(METH) acrylate, curable composition, cured product, laminate, optical article, lens and eyewear

Abstract

The purpose of the present invention is to provide a (meth) acrylate, a curable composition, a cured product, a laminate, an optical article, a lens, and eyeglasses, which are capable of achieving excellent performance of a functional dye. According to one embodiment, a (meth) acrylate represented by formula (1A) is provided. According to another embodiment, a curable composition is provided. The curable composition contains a (meth) acrylate according to the embodiment and a functional dye. According to another embodiment, a cured product is provided. The cured product is obtained by curing the curable composition according to the embodiment.

Description

TECHNICAL FIELD

[0001] The present application relates to (meth)acrylate, curable composition, cured product, laminate, optical article, lens, and eyeglasses. BACKGROUND

[0002] Photochromic compounds represented by naphthopyran compounds, fulgimide compounds, spirooxazine compounds, and the like are compounds that can reversibly take two isomers different in absorption spectrum by irradiation of light containing ultraviolet rays such as sunlight or light of a mercury lamp. They generally have the following characteristics: by irradiating ultraviolet rays to a colorless leuco state compound, the color rapidly changes, isomerizes to a colored colored state (coloration reaction), and returns to the original color when left in the dark after stopping the irradiation of light (hereinafter, also referred to as photochromism), and by utilizing this property, they are used for various purposes, particularly optical materials.

[0003] For example, photochromic eyeglass lenses endowed with photochromism by using photochromic compounds rapidly color in the outdoors where sunlight containing ultraviolet rays is irradiated to function as sunglasses, and decolorize in the indoors where such light is not irradiated to function as transparent ordinary eyeglasses, and in recent years, the demand for them has increased.

[0004] Photochromic eyeglass lenses are obtained, for example, by coating a photochromic curable composition on a plastic lens by spin coating or the like, and forming a photochromic coating layer by photocuring it.

[0005] Prior Art Documents

[0006] Patent Documents

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

[0008] Patent Document 2: U.S. 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

[0013] Patent Document 7: Japanese Patent Application Publication No. 2020-172565

[0014] Patent Document 8: Japanese Patent Application Publication No. 2022-120570

[0015] Patent Document 9: International Publication No. 2014 / 136804 Summary of the Invention

[0016] The problem the invention aims to solve

[0017] The object of the present invention is to provide (meth)acrylates, curable compositions, cured products, laminates, optical articles, lenses and eyeglasses that can achieve the excellent performance of functional pigments.

[0018] Solution for solving the problem

[0019] According to this disclosure, a (meth)acrylate of the following formula (1A) is provided.

[0020]

[0021] In formula (1A), Q 1 and Q 5 Each can be independently a hydrogen atom or a methyl group. Q 2 and Q 4 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 3A and Q 3B Each is an independent divalent group as shown in formula (1a) below. In Q 3A In the case of multiple Qs, multiple Qs 3A They can be chosen to be the same or different groups. 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. Z 3 The range is 1 to 100.

[0022]

[0023] In formula (1a), Q 6 and Q 10 It is an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. Q 7 and Q 9 It is an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. Q 6 and Q 7 These are distinct groups. Q 9 and Q 10 These are distinct groups. Q 8 It is a linear or branched alkylene group with 2 to 20 carbon atoms, optionally having substituents. d and h are 0 or more and 10 or less. e and g are 0 or more and 20 or less. f is 3 or more and 100 or less.

[0024] According to this disclosure, a curable composition is provided. The curable composition comprises (meth)acrylate and functional pigments as described in the embodiments.

[0025] According to the present disclosure, a cured product is provided. The cured product is obtained by curing the curable composition of the embodiments.

[0026] According to the present disclosure, a laminate is provided. The laminate includes the cured product of the embodiments on a surface of an optical substrate.

[0027] According to the present disclosure, an optical article is provided. The optical article includes the cured product of the embodiments.

[0028] According to the present disclosure, a lens is provided. The lens includes the cured product of the embodiments.

[0029] According to the present disclosure, a spectacle is provided. The spectacle includes the lens of the embodiments.

[0030] Effects of the Invention

[0031] According to the present disclosure, a (meth)acrylate, a curable composition, a cured product, a laminate, an optical article, a lens, and a spectacle, which can achieve excellent performance of a functional pigment, are provided. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 A cross-sectional view schematically showing an example of the laminate of the embodiments. DETAILED DESCRIPTION

[0033] According to the embodiments, a (meth)acrylate represented by Formula (1A) is provided. The (meth)acrylate can be suitably used as a material for forming a resin composition containing a functional pigment. The reason for this is described below.

[0034] First, the functional pigment contains a compound having selective absorption ability of visible light, and a compound that exhibits coloration, decoloration, or color change by energy such as light, heat, electric field, or pressure. Such a functional pigment can exert a specific function by undergoing a structural change under specific conditions. In general, the matrix of a plastic cured product has a rigid structure. Therefore, in the cured product, the free space provided for the functional pigment to undergo a structural change is small compared to that in a solution. Therefore, the functional pigment in the cured product is less likely to undergo a structural change compared to that in a solution, and its function is limited.

[0035] The (meth)acrylate represented by Formula (1A) is characterized by having a structure in which a Q 3A moiety and a Q 3B moiety are bonded by a carbonate bond. The Q 3A moiety and the Q 3B moiety each have a - (O-Q 8 ) fThe repeating structure shown is a first alkylene oxide chain with 2 or more but less than 20 carbon atoms. This first alkylene oxide chain is considered to function as a soft segment in the cured product, forming free space for functional pigments. Therefore, structural variations of functional pigments located in the soft segments composed of this first alkylene oxide chain are less likely to be hindered, enabling the achievement of excellent functionality. In the (meth)acrylate of the embodiment, it is believed that the presence of the first alkylene oxide chain functioning as a soft segment (Q) contributes to this effect. 3A Part of Q 3B Some of the bonds are formed through carbonate bonds, and the strong cohesive force between the carbonate bonds easily leads to the formation of agglomerated structures of soft segments. Furthermore, by using the (meth)acrylate of the embodiment, a cured product that balances high functionality and high hardness of the functional pigment can be achieved. That is, when a cured product with high hardness is desired, there is a tendency for a lower proportion of soft segments, narrower free space in the cured product, and reduced functionality of the functional pigment. As described above, the (meth)acrylate of the embodiment easily forms agglomerated structures between the first alkylene oxide chains, thus even in cured products with a low proportion of soft segments, a wide free space can be achieved within the agglomerated structure of soft segments, suppressing the reduction of functionality of the functional pigment. Therefore, by using this (meth)acrylate, a cured product that excels in both high hardness and the performance of the functional pigment can be achieved.

[0036] [The (meth)acrylate shown in formula (1A)]

[0037] The (meth)acrylate of the embodiments is represented by the following formula (1A). The (meth)acrylate is a diacrylate having two acryloyl groups, a dimethacrylate having two methacryloyl groups, or an acrylate methacrylate having one acryloyl group and one methacryloyl group. The (meth)acrylate has at least one carbonate bond in its molecule.

[0038]

[0039] In formula (1A), Q 1 and Q 5 Each atom is independently a hydrogen atom or a methyl group, preferably a methyl group.

[0040] Z 3 A value between 1 and 100. From the perspective of balancing functionality, hardness, and easily manageable viscosity, Z... 3 Preferably, the value is 1 or more and 85 or less, more preferably 1 or more and 70 or less, even more preferably 1 or more and 50 or less, and particularly preferably 2 or more and 25 or less.

[0041] Q 3A and Q 3Beach independently a bivalent group represented by the following formula (1a) in which Q 3A when a plurality of Q 3A are optionally the same or different groups.

[0042]

[0043] in formula (1a), Q 8 is a linear or branched alkylene group having 2 or more and 20 or less carbon atoms, optionally having a substituent. The number of carbon atoms of the alkylene group is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. The number of carbon atoms of the alkylene group can be 15 or less, can be 10 or less, or can be 6 or less. Q 8 is preferably a linear alkylene group having no substituent. The repeating unit - (OQ 8 ) - having a subscript f added thereto is a first alkylene oxy unit having 2 or more and 20 or less carbon atoms. The polymer site composed of the repeating unit can form a soft segment of the cured product. When the number of carbon atoms of the alkylene group is large, the functionality of the cured product is further improved. On the other hand, when the number of carbon atoms of the alkylene group is too large, the amount of the soft segment per unit mass decreases, and thus the functionality of the cured product can decrease.

[0044] f is 3 or more and 100 or less. From the viewpoint of balancing the functionality and the hardness, f is preferably 3 or more and 85 or less, more preferably 3 or more and 70 or less, further preferably 3 or more and 50 or less, and particularly preferably 3 or more and 25 or less.

[0045] Q 7 and Q 9 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 7 and Q 9 is preferably a hydrogen atom or a methyl group. e and g are 0 or more and 20 or less. e and g can be 1 or more and 15 or less, or can be 5 or more and 10 or less.

[0046] Q 6 and Q 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 6 and Q 10 is preferably a hydrogen atom or a methyl group. d and h are 0 or more and 10 or less. d and h can be 1 or more and 5 or less. When e and g are 0, d and h are 0.

[0047] Q 6 and Q 7 are different groups. Q 9 and Q 10 are different groups.

[0048] In other words, the (meth)acrylate of the embodiment can further have at least one of a repeating unit of e and g, i.e., a second alkyleneoxy unit, and a repeating unit of d and h, i.e., a third alkyleneoxy unit, added thereto. When the urethane (meth)acrylate of the embodiment has a diblock structure or a triblock structure including at least one of the second alkyleneoxy unit and the third alkyleneoxy unit, a microphase separation structure can be formed in a cured product.

[0049] Z 1 and Z 2 each independently is 0 or 1. Z 1 and Z 2 When at least one of a and b is 1, the (meth)acrylate represented by formula (1A) is a urethane (meth)acrylate having at least one urethane bond.

[0050] Q 2 and Q 4 each independently is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom.

[0051] a and b each independently are 0 or higher and 10 or lower, and are, for example, 1 or higher and 5 or lower, and are preferably 1 or 2.

[0052] From the viewpoint of having an easily handled viscosity, Z 1 and Z 2 of the (meth)acrylate of the embodiment is preferably 0. The (meth)acrylate is represented by, for example, the following formula (IB).

[0053]

[0054] In formula (IB),

[0055] Q 1 , Q 3A , Q 3B , Q 5 and Z 3 have the same meanings as in the aforementioned formula (1A).

[0056] From the viewpoint of obtaining more excellent performance of a functional pigment, the (meth)acrylate of the embodiment is preferably the following formula (1C).

[0057]

[0058] In formula (1C), Q 1 , Q 5 and Z 3 have the same meanings as in formula (1A).

[0059] Q 11is a divalent group represented by the following formula (1b), and a plurality of Q 11 are optionally the same or different groups.

[0060]

[0061] Q 8a is a linear or branched alkylene group having 1 to 7 carbon atoms, optionally having a substituent. The number of carbon atoms of the alkylene group is preferably 1 or more and 5 or less, more preferably 2 or more and 4 or less.

[0062] Q 6 , Q 7 , Q 9 , Q 10 , d, e, f, g, and h have the same meanings as in formula (1a).

