Thiourethane film, roll, lens, glasses, method for producing (THIO)urethane resin film, and method for producing multilayer lens

Abstract

Disclosed is a thiourethane film which contains a cured product of a photopolymerizable composition that contains a bifunctional or higher functional polythiol (A), an isocyanate compound (B), and a photopolymerization initiator (C), wherein the product E' × T of the storage elastic modulus E' at 40°C and the thickness T of the thiourethane film is 50 MPa∙mm to 1,800 MPa∙mm inclusive.

Description

Thiourethane film, roll-shaped wound product, lens, eyeglasses, method for producing (thio)urethane resin film, and method for producing laminated lens

[0001] The present invention relates to a thiourethane film, a roll, a lens, eyeglasses, a method for producing a (thio)urethane resin film, and a method for producing a laminated lens.

[0002] In some eyeglass lenses, a functional layer using a polymerizable composition is used on the lens substrate. Patent Document 1 is an example of a document relating to such a functional layer using a polymerizable composition.

[0003] Patent Document 1 describes a method for molding a transparent resin laminate having a functional resin layer on at least one surface of a transparent resin substrate, the method comprising the following steps (1) a first step of preparing a seat mold having a concave surface corresponding to the underside of the transparent resin substrate and dripping a monomer (including a prepolymer; the same applies hereinafter) of a thermosetting molding material onto the concave surface in an amount sufficient to form the functional resin layer; (2) a second step of exposing an assembly in which the transparent resin substrate is placed on the dripped monomer to an atmosphere at a temperature at which the molding material can gel for a predetermined period of time, thereby diffusing and gelling the monomer on the underside of the transparent resin substrate while removing air between the seat mold and the transparent resin substrate, thereby shaping the monomer; and (3) a third step of curing the gelled shaped material in the assembly after the second step and releasing it from the mold (Claim 1 of Patent Document 1). Patent Document 1 also describes a molding material composition for the functional resin layer or the upper and lower transparent resin layers used in the molding method, the molding material composition comprising an NCO component consisting mainly of or consisting of an alicyclic diisocyanate, an average functionality of the SH component being 3.0 or more, and further comprising EOPO or an EOPO chain-containing polyol as a modifying component, such that the viscosity of the dropped monomer is adjusted to the diffusible level when the transparent resin substrate is placed on the substrate (claim 8 of Patent Document 1). Patent Document 1 also describes that the molding method provides a method for molding a transparent resin laminate that does not require adhesive tape or gaskets to form cavities in the functional resin layer, which is expected to reduce the number of steps, suppresses the production of by-products of waste, and improves the adhesion of the functional resin layer to the transparent resin substrate.

[0004] Japanese Patent Application Laid-Open No. 2022-158759

[0005] The present invention provides a thiourethane film with improved winding properties and a method for producing a (thio)urethane resin film.

[0006] The present invention can be expressed, for example, as follows.

[0007] [1] A thiourethane film comprising a cured product of a photopolymerizable composition containing a difunctional or higher polythiol (A), an isocyanate compound (B), and a photopolymerization initiator (C), wherein the product E' x T of the storage modulus E' at 40°C and the thickness T of the thiourethane film is 50 MPa·mm or more and 1800 MPa·mm or less. [2] The thiourethane film according to [1] has a restoring force of 40.0 N / m or less, measured according to the following <Conditions>. <Conditions> The thiourethane film is cut into strips measuring 1 cm wide x 12 cm long, and one end (a) of the thiourethane film is fixed to a resin cylinder having an outer diameter of 10 cm with adhesive tape and wrapped around the resin cylinder. Next, a plate measuring 1 cm wide x 15 cm long is placed horizontally, with the end (b) of the thiourethane film opposite to the end (a) as the contact point. Next, one end (c) of the plate is overlapped longitudinally with the end of the thiourethane film on the side of the end (b) by 1 cm, and the end (d) of the plate opposite the end (c) is placed so that it is in contact with the upper side of the measurement axis of the digital force gauge. The plate is fixed with clay 7.5 cm from the end (d) and is set so that it can move around the point fixed with clay as a fulcrum. Next, the height of the resin cylinder is raised so that the thiourethane film rises along the underside of the plate, and the plate and the tangent to the outer circumference of the resin cylinder overlap. When the 1 cm overlapping portion of the plate and the thiourethane film are completely in contact, the value G (g) of the digital force gauge is read, and the restoring force (N / m) of the thiourethane film is calculated according to the following formula (1): Formula (1): Restoring force (N / m) = (G (g) × 9.80665 / 1000) × 100 The 9.80665 in the above formula (1) is the gravitational acceleration (m / s ２). [3] The thiourethane film according to [1] or [2], which contains elemental boron. [4] The thiourethane film according to [3], in which the elemental boron content in the thiourethane film is 5 ppm or more and 200 ppm or less. [5] The thiourethane film according to any one of [1] to [4], in which the photopolymerization initiator (C) contains boron. [6] The thiourethane film according to any one of [1] to [5], in which the photopolymerization initiator (C) contains a base generator composed of an organic boron anion and a counter cation. [7] The thiourethane film according to [6], in which the base generator contains one or more compounds selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2): (In formula (1), R １ ~R ４ each independently represents an alkyl group having 1 to 8 carbon atoms; R ５ ~R ８ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group. (In formula (2), R １ ~R ７ each independently represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms; R ８ ~R １１each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, the naphthyl group, the anthracenyl group, and the phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.) [8] The thiourethane film according to any one of [1] to [7], wherein the content of the photopolymerization initiator (C) is 250 ppm by mass or more relative to the total amount of the bifunctional or higher functional polythiol (A) and the isocyanate compound (B). [9] The thiourethane film according to any one of [1] to [8], wherein the total content of the bifunctional or higher functional polythiol (A) and the isocyanate compound (B) is 50% by mass or more and less than 100% by mass, when the total amount of the photopolymerizable composition is 100% by mass.

[10] The thiourethane film according to any one of [1] to [9], wherein the photopolymerizable composition further contains a metal catalyst (D).

[11] The thiourethane film according to any one of [1] to

[10] , wherein the photopolymerizable composition is irradiated with ultraviolet light to polymerize a portion of the photopolymerizable composition, and then the photopolymerizable composition is heated to further polymerize.

[12] The thiourethane film according to any one of [1] to

[11] , wherein the thickness T is 50 μm or more and 3000 μm or less.

[13] The difunctional or higher functional polythiol (A) is 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)- The thiourethane film according to any one of [1] to

[12] , which contains at least one selected from the group consisting of 1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.

[14] The thiourethane film according to any one of [1] to

[13] , wherein the isocyanate compound (B) comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

[15] The thiourethane film according to any one of [1] to

[14] , wherein the equivalent ratio (thiol group / isocyanato group) of the thiol group in the bifunctional or higher polythiol (A) to the isocyanato group in the isocyanate compound (B) is 0.8 or more and 1.2 or less.

[16] The thiourethane film according to any one of [1] to

[15] , wherein the difunctional or higher functional polythiol (A) comprises a difunctional polythiol and a trifunctional or higher functional polythiol.

[17] The thiourethane film according to any one of [1] to

[16] , further comprising one or more layers selected from the group consisting of a hard coat layer and an antireflection layer.

[18] The thiourethane film according to any one of [1] to

[17] , wherein the water contact angle on the surface of the thiourethane film is 50.0° or more and 90.0° or less.

[19] The thiourethane film according to any one of [1] to

[18] , further comprising an adhesive layer on one side of the thiourethane film.

[20] A rolled wound product comprising the thiourethane film according to any one of [1] to

[19] and a winding core, wherein the thiourethane film is wound around the winding core in a roll shape.

[21] A lens comprising the thiourethane film according to any one of [1] to

[19] .

[22] The lens according to

[21] , wherein the thiourethane film is in direct contact with the lens substrate.

[23] Eyeglasses equipped with the lens according to

[21] or

[22] .

[24] A method for producing a (thio)urethane resin film, comprising: a first polymerization step of irradiating a film of a photopolymerizable composition containing an active hydrogen compound, an isocyanate compound, a photopolymerization initiator, and a metal catalyst, provided on a substrate, with ultraviolet light to polymerize a portion of the photopolymerizable composition; and a second polymerization step of heating the photopolymerizable composition after the first polymerization step to further polymerize the photopolymerizable composition.

[25] A method for producing a (thio)urethane resin film according to

[24] , further comprising a viscosity adjustment step of adjusting the viscosity of a mixed liquid A containing the active hydrogen compound, the isocyanate compound, and the metal catalyst to 50 mPa·s or more and 2000 mPa·s or less.

[26] A method for producing a (thio)urethane resin film according to

[25] , further comprising, after the viscosity adjustment step, a step of mixing the mixed liquid A with a mixed liquid B containing the isocyanate compound and the photopolymerization initiator.

[27] The method for producing a (thio)urethane resin film according to any one of

[24] to

[26] , wherein the substrate is a release film.

[28] The method for producing a (thio)urethane resin film according to

[27] , wherein the release film comprises at least one selected from the group consisting of polyethylene terephthalate and fluororesin.

[29] The method for producing a (thio)urethane resin film according to any one of

[24] to

[28] , wherein the (thio)urethane resin film further comprises a protective film on the surface opposite to the substrate.

[30] A method for producing a laminated lens, comprising the steps of obtaining a (thio)urethane resin film by the method for producing a (thio)urethane resin film according to any one of

[24] to

[29] , and laminating the obtained (thio)urethane resin film to a lens substrate.

[31] The method for producing a laminated lens according to

[30] , wherein the lens substrate comprises at least one selected from the group consisting of poly(meth)acrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane.

[32] The method for producing a laminated lens according to

[30] or

[31] , wherein in the laminating step, the (thio)urethane resin film is laminated to the lens substrate by one or two methods selected from the group consisting of vacuum molding and pressure molding.

[0008] According to the present invention, it is possible to provide a thiourethane film and a method for producing a (thio)urethane resin film with improved winding properties.

[0009] 1A and 1B are schematic diagrams showing a state of measurement of restoring force (at the start of a test) and a state of measurement of restoring force (when reading a digital force gauge).

[0010] The present invention will be described below based on embodiments. In this embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. In this embodiment, the term "film" is a concept that includes what is generally called a "sheet." In this embodiment, thiourethane refers to a compound having a thiourethane bond formed by the reaction of a polythiol component and an isocyanate component.

[0011] <Thiourethane Film> The thiourethane film of the present embodiment is a thiourethane film containing a cured product of a photopolymerizable composition containing a difunctional or higher functional polythiol (A), an isocyanate compound (B), and a photopolymerization initiator (C), and the product E' x T of the storage modulus E' at 40°C and the thickness T of the thiourethane film is 50 MPa mm or more and 1800 MPa mm or less.

[0012] The inventors' investigations have revealed that the windability of a thiourethane film can be improved by producing the film using a photopolymerizable composition containing a specific polythiol, an isocyanate compound, and a photopolymerization initiator, and by setting the product E' x T of the storage modulus E' of the thiourethane film at 40°C and the thickness T of the thiourethane film within a specific range.

[0013] The product E' x T of the storage modulus E' at 40°C of the thiourethane film of this embodiment and the thickness T of the thiourethane film is 50 MPa·mm or more, preferably 100 MPa·mm or more, more preferably 300 MPa·mm or more, even more preferably 500 MPa·mm or more, even more preferably 700 MPa·mm or more, and even more preferably 800 MPa·mm or more, from the viewpoint of further improving the performance balance of the winding property of the thiourethane film, the anti-blocking property, and the releasability of the protective film described below; and from the viewpoint of further improving the winding property of the thiourethane film, it is 1800 MPa·mm or less, preferably 1600 MPa·mm or less, more preferably 1400 MPa·mm or less, even more preferably 1200 MPa·mm or less, and even more preferably 1150 MPa·mm or less. Furthermore, from the viewpoint of further improving the balance of the winding property, anti-blocking property, and releasability of the protective film described below, of the thiourethane film of this embodiment, the product E' x T of the storage modulus E' at 40°C and the thickness T of the thiourethane film is 50 MPa mm or more and 1800 MPa mm or less, preferably 100 MPa mm or more and 1600 MPa mm or less, more preferably 300 MPa mm or more and 1600 MPa mm or less, even more preferably 500 MPa mm or more and 1400 MPa mm or less, even more preferably 700 MPa mm or more and 1200 MPa mm or less, and even more preferably 800 MPa mm or more and 1150 MPa mm or less.

[0014] From the viewpoint of further improving the winding properties of the thiourethane film, the storage modulus E' of the thiourethane film at 40°C is preferably 1500 MPa or more, more preferably 2000 MPa or more, and even more preferably 2300 MPa or more, and is preferably 8000 MPa or less, more preferably 7500 MPa or less, even more preferably 7000 MPa or less, even more preferably 6500 MPa or less, even more preferably 6000 MPa or less, even more preferably 5700 MPa or less, even more preferably 5500 MPa or less, even more preferably 5000 MPa or less, even more preferably 4500 MPa or less, even more preferably 4000 MPa or less, preferably 3800 MPa or less, more preferably 3500 MPa or less, and even more preferably 3300 MPa or less. From the viewpoint of further improving the winding property of the thiourethane film, the storage modulus E' of the thiourethane film at 40°C is preferably 1500 MPa to 8000 MPa, more preferably 1500 MPa to 7500 MPa, even more preferably 1500 MPa to 7000 MPa, even more preferably 1500 MPa to 6500 MPa, even more preferably 2000 MPa to 6000 MPa, even more preferably 2000 MPa to 5500 MPa, even more preferably 2000 MPa to 5000 MPa, even more preferably 2300 MPa to 4500 MPa, and even more preferably 2300 MPa to 4000 MPa. The storage modulus of the thiourethane film at 40°C can be measured as follows. A test piece having a width of 5 mm and a length of 30 mm is cut from the thiourethane film, and solid viscoelastic temperature dispersion measurement is performed under the following conditions to measure the storage modulus E' (MPa) at 40°C. Apparatus: Dynamic viscoelasticity measuring device Deformation mode: Tensile Temperature increase rate: 2°C / min Frequency: 1Hz Set strain: 0.1% Environment: Air atmosphere

[0015] The thiourethane film of this embodiment preferably has a restoring force of 40.0 N / m or less, measured under the following conditions. Conditions: The thiourethane film is cut into strips measuring 1 cm wide and 12 cm long. One end (a) of the thiourethane film is fixed to a resin cylinder with an outer diameter of 10 cm with adhesive tape, and the film is then wrapped around the resin cylinder. The resin cylinder is fixed in place and does not rotate. Next, a plate measuring 1 cm wide and 15 cm long is placed horizontally, with the end (b) of the thiourethane film opposite the end (a) of the thiourethane film as the contact point. Next, one end (c) of the plate is overlapped by 1 cm longitudinally with the end of the thiourethane film near the end (b), and the end (d) of the plate opposite the end (c) is placed so that it is in contact with the upper side of the measurement axis of the digital force gauge. The plate is fixed with clay 7.5 cm from the end (d), and is positioned so that it can move around the point where it is fixed with clay as a fulcrum. Next, by raising the height of the resin cylinder, the thiourethane film rises along the underside of the plate, the plate and the tangent to the outer periphery of the resin cylinder overlap, and the value G (g) of the digital force gauge is read when the 1 cm overlapping portion between the plate and the thiourethane film is completely in close contact. The restoring force (N / m) of the thiourethane film is calculated according to the following formula (1): Formula (1): Restoring force (N / m) = (G (g) × 9.80665 / 1000) × 100 Note that 9.80665 in formula (1) is the gravitational acceleration (m / s ２ The above expression "complete adhesion of the 1 cm overlapping portion of the plate and the thiourethane film" means that the thiourethane film is pushed up from below the plate, and the portion of the plate measuring 1 cm in length and 1 cm in width from one end (c) and the portion of the thiourethane film measuring 1 cm in length and 1 cm in width from one end (b) are in contact with each other without any gaps over the entire surface.

[0016] The restoring force of the thiourethane film measured under the above conditions is, from the viewpoint of further improving the winding property of the film, preferably 40.0 N / m or less, more preferably 35.0 N / m or less, even more preferably 30.0 N / m or less, even more preferably 25.0 N / m or less, even more preferably 20.0 N / m or less, even more preferably 15.0 N / m or less, even more preferably 12.0 N / m or less, and even more preferably 10.0 N / m or less; from the viewpoint of further improving the performance balance of the winding property of the film, blocking property, and the releasability of the protective film described below, it is preferably 0 N / m or more, more preferably 0.3 N / m or more, even more preferably 0.5 N / m or more, even more preferably 0.8 N / m or more, even more preferably 1.0 N / m or more, even more preferably 1.5 N / m or more, even more preferably 3.0 N / m or more, even more preferably 5.0 N / m or more, and even more preferably 7.0 N / m or more.

[0017] In order to keep the E'xT and restoring force of the thiourethane film within the above ranges, it is important to consider the type and composition of the monomers used in the photopolymerizable composition, to irradiate the photopolymerizable composition with ultraviolet light to polymerize a portion of the photopolymerizable composition, and then to heat the photopolymerizable composition to further polymerize it and harden the photopolymerizable composition, and to adjust the thickness of the thiourethane film, etc., to within an appropriate range.

