Photochromic curable composition, photochromic laminate and method for producing same

Abstract

Provided are: a photochromic curable composition capable of providing a cured product having an excellent appearance; a photochromic optical article including this cured body; and a method for producing these. According to an embodiment, a photochromic curable composition is provided that includes: (A) a siloxane having an acyclic polysiloxane bond and at least one of a radically polymerizable group and a group reacting with a radically polymerizable group; (B) a radically polymerizable monomer component; and (C) a photochromic compound.

Description

[Technical Field]

[0001] The present invention relates to a photochromic curable composition, a photochromic laminate, and a method for producing the same. [Background technology]

[0002] Photochromic compounds, such as chromene compounds, fulgide compounds, and spirooxazine compounds, have the property of rapidly changing color when irradiated with ultraviolet light such as sunlight or light from a mercury lamp, and returning to their original color when the light irradiation is stopped and the compound is placed in a dark place, i.e., photochromic properties. Utilizing this property, photochromic compounds are used in a variety of applications, particularly in optical materials.

[0003] For example, photochromic eyeglasses containing a photochromic compound are functional eyeglasses that quickly become tinted outdoors where sunlight is irradiated, functioning as sunglasses, and fade to become colorless and transparent indoors where there is no sunlight. Demand for photochromic eyeglasses has been increasing in recent years.

[0004] Examples of methods for producing photochromic optical articles, including lenses for photochromic eyeglasses, include a kneading method, a binder method, and a coating method (Patent Documents 1, 2, and 3). The kneading method is a method for molding a photochromic optical article, such as a lens, by polymerizing a polymerizable composition containing a polymerizable monomer and a photochromic compound. The binder method is a method for obtaining a photochromic optical article by bonding a pair of optical sheets with an adhesive layer containing a photochromic compound and processing the resulting laminate into a lens or the like.

[0005] Compared with the above-mentioned methods, the coating method is a method with high productivity. In the coating method, first, a curable composition containing a photochromic compound and a polymerizable monomer is applied to the surface of a lens or the like by, for example, spin coating, to form a coating film. By curing this coating film, a laminate is obtained in which a photochromic resin layer is provided on the surface of the lens. This laminate can be used as a photochromic optical article. In the coating method, a leveling agent may be blended into the curable composition to uniformize the surface of the coating film.

[0006] In photochromic optical articles such as photochromic lenses obtained by the above-mentioned coating method, a protective film may be attached to the surface of the photochromic resin layer. That is, during the process of manufacturing optical devices such as photochromic sunglasses using photochromic lenses as components, and during storage and shipping of the manufactured optical devices, the photochromic resin layer of the lens may be scratched or have dust attached. Covering the surface of the photochromic resin layer of the lens with a protective film can prevent such scratches and dust attachment. Furthermore, a colored film may be used as the protective film. Since photochromic lenses are colorless and transparent when not irradiated with ultraviolet light, a colored protective film attached to their surface can function as an identification label. For example, a general-purpose protective film using an acrylic adhesive on the adhesive surface is used as the protective film. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2012 / 176439 [Patent Document 2] International Publication No. 2013 / 099640 [Patent Document 3] International Publication No. 2015 / 068798 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a photochromic curable composition capable of providing a cured product with excellent appearance, a photochromic optical article containing the cured product, and a method for producing the same. [Means for solving the problem]

[0009] The first embodiment is (A) a siloxane having an acyclic polysiloxane bond and at least one of a radical polymerizable group and a group reactive with a radical polymerizable group; (B) a radical polymerizable monomer component; (C) a photochromic compound; a reactive hindered amine compound having at least one reactive group selected from the group consisting of a radical polymerizable group and a group reactive with a radical polymerizable group; The photochromic curable composition comprises:

[0010] Furthermore, the first embodiment preferably takes the following aspects.

[0011] The amount of siloxane per 100 parts by mass of the radical polymerizable monomer component is preferably 0.01 parts by mass or more and 10 parts by mass or less.

[0012] The siloxane preferably contains a compound represented by the following formula (8).

[0013] [ka]

[0014] In formula (8), n is a number from 0 to 20. o is a number from 0 to 20. p is a number from 0 to 20. R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28, and R 29 are respectively a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group, and -(CH2) α OR 30 , -(CH2CH2O) α R 30 , -(CH(CH3)CH2O) α R 30 , -(CH2CH(CH3)O) α R 30 , -(CH2) q O-(CH2CH2O) r R 30 -, -(CH2) q O-(CH(CH3)CHO) r R 30 , -(CH2) q O-(CH2CH(CH3)O) r R 30 , -(CH2CH2O) q -(CH2CH(CH3)O) r R 30 , -(CH2CH(CH3)O) q -(CH2CH2O) r R 30 , -(CH2CH2O) q -(CH2CH(CH3)O) r -(CH2CH2O) s R 30 , -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s R 30 , -(CH2) q O-(CH2CH(CH3)O) r -(CH2CH2O) s R 30 , -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s -(CH2CH2O) z R 30 , acryloyl group, methacryloyl group, vinyl group, thiol group, amino group, -R 31 NH 2、It is an epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).

[0015] R 30 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. R 31 represents an alkylene group having 1 to 20 carbon atoms, or -(CH2) α It is O-. However, R 18 ~R 29 At least one of the groups is an acryloyl group, a methacryloyl group, a vinyl group, a thiol group, an amino group, -R 31 NH 2、 It is an epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).

[0016] [ka]

[0017] In equation (9), R 32 is an alkylene group having 1 to 20 carbon atoms, -(CH2) α O-, -(CH2CH2O) α - or -(CH2CH(CH3)O) α -R 33 is a hydrogen atom or a methyl group.

[0018] [ka]

[0019] In equation (10), R 34 is an oxygen atom, -(CH2) α O-, -(CH2CH2O) α -, -(CH(CH3)CH2O) α -, -(CH2CH(CH3)O) α -, -(CH2) q O-(CH2CH2O) r -, -(CH2) q O-(CH(CH3)CHO)r -, -(CH2) q O-(CH2CH(CH3)O) r -, -(CH2CH2O) q -(CH2CH(CH3)O) r -, -(CH2CH(CH3)O) q -(CH2CH2O) r -, -(CH2CH2O) q -(CH2CH(CH3)O) r -(CH2CH2O) s -, -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s -, -(CH2) q O-(CH2CH(CH3)O) r -(CH2CH2O) s - or -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s -(CH2CH2O) z -It is. R 35 is a hydrogen atom or a methyl group.

[0020] In formulas (8), (9), and (10), α is a number from 1 to 20, and q, r, s, and z are each a number from 0 to 20. q+r is a number from 1 to 40. q+r+s is a number from 1 to 60. q+r+s+z is a number from 1 to 80.

[0021] The radically polymerizable group of the siloxane and the group reactive with the radically polymerizable group preferably contain a (meth)acryloyl group.

[0022] The radically polymerizable monomer component preferably contains a polyrotaxane compound having a radically polymerizable group.

[0023] The radically polymerizable monomer component preferably contains a silsesquioxane having two or more functional (meth)acryloyl groups.

[0025] It is preferred that the composition further contains a non-reactive hindered amine compound that does not have a radical polymerizable group or a group that reacts with the radical polymerizable group.

[0026] It is preferable that the solvent further contains an organic compound having a boiling point of 80° C. or more and 200° C. or less and a Hildebrand SP value of 8.0 or more and 10.0 or less.

[0027] The second embodiment is an optical substrate; a photochromic resin layer that is a cured product of the curable composition according to the first embodiment; a polyurethane resin layer located between the optical substrate and the photochromic resin layer; A photochromic laminate comprising:

[0028] The third embodiment is A step of applying a coating liquid containing at least one compound selected from the group consisting of polyurethane resins and moisture-curable urethane resin precursors, and a solvent having a boiling point of 70°C or higher and a Hildebrand SP value of 8.0 or higher, onto one surface of an optical substrate, and removing the solvent from the coating film to form a polyurethane resin layer; a step of applying the photochromic curable composition according to the first embodiment onto the polyurethane resin layer and curing the coating to form a photochromic resin layer; The method for producing a photochromic laminate includes the steps of: [Effects of the Invention]

[0029] According to the present invention, there are provided a photochromic curable composition capable of providing a cured product with excellent appearance, a photochromic optical article containing the cured product, and a method for producing the same. [Brief explanation of the drawings]

[0030] [Figure 1] 1 is a schematic diagram showing an example of the molecular structure of polyrotaxane. DETAILED DESCRIPTION OF THE INVENTION

[0031] The photochromic curable composition according to the embodiment contains the following components (A), (B), and (C).

[0032] (A) a siloxane having an acyclic polysiloxane bond and at least one of a radically polymerizable group and a group reactive with a radically polymerizable group; (B) Radical polymerizable monomer component (C) Photochromic Compound By using the photochromic curable composition according to the embodiment, a cured product having high uniformity and excellent appearance, which can suppress the occurrence of wrinkle-like fine lines, can be obtained. Therefore, a photochromic optical article having excellent appearance can be obtained. The present inventors believe that the reason for this is as follows.

[0033] First, when the above-mentioned protective film is attached to the photochromic resin layer, the photochromic optical article may not achieve the desired color tone or may have poor appearance, such as wrinkle-like streaks. That is, in the photochromic optical article from which the above-mentioned protective film has been removed, the adhesive and colorant contained in the protective film may adhere to the surface of the photochromic resin layer. If such undesired adhesive and colorant remain on or penetrate into the surface of the photochromic resin layer, the color tone of the photochromic resin layer may change from the desired color tone. Furthermore, thin lines like wrinkles may appear inside the photochromic resin layer.

[0034] The inventors have discovered that these wrinkle-like thin lines are caused by an adhesive applied to the adhesive surface of the protective film. That is, it is believed that the acrylic adhesive used in the protective film permeates from the adhesive surface of the protective film into the photochromic resin layer and hardens inside the photochromic resin layer, causing the lines or stripes to appear.

[0035] As a result of further intensive research, the present inventors have found that the penetration of this acrylic adhesive is influenced by the leveling agent. Specifically, non-reactive silicone oils and the like are commonly used as leveling agents in curable compositions. Non-reactive silicone oils are siloxanes having a linear polysiloxane skeleton, with the end or side chain of this polysiloxane skeleton modified with a non-reactive organic functional group. The leveling agent orients to the coating film surface to reduce the surface tension of the coating film surface. This suppresses an increase in viscosity of the curable composition, eliminates unevenness in the coating film, and smooths the surface. Since the leveling agent cures while oriented on the coating film surface, it is believed to also be oriented on the surface of the photochromic resin layer. When the leveling agent is oriented on the surface of the resin layer in this way, components such as the adhesive of the protective film tend to be easily incorporated into the photochromic resin layer. Therefore, while the use of conventional leveling agents increases the smoothness of the coating film, it is believed that thin streaks or stripes of foreign matter originating from the protective film are observed inside the photochromic resin layer.

[0036] When a conventional curable composition not containing a leveling agent is used, a photochromic resin layer without such wrinkle-like fine lines can be obtained. On the other hand, the photochromic resin layer obtained from such a curable composition may have an uneven film thickness, and multiple irregularities may appear on the surface, resulting in a so-called orange peel appearance. Furthermore, when the curable composition is applied by spin coating, spiral traces may be observed in the photochromic resin layer due to the unevenness of the coating film.

[0037] The photochromic curable composition according to the present invention includes (A) a siloxane having an acyclic polysiloxane bond and at least one of a radically polymerizable group and a group reactive with the radically polymerizable group, and (B) a radically polymerizable monomer component. Hereinafter, at least one of the radically polymerizable group and the group reactive with the radically polymerizable group is also referred to as a radically reactive group. Because of the acyclic polysiloxane bond and the radically reactive group, component (A) functions as a leveling agent. The radically reactive group of component (A) reacts with component (B) upon curing of the curable composition. In a cured product of this composition, at least a portion of components (A) and (B) are believed to be in a polymerized composite state. Because component (A) in such a composite is polymerized with component (B), orientation toward the surface of the photochromic resin layer is believed to be reduced. That is, in a coating film of the photochromic curable composition, component (A) can be oriented toward the surface of the coating film, similar to conventional leveling agents, thereby reducing its surface tension. As a result, when the photochromic curable composition according to the embodiment is used, a highly uniform coating film can be obtained. When this coating film is cured, component (A) polymerizes with component (B) to form a complex, which is thought to suppress orientation toward the surface and increase random dispersion within the photochromic resin layer. This results in a photochromic resin layer that is less susceptible to the influence of the adhesive and colorant contained in the protective film attached to the surface. For these reasons, when the photochromic curable composition according to the embodiment is used, a photochromic resin layer that is highly uniform, is less likely to develop wrinkle-like streaks, and has excellent appearance can be formed. Each component contained in the curable composition will be described in detail below.

[0038] <Component (A)> Component (A) is a non-cyclic polysiloxane bond and a radical. reaction As described above, component (A) functions as a leveling agent.

[0039] The radical polymerizable group of component (A) may be at least one functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinyl group. A functional group containing at least one of an acryloyl group and a methacryloyl group may also be referred to as a (meth)acryloyl group. The group reactive with the radical polymerizable group may be at least one functional group selected from the group consisting of a thiol group, an amino group, and an epoxy group. These reactive groups are groups that polymerize or react with component (B), which will be described in detail below. A (meth)acryloyl group is particularly preferred. Component (A) may have both a radical polymerizable group and a group reactive with a radical polymerizable group, or one of them, as the radical reactive group. It is preferable that component (A) has a radical polymerizable group of the same type as the radical polymerizable group of component (B). By using similar functional groups for the radical polymerizable groups of component (A) and component (B), the reactivity between components (A) and (B) is enhanced, resulting in a cured product with excellent appearance. Here, the acryloyl group and the methacryloyl group are considered to be the same type of functional group. It is preferable to use at least one of silicone polyether acrylate and silicone acrylate as component (A).

[0040] The component (A) is chemically bonded to the matrix of the photochromic resin layer. Because the component (A) is present in the matrix of the photochromic resin layer, orientation of the component (A) toward the surface can be suppressed, the stability of the photochromic optical article can be maintained at a high level, and a photochromic optical article with good appearance can be obtained.

