Photochromic curable composition

Abstract

The present invention provides: a photochromic curable composition with which it is possible to provide a cured product having excellent durability and appearance; and particularly a cured product (photochromic laminate) having a favorable appearance. A photochromic curable composition according to an embodiment of the present invention comprises (A1) a first hindered amine compound which has at least one reactive group selected from the group consisting of radical-polymerizable groups and groups that react with radical-polymerizable groups, (B1) a polyrotaxane component which has a radical-polymerizable group, (B) a radical-polymerizable monomer which does not have a piperidyl group, and (C) a photochromic compound.

Description

[Technical Field]

[0001] The present invention relates to a novel photochromic curable composition, and further to a novel photochromic laminate obtained by laminating a cured product of the photochromic curable composition. [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. 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. 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. 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 hindered amine compound may be blended into the curable composition to increase the durability of the cured product. 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]

[0003] [Patent Document 1] International Publication No. 2012 / 176439 [Patent Document 2] International Publication No. 2013 / 099640 [Patent Document 3] International Publication No. 2015 / 068798 [Patent Document 4] International Publication No. 2011 / 125956 [Patent Document 5] International Publication No. 2013 / 058218 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a photochromic curable composition that can provide a cured product that is excellent in durability and appearance. [Means for solving the problem]

[0005] The object of the present invention is achieved by the following embodiments. 1. (A1) a first hindered amine compound having at least one reactive group selected from the group consisting of a radically polymerizable group and a group reactive with a radically polymerizable group; (A2) a secondary hindered amine compound having no reactive group, (B1) a polyrotaxane component having a radical polymerizable group, and (B) a radical polymerizable monomer having no piperidyl group; and (C) Photochromic Compound 1. A photochromic curable composition comprising: 2. The photochromic curable composition according to item 1 above, comprising 0.1 parts by mass or more and 5.0 parts by mass or less of the first hindered amine compound (A1) relative to 100 parts by mass of the radically polymerizable monomer component (B). 3. The photochromic curable composition according to item 1 or 2 above, wherein the ratio M1 / M2 of the mass M1 of the polyrotaxane component (B1) to the mass M2 of the first hindered amine compound (A1) is 0.1 or more and 40 or less. 4. The (A1) first hindered amine compound includes a compound represented by the following formula (X): The photochromic curable composition according to any one of items 1 to 3 above; [ka] 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, [ka] 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.

[0006] 5. The photochromic curable composition according to any one of items 1 to 4 above, wherein the proportion of the polyrotaxane component (B1) in the radically polymerizable monomer component (B) is 0.1% by mass or more and 50% by mass or less. 6. The photochromic curable composition according to any one of the above items 1 to 5, wherein the (B) radically polymerizable monomer component further contains (B2) a silsesquioxane having a di- or higher functional (meth)acryloyl group. 7. The photochromic curable composition according to any one of the above items 1 to 6, further comprising a leveling agent. 8 .before The second hindered amine compound (A2) includes a compound represented by the following formula (Y): Above 1~ 7 The photochromic curable composition according to any one of the above items; [ka] 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.

[0007] 9 (D) The above 1 to 3 further contain an organic compound having a boiling point of 80°C or more and 200°C or less and an SP value of 8.0 to 10.0. 8 10. The photochromic curable composition according to claim 1, wherein the photochromic curable composition is a photochromic curable composition. 1 0The above 1 to 100 parts by mass of the (B) radical polymerizable monomer component contains 0.10 parts by mass or more and 10.0 parts by mass or less of the (D) organic compound. 9 10. The photochromic curable composition according to claim 1, wherein the photochromic curable composition is a photochromic curable composition. 1 1 an optical substrate; 1-1 above 0 a photochromic resin layer that is a cured product of the photochromic curable composition according to any one of the above items; a polyurethane resin layer located between the optical substrate and the photochromic resin layer; 1. A photochromic laminate comprising: [Effects of the Invention]

[0008] According to the present invention, there is provided a photochromic curable composition that can provide a cured product that is excellent in durability and appearance.

[0009] Furthermore, even when the amount of a leveling agent (surfactant) added is reduced to highly prevent poor appearance due to the scratch-resistant protective film, a cured product with excellent appearance can be obtained. In addition, when the photochromic curable composition is used to laminate on a urethane resin layer on an optical substrate having a urethane resin layer on its surface to improve adhesion, a cured product (photochromic laminate) with particularly good appearance can be obtained. [Brief explanation of the drawings]

[0010] [Figure 1] Schematic diagram showing the molecular structure of polyrotaxane components. DETAILED DESCRIPTION OF THE INVENTION

[0011] The photochromic curable composition according to the present embodiment includes (A1) a first hindered amine compound, (B1) a polyrotaxane component having a radical polymerizable group, (B) a radical polymerizable monomer having no piperidyl group, and (C) a photochromic compound. The (A1) first hindered amine compound has at least one reactive group selected from the group consisting of a radical polymerizable group and a group reactive with the radical polymerizable group. By using the photochromic curable composition according to the embodiment, a cured product having high photochromic properties and capable of suppressing the occurrence of wrinkle-like fine lines and the like, and having excellent durability and appearance can be obtained. Therefore, a photochromic optical article having excellent durability and appearance can be obtained. The present inventors believe that the reason for this is as follows.

[0012] 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. 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. As a result of further intensive research, the present inventors discovered that the penetration of this acrylic adhesive is influenced by the hindered amine compound. Specifically, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is commonly used as the hindered amine compound in curable compositions. Hindered amine compounds can capture free radicals generated by ultraviolet light, thereby suppressing deterioration of the cured product. However, hindered amine compounds can separate from the resin of the cured product and bleed out to the surface. The presence of a hindered amine compound on the surface of the cured product tends to facilitate the incorporation of components such as the adhesive of the protective film into the photochromic resin layer. Therefore, while the use of conventional hindered amine compounds increases the durability of the cured product, it is believed that thin streaks or stripes of foreign matter originating from the protective film are observed inside the photochromic resin layer. When a conventional curable composition not containing a hindered amine compound is used, a photochromic resin layer free of these wrinkle-like fine lines can be obtained. However, the photochromic resin layer obtained from such a curable composition may have reduced durability and may undergo discoloration.

[0013] The photochromic curable composition according to the embodiment includes a hindered amine compound (A1) having at least one reactive group selected from the group consisting of radically polymerizable groups and groups reactive with radically polymerizable groups. The radically polymerizable group or the group reactive therewith of component (A1) reacts with component (B) during curing of the curable composition. In a cured product of this composition, component (A1) and at least a portion of component (B) are thought to be in a polymerized complex state. Because component (A1) in such a complex is polymerized with component (B), bleeding to the surface of the photochromic resin layer is thought to be reduced. Furthermore, the photochromic curable composition according to the embodiment includes a polyrotaxane component (B1) having a radically polymerizable group. Component (B1) does not interfere with the structural change of the photochromic compound in the cured product, enhancing the photochromic properties of the cured product. Component (B1) also increases the viscosity of the photochromic curable composition, contributing to the formation of a coating film of a desired thickness. The photochromic curable composition according to the embodiment contains the components (A1) and (B1), and therefore can provide a photochromic resin layer in which the hindered amine compound is less likely to bleed out and which has excellent photochromic properties. This photochromic resin layer is less susceptible to the effects of the adhesive and colorant contained in the protective film attached to the surface. For these reasons, the use of the photochromic curable composition according to the embodiment can form a photochromic resin layer that has excellent photochromic properties, is less likely to develop wrinkle-like streaks, and has excellent appearance. Each component will be described below.

[0014] Component (A) ((A) hindered amine component) The component (A) is a hindered amine component having a piperidyl group, and includes a first hindered amine compound (component (A1)) having at least one reactive group selected from the group consisting of a radically polymerizable group (A1) and a group reactive with the radically polymerizable group. The component (A) may contain (A2) a second hindered amine compound (component (A2)) other than the component (A1). Both the components (A1) and (A2) are compounds having a piperidyl group.

[0015] Component (A1) The component (A1) is a 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. Use of this component makes it possible to maintain high stability of the photochromic curable composition itself and the photochromic optical article, and to obtain a photochromic optical article with good appearance.

[0016] In the component (A1), examples of the radically polymerizable group include a (meth)acrylic group (methacrylic group and / or acrylic group) and a vinyl group. Examples of groups that react with the radically polymerizable group include a thiol group, an amino group, and an epoxy group. These reactive groups polymerize or react with the component (B), which will be described in detail below. In other words, the component (A1) is chemically bonded to the matrix of the photochromic optical article (a resin layer containing a photochromic compound). Because the component (A1) is present in the matrix, the stability of the photochromic curable composition itself and the stability of the photochromic optical article can be maintained at a high level, and a photochromic optical article with excellent appearance can be obtained.

