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

Abstract

The purpose of the present invention is to provide a urethane (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 urethane (meth) acrylate represented by formula (1) is provided. According to other embodiments, a curable composition is provided. The curable composition contains a urethane (meth) acrylate according to the embodiment and a functional dye. According to other embodiments, 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 invention relates to urethane (meth)acrylate, a curable composition, a cured product, a laminate, an optical article, a lens, and glasses. Background Art

[0002] Urethane (meth)acrylate is a monomer or oligomer containing a urethane bond and a (meth)acryloyl group. Urethane (meth)acrylate is obtained, for example, by reacting a urethane prepolymer obtained by reacting a polyol with an isocyanate compound with an acrylate having a hydroxyl group.

[0003] Urethane (meth)acrylate can be widely molecular-designed by changing the types of raw materials such as polyols. Urethane (meth)acrylate is widely used as a material for various coating agents, adhesives, paints, and plastic products.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: International Publication No. 2011 / 059117

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2018-035264

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 2021-055107

[0009] Patent Document 4: Japanese Patent Application Laid-Open No. 2005-097439

[0010] Patent Document 5: Japanese Patent Application Laid-Open No. 62-050321 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] An object of the present invention is to provide a urethane (meth)acrylate, a curable composition, a cured product, a laminate, an optical article, a lens, and glasses that can achieve excellent properties of a functional pigment.

[0013] Means for Solving the Problems

[0014] According to the present disclosure, there is provided a urethane (meth)acrylate represented by the following formula (1).

[0015]

[0016] In formula (1), Q 1 and Q 5 are each independently a hydrogen atom or a methyl group. Q2 and Q 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 3 is a divalent group represented by the following formula (1a). a and b are each independently 0 or more and 10 or less.

[0017]

[0018] In formula (1a), Q 6 and Q 10 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 7 and Q 9 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 6 and Q 7 are different groups from each other. Q 9 and Q 10 are different groups from each other. Q 8 is a linear or branched alkylene group having 1 to 7 carbon atoms which may optionally have a substituent. d and h are 0 or more and 10 or less. e and g are 0 or more and 20 or less. f is 2 or more and 100 or less.

[0019] Further, according to the present disclosure, there is provided a curable composition. The curable composition contains the urethane (meth)acrylate of the embodiment and a functional pigment.

[0020] Further, according to the present disclosure, there is provided a cured product. The cured product is obtained by curing the curable composition of the embodiment.

[0021] Further, according to the present disclosure, there is provided a laminate. The laminate includes an optical substrate and the cured product of the embodiment provided on the surface of the optical substrate.

[0022] Further, according to the present disclosure, there is provided an optical article. The optical article includes the cured product of the embodiment.

[0023] Further, according to the present disclosure, there is provided a lens. The lens includes the cured product of the embodiment.

[0024] Further, according to the present disclosure, there is provided a pair of glasses. The pair of glasses includes the lens of the embodiment.

[0025] Effects of the Invention

[0026] According to the present invention, there are provided a urethane (meth)acrylate, a curable composition, a cured product, a laminate, an optical article, a lens, and a pair of glasses that can achieve excellent properties of a functional pigment. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is a cross-sectional view schematically showing an example of the laminate of the embodiment. Detailed implementation mode

[0028] According to the implementation mode, a urethane (meth)acrylate represented by formula (1) is provided. This urethane (meth)acrylate can preferably be used as a material for forming a resin composition containing a functional pigment. The reasons therefor will be described below.

[0029] First, the functional pigment includes a compound having the ability to selectively absorb visible light, and a compound that develops color, fades, or changes color by energy such as light, heat, electric field, or pressure. Such a functional pigment can exhibit a specific function by undergoing a structural change under specific conditions. Generally, the matrix of a plastic cured product has a rigid structure. Therefore, in the cured product, the free space provided for the structural change of the functional pigment is smaller than in a solution. Therefore, the functional pigment in the cured product is less likely to undergo a structural change compared to in a solution, which limits its function.

[0030] The urethane (meth)acrylate represented by formula (1) has a repeating structure represented by -(O-CH2CH2Q 1 at the Q 8 ) f -, that is, it has a first alkyleneoxy chain having 3 or more and 9 or less carbon atoms. It is considered that the first alkyleneoxy chains aggregate in the cured product to form soft segments arranged by them. It is considered that the distance between the first alkyleneoxy chains in the soft segment is greater than the distance between the alkyleneoxy chains in the soft segment composed of alkyleneoxy chains having 2 or less carbon atoms. It is considered that the free space for the functional pigment in the soft segment composed of the first alkyleneoxy chains is relatively large. Therefore, the structural change of the functional pigment located in the soft segment composed of the first alkyleneoxy chains is not easily hindered, and excellent functionality can be achieved. In addition, it is considered that in a cured product using a curable composition containing urethane (meth)acrylate, hydrogen bonds are formed at the -NH- site contained in the urethane bond. Therefore, it is considered that the functional pigment is easily stabilized in the state of an isomer with a structural change.

[0031] And then, if use the carbamate (meth) acrylate of embodiment, then can realize the high functionality of functional pigment and the solidified material of high rigidity taking into account.That is, the flexibility of the solidified material soft segment that hardness is high is low or the ratio of soft segment is few, and there is the tendency that the functionality of functional pigment reduces.Think that the carbamate (meth) acrylate of embodiment has the more first alkylene oxy chain of carbonatoms, therefore the flexibility of its soft segment is lower than the flexibility of the soft segment that is constituted by the alkylene oxy chain below carbonatoms 2.On the other hand, as mentioned above, the distance between the first alkylene oxy chain is large, and therefore the free space in the soft segment is wide, can improve the functionality of functional pigment.Therefore, if use this carbamate (meth) acrylate, then can realize the solidified material of these two excellent performances of high rigidity and functional pigment.

[0032] [Urethane (meth)acrylate represented by formula (1)]

[0033] The urethane (meth)acrylate of the embodiment is represented by the following formula (1). The urethane (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 urethane (meth)acrylate has two urethane bonds.

[0034]

[0035] In formula (1), Q 1 and Q 5 Each is independently a hydrogen atom or a methyl group. 1 and Q 5 Preferred is methyl.

[0036] Q 2 and Q 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 2 and Q 4 A hydrogen atom is preferred. a and b are each independently 0 or more and 10 or less. a and b are, for example, 1 or more and 5 or less, and preferably 1.

[0037] Q 3 It is a divalent group represented by the following formula (1a).

[0038]

[0039] In formula (1a), Q 8 It is a linear or branched alkylene group having 1 or more and 7 or less carbon atoms, which may have a substituent. The number of carbon atoms in the alkylene group is preferably 2 or more, but may be 4 or less. 8Preferably a straight-chain alkylene group without substituents. The repeating unit -(OCH2CH2Q 8 )- with a subscript f is a first alkyleneoxy unit having 3 or more and 9 or less carbon atoms. The polymer part composed of this repeating unit can form a soft segment of the cured product. When the number of carbon atoms in the alkylene group is large, the functionality of the cured product is further improved. On the other hand, when the number of carbon atoms in the alkylene group is too large, the amount of the soft segment per unit mass decreases, so the functionality of the cured product may decrease.

[0040] f is a rational number of 2 or more and 100 or less. From the viewpoint of balancing functionality and hardness, f is preferably 3 or more and 85 or less, more preferably 4 or more and 70 or less, further preferably 5 or more and 50 or less, and particularly preferably 7 or more and 30 or less. f can be 10 or less, can also be 13 or less, and can also be 20 or less.

[0041] Q 7 and Q 9 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 7 and Q 9 are preferably a hydrogen atom or a methyl group. e and g are each 0 or more and 20 or less. e and g can each be 1 or more and 15 or less, and can also be 5 or more and 10 or less. The sum of e and g can be 2 or more and 5 or less.

[0042] Q 6 and Q 10 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Q 6 and Q 10 are preferably a hydrogen atom or a methyl group. Q 6 and Q 7 are groups having different structures from each other. Q 9 and Q 10 are groups having different structures from each other. d and h are each 0 or more and 10 or less. d and h can each be 1 or more and 5 or less. When e and g are 0, d and h are 0. The sum of d and h can be 2 or more and 10 or less.

[0043] In other words, the urethane (meth)acrylate of the embodiment may further include at least one of the repeating unit with e and g added, that is, the second alkyleneoxy unit, and the repeating unit with d and h added, that is, the third alkyleneoxy unit. If 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 the cured product.