[0041] Component (A) is not particularly limited as long as it is a siloxane having an acyclic polysiloxane bond and a radically polymerizable group. Component (A) may contain a non-reactive functional group in addition to the radically reactive group. Examples of such non-reactive functional groups include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 4 to 10 carbon atoms, and polymeric groups having 2 to 20 carbon atoms. Specific examples of polymeric groups having 2 to 20 carbon atoms include polypropylene groups, polyether groups, polyethylene groups, and polyolefin groups. Component (A) may contain multiple types of the non-reactive functional groups, and preferably contains at least one functional group selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and polymeric groups having 2 to 20 carbon atoms. More preferably, the non-reactive functional group is at least one selected from the group consisting of methyl groups, methoxy groups, ethoxy groups, phenyl groups, polypropylene groups, and polyether groups.

[0042] Of these, the compound represented by the following formula (8) is preferred, which may hereinafter be simply referred to as "component (A8)."

[0043] [ka]

[0044] In formula (8), n is a number from 0 to 20, and preferably a number from 1 to 15. o is a number from 0 to 20, and preferably a number from 1 to 15. p is a number from 0 to 20, and preferably a number from 1 to 15.

[0045] R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , and R 29are respectively a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group, and -(CH2) α OR 30 , -(CH2CH2O) α R 30 , -(CH(CH3)CH2O) α R 30 , -(CH2CH(CH3)O) α R 30 , -(CH2) q O-(CH2CH2O) r R 30 -, -(CH2) q O-(CH(CH3)CHO) r R 30 , -(CH2) q O-(CH2CH(CH3)O) r R 30 , -(CH2CH2O) q -(CH2CH(CH3)O) r R 30 , -(CH2CH(CH3)O) q -(CH2CH2O) r R 30 , -(CH2CH2O) q -(CH2CH(CH3)O) r -(CH2CH2O) s R 30 , -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s R 30 , -(CH2) q O-(CH2CH(CH3)O) r -(CH2CH2O) s R 30 , -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s -(CH2CH2O) z R 30 , acryloyl group, methacryloyl group, vinyl group, thiol group, amino group, -R 31 NH 2、 It is an epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).

[0046] The alkyl group having 1 to 20 carbon atoms is preferably a methyl group or an ethyl group, and the alkoxy group having 1 to 20 carbon atoms is preferably a methoxy group or an ethoxy group.

[0047] R 30 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. R 31 represents an alkylene group having 1 to 20 carbon atoms, or -(CH2) α It is O-. However, R 18 ~R 29 At least one of the groups is an acryloyl group, a methacryloyl group, a vinyl group, a thiol group, an amino group, -R 31 NH 2、 It is an epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).

[0048] [ka]

[0049] In equation (9), R 32 is an alkylene group having 1 to 20 carbon atoms, -(CH2) α O-, -(CH2CH2O) α - or -(CH2CH(CH3)O) α -R 32 is bonded to any Si in the above formula (8). R 33 is a hydrogen atom or a methyl group.

[0050] [ka]

[0051] In equation (10), R 34 is an oxygen atom, -(CH2) α O-, -(CH2CH2O) α -, -(CH(CH3)CH2O) α-, -(CH2CH(CH3)O) α -, -(CH2) q O-(CH2CH2O) r -, -(CH2) q O-(CH(CH3)CHO) r -, -(CH2) q O-(CH2CH(CH3)O) r -, -(CH2CH2O) q -(CH2CH(CH3)O) r -, -(CH2CH(CH3)O) q -(CH2CH2O) r -, -(CH2CH2O) q -(CH2CH(CH3)O) r -(CH2CH2O) s -, -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s -, -(CH2) q O-(CH2CH(CH3)O) r -(CH2CH2O) s - or -(CH2) q O-(CH2CH2O) r -(CH2CH(CH3)O) s -(CH2CH2O) z -R 34 is bonded to any of the Si in the above formula (8). R 35 is a hydrogen atom or a methyl group.

[0052] In formulas (8), (9), and (10), α is a number from 1 to 20, and preferably a number from 1 to 15. q, r, s, and z are each a number from 0 to 20. q+r is a number from 1 to 40. q+r+s is a number from 1 to 60. q+r+s+z is a number from 1 to 80.

[0053] The radically polymerizable group of the siloxane and the group reactive with the radically polymerizable group preferably contain a (meth)acryloyl group. The structure of the component (A8) and the type of functional group are, for example, ( 1It can be estimated by H-NMR analysis, infrared absorption spectroscopy (IR) analysis, and liquid chromatography mass spectrometry (LC-MS) analysis.

[0054] As the component (A8), commercially available products can be used. Examples of the component (A8) having at least one functional group selected from the group consisting of a group represented by formula (9), a group represented by formula (10), and an acryloyl group include TEGO (registered trademark) RAD2100 and TEGO (registered trademark) RAD2300 manufactured by Evonik Japan Co., Ltd., and BYK (registered trademark)-UV3505, BYK (registered trademark)-UV3505, BYK (registered trademark)-UV3510, and BYK (registered trademark)-UV3520 manufactured by BYK-Chemie Japan K.K. Examples of the acrylic acid ester include BYK (registered trademark)-UV3530, BYK (registered trademark)-3550, BYK (registered trademark)-3560, BYK (registered trademark)-UV3565, BYK (registered trademark)-3566, BYK (registered trademark)-UV3500, BYK (registered trademark)-UV3535, BYK (registered trademark)-UV3570, BYK (registered trademark)-UV3575, BYK (registered trademark)-UV3576, and KR-513 and X-22-2445 manufactured by Shin-Etsu Chemical Co., Ltd.

[0055] Examples of the component (A8) having a methacryloyl group include X-40-9296, X-22-164, X-22-164A, X-22-164B, X-22-164C, and X-22-164E manufactured by Shin-Etsu Chemical Co., Ltd.

[0056] An example of the component (A8) having a vinyl group is KR-511 manufactured by Shin-Etsu Chemical Co., Ltd.

[0057] Examples of the component (A8) having an amino group include KF-8010, KF-8012, X-22-161A, X-22-161B, and KF-8008 manufactured by Shin-Etsu Chemical Co., Ltd., and DOWSIL (registered trademark) BY16-205, DOWSIL (registered trademark) BY16-213, DOWSIL (registered trademark) 16-849 Fluid, DOWSIL (registered trademark) 16-853U, DOWSIL (registered trademark) 16-871, DOWSIL (registered trademark) 16-879B, DOWSIL (registered trademark) 16-892, DOWSIL (registered trademark) FZ-3705, DOWSIL (registered trademark) FZ-3710 Fluid, DOWSIL (registered trademark) FZ-3785, and DOWSIL (registered trademark) SF-8417 Fluid manufactured by Dow-Toray Industries, Inc.

[0058] Examples of the component (A8) having a thiol (mercapto) group include KR-518, X-22-167B, X-22-167C, X-22-173BX, and X-22-173DX manufactured by Shin-Etsu Chemical Co., Ltd.

[0059] Examples of the component (A8) having an epoxy group include KR-516, KR-517, X-24-9590, and X-41-1590A manufactured by Shin-Etsu Chemical Co., Ltd., and DOWSIL (registered trademark) BY16-839, DOWSIL (registered trademark) BY16-876, DOWSIL (registered trademark) FZ-3736 Fluid, DOWSIL (registered trademark) SF8411 Fluid, DOWSIL (registered trademark) SF8413 Fluid, DOWSIL (registered trademark) SF8421 Fluid, and DOWSIL (registered trademark) L-9300 manufactured by Dow-Toray Industries, Inc.

[0060] (A) Optimal blending ratio of component The amount of component (A) is not particularly limited. The amount of component (A) is preferably 0.01 to 10.0 parts by mass per 100 parts by mass of component (B). If the amount of component (A) is excessively large or small, the smoothness of the coating film of the curable composition may decrease, resulting in the appearance of multiple irregularities in the cured product. Furthermore, to improve the smoothness of the curable composition and improve the appearance of the cured product, the amount of component (A) is more preferably 0.05 to 5.0 parts by mass, and even more preferably 0.10 to 2.0 parts by mass. The amount of component (A) can be confirmed, for example, by the following method. When calculating the amount of component (A) from a cured product or curable composition that is a photochromic resin layer, first, the cured product or curable composition is dissolved in an organic solvent to obtain a sample. This sample is purified by gel filtration column chromatography or the like to isolate component (A). The isolated component (A) is then analyzed by the following method: 1 The structure of component (A) can be identified and its content calculated by H-NMR analysis, liquid chromatography mass spectroscopy (LC-MS), infrared absorption spectroscopy (IR), and gas chromatography mass spectroscopy (GC-MS).

[0061] When one type of component (B) is used, the amount of that component (B) is taken as 100 parts by mass. However, as explained below, the component (B) may contain multiple types of radical polymerizable monomers. When multiple types of radical polymerizable monomers are used as the component (B), the total amount of these multiple types of radical polymerizable monomers is taken as 100 parts by mass.

[0062] <(B) component> The component (B) can be the main component of the curable composition according to the embodiment. The component (B) can be the main component of the matrix in a cured product obtained from the curable composition. The component (B) is a radically polymerizable monomer. As the radically polymerizable monomer, a monomer having at least one radically polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinyl group can be used.

[0063] Component (B) preferably contains a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups in the molecule. In particular, it preferably contains a polyrotaxane having a (meth)acryloyl group and a weight-average molecular weight of 100,000 to 1,000,000. Hereinafter, this polyrotaxane will also be referred to as component (B1). Component (B) preferably contains a silsesquioxane having a radical polymerizable group and a weight-average molecular weight of 1,500 to 20,000. Hereinafter, this silsesquioxane will also be referred to as component (B2). Component (B) more preferably contains both component (B1) and component (B2). Using a curable composition containing at least one of component (B1) and component (B2), a cured product with excellent mechanical and photochromic properties can be obtained.

[0064] (B1) Component Component (B1) is a known compound and has a structure as shown in FIG. 1. FIG. 1 is a schematic diagram showing an example of the molecular structure of a polyrotaxane. Polyrotaxane 1 shown in FIG. 1 has multiple cyclic molecules 3, an axial molecule 2 that penetrates the inside of the rings of the multiple cyclic molecules 3, a bulky terminal group 4 that modifies the end of the axial molecule 2, and side chains 5 that bond to the multiple cyclic molecules 3. Note that, although one cyclic molecule 3 in FIG. 1 has multiple side chains 5, the cyclic molecule 3 may be bonded to only one side chain 5. Because component (B1) has the structure shown in FIG. 1, it can increase the flexibility of the matrix of the cured product. Therefore, when component (B1) is used, the structural change of the photochromic compound in the cured product is less likely to be hindered, and the photochromic properties of the cured product tend to be enhanced.

[0065] Various types of axial molecule 2 are known. For example, the axial molecule 2 may be a straight chain or a branched chain as long as it can penetrate the ring of the cyclic molecule 3, and is generally formed of a polymer.

[0066] In component (B1), the polymer forming the axial molecule is preferably polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, or polyvinyl methyl ether, with polyethylene glycol being most preferred.

[0067] Furthermore, the groups formed at both ends of the axial molecule are not particularly limited as long as they prevent the cyclic molecule from being detached from the axial molecule, but are preferably bulky groups (bulky terminal groups 4 in FIG. 1), such as adamantyl groups, trityl groups, fluoresceinyl groups, dinitrophenyl groups, and pyrenyl groups. The base Among these, an adamantyl group is particularly preferred in terms of ease of introduction.

[0068] The molecular weight of the axial molecule is not particularly limited, but if it is too large, compatibility with other components, such as other polymerizable monomers, tends to be poor, while if it is too small, the mobility of the cyclic molecule tends to decrease, resulting in poor photochromic properties. From this perspective, the weight-average molecular weight Mw of the axial molecule is preferably in the range of 1,000 to 100,000, particularly 5,000 to 80,000, and particularly preferably 8,000 to 30,000. Note that this weight-average molecular weight Mw is a value measured by the GPC measurement method described in the Examples below.

[0069] The cyclic molecule may be any molecule having a ring large enough to enclose the axial molecule, such as the above. Examples of such cyclic molecules include cyclodextrin rings, crown ether rings, benzocrown rings, dibenzocrown rings, and dicyclohexanocrown rings, with cyclodextrin rings being particularly preferred. Cyclodextrin rings include α-forms (inner ring diameter: 0.45-0.6 nm), β-forms (inner ring diameter: 0.6-0.8 nm), and γ-forms (inner ring diameter: 0.8-0.95 nm). Among these, α-cyclodextrin rings and γ-cyclodextrin rings are particularly preferred, with α-cyclodextrin rings being the most preferred.

[0070] A plurality of cyclic molecules having the above rings are included in one axial molecule. Generally, when the maximum number of cyclic molecules that can be included per axial molecule is 1, the inclusion number of the cyclic molecules is preferably in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, and even more preferably 0.003 to 0.4. If the inclusion number of the cyclic molecules is too high, the cyclic molecules are densely packed with one axial molecule, which reduces their mobility and tends to reduce the photochromic properties of the cured product. If the inclusion number is too low, the gap between the axial molecules becomes narrow, which reduces the flexibility that allows the photochromic compound molecules to undergo a reversible reaction, and tends to reduce the photochromic properties of the cured product.

[0071] As the component (B1), a polyrotaxane in which radical polymerizable groups have been introduced into the side chains 5 of the multiple cyclic molecules 3 shown in Fig. 1 is used. Such a component (B1) can be obtained, for example, by modifying a polyrotaxane in which the terminals of the side chains 5 are hydroxyl groups, using a known method.

[0072] The side chain having a hydroxyl group at its terminal is not particularly limited, but it is preferable to use a side chain formed by repeating an organic chain having a hydroxyl group at its terminal and a long chain carbon number in the range of 3 to 20. The average molecular weight of such a side chain is in the range of 300 to 10,000, preferably 350 to 8,000, more preferably 350 to 5,000, and most preferably 400 to 1,500. The average molecular weight of this side chain can be adjusted by the amount used when introducing the side chain, and can be determined by calculation, but 1 It can also be determined from H-NMR measurements.