[0018] The restoring force of the thiourethane film per 1 m width and 300 μm thickness is preferably 20.0 N / m or less, more preferably 15.0 N / m or less, even more preferably 12.0 N / m or less, and even more preferably 10.0 N / m or less, from the viewpoint of further improving the winding property of the film, blocking property, and the performance balance of the protective film described later, preferably 0 N / m or more, more preferably 0.5 N / m or more, even more preferably 0.8 N / m or more, even more preferably 1.0 N / m or more, even more preferably 1.5 N / m or more, even more preferably 2.0 N / m or more, even more preferably 3.0 N / m or more, and even more preferably 6.0 N / m or more. The restoring force of the thiourethane film per 1 m width and 300 μm thickness can be calculated using the following formula (2) using the digital force gauge value G (g) measured in the same manner as the restoring force per 1 m width described above and the thickness (μm) of the thiourethane film described later. Equation (2): Restoring force (N / m) = (G (g) × 9.80665 (m / s ２ ) / 1000 × 100) / thiourethane film thickness (μm) × 300 (μm)

[0019] The thickness T of the thiourethane film is preferably 50 μm or more, more preferably 70 μm or more, even more preferably 100 μm or more, even more preferably 130 μm or more, even more preferably 150 μm or more, even more preferably 200 μm or more, even more preferably 250 μm or more, even more preferably 300 μm or more, and preferably 3000 μm or less, more preferably 2000 μm or less, even more preferably 1000 μm or less, even more preferably 800 μm or less, even more preferably 650 μm or less, even more preferably 600 μm or less, even more preferably 500 μm or less, even more preferably 450 μm or less, even more preferably 400 μm or less. The thickness T of the thiourethane film is preferably 50 μm or more and 3000 μm or less, more preferably 70 μm or more and 2000 μm or less, even more preferably 100 μm or more and 1000 μm or less, even more preferably 130 μm or more and 800 μm or less, even more preferably 150 μm or more and 650 μm or less, even more preferably 200 μm or more and 600 μm or less, even more preferably 250 μm or more and 500 μm or less, even more preferably 300 μm or more and 450 μm or less, and even more preferably 300 μm or more and 400 μm or less. By setting the thickness T of the thiourethane film within the above range, the winding properties of the thiourethane film are further improved. Furthermore, by setting the thickness T of the thiourethane film at or above the lower limit, E' × T and the restoring force can be further improved, and by setting the thickness T of the thiourethane film at or below the upper limit, E' × T and the restoring force can be further reduced. The thickness T of the thiourethane film can be measured using a digimatic indicator.

[0020] [Difunctional or higher polythiol (A)] The photopolymerizable composition in the thiourethane film of this embodiment contains a difunctional or higher polythiol (A). This allows a thiourethane bond to be formed between the difunctional or higher polythiol (A) and the isocyanate compound (B) described below. The polythiol is highly nucleophilic and highly reactive with the isocyanate compound.

[0021] The difunctional or higher functional polythiol (A) is preferably 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, 4-mercaptomethyl-1,8-dimercapto-3, 6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, The compound contains one or more compounds selected from the group consisting of 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane, more preferably one or two or more compounds selected from the group consisting of bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and pentaerythritol tetrakis(3-mercaptopropionate), and even more preferably one or two compounds selected from the group consisting of bis(2-mercaptoethyl)sulfide and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0022] The difunctional or higher functional polythiol (A) preferably includes both a difunctional polythiol and a trifunctional or higher functional polythiol, which allows the flexibility of the resulting film to fall within a more appropriate range and makes it suitable for vacuum molding or pressure molding.

[0023] The thiol equivalent of the bifunctional polythiol can be appropriately selected depending on the type of isocyanate compound (B). From the viewpoint of appropriately improving the flexibility of the obtained film, the thiol equivalent is preferably 0% or more, more preferably 1% or more, even more preferably 5% or more, even more preferably 10% or more, even more preferably 15% or more, even more preferably 18% or more, even more preferably 20% or more, even more preferably 30% or more, and even more preferably 40% or more, relative to 100% of the total thiol equivalent of the bifunctional polythiol and the tri- or higher functional polythiol. From the viewpoint of appropriately hardening the obtained film, it is preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less.

[0024] (Bifunctional Polythiol) Examples of bifunctional polythiols include methanedithiol, ethanedithiol, 1,3-propanedithiol, 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)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;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; 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; 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 are also included.

[0025] Among these, it is more preferable that the bifunctional polythiol contains one or more selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0026] (Trifunctional or higher functional polythiols) Examples of trifunctional or higher functional polythiols 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, thioglycolic acid esters and mercaptopropionic acid esters thereof; 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; 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; 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.

[0027] Examples of tri- or higher functional polythiols include 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, 2-(2,2-bis(mercaptomethylthio)propane), ... The mercaptomethylthio-methyl ester preferably contains one or more selected from the group consisting of 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane, more preferably contains one or more selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and pentaerythritol tetrakis(3-mercaptopropionate), and even more preferably contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0028] The difunctional or higher functional polythiol (A) of the present embodiment preferably contains one or more difunctional polythiols selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, and 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is a trifunctional or higher functional polythiol, and more preferably contains bis(2-mercaptoethyl)sulfide and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0029] [Isocyanate Compound (B)] The photopolymerizable composition in the thiourethane film of this embodiment contains an isocyanate compound (B). The isocyanate compound (B) is preferably selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, The compound contains one or more selected from the group consisting of tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate, and more preferably contains one or more selected from the group consisting of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and xylylene diisocyanate.

[0030] The equivalent ratio of the thiol groups in the difunctional or higher polythiol (A) to the isocyanato groups in the isocyanate compound (B) (thiol groups / isocyanato groups) is preferably 0.8 or more, more preferably 0.85 or more, even more preferably 0.9 or more, and is preferably 1.2 or less, more preferably 1.15 or less, even more preferably 1.1 or less, thereby making it possible to obtain a thiourethane that is suitable for use as a lens material.

[0031] The total content of the difunctional or higher polythiol (A) and the isocyanate compound (B) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, even more preferably 99% by mass or more, and is preferably less than 100% by mass, when the entire photopolymerizable composition is taken as 100% by mass.

[0032] [Photopolymerization initiator (C)] The photopolymerizable composition in the thiourethane film of this embodiment contains a photopolymerization initiator (C). The photopolymerization initiator (C) is an initiator capable of photopolymerization, and preferably contains one or more selected from the group consisting of radical polymerization initiators and base generators, and more preferably contains a base generator from the viewpoint of further improving photopolymerizability.

[0033] (Base Generator) The base generator is preferably a compound comprising an organic boron anion and a counter cation. The organic boron anion preferably comprises one or more selected from the group consisting of a phenyl group, an alkyl group, and an aryl group, and more preferably comprises one or more selected from the group consisting of a phenyl group and an alkyl group. The counter cation preferably comprises one or more selected from the group consisting of ammonium or an ammonium salt, and more preferably comprises an ammonium salt.

[0034] The base generator more preferably contains one or more compounds selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2).

[0035]

[0036] In formula (1), R １ ~R ４ preferably each independently represents an alkyl group having 1 to 8 carbon atoms, and R ５ ~R ８ preferably each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0037] In formula (1), R １ ~R ４ are preferably identical. １ ~R ４is more preferably an alkyl group having 2 to 5 carbon atoms, even more preferably a linear alkyl group, and even more preferably an n-butyl group. ８ is more preferably an alkyl group having 2 to 5 carbon atoms, even more preferably a linear alkyl group, and even more preferably an n-butyl group. ５ ~R ７ are preferably identical. ５ ~R ７ is more preferably a phenyl group, a butylphenyl group, or a naphthyl group, and even more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. ５ ~R ７ When contains an aromatic ring, the aromatic ring may be substituted with an alkyl group, an aryl group, or the like.

[0038] The compound represented by formula (1) is preferably at least one selected from the group consisting of tetra(n-butyl)ammonium n-butyltriphenylborate, tetra(n-butyl)ammonium n-butyltri(4-tert-butylphenyl)borate, tetra(n-butyl)ammonium n-butyltri(1-naphthyl)borate, and tetra(n-butyl)ammonium n-butyltri(4-methyl-1-naphthyl)borate. The symbol "=" in the compound name indicates an ionic bond. Among these, from the viewpoint of further improving the performance balance of solubility, polymerizability, and pot life, the compound represented by formula (1) is more preferably at least one selected from the group consisting of tetra(n-butyl)ammonium n-butyltriphenylborate and tetra(n-butyl)ammonium n-butyltri(1-naphthyl)borate.

[0039]

[0040] In formula (2), R １ ~R ７ each independently represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms; R ８ ~R １１each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0041] In formula (2), R １ ~R ７ are preferably identical. １ ~R ７ is preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. １１ is more preferably an alkyl group having 2 to 5 carbon atoms, even more preferably a linear alkyl group, and even more preferably an n-butyl group. ８ ~R １０ are preferably identical. ８ ~R １０ is more preferably a phenyl group, a butylphenyl group, or a naphthyl group, and even more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. ８ ~R １０ When contains an aromatic ring, the aromatic ring may be substituted with an alkyl group, an aryl group, or the like.

[0042] The compound comprising the above-mentioned organic boron anion and counter cation may be commercially available, such as Karenz (registered trademark) N3B and Karenz (registered trademark) P3B (both manufactured by Resonac Corporation), WPBG-300, and WPBG-345 (both manufactured by Fujifilm Corporation).

[0043] (Radical Polymerization Initiator) As the radical polymerization initiator, known thermal radical polymerization initiators and photoradical polymerization initiators can be used. Examples of the thermal radical polymerization initiator include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, and ethyl-3,3-bis(t-butylperoxy). peroxy ketals such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate, t-butylperoxyacetate, and the like; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, and the like; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane, and the like; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, and the like.

[0044] Examples of photoradical polymerization initiators include benzoin alkyl ether, benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoyl formate, isopropyl thioxanthone, and mixtures of two or more thereof. Sensitizers can also be used in conjunction with these photoradical polymerization initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, and chloranil; nitro compounds such as nitrobenzene, p-dinitrobenzene, and 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene.

[0045] From the viewpoint of further improving photopolymerizability and making it possible to form a thiourethane film, the content of the photopolymerization initiator (C) is preferably 250 mass ppm or more, more preferably 300 mass ppm or more, even more preferably 500 mass ppm or more, and even more preferably 700 mass ppm or more, relative to the total amount of the bifunctional or higher polythiol (A) and the isocyanate compound (B), and is preferably 20,000 mass ppm or less, more preferably 15,000 mass ppm or less, even more preferably 12,000 mass ppm or less, even more preferably 10,000 mass ppm or less, even more preferably 8,000 mass ppm or less, and even more preferably 6,000 mass ppm or less. Furthermore, from the viewpoint of further reducing the Young's modulus of the obtained thiourethane film and further improving the winding property, the content of the photopolymerization initiator (C) is more preferably 1000 ppm by mass or more, more preferably 1200 ppm by mass or more, even more preferably 1300 ppm by mass or more, even more preferably 1400 ppm by mass or more, even more preferably 1500 ppm by mass or more, and even more preferably 2000 ppm by mass or more, relative to the total amount of the bifunctional or higher functional polythiol (A) and the isocyanate compound (B), Furthermore, from the viewpoint of further suppressing coloration of the film, the content is more preferably 5000 ppm by mass or less, even more preferably 4500 ppm by mass or less, and even more preferably 4000 ppm by mass or less; from the viewpoint of moderately increasing the Young's modulus of the film and further improving the winding property, the content is more preferably 2500 ppm by mass or less; and from the viewpoint of further reducing the yellowness index (YI value) of the film and further improving the appearance of the film, the content is more preferably 2300 ppm by mass or less, and even more preferably 2100 ppm by mass or less. Furthermore, from the viewpoint of further improving photopolymerizability and making it possible to form a thiourethane film, the content of the photopolymerization initiator (C) is preferably from 250 ppm by mass to 20,000 ppm by mass, more preferably from 300 ppm by mass to 15,000 ppm by mass, even more preferably from 500 ppm by mass to 10,000 ppm by mass, even more preferably from 700 ppm by mass to 8,000 ppm by mass, and even more preferably from 700 ppm by mass to 6,000 ppm by mass, relative to the total amount of the bifunctional or higher polythiol (A) and the isocyanate compound (B).Further, the content of the photopolymerization initiator (C) is more preferably 1000 mass ppm or more and 5000 mass ppm or less, more preferably 1200 mass ppm or more and 4500 mass ppm or less, more preferably 1300 mass ppm or more and 4500 mass ppm or less, more preferably 1400 mass ppm or more and 4000 mass ppm or less, more preferably 1500 mass ppm or more and 2500 mass ppm or less, more preferably 2000 mass ppm or more and 2300 mass ppm or less, based on the total amount of the difunctional or higher polythiol (A) and the isocyanate compound (B). By making the content of the photopolymerization initiator (C) 1000 mass ppm or more, the Young's modulus of the obtained thiourethane film can be further reduced, and the winding property can be further improved. Furthermore, by having the content of the photopolymerization initiator (C) be 5000 ppm by mass or less, the coloring of the film can be further suppressed, by having the content of the photopolymerization initiator (C) be 2500 ppm by mass or less, the Young's modulus of the film can be moderately increased and the winding property can be further improved, and by having the content of the photopolymerization initiator (C) be 2300 ppm by mass or less, the yellowness index (YI value) of the film can be further reduced and the appearance of the film can be further improved. Note that the unit of the content of the photopolymerization initiator (C) (ppm by mass) represents the content (mg) of the photopolymerization initiator (C) per 1 kg of the total of the difunctional or higher polythiol (A) and the isocyanate compound (B), i.e., mg / kg.

[0046] The thiourethane film of this embodiment preferably contains elemental boron. For example, when the thiourethane film contains the above-described photopolymerization initiator (C), the thiourethane film contains elemental boron derived from the photopolymerization initiator (C). The presence of elemental boron in the thiourethane film can be determined by combining elemental analysis such as X-ray fluorescence analysis or ICP atomic emission analysis with X-ray photoelectron spectroscopy (XPS / ESCA) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). For example, after acid decomposition of the thiourethane film using a microwave acid decomposition device, the boron content can be measured by the standard addition method using inductively coupled plasma mass spectrometry (ICP-MS). The boron content in the thiourethane film is preferably 10 ppm or more and 300 ppm or less. The unit of boron content, "ppm," represents the amount of boron (mg) per kg of thiourethane film, i.e., mg / kg.

[0047] From the viewpoint of further promoting the polymerization of the photopolymerizable composition, making it easier to form a thiourethane film, and further improving the appearance, the boron element content in the thiourethane film is preferably 5 ppm or more, more preferably 10 ppm or more, even more preferably 15 ppm or more, and even more preferably 20 ppm or more, and is preferably 200 ppm or less, more preferably 180 ppm or less, even more preferably 160 ppm or less, even more preferably 130 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, and even more preferably 50 ppm or less. Furthermore, from the viewpoint of further promoting the polymerization of the photopolymerizable composition, making it possible to form a thiourethane film, and further improving the appearance, the boron element content in the thiourethane film is preferably 5 ppm to 200 ppm, more preferably 5 ppm to 180 ppm, even more preferably 10 ppm to 160 ppm, even more preferably 10 ppm to 130 ppm, even more preferably 15 ppm to 100 ppm, even more preferably 15 ppm to 80 ppm, and even more preferably 20 ppm to 50 ppm. The boron element content in the thiourethane film can be measured, for example, by acid decomposition of the thiourethane film by a wet decomposition method, followed by inductively coupled plasma mass spectrometry (ICP-MS). Specific measurement methods are described in the Examples section.

[0048] [Metal Catalyst (D)] The photopolymerizable composition in the thiourethane film of this embodiment preferably further contains a metal catalyst (D). Examples of the metal catalyst (D) include organotin compounds, organolead compounds, organonickel compounds, organocupper compounds, organobismuth compounds, and potassium salts. Among these, it is preferable that the metal catalyst (D) contains an organotin compound.

[0049] Examples of organotin compounds include tin acetate, tin octoate, tin oleate, tin laurate, monobutyltin trioctate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dimethyltin dichloride, dibutyltin dichloride, and the like, and preferably includes one or two compounds selected from the group consisting of dimethyltin dichloride and dibutyltin dichloride.

[0050] From the viewpoint of further improving the polymerizability, the content of the metal catalyst (D) is preferably 0.1 ppm or more, more preferably 0.5 ppm or more, even more preferably 1 ppm or more, even more preferably 5 ppm or more, and is preferably 45 ppm or less, more preferably 40 ppm or less, even more preferably 35 ppm or less, relative to the total of the difunctional or higher polythiol (A) and the isocyanate compound (B). The unit (ppm) of the content of the metal catalyst (D) represents the content (mg) of the metal catalyst (D) per 1 kg of the total of the difunctional or higher polythiol (A) and the isocyanate compound (B), i.e., mg / kg.

[0051] [Other Components] The photopolymerizable composition of the present embodiment may further include an ultraviolet absorber, an antioxidant, a light stabilizer, a sensitizer, a release agent, a solvent, a bluing agent, an IR-cutting agent, a blue light-cutting agent, a reactive diluent, an oil-soluble dye, a pigment, a coloring matter, a fragrance, a filler, an adhesion improver such as a coupling agent, a chain extender, a crosslinking agent, an antifoaming agent, a suspending agent, a dispersing agent, a plasticizer, an anti-sagging agent, an antistaining agent, a preservative, a disinfectant, an antibacterial agent, an anti-mold agent, a matting agent, a thickener, a pigment dispersant, an anti-cracking agent, an agent for improving scratch resistance, a slip agent, a surface modifier, an agent for preventing color separation, an emulsifier, an anti-skinning agent, a desiccant, an antistatic agent, a conductive agent (electrostatic assistant), a flame retardant, a thermal conductivity improver, a plasticizer, an ion exchange resin, or the like.

[0052] Examples of the release agent include acidic phosphate ester compounds, polyether-modified silicones, alkyl-modified silicones, polyester-modified silicones, dimethylpolysiloxanes, polyoxyalkylene glycol monoalkyl ether compounds, polyoxyalkylene glycol monoester compounds, fluorine atom-containing compounds, surfactants, nonionic surfactants, and acrylic surfactants.