[0044] In the urethane (meth)acrylate of the embodiment, it is preferable that a and b are 1 and d, e, g, and h are 0, that is, it contains only the first alkyleneoxy unit. When such a urethane (meth)acrylate is used, the cured product tends to have a higher hardness. Such a urethane (meth)acrylate is represented by the following formula (1b), for example.

[0045]

[0046] In formula (1b), Q 1 , Q 2 , Q 4 , Q 5 , Q 8 and f have the same meanings as in formula (1).

[0047] From the viewpoint of improving the hardness of the cured product, the number-average molecular weight of the urethane (meth)acrylate of the embodiment is preferably 100 or more, more preferably 200 or more, and further preferably 400 or more. From the aspects of improving the functionality of the functional pigment and facilitating the handling of the viscosity of the obtained curable composition, the number-average molecular weight of the urethane (meth)acrylate is preferably 15,000 or less, more preferably 10,000 or less, and further preferably 7,500 or less. Such a number-average molecular weight can be calculated by nuclear magnetic resonance (NMR) spectroscopy, for example.

[0048] In the number-average molecular weight of the urethane (meth)acrylate, the proportion of the number-average molecular weight of the first alkyleneoxy chain is preferably 20% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more. When this proportion is high, the functionality of the functional pigment in the cured product tends to increase. This proportion is preferably 95% by mass or less, more preferably 90% by mass or less. When this proportion is low, the cured product tends to have a higher hardness. Such a proportion can be calculated by nuclear magnetic resonance (NMR) spectroscopy, for example.

[0049] The urethane (meth)acrylate of the embodiment can be produced by the following method, for example.

[0050] First, a polyol compound represented by the following formula (1c) is prepared. Q 6 , Q 7 , Q 8 , Q 9 , Q 10 , d, e, f, g, and h have the same meanings as in the above formula (1a).

[0051]

[0052] Next, prepare the compound represented by the following formula (1d). This compound contains one isocyanate group and one (meth)acryloyl group.

[0053]

[0054] In formula (1d), Q 1 , Q 2 , and a have the same meanings as in formula (1).

[0055] By bringing the polyol compound represented by formula (1c) into contact with the compound represented by formula (1d), the urethane (meth)acrylate represented by formula (1) is obtained.

[0056] This reaction can be carried out 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, and tetrahydrofuran can be used.

[0057] Among the above polyol compounds, polyol compounds in which d and h are 0 and e and g are 1 or more, that is, polyols having a second alkyleneoxy unit can be synthesized, for example, by the following method.

[0058] By reacting H-(OCH2CH2Q 8 ) f -OH with a cyclic ether compound such as ethylene oxide or propylene oxide, a polyol having a second alkyleneoxy unit can be synthesized. A polyol compound having a second alkyleneoxy unit can be synthesized, for example, by carrying out the reaction in a nitrogen-purged autoclave in the presence of a catalyst such as an alkali metal hydroxide like potassium hydroxide under high temperature and high pressure.

[0059] Among the above polyol compounds, polyol compounds in which d, e, g, and h are 1 or more, that is, polyols further containing second and third alkyleneoxy units can be synthesized, for example, by the following method.

[0060] By reacting a polyol compound having a second alkyleneoxy unit with a cyclic ether compound, a polyol compound having a third alkyleneoxy unit can be synthesized.

[0061] The urethane (meth)acrylate represented by formula (1) can be obtained by the following method.

[0062] The structure of the obtained urethane (meth)acrylate can be confirmed, for example, by combining infrared spectroscopy (IR) analysis and NMR spectroscopy analysis.

[0063] That is, the method for producing the urethane (meth)acrylate of the embodiment may include contacting a diol compound with a compound containing one isocyanate group and one (meth)acryloyl group.

[0064] [Curable composition]

[0065] According to the embodiment, a curable composition is provided. The curable composition contains the urethane (meth)acrylate of the embodiment and a functional pigment.

[0066] The curable composition of the embodiment can be used as a coating agent, an adhesive, a paint, a material for plastic products such as 3D printers, etc. This curable composition is particularly suitable for optical article applications.

[0067] The curable composition preferably further contains a radically polymerizable monomer. As the radically polymerizable monomer, the following first to third radically polymerizable monomers can be mentioned.

[0068] Hereinafter, each component will be described in detail.

[0069] <(A) Radically polymerizable monomer>

[0070] The radically polymerizable monomer (A) contains a first radically polymerizable monomer represented by formula (I) of (A-1). Hereinafter, the first radically polymerizable monomer represented by formula (1) will also be referred to as the component (A-1). The radically polymerizable monomer (A) will also be referred to as the component (A). The radically polymerizable monomer (A) may contain other radically polymerizable monomers according to the characteristics of the required cured product. As long as it is a polymerizable monomer capable of polymerizing with the component (A-1), there is no particular limitation, and known polymerizable monomers can be used. A radically polymerizable monomer having a (meth)acrylate group is preferred, and a radically polymerizable monomer (A-2) having three or more (meth)acryloyl groups in one molecule and a radically polymerizable monomer (A-3) having a (meth)acryloyl group are preferably used.

[0071] <(A-1) component: the radically polymerizable monomer represented by the following formula (I)>

[0072]

[0073] In the formula, R 1 and R 7 are each independently a hydrogen atom or a methyl group. That is, the component (A-1) can be a diacrylate, dimethacrylate or methacrylate acrylate represented by the above formula (I). When using the component (A-1) as a diacrylate, there is a tendency to obtain a cured product with a high fading rate of the photochromic pigment. If the component (A-1) is used as a dimethacrylate, there is a tendency to obtain a cured product with a high color development concentration of the photochromic pigment. R1 and R 7 is preferably methyl.

[0074] R 4 is a linear or branched alkylene group having 1 to 7 carbon atoms which may optionally have substituents. c1 is from 2 to 100. c1 is a number greater than a1, a number greater than b1, a number greater than d1, and a number greater than e1.

[0075] That is, the repeating unit -(OCH2CH2R 4 )- with a subscript c is a first alkyleneoxy unit having 3 or more and 9 or less carbon atoms. The polymer moiety composed of this repeating unit can form a soft segment of the cured product. R 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, 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 may decrease.

[0076] From the viewpoint of balancing functionality and hardness, c1 is preferably from 2 to 85, more preferably from 2 to 70, still more preferably from 3 to 50, and particularly preferably from 5 to 45. c1 can be from 9 to 30, or can be from 11 to 28.

[0077] R 2 、R 3 、R 5 、and R 6 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 2 、R 3 、R 5 and R 6 are each independently preferably a hydrogen atom or a methyl group. R 2 and R 3 are different groups. R 5 and R 6 are different groups. R 2 and R 6 can be the same group. R 3 and R 5 can be the same group.

[0078] a1 and e1 are from 0 to 10. From the viewpoint of balancing functionality and hardness, a1 and e1 are preferably from 0 to 5, more preferably from 0 to 2, still more preferably 0 or 1, and most preferably 0.

[0079] b1 and d1 are from 0 to 20. From the viewpoint of balancing functionality and hardness, it is preferably from 0 to 15, more preferably from 0 to 10, still more preferably from 0 to 5, and particularly preferably 0.

[0080] In other words, the component (A-1) may be a monomer further having at least one of a repeating unit having b1 and d1 added thereto, i.e., a second alkyleneoxy unit, and a repeating unit having a1 and e1 added thereto, i.e., a third alkyleneoxy unit.

[0081] Preferably, a1, b1, d1, and e1 in the component (A-1) are 0, that is, it contains only the first alkyleneoxy unit. When such a component (A-1) is used, there is a tendency for the hardness of the cured product to increase. c1 may be 4 or more and 20 or less, or may be 6 or more and 15 or less. The component (A-3) can be synthesized, for example, by the following method.

[0082] The component (A-1) is represented, for example, by the following formula (3).

[0083]

[0084] In the above formula (3), R 1 , R 7 , and c1 have the same meanings as in the formula (I).

[0085] R 11 is a linear alkylene having 1 to 7 carbon atoms. R 11 is preferably a linear alkylene having 1 to 5 carbon atoms, more preferably a linear alkylene having 1 to 3 carbon atoms, and most preferably a linear alkylene having 2 carbon atoms.

[0086] Specific examples of the compound represented by the above formula (3) include polytrimethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polypentamethylene glycol di(meth)acrylate, polyhexamethylene glycol di(meth)acrylate, and the like.

