Curable composition, cured product, laminate, optical article, lens, and eyeglasses

Abstract

This disclosure provides a curable composition, a cured product, a laminate, an optical article, a lens, and eyeglasses that can achieve excellent performance and hardness of a cured product with a functional pigment. According to an embodiment, a curable composition is provided. The curable composition comprises a first radical polymerizable monomer represented by formula (1) and a functional pigment. In formula (1), R... 1 and R 3 Each is an independent monovalent group as shown in formula (2), a2 is 1, or a number greater than 2 and less than 10, R 200 When R is a hydrogen atom or a methyl group and a2 is 1, 2 When R is a monovalent group as shown in formula (2), and a2 is 2 or more and 10 or less, 2 For the monovalent group or hydrogen atom shown in formula (2), multiple R 2 At least one of them is a monovalent group as shown in formula (2) below. The multiple monovalent groups shown in formula (2) may be the same as or different from each other.

Description

Technical Field

[0001] This invention relates to curable compositions, cured products, laminates, optical articles, lenses, and eyeglasses. Background Technology

[0002] Photochromic compounds, such as naphthopyran compounds, fumonisin anhydride compounds, and spiroxazine compounds, are compounds that can reversibly acquire two isomers with different absorption spectra when exposed to ultraviolet light, such as sunlight or mercury lamp light. They typically possess the following property (hereinafter also referred to as photochromism): when a colorless, achromatic compound is exposed to ultraviolet light, its color rapidly changes, isomerizing into a colored, chromogenic state (color reaction). When the light exposure is stopped and the compound is placed in the dark, it reverts to its original color. This property is utilized for various applications, particularly in optical materials.

[0003] For example, photochromic lenses, which are made photochromic by using photochromic compounds, rapidly color outdoors when exposed to sunlight containing ultraviolet light, thus functioning as sunglasses, and fade indoors when not exposed to such light, thus functioning as ordinary, transparent eyeglasses. In recent years, demand for them has increased.

[0004] One known method for imparting photochromic properties to optical materials is a coating method in which a photochromic curable composition is applied to a plastic lens by spin coating or similar means and then photocured to form a photochromic coating. The photochromic curable composition may contain, for example, various (meth)acrylates and urethane oligomers.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 98 / 37115

[0008] Patent Document 2: US Patent No. 5914174

[0009] Patent Document 3: International Publication No. 01 / 02449

[0010] Patent Document 4: International Publication No. 03 / 11967

[0011] Patent Document 5: International Publication No. 2015 / 054036

[0012] Patent Document 6: International Publication No. 2009 / 075388 Summary of the Invention

[0013] The problem the invention aims to solve

[0014] The purpose of this invention is to provide: a curable composition, a cured product, a laminate, an optical article, a lens, and eyeglasses that can achieve excellent performance and hardness of a cured product with functional pigments.

[0015] Solution for solving the problem

[0016] According to this disclosure, a curable composition is provided. The curable composition comprises a first radical polymerizable monomer as shown in formula (1) and a functional pigment.

[0017]

[0018] In equation (1), R 1 and R 3 Each is an independent monovalent group as shown in formula (2) below, where a2 is 1, or a number greater than 2 and less than 10, and R 200 When R is a hydrogen atom or a methyl group and a2 is 1, 2 When R is a monovalent group as shown in formula (2) below, and a2 is 2 or more and 10 or less, 2 For a monovalent group or hydrogen atom as shown in formula (2) below, multiple R 2 At least one of them is a monovalent group as shown in the following formula (2), and the multiple monovalent groups shown in the following formula (2) may be the same or different from each other.

[0019]

[0020] In equation (2), Q 1 It is a straight-chain or branched alkylene group having 1 or more but less than 6 carbon atoms, Q 2 b2 is a hydrogen atom or a methyl group, and b2 is 0, or 1 or more but less than 15.

[0021] According to this disclosure, a cured product is provided. The cured product is obtained by curing the curable composition of the embodiment.

[0022] According to this disclosure, a laminate is provided. The laminate includes an optical substrate and a cured product of an embodiment located on the surface of the optical substrate.

[0023] According to the present invention, a lens is provided. The lens comprises: a lens substrate and a cured product of an embodiment located on the surface of the optical substrate.

[0024] According to this disclosure, eyeglasses are provided. The eyeglasses include lenses according to embodiments.

[0025] The effects of the invention

[0026] According to the present invention, a curable composition, a cured product, a laminate, an optical article, a lens, and eyeglasses are provided, which can achieve a cured product with excellent functionality and hardness of functional pigments. Attached Figure Description

[0027] Figure 1 A cross-sectional view illustrating an example of a laminated body according to an embodiment. Detailed Implementation

[0028] The curable composition of the embodiment comprises a first radical polymerizable monomer and a functional pigment. The first radical polymerizable monomer is a compound having the structure shown in the following formula (1). The first radical polymerizable monomer is, for example, a tri(meth)acrylate containing a structure derived from glycerol. If such a curable composition is used, it is possible to achieve a cured product with excellent functionality of the functional pigment. The reason for this is not yet clear, but the inventors speculate as follows.

[0029] First, functional pigments such as photochromic compounds contain compounds that undergo structural changes through energy such as light to produce, decolorize, or change color. To facilitate structural changes in such functional pigments within a polymer matrix, it is important to configure the pigments within soft segments of the polymer matrix. Increasing the proportion of di(meth)acrylate in the curing composition is useful for increasing the proportion of soft segments in the cured product. However, if the proportion of di(meth)acrylate is too high, the number of crosslinking sites decreases, potentially reducing the curability of the polymer matrix. Therefore, curing compositions with further additions of polyfunctional radical polymerizable monomers with three or more functions are sometimes used. For example, by adding low-molecular-weight polyfunctional radical polymerizable monomers such as trimethylolpropane trimethacrylate (TMPT), the number of crosslinking sites increases, thereby improving the curability and hardness of the polymer matrix. However, in this cured material, although functional pigments may be present in the space around the crosslinking sites, especially in the space around the crosslinking sites where multifunctional free radical polymerizable monomers have reacted with each other, the space is insufficient to undergo structural changes, and therefore the performance of the functional pigments may be reduced.

[0030] The curable composition of the embodiment comprises a compound having the structure shown in formula (1) as a first radical polymerizable monomer. Such a compound is, for example, a polyfunctional (meth)acrylate having a structure derived from glycerol with three or more functions. In the (poly)glycerol structure, the distance between (meth)acrylate groups is smaller than that of polyfunctional radical polymerizable monomers such as TMPT. Therefore, it is believed that the space near the crosslinking site, especially the space formed by the reaction of the first radical polymerizable monomers with each other, is even smaller, and functional pigments are less likely to exist near the crosslinking site. As a result, the proportion of functional pigments that may exist near the crosslinking site decreases, while the proportion of functional pigments located in the soft chain segment increases, thereby the performance of the functional pigments is less likely to deteriorate, and the performance of the functional pigments in the cured product can be improved.

[0031] Furthermore, the high concentration of (meth)acryloyl groups per molecule of the first radical polymerizable monomer allows for an increase in the number of crosslinking sites. This, in turn, improves the hardness of the cured product. Therefore, it is possible to achieve a balance between the functionality and hardness of the functional pigments in the cured product.

[0032] The following is a detailed description of each ingredient.

[0033] <(A) Free radical polymerizable monomers>

[0034] The free radical polymerizable monomer (A) contains component (A-1), namely, the first free radical polymerizable monomer shown in formula (1). Hereinafter, the first free radical polymerizable monomer shown in formula (1) will also be referred to as component (A-1). The free radical polymerizable monomer (A) will also be referred to as component (A). The free radical polymerizable monomer (A) may contain other free radical polymerizable monomers depending on the desired properties of the cured product.

[0035] As for other free radical polymerizable monomers, there are no particular restrictions on any polymerizable monomer that can polymerize with component (A-1). Known free radical polymerizable monomers can be used, preferably free radical polymerizable monomers having (meth)acrylate groups. Suitable components include: component (A-2), i.e., free radical polymerizable monomers having two (meth)acryloyl groups in one molecule; component (A-3), i.e., free radical polymerizable monomers having three or more (meth)acryloyl groups in one molecule other than component (A-1); and component (A-4), i.e., other free radical polymerizable monomers having (meth)acryloyl groups.

[0036] <(A-1) Component; First radical polymerizable monomer>

[0037] The first free radical polymerizable monomer is a polyfunctional (meth)acrylate compound represented by the following formula (1).

[0038]

[0039] In equation (1), R 1 and R 3 Each is an independent monovalent group as shown in formula (2) below. R 2 This refers to a monovalent group or hydrogen atom as shown in formula (2) below. Multiple R 2 At least one of them is a monovalent group as shown in formula (2) below. a2 is 1, or a number greater than 2 and less than 10. R 200 It can be a hydrogen atom or a methyl group.

[0040]

[0041] In equation (2), Q 1It is a straight-chain or branched alkylene group with 1 to 6 carbon atoms. From the perspective of balancing the performance and hardness of functional pigments, Q... 1 Preferably, it is a straight-chain alkylene group with 1 or more and 6 or less carbon atoms, and more preferably, it is a straight-chain alkylene group with 2 or more and 4 or less carbon atoms.

[0042] b2 is 0, or 1 or more but less than 15. From the viewpoint of balancing the performance and hardness of functional pigments, b2 is preferably less than 12, more preferably less than 10, and most preferably less than 8.

[0043] Q 2 It can be a hydrogen atom or a methyl group. That is, component (A-1) can be a compound with only an acryloyl group as shown in formula (1) above, a compound with only a methacryloyl group, or a compound with both methacryloyl and acryloyl functional groups. If component (A-1) with a high proportion of methacryloyl groups is used, the color development concentration of the photochromic pigment is high, and there is a tendency to obtain a cured product with excellent repeatability and durability. If component (A-1) with a high proportion of methacryloyl groups is used, there is a tendency to obtain a cured product with excellent curability. Q 2 Methyl is preferred.

[0044] When a2 is 1, R 2 It is a monovalent group as shown in the above formula (2). That is, when a2 is 1, the first radical polymerizable monomer contains a monoglyceride (meth)acrylate compound as shown in the following formula (1a) (hereinafter, monoglyceride first radical polymerizable monomer).

[0045]

[0046] In equation (1a), R 200 It can be a hydrogen atom or a methyl group. From the viewpoint of ease of acquisition and balancing functionality and hardness, a hydrogen atom is preferred.

[0047] R 201 R 202 and R 203 Each is an alkylene group, either linear or branched, having 1 or more but 6 or fewer carbon atoms. From the viewpoint of balancing the performance and hardness of functional pigments, linear alkylene groups with 1 or more but 6 or fewer carbon atoms are preferred, and linear alkylene groups with 2 or more but 4 or fewer carbon atoms are even more preferred. 201 R 202 and R 203 They can have the same structure as each other, or they can have different structures.

[0048] b3, b4, and b5 are each independently 0, or 1 or more but less than 4. From the viewpoint of balancing the performance and hardness of functional pigments, it is preferable to be 3 or less, more preferably 2 or less, and most preferably 0.

[0049] R 204 R 205 and R 206 The atom is hydrogen or methyl. That is, component (A-1) can be triacrylate, trimethacrylate, dimethacrylate, or diacrylate methacrylate as shown in formula (1a) above. If component (A-1) with a high proportion of methacrylate groups is used, the color development concentration of the photochromic pigment is high, and there is a tendency to obtain a cured product with excellent repeatability and durability.

[0050] From the viewpoint of balancing functionality and hardness, the number-average molecular weight of the monoglyceride-based first radical polymerizable monomer shown in formula (1a) is preferably less than 850, more preferably 600 or less, more preferably 530 or less, even more preferably 460 or less, and particularly preferably 390 or less. The lower limit of the number-average molecular weight of the monoglyceride-based first radical polymerizable monomer is, for example, 254 or more, and according to another example, 296 or more. The number-average molecular weight can be determined, for example, by gel permeation chromatography (GPC) or mass spectrometry.

[0051] Specific examples of the monoglyceride-based first radical polymerizable monomers shown in formula (1a) above include glycerol trimethacrylate, glycerol triacrylate, glycerol dimethacrylate monoacrylate, glycerol diacrylate monomethacrylate, ethoxylated glycerol trimethacrylate, propoxylated glycerol trimethacrylate, butoxylated glycerol trimethacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, and butoxylated glycerol triacrylate.