[0017] The component (A1) is not particularly limited as long as it is a compound having a piperidyl group and at least one reactive group selected from the group consisting of a radically polymerizable group and a group reactive with a radically polymerizable group. Among these, the following compounds are preferred. Specifically, a compound represented by the following formula (X) (hereinafter sometimes referred to as component (A1X)) is preferred.

[0018] [ka] In formula (X), R100 , 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,

[0019] [ka] 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.

[0020] In the above formula, t, u, and v are shown as average values, because they are often obtained as a mixture during production.

[0021] In the formula (X), R 300 is preferably a methyl group. 100 is a hydrogen atom or a methyl group.

[0022] X is a divalent group represented by the formula (Z). 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.

[0023] 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 an average value of 0 to 10 is preferable, and an average value of 0 to 5 is more preferable. t may be 2 to 3.

[0024] u is a number having an average value of 0 to 20. In particular, in order to exert excellent effects, it is preferable that u is small, and an average value of 0 to 3 is preferable, and an average value of 0 to 2 is more preferable. u may be 1.

[0025] The component (A1X) is a known compound, and commercially available products can be used. Specifically, it can be synthesized according to the method described in Patent Document 5. Furthermore, compounds in which t, ​​u, and v are 0, i.e., X is an oxygen atom, can be commercially available products. Specific examples include LA-82 and LA-87 manufactured by ADEKA Corporation.

[0026] Among the components (A1X), those that exhibit particularly excellent effects include R 100 , and R 300 is a methyl group, and t, u, and v are 0 (X is an oxygen atom).

[0027] Specifically, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate is preferred. Among the (A1X) components, 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 at relatively small amounts. Furthermore, because it exhibits excellent effects even at relatively small amounts, when combined with the (A2) component described in detail below, it is possible to maintain high photochromic properties and sufficiently suppress poor appearance due to the scratch-resistant protective film. Furthermore, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate is a liquid at room temperature and is highly compatible with the (B) component described in detail below, which is why it is believed to exhibit excellent effects.

[0028] (A2) Component Component (A2) is a second hindered amine compound having a piperidyl group and other than component (A1). Component (A2) can be a known compound. Unlike component (A1), component (A2) is believed to exist in a dispersed state in the matrix of the photochromic optical article. Furthermore, by using component (A2) in combination with component (A1), the amount of component (A2) can be reduced relatively compared to using component (A2) alone. Furthermore, the use of component (A2) can maintain high stability of the photochromic curable composition itself and the photochromic optical article. Furthermore, the reduced amount of component (A1) is believed to contribute to the development of excellent photochromic properties.

[0029] The component (A2) 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 (A2Y)").

[0030] [ka] In formula (Y), R 500 , and R 600are each a hydrogen atom or a methyl group, W is an integer of 1 to 50.

[0031] Among the (A2Y) components, R 500 , and R 600 Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, in which ≡(A2Y) is a methyl group and w is 8, is preferred. When using component (A2Y), component (A2) can contain bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, which is component (A2Y), and the (1,2,2,6,6-pentamethyl-4-piperidyl)sebacate inevitably contained therein. In this case, the amount of component (A2) 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 (A2) other than component (A2Y).

[0032] Component (A2) preferably contains component (A2Y). Component (A2) may consist solely of component (A2Y), or may consist of component (A2Y) and (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Furthermore, component (A2) may contain component (A2Y) and (A2) components other than component (A2Y) and (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Component (A2) may also contain component (A2Y) and (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate plus other (A2) components. In order to achieve even better effects, the component (A2) contains bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate as the component (A2Y), and may also contain (1,2,2,6,6-pentamethyl-4-piperidyl)sebacate.

[0033] The component (A2Y), which is bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, can maintain the stability of the photochromic curable composition itself and the stability of the photochromic optical article at a high level, and can also exhibit excellent photochromic properties and an excellent appearance. Furthermore, the component (A2), which is primarily composed of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (component (A2Y)), is a liquid at room temperature and is highly compatible with component (B), which will be described in detail below, and is therefore thought to exhibit excellent effects.

[0034] (A1) Optimal blending ratio of component The blending amount of the (A1) component is not particularly limited, but is preferably the following blending amount. That is, it is preferable that the (A1) component be contained in an amount of 0.1 to 5.0 parts by mass per 100 parts by mass of the (B) radically polymerizable monomer component described in detail below. 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 blending amount is more preferably 0.5 to 4.0 parts by mass, and even more preferably 1.0 to 3.5 parts by mass. Among these, to achieve particularly excellent effects, the blending amount of the (A1) component is preferably 1.0 to 3.0 parts by mass, more preferably 1.0 to less than 3.0 parts by mass, and even more preferably 1.0 to 2.8 parts by mass per 100 parts by mass of the (B) component.

[0035] 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) is preferably used as a radically polymerizable composition (B') containing multiple types of radically polymerizable monomers (composition (B')). When the component (B') is used as the component (B), the total amount of the multiple types of component (B) (amount of composition (B')) is taken as 100 parts by mass.

[0036] Suitable blending ratio of components (A1) and (A2) in component (A) When the photochromic curable composition according to the embodiment includes the component (A2), i.e., when the component (A) is a mixture of the components (A1) and (A2), the blending ratios thereof are preferably as follows. Specifically, the component (A) may contain 10 to 500 parts by mass of the component (A2) per 100 parts by mass of the component (A1). Satisfying this range ensures good repeated use durability. Furthermore, in consideration of photochromic properties, storage stability, and other properties, the component (A2) is preferably contained in an amount of 10 to 300 parts by mass, more preferably 10 to 200 parts by mass, even more preferably 20 to 200 parts by mass, and particularly preferably 25 to 200 parts by mass, of 100 parts by mass of the component (A1). When the component (D) described in detail below is contained, the component (A) most preferably contains 25 to 150 parts by mass of the component (A2) per 100 parts by mass of the component (A1).When the component (D) described in detail below is not contained, the component (A) most preferably contains 25 to 150 parts by mass of the component (A2) per 100 parts by mass of the component (A1). On the other hand, when the photochromic curable composition according to the embodiment contains the (A2) component, the cured product tends to have fine lines similar to the wrinkles described above. Therefore, from the viewpoint of obtaining a cured product with excellent appearance, it is preferable that the content of the (A2) component is low, and it is more preferable that the (A2) component is not contained. Specifically, when the (A1) component is taken as 100 parts by mass, the amount of the (A2) component is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 75 parts by mass or less. The lower limit of the (A2) component is 0 parts by mass.

[0037] The blending amounts of the (A1) component and the (A2) component can be confirmed, for example, by the following method. When calculating the amounts of these components from a cured product or curable composition that is a photochromic resin layer, first, a sample is obtained by dissolving the cured product or the curable composition in an organic solvent. This sample is purified by gel filtration column chromatography or the like to isolate the (A1) component and the (A2) component. The isolated (A1) component and the (A2) component are then analyzed by the following method: 1 By H-NMR analysis, liquid chromatography mass spectrometry (LC-MS) analysis, and gas chromatography mass spectrometry (GC-MS) analysis, the structures of the components (A1) and (A2) can be identified and their respective contents can be calculated.

[0038] <Component (B); Radically Polymerizable Monomer ((B) Composition; Radically Polymerizable Monomer Composition)> Component (B) is not particularly limited, and any radically polymerizable monomer commonly used in conventional coating solutions can be used. Specifically, it preferably contains a polyfunctional (meth)acrylate having two or more (meth)acrylate groups in the molecule. Component (B) contains (B1) a polyrotaxane component having a radically polymerizable group. Component (B1) preferably has a weight-average molecular weight of 100,000 or more and 1,000,000 or less. Preferably, component (B) further contains (B2) a silsesquioxane component having a radical polymerizable group and a weight-average molecular weight of 1,500 to 20,000. When component (B) (composition (B')) contains at least one of component (B1) and component (B2), the resulting cured product and laminate exhibit excellent mechanical properties and photochromic properties. Next, these components will be described.

[0039] <Component (B1): Polyrotaxane component> The component (B1) preferably has a weight average molecular weight of 100,000 or more and 1,000,000 or less. The radically polymerizable group is preferably a (meth)acrylate group (a methacrylate group or an acrylate group, or in some cases both groups).

[0040] Component (B1) is a known compound and has a structure as shown in Figure 1. Figure 1 is a schematic diagram of component (B1) 1. In component (B1), various types of axial molecule 2 are known. Axial molecule 2 may be linear or branched as long as it can pass through the ring of cyclic molecule 3, and is generally composed of a polymer.

[0041] 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.

