coat layer is a coating layer intended to impart functions such as scratch resistance, abrasion resistance, humidity resistance, warm water resistance, heat resistance, and weather resistance to the lens surface. For forming the hard coat layer, a hard coat composition containing a curable organosilicon compound and one or more oxide fine particles containing an element selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti may be used; A hard coat composition may be used which contains a curable organosilicon compound and one or more fine particles of a composite oxide containing two or more elements selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti.

[0088] In addition to the above components, the hard coat composition preferably contains at least one selected from the group consisting of amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, acids, metal chlorides, and polyfunctional epoxy compounds. The hard coat composition may contain a solvent that does not affect the lens substrate, or may be solvent-free.

[0089] The hard coat layer is usually formed by applying a hard coat composition using a known application method such as spin coating or dip coating, followed by curing. Examples of curing methods include irradiation with energy rays such as ultraviolet light or visible light, and thermal curing. From the viewpoint of suppressing the occurrence of interference fringes, the refractive index of the hard coat layer preferably differs from that of the lens substrate by ±0.1. When forming the hard coat layer, the hard coat composition can be applied to the surface of the polythiourethane film using a bar coater, blade coater, or the like, cured, and then attached to the lens substrate. Alternatively, the polythiourethane film may be attached to the lens substrate in advance, and then the hard coat composition may be applied thereto using spin coating, dip coating, or the like.

[0090] (Anti-reflection layer) The spectacle lens of the first embodiment preferably includes an anti-reflection layer. Anti-reflection layers include inorganic and organic types. The inorganic anti-reflection layer is formed using inorganic oxides such as SiO2 and TiO2 by a dry method such as vacuum deposition, sputtering, ion plating, ion beam assist, or CVD. The organic anti-reflection layer is formed by a wet process using a composition containing an organosilicon compound and silica-based fine particles having internal cavities. An anti-reflection layer may be formed on the hard coat layer, if necessary.

[0091] The anti-reflection layer may be a multi-layer or a single layer. To effectively exhibit the antireflection function, the antireflection layer is preferably multi-layered, and in this case, it is preferable that low-refractive index layers and high-refractive index layers are alternately laminated. Furthermore, it is preferable that the difference in refractive index between the low-refractive index layers and the high-refractive index layers is 0.1 or more. Examples of high refractive index layers include layers of ZnO, TiO2, CeO2, Sb2O5, SnO2, ZrO2, and Ta2O5, and examples of low refractive index layers include layers of SiO2. When used as a single layer, it is preferable that the refractive index is at least 0.1 or more lower than the refractive index of the hard coat layer.

[0092] On the antireflection layer, an antifogging coating layer, an antifouling layer, a water-repellent layer, etc. may be formed as needed. The method for forming the antifogging layer, the antifouling layer, the water-repellent layer, etc. is not particularly limited, and a conventionally known method can be applied.

[0093] The eyeglass lens of the first embodiment preferably includes a hard coat layer or an anti-reflection layer. Specifically, for example, the eyeglass lens of the first embodiment includes a hard coat layer or an antireflection layer, and it is preferable that at least a portion of the hard coat layer or the antireflection layer be in contact with the polythiourethane film.

[0094] <<Method of manufacturing eyeglass lenses>> The method for manufacturing the eyeglass lens of the first embodiment is a method for manufacturing the eyeglass lens of the first embodiment. The method for manufacturing a spectacle lens of the first embodiment includes a step (also referred to as a bonding step) of attaching the spectacle lens material of the first embodiment to a spectacle lens substrate to obtain a spectacle lens.

[0095] The method for manufacturing a spectacle lens of the first embodiment preferably includes a step of attaching the spectacle lens material to a spectacle lens substrate using a vacuum / compressed air molding machine to obtain a spectacle lens.

[0096] The method for manufacturing the eyeglass lens of the first embodiment more preferably includes the step of heating the eyeglass lens material of the first embodiment to a surface temperature of 80°C to 150°C, and bonding the polyurethane adhesive layer of the eyeglass lens material to the eyeglass lens substrate under a reduced pressure of 10 kPa or less.

[0097] <Pasting process> The bonding step is preferably a step of heating the eyeglass lens material of the first embodiment so that the surface temperature is 80°C to 150°C, and bonding the polyurethane adhesive layer of the eyeglass lens material to the eyeglass lens substrate under a reduced pressure of 10 kPa or less. The bonding step will be specifically described below.

[0098] [Attachment using a vacuum / compressed air molding machine] The bonding step is preferably carried out using a vacuum / compressed air forming machine. The bonding using a vacuum / compressed air forming machine will be described with reference to FIG. FIG. 1 is a diagram for explaining lamination using a vacuum and pressure forming machine. First, the substrate 3 is placed on the lower substrate stage. The film 2 is placed on the film stage. At this time, the film 2 is placed so that the adhesive layer faces the substrate side. Next, the film 2 is heated to a predetermined temperature using the heater 1. The pressure in the upper film chamber and the lower mold chamber is reduced, and the lower mold chamber is placed in a vacuum state 4. After the film 2 is heated to a predetermined temperature, the pressure on the upper film chamber side is returned to normal pressure to apply pressure to the film 2. Thereafter, the substrate stage is raised (stage lift 5), and the pressure in the lower mold chamber is continuously reduced while the substrate 3 is struck against the film 2. Compressed air 6 is also sent into the upper film chamber to pressurize it. This state is maintained for 3 to 30 seconds. Next, the upper film chamber and the lower mold chamber are returned to normal pressure, and the substrate (i.e., lens) with the film attached thereto is removed. Any unnecessary parts of the film are trimmed 7, and the film is further heated to complete the application. Examples of vacuum and compressed air molding machines include the NGF series (manufactured by Fuse Vacuum Co., Ltd.) and the TFH series (manufactured by Asano Laboratory Co., Ltd.).

[0099] As a manufacturing method for the eyeglass lens of the first embodiment, the manufacturing method described in Japanese Patent No. 5417452 can be appropriately referred to and incorporated.

[0100] The first embodiment also includes the following embodiments. <1A> A polythiourethane film containing polythiourethane having a molecular weight between crosslinking points of 950 to 3,000. <2A> The polythiourethane film according to <1A>, wherein the polythiourethane is a reaction product of a bifunctional thiol compound, a tri- or higher functional thiol compound, and an isocyanate compound. <3A> The polythiourethane film according to <1A> or <2A>, wherein the bifunctional thiol compound has a thiol equivalent of 20% to 95% relative to 100% of the total thiol equivalent of the bifunctional thiol compound and the tri- or higher functional thiol compound. <4A> The polythiourethane film according to any one of <1A> to <3A>, further comprising a functional dye. <5A> The minimum storage modulus is between 30°C and 160°C, and the minimum storage modulus is 3.00 x 10 6 Pa~1.40×10 7 The polythiourethane film according to any one of <1A> to <4A>, wherein Pa. <6A> The poly(A) thiourethane film according to any one of <1A> to <5A>, which has a thickness of 100 μm to 600 μm. <7> A material for eyeglass lenses, comprising the polythiourethane film according to any one of <1A> to <6A> and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film. <8A> A spectacle lens comprising the spectacle lens material according to <7A> and a spectacle lens substrate adhered to the polyurethane adhesive layer of the spectacle lens material. <9A> The eyeglass lens according to <8A>, wherein the eyeglass lens substrate has a convex surface or a concave surface bonded to the polyurethane adhesive layer of the eyeglass lens material. <10A> The eyeglass lens according to <8A> or <9A>, wherein the eyeglass lens substrate has a radius of curvature of 62.5 mm to 125.0 mm. <11A> The eyeglass lens according to any one of <8A> to <10A>, which comprises two or more of the eyeglass lens materials. <12A> The eyeglass lens according to any one of <8A> to <11A>, wherein the eyeglass lens substrate contains at least one material selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane. <13A> The eyeglass lens according to any one of <8A> to <12A>, which comprises a hard coat layer or an antireflection layer, and at least a portion of the hard coat layer or the antireflection layer is in contact with the polythiourethane film.

[0101] (Second embodiment) <<Method of manufacturing eyeglass lenses>> The method for producing a spectacle lens of the second embodiment includes the steps of: forming a polycarbonate-based polyurethane adhesive layer made of a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one surface of a functional resin layer containing a functional dye to obtain a laminate (also referred to as a laminate production step in the second embodiment); a step of heating the laminate at 50°C to 150°C and attaching the laminate to a lens substrate under a reduced pressure of 20 kPa or less, with the polycarbonate-based polyurethane adhesive layer and the lens substrate facing each other, to obtain a spectacle lens (also referred to as a spectacle lens manufacturing step in the second embodiment); Including, The dried polyurethane aqueous dispersion has a storage modulus of 0.1 MPa to 80 MPa at 80° C. as measured under the following condition 1. [Condition 1] The storage modulus at 80°C is measured using a test piece made of a dried polyurethane aqueous dispersion, 3 cm long, 5 mm wide, and 500 μm thick, with a dynamic viscoelasticity measuring device, under conditions of strain control and tension at a frequency of 1 Hz, by raising the temperature from -102°C to 80°C at a rate of 3°C / min.

[0102] A known configuration of a functional lens is one in which a functional resin layer (for example, a film) containing a functional dye such as a photochromic compound is attached to a lens substrate. In a functional lens having the above configuration, the film is required to conform to the shape of the lens substrate. For example, when bonding the film to the lens substrate via an adhesive layer, the film including the adhesive layer may be heated and expanded. In such cases, the adhesive layer is required to expand and conform to the shape of the lens substrate, just like the film, and to adhere closely to the lens substrate. Furthermore, the functional lens having the above-described structure is also required to have alkali resistance. In the functional lens having the above-mentioned configuration, it is considered that a layer such as a hard coat layer is laminated on the film. In this case, treatment with an organic solvent, an alkaline aqueous solution, or the like is often carried out, and the adhesive layer is often damaged by the alkaline aqueous solution.

[0103] The second embodiment of the present disclosure can provide a method for producing a spectacle lens, a laminate, and a spectacle lens that can produce a spectacle lens including a polycarbonate-based polyurethane adhesive layer that has excellent adhesion to the lens substrate and excellent alkali resistance.

[0104] <Laminate manufacturing process> The laminate manufacturing process in the second embodiment is a process for obtaining a laminate by forming a polycarbonate-based polyurethane adhesive layer consisting of a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one side of a functional resin layer containing a functional dye.

[0105] In the method for manufacturing a spectacle lens of the second embodiment, the laminate is obtained by forming a polycarbonate-based polyurethane adhesive layer made of a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one side of a functional resin layer containing a functional dye. In the method for manufacturing a spectacle lens of the second embodiment, the laminate may include a functional resin layer containing a functional dye, and a polycarbonate-based polyurethane adhesive layer laminated on at least one side of the functional resin layer.

[0106] Before applying the aqueous polyurethane dispersion to the functional resin layer, the surface of the functional resin layer to which the aqueous polyurethane dispersion is to be applied may be subjected to a pretreatment. The pretreatment method is not particularly limited and may be appropriately selected from the viewpoint of, for example, adhesion. Examples of the pretreatment method include etching with an alkaline aqueous solution, etching with an alkaline surfactant aqueous solution, cleaning with a surfactant aqueous solution, cleaning with pure water, etching with UV ozone, etching with plasma, etching with corona discharge, polishing using fine particles, and grinding. When etching is performed using pure water or an aqueous solution, the chemical treatment can be performed more effectively by combining heating, ultrasonic irradiation, or the like. Among the above methods, etching by plasma or corona discharge is preferred as the pretreatment method.

[0107] The method for applying the aqueous polyurethane dispersion is not particularly limited, and any known application method can be used. For example, the aqueous polyurethane dispersion may be applied by spin coating, dip coating, die coating, spray coating, curtain (flow) coating, bar coating, or roll coating using a knife coater or gravure coater.

[0108] The temperature at which the aqueous polyurethane dispersion is dried is preferably 40°C to 130°C, more preferably 45°C to 110°C, and even more preferably 50°C to 100°C.

[0109] [Functional resin layer] The functional resin layer contains a functional dye. The functional resin layer contains a functional dye, and thereby has functions such as cutting off specific wavelengths (for example, ultraviolet light, visible light, near infrared light, etc.), photochromism, and polarization properties.

[0110] The thickness of the functional resin layer is preferably 10 μm to 700 μm, more preferably 13 μm to 600 μm, further preferably 15 μm to 400 μm, and particularly preferably 20 μm to 300 μm.

[0111] (functional dyes) Examples of functional dyes include dyes that cut off specific wavelengths (such as ultraviolet light, visible light, and near-infrared light), photochromic dyes (such as naphthopyran compounds), and dichroic dyes. The functional dye preferably contains at least one selected from the group consisting of an ultraviolet absorber, a visible light absorbing dye, a photochromic dye, and a dichroic dye.

[0112] (ultraviolet absorber) The ultraviolet absorber may be a dye that absorbs only ultraviolet light, or may be a dye that absorbs ultraviolet light and blue light (so-called blue light). Specific examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, diphenylacrylate-based ultraviolet absorbers, phenol-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and oxanilide-based ultraviolet absorbers. Among the above, the ultraviolet absorber preferably contains at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers.

[0113] Specific examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole and 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole. Commercially available benzotriazole-based ultraviolet absorbers include the VIOSORB series (Kyodo Pharmaceutical Co., Ltd.), the Tinuvin series (BASF), and the SEESORB series (Shipro Kasei Co., Ltd.).

[0114] Specific examples of triazine-based ultraviolet absorbers include 2-(4-phenoxy-2-hydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, etc. Commercially available triazine-based ultraviolet absorbers include the Tinuvin series (manufactured by BASF), the Adeka Stab series (manufactured by ADEKA Corporation), and the EVERSORB series (manufactured by EVER LIGHT).