[0052] The monoglyceride-based first radical polymerizable monomer preferably comprises at least one selected from the group consisting of glycerol trimethacrylate, glycerol triacrylate and ethoxylated glycerol trimethacrylate.

[0053] Glyceryl trimethacrylate is represented by the following formula (1-1A).

[0054]

[0055] Glyceryl triacrylate is represented by the following formula (1-2A).

[0056]

[0057] Ethoxylated glycerol trimethacrylate is represented by the following formula (1-3A).

[0058]

[0059] In equation (1), when a2 is greater than 2 and less than 10, R 2 This refers to a monovalent group or hydrogen atom as shown in formula (2) above. Multiple R... 2 At least one of them is a monovalent group as shown in formula (2) above. The multiple monovalent groups shown in formula (2) above may be identical or different from each other. From the viewpoint of obtaining a cured product with higher hardness, R 2 Preferably, it is a monovalent group as shown in formula (2) above. From the viewpoint of ease of acquisition, taking into account both the performance and hardness of functional pigments, a2 is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, and most preferably 2 or more and 4 or less.

[0060] That is, when a2 in formula (1) is 2 or more and 10 or less, the first free radical polymerizable monomer is a polyglycerol-based polyfunctional (meth)acrylate.

[0061] From the viewpoint of balancing functionality and hardness, and facilitating viscosity handling, the number average molecular weight of the first radical polymerizable monomer in a polyglycerol system is preferably less than 3000, more preferably 2500 or less, more preferably 2000 or less, further preferably 1700 or less, and particularly preferably 1500 or less. The lower limit of the number average molecular weight of the first radical polymerizable monomer in a polyglycerol system is, for example, 380 or more, and according to another example, 430 or more. The number average molecular weight can be determined, for example, by gel permeation chromatography (GPC) or mass spectrometry.

[0062] Specific examples of the first radical polymerizable monomer of the polyglycerol system shown in formula (1) above include diglycerol trimethacrylate, diglycerol triacrylate, diglycerol tetramethacrylate, diglycerol tetraacrylate, diglycerol dimethacrylate diacrylate, triglycerol pentaacrylate, triglycerol pentamethacrylate, triglycerol tetramethacrylate, triglycerol hexamethacrylate, tetraglycerol hexamethacrylate, tetraglycerol pentamethacrylate, tetraglycerol pentamethacrylate, ethoxylated tetraglycerol hexamethacrylate, propoxylated tetraglycerol hexamethacrylate, and butoxylated tetraglycerol hexamethacrylate. Acrylates, ethoxylated tetraglycerol hexaacrylate, propoxylated tetraglycerol hexaacrylate, butoxylated tetraglycerol hexaacrylate, ethoxylated triglycerol pentamethacrylate, propoxylated triglycerol pentamethacrylate, butoxylated triglycerol pentamethacrylate, propoxylated triglycerol pentamethacrylate, butoxylated triglycerol pentamethacrylate, ethoxylated diglycerol tetramethacrylate, propoxylated diglycerol tetramethacrylate, butoxylated diglycerol tetramethacrylate, ethoxylated diglycerol tetramethacrylate, propoxylated diglycerol tetramethacrylate, and butoxylated diglycerol tetramethacrylate, etc.

[0063] The first free radical polymerizable monomer of the polyglycerol system preferably comprises at least one selected from the group consisting of diglycerol tetraacrylate, diglycerol tetramethacrylate, ethoxylated diglycerol tetraacrylate, ethoxylated diglycerol tetramethacrylate, triglycerol tetramethacrylate and triglycerol pentamethacrylate.

[0064] Glyceryl tetramethacrylate is represented by the following formula (1-1).

[0065]

[0066] Ethoxylated glycerol tetramethacrylate is represented by the following formula (1-2).

[0067]

[0068] Triglyceride tetramethacrylate is represented by the following formula (1-3).

[0069]

[0070] Triglyceride pentamethacrylate is represented by the following formula (1-4).

[0071]

[0072] The first free radical polymerizable monomer can be a mixture of a monoglyceride trifunctional (meth)acrylate with a2 of 1 and a polyglyceride polyfunctional (meth)acrylate with a2 of 2 or more in formula (1).

[0073] <(A-2) Composition: A second radical polymerizable monomer with two (meth)acryloyl groups per molecule>

[0074] The curable composition of the embodiment preferably further comprises component (A-2): a second radical polymerizable monomer having two (meth)acryloyl groups in one molecule. If component (A-2) is included, there is a tendency to obtain a cured product with high performance of functional pigment.

[0075] (A-2) The component preferably has one or more methacryloyl groups, more preferably two methacryloyl groups. When methacryloyl groups are present, there is a tendency for the degradation of functional pigments to be suppressed and the appearance of the cured product to be improved.

[0076] Component (A-2) preferably contains alkylene oxide chains. Using such a component (A-2) tends to improve the functionality of the cured product. Particularly preferred is a second radical polymerizable monomer having at least one polyalkylene glycol chain structure with a number average molecular weight of 250 or more. The number of carbon atoms in the alkylene oxide chain is preferably 1 or more and 10 or less, more preferably 2 or more and 5 or less. The ratio of the number average molecular weight N2 of the alkylene oxide chain to the number average molecular weight N1 of component (A-2) is preferably 50% or more, more preferably 60% or more, and even more preferably 80% or more. This ratio can be 95% or less, or 90% or less.

[0077] Considering the performance of the functional pigments, hardness, and consequently the viscosity of the cured composition, the number average molecular weight of component (A-2) is preferably 350 or more and 9000 or less, more preferably 400 or more and 7000 or less, further preferably 500 or more and 6000 or less, and most preferably 600 or more and 3500 or less. The number average molecular weight of component (A-2) can be 400 or more and 3500 or less, or 600 or more and 2500 or less. The number average molecular weight can be determined, for example, by gel permeation chromatography (GPC).

[0078] The second radical polymerizable monomer may contain at least one structure selected from the group consisting of ester bonds, urethane bonds, urea bonds, carbonate bonds, and carbonyl groups. Preferably, the second radical polymerizable monomer does not contain at least one structure selected from the group consisting of ester bonds, urethane bonds, urea bonds, carbonate bonds, and carbonyl groups.

[0079] The second radical polymerizable monomer preferably comprises di(meth)acrylate as shown in formula (3) below.

[0080]

[0081] In equation (3), Q 3 and Q 6 Each molecule can be a hydrogen atom or a methyl group. That is, it can be a diacrylate, dimethacrylate, or methacrylate. Q 3 and Q 6 Methyl is preferred.

[0082] Q 4 and Q 5 Each is independently an alkyl group having 1 or more hydrogen atoms and 3 or fewer carbon atoms. Q 4 and Q 5 Each is preferably a hydrogen atom or a methyl group, with a particular preference for hydrogen atoms.

[0083] a and b are each independently 0 or more and 10 or less. a and b are preferably 0 or more and 5 or less, more preferably 0 or more and 3 or less, and particularly preferably 0 or more and 2 or less.

[0084] Z 1 and Z 2 Each is independently 0 or 1. From the viewpoint of having easily manageable viscosity, Z 1 and Z 2 The preferred value is 0.

[0085] Q 7 It is a divalent group with a number average molecular weight of 250 or more, as shown in the following formula (3a).

[0086]

[0087] Q in equation (3a) 7a Q 7b Q 7d and Q 7e Each is independently an alkyl group having 1 or more hydrogen atoms and 3 or fewer carbon atoms. Q 7a Q 7b Q 7d and Q 7e Each is preferably a hydrogen atom or a methyl group. Q 7a and Q 7b These are different groups from each other. Q 7d and Q 7e These are different groups from each other. Q 7a and Q 7e They can be the same group. Q 7b and Q 7d They can be the same group.

[0088] Q 7c It is an alkylene group with 2 or more carbon atoms and less than 20, which is either straight-chain or branched and has a substituent, and f is 3 or more and less than 100.

[0089] That is, repeating units with subscript f - (OQ 7c )- represents the first alkylene oxide unit. Polymer sites composed of this repeating unit can form soft segments of the cured product. Q 7c The preferred form is a linear alkylene group. The alkylene group preferably has 3 or more and 10 or less carbon atoms, more preferably 3 or more and 6 or less, and particularly preferably 3 or more and 4 or less. A higher number of carbon atoms in the alkylene group further improves the functionality of the cured product. On the other hand, an excessive number of carbon atoms in the alkylene group reduces the amount of soft segments per unit mass, which may decrease the functionality of the cured product.

[0090] From the perspective of balancing functionality and hardness, f is preferably 6~85, more preferably 7~60, even more preferably 8~45, and especially preferably 9~30.

[0091] d and h are 0~10. From the point of view of balancing functionality and hardness, d and h are preferably 0~5, more preferably 0~2, further preferably 0 or 1, and most preferably 0.

[0092] e and g are 0~20. From the point of view of balancing functionality and hardness, e and g are preferably 0~15, more preferably 0~10, even more preferably 0~5, and particularly preferably 0.

[0093] In other words, the di(meth)acrylate shown in formula (3) can be a monomer that also has at least one of the following units: a repeating unit with subscripts e and g, namely the second alkyleneoxy unit; and a repeating unit with subscripts d and h, namely the third alkyleneoxy unit.

[0094] The di(meth)acrylate shown in formula (3) is preferably Z. 1 and Z 2 The value is 0. Such compounds are represented by the following formula (3b).

[0095]

[0096] In the above equation (3b), Q 3 and Q 6 It can be a hydrogen atom or a methyl group. Q 7a Q 7b Q 7c Q 7d Q 7e The meanings of d, e, f, g and h are the same as those in equation (3a).

[0097] The di(meth)acrylate shown in formula (3b) preferably has d, e, g, and h of 0, i.e., contains only the first alkylene oxide unit. When using a di(meth)acrylate shown in formula (3b), there is a tendency for the hardness of the cured product to increase. Such a compound is represented, for example, by the following formula (3c). In the following formula (3c), f can be 6 or more and 85 or less, or 9 or more and 30 or less.

[0098]

[0099] In the above equation (3c), Q 3 Q 6 Q 7c f has the same meaning as equation (3b).

[0100] If we take specific examples of the compounds shown in formula (3c) above, examples include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytrimethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polypentamethylene glycol di(meth)acrylate, polyhexamethylene glycol di(meth)acrylate, etc.

[0101] When using a di(meth)acrylate of formula (3b) where d and h are 0 and e and g are 1 or more, that is, a di(meth)acrylate of formula (3b) that also contains a second alkylene oxide unit, there is a tendency to obtain a cured product with high functionality of functional pigment. In such a di(meth)acrylate of formula (3b), b and d can be 2 or more and 15 or less, or 4 or more and 10 or less.

[0102] Specific examples of di(meth)acrylates represented by such formula (3b) are described below.

[0103]

[0104]

[0105]

[0106] Furthermore, the di(meth)acrylate shown in formula (3b) can be a monomer in which d, e, g, and h are 1 or more, that is, it also possesses both a second alkylene oxide unit and a third alkylene oxide unit. In this case, the second alkylene oxide unit and the third alkylene oxide unit have different structures.

[0107] Specific examples of di(meth)acrylates represented by such formula (3b) are described below.

[0108]

[0109]

[0110] The di(meth)acrylate shown in formula (3) can be manufactured, for example, by the following method. First, prepare the isocyanate compound shown in formula (4). The compound contains an isocyanate group and a (meth)acryloyl group.

[0111]

[0112] In equation (4), Q 5 Q 6The meaning of 'b' is the same as in formula (3). The di(meth)acrylate shown in formula (3) can be obtained by reacting the isocyanate compound shown in formula (4) with the polyol compound shown in formula (3d) below. It should be noted that in the di(meth)acrylate shown in formula (3) obtained by the above method, Q... 4 and Q 5 The reactions are identical; a and b are the same. The reaction can be carried out in the presence of a solvent. Suitable solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide, and tetrahydrofuran.

[0113]

[0114] Q of polyol compounds of formula (3d) 7a Q 7b Q 7c Q 7d Q 7e , d, e, f, g, and h have the same meaning as in formula (3b). The polyol compound in formula (3d) can be derived from plants or from petroleum.

[0115] In equation (3), Z 1 and Z 2 When the value becomes 0, the di(meth)acrylate shown in formula (3b) can be manufactured, for example, by the following method.