[0053] The content of the release agent is preferably 20 ppm or more, more preferably 50 ppm or more, even more preferably 100 ppm or more, even more preferably 200 ppm or more, even more preferably 500 ppm or more, and even more preferably 1000 ppm or more, and is preferably 5000 ppm or less, more preferably 4500 ppm or less, even more preferably 4000 ppm or less, even more preferably 3500 ppm or less, even more preferably 3000 ppm or less, even more preferably 2000 ppm or less, even more preferably 1800 ppm or less, even more preferably 1500 ppm or less, and even more preferably 1300 ppm or less, based on the total of the difunctional or higher polythiol (A) and the isocyanate compound (B).

[0054] The thiourethane film of this embodiment is preferably produced by irradiating a photopolymerizable composition with ultraviolet light to polymerize a portion of the photopolymerizable composition, and then heating the photopolymerizable composition to further polymerize it. This makes it easier to set the E' x T and restoring force of the film of this embodiment within the above ranges, thereby further improving the winding ability of the thiourethane film when wound around a core. This also allows the thickness of the thiourethane film to be within an appropriate range.

[0055] Furthermore, by further heating after UV irradiation, the unpolymerized portions due to UV irradiation can be polymerized to obtain a completely polymerized polymer. This also prevents unreacted isocyanate groups in the isocyanate compound (B) from reacting, thereby preventing an increase in the hygroscopicity of the polymer of the photopolymerizable composition and preventing poor appearance due to the generation of bubbles or blisters when the thiourethane film is attached to a lens substrate.

[0056] There are two types of ultraviolet light: UVC with a wavelength of 250-260 nm and UVA with a wavelength of 320-390 nm, and it is UVC that affects photopolymerization. When using ultraviolet light, light sources such as sunlight, chemical lamps, mercury lamps, metal halide lamps, and UVLEDs can be used.

[0057] From the viewpoint of improving the appearance of the resulting film and further improving winding properties, the cumulative light amount of ultraviolet irradiation is preferably 500 mJ or more, more preferably 1000 mJ or more, even more preferably 1200 mJ or more, and even more preferably 1500 mJ or more, and is preferably 10,000 mJ or less, more preferably 9,500 mJ or less, even more preferably 9,000 mJ or less, even more preferably 6,000 mJ or less, even more preferably 5,000 mJ or less, even more preferably 4,000 mJ or less, even more preferably 3,800 mJ or less, even more preferably 3,500 mJ or less, and even more preferably 3,000 mJ or less. The cumulative light amount of ultraviolet irradiation represents the total cumulative light amount of UVC and UVA. From the viewpoints of improving the appearance of the resulting film and further improving winding properties, the irradiation intensity of the ultraviolet irradiation is preferably 100 mW or more, more preferably 150 mW or more, and even more preferably 200 mW or more, and is preferably 2000 mW or less, more preferably 1800 mW or less, even more preferably 1600 mW or less, even more preferably 1000 mW or less, more preferably 800 mW or less, even more preferably 600 mW or less, and even more preferably 400 mW or less. The irradiation intensity of ultraviolet irradiation refers to the total irradiation intensity of UVC and UVA.

[0058] From the viewpoint of improving the appearance of the resulting film and further improving winding properties, the integrated light amount of UVC in the ultraviolet irradiation is preferably 100 mJ or more, more preferably 200 mJ or more, and even more preferably 250 mJ or more, and is preferably 4000 mJ or less, more preferably 3000 mJ or less, more preferably 2500 mJ or less, more preferably 1200 mJ or less, more preferably 1000 mJ or less, more preferably 800 mJ or less, more preferably 600 mJ or less, even more preferably 500 mJ or less, and even more preferably 300 mJ or less. From the viewpoint of improving the appearance of the resulting film, the irradiation intensity of UVC in the ultraviolet irradiation is preferably 10 mW or more, more preferably 20 mW or more, more preferably 30 mW or more, more preferably 40 mW or more, more preferably 50 mW or more, and even more preferably 60 mW or more, and is preferably 200 mW or less, more preferably 150 mW or less, and even more preferably 100 mW or less.

[0059] The integrated light amount of UVA in ultraviolet irradiation is preferably 500 mJ or more, more preferably 1000 mJ or more, even more preferably 1300 mJ or more, and preferably 8000 mJ or less, even more preferably 7000 mJ or less, even more preferably 4000 mJ or less, even more preferably 3500 mJ or less, even more preferably 2000 mJ or less. The irradiation intensity of UVA in ultraviolet irradiation is preferably 50 mW or more, more preferably 100 mW or more, even more preferably 150 mW or more, and preferably 3000 mW or less, more preferably 2500 mW or less, even more preferably 800 mW or less, even more preferably 500 mW or less, even more preferably 300 mW or less.

[0060] UV irradiation of the photopolymerizable composition can be carried out after forming a film of a certain thickness using the photopolymerizable composition. The thickness of the film made of the photopolymerizable composition is preferably 50 μm or more, more preferably 100 μm or more, even more preferably 150 μm or more, even more preferably 200 μm or more, even more preferably 250 μm or more, and preferably 3000 μm or less, more preferably 1000 μm or less, even more preferably 600 μm or less, even more preferably 400 μm or less. By making the thickness of the photopolymerizable composition film within the above range, the thickness T of the obtained thiourethane film can be within the range described below. Note that the formation of a film using the photopolymerizable composition is not limited, and can be carried out, for example, by arranging two glass plates with a gap within the above range, placing a PTFE sheet around all four sides of the glass plates, injecting the photopolymerizable composition, and clamping the two glass plates with clips to secure them.

[0061] Furthermore, a film can be formed using the photopolymerizable composition by applying the composition to a substrate by a conventionally known method using a bar coater, a spin coater, a dip coater, etc. The substrate can be a release film, and the release film contains at least one material selected from the group consisting of polyethylene terephthalate and fluororesin.

[0062] Furthermore, when a film is formed using a photopolymerizable composition by applying it to a substrate, the film preferably further comprises a protective film on the side opposite the substrate when the film is heated after ultraviolet irradiation. By providing a protective film, contact with oxygen and moisture during polymerization of the photopolymerizable composition can be prevented, thereby preventing the formation of bubbles in the resulting thiourethane film. There are no limitations on the protective film as long as it can prevent the intrusion of oxygen and moisture and is heat-resistant, but a release film is preferred from the viewpoint of easy peeling after heating. For example, a polyethylene terephthalate film can be used as the release film. Furthermore, the thickness of the protective film is preferably 5 μm or more and 150 μm or less from the viewpoint of easy peeling after heating.

[0063] The heating temperature when heating the photopolymerizable composition is preferably 80° C. or higher, more preferably 100° C. or higher, and even more preferably 110° C. or higher, from the viewpoint of more fully polymerizing the photopolymerizable composition, and is preferably 140° C. or lower, more preferably 130° C. or lower, from the viewpoint of further improving the winding properties of the resulting thiourethane film. The heating time when heating the photopolymerizable composition is preferably 10 minutes or longer, more preferably 30 minutes or longer, even more preferably 50 minutes or longer, and even more preferably 60 minutes or longer, and is preferably 300 minutes or shorter, more preferably 150 minutes or shorter, even more preferably 120 minutes or shorter, even more preferably 100 minutes or shorter, and even more preferably 80 minutes or shorter.

[0064] The glass transition temperature Tg of the thiourethane film is preferably 60°C or higher, more preferably 70°C or higher, from the viewpoint of further improving heat resistance, and is preferably 130°C or lower, more preferably 120°C or lower, from the viewpoint of further improving flexibility.

[0065] The glass transition temperature of a thiourethane film can be measured as follows. A test piece 5 mm wide and 30 mm long is cut from the thiourethane film, and solid viscoelasticity temperature dispersion measurement is performed under the following conditions to measure the glass transition temperature Tg (°C). Tg is the peak temperature of tan δ. Apparatus: Dynamic viscoelasticity measuring apparatus Deformation mode: Tension Heating rate: 3°C / min Frequency: 1 Hz Set strain: 0.1% Environment: Nitrogen atmosphere

[0066] In the thiourethane film of this embodiment, the degree of polymerization is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and even more preferably 80% or more, and is preferably 100% or less, more preferably 90% or less. A degree of polymerization equal to or greater than the above-mentioned lower limit indicates that the photopolymerizable composition is more polymerized, making it possible to form a thiourethane film, and further reduces the Young's modulus, thereby further improving windability. A degree of polymerization equal to or less than the above-mentioned upper limit results in an appropriate increase in Young's modulus, thereby further improving windability. The degree of polymerization was calculated from the absorbance of the NCO absorption peak measured by FT-IR (ATR method) using the unpolymerized state as the reference. Specific examples are shown in the Examples section.

[0067] In the thiourethane film of the present embodiment, the yellowness index (YI value) measured in accordance with JIS K7373:2006 at a thickness of 2 mm is preferably less than 3.0, more preferably 2.5 or less, even more preferably 2.3 or less, even more preferably 2.0 or less, even more preferably 1.9 or less, even more preferably 1.5 or less, and even more preferably 1.3 or less, from the viewpoint of further suppressing yellowing and further improving appearance. There is no lower limit for the yellowness index (YI value) measured in accordance with JIS K7373:2006 at a thickness of 2 mm, but it may be, for example, -1.0 or more, -0.6 or more, 0.0 or more, or 0.3 or more.

[0068] In the thiourethane film of this embodiment, the haze measured at a thickness of 2 mm in accordance with JIS K7136:2000 is preferably 1.0% or less, more preferably 0.8% or less, and even more preferably 0.6% or less, from the viewpoint of further improving transparency. There is no lower limit for the haze measured at a thickness of 2 mm in accordance with JIS K7136:2000, but it may be, for example, 0.1% or more, 0.3% or more, or 0.5% or more.

[0069] In the thiourethane film of this embodiment, the Young's modulus measured using a tensile tester in accordance with JIS K7171:2016 on a test piece 65 mm long, 25 mm wide, and 2 mm thick under the conditions of a measurement temperature of 23°C, a measurement humidity of 50% RH, a tensile speed of 1 mm / min, and a support distance of 34 mm is preferably 100 MPa or more, more preferably 300 MPa or more, even more preferably 500 MPa or more, even more preferably 700 MPa or more, even more preferably 900 MPa or more, and preferably 5000 MPa or less, more preferably 4000 MPa or less, even more preferably 3500 MPa or less, even more preferably 3000 MPa or less, even more preferably 2500 MPa or less, and even more preferably 2300 MPa or less. When the Young's modulus is above the above lower limit, the thiourethane film becomes appropriately hard, and winding properties are further improved. When the Young's modulus is below the above upper limit, the thiourethane film becomes soft, and winding properties are further improved.

[0070] The yellowness index (YI value), haze, and Young's modulus of the 2 mm thick thiourethane film can also be measured by stacking multiple thiourethane films and press-molding them (temperature: 150°C, pressure: 5 MPa) to form a 2 mm film.

[0071] The thiourethane film of this embodiment can be used to impart functionality to lens substrates and the like. More specifically, optical properties can be imparted by incorporating a functional dye such as a photochromic dye, a polarizing dye, or a specific wavelength-blocking dye. Furthermore, a thiourethane film that does not contain a functional component such as a dye can be laminated to a lens substrate and thereby further improve the strength of the lens and the like. Furthermore, as will be described later, when a hard coat layer is formed on the thiourethane film of this embodiment by coating, the hard coat layer can be formed directly on the thiourethane film without an adhesive layer or the like.

[0072] The thiourethane film may further include one or more layers selected from the group consisting of a hard coat layer and an antireflection layer. When the thiourethane film includes a primer layer, the hard coat layer and the antireflection layer are preferably provided on the side of the thiourethane film opposite the primer layer. When both a hard coat layer and an antireflection layer are provided, the hard coat layer can be formed on the lens substrate, and then the antireflection layer can be formed on the hard coat layer.

[0073] The hard coat layer is a coating layer intended to impart functions such as scratch resistance, abrasion resistance, moisture resistance, warm water resistance, heat resistance, and weather resistance to the lens surface, and its film thickness is, for example, 0.3 μm to 30 μm. The hard coat layer generally uses a hard coat composition containing a curable organosilicon compound and one or more fine particles composed of one or more oxide fine particles of an element selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti and / or a composite oxide of two or more elements selected from this group.

[0074] The hard coat layer is formed, for example, by applying a hard coat composition by a known application method such as spin coating or dip coating, followed by curing. Examples of the curing method include thermal curing and curing by irradiation with energy rays such as ultraviolet rays or visible light. In order to suppress the occurrence of interference fringes, the difference in refractive index between the hard coat layer and the lens is preferably within ±0.1.

[0075] The anti-reflection layer may be formed on the hard coat layer as needed. The anti-reflection layer may be a single layer or a multi-layer. Anti-reflection layers are classified into inorganic and organic types. In the case of inorganic types, SiO ２ , TiO ２ The film is formed by a dry method such as vacuum deposition, sputtering, ion plating, ion beam assisted deposition, CVD, etc., using inorganic oxides such as silicon dioxide, silicon dioxide, silicon dioxide powder ...

[0076] 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 coating layer, the antifouling layer, the water-repellent layer, etc. is not particularly limited, and a conventionally known method can be applied.

[0077] The water contact angle of the surface of the thiourethane film is preferably 50.0° or more, more preferably 55.0° or more, even more preferably 60.0° or more, and preferably 90.0° or less, more preferably 85.0° or less, even more preferably 80.0° or less. When the water contact angle of the surface of the thiourethane film is within the above range, the interlayer adhesion between the thiourethane film and the hard coat layer or antireflection layer is further improved, even when the thiourethane film includes one or two layers selected from the group consisting of a hard coat layer and an antireflection layer, and the hard coat layer or antireflection layer is formed directly on the thiourethane film without an adhesive layer (described later). The water contact angle can be measured in an atmosphere of 23°C and 50% RH using a contact angle meter in accordance with JIS R3257:1999.

[0078] The thiourethane film of this embodiment may further include an adhesive layer on one side. This further improves interlayer adhesion between the thiourethane film and one or more layers selected from the group consisting of a lens substrate, a hard coat layer, and an anti-reflection layer. The adhesive layer is preferably made of a material that has high adhesion to one or more layers selected from the group consisting of a lens substrate, a hard coat layer, and an anti-reflection layer. Examples of the adhesive layer include adhesive compositions primarily composed of one or more resins selected from the group consisting of urethane resins, epoxy resins, polyester resins, melamine resins, and polyvinyl acetals, and preferably polyurethane-based aqueous dispersions. The adhesive layer preferably contains one or more resins selected from the group consisting of urethane (meth)acrylates, (meth)acrylic monomers, (meth)acrylic resins, urethane resins, and ester resins. The adhesive layer can be formed, for example, by a coating method or a dry process. In the coating method, the adhesive composition is applied by a known coating method, such as spin coating or dip coating, and then solidified to form the adhesive layer. In the dry process, the film is formed by a known dry process such as a CVD process or a vacuum deposition process.

[0079] When the thiourethane film has an adhesive layer and a hard coat layer, it is preferable to have the adhesive layer on the surface opposite the thio-hard coat layer. It is also preferable that the thiourethane film has an adhesive layer and a lens substrate, in this order, on the surface opposite the hard coat layer. The thiourethane film of this embodiment can be directly bonded to the hard coat layer. Furthermore, by bonding the lens substrate to the thiourethane film via an adhesive layer, the lens substrate can be more firmly bonded to the thiourethane film.

[0080] From the viewpoint of further improving strength, the lens substrate comprises at least one selected from the group consisting of polythiourethane, poly(meth)acrylate, polycarbonate, polyallyl carbonate, polyethylene terephthalate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, and polyurethane, more preferably at least one selected from the group consisting of polythiourethane, polyurethane, and polyepisulfide, and even more preferably polythiourethane. When the lens substrate comprises polythiourethane, because it is made of the same material as the thiourethane film, it becomes easy to polish the lens substrate into the shape of, for example, a spectacle lens after the thiourethane film is bonded to the lens substrate.

[0081] When the thiourethane film of the present embodiment includes one or more layers selected from the group consisting of a lens substrate, an adhesive layer, a hard coat layer, and an antireflection layer, the laminate structure can be, for example, thiourethane film / lens substrate, thiourethane film / adhesive layer, hard coat layer / thiourethane film, antireflection layer / hard coat layer / thiourethane film, hard coat layer / thiourethane film / adhesive layer, antireflection layer / hard coat layer / thiourethane film / adhesive layer, thiourethane film / adhesive layer / lens substrate, hard coat layer / thiourethane film / adhesive layer / lens substrate, antireflection layer / hard coat layer / thiourethane film / adhesive layer / lens substrate, etc.

[0082] [Uses of Thiourethane Film] The thiourethane film of the present embodiment can be used for various plastic lenses such as display components, display components for AR (Augmented Reality) and VR (Virtual Reality) devices, plastic eyeglass lenses, sunglasses, goggles, eyeglass lenses for vision correction, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, and lenticular lenses.

[0083] <Roll-shaped wound product> The roll-shaped wound product of this embodiment includes the thiourethane film of this embodiment and a winding core, with the thiourethane film wound into a roll around the winding core. The thiourethane film of this embodiment has improved winding properties when wound around the winding core.