[0042] Furthermore, the groups formed at both ends of the axial molecule are not particularly limited as long as they prevent the cyclic molecules from detaching from the axial molecule, but are preferably bulky groups (bulky terminal groups 4 in Figure 1). Examples of such groups include adamantyl groups, trityl groups, fluoresceinyl groups, dinitrophenyl groups, and pyrenyl groups, with the adamantyl group being particularly preferred in terms of ease of introduction.

[0043] The molecular weight of the axial molecule is not particularly limited. If the molecular weight is too large, compatibility with other components, such as other polymerizable monomers, tends to be poor. If the molecular weight is too small, the mobility of the cyclic molecule tends to decrease, and photochromic properties tend to decrease. 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. The weight-average molecular weight Mw is a value measured by the GPC measurement method described in the Examples below.

[0044] The cyclic molecule may have a ring large enough to encompass the axial molecule. 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 to 0.6 nm), β-forms (inner ring diameter: 0.6 to 0.8 nm), and γ-forms (inner ring diameter: 0.8 to 0.95 nm). Among these, α-cyclodextrin rings and γ-cyclodextrin rings are particularly preferred, with α-cyclodextrin rings being the most preferred.

[0045] 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 tends to reduce their mobility and photochromic properties. On the other hand, if the inclusion number is too low, the gap between the axial molecules becomes narrow, which reduces the gap that can allow the reversible reaction of the photochromic compound molecules, which also tends to reduce photochromic properties.

[0046] Component (B1) is a polyrotaxane compound obtained by modifying the hydroxyl group of a side chain having a terminal hydroxyl group in the cyclic molecule with a compound having a radical polymerizable group. This side chain is indicated by "5" in Figure 1.

[0047] The side chain having a hydroxyl group at its terminal is not particularly limited, but is preferably formed by repeating organic chains having a hydroxyl group at its terminal and having a 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.

[0048] Furthermore, the above-mentioned side chains are introduced by modifying the functional groups possessed by the cyclic molecules. For example, an α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and side chains are introduced via these hydroxyl groups. In other words, a maximum of 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 molecules 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%.

[0049] The side chains described above may be linear or branched as long as they have a terminal hydroxyl group. Furthermore, desired side chains can be obtained by introducing side chains into the functional groups of the cyclic molecules so as to have terminal hydroxyl groups, using ring-opening polymerization, radical polymerization, cationic polymerization, anionic polymerization, or living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, or NMP polymerization.

[0050] 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.

[0051] Among the 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). A lactone compound that is suitably used is preferably ε-caprolactone.

[0052] 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.

[0053] In the case of component (B1), when introducing a side chain having a hydroxyl group at its terminal into the cyclic molecule, it is preferable to adopt a method of introducing a side chain having a hydroxyl group at its terminal by ring-opening polymerization, taking into consideration the ease of introducing the side chain, the ease of adjusting the size (molecular weight) of the side chain, and the ability to modify the hydroxyl group.

[0054] (Component (B1) having a polymerizable group at the end (end of the side chain)) In the component (B1), a terminal hydroxyl group of a side chain of the polyrotaxane is reacted with a compound having a radical polymerizable group to form a side chain of the polyrotaxane compound. of A polymerizable group is introduced at the end of the polymer. This reaction is called "modification."

[0055] The compound having the radical polymerizable group is introduced by utilizing the side chain having a hydroxyl group at the terminal, and a compound that reacts with the hydroxyl group of the side chain can be appropriately used. In consideration of compatibility with other components, the compound having the radical polymerizable group is preferably a compound that does not have a hydroxyl group in the molecule. The radical polymerizable group is preferably a (meth)acrylate group.

[0056] The compound having the radical polymerizable group is a compound having both a functional group capable of reacting with a hydroxyl group in a side chain and the polymerizable group in one molecule. Examples of the functional group 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, the 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, the radical polymerizable group is introduced via an ester bond.

[0057] For the reaction between the compound having the radical polymerizable group and the hydroxyl group on the side chain, known reaction conditions for a functional group reactive with the hydroxyl group can be adopted.

[0058] For component (B1), the modification ratio of the radically polymerizable group relative to the terminal hydroxyl groups of the side chains, i.e., the reaction ratio of the compound having the radically polymerizable group relative to the total number of moles of hydroxyl groups in the side chains, is preferably 1 mol% or more and less than 100 mol%. In consideration of the yield, mechanical strength, photochromic properties, etc. of the resulting cured product, the modification ratio with the compound having the radically 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 ratio of 70 mol% or more and 95 mol% or less is particularly preferred.

[0059] 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 (B1) 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.

[0060] 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 the compound having the 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 the compound having the radical polymerizable group) may remain as hydroxyl groups or may be modified with a compound not having a radical polymerizable group.

[0061] The 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, the compound having no radical polymerizable group preferably 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 the 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 the radical polymerizable group."

[0062] As the 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 the 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.

[0063] 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%.

[0064] (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 hydroxyl group at the end introduced into the cyclic molecule by polycaprolactone.

[0065] 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 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.

[0066] 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 with (meth)acrylate groups in these side chains is 70% to 95% by mole. Based on these values, it is preferable to use a (B1) component having 10 to 1,000 (meth)acrylate groups per molecule of the (B1) component.

[0067] <Amount of component (B1)> The proportion of component (B1) in component (B) is preferably 0.1% by mass or more and 50% by mass or less. A high proportion of component (B1) tends to enhance the photochromic properties of the cured product. A low proportion of component (B1) tends to enhance the appearance of the cured product. The proportion of component (B1) in component (B) is more preferably 0.5% by mass or more and 45% by mass or less, and particularly preferably 1.0% by mass or more and 40% by mass or less. The ratio M1 / M2, where M1 is the mass of component (B1) and M2 is the mass of component (A1), is preferably 0.1 or more and 40 or less. By setting the ratio M1 / M2 within the above range, a cured product with better appearance can be obtained. The ratio M1 / M2 is more preferably 0.3 or more and 30 or less, even more preferably 0.5 or more and 25 or less, and particularly preferably 0.5 or more and 20 or less.

[0068] <Component (B2): Silsesquioxane component> The component (B) preferably contains a component (B2). The component (B2) is a silsesquioxane component having a weight-average molecular weight of 1,500 to 20,000 and having a radically polymerizable group. The radically polymerizable group is preferably a (meth)acrylate group (a methacrylate group, an acrylate group, or both groups in some cases).

[0069] The component (B2) is a polyfunctional polymerizable monomer having silicon in the molecule, and is not particularly limited, and known monomers can be used. Among them, a particularly suitable one is a silsesquioxane having multiple (meth)acrylate groups.

[0070] The component (B2) may be represented by the following formula (6):

[0071] [ka]

[0072] (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)acrylate groups. 15 does not include groups containing chain organosiloxane groups.) where R 15 In the above, the organic group containing a (meth)acrylate group includes those containing only a (meth)acrylate group (including those in which a (meth)acrylate group is directly bonded to a silicon atom). Specifically, the (meth)acrylate group may contain not only a (meth)acrylate group, but also a (meth)acryloxypropyl group or a (3-(meth)acryloxypropyl)dimethylsiloxy group. Among these, the (meth)acryloxypropyl group is particularly preferred because the raw material for producing the component (B2) is easily available and high film strength can be obtained while exhibiting excellent photochromic properties.

[0073] 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 (B) is a value measured by gel permeation chromatography (GPC).

[0074] Furthermore, the component (B2) preferably contains, on average, 10 or more (meth)acrylate groups per molecule, and more preferably 10 to 100 (meth)acrylate groups per molecule, and even more preferably 15 to 35 (meth)acrylate groups per molecule.

[0075] Silsesquioxanes generally can have a variety of structures, such as cage-like, ladder-like, and random structures. Component (B2) can be a compound of a single structure or a mixture of compounds with multiple structures. In the case of a mixture, the total mass of the mixture is considered to be the amount of component (B2). It is preferable that component (B2) be a mixture of compounds with multiple structures.

[0076] 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).

[0077] <Amount of ingredient (B2)> Although the component (B2) is not an essential component, use of the component (B2) can improve mechanical properties, photochromic properties, etc. Therefore, to further enhance these effects, 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, based on 100 parts by mass of the total amount of the components (B), that is, the amount of the composition (B').

[0078] Although the component (B1) and the component (B2) are not essential components, a photochromic curable composition containing at least one of them has excellent photochromic properties and physical properties, and in particular, has the effect of suppressing wrinkle defects, as described in detail below. Furthermore, the effect of including the component (A) is further enhanced. To produce a photochromic optical article in which the effects of the component (A) are further enhanced and the article has excellent photochromic properties and physical properties and suppresses wrinkle defects, it is preferable to include both the component (B1) and the component (B2).

