CN118541634A

CN118541634A - Polythiourethane film, material for spectacle lenses, spectacle lens, and method for producing spectacle lens

Info

Publication number: CN118541634A
Application number: CN202380017138.XA
Authority: CN
Inventors: 渡边诚; 追木基治; 河户伸雄
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 2022-03-18
Filing date: 2023-01-24
Publication date: 2024-08-23

Abstract

A polythiourethane film comprising a polythiourethane which is the reaction product of a 2-functional thiol compound, a 3-functional or more thiol compound, and an isocyanate compound.

Description

Polythiourethane film, material for spectacle lenses, spectacle lens, and method for producing spectacle lens

Technical Field

The present disclosure relates to polythiourethane films, materials for ophthalmic lenses, and methods for manufacturing ophthalmic lenses.

Background

Plastic lenses are lightweight and less prone to breakage than inorganic lenses, and therefore are rapidly spreading in optical elements such as spectacle lenses and camera lenses. In recent years, functional lenses having various functions are being studied.

Examples of the functional lens include a photochromic lens having photochromic performance.

The functional lens often contains a dye, a pigment, a visible light absorbing dye, a photochromic dye, or the like, or an ultraviolet absorber, for example.

Patent document 1 describes a film comprising a resin having a thiourethane bond, wherein the molar ratio (S/N) of sulfur to nitrogen contained in the resin is 0.8 or more and less than 3.

For example, patent document 2 describes an optical element comprising a lens substrate, an adhesive layer disposed on the lens substrate, and a functional film disposed on the adhesive layer, wherein the adhesive layer comprises an ester-based polyurethane, the adhesive layer has an elongation of 1050 to 1400%, and the adhesive layer has a young's modulus of 400N/mm ² or less.

For example, patent document 3 describes a method for producing a resin lens, in which a base lens is used as a first mold, a second mold is disposed on one or both sides of the first mold with a substantially constant predetermined gap therebetween, a peripheral surface gap between the first and second molds is sealed with a tape or a spacer to form a cavity, a liquid resin material containing a functional agent is injected into the cavity, a functional resin layer is cast-molded, and the base lens and the functional resin layer are integrated, the method being characterized in that the base lens having an adhesive layer of a thermoplastic elastomer formed on a side surface of the functional resin layer is used as the first mold.

Patent document 1: international publication No. 2011/058754

Patent document 2: japanese patent application laid-open No. 2014-202904

Patent document 3: international publication No. 2014/125738

Disclosure of Invention

Problems to be solved by the invention

The functional lens includes a laminated lens obtained by embedding a film in a lens substrate, a lens obtained by mixing a dye into a substrate, and the like. The material of the film used for the laminated lens includes polyethylene terephthalate film, acrylic film, polyvinyl alcohol film, and the like.

However, the following problems exist: if these films are heated and bonded to a lens substrate to obtain a functional lens, streak unevenness occurs in the films during bonding.

With such a background, as a film other than a polyethylene terephthalate film, an acrylic film, or the like, a thiourethane film has been studied (for example, see patent document 1).

In addition, in the functional lens, the film is required to follow the shape of the lens base material. The lens substrates are of various shapes, and it is particularly difficult to make the film follow the high curvature of the lens substrate.

In addition, in the functional lens having the above-described configuration, solvent resistance is required.

In the functional lens having the above-described configuration, it is conceivable to laminate a layer such as a hard coat layer on a film. In this case, the film is often damaged by the treatment with an organic solvent, an alkaline aqueous solution, or the like.

The problem to be solved by embodiment 1 of the present disclosure is to provide a polythiourethane film having excellent followability and solvent resistance, a material for a spectacle lens comprising the polythiourethane film, a spectacle lens, and a method for producing a spectacle lens.

Means for solving the problems

Means for solving the above problems include the following embodiments.

<1> A polythiourethane film comprising a polythiourethane which is the reaction product of a 2-functional thiol compound, a 3-functional or more thiol compound, and an isocyanate compound.

<2> The polythiourethane film according to <1>, wherein the thiol equivalent of the 2-functional thiol compound is 20 to 95% relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or more thiol compound.

<3> The polythiourethane film according to <1> or <2>, wherein the thickness is 100 μm to 600. Mu.m.

<4> The polythiourethane film according to any one of <1> to <3>, which has a minimum storage elastic modulus at 30℃to 160℃and the minimum storage elastic modulus is 3.00X 10 ⁶Pa～1.40×10⁷ Pa.

<5> The polythiourethane film according to any one of <1> to <4>, wherein the molecular weight between crosslinking points of the polythiourethane is 950 to 3000.

<6> The polythiourethane film according to any one of <1> to <5>, further comprising a functional dye.

<7> The polythiourethane film according to <6>, wherein the functional dye is a specific wavelength-cut dye or a photochromic dye.

<8> A material for a spectacle lens comprising the polythiourethane film according to any one of <1> to <7>, and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film.

<9> The material for a spectacle lens according to <8>, wherein the urethane adhesive layer comprises a polycarbonate urethane having an anionic functional group.

<10> The material for a spectacle lens according to <8> or <9>, further comprising a hard coat layer as an outermost layer.

<11> An ophthalmic lens comprising:

the material for a spectacle lens according to any one of <8> to <10>, and

And a spectacle lens base material bonded to the polyurethane bonding layer in the spectacle lens material.

<12> The spectacle lens according to <11>, wherein the convex surface or the concave surface of the spectacle lens base material is bonded to the polyurethane bonding layer in the spectacle lens material.

<13> The spectacle lens according to <11> or <12>, wherein the radius of curvature of the spectacle lens base material is 62.5mm to 125.0mm.

<14> The spectacle lens according to any one of <11> to <13>, which comprises 2 or more sheets of the above spectacle lens material.

The spectacle lens according to any one of <10> to <14>, wherein the spectacle lens base material comprises at least 1 selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polytriacetic acid cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxide (pol yepoxy), polyepisulfide (polyepisulfide), polyurethane, and polythiourethane.

<16> A method for producing a spectacle lens, comprising the step of adhering the material for a spectacle lens according to any one of <8> to <10> to a spectacle lens base material, thereby obtaining a spectacle lens.

<17> The method for producing a spectacle lens according to <16>, comprising a step of adhering the material for a spectacle lens to a spectacle lens base material by using a vacuum press molding machine to obtain a spectacle lens.

Effects of the invention

Embodiment 1 of the present disclosure can provide a polythiourethane film having excellent followability and solvent resistance, a material for a spectacle lens comprising the polythiourethane film, a spectacle lens, and a method for producing a spectacle lens.

Drawings

Fig. 1 is a view for explaining attachment by a vacuum-air forming machine.

Fig. 2 is a graph showing transmittance of the lens with a film in example 1.

Detailed Description

In the present disclosure, a numerical range indicated by "to" is a range including numerical values described before and after "to" as a lower limit value and an upper limit value.

In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

In the present disclosure, the amounts of the respective components contained in the composition, when a plurality of substances belonging to the respective components are present in the composition, refer to the total amount of the plurality of substances present in the composition unless otherwise specified.

In the numerical ranges described in stages in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. In addition, in the numerical ranges recited in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment.

In the present disclosure, the amounts of the respective components in the material refer to the total amount of the plurality of substances present in the material unless otherwise specified in the case where a plurality of substances belonging to the respective components in the material are present.

In the present disclosure, the term "poly (thio) urethane" refers to polyurethane or polythiourethane.

In the present disclosure, the term "polycarbonate-based polyurethane" refers to a polyurethane containing structural units derived from an active hydrogen compound having a polycarbonate structure.

In the present disclosure, "polycarbonate-based polyurethane having an anionic functional group" refers to a polycarbonate-based polyurethane containing a structural unit derived from an active hydrogen compound having an anionic functional group. Examples of the anionic functional group include a group containing a betaine structure such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a sulfobetaine.

The present disclosure includes embodiment 1 and embodiment 2 below.

Hereinafter, embodiment 1 and embodiment 2 will be described in detail.

(Embodiment 1)

Polythiourethane film

The polythiourethane film of embodiment 1 (also referred to simply as a film in embodiment 1) contains polythiourethane which is a reaction product of a thiol compound having 2 functions, a thiol compound having 3 functions or more, and an isocyanate compound.

Since the polythiourethane film of embodiment 1 includes the above-described configuration, the following property and the solvent resistance are excellent.

The functional lens includes a laminated lens obtained by embedding a film in a lens substrate, a lens obtained by mixing a dye into a substrate, and the like. The material of the film used for the laminated lens includes polyethylene terephthalate film, acrylic film, polyvinyl alcohol film, and the like. All of them are thermoplastic resin films.

However, the following problems exist: if the thermoplastic resin films are heated and bonded to a lens substrate to obtain a functional lens, streak unevenness occurs in the films during bonding or the adhesion to the hard coat layer is insufficient. In the case where the adhesion to the hard coat layer is insufficient, it is required to dispose a primer layer therebetween.

The inventors of the present application have conceived that adhesion to a hard coat layer can be obtained by providing the same material as a lens base material on the surface, and have studied a countermeasure for adhering a film to a lens focusing on a thiourethane film.

Since thermosetting resins polymerize when heated to form a polymer network structure and cure without recovery, it has not been conventionally studied to heat and stretch a film of the thermosetting resin and then attach the film to a lens substrate.

However, the inventors of the present application have paid attention to the above-described aspects and developed a thiourethane film which can be vacuum molded or pressure molded.

The polythiourethane film of embodiment 1 preferably contains a polythiourethane having a molecular weight between crosslinking points of 950 to 3000.

In a functional lens obtained by attaching a film containing a photochromic compound to a lens substrate, a method of imparting flexibility to the film is considered in order to improve the following property of the film. However, the higher the flexibility of the film, the lower the solvent resistance of the film tends to be. That is, the film follow-up property and solvent resistance are in a mutually restricted relationship, and it is difficult to realize them at the same time.

As a result of intensive studies, the inventors of the present application have found that by selecting polythiourethane as a material for a film and limiting the molecular weight between crosslinking points of the polythiourethane to a specific range, both the followability and solvent resistance of the film can be achieved.

According to the studies of the present inventors, when the molecular weight between the crosslinking points of polythiourethane is large, the crosslinking density becomes small, and the film becomes soft, so that the followability is improved and the solvent resistance is lowered.

On the other hand, when the molecular weight between the crosslinking points of polythiourethane is small, the crosslinking density increases, and the film becomes hard, so that the followability decreases and the solvent resistance improves.

The inventors of the present application have further studied and found that when the molecular weight between the crosslinking points of polythiourethane falls within a specific range, the following property and solvent resistance of the film can be simultaneously achieved, thereby obtaining the polythiourethane film of embodiment 1.

< Polythiourethane >

(Molecular weight between crosslinking points)

The polythiourethane of embodiment 1 has a molecular weight between crosslinking points of 950 to 3000.

The inter-crosslink molecular weight refers to the molecular weight between crosslink points.

The smaller the molecular weight between the crosslinking points, the harder the film and the greater the crosslinking point density.

The greater the molecular weight between the crosslinks, the softer the film and the less the crosslink density.

From the viewpoint of film follow-up properties, the molecular weight between the crosslinking points of the polythiourethane in embodiment 1 is preferably 1000 or more, and more preferably 1050 or more.

From the viewpoint of solvent resistance of the film, the molecular weight between crosslinking points of the polythiourethane in embodiment 1 is preferably 2800 or less, more preferably 2500 or less, and even more preferably 2000 or less.

The molecular weight between the crosslinking points can be adjusted by, for example, adjusting the content ratio of the 2-functional thiol compound to the 3-functional or higher thiol compound which can be used as a raw material of polythiourethane.

(Method for measuring molecular weight between crosslinking points)

The molecular weight between the crosslinking points is calculated from the following formula.

Inter-crosslinking point molecular weight mc=2 (1+μ) ρrt/E

Mu: poisson's ratio (poisson's ratio assumed to be 0.5.)

Ρ: density of polythiourethane (g/m ³)

R: gas constant (i.e. 8.314J/K/mol)

E: storage elastic modulus (Pa) of polythiourethane

T: absolute temperature (K)

Here, the temperature T is set to 150 ℃ (i.e., 423.15K), and the elastic modulus E is set to an elastic modulus at 150 ℃.

The temperature of 0℃was 273.15K, and the increase or decrease of 1℃was equal to the increase or decrease of 1K.

(Determination of softening temperature and storage elastic modulus)

The viscoelasticity of polythiourethane was measured using a dynamic viscoelasticity measuring device (for example, DMA8000 manufactured by PerkinElmer).

Polythiourethane having a size of 30mm×5mm and a thickness of 2.5mm was prepared as a test piece. The measurement system was a rectangular single cantilever, and the temperature was increased from 30℃to 160℃at a rate of 3℃per minute, and the measurement was performed at a frequency of 1.0 Hz. The temperature at which tan δ obtained by measurement was maximum was taken as softening temperature.

In addition, at the time of the above-mentioned temperature rise, the storage elastic modulus was measured every 1 minute.

Preferably, the polythiourethane film of embodiment 1 has a minimum storage elastic modulus at 30℃to 160℃of 3.00X 10 ⁶Pa～1.40×10⁷ Pa.

The term "having a minimum storage elastic modulus at 30℃to 160℃means that the temperature at which the storage elastic modulus is at a minimum value is in the range of 30℃to 160 ℃. The "minimum storage elastic modulus" refers to the storage elastic modulus at a temperature at which the storage elastic modulus is at a minimum.

The minimum storage elastic modulus is more preferably 4.00×10 ⁶ Pa or more, and still more preferably 6.00×10 ⁶ Pa or more.

The minimum storage elastic modulus is more preferably 1.30X10 ⁷ Pa or less, and still more preferably 1.25X10 ⁷ Pa or less.

The method for determining the minimum storage elastic modulus is as described above.

The polythiourethane may be used without particular limitation.

Polythiourethanes are the reaction product of 2-functional thiol compounds, 3-functional or more thiol compounds, and isocyanate compounds.

(Isocyanate Compound)

The isocyanate compound may be a chain isocyanate compound or a cyclic isocyanate compound.

Examples of the isocyanate compound include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, and aromatic aliphatic isocyanate compounds, and 1 or 2 or more of them may be used in combination. These isocyanate compounds may contain dimers, trimers, prepolymers, and the like.

Examples of the isocyanate compound include compounds exemplified in international publication No. 2011/055540.

The isocyanate compound preferably contains a chain isocyanate compound and a cyclic isocyanate compound, and more preferably contains an aliphatic isocyanate compound and an aromatic isocyanate compound.

Thus, for example, the glass transition temperature Tg and the refractive index can be easily adjusted to a desired range.

Among the above, the aliphatic isocyanate compound is preferably at least 1 selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatocyclohexyl) methane, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane.

Among the above, at least 1 selected from the group consisting of xylylene diisocyanate, toluene diisocyanate, 4' -diphenylmethane diisocyanate and phenylene diisocyanate is preferable as the aromatic isocyanate compound.

(Thiol Compound)

Examples of the thiol compound include a polythiol compound having 2 or more mercapto groups, a hydroxythiol compound having 1 or more mercapto groups and 1 or more hydroxyl groups, and the like, and 1 or a mixture of 2 or more thiol compounds may be used. Examples of the thiol compound include compounds exemplified in International publication No. 2016/125736.

(2 Functional thiol Compounds)

Examples of the 2-functional thiol compound include methyl dithiol, ethyl dithiol, 1, 3-propanedithiol, 1, 2-ethanedithiol, 1, 2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) 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-dicyclohexyl, 2, 5-dimercaptohexane, 1, 5-dimercaptohexane, and 1, 5-dimercaptohexane, 4-dimethylthio) propionate;

Aliphatic polythiol compounds such as 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 disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), thiodipropionate bis (2-mercaptoethyl ester), dithiodiacetic acid bis (2-mercaptoethyl ester), dithiodipropionate bis (2-mercaptomethyl thio) -1, 3-dithiocyclohexane;

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-toluene dithiol, 3, 4-toluene dithiol, 1, 5-naphthalene dithiol, and 2, 6-naphthalene dithiol;

heterocyclic polythiol compounds such as 2-methylamino-4, 6-dithiol-s-triazine, 3, 4-thiophenedichiol, bismuth reagent, 4, 6-bis (mercaptomethylthio) -1, 3-dithiocyclohexane, and 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiocyclobutane; etc.