[0084] <Lens> The lens of this embodiment is a lens containing the thiourethane film of this embodiment, for example, a lens substrate to which the thiourethane film of this embodiment is bonded. Furthermore, the lens of this embodiment may have direct contact between the thiourethane film and the lens substrate. Lens substrates made of the materials described above can be used. Examples of lenses include various plastic lenses such as the above-mentioned plastic eyeglass lenses, sunglasses, goggles, eyeglass lenses for vision correction, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, and lenticular lenses. Furthermore, when the lens includes a hard coat layer, an anti-reflection layer, or the like, the layer structure can have the above-mentioned layer order.

[0085] <Method for Manufacturing Laminated Lens> The method for manufacturing the laminated lens of this embodiment includes a step of obtaining the thiourethane film of this embodiment, and a laminating step of laminating the obtained thiourethane film to a lens substrate.

[0086] In the lamination step in the manufacturing method of the laminated lens of this embodiment, it is preferable to laminate the thiourethane film to the lens substrate by one or two methods selected from the group consisting of vacuum molding and pressure molding, and it is more preferable to carry out vacuum molding and pressure molding simultaneously.In addition, if necessary, heating may be carried out while vacuum molding or pressure molding is carried out.In the manufacturing method of the laminated lens of this embodiment, since the thiourethane film of this embodiment is used, the thiourethane film has appropriate flexibility and can be vacuum molded or pressure molded.

[0087] <Eyeglasses> The eyeglasses of this embodiment preferably include the lenses of this embodiment described above, that is, the eyeglasses include the thiourethane film of this embodiment.

[0088] <Method for Producing a (Thio)urethane Resin Film> The method for producing a (thio)urethane resin film of this embodiment includes a first polymerization step of irradiating a film made of a photopolymerizable composition containing an active hydrogen compound, an isocyanate compound, a photopolymerization initiator, and a metal catalyst and provided on a substrate with ultraviolet light to polymerize a portion of the photopolymerizable composition, and a second polymerization step of heating the photopolymerizable composition after the first polymerization step to further polymerize the photopolymerizable composition. The thiourethane film of this embodiment described above can be produced by using a polythiol described below as the active hydrogen compound in the method for producing a (thio)urethane resin film of this embodiment.

[0089] Although (thio)urethane resin films can be produced by a casting method, shrinkage marks sometimes occur during molding using this method. It is believed that these shrinkage marks occur due to the film shrinking during cooling. According to the method for producing a (thio)urethane resin film of this embodiment, the appearance of the resulting film is improved and production efficiency can be improved. The reason for this is unclear, but it is thought to be as follows. A (thio)urethane resin film can be polymerized by simply heating a photopolymerizable composition, but complete polymerization takes a long time. The polymerization time can be shortened by performing a photopolymerization step in which the photopolymerizable composition is irradiated with ultraviolet light before the heating step. Furthermore, when only the heating step is performed, shrinkage marks occur in the (thio)urethane resin film, resulting in poor appearance. On the other hand, when only photopolymerization is performed, the polymerization of the photopolymerizable composition is incomplete and the resulting polymer is hygroscopic. Therefore, when the (thio)urethane resin film is attached to a lens substrate after polymerization, air bubbles or water bubbles are trapped in the (thio)urethane resin film, resulting in poor appearance. It is believed that by subjecting the photopolymerizable composition to an ultraviolet irradiation step and then heat polymerization, the polymerization time can be shortened and the appearance of the resulting (thio)urethane resin film can be improved.

[0090] In this embodiment, the term "(thio)urethane-based resin" refers to one or more compounds selected from the group consisting of thiourethane, urethane, and urethane urea. Thiourethane refers to a compound having a thiourethane bond formed by the reaction of a polythiol component with an isocyanate component. Urethane refers to a compound having a urethane bond formed by the reaction of a polyol component with an isocyanate component. Urethane refers to a compound having a urethane urea bond formed by the reaction of a polyamine component with an isocyanate component. Among these, one or more compounds selected from the group consisting of thiourethane and urethane are preferred, with thiourethane being more preferred. Furthermore, among (thio)urethane-based resin films, one or more compounds selected from the group consisting of thiourethane films and urethane films are preferred, with thiourethane films being more preferred.

[0091] [Active hydrogen compound] The photopolymerizable composition in the method for producing a (thio)urethane resin film of this embodiment contains an active hydrogen compound. The active hydrogen compound preferably contains at least one selected from the group consisting of polythiol, polyol, and polyamine. This allows a thiourethane bond, urethane bond, or urea bond to be formed between the active hydrogen compound and an isocyanate compound described below, thereby forming a thiourethane, urethane, or urethane urea. The active hydrogen compound more preferably contains a polythiol, from the viewpoint of high nucleophilicity and further improving reactivity with an isocyanate compound.

[0092] (Polythiol) Preferred polythiols include 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5- The compound contains at least one selected from the group consisting of bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane. More preferably, it is one or more selected from the group consisting of bis(2-mercaptoethyl) sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and pentaerythritol tetrakis(3-mercaptopropionate), and even more preferably, it is one or two selected from the group consisting of bis(2-mercaptoethyl) sulfide and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0093] The polythiol preferably includes both a difunctional polythiol and a tri- or higher functional polythiol, which allows the flexibility of the resulting film to fall within a more appropriate range and makes it suitable for vacuum forming or pressure forming.

[0094] The thiol equivalent of the bifunctional polythiol can be selected appropriately depending on the type of isocyanate compound. From the viewpoint of making the obtained film suitably soft, it is preferably 15% or more, more preferably 30% or more, even more preferably 40% or more, even more preferably 50% or more, and even more preferably 60% or more, relative to 100% of the total thiol equivalent of the bifunctional polythiol and the tri- or higher functional polythiol. From the viewpoint of making the obtained film suitably hard, it is preferably 95% or less, more preferably 90% or less, and even more preferably 80% or less.

[0095] (Bifunctional Polythiol) Examples of bifunctional polythiols 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;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; 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; 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 are also included.

[0096] Among these, the bifunctional polythiol includes one or more selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0097] (Trifunctional or higher functional polythiols) Examples of trifunctional or higher functional polythiols 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, thioglycolic acid esters and mercaptopropionic acid esters thereof; 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; 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; 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.

[0098] Examples of tri- or higher functional polythiols include 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), penta It is preferable to use one or more selected from the group consisting of erythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane. Among these, it is more preferable to use one or more selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and pentaerythritol tetrakis(3-mercaptopropionate), and even more preferable to use 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0099] The polythiol of this embodiment preferably contains one or more bifunctional polythiols selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, and 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is a trifunctional or higher functional polythiol. It is more preferable that the polythiol contains bis(2-mercaptoethyl)sulfide and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0100] (Polyol) Examples of polyols include aliphatic polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, butanetriol, pentaerythritol, sorbitol, triethylene glycol, polyethylene glycol, cyclohexanediol, cyclohexanedimethanol, and tricyclo[5.2.1.02,6]decane-dimethanol; and aromatic polyols such as dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl)pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di(2-hydroxyethoxy)benzene, bisphenol A-bis-(2-hydroxyethyl ether), tetrabromobisphenol A, and tetrabromobisphenol A-bis-(2-hydroxyethyl ether).

[0101] (Polyamine) Examples of polyamines include low molecular weight diamines such as ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, hydrazine, o-, m-, or p-tolylenediamine (TDA, OTD), low molecular weight triamines such as diethylenetriamine, and low molecular weight polyamines having four or more amino groups such as triethylenetetramine and tetraethylenepentamine. These polyamines can be used alone or in combination of two or more.

[0102] [Isocyanate Compound] The photopolymerizable composition in the method for producing a (thio)urethane resin film of this embodiment contains an isocyanate compound. The isocyanate compound preferably includes at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate, and more preferably includes at least one selected from the group consisting of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and xylylene diisocyanate.

[0103] The equivalent ratio of thiol groups in the polythiol to the isocyanato groups in the isocyanate compound (thiol groups / isocyanato groups) is preferably 0.8 or more, more preferably 0.85 or more, even more preferably 0.9 or more, and preferably 1.2 or less, more preferably 1.15 or less, and even more preferably 1.1 or less. Also, the equivalent ratio of hydroxyl groups in the polyol to the isocyanato groups in the isocyanate compound (hydroxyl groups / isocyanato groups) is preferably 0.8 or more, more preferably 0.85 or more, even more preferably 0.9 or more, and preferably 1.2 or less, more preferably 1.15 or less, and even more preferably 1.1 or less. Also, the equivalent ratio of amino groups in the polyamine to the isocyanato groups in the isocyanate compound (amino groups / isocyanato groups) is preferably 0.8 or more, more preferably 0.85 or more, even more preferably 0.9 or more, and preferably 1.2 or less, more preferably 1.15 or less, and even more preferably 1.1 or less. When the equivalent ratio of the active hydrogen-generating functional group in the active hydrogen compound to the isocyanato group in the isocyanate compound is within the above range, it is possible to obtain a thiourethane, urethane, or urethane urea that is suitable for use as a lens material.

[0104] The total content of the active hydrogen compound and the isocyanate compound, when the entire photopolymerizable composition is taken as 100% by mass, is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, even more preferably 99% by mass or more, and is preferably 100% by mass or less, more preferably less than 100% by mass.

[0105] [Photopolymerization initiator] The photopolymerizable composition contains a photopolymerization initiator. The photopolymerization initiator is an initiator capable of photopolymerization, and preferably contains one or more types selected from the group consisting of radical polymerization initiators and base generators, and more preferably contains a base generator from the viewpoint of further improving photopolymerizability.

[0106] (Base Generator) The base generator is preferably a compound comprising an organic boron anion and a counter cation. The organic boron anion preferably comprises one or more selected from the group consisting of a phenyl group, an alkyl group, and an aryl group, and more preferably comprises one or more selected from the group consisting of a phenyl group and an alkyl group. The counter cation preferably comprises one or more selected from the group consisting of ammonium or an ammonium salt, and more preferably comprises an ammonium salt.

[0107] The base generator more preferably contains one or more compounds selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2).

[0108]

[0109] In formula (1), R １ ~R ４ preferably each independently represents an alkyl group having 1 to 8 carbon atoms, and R ５ ~R ８ preferably each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0110] In formula (1), R １ ~R ４ are preferably identical. １ ~R ４ is more preferably an alkyl group having 2 to 5 carbon atoms, even more preferably a linear alkyl group, and even more preferably an n-butyl group. ８ is more preferably an alkyl group having 2 to 5 carbon atoms, even more preferably a linear alkyl group, and even more preferably an n-butyl group. ５ ~R ７ are preferably identical. ５ ~R７ is more preferably a phenyl group, a butylphenyl group, or a naphthyl group, and even more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. ５ ~R ７ When contains an aromatic ring, the aromatic ring may be substituted with an alkyl group, an aryl group, or the like.

[0111] The compound represented by formula (1) is preferably at least one selected from the group consisting of tetra(n-butyl)ammonium n-butyltriphenylborate, tetra(n-butyl)ammonium n-butyltri(4-tert-butylphenyl)borate, tetra(n-butyl)ammonium n-butyltri(1-naphthyl)borate, and tetra(n-butyl)ammonium n-butyltri(4-methyl-1-naphthyl)borate. The symbol "=" in the compound name indicates an ionic bond. Among these, from the viewpoint of further improving the performance balance of solubility, polymerizability, and pot life, the compound represented by formula (1) is more preferably at least one selected from the group consisting of tetra(n-butyl)ammonium n-butyltriphenylborate and tetra(n-butyl)ammonium n-butyltri(1-naphthyl)borate.

[0112]

[0113] In formula (2), R １ ~R ７ each independently represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms; R ８ ~R １１ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

[0114] In formula (2), R １ ~R ７ are preferably identical.１ ~R ７ is preferably an alkyl group having 2 to 5 carbon atoms, more preferably a linear alkyl group, and even more preferably an n-butyl group. １１ is more preferably an alkyl group having 2 to 5 carbon atoms, even more preferably a linear alkyl group, and even more preferably an n-butyl group. ８ ~R １０ are preferably identical. ８ ~R １０ is more preferably a phenyl group, a butylphenyl group, or a naphthyl group, and even more preferably a phenyl group, a 4-tert-butylphenyl group, a 1-naphthyl group, or a 4-methyl-1-naphthyl group. ８ ~R １０ When contains an aromatic ring, the aromatic ring may be substituted with an alkyl group, an aryl group, or the like.

[0115] (Radical Polymerization Initiator) As the radical polymerization initiator, known thermal radical polymerization initiators and photoradical polymerization initiators can be used. Examples of the thermal radical polymerization initiator include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 2,5-bis(t-butylperoxy)2,5-dimethylhexane, 2,5-bis(t-butylperoxy)2,5-dimethylhexyne-3, di-t-butyl peroxide, isopropylcumyl-t-butyl peroxide, and bis(α-t-butylperoxyisopropyl)benzene; 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, and ethyl-3,3-bis(t-butylperoxy). peroxy ketals such as bis(t-butylperoxy)isophthalate, t-butylperoxybenzoate, t-butylperoxyacetate, and the like; hydroperoxides such as t-butyl hydroperoxide, t-hexyl hydroperoxide, cumin hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, and the like; bibenzyl compounds such as 2,3-dimethyl-2,3-diphenylbutane, and the like; and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, and the like.

[0116] Examples of photoradical polymerization initiators include benzoin alkyl ether, benzil dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methylbenzoyl formate, isopropyl thioxanthone, and mixtures of two or more thereof. Sensitizers can also be used in conjunction with these photoradical polymerization initiators. Examples of sensitizers include carbonyl compounds such as anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, and chloranil; nitro compounds such as nitrobenzene, p-dinitrobenzene, and 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; and nitrogen compounds such as nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, and tetracyanoethylene.

[0117] From the viewpoint of further improving photopolymerizability, the content of the photopolymerization initiator is preferably 250 ppm by mass or more, more preferably 300 ppm by mass or more, even more preferably 500 ppm by mass or more, even more preferably 700 ppm by mass or more, even more preferably 1000 ppm by mass or more, even more preferably 1200 ppm by mass or more, even more preferably 1300 ppm by mass or more, even more preferably 1400 ppm by mass or more, even more preferably 1500 ppm by mass or more, and even more preferably 2000 ppm by mass or more, based on the total amount of the active hydrogen compound and the isocyanate compound. Also, from the viewpoint of further suppressing coloration of the film, it is preferable or 20,000 ppm by mass or less, more preferably 15,000 ppm by mass or less, even more preferably 12,000 ppm by mass or less, even more preferably 10,000 ppm by mass or less, even more preferably 8,000 ppm by mass or less, even more preferably 6,000 ppm by mass or less, even more preferably 5,000 ppm by mass or less, even more preferably 4,500 ppm by mass or less, even more preferably 4,000 ppm by mass or less, even more preferably 3,500 ppm by mass or less, even more preferably 3,000 ppm by mass or less, even more preferably 2,500 ppm by mass or less, even more preferably 2,300 ppm by mass or less, and even more preferably 2,100 ppm by mass or less. Furthermore, from the viewpoint of further improving photopolymerizability and making it more possible to form a thiourethane film, the content of the photopolymerization initiator is preferably from 250 ppm by mass to 20,000 ppm by mass, more preferably from 300 ppm by mass to 15,000 ppm by mass, even more preferably from 500 ppm by mass to 10,000 ppm by mass, even more preferably from 700 ppm by mass to preferably 8,000 ppm by mass, and even more preferably from 700 ppm by mass to preferably 6,000 ppm by mass, relative to the total combined amount of the active hydrogen compound and the isocyanate compound.The content of the photopolymerization initiator is more preferably 1000 to 5000 ppm by mass, more preferably 1200 to 4500 ppm by mass, even more preferably 1300 to 4500 ppm by mass, even more preferably 1400 to 4000 ppm by mass, even more preferably 1500 to 2500 ppm by mass, and even more preferably 2000 to 2300 ppm by mass, based on the total combined amount of the active hydrogen compound and the isocyanate compound. By making the content of the photopolymerization initiator 1000 ppm by mass or more, the Young's modulus of the obtained film can be further reduced, and the winding property can be further improved. Furthermore, by setting the photopolymerization initiator content to 5000 ppm by mass or less, coloration of the film can be further suppressed, by setting the photopolymerization initiator content to 2500 ppm by mass or less, the Young's modulus of the film can be appropriately increased and winding properties can be further improved, and by setting the photopolymerization initiator content to 2300 ppm by mass or less, the yellowness index (YI value) of the film can be further reduced and the appearance of the film can be further improved. The unit of the photopolymerization initiator content (ppm by mass) represents the content (mg) of photopolymerization initiator per 1 kg of the total of the active hydrogen compound and the isocyanate compound, i.e., mg / kg.

[0118] [Metal Catalyst] The photopolymerizable composition contains a metal catalyst. Examples of the metal catalyst include organotin compounds, organolead compounds, organonickel compounds, organocopper compounds, organobismuth compounds, and potassium salts. Among these, it is preferable that the metal catalyst contains an organotin compound, from the viewpoint of adjusting the viscosity of the mixture A containing the active hydrogen compound, the isocyanate compound, and the metal catalyst to a more appropriate range, as described below.

[0119] Examples of organotin compounds include tin acetate, tin octoate, tin oleate, tin laurate, monobutyltin trioctoate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dimethyltin dichloride, and dibutyltin dichloride. Of these, one or more compounds selected from the group consisting of dimethyltin dichloride and dibutyltin dichloride are preferred.

[0120] The content of the metal catalyst is preferably 0.1 ppm or more, more preferably 0.5 ppm or more, even more preferably 1 ppm or more, and even more preferably 5 ppm or more, relative to the total total amount of the active hydrogen compound and the isocyanate compound, from the viewpoints of further improving polymerizability and further improving the viscosity of the mixture A described below, and is preferably 45 ppm or less, more preferably 40 ppm or less, and even more preferably 35 ppm or less, from the viewpoint of preventing an excessive increase in the viscosity of the mixture A described below. The unit of the content of the metal catalyst (ppm) represents the content (mg) of the metal catalyst per 1 kg of the total of the active hydrogen compound and the isocyanate compound, i.e., mg / kg.