[0073] The side chains having terminal hydroxyl groups as described above may be introduced by modifying the functional groups of the cyclic molecule. For example, an α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and side chains are introduced via these hydroxyl groups. That is, up to 18 side chains can be introduced to one α-cyclodextrin ring. To fully utilize the functions of the side chains described above, it is preferable that 6% or more, particularly 30% or more, of the total number of functional groups possessed by such rings be modified with side chains. Note that the functional groups possessed by the cyclic molecule may affect compatibility with other components, and in particular, hydroxyl groups have a significant impact on compatibility with other components. Therefore, the proportion of modified functional groups (modification degree) is preferably 6% to 80%, more preferably 30% to 70%.

[0074] The side chain having a terminal hydroxyl group as described above may be linear or branched, as long as it has a terminal hydroxyl group. Furthermore, a desired side chain can be obtained by introducing a side chain having a terminal hydroxyl group into a functional group of a cyclic molecule using living radical polymerization such as ring-opening polymerization, radical polymerization, cationic polymerization, anionic polymerization, atom transfer radical polymerization, RAFT polymerization, or NMP polymerization.

[0075] For example, a side chain derived from a cyclic compound such as a lactone or a cyclic ether can be introduced by ring-opening polymerization. The side chain introduced by ring-opening polymerization of a cyclic compound such as a lactone or a cyclic ether has a hydroxyl group introduced at the end of the side chain.

[0076] Among cyclic compounds, it is preferable to use cyclic ethers or lactone compounds from the viewpoints of easy availability, high reactivity, and ease of adjusting the size (molecular weight), and a lactone compound that is suitably used is preferably ε-caprolactone.

[0077] Furthermore, when introducing a side chain by reacting a cyclic compound by ring-opening polymerization, the functional group (e.g., hydroxyl group) attached to the ring has poor reactivity, and it may be difficult to directly react a large molecule, particularly due to steric hindrance. In such cases, for example, in order to react with caprolactone, a low molecular weight compound such as propylene oxide can be reacted with the functional group to hydroxypropylate it, introducing a highly reactive functional group (e.g., hydroxyl group) at the end, and then introducing a side chain by ring-opening polymerization using the aforementioned cyclic compound. In this case, the hydroxypropylated portion can also be considered a side chain.

[0078] In the component (B1), the terminal hydroxyl group of the side chain of the polyrotaxane is reacted with a compound having a radical polymerizable group to form the side chain of the polyrotaxane. of A polymerizable group is introduced at the end of the polymer. This reaction is called "modification."

[0079] The compound having a radical polymerizable group is introduced by utilizing a side chain having a hydroxyl group at the end, and a compound that reacts with the hydroxyl group of the side chain can be used appropriately. In addition, in consideration of compatibility with other components, the compound having this radical polymerizable group is preferably a compound that does not have a hydroxyl group in the molecule. As the radical polymerizable group, a (meth)acryloyl group is preferred.

[0080] A compound having a radical polymerizable group is a compound that has both a functional group capable of reacting with a hydroxyl group in a side chain and a polymerizable group in one molecule. Examples of functional groups capable of reacting with a hydroxyl group include an isocyanate group, a carboxyl group, and an acid chloride group (e.g., a -COCl group). By reacting a compound having an isocyanate group, a radical polymerizable group is introduced via a urethane bond. Alternatively, by reacting a compound having a carboxyl group, an acid chloride group, or the like, a radical polymerizable group is introduced via an ester bond.

[0081] For the reaction between a compound having a radical polymerizable group and a hydroxyl group on a side chain, known reaction conditions for a functional group reactive with a hydroxyl group and a hydroxyl group can be adopted.

[0082] For the component (B1), the modification ratio of the radical polymerizable group relative to the terminal hydroxyl groups of the side chain, i.e., the reaction ratio of the compound having the radical polymerizable group relative to the total number of moles of hydroxyl groups in the side chain, is preferably 1 mol % or more and less than 100 mol %. In consideration of the yield, mechanical strength, photochromic properties, etc. of the cured product obtained, the modification ratio with the compound having the radical polymerizable group is more preferably 10 mol % or more and 95 mol % or less, and even more preferably 30 mol % or more and 95 mol % or less. In consideration of the productivity of the polyrotaxane compound itself, a modification ratio of 70 mol % or more and 95 mol % or less is particularly preferred.

[0083] The modification ratio can be calculated by (number of moles of polymerizable groups introduced) / (number of moles of all hydroxyl groups in the side chains) × 100. As described in detail below, component (B2) can also be modified with a compound that does not have a radical polymerizable group. Therefore, the remaining hydroxyl groups in the side chains can also be modified with a compound that does not have a radical polymerizable group, as described in detail below. However, in this case, since the modification ratio is high, hydroxyl groups may remain.

[0084] It is essential that the component (B1) has the hydroxyl groups at the terminals of the side chains introduced into the cyclic molecule modified with a compound having a radical polymerizable group, and the remaining hydroxyl groups in the side chains (i.e., the hydroxyl groups at the terminals of the side chains introduced into the cyclic molecule that have not been modified with a compound having a radical polymerizable group) may remain as hydroxyl groups or may be modified with a compound that does not have a radical polymerizable group.

[0085] A compound having no radical polymerizable group has a functional group in one molecule that can react with a hydroxyl group in a side chain, but does not contain a radical polymerizable group in the molecule. Therefore, it is preferable that the compound having no radical polymerizable group has an alkyl group having 2 to 20 carbon atoms, an alkyleneoxy group having 2 to 30 carbon atoms, or an aryl group having 6 to 20 carbon atoms instead of a radical polymerizable group. Incidentally, examples of the functional group that can react with a hydroxyl group in a side chain include the same functional groups as those described in "compound having a radical polymerizable group."

[0086] As a compound having no radical polymerizable group, a compound having an isocyanate group is preferably an isocyanate compound having 2 to 20 carbon atoms (excluding the carbon atoms of the isocyanate group) from the viewpoints of easy availability of raw materials and high reactivity with hydroxyl groups. As a compound having no radical polymerizable group, a carboxylic acid chloride is preferably a carboxylic acid chloride having 2 to 20 carbon atoms (excluding the carbon atoms of the carbonyl group) from the viewpoints of easy availability of raw materials and high reactivity with hydroxyl groups.

[0087] The modification ratio with the compound having no radical polymerizable group can be calculated by (number of moles of the compound having no radical polymerizable group introduced) / (number of moles of all hydroxyl groups in the side chains) × 100. This modification ratio is not particularly limited. In particular, taking into consideration the yield, mechanical strength, photochromic properties, etc. of the cured product obtained, the modification ratio with the compound having no radical polymerizable group is preferably 0 to 99 mol%, more preferably 5 to 90 mol%, even more preferably 5 to 70 mol%, and particularly preferably 5 to 30 mol%.

[0088] Suitable structure and molecular weight of component (B1) Among the above-mentioned components, the (B1) component that is preferably used is preferably a cyclic molecule having an α-cyclodextrin ring and an axial molecule of polyethylene glycol bonded to both ends by adamantyl groups, and further having a side chain having a (meth)acryloyl group at the end introduced into the cyclic molecule by polycaprolactone.

[0089] Furthermore, the weight-average molecular weight Mw of component (B1) is preferably in the range of 100,000 to 1,000,000. Having the weight-average molecular weight Mw of component (B1) in this range improves compatibility with other components and further improves the transparency of the cured product. Considering compatibility with other components and the transparency of the cured product, the weight-average molecular weight Mw of component (B1) is more preferably in the range of 100,000 to 800,000, and even more preferably in the range of 100,000 to 500,000. This weight-average molecular weight Mw is a value measured using the GPC measurement method described in the Examples below.

[0090] Particularly suitable (B1) components are as follows: Preferably, the molecular weight of the axial molecule is 8,000 to 30,000, the ratio of α-cyclodextrin rings introduced is in the range of 0.003 to 0.4, and the ratio of α-cyclodextrin ring modification (modification degree) is 30% to 70%. The α-cyclodextrin rings preferably have side chains with an average molecular weight in the range of 400 to 1,500, and the ratio of modification of these side chains with (meth)acryloyl groups is 70% to 95% by mole. Based on these values, the number of (meth)acryloyl groups per molecule of (B1) component is preferably 10 to 1,000.

[0091] (B1) Amount of ingredient The amount of component (B1) is preferably 0 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (B).

[0092] (B2) Component Component (B2) is a radically polymerizable monomer containing silicon in the molecule and di- or higher-functional (meth)acryloyl groups. Component (B2) may be a silsesquioxane of a single structure, or a mixture of silsesquioxanes of multiple structures. Silsesquioxanes have a variety of molecular structures, including cage-like, ladder-like, and random structures. Because component (B2) has a cyclic siloxane structure, it can reduce the surface tension of the curable composition. Therefore, using a curable composition containing component (B2) tends to improve the smoothness of the coating film of the curable composition and produce a cured product with better appearance.

[0093] As the component (B2), it is preferable to use a silsesquioxane having a (meth)acryloyl group and a weight average molecular weight of 1,500 or more and 20,000 or less.

[0094] As the component (B2), it is preferable to use one represented by the following formula (6).

[0095] [ka]

[0096] (In the formula, k is the degree of polymerization and is an integer of 3 to 100, and 15 may be the same or different and are organic groups containing at least two or more (meth)acryloyl groups. 15 does not include groups containing chain organosiloxane groups.) where R 15In the above, the organic group containing a (meth)acryloyl group includes those containing only a (meth)acryloyl group (including those in which a (meth)acryloyl group is bonded directly to a silicon atom). Specifically, the (meth)acryloyl group may include not only a (meth)acryloyl group but also a (meth)acryloxypropyl group or a (3-(meth)acryloxypropyl)dimethylsiloxy group. Of these, the (meth)acryloxypropyl group is particularly preferred because the raw material for producing component (B2) is easily available and high film strength can be obtained while exhibiting excellent photochromic properties.

[0097] The weight average molecular weight Mw of the component (B2) is preferably 1,500 to 20,000, and the (meth)acrylic equivalent is preferably 150 to 800. The weight average molecular weight Mw of the component (B2) is a value measured by gel permeation chromatography (GPC).

[0098] Furthermore, the component (B2) preferably contains, on average, 10 or more (meth)acryloyl groups per molecule, and more preferably 10 to 100 (meth)acryloyl groups per molecule, and even more preferably 15 to 35 (meth)acryloyl groups per molecule.

[0099] The component (B2) can be synthesized, for example, according to the methods described in the cited literature (see Appl. Organometal. Chem. 2001, pp. 683-692) or patent documents (JP-A Nos. 2004-143449 and 1999-29640).

[0100] (B2) Amount of ingredients When the component (B) is taken as 100 parts by mass, the amount of the component (B2) is preferably 0 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.1 to 6 parts by mass.

[0101] Ingredient (B3) In addition to components (B1) and (B2), component (B) preferably contains component (B3) as another radically polymerizable monomer. The radically polymerizable group in component (B3) is preferably a (meth)acryloyl group. Examples of component (B3) include the following three types of acrylates:

[0102] a bifunctional (meth)acrylate having two (meth)acryloyl groups in the molecule (hereinafter also referred to simply as component (B31)), A polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule (hereinafter also referred to simply as component (B32)).

[0103] Monofunctional (meth)acrylate having one (meth)acryloyl group (hereinafter also referred to simply as component (B33)).

[0104] (B31) Ingredients Specific examples of the (B31) component include a component represented by the following formula (1) (hereinafter also referred to as the (B31a) component), a component represented by the following formula (2) (hereinafter also referred to as the (B31b) component), a component represented by the following formula (3) (hereinafter also referred to as the (B31c) component), and a bifunctional (meth)acrylate component having a urethane bond (hereinafter also referred to as the (B31d) component). Examples of the (B31) component include a bifunctional (meth)acrylate component other than the (B31a), (B31b), (B31c), and (B31d) components (hereinafter also referred to as the (B31e) component).

[0105] (B31a) Component [ka]

[0106] (In the formula, R 1 and R 2 are each a hydrogen atom or a methyl group, a and b are each independently an integer of 0 or greater, and a+b is an integer of 2 or greater. Specific examples of the compound represented by the above formula (1) are as follows.

[0107] Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate consisting of a mixture of polypropylene glycol and polyethylene glycol (having two repeating units of polyethylene and two repeating units of polypropylene), polyethylene glycol dimethacrylate (particularly a=4, b=0, average molecular weight 330), poly Polyethylene glycol dimethacrylate (especially a=9, b=0, average molecular weight 536), polyethylene glycol dimethacrylate (especially a=14, b=0, average molecular weight 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (especially a=0, b=7, average molecular weight 536), polyethylene glycol diacrylate (especially average molecular weight 258), polyethylene glycol diacrylate (especially a=4, b=0, average molecular weight 308), polyethylene glycol diacrylate (especially a=9, b=0, average molecular weight 508), polyethylene glycol diacrylate (especially a=14, b=0, average molecular weight 708), polyethylene glycol methacrylate acrylate (especially a=9, b=0, average molecular weight 522).

[0108] (B31b) Component [ka]

[0109] (In the formula, R 3 and R 4are each a hydrogen atom or a methyl group, R 5 and R 6 are each a hydrogen atom or a methyl group, R 7 is a hydrogen atom or a halogen atom, A is any one of -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, and -C(CH3)(C6H5)-; c and d are each an integer of 1 or greater, and c + d has an average value of 2 or greater and 30 or less.) The bifunctional (meth)acrylate represented by the above formula (2) is usually obtained in the form of a mixture of molecules with different molecular weights. Therefore, c and d are shown as average values.

[0110] A specific example of the bifunctional (meth)acrylate represented by the above formula (2) is the following bisphenol A di(meth)acrylate.

[0111] 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane (c+d=2, average molecular weight 452), 2,2-bis[4-(methacryloyloxydiethoxy)phenyl]propane (c+d=4, average molecular weight 540), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=7, average molecular weight 672), 2,2-bis[3,5-dibromo-4 -(methacryloyloxyethoxy)phenyl]propane (c+d=2, average molecular weight 768), 2,2-bis(4-(methacryloyloxydipropoxy)phenyl)propane (c+d=4, average molecular weight 596), 2,2-bis[4-(acryloyloxydiethoxy)phenyl]propane (c+d=4, average molecular weight 512), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=3, average molecular weight 466), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=7, average molecular weight 642), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=10, average molecular weight 804), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=17 , average molecular weight 1116), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=30, average molecular weight 1684), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=10, average molecular weight 776), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=20, average molecular weight 1216).