Among the above, the 2-functional thiol compound more preferably contains at least 1 selected from the group consisting of bis (mercaptoethyl) sulfide, 1, 3-propanedithiol, 2, 5-dimercaptomethyl-1, 4-dithiocyclohexane and 4, 6-bis (mercaptomethylthio) -1, 3-dithiocyclohexane.

(Thiol Compound of 3 functional groups or more)

Examples of the thiol compound having a 3-function or more include 1,2, 3-propanetrithiol, 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-mercaptopropylthio) propane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trimethylundecane, 4, 3-dimercaptomethyl-3, 8-dimercaptomethyl-3, 3-dimercaptomethyl-undecane, and tetramethyl-3, 3-mercaptomethyl-3-dimercaptomethyl-3-mercaptomethyl-undecane;

aliphatic polythiol compounds such as 1, 3-tetrakis (mercapto methylthio) propane, 1, 2-tetrakis (mercapto methylthio) ethane, tris (mercapto methylthio) methane, and tris (mercapto ethylthio) methane;

aromatic polythiol compounds such as 1,3, 5-trismercaptobenzene, 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-dithiacyclobutane; etc.

The thiol compound having 3 or more functions preferably contains at least 1 selected from the group consisting of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1, 3-tetrakis (mercaptomethylthio) propane, and 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiabutane.

As described above, the molecular weight between crosslinking points can be adjusted by, for example, adjusting the content ratio of the 2-functional thiol compound to the 3-functional or more thiol compound which can be used as a raw material of polythiourethane.

In embodiment 1, the larger the thiol equivalent of the 2-functional thiol compound in the polythiourethane, the larger the molecular weight between the crosslinking points tends to be. On the other hand, the larger the thiol equivalent of the thiol compound having 3 or more functions in polythiourethane, the smaller the molecular weight between crosslinking points tends to be.

For example, in the case of using a 2-functional thiol compound and a 3-functional or higher thiol compound as a raw material of polythiourethane, the thiol equivalent of the 2-functional thiol compound is preferably 20 to 95% relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or higher thiol compound.

Since the thiol equivalent of the 2-functional thiol compound is 20% or more relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or more thiol compound, the molecular weight between the crosslinking points can be made larger. As a result, the film was moderately soft and excellent in follow-up property.

From the above viewpoints, the thiol equivalent of the 2-functional thiol compound is more preferably 30% or more, and still more preferably 35% or more, relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or more thiol compound.

Since the thiol equivalent of the 2-functional thiol compound is 95% or less relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or more thiol compound, the molecular weight between the crosslinking points can be made smaller. As a result, the film was moderately hardened, and the solvent resistance was excellent.

From the above viewpoints, the thiol equivalent of the 2-functional thiol compound is more preferably 80% or less, and still more preferably 70% or less, relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or more thiol compound.

When the equivalent of all thiol compounds polymerized with isocyanate compounds is 1, the thiol equivalent of each thiol compound is calculated by integrating the number of moles and the number of functional groups.

The equivalent ratio of thiol groups in the thiol compound to isocyanate groups in the isocyanate compound (thiol groups/isocyanate groups) is preferably 0.8 to 1.2, more preferably 0.85 to 1.15, and even more preferably 0.9 to 1.1.

Within the above range, polythiourethane suitable for use as an optical material, particularly a plastic lens material for spectacles can be obtained.

< Functional pigment >

The polythiourethane film of embodiment 1 preferably further comprises a functional dye.

Examples of the functional dye include a dye that blocks a specific wavelength (for example, ultraviolet rays, visible rays, near infrared rays, and the like), a photochromic dye (for example, a tetrazaporphyrin compound, a naphthopyran compound, and the like), and an infrared absorbing dye.

(Ultraviolet absorber)

Specific examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, diphenylacrylate-based ultraviolet absorbers, phenol-based ultraviolet absorbers, malonate-based ultraviolet absorbers, and oxanilide-based ultraviolet absorbers.

A more preferred embodiment of the ultraviolet absorber comprises a malonate-based ultraviolet absorber and an oxanilide-based ultraviolet absorber.

Specific examples of the malonate-based ultraviolet absorber include tetraethyl p-phenylenedi (methylenemalonic acid), dimethyl p-methoxybenzylidene malonate, and the like.

As the malonate type ultraviolet absorber, HOSTAVIN PR-25, HOSTAVIN B-CAP (manufactured by CLARIANT CHEMICALS Co., ltd.) and the like are commercially available.

Specific examples of the oxanilide-based ultraviolet light absorber include 2-ethyl-2 '-ethoxyoxanilide and 2-isododecyl-2' -ethoxyoxanilide.

Commercially available products of the oxanilide-based ultraviolet absorber include trade names HO STAVIN VSU, HOSTAVIN 3206 (manufactured by CLARIANT CHEMICALS Co., ltd.), and TINUVIN 312 (manufactured by BASF Co., ltd.).

(Visible light absorbing pigment)

As the visible light absorbing pigment, commercially available products, preferably organic pigment compounds, can be used. Specifically, porphyrin compounds or tetrazaporphyrin compounds are mentioned. More specifically, PD-311S (manufactured by mountain chemical Co., ltd.) is exemplified.

(Near infrared ray absorption pigment)

Examples of the near infrared absorbing dye include a cyanine compound, a phthalocyanine compound, a naphthoquinone compound, an azo compound, and a silver nanoplate.

(Polarizing pigment)

Examples of the polarizing dye include anthraquinone-based dichroic dye and azo-based dichroic dye.

(Photochromic pigments)

The photochromic dye is not particularly limited, and any photochromic dye can be suitably selected from conventionally known compounds that can exhibit photochromic performance and used. For example, 1 or 2 or more kinds of compounds may be used from pyran-based compounds, oxazine-based compounds, fulgide-based compounds, bisimidazole-based compounds, and the like, depending on desired light-adjusting characteristics and coloring.

The photochromic dye is preferably at least 1 compound selected from the group consisting of a tetrazaporphyrin compound, a naphthopyran compound, a spiropyran compound, a spirooxazine compound, a fulgide compound, and a bisimidazole compound.

Among the photochromic dyes, a compound having at least 1 polymer chain selected from the group consisting of a polyalkyl group, a polyether group, a polyalkylene oxide group, a polysiloxane group, a polycaprolactone group, a polycarbonate group, a polyester group, a poly (meth) acrylate group, a poly (thio) urethane group, and a polyepoxide group is preferable.

The photochromic dye having a polymer chain can be obtained by a method described in, for example, international publication No. 2009/146509, international publication No. 2010/20770, international publication No. 2012/149599, or international publication No. 2012/162725.

Examples of the photochromic dye having a polymer chain include Re versacol series available from Vivimed, and 1 or 2 or more photochromic dyes may be used in combination. As the photochromic dye having a polymer chain, at least 1 selected from Reversacol Trent Blue、Rev ersacol Heath Green、Reversacol Chilli Red、Reversacol Wembley Grey、Reversacol Cayenne Red、Reversacol Peacock Blue、Reversa col Jalapeno Red、Reversacol Adriatic Blue、Reversacol Mendip Gr een、 and Reversacol Marine Blue is preferably used.

As the functional dye, commercially available products can be used, and examples thereof include specific wavelength-cut pigments such as PD-311S (manufactured by mountain chemical Co., ltd.);

dyes such as PLAST Blue 8514 (anthraquinone dyes available from chemical industries Co., ltd.), PLAST Red 8320 (anthraquinone dyes available from chemical industries Co., ltd.), PLAST YELL ow 8070 (methine dyes available from chemical industries Co., ltd.); etc.

The polythiourethane film of embodiment 1 has a thickness of preferably 100 μm to 600. Mu.m, more preferably 130 μm to 400. Mu.m, still more preferably 150 μm to 300. Mu.m, particularly preferably 170 μm to 250. Mu.m.

[ Use ]

The polythiourethane film of embodiment 1 can be used as a spectacle lens, a lamp cover, a window film, or the like.

Among the above, the polythiourethane film of embodiment 1 is preferably used for a spectacle lens.

Method for producing polythiourethane film

The polythiourethane film of embodiment 1 can be produced by a usual method.

For example, the polythiourethane film of embodiment 1 can be obtained by a casting (film coating-polymerization curing) method, a spin-coating-polymerization curing method, a casting polymerization method, or the like using a polymerizable composition containing the above components.

The casting method and the spin-coating-polymerization curing method are as follows: the film is obtained by extruding the viscosity-adjusted polymerizable composition from a die and casting the composition on a substrate, or by rotating the substrate on which the polymerizable composition is placed at a high speed to form a film, and then polymerizing and curing the film. The viscosity of the polymerizable composition at the time of casting (coating) may be appropriately selected depending on the coating method and the use thereof.

The casting polymerization method comprises the following steps: a film is obtained by injecting a polymerizable composition into a mold formed of a pair of inorganic glass, metal or resin plates having four edges sealed and having an interval of 200 μm or less between the surfaces, and polymerizing the mixture. The viscosity of the polymerizable composition at the time of injection may be appropriately selected according to the injection method, curing process, and the like.

In embodiment 1, the obtained film may be subjected to an annealing treatment. Further, fine particles of metal oxide or the like, filler or the like may be mixed with the polymerizable composition to form a film.

Material for spectacle lens

The material for a spectacle lens according to embodiment 1 comprises the polythiourethane film according to embodiment 1, and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film.

< Polyurethane adhesive layer >

The polyurethane adhesive layer is an adhesive layer containing polyurethane.

The polyurethane adhesive layer preferably contains a polycarbonate-based polyurethane containing an anionic functional group.

The polyurethane may be used without particular limitation.

The polyurethane may be commercially available, or may be produced from a raw material such as isocyanate or polyol.

As the polyurethane, TAKELAC WS-5100 (manufactured by Mitsui chemical Co., ltd.), SUPERFLEX 470 (manufactured by first Industrial pharmaceutical Co., ltd.), or the like can be specifically used.

The material for spectacle lenses preferably further comprises a hard coat layer as an outermost layer.

The material for a spectacle lens may comprise, for example, a hard coat layer, the polythiourethane film of embodiment 1, and a polyurethane adhesive layer in this order,

For example, the composition may contain a hard coat layer, a polyurethane adhesive layer, the polythiourethane film of embodiment 1, and a polyurethane adhesive layer in this order.

The composition of the hard coat layer may be appropriately selected.

Examples of the component of the hard coat layer include resins (for example, urethane resins, thiourethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, and the like), hard coat agents (silane compounds, and the like), visible light absorbers, infrared absorbers, and the like.

Glasses lens

The spectacle lens of embodiment 1 includes the spectacle lens material of embodiment 1 and a spectacle lens base material bonded to a polyurethane adhesive layer in the spectacle lens material.

The spectacle lens of embodiment 1 may comprise the polythiourethane film of embodiment 1, a polyurethane adhesive layer bonded to at least one surface of the polythiourethane film, and a spectacle lens base material bonded to the polyurethane adhesive layer.

< Spectacle lens substrate >

The spectacle lens base material is not particularly limited.

The spectacle lens substrate preferably comprises at least 1 selected from the group consisting of polyacrylates, polyethylene terephthalates, polycarbonates, polytriacet-celluloses, polyvinyl alcohols, polyesters, polyamides, polyepoxides, polyepisulfides, polyurethanes and polythiourethanes,

More preferably at least 1 selected from the group consisting of a polyepisulfide, a polyurethane and a polythiourethane,

It is further preferable to include at least 1 selected from the group consisting of polyurethane and polythiourethane.

The polyepisulfide is preferably composed of structural units derived from an episulfide compound or of structural units derived from an episulfide compound and structural units derived from a thiol compound.

The polyurethane is preferably composed of structural units derived from an isocyanate compound and structural units derived from a polyol compound.

The polythiourethane is preferably composed of a structural unit derived from an isocyanate compound and a structural unit derived from a thiol compound.

The method for producing the above-mentioned episulfide compound includes a method using an episulfide compound alone or an episulfide compound and a thiol compound.

As a method for producing polyurethane, a method using an isocyanate compound and a polyol compound can be mentioned.

As a method for producing polythiourethane, there can be mentioned a method using the above polyisocyanate compound and polythiol compound.

(Episulfide Compound)

Examples of the episulfide compound include episulfide ethyl sulfide, chain aliphatic 2, 3-episulfide propyl sulfide, cyclic aliphatic 2, 3-episulfide propyl sulfide, aromatic 2, 3-episulfide propyl sulfide, chain aliphatic 2, 3-episulfide propyl oxide, cyclic aliphatic 2, 3-episulfide propyl oxide, aromatic 2, 3-episulfide propyl oxide, and the like, and 1 or a mixture of 2 or more kinds may be used.

Examples of the episulfide compound include compounds exemplified in WO 2015/137401.

From the viewpoint of improving the solubility of the functional pigment in the resin, the episulfide compound is preferably at least 1 selected from the group consisting of bis (2, 3-cyclopropylsulfanyl) sulfide, bis (2, 3-cyclopropylsulfanyl) disulfide, bis (1, 2-cyclosulfanyl) sulfide, bis (1, 2-cyclosulfanyl) disulfide, and bis (2, 3-cyclopropylsulfanyl) methane, and more preferably bis (2, 3-cyclopropylsulfanyl) disulfide.

(Thiol Compound)

Specific examples, preferred modes, and the like of the thiol compound are the same as those described in the above item (thiol compound).

(Isocyanate Compound)

The specific examples, preferred modes, and the like of the isocyanate compound are the same as those described in the above item (isocyanate compound).

(Polyol Compound)

The alcohol compound is 1 or more aliphatic or alicyclic alcohol, and specifically, a linear or branched aliphatic alcohol, alicyclic alcohol, alcohol obtained by adding ethylene oxide, propylene oxide, and epsilon-caprolactone to these alcohols, and specifically, a compound exemplified in WO2016/125736 can be used.

The polyhydric alcohol compound is preferably at least 1 selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-cyclopentanediol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, and 1, 4-cyclohexanediol.

In the spectacle lens of embodiment 1, the convex or concave surface of the spectacle lens base material is preferably bonded to the polyurethane adhesive layer in the spectacle lens material.

The polythiourethane film of embodiment 1 can be bonded to a spectacle lens base material via a polyurethane adhesive layer.

In general, the smaller the radius of curvature of the convex or concave curved surface, the steeper the curved surface of the lens is, and the harder it is to bond the polythiourethane film to the spectacle lens substrate. The polythiourethane film of embodiment 1 exhibits good adhesion even when applied to a spectacle lens substrate having a small radius of curvature.

In the eyeglass lens of embodiment 1, the radius of curvature of the convex or concave surface of the eyeglass lens base material may be small.

For example, the radius of curvature of the spectacle lens base material is preferably 62.5mm to 125.0mm, more preferably 70.0mm to 100.0mm, and further preferably 75.0mm to 90.0mm.

The polythiourethane film of embodiment 1 exhibits good curve following property and adhesion even when applied to a spectacle lens base material having a radius of curvature in the above-described range.

The spectacle lens of embodiment 1 may contain 2 or more sheets of a material for spectacle lenses.

< Coating layer >

The spectacle lens of embodiment 1 may comprise a coating layer.

Specifically, examples of the coating layer include a hard coat layer, an antireflection layer, an antifogging coating layer, an anti-contamination layer, and a water-repellent layer.

These coating layers may be used alone or as a plurality of layers. In the case of applying the coating layers on both sides, the same coating layer may be applied to each side, or different coating layers may be applied.

In the case of performing the coating treatment, a treatment with a solvent may be performed before the coating composition is applied to the film. Examples of such a process include: wiping a coated surface of a coating composition of a lens to be coated with an organic solvent; etching the coated surface with an aqueous alkali solution; immersing the lens in a coating liquid containing a solvent; etc.

In this case, when the solvent resistance of the film is poor, the film is damaged by the solvent, and the coating layer cannot be properly laminated.

Since the polythiourethane film of embodiment 1 has excellent solvent resistance, even when treated with a solvent such as an organic solvent or an aqueous alkali solution, the coating layer can be laminated well.

As a result, the spectacle lens according to embodiment 1 can be directly formed by laminating the coating layer on the polythiourethane film according to embodiment 1 of embodiment 1 without interposing any other layer.

(Hard coat)

The spectacle lens of embodiment 1 preferably includes a hard coat layer.