[0087] From the viewpoint of achieving both photochromism and hardness, and further considering the viscosity of the resulting curable composition, etc., the number-average molecular weight of the component (A-1) represented by the formula (3) is preferably 200 or more and 9000 or less, more preferably 200 or more and 7000 or less, still more preferably 200 or more and 6000 or less, and most preferably 250 or more and 5000 or less. The number-average molecular weight of the component (A-1) may be 400 or more and 1500 or less, or may be 600 or more and 1000 or less.

[0088] If a component (A-1) in which a1 and e1 are 0 and b1 and d1 are 1 or more, that is, a component (A-1) further containing a second alkyleneoxy unit, is used, there is a tendency to obtain a cured product having high functionality of the functional pigment. b1 and d1 may be 2 or more and 15 or less, or may be 4 or more and 10 or less.

[0089] Specific examples of such component (A-1) are described below.

[0090]

[0091] In addition, the component (A-1) can be a monomer in which a1, b1, d1, and e1 are 1 or more, that is, further having both a second alkyleneoxy unit and a third alkyleneoxy unit. At this time, the second alkyleneoxy unit and the third alkyleneoxy unit have different structures from each other.

[0092] Specific examples of such component (A-1) are described below.

[0093]

[0094] The component (A-1) can be produced, for example, by the following method.

[0095] The (A-1) component having an acryloyl group can be synthesized by esterification of the following polyol compound with acrylic acid. In the following polyol compound, R 2 , R 3 , R 4 , R 5 , R 6 , a1, b1, c1, d1, and e1 have the same meanings as in formula (I).

[0096]

[0097] Specifically, in the presence of an inorganic acid such as sulfuric acid or hydrochloric acid, an organic acid such as an aromatic sulfonic acid, or a Lewis acid such as boron fluoride etherate, the above polyol compound dissolved in a solvent such as toluene and acrylic acid are stirred while heating as needed, and the water generated is removed by azeotropic distillation to cause a reaction. It should be noted that in the esterification reaction, as a method for removing water, a method of removing water using a desiccant such as anhydrous magnesium sulfate or molecular sieve, or a method of removing water in the presence of a dehydrating agent represented by dicyclohexylcarbodiimide can be cited.

[0098] In addition, it can also be synthesized by carrying out an esterification reaction using an acryloyl halide. Specifically, a method such as stirring the above polyol compound and acrylic acid dissolved in an ether solvent such as tetrahydrofuran while heating as needed in the presence of a base such as pyridine or dimethylaniline to remove the generated hydrogen halide can be adopted.

[0099] Furthermore, it can also be synthesized by carrying out a transesterification reaction with an ester compound such as acrylic anhydride or methyl acrylate. Specifically, a method such as stirring the above polyol compound and acrylic acid dissolved in a solvent such as toluene while heating as needed in the presence of an acidic catalyst such as an aromatic sulfonic acid or a basic catalyst such as sodium acetate or pyridine can be adopted.

[0100] The component (A-1) having a methacryloyl group can be synthesized in the same manner as described above by using methacrylic acid instead of acrylic acid.

[0101] Among the above polyol compounds, a polyol compound in which a1 and e1 are 0 and b1 and d1 are 1 or more, that is, a polyol having a second alkyleneoxy unit can be synthesized, for example, by the following method.

[0102] By reacting H-(OCH2CH2R 4 )c-OH with a cyclic ether compound such as ethylene oxide and propylene oxide, a polyol having a second alkyleneoxy unit can be synthesized. A polyol compound having a second alkyleneoxy unit can be synthesized, for example, by reacting in a nitrogen-purged autoclave in the presence of a catalyst such as an alkali metal hydroxide such as potassium hydroxide under high temperature and high pressure.

[0103] Among the above polyol compounds, a polyol compound in which a1, b1, d1, and e1 are 1 or more, that is, the component (A-1) further containing second and third alkyleneoxy units can be synthesized, for example, by the following method.

[0104] A polyol compound having a third alkyleneoxy unit is synthesized by reacting a polyol compound having a second alkyleneoxy unit with a cyclic ether compound, and the component (A-1) further containing second and third alkyleneoxy units can be synthesized by reacting the obtained polyol compound having a third alkyleneoxy unit with acrylic acid or methacrylic acid in the same manner as the method described above.

[0105] <The second radically polymerizable monomer having three or more (meth)acryloyl groups in one molecule>

[0106] The curable composition of the embodiment may further contain a second radically polymerizable monomer having three or more (meth)acryloyl groups in one molecule. Hereinafter, the second radically polymerizable monomer having three or more (meth)acryloyl groups in one molecule is also referred to as the component (A-2). If a polyfunctional (meth)acrylate is contained, the hardness of the cured product tends to increase.

[0107] Examples of the component (A-2) include polyfunctional (meth)acrylates represented by the following formula (Ia), polyfunctional (meth)acrylates having a urethane bond, and polyfunctional (meth)acrylates not belonging to the foregoing. Particularly preferred is the polyfunctional (meth)acrylate represented by the following formula (Ia).

[0108] <The polyfunctional (meth)acrylate represented by the following formula (Ia)>

[0109]

[0110] In formula (Ia), Q 10 is methylene. a1 is an integer of 0 or 1.

[0111] Q 11 is a linear or branched alkylene group having 1 or more and 3 or less carbon atoms. Q 11 is preferably a linear alkylene group. Q 11 is preferably an alkylene group having 2 or 3 carbon atoms. Q 11 More preferably, it is ethylene, n-propylene group or n-butylene group.

[0112] a2 is 0, 1, 2 or 3. a2 is preferably 1, 2 or 3.

[0113] Q 12 is a hydrogen atom or a methyl group. Q 12 is preferably a methyl group.

[0114] Q 13 is an organic group having a valence of 3 to 6 and 1 to 10 carbon atoms. As the Q 13 shown organic group, a group derived from a polyol, a hydrocarbon group having a valence of 3 to 6, and an organic group containing a urethane bond having a valence of 3 to 6 can be mentioned. Q 13 is preferably a tetravalent hydrocarbon group or a hexavalent hydrocarbon group. Q 13 can be a group derived from trimethylolpropane, a group derived from glycerol, a group derived from pentaerythritol, a group derived from ditrimethylolpropane or a group derived from dipentaerythritol.

[0115] a3 is 3, 4, 5 or 6. a3 is preferably 3 or 4.

[0116] The polyfunctional (meth)acrylate represented by formula (Ia) more preferably contains a 3- to 4-functional (meth)acrylate represented by the following formula (II).

[0117]

[0118] In formula (II), Q 20 , Q 21 , Q 22 and Q 23 are each independently methylene. a4, a5, a6 and a7 are each independently an integer of 0 or 1.

[0119] Q 24 , Q 25 and Q 26 are each independently a monovalent group represented by the following formula (III).

[0120]

[0121] In formula (III), Q 11 , Q 12 , a2 have the same meanings as in formula (Ia).

[0122] Q 24 , Q 25 and Q 26 may have structures different from each other or may have the same structure. Q 24 , Q 25 and Q 26 preferably have the same structure.

[0123] Q 27 is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms, or a monovalent group represented by formula (III). Q 27 Preferably, it is a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a monovalent group represented by formula (III).

[0124] Specific examples of the polyfunctional (meth)acrylate represented by the above formula (Ia) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, bis-trimethylolpropane tetramethacrylate, bis-trimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, glycerol trimethacrylate, glycerol triacrylate, ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, butoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, butoxylated trimethylolpropane triacrylate, ethoxylated glycerol trimethacrylate, propoxylated glycerol trimethacrylate, butoxylated glycerol trimethacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, butoxylated glycerol triacrylate, ethoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetramethacrylate, butoxylated pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, and butoxylated pentaerythritol tetraacrylate, etc.

[0125] <Polyfunctional (meth)acrylate having a urethane bond>

[0126] The polyfunctional (meth)acrylate having a urethane bond has a structure different from that of the urethane (meth)acrylate represented by the formula (1). The polyfunctional (meth)acrylate having a 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 hydroxyl group-containing (meth)acrylate. The polyfunctional (meth)acrylate having a urethane bond is preferably a polyfunctional (meth)acrylate having a urethane bond and 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), and U-15HA (molecular weight 2,300, number of functional groups 15) manufactured by Shin-Nakamura Chemical Co., Ltd. can be cited.