[0115] Specific examples of benzophenone-based ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. Commercially available benzophenone-based ultraviolet absorbers include the Tinuvin series (manufactured by BASF), the SEESORB series (manufactured by Shipro Kasei Co., Ltd.), and the EVERSORB series (manufactured by EVER LIGHT).

[0116] Specific examples of malonic acid ester-based ultraviolet absorbers include p-phenylenebis(methylenemalonic acid) tetraethyl ester, dimethyl p-methoxybenzylidenemalonate, and the like.

[0117] Examples of commercially available malonic acid ester-based ultraviolet absorbers include Hostavin PR-25 and Hostavin B-CAP (both manufactured by Clariant Chemicals Co., Ltd.).

[0118] Specific examples of oxanilide-based ultraviolet absorbers include 2-ethyl-2'-ethoxy-oxanilide and 2-isododecyl-2'-ethoxyoxanilide.

[0119] Examples of commercially available oxanilide-based ultraviolet absorbers include those under the trade names Hostavin VSU and Hostavin 3206 (both manufactured by Clariant Chemicals Co., Ltd.), and Tinuvin 312 (both manufactured by BASF).

[0120] (visible light absorbing pigment) Examples of visible light absorbing dyes include porphyrin dyes, tetraazaporphyrin dyes, phthalocyanine dyes, merocyanine dyes, anthraquinone dyes, methine dyes, and azo dyes. As the visible light absorbing dye, porphyrin dyes, tetraazaporphyrin dyes, phthalocyanine dyes and anthraquinone dyes are preferred. The visible light absorbing dyes may be used alone or in combination of two or more.

[0121] Commercially available porphyrin dyes include UVY-0026 (manufactured by Yamamoto Chemical Industry Co., Ltd., maximum absorption wavelength: 449 nm) and UVY-1023 (manufactured by Yamamoto Chemical Industry Co., Ltd., maximum absorption wavelength: 479 nm). An example of a commercially available tetraazaporphyrin dye is PD-311S (manufactured by Yamamoto Chemical Industry Co., Ltd., maximum absorption wavelength: 585 nm). Commercially available anthraquinone dyes include the Plast Color series (manufactured by Arimoto Chemical Industry Co., Ltd.). Commercially available methine dyes include the Plast Color series (manufactured by Arimoto Chemical Industry Co., Ltd.).

[0122] (near infrared absorbing dye) Examples of near-infrared absorbing dyes include phthalocyanine dyes, squarylium dyes, diimonium dyes, dithiolene complex dyes, and cyanine dyes.

[0123] (photochromic dye) The photochromic dye is not particularly limited, and any one can be appropriately selected from conventionally known compounds capable of exhibiting photochromic properties. For example, one or more of pyran compounds, oxazine compounds, fulgide compounds, fulgimide compounds, bisimidazole compounds, etc. can be used depending on the desired photochromic properties and coloring.

[0124] The photochromic dye is preferably at least one compound selected from spiropyran compounds, spirooxazine compounds, fulgide compounds, and bisimidazole compounds.

[0125] Among photochromic dyes, compounds having at least one polymer chain selected from a polyalkyl group, a polyether group, a polyalkyleneoxy group, a polysiloxane group, a polycaprolactone group, a polycarbonate group, a polyester group, a poly(meth)acrylate group, a poly(thio)urethane group, and a polyepoxy group are preferred.

[0126] Photochromic dyes having polymer chains can be obtained by the methods described in, for example, WO 2009 / 146509, WO 2010 / 20770, WO 2012 / 149599, or WO 2012 / 162725.

[0127] Examples of photochromic dyes having polymer chains include the Reversacol series from Vivimed, and these can be used alone or in combination of two or more. As the photochromic dye having a polymer chain, it is preferable to use at least one selected from Reversacol Trent Blue, Reversacol Heath Green, Reversacol Chilli Red, Reversacol Wembley Grey, Reversacol Cayenne Red, Reversacol Peacock Blue, Reversacol Jalapeno Red, Reversacol Adriatic Blue, Reversacol Mendip Green, and Reversacol Marine Blue.

[0128] (dichroic dye) Examples of dichroic dyes include iodine, azo dyes, anthraquinone dyes, and dioxazine dyes.

[0129] (resin) The functional resin layer may contain a resin as a substrate. Examples of the resin include thermoplastic resin and thermosetting resin.

[0130] (thermoplastic resin) The thermoplastic resin is not particularly limited, but examples thereof include polyacrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyurethane, and the like.

[0131] Among the above, polyacrylate, polyethylene terephthalate, and polyacetyl cellulose are preferred as the thermoplastic resin.

[0132] The softening temperature of the thermoplastic resin is preferably 50°C to 150°C, more preferably 55°C to 140°C, and even more preferably 60°C to 130°C. For example, the functional resin layer may contain a thermoplastic resin having a softening temperature of 50°C to 150°C. The softening temperature is determined as the temperature at which the tan δ curve shows a maximum value in measurement using a dynamic viscoelasticity measuring device.

[0133] (thermosetting resin) The thermosetting resin is not particularly limited, but preferably contains at least one selected from the group consisting of polyepoxy, polyepisulfide, and poly(thio)urethane.

[0134] The functional resin layer may be a commercially available product, or may be produced by curing a polymerizable composition. Commercially available products include, for example, the Acriplene series (polyacrylate, manufactured by Mitsubishi Chemical Corporation).

[0135] The functional resin layer may be a single layer or multiple layers. When the functional resin layer is a multilayer, it may be made of a single resin type or multiple resin types. Furthermore, when the functional resin layer is a multilayer, it may be bonded together with an adhesive or the like.

[0136] The functional resin layer can be produced by a conventional method. For example, the functional resin layer can be obtained using the above-mentioned components by a casting method (thin film coating-solvent evaporation), a casting method (extrusion molding-cooling), a stretching method, a thin film coating-polymerization curing method, a cast polymerization method, or the like. As a method for incorporating a functional dye into a functional resin layer, the functional dye may be added to a resin in advance to form a functional resin layer, or the functional resin layer may be formed by providing a dye to the resin layer after the resin layer is obtained by solvent dyeing, sublimation dyeing, coating, or the like.

[0137] The casting (thin film coating-solvent evaporation) method involves pouring a solution of resin in a solvent into a sheet, and then evaporating the solvent to obtain a film. The casting (extrusion molding-cooling) method is a method in which molten resin is extruded into a film shape through a T-die attached to the tip of an extruder, and then cooled with a cooling roll to obtain a film. The stretching method is a method in which molten resin is extruded into a film shape through a T-die attached to the tip of an extruder, and then stretched to obtain a film. The thin film coating-polymerization curing method is a method in which a polymerizable composition coated in the form of a thin film is polymerized and cured to obtain a film. The polymerization and curing is carried out by irradiation with ultraviolet light or heating. The substrate on which the thin film is coated may be a release film. In the cast polymerization method, a polymerizable composition is cast into a cavity formed by a plate-like mold and a spacer, and after the polymerizable composition is polymerized and cured, it is released from the mold to obtain a film. Polymerization and curing are carried out by irradiation with ultraviolet light or heating. In addition, in the second embodiment, the obtained film may be subjected to an annealing treatment. Furthermore, the functional resin layer may contain fine particles such as metal oxides, fillers, and the like.

[0138] <Functional resin layer manufacturing process> The method for manufacturing the eyeglass lens of the second embodiment preferably includes a functional resin layer manufacturing step before the laminate manufacturing step. The functional resin layer manufacturing process in the second embodiment is carried out before the process of obtaining the laminate, and is a process of applying a polymerizable composition containing a functional dye to a release film and then curing it to obtain a functional resin layer.

[0139] Specifically, the functional resin layer manufacturing step may be carried out, for example, by the following method. A polymerizable composition containing a functional dye is applied to a release film, and then the composition is cured by heat or light to form a functional resin layer. The method for applying the polymerizable composition to the release film can be any known application method without any particular limitation, for example, spin coating, dip coating, die coating, spray coating, curtain (flow) coating, bar coating, or roll coating using a knife coater or gravure coater. When photocuring the polymerizable composition, it is desirable to use light containing light with a wavelength of 200 nm to 450 nm.

[0140] When photocuring the polymerizable composition, light sources such as sunlight, chemical lamps, mercury lamps, metal halide lamps, UV LEDs, etc. may be used. If necessary, a specific wavelength cut filter, a heat ray cut filter, or a wavelength cut filter that suppresses ozone generation may be used, or the coating agent may be cooled or heated during ultraviolet irradiation.

[0141] An example of ultraviolet irradiation conditions is an irradiation intensity of 0.1 mW / cm 2 ~1,000mW / cm 2 , the cumulative light intensity is 10 mJ / cm 2 ~5,000mJ / cm 2 The irradiation time may be 0.1 seconds to 500 seconds.

[0142] When the polymerizable composition is thermally cured, it may be heated at a constant temperature, or may be heated and cooled by combining heating, temperature increase, cooling, and temperature decrease to a predetermined temperature for a predetermined time using a temperature controller or polymerization furnace capable of temperature control based on a temperature program. Heating may be performed at a temperature of 10°C to 300°C for 0.1 to 80 hours.

[0143] Examples of materials for the release film include polyolefins such as polyethylene terephthalate and polypropylene, and polycarbonates. The thickness of the release film is preferably 10 μm to 250 μm, more preferably 15 μm to 200 μm, and even more preferably 20 μm to 150 μm.

[0144] [Polycarbonate-based polyurethane adhesive layer] The polycarbonate-based polyurethane adhesive layer is a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group. That is, the polycarbonate-based polyurethane adhesive layer contains a polycarbonate-based polyurethane having an anionic functional group. The polycarbonate-based polyurethane adhesive layer may further contain additives such as inorganic nanoparticles, leveling agents, ultraviolet absorbers, silane coupling agents, and plasticizers. The content of the additive may be 30% by mass or less, and preferably 20% by mass or less, based on the total mass of the polycarbonate-based polyurethane adhesive layer.

[0145] [Mass increase rate in hot water resistance test] The polycarbonate-based polyurethane adhesive layer preferably has a mass increase rate of 1% to 50% in a hot water resistance test measured under the following condition 3. [Condition 3] A test piece made of a dried aqueous polyurethane dispersion containing polycarbonate-based polyurethane, measuring 4 cm in length, 2 cm in width, and 500 μm in thickness, is immersed in hot water at 40°C for 24 hours, and the mass of the test piece is measured before and after immersion. The mass increase rate in the hot water resistance test is calculated using the mass of the test piece before and after immersion using the following formula. Mass increase rate = ((mass of test piece after immersion - mass of test piece before immersion) / (mass of test piece before immersion)) x 100 The mass increase rate is expressed in %.

[0146] The mass increase rate in the hot water resistance test is 50% or less, which means that the material has excellent alkali resistance. From the above viewpoint, the mass increase rate in the hot water resistance test is more preferably 40% or less, and even more preferably 20% or less. A mass increase rate of 1% or more in a hot water resistance test provides excellent adhesion to the lens substrate. From the above viewpoint, the mass increase rate in the hot water resistance test is more preferably 3% or more, and even more preferably 5% or more.

[0147] The mass increase rate in the hot water resistance test is measured, for example, by the following method. The aqueous polyurethane dispersion is applied to a PET film and heated and dried in an electric oven set at 80°C to obtain a dried aqueous polyurethane dispersion. Heat drying is continued until the mass change of the dried aqueous polyurethane dispersion is less than 1% per hour. The initial mass of a test piece (500 μm thick, 4 cm long, 2 cm wide) of the dried aqueous polyurethane dispersion peeled from the PET film is measured. The resulting test piece is then immersed in 40°C warm water for 24 hours, after which its mass is measured. The mass gain is calculated as ((mass of test piece after immersion - mass of test piece before immersion) / (mass of test piece before immersion)) × 100.

[0148] The polycarbonate-based polyurethane adhesive layer preferably has a thickness of 1 μm to 100 μm, more preferably 2 μm to 70 μm, even more preferably 3 μm to 50 μm, and particularly preferably 4 μm to 20 μm.

[0149] (Polyurethane aqueous dispersion) The aqueous polyurethane dispersion contains a polycarbonate-based polyurethane having an anionic functional group and water. The aqueous polyurethane dispersion may further contain inorganic nanoparticles, a leveling agent, an ultraviolet absorber, a silane coupling agent, a plasticizer, a solvent, and the like.

[0150] (Polycarbonate-based polyurethane) The polycarbonate-based polyurethane has anionic functional groups. Examples of the anionic functional group include a carboxy group, a sulfonic acid group, a phosphate group, and a group containing a betaine structure such as sulfobetaine. Of the above, the anionic functional group preferably contains a carboxy group. The polycarbonate-based polyurethane preferably contains a non-yellowing isocyanate as a constituent raw material of the urethane. The non-yellowing isocyanate is an isocyanate that does not have an aromatic skeleton, and preferably has an aliphatic skeleton or an alicyclic skeleton. Polycarbonate-based polyurethanes contain non-yellowing isocyanates, which can prevent yellowing when heated and have excellent light resistance.

[0151] [Storage modulus] The dried polyurethane aqueous dispersion has a storage modulus of 0.1 MPa to 80 MPa at 80° C. as measured under the following condition 1. [Condition 1] The storage modulus at 80°C is measured using a test piece made of a dried polyurethane aqueous dispersion, 3 cm long, 5 mm wide, and 500 μm thick, with a dynamic viscoelasticity measuring device, at a frequency of 1 Hz, under strain-controlled tensile conditions, by raising the temperature from -102°C to 80°C at a rate of 3°C / min.