[0079] The component (B) preferably contains the component (B1) and another radically polymerizable monomer component (B3) other than the component (B2). The other radically polymerizable monomer component (B3) (hereinafter sometimes simply referred to as component (B3)) will be described below.

[0080] <Component (B3): Other radically polymerizable monomer components> The component (B) is preferably a composition (B') containing multiple types of radically polymerizable monomers. The composition (B') preferably contains a component (B3) in addition to the components (B1) and (B2). The radically polymerizable group in the component (B3) is preferably a (meth)acrylate group. In particular, the component (B3) preferably contains the following two components:

[0081] (B31) a bifunctional (meth)acrylate having two (meth)acrylate groups in the molecule (hereinafter also referred to simply as component (B31)), (B32) A polyfunctional (meth)acrylate having three or more (meth)acrylate groups in the molecule (hereinafter also referred to simply as component (B32)).

[0082] (B33) Monofunctional (meth)acrylate having one (meth)acrylate group (hereinafter also referred to simply as component (B33)). These components will be described below.

[0083] <Component (B31): Difunctional (meth)acrylate> The composition (B') preferably contains a component (B31). Specific examples are shown below. Specifically, a component represented by the following formula (1) (hereinafter also referred to as component (B31a)), a component represented by the following formula (2) (hereinafter also referred to as component (B31b)), and a component represented by the following formula (3) (hereinafter also referred to as component (B31c)) are preferred. Other examples include a bifunctional (meth)acrylate component having a urethane bond (hereinafter also referred to as component (B31d)), and a bifunctional (meth)acrylate component other than the aforementioned components (B31a), (B31b), (B31c), and (B31d) (hereinafter also referred to as component (B31e)). These (B31) components will be explained below.

[0084] <Component (B31a): a component represented by the following formula (1)> [ka] (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.

[0085] 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).

[0086] <(B31b) component: a component represented by the following formula (2) [ka]

[0087] (In the formula, R 3 and R 4 are each a hydrogen atom or a methyl group, R 5 and R 6are 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.

[0088] A specific example of the bifunctional (meth)acrylate represented by the above formula (2) is the following bisphenol A di(meth)acrylate.

[0089] 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).

[0090] Component (B31c): a component represented by the following formula (3) [ka]

[0091] (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.

[0092] The bifunctional (meth)acrylate represented by the above formula (3) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0093] 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.

[0094] Component (B31d): Bifunctional (meth)acrylate having a urethane bond 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.

[0095] On the other hand, 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.

[0096] 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 the diisocyanates with 2-hydroxy(meth)acrylate, such as a urethane(meth)acrylate, can also be used.

[0097] 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.

[0098] Component (B31e): Bifunctional (meth)acrylate not corresponding to the above components Examples of the component (B31e) include compounds having (meth)acrylate groups at both ends of an alkylene group that may have a substituent. Among these, compounds having an alkylene group having 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.

[0099] Furthermore, the component (B31e) can also include butadiene di(meth)acrylate represented by the following formula (4).

[0100] [ka] (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.

[0101] 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.

[0102] The component (B31e) may also be 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.

[0103] The components (B31a), (B31b), (B31c), (B31d), and (B31e) can be used either individually or in combination as described above. 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, it is preferable that the (B31a) component be 30 to 100 parts by mass, the (B31b) component be 0 to 70 parts by mass, the (B31c) component be 0 to 70 parts by mass, the (B31d) component be 0 to 70 parts by mass, and the (B31e) component be 0 to 70 parts by mass, and it is more preferable that the (B31a) component be 40 to 95 parts by mass, the (B31b) component be 5 to 60 parts by mass, the (B31c) component be 5 to 60 parts by mass, the (B31d) component be 5 to 60 parts by mass, and the (B31e) component be 5 to 60 parts by mass. Next, (B32) polyfunctional (meth)acrylate will be described.

[0104] <Component (B32): Polyfunctional (meth)acrylate> 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).

[0105] <Component (B32a): Compound represented by the following formula (5)> [ka] (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.

[0106] R 13 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:

[0107] 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.

[0108] <Component (B32b): Polyfunctional (meth)acrylate having a urethane bond> 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)acrylate 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.

[0109] <Component (B32c): Polyfunctional (meth)acrylate not falling under the above-mentioned components> Examples of the (B32c) component include compounds in which the terminals of polyester compounds are modified with (meth)acrylate 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 modification with the (meth)acrylate groups. 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.

[0110] 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.

[0111] The above components (B32a), (B32b), and (B32c) can be used either individually or in combination as described above. When multiple components are used, the reference mass of component (B32) is the total mass of the multiple components. While not particularly limited, it is preferable that, when the total mass 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. Next, the component (B33) will be explained.

[0112] <Component (B33): Monofunctional (meth)acrylate> The component (B33) may be a compound represented by the following formula (7). [ka] (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:

[0113] Methoxypolyethylene glycol methacrylate (particularly average molecular weight 293), methoxypolyethylene glycol methacrylate (particularly average molecular weight 468), methoxypolyethylene glycol acrylate (particularly average molecular weight 218), methoxypolyethylene glycol acrylate (particularly 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.

[0114] <(B') Suitable blending ratio and characteristics of the composition> The component (B) (the composition (B')) preferably contains the components (B1), (B2), and (B3). However, since the components (B1) and (B2) are not essential components, the composition may consist solely of the component (B3).

[0115] When the composition consists solely of the component (B3), the blending ratio of each component preferably satisfies the following blending ratio, taking into consideration the hardness and mechanical properties of the resulting photochromic cured body, as well as photochromic properties such as color density and color fading speed: That is, when the total amount of the component (B3) (the total amount of the components (B31), (B32), and (B33), or the amount of the composition (B')) is taken as 100 parts by mass, Preferably, the amount of the (B31) component is 30 to 80 parts by mass, the amount of the (B32) component is 10 to 60 parts by mass, and the amount of the (B33) component is 0.1 to 20 parts by mass. It is even more preferable that the amount of the (B31) component is 40 to 75 parts by mass, the amount of the (B32) component is 15 to 55 parts by mass, and the amount of the (B33) component is 0.5 to 10 parts by mass. Naturally, the total amount of each component is 100 parts by mass. However, it is preferable that at least one of the component (B1) and the component (B2) is contained.

[0116] When the (B1) component is included, it is preferable to satisfy the following blending ratios in order to maintain high hardness and mechanical properties of the resulting photochromic cured body and to achieve particularly high photochromic properties such as color density and color fading speed. That is, when the amount of the (B') composition is taken as 100 parts by mass, it is preferable to use 0.1 to 20 parts by mass of the (B1) component, 30 to 80 parts by mass of the (B31) component, 10 to 60 parts by mass of the (B32) component, and 0.1 to 10 parts by mass of the (B33) component. It is even more preferable to use 0.5 to 10 parts by mass of the (B1) component, 40 to 75 parts by mass of the (B31) component, 15 to 55 parts by mass of the (B32) component, and 0.5 to 10 parts by mass of the (B33) component. Naturally, the total amount of each component is 100 parts by mass.

[0117] When the (B2) component is included, it is preferable to satisfy the following blending ratios in order to enhance the hardness and mechanical properties of the resulting photochromic cured product and maintain high levels of photochromic properties such as color density and color fading speed. That is, when the amount of the (B') composition is taken as 100 parts by mass, it is preferable to use 0.1 to 8 parts by mass of the (B2) component, 30 to 80 parts by mass of the (B31) component, 10 to 60 parts by mass of the (B32) component, and 0.1 to 20 parts by mass of the (B33) component. It is even more preferable to use 0.1 to 6 parts by mass of the (B2) component, 40 to 75 parts by mass of the (B31) component, 15 to 55 parts by mass of the (B32) component, and 0.5 to 10 parts by mass of the (B33) component. Naturally, the total amount of each component is 100 parts by mass.

[0118] When both the (B1) component and the (B2) component are included, in order to improve the hardness and mechanical properties of the resulting photochromic cured body and to improve photochromic properties such as color density and color fading speed, it is preferable to satisfy the following blending ratios. That is, when the amount of the (B') composition is taken as 100 parts by mass, it is preferable that the amounts are 0.1 to 20 parts by mass of the (B1) component, 0.1 to 8 parts by mass of the (B2) component, 30 to 80 parts by mass of the (B31) component, 10 to 60 parts by mass of the (B32) component, and 0.1 to 20 parts by mass of the (B33) component. It is even more preferable that the amounts are 0.5 to 10 parts by mass of the (B1) component, 0.1 to 6 parts by mass of the (B2) component, 40 to 75 parts by mass of the (B31) component, 15 to 55 parts by mass of the (B32) component, and 0.5 to 10 parts by mass of the (B33) component. Naturally, the total amount of each component is 100 parts by mass. The photochromic laminate obtained exhibits particularly excellent effects when it contains both the component (B1) and the component (B2).