[0116] The diacrylate of formula (3b) having an acryloyl group can be synthesized by esterification of acrylic acid with a polyol compound of formula (3d).

[0117] Specifically, the above-mentioned polyol compound dissolved in solvents such as toluene can be reacted with acrylic acid in the presence of inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as aromatic sulfonic acids, or Lewis acids such as boron fluoride ethers, while being heated and stirred as needed. The water generated is removed by azeotropic reaction. It should be noted that, in the esterification reaction, methods for removing water include using desiccants such as anhydrous magnesium sulfate or molecular sieves, or removing water in the presence of dehydrating agents such as dicyclohexylcarbodiimide.

[0118] Alternatively, it can be synthesized by esterification of acryloyl halides. Specifically, this can be achieved by reacting the aforementioned polyol compound dissolved in an ether solvent such as tetrahydrofuran with acrylic acid in the presence of a base such as pyridine or dimethylaniline, while heating and stirring as needed to remove the generated hydrogen halide.

[0119] Furthermore, it can also be synthesized by transesterification with ester compounds such as acrylic anhydride and methyl acrylate. Specifically, the polyol compound dissolved in a solvent such as toluene can be reacted with acrylic acid in the presence of an acidic catalyst such as aromatic sulfonic acid or a basic catalyst such as sodium acetate or pyridine, while being heated and stirred as needed.

[0120] Compounds of formula (3b) having a methacryloyl group can be synthesized, for example, by using methacrylic acid instead of acrylic acid, in the same manner as described above.

[0121] Among the above-mentioned polyol compounds, polyol compounds in which d and h are 0 and e and g are 1 or more, i.e. polyols having a second alkylene oxide unit, can be synthesized, for example, by the following method.

[0122] By making H-(OQ) 7c ) f -OH groups react with cyclic ether compounds such as ethylene oxide and propylene oxide to synthesize polyols having a second alkylene oxide unit. These polyols can be synthesized, for example, by reacting them in a nitrogen-purged autoclave under high temperature and pressure in the presence of a catalyst such as an alkali metal hydroxide like potassium hydroxide.

[0123] Among the above polyol compounds, polyol compounds in which d, e, g, and h are 1 or more, i.e., di(meth)acrylates of formula (3b) that also contain a second and a third alkyleneoxy unit, can be synthesized, for example, by the following method.

[0124] A polyol compound having a second alkylene oxide unit is reacted with a cyclic ether compound to synthesize a polyol compound having a third alkylene oxide unit. The resulting polyol compound having a third alkylene oxide unit is then reacted with acrylic acid and methacrylic acid in the same manner as described above to synthesize a di(meth)acrylate of formula (3b) that also contains the second and third alkylene oxide units.

[0125] (A-2) component may contain di(meth)acrylate as shown in formula (5) below.

[0126]

[0127] R in equation (5) 14 and R 15 Each is either a hydrogen atom or a methyl group. R 16 and R 17 Each is either a hydrogen atom or a methyl group.

[0128] A is a divalent organic group. A is a straight-chain or branched alkylene group having 1 or more carbon atoms and less than 20 carbon atoms, or a phenylene group, cycloalkylene group, dicycloalkylene group, tricycloalkylene group, or any group shown in the following formulas, optionally having a halogen or an alkyl group having 1 or more carbon atoms and less than 5 carbon atoms as a substituent.

[0129]

[0130]

[0131]

[0132]

[0133]

[0134] In the above formula, R 18A R 18B It consists of hydrogen atoms, alkyl or halogen atoms with 1 or more but less than 5 carbon atoms. xx and xy are 0~4 or 0~10. Ring X is a benzene ring or a cyclohexane ring. YY is a group represented by -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, -C(CH3)(C6H5)-, or any of the following formulas.

[0135]

[0136]

[0137] In equation (5), l and m are integers greater than or equal to 0 or 1, and l+m is an average value of 2 or greater and less than 30.

[0138] Specific examples of the difunctional (meth)acrylates shown in formula (5) include alkoxylated bisphenol A diacrylate, alkoxylated bisphenol A dimethacrylate, etc.

[0139] (A-2) component may contain di(meth)acrylate as shown in formula (6) below.

[0140]

[0141] R in equation (6) 19 and R 20 Each is either a hydrogen atom or a methyl group.

[0142] n is a number whose average value is between 1 and 20.

[0143] B and B' are each independently a straight-chain or branched alkylene group having 2 or more but less than 15 carbon atoms. B and B' can be the same or different from each other. In the presence of multiple Bs, the multiple Bs can be the same group or different groups.

[0144] The difunctional (meth)acrylate shown in formula (6) above can be manufactured by reacting polycarbonate diol with (meth)acrylate.

[0145] Here, the polycarbonate diol used can be exemplified by the following polycarbonate diols. Specifically, examples include polycarbonate diols obtained by phosgenation of trimethylene glycol (average molecular weight 800-2000), polycarbonate diols obtained by phosgenation of tetramethylene glycol (average molecular weight 800-2000), polycarbonate diols obtained by phosgenation of pentamethylene glycol (average molecular weight 800-2000), polycarbonate diols obtained by phosgenation of hexamethylene glycol (average molecular weight 800-2000), polycarbonate diols obtained by phosgenation of octamethylene glycol (average molecular weight 800-2000), polycarbonate diols obtained by phosgenation with nonamethylene glycol (average molecular weight 800-2000), and polycarbonate diols obtained by phosgenation of triethylene glycol and tetramethylene glycol. Polycarbonate diol (average molecular weight 800-2000) obtained by phosgenation of tetramethylene glycol and hexamethylene diethylene glycol; polycarbonate diol (average molecular weight 800-2000) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol; polycarbonate diol (average molecular weight 800-2000) obtained by phosgenation of tetramethylene glycol and octamethylene glycol; polycarbonate diol (average molecular weight 800-2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol; and polycarbonate diol (average molecular weight 800-2000) obtained by phosgenation with 1-methyltrimethylene glycol.

[0146] (A-2) Component may contain di(meth)acrylates having urethane bonds. As urethane di(meth)acrylates, they are obtained by reacting a polyisocyanate compound having two isocyanate groups in the molecule with a polyol compound having two hydroxyl groups in the molecule and a hydroxyl-containing (meth)acrylate.

[0147] Examples of suitable polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis(4-cyclohexyl) isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, or methylcyclohexane diisocyanate.

[0148] Examples of polyols include polyalkylene glycols such as ethylene oxide, propylene oxide, and hexane, which have repeating units of carbon atoms of 2 or more but less than 4, or polyester glycols such as polycaprolactone glycol. Other examples include polycarbonate glycol, polybutadiene glycol, pentaerythritol, ethylene glycol, 1,2-propanediol, 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-cyclohexanediol, glycerol, and trimethylolpropane.

[0149] Alternatively, a reaction mixture obtained by further reacting a urethane prepolymer with terminal isocyanate groups, obtained by reacting these polyisocyanates and polyols, with 2-hydroxy(meth)acrylate can be used; or a reaction mixture obtained by directly reacting the aforementioned diisocyanate with 2-hydroxy(meth)acrylate, i.e., urethane(meth)acrylate monomers, can be used.

[0150] Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0151] Difunctional (meth)acrylates with urethane bonds can be used without any restrictions in commercially available products, such as UA-122P (molecular weight 1,100) and U-122P (molecular weight 1,100).

[0152] (A-2) Components may include difunctional (meth)acrylates other than those described above. Examples of difunctional (meth)acrylates other than those described above include difunctional (meth)acrylates containing sulfur atoms, di(meth)acrylate bodies of alkylene glycols, etc. In difunctional (meth)acrylates containing sulfur atoms, the sulfur atom is preferably formed as a thioether group as part of the molecular chain. Specifically, examples include bis(2-methacryloyloxyethyl thioethyl) sulfide, bis(methacryloyloxyethyl) sulfide, bis(acryloyloxyethyl) sulfide, 1,2-bis(methacryloyloxyethyl thio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethyl thioethyl) sulfide, bis(2-acryloyloxyethyl thioethyl) sulfide, 1,2-bis(methacryloyloxyethyl thioethyl thio)ethane, 1,2-bis(acryloyloxyethyl thioethyl thio)ethane, 1,2-bis(methacryloyloxyisopropyl thioisopropyl) sulfide, and 1,2-bis(acryloyloxyisopropyl thioisopropyl) sulfide.

[0153] As the di(meth)acrylate body of an alkyl diol, a linear or branched alkylene diol having 2 or more but less than 30 carbon atoms is preferred. Specifically, examples include ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate.

[0154] <(A-3): A third radical polymerizable monomer with a structure different from that of (A-1) and having three or more (meth)acryloyl groups in one molecule>

[0155] The curable composition of the embodiment may further comprise a third radical polymerizable monomer having a structure different from that of component (A-1) and having three or more (meth)acryloyl groups per molecule as component (A-3). Hereinafter, the third radical polymerizable monomer having a structure different from that of component (A-1) and having three or more (meth)acryloyl groups per molecule will also be referred to as component (A-3). If a third radical polymerizable monomer is included, there is a tendency for the hardness of the cured product to increase.

[0156] Examples of components (A-3) include polyfunctional (meth)acrylates represented by formula (I), polyfunctional (meth)acrylates represented by formula (II), polyfunctional (meth)acrylates having urethane bonds, and polyfunctional (meth)acrylates not included in the foregoing. Component (A-3) is particularly preferably a polyfunctional (meth)acrylate represented by formula (I).

[0157] <The polyfunctional (meth)acrylate shown in formula (I) below>

[0158]

[0159] In equation (I), Q 10 It is a straight-chain or branched alkylene group having 1 or more but less than 3 carbon atoms. Q 10 Preferably, it is a straight-chain alkylene group with 1 or more but less than 3 carbon atoms, and particularly preferably a methylene group.

[0160] Q 11 It is a straight-chain or branched alkylene group having 1 or more but less than 10 carbon atoms. Q 11 Preferably, it is a straight-chain alkylene group with 1 or more and 10 or less carbon atoms, more preferably a straight-chain alkylene group with 2 or more and 6 or less carbon atoms, and particularly preferably a straight-chain alkylene group with 2 or more and 4 or less carbon atoms.

[0161] Q 12 It can be a hydrogen atom or a methyl group. Q 12 Methyl is preferred.

[0162] Q 13 It is an organic group with 1 or more but less than 10 carbon atoms, exhibiting a valence of 3 to 6. As Q 13 Examples of organic groups shown include groups derived from polyols, 3-6 valent hydrocarbon groups, and 3-6 valent organic groups containing urethane bonds. Q 13 Preferably, the group is derived from a polyol or is a 3- to 6-valent hydrocarbon group, and more preferably, it is derived from trimethylolpropane, pentaerythritol, bis(trimethylolpropane), or dipentaerythritol.

[0163] b1 is a number of 0 or more and 15 or less. When it is desired to further increase the hardness of the obtained cured material, b1 is preferably a number of 0 or more and 6 or less, more preferably a number of 0 or more and 4 or less, even more preferably a number of 0 or more and 2 or less, and particularly preferably 0.

[0164] Furthermore, when it is desired to improve the performance of the functional pigment in the obtained cured product, b1 is preferably a number of 5 or more and 15 or less, more preferably a number of 5 or more and 13 or less, even more preferably a number of 6 or more and 12 or less, and particularly preferably a number of 6 or more and 11 or less.

[0165] c1 is 3 or higher and 6 or lower.

[0166] The polyfunctional (meth)acrylates shown in formula (I) below may contain the 3- to 4-functional (meth)acrylates shown in formula (II) below.

[0167]

[0168] In equation (II), Q 20 Q 21 Q 22 and Q 23 Each is independently an alkylene group having 1 or more but less than 3 carbon atoms. Q 20 Q 21 Q 22 and Q 23 The preferred form is methylene. a4, a5, a6, and a7 are each an independent integer of 0 or 1.

[0169] Q 24 Q 25 and Q 26 Each is an independent monovalent group as shown in formula (III) below.

[0170]

[0171] In equation (III), Q 11 Q 12 b1 has the same meaning as in equation (I).

[0172] Q 24 Q 25 and Q 26 They can have different structures from each other, or they can have the same structure. Q 24 Q 25 and Q 26 Preferably, they have the same structure.