[0063] The (meth)acrylate of the embodiment is preferably one in which d, e, g, and h are 0, i.e., one containing only the first alkyleneoxy unit. When such a (meth)acrylate is used, there is a tendency that more excellent performance of the functional pigment and the hardness of the cured product can be balanced.

[0064] The (meth)acrylate is represented by, for example, the following formula (1D).

[0065]

[0066] In formula (1D), Q 1 , Q 5 , and Z 3 have the same meanings as in formula (1A), and f has the same meaning as in formula (1a).

[0067] Q 8b is a linear alkylene group having 1 to 7 carbon atoms. Q 8b is preferably a linear alkylene group having 1 to 5 carbon atoms, more preferably a linear alkylene group having 1 to 3 carbon atoms, and most preferably a linear alkylene group having 2 carbon atoms.

[0068] a plurality of - (CH2CH2Q 8b O) f are optionally the same or different, but are preferably the same in view of ease of synthesis.

[0069] From the viewpoint of the hardness of the cured product, the number average molecular weight of the (meth)acrylate of the embodiment is preferably 100 or greater, more preferably 200 or greater, and further preferably 400 or greater. From the viewpoint of improving the functionality of the functional pigment and the ease of handling the viscosity of the obtained curable composition, the number average molecular weight of the (meth)acrylate is preferably 10,000 or less, more preferably 8,000 or less, further preferably 6,000 or less, and particularly preferably 4,500 or less. The number average molecular weight can be calculated, for example, by nuclear magnetic resonance (NMR) spectroscopy.

[0070] In the number average molecular weight of the (meth)acrylate, the proportion of the number average molecular weight of the first alkyleneoxy chain is preferably 20% by mass or greater, more preferably 40% by mass or greater, and further preferably 60% by mass or greater. When the proportion is high, there is a tendency for the functionality of the functional pigment in the cured product to improve. The proportion can be calculated, for example, by nuclear magnetic resonance (NMR) spectroscopy.

[0071] The (meth)acrylate of the embodiment can be produced, for example, by the following method. The case of the (meth)acrylate represented by formula (1A) is described.

[0072] First, a polyol compound represented by the following formula (1c) is prepared. The polyol compound can be derived from a plant or derived from petroleum. 3A and Q 3B , and Z 3 have the same meanings as in the formula (1A) described above.

[0073]

[0074] Next, a compound represented by the following formula (1d) is prepared. The compound contains one isocyanate group and one (meth)acryloyl group.

[0075]

[0076] In formula (1d), Q 1 , Q 2 , and a have the same meanings as in formula (1A).

[0077] The (meth)acrylate represented by formula (1A) can be obtained by reacting the polyol compound represented by formula (1c) with the isocyanate compound represented by formula (1d).

[0078] The reaction can be performed in the presence of a solvent. As the solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide, tetrahydrofuran is used.

[0079] As another synthetic method, it can also be synthesized through esterification with (meth)acrylic acid. Specifically, the above-mentioned polyol compound dissolved in a solvent such as toluene can be reacted with (meth)acrylic acid under heating and stirring as needed 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, to remove the generated water 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.

[0080] Alternatively, it can be synthesized by esterification using (meth)acryloyl halide. Specifically, it can be achieved by heating and stirring 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 removing the generated hydrogen halide.

[0081] Furthermore, it can also be synthesized by transesterification with ester compounds such as (meth)acrylic anhydride and (meth)acrylate. Specifically, it can be synthesized by heating and stirring the above-mentioned polyol compound dissolved in a solvent such as toluene 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, as needed.

[0082] The aforementioned polyol compounds can be synthesized using the methods described in Patent Documents 7 and 8.

[0083] Specifically, this can be achieved by making HQ 3A The polyol compound represented by -H is synthesized by transesterification with alkylene carbonate, dialkyl carbonate, diaryl carbonate, cyclic carbonate, and other carbonate diesters in the presence of an ester exchange catalyst such as an acetate, nitrate, sulfate, carbonate, phosphate, hydroxide, halide, acetylacetone salt, or alkoxide of at least one metal selected from Group II of the periodic table, at a temperature of 70°C to 250°C, preferably 80°C to 220°C.

[0084] In HQ 3A When the structure of the polyol compound represented by -H is as shown in the following formula (1f), it can be synthesized, for example, by the following method.

[0085]

[0086] In the case of polyol compounds where d and h are 0 and e and g are 1 or more, i.e., polyol compounds having a second alkylene oxide unit, by making H-(OQ) 8 ) f-OH and a cyclic ether compound such as an oxirane or an oxetane, to synthesize a polyol compound having a second alkyleneoxy unit. The polyol compound having a second alkyleneoxy unit can be synthesized, for example, by performing a reaction in a high-pressure autoclave replaced with nitrogen, in the presence of an alkali metal hydroxide such as potassium hydroxide or the like as a catalyst, at high temperature and high pressure.

[0087] In the case of the polyol compound in which d, e, g, and h are 1 or more, that is, the polyol compound further containing a second and a third alkyleneoxy unit, a polyol compound having a third alkyleneoxy unit can be synthesized by reacting the polyol compound having a second alkyleneoxy unit with a cyclic ether compound.

[0088] [Curable composition]

[0089] According to the embodiment, a curable composition is provided. The curable composition contains the (meth)acrylate of the embodiment and a functional pigment.

[0090] The curable composition of the embodiment can be used as a coating agent, an adhesive, a paint, a material for a plastic product of a 3D printer, or the like. The curable composition is particularly suitable for use in an optical article application.

[0091] The curable composition preferably further contains a radically polymerizable monomer. As the radically polymerizable monomer, the following first to fifth radically polymerizable monomers can be given.

[0092] Hereinafter, each component will be described in detail.

[0093] < (A) Radically polymerizable monomer>

[0094] The radically polymerizable monomer (A) contains a (A-1) component: a first radically polymerizable monomer represented by Formula (I). Hereinafter, the first radically polymerizable monomer represented by Formula (I) is also referred to as the (A-1) component. The radically polymerizable monomer (A) is also referred to as the (A) component. The radically polymerizable monomer (A) can contain other radically polymerizable monomers depending on the properties of the cured product required. As long as it is a polymerizable monomer capable of polymerizing with the (A-1) component, there is no particular limitation, and a publicly known polymerizable monomer can be used, and a radically polymerizable monomer having a (meth)acrylate group is preferred, and a (A-2) component: a radically polymerizable monomer having three or more (meth)acryloyl groups in one molecule and a (A-3) component: another radically polymerizable monomer having a (meth)acryloyl group are preferably used.

[0095] < (A-1) Component: first radically polymerizable monomer>

[0096]

[0097] In formula (I), R 1 and R 7 each independently is a hydrogen atom or a methyl group. That is, the (A-1) component can be a diacrylate, a dimethacrylate, or a methacrylate acrylate represented by the above formula (I). When the (A-1) component is used as a diacrylate, there is a tendency to obtain a cured product in which the fading speed of the photochromic pigment is high. If the (A-1) component is used as a dimethacrylate, there is a tendency to obtain a cured product in which the color development concentration of the photochromic pigment is high. 1 and R 7 is preferably a methyl group.

[0098] R 4 is a linear or branched alkylene group having 1 to 7 carbon atoms, which optionally has a substituent. c1 is 2 or more and 100 or less. c1 is a larger number than a1, a larger number than b1, a larger number than d1, and a larger number than e1.

[0099] That is, the repeating unit - (OCH2CH2R 4 ) - with subscript c1 added is a first alkylene oxy unit having 4 or more and 9 or less carbon atoms. The polymer site composed of this repeating unit can form a soft segment of the cured product. 4 is preferably a linear alkylene group. The number of carbon atoms of the alkylene group is preferably 1 or more and 4 or less, and more preferably 2 or more and 4 or less. When the number of carbon atoms of the alkylene group is large, the functionality of the cured product is further improved. On the other hand, when the number of carbon atoms of the alkylene group is too large, the amount of the soft segment per unit mass decreases, and thus the functionality of the cured product can decrease.

[0100] From the viewpoint of balancing the functionality and the hardness, c1 is preferably 2 or more and 85 or less, more preferably 2 or more and 70 or less, further preferably 3 or more and 50 or less, and particularly preferably 5 or more and 45 or less.

[0101] R 2 , R 3 , R 5 , and R 6 each independently is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 2 , R 3 , R 5 , and R 6 each independently is preferably a hydrogen atom or a methyl group. 2 and R 3 are different groups from each other. 5 and R 6 are different groups from each other. 2 and R 6 may be the same group. 3 and R 5may be the same group.

[0102] a1 and e1 are 0 or more and 10 or less. From the viewpoint of balancing functionality and hardness, a1 and e1 are preferably 0 or more and 5 or less, more preferably 0 or more and 2 or less, further preferably 0 or 1, most preferably 0.

[0103] b1 and d1 are 0 or more and 20 or less. From the viewpoint of balancing functionality and hardness, they are preferably 0 or more and 15 or less, more preferably 0 or more and 10 or less, further preferably 0 or more and 5 or less, particularly preferably 0.

[0104] In other words, the (A-1) component can be a monomer further having at least one of a second alkyleneoxy unit in which b1 and d1 are added as a repeating unit and a third alkyleneoxy unit in which a1 and e1 are added as a repeating unit.

[0105] The (A-1) component preferably has a1, b1, d1 and e1 of 0, that is, contains only the first alkyleneoxy unit. When such a (A-1) component is used, there is a tendency that the hardness of the cured product increases. c1 can be 4 or more and 20 or less, or 6 or more and 15 or less.

[0106] The (A-1) component is represented by, for example, the following formula (3).

[0107]

[0108] In the above formula (3), R 1 , R 7 and c1 have the same meanings as in formula (I).

[0109] R 11 is a linear alkylene group having 1 to 7 carbon atoms. R 11 is preferably a linear alkylene group having 1 to 5 carbon atoms, more preferably a linear alkylene group having 1 to 3 carbon atoms, most preferably a linear alkylene group having 2 carbon atoms.

[0110] If the compound represented by the above formula (3) is specifically exemplified, polytrimethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, poly- pentamethylene glycol di(meth)acrylate, polyhexamethylene glycol di(meth)acrylate and the like can be mentioned.

[0111] If the light-induced color change, the hardness, and the viscosity of the cured composition obtained therefrom are taken into consideration, the number average molecular weight of the (A-1) component represented by Formula (3) is preferably 200 or greater and 9000 or less, more preferably 200 or greater and 7000 or less, further preferably 200 or greater and 6000 or less, and most preferably 250 or greater and 5000 or less. The number average molecular weight of the (A-1) component can be 400 or greater and 1500 or less, or 600 or greater and 1000 or less.

[0112] If the (A-1) component in which a1 and e1 are 0 and b1 and d1 are 1 or greater, i.e., the (A-1) component further containing a second alkyleneoxy unit is used, there is a tendency to obtain a cured product having a high function of functional pigments. b1 and d1 can be 2 or greater and 15 or less, or 4 or greater and 10 or less.

[0113] Specific examples of such (A-1) components are described below.

[0114]

[0115]

[0116] In addition, the (A-1) component can be a monomer in which a1, b1, d1, and e1 are 1 or greater, i.e., further having both a second alkyleneoxy unit and a third alkyleneoxy unit. In this case, the second alkyleneoxy unit and the third alkyleneoxy unit have different structures from each other.

[0117] Specific examples of such (A-1) components are described below.