[0119] The SP value of composition (B') is not particularly limited. In particular, taking into consideration compatibility with other components, solubility, 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 of composition (B') is preferably 7.0 to 12.0. The SP value of composition (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 (1973 edition) edited by the Chemical Society of Japan and Polymer Handbook (4th edition, edited by Johannes Brandrup and EH Immergut, 1998).

[0120] Although it is only a guess, it is believed that the excellent effect is exhibited because the SP value of composition (B') is close to the SP value of component (A). In order to exhibit even more excellent effects, the SP value of composition (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.

[0121] <Component (C): Photochromic compound> As the (C) photochromic compound (component (C)), any known compound can be used without any limitation, and these can be used alone or in combination of two or more types.

[0122] Representative examples of such 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.

[0123] 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.

[0124] The chromene compounds shown below are examples of particularly suitable chromene compounds, but are not limited to these.

[0125] [ka]

[0126] 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.

[0127] [ka]

[0128] Considering the photochromic properties such as the color density and fading rate of the resulting photochromic cured body, the blending amount of the component (C) is preferably the following amount: That is, when the total amount of the component (B) (the amount of the composition (B')) is taken as 100 parts by mass, the blending amount of the component (C) is preferably from 0.001 to 20 parts by mass, more preferably from 0.05 to 15 parts by mass, and even more preferably from 0.1 to 10 parts by mass.

[0129] The photochromic curable composition contains the component (A), the component (B) (the (B') composition), and the component (C) as essential components. However, it may contain other additive components such as other known additives, compounding agents, and polymerization initiators. Next, these other additive components will be described.

[0130] <Component (D): an organic compound with a boiling point of 80°C or higher and 200°C or lower and an SP value of 8.0 to 10.0> The photochromic curable composition may further contain an organic compound (component (D)) having a boiling point of 80°C or higher and 200°C or lower and an SP value of 8.0 to 10.0. The SP value here is a value that is sometimes called the solubility parameter or Hildebrand parameter. When the photochromic curable composition contains component (D), poor appearance during coating is suppressed and the storage stability of the photochromic curable composition is also improved.

[0131] If the SP value of component (D) is less than 8.0, its compatibility with component (B) may decrease, resulting in poor coatability (wettability) and poor coating ease (coating workability) on the polyurethane resin layer. On the other hand, if the SP value of component (D) exceeds 10.0, its compatibility with component (B) may decrease, improving compatibility with scratch-resistant protective films, but it may also increase the likelihood of wrinkled appearance defects. In consideration of compatibility with component (B) and the effect of improving the above-mentioned issues, the SP value of component (D) is preferably 8.0 to 9.5, more preferably 8.0 to 9.0.

[0132] The boiling point of component (D) is preferably 80°C or higher and 200°C or lower. If the boiling point of component (D) is lower than 80°C, defects are likely to occur when the photochromic curable composition is cured, and the resulting cured product (photochromic laminate) is likely to have poor appearance. On the other hand, if the boiling point of component (D) is higher than 200°C, the resulting cured product (photochromic laminate) tends to have poor adhesion and durability. Adhesion refers to the adhesion between the photochromic layer formed from the cured product and the optical substrate. Considering the wettability and ease of coating (workability) on the optical substrate (or on the polyurethane resin layer), and the appearance and properties of the resulting cured product (photochromic laminate), 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.

[0133] The inclusion of this component (D) improves the compatibility of the photochromic compound, particularly when producing a photochromic cured product, resulting in a uniformly mixed photochromic curable composition, improving the wettability and ease of coating on the polyurethane resin layer. This improves the smoothness of the resulting photochromic layer, resulting in a good appearance. As a result, it is believed that a photochromic laminate with excellent appearance can be obtained even when the leveling agent (surfactant), which may have a negative effect when protected with a scratch-resistant protective film, is reduced from the photochromic curable composition. In other words, even when the leveling agent (surfactant) is reduced, the smoothness of the photochromic layer can be improved as described above, resulting in a photochromic laminate with excellent appearance. Therefore, when component (D) is used, a photochromic cured product (photochromic laminate) with excellent properties can be obtained without the addition of a leveling agent (surfactant).

[0134] The component (D) is not particularly limited as long as its SP value and boiling point fall within the above 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.

[0135] 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.

[0136] These components (D) can be used alone or in combination of two or more. When two or more components are used, the reference amount of component (D) is the total amount of these components (D). In addition, although styrene and methyl methacrylate listed here have radically polymerizable groups, they are also considered to be components (D).

[0137] The amount of the component (D) used is preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the component (B) (the amount of the composition (B')). When the amount of the component (D) used satisfies this range, compatibility with the component (B) can be enhanced, and the smoothness of the resulting photochromic layer can be further improved. As a result, the occurrence of defective appearance can be further suppressed. The adhesion and durability of the photochromic laminate can also be improved. From the viewpoints of compatibility and solubility with the component (B), the coatability of the photochromic curable composition, the wettability and coatability of a polyurethane resin layer laminated on an optical substrate, and the influence of residual organic compounds, the amount of the 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 the total amount of the component (B) (the amount of the composition (B')).

[0138] <Other added ingredients> The photochromic curable composition used in the present invention may contain various known compounding agents, such as various stabilizers such as polymerization initiators, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances, as needed, within the range that does not impair the effects of the present invention.

[0139] The amount of the other additive components used is not particularly limited as long as it does not impair the effects of the present invention, but is usually in the range of 0.001 to 10 parts by mass, particularly 0.01 to 7.5 parts by mass, and furthermore 0.05 to 6 parts by mass, per 100 parts by mass of the total amount of component (B) (amount of composition (B')). However, as mentioned above, when component (D) is blended, excellent effects are exhibited even without the inclusion of a leveling agent (surfactant).

[0140] (Polymerization initiator) The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator, and specific examples thereof are as follows:

[0141] 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.

[0142] 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:

[0143] When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine can also be used in combination.

[0144] (UV stabilizer) 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). Known 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.

[0145] The amount of the 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 the total amount of component (B) (amount of composition (B')).

[0146] (Leveling agent) The photochromic curable composition may also contain a leveling agent, provided that the effects of the present invention are not impaired. A non-reactive silicone oil may be used as the leveling agent. The non-reactive silicone oil is a siloxane having a linear polysiloxane skeleton, with the end or side chain of the polysiloxane skeleton modified with a non-reactive organic functional group. When a scratch-resistant protective film is attached to the surface of the photochromic cured body, the non-reactive silicone oil can prevent the adhesive of the scratch-resistant protective film from adhering to the surface of the photochromic cured body. 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. may be used.

[0147] The leveling agent may be a siloxane having an acyclic polysiloxane bond and a radical reactive group. The use of such a leveling agent results in a cured product with excellent appearance. The radical reactive group may be the same as the radical polymerization group used in component (A1) and the group reactive therewith. The leveling agent may contain a non-reactive functional group in addition to the radical 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. The leveling agent 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. The non-reactive functional group is more preferably at least one selected from the group consisting of a methyl group, a methoxy group, an ethoxy group, a phenyl group, a polypropylene group, and a polyether group. Among them, a compound represented by the following formula (8) is preferred.

[0148] [ka] 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. 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 OR30 , -(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).

[0149] 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. 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 NH2, an epoxy group, a group represented by the following formula (9), or a group represented by the following formula (10).

[0150] [ka] 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.

[0151] [ka] 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) qO-(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.

[0152] 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. The radically polymerizable group of the siloxane and the group reactive with the radically polymerizable group preferably contain a (meth)acryloyl group.

[0153] As the leveling agent represented by formula (8), commercially available products can be used. Examples of the leveling agent represented by formula (8) 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., BYK (registered trademark)-UV3505, BYK (registered trademark)-UV3505, and BYK (registered trademark)-UV3510 manufactured by BYK-Chemie Japan K.K., Examples of such an antibacterial agent 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.

[0154] Examples of the leveling agent having a methacryloyl group and represented by formula (8) 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. An example of the leveling agent having a vinyl group and represented by formula (8) is KR-511 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of leveling agents having an amino group and represented by formula (8) 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. Examples of the leveling agent having a thiol (mercapto) group and represented by formula (8) include KR-518, X-22-167B, X-22-167C, X-22-173BX, and X-22-173DX manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the leveling agent having an epoxy group and represented by formula (8) include KR-516, KR-517, X-24-9590, and X-41-1590A manufactured by Shin-Etsu Chemical Co., Ltd. Examples include 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, all of which are manufactured by Dow-Toray Industries, Inc.