[0127] <Not belonging to the aforementioned polyfunctional (meth)acrylate>

[0128] As polyfunctional (meth)acrylates other than the polyfunctional (meth)acrylate represented by the formula (Ia) and the polyfunctional (meth)acrylate having a urethane bond, compounds obtained by modifying the terminals of a polyester compound with a (meth)acryloyl group can be cited. As such polyester (meth)acrylate compounds, various polyester (meth)acrylate compounds having different molecular weights of the polyester compound as a raw material and different modification amounts of the (meth)acryloyl group are commercially available, and they can be used. Specifically, 4-functional polyester oligomers (molecular weight 2,500 to 3,500, Daicel-UCB, EB80, etc.), 6-functional polyester oligomers (molecular weight 6,000 to 8,000, DAICEL-ALLNEX LTD., EB450, etc.), 6-functional polyester oligomers (molecular weight 45,000 to 55,000, DAICEL-ALLNEX LTD., EB1830, etc.), 4-functional polyester oligomers (especially the first industrial pharmaceutical company with a molecular weight of 10,000, GX8488B, etc.) can be cited.

[0129] <(A-3) Other radically polymerizable monomers having a (meth)acryloyl group>

[0130] As other radically polymerizable monomers having a (meth)acryloyl group, radically polymerizable monomers having a (meth)acryloyl group in the molecular structure and not belonging to (A-1) and (A-2) are not particularly limited, and known radically polymerizable monomers can be used, and it can also include bifunctional (meth)acrylates having 2 (meth)acryloyl groups in the molecule and monofunctional (meth)acrylates having only 1 (meth)acryloyl group.

[0131] 2-functional (meth)acrylate having two (meth)acryloyl groups in the molecule

[0132] The curable composition of the embodiment may contain the 2-functional (meth)acrylate shown below. If a 2-functional (meth)acrylate other than the first radically polymerizable compound is included, the functionality of the functional pigment can be improved. Specifically, examples thereof include 2-functional (meth)acrylates represented by the following formula (4), the following formula (5), or formula (6), 2-functional (meth)acrylates having a urethane bond, and 2-functional (meth)acrylates not belonging to the foregoing.

[0133] 2-functional (meth)acrylate compound represented by the following formula (4)

[0134]

[0135] R 12 and R 13 Each is a hydrogen atom or a methyl group. j and k are each independently 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 (4) is mostly obtained in the form of a mixture in production. Therefore, j + k is 2 or more on average, preferably 2 or more and 50 or less on average.

[0136] Specific examples of the compound represented by the above formula (4) are as follows.

[0137] 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.

[0138] 2-functional (meth)acrylate represented by the following formula (5)

[0139]

[0140] R 14 and R 15 Each is a hydrogen atom or a methyl group. R 16 and R 17 Each is a hydrogen atom or a methyl group.

[0141] A is a divalent organic group. A is a linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group optionally having a halogen or an alkyl group having 1 to 5 carbon atoms as a substituent, a cycloalkylene group, a bicycloalkylene group, a tricycloalkylene group, or a group represented by any of the following formulas.

[0142]

[0143]

[0144] In the above formulas, R 18A , R 18B are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. xx and xy are 0 to 4 or 0 to 10. Ring X is a benzene ring or a cyclohexane ring. YY is -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, -C(CH3)(C6H5)-, or any of the groups represented by the following formulas.

[0145]

[0146] l and m are each an integer of 1 or more, and the average value of l + m is 2 or more and 30 or less.

[0147] As specific examples of the bifunctional (meth)acrylate represented by the above formula (5), for example, the following bisphenol A di(meth)acrylates can be cited.

[0148] 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis(4-(methacryloyldipropoxy)phenyl)propane, 2,2-bis[4-(acryloyldiethoxy)phenyl]propane, 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane, 1,3-adamantanediol dimethacrylate, di(trishydroxymethyl)cyclodecane diacrylate.

[0149] <The bifunctional (meth)acrylate represented by the following formula (6)>

[0150]

[0151] R 19 and R 20 are each a hydrogen atom or a methyl group.

[0152] n is a number of 1 to 20 on average.

[0153] B and B’ are each independently a linear or branched alkylene group having 2 to 15 carbon atoms. B and B’ may be the same or different from each other. When there are multiple Bs, the multiple Bs may be the same group or different groups.

[0154] The bifunctional (meth)acrylate shown in the above formula (6) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0155] Here, examples of the polycarbonate diol used include the following polycarbonate diols. 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 diglycol (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).

[0156] <Bifunctional (meth)acrylate having a urethane bond>

[0157] The bifunctional (meth)acrylate having a urethane bond has a structure different from that of the urethane (meth)acrylate shown in formula (1). As the bifunctional (meth)acrylate having a urethane bond, it is obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the molecule, a polyol compound having two or more hydroxyl groups in the molecule, and a hydroxyl group-containing (meth)acrylate.

[0158] 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 cited.

[0159] As the polyol, polyalkylene glycols having repeating units of ethylene oxide, propylene oxide, or hexylene oxide with 2 to 4 carbon atoms, or polyester diols such as polycaprolactone diol can be cited. In addition, polycarbonate diol, polybutadiene diol, 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-cyclohexanedimethanol, glycerin, trimethylolpropane, etc. can also be exemplified.

[0160] In addition, a reaction mixture obtained by further reacting a urethane prepolymer formed by the reaction of these polyisocyanate and polyol with 2-hydroxy(meth)acrylate, a urethane (meth)acrylate monomer which is a reaction mixture obtained by directly reacting the aforementioned diisocyanate with 2-hydroxy(meth)acrylate, etc. can also be used.

[0161] As the hydroxy-containing (meth)acrylate, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. can be cited.

[0162] As the bifunctional (meth)acrylate having a urethane bond, commercially available products can be used without any limitation. For example, as the commercially available products, 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 LTD. can be cited.

[0163] <Not belonging to the aforementioned bifunctional (meth)acrylate>

[0164] It is also possible to cite difunctional (meth)acrylates containing a sulfur atom. The sulfur atom preferably forms part of the molecular chain in the form of a thioether group. Specifically, bis(2-methacryloyloxyethyl thioethyl) sulfide, bis(methacryloyloxyethyl) sulfide, bis(acryloyloxyethyl) sulfide, 1,2-bis(methacryloyloxyethyl thio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethyl thioethyl) sulfide, bis(2-acryloyloxyethyl thioethyl) sulfide, 1,2-bis(methacryloyloxyethyl thioethyl thio)ethane, 1,2-bis(acryloyloxyethyl thioethyl thio)ethane, 1,2-bis(methacryloyloxyisopropyl thioisopropyl) sulfide, 1,2-bis(acryloyloxyisopropyl thioisopropyl) sulfide can be cited.

[0165] The above difunctional (meth)acrylate compounds can be used alone with each of the components described separately, or multiple components can be used. In addition, multiple components described separately can be used in combination. In the case of using multiple components or multiple combinations, the reference mass is the total measurement of the multiple components.

[0166] <The third radically polymerizable monomer having one (meth)acryloyl group in one molecule>

[0167] The curable composition of the embodiment can further contain a third radically polymerizable monomer having one (meth)acryloyl group in one molecule. The third radically polymerizable monomer can be a monofunctional (meth)acrylate.

[0168] As the monofunctional (meth)acrylate, the monofunctional (meth)acrylate represented by the following formula (7) can be cited.

[0169]

[0170] In the above formula (7), R 21 is a hydrogen atom, methyldimethoxysilyl, trimethoxysilyl, glycidyl, pentamethylpiperidyl, 2,2,6,6-tetramethylpiperidyl or piperidyl. R 22 is a hydrogen atom or a methyl group. o is an integer from 0 to 10. p is an integer from 0 to 20.

[0171] R 21 is preferably methyldimethoxysilyl, trimethoxysilyl or glycidyl. When a monofunctional acrylate having such a functional group is included, there is a tendency for the adhesion between the cured product and the substrate to be improved.

[0172] When specifically showing the monofunctional (meth)acrylate shown in the above formula (7), examples thereof include 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.

[0173] <Other radically polymerizable monomers>

[0174] The curable composition of the embodiment may further contain other radically polymerizable monomers. As long as it is a radically polymerizable monomer capable of polymerizing with the component (A-1), there is no particular limitation, and known radically polymerizable monomers can be used. For example, radically polymerizable polyrotaxanes, radically polymerizable silsesquioxane compounds, allyl-based compounds, and vinyl-based compounds are preferably used.