[0121] [Other Components] The photopolymerizable composition of the present embodiment may further include an ultraviolet absorber, an antioxidant, a light stabilizer, a sensitizer, a release agent, a solvent, a bluing agent, an IR-cutting agent, a blue light-cutting agent, a reactive diluent, an oil-soluble dye, a pigment, a coloring matter, a fragrance, a filler, an adhesion improver such as a coupling agent, a chain extender, a crosslinking agent, an antifoaming agent, a suspending agent, a dispersing agent, a plasticizer, an anti-sagging agent, an antistaining agent, a preservative, a bactericide, an antibacterial agent, an anti-mold agent, a matting agent, a thickener, a pigment dispersant, an anti-cracking agent, an agent for improving scratch resistance, a slip agent, a surface modifier, an agent for preventing color separation, an emulsifier, an anti-skinning agent, a desiccant, an antistatic agent, a conductive agent (electrostatic assistant), a flame retardant, a thermal conductivity improver, a plasticizer, an ion exchange resin, or the like.

[0122] Examples of the release agent include acidic phosphate ester compounds, polyether-modified silicones, alkyl-modified silicones, polyester-modified silicones, dimethylpolysiloxanes, polyoxyalkylene glycol monoalkyl ether compounds, polyoxyalkylene glycol monoester compounds, fluorine atom-containing compounds, surfactants, nonionic surfactants, and acrylic surfactants.

[0123] The content of the release agent is preferably 20 ppm or more, more preferably 50 ppm or more, even more preferably 100 ppm or more, even more preferably 200 ppm or more, even more preferably 500 ppm or more, and even more preferably 1000 ppm or more, and is preferably 5000 ppm or less, more preferably 3000 ppm or less, even more preferably 2000 ppm or less, even more preferably 1800 ppm or less, even more preferably 1500 ppm or less, and even more preferably 1300 ppm or less, based on the total amount of the active hydrogen compound and the isocyanate compound.

[0124] [First Polymerization Step] The first polymerization step is a step of irradiating a film of a photopolymerizable composition provided on a substrate with ultraviolet light to polymerize a portion of the photopolymerizable composition. In the method for producing a (thio)urethane resin film of this embodiment, the polymerization time can be shortened by including a step of irradiating the photopolymerizable composition with ultraviolet light. Ultraviolet light includes UVC with a wavelength of 250 to 260 nm and UVA with a wavelength of 320 to 390 nm. Of the ultraviolet light irradiated in the first polymerization step, it is UVC that affects photopolymerization. When ultraviolet light is used, light sources such as sunlight, chemical lamps, mercury lamps, metal halide lamps, and UVLEDs can be used.

[0125] From the viewpoint of improving the appearance of the resulting film, the cumulative light amount of ultraviolet irradiation in the first polymerization step is preferably 500 mJ or more, more preferably 1000 mJ or more, even more preferably 1200 mJ or more, and even more preferably 1500 mJ or more, and is preferably 10,000 mJ or less, more preferably 9,500 mJ or less, even more preferably 9,000 mJ or less, even more preferably 6,000 mJ or less, even more preferably 5,000 mJ or less, even more preferably 4,000 mJ or less, more preferably 3,800 mJ or less, even more preferably 3,500 mJ or less, and even more preferably 3,000 mJ or less. The cumulative light amount of ultraviolet irradiation represents the total cumulative light amount of UVC and UVA. From the viewpoint of improving the appearance of the resulting film, the irradiation intensity of ultraviolet irradiation in the first polymerization step is preferably 100 mW or more, more preferably 150 mW or more, even more preferably 200 mW or more, and is preferably 2000 mW or less, more preferably 1800 mW or less, even more preferably 1600 mW or less, even more preferably 1000 mW or less, more preferably 800 mW or less, even more preferably 600 mW or less, even more preferably 400 mW or less. The irradiation intensity of ultraviolet irradiation refers to the total irradiation intensity of UVC and UVA.

[0126] From the viewpoint of improving the appearance of the resulting film, the integrated amount of UVC light in the ultraviolet irradiation in the first polymerization step is preferably 100 mJ or more, more preferably 150 mJ or more, even more preferably 200 mJ or more, and even more preferably 250 mJ or more, and is preferably 4000 mJ or less, more preferably 3500 mJ or less, even more preferably 3000 mJ or less, even more preferably 2500 mJ or less, even more preferably 2000 mJ or less, even more preferably 1200 mJ or less, even more preferably 1000 mJ or less, even more preferably 800 mJ or less, even more preferably 600 mJ or less, even more preferably 500 mJ or less, and even more preferably 300 mJ or less. From the viewpoint of improving the appearance of the resulting film, the irradiation intensity of UVC in the ultraviolet irradiation in the first polymerization step is preferably 10 mW or more, more preferably 20 mW or more, even more preferably 30 mW or more, even more preferably 40 mW or more, even more preferably 50 mW or more, even more preferably 60 mW or more, and is preferably 200 mW or less, more preferably 150 mW or less, even more preferably 100 mW or less.

[0127] The integrated light dose of UVA in the ultraviolet irradiation in the first polymerization step is preferably 500 mJ or more, more preferably 1000 mJ or more, even more preferably 1300 mJ or more, and preferably 8000 mJ or less, more preferably 7500 mJ or less, even more preferably 7000 mJ or less, even more preferably 5000 mJ or less, even more preferably 4000 mJ or less, more preferably 3800 mJ or less, even more preferably 3500 mJ or less, even more preferably 2000 mJ or less. The irradiation intensity of UVA in the ultraviolet irradiation in the first polymerization step is preferably 50 mW or more, more preferably 100 mW or more, even more preferably 150 mW or more, and preferably 3000 mW or less, more preferably 2500 mW or less, even more preferably 800 mW or less, even more preferably 500 mW or less, even more preferably 300 mW or less.

[0128] The first polymerization step preferably further includes a step of applying the photopolymerizable composition to a substrate to form a film. The thickness of the photopolymerizable composition applied to the substrate is preferably 50 μm or more, more preferably 100 μm or more, even more preferably 150 μm or more, even more preferably 200 μm or more, even more preferably 250 μm or more, and preferably 3 mm or less, more preferably 2 mm or less, even more preferably 1 mm or less, even more preferably 600 μm or less, even more preferably 400 μm or less. By adjusting the thickness of the photopolymerizable composition applied to the substrate to be equal to or greater than the above-mentioned lower limit, it is possible to easily peel the (thio)urethane resin film from the substrate. Furthermore, by adjusting the thickness of the photopolymerizable composition applied to the substrate to be equal to or less than the above-mentioned upper limit, it is possible to apply the composition with a uniform thickness. Furthermore, by applying the composition within the above-mentioned range, it is possible to achieve a thickness of the resulting (thio)urethane resin film within the range described below. The photopolymerizable composition can be applied using a conventionally known method, such as a bar coater, spin coater, or dip coater.

[0129] The substrate used in the first polymerization step is preferably a release film. The release film contains at least one material selected from the group consisting of polyethylene terephthalate and fluororesin, more preferably polyethylene terephthalate. The release film is preferably silicone-coated or non-silicone-coated, more preferably a non-silicone-coated polyethylene terephthalate film. An example of a commercially available non-silicone-coated polyethylene terephthalate film is Cerapeel (registered trademark) manufactured by Toray Industries, Inc. The thickness of the substrate used in the first polymerization step is preferably 30 μm or more, more preferably 100 μm or more, even more preferably 150 μm or more, even more preferably 200 μm or more, and preferably 1 mm or less, more preferably 800 μm or less, even more preferably 500 μm or less, and even more preferably 300 μm or less.

[0130] In the substrate used in the first polymerization step, the water contact angle on the surface of the substrate is preferably 60.0° or more, more preferably 63.0° or more, even more preferably 65.0° or more, and even more preferably 68.0° or more, from the viewpoint of further improving the releasability of the substrate and making it easier to peel off the substrate after complete polymerization of the photopolymerizable composition; and is preferably 100.0° or less, more preferably 90.0° or less, even more preferably 80.0° or less, and even more preferably 75.0° or less, from the viewpoint of further improving the wettability of the substrate and making it easier to apply the photopolymerizable composition.

[0131] The method for producing a (thio)urethane resin film of this embodiment preferably further includes a viscosity adjustment step of adjusting the viscosity of a mixed solution A containing an active hydrogen compound, an isocyanate compound, and a metal catalyst. The viscosity adjustment step is preferably performed before the first polymerization step. The viscosity of mixed solution A in the viscosity adjustment step is preferably 50 mPa·s or more, more preferably 80 mPa·s or more, even more preferably 100 mPa·s or more, even more preferably 130 mPa·s or more, even more preferably 150 mPa·s or more, and even more preferably 170 mPa·s or more, and preferably 2000 mPa·s or less, more preferably 1500 mPa·s or less, even more preferably 1000 mPa·s or less, even more preferably 700 mPa·s or less, even more preferably 600 mPa·s or less, even more preferably 500 mPa·s or less, even more preferably 400 mPa·s or less, even more preferably 300 mPa·s or less, and even more preferably 200 mPa·s or less. When the viscosity of the mixed liquid A is equal to or greater than the above lower limit, the photopolymerizable composition can be applied thickly and uniformly, and when the viscosity of the mixed liquid A is equal to or less than the above upper limit, the coatability of the photopolymerizable composition when applied can be improved and the usable time can be extended. The viscosity of the mixed liquid A in the viscosity adjustment step is measured at 23°C using a vibration viscometer. The vibration viscometer that can be used is a VM-10A-M model manufactured by Secomic Co., Ltd.

[0132] In the viscosity adjustment step, the mixed liquid A containing the active hydrogen compound, the isocyanate compound, and the metal catalyst is heated to form a prepolymer, thereby adjusting the viscosity to within the above range. The heating temperature of the mixed liquid A in the viscosity adjustment step is preferably 70°C or higher, more preferably 75°C or higher, from the viewpoint of appropriately increasing the viscosity of the mixed liquid A, and is preferably 90°C or lower, more preferably 85°C or lower, from the viewpoint of preventing the viscosity of the mixed liquid A from increasing too much. The heating time of the mixed liquid A in the viscosity adjustment step is preferably 120 minutes or longer, more preferably 150 minutes or longer, even more preferably 200 minutes or longer, and even more preferably 220 minutes or longer, from the viewpoint of appropriately increasing the viscosity of the mixed liquid A, and is preferably 300 minutes or shorter, more preferably 280 minutes or shorter, from the viewpoint of preventing the viscosity of the mixed liquid A from increasing too much. By setting the heating time of the mixed liquid A to the above upper limit or less, the reaction rate of the active hydrogen compound and the isocyanate compound in the mixed liquid A is slowed, and an increase in viscosity can be suppressed.

[0133] The method for producing a (thio)urethane resin film of this embodiment preferably further includes, after the viscosity adjusting step, a step of mixing the mixed liquid A with a mixed liquid B containing an isocyanate compound and a photopolymerization initiator. The step of mixing the mixed liquid A and the mixed liquid B can be carried out before the first polymerization step.

[0134] Furthermore, by separately preparing a mixed solution A containing an active hydrogen compound, an isocyanate compound, and a metal catalyst, and a mixed solution B containing an isocyanate compound and a photopolymerization initiator, and then mixing them, it is possible to adjust the viscosity using only the mixed solution A containing only the metal catalyst as a catalyst. Mixing mixed solutions A and B immediately before application of the photopolymerizable composition makes it easier to maintain the viscosity of the entire photopolymerizable composition within an appropriate range during application. Furthermore, by adjusting the heating temperature and heating time to maintain the viscosity of mixed solution A within an appropriate range, viscosity increase is suppressed even during long-term storage, and when mixed with mixed solution B and applied, viscosity sufficient for a thick, uniform coating can be maintained. Furthermore, by adjusting the viscosity of mixed solution A within an appropriate range, viscosity increase is suppressed during storage, making it possible to produce, transport, and store mixed solution A alone.

[0135] [Second Polymerization Step] The method for producing a (thio)urethane-based resin film of this embodiment includes a second polymerization step in which the photopolymerizable composition after the first polymerization step is heated to further polymerize the photopolymerizable composition. The second polymerization step is a step in which the unpolymerized portion in the first polymerization step is polymerized to obtain a completely polymerized polymer. By performing the second polymerization step, unreacted isocyanate groups in the isocyanate compound are reacted, and an increase in the hygroscopicity of the polymerized photopolymerizable composition is suppressed, and poor appearance due to the generation of bubbles or water blisters can be suppressed in the step of attaching the (thio)urethane-based resin film to a lens substrate.

[0136] The heating temperature in the second polymerization step is preferably 80° C. or higher, more preferably 85° C. or higher, even more preferably 90° C. or higher, even more preferably 100° C. or higher, and even more preferably 110° C. or higher, from the viewpoint of more sufficiently polymerizing the photopolymerizable composition, and is preferably 140° C. or lower, more preferably 130° C. or lower, and even more preferably 125° C. or lower, from the viewpoint of further improving the winding property of the resulting (thio)urethane resin film. The heating time in the second polymerization step is preferably 10 minutes or longer, more preferably 20 minutes or longer, even more preferably 30 minutes or longer, and even more preferably 50 minutes or longer, and is preferably 300 minutes or shorter, more preferably 150 minutes or shorter, even more preferably 120 minutes or shorter, even more preferably 100 minutes or shorter, and even more preferably 80 minutes or shorter.

[0137] The (thio)urethane resin film preferably further comprises a protective film on the surface opposite the substrate. By providing a protective film, contact with oxygen and moisture during polymerization of the photopolymerizable composition can be prevented, thereby preventing the formation of bubbles in the resulting (thio)urethane resin film. The protective film can be any film capable of preventing the intrusion of oxygen and moisture and is heat-resistant. However, from the viewpoint of easy peeling after the second polymerization step, a release film is preferred. The higher the release property, the thinner the thickness of the (thio)urethane resin film can be, which is preferable. For example, a polyethylene terephthalate film can be used as the release film. Furthermore, from the viewpoint of easy peeling after the second polymerization step, the thickness of the protective film can be preferably 5 μm or more and 150 μm or less.

[0138] The contact angle of the substrate used in the first polymerization step with the mixed liquid A is preferably 10° or more, more preferably 13° or more, even more preferably 15° or more, and preferably 90° or less, more preferably 70° or less, even more preferably 50° or less, and even more preferably 30° or less. Having the contact angle of the substrate with the mixed liquid A in the above range facilitates application of the photopolymerizable composition to the substrate. The contact angle (°) of the substrate with the mixed liquid A is calculated by measuring the arithmetic mean value of contact angles at five points on the same sample of the substrate cut into 9 cm x 9 cm using the mixed liquid A containing an active hydrogen compound, an isocyanate compound, and a metal catalyst, in accordance with JIS R 3257:1999.

[0139] The thickness of the (thio)urethane resin film is preferably 50 μm or more, more preferably 70 μm or more, even more preferably 100 μm or more, even more preferably 130 μm or more, even more preferably 150 μm or more, even more preferably 200 μm or more, even more preferably 250 μm or more, even more preferably 300 μm or more, and is preferably 3 mm or less, more preferably 2 mm or less, even more preferably 1 mm or less, even more preferably 800 μm or less, even more preferably 650 μm or less, even more preferably 600 μm or less, even more preferably 500 μm or less, even more preferably 400 μm or less. The thickness of the (thio)urethane resin film is preferably 50 μm or more and 3000 μm or less, more preferably 70 μm or more and 2000 μm or less, even more preferably 100 μm or more and 1000 μm or less, even more preferably 130 μm or more and 800 μm or less, even more preferably 150 μm or more and 650 μm or less, even more preferably 200 μm or more and 600 μm or less, even more preferably 250 μm or more and 500 μm or less, even more preferably 300 μm or more and 450 μm or less, and even more preferably 300 μm or more and 400 μm or less.

[0140] The (thio)urethane resin film may further include a primer layer, preferably on the surface opposite the substrate. The (thio)urethane resin film of this embodiment can be bonded to an eyeglass lens substrate via the primer layer. The primer layer is preferably made of a material that has high adhesion to the lens substrate, such as a primer composition containing a urethane resin, an epoxy resin, a polyester resin, a melamine resin, or polyvinyl acetal as its main component, and preferably contains a polyurethane aqueous dispersion. The primer layer is formed, for example, by a coating method or a dry method. In the coating method, the primer composition is applied by a known coating method such as spin coating or dip coating, and then solidified to form the primer layer. In the dry method, the primer layer is formed by a known dry method such as a CVD method or a vacuum deposition method.

[0141] The (thio)urethane resin film preferably further comprises at least one layer selected from the group consisting of a hard coat layer and an antireflection layer. When the (thio)urethane resin film comprises a primer layer, the hard coat layer and the antireflection layer are preferably provided on the side of the (thio)urethane resin film opposite to the primer layer. When both a hard coat layer and an antireflection layer are provided, the hard coat layer can be formed on the lens substrate, and then the antireflection layer can be formed on the hard coat layer.

[0142] The hard coat layer is a coating layer intended to impart functions such as scratch resistance, abrasion resistance, moisture resistance, warm water resistance, heat resistance, and weather resistance to the lens surface, and its film thickness is, for example, 0.3 μm to 30 μm. The hard coat layer generally uses a hard coat composition containing a curable organosilicon compound and one or more fine particles composed of one or more oxide fine particles of an element selected from the group consisting of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti and / or a composite oxide of two or more elements selected from this group.