[0173] Q 27 It is a hydrogen atom, a straight-chain or branched alkyl group having 1 or more but 5 or fewer carbon atoms, a straight-chain or branched alkoxy group having 1 or more but 5 or fewer carbon atoms, or a monovalent group represented by formula (III). Q 27 Preferably, it is a straight-chain alkyl group with 1 or more but less than 3 carbon atoms, or a monovalent group as shown in formula (III).

[0174] Specific examples of the polyfunctional (meth)acrylates shown in formula (I) above include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, bis(trimethylolpropane tetramethacrylate), bis(trimethylolpropane tetramethacrylate), dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexamethacrylate. Dipentaerythritol pentamethacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, butoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, butoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetramethacrylate, butoxylated pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, and butoxylated pentaerythritol tetraacrylate, etc.

[0175] <Polyfunctional (meth)acrylates with urethane bonds>

[0176] Polyfunctional (meth)acrylates with urethane bonds are obtained by reacting polyisocyanate compounds with three or more isocyanate groups in the molecule with polyol compounds with two or more hydroxyl groups in the molecule and hydroxyl-containing (meth)acrylates. Suitable polyfunctional (meth)acrylates with urethane bonds are those with four or more (meth)acryloyl groups in the molecule. Commercially available examples include U-4HA (molecular weight 596, functional group number 4), U-6HA (molecular weight 1,019, functional group number 6), U-6LPA (molecular weight 818, functional group number 6), and U-15HA (molecular weight 2,300, functional group number 15) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0177] <Not belonging to the aforementioned polyfunctional (meth)acrylates>

[0178] Other than the polyfunctional (meth)acrylates shown in formula (I) and polyfunctional (meth)acrylates having urethane bonds, examples of polyfunctional (meth)acrylates include compounds obtained by modifying the ends of polyester compounds with (meth)acryloyl groups. Various commercially available polyester (meth)acrylate compounds with different molecular weights and amounts of (meth)acryloyl group modification are available as such polyester (meth)acrylate compounds, and these can be used. Specifically, examples include 4-functional polyester oligomers (molecular weight 2,500-3,500, Daicel-UCB, EB80, etc.), 6-functional polyester oligomers (molecular weight 6,000-8,000, Daicel-UCB, EB450, etc.), 6-functional polyester oligomers (molecular weight 45,000-55,000, Daicel-UCB, EB1830, etc.), and 4-functional polyester oligomers (especially those with a molecular weight of 10,000, such as Daiichi Kogyo Pharmaceutical Co., Ltd., GX8488B, etc.).

[0179] When the proportion of the third radical polymerizable monomer in the curable composition of the embodiment is high, there is a tendency for the hardness of the cured product to increase. This proportion can be 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more. On the other hand, when this proportion is too high, there is a tendency for the performance of the functional pigment to decrease. This proportion can be 95% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

[0180] <(A-4) Ingredients: Other radical polymerizable monomers with (meth)acryloyl groups>

[0181] Other free radical polymerizable monomers having a (meth)acrylyl group include free radical polymerizable monomers that have a (meth)acrylyl group in their molecular structure and do not belong to (A-1), (A-2), and (A-3). There are no particular limitations on such free radical polymerizable monomers; known free radical polymerizable monomers can be used, and monofunctional (meth)acrylates containing only one (meth)acrylyl group can also be used.

[0182] As a monofunctional (meth)acrylate, examples of monofunctional (meth)acrylates shown in the following formula (7) can be cited.

[0183]

[0184] R in equation (7) 21 It can be a hydrogen atom, methyldimethoxysilyl, trimethoxysilyl, glycidyl, pentamethylpiperidinyl, or 2,2,6,6-tetramethylpiperidinyl. R 22 It represents a hydrogen atom or a methyl group. o is an integer from 0 to 10. p is an integer from 0 to 20.

[0185] R 21 Preferably, it is methyldimethoxysilyl, trimethoxysilyl, or glycidyl. When a monofunctional acrylate containing such a functional group is included, there is a tendency for improved adhesion between the cured product and the substrate.

[0186] If a monofunctional (meth)acrylate represented by formula (7) above is specifically shown, examples include methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol acrylate, stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, etc.

[0187] <Other free radical polymerizable monomers>

[0188] The curable composition of the embodiments may also contain other radical polymerizable monomers. There are no particular limitations as long as the monomer is capable of polymerizing with the first radical polymerizable monomer, and known monomers can be used. For example, radical polymerizable polyrotaxanes, radical polymerizable silsesquioxane compounds, allyl compounds, and vinyl compounds are preferred.

[0189] <Polyrotaxane with free radical polymerization properties>

[0190] Polyrotaxanes have a complex molecular structure consisting of an axial molecule and multiple cyclic molecules surrounding the axial molecule. Large terminal groups are formed at both ends of the axial molecule to prevent the cyclic molecules from detaching from the axial molecule. Polyrotaxanes with free radical polymerizability are those in which free radical polymerizable groups are introduced into the side chains of the cyclic molecules. These free radical polymerizable groups are introduced, for example, by modifying 1 mol% or more but less than 100 mol% of the hydroxyl groups of the cyclic molecules into free radical polymerizable groups. The modification ratio can be calculated by (moles of polymerizable groups introduced) / (moles of all OH groups in the side chains) × 100. It should be noted that, from the viewpoints of adhesion, the mechanical strength of the resulting cured product, and functionality, the modification ratio is preferably set to 10 mol% or more and 95 mol% or less.

[0191] When the weight-average molecular weight of the axial molecules is too high, there is a tendency for reduced compatibility with other polymerizable monomers, etc.; when it is too low, there is a tendency for reduced mobility of cyclic molecules. The weight-average molecular weight of the axial molecules is preferably in the range of 1,000 to 100,000, more preferably in the range of 5,000 to 80,000, and most preferably in the range of 8,000 to 50,000.

[0192] The cyclic molecules are preferably cyclodextrin rings, crown ether rings, benzo[a] crown rings, dibenzo[a] crown rings, and dicyclohexane[a] crown rings, particularly preferably cyclodextrin rings and crown ether rings, and most preferably cyclodextrin rings. Furthermore, the cyclodextrin rings may have an α-form (ring inner diameter 0.45~0.6 nm), a β-form (ring inner diameter 0.6~0.8 nm), or a γ-form (ring inner diameter 0.8~0.95 nm), with α-cyclodextrin rings and β-cyclodextrin rings being preferred, and α-cyclodextrin rings being most preferred. When the inclusion number of all cyclic molecules introduced onto the axial molecule is set to 1, the inclusion number of the cyclic molecules is preferably in the range of 0.001~0.6, further preferably in the range of 0.002~0.5, and most preferably in the range of 0.003~0.4.

[0193] When considering reactivity with other polymerizable monomers, the (meth)acryloyl group is preferred as a free radical polymerizable group. The number of free radical polymerizable groups is not particularly limited, but is preferably 0 to 5000 per molecule.

[0194] Polyrotaxanes having (meth)acryloyl groups, as described above, are illustrated, for example, in International Publication No. 2018 / 030257.

[0195] <Silsesquioxane free radical polymerizable compounds>

[0196] Silsesquioxane free radical polymerizable compounds adopt various molecular structures such as cage-like, ladder-like, and random structures, and have free radical polymerizable groups such as (meth)acryloyl groups.

[0197] Examples of such polymerizable silsesquioxane compounds include the compound shown in formula (8).

[0198]

[0199] In equation (8), q is the degree of aggregation, which is an integer from 3 to 100.

[0200] Multiple R 23 The following are optional and may be the same or different from each other: a free radical polymerizable group, an organic group containing a free radical polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, and at least one R. 23 It is a free radical polymerizable group or an organic group containing a free radical polymerizable group.

[0201] Here, as R 23 Examples of free radical polymerizable groups or organic groups containing free radical polymerizable groups include (meth)acryloyl; (meth)acryloyloxypropyl, (3-(meth)acryloyloxypropyl)dimethylsiloxy, and other organic groups having a (meth)acryloyl group; allyl; allylpropyl, allylpropyldimethylsiloxy, and other organic groups having an allyl group; vinyl; vinylpropyl, vinyldimethylsiloxy, and other organic groups having a vinyl group.

[0202] <Allyl polymeric compounds>

[0203] Examples of allyl-based polymeric compounds containing an allyl group include the following compounds: diethylene glycol dielyl carbonate, methoxy polyethylene glycol allyl ether, methoxy polyethylene glycol-polypropylene glycol allyl ether, butoxy polyethylene glycol-polypropylene glycol allyl ether, phenoxy polyethylene glycol allyl ether, ethyleneoxy polyethylene glycol allyl ether, styreneoxy polyethylene glycol allyl ether, and methoxy polyethylene dithiols allyl sulfide.

[0204] Vinyl polymers

[0205] Examples of vinyl polymeric compounds containing vinyl groups include methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinylcyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, 1,3-divinyl-1,1,3,3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, divinyl adipate, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl sulfide, dimethyldivinylsilane, 1,2,4-trivinylcyclohexane, methyltrivinylsilane, α-methylstyrene, and α-methylstyrene dimers.

[0206] <Formulation ratio in the curing composition>

[0207] When the proportion of the first free radical polymerizable monomer in the curable composition of the embodiment is high, there is a tendency for the hardness of the cured product to increase and the performance of the functional pigment to improve. This proportion can be 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more. On the other hand, when this proportion is too high, there is a tendency for the performance of the functional pigment to decrease. This proportion can be 95% by mass or less, preferably 80% by mass or less, and more preferably 60% by mass or less.

[0208] The proportion of the second free radical polymerizable monomer in the curable composition of the embodiment is, for example, 10% by mass or more and 90% by mass or less. A higher proportion tends to improve the performance of the functional pigments in the cured product. This proportion can be 35% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. On the other hand, if this proportion is too high, there is a tendency for the hardness of the cured product to decrease. This proportion is preferably 85% by mass or less, more preferably 80% by mass or less.

[0209] In the curable composition of the embodiment, the content of di(meth)acrylate other than the second radical polymerizable monomer is preferably 50% by mass or less. That is, when the content of di(meth)acrylate such as polyalkylene carbonate polyol di(meth)acrylate is high, the performance of the functional pigment of the cured product may be reduced. The content of di(meth)acrylate other than the second radical polymerizable monomer is more preferably 30% by mass or less, and even more preferably 20% by mass or less. The lower limit of this content is 0% by mass in one example and 5% by mass or more in another example.

[0210] From the perspective of improving the curability of the cured product, the curable composition of the embodiment preferably further comprises a third radical polymerizable monomer. The proportion of the third radical polymerizable monomer in the curable composition of the embodiment is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more. On the other hand, if this proportion is too high, there is a tendency for the performance of the functional pigments in the cured product to decrease. This proportion is preferably 95% by mass or less, more preferably 85% by mass or less, and further preferably 75% by mass or less.

[0211] In the curable composition of the embodiments, from the perspective of improving the appearance and adhesion of the cured product, it is preferable to include monofunctional (meth)acrylates. The proportion of monofunctional (meth)acrylates in the curable composition of the embodiments is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. On the other hand, if this proportion is too high, there is a tendency for the performance of the functional pigments in the cured product to decrease. This proportion is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less.

[0212] In a curable composition containing first to third free radical polymerizable monomers, the content of the first free radical polymerizable monomer may be 5% by mass or more and 80% by mass or less, the content of the second free radical polymerizable monomer may be 10% by mass or more and 80% by mass or less, the content of the third free radical polymerizable monomer may be 5% by mass or more and 75% by mass or less, and the remainder may be the proportion of functional pigments and additives.

[0213] The proportion of methacrylate in the curable composition of the embodiment is preferably 30% by mass or more. A higher proportion tends to result in a cured product with high functionality of the functional pigment. This proportion is preferably 60% by mass or more. The upper limit of this proportion is 100% by mass in one example and 90% by mass or less in another example.

[0214] The ratio M2 / M1 of the mass of the second radical polymerizable monomer (M2) to the mass of the first radical polymerizable monomer (M1) is preferably 0.1 or more and 20 or less. If a curable composition with an M2 / M1 ratio within this range is used, there is a tendency for further improvements in the performance and hardness of the functional pigments in the cured product. A more preferred M2 / M1 ratio is 0.5 or more and 10 or less, and even more preferably 1 or more and 5 or less.

[0215] The ratio M1 / M3 of the mass of the first free radical polymerizable monomer (M1) to the mass of the third free radical polymerizable monomer (M3) is preferably 0.1 or more and 20 or less. If a curable composition with a ratio M1 / M3 within this range is used, there is a tendency for further improvement in the performance and hardness of the functional pigments in the cured product. A ratio M1 / M3 is more preferably 0.5 or more and 10 or less, and even more preferably 1 or more and 5 or less.