The hard coat layer is a coating layer for imparting functions such as scratch resistance, abrasion resistance, moisture resistance, hot water resistance, heat resistance, and weather resistance to the lens surface.

In order to form the hard coat layer, a hard coat layer composition containing an organic silicon compound having curability and 1 or more kinds of oxide fine particles containing an element selected from the group consisting of Si, al, sn, sb, ta, ce, la, fe, zn, W, zr, in and Ti may be used,

A hard coat composition containing fine particles of a curable organosilicon compound and 1 or more kinds of composite oxides containing 2 or more elements selected from the group consisting of Si, al, sn, sb, ta, ce, la, fe, zn, W, zr, in and Ti may also be used.

The hard coat composition preferably contains at least 1 selected from the group consisting of amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, metal chlorides, and polyfunctional epoxy compounds in addition to the above-mentioned components.

The hard coat composition may or may not contain a solvent that does not affect the lens substrate.

The hard coat layer is generally formed by applying a hard coat composition by a known coating method such as spin coating or dip coating, and then curing the composition. The curing method includes irradiation with energy rays such as ultraviolet rays and visible rays, heat curing, and the like. From the viewpoint of suppressing the occurrence of interference fringes, it is preferable that the difference between the refractive index of the hard coat layer and the refractive index of the lens base material is within ±0.1. In forming the hard coat layer, the hard coat layer composition may be applied to the surface of the polythiourethane film by a bar coater, a blade coater, or the like, cured, and then attached to the lens substrate. Alternatively, the polythiourethane film may be attached to the lens substrate in advance, and then the hard coat composition may be applied by spin coating, dip coating, or the like.

(Anti-reflection layer)

The spectacle lens of embodiment 1 preferably includes an antireflection layer.

The anti-reflection layer is inorganic and organic.

The inorganic antireflection layer can be formed by a dry method such as a vacuum deposition method, a sputtering method, an ion plating method, an ion beam assist method, or a CVD method using an inorganic oxide such as SiO ₂、TiO₂.

The organic anti-reflective layer may be formed by a wet method using a composition including an organosilicon compound and silica-based particles having an internal cavity.

The anti-reflection layer may be formed on the hard coat layer as needed.

The anti-reflection layer may be a plurality of layers or a single layer.

The antireflection layer is preferably a multilayer from the viewpoint of effectively exhibiting an antireflection function, and in this case, it is preferable to alternately laminate a low refractive index layer and a high refractive index layer. The refractive index difference between the low refractive index layer and the high refractive index layer is preferably 0.1 or more.

The high refractive index layer includes a layer of ZnO, tiO ₂、CeO₂、Sb₂O₅、SnO₂、ZrO₂、Ta₂O₅, or the like, and the low refractive index layer includes a layer of SiO ₂, or the like.

When used in a single-layer form, the refractive index is preferably lower than that of the hard coat layer by at least 0.1 or more.

On the antireflection layer, an antifogging coating layer, an anti-pollution layer, a waterproof layer, and the like may be formed as needed. The method for forming the anti-fog layer, anti-contamination layer, waterproof layer, etc. is not particularly limited, and conventionally known methods can be applied.

The spectacle lens of embodiment 1 preferably comprises a hard coat layer or an antireflection layer.

Specifically, for example, it is preferable that the spectacle lens of embodiment 1 includes a hard coat layer or an antireflection layer, and at least a part of the hard coat layer or the antireflection layer is in contact with the polythiourethane film.

Method for producing spectacle lens

The method for manufacturing the spectacle lens of embodiment 1 is the method for manufacturing the spectacle lens of embodiment 1.

The method for manufacturing a spectacle lens according to embodiment 1 includes a step of attaching the spectacle lens material according to embodiment 1 to a spectacle lens base material to obtain a spectacle lens (also referred to as an attaching step).

The method for producing a spectacle lens according to embodiment 1 preferably includes a step of adhering the material for a spectacle lens to a spectacle lens base material using a vacuum press molding machine to obtain a spectacle lens.

The method for manufacturing an eyeglass lens according to embodiment 1 further preferably includes the steps of: the material for a spectacle lens according to embodiment 1 is heated so that the surface temperature becomes 80 to 150 ℃, and the polyurethane adhesive layer in the material for a spectacle lens is adhered to the spectacle lens base material under reduced pressure of 10kPa or less.

< Attaching Process >

The attaching step is preferably the following step: the material for a spectacle lens according to embodiment 1 is heated so that the surface temperature becomes 80 to 150 ℃, and the polyurethane adhesive layer in the material for a spectacle lens is adhered to the spectacle lens base material under reduced pressure of 10kPa or less.

The attaching step is specifically described below.

Attachment based on vacuum pressure Forming machine

The attaching step is preferably performed using a vacuum-air molding machine.

Attachment by a vacuum-air forming machine will be described with reference to fig. 1.

Fig. 1 is a view for explaining attachment by a vacuum-air forming machine.

First, the substrate 3 is placed on a substrate stage at the lower part. The film 2 is disposed on the film stage. At this time, the film 2 is disposed so that the adhesive layer is on the substrate side.

Next, the film 2 is heated to a predetermined temperature using the heater 1. In addition, the upper film chamber and the lower mold chamber are depressurized. The lower mold chamber is brought into a vacuum 4 state.

After the membrane 2 is heated to a predetermined temperature, the upper membrane chamber side is returned to normal pressure, and the membrane 2 is pressurized.

Then, the substrate stage is raised 5, and the lower die chamber is continuously depressurized while the substrate 3 is collided with the film 2. In addition, compressed air 6 is fed into the upper membrane chamber to pressurize the same. This state is maintained for 3 to 30 seconds.

Then, the upper film chamber and the lower mold chamber are returned to normal pressure, and the film-attached substrate (i.e., lens) is taken out.

The unwanted parts of the film are trimmed 7 and further heated to complete the attachment.

Examples of the vacuum pressure air forming machine include NGF series (manufactured by bushi vacuum co., ltd.) and TFH series (manufactured by shallow research institute, manufactured by co., ltd.).

As a method for manufacturing an eyeglass lens according to embodiment 1, the manufacturing method described in japanese patent No. 5417452 can be appropriately referred to and incorporated.

Embodiment 1 also includes the following embodiments.

<1A > a polythiourethane film comprising a polythiourethane having a molecular weight between crosslinking points of 950 to 3000.

<2A > the polythiourethane film according to <1A >, wherein the polythiourethane is a reaction product of a 2-functional thiol compound, a 3-functional or more thiol compound, and an isocyanate compound.

The polythiourethane film according to <1A > or <2A >, wherein the thiol equivalent of the 2-functional thiol compound is 20 to 95% relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or more thiol compound.

The polythiourethane film according to any one of <1A > to <3A >, which further comprises a functional dye.

The polythiourethane film according to any one of <1A > to <4A >, which has a minimum storage elastic modulus at 30 to 160 ℃, and the minimum storage elastic modulus is 3.00X 10 ⁶Pa～1.40×10⁷ Pa.

The polythiourethane film according to any one of <1A > to <5A >, wherein the thickness is 100 μm to 600. Mu.m.

<7> A material for a spectacle lens comprising the polythiourethane film according to any one of <1A > to <6A >, and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film.

<8A > a spectacle lens comprising the material for a spectacle lens described in <7A >, and a spectacle lens base material bonded to the polyurethane bonding layer in the material for a spectacle lens.

The spectacle lens according to <8A >, wherein the convex or concave surface of the spectacle lens base material is bonded to the polyurethane bonding layer of the spectacle lens material.

The spectacle lens according to <8A > or <9A >, wherein the radius of curvature of the spectacle lens base material is 62.5mm to 125.0mm.

The spectacle lens according to any one of <8A > to <10A >, which comprises 2 or more sheets of the above spectacle lens material.

The spectacle lens according to any one of <8A > to <11A >, wherein the spectacle lens base material comprises at least 1 selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polytriacetic acid cellulose, polyvinyl alcohol, polyester, polyamide, polyepoxide, polyepisulfide, polyurethane and polythiourethane.

The spectacle lens according to any one of <8A > to <12A >, which comprises a hard coat layer or an antireflection layer, wherein at least a part of the hard coat layer or the antireflection layer is in contact with the polythiourethane film.

(Embodiment 2)

Method for producing spectacle lens

The method for manufacturing an eyeglass lens according to embodiment 2 includes the steps of:

A step of forming a polycarbonate-based polyurethane adhesive layer formed from a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one surface of a functional resin layer containing a functional pigment (also referred to as a laminate manufacturing step in embodiment 2); and

A step of heating the laminate at 50 to 150 ℃ and adhering the laminate to a lens substrate in an orientation in which the polycarbonate urethane adhesive layer is in contact with the lens substrate under reduced pressure of 20kPa or less to obtain a spectacle lens (also referred to as a spectacle lens manufacturing step in embodiment 2),

The storage elastic modulus of the dried polyurethane aqueous dispersion at 80 ℃ measured under the following condition 1 is 0.1MPa to 80MPa.

[ Condition 1]

The storage elastic modulus at 80℃was measured by using a test piece made of a dried polyurethane aqueous dispersion having a length of 3cm, a width of 5mm and a thickness of 500. Mu.m, and heating from-102℃to 80℃at a rate of 3℃per minute under conditions of a frequency of 1Hz, strain control and stretching by a dynamic viscoelasticity measuring apparatus.

As a configuration of a functional lens, a configuration is known in which a functional resin layer (e.g., a film) containing a functional pigment such as a photochromic compound is attached to a lens substrate.

In the functional lens having the above-described configuration, the film is required to follow the shape of the lens base material. For example, when a film is adhered to a lens base material via an adhesive layer, the film may be heated together with the film having the adhesive layer and may be expanded. In such a case, the adhesive layer is required to expand to follow the shape of the lens base material and adhere to the lens base material, as in the case of the film.

In addition, in the functional lens having the above-described configuration, alkali resistance is required.

In the functional lens having the above-described configuration, it is conceivable to laminate a layer such as a hard coat layer on a film. In this case, the adhesive layer is often damaged by the treatment with an organic solvent, an alkaline aqueous solution, or the like.

Embodiment 2 of the present disclosure can provide a method for producing a spectacle lens capable of producing a spectacle lens comprising a polycarbonate-based polyurethane adhesive layer excellent in adhesion to a lens substrate and alkali resistance, a laminate, and a spectacle lens.

< Procedure for producing laminate >

The laminate manufacturing process in embodiment 2 is as follows: a laminate is obtained by forming a polycarbonate-based polyurethane adhesive layer formed from a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one surface of a functional resin layer containing a functional pigment.

In the method for producing a spectacle lens according to embodiment 2, the laminate is obtained by forming a polycarbonate-based polyurethane adhesive layer formed from a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group on at least one surface of a functional resin layer containing a functional dye.

In the method for producing a spectacle lens according to embodiment 2, the laminate may contain a functional resin layer containing a functional dye and a polycarbonate-based polyurethane adhesive layer laminated on at least one surface of the functional resin layer.

Before the aqueous polyurethane dispersion is applied to the functional resin layer, the surface of the functional resin layer to be coated with the aqueous polyurethane dispersion may be subjected to pretreatment.

The method of pretreatment is not particularly limited, and may be appropriately selected from the viewpoint of adhesion, for example. Examples of the pretreatment method include an etching treatment with an alkaline aqueous solution, an etching treatment with an alkaline surfactant aqueous solution, a washing treatment with a surfactant aqueous solution, a washing treatment with pure water, an etching treatment with UV ozone, an etching treatment with plasma, an etching treatment with corona discharge, a polishing treatment with fine particles, and a polishing treatment.

In the case of performing etching treatment with pure water or an aqueous solution, chemical treatment can be performed more effectively by combining heating, ultrasonic irradiation, and the like.

Among the above, as a method of pretreatment, etching treatment by plasma or corona discharge is preferable.

As a method for coating the aqueous polyurethane dispersion, there is no particular limitation, and known coating methods can be applied. For example, the aqueous polyurethane dispersion may be applied by a roll coating method such as spin coating, dip coating, die coating, spray coating, curtain (flow) coating, bar coating, blade coating, gravure coating, or the like.

The temperature at which the aqueous polyurethane dispersion is dried is preferably 40 to 130 ℃, more preferably 45 to 110 ℃, and even more preferably 50 to 100 ℃.

[ Functional resin layer ]

The functional resin layer contains a functional dye.

The functional resin layer contains a functional dye, and thus has functions such as blocking of a specific wavelength (for example, ultraviolet rays, visible rays, near infrared rays, and the like), photochromic, and polarizing properties.

The thickness of the functional resin layer is preferably 10 μm to 700. Mu.m, more preferably 13 μm to 600. Mu.m, still more preferably 15 μm to 400. Mu.m, particularly preferably 20 μm to 300. Mu.m.

(Functional pigment)

Examples of the functional dye include a dye that blocks a specific wavelength (for example, ultraviolet rays, visible rays, near infrared rays, and the like), a photochromic dye (for example, a naphthopyran compound, and the like), and a dichromatic dye.

The functional dye preferably contains at least 1 selected from the group consisting of an ultraviolet absorber, a visible light absorbing dye, a photochromic dye and a dichroic dye.

(Ultraviolet absorber)

The ultraviolet absorber may be a dye that absorbs only ultraviolet light, or may be a dye that absorbs ultraviolet light and blue light (so-called blue light).

Among the above, the ultraviolet absorber preferably contains at least 1 selected from the group consisting of benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers.

Specific examples of the benzotriazole-based ultraviolet absorber include 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole.

Examples of the commercial products of benzotriazole-based ultraviolet absorbers include VIOSORB series (manufactured by co-pharmaceuticals Co., ltd.), tinuvin series (manufactured by BASF corporation), SEES ORB series (manufactured by SHIPRO KASEI KAISHA, LTD.), and the like.

Specific examples of the triazine-based ultraviolet light absorber include 2- (4-phenoxy-2-hydroxy-phenyl) -4, 6-diphenyl-1, 3, 5-triazine and the like. Examples of commercial products of the triazine ultraviolet light absorber include Tinuvin series (manufactured by BASF corporation), ADK STAB series (manufactured by ADEKA, co., ltd.), EVERSORB series (manufactured by EVER LIGHT corporation), and the like.

Specific examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, and 2,2 '-dihydroxy-4, 4' -dimethoxybenzophenone.

Examples of commercial products of benzophenone-based ultraviolet absorbers include Tinuvin series (manufactured by BASF corporation), SEESORB series (manufactured by SHIPRO KASEI KAISHA, LT D. System), EVERSORB series (manufactured by EVER LIGHT corporation), and the like.

Examples of commercial products of the oxanilide-based ultraviolet absorber include trade names HO STAVIN VSU, HOSTAVIN 3206 (manufactured by CLARIANT CHEMICALS Co., ltd.), and TINUVIN 312 (manufactured by BASF Co., ltd.).

(Visible light absorbing pigment)

Examples of the visible light absorbing pigment include porphyrin-based pigments, tetrazaporphyrin-based pigments, phthalocyanine-based pigments, merocyanine-based pigments, anthraquinone-based pigments, methine-based pigments, azo-based pigments, and the like.

The visible light absorbing dye is preferably a porphyrin-based dye, a tetraazaporphyrin-based dye, a phthalocyanine-based dye or an anthraquinone-based dye.

One kind of visible light absorbing pigment may be used alone, or two or more kinds of visible light absorbing pigments may be used in combination.

As commercial products of porphyrin-based pigments, UVY-0026 (manufactured by Kagaku Co., ltd., maximum absorption wavelength 449 nm) and UVY-1023 (manufactured by Kagaku Co., ltd., maximum absorption wavelength 479 nm) are mentioned.

As a commercially available product of the porphyrazine coloring matter, PD-311S (manufactured by Kagaku Co., ltd., maximum absorption wavelength 585 nm) is mentioned.

As a commercially available product of anthraquinone pigments, there is a Plast Color series (available from chemical industries Co., ltd.).

As a commercially available product of the methine-based coloring matter, there is a Plast Color series (available from Kagaku Kogyo Co., ltd.).

(Near infrared ray absorption pigment)

Examples of the near infrared absorbing dye include phthalocyanine dyes, squarylium dyes, diimmonium dyes, disulfide complex (dithiolene complex) dyes, and cyanine dyes.

(Photochromic pigments)

The photochromic dye is preferably at least 1 compound selected from the group consisting of spiropyran-based compounds, spirooxazine-based compounds, fulgide-based compounds, and bisimidazole compounds.