[0143] In addition to the above components, the hard coat composition preferably contains at least one 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 be used in an appropriate solvent that does not affect the lens, or may be used without a solvent.

[0144] 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. Examples of the curing method include thermal curing and curing by irradiation with energy rays such as ultraviolet rays or visible light. In order to suppress the occurrence of interference fringes, the difference in refractive index between the hard coat layer and the lens is preferably within ±0.1.

[0145] An anti-reflection layer is usually formed on the hard coat layer as needed. The anti-reflection layer may be a single layer or a multi-layer. Anti-reflection layers are classified into inorganic and organic types. In the case of inorganic types, SiO ２ , TiO ２ The film is formed by a dry method such as vacuum deposition, sputtering, ion plating, ion beam assisted deposition, CVD, etc., using inorganic oxides such as silicon dioxide, silicon dioxide, silicon dioxide powder ...

[0146] 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.

[0147] <Method for manufacturing laminated lens> The method for manufacturing a laminated lens of the present embodiment includes a step of obtaining a (thio)urethane resin film by the method for manufacturing a (thio)urethane resin film of the present embodiment, and a lamination step of laminating the obtained (thio)urethane resin film to a lens substrate.

[0148] In the laminating step in the method for producing a laminated lens of this embodiment, it is preferable to laminate the (thio)urethane resin film to the lens substrate by one or two methods selected from the group consisting of vacuum molding and pressure molding, and it is more preferable to perform vacuum molding and pressure molding simultaneously. Furthermore, heating may be performed while vacuum molding or pressure molding is performed, as necessary. In the method for producing a laminated lens of this embodiment, the (thio)urethane resin film obtained by the method for producing a (thio)urethane resin film of this embodiment is used, so the (thio)urethane resin film has appropriate flexibility and can be vacuum molded or pressure molded. The vacuum conditions for vacuum molding can be, for example, a vacuum state of 0.2 kPa or more and 3 kPa or less. The pressure conditions for pressure molding can be, for example, a pressure state of about 100 kPa or more and 300 kPa or less. The heating temperature can be, for example, about 100°C or more and 140°C or less.

[0149] The lens substrate used in the method for manufacturing a laminated lens of the present embodiment preferably contains at least one selected from the group consisting of poly(meth)acrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane, more preferably contains at least one selected from the group consisting of polyepisulfide, polyurethane, and polythiourethane, and even more preferably contains at least one selected from the group consisting of polyurethane and polythiourethane.

[0150] [Uses of (thio)urethane-based resin film] The (thio)urethane-based resin film obtained by the method for producing a (thio)urethane-based resin film of the present embodiment can be used for various plastic lenses such as display members, plastic eyeglass lenses, sunglasses, goggles, eyeglass lenses for vision correction, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, and lenticular lenses.

[0151] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements that do not impair the effects of the present invention are included in the present invention.

[0152] The present embodiment will be described in detail below with reference to examples, etc. However, the present embodiment is not limited to the descriptions of these examples.

[0153] <Examples 1a to 6a and Comparative Examples 1a and 2a>

[0154] (Raw materials) Polythiol 1: bis(2-mercaptoethyl) sulfide Polythiol 2: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane Polythiol 3: pentaerythritol tetrakis(3-mercaptopropionate) Isocyanate compound 1: mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane Isocyanate compound 2: xylylene diisocyanate Base generator 1: tetra(n-butyl)ammonium=n-butyltri(1-naphthyl)borate Mold release agent 1: polyether-modified silicone (DOWSIL SH-3749, manufactured by Dow Toray Industries, Inc.)

[0155] Example 1a: A mixed solution was prepared by adding 100 parts by mass of a mixture of isocyanate compound 1: 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 84.2 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 3000 ppm of base generator 1 relative to the total of polythiol compound (A) and isocyanate compound (B), and 3000 ppm of release agent 1. This mixed solution was stirred at 25°C for 10 minutes to completely dissolve the mixture, degassed at 600 Pa for 1 hour, and filtered using a 1 µm PTFE filter to obtain a prepared liquid (photopolymerizable composition). Two glass plates, each 15 cm on a side and 2 mm thick, were placed at a distance of 350 μm. A 200 μm thick PTFE sheet was placed around the four sides of the glass plates with a width of 1 cm. The resulting preparation was poured into the glass plate, sandwiched between the pair of glass plates, and secured with clips. UV irradiation was performed with UVA at an irradiation intensity of 200 mW and an irradiation dose of 6000 mJ, and UVC at an irradiation intensity of 70 mW and an irradiation dose of 2100 mJ, polymerizing the surface of the preparation and obtaining a semi-cured product sandwiched between the glass plates. This semi-cured product was heated at 120 ° C. for 2 hours and then peeled from the glass plates to obtain a thiourethane film measuring approximately 13 cm x 13 cm. A 30 cm x 30 cm thiourethane film was obtained in the same manner as above, except that two glass plates, each 40 cm on a side and 2 mm thick, were used.

[0156] Examples 2a to 6a and Comparative Example 2a Thiourethane films were obtained in the same manner as in Example 1a, except that the formulation and conditions shown in Table 1 were used.

[0157] Comparative Example 1a In Comparative Example 1a, a polyester film, Lumirror H10 (thickness: 500 μm), manufactured by Toray Industries, Inc. was used.

[0158] For each example film, the storage modulus E', glass transition temperature Tg, thickness T, water contact angle, presence or absence of boron element, and restoring force were evaluated using a thiourethane film measuring approximately 13 cm x 13 cm. Furthermore, E' x T was calculated from the storage modulus E' and thickness T. Furthermore, a thiourethane film measuring 5 cm wide and 30 cm long was cut from the 30 cm x 30 cm thiourethane film, and winding properties (1) and (2) were evaluated. The results are shown in Table 1.

[0159] [Storage Modulus E' and Glass Transition Temperature Tg] Test pieces measuring 5 mm in width and 30 mm in length were cut out from the films of each example under the following conditions, and solid viscoelastic temperature dispersion measurements were performed to measure the storage modulus E' (MPa) at 40°C and the glass transition temperature Tg (°C). Tg was taken as the peak temperature of tan δ. Apparatus: Dynamic viscoelasticity measuring apparatus RSA-III (manufactured by TA Instruments) Deformation mode: Tensile Heating rate: 2°C / min Frequency: 1 Hz Set strain: 0.1% Environment: Air atmosphere

[0160] [Thickness Measurement] The thickness T of the film in each example was determined by measuring the thickness at 10 arbitrary locations on each film using a Digimatic Indicator (ID-H0560, manufactured by Mitutoyo Corporation) and using the average value of these measurements.

[0161] [Water Contact Angle] The water contact angle of the film of each example was measured in an atmosphere of 23°C and 50% RH using a contact angle meter (Model DMs-401, manufactured by Kyowa Interface Science Co., Ltd.) in accordance with JIS R3257:1999. The film was cut into a 10 cm square, and the arithmetic mean value of contact angles at five points within the same sample was taken as the water contact angle (°).

[0162] [Presence or Absence of Boron Element] The presence or absence of boron element on the film surface of each example was confirmed by elemental analysis using ICP emission spectrometry.

[0163] [Elemental Boron Content] The film of each example was cut into a size of 20 mm x 20 mm using a cutter to prepare a sample. The sample had a shape close to a square with sides of 20 mm. 5 g of the obtained sample was added to a hydrogen fluoride solution, and then the sample was dissolved under sealed conditions using a microwave wet decomposition method to obtain a measurement solution. The obtained measurement solution was diluted to a constant volume and appropriately diluted, and the content (ppm) of elemental boron in the film was quantitatively analyzed using an ICP-AES: 720-ES (manufactured by Agilent Technologies, Inc.). A calibration curve for boron was prepared, and the content (ppm) of elemental boron in the film was determined using the external standard method.

[0164] [Restoring Force] The method for measuring the restoring force will be described with reference to Figures 1 and 2. Each film was cut into a strip measuring 1 cm wide x 12 cm long from the center of the film widthwise to prepare a test piece (101). One end (a) of the test piece (101) was fixed to a resin cylinder (material: ABS) (102) with an outer diameter of 10 cm with adhesive tape (not shown), and the test piece was then wrapped around the resin cylinder (102). The resin cylinder (102) was fixed on a height-adjustable jack (105) to prevent it from rotating. Next, a rectangular parallelepiped plate (103) measuring 1 cm wide x 15 cm long x 0.1 cm thick (material: stainless steel, weight: 7.3 g) was placed horizontally, with the end (b) of the test piece (101) opposite to the end (a) as the contact point. One end (c) of the plate (103) was overlapped by 1 cm in the longitudinal direction with the end of the test piece (101) on the side of the end (b), and the end (d) of the plate (103) opposite the end (c) was placed in contact with the upper side of the measurement axis of a digital force gauge (104) (manufactured by Nidec-Shimpo Corporation, product name: FGP-0.2). The plate (103) was fixed 7.5 cm from the end (d) using a stand, clamps, and clay (not shown), and was set so that it could move around the point fixed by the clay as a fulcrum. This state was the start of the test and is shown in Figure 1. Next, as shown by the arrow in Figure 1, the jack (105) was moved to raise the height of the resin cylinder (102), so that the test piece (101) rose along the underside of the plate (103), and the plate (103) and the tangent to the outer periphery of the resin cylinder (102) overlapped. The value G (g) of the digital force gauge (104) was read when the 1 cm overlapping portion of the plate (103) and the test piece (101) were completely in contact (this state is shown in Figure 2). Note that the above-mentioned "the 1 cm overlapping portion of the plate (103) and the test piece (101) are completely in contact" means that, as shown in Figure 2, the test piece (101) was pushed up from below the plate (103), and a portion 1 cm long and 1 cm wide from one end (c) of the plate (103) and a portion 1 cm long and 1 cm wide from one end (b) of the test piece (101) were in contact with each other without any gaps over the entire surface. The restoring force (N / m) per meter of width of the test piece (101) was calculated according to the following formula (1).Formula (1): Restoring force (N / m) = (G (g) x 9.80665 / 1000) x 100 Furthermore, the restoring force (N / m) per 1 m width and 300 μm thickness of the test piece (101) was calculated according to the following formula (2): Formula (2): Restoring force (N / m) = (G (g) x 9.80665 / 1000 x 100) / thickness of test piece (μm) x 300 (μm) Note that 9.80665 in the above formulas (1) and (2) is the acceleration of gravity (m / s). ２ ) represents

[0165] [Winding property evaluation (1)] A film having a width of 5 cm and a length of 30 cm of each example was wound into a roll on a winding core (large winding core) (material: ABS) having an outer diameter of 7.62 cm and a width of 20 cm, and a winding core (small winding core) (material: ABS) having an outer diameter of 4 cm and a width of 20 cm, respectively, at a winding speed of 100 cm / min. The end of the wound film was fixed with adhesive tape (Scotch tape manufactured by 3M) having a width of 18 mm and a length of 3 cm, and after leaving it for 30 minutes, the presence or absence of rewinding of the film was confirmed. Rewinding of the film refers to the adhesive tape coming off or the part fixed with the adhesive tape shifting. The roll-shaped wound product was observed after winding, and the winding property was evaluated according to the following criteria. A and B were considered to be acceptable. (Criteria) A (best): No rewinding occurred on either the large or small winding core. B (good): Rewinding occurred on either the large or small winding core. C (poor): Rewinding occurred on both the large and small winding core.

[0166] [Windability Evaluation (2)] For each example thiourethane film, the windability was evaluated based on the obtained restoring force (N / m) per meter of width, according to the following criteria: A (best): restoring force per meter of width less than 1.0 N / m (easy to wind, no rewinding) B (good): restoring force per meter of width 1.0 N / m or more and less than 30 N / m (windable) C (poor): restoring force per meter of width 30 N / m or more (difficult to wind)

[0167]

[0168] <Examples 1b to 6b and Comparative Example 1b>

[0169] (Raw materials) Polythiol 1: bis(2-mercaptoethyl) sulfide Polythiol 2: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane Isocyanate compound 1: a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane Base generator 1: tetra(n-butyl)ammonium = n-butyltri(1-naphthyl)borate, manufactured by Resonac Co., Ltd., Karenz (registered trademark) N3B, a compound represented by the following formula (X)

[0170]

[0171] Release agent 2: Polyether-modified silicone (KF-351A, manufactured by Shin-Etsu Silicones Co., Ltd.)

[0172] Example 1b Thiourethane plates and films were prepared as follows. A mixed solution was prepared by adding 100 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, 42.1 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 37.4 parts by mass of bis(2-mercaptoethyl)sulfide, 750 ppm of base generator 1 relative to the total of polythiol compound (A) and isocyanate compound (B), and 2000 ppm of release agent 2. This mixed solution was stirred at 25°C for 10 minutes to completely dissolve the mixture, degassed at 600 Pa for 1 hour, and then filtered through a 1 μm PTFE filter to obtain a prepared solution (photopolymerizable composition). The thiourethane plate was prepared as follows. Two glass molds with a diameter of 7.7 cm and a thickness of 5 mm were fixed with tape so that the gap between them was 2 mm to prepare a casting mold. The obtained preparation was poured into the obtained casting mold, and ultraviolet light was irradiated at a UVA irradiation intensity of 186 mW, an accumulated light quantity of 1488 mJ, and a UVC irradiation intensity of 32.5 mW, an accumulated light quantity of 260 mJ, to obtain a semi-cured product sandwiched between glass plates. The obtained semi-cured product was heated at 120°C for 3 hours and then released from the glass mold to obtain a thiourethane plate with a thickness of 2 mm. The thiourethane film was prepared as follows. Two 15 cm x 2 mm thick glass plates were placed at a distance of 200 μm, and a 200 μm thick PTFE sheet was placed around the four sides of the glass plates with a width of 1 cm. The resulting mixture was poured into the glass plates, sandwiched between the pair of glass plates and fixed with clips. UV irradiation was performed with a UVA irradiation intensity of 186 mW, an accumulated light quantity of 1488 mJ, and a UVC irradiation intensity of 32.5 mW, an accumulated light quantity of 260 mJ, to obtain a semi-cured product sandwiched between the glass plates. The resulting semi-cured product was heated at 120 ° C for 3 hours, and then released from the glass mold to obtain a 220 μm thick thiourethane film.

[0173] Examples 2b to 6b and Comparative Example 1b Thiourethane plates and thiourethane films of each example were obtained in the same manner as in Example 1b, except that the formulations and production conditions shown in Table 2 were used.

[0174] For each example of thiourethane flat plate, the degree of polymerization, boron element content, flat plate thickness, haze, yellowness index (YI value), and Young's modulus were measured as follows. For each example of thiourethane film, the film thickness T, restoring force, and storage modulus E' were measured as follows. For the thiourethane film, E' x T was calculated from the storage modulus E' and thickness T. Furthermore, winding properties (1), winding properties (2), appearance evaluation, and hue evaluation were performed. The results are shown in Table 2.

[0175] [Polymerization Degree] The polymerization degree (%) of the thiourethane flat plate of each example was measured using FT-IR (ATR method). For the thiourethane flat plate of each example, the 2254 cm －１ The absorbance of the peak was measured. The degree of polymerization was calculated according to the following formula (4), with the absorbance measured for the unpolymerized monomer solution being taken as the standard for a degree of polymerization of 0%. Formula (4): Degree of polymerization (%) = (absorbance of unpolymerized monomer - absorbance of each thiourethane plate) / absorbance of unpolymerized monomer × 100. The absorbance in the above formula (4) was calculated at 2254 cm －１ This is the peak absorbance.

[0176] [Content of Boron in Thiourethane Plates] The thiourethane plates of each example were cut with a cutter to a size of 20 mm x 20 mm to prepare samples. The samples were approximately square with sides of 20 mm. Five grams of the obtained sample was added to a hydrogen fluoride solution, and then dissolved under sealed conditions using a microwave wet decomposition method to obtain a measurement solution. The obtained measurement solution was diluted to a constant volume and appropriately diluted, and the content of boron (ppm) in the thiourethane plates was quantitatively analyzed using an ICP-AES: 720-ES (Agilent Technologies, Inc.). A calibration curve for boron was created, and the content of boron (ppm) was determined using the external standard method. Comparative Example 1b was uncured, but the boron content was measured using the above method.

[0177] [Thickness of Plate and Film] The thickness T of the plate and film in each example was determined by measuring the thickness at 10 arbitrary locations on each plate and each film using a Digimatic Indicator (ID-H0560, manufactured by Mitutoyo Corporation), and then using the average value.

[0178] [Haze] The haze (%) of each thiourethane plate was measured in accordance with JIS K 7136:2000 (ISO 14782:1999) using a HazeMeter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0179] [Yellowness Index (YI Value)] The yellowness index (YI value) of each thiourethane plate was measured in accordance with JIS K 7373:2006 using a spectrophotometer CM-5 (manufactured by Konica Minolta, Inc.).

[0180] [Young's Modulus] The thiourethane plate of each example was cut into a test piece having a length of 65 mm and a width of 25 mm, and the Young's modulus was measured for the test piece in accordance with JIS K7171:2016 using a tensile tester (Autograph AGS-X (5 kN), manufactured by Shimadzu Corporation) under the conditions of a measurement temperature of 23°C, a measurement humidity of 50% RH, a tensile speed of 1 mm / min, and a distance between supports of 34 mm.