[0216] The ratio M2 / M3 of the second free radical polymerizable monomer (M2) to the third free radical polymerizable monomer (M3) is preferably 0.1 or more and 20 or less. If a curable composition with an M2 / M3 ratio within this range is used, there is a tendency for further improvements in the performance and hardness of the functional pigments in the cured product. A more preferred M2 / M3 ratio is 0.5 or more and 10 or less, and even more preferably 1 or more and 5 or less.

[0217] (B) Functional Pigments

[0218] Functional pigments include compounds that selectively absorb visible light, and compounds that develop, decolorize, or change color upon exposure to energy such as light, heat, electric fields, or pressure. Such functional pigments can perform specific functions by undergoing structural changes under specific conditions. Functional pigments may include, for example, at least one selected from the group consisting of photochromic compounds, ultraviolet absorbers, blue light absorbers, infrared absorbers, and electrochromic compounds. The content of the functional pigment in the curable composition is, for example, 0.01% by mass or more and 10% by mass or less. Preferably, the content of the functional pigment is 0.1% by mass or more and 8% by mass or less, more preferably 1% by mass or more and 5% by mass or less.

[0219] <Photochromic compounds>

[0220] The photochromic compound is used in a formulation amount that yields the desired photochromic properties. The photochromic compound is preferably used in a formulation of 0.01 to 10 parts by weight relative to 100 parts by weight of component (A).

[0221] The mixing amount is preferably adjusted to the optimal mixing amount according to the intended use. Specifically, when the curable composition containing the photochromic compound is made into a thin film such as a coating, for example, a film of about 100 μm (a polymer film formed by polymerizing the curable composition containing the photochromic compound), it is advisable to mix 0.1 to 10 parts by mass of the photochromic compound relative to 100 parts by mass of component (A) to adjust the hue.

[0222] In addition, when producing a thick cured product (a polymer molded body formed by polymerizing a curable composition containing a photochromic compound), for example, when the cured product has a thickness of 1 mm or more, it is advisable to mix 0.01 to 1 part by mass of the photochromic compound relative to 100 parts by mass of the thick cured product or 100 parts by mass of component (A) of the thick cured product to adjust the hue.

[0223] There are no restrictions on the photochromic compounds used; known compounds can be used alone or in combination of two or more. Representative examples of such photochromic compounds include chromene compounds, succinic anhydride compounds, succinic imide compounds, and spirooxazine compounds. Among these photochromic compounds, chromene compounds and spirooxazine compounds are preferred. Chromene compounds are particularly preferred. Examples of chromene compounds include compounds having a 1-benzopyran skeleton, spiropyran compounds containing a spiropyran skeleton, and naphthopyran compounds having a naphthopyran skeleton.

[0224] As a naphthopyran compound, it is preferred to include at least any one of the compounds shown in formula (9), formula (10), formula (11), formula (12), formula (13) and formula (14).

[0225]

[0226] In formula (9), ring AA is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with aromatic rings or aromatic heterocycles fused to these rings. Ring AA may also be absent. Ring AB is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with aromatic rings or aromatic heterocycles fused to these rings.

[0227] R 24 and R 25 Each can be a hydrogen atom or a substituent independently, and two or more substituents can bond together to form a ring structure.

[0228] As a substituent, it is at least one selected from the group consisting of hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, alkoxyalkyl, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, halogen atom, optionally substituted aralkyl, optionally substituted aralkoxy, optionally substituted aroxy, alkylthio, optionally substituted arthio, optionally substituted aryl, amino, substituted amino, optionally substituted heterocyclic group, preferably at least one selected from the group consisting of haloalkylthio, optionally substituted cycloalkylthio, oligomer group and group represented by formula (15) below.

[0229] -Q 1 -(P 1 Q 2 ) aa -P 2 Q 3 (15)

[0230] In equation (15), Q 1 The substituent may optionally be an alkylene group containing a halogen atom. Q 2 The substituent may optionally be an alkylene group containing a halogen atom. Q 3 The substituent may optionally contain a halogen atom. P 1 and P 2 Each is independently O, S, NR 700 PR 701 Or P (=O). R 700 R is a hydrogen atom, optionally an alkyl group with substituents, optionally a cycloalkyl group with substituents, optionally an aryl group with substituents, or optionally a heteroaryl group with substituents. 701It is a hydrogen atom, optionally an alkyl group with a substituent, optionally a cycloalkyl group with a substituent, optionally an aryl group with a substituent, or optionally a heteroaryl group with a substituent. aa is 0, or is more than 1 and less than 10.

[0231] In equation (9), M is CR 26 R 27 SiR 26 R 27 GeR 26 R 27 or NR 26 R 26 and R 27 Each can be a hydrogen atom or a substituent independently, and two or more substituents can bond together to form a ring structure.

[0232] As a substituent, it is preferably selected from at least one of the following groups: hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, alkoxyalkyl, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, halogen atom, optionally substituted aralkyl, optionally substituted aralkyloxy, optionally substituted aroxy, alkylthio, optionally substituted aryl, optionally substituted aryl, amino, substituted amino, optionally substituted heterocyclic group, and groups represented by formula (15) above. Additionally, R 26 and R 27 When two ring structures are formed together, it is preferable to form an aliphatic ring with 3 or more but less than 20 ring carbon atoms, a fused polycyclic ring with an aromatic ring or an aromatic heterocyclic ring fused to an aliphatic ring, a heterocyclic ring with 3 or more but less than 20 ring atoms, or a fused polycyclic ring with an aromatic ring or an aromatic heterocyclic ring fused to a heterocyclic ring.

[0233]

[0234] In equation (10), R 1000 R 1001 and R 1002 Each substituent is an independent hydrogen atom or a substituent, and two or more substituents can bond together to form a ring structure. Substituents can be the same type of group as those described in formula (9). mm is 1 to 10.

[0235]

[0236] In equation (11), R 1003 R 1004 and R 1005 Each substituent is an independent hydrogen atom or a substituent, and two or more substituents can bond together to form a ring structure. Substituents can be the same type of group as those described in formula (9). nn is 1 to 10.

[0237]

[0238] In equation (12), R 1006 R 1007 and R 1008 Each substituent is an independent hydrogen atom or a substituent, and two or more substituents can bond together to form a ring structure. Substituents can be the same type of group as those described in formula (9). oo is 1 to 12.

[0239]

[0240] In equation (13), R 1009 R 1010 and R 1011 Each substituent is an independent hydrogen atom or a substituent, and two or more substituents can bond together to form a ring structure. Substituents can be the same type of group as those described in formula (9). pp is 1 to 12.

[0241]

[0242] In equation (14), R 1012 R 1013 and R 1014 Each substituent is an independent hydrogen atom or a substituent, and two or more substituents can bond together to form a ring structure. Substituents can be the same type of group as those described in formula (9). qq is 1 to 12.

[0243] Examples of indo-naphtho-pyran compounds include those having an indo-naphtho-pyran skeleton. Indo-naphtho-pyran compounds preferably have an indo-[2,1-f]naphtho-[1,2-b]pyran skeleton.

[0244] The indo-naphtho-pyran compounds preferably comprise compounds represented by the following formula (16).

[0245]

[0246] In equation (16), R 24 R 25 R 26 and R 27 Same as above.

[0247] r is an integer from 0 to 4. s is an integer from 0 to 4. When r is 2 to 4, multiple R... 28 They can be the same or different. When s is 2~4, multiple R... 29 They can be the same or different. Furthermore, in R where r is 2~4 and there are adjacent pairs... 28 In the case of two adjacent R 28 Can be used together with these R 28The bonded carbon atoms together form a ring optionally containing at least one heteroatom selected from the group consisting of oxygen, carbon, sulfur, and nitrogen atoms, and the ring optionally has substituents. Additionally, in cases where s is 2 to 4 and adjacent R atoms are present... 29 In the case of two adjacent R 29 Can be used together with these R 29 The bonded carbon atoms together form a ring that optionally contains at least one heteroatom selected from the group consisting of oxygen, carbon, sulfur, or nitrogen atoms, and the ring optionally has substituents.

[0248] R 28 and R 29 Each of the following groups independently represents a group of formula (15), a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group optionally having a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group optionally having a substituent, a cyano group, a halogen atom, an alkylthio group optionally having a substituent, an arylthio group optionally having a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group optionally having a substituent, an aryl alkoxy group optionally having a substituent, an aryl group optionally having a substituent, a heteroaryl group optionally having a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group optionally having a substituent, a silyl group optionally having a substituent, an oxysilyl group optionally having a substituent, a group of formula (17) below, or LR 400 The group shown.

[0249]

[0250] In equation (17), E is an oxygen atom or NR. 101 R 101 F is a hydrogen atom or an alkyl group. F is an oxygen atom or a sulfur atom. G is an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl group. gg is an integer of 0 or 1. R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. When G is an oxygen atom or a sulfur atom, R... 201 It is a group other than a hydrogen atom.

[0251] LR 400 In the indicated group, R 400 It can be a hydrogen atom, alkyl, aryl, silyl group with substituents, polymeric group, or photochromic group. The substituent of the silyl group is alkyl, alkoxy, or aryl. L is a group represented by the following formula (18).

[0252]

[0253] In formula (18), J is a divalent group, which can be directly bonded, substituted methylene, oxygen atom, sulfur atom or NR. 301 R 301 R is a hydrogen atom or an alkyl group. In formula (18), L is an oxygen atom or a sulfur atom. 300 It is an alkylene group, or a silylene group having alkyl or aryl substituents. R 302 R 303 and R 304 For alkylene groups. hh, jj, kk, and ll are integers of 0 or 1. ii are integers from 1 to 200. When ii is 2 or more, multiple units of ii can be the same or different. Dashed lines indicate the presence of R. 400 . bond.

[0254] <Other Additives>

[0255] In curable compositions, various known compounding agents can be formulated without impairing the effect. These compounding agents include, for example, release agents, UV absorbers, infrared absorbers, UV stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and various other stabilizers. Additionally, solvents and leveling agents can also be formulated. Thiols such as tert-dodecyl mercaptan can be formulated as polymerization modifiers.

[0256] UV stabilizers

[0257] The durability of photochromic compounds can be further improved by using a mixture of UV stabilizers, therefore, a compounding is preferred. Hindered amine light stabilizers, hindered phenolic antioxidants, and sulfur-based antioxidants are suitable as UV stabilizers. There are no particular limitations on the hindered amine light stabilizer, but bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate is preferred, especially from the perspective of preventing the degradation of photochromic compounds. Alternatively, hindered amine light stabilizers commercially available from ADEKA Corporation under trade names such as Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, and LA-87 are also suitable.

[0258] In preventing the degradation of photochromic compounds, it is preferred as a hindered phenolic antioxidant. Examples include: 2,6-di-tert-butyl-4-methylphenol; IRGANOX 245 (manufactured by BASF Japan Ltd.): ethylene bis(oxyethylene)bis[3,5-tert-butyl-4-hydroxy-m-tolyl]propionate; IRGANOX 1076 (manufactured by BASF Japan Ltd.): octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; IRGANOX 1010 (manufactured by BASF Japan Ltd.): pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; and IRGANOX 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565 (manufactured by BASF Japan Ltd.).

[0259] There are no particular restrictions on the amount of such UV stabilizer used, as long as it does not impair the effect. It is usually in the range of 0.001 to 10 parts by weight, especially 0.01 to 1 part by weight, relative to 100 parts by weight of the curing composition.

[0260] <Polymerization initiator>

[0261] Polymerization initiators include thermal polymerization initiators and photopolymerization initiators, and their specific examples are described below.

[0262] Examples of thermal polymerization initiators include:

[0263] Diacyl peroxides: benzoyl peroxide, p-chlorobenzoyl peroxide, decyl peroxide, lauroyl peroxide, acetyl peroxide;

[0264] Peroxide esters: tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-neodecanate, cumyl peroxide-neodecanate, tert-butyl peroxide;

[0265] Peroxide carbonate; diisopropyl peroxide dicarbonate, disec-butyl peroxide dicarbonate;

[0266] Azo compounds: azobisisobutyronitrile; etc.