[0152] When the storage modulus is 0.1 MPa or more, the dried product of the aqueous polyurethane dispersion can be prevented from becoming too liquid, resulting in excellent adhesion. From the above viewpoint, the storage modulus is preferably 0.5 MPa or more, more preferably 0.7 MPa or more, and even more preferably 1.0 MPa or more.

[0153] When the storage modulus is 80 MPa or less, the dried product of the aqueous polyurethane dispersion can be prevented from becoming excessively solid, resulting in excellent adhesion. From the above viewpoint, the storage modulus is preferably 70 MPa or less, more preferably 50 MPa or less, and even more preferably 30 MPa or less.

[0154] (Measurement of storage modulus) The viscoelasticity of the dried polyurethane aqueous dispersion is measured using a dynamic viscoelasticity measuring device (for example, DMA8000 manufactured by PerkinElmer). The aqueous polyurethane dispersion was applied to a PET film and then heated and dried in an electric oven set at 80°C to obtain a dried aqueous polyurethane dispersion. Heat drying was continued until the mass change of the dried aqueous polyurethane dispersion was less than 1% per hour. A test piece (3 cm x 5 mm, 500 μm thick) was prepared from the dried aqueous polyurethane dispersion peeled from the PET film. A dried polyurethane aqueous dispersion specimen measuring 3 cm x 5 mm and 500 μm thick is prepared and measured under tensile conditions at a frequency of 1.0 Hz, strain control, and a heating rate of 3°C / min from -102°C to 80°C. The test piece made of the dried product of the aqueous polyurethane dispersion may be produced, for example, from the aqueous polyurethane dispersion. Furthermore, the test piece made of the dried product of the polyurethane aqueous dispersion may contain, in addition to the polycarbonate-based polyurethane, additives such as inorganic nanoparticles, leveling agents, ultraviolet absorbers, silane coupling agents, plasticizers, etc. The content of the additives may be 30% by mass or less, and preferably 20% by mass or less, based on the total mass of the polycarbonate-based polyurethane adhesive layer.

[0155] [Outflow start temperature] The dried product of the aqueous polyurethane dispersion preferably has an outflow starting temperature of 160°C to 220°C as measured under the following condition 2. [Condition 2] The outflow start temperature was measured using a flow tester. A test vessel containing a 1mm inner diameter and 1mm long orifice was placed in the test vessel, and a load of 10kgf / cm was applied. 2 Under the above conditions, the temperature is increased at a rate of 3°C / min until the temperature reaches a point where the dried polyurethane aqueous dispersion begins to flow out of the orifice. The unit of the outflow start temperature is °C.

[0156] The flow onset temperature tends to depend on the flow characteristics of the polymer when heated. With an outflow start temperature of 160°C or higher, it has excellent heat resistance. From the above viewpoint, it is more preferable that the outflow starting temperature is 165°C or higher. By keeping the flow start temperature at 220°C or less, excellent adhesion to the lens substrate is achieved. From the above viewpoint, the outflow starting temperature is more preferably 210°C or lower, and even more preferably 200°C or lower.

[0157] The outflow starting temperature is measured, for example, by the following method. The polyurethane aqueous dispersion is applied to a PET film and heated and dried in an electric furnace set at 80°C to obtain a dried polyurethane aqueous dispersion. Heat drying is continued until the mass change of the dried polyurethane aqueous dispersion is less than 1% per hour. The dried polyurethane aqueous dispersion peeled from the PET film is placed in a test container containing an orifice (inner diameter 1 mm, length 1 mm) at the end, and a load of 10 kgf / cm is applied using a flow tester CFT-500D manufactured by Shimadzu Corporation. 2 Under the conditions, the temperature is increased at a rate of 3°C / min, and the temperature (°C) is measured when the dried polyurethane aqueous dispersion begins to flow out of the orifice.

[0158] The dried polyurethane aqueous dispersion preferably has a glass transition temperature of -45°C to 0°C. When the glass transition temperature is −45° C. or higher, the dried product of the polyurethane aqueous dispersion has excellent heat resistance. From the above viewpoint, the glass transition temperature is more preferably −35° C. or higher, further preferably −25° C. or higher, and particularly preferably −20° C. or higher.

[0159] When the glass transition temperature is 0°C or lower, the dried product of the polyurethane aqueous dispersion has excellent adhesion. From the above viewpoint, the glass transition temperature is more preferably −3° C. or lower, and even more preferably −5° C. or lower.

[0160] The glass transition temperature is measured using a dynamic viscoelasticity measuring device (for example, DMA 8000 manufactured by PerkinElmer). Specifically, the aqueous polyurethane dispersion is applied to a PET film and then heated and dried in an electric oven set at 80°C to obtain a dried aqueous polyurethane dispersion. The heated drying is carried out until the mass loss of the dried aqueous polyurethane dispersion per hour is less than 1%. The polycarbonate-based polyurethane is peeled from the PET film, and the glass transition temperature of the dried polyurethane aqueous dispersion is measured using a dynamic viscoelasticity measuring device (PerkinElmer, DMA 8000). The glass transition temperature is determined as the temperature at which the tan δ graph shows a maximum value. If multiple temperatures show maximum values, the lowest temperature is determined as the glass transition temperature.

[0161] The polycarbonate polyurethane is not particularly limited as long as it has an anionic functional group. The polycarbonate-based polyurethane may be a commercially available product or may be produced by synthesis from raw materials. Commercially available aqueous polyurethane dispersions include, for example, Superflex 470 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Evaphanol HA-170 (manufactured by Nicca Chemical Co., Ltd.), Takelac series (manufactured by Mitsui Chemicals, Inc.), and Hydran series (manufactured by DIC Corporation). Preferred commercially available products are Superflex 470 and Evaphanol HA-170.

[0162] The content of the polycarbonate-based polyurethane having an anionic functional group is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 45% by mass, and even more preferably 20% by mass to 40% by mass, relative to the total mass of the aqueous polyurethane dispersion. From the viewpoint of improving the transparency of the adhesive layer, the particle size of the polyurethane particles contained in the aqueous polyurethane dispersion is preferably 5 nm to 100 nm, more preferably 10 nm to 80 nm, and even more preferably 15 nm to 50 nm. The particle size of the polyurethane particles contained in the aqueous polyurethane dispersion is measured by a dynamic light scattering method.

[0163] (water) The aqueous polyurethane dispersion contains water. The water content is not particularly limited, and is, for example, preferably 40% by mass to 90% by mass, more preferably 50% by mass to 75% by mass, and even more preferably 60% by mass to 80% by mass, relative to the total mass of the aqueous polyurethane dispersion.

[0164] <Eyeglass lens manufacturing process> The eyeglass lens manufacturing process in the second embodiment is a process in which the laminate is heated to 50°C to 150°C and attached to a lens substrate under a reduced pressure of 20 kPa or less, with the polycarbonate-based polyurethane adhesive layer and the lens substrate in contact with each other, to obtain an eyeglass lens.

[0165] The eyeglass lens manufacturing process will be specifically described below.

[0166] The eyeglass lens manufacturing process is preferably carried out by attaching the laminate to the lens substrate using a vacuum molding machine, a pressure molding machine, or a vacuum / pressure molding machine. The laminate may be heated using an infrared heater, a ceramic heater, hot air, water vapor, or the like. When attaching the laminate to the lens substrate, air, compressed air, a silicone pad, a rubber pad, or the like may be used.

[0167] [Attached using a vacuum / compressed air molding machine] For example, the bonding of a polycarbonate-based polyurethane adhesive layer to a lens substrate using a vacuum / compressed air molding machine will be described with reference to FIG. FIG. 1 is a diagram for explaining the application using a vacuum / compressed air forming machine. First, the substrate 3 is placed on the lower substrate stage. The film 2 is placed on the film stage. At this time, the film 2 is placed so that the adhesive layer faces the substrate side. Next, the film 2 is heated to a predetermined temperature using the heater 1. The pressure in the upper film chamber and the lower mold chamber is reduced, and the lower mold chamber is placed in a vacuum state 4. After the film 2 is heated to a predetermined temperature, the pressure on the upper film chamber side is returned to normal pressure to apply pressure to the film 2. Thereafter, the substrate stage is raised (stage lift 5), and the pressure in the lower mold chamber is reduced while the substrate 3 is struck against the film 2. Compressed air 6 is also sent into the upper film chamber to pressurize it. This state is maintained for several seconds. Next, the upper film chamber and the lower mold chamber are returned to normal pressure, and the substrate (i.e., lens) with the film attached thereto is removed. Any unnecessary portions of the film are trimmed 7, and the film is further heated to complete the application. Examples of vacuum and compressed air molding machines include the NGF series (manufactured by Fuse Vacuum Co., Ltd.) and the TFH series (manufactured by Asano Laboratory Co., Ltd.).

[0168] (eyeglass lenses) The eyeglass lens is obtained by heating the laminate at 50°C to 150°C and attaching it to a lens substrate under a reduced pressure of 20 kPa or less, with the polycarbonate-based polyurethane adhesive layer and the lens substrate in contact with each other. That is, the eyeglass lens includes the laminate of the second embodiment and a lens substrate adhered to the polycarbonate-based polyurethane adhesive layer side of the laminate. The eyeglass lens may include a functional resin layer containing a functional dye, a polycarbonate-based polyurethane adhesive layer laminated on at least one side of the functional resin layer, and a lens substrate adhered to the side of the polycarbonate-based polyurethane adhesive layer.

[0169] <Lens substrate> The lens substrate is not particularly limited. The lens substrate preferably contains at least one material selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane, More preferably, the polymer contains at least one selected from the group consisting of polyepisulfide, polyurethane, and polythiourethane, It is more preferable that the material contains at least one selected from the group consisting of polyurethane and polythiourethane.

[0170] The polyepisulfide preferably comprises a constituent unit derived from an episulfide compound, or comprises a constituent unit derived from an episulfide compound and a constituent unit derived from a thiol compound. The polyurethane preferably comprises a structural unit derived from an isocyanate compound and a structural unit derived from an alcohol compound. The polythiourethane preferably comprises a structural unit derived from an isocyanate compound and a structural unit derived from a thiol compound.

[0171] The method for producing the polyepisulfide may include a method using an episulfide compound alone or a method using an episulfide compound and a thiol compound. As a method for producing polyurethane, a method using an isocyanate compound and an alcohol compound can be mentioned. The polythiourethane can be produced by a method using the above-mentioned isocyanate compound and thiol compound.

[0172] (episulfide compounds) Examples of the episulfide compound include epithioethylthio compounds, chain aliphatic 2,3-epithiopropylthio compounds, cyclic aliphatic 2,3-epithiopropylthio compounds, aromatic 2,3-epithiopropylthio compounds, chain aliphatic 2,3-epithiopropyloxy compounds, cyclic aliphatic 2,3-epithiopropyloxy compounds, and aromatic 2,3-epithiopropyloxy compounds, and these may be used alone or in combination of two or more. Examples of the episulfide compound include the compounds exemplified in WO2015 / 137401.

[0173] The episulfide compound is preferably at least one selected from the group consisting of bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropyl) disulfide, bis(1,2-epithioethyl) sulfide, bis(1,2-epithioethyl) disulfide, and bis(2,3-epithiopropylthio)methane, and more preferably bis(2,3-epithiopropyl) disulfide.

[0174] (Isocyanate compounds) The isocyanate compound may be a chain isocyanate compound or a cyclic isocyanate compound. Examples of the isocyanate compound include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, and aromatic aliphatic isocyanate compounds, and these compounds may be used alone or in combination. These isocyanate compounds may include dimers, trimers, prepolymers, etc. Examples of the isocyanate compound include the compounds exemplified in WO 2011 / 055540.

[0175] Among the above, the aliphatic isocyanate compound is preferably at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane.

[0176] Among the above, the aromatic isocyanate compound is preferably at least one selected from the group consisting of xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0177] (Thiol compounds) Examples of the thiol compound include a polythiol compound having two or more mercapto groups, a hydroxythiol compound having one or more mercapto groups and one or more hydroxyl groups, and the like, and these compounds are used alone or in combination. Examples of these thiol compounds include the compounds exemplified in WO 2016 / 125736.

[0178] (Bifunctional thiol compounds) Examples of bifunctional thiol compounds include methanedithiol, 1,3-propanedithiol, 1,2-ethanedithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl)ether, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)ether, bis(mercaptomethyl ... mercaptomethylthio) disulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters of thioglycolic acid and mercaptopropionic acid;

[0179] Bis(2-mercaptoethyl) sulfide, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl aliphatic polythiol compounds such as ethyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), and 4,6-bis(mercaptomethylthio)-1,3-dithiane;

[0180] aromatic polythiol compounds such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol;

[0181] Heterocyclic polythiol compounds such as 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane; and the like.

[0182] Among the above, the bifunctional thiol compound more preferably includes at least one selected from bis(mercaptoethyl) sulfide, 1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0183] (Trifunctional or higher thiol compounds) Examples of trifunctional or higher functional thiol compounds include 1,2,3-propane trithiol, tetrakis(mercaptomethyl)methane, trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptomethylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl) sulfide, and their thioglycolic acid esters and mercaptopropionic acid esters;

[0184] Aliphatic polythiol compounds such as 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane;

[0185] Aromatic polythiol compounds such as 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, and 1,3,5-tris(mercaptoethyleneoxy)benzene;

[0186] Heterocyclic polythiol compounds such as 2,4,6-trimercapto-s-triazine, 2,4,6-trimercapto-1,3,5-triazine, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane; and the like.

[0187] The tri- or higher functional thiol compound preferably includes at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.