[0181] [Restoring Force] The method for measuring the restoring force will be described with reference to Figures 1 and 2. Each film was cut into a strip measuring 1 cm wide x 12 cm long from the center of the film widthwise to prepare a test piece (101). One end (a) of the test piece (101) was fixed to a resin cylinder (material: ABS) (102) with an outer diameter of 10 cm with adhesive tape (not shown), and the test piece was then wrapped around the resin cylinder (102). The resin cylinder (102) was fixed on a height-adjustable jack (105) to prevent it from rotating. Next, a rectangular parallelepiped plate (103) measuring 1 cm wide x 15 cm long x 0.1 cm thick (material: stainless steel, weight: 7.3 g) was placed horizontally, with the end (b) of the test piece (101) opposite to the end (a) as the contact point. One end (c) of the plate (103) was overlapped by 1 cm in the longitudinal direction with the end of the test piece (101) on the side of the end (b), and the end (d) of the plate (103) opposite the end (c) was placed in contact with the upper side of the measurement axis of a digital force gauge (104) (manufactured by Nidec-Shimpo Corporation, product name: FGP-0.2). The plate (103) was fixed 7.5 cm from the end (d) using a stand, clamps, and clay (not shown), and was set so that it could move around the point fixed by the clay as a fulcrum. This state was the start of the test and is shown in Figure 1. Next, as shown by the arrow in Figure 1, the jack (105) was moved to raise the height of the resin cylinder (102), so that the test piece (101) rose along the underside of the plate (103), and the plate (103) and the tangent to the outer periphery of the resin cylinder (102) overlapped. The value G (g) of the digital force gauge (104) was read when the 1 cm overlapping portion of the plate (103) and the test piece (101) were completely in contact (this state is shown in Figure 2). Note that the above-mentioned "the 1 cm overlapping portion of the plate (103) and the test piece (101) are completely in contact" means that, as shown in Figure 2, the test piece (101) was pushed up from below the plate (103), and a portion 1 cm long and 1 cm wide from one end (c) of the plate (103) and a portion 1 cm long and 1 cm wide from one end (b) of the test piece (101) were in contact with each other without any gaps over the entire surface. The restoring force (N / m) per meter of width of the test piece (101) was calculated according to the following formula (2).Formula (2): Restoring force (N / m) = G (g) × 9.80665 / 1000 × 100 Furthermore, the restoring force (N / m) per 1 m width and 300 μm thickness of the test piece (101) was calculated according to the following formula (3): Formula (3): Restoring force (N / m) = (G (g) × 9.80665 / 1000 × 100) / Thickness of test piece (μm) × 300 (μm) The number 9.80665 in the above formulas (2) and (3) is the acceleration of gravity (m / s). ２ ) represents

[0182] [Storage Modulus E'] A test piece measuring 5 mm in width and 30 mm in length was cut out from the film of each example under the following conditions, and solid viscoelastic temperature dispersion measurement was performed to measure the storage modulus E' (MPa) at 40°C. Apparatus: Dynamic viscoelasticity measuring apparatus RSA-III (manufactured by TA Instruments) Deformation mode: Tension Heating rate: 2°C / min Frequency: 1 Hz Set strain: 0.1% Environment: Air atmosphere

[0183] [Winding property evaluation (1)] From each example film, a film measuring 5 cm wide and 30 cm long was cut out and wound onto a winding core (large winding core) (material: ABS) with an outer diameter of 7.62 cm and a width of 20 cm, and a winding core (small winding core) (material: ABS) with an outer diameter of 4 cm and a width of 20 cm, respectively, at a winding speed of 100 cm / min. The end of the wound film was fixed with adhesive tape (3M Scotch tape) with a width of 18 mm and a length of 3 cm, and after leaving it for 30 minutes, the presence or absence of film rewinding was confirmed. Film rewinding refers to the adhesive tape coming off or the part fixed with the adhesive tape shifting. The rolled wound product was observed, and the winding property was evaluated according to the following criteria. A and B were considered to be acceptable. (Criteria) A (best): No rewinding occurred on either the large or small winding core. B (good): Rewinding occurred on either the large or small winding core. C (poor): Rewinding occurred on both the large and small winding core.

[0184] [Windability Evaluation (2)] For each example thiourethane film, the windability was evaluated based on the obtained restoring force (N / m) per meter of width, according to the following criteria: A (best): restoring force per meter of width less than 1.0 N / m (easy to wind, no rewinding) B (good): restoring force per meter of width 1.0 N / m or more and less than 30 N / m (windable) C (poor): restoring force per meter of width 30 N / m or more (difficult to wind)

[0185] [Evaluation of Appearance (Presence or Absence of Foaming)] The appearance (presence or absence of foaming) of each thiourethane film was visually evaluated based on the following criteria: A (best): No foaming B (good): Foaming present in some areas C (poor): Foaming present throughout the film

[0186] [Evaluation of Hue] The hue of each thiourethane film was evaluated based on the obtained yellowness index (YI value) according to the following criteria: A (best): YI value less than 2.0 B (good): YI value 2.0 or more and less than 3.0 C (poor): YI value 3.0 or more

[0187]

[0188] Examples 1c to 6c

[0189] (Raw materials) Polythiol 1: bis(2-mercaptoethyl) sulfide Polythiol 2: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane Isocyanate compound 1: a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane Isocyanate compound 2: xylylene diisocyanate Base generator 1: tetra(n-butyl)ammonium=n-butyltri(1-naphthyl)borate Metal catalyst 1: dimethyltin dichloride Mold release agent 1: polyether-modified silicone (DOWSIL SH-3749, manufactured by Dow-Toray Industries, Inc.) Mold release agent 2: polyether-modified silicone (KF-351A, manufactured by Shin-Etsu Chemical Co., Ltd.) Release agent 3: Phosphate ester (Zelec (registered trademark) UN, manufactured by STEPAN)

[0190] Example 1c [Preparation of Photopolymerizable Composition] A mixed solution was prepared by adding 0.006 parts by mass of dimethyltin dichloride, 100 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, 27.7 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 57.5 parts by mass of bis(2-mercaptoethyl)sulfide, and 0.19 parts by mass of a release agent. The resulting mixed solution was stirred at 25°C for 10 minutes to completely dissolve the components, degassed at 600 Pa for 1 hour, and filtered through a 1 μm PTFE filter to obtain mixed solution A. The resulting mixed solution A was heated at 80°C for 4.5 hours to obtain a prepolymerized polymerizable composition having a viscosity of 182 mPa s. To the obtained prepolymerized polymerizable composition, a solution (mixed solution B) in which 0.49 parts by mass of base generator 1 was dissolved in 9.3 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 added, thereby obtaining a prepared solution (photopolymerizable composition).

[0191] [Laminate Manufacturing Step] The obtained preparation was applied to a release film cut into a size of 9 x 9 cm using a bar coater to a thickness of 300 µm.

[0192] [First polymerization step] The prepared liquid applied onto the release film was irradiated with ultraviolet light at a UVA irradiation intensity of 200 mW and an irradiation amount of 1000 mJ, and at a UVC irradiation intensity of 70 mW and an irradiation amount of 360 mJ, thereby polymerizing the vicinity of the surface of the prepared liquid and obtaining a semi-cured product.

[0193] [Second polymerization step] A 125 μm thick PET (polyethylene terephthalate) film was laminated as a protective film on the surface of the release film on which the semi-cured material layer was formed, and the film was heated at 120° C. for 1 hour. The release film and protective film were then peeled off to obtain a thiourethane film having a size of approximately 9 cm × 9 cm.

[0194] [Evaluation of production efficiency] Based on the time required to obtain a thiourethane film of 8 cm x 8 cm size, i.e., the time required from the start of preparation of the mixed solution in [Preparation of photopolymerizable composition] to the time required to peel off the release film and protective film from the thiourethane film in [Second polymerization step], production efficiency was evaluated according to the following criteria: A (best): Within 7 hours B (good): More than 7 hours but less than 10 hours C (poor): More than 10 hours

[0195] [Evaluation of shrinkage marks] The appearance of the resulting thiourethane film surface was visually evaluated for shrinkage marks according to the following criteria: A (best): No shrinkage marks at all. B (good): Slight shrinkage marks were observed around the edges of the film. C (poor): Large shrinkage marks were observed from the edges to the center of the film.

[0196] [Evaluation of Appearance After Heating at 145°C for 15 Minutes] The obtained thiourethane film was heated at 145°C for 15 minutes, and the presence or absence of bubbles on the film surface was visually evaluated according to the following criteria. A and B were rated as acceptable. A (best): No bubbles were generated. B (good): A few bubbles were generated. C (poor): Many bubbles were generated.

[0197] Examples 2c to 6c Thiourethane films were obtained in the same manner as in Example 1c, except for the formulation and conditions shown in Table 3. For Example 3c, the bar coater was set to achieve a thickness of 300 μm in the laminate production process, but due to the low viscosity, the thickness was in the range of 50 to 150 μm.

[0198] The thiourethane films obtained in each example were evaluated as follows.

[0199] [Evaluation Method] In the present examples, the films and lenses were evaluated as follows.

[0200] [Viscosity] The viscosity (mPa·s) of the mixed solution A at 23° C. was measured using a vibration viscometer VM-10A-M manufactured by Secomic Co., Ltd.

[0201] [Thickness Measurement] The thickness T of the obtained thiourethane film was determined by measuring the thickness at 10 arbitrary locations on each film using a Digimatic Indicator (ID-H0560, manufactured by Mitutoyo Corporation), and then using the average value of these measurements.

[0202] [Water Contact Angle of Substrate] The water contact angle of the release film was measured in an atmosphere of 23°C and 50% RH using a contact angle meter (DMs-401 model, manufactured by Kyowa Interface Science Co., Ltd.) in accordance with JIS R3257: 1999. The substrate was cut into 10 cm squares, and the arithmetic mean value of contact angles at five points within the same sample was taken as the water contact angle (°).

[0203] [Contact angle of substrate with mixed liquid A] The contact angles with mixed liquid A obtained in Examples 1c, 2c, and 6c were measured. The substrates were cut into 9 cm squares, and the arithmetic mean value of contact angles measured at five points on the same sample in accordance with JIS R 3257:1999 was taken as the contact angle (°) with mixed liquid A.

[0204] [Content of Boron in Film] The film of each example was cut into a size of 20 mm x 20 mm using a cutter to prepare a sample. The sample had a shape close to a square with sides of 20 mm. 5 g of the obtained sample was added to a hydrogen fluoride solution, and then the sample was dissolved under sealed conditions using a microwave wet decomposition method to obtain a measurement solution. The obtained measurement solution was diluted to a constant volume and appropriately diluted, and the content of boron (ppm) in the film was quantitatively analyzed using an ICP-AES: 720-ES (manufactured by Agilent Technologies, Inc.). A calibration curve for boron was prepared, and the content of boron (ppm) in the film was determined using the external standard method.

[0205] [Storage Modulus E'] A test piece measuring 5 mm in width and 30 mm in length was cut out from the film of each example under the following conditions, and solid viscoelastic temperature dispersion measurement was performed to measure the storage modulus E' (MPa) at 40°C. Apparatus: Dynamic viscoelasticity measuring apparatus RSA-III (manufactured by TA Instruments) Deformation mode: Tensile Heating rate: 2°C / min Frequency: 1 Hz Set strain: 0.1% Environment: Air atmosphere Furthermore, E' x T was calculated from the results of storage modulus E' and thickness T.

[0206] [Restoring Force] The method for measuring the restoring force will be described with reference to Figures 1 and 2. Each film was cut into a strip measuring 1 cm wide x 12 cm long from the center of the film widthwise to prepare a test piece (101). One end (a) of the test piece (101) was fixed to a resin cylinder (material: ABS) (102) with an outer diameter of 10 cm with adhesive tape (not shown), and the test piece was then wrapped around the resin cylinder (102). The resin cylinder (102) was fixed on a height-adjustable jack (105) to prevent it from rotating. Next, a rectangular parallelepiped plate (103) measuring 1 cm wide x 15 cm long x 0.1 cm thick (material: stainless steel, weight: 7.3 g) was placed horizontally, with the end (b) of the test piece (101) opposite to the end (a) as the contact point. One end (c) of the plate (103) was overlapped by 1 cm in the longitudinal direction with the end of the test piece (101) on the side of the end (b), and the end (d) of the plate (103) opposite the end (c) was placed in contact with the upper side of the measurement axis of a digital force gauge (104) (manufactured by Nidec-Shimpo Corporation, product name: FGP-0.2). The plate (103) was fixed 7.5 cm from the end (d) using a stand, clamps, and clay (not shown), and was set so that it could move around the point fixed by the clay as a fulcrum. This state was the start of the test and is shown in Figure 1. Next, as shown by the arrow in Figure 1, the jack (105) was moved to raise the height of the resin cylinder (102), so that the test piece (101) rose along the underside of the plate (103), and the plate (103) and the tangent to the outer periphery of the resin cylinder (102) overlapped. The value G (g) of the digital force gauge (104) was read when the 1 cm overlapping portion of the plate (103) and the test piece (101) were completely in contact (this state is shown in Figure 2). Note that the above-mentioned "the 1 cm overlapping portion of the plate (103) and the test piece (101) are completely in contact" means that, as shown in Figure 2, the test piece (101) was pushed up from below the plate (103), and a portion 1 cm long and 1 cm wide from one end (c) of the plate (103) and a portion 1 cm long and 1 cm wide from one end (b) of the test piece (101) were in contact with each other without any gaps over the entire surface. The restoring force (N / m) per meter of width of the test piece (101) was calculated according to the following formula (2): Formula (2): restoring force (N / m) = G (g) × 9.80665 / 1000 × 100

[0207] [Winding property evaluation (1)] From each example of thiourethane film, a film measuring 5 cm wide and 30 cm long was cut out and wound onto a core (large core) (material: ABS) with an outer diameter of 7.62 cm and a width of 20 cm, and a core (small core) (material: ABS) with an outer diameter of 4 cm and a width of 20 cm, at a winding speed of 100 cm / min. The end of the wound film was fixed with adhesive tape (3M Scotch tape) with a width of 18 mm and a length of 3 cm, and after leaving it for 30 minutes, the presence or absence of film rewinding was confirmed. Film rewinding refers to the adhesive tape coming off or the part fixed with the adhesive tape shifting. The rolled wound product was observed, and the winding property was evaluated according to the following criteria. A and B were considered to be acceptable. (Criteria) A (best): No rewinding occurred on either the large or small winding core. B (good): Rewinding occurred on either the large or small winding core. C (poor): Rewinding occurred on both the large and small winding core.

[0208] [Windability Evaluation (2)] For each example thiourethane film, the windability was evaluated based on the obtained restoring force (N / m) per meter of width, according to the following criteria: A (best): restoring force per meter of width less than 1.0 N / m (easy to wind, no rewinding) B (good): restoring force per meter of width 1.0 N / m or more and less than 30 N / m (windable) C (poor): restoring force per meter of width 30 N / m or more (difficult to wind)

[0209]

[0210] Examples of reference embodiments are listed below. A1. A thiourethane film comprising a cured product of a photopolymerizable composition containing a di- or higher functional polythiol (A), an isocyanate compound (B), and a photopolymerization initiator (C), wherein the product E' x T of the storage modulus E' at 40°C and the thickness T of the thiourethane film is 50 MPa·mm or more and 1800 MPa·mm or less. A2. A thiourethane film comprising a cured product of a photopolymerizable composition containing a di- or higher functional polythiol (A), an isocyanate compound (B), and a photopolymerization initiator (C), wherein the restoring force measured according to the following <Conditions> is 40.0 N / m or less. <Conditions> The thiourethane film is cut into strips measuring 1 cm wide and 12 cm long, and one end (a) of the thiourethane film is fixed to a resin cylinder having an outer diameter of 10 cm with adhesive tape, and the film is wrapped around the resin cylinder. Next, a plate measuring 1 cm wide and 15 cm long was placed horizontally, with the end (b) of the thiourethane film opposite the end (a) as the contact point. Next, one end (c) of the plate was overlapped by 1 cm longitudinally with the end of the thiourethane film on the side of the end (b), and the end (d) of the plate opposite the end (c) was placed so that it was in contact with the upper side of the measurement axis of the digital force gauge. The plate was fixed with clay at a section 7.5 cm from the end (d) and was set so that it could move around the point fixed with clay as a fulcrum. Next, the height of the resin cylinder was raised, causing the thiourethane film to rise along the underside of the plate, and the plate and the tangent to the outer circumference of the resin cylinder overlapped. When the 1 cm overlapping portion of the plate and the thiourethane film were completely in contact, the value G (g) of the digital force gauge was read, and the restoring force (N / m) of the thiourethane film was calculated according to the following formula (1): Formula (1): Restoring force (N / m) = (G (g) × 9.80665 / 1000) × 100 The 9.80665 in the above formula (1) is the gravitational acceleration (m / s ２A3. The thiourethane film according to A1 or A2, wherein the photopolymerization initiator (C) contains a base generator consisting of an organoboron anion and a counter cation. A4. The thiourethane film according to A3, wherein the base generator contains a compound represented by the following formula (1): A5. The thiourethane film according to any one of A1. to A4., which contains boron element. A6. The thiourethane film according to any one of A1. to A5., in which the content of the photopolymerization initiator (C) is 500 ppm to 5,000 ppm, based on the total of the bifunctional or higher polythiol (A) and the isocyanate compound (B). A7. The thiourethane film according to any one of A1. to A6., in which the photopolymerizable composition further contains a metal catalyst (D). A8. The thiourethane film according to any one of A1. to A7., which is obtained by irradiating the photopolymerizable composition with ultraviolet light to polymerize a portion of the photopolymerizable composition, and then heating the photopolymerizable composition to further polymerize it. A9. The thiourethane film according to any one of A1. to A8., which has a thickness of 50 μm to 1,000 μm. A10. The polythiol (A) is 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis( The thiourethane film according to any one of A1 to A9, comprising at least one selected from the group consisting of 1,2-bis(mercaptomethylthio)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.A11. The thiourethane film according to any one of A1 to A10, wherein the isocyanate compound (B) comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. A12. The thiourethane film according to any one of A1 to A11, further comprising one or two selected from the group consisting of a hard coat layer and an antireflection layer. A13. A thiourethane film according to any one of A1. to A12., wherein the surface of the thiourethane film has a water contact angle of 50.0° or more and 90.0° or less. A14. A thiourethane film according to any one of A1. to A13., further comprising an adhesive layer on one side of the thiourethane film. A15. A roll-shaped wound product comprising the thiourethane film according to any one of A1. to A14. and a winding core, wherein the thiourethane film is wound around the winding core in a roll shape. A16. A lens comprising the thiourethane film according to any one of A1. to A14.. A17. A lens according to A16., wherein the thiourethane film and lens substrate are in direct contact.