[0118]

[0119] The (A-1) component can be produced, for example, by the following method.

[0120] The (A-1) component having an acryloyl group can be synthesized by esterification of a polyol compound represented by the following formula with acrylic acid. R 2 , R 3 , R 4 , R 5 , R 6 , a1, b1, c1, d1, and e1 have the same meanings as in Formula (I).

[0121]

[0122] 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, to remove the generated water through 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.

[0123] Alternatively, it can be synthesized by esterification of acryloyl halides. Specifically, this can be achieved by heating and stirring 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 removing the generated hydrogen halide.

[0124] Furthermore, it can also be synthesized through transesterification with ester compounds such as acrylic anhydride and methyl acrylate. Specifically, it can be achieved by heating and stirring the aforementioned polyol compound dissolved in a solvent such as toluene 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, as needed.

[0125] The (A-1) component having a methacryloyl group can be synthesized in the same manner as described above, for example, by using methacrylic acid instead of acrylic acid.

[0126] Among the above-mentioned polyol compounds, polyol compounds in which a1 and e1 are 0 and b1 and d1 are 1 or more, i.e. polyols having a second alkylene oxide unit, can be synthesized, for example, by the following method.

[0127] By making H-(OCH2CH2R) 4 The reaction of c1-OH with cyclic ether compounds such as ethylene oxide and propylene oxide can synthesize polyols containing a second alkylene oxide unit. Polyols containing a second alkylene oxide unit 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.

[0128] Among the above-mentioned polyol compounds, polyol compounds in which a1, b1, d1 and e1 are 1 or more, that is, (A-1) components further containing second and third alkylene oxide units, can be synthesized, for example, by the following method.

[0129] The polyol compound having the second alkylene oxide unit is reacted with a cyclic ether compound, thereby synthesizing a polyol compound having a third alkylene oxide unit. The resulting polyol compound further having the third alkylene oxide unit is reacted with acrylic acid or methacrylic acid by the same method as the above-described method, thereby a component (A-1) further containing the second and third alkylene oxide units can be synthesized.

[0130] < (A-2) : Second Radical Polymerizable Monomer >

[0131] The curable composition of the embodiment can further contain a second radical polymerizable monomer having three or more (meth)acryloyl groups in one molecule. Hereinafter, the second radical polymerizable monomer having three or more (meth)acryloyl groups in one molecule is also referred to as a component (A-2). If a multifunctional (meth)acrylate is contained, there is a tendency that the hardness of the cured product increases.

[0132] As the component (A-2), a multifunctional (meth)acrylate represented by the following formula (2), a multifunctional (meth)acrylate having a urethane bond, a multifunctional (meth)acrylate not belonging to the foregoing, and the like can be exemplified, and a multifunctional (meth)acrylate represented by the following formula (2) is particularly preferred.

[0133] < Multifunctional (Meth)acrylate represented by the following formula (2) >

[0134]

[0135] R 8 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. R 8 is preferably a methyl group. i1 is a number of 0 or more and 3 or less. i1 is preferably 0.

[0136] j1 is a number of 0 or more and 3 or less. j1 is preferably 0 or 1.

[0137] R 9 is a hydrogen atom or a methyl group. R 9 is preferably a methyl group.

[0138] R 10 is a 3- to 6-valent organic group having 1 to 10 carbon atoms. h1 is a number of 3 or more and 6 or less. h1 is preferably 3 or more and 5 or less.

[0139] As the organic group represented by R 10 , a group derived from a polyol, a 3- to 6-valent hydrocarbon group, and a 3- to 6-valent organic group containing a urethane bond can be exemplified.

[0140] As the multifunctional (meth)acrylate represented by the above formula (2), specifically, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, glycerol trimethacrylate, glycerol triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol penta- methacrylate, and the like can be exemplified.

[0141] < Multifunctional (Meth)acrylate Having Urethane Bond >

[0142] The multifunctional (meth)acrylate having urethane bond has a structure different from that of the urethane (meth)acrylate represented by formula (I). The multifunctional (meth)acrylate having urethane bond is obtained by reacting a polyisocyanate compound having three or more isocyanate groups in the molecule, a polyol compound having two or more hydroxyl groups in the molecule, and a (meth)acrylate containing a hydroxyl group. The multifunctional (meth)acrylate having urethane bond is preferably a multifunctional (meth)acrylate having urethane bond having four or more (meth)acryloyl groups in the molecule. As commercially available products, U-4HA (molecular weight 596, number of functional groups 4), U-6HA (molecular weight 1,019, number of functional groups 6), U-6LPA (molecular weight 818, number of functional groups 6), U-15HA (molecular weight 2,300, number of functional groups 15) manufactured by Shin-Nakamura Chemical Co., Ltd. can be exemplified.

[0143] < Multifunctional (Meth)acrylate Not Belonging to the Above >

[0144] As the multifunctional (meth)acrylate other than the multifunctional (meth)acrylate represented by Formula (2) and the multifunctional (meth)acrylate having a urethane bond, a compound in which a terminal of a polyester compound is modified with a (meth)acryloyl group can be exemplified. As such a polyester (meth)acrylate compound, various polyester (meth)acrylate compounds differing in the molecular weight of the polyester compound as a raw material and the modification amount of the (meth)acryloyl group are commercially available, and they can be used. Specifically, 4-functional polyester oligomer (molecular weight 2,500 to 3,500, Daicel-Allnex, Inc., EB80, etc.), 6-functional polyester oligomer (molecular weight 6,000 to 8,000, Daicel-Allnex, Inc., EB450, etc.), 6-functional polyester oligomer (molecular weight 45,000 to 55,000, Daicel-Allnex, Inc., EB1830, etc.), 4-functional polyester oligomer (in particular, GX8488B, etc., of Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like can be exemplified.

[0145] <(A-3) Other radical polymerizable monomer having a (meth)acryloyl group>

[0146] As the other radical polymerizable monomer having a (meth)acryloyl group, a radical polymerizable monomer having a (meth)acryloyl group in the molecular structure and not belonging to (A-1) and (A-2) can be exemplified. The above radical polymerizable monomer is not particularly limited, and a publicly known radical polymerizable monomer can be used, and a third radical polymerizable monomer having only one (meth)acryloyl group, a fourth radical polymerizable monomer having a 2-functional (meth)acryloyl group having a different structure from the first radical polymerizable compound, and a fifth radical polymerizable monomer having at least one (meth)acryloyl group in the molecule having a different structure from the first to fourth radical polymerizable monomers can be contained.

[0147] <Third radical polymerizable monomer>

[0148] The curable composition of the embodiment can further contain a third radical polymerizable monomer having one (meth)acryloyl group in one molecule. The third radical polymerizable monomer can be a monofunctional (meth)acrylate.

[0149] As the monofunctional (meth)acrylate, a monofunctional (meth)acrylate represented by the following Formula (4) can be exemplified.

[0150]

[0151] R 21a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, a glycidyl group, a pentamethylpiperidyl group, or a 2,2,6,6-tetramethylpiperidyl group. R 22 a hydrogen atom or a methyl group. o is an integer of 0 to 10. p is an integer of 0 to 20.

[0152] R 21 a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group. When a monofunctional acrylate having such a functional group is contained, there is a tendency that adhesion of a cured product to a substrate is improved.

[0153] If the monofunctional (meth)acrylate represented by the above formula (4) is specifically shown, methoxypolyethylene glycol methacrylate, methoxypolyethylene 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-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, and the like can be exemplified.

[0154] <2-functional (meth)acrylate having two (meth)acryloyl groups in a molecule>

[0155] The curable composition of the embodiment can contain a fourth radical polymerizable monomer having a 2-functional (meth)acryloyl group other than the first radical polymerizable compound shown below. If the fourth radical polymerizable monomer is contained, the functionality of a functional pigment can be improved. Specifically, a 2-functional (meth)acrylate represented by the following formula (5), the following formula (6) or (7), a 2-functional (meth)acrylate having a urethane bond, and a 2-functional (meth)acrylate not belonging to the foregoing can be exemplified.

[0156] <2-functional (meth)acrylate compound represented by the following formula (5)>

[0157]

[0158] R 12 and R 13 each is a hydrogen atom or a methyl group. j and k each independently are an integer of 0 or more, and j + k is an integer of 2 or more. In addition, the 2-functional (meth)acrylate compound represented by formula (5) is mostly obtained in the form of a mixture in terms of production. Therefore, j + k is an integer of 2 or more on average, and preferably an integer of 2 or more and 50 or less on average.

[0159] Specific examples of the compound represented by the above formula (5) are as follows.

[0160] Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate formed from a mixture of polypropylene glycol and polyethylene glycol (polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate acrylate).

[0161] <The difunctional (meth)acrylate shown in formula (6) below>

[0162]

[0163] R 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.

[0164] A is a divalent organic group. A is a straight-chain or branched alkylene group having 1 to 20 carbon atoms, optionally a phenylene group having a halogen or an alkyl group having 1 to 5 carbon atoms as a substitute, a cycloalkylene group, a bicycloalkylene group, a tricycloalkylene group, or any group shown in any of the following formulas.

[0165]

[0166]

[0167]

[0168]

[0169]

[0170] In the above formula, R 18A R 18B It consists of hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, or halogen atoms. xx and xy are 0 to 4. 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.

[0171]

[0172]

[0173] l and m are each an integer of 1 or more, and l+m is 2 or more and 30 or less on average.

[0174] As specific examples of the 2-functional (meth)acrylate represented by the above formula (6), for example, bisphenol A di(meth)acrylate, 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxidipropoxy)phenyl]propane, 2,2-bis[4-(acryloyloxydiethoxy)phenyl]propane, 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane, 1,3-adamantanedimethacrylate, dimethylolcyclo-decanediacrylate can be given.

[0175] <2-functional (meth)acrylate represented by the following formula (7)>

[0176]

[0177] R 19 and R 20 are each a hydrogen atom or a methyl group.

[0178] n is a number of 1 or more and 20 or less on average.

[0179] B and B' are each independently a linear or branched alkylene group having 2 to 15 carbon atoms. B and B' can be the same as or different from each other. In the case where a plurality of B's are present, the plurality of B's can be the same group or different groups.

[0180] The 2-functional (meth)acrylate represented by the above formula (7) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0181] Here, as the polycarbonate diol used, the following polycarbonate diols can be exemplified. Specifically, polycarbonate diols obtained by phosgenation of trimethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of tetramethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of pentamethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of hexamethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of octamethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of nonamethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of triethylene glycol and tetramethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of tetramethylene glycol and hexamethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of tetramethylene glycol and octamethylene glycol (average molecular weight 500 to 2000), polycarbonate diols obtained by phosgenation of hexamethylene glycol and octamethylene glycol (average molecular weight 500 to 2000), and polycarbonate diols obtained by phosgenation of 1-methyltrimethylene glycol (average molecular weight 500 to 2000) can be exemplified.

[0182] <2-functional (meth)acrylate having urethane bond>

[0183] The 2-functional (meth)acrylate having urethane bond is obtained by reacting a polyisocyanate compound having 2 or more isocyanate groups in the molecule, a polyol compound having 2 or more hydroxyl groups in the molecule, and a (meth)acrylate containing a hydroxyl group.

[0184] As the polyisocyanate, for example, 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 can be suitably exemplified.