(Dichroism pigment)

Examples of the dichroic dye include iodine, azo dye, anthraquinone dye, and dioxazine dye.

(Resin)

The functional resin layer may contain a resin as a base material.

Examples of the resin include thermoplastic resins and thermosetting resins.

(Thermoplastic resin)

The thermoplastic resin is not particularly limited, and examples thereof include polyacrylate, polyethylene terephthalate, polycarbonate, cellulose polytriacetate, polyvinyl alcohol, polyester, polyamide, polyurethane, and the like.

Among the above, preferable thermoplastic resins are polyacrylate, polyethylene terephthalate and polytriacetic acid cellulose.

The softening temperature of the thermoplastic resin is preferably 50 to 150 ℃, more preferably 55 to 140 ℃, and still more preferably 60 to 130 ℃.

For example, the functional resin layer may comprise a thermoplastic resin having a softening temperature of 50 ℃ to 150 ℃.

The softening temperature can be obtained as a temperature at which the tan delta curve shows a maximum value in the measurement using the dynamic viscoelasticity measuring device.

(Thermosetting resin)

The thermosetting resin is not particularly limited, but preferably contains at least 1 selected from the group consisting of polyepoxide, polyepisulfide, and poly (thio) urethane.

The functional resin layer may be commercially available, or may be produced by curing a polymerizable composition.

Commercially available products include ACRYPLEN series (polyacrylate, manufactured by Mitsubishi Chemical Group Corporation) and the like.

The functional resin layer may be a single layer or a plurality of layers. In the case where the functional resin layer is a plurality of layers, the functional resin layer may be composed of a single resin species or may be composed of a plurality of resin species. In addition, when the functional resin layer is a plurality of layers, bonding may be performed by an adhesive or the like.

The functional resin layer can be produced by a usual method.

For example, the functional resin layer can be obtained by a casting (film coating-solvent evaporation) method, a casting (extrusion molding-cooling) method, a stretching method, a film coating-polymerization curing method, a casting polymerization method, or the like using the above-described components.

As a method for incorporating the functional pigment into the functional resin layer, the functional resin layer may be prepared by adding the functional pigment to the resin in advance, or the functional resin layer may be prepared by adding the pigment by solvent dyeing, sublimation dyeing, coating, or the like after the resin layer is obtained.

The casting (film coating-solvent evaporation) method is the following method: after a solution obtained by dissolving a resin in a solvent is cast in a sheet form, the solvent is evaporated to obtain a film.

The casting (extrusion-cooling) method is the following method: the molten resin was discharged in a film shape through a T die attached to the front end of the extruder, and then cooled by a cooling roll to obtain a film.

The stretching method comprises the following steps: the molten resin was discharged in a film shape through a T die attached to the front end of an extruder, and then stretched to obtain a film.

The film coating-polymerization curing method comprises the following steps: the film is obtained by polymerizing and curing the polymerizable composition applied in the form of a film. The polymerization curing may be performed by irradiation with ultraviolet rays and heating. The substrate to which the film is applied may be a release film.

The casting polymerization method comprises the following steps: the film is obtained by casting a polymerizable composition between a plate-shaped mold and a cavity formed by a gasket, polymerizing and curing the polymerizable composition, and then releasing the composition from the mold. The polymerization curing may be performed by irradiation with ultraviolet rays and heating.

In embodiment 2, the obtained film may be subjected to an annealing treatment. The functional resin layer may contain fine particles of metal oxide or the like, a filler, and the like.

< Step of producing functional resin layer >

The method for manufacturing an eyeglass lens according to embodiment 2 preferably includes a functional resin layer manufacturing step before the laminate manufacturing step.

The functional resin layer manufacturing step in embodiment 2 is a step of obtaining a functional resin layer by applying a polymerizable composition containing a functional dye to a release film and then curing the composition, before the step of obtaining the laminate.

Specifically, the functional resin layer manufacturing process can be performed by, for example, the following method.

After a polymerizable composition containing a functional dye is applied to the release film, the composition is thermally cured or photo-cured to form a functional resin layer.

As a method of coating the polymerizable composition on the release film, a known coating method can be applied without particular limitation. For example, the polymerizable composition can be applied by a roll coating method such as spin coating, dip coating, die coating, spray coating, curtain (flow) coating, bar coating, blade coating, gravure coating, or the like.

In the case of photocuring the polymerizable composition, it is desirable to use light including light having a wavelength of 200nm to 450 nm.

In the case of photocuring the polymerizable composition, a light source such as sunlight, a chemical lamp, a mercury lamp, a metal halide lamp, or a UVLED may be used. If necessary, a specific wavelength cut filter, a heat ray cut filter, a wavelength cut filter for suppressing ozone generation, or a coating agent cooling or heating in ultraviolet irradiation may be used.

Examples of the ultraviolet irradiation conditions include an irradiation intensity of 0.1mW/cm ²～1,000mW/cm², an accumulated light amount of 10mJ/cm ²～5,000mJ/cm², and an irradiation time of 0.1 to 500 seconds.

When the polymerizable composition is thermally cured, the heating may be performed at a constant temperature, or a temperature regulator or a polymerization furnace capable of temperature adjustment based on a temperature program may be used to perform heating and cooling by combining heating, cooling, and cooling for a predetermined time and at a predetermined temperature. The heating may be performed at a temperature of 10 to 300℃for 0.1 to 80 hours.

Examples of the material of the release film include polyolefin such as polyethylene terephthalate and polypropylene, polycarbonate, and the like.

The film thickness of the release film is preferably 10 μm to 250. Mu.m, more preferably 15 μm to 200. Mu.m, and still more preferably 20 μm to 150. Mu.m.

[ Polycarbonate-based polyurethane adhesive layer ]

The polycarbonate-based polyurethane adhesive layer is a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group.

That is, the polycarbonate-based polyurethane adhesive layer contains a polycarbonate-based polyurethane having an anionic functional group.

The polycarbonate-based polyurethane adhesive layer may further contain additives such as inorganic nanoparticles, leveling agents, ultraviolet absorbers, silane coupling agents, plasticizers, and the like.

The content of the additive may be 30 mass% or less, preferably 20 mass% or less, relative to the total mass of the polycarbonate-based polyurethane adhesive layer.

[ Mass increase Rate in temperature Water resistance test ]

The mass increase rate of the polycarbonate-based polyurethane adhesive layer in the hot water resistance test measured under the following condition 3 is preferably 1% to 50%.

[ Condition 3]

A test piece having a length of 4cm, a width of 2cm and a thickness of 500 μm and formed of a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane was immersed in warm water at 40℃for 24 hours, and the mass of the test piece before and after the immersion was measured. The mass increase rate in the hot water resistance test was calculated from the following formula using the mass of the test piece before and after immersion.

Mass increase rate= ((mass of test piece after impregnation-mass of test piece before impregnation)/(mass of test piece before impregnation)) ×100

The unit of the mass increase rate is%.

The alkali resistance is excellent by setting the mass increase rate in the hot water resistance test to 50% or less.

From the above point of view, the mass increase rate in the hot water resistance test is more preferably 40% or less, and still more preferably 20% or less.

The mass increase rate in the heat resistance test was 1% or more, and thus the adhesion to the lens base material was excellent.

From the above point of view, the mass increase rate in the hot water resistance test is more preferably 3% or more, and still more preferably 5% or more.

The mass increase rate in the hot water resistance test is measured by the following method, for example.

The aqueous polyurethane dispersion was coated on a PET film, and the film was heated and dried in an electric furnace set at 80 ℃ to obtain a dried product of the aqueous polyurethane dispersion. The heat drying is carried out until the mass change of the dry matter of the aqueous polyurethane dispersion is less than 1%/hour. The initial mass of a test piece (thickness 500 μm, length 4cm, width 2 cm) of the dried polyurethane aqueous dispersion after peeling from the PE T film was measured. Next, the mass of the obtained test piece was measured after immersing it in warm water at 40 ℃ for 24 hours. The mass increase rate= ((mass of test piece after impregnation-mass of test piece before impregnation)/(mass of test piece before impregnation)) ×100 was set.

The thickness of the polycarbonate-based polyurethane adhesive layer is preferably 1 μm to 100. Mu.m, more preferably 2 μm to 70. Mu.m, still more preferably 3 μm to 50. Mu.m, particularly preferably 4 μm to 20. Mu.m.

(Polyurethane aqueous dispersion)

The polyurethane aqueous dispersion contains a polycarbonate-based polyurethane having an anionic functional group and water.

The polyurethane aqueous dispersion may further contain inorganic nanoparticles, leveling agents, ultraviolet absorbers, silane coupling agents, plasticizers, solvents, and the like.

(Polycarbonate-based polyurethane)

The polycarbonate-based polyurethane has an anionic functional group.

Examples of the anionic functional group include a group containing a betaine structure such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a sulfobetaine. Among the above, the anionic functional group preferably contains a carboxyl group.

The polycarbonate-based polyurethane preferably contains a non-yellowing isocyanate as a constituent material of the urethane. The non-yellowing isocyanate is an isocyanate having no aromatic skeleton, preferably an aliphatic skeleton or an alicyclic skeleton.

By including the non-yellowing isocyanate in the polycarbonate polyurethane, yellowing upon heating can be suppressed, and the polycarbonate polyurethane is excellent in light resistance.

[ Storage elastic modulus ]

[ Condition 1]

When the storage elastic modulus is 0.1MPa or more, excessive fluidization of the dried polyurethane aqueous dispersion can be suppressed, and thus the adhesion is excellent.

From the above point of view, the storage elastic modulus is preferably 0.5MPa or more, more preferably 0.7MPa or more, and still more preferably 1.0MPa or more.

When the storage elastic modulus is 80MPa or less, the polyurethane aqueous dispersion can be prevented from being excessively solidified, and thus the adhesion is excellent.

From the above point of view, the storage elastic modulus is preferably 70MPa or less, more preferably 50MPa or less, and still more preferably 30MPa or less.

(Determination of storage elastic modulus)

The viscoelasticity of the dried polyurethane aqueous dispersion was measured using a dynamic viscoelasticity measuring apparatus (for example, DMA8000 manufactured by PerkinElmer).

The aqueous polyurethane dispersion was coated on a PET film, and the film was heated and dried in an electric furnace set at 80 ℃ to obtain a dried product of the aqueous polyurethane dispersion. The heat drying is carried out until the mass change of the dry matter of the aqueous polyurethane dispersion is less than 1%/hour. Test pieces (3 cm. Times.5 mm, 500 μm thick) were prepared from the dried polyurethane aqueous dispersion after peeling from the PET film.

A dried product of a polyurethane aqueous dispersion having a size of 3cm by 5mm and a thickness of 500 μm was prepared as a test piece. The temperature was increased from-102℃to 80℃at a rate of 3℃per minute under conditions of a frequency of 1.0Hz, strain control and stretching.

The test piece formed of the dried polyurethane aqueous dispersion may be produced from, for example, a polyurethane aqueous dispersion.

The test piece formed of the dried polyurethane aqueous dispersion may contain additives such as inorganic nanoparticles, leveling agents, ultraviolet absorbers, silane coupling agents, plasticizers, and the like, in addition to the polycarbonate-based polyurethane. The content of the additive may be 30 mass% or less, preferably 20 mass% or less, relative to the total mass of the polycarbonate-based polyurethane adhesive layer.

[ Outflow start temperature ]

The outflow start temperature of the dried polyurethane aqueous dispersion, which is measured under the following condition 2, is preferably 160 to 220 ℃.

Condition 2

The outflow start temperature was measured using a rheometer and was the following temperature: a test vessel having an orifice of an inner diameter of 1mm and a length of 1mm at the end was filled with a polycarbonate-based polyurethane, and the temperature was raised at a temperature rise rate of 3℃per minute under a load of 10kgf/cm ², whereby the dried polyurethane aqueous dispersion began to flow out from the orifice.

The outflow start temperature is in units of c.

There is a tendency that the outflow starting temperature depends on the flow characteristics upon heating of the polymer.

When the outflow start temperature is 160 ℃ or higher, the heat resistance is excellent.

From the above point of view, the outflow start temperature is more preferably 165 ℃ or higher.

When the outflow start temperature is 220 ℃ or lower, the adhesion to the lens base material is excellent.

From the above point of view, the outflow start temperature is more preferably 210 ℃ or less, and still more preferably 200 ℃ or less.

The outflow start temperature is measured by the following method, for example.

The aqueous polyurethane dispersion was coated on a PET film, and the film was heated and dried in an electric furnace set at 80 ℃ to obtain a dried product of the aqueous polyurethane dispersion. The heat drying is carried out until the mass change of the dry matter of the aqueous polyurethane dispersion is less than 1%/hour. The dried polyurethane aqueous dispersion obtained by peeling from the PET film was placed in a test vessel having an orifice (inner diameter 1mm, length 1 mm) at the end thereof, and the temperature was raised at a temperature rise rate of 3℃per minute under a load of 10kgf/cm ² by using a rheometer CFT-500D manufactured by Shimadzu corporation, to measure the temperature (. Degree.C.) at which the dried polyurethane aqueous dispersion began to flow out of the orifice.

The glass transition temperature of the dried polyurethane aqueous dispersion is preferably-45 ℃ to 0 ℃.

The dry product of the aqueous polyurethane dispersion is excellent in heat resistance by setting the glass transition temperature to-45 ℃ or higher.

From the above point of view, the glass transition temperature is more preferably-35℃or higher, still more preferably-25℃or higher, particularly preferably-20℃or higher.

When the glass transition temperature is 0 ℃ or lower, the adhesion of the dried polyurethane aqueous dispersion is excellent.

From the above point of view, the glass transition temperature is more preferably-3℃or lower, and still more preferably-5℃or lower.

The glass transition temperature was measured using a dynamic viscoelasticity measuring device (for example, DMA 8000 manufactured by PerkinElmer).

Specifically, the aqueous polyurethane dispersion was coated on a PET film, and the film was heated and dried in an electric furnace set at 80 ℃ to obtain a dried product of the aqueous polyurethane dispersion. The heat drying is carried out until the mass reduction per 1 hour of the dried product of the aqueous polyurethane dispersion is less than 1%.

The polycarbonate-based polyurethane was peeled from the PET film, and the glass transition temperature of the dried product of the polyurethane aqueous dispersion was measured using a dynamic viscoelasticity measuring apparatus (DMA 8000, manufactured by PerkinElmer). The graph of the glass transition temperature as tan delta shows the maximum temperature. In the case where there are maxima at a plurality of temperatures, a lower temperature is taken as the glass transition temperature.

The polycarbonate-based polyurethane is not particularly limited as long as it has an anionic functional group.

The polycarbonate-based polyurethane may be commercially available, or may be produced by synthesis from a raw material.

Examples of commercial products of the aqueous polyurethane dispersion include SUPERFLEX 470 (manufactured by first Industrial pharmaceutical Co., ltd.), EVAFANOL HA-170 (manufactured by Nikka chemical Co., ltd.), TAKELAC series (manufactured by Sanwell chemical Co., ltd.), HYDRA N series (manufactured by DIC Co., ltd.). As a commercial product, SUPERFLEX 470 and EVAFANOL HA-170 are preferable.

The content of the polycarbonate-based polyurethane having an anionic functional group is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass, based on the total mass of the polyurethane aqueous dispersion.

The particle diameter of the polyurethane particles contained in the aqueous polyurethane dispersion is preferably 5nm to 100nm, more preferably 10nm to 80nm, and even more preferably 15nm to 50nm, from the viewpoint of improving the transparency of the adhesive layer.

The particle size of the polyurethane particles contained in the polyurethane aqueous dispersion can be measured by a dynamic light scattering method.

(Water)

The aqueous polyurethane dispersion comprises water.

The content of water is not particularly limited, and is, for example, preferably 40 to 90% by mass, more preferably 50 to 75% by mass, and still more preferably 60 to 80% by mass, relative to the total mass of the aqueous polyurethane dispersion.

< Procedure for producing spectacle lens >

The spectacle lens manufacturing process in embodiment 2 is as follows: the laminate is heated at 50-150 ℃, and the polycarbonate polyurethane adhesive layer is attached to the lens substrate in the direction in which the polycarbonate polyurethane adhesive layer is in contact with the lens substrate under reduced pressure of 20kPa or less, thereby obtaining a spectacle lens.