[0267] Examples of photopolymerization initiators include:

[0268] Acetophenone compounds: 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one;

[0269] α-Dicarbonyl compounds: 1,2-diphenylethylenedione, methyl phenyl glyoxylate;

[0270] Acylphosphine oxide compounds: 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, methyl 2,4,6-trimethylbenzoyl diphenylphosphonate, 2,6-dichlorobenzoyl diphenylphosphine oxide, 2,6-dimethoxybenzoyl diphenylphosphine oxide.

[0271] It should be noted that when using photopolymerization initiators, well-known polymerization and curing accelerators such as tertiary amines can also be used in combination.

[0272] <surfactants>

[0273] Adding a surfactant can improve the wettability of optical substrates and primer layers, and prevent the formation of appearance defects. Examples of surfactants include known surfactants such as silicone surfactants with hydrophobic groups consisting of silicone chains (polyalkylsiloxane units) and fluorosurfactants with fluorinated carbon chains. When using surfactants, two or more can be mixed. Furthermore, the surfactant can be either polymerizable with component (A) or non-polymerizable.

[0274] If specific examples of suitable silicone surfactants and fluorinated surfactants are to be cited, they include: L-7001, L-7002, L-7604, FZ-2123, and FZ-2110 manufactured by DowToray Co., Ltd.; MEGAFAC F-470, MEGAFAC F-1405, and MEGAFAC F-479 manufactured by DIC Corporation; Fluorad FC-430 manufactured by 3M Japan Ltd.; TEGORAD2100 and TEGORAD2300 manufactured by Evonik Japan Co., Ltd.; and BYK-Chemie... The following models are manufactured by Japan: BYK-UV3505, BYK-UV3505, BYK-UV3510, BYK-UV3530, BYK-3550, BYK-3560, BYK-UV3565, BYK-3566, BYK-UV3500, BYK-UV3535, BYK-UV3570, BYK-UV3575, and BYK-UV3576; and Shin-Etsu Chemical Industry Co., Ltd., which manufactures: KR-513, X-22-2445, X-40-9296, X-22-164, X-22-164A, X-22-164B, X-22-164C, and X-22-164E.

[0275] <UV absorber>

[0276] As a UV absorber, known UV absorbers such as benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, benzoate compounds, cinnamic acid ester compounds, and oxaloyl aniline compounds can be used, with cyanoacrylate compounds, benzophenone compounds, benzotriazole compounds, and cinnamic acid ester compounds being particularly preferred. The UV stabilizer is preferably used in the range of 0.001 to 5 parts by weight relative to 100 parts by weight of the curable composition containing the photochromic compound and the polymerizable compound.

[0277] <Cured product>

[0278] The cured product is obtained by curing the curable composition. The curing of the curable composition is carried out by inducing a free radical polymerization reaction through irradiation with active energy rays such as ultraviolet light, alpha rays, beta rays, gamma rays, or LEDs, heat, or a combination of both. That is, an appropriate curing method can be used depending on the type of polymerizable monomer, the type of polymerization accelerator, and the morphology of the resulting cured product. When forming a laminate using the coating method described later, photopolymerization is preferred for the purpose of obtaining a uniform film thickness.

[0279] When a curable composition containing a polymerizable compound is thermally polymerized, the thermal polymerization temperature affects the properties of the resulting cured product. This temperature condition is influenced by the type and amount of the thermal polymerization initiator and the type of polymerizable compound, and therefore cannot be uniformly defined. Generally, it is preferable to begin polymerization at a relatively low temperature and then slowly increase the temperature. The polymerization time, like the temperature, varies for various reasons, so it is preferable to predetermine the optimal time corresponding to these conditions, but it is generally preferred to select conditions in a manner that completes polymerization within 2 to 48 hours. In the case of obtaining photochromic laminates, polymerization is preferably carried out at a temperature at which the polymerizable functional groups react with each other; in this case, the optimal temperature and time are determined in a manner that achieves the target molecular weight.

[0280] Furthermore, during photopolymerization of the curable composition, the polymerization conditions, particularly the UV intensity, affect the properties of the resulting photochromic cured product. These irradiation conditions vary depending on the type and amount of the photopolymerization initiator and the type of polymerizable monomer, and therefore cannot be uniformly limited. Generally, irradiation at a wavelength of 365 nm for 0.5 to 5 minutes at a rate of 50 to 500 mW / cm² is preferred. 2 The selection criteria for UV light mode.

[0281] The biomass plasticity of the solidified material is preferably 25% by mass or more. The biomass plasticity can be calculated according to the method of ISO standard 16620-3. The biomass plasticity of the solidified material is preferably 30% by mass or more, and more preferably 40% by mass or more. There is no particular upper limit to this biomass plasticity; according to one example, it is 100% by mass or less, and according to another example, it is 80% by mass or less.

[0282] <Layered Body>

[0283] According to another embodiment, a laminate is provided. The laminate includes an optical substrate and a cured product of the embodiment located on the surface of the optical substrate. The optical substrate includes, for example, a resin such as diallyl carbonate resin, urethane resin, or thiourethane resin. The optical substrate may be a lens substrate. A primer layer may be provided between the laminate and the cured product. The primer layer includes urethane resin.

[0284] The biomass plasticity of the optical substrate is preferably 25% by mass or more. The biomass plasticity can be calculated according to ISO standard 16620-3. The biomass plasticity of the optical substrate is preferably 30% by mass or more, more preferably 40% by mass or more. There is no particular upper limit to this biomass plasticity; in one example, it is 100% by mass or less, and in another example, it is 80% by mass or less.

[0285] Figure 1 This is a cross-sectional view illustrating an example of a laminated structure in an embodiment. Figure 1 The laminate 10 shown includes an optical substrate 11, a primer layer 1 disposed on a main surface of the optical substrate 11, and a functional resin layer 12 disposed on the main surface of the primer layer 1. The functional resin layer 12 contains the cured product of the embodiment. The optical substrate 11 is a convex meniscus lens with an uneven shape.

[0286] <Optical Items>

[0287] The cured product of the embodiment can be widely used as an optical article, for example, as a substitute for silver halide photosensitive materials in various storage materials, photocopying materials, photosensitive materials for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, and other storage materials, as well as lenses. Lenses are suitable for eyeglasses. Photochromic cured products containing photochromic compounds can also be used as photochromic lens materials, optical filter materials, display materials, photometers, decorative materials, etc.

[0288] The cured product of this embodiment is particularly suitable for use in photochromic lenses. Photochromic lenses are suitable for use as lenses in eyeglasses such as sunglasses. Any known method can be used to manufacture photochromic lenses as long as it achieves uniform light-adjusting performance.

[0289] When photochromic properties are manifested by mixing, the above-mentioned curable composition can be injected into a glass mold held by an elastomer gasket or spacer. Depending on the type of polymerizable compound and polymerization curing accelerator, the mixture is cast and polymerized by heating in an air furnace and irradiation with active energy rays such as ultraviolet light, thereby obtaining a photochromic cured product shaped into an optical material such as a lens.

[0290] When photochromic properties are manifested by a lamination method, a coating liquid can be prepared by appropriately dissolving the curable composition in an organic solvent. The coating liquid is then applied to the surface of an optical substrate such as a lens substrate by spin coating or dipping. After drying to remove the organic solvent, the coating liquid is polymerized and cured by UV irradiation or heating in an inactive gas such as nitrogen. This forms a photochromic layer (coating method) on the surface of the optical substrate, which is composed of a photochromic cured product.

[0291] Alternatively, an optical substrate such as a lens substrate can be arranged face-to-face with a glass mold to form a specified gap, and a curable composition can be injected into the gap. In this state, a mold-based casting polymerization is carried out by polymerization and curing using UV irradiation, heating, etc., thereby forming a photochromic layer formed by the photochromic cured material on the surface of the optical substrate (casting polymerization method).

[0292] When a photochromic layer is formed on the surface of an optical substrate using the lamination method (coating method and casting polymerization method) as described above, the adhesion between the photochromic layer and the optical substrate can be improved by pre-treating the surface of the optical substrate with chemical treatment based on alkaline solutions, acidic solutions, etc., or by physical treatment using corona discharge, plasma discharge, grinding, etc. Alternatively, a transparent adhesive resin layer can be pre-formed on the surface of the optical substrate.

[0293] Furthermore, the cured product formed from the curable composition can be post-processed according to its intended use. Examples of post-processing include dyeing using dyes such as disperse dyes, lamination of protective layers containing urethane resins, epoxy resins, etc., formation of hard coating films using silane coupling agents and hard coating agents with silicon, zirconium, antimony, aluminum, tin, tungsten, etc. as the main components, thin film formation based on the vapor deposition of metal oxides such as SiO2, TiO2, ZrO2, etc., anti-reflective treatment of thin films based on coated organic polymers, and antistatic treatment.

[0294] Example

[0295] 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 description of each component and the evaluation method are as follows.

[0296] <Each ingredient>

[0297] (A) Ingredients

[0298] (A-1) Ingredients

[0299] GT-A: Glyceryl Triacrylate

[0300] GT-MA: Glyceryl Trimethacrylate

[0301] GT-MA1A: Glyceryl dimethacrylate acrylate

[0302] GT-MA3EO: Ethoxylated glycerol trimethacrylate (number average molecular weight 428)

[0303] G2-4A: Diglyceride Tetraacrylate

[0304] G2-4MA: Tetramethyldiglyceride

[0305] G2-4AE: Ethoxylated diglyceride tetraacrylate (number average molecular weight 559)

[0306] G2-4MAE: Ethoxylated diglycerol tetramethacrylate (number average molecular weight 615)

[0307] G2-4MA6E: Ethoxylated diglyceride tetramethacrylate (number average molecular weight 1438)

[0308] G3-4MA: A mixture of tetramethyltriglyceride and pentamethyltriglyceride in a ratio of 78:22.

[0309] G3-5MA: Triglyceride Pentamethacrylate

[0310] (A-2) Ingredients

[0311] 14G: Polyethylene glycol dimethacrylate (number average molecular weight 770)

[0312] A-PTMG65: Polytetramethylene glycol diacrylate (number average molecular weight 775)

[0313] M-PTMG65: Polytetramethylene glycol dimethacrylate (number average molecular weight 803)

[0314] M-PTMG65Bio: Polytetramethylene glycol dimethacrylate (number average molecular weight 803, biomass plasticity 76.8% by mass) with 95% biomass plasticity.

[0315] A-PTMG100: Polytetramethylene glycol diacrylate (number average molecular weight 1128)

[0316] M-PTMG100: Polytetramethylene glycol dimethacrylate (number average molecular weight 1156)

[0317] M-PTMG100Bio: Polytetramethylene glycol dimethacrylate (number average molecular weight 1171, biomass plasticity 82.5% by mass) with 95% biomass plasticity.

[0318] A-PTMG200Bio: Polytetramethylene glycol diacrylate (number average molecular weight 2123, biomass plasticity 90.1% by mass) with 95% biomass plasticity.

[0319] M-EGTMG160: Dimethacrylate of the following formula

[0320]

[0321] M-EGTMG130: Dimethacrylate of the following formula

[0322]

[0323] PTG25CD100: Dimethacrylate of the following formula

[0324]

[0325] (Synthesis of PTG25CD100)

[0326] 100g of NT1002 (manufactured by Mitsubishi Chemical Corporation), with a molecular weight of 1000 determined by hydroxyl value, was mixed with 330mL of dehydrated toluene, 1.0mg of p-methoxyphenol, and 2.86g of p-toluenesulfonic acid monohydrate, and stirred. 18.9g of methacrylic acid was then added, and the mixture was reacted at an azeotropic temperature for 20 hours. After the reaction was complete, 1000mL of 5% sodium bicarbonate solution was added, and the mixture was separated. Diatomaceous earth was added to the resulting organic layer, stirred, and filtered. 20g of WakoGel 60N was added to the resulting organic layer, stirred, and filtered. 1mL of a 0.1mg / mL p-methoxyphenol toluene solution was added to the resulting organic layer, and the mixture was concentrated to synthesize PTG25CD100.

[0327] The proton nuclear magnetic resonance spectrum was measured, and the results showed a peak of about 55H based on tetramethyleneoxy and methacryloyl groups in the vicinity of δ1.0~2.5ppm, a peak of about 49H based on tetramethyleneoxy groups in the vicinity of δ3.0~4.5ppm, and a peak of 4H based on acryloyl groups in the protons in the vicinity of δ5.5~6.5ppm.