[0112] (B31c) Component [ka]

[0113] (In the formula, R 8 and R 9 are each a hydrogen atom or a methyl group, e is the average value and is a number between 1 and 20. B and B' may be the same or different and each represents a linear or branched alkylene group having 2 to 15 carbon atoms, and when there are multiple B's, the multiple B's may be the same or different groups.

[0114] The bifunctional (meth)acrylate represented by the above formula (3) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0115] Examples of the polycarbonate diol that can be used include the following: Specifically, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of trimethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of tetramethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of pentamethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of hexamethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of octamethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of nonamethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of triethylene glycol and tetramethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of tetramethylene glycol and hexamethylene glycol, ng Polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation with glycerol, polycarbonate obtained by phosgenation with pentamethylene glycol and hexamethylene glycol to Polycarbonate obtained by phosgenation of diol (average molecular weight 500-2000), tetramethylene glycol and octamethylene glycol todiol (average molecular weight 500 to 2000), polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of 1-methyltrimethylene glycol.

[0116] Ingredient (B31d) Component (B31d) is typically a reaction product of a polyol and a polyisocyanate, such as hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, or methylcyclohexane diisocyanate.

[0117] The polyol may be a polyalkylene glycol having a repeating unit of ethylene oxide, propylene oxide, or hexamethylene oxide having 2 to 4 carbon atoms. R Examples of the diol include polyester diols such as polyethylene glycol and polycaprolactone diol, polycarbonate diol, polybutadiene diol, pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, and trimethylolpropane.

[0118] In addition, a reaction mixture obtained by further reacting a urethane prepolymer obtained by the reaction of these polyisocyanates and polyols with 2-hydroxy(meth)acrylate, or a reaction mixture obtained by directly reacting a diisocyanate with 2-hydroxy(meth)acrylate, such as a urethane(meth)acrylate, can also be used.

[0119] Commercially available bifunctional copolymers include U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), and U-122P (molecular weight 1,100) manufactured by Shin-Nakamura Chemical Co., Ltd., EB4858 (molecular weight 454) manufactured by Daicel-UCB Ltd., TEAI-1000 and TE-2000 manufactured by Nippon Soda Co., Ltd., and CN9014 manufactured by Arkema.

[0120] (B31e) component Examples of the component (B31e) include compounds having (meth)acryloyl groups at both ends of an alkylene group that may have a substituent. Among these, compounds having an alkylene group with 6 to 20 carbon atoms are preferred. Specific examples include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, and 1,10-decanediol dimethacrylate.

[0121] Furthermore, the component (B31e) can also include butadiene di(meth)acrylate represented by the following formula (4).

[0122] [ka]

[0123] (In the formula, R 10 and R 11 are each a hydrogen atom or a methyl group, f, g, and h are each independently an integer of 0 or greater, and f+g+h is an integer of 1 or greater.

[0124] The bifunctional (meth)acrylate represented by the above formula (4) is not particularly limited, and examples of commercially available products include butadiene di(meth)acrylates such as BAC-45 manufactured by Osaka Organic Chemical Industry Co., Ltd. and CN307 manufactured by Arkema.

[0125] Further, the component (B31e) may also include a bifunctional (meth)acrylate containing a sulfur atom. Preferably, the sulfur atom forms part of the molecular chain as a sulfide group. Specific examples include bis(2-methacryloyloxyethylthioethyl)sulfide, bis(methacryloyloxyethyl)sulfide, bis(acryloyloxyethyl)sulfide, 1,2-bis(methacryloyloxyethylthio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2-bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyethylthioisopropyl)sulfide, and 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide.

[0126] The components (B31a), (B31b), (B31c), (B31d), and (B31e) can be used singly or in combination. When multiple components are used, the reference mass of component (B31) is the total mass of the multiple components. Although there are no particular limitations, when the total amount of the (B31) component is taken as 100 parts by mass, the (B31a) component is preferably 30 to 100 parts by mass, the (B31b) component is 0 to 70 parts by mass, the (B31c) component is 0 to 70 parts by mass, the (B31d) component is 0 to 70 parts by mass, and the (B31e) component is 0 to 70 parts by mass, and more preferably the (B31a) component is 40 to 95 parts by mass, the (B31b) component is 0 to 50 parts by mass, the (B31c) component is 5 to 60 parts by mass, the (B31d) component is 0 to 50 parts by mass, and the (B31e) component is 0 to 50 parts by mass.

[0127] (B32) Ingredients Examples of the (B32) component include a component represented by the following formula (5) (hereinafter also simply referred to as the (B32a) component), a polyfunctional (meth)acrylate having a urethane bond (hereinafter also simply referred to as the (B32b) component), and a polyfunctional (meth)acrylate that does not fall under the category of the (B32a) component or the (B32b) component (hereinafter also simply referred to as the (B32c) component).

[0128] Ingredient (B32a) [ka]

[0129] (In the formula, R 12 is a hydrogen atom or a methyl group, R 13 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R 14 is a trivalent to hexavalent organic group having 1 to 10 carbon atoms, i is the average value and is a number between 0 and 3, and j is a number between 3 and 6.

[0130] R13 The alkyl group having 1 to 2 carbon atoms represented by R is preferably a methyl group. 14 Examples of the organic group represented by the formula (I) include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and an organic group containing a trivalent to hexavalent urethane bond. Specific examples of the compound represented by the above formula (5) are as follows:

[0131] Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.

[0132] (B32b) Component Component (B32b) is obtained by reacting the polyisocyanate compound described in component (B31d) with a polyol compound, and is a compound having three or more (meth)acryloyl groups in the molecule. Commercially available products include U-4HA (molecular weight 596, number of functional groups 4), U-6HA (molecular weight 1,019, number of functional groups 6), U-6LPA (molecular weight 818, number of functional groups 6), and U-15HA (molecular weight 2,300, number of functional groups 15), all manufactured by Shin-Nakamura Chemical Co., Ltd.

[0133] (B32c) Component Examples of the (B32c) component include compounds in which the terminals of polyester compounds are modified with (meth)acryloyl groups. Various commercially available polyester (meth)acrylate compounds can be used, depending on the molecular weight of the raw polyester compound and the amount of (meth)acryloyl group modification. Specific examples include tetrafunctional polyester oligomers (molecular weight 2,500 to 3,500, Daicel-UCB, EB80, etc.), hexafunctional polyester oligomers (molecular weight 6,000 to 8,000, Daicel-UCB, EB450, etc.), hexafunctional polyester oligomers (molecular weight 45,000 to 55,000, Daicel-UCB, EB1830, etc.), and tetrafunctional polyester oligomers (e.g., GX8488B, Dai-ichi Kogyo Seiyaku, molecular weight 10,000, etc.). Other commercially available products include CN2300, CN2301, CN2302, CN2303, CN2304, SB401, SB402, SB404, SB500E50, SB500K60, SB510E35, SB520E35, SB520M35, CN550, and CN551 manufactured by Arkema, and A-DPH-6E, A-DPH-12E, A-DPH-6EL, A-DPH-12EL, and A-DPH-6P manufactured by Shin-Nakamura Chemical Co., Ltd.

[0134] The use of the above-exemplified (B32) components (component (B32a), component (B32b), and component (B32c)) improves the crosslink density through polymerization, thereby increasing the surface hardness of the resulting cured product. Therefore, it is particularly preferable to include component (B32) when preparing a photochromic cured product (laminate) obtained by a coating method.

[0135] The above components (B32a), (B32b), and (B32c) can be used either individually or in combination. When multiple components are used, the reference mass of component (B32) is the total mass of the multiple components. While not subject to any particular limitations, it is preferred that, when the total amount of component (B32) is 100 parts by mass, component (B32a) be 50 to 100 parts by mass, component (B32b) be 0 to 50 parts by mass, and component (B32c) be 0 to 50 parts by mass.

[0136] (B33) ingredient The component (B33) may be a compound represented by the following formula (7). [ka]

[0137] (In the formula, R 16 is a hydrogen atom or a methyl group, R 17 is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group, l is an integer from 0 to 10, and m is an integer from 0 to 20. Specific examples of the compound represented by the above formula (7) are as follows:

[0138] Methoxypolyethylene glycol methacrylate (especially average molecular weight 293), methoxypolyethylene glycol methacrylate (especially average molecular weight 468), methoxypolyethylene glycol acrylate (especially average molecular weight 218), methoxypolyethylene glycol acrylate (especially average molecular weight 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate, tridecyl acrylate, tridecyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate.

[0139] (B) Optimal blending ratio of ingredients The component (B) preferably includes the components (B1), (B2), and (B3).

[0140] When component (B) contains only component (B3), the amounts of component (B31) are preferably 30 to 80 parts by mass, component (B32) are 10 to 60 parts by mass, and component (B33) are 0.1 to 20 parts by mass, and the amounts of component (B31) are preferably 40 to 75 parts by mass, component (B32) are 15 to 55 parts by mass, and component (B33) are 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of component (B).

[0141] When the composition contains component (B1) but does not contain component (B2), the amounts of component (B1), component (B31), component (B32), component (B33), and component (B33) are preferably 0.1 to 20 parts by mass, 30 to 80 parts by mass, 10 to 60 parts by mass, and 0.1 to 10 parts by mass, respectively, based on 100 parts by mass of component (B). The amounts of component (B1), component (B31), component (B32), component (B33), and component (B33) are preferably 0.5 to 10 parts by mass, 40 to 75 parts by mass, 15 to 55 parts by mass, and 0.5 to 10 parts by mass, respectively.

[0142] When the composition contains component (B2) but does not contain component (B1), the amounts of component (B2), component (B31), component (B32), and component (B33) are preferably 0.1 to 8 parts by mass, 30 to 80 parts by mass, 10 to 60 parts by mass, and 0.1 to 20 parts by mass, respectively, based on 100 parts by mass of component (B). The amounts of component (B2), component (B31), component (B32), and component (B33) are preferably 0.1 to 6 parts by mass, 40 to 75 parts by mass, 15 to 55 parts by mass, and 0.5 to 10 parts by mass, respectively.

[0143] When both component (B1) and component (B2) are contained, the amounts of component (B1), component (B2), component (B3), component (B31), component (B32), component (B33), and component (B33) are preferably 0.1 to 20 parts by mass, 0.1 to 8 parts by mass, 30 to 80 parts by mass, 10 to 60 parts by mass, and 0.1 to 20 parts by mass, respectively, based on 100 parts by mass of component (B).More preferably, the amounts of component (B1), component (B2), component (B31), component (B32), component (B32), component (B33) are preferably 0.5 to 10 parts by mass, 0.1 to 6 parts by mass, 40 to 75 parts by mass, 15 to 55 parts by mass, and 0.5 to 10 parts by mass, respectively.

[0144] Considering compatibility with other components, solubility, coating properties of the photochromic curable composition, and wetting properties of the polyurethane resin layer laminated on an optical substrate, the SP value of component (B) is preferably 7.0 to 12.0. The SP value of component (B) can be determined by titration using the turbidimetric titration method described in detail below. The SP value can be calculated in accordance with the description of the solubility parameter δ in the Applied Chemistry Handbook (Applied Edition) edited by the Chemical Society of Japan (published in 1973) and Polymer Handbook (4th edition, edited by Johannes Brandrup and EH Immergut, published in 1998).

[0145] Although it is only a guess, it is believed that the excellent effect is achieved because the SP value of component (B) is close to the SP value of component (A). In order to achieve even better effects, the SP value of component (B) is more preferably 7.5 to 12.0, even more preferably 7.5 to 11.5, and particularly preferably 8.0 to 11.0.

[0146] <(C) component> As the component (C), there are no limitations and any known substance can be used, and these can be used alone or in combination of two or more types.

[0147] Representative photochromic compounds include fulgide compounds, chromene compounds, and spirooxazine compounds, which are disclosed in many documents, such as JP-A-2-28154, JP-A-62-288830, WO94 / 22850, and WO96 / 14596.

[0148] Among known photochromic compounds, it is more preferable to use chromene compounds having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton from the viewpoint of photochromic properties such as color density, initial coloring, durability, and color fading speed. In particular, chromene compounds having a molecular weight of 540 or more are preferably used because they are particularly excellent in color density and color fading speed.

[0149] The chromene compounds shown below are examples of chromene compounds that are particularly suitable for use in the present invention, but the present invention is not limited to these.

[0150] [ka]

[0151] In addition to the above, photochromic compounds having an oligomer chain group in the molecule can also be suitably used. Such photochromic compounds having an oligomer chain group are disclosed in many documents, such as WO2000 / 015630 pamphlet, WO2004 / 041961 pamphlet, WO2009 / 146509 pamphlet, WO2012 / 149599 pamphlet, WO2012 / 162725 pamphlet, WO2013 / 078086 pamphlet, WO2019 / 013249 pamphlet, and WO2019 / 203205 pamphlet. Among these photochromic compounds having an oligomer chain group in the molecule, it is preferable to use photochromic compounds having an oligomer chain group described in WO2019 / 013249 pamphlet and WO2019 / 203205 pamphlet, as they exhibit better photochromic properties and durability. The photochromic compounds having oligomer chain groups shown below are particularly suitable examples of compounds that can be used, but are not limited to these.

[0152] [ka]

[0153] Component (C) may also be a compound having, as a substituent, a group containing a long chain with a molecular weight of 300 or more. A molecular weight of 300 or more refers to the molecular weight of only the long chain portion. Such a long chain is preferably at least one group selected from a polysiloxane chain, a polyoxyalkylene chain, a polyester chain, and a polyester polyether chain. A long chain with a molecular weight of 300 or more may be composed of a single repeating structure or may be a block copolymer or graft copolymer of multiple repeating structures. When the long chain is a copolymer of multiple repeating structures, the molecular weight of the long chain refers to the average molecular weight of each repeating structure. This average value is the number-average molecular weight. This molecular weight can be confirmed based on the type of raw material used in the production of the photochromic compound. When checking the product, it can be confirmed by known means such as NMR, IR, or mass spectrometry.