[0185] As the polyhydric alcohol, polyalkylene glycols having repeating units of ethylene oxide, propylene oxide, or hexylene oxide having 2 to 4 carbon atoms, or polyester diols such as polycaprolactone diol can be mentioned. In addition, polycarbonate diols, polybutadiene diols, or 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-cyclohexane dimethanol, glycerol, trimethylolpropane, and the like can be exemplified.

[0186] In addition, reaction mixtures obtained by further reacting a urethane prepolymer produced by the reaction of these polyisocyanates and polyhydric alcohols with 2-hydroxy (meth) acrylate, urethane (meth) acrylate monomers which are reaction mixtures obtained by directly reacting the aforementioned diisocyanates with 2-hydroxy (meth) acrylate, and the like can also be used.

[0187] As the (meth) acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like can be mentioned.

[0188] The 2-functional (meth) acrylate having a urethane bond can be used without any limitation using a commercially available material. As a commercially available product, for example, U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), U-122P (molecular weight 1,100) manufactured by Shin-Nakamura Chemical Co., Ltd., and EB4858 (molecular weight 454) manufactured by DAICEL-ALLNEX Corporation can be mentioned.

[0189] <2-functional (meth) acrylates not belonging to the aforementioned>

[0190] A 2-functional (meth) acrylate containing a sulfur atom can also be mentioned. The sulfur atom is preferably in the form of a sulfide group to form a part of the molecular chain. Specifically, bis (2-methacryloyloxyethyl thioethyl) sulfide, bis (methacryloyloxyethyl) sulfide, bis (acryloyloxyethyl) sulfide, 1,2-bis (methacryloyloxyethylthio) ethane, 1,2-bis (acryloyloxyethyl) ethane, bis (2-methacryloyloxyethyl thioethyl) sulfide, bis (2-acryloyloxyethyl thioethyl) sulfide, 1,2-bis (methacryloyloxyethyl thioethylthio) ethane, 1,2-bis (acryloyloxyethyl thioethylthio) ethane, 1,2-bis (methacryloyloxyisopropyl thioisopropyl) sulfide, 1,2-bis (acryloyloxyisopropyl thioisopropyl) sulfide can be mentioned.

[0191] The 2-functional (meth)acrylate compound above can use a single component of each component described separately, or can use a plurality of components. In addition, a plurality of components described separately can also be used in combination. In the case of a plurality of components, a plurality of combinations, the mass as a reference is the total amount of the plurality of components.

[0192] <Other radical polymerizable monomer>

[0193] The curable composition of the embodiment can further include other radical polymerizable monomers as a fifth radical polymerizable monomer. As long as it is a radical polymerizable monomer that can be polymerized with the (A-1) component, there is no particular limitation, and a publicly known monomer can be used. For example, it is preferable to use a radical polymerizable polyrotaxane, a radical polymerizable silsesquioxane compound, an allyl-based compound, a vinyl-based compound.

[0194] <Polylotaxane having radical polymerizability>

[0195] The polyrotaxane has a complex molecular structure composed of an axle molecule and a plurality of ring molecules that enclose the axle molecule. A bulky end group is formed at both ends of the axle molecule, preventing the ring molecules from falling off the axle molecule. The polyrotaxane having radical polymerizability is a polyrotaxane in which a radical polymerizable group is introduced into the side chain of the ring molecule. The radical polymerizable group is introduced, for example, by modifying 1% or more and less than 100% of the hydroxyl group of the ring molecule to a radical polymerizable group. The modification ratio can be calculated by (the number of moles of the introduced polymerizable group) / (the total number of moles of OH groups in the side chain) x 100. Note that from the viewpoints of adhesion, mechanical strength of the obtained cured product, and functionality, the modification ratio is preferably 10% or more and 95% or less.

[0196] When the weight average molecular weight of the axle molecule is too large, there is a tendency for compatibility with other polymerizable monomers and the like to decrease, and when it is too small, there is a tendency for the mobility of the ring molecules to decrease. The weight average molecular weight of the axle molecule is preferably in the range of 1,000 to 100,000, further preferably in the range of 5,000 to 80,000, and most preferably in the range of 8,000 to 50,000.

[0197] The cyclic molecule is preferably a cyclodextrin ring, a crown ether ring, a benzo crown ring, a dibenzo crown ring, and a dicyclohexane crown ring, particularly preferably a cyclodextrin ring, and most preferably a cyclodextrin ring. Among cyclodextrin rings, there are α- (ring inner diameter: 0.45 to 0.6 nm), β- (ring inner diameter: 0.6 to 0.8 nm), and γ- (ring inner diameter: 0.8 to 0.95 nm), and preferably α-cyclodextrin ring and β-cyclodextrin ring, and most preferably α-cyclodextrin ring. When the number of inclusion of the cyclic molecule in the axial molecule is set to 1, the number of inclusion of the cyclic molecule is preferably in the range of 0.001 to 0.6, further preferably in the range of 0.002 to 0.5, and most preferably in the range of 0.003 to 0.4.

[0198] As the radical polymerizable group, a (meth)acryloyl group is preferable in consideration of reactivity with other polymerizable monomers, and the like. The number of radical polymerizable groups is not particularly limited, and is preferably 0 to 5000 per molecule.

[0199] The polyrotaxane having a (meth)acryloyl group described above is described in International Publication No. 2018 / 030257.

[0200] <Silsequioxane Radical Polymerizable Compound>

[0201] The silsequioxane radical polymerizable compound has a cage shape, a ladder shape, a random shape, and the like, and has a radical polymerizable group such as a (meth)acryloyl group.

[0202] As an example of such a silsequioxane polymerizable compound, a compound represented by the following formula (8) can be given.

[0203]

[0204] In formula (8), q is a polymerization degree, and is an integer of 3 to 100.

[0205] A plurality of R 23 Optionally, the same or different, is a radical polymerizable group, an organic group containing a radical polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, at least one R 23 is a radical polymerizable group, or an organic group containing a radical polymerizable group.

[0206] Here, as R 23As the radical polymerizable group, or the organic group containing the radical polymerizable group, there can be mentioned (meth)acryloyl group; (meth)acryloyloxypropyl, (3- (meth)acryloyloxypropyl)dimethylsiloxy group, and the like organic groups having (meth)acryloyl group; allyl group; allylpropyl, allylpropyldimethylsiloxy group, and the like organic groups having allyl group; vinyl group; vinylpropyl, vinyl dimethylsiloxy group, and the like organic groups having vinyl group; and the like.

[0207] <Allyl-based polymerizable compound>

[0208] As the allyl-based polymerizable compound having an allyl group, there can be mentioned the following compounds. Diethyleneglycol bisallyl carbonate, methoxypolyethyleneglycol allyl ether, methoxypolyethyleneglycol-polypropyleneglycol allyl ether, butoxypolyethyleneglycol-polypropyleneglycol allyl ether, phenoxy polyethyleneglycol allyl ether, vinyloxy polyethyleneglycol allyl ether, styryloxy polyethyleneglycol allyl ether, methoxypolyethylenedithiol allyl thioether.

[0209] <Vinyl-based polymerizable compound>

[0210] As the vinyl-based polymerizable compound having a vinyl group, there can be mentioned 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-tetramethylpropane disiloxane, diethyleneglycol divinyl ether, divinyl adipate, divinyl sebacate, ethyleneglycol divinyl ether, divinyl sulfoxide, divinyl sulfide, dimethyl divinyl silane, 1,2,4-trivinylcyclohexane, methyltrivinylsilane, α-methyl styrene, and α-methyl styrene dimer, and the like.

[0211] <Blending ratio in curable composition>

[0212] In the curable composition of the embodiment, the proportion of the (meth)acrylate represented by Formula (1A) is, for example, 5% by mass or more and 99% by mass or less. When the proportion is high, there is a tendency that the performance of the functional pigment in the cured product is improved. The proportion can be 15% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more. On the other hand, if the proportion is too high, there is a tendency that the hardness of the cured product is reduced. The proportion is preferably 90% by mass or less, and more preferably 80% by mass or less.

[0213] The proportion of the first radical polymerizable monomer in the curable composition of the embodiment is preferably 15% by mass or more. When the proportion is high, there is a tendency for the performance of the functional pigment in the cured product to improve. The proportion is more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, if the proportion is too high, there is a tendency for the hardness of the cured product to decrease. The proportion is preferably 90% by mass or less, and more preferably 80% by mass or less.

[0214] From the viewpoint of improving the hardness of the cured product, the curable composition of the embodiment preferably further contains a second radical polymerizable monomer. The proportion of the second radical polymerizable monomer is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more. On the other hand, if the proportion is too high, there is a tendency for the performance of the functional pigment in the cured product to decrease. The proportion is preferably 85% by mass or less, more preferably 65% by mass or less, and further preferably 55% by mass or less.

[0215] In the curable composition of the embodiment, a fourth radical polymerizable monomer is preferably contained from the viewpoint of adjusting the viscosity of the curable composition and improving the compatibility of the curable composition. The proportion of the fourth radical polymerizable monomer is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. On the other hand, if the proportion is too high, there is a tendency for the performance of the functional pigment in the cured product to decrease. The proportion is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

[0216] From the viewpoint of adjusting the viscosity of the curable composition and improving the adhesion of the cured product, the curable composition of the embodiment preferably contains a third radical polymerizable monomer. The proportion of the third radical polymerizable monomer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. On the other hand, if the proportion is too high, there is a tendency for the performance of the functional pigment in the cured product to decrease. The proportion is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less.

[0217] From the viewpoint of adjusting the viscosity of the curable composition and adjusting the polymerizability, the curable composition of the embodiment preferably contains a fifth radical polymerizable monomer. The proportion of the fifth radical polymerizable monomer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. On the other hand, if the proportion is too high, there is a tendency for the performance of the functional pigment in the cured product to decrease. The proportion is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less.

[0218] In the curable composition containing the first to fifth radically polymerizable monomers, the content of the first radically polymerizable monomer can be 40 mass% or more and 80 mass% or less, the content of the second radically polymerizable monomer can be 10 mass% or more and 40 mass% or less, the content of the third radically polymerizable monomer can be 1 mass% or more and 10 mass% or less, the content of the fourth radically polymerizable monomer can be 5 mass% or more and 50 mass% or less, the content of the fifth radically polymerizable monomer can be 1 mass% or more and 10 mass% or less, and the balance can be the functional pigment and the additive.

[0219] In the curable composition of the embodiment, the proportion of the methacrylate is preferably 50 mass% or more. When the proportion is high, there is a tendency to obtain a cured product having a high function of the functional pigment. The proportion is preferably 60 mass% or more, more preferably 70 mass% or more, and further preferably 90 mass% or more. The upper limit of the proportion is 99 mass% or less according to one example, and 95 mass% or less according to another example.

[0220] In the curable composition of the embodiment, the ratio M100 / M101 of the mass M100 of the methacrylate to the mass M101 of the acrylate can be 0.1 or more and 20 or less, can be 0.5 or more and 10 or less, or can be 1 or more and 8 or less. Here, the methacrylate refers to a compound having a methacryloyl group and not having an acryloyl group in the curable composition. The acrylate refers to a compound having an acryloyl group and not having a methacryloyl group in the curable composition.