[0155] Suitable mixing ratio of leveling agent The amount of the leveling agent is not particularly limited. The amount of the leveling agent is preferably 0.01 to 10.0 parts by mass per 100 parts by mass of component (B). If the amount of the leveling agent is too much or too little, the smoothness of the coating film of the curable composition may decrease, and multiple irregularities may appear in the cured product, resulting in poor appearance. Furthermore, in order to improve the smoothness of the curable composition and improve the appearance of the cured product, the amount of the leveling agent is more preferably 0.05 to 5.0 parts by mass, and even more preferably 0.10 to 2.0 parts by mass.

[0156] <Production method / properties of photochromic curable composition> The photochromic curable composition can be produced by mixing the components (A), (B), and (C), and other additive components (including component (D)) 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 (A) and, if necessary, the component (D) can be blended after the component (C) is sufficiently dispersed in the component (B). In this case, the other additive components may be blended at any time.

[0157] The SP value of the photochromic curable composition is not particularly limited. In particular, 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. This SP value is determined by titration using the turbidimetric titration method described in detail below.

[0158] <Photochromic cured product and laminate> A photochromic cured product can be produced by curing the photochromic curable composition produced by the above-mentioned method. By producing this cured product on an optical substrate, a laminate having a photochromic layer made of the cured product of the photochromic curable composition can be produced.

[0159] Curing to produce a photochromic laminate is carried out by a radical polymerization reaction using irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, γ-rays, and LEDs, heat, or a combination of both. That is, appropriate curing means may be adopted depending on the types of polymerizable monomers and polymerization curing accelerators used and the form of the photochromic laminate to be formed. When forming a photochromic laminate by the coating method described below, it is preferable to adopt photopolymerization because a uniform film thickness can be obtained.

[0160] 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 for irradiation with UV light for 0.1 to 5 minutes. Note that, according to the present invention, the effects of component (A) can be maintained while bleed-out of component (A) can be suppressed, allowing for a wide range of UV light intensity during production. In other words, sufficient curing can be achieved and bleed-out can be suppressed without increasing the UV light intensity too much, thereby widening the range of production.

[0161] When a photochromic laminate is obtained by a lamination method (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 are carried out by UV irradiation or heating in an inert gas such as nitrogen, thereby laminating a photochromic layer consisting of a photochromic cured product on the surface of the optical substrate.

[0162] Examples of optical substrates include substrates made of known materials, such as those used for eyeglass lenses, window glass for houses and automobiles, etc. Specific materials include plastic materials such as (meth)acrylic resins, polycarbonate resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins, as well as glass.

[0163] When forming a photochromic laminate on the surface of an optical substrate by the lamination method (coating method) described above, the adhesion between the photochromic laminate and the optical substrate can be improved 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. Of course, a transparent adhesive resin layer can also be provided on the surface of the optical substrate. This transparent adhesive resin layer is preferably a polyurethane resin layer. That is, it is preferable to use 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. When producing such a laminate, it is preferable to use the photochromic curable composition of the present invention. A detailed description will be given below.

[0164] <Method of forming a photochromic layer on a polyurethane resin layer> 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.

[0165] 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.

[0166] The coating liquid can be a commercially available product. 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 precursors of moisture-curable urethane resins 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 the above ranges are when the total amount of the solid content and solvent is taken as 100 mass %, and the coating liquid may contain any other known components).

[0167] Examples of solvents having an SP value of 8.0 or greater include the same organic compounds (solvents) in component (D) that have an SP value of 8.0 or greater. Among these, the following solvents are preferred because they contain urethane resin, moisture-curable urethane, and / or a precursor of moisture-curable urethane. Specifically, solvents having a boiling point of 70°C or greater and an SP value of 8.0 or greater 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), 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.

[0168] The coating liquid is applied to an optical substrate, and a polyurethane resin layer can be formed by removing the solvent having an SP value of 8.0 or more. When the coating liquid contains a moisture-curing urethane resin precursor, the polyurethane resin layer can be formed by curing with moisture in the air.

[0169] The thickness of the polyurethane resin layer on the optical substrate is not particularly limited, but is preferably 3.5 to 10.0 μm.

[0170] Next, the photochromic curable composition is applied onto the polyurethane resin layer, and then the photochromic curable composition is cured to form a cured product, thereby producing a photochromic laminate. A photochromic layer consisting of a cured product of the photochromic curable composition can be formed on the polyurethane resin layer. The applied photochromic curable composition can be cured by the method described above. The thickness of the photochromic layer is not particularly limited, but is 30 to 50 μm.

[0171] An excellent effect is exhibited when a photochromic layer is formed on such a polyurethane resin layer. While the reason for this is unclear, it is believed to be due to the low bleed-out of component (A). Additionally, it is presumed that when component (D) is incorporated, component (D) has an SP value similar to that of the solvent used in the coating liquid and the polyurethane resin layer formed. In other words, the photochromic curable composition is believed to have excellent wetting properties with the urethane resin layer formed from the coating liquid. As a result, even if the photochromic curable composition contains a reduced amount of leveling agent (surfactant), it is believed to exhibit excellent effects.

[0172] Furthermore, it is believed that a small amount of the solvent (a 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 when the photochromic curable composition is applied. Because this small amount of solvent may remain, when component (D) is added, it is believed that a photochromic laminate with excellent properties can be produced and productivity can be improved.

[0173] The photochromic curable composition can exhibit photochromic properties excellent in color density, color fading speed, etc., and can give a cured product imparted with good photochromic properties without reducing properties such as mechanical strength, etc. Although the coating method has been described above, the photochromic curable composition can also be used to produce a photochromic cured product by cast polymerization, dip coating, flow coating, spraying, binder method, etc.

[0174] In addition, photochromic cured bodies and laminates formed from the photochromic curable composition can be dyed with dyes such as disperse dyes depending on their intended use. A hard coat film can also be laminated thereon using a hard coat agent primarily composed of a silane coupling agent or an oxide sol of silicon, zirconium, antimony, aluminum, tin, tungsten, or the like. Furthermore, a thin film of a metal oxide such as SiO2, TiO2, or ZrO2 can be formed by vapor deposition directly or on the hard coat film. In addition, post-processing such as antireflection treatment or antistatic treatment using a thin film coated with an organic polymer is also possible.

[0175] From the viewpoint of improving the appearance of the photochromic laminate, the Vickers hardness of the photochromic cured body (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.

[0176] A scratch-resistant protective film may be attached to the photochromic laminate for the purpose of protecting the surface.

[0177] When a scratch-resistant protective film is attached to the surface of the photochromic cured body (at least on the photochromic layer) as described above, it is preferable that the SP values ​​of the photochromic curable composition and the adhesive be different by a certain amount, from the viewpoint of preventing the adhesive of the scratch-resistant protective film from adhering to the surface of the cured body and preventing the cured body from having wrinkled appearance due to the adhesive.

[0178] The upper limit of the difference in SP value between the photochromic curable composition and the adhesive of the scratch-resistant protective film is not particularly limited, but from the viewpoint of adhesiveness, it is preferably 5 or less. The difference in SP value between the photochromic curable composition and the adhesive of the scratch-resistant protective film is preferably 0.05 to 5.0, more preferably 0.075 to 4.0, and particularly preferably 0.1 to 3.0. The SP value of the photochromic curable composition and the SP value of the adhesive can be determined by titration using the turbidimetric titration method described in the Examples, as described in detail below.

[0179] Furthermore, when a scratch-resistant protective film is attached to the photochromic laminate, it is preferable that the photochromic cured product have a high contact angle with ethylene glycol in order to improve appearance defects caused by the adhesive of the scratch-resistant protective film adhering to the surface of the cured product. Specifically, the contact angle is preferably 50 degrees or more. By having the contact angle be 50 degrees or more, the above-mentioned appearance defects can be reduced. The upper limit of the contact angle between the photochromic cured product and ethylene glycol is not particularly limited, but 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]

[0180] 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.

[0181] Component (A) <(A1) component ((A1X) component)> 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: A hindered amine (molecular weight 370) having a methacrylate group and a piperidyl group, represented by the following formula (HALS-3):

[0182] [ka] The HALS-3 was prepared under the following conditions.

[0183] Synthesis of "HALS-3"; 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.

[0184] 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%.

[0185] 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 methacryl group and one proton due to the hydrogen atom at the 4th position of the piperidyl group were observed between 5 and 7 ppm.

[0186] From the above, it was confirmed that the compound was represented by the formula (HALS-3). The yield was 92%.

[0187] <(A2) component ((A2Y) component> HALS-1: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508). In the formula (Y), R 500 , and R 600 A compound where is a methyl group and W is 8.