[0175] <Radically polymerizable polyrotaxane>

[0176] A polyrotaxane has a composite molecular structure composed of an axle molecule and a plurality of cyclic molecules that encapsulate the axle molecule. Bulky end groups are formed at both ends of the axle molecule to prevent the cyclic molecules from falling off the axle molecule. A radically polymerizable polyrotaxane is a polyrotaxane in which a radically polymerizable group is introduced into the side chain of the cyclic molecule. The radically polymerizable group is introduced, for example, by modifying 1 mol% or more and less than 100 mol% of the hydroxyl groups of the cyclic molecule into radically polymerizable groups. The modification ratio can be calculated by (the number of moles of the introduced polymerizable group) / (the total number of OH groups in the side chain) × 100. It should be noted that from the viewpoints of adhesion, the mechanical strength of the obtained cured product, and functionality, the modification ratio is preferably 10 mol% or more and 95 mol% or less.

[0177] When the weight average molecular weight of the axle molecule is too large, there is a tendency for the 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 cyclic molecules to decrease. The weight average molecular weight of the axle molecule is preferably in the range of 1,000 to 100,0000, more preferably in the range of 5,000 to 80,000, and most preferably in the range of 8,000 to 50,000.

[0178] The cyclic molecule is preferably a cyclodextrin ring, a crown ether ring, a benzo crown ring, a dibenzo crown ring, or a dicyclohexano crown ring, particularly preferably a cyclodextrin ring or a crown ether ring, and most preferably a cyclodextrin ring. Further, in the cyclodextrin ring, there are an α-form (inner ring diameter: 0.45 to 0.6 nm), a β-form (inner ring diameter: 0.6 to 0.8 nm), and a γ-form (inner ring diameter: 0.8 to 0.95 nm). The α-cyclodextrin ring and the β-cyclodextrin ring are preferred, and the α-cyclodextrin ring is most preferred. When the inclusion number when all cyclic molecules are introduced into the shaft molecule is set to 1, the inclusion number of the cyclic molecule is preferably in the range of 0.001 to 0.6, more preferably in the range of 0.002 to 0.5, and most preferably in the range of 0.003 to 0.4.

[0179] As the radically polymerizable group, when considering the reactivity with other polymerizable monomers, etc., a (meth)acryloyl group is preferred. The number of radically polymerizable groups is not particularly limited, and is preferably 0 to 5000 in one molecule.

[0180] The above-mentioned polyrotaxane having a (meth)acryloyl group is described in International Publication No. 2018 / 030257.

[0181] <Sesquisiloxane radically polymerizable compound>

[0182] The sesquisiloxane radically polymerizable compound has various molecular structures such as a cage-like structure, a ladder-like structure, and a random structure, and has a radically polymerizable group such as a (meth)acryloyl group.

[0183] As an example of such a sesquisiloxane polymerizable compound, a compound represented by the following formula (8) can be cited.

[0184]

[0185] In the formula, q is the degree of polymerization and is an integer of 3 to 100.

[0186] A plurality of Rs 23 may be the same or different from each other and are a radically polymerizable group, an organic group containing a radically polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group. At least one of the plurality of Rs 23 is a radically polymerizable group or an organic group containing a radically polymerizable group. 23 Here, as R

[0187] 23 ​Examples of the radical polymerizable group or the organic group containing a radical polymerizable group include (meth)acryloyl group; organic groups having a (meth)acryloyl group such as (meth)acryloyloxypropyl group and (3-(meth)acryloyloxypropyl)dimethylsiloxy group; allyl group; organic groups having an allyl group such as allylpropyl group and allylpropyldimethylsiloxy group; vinyl group; organic groups having a vinyl group such as vinylpropyl group and vinyldimethylsiloxy group, etc.

[0188] <Allyl-based polymerizable compound>

[0189] Examples of the allyl-based polymerizable compound having an allyl group include the following compounds. Diethylene glycol diallyl carbonate, methoxypolyethylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether, phenoxypolyethylene glycol allyl ether, vinyloxypolyethylene glycol allyl ether, styryloxypolyethylene glycol allyl ether, methoxypolyethylene dithiol allyl sulfide.

[0190] <Vinyl-based polymerizable compound>

[0191] Examples of the vinyl-based polymerizable compound having a vinyl group include methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinylcyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, 1,3-divinyl-1,1,3,3-tetramethylpropanedisiloxane, diethylene glycol divinyl ether, divinyl adipate, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl sulfide, dimethyldivinylsilane, 1,2,4-trivinylcyclohexane, methyltrivinylsilane, α-methylstyrene and α-methylstyrene dimer, etc.

[0192] <Blending ratio in the curable composition>

[0193] In the curable composition of the embodiment, the proportion of the urethane (meth)acrylate represented by the formula (1) is, for example, 10% by mass or more and 99% by mass or less. When this proportion is high, there is a tendency for the performance of the functional pigment in the cured product to improve. This proportion may be 35% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. On the other hand, if this proportion is too high, there is a tendency for the hardness of the cured product to decrease. This proportion is preferably 90% by mass or less, more preferably 80% by mass or less.

[0194] In the curable composition of the embodiment, the proportion of the first radically polymerizable monomer is preferably 15% by mass or more. When this proportion is high, there is a tendency for the performance of the functional pigment in the cured product to improve. This proportion is more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, if this proportion is too high, there is a tendency for the hardness of the cured product to decrease. This proportion is preferably 90% by mass or less, and more preferably 80% by mass or less.

[0195] From the aspect of improving the hardness of the cured product, the curable composition of the embodiment preferably further contains a second radically polymerizable monomer. The proportion of the second radically 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, when this proportion is too high, there is a tendency for the performance of the functional pigment in the cured product to decrease. This proportion is preferably 85% by mass or less, more preferably 50% by mass or less, and further preferably 35% by mass or less.

[0196] From the aspect of improving the adhesion of the cured product, the curable composition of the embodiment preferably contains a third radically polymerizable monomer. The proportion of the third radically 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, when this proportion is too high, there is a tendency for the performance of the functional pigment in the cured product to decrease. This proportion is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less.

[0197] In the curable composition of the embodiment, the content of the di(meth)acrylate other than the urethane (meth)acrylate and the first radically polymerizable monomer represented by the formula (1) is preferably 70% by mass or less. That is, when the content of the di(meth)acrylate such as (meth)acrylate having an alkyleneoxy chain with 2 or less carbon atoms and polyalkylene carbonate polyol di(meth)acrylate is large, the performance of the functional pigment in the cured product may decrease. The content of the di(meth)acrylate other than the urethane (meth)acrylate and the first radically polymerizable monomer represented by the formula (1) is more preferably 30% by mass or less, and further preferably 20% by mass or less. The lower limit value of this content is 0% by mass according to one example, and 5% by mass or more according to another example. In particular, it is preferable that the content of (poly)ethylene glycol di(meth)acrylate is 30% by mass or less. The content of (poly)ethylene glycol di(meth)acrylate is preferably 20% by mass or less, and more preferably 10% by mass or less. The lower limit value of this content is 0% by mass according to one example, and 5% by mass or more according to another example.

[0198] In the curable composition containing the first to third radically polymerizable monomers, the content of the first radically polymerizable monomer is 40% by mass or more and 80% by mass or less, the content of the second radically polymerizable monomer is 10% by mass or more and 40% by mass or less, the content of the third radically polymerizable monomer is 1% by mass or more and 10% by mass or less, and the balance can be the ratio of the functional pigment and the additive.

[0199] In the curable composition of the embodiment, the proportion of the acrylate is preferably 50% by mass or more. When this proportion is high, there is a tendency to obtain a cured product with high functionality of the functional pigment. This proportion is preferably 60% by mass or more. The upper limit value of this proportion is 80% by mass or less according to one example and 70% by mass or less according to another example.

[0200] The ratio M10 / M3 of the mass M10 of the urethane (meth)acrylate represented by the formula (1) to the mass M3 of the second radically polymerizable monomer is preferably 0.1 or more and 20 or less. If a curable composition having a ratio M10 / M3 within this range is used, there is a tendency for the performance and hardness of the functional pigment of the cured product to be further improved. The ratio M10 / M3 is more preferably 0.5 or more and 10 or less, and further preferably 1 or more and 5 or less.

[0201] The ratio M10 / M4 of the mass M10 of the urethane (meth)acrylate represented by the formula (1) to the mass M4 of the third radically polymerizable monomer is preferably 0.1 or more and 50 or less. If a curable composition having a ratio M10 / M4 within this range is used, there is a tendency for the performance and hardness of the functional pigment of the cured product to be further improved. The ratio M10 / M4 is more preferably 0.5 or more and 10 or less, and further preferably 1 or more and 5 or less.