[0211] B1. A polymerizable composition for forming a thiourethane film, comprising a difunctional or higher polythiol (A), an isocyanate compound (B), and a photopolymerization initiator (C), wherein the content of the photopolymerization initiator (C) relative to the total amount of the difunctional or higher polythiol (A) and the isocyanate compound (B) is 250 mass ppm or more. B2. The polymerizable composition for forming a thiourethane film according to B1., wherein the photopolymerization initiator (C) contains boron. B3. The polymerizable composition for forming a thiourethane film according to B1. or B2., wherein the photopolymerization initiator (C) contains a base generator composed of an organic boron anion and a counter cation. B4. The polymerizable composition for forming a thiourethane film according to B3., wherein the base generator contains a compound represented by the following formula (1): (In formula (1), R １ ~R ４ each independently represents an alkyl group having 1 to 8 carbon atoms; R ５ ~R ８each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.) B5. The polymerizable composition for forming a thiourethane film according to any one of B1. to B4., wherein the difunctional or higher functional polythiol (A) includes a difunctional polythiol and a trifunctional or higher functional polythiol. B6. The bifunctional or higher functional polythiol (A) may be 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5- The polymerizable composition for forming a thiourethane film according to any one of B1 to B5, comprising at least one selected from the group consisting of bis(mercaptomethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.B7. The polymerizable composition for forming a thiourethane film according to any one of B1 to B6, wherein the isocyanate compound (B) comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. B8. The polymerizable composition for forming a thiourethane film according to any one of B1. to B7., wherein the equivalent ratio of thiol groups in the difunctional or higher polythiol (A) to the isocyanato groups in the isocyanate compound (B) (thiol groups / isocyanato groups) is 0.8 or more and 1.2 or less. B9. The polymerizable composition for forming a thiourethane film according to any one of B1. to B8., wherein the total content of the difunctional or higher polythiol (A) and the isocyanate compound (B) is 50% by mass or more and less than 100% by mass, when the total content of the polymerizable composition for forming a thiourethane film is taken as 100% by mass. B10. The polymerizable composition for forming a thiourethane film according to any one of B1. to B9., wherein the yellowness index (YI value) measured by the following Method 1 is less than 3.0. (Method 1) A casting mold was prepared by fixing two 7.7 cm diameter, 5 mm thick glass molds with tape so that they were spaced 2 mm apart. The polymerizable composition for forming a thiourethane film was then poured into the casting mold. The composition was then irradiated with UV light at a UVA irradiation intensity of 186 mW and an accumulated light dose of 1488 mJ, and a UVC irradiation intensity of 32.5 mW and an accumulated light dose of 260 mJ, yielding a semi-cured product sandwiched between the glass plates. The resulting semi-cured product was heated at 120°C for 3 hours and then released from the glass mold to produce a 2 mm thick thiourethane plate. The yellowness index (YI value) of the thiourethane plate was measured in accordance with JIS K7373:2006.B11. The polymerizable composition for forming a thiourethane film according to any one of B1. to B10., wherein the haze measured by Method 2 below is 1.0% or less. (Method 2) A casting mold is prepared by fixing two 7.7 cm diameter, 5 mm thick glass molds with tape at a 2 mm gap between them. The polymerizable composition for forming a thiourethane film is then poured into the casting mold and irradiated with ultraviolet light at a UVA irradiation intensity of 186 mW and an accumulated light dose of 1488 mJ, and a UVC irradiation intensity of 32.5 mW and an accumulated light dose of 260 mJ, to obtain a semi-cured product sandwiched between the glass plates. The resulting semi-cured product is heated at 120°C for 3 hours and then released from the glass mold to produce a 2 mm thick thiourethane plate. The haze of the thiourethane plate is measured in accordance with JIS K7136:2000. B12. The polymerizable composition for forming a thiourethane film according to any one of B1. to B11., wherein the Young's modulus, measured by Method 3 below, is 100 MPa or more and 5000 MPa or less. (Method 3) A casting mold is prepared by fixing two 7.7 cm diameter, 5 mm thick glass molds with tape so that they are spaced 2 mm apart. The polymerizable composition for forming a thiourethane film is then poured into the casting mold and irradiated with UV light at a UVA irradiation intensity of 186 mW and an accumulated light dose of 1488 mJ, and a UVC irradiation intensity of 32.5 mW and an accumulated light dose of 260 mJ, to obtain a semi-cured product sandwiched between the glass plates. The resulting semi-cured product is heated at 120°C for 3 hours and then released from the glass mold to produce a 2 mm thick thiourethane plate. A test piece measuring 65 mm long, 25 mm wide, and 2 mm thick is then cut from the resulting thiourethane plate. The Young's modulus of the obtained test piece is measured using a tensile tester in accordance with JIS K7171:2016 under conditions of measurement temperature: 23°C, measurement humidity: 50% RH, tensile speed: 1 mm / min, and support distance: 34 mm. B13. A thiourethane film comprising a cured product of the polymerizable composition for molding a thiourethane film described in any one of B1. to B12. B14. The thiourethane film described in B13., having a thickness of 50 μm or more and 1000 μm or less. B15. The thiourethane film described in either B13. or B14., which has an adhesive layer on one side of the thiourethane film.B16. The thiourethane film according to B15, wherein the adhesive layer comprises one or more materials selected from the group consisting of urethane (meth)acrylate, (meth)acrylic monomer, (meth)acrylic resin, urethane resin, and ester resin. B17. The thiourethane film according to any one of B13 to B16, wherein a hard coat layer is provided on one surface of the thiourethane film. B18. The thiourethane film according to B17, wherein the hard coat layer is provided on one surface of the thiourethane film, and an adhesive layer and an optical substrate are provided, in this order, on the surface opposite the hard coat layer. B19. The thiourethane film according to B18, wherein the optical substrate comprises at least one material selected from the group consisting of polythiourethane, poly(meth)acrylate, polycarbonate, polyallyl carbonate, polyethylene terephthalate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, and polyurethane. B20. B13 to B19. B21. A lens comprising the thiourethane film according to any one of B20. B22. Eyeglasses equipped with the lens according to B20.

[0212] C1. A method for producing a (thio)urethane resin film, comprising: a first polymerization step of irradiating a film of a photopolymerizable composition containing an active hydrogen compound and an isocyanate compound, the film being formed on a substrate, with ultraviolet light to polymerize a portion of the photopolymerizable composition; and a second polymerization step of heating the photopolymerizable composition after the first polymerization step to further polymerize the photopolymerizable composition. C2. A method for producing a (thio)urethane resin film according to C1., wherein the photopolymerizable composition further contains a photopolymerization initiator. C3. A method for producing a (thio)urethane resin film according to C1. or C2., wherein the photopolymerizable composition further contains a metal catalyst. C4. A method for producing a (thio)urethane resin film according to C3., further comprising a viscosity adjusting step of adjusting the viscosity of mixed liquid A containing the active hydrogen compound, the isocyanate compound, and the metal catalyst to 50 mPa·s or more and 700 mPa·s or less. C5. C4., a method for producing a (thio)urethane resin film, further comprising, after the viscosity adjusting step, a step of mixing the mixed liquid A with a mixed liquid B containing the isocyanate compound and the photopolymerization initiator. C6. A method for producing a (thio)urethane resin film according to any one of C1. to C5., wherein the first polymerization step involves irradiating with ultraviolet light at an integrated light dose of 1,000 mJ or more and 4,000 mJ or less. C7. A method for producing a (thio)urethane resin film according to any one of C1. to C6., wherein the second polymerization step involves heating at a temperature of 80°C or more and 140°C or less. C8. A method for producing a (thio)urethane resin film according to any one of C1. to C7., wherein the (thio)urethane resin film has a thickness of 50 μm or more and 3 mm or less. C9. A method for producing a (thio)urethane resin film according to any one of C1. to C8., wherein the surface of the substrate has a water contact angle of 60.0° or more and 100.0° or less. C10. The method for producing a (thio)urethane resin film according to any one of C1. to C9., wherein the substrate is a release film. C11. The method for producing a (thio)urethane resin film according to C10., wherein the release film comprises at least one selected from the group consisting of polyethylene terephthalate and fluororesin.C12. The method for producing a (thio)urethane resin film according to any one of C1. to C11., wherein the (thio)urethane resin film further comprises a protective film on the surface opposite to the substrate. C13. The method for producing a (thio)urethane resin film according to any one of C1. to C12., wherein the isocyanate compound comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. C14. A method for producing a (thio)urethane resin film according to any one of C1. to C13., wherein the active hydrogen compound comprises at least one selected from the group consisting of polythiol, polyol, and polyamine. C15. A method for producing a (thio)urethane resin film according to any one of C1. to C14., wherein the (thio)urethane resin film further comprises a primer layer on the surface opposite to the substrate. C16. A method for producing a (thio)urethane resin film according to C15., wherein the primer layer comprises a polyurethane aqueous dispersion. C17. A method for producing a (thio)urethane resin film according to C15. or C16., wherein the (thio)urethane resin film further comprises at least one layer selected from the group consisting of a hard coat layer and an antireflection layer. C18. A method for producing a laminated lens, comprising: obtaining a (thio)urethane resin film by the method for producing a (thio)urethane resin film according to any one of C1. to C17.; and laminating the obtained (thio)urethane resin film to a lens substrate.C19. The method for manufacturing a laminated lens according to C18., wherein the lens substrate contains at least one selected from the group consisting of poly(meth)acrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane. C20. The method for manufacturing a laminated lens according to C18. or C19., wherein in the laminating step, the (thio)urethane resin film is laminated to the lens substrate by one or two methods selected from the group consisting of vacuum molding and pressure molding.

[0213] This application claims priority based on Japanese Patent Application Nos. 2023-081879 and 2023-081880, filed May 17, 2023, and Japanese Patent Application No. 2023-170313, filed September 29, 2023, the disclosures of which are incorporated herein in their entireties.

[0214] 101 Thiourethane film test piece 102 Resin cylinder 103 Plate 104 Digital force gauge 105 Jack

Claims

1. A thiourethane film comprising a cured product of a photopolymerizable composition comprising a difunctional or higher functional polythiol (A), an isocyanate compound (B), and a photopolymerization initiator (C), A thiourethane film having a product E' x T of the storage modulus E' at 40°C and the thickness T of the thiourethane film of 50 MPa·mm or more and 1800 MPa·mm or less.

2. 2. The thiourethane film according to claim 1, which has a restoring force of 40.0 N / m or less when measured according to the following conditions: <Conditions> The thiourethane film was cut into strips measuring 1 cm wide x 12 cm long, and one end (a) of the thiourethane film was fixed to a resin cylinder with an outer diameter of 10 cm with adhesive tape and wrapped around the resin cylinder. Next, a plate measuring 1 cm wide x 15 cm long was placed horizontally, with the end (b) of the thiourethane film opposite the end (a) as the contact point. Next, one end (c) of the plate was overlapped by 1 cm longitudinally with the end of the thiourethane film on the side of the end (b), and the end (d) of the plate opposite the end (c) was placed so that it was in contact with the upper side of the measurement axis of a digital force gauge. The plate is fixed with clay at a portion 7.5 cm from the end (d), and is set so that it can move around the point fixed with clay as a fulcrum. Next, the height of the resin cylinder is raised so that the thiourethane film rises along the underside of the plate, and the plate and the tangent to the outer periphery of the resin cylinder overlap. When the 1 cm overlapping portion of the plate and the thiourethane film are completely in close contact, the value G (g) of the digital force gauge is read, and the restoring force (N / m) of the thiourethane film is calculated according to the following formula (1). Formula (1): Restoring force (N / m) = (G (g) × 9.80665 / 1000) × 100 The 9.80665 in the above formula (1) is the gravitational acceleration (m / s ２ ) represents

3. The thiourethane film of claim 1 or 2, which contains elemental boron.

4. The thiourethane film according to claim 3 , wherein the boron element content in the thiourethane film is 5 ppm or more and 200 ppm or less.

5. The thiourethane film according to claim 1 or 2, wherein the photopolymerization initiator (C) contains boron.

6. The thiourethane film according to claim 1 or 2, wherein the photopolymerization initiator (C) comprises a base generator comprising an organic boron anion and a counter cation.

7. The thiourethane film according to claim 6, wherein the base generator comprises one or more compounds selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2): 【Chemistry 1】 (In formula (1), R １ ~R ４ each independently represents an alkyl group having 1 to 8 carbon atoms; R ５ ~R ８ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, naphthyl group, anthracenyl group, and phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group. 【Chemistry 2】 (In formula (2), R １ ~R ７ each independently represents an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms; R ８ ~R １１ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthryl group, and the phenyl group, the naphthyl group, the anthracenyl group, and the phenanthryl group may be substituted with a halogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group.

8. 3. The thiourethane film according to claim 1, wherein the content of the photopolymerization initiator (C) is 250 mass ppm or more relative to the total amount of the difunctional or higher polythiol (A) and the isocyanate compound (B).

9. 3. The thiourethane film according to claim 1, wherein the total content of the difunctional or higher polythiol (A) and the isocyanate compound (B) is 50% by mass or more and less than 100% by mass, when the entire photopolymerizable composition is taken as 100% by mass.

10. The thiourethane film of claim 1 or 2, wherein the photopolymerizable composition further comprises a metal catalyst (D).

11. The thiourethane film according to claim 1 or 2, which is obtained by irradiating the photopolymerizable composition with ultraviolet light to polymerize a portion of the photopolymerizable composition, and then heating the photopolymerizable composition to further polymerize it.

12. The thiourethane film according to claim 1 or 2, wherein the thickness T is 50 μm or more and 3000 μm or less.

13. The di- or higher functional polythiol (A) is selected from the group consisting of 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl 3. The thiourethane film according to claim 1, further comprising at least one member selected from the group consisting of 1,2,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.

14. The thiourethane film according to claim 1 or 2, wherein the isocyanate compound (B) comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

15. 3. The thiourethane film according to claim 1, wherein the equivalent ratio (thiol group / isocyanato group) of the thiol group in the bifunctional or higher polythiol (A) to the isocyanato group in the isocyanate compound (B) is 0.8 or more and 1.2 or less.

16. The thiourethane film according to claim 1 or 2, wherein the difunctional or higher functional polythiol (A) includes a difunctional polythiol and a trifunctional or higher functional polythiol.

17. The thiourethane film according to claim 1 or 2, further comprising one or more layers selected from the group consisting of a hard coat layer and an anti-reflection layer.

18. 3. The thiourethane film according to claim 1, wherein the water contact angle of the surface of the thiourethane film is 50.0° or more and 90.0° or less.

19. The thiourethane film according to claim 1 or 2, further comprising an adhesive layer on one side of the thiourethane film.

20. A rolled product comprising the thiourethane film according to claim 1 or 2 and a winding core, the thiourethane film being wound around the winding core in a roll shape.

21. A lens comprising the thiourethane film of claim 1 or 2.

22. 22. The lens of claim 21, wherein the thiourethane film and the lens substrate are in direct contact.

23. Eyeglasses comprising a lens according to claim 21.

24. a first polymerization step of irradiating a film made of a photopolymerizable composition provided on a substrate with ultraviolet light, the film including an active hydrogen compound, an isocyanate compound, a photopolymerization initiator, and a metal catalyst, to polymerize a portion of the photopolymerizable composition; a second polymerization step of heating the photopolymerizable composition after the first polymerization step to further polymerize the photopolymerizable composition.

25. The method for producing a (thio)urethane resin film according to claim 24, further comprising a viscosity adjusting step of adjusting the viscosity of the mixed solution A containing the active hydrogen compound, the isocyanate compound, and the metal catalyst to 50 mPa·s or more and 2000 mPa·s or less.

26. The method for producing a (thio)urethane resin film according to claim 25, further comprising, after the viscosity adjusting step, a step of mixing the mixed liquid A with a mixed liquid B containing the isocyanate compound and the photopolymerization initiator.

27. The method for producing a (thio)urethane resin film according to any one of claims 24 to 26, wherein the substrate is a release film.

28. The method for producing a (thio)urethane resin film according to claim 27, wherein the release film comprises at least one selected from the group consisting of polyethylene terephthalate and fluororesin.

29. The method for producing a (thio)urethane resin film according to any one of claims 24 to 26, wherein the (thio)urethane resin film further comprises a protective film on a surface opposite to the substrate.

30. A step of obtaining a (thio)urethane resin film by the (thio)urethane resin film manufacturing method according to any one of claims 24 to 26; a step of laminating the obtained (thio)urethane resin film to a lens substrate; A method for manufacturing a laminated lens, comprising:

31. 31. The method for producing a laminated lens according to claim 30, wherein the lens substrate comprises at least one selected from the group consisting of poly(meth)acrylate, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxy, polyepisulfide, polyurethane, and polythiourethane.

32. The method for producing a laminated lens according to claim 30, wherein in the bonding step, the (thio)urethane resin film is bonded to the lens substrate by one or two methods selected from the group consisting of vacuum molding and pressure molding.

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