[0154] It is believed that component (C) can exhibit higher photochromic properties in component (B) by having a long-chain group with a molecular weight of 300 or more. Taking into consideration the photochromic properties, the amount of the long-chain group added, and the productivity of component (C) itself, the molecular weight of the long-chain group is preferably 300 to 25,000, more preferably 400 to 20,000, even more preferably 440 to 15,000, and particularly preferably 500 to 10,000. The number of long-chain groups per molecule of the photochromic compound is preferably at least 0.5 or more. That is, a photochromic compound having a structure in which two photochromic moieties are bonded via a group containing a long chain may be used. In consideration of the balance with the molecular weight of the molecular chain, photochromic properties, etc., the number of long-chain groups per molecule of the photochromic moiety is preferably 4 or less, more preferably 2 or less, and even more preferably 1.

[0155] Considering the photochromic properties such as the color density and fading rate of the resulting photochromic cured product, the blending amount of component (C) is preferably the following amount: That is, when component (B) is taken as 100 parts by mass, the blending amount of component (C) is preferably 0.001 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, and even more preferably 0.1 to 10 parts by mass.

[0156] <(D) component> The photochromic curable composition according to the embodiment may further contain an organic compound having a boiling point of 80°C or higher and 200°C or lower and an SP value of 8.0 to 10.0. Hereinafter, this organic compound is also referred to as component (D). The SP value referred to here is a value that is sometimes called the solubility parameter or Hildebrand parameter.

[0157] The use of a curable composition containing component (D) can improve the appearance of the cured product. Specifically, component (D) has a relatively high boiling point, so trace amounts may remain in the cured product. Because component (D) has an SP value within the above range, it is highly compatible with the acrylic adhesive of the protective film described above. Therefore, when the acrylic adhesive that has flowed out from the adhesive surface of the protective film penetrates into the photochromic resin layer, the trace amount of component (D) remaining in the photochromic resin layer can be compatible with the acrylic adhesive, which is a foreign substance. This can prevent the acrylic adhesive from aggregating within the photochromic resin layer. Therefore, the appearance defects such as thin lines and stripes that are often seen within the photochromic resin layer due to the acrylic adhesive described above are less likely to occur.

[0158] The SP value of component (D) is preferably 8.0 to 9.5, and more preferably 8.0 to 9.0. When the SP value of component (D) is within this range, the curable composition tends to be easier to coat, and production efficiency tends to be improved.

[0159] The boiling point of component (D) is preferably 85°C or higher and 200°C or lower, more preferably 95°C or higher and 200°C or lower, and even more preferably 110°C or higher and 170°C or lower. A high boiling point of component (D) tends to improve the appearance of the cured product. A low boiling point of component (D) tends to improve the adhesion and durability of the cured product.

[0160] There are no particular limitations on the component (D) as long as its SP value and boiling point fall within the ranges, but considering compatibility with the preferred component (B) described below, the following organic compounds are preferred. Aromatic compounds such as toluene (boiling point 111°C, SP value 8.8), xylene (boiling point 138°C, SP value 8.7), and styrene (boiling point 145°C, SP value 8.5); Ketone compounds such as methyl propyl ketone (boiling point 105°C, SP value 8.7), methyl isopropyl ketone (boiling point 95°C, SP value 8.5), diethyl ketone (boiling point 101°C, SP value 8.8), and methyl isobutyl ketone (boiling point 116°C, SP value 8.4); Ester compounds such as butyl acetate (boiling point 124°C, SP value 8.5), isopropyl acetate (boiling point 89°C, SP value 8.4), isobutyl acetate (boiling point 116°C, SP value 8.3), and ethyl acetate (boiling point 80°C, SP value 9.1); Ether compounds such as diethylene glycol dimethyl ether (boiling point 162°C, SP value 9.9) and propylene glycol monomethyl ether (boiling point 120°C, SP value 9.1); Suitable organic compounds include cyclic alkyl compounds such as cyclohexane (boiling point 81° C., SP value 8.2), etc. Commercially available products can be used.

[0161] Among these, from the viewpoint of compatibility with component (B), component (D) preferably contains at least one selected from the group consisting of ether compounds, ester compounds, aromatic compounds, ketone compounds, and cyclic alkyl compounds, and more preferably contains at least one selected from the group consisting of ester compounds and aromatic compounds. Among these, butyl acetate, toluene, or xylene is preferred, toluene or xylene is more preferred, and xylene is particularly preferred. Xylene may be a mixture containing isomers.

[0162] These (D) components can be used alone or in combination of two or more. When two or more components are used, the reference amount of (D) component is the total amount of these (D) components. In addition, styrene and methyl methacrylate listed here have radical polymerizable groups, but are also included in the (D) component.

[0163] The amount of component (D) used is preferably 0.1 to 10 parts by mass, based on 100 parts by mass of component (B). When the amount of component (D) used satisfies this range, compatibility with component (B) can be enhanced, and the smoothness of the resulting photochromic layer can be further improved. As a result, the occurrence of poor appearance can be further suppressed. The adhesion and durability of the photochromic resin layer can also be improved. The amount of component (D) used is more preferably 0.5 to 9 parts by mass, and particularly preferably 1.0 to 6 parts by mass, based on 100 parts by mass of component (B).

[0164] <(E) component> The curable composition according to the embodiment may further include a hindered amine component as the component (E). The hindered amine functions as a light stabilizer. Use of a curable composition containing the component (E) improves the durability of the cured product. Examples of the component (E) include the following components (E1) and (E2). The component (E) may include either the component (E1) or the component (E2), but preferably includes both.

[0165] Component (E1) Component (E1) is a reactive hindered amine compound having at least one reactive group selected from the group consisting of a radically polymerizable group and a group reactive with the radically polymerizable group. The use of such component (E1) tends to improve the appearance of the cured product. The reasons for this are explained below. First, hindered amine light stabilizers (HALS) can bleed out, meaning that they exude from the cured product to its surface over time. HALS is also thought to have a high affinity with the acrylic adhesive used in the protective film. Therefore, the use of a curable composition containing HALS not only improves light stability but also facilitates penetration of the acrylic adhesive into the photochromic resin layer. To address this issue, component (E1) contains a radically reactive group. Therefore, like component (A), component (E1) forms a complex with component (B) in the cured product, which is thought to reduce bleed-out to the surface of the photochromic resin layer. Therefore, when the component (E1) is contained, the acrylic adhesive derived from the protective film described above becomes more difficult to penetrate into the photochromic resin layer, and poor appearance of the cured product becomes less likely to occur.

[0166] In the component (E1), examples of the radically polymerizable group include a (meth)acryloyl group (a methacryloyl group and / or an acryloyl group), a vinyl group, etc. Examples of the group that reacts with the radically polymerizable group include a thiol group, an amino group, an epoxy group, etc.

[0167] The component (E1) is 1, It preferably has a 2,2,6,6-pentamethyl-4-piperidyl structure, and more specifically, it is preferably a compound represented by the following formula (X) (hereinafter, sometimes referred to as component (E1X)).

[0168] [ka]

[0169] In formula (X), R 100 , and R 300 are each a hydrogen atom or a methyl group, X is a group represented by the following formula (Z): R 200 is an alkylene group having 1 to 5 carbon atoms, t is a number between 0 and 20 with an average value, u is a number between 0 and 20 with an average value,

[0170] [ka]

[0171] In formula (Z), R 400 is an alkylene group having 1 to 20 carbon atoms, v is a number between 0 and 20 with an average value.

[0172] In the above formula, t, u, and v are shown as average values, because they are often obtained as a mixture during production.

[0173] In formula (X), R 300 is preferably a methyl group. 100 is a hydrogen atom or a methyl group.

[0174] X is a divalent group represented by formula (Z). In formula (Z), R 400 is an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be linear or branched. 400 is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and more preferably a linear or branched alkylene group having 1 to 3 carbon atoms. In order to exert excellent effects, v is preferably small, and is preferably a number from 0 to 10 on average, and more preferably a number from 0 to 5 on average.

[0175] R 200is an alkylene group having 1 to 10 carbon atoms, and the alkylene group may be linear or branched. In order to exert excellent effects, a linear or branched alkylene group having 1 to 5 carbon atoms is more preferable. In order to exert excellent effects, it is preferable that t is small, and it is preferably a number from 0 to 10 on average, and more preferably a number from 0 to 5 on average.

[0176] u is a number on average from 0 to 20. In particular, in order to exert excellent effects, it is preferable that u is small, and it is preferably a number on average from 0 to 3, and more preferably a number on average from 0 to 2.

[0177] The component (E1X) is a known compound, and commercially available products can be used, such as LA-82 and LA-87 manufactured by ADEKA Corporation.

[0178] Among the (E1X) ingredients, R is particularly effective. 100 , and R 300 is a methyl group, and t, u, and v are 0 (X is an oxygen atom).

[0179] Specifically, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate is preferred. Among the components (E1X), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate can maintain high stability of the photochromic curable composition itself and the photochromic optical article, even when used in a relatively small amount.

[0180] When the curable composition according to the embodiment contains the (E1) component, the amount of the (E1) component per 100 parts by mass of the (B) component is preferably 0.5 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 3.0 parts by mass or less.

[0181] (E2) Component Component (E2) is a non-reactive hindered amine compound that does not have a reactive group selected from the group consisting of a radically polymerizable group and a group that reacts with a radically polymerizable group. In other words, component (E2) is a conventionally commonly used HALS. Component (E2) is thought to have a higher light stability effect than component (E1) in the photochromic resin layer that is the cured product of the curable composition. From the viewpoint of further improving the appearance of the cured product, it is preferable to incorporate component (E1) in addition to component (E2) into the curable composition.

[0182] The component (E2) is not particularly limited, but it is preferable to use a compound represented by the following formula (Y) (hereinafter sometimes simply referred to as "component (E2Y)").

[0183] [ka]

[0184] In formula (Y), R 500 , and R 600 are each a hydrogen atom or a methyl group, W is an integer of 1 to 50.

[0185] Among the (E2Y) components, R 500 , and R 600Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, in which ≡ is a methyl group and w is 8, is preferred. When using component (E2Y), component (E2) can contain bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, which is component (E2Y), and the (1,2,2,6,6-pentamethyl-4-piperidyl)sebacate inevitably contained therein. In this case, the amount of component (E2) is based on the total amount of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and (1,2,2,6,6-pentamethyl-4-piperidyl)sebacate. Naturally, (1,2,2,6,6-pentamethyl-4-piperidyl)sebacate falls under component (E2) other than component (E2Y).

[0186] The component (E2) may consist solely of the component (E2Y), or may consist of the component (E2Y) and (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Furthermore, the component (E2) may contain the component (E2Y) and a component (E2) other than the component (E2Y) and (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Furthermore, the component (E2) may contain the component (E2Y) and (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, plus a component (E2) other than these. To achieve even better effects, the component (E2) may contain bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as the component (E2Y), and may also contain (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

[0187] When the curable composition according to the embodiment contains the (E2) component, the amount of the (E2) component per 100 parts by mass of the (B) component is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 3.0 parts by mass or less.

[0188] Suitable blending ratio of components (E1) and (E2) in component (E) The (E) component preferably contains 0 to 500 parts by mass of the (E2) component relative to 100 parts by mass of the (E1) component. By satisfying this range, it is possible to achieve good repeated use durability while sufficiently suppressing poor appearance due to the scratch-resistant protective film. Furthermore, in consideration of photochromic properties, storage stability, and other properties, it is preferable to contain both the (E1) component and the (E2) component. When the curable composition according to the embodiment contains both the (E1) and (E2) components, it preferably contains 1 to 300 parts by mass of the (E2) component relative to 100 parts by mass of the (E1) component, more preferably 1 to 200 parts by mass, even more preferably 1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass.

[0189] (E) Optimal blending ratio of ingredients The amount of component (E) per 100 parts by mass of component (B) is preferably 0.1 parts by mass or more and 5.0 parts by mass or less. By satisfying this range, good photochromic properties and repeated use durability can be obtained, and good storage stability can be achieved. Furthermore, to improve storage stability, the amount is more preferably 0.5 parts by mass or more and 4.0 parts by mass or less, even more preferably 1.0 parts by mass or more and 3.5 parts by mass or less, and particularly preferably 1.0 parts by mass or more and 2.8 parts by mass or less.

[0190] <Additives> The photochromic curable composition according to the embodiment may contain various known additives within a range that does not impair the effects of the composition, such as a polymerization initiator, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, a stabilizer, a solvent, and a leveling agent.

[0191] The amount of the additive used is, for example, in the range of 0.001 to 10 parts by mass, particularly 0.01 to 7.5 parts by mass, and even more particularly 0.05 to 6 parts by mass, per 100 parts by mass of the component (B).

[0192] polymerization initiator The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator, and specific examples thereof are as follows:

[0193] Examples of thermal polymerization initiators include: Diacyl peroxide; benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, Peroxyesters: t-butyl peroxy-2-ethylhexanate, t-butyl peroxyneodecanate, cumyl peroxyneodecanate, t-butyl peroxybenzoate, Peroxydicarbonate; diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, Azo compounds; Azobisisobutyronitrile etc.

[0194] Photopolymerization initiators include: Acetophenone compounds; 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, α-Dicarbonyl compounds; 1,2-diphenylethanedione, methylphenylglycoxylate, Acylphosphine oxide compounds: 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, Examples include:

[0195] When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine can also be used in combination.

[0196] UV stabilizers UV stabilizers are preferably used because they can improve the durability of the photochromic compound. The UV stabilizer referred to here does not include component (A). Examples of such UV stabilizers include hindered phenol antioxidants and sulfur-based antioxidants. Particularly suitable UV stabilizers include 2,6-di-t-butyl-4-methylphenol, ethylene bis(oxyethylene) bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], and IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, 254, and 245 manufactured by Ciba Specialty Chemicals.

[0197] The amount of UV stabilizer used is not particularly limited as long as it does not impair the effects of the present invention, but is in the range of 0.001 to 10 parts by mass, particularly 0.01 to 3 parts by mass, per 100 parts by mass of component (B).