[0188] The equivalent ratio of the thiol group in the thiol compound to the isocyanato group in the isocyanate compound (thiol group / isocyanato group) is preferably 0.8 to 1.2, more preferably 0.85 to 1.15, and even more preferably 0.9 to 1.1. Within the above range, a polythiourethane suitable for use as an optical material, particularly as a plastic lens material for spectacles, can be obtained.

[0189] (Polyol compound) The alcohol compound is one or more aliphatic or alicyclic alcohols. Specific examples include linear or branched aliphatic alcohols, alicyclic alcohols, and alcohols obtained by adding ethylene oxide, propylene oxide, or ε-caprolactone to these alcohols. Specific examples of the compounds that can be used include the compounds exemplified in WO2016 / 125736.

[0190] The polyol compound is preferably at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol.

[0191] Before the functional resin layer is attached to the lens substrate, the lens surface to which the functional resin layer is to be attached may be subjected to a pretreatment. The pretreatment method is not particularly limited and may be appropriately selected from the viewpoint of, for example, adhesion. Examples of the pretreatment method include etching with an alkaline aqueous solution, etching with an alkaline surfactant aqueous solution, cleaning with a surfactant aqueous solution, cleaning with pure water, etching with UV ozone, etching with plasma, polishing using fine particles, and grinding. When etching is performed using pure water or an aqueous solution, the chemical treatment can be performed more effectively by combining heating, ultrasonic irradiation, or the like.

[0192] The method for manufacturing a spectacle lens of the second embodiment preferably further includes the step of forming a coating layer on at least the surface of the functional resin layer of the spectacle lens. It is more preferable that the method for manufacturing a spectacle lens of the second embodiment further includes the step of forming a hard coat layer on at least the surface of the functional resin layer of the spectacle lens.

[0193] [Coating layer] Specific examples of the coating layer include a hard coat layer, an anti-reflection layer, an anti-fogging coat layer, an anti-fouling layer, and a water-repellent layer. These coating layers can be used alone or in combination. When coating layers are applied to both sides, the same coating layer or different coating layers can be applied to each side.

[0194] (Hard coat layer) The eyeglass lens of the second embodiment preferably includes a hard coat layer. The hard coat layer is a coating layer intended to impart functions such as scratch resistance, abrasion resistance, humidity resistance, warm water resistance, heat resistance, and weather resistance to the lens surface. For forming the hard coat layer, a hard coat composition containing a curable organosilicon compound and one or more oxide fine particles containing an element selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti may be used; A hard coat composition may be used which contains a curable organosilicon compound and one or more fine particles of a composite oxide containing two or more elements selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti.

[0195] In addition to the above components, the hard coat composition preferably contains at least one selected from the group consisting of amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, acids, metal chlorides, and polyfunctional epoxy compounds. The hard coat composition may contain a solvent that does not affect the lens substrate, or may be solvent-free.

[0196] The hard coat layer is usually formed by applying a hard coat composition by a known application method such as spin coating or dip coating, followed by curing. Curing methods include irradiation with energy rays such as ultraviolet light or visible light, and thermal curing. From the viewpoint of suppressing the occurrence of interference fringes, it is preferable that the difference in refractive index between the hard coat layer and the lens substrate is within ±0.1.

[0197] Before applying the hard coating agent, the surface to be coated with the hard coating agent may be subjected to a pretreatment. Examples of pretreatment methods include etching with an alkaline aqueous solution, etching with an alkaline surfactant aqueous solution, cleaning with a surfactant aqueous solution, cleaning with pure water, etching with UV ozone, etching with plasma, polishing using fine particles, and grinding. When etching is performed using pure water or an aqueous solution, the chemical treatment can be performed more effectively by combining heating, ultrasonic irradiation, or the like.

[0198] (Anti-reflection layer) The spectacle lens of the second embodiment preferably includes an anti-reflection layer. Anti-reflection layers include inorganic and organic types. The inorganic anti-reflection layer is formed using inorganic oxides such as SiO2 and TiO2 by a dry method such as vacuum deposition, sputtering, ion plating, ion beam assist, or CVD. The organic anti-reflection layer is formed by a wet process using a composition containing an organosilicon compound and silica-based fine particles having internal cavities. An anti-reflection layer may be formed on the hard coat layer, if necessary.

[0199] The anti-reflection layer may be a multi-layer or a single layer. To effectively exhibit the antireflection function, the antireflection layer is preferably multi-layered, and in this case, it is preferable that low-refractive index layers and high-refractive index layers are alternately laminated. Furthermore, it is preferable that the difference in refractive index between the low-refractive index layers and the high-refractive index layers is 0.1 or more. Examples of high refractive index layers include layers of ZnO, TiO2, CeO2, Sb2O5, SnO2, ZrO2, and Ta2O5, and examples of low refractive index layers include layers of SiO2. When used as a single layer, it is preferable that the refractive index is at least 0.1 or more lower than the refractive index of the hard coat layer.

[0200] On the antireflection layer, an antifogging coating layer, an antifouling layer, a water-repellent layer, etc. may be formed as needed. The method for forming the antifogging layer, the antifouling layer, the water-repellent layer, etc. is not particularly limited, and a conventionally known method can be applied.

[0201] <Reheating process> The method for manufacturing a spectacle lens according to the second embodiment preferably further comprises a reheating step of reheating the spectacle lens at a temperature of 50°C to 150°C. The reheating is preferably carried out at a temperature of 90 to 140°C, more preferably 100 to 130°C.

[0202] <Laminate> The laminate of the second embodiment includes a polycarbonate-based polyurethane adhesive layer made of a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group, a functional resin layer containing a functional dye, and The dried polyurethane aqueous dispersion has a storage modulus of 0.1 MPa to 80 MPa at 80° C. as measured under the following condition 1. [Condition 1] The storage modulus at 80°C is measured using a test piece made of a dried polyurethane aqueous dispersion, 3 cm long, 5 mm wide, and 500 μm thick, with a dynamic viscoelasticity measuring device, at a frequency of 1 Hz, under strain-controlled tensile conditions, by raising the temperature from -102°C to 80°C at a rate of 3°C / min.

[0203] The laminate of the second embodiment may be a laminate manufactured by the laminate manufacturing process of the second embodiment.

[0204] Details of the dried product of the aqueous polyurethane dispersion, the polycarbonate-based polyurethane adhesive layer, the functional dye, the functional resin layer, and the storage modulus at 80°C measured under condition 1, including specific examples, preferred specific examples, specific aspects, preferred aspects, and measurement methods, are as described above.

[0205] The dried polyurethane aqueous dispersion preferably has a mass increase rate of 1% to 50% in a hot water resistance test measured under the following condition 3. [Condition 3] A test piece made of a dried polyurethane aqueous dispersion, 4 cm long, 2 cm wide, and 500 μm thick, is immersed in hot water at 40°C for 24 hours, and the mass of the test piece is measured before and after immersion. The mass increase rate in the hot water resistance test is calculated using the mass of the test piece before and after immersion using the following formula. Mass increase rate = ((mass of test piece after immersion - mass of test piece before immersion) / (mass of test piece before immersion)) x 100

[0206] The specific aspects and preferred ranges of the mass increase rate in the hot water resistance test are as described above.

[0207] <Eyeglass lenses> The eyeglass lens of the second embodiment includes the laminate of the second embodiment and a lens substrate adhered to the polycarbonate-based polyurethane adhesive layer side of the laminate.

[0208] The eyeglass lens of the second embodiment may be a eyeglass lens manufactured by the eyeglass lens manufacturing method of the second embodiment.

[0209] The specific and preferred embodiments of the lens substrate are as described above.

[0210] The second embodiment also includes the following implementations. <1B> A method for producing a spectacle lens, comprising the steps of: forming a polycarbonate-based polyurethane adhesive layer made of a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one surface of a functional resin layer containing a functional dye, to obtain a laminate; and heating the laminate at 50°C to 150°C and attaching the laminate to a lens substrate under a reduced pressure of 20 kPa or less, with the polycarbonate-based polyurethane adhesive layer and the lens substrate in a contacting orientation, to obtain a spectacle lens, wherein the dried product of the aqueous polyurethane dispersion has a storage modulus at 80°C of 0.1 MPa to 80 MPa, as measured under the following condition 1. [Condition 1] The storage modulus at 80°C is measured using a test piece made of a dried product of the polyurethane aqueous dispersion, 3 cm in length, 5 mm in width, and 500 μm in thickness, with a dynamic viscoelasticity measuring device, at a frequency of 1 Hz under strain-controlled tensile conditions, by raising the temperature from -102°C to 80°C at a rate of 3°C / min. <2B> The method for producing a spectacle lens according to <1B>, wherein the dried product of the aqueous polyurethane dispersion has an outflow start temperature of 160°C to 220°C as measured under the following condition 2: [Condition 2] The flow-out starting temperature was measured using a flow tester. The dry polyurethane aqueous dispersion was placed in a test vessel having an orifice with an inner diameter of 1 mm and a length of 1 mm at the end, and the temperature was measured under a load of 10 kgf / cm. 2 Under the above conditions, the temperature is increased at a rate of 3°C / min until the temperature reaches a point where the dried polyurethane aqueous dispersion begins to flow out of the orifice. <3B> The method for producing a spectacle lens according to <1B> or <2B>, further comprising the step of forming a hard coat layer on at least the surface of the functional resin layer in the spectacle lens. <4B> The method for producing a spectacle lens according to any one of <1B> to <3B>, wherein the dried product of the aqueous polyurethane dispersion has a mass increase rate of 1% to 50% in a hot water resistance test measured under the following condition 3: [Condition 3] A test piece made of the dried polyurethane aqueous dispersion, measuring 4 cm in length, 2 cm in width, and 500 μm in thickness, is immersed in hot water at 40° C. for 24 hours, and the mass of the test piece is measured before and after immersion. The mass increase rate in the hot water resistance test is calculated from the masses of the test piece before and after immersion using the following formula: Mass increase rate = ((mass of test piece after immersion - mass of test piece before immersion) / (mass of test piece before immersion)) x 100 <5B> The method for producing a spectacle lens according to any one of <1B> to <4B>, wherein the polycarbonate-based polyurethane adhesive layer has a thickness of 1 μm to 100 μm. <6B> The method for producing a spectacle lens according to any one of <1B> to <5B>, wherein the dried product of the aqueous polyurethane dispersion has a glass transition temperature of -45°C to 0°C. <7B> The method for producing a spectacle lens according to any one of <1B> to <6B>, wherein the functional resin layer has a thickness of 10 μm to 700 μm. <8B> The method for manufacturing a spectacle lens according to any one of <1B> to <7B>, wherein the functional resin layer contains a thermoplastic resin having a softening temperature of 50°C to 150°C. <9B> The method for producing a spectacle lens according to any one of <1B> to <7B>, wherein the functional resin layer contains a thermosetting resin including at least one selected from the group consisting of polyepoxy, polyepisulfide, and poly(thio)urethane. <10B> The method for producing a spectacle lens according to any one of <1B> to <9B>, comprising a step, which is carried out before the step of obtaining the laminate, of applying a polymerizable composition containing the functional dye to a release film, followed by curing the composition to obtain the functional resin layer. <11B> Any of <1B> to <10B>, wherein the functional dye contains at least one selected from the group consisting of an ultraviolet absorber, a visible light absorbing dye, a photochromic dye, and a dichroic dye. 1. A method for manufacturing eyeglass lenses according to any one of the preceding items. <12B> A laminate comprising: a polycarbonate-based polyurethane adhesive layer made of a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group; and a functional resin layer containing a functional dye, wherein the dried product of the aqueous polyurethane dispersion has a storage modulus of 0.1 MPa to 80 MPa at 80°C as measured under the following condition 1. [Condition 1] The storage modulus at 80°C is measured using a test piece made of a dried product of the polyurethane aqueous dispersion, 3 cm in length, 5 mm in width, and 500 μm in thickness, with a dynamic viscoelasticity measuring device, at a frequency of 1 Hz under strain-controlled tensile conditions, by raising the temperature from -102°C to 80°C at a rate of 3°C / min. <13B> The laminate according to <12B>, wherein the dried product of the aqueous polyurethane dispersion has a mass increase rate of 1% to 50% in a hot water resistance test measured under the following condition 3. [Condition 3] A test piece made of the dried polyurethane aqueous dispersion, measuring 4 cm in length, 2 cm in width, and 500 μm in thickness, is immersed in hot water at 40° C. for 24 hours, and the mass of the test piece is measured before and after immersion. The mass increase rate in the hot water resistance test is calculated from the masses of the test piece before and after immersion using the following formula: Mass increase rate = ((mass of test piece after immersion - mass of test piece before immersion) / (mass of test piece before immersion)) x 100 <14B> The laminate according to <12B> or <13B>, wherein the functional dye comprises at least one selected from an ultraviolet absorber, a visible light absorbing dye, a photochromic dye, and a dichroic dye. <15B> A spectacle lens comprising the laminate according to any one of <12B> to <14B> and a lens substrate adhered to the polycarbonate-based polyurethane adhesive layer side of the laminate. [Example]

[0211] The first embodiment will be described in detail below with reference to examples, but the invention of the first embodiment is not limited to the descriptions of these examples.

[0212] In this example, the details of each component used are as follows:

[0213] Specific wavelength blocking dye PD-311S Yamamoto Kasei Co., Ltd.

[0214] ·dye Plast Blue 8514 Anthraquinone dye manufactured by Arimoto Chemical Industry Co., Ltd. Plast Red 8320 Anthraquinone dye manufactured by Arimoto Chemical Industry Co., Ltd. Plast Yellow 8070 Methine dye manufactured by Arimoto Chemical Industry Co., Ltd.