[0221] The (meth)acrylate represented by Formula (1A), the (A-1) component, the (A-2) component, and the (A-3) component are collectively referred to as the (A) component, and when the (A) component is 100 parts by mass, the (meth)acrylate can be 15 to 100 parts by mass, can be 20 to 90 parts by mass, can be 30 to 80 parts by mass, or can be 35 to 65 parts by mass.

[0222] When the (A-1) component is compounded, the amount of the (A-1) component can be 15 parts by mass to 85 parts by mass, can be 20 parts by mass to 80 parts by mass, can be 30 parts by mass to 70 parts by mass, or can be 35 parts by mass to 65 parts by mass, when the (A) component is 100 parts by mass.

[0223] When the (A-2) component is compounded, the amount of the (A-2) component can be 1 to 85 parts by mass, can be 3 to 75 parts by mass, can be 5 to 70 parts by mass, or can be 10 to 65 parts by mass, when the (A) component is 100 parts by mass.

[0224] When the (A-3) component is further included, the amount of the (A-3) component can be 0.01 to 20 parts by mass, or 0.1 to 17 parts by mass, or 0.5 to 15 parts by mass, based on 100 parts by mass of the (A) component.

[0225] < (B) Functional Pigment >

[0226] The functional pigment includes a compound having a selective absorption ability of visible light, and a compound that exhibits coloration, decoloration, or color change by energy such as light, heat, electric field, or pressure. Such a functional pigment is capable of exerting a specific function by undergoing a structural change under specific conditions. The functional pigment includes, for example, at least one selected from the group consisting of a photochromic compound, an ultraviolet absorber, a blue light absorber, an infrared absorber, and an electrochromic compound.

[0227] The ratio M1 / M2 of the mass M1 of the (meth)acrylate represented by Formula (I) to the mass M2 of the functional pigment is, for example, 1 or more and 10,000 or less. The ratio M1 / M2 is preferably 1 or more and 2,500 or less, more preferably 5 or more and 1,000 or less, and further preferably 5 or more and 1,000 or less.

[0228] The content of the functional pigment in the curable composition is, for example, 0.001% by mass or more and 10% by mass or less. The content of the functional pigment is preferably 0.1% by mass or more and 8% by mass or less, and more preferably 1% by mass or more and 5% by mass or less.

[0229] < Photochromic Compound >

[0230] The photochromic compound is used in a compounding amount that enables desired photochromic properties to be obtained. It is preferably used in an amount of 0.001 to 10 parts by mass with respect to 100 parts by mass of the (A) component.

[0231] The compounding amount is preferably adjusted to an optimum compounding amount according to the use.

[0232] Specifically, in the case where the curable composition including the photochromic compound is made into a thin film such as a film of about 100 μm (a polymer film obtained by polymerizing the photochromic curable composition) like a coating material, it is appropriate to adjust the color tone by compounding 0.1 to 10 parts by mass of the photochromic compound with respect to 100 parts by mass of the polymerizable compound.

[0233] In addition, in the case where a thick cured product (a polymer molded body obtained by polymerizing the photochromic curable composition) is made, for example, in the case of a cured product having a thickness of 1 mm or more, it is appropriate to adjust the color tone by compounding 0.001 to 1 parts by mass of the photochromic compound with respect to 100 parts by mass of the thick cured product or 100 parts by mass of the polymerizable compound that provides the thick cured product.

[0234] As the photochromic compound, there is no particular limitation, and publicly known compounds can be used, and one kind can be used alone or two or more kinds can be used in combination. As representative compounds of such photochromic compounds, there are chromene compounds, fulgimide compounds, spirooxazine compounds, and spiroxanthene compounds, which are disclosed in, for example, Japanese Patent Application Publication No. 2-28154, Japanese Patent Application Publication No. 62-288830, International Publication No. 94 / 22850, International Publication No. 96 / 14596, International Publication No. 2022 / 075330, International Publication No. 2022 / 168989, and many other documents.

[0235] Among these photochromic compounds, chromene compounds, spiroxanthene compounds are preferably used. Chromene compounds are particularly preferred. Chromene compounds include compounds having a 1-benzopyran skeleton, spiro-pyran compounds including a spiro-pyran skeleton, and naphthopyran compounds having a naphthopyran skeleton.

[0236] The naphthopyran compound preferably includes a compound represented by the following formula (9), the following formula (10), the following formula (11), the following formula (12), the following formula (13), and the following formula (14).

[0237]

[0238] In formula (9), ring AA is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on these rings. Ring AA can also be absent.

[0239] Ring AB is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on these rings.

[0240] R 24 and R 25 Each independently is a hydrogen atom or a substituent, and two or more substituents can be bonded to form a ring structure.

[0241] As the substituent, there are a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group optionally having a substituent, an aralkoxy group optionally having a substituent, an aryloxy group optionally having a substituent, an alkylthio group, an arylthio group optionally having a substituent, an aryl group optionally having a substituent, an amino group, a substituted amino group, a heterocyclic group optionally having a substituent, and preferably at least one selected from the group consisting of a haloalkylthio group, a cycloalkylthio group optionally having a substituent, an oligomer group, and a group represented by the following formula (15).

[0242] -Q 1 -(P 1 Q 2 ) aa -P 2 Q 3 (15)

[0243] 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. 701 It 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 more than 1 and less than 10.

[0244] 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.

[0245] 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 arylalkyl with a substituent, optionally arylalkoxy with a substituent, optionally aryloxy with a substituent, alkylthio, optionally arylthio with a substituent, optionally aryl, amino, substituted amino, optionally heterocyclic group with a substituent, and groups represented by the above formula (15).

[0246] Additionally, R 26 and R 27 When two ring structures are formed together, it is preferable to form an aliphatic ring with 3 to 20 carbon atoms, a fused polycyclic ring with an aromatic ring or an aromatic heterocyclic ring fused on the aliphatic ring, a heterocyclic ring with 3 to 20 carbon atoms, or a fused polycyclic ring with an aromatic ring or an aromatic heterocyclic ring fused on the heterocyclic ring.

[0247]

[0248] In formula (10), R 1000 , R 1001 , and R 1002 each independently are a hydrogen atom or a substituent, and two or more substituents can be bonded to form a ring structure. The substituents can use the same groups as those described in formula (9). mm is 1 to 10.

[0249]

[0250] In formula (11), R 1003 , R 1004 , and R 1005 each independently are a hydrogen atom or a substituent, and two or more substituents can be bonded to form a ring structure. The substituents can use the same groups as those described in formula (9). nn is 1 to 10.

[0251]

[0252] In formula (12), R 1006 , R 1007 , and R 1008 each independently are a hydrogen atom or a substituent, and two or more substituents can be bonded to form a ring structure. The substituents can use the same groups as those described in formula (9). oo is 1 to 12.

[0253]

[0254] In formula (13), R 1009 , R 1010 , and R 1011 each independently are a hydrogen atom or a substituent, and two or more substituents can be bonded to form a ring structure. The substituents can use the same groups as those described in formula (9). pp is 1 to 12.

[0255]

[0256] In formula (14), R 1012 , R 1013 , and R 1014 each independently are a hydrogen atom or a substituent, and two or more substituents can be bonded to form a ring structure. The substituents can use the same groups as those described in formula (9). qq is 1 to 12.

[0257] The naphthopyran compound includes an indenonaphthopyran compound having an indenonaphthopyran skeleton. The indenonaphthopyran compound preferably has an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.

[0258] As the indeno[2,1-f]naphtho[1,2-b]pyran, for example, the compounds described in International Publication No. 1996 / 014596, International Publication No. 2001 / 019813, International Publication No. 2001 / 060811, International Publication No. 2005 / 028465, International Publication No. 2006 / 110221, International Publication No. 2007 / 073462, International Publication No. 2007 / 140071, International Publication No. 2008 / 054942, International Publication No. 2010 / 065393, International Publication No. 2011 / 10744, International Publication No. 2011 / 016582, International Publication No. 2011 / 025056, International Publication No. 2011 / 034202, International Publication No. 2011 / 078030, International Publication No. 2012 / 102409, International Publication No. 2012 / 102410, International Publication No. 2012 / 121414, and the like can be used without any limitation.

[0259] In addition to the above, it is also preferable to use a photochromic compound having an oligomer chain group in the molecule. As such a photochromic compound having an oligomer chain group, there are disclosed in many documents such as International Publication No. 2000 / 015630, International Publication No. 2004 / 041961, International Publication No. 2009 / 146509, International Publication No. 2012 / 149599, International Publication No. 2012 / 162725, International Publication No. 2013 / 078086, International Publication No. 2019 / 013249, International Publication No. 2019 / 203205, and the like. Among these photochromic compounds having an oligomer chain group in the molecule, in order to exhibit more excellent photochromism and durability, it is preferable to use the photochromic compound having an oligomer chain group described in International Publication No. 2019 / 013249, International Publication No. 2019 / 203205.

[0260] The indenonaphthopyran compound preferably contains a compound represented by the following formula (16).

[0261]

[0262] In the formula, R 24 , R 25 , R 26 , and R 27 are the same as described above.

[0263] r is an integer of 0 to 4. s is an integer of 0 to 4. In the case where r is 2 to 4, a plurality of R 28 may be the same as or different from each other. In the case where s is 2 to 4, a plurality of R 29Each of R1and R2may be the same or different. In addition, in the case where r is 2 to 4 and there are adjacent R 28 groups, the two adjacent R 28 groups together with the carbon atom to which these R 28 groups are bonded can form a ring optionally containing at least one hetero atom selected from the group consisting of an oxygen atom, a carbon atom, a sulfur atom, and a nitrogen atom, and the ring can optionally have a substituent. In addition, in the case where s is 2 to 4 and there are adjacent R 29 groups, the two adjacent R 29 groups together with the carbon atom to which these R 29 groups are bonded can form a ring optionally containing at least one hetero atom selected from the group consisting of an oxygen atom, a carbon atom, a sulfur atom, and a nitrogen atom, and the ring can optionally have a substituent.

[0264] R 28 and R 29 each independently are a group represented by formula (15), a hydroxyl group, an alkyl group, a halogenated alkyl 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, an arylthio group optionally having a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group optionally having a substituent, an aralkyloxy group optionally having a substituent, an aryloxy 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 halogenated alkylthio 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 represented by formula (17) below, or a group represented by formula L-R 400 .

[0265]

[0266] E is an oxygen atom or NR 101 , R 101 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 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. gg is an integer of 0 or 1. R 201 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. In the case where G is an oxygen atom or a sulfur atom, R 201 is a group other than a hydrogen atom.

[0267] R 400 is a hydrogen atom, an alkyl group, an aryl group, a silyl group having a substituent, a polymerizable group, or a photochromic group. The substituent of the silyl group is an alkyl group, an alkoxy group, or an aryl group. L is a group represented by formula (18) below.

[0268]

[0269] J is a divalent group, each independently a direct bond, a substituted methylene group, an oxygen atom, a sulfur atom, or NR 301 . R 301 is a hydrogen atom or an alkyl group. L in formula (18) is an oxygen atom or a sulfur atom. R 300 is an alkylene group, or a silyl ene group having an alkyl group or an aryl group as a substituent. R 302 , R 303 , and R 304 are alkylene groups. hh, jj, kk, and ll are integers of 0 or 1. ii is an integer of 1 to 200. The plurality of units of ii can be the same or different. The dotted line indicates bonding to R 400 .