[0328] PTG65CD200: Dimethacrylate of the following formula

[0329]

[0330] (Synthesis of PTG65CD200)

[0331] In the synthesis of PTG25CD100, NT2006 was used instead of NT1002, and the reaction was carried out in the same manner to synthesize PTG65CD200.

[0332] The proton nuclear magnetic resonance spectrum was measured, and the results showed a peak of about 114H based on tetramethyleneoxy and methacryloyl groups in the vicinity of δ1.0~2.5ppm, a peak of about 108H based on tetramethyleneoxy groups in the vicinity of δ3.0~4.5ppm, and a peak of 4H based on acryloyl groups in the protons in the vicinity of δ5.5~6.5ppm.

[0333] UA-PTMG65: Diacrylate of the following formula

[0334]

[0335] (Synthesis of UA-PTMG65)

[0336] 65g of polytetramethylene ether glycol (molecular weight 650, determined by hydroxyl value) was added to 250mL of dehydrated toluene for azeotropic dehydration. After distilling off 50mL of toluene from the azeotropically dehydrated toluene solution, the solution was cooled to 60°C. 19.5mg of p-methoxyphenol and 6.5mg of dibutyltin dilaurate were added to the cooled solution. 13.9g of 2-acryloyloxyethyl isocyanate was slowly added dropwise to this solution. After the addition, the reaction was carried out at 60-65°C for 10 hours to obtain a reaction solution. 100mL of water was added to the reaction solution, and the mixture was separated. Diatomaceous earth was added to the obtained organic layer, stirred, and then filtered. The obtained organic layer was concentrated to obtain UA-PTMG65.

[0337] For the obtained concentrate, proton nuclear magnetic resonance spectra were measured. The results showed a peak of about 36H based on tetramethylene group in the vicinity of δ1.0~2.0 ppm, a peak of about 44H based on tetramethylene group and ethylene group in the vicinity of δ3.0~4.5 ppm, and a peak of 6H based on acryloyl group proton in the vicinity of δ5.5~6.5 ppm.

[0338] APC56: A diacrylate of polycarbonate diol (number average molecular weight 606) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol.

[0339] (A-3)

[0340] A-TMPT: Trimethylolpropane triacrylate

[0341] TMPT: Trimethylolpropane trimethacrylate

[0342] TMPT-20E: Ethoxylated trimethylolpropane trimethacrylate (number average molecular weight 1218)

[0343] DPE6MA-6EO: Ethoxylated dipentaerythritol hexamethacrylate (number average molecular weight 927)

[0344] D-TMP: Di(trimethylolpropanetetramethacrylate)

[0345] (A-4)

[0346] LA82: 1,2,2,6,6'-Pentamethyl-4-piperidinyl methacrylate

[0347] TSL: γ-methacryloyloxypropyltrimethoxysilane

[0348] (Other free radical polymerizable monomers)

[0349] RX-1: Polyrotaxane with acryloyl groups

[0350] Polyrotaxanes with acryloyl groups were synthesized according to the method described in International Publication No. 2018 / 030257, which satisfy the following properties.

[0351] The weight-average molecular weight (Mw) of polyrotaxane (RX-1) with acryloyl groups is 180,000.

[0352] Acryloyl group modification ratio in the side chain: 80 mol%.

[0353] The proportion of OH groups remaining in the side chain: 20 mol%.

[0354] Axial molecule: linear polyethylene glycol (PEG) with a molecular weight of 11,000.

[0355] Encapsulation ring: α-cyclodextrin (α-CD) introduction ratio 0.25.

[0356] End of the axial molecule: end-capped with adamantane.

[0357] The side chain is introduced into the encapsulation ring; the (average) molecular weight of the side chain is approximately 500.

[0358] Number of acryloyl groups per molecule: approximately 90.

[0359] The weight-average molecular weight (Mw) of polyrotaxane (RX-1) was determined by gel permeation chromatography (GPC). A liquid chromatography apparatus (Waters Corporation, Japan) was used. Two TSKgel SuperHM-M columns (size exclusion limit molecular weight: 4,000,000, Tosoh Corporation) were used in series as columns.

[0360] In addition, tetrahydrofuran was used as the developing solvent, and the determination was carried out at a flow rate of 0.6 ml / min and a temperature of 40 °C. Polystyrene was used as the standard sample, and the weight-average molecular weight was calculated by comparison. The result showed that the weight-average molecular weight of RX-1 was 180,000.

[0361] SO-1: A sesquioxane having a methacryloyl group and the following properties.

[0362] Number of methacrylate groups per molecule: 20.

[0363] Weight-average molecular weight: 4,800.

[0364] It should be noted that SO-1 is synthesized via the following method. First, 248 g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate is mixed with 248 ml of ethanol and 54 g (3.0 mol) of water, and 0.20 g (0.005 mol) of sodium hydroxide is added as a catalyst. The reaction is carried out at 30°C for 3 hours. 1 After confirming the disappearance of the starting material by H-NMR, the mixture was neutralized with dilute hydrochloric acid, and 174 ml of toluene, 174 ml of heptane, and 174 g of water were added to remove the aqueous layer. The organic layer was then washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain SO₂. It should be noted that... 29 Si-NMR confirmed that SO-1 is a mixture of cage-like, ladder-like, and random structures.

[0365] The weight-average molecular weight (Mw) of SO-1 was determined by gel permeation chromatography (GPC). A liquid chromatography apparatus (Waters Corporation, Japan) was used. Three columns were used in series: Shodex GPC KF-802 (size-limiting molecular weight: 5000, Showa Denko Corporation), Shodex GPC KF802.5 (size-limiting molecular weight: 20000, Showa Denko Corporation), and Shodex GPC KF-803 (size-limiting molecular weight: 70000, Showa Denko Corporation). Tetrahydrofuran was used as the developing solvent, and the determination was performed at a flow rate of 1 ml / min and a temperature of 40°C. Polystyrene was used as the standard sample, and the weight-average molecular weight was calculated by comparison.

[0366] (B) Components

[0367] PC1: The compound shown in the following formula. In the following formula, "Me" represents a methyl group.

[0368]

[0369] PC2: The compound shown in the following formula. In the following formula, "Me" represents a methyl group.

[0370]

[0371] (Other compounding agents)

[0372] (Stabilizer)

[0373] HALS: Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate

[0374] HP: Ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxym-tolyl)propionate] (manufactured by BASF Japan Ltd., Irganox 245).

[0375] (Photopolymerization initiator)

[0376] PI: Phenylenol bis(2,4,6-trimethylbenzoyl)-phosphine oxide (IGM Corporation, Omnirad 819)

[0377] <Example 1>

[0378] (Preparation of photochromic curable composition)

[0379] First, prepare the ingredients according to the following recipe.

[0380] (A) Ingredients

[0381] (A-1) Ingredients: GT-A 28.3 parts by weight.

[0382] (A-2) Ingredients: 14g 66.1 parts by weight.

[0383] (A-4) Ingredients: 5.6 parts by weight of TSL.

[0384] (B) Ingredients: PC1 2.0 parts by weight.

[0385] (Other compounding agents)

[0386] (Polymerization initiator): 0.3 parts by weight of PI.

[0387] Next, all the compounds equivalent to component (A) were mixed together, and then component (B) and other additives were mixed in to obtain a mixture. 1000 ppm of Dow Toray Co., Ltd. leveling agent L-7001 was added to the obtained mixture, and the mixture was further mixed to obtain a photochromic curable composition.

[0388] (Manufacturing of optical items)

[0389] Using this photochromic curable composition, a polymerization reaction is carried out as follows, and a photochromic laminate is obtained by a lamination method.

[0390] First, a thiocarbamate-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as the optical substrate. It should be noted that the thiocarbamate-based plastic lens was first subjected to alkaline etching at 50°C for 5 minutes using a 5% sodium hydroxide aqueous solution, and then thoroughly cleaned with distilled water.

[0391] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by TOKUYAMA CORPORATION) was applied to the surface of the aforementioned plastic lens at a spin speed of 70 rpm for 15 seconds, followed by application at 700 rpm for 10 seconds. Then, approximately 1 g of the aforementioned photochromic curable composition was spin-coated to achieve a photochromic coating thickness of 40 μm.

[0392] A lens with a photochromic curable composition (photochromic coating) coated on its surface was used in a nitrogen atmosphere with an output power of 200mW / cm. 2 The coating was irradiated with a metal halide lamp for 90 seconds to cure it. Then, it was further heated at 90°C for 1 hour to produce a photochromic laminate with a photochromic layer.

[0393] <Examples 2-4 and Comparative Examples 1-3>

[0394] The photochromic curable compositions described in Tables 1 to 3 were used to prepare photochromic cured products in the same manner as in Example 1, except that...

[0395] <Examples 5-27 and Comparative Examples 4-6>

[0396] Using the photochromic curable compositions described in Tables 4 to 8, PC2 was used as component (B), and other compounding agents were used in the same manner as in Example 1, with 0.3 parts by weight of PI, 3 parts by weight of HALS, and 1 part by weight of HP.

[0397] <Evaluation Methods>

[0398] The photochromic laminates obtained in the examples and comparative examples were evaluated using the methods shown below. The results are shown in Tables 1 to 8.

[0399] (1) Photochromic properties

[0400] [1] Maximum absorption wavelength (λmax (nm)):

[0401] The maximum absorption wavelength after color development is determined using a spectrophotometer (MCPD3000 instantaneous multichannel photodetector) manufactured by Otsuka Electronics Co., Ltd., and is used as an indicator of the hue during color development.

[0402] [2] Colorimetric concentration at 23℃ (A) 23 ):

[0403] The difference between the absorbance {ε(240)} at the aforementioned maximum absorption wavelength after 240 seconds of light irradiation at 23°C and the absorbance ε(0) without irradiation is used as an indicator of colorimetric concentration. The higher this value, the better the photochromic properties.

[0404] [3] Fading half-life at 23℃ [τ1 / 2 (sec.)]:

[0405] The fading rate is the time required for the absorbance of the sample at the aforementioned maximum absorption wavelength to decrease to half of {ε(300)-ε(0)} after 300 seconds of light irradiation at 23°C and then the light irradiation is stopped. The shorter this time, the faster the fading rate.

[0406] (2) Vickers hardness

[0407] Vickers hardness was measured using a micro Vickers hardness tester, PMT-X7A (manufactured by Matsuzawa Co., Ltd). A pyramidal diamond indenter was used, and the measurement was performed under a load of 10 gf and a holding time of 30 seconds. The results were performed in a total of 4 measurements, and the average of the 3 measurements after removing the first measurement with the largest measurement error was expressed.

[0408] [Table 1]

[0409]

[0410] [Table 2]

[0411]

[0412] [Table 3]

[0413]

[0414] [Table 4]

[0415]

[0416] [Table 5]

[0417]

[0418] [Table 6]

[0419]

[0420] [Table 7]

[0421]

[0422] [Table 8]

[0423]

[0424] <Example 28>

[0425] (Preparation of photochromic curable composition)

[0426] First, prepare the ingredients according to the following recipe.

[0427] (A) Ingredients

[0428] (A-1) Ingredients: G2-4A 28.3 parts by weight.

[0429] (A-2) Ingredients: 14g 66.1 parts by weight.

[0430] (A-4) Ingredients: 5.6 parts by weight of TSL.

[0431] (B) Ingredients: PC1 2.0 parts by weight.

[0432] (Other compounding agents)

[0433] (Polymerization initiator): 0.3 parts by weight of PI.

[0434] Next, all the compounds equivalent to component (A) were mixed together, and then component (B) and other additives were mixed in to obtain a mixture. 1000 ppm of Dow Toray Co., Ltd. leveling agent L-7001 was added to the obtained mixture, and the mixture was further mixed to obtain a photochromic curable composition.

[0435] (Manufacturing of optical items)

[0436] Using this photochromic curable composition, a polymerization reaction is carried out as follows, and a photochromic laminate is obtained by a lamination method.

[0437] First, a thiocarbamate-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as the optical substrate. It should be noted that the thiocarbamate-based plastic lens was first subjected to alkaline etching at 50°C for 5 minutes using a 5% sodium hydroxide aqueous solution, and then thoroughly cleaned with distilled water.

[0438] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by TOKUYAMA CORPORATION) was applied to the surface of the aforementioned plastic lens at a spin speed of 70 rpm for 15 seconds, followed by application at 700 rpm for 10 seconds. Then, approximately 1 g of the aforementioned photochromic curable composition was spin-coated to achieve a photochromic coating thickness of 40 μm.