[0215] Urethane primer Urethane primer 1: Takelac WS-5100 (Mitsui Chemicals, Inc.) Urethane primer 2: Superflex 470 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Urethane primer 3: Evaphanol HA-170 (manufactured by Nicca Chemical Co., Ltd.)

[0216] Isocyanate compounds Isocyanate 1: Mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane Isocyanate 2: Hexamethylene diisocyanate Isocyanate 3: meta-xylylene diisocyanate

[0217] Thiol compounds Thiol 1: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane Thiol 2: Bis(2-mercaptoethyl) sulfide Thiol 3: Pentaerythritol tetrakis(3-mercaptopropionate)

[0218] [Evaluation method] In the present examples, the films and lenses were evaluated as follows. (Film thickness measurement) The thickness of each film was measured using a thickness gauge. Specifically, a digital gauge (DIGIMICRO ME-50HA, manufactured by Nikon Corporation) was used to measure the thickness at any point on the film.

[0219] (Measurement of softening temperature and elastic modulus of film resin) The measurements were carried out by the method described in the above section (Measurement of softening temperature and storage modulus).

[0220] (Calculation of molecular weight between crosslinking points of film resin) The measurement was carried out by the method described in the above section (Method for measuring molecular weight between crosslink points).

[0221] (Film tracking ability) The lens to which the film was attached was visually inspected and evaluated for conformability of the film to the substrate. Rank 1: The film was not attached to the curved surface of the substrate, or air bubbles were found between the substrate and the film. Rank 2: The film was attached to the curved surface of the substrate so as to conform to the curved surface, and no air bubbles were observed between the substrate and the film.

[0222] (Film bag breaks) The film was visually inspected to see if any tears had occurred.

[0223] (Adhesion test) Eleven lines were drawn vertically and eleven lines horizontally at 1 mm intervals on the periphery of the convex surface of the lens using a cutter, creating a grid of 100 squares. Nichiban cellophane tape was applied over the 100 squares, and the tape was then peeled off vertically to check the state of peeling of the film or coating film. The number of squares out of 100 that did not peel off was visually confirmed to evaluate the adhesion. Table 1 shows the number of squares out of 100 that did not experience peeling.

[0224] If peeling did not occur, the tape was reattached and peeled off in the same manner twice. When the above adhesion test is carried out on a lens having a hard coat layer laminated on a film, and peeling occurs, this means that the film has poor solvent resistance. That is, if the film is damaged by the solvent used in the hard coating treatment, the film and the hard coating layer cannot be sufficiently adhered to each other, resulting in the above-mentioned peeling.

[0225] (Scratch resistance test) Using #0000 steel wool, a 1 kg weight was placed directly above the lens, and the lens was moved back and forth 10 times to visually evaluate scratches on the coating surface and rank them on a 5-point scale. The evaluation criteria are as follows: Evaluation criteria Rank 1: The steel wool was scratched across its entire width, and the coating film had completely peeled off. Rank 2: There was a deep scratch across the entire width of the steel wool, but the coating film remained. Rank 3: There were several to several dozen thick scratches. Rank 4: There were several to several dozen thin scratches. Rank 5: Almost no visible damage.

[0226] (cloudy) The coated lenses were visually inspected to see if any cloudiness occurred. If the film surface is corroded and damaged by the solvent in the hard coat treatment, cloudiness occurs. In other words, the occurrence of cloudiness indicates that the film has poor solvent resistance.

[0227] (Heat resistance test) The film or lens was placed on a tray and heated in an electric furnace at a constant temperature of 60°C for 10 minutes. The lens was observed immediately after being removed from the furnace and after the temperature had sufficiently cooled to around room temperature to check for the presence or absence of cracks. If no cracks occurred, the temperature of the electric furnace was increased by another 10°C and the same evaluation was carried out. The same procedure was repeated until cracks occurred, and the maximum temperature at which no cracks occurred was taken as the heat resistance temperature and used as an index of heat resistance.

[0228] (Transmittance measurement) The transmittance of the film or lens was measured using a UV-Vis spectrophotometer (Shimadzu Corporation). The measurement wavelength was in the range of 350 nm to 800 nm, and the effect of the functional dye absorbing specific wavelengths was confirmed from the obtained transmittance spectrum.

[0229] <<Preparation of lens substrate>> A mixed solution was prepared by adding 0.03 parts by weight of dimethyltin dichloride, 0.1 parts by weight of ZelecUN (STEPAN), 50.6 parts by weight of a mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, and 0.05 parts by weight of 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole as a UV absorber. This mixed solution was stirred at 25°C for 1 hour to achieve complete dissolution. Subsequently, 25.5 parts by weight of a thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by weight of a thiol composition containing pentaerythritol tetrakis(3-mercaptopropionate) were added to this mixture, and the mixture was stirred at 25°C for 30 minutes to obtain a homogeneous solution (polymerizable composition). This polymerizable composition was degassed at 600 Pa for 1 hour and filtered through a 1 μm PTFE filter to obtain a prepared liquid. Next, to mold a lens with a high curvature on the convex side, a casting mold was prepared in which a front glass mold (concave surface R facing the back glass mold: 86 mm) and a back glass mold (convex surface R facing the front glass mold: 250 mm) were secured with tape so that they faced each other. The gap at the outermost periphery of the mold was approximately 1 mm, and a prepared liquid was poured into the gap formed by the mold and tape, and the temperature was raised from 25°C to 120°C over 16 hours. After cooling to room temperature, the glass mold was removed, yielding a lens with a diameter of 81 mm. This lens was then machined to a diameter of 75 mm, yielding a lens substrate with a diopter of +4.50 and a refractive index of 1.597. Separately from the above, to mold a lens with a high curvature on the concave side, a casting mold was prepared in which a front glass mold (concave surface R facing the back glass mold: 253 mm) and a back glass mold (convex surface R facing the front glass mold: 86 mm) were fixed with tape so that they faced each other. A prepared liquid was poured into the gap between the molds (separation distance of the approximate circular centers: 1.5 mm), and the temperature was raised from 25°C to 120°C over 16 hours. After cooling to room temperature, the glass mold was removed from the glass mold to obtain a lens with a diameter of 81 mm. This lens was then processed to a diameter of 75 mm to obtain a lens substrate with a diopter of -4.50 and a refractive index of 1.597.

[0230] Example 1A [Preparation of polythiourethane film] A mixed solution was prepared by adding 0.04 parts by mass of dimethyltin dichloride, 0.2 parts by mass of ZelecUN manufactured by STEPAN Corporation, 0.007 parts by mass of PD-311S manufactured by Yamamoto Chemical Industries, Ltd. as a dye, 31.9 parts by mass of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 17.3 parts by mass of hexamethylene diisocyanate, and 0.05 parts by mass of 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole as a UV absorber. This mixed solution was stirred at 25°C for 1 hour to completely dissolve the solution. Then, 26.8 parts by mass of a thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 15.9 parts by mass of bis(2-mercaptoethyl) sulfide were added to this preparation, and the mixture was stirred at 25°C for 30 minutes to obtain a homogeneous solution (polymerizable composition). This polymerizable composition was degassed at 600 Pa for 1 hour and filtered through a 1 μm PTFE filter to obtain a preparation. A film molding mold was assembled by sandwiching a 200 μm thick PTFE sheet between two 36 cm long, 27 cm wide, 5 mm thick glass plates, with the PTFE sheet wrapped around all four sides of the glass plates to a width of 1.5 cm. The pair of glass plates was secured with tape covering the periphery. The prepared solution was poured into the gap between the film molding mold, the pouring port was sealed with tape, and the temperature was raised from 30 °C to 120 °C over 12 hours. The film was cooled to room temperature and removed from the glass mold to obtain an A4-sized polythiourethane film having the thickness listed in Table 1. Separately, two φ80 mm glass plates were prepared and secured with tape so that they faced each other to create a casting mold. The prepared liquid was poured into the gap between the molds (2.5 mm separation between the centers of the approximately circular plates), and the temperature was raised from 25°C to 120°C over 16 hours. The plate was then cooled to room temperature and removed from the glass mold, yielding a φ80 mm polythiourethane plate. A portion of the resulting plate was cut to obtain a 30 mm x 5 mm, 2.5 mm thick test piece for measuring the softening temperature and elastic modulus. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus rose steadily to the right with a gradient of 10,000 or more in the range of 130 to 150°C. The results are shown in Table 1.

[0231] [Adhesive layer application] The obtained film was wiped with acetone, and then Urethane Primer 1 was applied thereto as an adhesive layer for bonding the substrate and the film. Urethane Primer 1 was dropped onto the film using a dropper and applied using a gap coater. After application, the film with primer was placed in an electric furnace set to 70°C and dried for 15 minutes. A protective film was then attached to the surface coated with the urethane primer, and the film was stored as a film for application.

[0232] [Attachment using a vacuum / compressed air molding machine] The lens was wiped with acetone-soaked Silbon paper, then immersed in a 10% caustic soda bath at 55°C for 5 minutes while applying ultrasonic waves, then rinsed and cleaned in a pure water bath for 15 minutes while applying ultrasonic waves, and then dried with warm air at 70°C to prepare the substrate. Next, the cleaned lens was placed on the substrate stage of a vacuum pressurized air forming machine NGF-0404-T (manufactured by Fuse Vacuum Co., Ltd.), and an A4-sized polythiourethane film coated with an adhesive layer was placed on the film stage. The protective film was peeled off, and the polythiourethane film was placed so that the adhesive layer faced the substrate. Next, the vacuum chamber containing the film and substrate was sealed and the pressure was reduced to 3 kPa using a vacuum pump. At this time, the upper film chamber, which is the space above the film, and the lower mold chamber, which is the space containing the substrate below, were separated by the film, and both the upper and lower spaces were reduced in pressure. The film was heated from above using a heater until the surface temperature reached the temperature listed in Table 1. After the film reached 145°C, a small amount of air was pumped into the upper film chamber to increase the pressure, causing the film to expand slightly toward the substrate below. In this state, the substrate stage was raised from below toward the film, bonding the substrate and film surfaces together. After bonding, compressed air was pumped into the upper film chamber, pressurizing it to 300 kPa while keeping the lower mold chamber vacuum, and this was maintained for approximately 5 seconds. The space above and below the film was then returned to normal pressure, the sealed state was released, and the lens with the film attached was removed.

[0233] When the lens was removed, the film was attached to the curved surface of the lens, and no air bubbles were observed between the substrate and the film. Next, the film was cut out circumferentially along the outer periphery of the lens, and the lens portion to which the film was attached was separated from the remaining film portion. Next, the lens with the film attached was heated in an electric furnace at 120° C. for 1 hour to completely cure the primer, thereby obtaining a lens with a film in which the substrate surface and the film were completely bonded.

[0234] [Hard coating treatment] The obtained lens with the film was wiped with Silbon paper soaked in acetone as a solvent, and then immersed in a bath of 10% caustic soda at a liquid temperature of 55°C for 5 minutes while applying ultrasonic waves. The lens was then rinsed for 15 minutes in a pure water bath while applying ultrasound, and then dried with warm air at 70° C. The lens was then immersed in a hard coating solution, Crystal Coat IM-9060 (manufactured by SDC Technologies), for 10 seconds, pulled out at 2 mm / second, and dried for 15 minutes at 80° C. The lens was removed from the jig and further heated and cured at 120° C. for 3 hours to obtain a hard-coated lens with a film. The transmittance spectrum of the obtained lens was measured using a spectrophotometer, and as shown in Figure 2, it showed maximum absorption around 585 nm, which is the absorption wavelength of the functional dye. FIG. 2 is a graph showing the transmittance of the lens with a film in Example 1A.

[0235] [Anti-reflective coating] A five-layer anti-reflection layer consisting of silicon oxide / zirconium oxide was formed on the hard-coated lens using a vacuum deposition device. When the appearance of the obtained lens was checked visually, no streaky spots (streaks) were found. The evaluation results are shown in Table 1.

[0236] Example 2A A colorless, transparent, A4-sized polythiourethane film having the thickness shown in Table 1, and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm × 5 mm and 2.5 mm thick, were obtained in the same manner as in Example 1A, except that no dye was added in [Film Preparation]. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus rose steadily to the right with a slope of 10,000 or more in the range of 130°C to 150°C.

[0237] Furthermore, the same procedures as in Example 1A were carried out: [adhesive layer application], [attachment using a vacuum / pressure molding machine], [hard coating treatment], and [anti-reflection coating treatment], to obtain a lens with a film that was hard-coated and anti-reflection coated. When the appearance of the obtained lens was visually confirmed, no streaky spots were found. The evaluation results are shown in Table 1.

[0238] Example 3A In [Film Production], the content of the mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane was changed to 53.1 parts by mass. The content of hexamethylene diisocyanate was changed to 0 parts by mass. The content of the thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was changed to 17.9 parts by mass, Except for changing the content of bis(2-mercaptoethyl) sulfide to 23.8 parts by mass, Using the same procedures as in Example 1A, a colorless, transparent, A4-sized polythiourethane film having the thickness shown in Table 1, and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm × 5 mm and 2.5 mm thick, were obtained. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus rose steadily to the right with a slope of 4000 or more in the range of 130°C to 150°C.

[0239] Furthermore, the same procedures as in Example 1A were carried out for [adhesive layer application], [lamination using a vacuum / pressure molding machine], [hard coating treatment], and [anti-reflection coating treatment], except that in [lamination using a vacuum / pressure molding machine], the heating temperature of the film was set to the temperature shown in Table 1, thereby obtaining a lens with a film that was hard coated and anti-reflection coated. When the appearance of the obtained lens was visually inspected, no streaky spots were observed. The evaluation results are shown in Table 1.