[0198] Leveling Agent The photochromic curable composition according to the embodiment may also contain a leveling agent such as a non-reactive silicone oil, provided that the effect is not impaired. The non-reactive silicone oil is not particularly limited, and commercially available products such as KF-351A, KF-352A, FL-5, X-22-821, X-22-822, KF-412, and KF-414 manufactured by Shin-Etsu Chemical Co., Ltd., and L7001, FZ2104, and FZ2110 manufactured by Dow Corning Toray Co., Ltd., may be used. A reactive leveling agent without a siloxane bond may also be used. The reactive leveling agent is not particularly limited, and commercially available products such as ADEKA REASOAP SR-10, SR-20, SR-1025, SR-3025, ER-10, ER-20, ER-30, ER-40, NE-10, and NE-20 manufactured by ADEKA Corporation may be used. As mentioned above, the use of these leveling agents can degrade the appearance of the photochromic cured product. In the photochromic curable composition according to the embodiment, component (A) functions as a leveling agent, so a photochromic resin layer with excellent smoothness can be obtained even if the amount of these conventional leveling agents used is reduced or not used at all. When the curable composition according to the embodiment contains a non-reactive silicone oil, the amount is preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, per 100 parts by mass of component (B). It is even more preferable that the curable composition according to the embodiment does not contain a non-reactive silicone oil, and that the amount is 0 parts by mass per 100 parts by mass of component (B).

[0199] catalyst Furthermore, the photochromic curable composition according to the embodiment may contain a catalyst to react the radically polymerizable group with a group reactive with the radically polymerizable group, as long as the effect is not impaired. The catalyst is not particularly limited, and examples thereof include triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri-n-propylphosphine, hexylamine, dipropylamine, triethylamine, 1,8-bis(dimethylamino)naphthalene, diazabicycloundecene, and diazabicyclononene. The use of these catalysts may reduce the durability of the photochromic cured product. When the curable composition according to the embodiment contains a catalyst, the amount is not particularly limited, but the amount is preferably 0.000001 parts by mass or less per 100 parts by mass of component (A). amount The content is preferably from 0.00001 to 3 parts by mass, and particularly preferably from 0.00001 to 2 parts by mass.

[0200] <Method for producing photochromic curable composition> The photochromic curable composition according to the embodiment can be produced by mixing the components (A), (B), and (C), as well as other additive components (including components (D) and (E)) that are blended as needed. The procedure for blending the components is not particularly limited. In particular, the components (B) and (C) can be blended together in advance, and then the component (E) can be added as needed once the component (C) is sufficiently dispersed in the component (B). It is also possible to further blend the component (A) and, as needed, the component (D). In this case, the other additive components may be blended at any time.

[0201] The SP value of the photochromic curable composition is not particularly limited. In consideration of the uniform dispersion of each component, the coating properties of the photochromic curable composition, and the wettability of the composition to a polyurethane resin layer laminated on an optical substrate, the SP value is preferably 7.0 to 12.0, more preferably 7.5 to 12.0, even more preferably 7.5 to 11.5, and particularly preferably 8.0 to 11.0. The SP value is determined by titration using the turbidimetric titration method described in detail below.

[0202] <Photochromic cured material> The photochromic cured product can be obtained by curing the photochromic curable composition.

[0203] The photochromic curable composition is cured by inducing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, γ-rays, and LEDs, or by heat, or by a combination of both. That is, an appropriate curing method may be adopted depending on the types of polymerizable monomers and polymerization curing accelerators used and the form of the photochromic cured product to be formed. When the photochromic laminate is formed by the coating method described below, it is preferable to adopt photopolymerization because a uniform film thickness can be obtained.

[0204] When photopolymerizing a photochromic curable composition, the curing conditions, particularly UV intensity, affect the properties of the resulting photochromic laminate. The illuminance conditions cannot be generally limited because they are affected by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, but are generally 10 to 500 mW / cm at a wavelength of 365 nm. 2 It is preferable to select conditions such that the UV light is irradiated for 0.1 to 5 minutes. The curable composition according to the embodiment contains component (A), which can suppress the orientation of the leveling agent on the surface of the cured product. Therefore, the curable composition can be sufficiently cured without excessively increasing the intensity of the UV light, which can suppress the orientation of the leveling agent and improve production efficiency.

[0205] <Photochromic laminate> The photochromic laminate includes an optical substrate, a photochromic resin layer which is a cured product of a curable composition, and a polyurethane resin layer located between the optical substrate and the photochromic resin layer. The polyurethane resin layer may be omitted.

[0206] When a photochromic laminate is obtained by a coating method, a photochromic curable composition is used as a coating liquid, and the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and then polymerization and curing is carried out by UV irradiation, heating, or the like in an inert gas such as nitrogen, thereby obtaining a laminate in which a photochromic layer made of a photochromic cured product is laminated on the surface of the optical substrate.

[0207] Examples of optical substrates include those used in eyeglass lenses, window glass for houses and automobiles, etc. Specific materials for optical substrates include plastic materials such as (meth)acrylic resins, polycarbonate resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins, as well as glass.

[0208] When forming a photochromic laminate on the surface of an optical substrate by the above-mentioned coating method, it is preferable to enhance the adhesion between the photochromic laminate and the optical substrate by previously subjecting the surface of the optical substrate to a chemical treatment using an alkaline solution, an acid solution, or the like, or a physical treatment using corona discharge, plasma discharge, polishing, or the like. It is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate. This transparent adhesive resin layer is preferably a polyurethane resin layer. That is, it is preferable to form a photochromic laminate having a laminate structure in which a polyurethane resin layer and a resin layer containing a photochromic compound are laminated in this order on the surface of the optical substrate.

[0209] The polyurethane resin layer is preferably formed by applying a coating liquid containing at least one component selected from the group consisting of polyurethane resins and moisture-curable urethane resin precursors that can be cured by moisture in the air, and a solvent having a boiling point of 70°C or higher and an SP value of 8.0 or higher, to the surface of the optical substrate, and then removing the solvent.

[0210] Specifically, it is preferable to manufacture a photochromic laminate through the following steps: First, a coating liquid containing at least one component selected from the group consisting of polyurethane resins and moisture-curable urethane resin precursors that can be cured by moisture in the air, and a solvent with a boiling point of 70°C or higher and an SP value of 8.0 or higher is applied to the surface of an optical substrate, and then the solvent is removed to form a polyurethane resin layer.

[0211] A commercially available coating liquid can be used. It is particularly preferable to use a coating liquid having a solid content of 15 to 40 mass % containing at least one component selected from the group consisting of polyurethane resins and moisture-curable urethane resin precursors that can be cured by moisture in the air, and a solvent having an SP value of 8.0 or more of 60 to 85 mass % (note that this range is when the total amount of the solid content and solvent is taken as 100 mass %, and any other known components may be blended into the coating liquid).

[0212] As the solvent having an SP value of 8.0 or more, the same organic compounds as those exemplified as those having an SP value of 8.0 or more in component (D) can be used. Specifically, solvents having a boiling point of 70°C or more and an SP value of 8.0 or more include toluene (boiling point 111°C, SP value 8.8), xylene (boiling point 138°C, SP value 8.7), ethyl acetate (boiling point 77°C, SP value 9.0), methyl propyl ketone (boiling point 105°C, SP value 8.7), butyl acetate (boiling point 124°C, SP value 8.5), methyl isopropyl ketone (boiling point 95°C, SP value 8.5), isopropyl acetate (boiling point 89°C, SP value 9.0), ...methyl propyl ketone (boiling point 95°C, SP value 8.5), methyl propyl ketone (boiling point 95°C, SP value 8.5), methyl propyl ketone (boiling point 95°C, SP value 8.5), methyl propyl ketone (boiling point 95°C, SP value 8.5), methyl propyl ketone (boiling point 95°C, SP value 8.5), methyl propyl ketone (boiling point Examples of solvents include isobutyl acetate (boiling point 116°C, SP value 8.4), isobutyl acetate (boiling point 116°C, SP value 8.3), methyl isobutyl ketone (boiling point 116°C, SP value 8.5), ethylene glycol dimethyl ether (boiling point 85°C, SP value 8.6), propylene glycol monoethyl ether acetate (boiling point 146°C, SP value 8.6), methyl acetoacetate (boiling point 170°C, SP value 8.4), and diethyl ketone (boiling point 101°C, SP value 8.8). These solvents may be used alone or in combination with two or more solvents. When a mixed solvent is used, the total amount of the mixed solvent is used as the basis. The SP value of the mixture is also used.

[0213] The polyurethane resin layer can be formed by applying the coating liquid to the optical substrate and then removing the solvent. When the coating liquid contains a moisture-curing urethane resin precursor, the polyurethane resin layer can be formed by curing the precursor with moisture in the air.

[0214] The thickness of the polyurethane resin layer is not particularly limited, but is preferably 2.0 to 10.0 μm.

[0215] Next, a photochromic curable composition is applied onto the polyurethane resin layer, and the coating is cured to form a photochromic resin layer. This allows for the production of a photochromic laminate in which the optical substrate and the photochromic resin layer are bonded via the polyurethane resin layer. The thickness of the photochromic resin layer is not particularly limited, but is generally 30 to 50 μm.

[0216] Furthermore, when the photochromic curable composition is applied onto a polyurethane resin layer, it is believed that a trace amount of solvent having a boiling point of 70°C or higher and an SP value of 8.0 or higher may remain in the polyurethane resin layer. Because this trace amount of remaining solvent is highly compatible with component (D) contained in the curable composition, when component (D) is blended, a photochromic resin layer with superior smoothness can be obtained and production efficiency tends to be improved.

[0217] Although the coating method has been described, the photochromic curable composition according to the embodiment can also be used to produce a photochromic cured product by known methods such as cast polymerization, lamination, dip coating, flow coating, spraying, and binder methods.

[0218] The photochromic cured body and laminate according to the embodiment may contain a dye such as a disperse dye depending on the intended use. A hard coat layer may be further laminated on the photochromic resin layer of the laminate. The hard coat layer may be obtained by applying a hard coat agent containing, for example, an oxide sol of silicon, zirconium, antimony, aluminum, tin, tungsten, or the like as a main component and including a silane coupling agent to the photochromic resin layer and curing the resulting film. Alternatively, the hard coat layer may be formed by vapor-depositing a metal oxide such as SiO2, TiO2, or ZrO2 onto the photochromic resin layer. The photochromic resin layer of the laminate may also be subjected to post-treatments such as anti-reflection treatment and anti-static treatment. These post-treatments are performed, for example, by applying a coating liquid containing an organic polymer to the photochromic resin layer or hard coat layer and drying it to form a thin film.

[0219] The Vickers hardness of the photochromic cured product (in a state where a hard coat film or the like is not formed) is preferably 3.0 or more and 8.0 or less, more preferably 3.5 or more and 7.5 or less, and particularly preferably 4.0 or more and 7.5 or less.

[0220] A protective film may be attached to the surface of the photochromic resin layer of the photochromic laminate for the purposes of protecting the surface and preventing the adhesion of dust. As described above, the photochromic cured product according to the embodiment contains component (A), and therefore is less likely to suffer from poor appearance due to the acrylic adhesive contained in the protective film. To further reduce the likelihood of poor appearance, it is preferable that the SP value of the photochromic curable composition and the SP value of the pressure-sensitive adhesive have a certain difference. While there is no particular upper limit for this SP value difference, it is preferably 5 or less from the viewpoint of adhesiveness. This SP value difference is preferably 0.05 to 5.0, more preferably 0.075 to 4.0, and particularly preferably 0.1 to 3.0. The SP values ​​of the photochromic curable composition and the pressure-sensitive adhesive can be determined by titration using the turbidimetric titration method described in the Examples, as described in detail below.

[0221] Furthermore, in order to further reduce the occurrence of poor appearance, it is preferable that the photochromic cured product has a high contact angle with the solvent contained in the adhesive surface of the protective film. An example of the solvent contained in the adhesive surface of the protective film is ethylene glycol. Specifically, the contact angle with this solvent is preferably 50 degrees or more. By having a contact angle of 50 degrees or more, the above-mentioned poor appearance can be reduced. The upper limit of the contact angle of the photochromic cured product with the solvent is not particularly limited, but it is preferably less than 90 degrees. The contact angle is more preferably 50 degrees or more but less than 90 degrees, and even more preferably 50 degrees or more but less than 85 degrees. [Example]

[0222] EXAMPLES Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. The notation of each component and the evaluation methods are as follows.

[0223] <Ingredients> Component (A) A1: (Product name: TEGORAD2100, manufactured by Evonik Japan Co., Ltd.) A2: (Product name: TEGORAD2300, manufactured by Evonik Japan Co., Ltd.) A3: (Product name: BYK-UV3500, manufactured by BYK Japan Co., Ltd.) A4: (Product name: BYK-UV3505, manufactured by BYK Japan Co., Ltd.) A5: (Product name: BYK-UV3510, manufactured by BYK Japan Co., Ltd.) A6: (Product name: BYK-UV3530, manufactured by BYK Japan Co., Ltd.) A7: (Product name: BYK-UV3535, manufactured by BYK Japan Co., Ltd.) A8: (Product name: BYK-UV3570, manufactured by BYK Japan Co., Ltd.) A9: (Product name: BYK-UV3575, manufactured by BYK Japan Co., Ltd.) A10: (Product name: BYK-UV3576, manufactured by BYK Japan Co., Ltd.) A11: (Product name: BYK-3550, manufactured by BYK Japan Co., Ltd.) A12: (Product name: BYK-3560, manufactured by BYK Japan Co., Ltd.) A13: (Product name: BYK-3565, manufactured by BYK Japan Co., Ltd.) A14: (Product name: BYK-3566, manufactured by BYK Japan Co., Ltd.) A15: (Product name: KR-511, manufactured by Shin-Etsu Chemical Co., Ltd.) A16: (Product name: KR-513, manufactured by Shin-Etsu Chemical Co., Ltd.) A17: (Product name: X-40-9296, manufactured by Shin-Etsu Chemical Co., Ltd.) A18: (Product name: KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd.) A19: (Product name: DOWSIL BY16-205, manufactured by Dow Toray Industries, Inc.) A20: (Product name: KR-518, manufactured by Shin-Etsu Chemical Co., Ltd.) A21: (Product name: KR-516, manufactured by Shin-Etsu Chemical Co., Ltd.) A22: (Product name: DOWSIL BY16-876, manufactured by Dow Toray Industries, Inc.) (B) Component (B1) Component RX-1: Polyrotaxane containing acryloyl groups and having the following properties: Weight average molecular weight Mw (GPC); 180,000. The proportion of acryloyl groups modified in the side chains was 80 mol %. Proportion of OH groups remaining in side chains: 20 mol %. Axial molecule: linear polyethylene glycol (PEG) with a molecular weight of 11,000. Inclusion ring: α-cyclodextrin (α-CD) introduction ratio: 0.25. End of axial molecule; capped with adamantane. Side chains introduced into the inclusion ring; the (average) molecular weight of the side chains is approximately 500. Number of acryloyl groups per molecule: approximately 90.