[0202] The ratio M1 / M4 of the mass M1 of the first radically polymerizable monomer to the mass M4 of the third radically polymerizable monomer is preferably 0.1 or more and 50 or less. If a curable composition having a ratio M1 / M4 within this range is used, there is a tendency for the performance and hardness of the functional pigment of the cured product to be further improved. The ratio M1 / M4 is more preferably 1 or more and 30 or less, and further preferably 5 or more and 15 or less.

[0203] The urethane (meth)acrylate represented by the formula (1), the component (A-1), the component (A-2), and the component (A-3) are collectively referred to as the component (A). When the component (A) is 100 parts by mass, the urethane (meth)acrylate can be 15 to 100 parts by mass, can be 20 to 95 parts by mass, can be 30 to 95 parts by mass, or can be 35 to 90 parts by mass.

[0204] The content of component (A-1) can be 15 to 100 parts by mass, can be 20 to 95 parts by mass, can be 30 to 95 parts by mass, or can be 35 to 90 parts by mass.

[0205] When compounding component (A-2), when the content of component (A-1) is 100 parts by mass, the content of component (A-2) can be 1 to 500 parts by mass, can be 1 to 300 parts by mass, can be 3 to 300 parts by mass, or can be 5 to 250 parts by mass.

[0206] When further containing component (A-3), when the content of component (A) is 100 parts by mass, the content of component (A-3) can be 0.01 to 20 parts by mass, can be 0.1 to 17 parts by mass, or can be 0.5 to 15 parts by mass.

[0207] <(B) Functional pigment>

[0208] The functional pigment includes a compound having an ability to selectively absorb visible light, and a compound that develops color, fades, or changes color by energy such as light, heat, an electric field, or pressure. Such a functional pigment can exhibit 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.

[0209] The ratio M10 / M2 of the mass M10 of the urethane (meth)acrylate represented by formula (1) to the mass M2 of the functional pigment is, for example, 10 or more and 10000 or less. This ratio M10 / M2 is preferably 15 or more and 1000 or less, and more preferably 20 or more and 100 or less.

[0210] The content of the functional pigment in the curable composition is, for example, 0.01% by mass or more and 10% by mass or less. 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.

[0211] <Photochromic compound>

[0212] The photochromic compound is used in a compounding amount capable of obtaining desired photochromic properties. Relative to 100 parts by mass of component (A), it is preferably used in an amount of 0.01 to 10 parts by mass.

[0213] This compounding amount is preferably adjusted to an optimal compounding amount according to the intended use.

[0214] Specifically, when the curable composition containing a photochromic compound is formed into a thin film such as a coating film, for example, a thin film of about 100 μm (a polymer film formed by polymerization of the photochromic curable composition), the hue can be adjusted by blending 0.1 to 10 parts by mass of the photochromic compound with respect to 100 parts by mass of the polymerizable compound.

[0215] In addition, when a thick cured product (a polymer molded body formed by polymerization of the photochromic curable composition) is formed, for example, in the case of a cured product having a thickness of 1 mm or more, the hue can be adjusted by blending 0.01 to 1 part 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 imparted to the thick cured product.

[0216] There are no restrictions on the photochromic compound, and known compounds can be used. They can be used alone or in combination of two or more. As such photochromic compounds, representative compounds are chromene compounds, fulgide compounds, fulgimide compounds, and spirooxazine compounds.

[0217] Among these photochromic compounds, chromene compounds and spirooxazine compounds are preferably used. Chromene compounds are particularly preferred. Chromene compounds include compounds having a 1-benzopyran skeleton, spiropyran compounds having a spiropyran skeleton, and naphthopyran compounds having a naphthopyran skeleton.

[0218] The naphthopyran compound preferably includes compounds 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).

[0219]

[0220] 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 fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to these rings. Ring AA may also be absent.

[0221] Ring AB is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to these rings.

[0222] R 24 and R 25 are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure.

[0223] As a substituent, it is 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 is 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).

[0224] -Q 1 -(P 1 Q 2 ) aa -P 2 Q 3 (15)

[0225] Q 1 is an alkylene group optionally containing a halogen atom in the substituent. Q 2 is an alkylene group optionally containing a halogen atom in the substituent. Q 3 is an alkyl group optionally containing a halogen atom in the substituent. P 1 and P 2 each independently is O, S, NR 700 , PR 701 or P(=O). R 700 is a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an aryl group optionally having a substituent, or a heteroaryl group optionally having a substituent. R 701 is a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an aryl group optionally having a substituent, or a heteroaryl group optionally having a substituent. aa is 0 or 1 or more and 10 or less.

[0226] M is CR 26 R 27 , SiR 26 R 27 , GeR 26 R 27 or NR 26 . R 26 and R 27 each independently is a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure.

[0227] As a substituent, it is preferably at least one selected from the group consisting of 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 aralkyloxy 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 the group represented by the above formula (15).

[0228] In addition, when R 26 and R 27 form a ring structure together, it is preferably an aliphatic ring having 3 to 20 carbon atoms in the ring, a fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to the aliphatic ring, a heterocyclic ring having 3 to 20 ring atoms, or a fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to the heterocyclic ring.

[0229]

[0230] In formula (10), R 1000 , R 1001 and R 1002 are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The substituents may be the same as the groups described in formula (9). mm is 1 to 10.

[0231]

[0232] In formula (11), R 1003 , R 1004 and R 1005 are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The substituents may be the same as the groups described in formula (9). nn is 1 to 10.

[0233]

[0234] In formula (12), R 1006 , R 1007 and R 1008 are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The substituents may be the same as the groups described in formula (9). oo is 1 to 12.

[0235]

[0236] In formula (13), R 1009 , R 1010 and R 1011Each independently represents a hydrogen atom or a substituent, and two or more substituents may bond to form a ring structure. The substituent may be the same type of group as the group described in Formula (9). pp is an integer from 1 to 12.

[0237]

[0238] In Formula (14), R 1012 , R 1013 and R 1014 each independently represents a hydrogen atom or a substituent, and two or more substituents may bond to form a ring structure. The substituent may be the same type of group as the group described in Formula (9). qq is an integer from 1 to 12.

[0239] The naphthopyran compound includes an indeno[2,1-f]naphtho[1,2-b]pyran compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton. The indeno[2,1-f]naphtho[1,2-b]pyran compound preferably has an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.

[0240] The indeno[2,1-f]naphtho[1,2-b]pyran compound preferably includes a compound represented by the following Formula (16).

[0241]

[0242] In the formula, R 24 , R 25 , R 26 and R 27 are the same as above.

[0243] r is an integer from 0 to 4. s is an integer from 0 to 4. When r is 2 to 4, the plurality of R 28 may be the same as or different from each other. When s is 2 to 4, the plurality of R 29 may be the same as or different from each other. Further, when r is 2 to 4 and there are adjacent R 28 , two adjacent R 28 may together with the carbon atom bonded to these R 28 form a ring optionally containing at least one heteroatom selected from an oxygen atom, a carbon atom, a sulfur atom, and a nitrogen atom, and further the ring may have a substituent. Further, when s is 2 to 4 and there are adjacent R 29 , two adjacent R 29 may together with the carbon atom bonded to these R 29 form a ring optionally containing at least one heteroatom selected from an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and further the ring may have a substituent.

[0244] R 28 and R 29Each independently is a group represented by formula (15), a hydroxyl group, an alkyl group, a haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, an optionally substituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an optionally substituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an optionally substituted aralkyl group, an optionally substituted aralkoxy group, an optionally substituted aryloxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a mercapto group, an alkoxyalkylthio group, a haloalkylthio group, or an optionally substituted cycloalkylthio group, an optionally substituted silyl group, an optionally substituted oxysilyl group, a group represented by the following formula (17) or L1-R 400 The group shown.

[0245]

[0246] 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. When G is an oxygen atom or a sulfur atom, R 201 is a group other than a hydrogen atom.

[0247] R 400 is a hydrogen atom, an alkyl group, an aryl group, a substituted silyl group, a polymer group or a photochromic group. The substituent of the silyl group is an alkyl group, an alkoxy group or an aryl group. L1 is a group represented by the following formula (18).

[0248]

[0249] 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. In formula (18), L is an oxygen atom or a sulfur atom. R 300 is an alkylene group, or a silylene 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 from 1 to 200. The units of multiple i may be the same or different. The dashed line represents the bond to R 400 .