The following describes the steps of producing the ophthalmic lens in detail.

The spectacle lens manufacturing process is preferably performed by attaching the laminate to the lens base material using a vacuum molding machine, a pressure air molding machine or a vacuum pressure air molding machine. Heating of the laminate may be performed using an infrared heater, a ceramic heater, hot air, steam, or the like.

When the laminate is attached to the lens base material, air, compressed air, a silicone pad, a rubber pad, or the like may be used.

Attachment based on vacuum pressure Forming machine

For example, the adhesion of a polycarbonate-based polyurethane adhesive layer to a lens substrate by a vacuum-air molding machine will be described with reference to fig. 1.

Fig. 1 is a view for explaining attachment by a vacuum-air forming machine.

Then, the substrate stage is raised 5, and the lower die chamber is continuously depressurized while the substrate 3 is collided with the film 2. In addition, compressed air 6 is fed into the upper membrane chamber to pressurize the same. This state was maintained for several seconds.

(Spectacle lens)

In the case of a spectacle lens, the laminate is heated at 50 to 150 ℃ and is adhered to a lens substrate in the direction in which the polycarbonate-based polyurethane adhesive layer is in contact with the lens substrate under reduced pressure of 20kPa or less.

That is, the spectacle lens includes the laminate of embodiment 2 and the lens base material bonded to the polycarbonate urethane adhesive layer side of the laminate.

The spectacle lens may include a functional resin layer containing a functional dye, a polycarbonate urethane adhesive layer laminated on at least one surface of the functional resin layer, and a lens base material adhered to the polycarbonate urethane adhesive layer side.

< Lens substrate >

The lens substrate is not particularly limited.

The lens substrate preferably comprises at least 1 selected from the group consisting of polyacrylate, polyethylene terephthalate, polycarbonate, polyamide, polyepoxide, polyepisulfide, polyurethane, and polythiourethane,

The polyurethane is preferably composed of structural units derived from an isocyanate compound and structural units derived from an alcohol compound.

As a method for producing polyurethane, a method using an isocyanate compound and an alcohol compound is exemplified.

As a method for producing polythiourethane, there is a method using the above-mentioned isocyanate compound and thiol compound.

(Episulfide Compound)

The episulfide compound is preferably at least 1 selected from the group consisting of bis (2, 3-episulfide propyl) sulfide, bis (2, 3-episulfide propyl) disulfide, bis (1, 2-episulfide ethyl) sulfide, bis (1, 2-episulfide ethyl) disulfide, and bis (2, 3-episulfide propyl sulfide) methane, more preferably bis (2, 3-episulfide propyl) disulfide.

(Isocyanate Compound)

(Thiol Compound)

(2 Functional thiol Compounds)

Examples of the 2-functional thiol compound include methyl dithiol, 1, 3-propanedithiol, 1, 2-ethanedithiol, 1, 2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) 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-dithiocyclohexane, 2, 5-dimercaptohexane, 1, 5-dimercaptohexane, and 1, 5-dimercaptohexane, 4-dimethylthio) propionate;

(Thiol Compound of 3 functional groups or more)

(Polyol Compound)

Before the functional resin layer is attached to the lens base material, the lens surface to be attached with the functional resin layer may be subjected to pretreatment.

The method of pretreatment is not particularly limited, and may be appropriately selected from the viewpoint of adhesion, for example. Examples of the pretreatment method include an etching treatment with an alkaline aqueous solution, an etching treatment with an alkaline surfactant aqueous solution, a washing treatment with a surfactant aqueous solution, a washing treatment with pure water, an etching treatment with UV ozone, an etching treatment with plasma, a polishing treatment with fine particles, and a polishing treatment.

The method for manufacturing an ophthalmic lens according to embodiment 2 preferably further includes a step of forming a coating layer on at least a surface of the functional resin layer in the ophthalmic lens.

The method for manufacturing an ophthalmic lens according to embodiment 2 further preferably includes a step of forming a hard coat layer on at least the surface of the functional resin layer in the ophthalmic lens.

[ Coating layer ]

(Hard coat)

The spectacle lens of embodiment 2 preferably comprises a hard coat layer.

The hard coat layer is generally formed by applying a hard coat composition by a known coating method such as spin coating or dip coating, and then curing the composition. The curing method includes irradiation with energy rays such as ultraviolet rays and visible rays, heat curing, and the like. From the viewpoint of suppressing the occurrence of interference fringes, it is preferable that the difference between the refractive index of the hard coat layer and the refractive index of the lens base material is within ±0.1.

Before the hard coat agent is applied, the surface to be applied with the hard coat agent may be subjected to a pretreatment.

Examples of the pretreatment method include an etching treatment with an alkaline aqueous solution, an etching treatment with an alkaline surfactant aqueous solution, a washing treatment with a surfactant aqueous solution, a washing treatment with pure water, an etching treatment with UV ozone, an etching treatment with plasma, a polishing treatment with fine particles, and a polishing treatment.

(Anti-reflection layer)

The spectacle lens of embodiment 2 preferably includes an antireflection layer.

The anti-reflection layer is inorganic and organic.

The anti-reflection layer may be formed on the hard coat layer as needed.

The anti-reflection layer may be a plurality of layers or a single layer.

< Reheating Process >

The method for producing an ophthalmic lens according to embodiment 2 preferably further includes a reheating step of reheating the ophthalmic lens at 50 to 150 ℃.

The reheating is preferably carried out at 90℃to 140℃and more preferably at 100℃to 130 ℃.

Laminate (laminated body)

The laminate of embodiment 2 comprises a polycarbonate-based polyurethane adhesive layer formed from a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group, and a functional resin layer containing a functional pigment, and the storage elastic modulus of the dried product of the polyurethane aqueous dispersion at 80 ℃ is 0.1MP a to 80MPa, measured under the following condition 1.

[ Condition 1]

The laminate of embodiment 2 may be produced by the laminate production process of embodiment 2.

Details of the dried polyurethane dispersion, the polycarbonate-based polyurethane adhesive layer, the functional pigment, the functional resin layer, and specific examples, preferred embodiments, measurement methods, and the like of the storage elastic modulus at 80 ℃ measured under condition 1 are as described above.

The mass increase rate of the dried polyurethane aqueous dispersion in the hot water resistance test under the following condition 3 is preferably 1% to 50%.

[ Condition 3]

Test pieces having a length of 4cm, a width of 2cm and a thickness of 500 μm and formed from a dried polyurethane aqueous dispersion were immersed in warm water at 40℃for 24 hours, and the mass of the test pieces before and after immersion was measured. The mass increase rate in the hot water resistance test was calculated from the following formula using the mass of the test piece before and after immersion.

Details of the specific mode, preferable range, and the like of the mass increase rate in the heat resistance water test are as described above.

Glasses lens

The spectacle lens of embodiment 2 includes the laminate of embodiment 2 and a lens substrate bonded to the polycarbonate urethane adhesive layer side in the laminate.

The eyeglass lens of embodiment 2 may be manufactured by the method for manufacturing an eyeglass lens of embodiment 2.

Details of the specific mode, preferred mode, and the like of the lens base material are as described above.

Embodiment 2 also includes the following embodiments.

<1B > a method for manufacturing a spectacle lens, comprising the steps of: a step of forming a polycarbonate-based polyurethane adhesive layer on at least one surface of a functional resin layer containing a functional pigment, the polycarbonate-based polyurethane adhesive layer being formed from a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group; and a step of adhering the laminate to a lens substrate with the polycarbonate-based polyurethane adhesive layer in contact with the lens substrate under reduced pressure of 20kPa or less at a temperature of 50 to 150 ℃ to obtain a spectacle lens, wherein the storage elastic modulus of the polyurethane aqueous dispersion dried at 80 ℃ is 0.1 to 80MPa, measured under the following condition 1.

[ Condition 1]

The storage elastic modulus at 80℃was measured by using a test piece having a length of 3cm, a width of 5mm and a thickness of 500. Mu.m, which was formed from a dried polyurethane aqueous dispersion, and heating the test piece from-102℃to 80℃at a rate of 3℃per minute under conditions of a frequency of 1Hz, strain control and stretching by a dynamic viscoelasticity measuring apparatus.

<2B > the method for producing a spectacle lens according to <1B >, wherein the outflow starting temperature of the dried polyurethane aqueous dispersion measured under the following condition 2 is 160 ℃ to 220 ℃.

Condition 2

The aforementioned outflow start temperature was measured using a rheometer, and was the following temperature: the dried polyurethane aqueous dispersion was charged into a test vessel having an orifice of 1mm in inner diameter and 1mm in length at the end, and the temperature was raised at a temperature rise rate of 3℃per minute under a load of 10kgf/cm ², whereby the dried polyurethane aqueous dispersion started to flow out from the orifice.

<3B > the method for producing an ophthalmic lens according to <1B > or <2B >, further comprising a step of forming a hard coat layer on at least the surface of the functional resin layer in the ophthalmic lens.

<4B > the method for producing a spectacle lens according to any one of <1B > to <3B >, wherein the mass increase rate in the heat resistance water test of the dried polyurethane aqueous dispersion under the following condition 3 is 1% to 50%.

[ Condition 3]

A test piece having a length of 4cm, a width of 2cm and a thickness of 500 μm and formed from a dried product of the aqueous polyurethane dispersion was immersed in warm water at 40℃for 24 hours, and the mass of the test piece before and after immersion was measured. The mass increase rate in the hot water resistance test was calculated from the following equation using the mass of the test piece before and after immersion.

The method for producing a spectacle lens according to any one of <1B > to <4B >, wherein the thickness of the polycarbonate-based polyurethane adhesive layer is 1 μm to 100. Mu.m.

The method for producing a spectacle lens according to any one of <1B > to <5B >, wherein the glass transition temperature of the dried polyurethane aqueous dispersion is-45 ℃ to 0 ℃.

<7B > the method for producing a spectacle lens according to any one of <1B > to <6B >, wherein the functional resin layer has a thickness of 10 μm to 700. Mu.m.

The method for producing a spectacle lens according to any one of <1B > to <7B >, wherein the functional resin layer comprises a thermoplastic resin having a softening temperature of 50 to 150 ℃.

The method for producing a spectacle lens according to any one of <1B > to <7B >, wherein the functional resin layer contains a thermosetting resin containing at least 1 selected from the group consisting of polyepoxides, polyepisulfides, and poly (thio) urethanes.

The method for producing an ophthalmic lens according to any one of <1B > to <9B >, which comprises a step of applying a polymerizable composition containing the functional dye to a release film and then curing the composition to obtain the functional resin layer, wherein the step is provided before the step of obtaining the laminate.

The method for producing a spectacle lens according to any one of <1B > to <10B >, wherein the functional dye comprises at least 1 selected from the group consisting of an ultraviolet absorber, a visible light absorbing dye, a photochromic dye and a dichroic dye.

<12B > a laminate comprising a polycarbonate-based polyurethane adhesive layer formed from a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group, and a functional resin layer containing a functional pigment, wherein the storage elastic modulus of the dried product of the polyurethane aqueous dispersion at 80 ℃ is 0.1MP a to 80MPa, measured under the following condition 1.

[ Condition 1]

<13B > the laminate according to <12B >, wherein the mass increase rate of the dried polyurethane aqueous dispersion in the hot water resistance test under the following condition 3 is 1% to 50%.

[ Condition 3]

The laminate according to claim 12B or 13B, wherein the functional dye comprises at least 1 selected from the group consisting of an ultraviolet absorber, a visible light absorbing dye, a photochromic dye and a dichroic dye.

<15B > an ophthalmic lens comprising the laminate of any one of <12B > to <14B >, and a lens substrate bonded to the polycarbonate urethane adhesive layer side in the laminate.

Examples

Hereinafter, embodiment mode according to embodiment 1 will be described in detail with reference to examples. The invention of embodiment 1 is not limited to the description of these examples.

In this example, the details of the respective components used are as follows.

Specific wavelength cut-off pigments

PD-311S manufactured by Shanzhu Cheng Co Ltd

Dyes and dyes

The pigment Blue 8514 anthraquinone dye is available from chemical industry Co., ltd

The anthraquinone dye of Plast Red 8320 is available from chemical industry Co., ltd

Plast Yellow 8070 methine dyes available from chemical industries Co., ltd

Urethane primer

Urethane primer 1: TAKELAC WS-5100 (Sanjing chemical Co., ltd.)

Urethane primer 2: SUPERFLEX 470 (manufactured by first industry pharmaceutical Co., ltd.)

Urethane primer 3: EVAFANOL HA-170 (manufactured by Rihua chemical Co., ltd.)

Isocyanate Compound

Isocyanate 1: mixtures of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane with 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane

Isocyanate 2: hexamethylene diisocyanate

Isocyanate 3: m-xylylene diisocyanate

Thiol Compounds

Thiol 1: 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane

Thiol 2: bis (2-mercaptoethyl) sulfide

Thiol 3: pentaerythritol tetrakis (3-mercaptopropionate)

[ Evaluation method ]

In this example, the evaluation of each film and lens was performed as follows.

(Measurement of film thickness)

The thickness of each film was measured by a thickness gauge. Specifically, any point on the film was measured using a digital gauge (DIGIMICRO ME-50HA, manufactured by NIKON, inc.).

(Determination of softening temperature and elastic modulus of film resin)

The measurement was performed by the method described in the above item (measurement of softening temperature and storage elastic modulus).

(Calculation of molecular weight between crosslinking points of film resin)

The measurement was performed by the method described in the above item (method for measuring molecular weight between crosslinking points).

(Film following Property)

The following property of the film to the substrate was visually confirmed and evaluated for the lens to which the film was attached.

Stage 1: the film was not attached so as to follow the curved surface of the substrate, or bubbles were confirmed between the substrate and the film.

2 Stages: the film was attached so as to follow the curved surface of the substrate, and no bubbles were observed between the substrate and the film.

(Bag breaking of film)

Whether or not breakage occurred in the film was visually confirmed.

(Test of adhesion)

At the convex peripheral edge of the lens, lines at 1mm intervals were cut out by a cutter so as to be 11 lines in the vertical direction and 11 lines in the horizontal direction, and 100 checkers were provided in a checkerboard pattern. A NICHIBAN-made transparent adhesive tape was attached from above the 100 squares, and the adhesive tape was peeled vertically, and the peeled state of the film or the coating film was confirmed.

The number of non-peeled squares out of the 100 squares was visually checked and the adhesion was evaluated.

The number of non-peeled squares out of the 100 squares is shown in table 1.

When peeling did not occur, the operation of attaching the tape again and peeling by the same method was repeated 2 times.

When the adhesion test was performed on the lens having the hard coat layer laminated on the film and peeling was performed, this means that the film had poor solvent resistance.

That is, if the film is damaged by the solvent used in the treatment in the hard coat treatment, the film and the hard coat layer cannot be sufficiently adhered, and the peeling occurs.

(Scratch resistance test)

By placing a 1kg weight directly above the lens and applying a load using steel wool #0000, and performing a reciprocating motion 10 times, the flaws generated on the surface of the coating film were visually evaluated, and 5 grades were performed. The evaluation criteria are as follows.

Evaluation criterion

Stage 1: in order to introduce flaws into the whole width of the steel wool and to peel off the whole surface of the coating film.

2 Stages: in order to introduce deep flaws into the whole width of the steel wool, the coating film remains.

3 Stages: in order to introduce a state of several to tens of coarse flaws.

4 Stages: in order to introduce a state of several to tens of shallow scratches.

5 Stages: the state is almost no visually recognizable flaw.

(White turbidity)

In the coated lens, whether or not cloudiness was generated was visually confirmed.

When the film surface is damaged by etching with the solvent in the hard coat process, cloudiness is generated. That is, the occurrence of cloudiness means that the solvent resistance of the film is poor.

(Heat resistance test)

The film or lens was placed on a tray, heated in an electric furnace at a constant temperature of 60 ℃ for 10 minutes, and the lens immediately after removal from the electric furnace and the lens in a state where the temperature was sufficiently lowered to the vicinity of room temperature were observed to confirm the presence or absence of cracks.

If no crack was generated, the temperature of the electric furnace was further increased by 10℃and the same evaluation was performed. The same operation was repeated until cracks were generated, and the maximum temperature at which no crack was generated was used as a heat-resistant temperature as an index of heat resistance.