[0224] RX-1 was synthesized by the method described in International Publication No. WO2018 / 030275. The weight-average molecular weight Mw of RX-1 was measured by gel permeation chromatography (GPC). A liquid chromatograph (manufactured by Nihon Waters) was used as the apparatus. Two TSKgel SuperHM-M columns (exclusion limit molecular weight: 4,000,000, manufactured by Tosoh Corporation) were used in series. Tetrahydrofuran was used as the developing solution, and measurements were performed at a flow rate of 0.6 ml / min and a temperature of 40°C. Polystyrene was used as a standard sample, and the weight-average molecular weight was determined by comparative conversion.

[0225] (B2) Component SO-1: Silsesquioxane having the following properties and having a methacryloyl group: Number of methacrylate groups per molecule: 20. Weight average molecular weight; 4,800. Acid value: 1.1mgKOH / g. SO-2: "Product name: AC-SQ SI-20, manufactured by Toagosei Co., Ltd." Number of acryloyl groups per molecule: approximately 4. Weight average molecular weight: 2,000.

[0226] SO-1 was synthesized by the following method. First, 248 g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate was added with 248 ml of ethanol and 54 g (3.0 mol) of water, and 0.20 g (0.005 mol) of sodium hydroxide was added as a catalyst. The reaction was carried out at 30°C for 3 hours. 1 After confirmation by H-NMR, the mixture was neutralized with dilute hydrochloric acid, 174 ml of toluene, 174 ml of heptane, and 174 g of water were added, and the aqueous layer was removed. The organic layer was then washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain SO-1. 29 Si-NMR analysis confirmed that SO-1 is a mixture of cage, ladder and random structures.

[0227] The acid value contained in SO-1 was calculated using the following method. First, a 0.1 mol / L potassium hydroxide alcohol solution (ethanolic) (hereinafter referred to as the measurement solution) was placed in a 2 ml microburet, and a stirrer was prepared. 50 ml each of ethanol and toluene were precisely weighed using a measuring cylinder and placed in a 200 ml beaker, followed by stirring and mixing using the stirrer. Three drops of phenolphthalein solution were added, and blank titration was performed using the titrant. 20 g of sample was added to the solution after blank titration, followed by stirring and mixing using the stirrer. Furthermore, three drops of phenolphthalein solution were added, and the sample was titrated using the titrant to obtain the titration amount. The acid value was calculated using the following formula. Acid value (mgKOH / g) = titration volume (ml) × titrant f × 5.6 ÷ sample volume (g) Here, f is the titrant factor determined using a standard hydrochloric acid solution. The f of the N / 10 potassium hydroxide alcohol solution used in the above method was 0.094. The sample amount is the weight of silsesquioxane contained in the sample.

[0228] The weight-average molecular weight Mw of SO-1 was measured by gel permeation chromatography (GPC). A liquid chromatograph (manufactured by Nihon Waters) was used. Three columns were used in series: Shodex GPC KF-802 (molecular weight exclusion limit: 5000, manufactured by Showa Denko K.K.), Shodex GPC KF802.5 (molecular weight exclusion limit: 20000, manufactured by Showa Denko K.K.), and Shodex GPC KF-803 (molecular weight exclusion limit: 70000, manufactured by Showa Denko K.K.).

[0229] Tetrahydrofuran was used as the developing liquid, and measurements were performed at a flow rate of 1 ml / min and a temperature of 40° C. Polystyrene was used as a standard sample, and the weight average molecular weight was calculated by comparative conversion.

[0230] Ingredient (B3) (B31) Ingredients (B31a) Component 9G: Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain: 9, average molecular weight: 536). 14G: Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain: 14, average molecular weight: 736). A-400: Polyethylene glycol diacrylate (average chain length of ethylene glycol chain: 9, average molecular weight: 508). (B31b) Component BPE800: 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=10, average molecular weight 804). (B31c) Component APC56: Polycarbonate obtained by phosgenation of pentamethylene glycol and hexamethylene glycol to Diol (average molecular weight 1000)

[0231] (B32) Ingredients Ingredient (B32a) TMPT; Trimethylolpropane trimethacrylate. D-TMP; ditrimethylolpropane tetraacrylate.

[0232] (B33) ingredient TSL-1: γ-methacryloyloxypropyltrimethoxysilane. GMA: glycidyl methacrylate.

[0233] (C) Component PC1: A compound represented by the following formula: [ka]

[0234] PC2: A compound represented by the following formula, synthesized with reference to the method described in WO2019 / 013249

[0235] [ka]

[0236] PC3: A compound represented by the following formula, in which photochromic compounds are bound to both ends of a polypropylene glycol chain having a molecular weight of 2000, synthesized by the method described in WO2012 / 149599.

[0237] [ka]

[0238] PC4: A compound represented by the following formula: [ka]

[0239] PC5: A compound represented by the following formula: [ka]

[0240] PC6: A compound represented by the following formula: [ka]

[0241] (D) Component OC-1: Xylene (boiling point 138°C, SP value 8.7). OC-2: Toluene (boiling point 111°C, SP value 8.8). OC-3: Ethyl acetate (boiling point 80°C, SP value 9.1). OC-4: Propylene glycol monoethyl ether (boiling point 120°C, SP value 9.1).

[0242] (E) Component Component (E1) HALS-2: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (molecular weight 239). In formula (X), R 100 , and R 300 is a methyl group and t, u, and v are 0. HALS-3: Hindered amine (molecular weight 370) represented by the following formula (HALS-3)

[0243] [ka]

[0244] HALS-3 was prepared by the following method. Equip a 200 mL four-neck flask with a stirring blade, thermometer, and dropping funnel. 1,2,2,6,6-pentamethyl-4-hydroxypiperidine; 17.0 g (0.1 mol), Dibutyltin dilaurate: 7.4 mg, Dibutylhydroxytoluene: 6.1 g (0.05 mol), Dehydrated toluene: 60 mL The mixture was heated to 60°C, and 19.9 g (0.1 mol) of 2-(2-methacryloyloxyethyloxy)ethyl isocyanate was added portionwise. The mixture was stirred at 60-65°C for 1 hour. The mixture was then washed three times with 50 mL of water and extracted with toluene. After drying over magnesium sulfate, the solvent was distilled off. The resulting white solid was purified using a neutral alumina column {developing solvent: chloroform / ethyl acetate = 3 / 1 (v / v)} to obtain 36.3 g of a white solid.

[0245] The elemental analysis of this product was C 65.09%, H 9.75%, N 7.70%, O 17.47%. 20 H 35 This was in excellent agreement with the calculated values ​​for N2O4: C 65.19%, H 9.85%, N 7.60%, and O 17.37%.

[0246] In addition, when the proton nuclear magnetic resonance spectrum was measured, a peak corresponding to 32 protons was observed between 1 and 5 ppm, and a peak corresponding to two protons due to the methacryloyl group and one proton due to the hydrogen atom at the 4th position of the piperidyl group were observed between 5 and 7 ppm.

[0247] From the above, it was confirmed that the compound was represented by the formula (HALS-3). The yield was 92%.

[0248] (E2) Component HALS-1: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508). In formula (Y), R 500 , and R 600 A compound where is a methyl group and W is 8.

[0249] Other additives polymerization initiator CGI1: phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (trade name: Omnirad819, manufactured by IGM). CGI2: 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad184, manufactured by IGM).

[0250] stabilizers HP: ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (Ciba Specialty Chemicals, Irganox 245).

[0251] Leveling Agent L7001: (Product name: L7001, manufactured by Dow Corning Toray Co., Ltd.). ER-10: (Product name: ER-10, manufactured by ADEKA Corporation) NE-10: (Product name: NE-10, manufactured by ADEKA Corporation) catalyst CA-1: dimethylphenylphosphine Example 1 (Production of Photochromic Curable Composition) First, the ingredients were prepared according to the following formulation. (A) Component: A1 0.1 part by mass. (B1) Component: 3 parts by mass of RX-1. (B2) Component: SO-1 0.1 part by mass. (B31a) Ingredients: 9G 40 parts by mass. (B31a) Ingredient: 25 parts by mass of A-400. (B32a) Component: 25 parts by mass of TMPT. (B33) Ingredients: 5.9 parts by mass of TSL-1, 1 part by mass of GMA. (C) Component: 2 parts by mass of PC1. (E) Component: (E1) component; HALS-2 1.5 parts by mass; (E2) component; HALS-1 1 part by mass. (Polymerization initiator): CGI-1 0.3 parts by mass, CGI-2 0.3 parts by mass. (stabilizer); HP 1 part by mass.

[0252] Next, all compounds corresponding to component (B) were mixed together, and then components (C), (E), and other additives were mixed therewith to obtain a mixture, which was then further mixed with component (A) to obtain a photochromic curable composition.

[0253] (Production of photochromic laminate) A photochromic laminate was produced by a coating method using the photochromic curable composition obtained by the above method. Specifically, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was first prepared as an optical substrate. The thiourethane-based plastic lens was subjected to alkaline etching using a 5% aqueous sodium hydroxide solution at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0254] Next, using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the plastic lens was coated with the coating liquid at 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds, to obtain a 6 μm polyurethane resin layer. The coating liquid used was a moisture-curing primer liquid containing a moisture-curing urethane resin precursor and a solvent. The solvent contained toluene (boiling point 111°C, SP value 8.8) and ethyl acetate (boiling point 77°C, SP value 9.0), with 185 parts by weight of ethyl acetate per 100 parts by weight of toluene.

[0255] Next, about 2 g of the photochromic curable composition obtained above was applied onto the polyurethane resin layer by spin coating to obtain a coating film with a thickness of 40 μm. In the spin coating, the lens was first rotated at 100 rpm for 30 seconds to form a coating film, and then the rotation speed was increased to 900 rpm and the lens was further rotated for 5 to 15 seconds to remove excess photochromic curable composition.

[0256] Next, the lens on which the coating film of the photochromic curable composition was formed was exposed to a nitrogen gas atmosphere with an output of 200 mW / cm 2 The coating was cured by irradiating it with light for 90 seconds using a metal halide lamp. It was then heated at 90°C for an additional hour to produce a photochromic laminate having a photochromic resin layer. The same method was repeated to produce 20 photochromic laminates.

[0257] <Examples 2 to 18, Comparative Examples 1 and 2> Photochromic curable compositions and photochromic laminates were prepared in the same manner as in Example 1, except that the blending of the components and the output of the metal halide lamp were changed as shown in Table 1 or Table 2. <Examples 19 to 55> Photochromic curable compositions and photochromic laminates were prepared in the same manner as in Example 1, except that the blending of each component and the output of the metal halide lamp were changed as shown in Table 4, Table 5, or Table 6. When a catalyst was added, it was added immediately before producing the photochromic laminate.

[0258] <Evaluation method> (Photochromic properties) The photochromic laminates obtained in the examples and comparative examples were used as samples, and were irradiated with a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics K.K. through an Aeromass filter (manufactured by Corning) at 23±1°C, with a beam intensity of 365 nm = 2.4 mW / cm on the surface of the photochromic optical article. 2 , 245nm=24μW / cm 2 The photochromic laminate was irradiated with light for 300 seconds to develop color, and the maximum absorption wavelength, color density, and fading rate were measured. This measurement was performed on 20 sheets of the photochromic laminate, and the average values ​​were calculated. These average values ​​are shown in Table 3, Table 7, or Table 8. Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development, determined using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone during color development. Color density {ε(300)-ε(0)}: The difference between the absorbance {ε(300)} after 300 seconds of light irradiation at the maximum absorption wavelength and the absorbance ε(0) before light irradiation. The higher this value, the better the photochromic properties. ·Fading speed〔t1 / 2(sec.)〕: This is the time required for the absorbance at the maximum absorption wavelength of a sample to decrease to half of {ε(300) - ε(0)} after 300 seconds of light irradiation and then the light irradiation is stopped. The shorter this time, the better the photochromic properties.

[0259] (Repeated durability) The following accelerated deterioration test was carried out to evaluate the durability of the color development of the photochromic compound under repeated irradiation with light. First, the obtained photochromic laminate was accelerated for 200 hours using a xenon weather meter (X25, manufactured by Suga Test Instruments Co., Ltd.). The color density was evaluated before and after the deterioration, and the color density before the test (A0) and the color density after the test (A 200 ) was measured.

[0260] From the measurement results, the residual rate, which is an index of the durability against repeated use, was calculated. The results are shown in Table 3, Table 6, or Table 7. Survival rate (%)={(A 200 / A0)×100} During the ceremony, A0 is the color density before the test, A 200 is the color density after the test.

[0261] Further, the yellowing index (ΔYI) was determined using a color difference meter {SM-4, manufactured by Suga Test Instruments Co., Ltd.}. ΔYI=YI 200 -YI0 During the ceremony, YI 200 is the YI after 200 hours of accelerated aging, YI0 is the YI before accelerated degradation.

[0262] The higher the residual rate and the smaller the degree of yellowing, the higher the durability against repeated use and the more excellent the photochromic properties.

[0263] (Appearance evaluation) First, a protective film was attached to the photochromic resin layer of the photochromic laminate obtained in the Examples and Comparative Examples. The adhesive layer of the protective film was 0.1 mm thick and made of an acrylic adhesive. Next, the photochromic laminate with the attached protective film was heated at 70°C for 1 hour.