[0270] <Other additives>

[0271] The curable composition is essential in the above (A) component, (B) component. In the curable composition, various compounding agents known in the art can be compounded within a range not impairing the effects. The compounding agents include, for example, mold release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, perfumes, and various stabilizers. In addition, solvents, leveling agents can be compounded. Mercaptans such as tert-dodecyl mercaptan can be compounded as polymerization regulators.

[0272] <Ultraviolet stabilizers>

[0273] If an ultraviolet stabilizer is used in combination, the durability of the photochromic compound can be further improved, and thus compounding is preferred. As the ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, a sulfur antioxidant can be preferably used. As the hindered amine light stabilizer, there is no particular limitation, and in particular, from the aspect of preventing deterioration of the photochromic compound, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is preferred. In addition, a hindered amine light stabilizer commercially available under the trade names of Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-87, and the like from ADEKA CORPORATION can also be preferably used.

[0274] As a hindered phenol antioxidant, it is preferable in terms of the deterioration prevention of the photochromic compound. For example, 2, 6-di-tert-butyl-4-methyl-phenol, 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], IRGANOX 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, etc. manufactured by BASF Japan Ltd. can also be mentioned. The amount of use of such an ultraviolet stabilizer is not particularly limited as long as the effect is not impaired, and is usually in the range of 0.001 to 10 parts by mass, particularly 0.01 to 1 parts by mass, with respect to 100 parts by mass of the curable composition.

[0275] <Polymerization initiator>

[0276] The polymerization initiator is a thermal polymerization initiator and a photopolymerization initiator, which are specifically exemplified below.

[0277] As the thermal polymerization initiator, for example, the following can be mentioned.

[0278] Diacyl peroxide: benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, acetyl peroxide,

[0279] Peroxide ester: tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanate, cumyl peroxyneodecanate, tert-butyl peroxybenzoate,

[0280] Peroxide carbonate; diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate,

[0281] Azo compound: azobisisobutyronitrile

[0282] and the like.

[0283] As the photopolymerization initiator, for example, the following can be mentioned.

[0284] Acetophenone-based compound: 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one,

[0285] α-Dicarbonyl-based compound: 1, 2-diphenylethanediol, methylphenyl glyoxylate,

[0286] Acylphosphine oxide-based compounds: 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethyl diphenylphosphine, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide.

[0287] Note that, when a photopolymerization initiator is used, a known polymerization-curing promoting aid such as a tertiary amine can also be used in combination.

[0288] <Surfactant>

[0289] When a surfactant is added, the wettability to the optical substrate, the primer layer can be improved, and the occurrence of appearance defects can be prevented. As the surfactant, known surfactants such as a silicone surfactant in which a silicone chain (polyalkylsiloxane unit) is used as a hydrophobic group, a fluorine surfactant having a fluorocarbon chain, and the like can be exemplified. When a surfactant is used, two or more kinds can be used in combination. Furthermore, the surfactant can be one that can be polymerized with the (A) component, or one that cannot be polymerized.

[0290] If specific examples of the silicone surfactants and the fluorine surfactants that can be preferably used are exemplified, L-7001, L-7002, L-7604, FZ-2123, FZ-2110 manufactured by Dow Toray Co., Ltd., MEGAFAC F-470, MEGAFAC F-1405, MEGAFAC F-479 manufactured by DIC Corporation, Fluorad FC-430 manufactured by 3M Japan Ltd., TEGORAD 2100, TEGORAD 2300 manufactured by Evonik Japan Co., Ltd., BYK-UV3505, BYK-UV3505, BYK-UV3510, BYK-UV3530, BYK-3550, BYK-3560, BYK-UV3565, BYK-3566, BYK-UV3500, BYK-UV3535, BYK-UV3570, BYK-UV3575, BYK-UV3576 manufactured by BYK-Chemie Japan, KR-513, X-22-2445, X-40-9296, X-22-164, X-22-164A, X-22-164B, X-22-164C, X-22-164E manufactured by Shin-Etsu Chemical Co., Ltd., and the like can be exemplified.

[0291] <Ultraviolet absorber>

[0292] As the ultraviolet absorber, known ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, cyano acrylate-based compounds, triazine-based compounds, benzoate-based compounds, cinnamate-based compounds, oxanilide-based compounds, and the like can be used, and particularly, cyano acrylate-based compounds, benzophenone-based compounds, benzotriazole-based compounds, and cinnamate-based compounds are preferable. The above-described ultraviolet stabilizer is preferably used in a range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the curable composition containing the photochromic compound and the polymerizable compound.

[0293] <Curable product>

[0294] The curable product is obtained by curing the curable composition. The curing of the curable composition is performed by causing a radical polymerization reaction using irradiation of active energy rays such as ultraviolet rays, α-rays, β-rays, γ-rays, LEDs, or the like, heat, or a combination of both. That is, depending on the kind of the polymerizable monomer, the kind of the polymerization curing accelerator used, and the form of the curable product formed, an appropriate curing means is employed. In the case where a laminate is formed by the coating method described later, from the reason of obtaining a uniform film thickness, photopolymerization is preferably employed.

[0295] In the case where the curable composition in which the polymerizable compound is compounded is subjected to thermal polymerization, the thermal polymerization temperature has an influence on the properties of the curable product obtained. This temperature condition is influenced by the kind and amount of the thermal polymerization initiator, the kind of the polymerizable compound, and thus cannot be generally defined, and generally, it is preferable to start polymerization at a relatively low temperature and to slowly increase the temperature. The polymerization time also differs depending on various reasons as with the temperature, and thus it is preferable to decide the optimum time corresponding to these conditions in advance, but generally, it is preferable to select the conditions in such a manner that the polymerization is completed in 2 to 48 hours. In the case where a photochromic laminate is obtained, it is preferable to perform polymerization at a temperature at which the reaction of the polymerizable functional groups with each other proceeds, and at this time, the optimum temperature and time are decided in such a manner that the target molecular weight is obtained.

[0296] In addition, in the case where the curable composition is subjected to photopolymerization, the intensity of the UV light in the polymerization conditions has an influence on the properties of the photochromic curable product obtained. This intensity condition is influenced by the kind and amount of the photopolymerization initiator, the kind of the polymerizable monomer, and thus cannot be generally defined, and generally, it is preferable to select the conditions in such a manner that 50 to 500 mW / cm 2 of UV light is irradiated for 0.5 to 5 minutes at a wavelength of 365 nm.

[0297] <Laminate>

[0298] According to another embodiment, a laminate is provided. The laminate includes an optical substrate and the cured product of the embodiment on a surface of the optical substrate. The optical substrate includes, for example, a diallyl carbonate resin, a urethane resin, a thio urethane resin, or the like. The optical substrate can be a lens substrate. A primer layer can be provided between the laminate and the cured product. The primer layer includes a urethane resin.

[0299] Figure 1 is a cross-sectional view schematically showing an example of the laminate of the embodiment. Figure 1 The laminate 10 shown includes an optical substrate 11, a primer layer 1 provided on one main surface of the optical substrate 11, and a functional resin layer 12 provided on a main surface of the primer layer 1. The functional resin layer 12 includes the cured product of the embodiment. The optical substrate 11 is a convex meniscus lens having a concave-convex shape.

[0300] <Optical article>

[0301] The cured product of the embodiment can be widely used as an optical article, for example, as various storage materials such as silver halide photosensitive materials, copying materials, photosensitive bodies for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holograms, and the like, and lenses. The lenses are suitable for use in eyeglasses. The photochromic cured product including the photochromic compound can also be used as a photochromic lens material, an optical filter material, a display material, a light meter, a decorative material, and the like.

[0302] The cured product of the embodiment is particularly suitable for photochromic lens applications. The photochromic lenses are suitable as lenses for eyeglasses such as sunglasses. The method for producing the photochromic lenses can employ a known method as long as a method that can provide uniform light adjustment performance.

[0303] In a case where the photochromic property is exhibited by a mixing method, the above-mentioned curable composition is injected between glass molds held by an elastomer gasket or a spacer, and a photochromic cured product shaped as an optical material such as a lens can be obtained by casting polymerization using heating in an air oven, irradiation of active energy rays such as ultraviolet rays, depending on the kind of the polymerizable compound, the polymerization curing accelerator.

[0304] In a case where the photochromic property is exhibited by a lamination method, a coating liquid is prepared by dissolving the curable composition in an organic solvent as appropriate, the coating liquid is coated on a surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and the organic solvent is removed by drying, and then polymerization curing is performed by UV irradiation in a non-active gas such as nitrogen, heating, or the like, whereby a photochromic layer formed of a photochromic cured product is formed on the surface of the optical substrate (coating method).

[0305] In addition, the optical substrate such as a lens substrate is arranged so as to form a prescribed gap with a glass mold, a curable composition is injected into the gap, and in this state, polymerization and curing are performed by UV irradiation, heating, or the like, and based on the inner mold, casting polymerization, and thus a photochromic layer formed of a photochromic cured product can also be formed on the surface of the optical substrate (casting polymerization method).

[0306] In the case where the photochromic layer is formed on the surface of the optical substrate by the above-described lamination method (coating method and casting polymerization method), the adhesion of the photochromic layer to the optical substrate can also be improved by performing chemical treatment based on an alkali solution, an acid solution, or the like, physical treatment using corona discharge, plasma discharge, polishing, or the like, on the surface of the optical substrate in advance. Of course, a transparent adhesive resin layer can also be provided on the surface of the optical substrate in advance.

[0307] In addition, the cured product formed of the curable composition can be subjected to post-processing according to its use. In the post-processing, dyeing using a dye such as a disperse dye, formation of a hard coat film using a silane coupling agent, a hard coat agent having a sol of silicon, zirconium, antimony, aluminum, tin, tungsten, or the like as a main component, thin film formation based on evaporation of a metal oxide such as SiO2, TiO2, ZrO2, antireflection treatment based on coating of an organic high molecule, antistatic treatment, or the like can be cited.

[0308] Example

[0309] Next, the present application will be described in detail using examples and comparative examples, but the present application is not limited to the present examples. The description of each component and the evaluation method, and the like are described below.

[0310] [Synthesis of (urethane) (meth) acrylate]

[0311] Example 1

[0312] (Synthesis of PTG25CD100)

[0313] The methacrylate PTG25CD100 of the following formula was synthesized by the following method.

[0314]

[0315] To 100 g of NT1002 (manufactured by Mitsubishi Chemical Corporation) having a molecular weight of 1000 calculated from the hydroxyl value, 330 mL of dehydrated toluene, 1.0 mg of p-methoxyphenol, and 2.86 g of p-toluenesulfonic acid monohydrate were added, and stirred. To this, 18.9 g of methacrylic acid was added, and reacted for 20 hours under azeotropy. After the reaction, 1000 mL of 5% sodium bicarbonate aqueous solution was added, and subjected to liquid separation. To the obtained organic layer, diatomaceous earth was added, stirred, and filtered. To the obtained organic layer, 20 g of Wako Gel 60N was added, stirred, and filtered. To the obtained organic layer, 1 mL of 0.1 mg / mL p-methoxyphenol toluene solution was added, and concentrated, thereby synthesizing PTG25CD100.