[0188] (B) Component (B1) Ingredients: RX-1: Polyrotaxane with acrylate groups According to the method described in International Publication No. WO2018 / 030257, a polyrotaxane having an acrylate group satisfying the following properties was synthesized. Weight average molecular weight Mw (GPC) of polyrotaxane (RX-1) having acrylate groups: 180,000. Proportion of acrylate group modification in side chains: 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 acrylate groups per molecule: approximately 90.

[0189] The weight average molecular weight Mw of RX-1 was determined by GPC under the following conditions.

[0190] <Measurement of weight average molecular weight Mw of component (B1): RX-1> The weight-average molecular weight Mw of the (B1) component, polyrotaxane (RX-1), was measured by gel permeation chromatography (GPC). A liquid chromatograph (manufactured by Nihon Waters) was used. Two TSKgel SuperHM-M columns (molecular weight exclusion limit: 4,000,000, manufactured by Tosoh Corporation) were used in series.

[0191] Furthermore, tetrahydrofuran was used as the developing liquid, and measurements were made at a flow rate of 0.6 ml / min and a temperature of 40° C. Using polystyrene as a standard sample, the weight average molecular weight was calculated by comparative conversion, and the weight average molecular weight of RX-1 was found to be 180,000.

[0192] (B2) Component SO-1: Silsesquioxane having a methacrylate group synthesized by the following method. Number of methacrylate groups per molecule: 20. Weight average molecular weight of silsesquioxane having methacrylate groups: 4,800.

[0193] <Component (B2): Method for producing SO-1> 248 ml of ethanol and 54 g (3.0 mol) of water were added to 248 g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate, and 0.20 g (0.005 mol) of sodium hydroxide was added as a catalyst, followed by a reaction at 30°C for 3 hours. After confirming the disappearance of the raw materials, the mixture was neutralized with dilute hydrochloric acid, and 174 ml of toluene, 174 ml of heptane, and 174 g of water were added, followed by removal of the aqueous layer. The organic layer was then washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain the silsesquioxane (PMS-1) used in the present invention. 1 H-NMR confirmed that the raw material was completely consumed. 29 Si-NMR confirmed that the structure was a mixture of cage, ladder and random structures.

[0194] <Confirmation of the acid value of component (B2): SO-1> The acidic components contained in SO-1 were evaluated by quantifying the acid value using the titration method described below. A 2 ml microburet was loaded with 0.1 mol / L potassium hydroxide alcohol solution (ethanolic) (hereinafter referred to as the measurement solution), 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. Three drops of phenolphthalein solution were then 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. The acid value of SO-1 measured using this method was 1.1 mg KOH / g.

[0195] <Measurement of weight average molecular weight Mw of component (B2): SO-1> The weight-average molecular weight Mw of component (B2): 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.).

[0196] The measurement was also carried out using tetrahydrofuran as the developing liquid at a flow rate of 1 ml / min and a temperature of 40° C. Using polystyrene as the standard sample, the weight average molecular weight was calculated by comparative conversion, and the weight average molecular weight of SO-1 was found to be 4,800.

[0197] (B2) Component SO-2: "Product name: AC-SQ SI-20, manufactured by Toagosei Co., Ltd." Silsesquioxane. Number of acrylate groups per molecule: approximately 4. Weight average molecular weight of silsesquioxane having acrylate groups: 2,000.

[0198] Ingredient (B3) Component (B31): Bifunctional (meth)acrylate (B31a) Ingredients: 9G: Polyethylene glycol dimethacrylate (average difference length of ethylene glycol chains: 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).

[0199] (B31b) Ingredients: BPE800: 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=10, average molecular weight 804).

[0200] Component (B32): Polyfunctional (meth)acrylate (B32a) Ingredients: TMPT; Trimethylolpropane trimethacrylate. D-TMP; ditrimethylolpropane tetraacrylate. (B31c) Ingredients: APC56: Polycarbonate obtained by phosgenation of pentamethylene glycol and hexamethylene glycol to Diol (average molecular weight 1000)

[0201] (B33) Component: Monofunctional (meth)acrylate TSL-1: γ-methacryloyloxypropyltrimethoxysilane. GMA: glycidyl methacrylate.

[0202] (C) Component PC1: A compound represented by the following formula: [ka] PC2: A compound represented by the following formula, synthesized with reference to the method described in WO2019 / 013249

[0203] [ka] 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.

[0204] [ka]

[0205] (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).

[0206] (Other added ingredients) polymerization initiator CGI-1: phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (trade name: Omnirad819, manufactured by IGM) (polymerization initiator). CGI-2: 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM) (polymerization initiator).

[0207] (Other added ingredients) Stabilizer, leveling agent (surfactant) HP: Ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (Ciba Specialty Chemicals, Irganox 245) (stabilizer). L7001: (Product name: L7001, manufactured by Toray Dow Corning Co., Ltd.) (Leveling agent).

[0208] Example 1 Regarding the preparation of the photochromic curable composition and the production and evaluation of the photochromic cured product (photochromic cured product), the components were thoroughly mixed according to the following recipe to prepare a photochromic curable composition.

[0209] Prescription; (Photochromic curable composition) Component (A); Component (A2); 1 part by mass of HALS-1; Component (A1); 1.5 parts by mass of HALS-2. (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) Ingredient: 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. Other added ingredients: (Polymerization initiator): CGI-1 0.3 parts by mass, CGI-2 0.3 parts by mass. (stabilizer); HP 1 part by mass.

[0210] In the manufacturing method, component (A), composition (B'), component (C), and other additive components are first mixed. In the examples and comparative examples using component (D), component (D) is further mixed with the resulting mixture to form a uniform photochromic curable composition.

[0211] (Measurement of SP value of photochromic curable composition) The SP value of the obtained photochromic curable composition was evaluated by turbidity titration. 2.0 g of the photochromic curable composition was dissolved in 10 ml of acetone. The obtained photochromic curable composition solution was titrated with deionized water and n-hexane, and the titration amount at which the solution became turbid was calculated. The SP value was calculated from the obtained value 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. VL: 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.

[0212] (Production and evaluation of photochromic laminates (cured photochromic materials)) The photochromic curable composition was used to obtain a photochromic laminate by a lamination method. The curing method is as follows.

[0213] First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 5% aqueous solution of sodium hydroxide at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0214] Using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the plastic lens was coated with a moisture-curable primer (coating liquid) at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds, to obtain a 6 μm polyurethane resin layer. The moisture-curable primer (coating liquid) used contained a moisture-curable 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 mass of ethyl acetate per 100 parts by mass of toluene.

[0215] Thereafter, approximately 2 g of the photochromic curable composition obtained above was spin-coated onto the polyurethane resin layer at a rotation speed of 100 rpm for 30 seconds, and then at 900 rpm for 5 to 15 seconds, so that the photochromic layer had a thickness of 40 μm.

[0216] The lens having the photochromic curable composition applied to its surface was then heated in a nitrogen gas atmosphere at 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 (photochromic optical article) having a photochromic layer. The same method was repeated to produce 20 photochromic laminates (photochromic optical articles). The evaluation was carried out according to the following evaluation methods, and the results are shown in Table 5.

[0217] (Evaluation method) (1) Photochromic properties The obtained photochromic optical article was used as a sample, and was irradiated with a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. through an Aeromass filter (manufactured by Corning) at 20±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 properties were measured by irradiating the solution with light for 300 seconds to develop color.

[0218] 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 and the absorbance ε(0) before light irradiation at the maximum absorption wavelength. The higher this value, the better the photochromic properties. ·Fading speed〔t1 / 2(sec.)〕: The time required for the absorbance of a sample at the maximum absorption wavelength 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. The above evaluation was carried out by measuring the 20 sheets produced, and the average values ​​are shown in the table.

[0219] (2) Repeated durability The following accelerated deterioration test was conducted to evaluate the durability of the color development due to repeated exposure to light. The test method is as follows. The obtained photochromic laminate (photochromic optical article) was subjected to accelerated deterioration 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 as described above, and the color density before the test (A0) and the color density after the test (A 200 ) was measured.

[0220] From the measurement results, the residual rate, which is an index of the durability against repeated use, was calculated. 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.

[0221] 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.

[0222] 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.