[0264] After the protective film was peeled off from the photochromic laminate after heating, the exposed photochromic resin layer was observed using an optical microscope and lighting device (QC X75, manufactured by Valvetronics) and its appearance was evaluated. Next, a protective film was again attached to the photochromic resin layer, and the laminate was further heated at 70°C for 1 hour with the protective film attached. After heating for a total of 2 hours, the protective film was peeled off from the photochromic laminate, and the exposed photochromic resin layer was again observed using an optical microscope and lighting device and its appearance was evaluated. This appearance evaluation was performed on all 20 photochromic laminates.

[0265] If the appearance is good after heating for 2 hours, it means that even if the protective film has been attached for a long period of time, a photochromic laminate with excellent appearance can be obtained after peeling it off.

[0266] The appearance was evaluated by four methods: smoothness (appearance), cracks, cloudiness, and wrinkle defects. The evaluation criteria are as follows. The results are shown in Table 3, Table 7, or Table 8.

[0267] smoothness A: The surfaces of all 20 photochromic laminates were uniform, with no irregularities observed. B: Among 20 photochromic laminates, one or more photochromic laminates had fine irregularities on the surface, and the remaining photochromic laminates were rated A above. C: Among the 20 photochromic laminates, one or more photochromic laminates had slight irregularities on the surface, and the remaining photochromic laminates were rated A or B above. D: Of the 20 photochromic laminates, one or more photochromic laminates had irregularities on a portion of the surface, and the remaining photochromic laminates were rated as any one of A to C above. E: Among 20 photochromic laminates, there is at least one photochromic laminate having irregularities on the entire surface.

[0268] crack A: The surfaces of all 20 photochromic laminates were uniform and no cracks were observed. B: Of the 20 photochromic laminates, one or more photochromic laminates had very slight cracks on the surface, and the remaining photochromic laminates were rated A above. C: Among 20 photochromic laminates, one or more photochromic laminates had slight cracks on the surface, and the remaining photochromic laminates were rated A or B above. D: Of the 20 photochromic laminates, one or more photochromic laminates had cracks in part of the surface, and the remaining photochromic laminates were rated any one of A to C above. E: Among 20 photochromic laminates, there is at least one photochromic laminate in which cracks are observed over the entire surface.

[0269] Milky white A: The surfaces of all 20 photochromic laminates were uniform and no cloudiness was observed. B: Of the 20 photochromic laminates, one or more photochromic laminates exhibited very slight white turbidity, and the remaining photochromic laminates were rated A above. C: Among the 20 photochromic laminates, one or more photochromic laminates were slightly cloudy, and the remaining photochromic laminates were rated A or B above. D: Of the 20 photochromic laminates, one or more photochromic laminates were partially cloudy, and the remaining photochromic laminates were rated as any one of A to C above. E: Among 20 photochromic laminates, there is at least one photochromic laminate that is entirely cloudy.

[0270] Poor wrinkles A: In all 20 photochromic laminates, no wrinkle defects, i.e., no fine lines or stripes like wrinkles, were observed in the photochromic resin layer. B: Of the 20 photochromic laminates, one or more photochromic laminates had very slight wrinkle defects in the photochromic resin layer, and the remaining photochromic laminates were rated A above. C: Among the 20 photochromic laminates, one or more photochromic laminates exhibited slight wrinkle defects, and the remaining photochromic laminates were rated A or B above. D: Of the 20 photochromic laminates, one or more photochromic laminates had partial wrinkle defects in the photochromic resin layer, and the remaining photochromic laminates were rated any one of A to C above. E: Among the 20 photochromic laminates, there is one or more photochromic laminates in which wrinkle defects are observed throughout the photochromic resin layer.

[0271] (yield) The yield was calculated by counting the number of 20 photochromic optical articles that showed no defects in appearance and dividing this number by 20. The results are shown in Table 3, Table 6, or Table 7.

[0272] (adhesion) The adhesion of the photochromic laminate was evaluated by a cross-cut tape test in accordance with JIS D-0202. Specifically, a cutter knife was used to make cuts at 1 mm intervals on the surface of the obtained photochromic laminate, forming 100 squares. Cellophane adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was firmly attached thereon, and then the tape was pulled in a 90° direction from the surface to peel it off. The number of squares remaining on the photochromic optical article was calculated. This test was performed on 20 photochromic laminates, and the average value was taken as the number of remaining squares. The number of remaining squares is shown in Table 3, Table 7, or Table 8 as an index of adhesion.

[0273] (Vickers hardness) The Vickers hardness of the photochromic laminate was measured using a micro Vickers hardness tester PMT-X7A (manufactured by Matsuzawa Corporation). A square pyramidal diamond indenter was used as the indenter, and measurements were taken under conditions of a load of 10 gf and a holding time of 30 seconds. A total of four measurements were taken, and the measurement results were shown as the average of three measurements, excluding the first measurement value, which had a large measurement error. This test was performed on 20 photochromic laminates, and the average value was taken as the Vickers hardness. The results are shown in Table 3, Table 7, or Table 8.

[0274] (contact angle) First, ethylene glycol (2.0 μl) was dropped onto the photochromic resin layer of the photochromic laminate to form a droplet. Five seconds after the drop, the contact angle of the droplet was measured five times using an automatic contact angle meter DM500 (manufactured by Kyowa Interface Science Co., Ltd.) to obtain an average value. This test was performed on 20 photochromic laminates, and the average value was used as the contact angle. The results are shown in Table 3, Table 7, or Table 8.

[0275] (SP value difference) The difference between the SP value of the photochromic curable composition and the SP value of the adhesive of the protective film was calculated by the following method.

[0276] First, the SP values ​​of the photochromic curable compositions obtained in the Examples and Comparative Examples were calculated by turbidity titration. Specifically, 2.0 g of the photochromic curable composition was dissolved in 10 ml of acetone. The resulting photochromic curable composition solution was titrated with deionized water and n-hexane, and the titration amount at which the solution became turbid was calculated. From the obtained values, the SP value was calculated using the following formula. SP value = ((VH) 1 / 2 ×δH+(VL) 1 / 2 ×δL) / ((VH) 1 / 2 +(VL) 1 / 2 ). VH=H / (S+H). VL=L / (S+L). δH=A×S / (S+H)+B×H(S+H). δL=A×S / (S+L)+C×H(S+L). H: n-hexane titration volume (ml). L: deionized water titration (ml). VH: volume fraction of hexane. VD: volume fraction of deionized water. S: Amount of acetone used (ml). A: SP value of acetone. B: SP value of n-hexane. C: SP value of deionized water.

[0277] Next, the SP value of the adhesive for the protective film was calculated in the same manner as above. The SP value of the adhesive for the protective film was then divided by the SP value of the photochromic curable composition to obtain the difference. The absolute value of this difference is shown in Table 3, Table 7, or Table 8 as the SP value difference.

[0278] (Muddy) The following accelerated storage test was conducted to evaluate the surface turbidity of the photochromic composition after long-term storage. The photochromic laminate was placed in a thermo-hygrostat at 60°C and 98% RH for 24 hours. A haze meter was used to determine the difference in haze (ΔHAZE) between before and after the test. The results are shown in Table 3, Table 7, or Table 8. ΔHAZE=HAZE 24 -HAZE0 During the ceremony, HAZE 24 represents the haze after 24 hours, HAZE0 represents the haze before placing in the temperature and humidity chamber.

[0279] [Table 1]

[0280] [Table 2]

[0281] [Table 3]

[0282] [Table 4]

[0283] [Table 5]

[0284] [Table 6]

[0285] [Table 7]

[0286] [Table 8] [Explanation of symbols]

[0287] 1: Polyrotaxane 2: Axial molecule 3: Cyclic molecules 4: Bulky end groups 5: Side chain

Claims

1. (A) a siloxane having an acyclic polysiloxane bond and at least one of a radical polymerizable group and a group reactive with a radical polymerizable group; (B) a radical polymerizable monomer component; (C) a photochromic compound; a reactive hindered amine compound having at least one reactive group selected from the group consisting of a radical polymerizable group and a group reactive with a radical polymerizable group; 1. A photochromic curable composition comprising:

2. 2. The photochromic curable composition according to claim 1, wherein the amount of the siloxane is 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the radical polymerizable monomer component.

3. The photochromic curable composition according to claim 1 or 2, wherein the siloxane comprises a compound represented by the following formula (8): 【Chemical 1】 In the formula (8), n is a number from 0 to 20, o is a number from 0 to 20, p is a number from 0 to 20, R １８ , R １９ , R ２０ , R ２１ , R ２２ , R ２３ , R ２４ , R ２５ , R ２６ , R ２７ , R ２８ , and R ２９ are respectively a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group, and -(CH ２ ) α OR ３０ , -(CH ２ CH ２ O) α R ３０ , -(CH(CH ３ ) CH ２ O) α R ３０ , -(CH ２ CH (CH ３ ) O) α R ３０ , -(CH ２ ) ｑ O-(CH ２ CH ２ O) ｒ R ３０ -, -(CH ２ ) ｑ O-(CH(CH ３ ) CH ２ O) ｒ R ３０ , -(CH ２ ) ｑ O-(CH ２ CH (CH ３ ) O) ｒ R ３０ , -(CH ２ CH ２ O) ｑ - (CH ２ CH (CH ３ ) O) ｒ R ３０ , -(CH ２ CH (CH ３ ) O) ｑ - (CH ２ CH ２ O) ｒ R ３０ , -(CH ２ CH ２ O) ｑ - (CH ２ CH (CH ３ ) O) ｒ - (CH ２ CH ２ O) ｓ R ３０ , -(CH ２ ) ｑ O-(CH ２ CH ２ O) ｒ - (CH ２ CH (CH ３ ) O) ｓ R ３０ , -(CH ２ ) ｑ O-(CH ２ CH (CH ３ ) O) ｒ - (CH ２ CH ２ O) ｓ R ３０ , -(CH ２ ) ｑ O-(CH ２ CH ２ O) ｒ - (CH ２ CH (CH ３ ) O) ｓ - (CH ２ CH ２ O) ｚ R ３０ , acryloyl group, methacryloyl group, vinyl group, thiol group, amino group, -R ３１ NH ２、 an epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10): R ３０ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, R ３１ represents an alkylene group having 1 to 20 carbon atoms, or —(CH ２ ) α O-, However, R １８ ~R ２９ At least one of the groups is an acryloyl group, a methacryloyl group, a vinyl group, a thiol group, an amino group, or —R ３１ NH ２、 an epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10): 【Chemistry 2】 In the formula (9), R ３２ represents an alkylene group having 1 to 20 carbon atoms, -(CH ２ ) α O-, -(CH ２ CH ２ O) α - or -(CH ２ CH (CH ３ ) O) α - and R ３３ is a hydrogen atom or a methyl group, 【Chemistry 3】 In the formula (10), R ３４ is an oxygen atom, -(CH ２ ) α O-, -(CH ２ CH ２ O) α -, -(CH(CH ３ ))CH ２ O) α -, -(CH ２ CH(CH ３ ))O) α -, -(CH ２ )) ｑ O-(CH ２ CH ２ O) ｒ -, -(CH ２ )) ｑ O-(CH(CH ３ ))CH ２ O) ｒ -, -(CH ２ )) ｑ O-(CH ２ CH(CH ３ ))O) ｒ -, -(CH ２ CH ２ O) ｑ -(CH ２ CH(CH ３ ))O) ｒ -, -(CH ２ CH(CH ３ ))O) ｑ -(CH ２ CH ２ O) ｒ -, -(CH ２ CH ２ O) ｑ -(CH ２ CH(CH ３ ))O) ｒ -(CH ２ CH ２ O) ｓ -, -(CH ２ )) ｑ O-(CH ２ CH ２ O) ｒ [[ID=mathbf{106}]]-(CH ２ CH(CH ３ ))O) ｓ -, -(CH ２ )) ｑ O-(CH ２ CH(CH ３ )(O) ｒ -(CH ２ CH ２ )(O) ｓ -, or, -(CH ２ )( ｑ O-(CH ２ CH ２ )(O) ｒ -(CH ２ CH(CH ３ )(O) ｓ -(CH ２ CH ２ )(O) ｚ - and R ３５ is a hydrogen atom or a methyl group, In the formulas (8), (9), and (10), α is a number from 1 to 20, q, r, s, and z are each a number from 0 to 20, q+r is a number from 1 to 40, q+r+s is a number from 1 to 60, and q+r+s+z is a number from 1 to 80.

4. The photochromic curable composition according to any one of claims 1 to 3, wherein the radical polymerizable group and the group reactive with the radical polymerizable group of the siloxane contain a (meth)acryloyl group.

5. 5. The photochromic curable composition according to claim 1, wherein the radical polymerizable monomer component comprises a polyrotaxane compound having a radical polymerizable group.

6. 6. The photochromic curable composition according to claim 1, wherein the radical polymerizable monomer component contains a silsesquioxane having a di- or higher functional (meth)acryloyl group.

7. The photochromic curable composition according to any one of claims 1 to 6, further comprising a non-reactive hindered amine compound having neither a radical polymerizable group nor a group reactive with the radical polymerizable group.

8. The photochromic curable composition according to any one of claims 1 to 7, further comprising an organic compound having a boiling point of 80°C or more and 200°C or less and a Hildebrand SP value of 8.0 or more and 10.0 or less.

9. an optical substrate; A photochromic resin layer that is a cured product of the photochromic curable composition according to any one of claims 1 to 8; a polyurethane resin layer located between the optical substrate and the photochromic resin layer; 1. A photochromic laminate comprising:

10. a step of applying a coating liquid containing at least one compound selected from the group consisting of polyurethane resins and moisture-curable urethane resin precursors, and a solvent having a boiling point of 70°C or higher and a Hildebrand SP value of 8.0 or higher, onto one surface of an optical substrate, and removing the solvent from the coating film to form a polyurethane resin layer; a step of applying the photochromic curable composition according to any one of claims 1 to 8 onto the polyurethane resin layer and curing the coating to form a photochromic resin layer; A method for producing a photochromic laminate, comprising:

Images