[0316] The proton nuclear magnetic resonance spectrum was measured, and as a result, peaks of about 55H based on tetramethyleneoxy group and methacryloyl group were shown around δ 1.0 to 2.5 ppm, peaks of about 49H based on tetramethyleneoxy group were shown around δ 3.0 to 4.5 ppm, and peaks of 4H based on the protons of acryloyl group were shown around δ 5.5 to 6.5 ppm.

[0317] (Example 2)

[0318] (Synthesis of PTG25CD200)

[0319] The methacrylate PTG25CD200 of the following formula was synthesized by the following method.

[0320]

[0321] In Example 1, instead of NT1002, NT2002 was used, and otherwise the reaction was carried out in the same manner, thereby synthesizing PTG25CD200.

[0322] The proton nuclear magnetic resonance spectrum was measured, and as a result, peaks of about 103H based on tetramethyleneoxy group and methacryloyl group were shown around δ 1.0 to 2.5 ppm, peaks of about 96H based on tetramethyleneoxy group were shown around δ 3.0 to 4.5 ppm, and peaks of 4H based on the protons of acryloyl group were shown around δ 5.5 to 6.5 ppm.

[0323] (Example 3)

[0324] (Synthesis of PTG65CD200)

[0325] The methacrylate PTG65CD200 of the following formula was synthesized by the following method.

[0326]

[0327] In Example 1, the reaction was carried out in the same manner as in the above except that NT2006 was used instead of NT1002, to synthesize PTG65CD200.

[0328] The proton nuclear magnetic resonance spectrum was measured, and as a result, a peak of about 114H based on tetramethyleneoxy, methacryloyl was shown around δ 1.0 to 2.5 ppm, a peak of about 108H based on tetramethyleneoxy was shown around δ 3.0 to 4.5 ppm, and a peak of 4H based on the proton of acryloyl was shown around δ 5.5 to 6.5 ppm.

[0329] Example 4

[0330] (Synthesis of UA-PTG25CD100)

[0331] The urethane acrylate UA-PTG25CD100 of the following formula was synthesized by the following method.

[0332]

[0333] To 97.5 g of NT1002, dehydrated toluene 350 mL was added, and subjected to azeotropic dehydration. After distilling off 50 mL, it was cooled to 60 degrees, and p-methoxyphenol 19.5 mg, dibutyltin dilaurate 6.5 mg were added. 27.2 g of 2-acryloyloxyethyl isocyanate was added dropwise slowly. After the dropwise addition, it was reacted at 60 to 65 degrees for 8 hours. After the end of the reaction, 100 mL of water was added, and subjected to liquid separation. To the obtained organic layer, diatomaceous earth was added, and after stirring, it was filtered. The obtained organic layer was concentrated, whereby UA-PTG25CD100 was synthesized.

[0334] The proton nuclear magnetic resonance spectrum was measured, and as a result, a peak of about 49H based on tetramethyleneoxy was shown around δ 1.0 to 2.5 ppm, a peak of about 57H based on tetramethyleneoxy, ethyleneoxy was shown around δ 3.0 to 4.5 ppm, and a peak of 9H based on the proton of acryloyl was shown around δ 5.5 to 6.5 ppm.

[0335] [Photochromic curable composition and manufacturing of optical article]

[0336] [Components]

[0337] (A) Component

[0338] (Formula (1A) Component)

[0339] PTG25CD100: methacrylate of Example 1

[0340] PTG25CD200: methacrylate of Example 2

[0341] PTG65CD200: methacrylate ester of Example 3

[0342] UA-PTG25CD100: urethane acrylate ester of Example 4

[0343] (A-1)

[0344] M-PTMG65: polytetramethylene glycol dimethacrylate (average molecular weight 786)

[0345] (A-2)

[0346] TMPT: trimethylolpropane trimethacrylate

[0347] D-TMP: ditrimethylolpropane tetramethacrylate

[0348] M-TMMT: pentaerythritol tetramethacrylate

[0349] M-TMMT-80: pentaerythritol trimethacrylate: pentaerythritol tetramethacrylate = 18:82 (weight ratio) mixture

[0350] (A-3)

[0351] TSL: γ-methacryloyloxypropyltrimethoxysilane

[0352] LA82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate

[0353] (A-4)

[0354] 14G: polyethylene glycol dimethacrylate (average molecular weight 770)

[0355] 23G: polyethylene glycol dimethacrylate (average molecular weight 1170)

[0356] MPCD100: polycarbonate diol dimethacrylate (average molecular weight 1156) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol

[0357] (A-5)

[0358] RX-1: polyrotaxane having an acryloyl group, having the following properties

[0359] Weight average molecular weight Mw (GPC): 180,000

[0360] Proportion of acryloyl group modification in side chain: 80 mol%

[0361] Proportion of OH group remaining in side chain: 20 mol%

[0362] Axle molecule: linear polyethylene glycol (PEG) having a molecular weight of 11,000

[0363] Inclusion ring: α-cyclodextrin (α-CD) Introduction ratio 0.25

[0364] End of axle molecule: capped with adamantane

[0365] Side chain introduced into inclusion ring; (average) molecular weight of side chain is about 500

[0366] Number of acryloyl groups per 1 molecule: about 90

[0367] RX-1 was synthesized by the method described in International Publication No. 2018 / 030275. The weight average molecular weight Mw of RX-1 was measured by gel permeation chromatography (GPC method). As the device, a liquid chromatograph device (manufactured by Japan Waters Corporation) was used. As the column, two TSKgel Super HM-M (exclusion limit molecular weight: 4,000,000, manufactured by Tosoh Corporation) were used in series. In addition, tetrahydrofuran was used as the developing solvent, and the measurement was performed at a flow rate of 0.6 ml / min, a temperature of 40°C. The standard sample used polystyrene, and the weight average molecular weight was calculated by comparison.

[0368] SO-1: silsesquioxane having a methacryloyl group, having the following properties

[0369] Number of methacrylate groups per 1 molecule: 20

[0370] Weight average molecular weight: 4,800

[0371] In addition, SO-1 was synthesized by the following method. First, 3- trimethoxysilylpropyl methacrylate 248 g (1.0 mol) was added with ethanol 248 ml and water 54 g (3.0 mol), and 0.20 g (0.005 mol) of sodium hydroxide as a catalyst was added, and reacted at 30°C for 3 hours. After confirming the disappearance of the raw material by 1 After confirming the disappearance of the raw material by H-NMR, neutralization was performed with dilute hydrochloric acid, and toluene 174 ml, heptane 174 ml, and water 174 g were added, and the water layer was removed. Then, the organic layer was washed with water until the water layer became neutral, and the solvent was concentrated, thereby obtaining SO-1. Note that the molecular weight of SO-1 was measured by GPC method. 29 Si-NMR, SO-1 was confirmed to be a mixture of a cage structure, a ladder structure, and a random structure.

[0372] The weight average molecular weight Mw of SO-1 was measured by gel permeation chromatography (GPC method). As the device, a liquid chromatograph device (manufactured by Waters Corporation, Japan) was used. As the column, three of Shodex GPC KF-802 (exclusion limit molecular weight: 5000, manufactured by Showa Denko K.K.), Shodex GPC KF802.5 (exclusion limit molecular weight: 20000, manufactured by Showa Denko K.K.), and Shodex GPC KF-803 (exclusion limit molecular weight: 70000, manufactured by Showa Denko K.K.) were used in series. In addition, tetrahydrofuran was used as the developing liquid, and the measurement 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.

[0373] (B) Component

[0374] PC1: a compound represented by the following formula.

[0375]

[0376] PC2: a compound represented by the following formula.

[0377]

[0378] PC3: a compound represented by the following formula.

[0379]

[0380] PC4: a compound represented by the following formula.

[0381]

[0382] (Other compounding agents)

[0383] (Stabilizer)

[0384] HALS: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate

[0385] HP: Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (manufactured by BASF Japan Ltd., Irganox 245).

[0386] (Photo-polymerization initiator)

[0387] PI: Phenyl bis (2,4,6-trimethylbenzoyl) -phosphine oxide (manufactured by IGM, Omnirad 819)

[0388] Example 5

[0389] (Production of photochromic curable composition)

[0390] First, each component was prepared according to the following formulation.

[0391] (A) Component

[0392] PTG 25 CD 100 47.2 parts by mass

[0393] TMPT 47.2 parts by mass

[0394] TSL 5.6 parts by mass

[0395] (B) Component

[0396] PC 11.7 parts by mass

[0397] (Other additives)

[0398] (Polymerization initiator) PI 0.3 parts by mass

[0399] (Stabilizer) HP 1 part by mass

[0400] HALS 3 parts by mass

[0401] Next, the compounds equivalent to the (A) component were mixed together, and then the (B) component and other additives were mixed in the mixture, to obtain a mixture. To the obtained mixture, 1000 ppm of a leveling agent FZ2110 manufactured by Dow-Toray Co., Ltd. was added, and mixed, whereby a photochromic curable composition was obtained.

[0402] (Manufacture of optical article)

[0403] Using the photochromic curable composition, a photochromic laminate was obtained by a lamination method.

[0404] First, as an optical substrate, a thiourethane-based plastic lens having a center thickness of 2 mm and a refractive index of 1.60 was prepared. Note that the thiourethane-based plastic lens was subjected to alkaline etching using a 5% sodium hydroxide aqueous solution at 50°C for 5 minutes in advance, and then washed thoroughly with distilled water.

[0405] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curable primer (product name; TR-SC-P, manufactured by Tokuyama Corp.) was applied to the surface of the above plastic lens at a rotation speed of 70 rpm for 15 seconds, and then at 700 rpm for 10 seconds. Then, about 1 g of the photochromic curable composition obtained above was spin-coated, so that the film thickness of the photochromic coating layer was 40 μm.

[0406] The lens on which the photochromic curable composition (photochromic coating layer) was applied to the surface was irradiated with ultraviolet light having an output power of 200 mW / cm 2The metal halide lamp was irradiated for 90 seconds to cure the coating film. Then, further heating was performed at 90°C for 1 hour to produce a photochromic laminate having a photochromic layer.

[0407] Examples 6 to 18

[0408] A photochromic cured product was produced in the same manner as in Example 5 except that the photochromic curable composition described in Table 1 was used, and evaluation was performed in accordance with the same evaluation items.

[0409] Comparative Examples 1 to 4

[0410] A photochromic cured product was produced in the same manner as in Example 5 except that the photochromic curable composition described in Table 2 was used, and evaluation was performed in accordance with the same evaluation items.

[0411] [evaluation]

[0412] The laminates obtained in the examples and comparative examples were evaluated in accordance with the following evaluation methods, and the results are described in Table 3.

[0413] (1) Photochromic properties

[0414] [1] Maximum absorption wavelength (λmax):

[0415] was the maximum absorption wavelength after coloration, which was obtained by a spectrophotometer (instantaneous multi-channel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., and was used as an index of the color tone at the time of coloration.

[0416] [2] Coloration concentration at 23°C (A 23 ):

[0417] was the difference between the absorbance at the maximum absorption wavelength {ε(300)} after 300 seconds of light irradiation at 23°C and the absorbance ε(0) in the absence of light irradiation, and was used as an index of the coloration concentration. The higher the value, the more excellent the photochromic properties.

[0418] [3] Fading half-life at 23°C (τ1 / 2 (sec.)):

[0419] was the time required for the absorbance at the maximum absorption wavelength of the sample to decrease to 1 / 2 of {ε(300)-ε(0)} when the light irradiation was stopped after 300 seconds of light irradiation at 23°C, and was used as an index of the fading speed. The shorter the time, the faster the fading speed.