[0439] A lens with a photochromic curable composition (photochromic coating) coated on its surface was used in a nitrogen atmosphere with an output power of 200mW / cm. 2 The coating was irradiated with a metal halide lamp for 90 seconds to cure it. Then, it was further heated at 90°C for 1 hour to produce a photochromic laminate with a photochromic layer.

[0440] The same method was used to evaluate the results, which are recorded in Table 9.

[0441] <Examples 29-31, 44 and 45 and Comparative Examples 6-8>

[0442] The photochromic curable compositions described in Tables 9-11 and 13 were used to prepare photochromic cured products in the same manner as in Example 28, except that...

[0443] <Examples 32-43, 46-50 and Comparative Examples 9-10>

[0444] Using the photochromic curable compositions described in Tables 12 and 13, PC2 was used as component (B), and other compounding agents were used in the same manner as in Example 28, with 0.3 parts by weight of PI, 3 parts by weight of HALS, and 1 part by weight of HP.

[0445] [Table 9]

[0446]

[0447] [Table 10]

[0448]

[0449] [Table 11]

[0450]

[0451] [Table 12]

[0452]

[0453] [Table 13]

[0454]

[0455] As shown in Tables 1 to 13, in the comparison between the examples and comparative examples using the same photochromic compound, the curable composition of the present invention using the first free radical polymerizable monomer shown in formula (1) exhibits excellent photochromic properties, especially excellent fading speed. In addition, the hardness of the cured product is also high.

[0456] The following illustrates preferred embodiments of this disclosure. [1]

[0458] A curable composition comprising a first radical polymerizable monomer as shown in formula (1) and a functional pigment,

[0459]

[0460] R 1 and R 3 Each is an independent monovalent group as shown in the following formula (2).

[0461] a2 is 1, or a number greater than 2 and less than 10.

[0462] R 200 It can be a hydrogen atom or a methyl group.

[0463] When a2 is 1, R 2 The monovalent group is represented by the following formula (2).

[0464] When a2 is greater than 2 and less than 10, R 2 For a monovalent group or hydrogen atom as shown in formula (2) below, multiple R 2 At least one of them is a monovalent group as shown in the following formula (2),

[0465] The multiple monovalent groups shown in the following formula (2) may be chosen to be the same or different from each other.

[0466]

[0467] In the aforementioned formula (2),

[0468] Q 1 It is a straight-chain or branched alkylene group having 1 or more but less than 6 carbon atoms.

[0469] Q 2 It can be a hydrogen atom or a methyl group.

[0470] b2 is 0, or is greater than 1 and less than 15. [2]

[0472] According to the curable composition described in [1], the proportion of the first free radical polymerizable monomer in the curable composition is more than 5% by mass and less than 95% by mass. [3]

[0474] According to the curable composition described in [1] or [2], the aforementioned functional pigment is present in a proportion of 0.001% by mass or more and 10% by mass or less in the aforementioned curable composition. [4]

[0476] The curable composition according to any one of [1] to [3], wherein the aforementioned first free radical polymerizable monomer comprises a compound represented by the following formula (1a),

[0477]

[0478] In the aforementioned equation (1a),

[0479] R 200 It can be a hydrogen atom or a methyl group.

[0480] R 201 R 202 and R 203 Each is an independent straight-chain or branched alkylene group having 1 or more but less than 6 carbon atoms.

[0481] R 204 R 205 and R 206 Each can be independently a hydrogen atom or a methyl group.

[0482] b3, b4, and b5 are each independently 0, or 1 or more and 4 or less. [5]

[0484] The curable composition according to any one of [1] to [4] further comprises a second radical polymerizable monomer having at least one polyalkylene glycol chain structure with a number average molecular weight of more than 250 and two (meth)acryloyl groups in one molecule. [6]

[0486] According to the curable composition described in [5], wherein the aforementioned second radical polymerizable monomer comprises a di(meth)acrylate as shown in formula (3),

[0487]

[0488] In the aforementioned formula (3),

[0489] Q 3 and Q 6 Each can be independently a hydrogen atom or a methyl group.

[0490] Q 4 and Q 5 Each is independently an alkyl group having 1 or more hydrogen atoms and 3 or fewer carbon atoms.

[0491] Q 7 For divalent groups with a number average molecular weight of 250 or more, as shown in formula (3a) below,

[0492] a and b are each independently greater than 0 and less than 10.

[0493] Z 1 and Z 2 Each is independently either 0 or 1.

[0494]

[0495] In the aforementioned equation (3a),

[0496] Q 7a Q 7b Q 7d and Q 7e Each is independently an alkyl group having 1 or more hydrogen atoms and 3 or fewer carbon atoms.

[0497] Q 7d and Q 7e For groups that are different from each other, Q 7a and Q 7e For different groups of groups,

[0498] Q 7c It can be a linear or branched alkylene group with 2 or more but less than 20 carbon atoms, optionally with substituents.

[0499] d and h are both greater than 0 and less than 10.

[0500] e and g are greater than 0 and less than 20.

[0501] f is 3 or higher and 100 or lower. [7]

[0503] The curable composition according to any one of [1] to [6] further comprises a third radical polymerizable monomer having three or more (meth)acryloyl groups in one molecule. [8]

[0505] According to the curable composition described in [7], wherein the aforementioned third radical polymerizable monomer comprises a polyfunctional (meth)acrylate represented by formula (I) below,

[0506]

[0507] In the aforementioned formula (I),

[0508] Q 10 It is a straight-chain or branched alkylene group having 1 or more but less than 3 carbon atoms.

[0509] Q 11 It is a straight-chain or branched alkylene group having 1 or more but less than 10 carbon atoms.

[0510] Q 12 It can be a hydrogen atom or a methyl group.

[0511] Q 13 Organic groups with a carbon number of 1 or more but less than 10, exhibiting a valence of 3 to 6.

[0512] a1 is 0 or 1.

[0513] b1 is greater than 0 and less than 15.

[0514] c1 is 3 or higher and 6 or lower. [9]

[0516] According to the curable composition described in [5] or [6], the proportion of the aforementioned second free radical polymerizable monomer in the aforementioned curable composition is more than 10% by mass and less than 90% by mass.

[10]

[0518] According to the curable composition described in [7], the proportion of the aforementioned third free radical polymerizable monomer in the aforementioned curable composition is more than 5% by mass and less than 95% by mass.

[11]

[0520] The curable composition according to any one of [1] to

[10] , wherein the aforementioned functional pigment comprises a photochromic compound.

[12]

[0522] The curable composition according to any one of [1] to

[11] , wherein, in the aforementioned formula (2), Q 2 It is a methyl group.

[13]

[0524] The curable composition according to any one of [1] to

[12] , wherein b2 is 0 in the aforementioned formula (2).

[14]

[0526] A cured material is formed by curing any one of the curable compositions described in [1] to

[13] .

[15]

[0528] A layered body having:

[0529] Optical substrate; and,

[0530] A resin layer comprising the cured material described in

[14] .

[16]

[0532] An optical article comprising the cured material described in

[14] .

[17]

[0534] A lens comprising the cured material described in

[14] .

[18]

[0536] A pair of eyeglasses comprising the lens described in

[17] .

[19]

[0538] According to

[14] , the solidified material obtained by means of ISO standard 16620-3 has a biomass plasticity of 10% by mass or more.

[20]

[0540] According to the laminate described in

[15] , the biomass plasticity of the aforementioned optical substrate obtained by means of ISO standard 16620-3 is 25% by mass or more.

Claims

1. A curable composition comprising a first free radical polymerizable monomer as shown in formula (1) and a functional pigment, In the above formula (1), R 1 and R 3 Each is an independent monovalent group as shown in the following formula (2). a2 is 1, or a number greater than 2 and less than 10. R 200 It can be a hydrogen atom or a methyl group. When a2 is 1, R 2 The monovalent group is represented by the following formula (2). When a2 is greater than 2 and less than 10, R 2 For a monovalent group or hydrogen atom as shown in formula (2) below, multiple R 2 At least one of them is a monovalent group as shown in the following formula (2), The multiple monovalent groups shown in the following formula (2) may be chosen to be the same or different from each other. In the above formula (2), Q 1 It is a straight-chain or branched alkylene group having 1 or more but less than 6 carbon atoms. Q 2 It can be a hydrogen atom or a methyl group. b2 is 0, or is greater than 1 and less than 15.

2. The curable composition according to claim 1, wherein, The proportion of the first free radical polymerizable monomer in the cured composition is more than 5% by mass and less than 95% by mass.

3. The curable composition according to claim 1, wherein, The functional pigment is present in a proportion of 0.001% by mass or more and 10% by mass or less in the curable composition.

4. The curable composition according to claim 1, wherein, The first radical polymerizable monomer comprises a compound represented by the following formula (1a), In the aforementioned formula (1a), R 200 It can be a hydrogen atom or a methyl group. R 201 R 202 and R 203 Each is an independent straight-chain or branched alkylene group having 1 or more but less than 6 carbon atoms. R 204 R 205 and R 206 Each can be independently a hydrogen atom or a methyl group. b3, b4, and b5 are each independently 0, or 1 or more and 4 or less.

5. The curable composition according to claim 1, further comprising a second radical polymerizable monomer having in one molecule at least one polyalkylene glycol chain structure with a number average molecular weight of 250 or more and two (meth)acryloyl groups.

6. The curable composition according to claim 5, wherein, The second radical polymerizable monomer comprises a di(meth)acrylate as shown in formula (3). In the aforementioned formula (3), Q 3 and Q 6 Each can be independently a hydrogen atom or a methyl group. Q 4 and Q 5 Each is independently an alkyl group having 1 or more hydrogen atoms and 3 or fewer carbon atoms. Q 7 For divalent groups with a number average molecular weight of 250 or more, as shown in formula (3a) below, a and b are each independently greater than 0 and less than 10. Z 1 and Z 2 Each is independently either 0 or 1. In the aforementioned formula (3a), Q 7a Q 7b Q 7d and Q 7e Each is independently an alkyl group having 1 or more hydrogen atoms and 3 or fewer carbon atoms. Q 7d and Q 7e For groups that are different from each other, Q 7a and Q 7e For different groups of groups, Q 7c It can be a linear or branched alkylene group with 2 or more but less than 20 carbon atoms, optionally with substituents. d and h are both greater than 0 and less than 10. e and g are greater than 0 and less than 20. f is 3 or higher and 100 or lower.

7. The curable composition according to claim 1, further comprising a third radical polymerizable monomer having three or more (meth)acryloyl groups in one molecule.

8. The curable composition according to claim 7, wherein, The third radical polymerizable monomer comprises a polyfunctional (meth)acrylate as shown in formula (I). In the aforementioned formula (I), Q 10 It is a straight-chain or branched alkylene group having 1 or more but less than 3 carbon atoms. Q 11 It is a straight-chain or branched alkylene group having 1 or more but less than 10 carbon atoms. Q 12 It can be a hydrogen atom or a methyl group. Q 13 Organic groups with a carbon number of 1 or more but less than 10, exhibiting a valence of 3 to 6. a1 is 0 or 1. b1 is greater than 0 and less than 15. c1 is 3 or higher and 6 or lower.

9. The curable composition according to claim 5, wherein, The proportion of the second free radical polymerizable monomer in the cured composition is more than 10% by mass and less than 90% by mass.

10. The curable composition according to claim 7, wherein, The third free radical polymerizable monomer accounts for more than 5% by mass and less than 95% by mass in the cured composition.

11. The curable composition according to claim 1, wherein, The functional pigment contains a photochromic compound.

12. The curable composition according to claim 1, wherein, In the above equation (2), Q 2 It is a methyl group.

13. The curable composition according to claim 1, wherein, In the formula (2), b2 is 2, 3 or 4.

14. A cured product formed by curing the curable composition of claim 1.

15. A laminated body comprising: Optical substrate; and, A resin layer comprising the cured product of claim 14.

16. An optical article comprising the cured material of claim 14.

17. A lens comprising the cured material of claim 14.

18. A pair of eyeglasses comprising the lens of claim 17.

19. The solidified material according to claim 14, wherein the biomass plasticity obtained by means of the method according to ISO standard 16620-3 is 10% by mass or more.

20. The laminate according to claim 15, wherein the biomass plasticity of the optical substrate obtained by means of ISO standard 16620-3 is 25% by mass or more.

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