[0250] <Other additives>

[0251] In the curable composition, various known compounding agents can be compounded within a range that does not impair the effects. The compounding agents include, for example, various stabilizers such as mold release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances. In addition, a solvent and a leveling agent can also be compounded. Mercaptans such as tert-dodecyl mercaptan can be compounded as a polymerization regulator.

[0252] <Ultraviolet stabilizer>

[0253] If an ultraviolet stabilizer is used in combination, the durability of the photochromic compound can be further improved, and thus it is preferably compounded. As the ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, and a sulfur-based antioxidant can be preferably used. As the hindered amine light stabilizer, there is no particular limitation. Especially from the aspect of preventing the deterioration of the photochromic compound, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is preferred. In addition, hindered amine-based light stabilizers commercially available under the trade names Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-87, etc. by ADEKA Corporation can also be preferably used.

[0254] Hindered phenol antioxidants are preferred in terms of preventing the deterioration of the photochromic compound. For example, 2,6-di-tert-butyl-4-methylphenol, IRGANOX245 manufactured by BASF Japan Ltd.: ethylenebis(oxyethylene)bis[3,5-di-tert-butyl-4-hydroxy-m-tolyl]propionate, IRGANOX1076 manufactured by BASF Japan Ltd.: octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, IRGANOX1010 manufactured by BASF Japan Ltd.: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and IRGANOX1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, etc. manufactured by BASF Japan Ltd. can also be cited.

[0255] The amount of such an ultraviolet stabilizer used is not particularly limited as long as the effects are not impaired, and is usually in the range of 0.001 to 10 parts by mass, particularly 0.01 to 1 part by mass, relative to 100 parts by mass of the curable composition.

[0256] <Polymerization initiator>

[0257] There are thermal polymerization initiators and photopolymerization initiators for the polymerization initiator, and specific examples thereof are described below.

[0258] As thermal polymerization initiators, examples include: diacyl peroxides: benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide,

[0259] peroxyesters: tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, cumyl peroxypivalate, tert-butyl peroxybenzoate,

[0260] peroxycarbonates: diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, azo compounds: azobisisobutyronitrile;

[0261] etc.

[0262] As photoinitiators, examples include acetophenone-based compounds: 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,

[0263] α-dicarbonyl-based compounds: 1,2-diphenylethane-1,2-dione, methyl phenylglyoxylate,

[0264] acylphosphine oxide-based compounds: 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, methyl 2,4,6-trimethylbenzoyl diphenylphosphonate, 2,6-dichlorobenzoyl diphenylphosphine oxide, 2,6-dimethoxybenzoyl diphenylphosphine oxide.

[0265] It should be noted that when using photoinitiators, known polymerization and curing promoting aids such as tertiary amines can also be used in combination.

[0266] <Surfactant>

[0267] When adding a surfactant, the wettability to the optical substrate and the primer layer can be improved, and the occurrence of appearance defects can be prevented. As surfactants, known surfactants such as silicone surfactants having a silicone chain (polyalkylsiloxane unit) as a hydrophobic group and fluorosurfactants having a fluorocarbon chain can be cited. When using surfactants, two or more kinds can be mixed and used. Furthermore, it can be a surfactant capable of polymerizing with component (A), or a surfactant incapable of polymerizing.

[0268] Examples of silicone surfactants and fluorosurfactants that can be preferably used in specific examples include L-7001, L-7002, L-7604, FZ-2123, FZ-2110 manufactured by DowToray Co., Ltd., MEGAFAC F-470, MEGAFAC F-1405, MEGAFAC F-479 manufactured by DIC Corporation, Fluorad FC-430 manufactured by 3M Japan Ltd., TEGORAD2100, TEGORAD2300 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 Co., Ltd., KR-513, X-22-2445, X-40-9296, X-22-164, X-22-164A, X-22-164B, X-22-164C, X-22-164E, etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0269] <Ultraviolet absorber>

[0270] As the ultraviolet absorber, known ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, benzoate compounds, cinnamate compounds, and oxanilide compounds can be used. Cyanoacrylate compounds, benzophenone compounds, benzotriazole compounds, and cinnamate compounds are particularly preferred. With respect to 100 parts by mass of the curable composition containing the photochromic compound and the polymerizable compound, the above ultraviolet stabilizer is preferably used in the range of 0.001 to 5 parts by mass.

[0271] <Cured product>

[0272] The cured product is obtained by curing the curable composition. The curing of the curable composition is carried out by causing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, γ-rays, LEDs, heat, or a combination of both. That is, depending on the type of the polymerizable monomer and the polymerization curing accelerator used and the form of the cured product formed, an appropriate curing means can be adopted. In the case of forming a laminate by the coating method described later, photopolymerization is preferably adopted for the reason of obtaining a uniform film thickness.

[0273] When thermally polymerizing a curable composition compounded with a polymerizable compound, the thermal polymerization temperature affects the properties of the resulting cured product. This temperature condition is affected by the type and amount of the thermal polymerization initiator and the type of the polymerizable compound, and thus cannot be generally defined. However, a method of initiating polymerization at a relatively low temperature and gradually increasing the temperature is usually preferred. The polymerization time also varies depending on various factors like the temperature, and thus it is preferred to pre-determine the optimal time corresponding to these conditions. However, conditions are usually selected such that the polymerization is completed within 2 to 48 hours. When obtaining a photochromic laminate, polymerization is preferably carried out at a temperature at which the reaction between the polymerizable functional groups proceeds. At this time, the optimal temperature and time are determined so as to achieve the target molecular weight.

[0274] In addition, when photopolymerizing the curable composition, among the polymerization conditions, particularly the UV intensity affects the properties of the resulting photochromic cured product. This illuminance condition is affected by the type and amount of the photopolymerization initiator and the type of the polymerizable monomer, and thus cannot be generally defined. However, conditions are usually selected such that UV light with a wavelength of 365 nm is irradiated for 0.5 to 5 minutes at 50 to 500 mW / cm 2 .

[0275] The bioplastic degree of the cured product is preferably 10% by mass or more. The bioplastic degree can be calculated by the method according to ISO standard 16620-3. The bioplastic degree of the cured product is preferably 30% by mass or more, more preferably 40% by mass or more. There is no particular upper limit for this bioplastic degree. According to one example, it is 100% by mass or less, and according to another example, it is 80% by mass or less.

[0276] <Laminate>

[0277] According to another embodiment, a laminate is provided. The laminate includes an optical substrate and the cured product of the embodiment located on the surface of the optical substrate. The optical substrate includes resins such as diallyl carbonate resin, urethane resin, and thiourethane resin, for example. 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 urethane resin.

[0278] The bioplastic degree of the optical substrate is preferably 25% by mass or more. The bioplastic degree can be calculated by the method according to ISO standard 16620-3. The bioplastic degree of the optical substrate is preferably 30% by mass or more, more preferably 40% by mass or more. There is no particular upper limit for this bioplastic degree. According to one example, it is 100% by mass or less, and according to another example, it is 80% by mass or less.

[0279] 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 the main surface of the primer layer 1. The functional resin layer 12 contains the cured product of the embodiment. The optical substrate 11 is a convex meniscus lens having an uneven shape.

[0280] <Optical article>

[0281] The cured product of the embodiment can be widely used as an optical article. For example, it can be used as various storage materials, copying materials, photosensitive members for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, etc., which can replace silver salt photosensitive materials, as well as lenses. The lens is suitable for glasses. A photochromic cured product containing a photochromic compound can also be used as a photochromic lens material, an optical filter material, a display material, a light meter, a decorative material, etc.

[0282] The cured product of the embodiment is particularly suitable for photochromic lens applications. The photochromic lens is suitable as a lens for glasses such as sunglasses. As long as the manufacturing method of the photochromic lens can obtain uniform light control performance, a known method can be adopted.

[0283] In the case where photochromism is exhibited by a kneading method, the above-mentioned curable composition is injected between glass molds held by an elastomeric gasket or spacer, and depending on the types of the polymerizable compound and the polymerization curing accelerator, casting polymerization is carried out by heating in an air furnace, irradiation with active energy rays such as ultraviolet rays, whereby a photochromic cured product formed in the form of an optical material such as a lens can be obtained.

[0284] In the case where photochromism is exhibited by a lamination method, a coating solution is prepared by appropriately dissolving the curable composition in an organic solvent, the coating solution is coated on the surface of an optical substrate such as a lens substrate by spin coating, dipping, etc., and the organic solvent is removed by drying. Then, polymerization curing is carried out by UV irradiation, heating, etc. in an inert gas such as nitrogen, whereby a photochromic layer formed of a photochromic cured product is formed on the surface of the optical substrate (coating method).