[0240] Example 4A In [Film Preparation], 0.007 parts by mass of PD-311S manufactured by Yamamoto Chemical Industry Co., Ltd. was replaced with 0.018 parts by mass of Plast Red 8320 manufactured by Arimoto Chemical Industry Co., Ltd. and 0.012 parts by mass of Plast Yellow 8070 manufactured by Arimoto Chemical Industry Co., Ltd. As the isocyanate composition, 31.9 parts by mass of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane was replaced with 52.0 parts by mass of xylylene diisocyanate, The content of hexamethylene diisocyanate was changed to 0 parts by mass. The content of the thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was changed to 28.8 parts by mass, Except for changing the content of bis(2-mercaptoethyl) sulfide to 17.1 parts by mass, Using the same procedure as in Example 1A, an A4-sized polythiourethane film having the thickness shown in Table 1 and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm x 5 mm and 2.5 mm thick, were obtained. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus rose steadily to the right with a slope of 27,000 or more in the range of 130°C to 150°C.

[0241] Furthermore, the same procedures as in Example 1A were carried out: [adhesive layer application], [attachment using a vacuum / pressure molding machine], [hard coating treatment], and [anti-reflection coating treatment], to obtain a lens with a film that was hard-coated and anti-reflection coated. When the appearance of the obtained lens was visually confirmed, no streaky spots were found. The evaluation results are shown in Table 1.

[0242] Example 5A A film was prepared in the same manner as in [Film Preparation] of Example 1A (referred to as Film 5A). Next, in the [Film Preparation] step, the same procedure as in Example 1A was used, except that 0.007 parts by mass of PD-311S manufactured by Yamamoto Chemical Industry Co., Ltd. was replaced with 0.046 parts by mass of Plast Yellow 8070 manufactured by Arimoto Chemical Industry Co., Ltd., to obtain a polythiourethane film 5B having an A4 size and the thickness shown in Table 2. Details and evaluation of Film 5B are shown in Table 2. Next, the adhesive layer coating process was carried out on each of the films 5A and 5B in the same manner as in Example 1A to obtain a film for application.

[0243] [Attachment using a vacuum / compressed air molding machine] The lens was wiped with acetone-soaked Silbon paper, then immersed in a 10% caustic soda bath at 55°C for 5 minutes while applying ultrasonic waves, then rinsed and cleaned in a pure water bath for 15 minutes while applying ultrasonic waves, and then dried with warm air at 70°C to prepare the substrate. Next, the cleaned lens was placed on the substrate stage of a vacuum pressurized air forming machine NGF-0404-T (manufactured by Fuse Vacuum Co., Ltd.), and polythiourethane film 5A with an adhesive layer applied was placed on the film stage. At this time, the protective film was peeled off and polythiourethane film 5A was placed so that the adhesive layer faced the substrate side. Next, the vacuum chamber containing the film and substrate was sealed and the pressure was reduced to 3 kPa using a vacuum pump. At this time, the upper film chamber, which is the space above the film, and the lower mold chamber, which is the space containing the substrate below, were separated by the film, and both the upper and lower spaces were reduced in pressure. The film was heated from above using a heater until the surface temperature reached the temperature listed in Table 2. After the film reached the temperature listed in Table 2, a small amount of air was sent into the upper film chamber to increase the pressure, causing the film to expand slightly toward the substrate below. In this state, the substrate stage was raised from below toward the film, bonding the substrate surface and film surface together. After bonding, compressed air was sent into the upper film chamber, while the lower mold chamber remained decompressed, creating a pressurized state of 300 kPa, which was maintained for approximately 5 seconds. The space above and below the film was then returned to normal pressure, the sealed state was released, and the lens with the film attached was removed.

[0244] When the lens was removed, the film was attached to it so as to conform to the lens's curvature, and no air bubbles were found between the substrate and the film. Next, the film was cut out in a circular shape along the outer periphery of the lens, and the lens portion to which the film was attached was separated from the remaining film portion, thereby obtaining a lens to which the 5A film was attached.

[0245] The lens surface with the 5A film attached was then air-blown and placed on the substrate stage of the NGF-0404-T vacuum / pressure forming machine. The polythiourethane film 5B with an adhesive layer applied was then placed on the film stage with the protective film removed, so that the adhesive layer faced the substrate. Next, the decompression chamber containing film 5B and the lens with film 5A attached thereto was sealed, and the pressure was reduced to 3 kPa using a vacuum pump. At this time, the upper film chamber, which is the space above the film, and the lower mold chamber, which is the space containing the lower substrate, were separated by the film, and both the upper and lower spaces were reduced in pressure. The film was heated from above by a heater until the surface temperature reached the temperature shown in Table 2. After the film reached the temperature listed in Table 2, a small amount of air was pumped into the upper film chamber to increase the pressure, causing the film to expand slightly toward the substrate below. In this state, the substrate stage was raised from below toward the film, bonding the substrate surface and film surface together. After bonding, while the lower mold chamber remained depressurized, compressed air was pumped into the upper film chamber to create a pressurized state of 300 kPa, which was maintained for approximately 5 seconds. The space above and below the film was then returned to normal pressure, the sealed state was released, and the lens with Film 5B further attached was removed.

[0246] When the lens was removed, the film was attached to it, following the curvature of the lens, and no air bubbles were found between the substrate and the film. Next, the film was cut out circumferentially along the outer periphery of the lens, and the lens portion to which the film was attached was separated from the remaining film portion. Next, the lens with the film attached was heated in an electric furnace at 120° C. for 1 hour to completely cure the primer, thereby obtaining a lens with the substrate, film 5A and film 5B completely bonded together.

[0247] Furthermore, the same procedures as in Example 1A were carried out: [adhesive layer application], [attachment using a vacuum / pressure molding machine], [hard coating treatment], and [anti-reflection coating treatment], to obtain a lens with a film that was hard-coated and anti-reflection coated. When the appearance of the obtained lens was visually confirmed, no streaky spots were observed. The evaluation results are shown in Table 2.

[0248] Example 6A In [Film Production], the content of the mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane was changed to 53.1 parts by mass. The content of hexamethylene diisocyanate was changed to 0 parts by mass. The content of the thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was changed to 8.9 parts by mass, The content of bis(2-mercaptoethyl) sulfide was changed to 31.8 parts by mass. Except that no dye was added. Using the same procedures as in Example 1A, a colorless, transparent, A4-sized polythiourethane film having the thickness shown in Table 2, and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm × 5 mm and 2.5 mm thick, were obtained. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus was almost flat with a gradient of -21000 or more in the range of 130°C to 150°C.

[0249] Furthermore, the same procedures as in Example 1A were carried out for [adhesive layer application], [lamination using a vacuum / pressure molding machine], [hard coating treatment], and [anti-reflection coating treatment], except that in [lamination using a vacuum / pressure molding machine], the heating temperature of the film was set to the temperature shown in Table 2, and a lens with a hard coating and an anti-reflection coating treatment was obtained. When the appearance of the obtained lens was visually confirmed, no streaky spots were found. The evaluation results are shown in Table 2.

[0250] Example 7A A lens with a film was obtained in the same manner as in Example 1A, except that Urethane Primer 1 was replaced with Urethane Primer 2. When the appearance of the obtained lens was visually inspected, no streaky spots were observed. The evaluation results are shown in Table 2.

[0251] (Comparative Example 1A) In the [Film Preparation] step, 0.007 parts by mass of Yamamoto Kasei Co., Ltd.'s PD-311S dye was replaced with 0.030 parts by mass of Arimoto Chemical Industry Co., Ltd.'s Plast Blue 8514 dye. 31.9 parts by mass of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane was replaced with 43.5 parts by mass of xylylene diisocyanate, The content of hexamethylene diisocyanate was changed to 0 parts by mass. 26.8 parts by mass of the thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was replaced with 56.5 parts by mass of a thiol compound containing pentaerythritol tetrakis(3-mercaptopropionate), Except for changing the content of bis(2-mercaptoethyl) sulfide to 0 parts by mass, Using the same procedure as in Example 1A, an A4-sized polythiourethane film having the thickness shown in Table 3 and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm x 5 mm and 2.5 mm thick, were obtained. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus rose steadily to the right with a slope of 72,000 or more in the range of 130°C to 150°C.

[0252] Furthermore, in the [Laminating by vacuum and pressure molding machine], the same procedures as in Example 1A were carried out for [Coating of adhesive layer] and [Laminating by vacuum and pressure molding machine], except that the heating temperature of the film was set to the temperature shown in Table 3. We carried out the following method: pasting. In the case of application using a vacuum / compressed air molding machine, the film was unable to withstand the impact of application and cracks occurred around the periphery of the lens. Furthermore, the film was unable to conform to the curvature of the lens, and air got trapped between the substrate and the film, preventing the film from adhering to the substrate surface. The evaluation results are shown in Table 3.

[0253] (Comparative example 2A) In the [Film Preparation] step, 0.007 parts by mass of PD-311S manufactured by Yamamoto Chemical Industry Co., Ltd. was replaced with 0.018 parts by mass of Plast Red 8320 and 0.012 parts by mass of Plast Yellow 8070 manufactured by Arimoto Chemical Industry Co., Ltd. 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane mixture 31.9 parts by mass was replaced with xylylene diisocyanate 52.0 parts by mass, The content of hexamethylene diisocyanate was changed to 0 parts by mass. The content of the thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was changed to 48.0 parts by mass, Except for changing the content of bis(2-mercaptoethyl) sulfide to 0 parts by mass, Using the same procedure as in Example 1A, an A4-sized polythiourethane film having the thickness shown in Table 3 and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm x 5 mm and 2.5 mm thick, were obtained. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus rose steadily to the right with a gradient of 55,000 or more in the range of 130°C to 150°C.

[0254] Furthermore, in [Attachment using a vacuum and pressure-sensitive molding machine], [Application of adhesive layer] and [Attachment using a vacuum and pressure-sensitive molding machine] were carried out in the same manner as in Example 1A, except that the heating temperature of the film was set to the temperature listed in Table 3. In the [Attachment using a vacuum / compressed air molding machine], the film was unable to conform to the curvature of the lens, and air got trapped between the substrate and the film, making it impossible to bond the film to the substrate surface. The evaluation results are shown in Table 3.

[0255] (Comparative example 3A) In the [Film Preparation] step, 0.007 parts by mass of Yamamoto Kasei Co., Ltd.'s PD-311S dye was replaced with 0.030 parts by mass of Arimoto Chemical Industry Co., Ltd.'s Plast Blue 8514 dye. The content of the mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane was changed to 26.5 parts by mass, The content of hexamethylene diisocyanate was changed to 21.6 parts by mass. The content of the thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was changed to 44.5 parts by mass, Except for changing the content of bis(2-mercaptoethyl) sulfide to 0 parts by mass, Using the same procedure as in Example 1A, an A4-sized polythiourethane film having the thickness shown in Table 3 and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm x 5 mm and 2.5 mm thick, were obtained. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus rose steadily to the right with a slope of 51,000 or more in the range of 130°C to 150°C.

[0256] Furthermore, in [Attachment using a vacuum and pressure-sensitive molding machine], [Application of adhesive layer] and [Attachment using a vacuum and pressure-sensitive molding machine] were carried out in the same manner as in Example 1A, except that the heating temperature of the film was set to the temperature listed in Table 3. In the [Attachment using a vacuum / compressed air molding machine], the film was unable to conform to the curvature of the lens, and air got trapped between the substrate and the film, making it impossible to bond the film to the substrate surface. The evaluation results are shown in Table 3.

[0257] (Comparative example 4A) In [Film Production], the content of the mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane was changed to 53.1 parts by mass. The content of hexamethylene diisocyanate was changed to 0 parts by mass. The content of the thiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is changed to 0 parts by mass, The content of bis(2-mercaptoethyl) sulfide was changed to 39.7 parts by mass. Except that no dye was added. Using the same procedures as in Example 1A, a colorless, transparent, A4-sized polythiourethane film having the thickness shown in Table 3, and a test piece for measuring the softening temperature and elastic modulus, measuring 30 mm × 5 mm and 2.5 mm thick, were obtained. The elastic modulus of the obtained test piece was measured, and it was found that the approximate line of temperature and elastic modulus had a slope of -51000 or more and was downward sloping to the right in the range of 130°C to 150°C.

[0258] Furthermore, in the [Attachment using a vacuum and pressure-molding machine], the film was heated to the temperature shown in Table 3. The same procedures as in Example 1A were then used for [Coating of adhesive layer], [Attachment using a vacuum and pressure-molding machine], and [Hard coat treatment]. The surface of the hard-coated lens was corroded by the solvent used in the hard-coating process, causing it to become cloudy. This resulted in the film having poor solvent resistance. The evaluation results are shown in Table 3.

[0259] (Reference Example 1A) The film used was a PET film (Lumirror T-60, film thickness 50μ) manufactured by Toray Industries, Inc. In the [Attachment using a vacuum / compressed air molding machine], the film was heated to the temperature shown in Table 3. The same procedures as in Example 1A were carried out for [film production], [adhesive layer application], [bonding using a vacuum / compressed air molding machine], and [hard coat treatment]. In the adhesion test, the hard-coated lens did not achieve good adhesion between the film and the hard-coat layer. Visual inspection of the lens revealed streaky spots across the entire surface. Furthermore, due to the soft film, the lens had poor scratch resistance, with thick scratches across the entire width of the steel wool. The evaluation results are shown in Table 3.