[0223] (3) Appearance evaluation (appearance, cracks, cloudiness, wrinkle defects) All of the obtained photochromic optical articles were observed and evaluated using an optical microscope and an illumination device (QC X75, manufactured by Valvetronics) for appearance (orange peel, spiral defects), cracks, the presence or absence of cloudiness, and wrinkle defects (referring to wrinkle-like appearance defects that occur on the surface of the photochromic optical article). These evaluations were performed by attaching a scratch-resistant protective film (acrylic adhesive, 0.1 mm thick) to the photochromic layer of the obtained photochromic optical article, and checking the condition after heating at 70°C for 1 hour and after heating at 70°C for 2 hours. By heating, the evaluation results of the accelerated condition can be obtained. If the appearance is good after 2 hours of heating, it means that a photochromic optical article (photochromic laminate) with excellent appearance can be obtained after peeling off the scratch-resistant protective film, even if it has been attached for a long period of time. The appearance, cracks, cloudiness, and wrinkle defects were evaluated by peeling off the scratch-preventing protective film and observing the photochromic optical article with an optical microscope and a lighting device (QC X75, manufactured by Valvetronics). The evaluation criteria are shown below.

[0224] <Appearance> A: All photochromic optical articles were uniform and no defects in appearance were observed. B: Very slight defects in appearance are observed (one or more sheets present). C: Slight defects in appearance (one or more sheets present). D: Partially defective appearance (one or more sheets present). E: Overall appearance is poor (one or more sheets present). In this evaluation, if even one of the 20 photochromic optical articles produced had the above-mentioned appearance defects, the corresponding evaluation (lowest evaluation) was shown in the table.

[0225] <Crack> A: All photochromic optical articles are uniform and no cracks are observed. B: Very few fine cracks are observed (one or more sheets present). C: Slight cracks are observed (one or more sheets present). D: Cracks are partially observed (one or more sheets present). E: Cracks are observed throughout the entire surface (one or more sheets present). In this evaluation, if even one of the 20 photochromic optical articles produced had the above-mentioned cracks, the corresponding evaluation (lowest evaluation) was shown in the table.

[0226] <Cloudy> A: All photochromic optical products are uniform and no opacity is observed. B: Very slight white turbidity is observed (one or more sheets present). C: Slight cloudiness is observed (one or more sheets present). D: Partial clouding is observed (one or more sheets present). E: Overall cloudiness is observed (one or more sheets are present). In this evaluation, if even one of the 20 photochromic optical articles produced had the above-mentioned cloudiness, the corresponding evaluation (lowest evaluation) was shown in the table.

[0227] <Wrinkle defects> A: All photochromic optical articles were uniform and no wrinkle defects were observed. B: Very slight wrinkle defects are observed (one or more sheets present). C: Slight wrinkle defects are observed (one or more sheets present). D: Wrinkles are partially observed (one or more sheets present). E: Wrinkles are observed throughout the entire sheet (one or more sheets are present). In this evaluation, if even one of the 20 photochromic optical articles produced had the above-mentioned wrinkle defect, the corresponding evaluation (the lowest evaluation) was shown in the table. This "wrinkle defect" is thought to be caused by the adhesive transferred from the scratch-resistant protective film.

[0228] The above evaluations were carried out after heating at 70°C for 1 hour and after heating at 70°C for 2 hours. M The test pieces were evaluated after peeling off the film. As a result, the evaluations of "appearance", "cracking", and "cloudiness" were the same after heating at 70°C for 1 hour and after heating at 70°C for 2 hours. However, the evaluation of "wrinkle defects" showed different results after heating at 70°C for 1 hour and after heating at 70°C for 2 hours, so Table 5 shows the results for both.

[0229] (4) Yield Of the 20 photochromic optical articles produced, the number of those that were uniform and had no defects such as cracks, cloudiness, or wrinkles was observed and evaluated, and the number of those was calculated as the yield. The results of this yield after heating at 70°C for 2 hours are shown in Table 5.

[0230] (5) Adhesion The cross-cut tape test was conducted in accordance with JISD-0202. Specifically, a cutter knife was used to make cuts at 1 mm intervals on the surface of the obtained photochromic optical article, forming 100 grids. Cellophane adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was firmly attached thereon, and then pulled in a 90° direction from the surface to peel it off, and the grids where the photochromic optical article remained were evaluated. The average values ​​for 20 sheets are shown in the table.

[0231] (6) Vickers hardness The Vickers hardness was measured using a micro Vickers hardness tester PMT-X7A (manufactured by Matsuzawa Corporation). A square pyramidal diamond indenter was used, 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 value, which had a large measurement error. The average values ​​of 20 sheets are shown in the table.

[0232] (7) Contact angle with ethylene glycol For the photochromic laminate, an automatic contact angle meter DM500 (manufactured by Kyowa Interface Science Co., Ltd.) was used to drop ethylene glycol (2.0 μl) onto the photochromic layer, and the drop of ethylene glycol (2.0 μl) formed on the photochromic laminate was measured 5 seconds after the drop. ethylene The contact angle with glycol was measured five times and the average value was used as the result. The average value of 20 sheets is shown in the table.

[0233] (8) SP value difference The difference in adhesive strength between the photochromic curable composition and the scratch-preventing protective film was calculated, and the average values ​​for 20 sheets are shown in the table.

[0234] (9) Turbidity To evaluate the surface turbidity after long-term storage, the following accelerated storage test was conducted. Specifically, the obtained photochromic laminate (photochromic optical article) was placed in a thermo-hygrostat chamber at 60°C and 98% RH for 24 hours. Using a haze meter, the difference in haze value before and after the test (ΔHAZE) was determined. 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.

[0235] <Examples 2 to 23 and Comparative Examples 1 to 3> Photochromic curable compositions were prepared in the same manner as in Example 1, except that the components shown in Tables 1 to 4 were used and the curing outputs shown in Tables 1 to 4 were used, and photochromic laminates were produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 5 and 6.

[0236] In all Examples and Comparative Examples, the evaluations of "appearance", "cracking", and "cloudiness" were the same after heating at 70°C for 1 hour and after heating at 70°C for 2 hours, as in Example 1. However, the evaluation of "wrinkle defect" showed different results after heating at 70°C for 1 hour and after heating at 70°C for 2 hours, so both the results are shown in Tables 5 and 6.

[0237] [Table 1]

[0238] [Table 2]

[0239] [Table 3]

[0240] [Table 4]

[0241] [Table 5]

[0242] [Table 6]

[0243] <Examples 24 to 34, Comparative Examples 4 and 5> Photochromic curable compositions and photochromic laminates were prepared and evaluated in the same manner as in Example 1, except that the components shown in Table 7 were used. The results are shown in Table 8.

[0244] [Table 7]

[0245] [Table 8] [Explanation of symbols]

[0246] 1: Polyrotaxane 2: Axial molecule 3: Cyclic molecules 4: Bulky end groups 5: Side chain

Claims

1. (A1) a first hindered amine compound having at least one reactive group selected from the group consisting of a radically polymerizable group and a group reactive with a radically polymerizable group; (A2) a secondary hindered amine compound having no reactive group, (B1) a polyrotaxane component having a radical polymerizable group, and (B) a radical polymerizable monomer having no piperidyl group; and (C) Photochromic compound 1. A photochromic curable composition comprising:

2. 2. The photochromic curable composition according to claim 1, comprising 0.1 parts by mass or more and 5.0 parts by mass or less of the first hindered amine compound (A1) relative to 100 parts by mass of the radical polymerizable monomer component (B).

3. 3. The photochromic curable composition according to claim 1, wherein a ratio M1 / M2 of a mass M1 of the polyrotaxane component (B1) to a mass M2 of the first hindered amine compound (A1) is 0.1 or more and 40 or less.

4. The first hindered amine compound (A1) includes a compound represented by the following formula (X): The photochromic curable composition according to any one of claims 1 to 3; 【Chemical 1】 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 on average, 【Chemistry 2】 In formula (Z), R ４００ is an alkylene group having 1 to 20 carbon atoms, v is a number between 0 and 20 on average.

5. 5. The photochromic curable composition according to claim 1, wherein a ratio of the polyrotaxane component (B1) to the radical polymerizable monomer component (B) is 0.1 mass% or more and 50 mass% or less.

6. The photochromic curable composition according to any one of claims 1 to 5, wherein the (B) radically polymerizable monomer component further contains (B2) 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 leveling agent.

8. The second hindered amine compound (A2) includes a compound represented by the following formula (Y): The photochromic curable composition according to any one of claims 1 to 7; 【Chemistry 3】 In formula (Y), R ５００ , and R ６００ are each a hydrogen atom or a methyl group, W is an integer from 1 to 50.

9. The photochromic curable composition according to any one of claims 1 to 8, further comprising (D) 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.

10. The photochromic curable composition according to any one of claims 1 to 9, comprising 0.10 parts by mass or more and 10.0 parts by mass or less of the organic compound (D) relative to 100 parts by mass of the radical polymerizable monomer component (B).

11. 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 10; a polyurethane resin layer located between the optical substrate and the photochromic resin layer; 1. A photochromic laminate comprising:

Images