[0420] (2) Vickers hardness

[0421] The Vickers hardness was measured using a micro Vickers hardness tester PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A four-pyramid diamond indenter was used, and the measurement was performed under conditions of a load of 10 gf and a holding time of the indenter of 30 seconds. The measurement results were averaged for a total of 4 times of measurement, and the average value of a total of 3 times of measurement excluding the value of the first time which had a large measurement error was represented.

[0422] [Table 1]

[0423]

[0424] [Table 2]

[0425]

[0426] [Table 3]

[0427]

[0428] The following describes preferred modes of the present application. [1]

[0430] A (meth)acrylate represented by the following formula (1A):

[0431]

[0432] In the aforementioned formula (1A),

[0433] Q 1 and Q 5 each independently is a hydrogen atom or a methyl group,

[0434] Q 2 and Q 4 each independently is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0435] Q 3A and Q 3B each independently is a divalent group represented by the following formula (1a),

[0436] In the case where a plurality of Q 3A are present, the plurality of Q 3A are optionally the same group or different groups,

[0437] a and b each independently are 0 or higher and 10 or lower,

[0438] Z 1 and Z 2 each independently is 0 or 1,

[0439] Z 3 is 1 or higher and 100 or lower,

[0440]

[0441] in the aforementioned formula (1a),

[0442] Q 6 and Q 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0443] Q 7 and Q 9 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0444] Q 6 and Q 7 are different groups, Q 9 and Q 10 are different groups,

[0445] Q 8 is a linear or branched alkylene group having 2 to 20 carbon atoms which optionally has a substituent,

[0446] d and h are 0 or more and 10 or less,

[0447] e and g are 0 or more and 20 or less,

[0448] f is 3 or more and 100 or less. [2]

[0450] The (meth)acrylate according to [1], wherein in the aforementioned formula (1a), d, e, g and h are each 0. [3]

[0452] The (meth)acrylate according to [1], which is represented by the following formula (1B):

[0453]

[0454] in the aforementioned formula (1B),

[0455] Q 1 , Q 3A , Q 3B , Q 5 and Z 3 have the same meanings as in the aforementioned formula (1A). [4]

[0457] The (meth)acrylate according to [3], wherein in the aforementioned formula (1a), Q 8 is a linear alkylene group having 3 to 9 carbon atoms which optionally has a substituent. [5]

[0459] The (meth)acrylate according to [1], which is represented by the following formula (1D):

[0460]

[0461] In the aforementioned formula (1D),

[0462] Q 1 , Q 5 , Z 3 and f have the same meanings as in the aforementioned formula (1A),

[0463] Q 8b is a linear alkylene group having 1 to 7 carbon atoms. [6]

[0465] The (meth)acrylate according to [1] has a number average molecular weight of 100 or more and 10,000 or less. [7]

[0467] A curable composition comprising the (meth)acrylate according to any one of [1] to [6] and a functional pigment. [8]

[0469] The curable composition according to [7], wherein the proportion of the aforementioned functional pigment in the aforementioned curable composition is 0.001 mass% or more and 10 mass% or less. [9]

[0471] The curable composition according to [7] or [8], wherein the content of the aforementioned (meth)acrylate is 5 mass% or more and 99 mass% or less.

[10]

[0473] The curable composition according to any one of [7] to [9], further comprising a first radical polymerizable monomer represented by the following formula (I).

[0474]

[0475] In the aforementioned formula (I),

[0476] R 1 and R 7 are each independently a hydrogen atom or a methyl group,

[0477] R 2 and R 6 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0478] R 3 and R 5 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0479] R 2 and R 3R are mutually different groups, and 6 R are mutually different groups, 7 R are mutually different groups,

[0480] R 4 R is a linear or branched alkylene group having 1 to 7 carbon atoms optionally having a substituent,

[0481] a1 and e1 are 0 or more and 10 or less,

[0482] b1 and d1 are 0 or more and 20 or less,

[0483] c1 is 2 or more and 100 or less, and is a number larger than each of a1, b1, d1, and e1.

[11]

[0485] The curable composition according to any one of [7] to

[10] , further comprising a second radical polymerizable monomer having three or more (meth)acryloyl groups in one molecule.

[12]

[0487] The curable composition according to

[11] , wherein the aforementioned second radical polymerizable monomer comprises a polyfunctional (meth)acrylate represented by the following formula (2).

[0488]

[0489] In the aforementioned formula (2),

[0490] R 8 R is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,

[0491] R 9 R is a hydrogen atom or a methyl group,

[0492] R 10 R is a 3- to 6-valent organic group having 1 to 10 carbon atoms,

[0493] i1 is 0 or more and 3 or less,

[0494] j1 is 0 or more and 3 or less,

[0495] h1 is 3 or more and 6 or less.

[13]

[0497] The curable composition according to any one of [7] to

[12] , further comprising a third radical polymerizable monomer having one (meth)acryloyl group in one molecule.

[14]

[0499] The curable composition according to any one of [7] to

[13] , further comprising a polyethylene glycol di(meth)acrylate.

[15]

[0501] The curable composition according to any one of [7] to

[14] , wherein the aforementioned functional pigment comprises at least one compound selected from the group consisting of a chromene compound and a spirooxazine compound.

[16]

[0503] A cured product obtained by curing the curable composition according to any one of [7] to

[15] .

[17]

[0505] A laminate comprising an optical substrate, and the cured product according to

[16] on a surface of the aforementioned optical substrate.

[18]

[0507] An optical article comprising the cured product according to

[16] .

[19]

[0509] A lens comprising the cured product according to

[16] .

[20]

[0511] Eyeglasses comprising the lens according to

[19] .

Claims

1. A (meth)acrylate represented by the following formula (1A): ###0001### wherein a and b are each independently 0 or more and 10 or less, and wherein the formula (1A) is represented by the following formula (1a): ###0002### wherein d and h are each independently 0 or more and 10 or less, and wherein the formula (1a) is represented by the following formula (1b): ###0003### wherein e and g are each independently 0 or more and 20 or less, and wherein the formula (1b) is represented by the following formula (1c): ###0004### wherein f is 3 or more and 100 or less.

2. The (meth)acrylate according to claim 1, wherein each of d, e, g, and h is 0 in the formula (1a). Q 1 and Q 5 each independently is a hydrogen atom or a methyl group, Q 2 and Q 4 each independently is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 3A and Q 3B each independently is a divalent group represented by the following formula (1a), In Q 3A In the case of a plurality, the plurality of Q 3A are optionally identical radicals or different radicals, 3. The (meth)acrylate according to claim 1, represented by the following formula (1B): ###0005### wherein a and b are each independently 0 or more and 10 or less, and wherein the formula (1B) is represented by the following formula (1B1): ###0006### wherein d and h are each independently 0 or more and 10 or less, and wherein the formula (1B1) is represented by the following formula (1B2): ###0007### wherein e and g are each independently 0 or more and 20 or less, and wherein the formula (1B2) is represented by the following formula (1B3): ###0008### wherein f is 3 or more and 100 or less. Z 1 and Z 2 each independently is 0 or 1, Z 3 is 1 or more and 100 or less, 5. The (meth)acrylate according to claim 1, represented by the following formula (1D): ###0010### wherein a and b are each independently 0 or more and 10 or less, and wherein the formula (1D) is represented by the following formula (1D1): ###0011### wherein d and h are each independently 0 or more and 10 or less, and wherein the formula (1D1) is represented by the following formula (1D2): ###0012### wherein e and g are each independently 0 or more and 20 or less, and wherein the formula (1D2) is represented by the following formula (1D3): ###0013### wherein f is 3 or more and 100 or less. Q 6 and Q 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 7 and Q 9 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 6 and Q 7 are different from each other, Q 9 and Q 10 are different from each other, Q 8 a straight-chain or branched-chain alkylene group having 2 to 20 carbon atoms optionally having a substituent, 6. The (meth)acrylate according to claim 1, having a number average molecular weight of 100 or more and 10,000 or less.

7. A curable composition comprising the (meth)acrylate according to claim 1 and a functional pigment.

8. The curable composition according to claim 7, wherein the proportion of the functional pigment is 0.001 mass% or more and 10 mass% or less.

2. The (meth)acrylate according to claim 1, wherein 9. The curable composition according to claim 7, wherein the content of the (meth)acrylate is 5 mass% or more and 99 mass% or less.

10. The curable composition according to claim 7, further comprising a first radical polymerizable monomer represented by the following formula (I): ###0014### wherein a1 and e1 are each independently 0 or more and 10 or less, and wherein the formula (I) is represented by the following formula (I1): ###0015### wherein b1 and d1 are each independently 0 or more and 20 or less, and wherein the formula (I1) is represented by the following formula (I2): ###0016### wherein c1 is 2 or more and 100 or less, and is a number larger than each of a1, b1, d1, and e1.

11. The curable composition according to claim 7, further comprising a second radical polymerizable monomer having three or more (meth)acryloyl groups in one molecule. Q 1 , Q 3A , Q 3B , Q 5 and Z 3 have the same meaning as in formula (1A).

4. The (meth)acrylate of claim 3, wherein, In the formula (1a), Q 8 is an optionally substituted straight-chain alkylene group having 3 to 9 carbon atoms.

12. The curable composition according to claim 11, wherein the second radical polymerizable monomer comprises a multifunctional (meth)acrylate represented by the following formula (2): ###0017### wherein i1 is 0 or more and 3 or less, and wherein the formula (2) is represented by the following formula (2-1): ###0018### wherein j1 is 0 or more and 3 or less, and wherein the formula (2-1) is represented by the following formula (2-2): ###0019### wherein h1 is 3 or more and 6 or less.

13. The curable composition according to claim 7, further comprising a third radical polymerizable monomer having one (meth)acryloyl group in one molecule. Q 1 , Q 5 , Z 3 and f have the same meaning as in said formula (1 A), Q 8b R1is a straight-chain alkylene group having 1 to 7 carbon atoms.

14. The curable composition according to claim 7, further comprising a polyethylene glycol di(meth)acrylate.

15. The curable composition according to claim 7, wherein the functional pigment comprises at least one compound selected from the group consisting of a chromene compound and a spirooxazine compound.

8. The curable composition according to claim 7, wherein, 16. A cured product obtained by curing the curable composition according to claim 7.

9. The curable composition according to claim 7, wherein, 17. A laminate comprising an optical substrate, and the cured product according to claim 16 on a surface of the optical substrate.

18. An optical article comprising the cured product according to claim 16.

19. A lens comprising the cured product according to claim 16. R 1 and R 7 each independently is a hydrogen atom or a methyl group, R 2 and R 6 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 3 and R 5 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2 and R 3 are different from each other, R 6 and R 7 are different from each other, R 4 R is a straight-chain or branched alkylene group having 1 to 7 carbon atoms optionally having substituents, 20. Eyeglasses comprising the lens according to claim 19. ​ ​ ​ 12. The curable composition of claim 11, wherein, ​ ​ R 8 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R 9 is a hydrogen atom or a methyl group, R 10 R is a 3-6 valent organic group having 1-10 carbon atoms, ​ ​ ​ ​ ​ 15. The curable composition according to claim 7, wherein, ​ ​ ​ ​ ​ ​

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