(Determination of transmittance)

The transmittance of the film or lens was measured by a UV-Vis spectrophotometer (manufactured by Shimadzu corporation). The measurement wavelength was set to a range of 350nm to 800nm, and the effect of the functional dye on absorbing a specific wavelength was confirmed from the obtained transmittance spectrum.

Manufacture of lens base Material

A mixed solution was prepared by charging 0.03 part by mass of dimethyltin dichloride, zelecUN 0.1.1 parts by mass of STEPAN Co., ltd., 50.6 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, and 0.05 part by mass of 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole as a UV absorber. The mixed solution was stirred at 25 ℃ for 1 hour to be completely dissolved. Then, 25.5 parts by mass of a thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 23.9 parts by mass of a thiol composition containing pentaerythritol tetrakis (3-mercaptopropionate) were added to the prepared solution, and the mixture was stirred at 25℃for 30 minutes to obtain a homogeneous solution (polymerizable composition). The polymerizable composition was defoamed at 600Pa for 1 hour, and filtered through a 1. Mu.mPTFE filter to obtain a blended liquid.

Next, in order to mold a lens having a high curvature on the convex side, a casting mold in which a front glass mold (R of a concave surface facing a rear glass mold is 86 mm) and a rear glass mold (R of a convex surface facing the front glass mold is 250 mm) are fixed to each other with an adhesive tape so as to face each other was produced. The gap of the outermost periphery of the mold was set to about 1mm, and the solution was cast into the gap formed between the mold and the tape, and the temperature was raised from 25℃to 120℃over 16 hours. The mixture was cooled to room temperature and removed from the glass mold to obtain a lens having a diameter of 81 mm. The lens was processed to have a diameter of 75mm, and a lens substrate having a power of +4.50 and a refractive index of 1.597 was obtained.

Separately from the above, in order to mold a lens having a high curvature on the concave side, a casting mold in which a front glass mold (R of 253mm for a concave surface opposing a rear glass mold) and a rear glass mold (R of 86mm for a convex surface opposing the front glass mold) are fixed by tape so as to oppose each other was produced. The solution was cast in the gap between the molds (the distance between the center portions of the substantially circles was 1.5 mm), and the temperature was raised from 25℃to 120℃over 16 hours. The mixture was cooled to room temperature and removed from the glass mold to obtain a lens having a diameter of 81 mm. The lens was processed to have a diameter of 75mm to obtain a lens substrate having a power of-4.50 and a refractive index of 1.597.

Example 1A

[ Production of polythiourethane film ]

A mixed solution was prepared by charging 0.04 part by mass of dimethyltin dichloride, zelecUN 0.2.2 parts by mass of STEPAN, 0.007 part by mass of PD-311S (manufactured by ShandomiKagaku chemical Co., ltd.) as a dye, 31.9 parts by mass of a mixture of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 17.3 parts by mass of hexamethylene diisocyanate, and 0.05 part by mass of 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole as a UV absorber. The mixed solution was stirred at 25 ℃ for 1 hour to be completely dissolved. Then, 26.8 parts by mass of a thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane and 15.9 parts by mass of bis (2-mercaptoethyl) sulfide were added to the prepared solution, and the mixture was stirred at 25℃for 30 minutes to obtain a homogeneous solution (polymerizable composition). The polymerizable composition was defoamed at 600Pa for 1 hour, and filtered through a 1. Mu. MPT FE filter to obtain a blended liquid.

A film forming mold was assembled by sandwiching a 200 μm thick PTFE sheet (which was processed so as to surround the glass plate 4 by a width of 1.5 cm) between 2 glass plates having a longitudinal direction of 36cm, a transverse direction of 27cm and a plate thickness of 5mm, and fixing the peripheries of the pair of glass plates so as to cover them with an adhesive tape. The gap between the film forming molds was filled with the blending liquid, and after the casting nozzle was closed with the tape, the temperature was raised from 30℃to 120℃over 12 hours. The resultant film was cooled to room temperature and removed from the glass mold to obtain a polythiourethane film having A4 size and a thickness as shown in table 1.

In addition, 2 glass plates having a diameter of 80mm were separately prepared and fixed with tape so as to face each other, thereby producing a casting mold. The solution was cast in the gap between the molds (the distance between the center portions of the substantially circles was 2.5 mm), and the temperature was raised from 25℃to 120℃over 16 hours. Then, the mixture was cooled to room temperature, and removed from the glass mold to obtain a polythiourethane plate having a diameter of 80 mm. A part of the obtained flat plate was subjected to cutting processing to obtain a test piece having a softening temperature and a modulus of elasticity measuring dimension of 30mm X5 mm and a thickness of 2.5 mm.

As a result of measuring the elastic modulus of the obtained test piece, the fitted line between the temperature and the elastic modulus was increased continuously with a slope of 10000 or more in the range of 130 to 150 ℃.

The results are shown in Table 1.

[ Coating of adhesive layer ]

After wiping the obtained film with acetone, the urethane primer 1 was applied as an adhesive layer for bonding the substrate to the film.

The urethane primer 1 was dropped onto the film by a dropper, and the film was coated by a gap coater. After coating, the primed film was put into an electric oven set at 70 ℃ and dried for 15 minutes. Next, a protective film is attached to the coated surface of the urethane primer, and the urethane primer is stored as an attaching film.

Attachment based on vacuum pressure Forming machine

The lens wiped with Silbon paper containing acetone was immersed in a tank containing sodium hydroxide at a concentration of 10% at a liquid temperature of 55℃for 5 minutes while applying ultrasonic waves, and then rinsed in a pure water tank for 15 minutes while applying ultrasonic waves, and then dried with hot air at 70℃to prepare a substrate.

Next, a washed lens was placed on a substrate stage of a vacuum press molding machine NGF-0404-T (manufactured by cloth vacuum), and an A4-sized polythiourethane film coated with an adhesive layer was placed on a film stage. At this time, the protective film was peeled off, and the polythiourethane film was disposed so that the adhesive layer was on the substrate side.

Next, the pressure reduction chamber in which the film and the substrate were disposed was sealed, and the pressure was reduced by a vacuum pump until the pressure became 3kPa. At this time, the upper film chamber, which is the upper space for sandwiching the film, is partitioned by the film from the lower die chamber, which is the space for disposing the lower substrate, and the upper and lower spaces are depressurized together.

From the upper part of the film, the film was heated by a heater to a surface temperature as shown in table 1. After the film reached 145 ℃, a small amount of air was introduced into the upper film chamber to raise the pressure, and the film was inflated slightly toward the substrate side below. In this state, the substrate stage is raised from below toward the film, and the substrate surface is bonded to the film surface. After bonding, the lower mold chamber was kept under reduced pressure, and compressed air was supplied to the upper film chamber to be in a pressurized state of 300kPa, and the pressure was maintained for about 5 seconds. Then, the upper and lower spaces of the film are returned to normal pressure, the sealed state is released, and the lens with the film attached thereto is taken out.

In the lens taken out, the film was attached so as to follow the curved surface of the lens, and no air bubbles were observed between the substrate and the film.

Next, the film is cut out circumferentially along the outer periphery of the lens, and the lens portion to which the film is attached is separated from the remaining film portion.

Then, the lens with the film attached thereto was heated in an electric furnace at 120 ℃ for 1 hour to completely cure the primer, thereby obtaining a lens with a film having a substrate surface and a film bonded completely.

[ Hard coating treatment ]

The resulting film-equipped lens was wiped with Silbon paper containing acetone as a solvent, and immersed in a tank of 10% sodium hydroxide at a liquid temperature of 55℃for 5 minutes with ultrasonic waves.

Then, the washing was performed by rinsing for 15 minutes while applying ultrasonic waves to the pure water tank, and further drying was performed by hot air at 70 ℃. The lens was immersed in a hard coat solution Crysta l Coat IM-9060 (SDC Technologies Co.) for 10 seconds, lifted at 2 mm/sec, coated, and dried at 80℃for 15 minutes. The lens was removed from the jig and further heat-cured at 120℃for 3 hours to obtain a hard-coated lens with a film.

The transmittance spectrum of the obtained lens was measured by a spectrophotometer, and as a result, as shown in fig. 2, the maximum absorption was exhibited in the vicinity of 585nm, which is the absorption wavelength of the functional dye.

Fig. 2 is a graph showing transmittance of the lens with a film in example 1A.

[ Anti-reflection coating treatment ]

On the hard-coated lens with film, a 5-layer multilayer antireflection layer formed of silicon oxide/zirconium oxide was formed using a vacuum evaporation apparatus.

The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots (streak unevenness) were not completely confirmed.

The evaluation results are shown in table 1.

Example 2A

A colorless transparent polythiourethane film having the dimensions of A4 and the thickness shown in Table 1, and a test piece for measuring the softening temperature and the elastic modulus having dimensions of 30 mm. Times.5 mm and a thickness of 2.5mm were obtained by the same procedure as in example 1A, except that no coloring matter was added to the film.

As a result of measuring the elastic modulus of the obtained test piece, the fitted line of the temperature and the elastic modulus was increased continuously with a slope of 10000 or more in the range of 130 to 150 ℃.

Further, by the same procedure as in example 1A, [ adhesive layer coating ], [ attachment by a vacuum pressure air forming machine ], [ hard coating treatment ], and [ antireflection coating treatment ], a lens with a film subjected to the hard coating treatment and the antireflection coating treatment was obtained. The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were not completely confirmed. The evaluation results are shown in table 1.

Example 3A

In [ preparation of film ], the content of the mixture of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane was changed to 53.1 parts by mass,

The content of hexamethylene diisocyanate was changed to 0 parts by mass,

The content of the thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was changed to 17.9 parts by mass,

The content of bis (2-mercaptoethyl) sulfide was changed to 23.8 parts by mass, and in addition,

A colorless transparent polythiourethane film having the dimensions of A4 and the thickness shown in Table 1, and a test piece for measuring softening temperature and elastic modulus having dimensions of 30mm by 5mm and a thickness of 2.5mm were obtained by the same procedure as in example 1A.

As a result of measuring the elastic modulus of the obtained test piece, the fitted line of the temperature and the elastic modulus was increased continuously at a gradient of 4000 or more in the range of 130 to 150 ℃.

Further, in [ adhesion by vacuum air-pressure molding machine ], the film-attached lens subjected to the hard coating treatment and the antireflection coating treatment was obtained by performing [ adhesive layer coating ], [ adhesion by vacuum air-pressure molding machine ], [ hard coating treatment ] and [ antireflection coating treatment ] in the same manner as in example 1A, except that the heating temperature of the film was set to the temperature described in table 1. The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were not completely confirmed.

The evaluation results are shown in table 1.

Example 4A

In [ preparation of film ], PD-311S0.007 parts by mass of mountain chemical Co., ltd., which is a pigment, was changed to 0.018 parts by mass of Plast Red8320 parts by mass of Chemie Co., ltd., plast Yellow 8070.012 parts by mass of Plast Yellow8070 parts by Chemie Co., ltd.,

As an isocyanate composition, instead of 31.9 parts by mass of a mixture of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 52.0 parts by mass of xylylene diisocyanate was used,

The content of hexamethylene diisocyanate was changed to 0 parts by mass,

The content of the thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was changed to 28.8 parts by mass,

The content of bis (2-mercaptoethyl) sulfide was changed to 17.1 parts by mass, and in addition,

A polythiourethane film having a size of A4 and a thickness as shown in Table 1, and a test piece for measuring a softening temperature and an elastic modulus having a size of 30mm by 5mm and a thickness of 2.5mm were obtained by the same procedure as in example 1A.

As a result of measuring the elastic modulus of the obtained test piece, the fitted line of the temperature and the elastic modulus was increased at a gradient of 27000 or more in the range of 130 to 150 ℃.

Example 5A

A film (referred to as film 5A) was produced by the same procedure as in [ film production ] of example 1A.

Next, a polythiourethane film 5B having A4 size and a thickness as shown in table 2 was obtained in the same manner as in example 1A, except that 0.007 parts by mass of PD-311S manufactured by kayaku chemical corporation was changed to 0.046 parts by mass of plastic Yellow8070 manufactured by shimeji chemical corporation in [ film manufacturing ].

Details, evaluations, and the like of the film 5B are described in table 2.

Next, the adhesive films 5A and 5B were each obtained by the same procedure as in example 1A [ adhesive layer coating ].

Attachment based on vacuum pressure Forming machine

Next, a washed lens was placed on a substrate stage of a vacuum press molding machine NGF-0404-T (manufactured by vacuum application), and a polythiourethane film 5A coated with an adhesive layer was placed on a film stage. At this time, the protective film is peeled off, and the polythiourethane film 5A is disposed so that the adhesive layer is on the substrate side.

From the upper part of the film, the film was heated by a heater to a surface temperature as shown in table 2. After the film reached the temperature shown in table 2, a small amount of air was introduced into the upper film chamber to raise the pressure, and the film was inflated slightly toward the substrate side below. In this state, the substrate stage is raised from below toward the film, and the substrate surface is bonded to the film surface. After bonding, the lower mold chamber was kept under reduced pressure, and compressed air was supplied to the upper film chamber to be in a pressurized state of 300kPa, and the pressure was maintained for about 5 seconds. Then, the upper and lower spaces of the film are returned to normal pressure, the sealed state is released, and the lens with the film attached thereto is taken out.

In the lens taken out, the film was attached so as to follow the curvature, and no bubbles were observed between the substrate and the film.

Next, the film was cut out circumferentially along the outer periphery of the lens, and the lens portion to which the film was attached was separated from the remaining film portion, to obtain a lens to which a 5A film was attached.

Then, the surface of the lens having the 5A film attached thereto was blown, and the lens was placed on a substrate stage of a vacuum air-compression molding machine NGF-0404-T again. On the film stage, the polythiourethane film 5B coated with the adhesive layer is disposed so that the protective film is peeled off and the adhesive layer is on the substrate side.

Next, the vacuum chamber in which the film 5B and the lens to which the film 5A was attached were placed was sealed, and the pressure was reduced by a vacuum pump until the pressure became 3kPa. At this time, the upper film chamber, which is the upper space for sandwiching the film, is partitioned by the film from the lower die chamber, which is the space for disposing the lower substrate, and the upper and lower spaces are depressurized together.

From the upper part of the film, the film was heated by a heater to a surface temperature as shown in table 2.

After the film reached the temperature shown in table 2, a small amount of air was introduced into the upper film chamber to raise the pressure, and the film was inflated slightly toward the substrate side below. In this state, the substrate stage is raised from below toward the film, and the substrate surface is bonded to the film surface. After bonding, the lower mold chamber was kept under reduced pressure, and compressed air was supplied to the upper film chamber to be in a pressurized state of 300kPa, and the pressure was maintained for about 5 seconds. Then, the upper and lower spaces of the film were returned to normal pressure, the sealed state was released, and the lens to which the film 5B was further attached was taken out.

Next, the lens with the film attached thereto was heated in an electric furnace at 120 ℃ for 1 hour to completely cure the primer, thereby obtaining a lens in which the base material, the film 5A, and the film 5B were completely bonded.

Further, by the same procedure as in example 1A, [ adhesive layer coating ], [ attachment by a vacuum pressure air forming machine ], [ hard coating treatment ], and [ antireflection coating treatment ], a lens with a film subjected to the hard coating treatment and the antireflection coating treatment was obtained. The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were not completely confirmed. The evaluation results are shown in table 2.

Example 6A

The content of hexamethylene diisocyanate was changed to 0 parts by mass,

The content of the thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was changed to 8.9 parts by mass,

The content of bis (2-mercaptoethyl) sulfide was changed to 31.8 parts by mass,

In addition to the fact that no pigment is added,

A colorless transparent polythiourethane film having the dimensions of A4 and the thickness shown in Table 2, and a test piece for measuring softening temperature and elastic modulus having dimensions of 30mm by 5mm and a thickness of 2.5mm were obtained by the same procedure as in example 1A.

As a result of measuring the elastic modulus of the obtained test piece, the fitted line between the temperature and the elastic modulus was substantially flat at a slope of-21000 or more in the range of 130℃to 150 ℃.

Further, in [ adhesion by vacuum air-pressure molding machine ], the film-attached lens subjected to the hard coating treatment and the antireflection coating treatment was obtained by performing [ adhesive layer coating ], [ adhesion by vacuum air-pressure molding machine ], [ hard coating treatment ] and [ antireflection coating treatment ] in the same manner as in example 1A, except that the heating temperature of the film was set to the temperature described in table 2. The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were not completely confirmed. The evaluation results are shown in table 2.