[0260] (Reference example 2A) The film used was an acrylic film (Acryplene HBS-006, film thickness 75 μm) manufactured by Mitsubishi Chemical Corporation. In the [Attachment using a vacuum / compressed air molding machine], the film was heated to the temperature shown in Table 3. The same procedures as in Example 1A were carried out for [film production], [adhesive layer application], [bonding using a vacuum / compressed air molding machine], and [hard coat treatment]. When the appearance of the obtained lens was visually inspected, streaky spots were observed over the entire surface of the lens. In the adhesion test, the hard-coated lens did not show good adhesion between the film and the hard-coat layer. In addition, the soft film caused poor scratch resistance, resulting in thick scratches across the entire width of the steel wool. The evaluation results are shown in Table 3.

[0261] [Table 1]

[0262] [Table 2]

[0263] [Table 3]

[0264] As shown in Tables 1 to 3, the Examples using polythiourethane films containing polythiourethane with a molecular weight between crosslinks of 950 to 3000 exhibited excellent conformability. Furthermore, the Examples were free of cloudiness and were excellent in the adhesion evaluation, indicating excellent solvent resistance. On the other hand, Comparative Examples 1A to 3A, which used polythiourethane films containing polythiourethane with a molecular weight between crosslinks of less than 950, were poor in conformability. Furthermore, Comparative Example 4A, which used a polythiourethane film containing polythiourethane with a molecular weight between crosslinks of more than 3000, was cloudy, indicating that the film surface was eroded and damaged by the solvent in the hard coat treatment, and exhibited poor solvent resistance. In addition, in Reference Examples 1A and 2A, in which films other than polythiourethane films were used, when the appearance of the obtained lenses was visually inspected, streaky spots were observed over the entire surface of the lenses. For laminated lenses using PET film, acrylic film, etc., it was necessary to formulate and use a special hard coating solution, which was cumbersome as it required an additional process. By forming a laminated lens having a polythiourethane film as a surface layer, higher adhesion can be achieved without limiting the type of hard coating liquid, and eyeglass lenses with a good appearance free of streaks can be obtained. In Examples 1A to 7A, by using polythiourethane as the film, it was possible to obtain adhesion without changing the hard coat used in the polythiourethane lens.

[0265] The second embodiment will be described in detail below with reference to examples, but the invention of the second embodiment is not limited to the descriptions of these examples.

[0266] [Evaluation method] In this example, each evaluation was carried out as follows. (Outflow start temperature) The onset temperature of the flow was measured as described above.

[0267] (Mass increase rate in hot water resistance test) The mass increase rate in the hot water resistance test was measured as described above.

[0268] (Glass transition temperature of dried aqueous polyurethane dispersion) The glass transition temperature of the dried aqueous polyurethane dispersion was measured as described above.

[0269] (Thickness measurement) The thickness of each layer was measured using a Digimatic Indicator ID-H and a Comparator Stand BSB-20X manufactured by Mitutoyo Corporation.

[0270] (Measurement of storage modulus) The measurement was carried out by the method described in the above section (Measurement of storage modulus).

[0271] (Measurement of softening temperature of thermoplastic resin) The measurement was carried out by the method described in the above section (Thermoplastic resin).

[0272] (Evaluation of eyeglass lens adhesion) Using Cellotape (registered trademark) CT405AP-18 manufactured by Nichiban Co., Ltd., a peel test was carried out in accordance with JIS K5400-8.5 (1999) by making 100 square cuts on the surface of the eyeglass lens. The number (%) of squares out of 100 that did not peel off was visually confirmed to evaluate the adhesion.

[0273] (Adhesion after peripheral processing of eyeglass lenses) Using a NIDEK Co., Ltd. patternless edger LE-1200, the outer periphery of the eyeglass lens was ground into a circle with a radius of 37.5 mm (half the maximum length in plan view) by spraying water onto the outer periphery of the lens at high speed, centered on the geometric center of the lens. After polishing, the eyeglass lenses were visually inspected under fluorescent light to check for peeling of the functional resin layer. The case where the functional resin layer did not peel off was evaluated as A, and the case where peeling occurred was evaluated as B.

[0274] (Evaluation of Scratch Resistance of Hard Coat Layer) A piece of Bonstar #0000 steel wool manufactured by Japan Steel Wool Co., Ltd., cut to approximately 3cm in length and width, was attached using double-sided tape to a HEIDON Tribogear TYPE:30S reciprocating abrasion tester manufactured by Shinto Scientific Co., Ltd. The steel wool was rubbed back and forth across the hard coat surface 10 times with a load of 1kg, and the rubbed area was visually inspected to confirm and evaluate the number and depth of scratches on the coat surface.

[0275] (Alkali resistance test) An ultrasonic cleaner MCS-6 manufactured by AS ONE Corporation was charged with a 10% by mass aqueous solution of potassium hydroxide. The eyeglass lenses were immersed in this aqueous solution and irradiated with ultrasonic waves at 60°C to 63°C for 20 minutes. After the ultrasonic irradiation, the eyeglass lenses were removed and washed with running water for 3 minutes. The eyeglass lenses were then immersed in a container equipped with an ultrasonic generator and charged with ion-exchanged water, and irradiated with ultrasonic waves at 45°C for 5 minutes. After the ultrasonic irradiation, the eyeglass lens was removed and the adhesion of the adhesive layer was evaluated. The adhesion was evaluated by a peel test using Cellotape (registered trademark) CT405AP-18 manufactured by Nichiban Co., Ltd., in accordance with JIS K5400-8.5 (1999), in which 100 squares were cut into the surface of the eyeglass lens. The number (%) of squares out of 100 that did not peel off was visually confirmed to evaluate the adhesion.

[0276] <Preparation of Lens Substrate A> To a 100 mL sample bottle, 0.02 parts by mass (1,000 ppm by mass) of Zelec (registered trademark) UN manufactured by Stepan GmbH was added as an internal release agent, 0.01 parts by mass (500 ppm by mass) of dibutyltin(II) dichloride as a catalyst, and 10.12 parts by mass of 2,5(6)-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane as a polymerizable compound, and the mixture was stirred and mixed at 20°C to obtain a homogeneous solution. To this homogeneous solution, 4.78 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) and 5.1 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were further added as polymerizable compounds, and the mixture was stirred and mixed at 20° C. to obtain a homogeneous polymerizable composition. The obtained polymerizable composition was degassed for 30 minutes to 1 hour under a reduced pressure of 400 Pa or less, and then filtered through a PTFE membrane filter with a pore size of 1 μm. The composition was then poured into a cavity consisting of a glass mold and tape (circular plano shape, radius (half the maximum length in plan view): 40.5 mm, curved shape: radius of curvature of both the convex and concave surfaces: 128 mm, center thickness: 2 mm) and sealed with tape. The mold with the polymerizable composition sealed in the cavity was placed in a polymerization oven, and the temperature was gradually increased from 25°C to 120°C over 19 hours, and then the oven was maintained at 120°C for 2 hours to polymerize. After cooling, the glass mold and tape were peeled off, and lens substrate A, a molded body made of the cured resin formed inside, was removed. The obtained molded product was colorless and transparent, and had a refractive index of ne 1.60, nd 1.59, Abbe numbers νe 40, νd 42, and a glass transition temperature of 121°C.

[0277] (Refractive index (ne, nd) and Abbe number (νe, νd) of lens substrate) Measurements were performed at 20°C using a Pulfrich refractometer KPR-30 manufactured by Kalnew Optical Co., Ltd. The refractive index and Abbe number were measured by transmitting F' line (a Cd spectral line with a wavelength of 479.99 nm), C' line (a Cd spectral line with a wavelength of 643.85 nm), F line (a H spectral line with a wavelength of 486.13 nm), C line (a H spectral line with a wavelength of 656.27 nm), e line (a Hg spectral line with a wavelength of 546.07 nm), and d line (a He spectral line with a wavelength of 587.56 nm) through the molded product. The refractive index (ne) and Abbe number (νe) at the wavelength of the e line, and the refractive index (nd) and Abbe number (νd) at the wavelength of the d line were calculated in accordance with JIS B 7090:1999 and ISO 7944:1998.

[0278] (glass transition temperature of lens substrate) Measurement was carried out by the TMA penetration method (50 g load, pin tip 0.5 mmφ, temperature rise rate 10°C / min, heating temperature range from room temperature to 140°C) using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation.

[0279] Furthermore, the lens substrate A was subjected to alkaline cleaning in the following manner. A 10% by mass aqueous solution of potassium hydroxide was charged into an ultrasonic cleaner MCS-6 manufactured by AS ONE Corp. The ultrasonic cleaner had an oscillation frequency of 40 kHz and an ultrasonic output of 150 W. Lens substrate A was immersed in this solution and irradiated with ultrasound at 50°C to 55°C for 5 minutes. After ultrasound irradiation, the lens substrate was removed and washed with running water for 3 minutes. The lens substrate was then immersed in a container equipped with an ultrasonic generator and charged with ion-exchanged water, and irradiated with ultrasound at 45°C for 5 minutes. After ultrasound irradiation, the lens substrate was removed and heated for approximately 30 minutes in a forced air circulation constant temperature oven set at 110°C. Once heating was complete, the substrate was removed from the oven and left to cool at room temperature of 18 to 30°C for at least 30 minutes.

[0280] <Synthesis Example of Polyurethane Aqueous Dispersion 1> A four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 205.6 g of UH-CARB200 (polycarbonate diol, average molecular weight 2000, manufactured by Ube Industries, Ltd.) as an active hydrogen compound, 15.4 g of triethylene glycol, 11.2 g of dimethylolpropionic acid, 1.8 g of trimethylolpropane, and 145.0 g of acetonitrile as a solvent. Then, 91.1 g of 1,3-(bisisocyanatomethyl)cyclohexane was added as an isocyanate compound to the four-neck flask, and the mixture was allowed to react for 6 hours at 75° C. After the isocyanate content (NCO%) of the reaction solution reached 2.9 mol%, 4.8 g of 2-hydroxyethyl acrylate and 0.017 g of stannous octoate were added to the four-neck flask, and the mixture was allowed to react for 2 hours at 70° C., yielding a urethane prepolymer (NCO%=2.45%). After cooling the reaction mixture to 40°C, it was neutralized with 8.3 g of triethylamine and dispersed in water by gradually adding 650 g of ion-exchanged water. Next, an amine aqueous solution prepared by dissolving 4.9 g of hydrazine monohydrate and 6.8 g of KBM602 (N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) in 46.8 g of ion-exchanged water was added to the aqueous dispersion of the urethane prepolymer to carry out a chain extension reaction. Further, acetonitrile was distilled off to obtain an aqueous polyurethane dispersion 1, which was an aqueous dispersion of an aqueous polyurethane resin with a solids content of 35% by mass and contained a polycarbonate-based polyurethane having anionic functional groups.

[0281] <Spectral Measurement> The spectral characteristics of the functional resin layer and the functional dye were measured at room temperature using a UV-Vis spectrophotometer UV-1800 manufactured by Shimadzu Corporation. The measurement wavelength range was 350 nm to 800 nm.

[0282] Example 1B (Preparation of functional resin layer) As the functional resin layer, an acrylic film having an ultraviolet blocking function (manufactured by Mitsubishi Chemical Corporation, Acryplene HBA007P, thickness 75 μm, transmittance at 380 nm 6%, length 297 mm, width 210 mm) was used. The functional resin layer was subjected to a plasma treatment by the following method.

[0283] <Plasma treatment> A small plasma device with a capacitor-type two-part electrode structure (PM100, manufactured by Yamato Scientific Co., Ltd.) was used. For plasma treatment, the chamber containing the sample was evacuated, and oxygen gas was introduced at a rate of 50 mL / min. The sample was irradiated for 15 seconds at an output of 15 W.

[0284] (Laminate preparation) The plasma-treated functional resin layer was fixed on a flat glass plate, and a polyurethane aqueous dispersion, Superflex 470 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), was dropped onto the functional resin layer using a dropper. The dropped polyurethane aqueous dispersion was applied to the functional resin layer using a bar coater (No. 10), and then dried for 5 minutes in an electric oven set at 60°C to obtain a laminate including the functional resin layer and a polycarbonate-based polyurethane adhesive layer. The thickness of the polycarbonate-based polyurethane adhesive layer is as shown in Table 4.

[0285] (Attaching lens substrate) The resulting laminate (i.e., adhesive film) was cooled to room temperature and then attached to lens substrate A using a vacuum molding device to obtain a spectacle lens comprising, in this order, a functional resin layer, a polycarbonate-based polyurethane adhesive layer, and a lens substrate. Specifically, a vacuum forming device (NGF-0404-T) manufactured by Fuse Vacuum Co., Ltd. was used. In this device, a laminate that has been heated and softened is attached to a substrate in a vacuum chamber, and then the film is pressed against the substrate using compressed air. With this device, the molding parameters can be adjusted appropriately depending on the material of the functional resin layer, the material of the release film, etc. The lamination was performed so that the polycarbonate-based polyurethane adhesive layer was attached to the convex surface of lens substrate A. When laminating, the heating temperature of the laminate was set to 115°C, and the air pressure inside the chamber was set to 1 kPa.

[0286] After bonding, the eyeglass lens was cooled to room temperature, and any laminate that protruded from the lens substrate was cut off. The eyeglass lens was then reheated for 1 hour in an electric furnace set to 120°C to produce an eyeglass lens.

[0287] Example 2B (Preparation of functional resin layer) 0.10 parts by mass of a tetraazaporphyrin compound (manufactured by Yamamoto Chemical Industry Co., Ltd., PD-311S, maximum absorption wavelength 585 nm) as a visible light absorbing dye, 0.10 parts by mass of a polyether-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KF-352A) as a leveling agent, 1.0 parts by mass of 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole (manufactured by Kyodo Pharmaceutical Co., Ltd., VIOSORB 583) as an ultraviolet absorber, 0.5 parts by mass of a sulfonium salt compound (manufactured by San-Apro Co., Ltd., CPI-210S, details are described below) as a cationic polymerization initiator, and 70 parts by mass of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, CELLOXIDE 2021P, details are described below) as a cationic polymerizable compound were weighed into a glass vial.

[0288] CPI-210S: a cationic polymerization initiator, a triarylsulfonium salt represented by the following formula, in which Rf is a perfluoroalkyl group and n is an integer of 1 to 5.

[0289] [ka]

[0290] Celloxide 2021P: Cationic polymerizable compound, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by the following formula:

[0291] [ka]

[0292] A stirring bar was placed in the vial, and the mixture was stirred and mixed using a magnetic stirrer at a rotation speed of 100 to 300 rpm (revolutions per minute) for 2 hours. During mixing, the glass vial was capped to prevent contact with the outside air. After visually confirming that the mixture had become a homogeneous solution, 30 parts by mass of a poloxamer compound composed of an ethyleneoxy group and a propyleneoxy group, which is a cationic polymerizable compound (manufactured by Adeka Corporation, Adeka Pluronic (registered trademark) L-64, average molecular weight 2,900), was added to this homogeneous solution, and the mixture was stirred and mixed at a rotational speed of 100 rpm to 300 rpm over 30 minutes to 2 hours. During mixing, if necessary, it was heated to 30°C to 60°C using a ceramic heater or an oil bath. After visually confirming that the mixture had become a homogeneous solution, it was cooled to room temperature to obtain a polymerizable composition for a homogeneous functional resin layer. The obtained polymerizable composition was filtered using a PTFE membrane filter manufactured by Advantec with a pore size of 1 μm to 5 μm.

[0293] A uniaxially stretched polypropylene film (thickness 50 μm, longitudinal length 297 mm, transverse length 210 mm), which is a release film, was fixed on a flat and UV-transmissive glass plate. On the release film, the polymerizable composition for the functional resin layer was dropped with a dropper, applied onto the release film using a bar coater (No. 20), and UV-cured using a UV curing device to obtain a functional resin layer provided with a release film. The detailed conditions for UV curing are as follows.

[0294] <UV Curing Device> A batch-type UV curing device having a power supply for UV irradiation UB012-0BM-60Hz manufactured by Eye Graphics Co., Ltd. was used. Inside the box-shaped housing of this curing device, there are a sample holder and metal halide lamps M01-L212 (arc length 122 mm, lamp output 80 W / cm) manufactured by Eye Graphics Co., Ltd. at the upper and lower parts of the sample holder, respectively. The irradiation time of the UV light of this curing device can be changed, and the output of the lamp can be switched in two steps of 750 W and 1,000 W. Also, the distance between the sample and the metal halide lamp is variable.

[0295] <Measurement of UVA Ultraviolet Intensity> The ultraviolet intensity in the wavelength range of UVA (320 nm to 390 nm) was measured using the UVA single-band light meter UVICURE (registered trademark) Plus II manufactured by EIT, INC.

[0296] <Measurement of UVC Ultraviolet Intensity> The ultraviolet intensity in the wavelength range of UVC (250 nm to 260 nm) was measured using the UVC single-band light meter UVICURE Plus II manufactured by EIT, INC.

[0297] In UV curing, UV light was irradiated from both the upper and lower surfaces (glass plate surfaces) of the polymerizable composition for the functional resin layer. Details of the UV light irradiated from the upper surface are as follows. Irradiation intensity of UV light in the UVA wavelength region: 110 mW / cm 2 、 Irradiation intensity of UV light in the UVC wavelength region: 30 mW / cm 2 Integrated light quantity of UV light in the UVA wavelength region: 3,300 mJ / cm 2 Integrated light quantity of UV light in the UVC wavelength region: 1,000 mJ / cm 2

[0298] Details of the UV light irradiated from the lower surface are as follows. Irradiation intensity of UV light in the UVA wavelength region: 100 mW / cm 2 Irradiation intensity of UV light in the UVC wavelength region: 25 mW / cm 2 Integrated light quantity of UV light in the UVA wavelength region: 3,000 mJ / cm 2 Integrated light quantity of UV light in the UVC wavelength region: 800 mJ / cm 2

[0299] Irradiation of UV on the polymerizable composition for the functional resin layer was performed in an atmosphere with a relative humidity of 30% to 70% and a temperature of 18°C to 30°C. The thickness of the obtained functional resin layer (the cured product of the polymerizable composition for the functional resin layer) is as described in Table 4. The temperature and relative humidity were measured using a tabletop thermo-hygrometer testo 608-H2 manufactured by Testo Corporation.

[0300] The spectrum of this functional resin layer was measured, and as a result, it was found that this functional resin layer had a peak at a wavelength of 585 nm and a transmittance of 37% at 585 nm, and thus had a wavelength cutting function. The spectrum was measured at room temperature using a UV-Vis spectrophotometer UV-1800 manufactured by Shimadzu Corporation, with the measurement wavelength range being 350 nm to 800 nm.

[0301] The resulting functional resin layer provided with the release film was subjected to plasma treatment in the same manner as described above.

[0302] (Laminate preparation) After the plasma treatment, polyurethane aqueous dispersion 1 was dropped onto the surface of the functional resin layer using a dropper and applied using a bar coater (No. 10), and then dried for 5 minutes in an electric furnace set at 60°C to obtain a laminate comprising a functional resin layer and a polycarbonate-based polyurethane adhesive layer. The thickness of the polycarbonate-based polyurethane adhesive layer is as shown in Table 1.

[0303] (Attaching lens substrate) The resulting laminate (i.e., adhesive film) was cooled to room temperature and then attached to lens substrate A using a vacuum molding device to obtain a spectacle lens comprising, in this order, a functional resin layer, a polycarbonate-based polyurethane adhesive layer, and a lens substrate. The specific method was the same as that described in Example 1B, except that the heating temperature of the laminate was 85°C.

[0304] After bonding, the eyeglass lens was cooled to room temperature, and any laminate that protruded from the lens substrate was cut off. The eyeglass lens was then reheated for 1 hour in an electric furnace set to 120°C to produce an eyeglass lens.

[0305] (cleaning eyeglass lenses) An ultrasonic cleaner MCS-6 manufactured by AS ONE Corporation was charged with a 10% by mass aqueous solution of potassium hydroxide. The eyeglass lenses obtained above were immersed in this solution and irradiated with ultrasonic waves at 55°C to 60°C for 10 minutes. After ultrasonic irradiation, the eyeglass lenses were removed and washed with running water for 3 minutes. The eyeglass lenses were then immersed in a container equipped with an ultrasonic generator and charged with ion-exchanged water, and irradiated with ultrasonic waves at 45°C for 5 minutes. After the ultrasonic irradiation, the eyeglass lens was removed and heated for approximately 10 minutes in a forced air circulation constant temperature oven set at 80°C. After heating was completed, the eyeglass lens was removed from the oven and left at room temperature of 18°C ​​to 30°C for 30 minutes or more to cool the eyeglass lens.

[0306] (Formation of hard coat layer) The eyeglass lens, cooled to room temperature, was fixed with a vacuum chuck to a spin coater MS-150A manufactured by Mikasa Co., Ltd., equipped with a rotating jig, and rotated at a constant rotation speed. 5 to 10 mL of MP-1179, a hard coating liquid manufactured by SDC Technologies Inc., was applied to the functional resin layer of the rotating eyeglass lens using a dropper over a period of 10 to 20 seconds. The rotation speed of the eyeglass lens was adjusted appropriately within the range of 300 rpm to 400 rpm so that the thickness of the hard coat layer would be 3 μm. When applying the hard coating liquid, the dropper was dropped without moving from the center of the eyeglass lens, or while moving the dropper from the center of the eyeglass lens to the outside. After the hard coating liquid had been dropped, the eyeglass lens was rotated at a constant speed for a further 160 to 170 seconds, so that the hard coating liquid was applied evenly to the surface of the eyeglass lens. After application of the hard coating liquid was completed, the eyeglass lens was heated for approximately 2 hours in a forced air circulation type thermostatic oven set at a temperature of 110° C. After heating was completed, the eyeglass lens was removed from the oven and cooled to room temperature, yielding an eyeglass lens having a hard coating layer on its surface.

[0307] The adhesion of the hard coat layer of the obtained eyeglass lens was evaluated according to the method for evaluating adhesion described above. The number (%) of squares where peeling of the functional resin layer was not observed was 100%, and no peeling was observed between the functional resin layer and the hard coat layer.

[0308] When the above adhesion test is carried out on a lens having a hard coat layer laminated on a functional resin layer, and peeling occurs, this means that the film has poor alkali resistance. That is, if the functional resin layer is damaged by a solvent such as an alkali used in the pretreatment in the hard coat treatment, the functional resin layer and the hard coat layer cannot be sufficiently adhered to each other, resulting in the above-mentioned peeling.

[0309] The scratch resistance of the hard coat layer of the obtained eyeglass lens was evaluated according to the method described above for evaluating the scratch resistance of the hard coat layer. No deep scratches were observed on the resulting hard coat layer.

[0310] Example 3B Spectacle lenses were produced in the same manner as in Example 1B, except that the polyurethane aqueous dispersion, Superflex 470, was changed to Evaphanol HA-170 (manufactured by Nicca Chemical Co., Ltd.).

[0311] [Comparative example 1B] Spectacle lenses were produced in the same manner as in Example 1B, except that Superflex 470, an aqueous polyurethane dispersion, was changed to Superflex 620 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0312] [Table 4]

[0313] As shown in Table 4, in examples using a method for producing eyeglass lenses that includes the steps of forming a polycarbonate-based polyurethane adhesive layer made of a dried product of an aqueous polyurethane dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one side of a functional resin layer containing a functional dye to obtain a laminate, and heating the laminate at 50°C to 150°C and attaching the polycarbonate-based polyurethane adhesive layer to a lens substrate under a reduced pressure of 20 kPa or less so that the polycarbonate-based polyurethane adhesive layer and the lens substrate are in contact with each other, and in which the dried product of the aqueous polyurethane dispersion has a storage modulus at 80°C measured under condition 1 of 0.1 MPa to 80 MPa, the results showed excellent results for adhesion of the eyeglass lenses and adhesion after processing of the eyeglass lenses' periphery. Therefore, eyeglass lenses containing a polycarbonate-based polyurethane adhesive layer with excellent adhesion to the lens substrate could be produced. Furthermore, the Examples showed excellent results in the alkali resistance test, which means that eyeglass lenses including a polycarbonate-based polyurethane adhesive layer with excellent alkali resistance could be manufactured. On the other hand, Comparative Example 1B, which used a dried product of an aqueous polyurethane dispersion with a storage modulus of more than 80 MPa at 80°C, exhibited poor adhesion to the eyeglass lens. As a result, it was not possible to produce an eyeglass lens including a polycarbonate-based polyurethane adhesive layer with excellent adhesion to the lens substrate. Comparative Example 1B also showed poor results in the alkali resistance test, making it impossible to produce eyeglass lenses including a polycarbonate-based polyurethane adhesive layer with excellent alkali resistance.

[0314] The disclosures of Japanese Patent Application No. 2022-044196, filed on March 18, 2022, and Japanese Patent Application No. 2022-044197, filed on March 18, 2022, are incorporated herein by reference in their entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference. [Explanation of symbols]

[0315] 1. Heater 2. Film 3...Base material 4...vacuum 5. Stage Up 6. Compressed air 7. Trimming

Claims

1. Contains polythiourethane, the polythiourethane is a reaction product of a difunctional thiol compound, a tri- or higher functional thiol compound, and an isocyanate compound; The minimum storage modulus is between 30°C and 160°C, and the minimum storage modulus is between 4.00 x 10 Pa and 1.40 x 10 Pa; A polythiourethane film having a thickness of 100 μm to 400 μm.

2. The polythiourethane film according to claim 1, wherein the bifunctional thiol compound has a thiol equivalent of 20% to 95% relative to 100% of the total thiol equivalent of the bifunctional thiol compound and the trifunctional or higher thiol compound.

3. The polythiourethane film according to claim 1, wherein the polythiourethane has a molecular weight between crosslinks of 950 to 3,000.

4. The polythiourethane film according to claim 1 , further comprising a functional dye.

5. 5. The polythiourethane film according to claim 4, wherein the functional dye is a specific wavelength-cutting dye or a photochromic dye.

6. A material for eyeglass lenses, comprising the polythiourethane film according to any one of claims 1 to 5 and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film.

7. 7. The eyeglass lens material according to claim 6, wherein the polyurethane adhesive layer comprises a polycarbonate-based polyurethane containing an anionic functional group.

8. 7. The eyeglass lens material according to claim 6, further comprising a hard coat layer as the outermost layer.

9. The eyeglass lens material according to claim 6, and a spectacle lens substrate adhered to the polyurethane adhesive layer of the spectacle lens material.

10. The eyeglass lens according to claim 9 , wherein the eyeglass lens substrate has a convex surface or a concave surface bonded to the polyurethane adhesive layer of the eyeglass lens material.

11. The eyeglass lens according to claim 9, wherein the eyeglass lens substrate has a radius of curvature of 62.5 mm to 125.0 mm.

12. The eyeglass lens according to claim 9, comprising two or more eyeglass lens materials.

13. 10. The eyeglass lens according to claim 9, wherein the eyeglass lens substrate comprises at least one selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane.

14. A method for manufacturing eyeglass lenses, comprising the step of attaching the eyeglass lens material according to claim 6 to an eyeglass lens substrate to obtain an eyeglass lens.

15. The method for manufacturing eyeglass lenses according to claim 14, further comprising the step of attaching the eyeglass lens material to an eyeglass lens substrate using a vacuum / compressed air molding machine to obtain an eyeglass lens.

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