Example 7A

A lens with a film was obtained in the same manner as in example 1A, except that the urethane primer 1 was changed to the urethane primer 2. The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were not completely confirmed. The evaluation results are shown in table 2.

Comparative example 1A

In [ film production ], PD-311S0.007 parts by mass of mountain chemical Co., ltd., which is a pigment, was changed to PLAST Blue 8514, 0.030 parts by mass of the pigment,

Instead of 31.9 parts by mass of a mixture of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 43.5 parts by mass of xylylene diisocyanate was used,

The content of hexamethylene diisocyanate was changed to 0 parts by mass,

Instead of 26.8 parts by mass of the thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 56.5 parts by mass of a thiol compound containing pentaerythritol tetrakis (3-mercaptopropionate) was used,

The content of bis (2-mercaptoethyl) sulfide was changed to 0 parts by mass, and in addition to this,

A polythiourethane film having a size of A4 and a thickness as shown in Table 3, and a test piece for measuring a softening temperature and an elastic modulus having a size of 30mm by 5mm and a thickness of 2.5mm were obtained by the same procedure as in example 1A.

As a result of measuring the elastic modulus of the obtained test piece, the fitted line between the temperature and the elastic modulus was increased at a slope of 72000 or more in the range of 130℃to 150 ℃.

Further, in [ adhesion by a vacuum-air forming machine ], the same procedure as in example 1A was followed to carry out [ adhesion by a vacuum-air forming machine ].

In [ attachment by a vacuum pressure molding machine ], the film cannot withstand the impact at the time of attachment, and cracks occur in the peripheral portion of the lens. In addition, the film cannot follow the curvature surface of the lens, and air enters between the substrate and the film, so that the film cannot be bonded to the substrate surface. The evaluation results are shown in table 3.

Comparative example 2A

In [ preparation of film ], PD-311S0.007 parts by mass of mountain chemical Co., ltd., which is a pigment, was changed to 0.018 parts by mass of glass Red 8320 parts by mass of glass Yellow 8070.012 parts by mass of the chemical Co., ltd.,

Instead of 31.9 parts by mass of a mixture of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 52.0 parts by mass of xylylene diisocyanate was used,

The content of hexamethylene diisocyanate was changed to 0 parts by mass,

The content of the thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was changed to 48.0 parts by mass,

As a result of measuring the elastic modulus of the obtained test piece, the fitted line between the temperature and the elastic modulus was increased at a slope of 55000 or more in the range of 130 to 150 ℃.

In the case of [ attachment by a vacuum-air molding machine ], the film cannot follow the curvature surface of the lens, and air enters between the substrate and the film, so that the film cannot be bonded to the substrate surface. The evaluation results are shown in table 3.

Comparative example 3A

In the case of the [ fabrication of a film ], the pigment was changed from PD-311S0.007 parts by mass to Plast Blue 8514, manufactured by Chemie Co., ltd.,

The content of the mixture of 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane was changed to 26.5 parts by mass,

The content of hexamethylene diisocyanate was changed to 21.6 parts by mass,

The content of the thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was changed to 44.5 parts by mass,

As a result of measuring the elastic modulus of the obtained test piece, the fitted line between the temperature and the elastic modulus was increased with a gradient of 51000 or more in the range of 130℃to 150 ℃.

Comparative example 4A

The content of hexamethylene diisocyanate was changed to 0 parts by mass,

The content of the thiol composition containing 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane was changed to 0 parts by mass,

The content of bis (2-mercaptoethyl) sulfide was changed to 39.7 parts by mass,

In addition to the fact that no pigment is added,

A colorless transparent polythiourethane film having the dimensions of A4 and the thickness shown in Table 3, and a test piece for measuring softening temperature and elastic modulus having dimensions of 30mm by 5mm and a thickness of 2.5mm were obtained by the same procedure as in example 1A.

As a result of measuring the elastic modulus of the obtained test piece, the fitted line of the temperature and the elastic modulus was gradually decreased at a slope of-51000 or more in the range of 130℃to 150 ℃.

Further, in [ adhesion by a vacuum-air forming machine ], the adhesive layer coating ], [ adhesion by a vacuum-air forming machine ], and [ hard coat treatment ] were performed in the same manner as in example 1A except that the heating temperature of the film was set to the temperature shown in table 3.

The hard-coated lens is subjected to clouding due to the surface being etched by the solvent in the hard coating process. Therefore, the solvent resistance of the film is poor.

The evaluation results are shown in table 3.

Reference example 1A

As the film, PET film (Lumiror T-60, film thickness 50 μm) manufactured by Toli Co., ltd was used,

In [ adhesion by vacuum air molding machine ], except that the heating temperature of the film was set to the temperature shown in Table 3,

The same procedures as in example 1A were carried out [ film production ], [ adhesive layer coating ], [ adhesion by a vacuum pressure air forming machine ], [ hard coating treatment ].

In the case of the hard-coated lens, adhesion between the film and the hard coating layer was not obtained in the adhesion test. The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were confirmed on the entire surface of the lens. Further, the abrasion resistance was poor due to the influence of the soft film, and coarse flaws were introduced into the entire width of the steel wool.

The evaluation results are shown in table 3.

Reference example 2A

As the film, mitsubishi Chemical Group Corporation acrylic films (ACRYPLEN HBS-006, film thickness 75 μm) were used,

The appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were confirmed on the entire surface of the lens.

In the case of the hard-coated lens, adhesion between the film and the hard coating layer was not obtained in the adhesion test. Further, the abrasion resistance was poor due to the influence of the soft film, and coarse flaws were introduced into the entire width of the steel wool.

The evaluation results are shown in table 3.

TABLE 1

TABLE 2

TABLE 3

As shown in tables 1 to 3, the following properties were excellent in examples using polythiourethane films containing polythiourethane having a molecular weight between crosslinking points of 950 to 3000. In the examples, no cloudiness was observed, and the evaluation of adhesion was excellent, so that the solvent resistance was excellent.

On the other hand, comparative examples 1A to 3A using polythiourethane films containing polythiourethane having a molecular weight of less than 950 between crosslinking points have poor followability.

In comparative example 4A using a polythiourethane film containing a polythiourethane having a molecular weight of more than 3000 between crosslinking points, cloudiness was found. Therefore, the film surface is damaged by the solvent etching in the hard coat treatment, and the solvent resistance is poor.

In reference examples 1A and 2A, which used films other than the polythiourethane film, the appearance of the obtained lens was visually confirmed, and as a result, streak-like spots were confirmed on the entire surface of the lens.

In laminated lenses using PET films, acrylic films, and the like, it is necessary to prepare a hard coating liquid for exclusive use, and it is complicated to add additional steps.

By forming a laminated lens having a polythiourethane film on the surface layer, a higher adhesion can be obtained without limiting the kind of hard coating liquid, and a spectacle lens having a good appearance and free from streak-like spots can be obtained.

In examples 1A to 7A, the use of polythiourethane as a film can provide adhesion without changing the hard coat layer used for the polythiourethane lens.

Hereinafter, embodiment mode according to embodiment 2 will be described in detail with reference to examples. The invention of embodiment 2 is not limited to the description of these examples.

[ Evaluation method ]

In this example, each evaluation was performed as follows.

(Outflow starting temperature)

The outflow start temperature was measured as described above.

(Mass increase Rate in temperature Water resistance test)

The mass increase rate in the hot water resistance test was measured as described above.

(Glass transition temperature of dried polyurethane aqueous dispersion)

The glass transition temperature of the dried polyurethane aqueous dispersion was measured as described above.

(Thickness measurement)

The thickness of each layer was measured using a digital display meter ID-H and a Comparator Stand (BSB-20X, manufactured by Mitutoyo, inc.).

(Determination of storage elastic modulus)

The measurement was performed by the method described in the above item (measurement of the storage elastic modulus).

(Determination of softening temperature of thermoplastic resin)

The measurement was performed by the method described in the item (thermoplastic resin) above.

(Evaluation of adhesion of spectacle lens)

A peel test was performed by using CT405AP-18 (registered trademark) manufactured by NICHIBAN Co., ltd. CELLOTAPE, and cutting lines of 100 squares were cut on the surface of the spectacle lens in accordance with JIS K5400-8.5 (1999).

The number (%) of squares which did not peel out of the 100 squares was visually checked and the adhesion was evaluated.

(Adhesion after the lens periphery of the spectacles is processed)

A template-free edge grinder (PATTERNLESS EDGER) LE-1200 manufactured by NIDEK was used, and the outer peripheral portion of the lens was cut by a rotary blade rotating at high speed while water was sprayed around the geometric center of the spectacle lens, and ground into a circular shape having a radius (half of the maximum length in a plane view) of 37.5 mm.

The presence or absence of peeling of the functional resin layer was visually confirmed under a fluorescent lamp for the spectacle lens after polishing.

The case where the functional resin layer was not peeled was evaluated as a, and the case where the functional resin layer was peeled was evaluated as B.

(Evaluation of scratch resistance of hard coating)

Reciprocating abrasion tester HEIDON TriboGear TYPE manufactured by new eastern science co., ltd: on 30S, steel wool manufactured to be bos STAR #0000 manufactured by NIHON STEEL WOOL co., ltd. Having a longitudinal and transverse direction of about 3cm was mounted using a double-sided tape. The steel wool was rubbed back and forth on the hard coat surface 10 times under a load of 1kg, and the rubbed position was visually observed to confirm and evaluate the number and depth of flaws generated on the coat surface.

(Alkali resistance test)

An ultrasonic washer MCS-6 manufactured by AS ONE Co., ltd was charged with a 10 mass% aqueous potassium hydroxide solution.

The spectacle lens is immersed in the aqueous solution, and irradiated with ultrasonic waves at 60 to 63 ℃ for 20 minutes. After the ultrasonic irradiation, the spectacle lens was taken out and washed with running water for 3 minutes. Next, the spectacle lens was immersed in a container equipped with an ultrasonic wave generating device in which ion-exchanged water was filled, and irradiated with ultrasonic waves at 45 ℃ for 5 minutes.

After the ultrasonic irradiation, the spectacle lens was removed, and the adhesion of the adhesive layer was evaluated. For the evaluation of adhesion, a peel test was performed by using a peel test of CELL OTAPE (registered trademark) CT405AP-18 manufactured by NICHIBAN company, and cutting lines of 100 squares were cut on the surface of a spectacle lens in accordance with JIS K5400-8.5 (1999).

< Production of lens base A >

To a sample bottle having a capacity of 100mL, 0.02 parts by mass (1,000 parts by mass) of Zelec (registered trademark) UN (manufactured by Stepan corporation), 0.01 parts by mass (500 parts by mass) of dibutyltin (II) dichloride (a catalyst), and 10.12 parts by mass of 2,5 (6) -bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane (a polymerizable compound) were added and mixed by stirring at 20℃to obtain a homogeneous solution.

Further, 4.78 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) and 5.1 parts by mass of 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane were added as polymerizable compounds to the homogeneous solution, and the mixture was stirred and mixed at 20℃to obtain a homogeneous polymerizable composition.

The resulting polymerizable composition was defoamed under reduced pressure of 400Pa or less for 30 minutes to 1 hour, then filtered through a PTFE membrane filter having a pore size of 1 μm, and poured into a cavity (circular planar lens (plane) shape having a radius (half of the maximum length in a plan view) of 40.5mm, a curved surface shape having a radius of curvature of 128mm and a center thickness of 2 mm) formed by a glass mold and an adhesive tape, and sealed with the adhesive tape.

The mold having the polymerizable composition sealed in the cavity was placed in a polymerization furnace, gradually heated from 25℃to 120℃over 19 hours, and then kept at 120℃for 2 hours, followed by polymerization. After cooling, the glass mold and the tape were peeled off, and the lens substrate a, which is a molded body formed of a cured resin and formed inside, was taken out.

The resulting molded article was colorless and transparent, had a refractive index ne of 1.60, nd of 1.59, abbe number ve of 40, vd of 42 and glass transition temperature of 121 ℃.

(Refractive index (ne, nd), abbe numbers (ve, vd)) of the lens base material

The measurement was performed at 20℃using a Porphyra refractometer KPR-30 manufactured by Kalnew Optical Industrial Co., ltd. The refractive index and Abbe number were measured by passing F '(a Cd spectral line at a wavelength of 479.99 nm), C' (a Cd spectral line at a wavelength of 643.85 nm), F (a H spectral line at a wavelength of 486.13 nm), C (a H spectral line at a wavelength of 656.27 nm), e (a Hg spectral line at a wavelength of 546.07 nm) and d (a He spectral line at a wavelength of 587.56) through the molded article. The refractive index (ne) and abbe number (ve) at the wavelength of the e-line, the refractive index (nd) and abbe number (vd) at the wavelength of the d-line are calculated in accordance with JIS B7090: 1999 and ISO7944:1998.

(Glass transition temperature of lens substrate)

The measurement was performed by TMA penetration method (50 g load, 0.5mm phi at a tip of needle, 10℃/min at a heating rate of 10℃and a heating temperature of room temperature to 140 ℃) using a thermo-mechanical analyzer TMA-60 manufactured by Shimadzu corporation.

The lens substrate a was further alkali-washed by the following procedure.

An ultrasonic washer MCS-6 manufactured by AS ONE Co., ltd was charged with a 10 mass% aqueous potassium hydroxide solution. The emission frequency of the ultrasonic scrubber was 40kHz, and the output power of the ultrasonic wave was 150W.

The lens substrate A is immersed in the solution, and ultrasonic waves are irradiated at 50 to 55 ℃ for 5 minutes. After the ultrasonic irradiation, the lens substrate was taken out, washed with running water for 3 minutes, and then immersed in a container equipped with an ultrasonic wave generating device in which ion-exchanged water was filled, and irradiated with ultrasonic waves at 45 ℃ for 5 minutes. After the ultrasonic irradiation, the lens substrate was taken out and heated in a forced air circulation type constant temperature oven set at 110℃for about 30 minutes. When the heating is completed, the substrate is taken out of the oven and left at room temperature of 18 to 30 ℃ for 30 minutes or more, and the lens substrate a is cooled.

< Synthetic example of polyurethane aqueous Dispersion 1 >

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen inlet tube, 205.6g of UH-CARB200 (polycarbonate diol, average molecular weight 2000, manufactured by Yu Zu Xin Co., ltd.), 15.4g of triethylene glycol, 11.2g of dimethylolpropionic acid, 1.8g of trimethylolpropane and 145.0g of acetonitrile as a solvent were charged.

Then, 91.1g of 1, 3-bis (isocyanatomethyl) cyclohexane as an isocyanate compound was added to a four-necked flask, and the reaction was carried out at 75℃for 6 hours. After the isocyanate content (NCO%) of the reaction liquid was set to 2.9 mol%, 4.8g of 2-hydroxyethyl acrylate and 0.017g of stannous octoate were added to a four-necked flask, and the reaction was performed at 70 ℃ for 2 hours to obtain a urethane prepolymer (NCO% =2.45%).

After the reaction solution was cooled to 40 ℃, 8.3g of triethylamine was used for neutralization, 650g of ion-exchanged water was slowly added thereto, and the mixture was dispersed in water. Next, an aqueous amine solution obtained by dissolving 4.9g of hydrazine monohydrate and 6.8g of KBM602 (N-. Beta. -aminoethyl-. Gamma. -aminopropyl methyldimethoxysilane, manufactured by Xinyue chemical Co., ltd.) in 46.8g of ion-exchanged water was added to the aqueous dispersion of the urethane prepolymer to conduct a chain extension reaction. The acetonitrile was further distilled off to obtain an aqueous polyurethane dispersion 1 containing a polycarbonate-based polyurethane having an anionic functional group, and the aqueous polyurethane dispersion 1 was an aqueous polyurethane resin dispersion having a solid content of 35 mass%.

< Measurement of spectroscopic Spectrum >

The spectroscopic properties of the functional resin layer and the functional dye were measured at room temperature using a UV-Vis spectrophotometer UV-1800 manufactured by Shimadzu corporation. The measurement wavelength range was set to 350nm to 800nm.

Example 1B

(Preparation of functional resin layer)

An acrylic film (Mitsubishi Chemical Group Corporation, ACRYPLEN HBA007P, thickness 75 μm, transmittance 6% at 380nm, length 297mm in the machine direction, length 210mm in the transverse direction) having an ultraviolet ray blocking function was used as the functional resin layer.

The functional resin layer was subjected to plasma treatment by the following method.

< Plasma treatment >

A small-sized plasma device (Ya mato Scientific co., ltd., manufactured by ltd.) having a capacitor-shaped two-divided electrode structure was used as the PM 100. In the plasma treatment, after the vacuum suction was performed in the chamber containing the sample, oxygen was introduced at a rate of 50 mL/min, and the sample was irradiated with 15W for 15 seconds.

(Preparation of laminate)

The functional resin layer subjected to plasma treatment was fixed on a flat glass plate, and SUPERFLE X470 (manufactured by first industrial pharmaceutical co.) as an aqueous polyurethane dispersion was added dropwise to the functional resin layer using a dropper.

The aqueous polyurethane dispersion thus added was applied to a functional resin layer by a bar coater (No. 10), and then dried in an electric oven set at 60℃for 5 minutes, to obtain a laminate comprising the functional resin layer and a polycarbonate-based polyurethane adhesive layer. The thicknesses of the polycarbonate-based polyurethane adhesive layers are shown in table 4.

(Attachment of lens base material)

The obtained laminate (i.e., adhesive film) was cooled to room temperature and then attached to the lens substrate a using a vacuum molding apparatus, whereby a spectacle lens comprising a functional resin layer, a polycarbonate-based polyurethane adhesive layer and a lens substrate in this order was obtained.

Specifically, a vacuum forming apparatus (NGF-0404-T) manufactured by Bruce vacuum Co., ltd was used.

In the present apparatus, the laminate softened by heating is attached to a substrate in a vacuum-pumped chamber, and the film is pressed against the substrate by compressed air. In the present apparatus, the molding parameters may be appropriately changed depending on the material of the functional resin layer, the material of the release film, and the like.

In the case of attaching, a polycarbonate-based polyurethane adhesive layer was attached to the convex surface of the lens base material a. In the adhesion, the heating temperature of the laminate was set to 115℃and the air pressure in the chamber was set to 1kPa.

After the attachment, the spectacle lens was cooled to room temperature, and then the laminate protruding from the lens base material was cut off. Then, the spectacle lens was heated in an electric furnace set to 120 ℃ for 1 hour, thereby manufacturing the spectacle lens.

Example 2B

(Preparation of functional resin layer)

0.10 Parts by mass of a tetraazaporphyrin compound (PD-311S, manufactured by Shando chemical Co., ltd., maximum absorption wavelength: 585 nm) as a visible light absorbing pigment, 0.10 parts by mass of a polyether-modified silicone (KF-352A, manufactured by Xinyue chemical Co., ltd.), 1.0 parts by mass of 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole (manufactured by Co-medicine Co., ltd., VIOSORB 583) as an ultraviolet absorber, 0.5 parts by mass of a sulfonium salt compound (San-Apro Co., CPI-210S, details described below) as a cationic polymerization initiator, and 70 parts by mass of 3',4' -epoxycyclohexyl methyl 3, 4-epoxycyclohexane carboxylate (manufactured by Daicel Co., ltd., CELLOXIDE 2021P, details described below) as a cationic polymerization compound were weighed in a glass vial.

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

[ Chemical formula 1]

CELLOXIDE 2021P: cationic polymerizable compound, 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate represented by the following formula

[ Chemical formula 2]

The vial was filled with a stirrer and stirred and mixed using a magnetic stirrer at a rotational speed of 100rpm (revolutions per minute rpm) to 300rpm over 2 hours. During mixing, the cap of the glass vial is closed to prevent contact with the outside air.

After confirming visually that the mixture was a homogeneous solution, 30 parts by mass of a Poloxamer (Poloxamer) compound (ADEKA, ADEKA noil (registered trademark) L-64, manufactured by ADEKA corporation) composed of an ethyleneoxy group and a propyleneoxy group was added as a cationically polymerizable compound to the homogeneous solution, and the mixture was stirred and mixed at a rotation speed of 100rpm to 300rpm over a period of 30 minutes to 2 hours.

When mixing, a ceramic heater or an oil bath is used as necessary, and the mixture is heated to 30 to 60 ℃. The mixture was visually confirmed to be a homogeneous solution, and cooled to room temperature to obtain a homogeneous polymerizable composition for a functional resin layer.

The obtained polymerizable composition was filtered using a membrane filter made of PTFE manufactured by Advantec Co., ltd. Having a pore size of 1 μm to 5. Mu.m.

A uniaxially stretched polypropylene film (thickness 50 μm, length 297mm in the machine direction, length 210mm in the transverse direction) as a release film was fixed to a flat and UV-permeable glass plate.

A polymerizable composition for a functional resin layer was dropped onto a release film by a dropper, the resultant was applied onto the release film by a bar coater (No. 20), and UV-cured by a UV-curing device to obtain a functional resin layer having a release film.

The detailed conditions for UV curing are as follows.

< UV curing apparatus >

A batch-type UV curing apparatus having a UV irradiation power supply UB012-0BM-60Hz manufactured by EYE GRAPHICS Co., ltd was used. The inside of the box-shaped case of the curing apparatus was provided with a sample holder and metal halide lamps M01-L212 (arc length 122mm, lamp output 80W/cm) manufactured by EYE GRAPHICS Co., ltd. And located at the upper and lower parts of the sample holder, respectively. The irradiation time of the UV light of the curing device can be changed, and the output power of the lamp can be switched between 2 levels of 750W and 1,000W. In addition, the distance between the sample and the metal halide lamp may also be varied.

< Measurement of UVA ultraviolet intensity >

The ultraviolet intensity in the wavelength range of UVA (320 nm to 390 nm) was measured using UVA single band photometer UVICURE (registered trademark) Plus II manufactured by EIT, INC.

< Measurement of UVC ultraviolet intensity >

The ultraviolet intensity in the wavelength range of UVC (250 nm to 260 nm) was measured using a UVC single band photometer UVICURE Plus II manufactured by EIT, INC.

In UV curing, UV light is irradiated from both the upper surface and the lower surface (glass plate surface) of the polymerizable composition for a functional resin layer.

The details of the UV light irradiated from the upper surface are as follows.

UV light irradiation intensity in UVA wavelength region: 110mW/cm ² of the total weight,

UV light irradiation intensity in the UVC wavelength region: 30mW/cm ²

Cumulative amount of UV light in the UVA wavelength region: 3,300mJ/cm ²

Cumulative amount of UV light in the UVC wavelength region: 1,000mJ/cm ²

The details of the UV light irradiated from the lower surface are as follows.

UV light irradiation intensity in UVA wavelength region: 100mW/cm ²

UV light irradiation intensity in the UVC wavelength region: 25mW/cm ²

Cumulative amount of UV light in the UVA wavelength region: 3,000mJ/cm ²

Cumulative amount of UV light in the UVC wavelength region: 800mJ/cm ²

The UV irradiation of the polymerizable composition for a functional resin layer is performed under an atmosphere of air having a relative humidity of 30 to 70% and an air temperature of 18 to 30 ℃. The thickness of the obtained functional resin layer (cured product of the polymerizable composition for a functional resin layer) is as shown in table 4.

The air temperature and the relative humidity were measured using a bench hygrothermograph testo-H2 manufactured by Kagaku testo.

As a result of measurement of the spectroscopic spectrum of the functional resin layer, the functional resin layer had a peak at a wavelength of 585nm, and the transmittance at 585nm was 37%, and the functional resin layer had a wavelength cut-off function.

The spectroscopic spectrum was measured at room temperature using a UV-Vis spectrophotometer UV-1800 manufactured by Shimadzu corporation. The measurement wavelength range was set to 350nm to 800nm.

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

(Preparation of laminate)

After the plasma treatment, the aqueous polyurethane dispersion 1 was dropped onto the surface of the functional resin layer by a dropper, and after coating by a bar coater (No. 10), the resultant was dried in an electric oven set at 60 ℃ for 5 minutes to obtain a laminate comprising the functional resin layer and the polycarbonate-based polyurethane adhesive layer. The thicknesses of the polycarbonate-based polyurethane adhesive layers are as shown in table 1.

(Attachment of lens base material)

The specific method was the same as that described in example 1B, except that the heating temperature of the laminate was 85 ℃.

(Washing of spectacle lenses)

The spectacle lens obtained in the above was immersed in the solution, and irradiated with ultrasonic waves at 55℃to 60℃for 10 minutes. After the ultrasonic irradiation, the spectacle lens was taken out and washed with running water for 3 minutes. Next, the spectacle lens was immersed in a container equipped with an ultrasonic wave generating device in which ion-exchanged water was filled, and irradiated with ultrasonic waves at 45 ℃ for 5 minutes.

After the ultrasonic irradiation, the spectacle lens was taken out and heated in a forced air circulation type constant temperature oven set at 80℃for about 10 minutes. After the heating is finished, the spectacle lens is taken out of the oven and left at the room temperature of 18-30 ℃ for more than 30 minutes, so that the spectacle lens is cooled.

(Formation of hard coating)

The spectacle lens cooled to room temperature was fixed to a spin coater MS-150A manufactured by MIKASA corporation, to which a spin chuck was attached, by using a vacuum chuck, and rotated at a constant rotational speed. A hard coat liquid MP-1179 made by SDC Technologies Inc. was applied to the functional resin layer of the rotary spectacle lens with a dropper for 10 to 20 seconds in an amount of 5 to 10 mL.

The rotational speed of the spectacle lens is suitably adjusted in the range of 300rpm to 400rpm so that the thickness of the hard coat layer becomes 3 μm.

When the hard coating liquid is coated, the dropper does not move from the center of the eyeglass lens, or the dropper is dripped while moving outwards from the center of the eyeglass lens.

After the end of the dripping of the hard coating liquid, the spectacle lens is further rotated for about 160 seconds to 170 seconds while maintaining the constant speed, and the hard coating liquid is uniformly applied to the surface of the spectacle lens.

After the hard coating liquid application was completed, the spectacle lens was heated in a forced air circulation type constant temperature oven set to a temperature of 110 ℃ for about 2 hours. After the heating was completed, the spectacle lens was taken out of the oven and cooled to room temperature to obtain a spectacle lens having a hard coating layer on the surface.

The adhesion of the hard coat layer was evaluated for the obtained spectacle lens according to the method described in the above evaluation of adhesion.

The number (%) of squares in which peeling of the functional resin layer was not observed was 100%, and peeling was not observed between the functional resin layer and the hard coat layer.

When the adhesion test was performed on the lens having the hard coat layer laminated on the functional resin layer and peeling was generated, this means that the film had poor alkali resistance.

That is, if the functional resin layer is damaged by a solvent such as an alkali used in the lower treatment in the hard coat treatment, the functional resin layer and the hard coat layer cannot be sufficiently adhered, and the peeling occurs.

The scratch resistance of the hard coat layer was evaluated for the obtained spectacle lens according to the method described in the above evaluation of scratch resistance of the hard coat layer.

No deep flaws were generated in the resulting hard coat layer.

Example 3B

An ophthalmic lens was produced in the same manner as in example 1B except that SUPERFLEX 470 as an aqueous polyurethane dispersion was changed to EVAFAN OL HA-170 (manufactured by Rihua chemical Co., ltd.).

Comparative example 1B

A spectacle lens was produced in the same manner as in example 1B except that SUPERFLEX 470, which is an aqueous polyurethane dispersion, was changed to SUPERFL EX 620,620 (manufactured by first industrial pharmaceutical co.).

TABLE 4

As shown in table 4, the adhesion of the spectacle lens and the adhesion after the outer periphery processing of the spectacle lens are excellent in the examples using the following method for manufacturing the spectacle lens, which comprises the following steps: a step of forming a polycarbonate-based polyurethane adhesive layer on at least one surface of a functional resin layer containing a functional pigment, the polycarbonate-based polyurethane adhesive layer being formed from a dried product of a polyurethane aqueous dispersion containing a polycarbonate-based polyurethane having an anionic functional group; and a step of adhering the laminate to a lens substrate in a direction in which the polycarbonate-based polyurethane adhesive layer is in contact with the lens substrate under reduced pressure of 20kPa or less at 50 to 150 ℃ to obtain a spectacle lens, wherein the storage elastic modulus of the polyurethane aqueous dispersion dried at 80 ℃ is 0.1 to 80MPa, measured under condition 1. Accordingly, a spectacle lens comprising a polycarbonate polyurethane adhesive layer excellent in adhesion to a lens substrate can be produced.

In addition, the results of the alkali resistance test in the examples are excellent. Accordingly, a spectacle lens comprising a polycarbonate-based polyurethane adhesive layer excellent in alkali resistance can be produced.

On the other hand, the spectacle lens in comparative example 1B using a dried polyurethane aqueous dispersion having a storage elastic modulus at 80 ℃ of more than 80MPa had poor adhesion. Therefore, it is not possible to produce a spectacle lens comprising a polycarbonate-based polyurethane adhesive layer excellent in adhesion to a lens substrate.

In addition, the results of the alkali resistance test in comparative example 1B were also poor. Therefore, it is also impossible to produce a spectacle lens comprising a polycarbonate-based polyurethane adhesive layer excellent in alkali resistance.

The entire disclosures of japanese patent application No. 2022-044196 filed on month 3 of 2022 and japanese patent application No. 2022-044197 filed on month 3 of 2022 are incorporated herein by reference.

All documents, patent applications and technical standards described in the present specification are incorporated in the present specification by reference, and the degree to which each document, patent application and technical standard is incorporated by reference is the same as in the case of specific and individual descriptions.

Description of the reference numerals

1- & Gt heater

2. Membrane

3. Substrate

4. Vacuum

5. Carrier lifting the platform

6. Compressed air

7. Trimming

Claims

1. A polythiourethane film comprising a polymer of a polythiourethane, which comprises a polythiourethane and a polythiourethane,

The polythiourethane is the reaction product of a 2-functional thiol compound, a 3-functional or more thiol compound, and an isocyanate compound.

2. The polythiourethane film according to claim 1, wherein the thiol equivalent of the 2-functional thiol compound is 20 to 95% relative to 100% of the total thiol equivalent of the 2-functional thiol compound and the 3-functional or higher thiol compound.

3. The polythiourethane film according to claim 1, which has a thickness of 100 μm to 600. Mu.m.

4. The polythiourethane film according to claim 1, which has a minimum storage elastic modulus at 30 to 160 ℃, the minimum storage elastic modulus being 3.00 x 10 ⁶Pa～1.40×10⁷ Pa.

5. The polythiourethane film according to claim 1, wherein the molecular weight between crosslinking points of the polythiourethane is 950 to 3000.

6. The polythiourethane film of claim 1 further comprising a functional pigment.

7. The polythiourethane film according to claim 6, wherein the functional dye is a specific wavelength-cut dye or a photochromic dye.

8. A material for a spectacle lens comprising the polythiourethane film according to any one of claims 1 to 7, and a polyurethane adhesive layer adhered to at least one surface of the polythiourethane film.

9. The material for a spectacle lens according to claim 8, wherein the polyurethane adhesive layer comprises a polycarbonate-based polyurethane having an anionic functional group.

10. The material for a spectacle lens according to claim 8, further comprising a hard coat layer as an outermost layer.

11. An ophthalmic lens comprising:

the material for a spectacle lens according to claim 8, and

12. The spectacle lens of claim 11 wherein the convex or concave surface of the spectacle lens substrate is bonded to the polyurethane bonding layer in the spectacle lens material.

13. The ophthalmic lens of claim 11, wherein the ophthalmic lens substrate has a radius of curvature of 62.5mm to 125.0mm.

14. The spectacle lens according to claim 11, comprising 2 or more sheets of the material for spectacle lenses.

15. The ophthalmic lens of claim 11, wherein the ophthalmic lens substrate comprises at least 1 selected from the group consisting of polyacrylates, polyethylene terephthalate, polycarbonates, polytriacet-cellulose, polyvinyl alcohol, polyesters, polyamides, polyepoxides, polyepisulfides, polyurethanes, and polythiourethanes.

16. A method for producing a spectacle lens, comprising the step of adhering the material for a spectacle lens according to claim 8 to a spectacle lens base material to obtain a spectacle lens.

17. The method for producing a spectacle lens according to claim 16, comprising a step of adhering the material for a spectacle lens to a spectacle lens base material by using a vacuum press molding machine to obtain a spectacle lens.