[0285] In addition, an optical substrate such as a lens substrate is disposed opposite to a glass mold so as to form a predetermined gap, the curable composition is injected into the gap, and in this state, casting polymerization using an inner mold is carried out by polymerization curing by UV irradiation, heating, etc., and a photochromic layer composed of a photochromic cured product can also be formed on the surface of the optical substrate (casting polymerization method).

[0286] When forming a photochromic layer on the surface of an optical substrate by the above-described lamination method (coating method and casting polymerization method), the adhesion between the photochromic layer and the optical substrate can also be improved by previously subjecting the surface of the optical substrate to chemical treatment using an alkali solution, an acid solution, etc., or physical treatment using corona discharge, plasma discharge, polishing, etc. Of course, a transparent adhesive resin layer may be provided on the surface of the optical substrate.

[0287] In addition, the cured product formed from the curable composition can be post-processed according to its use. Examples of the post-processing include dyeing using a dye such as a disperse dye, lamination of a protective layer containing a urethane resin, an epoxy resin, etc., formation of a hard coating film of a hard coat agent mainly composed of a silane coupling agent and a sol of silicon, zirconium, antimony, aluminum, tin, tungsten, etc., formation of a thin film by vapor deposition of a metal oxide such as SiO2, TiO2, ZrO2, antireflection treatment of a thin film formed by coating an organic polymer, antistatic treatment, etc.

[0288] Examples

[0289] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. The description of each component and the evaluation method, etc. are as follows.

[0290] <Each component>

[0291] (A) component

[0292] (UA)

[0293] UA-PTMG65: urethane acrylate of the following formula

[0294]

[0295] UMA-PTMG100 and UMA-BioPTMG100: urethane methacrylate of the following formula

[0296]

[0297] UMA-EG-PTMG65: urethane methacrylate of the following formula

[0298]

[0299] UMA-PEGTMG160: urethane methacrylate of the following formula

[0300]

[0301] UMA-PEGPGTMG80: urethane methacrylate of the following formula (where d + h = 7, e + g = 4)

[0302]

[0303] UMA - PPG90: Carbamate methacrylate of the following formula

[0304]

[0305] UMA - PTMG130: Carbamate methacrylate of the following formula

[0306]

[0307] UMA - BioPTMG200: Carbamate methacrylate of the following formula

[0308]

[0309] UMA - PTMG65: Carbamate methacrylate of the following formula

[0310]

[0311] (A - 1)

[0312] M - PTMG65: Polytetramethylene glycol dimethacrylate (average molecular weight 803)

[0313] M - PTMG65Bio: Polytetramethylene glycol dimethacrylate using polytetramethylene glycol with a biomass content of 95% by mass (average molecular weight 803, biomass content 76.8% by mass)

[0314] M - PTMG100: Polytetramethylene glycol dimethacrylate (average molecular weight 1156)

[0315] M - PTMG100Bio: Polytetramethylene glycol dimethacrylate using polytetramethylene glycol with a biomass content of 95% by mass (average molecular weight 1171, biomass content 82.5% by mass)

[0316] (A - 2)

[0317] TMPT: Trimethylolpropane trimethacrylate

[0318] M - DTMP: Di(trimethylolpropane) tetramethacrylate

[0319] M - TMMT: Pentaerythritol tetramethacrylate

[0320] A - DPEHA: Dipentaerythritol hexaacrylate

[0321] M-TMMT-80: A mixture of trimethylolpropane trimethacrylate and pentaerythritol tetramethacrylate at a weight ratio of 18:82

[0322] A-TMMT-43: A mixture of trimethylolpropane triacrylate and pentaerythritol tetraacrylate at a weight ratio of 57:43

[0323] A-TMMT: Pentaerythritol tetraacrylate

[0324] (A-3)

[0325] TSL: γ-Methacryloxypropyltrimethoxysilane

[0326] 9G: Polyethylene glycol dimethacrylate (average molecular weight 550)

[0327] 14G: Polyethylene glycol dimethacrylate (average molecular weight 770)

[0328] APC56: Dimethacrylate of polycarbonate diol obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (average molecular weight 606)

[0329] MPCD56: Dimethacrylate of polycarbonate diol obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (average molecular weight 634)

[0330] LA82: 1,2,2,6,6-Pentamethyl-4-piperidyl methacrylate

[0331] (Other radically polymerizable monomers)

[0332] RX-1: Polyrotaxane having an acryloyl group

[0333] According to the method described in International Publication No. WO2018 / 030257, a polyrotaxane having an acryloyl group satisfying the following characteristics was synthesized.

[0334] The weight-average molecular weight Mw (GPC) of the polyrotaxane (RX-1) having an acryloyl group: 180,000.

[0335] The modification ratio of the acryloyl group in the side chain: 80 mol%.

[0336] The ratio of OH groups remaining in the side chain: 20 mol%.

[0337] The axle molecule: Linear polyethylene glycol (PEG) with a molecular weight of 11,000.

[0338] The inclusion ring: The inclusion ratio of α-cyclodextrin (α-CD) is 0.25.

[0339] The end of the axle molecule: capped with adamantane.

[0340] Introduced into the side chain of the inclusion ring; the (average) molecular weight of the side chain is about 500.

[0341] The number of acryloyl groups per molecule: about 90.

[0342] The weight-average molecular weight Mw of the polyrotaxane (RX-1) was measured by gel permeation chromatography (GPC method). As the apparatus, a liquid chromatography apparatus (manufactured by Waters Corporation, Japan) was used. As the columns, two TSKgel SuperHM-M (exclusion limit molecular weight: 4,000,000, manufactured by Tosoh Corporation) were used in series.

[0343] In addition, tetrahydrofuran was used as the developing solution, and the measurement was carried out under the conditions of a flow rate of 0.6 ml / min and a temperature of 40°C. Polystyrene was used as the standard sample, and the weight-average molecular weight was obtained by comparison conversion. As a result, the weight-average molecular weight of RX-1 was 180,000.

[0344] SO-1: A silsesquioxane having a methacryloyl group and having the following characteristics.

[0345] The number of methacrylate groups per molecule: 20.

[0346] Weight-average molecular weight: 4,800.

[0347] In addition, SO-1 was synthesized by the following method. First, 248 g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate was added with 248 ml of ethanol and 54 g (3.0 mol) of water, and 0.20 g (0.005 mol) of sodium hydroxide as a catalyst was added, and the reaction was carried out at 30°C for 3 hours. After 1 confirmation of the disappearance of the raw materials by 1H-NMR, it was neutralized with dilute hydrochloric acid, 174 ml of toluene, 174 ml of heptane and 174 g of water were added, and the aqueous layer was removed. Then, the organic layer was washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain SO-1. It should be noted that by 29 Si-NMR, it was confirmed that SO-1 was a mixture of a cage structure, a ladder structure and a random structure.

[0348] The weight-average molecular weight Mw of SO-1 was measured by gel permeation chromatography (GPC method). As the apparatus, a liquid chromatography apparatus (manufactured by Waters Corporation, Japan) was used. As the columns, three columns 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.

[0349] In addition, tetrahydrofuran was used as the eluent, and the measurement was carried out under the conditions of 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 obtained by comparison conversion.

[0350] (Component (B))

[0351] PC1: The compound represented by the following formula.

[0352]

[0353] (Other compounding agents)

[0354] (Stabilizer)

[0355] HALS: Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate

[0356] HP: Ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] (manufactured by BASF Japan Ltd., Irganox 245).

[0357] (Photoinitiator)

[0358] PI: Phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (manufactured by IGM Company, Omnirad 819)

[0359] Example 1

[0360] (Synthesis of UA-PTMG65)

[0361] 65 g of polytetramethylene ether glycol with a molecular weight of 650 determined from the hydroxyl value was added with 250 mL of dehydrated toluene, and azeotropic dehydration was carried out. After distilling off 50 mL of toluene from the toluene solution after azeotropic dehydration, the solution was cooled to 60 °C. 19.5 mg of p-methoxyphenol and 6.5 mg of dibutyltin dilaurate were added to the cooled solution. 13.9 g of 2-acryloyloxyethyl isocyanate was slowly added dropwise to the solution. After the addition, the reaction was carried out at 60 °C - 65 °C for 10 hours to obtain a reaction solution. 100 mL of water was added to the reaction solution, and liquid separation was carried out. Siliceous cerite was added to the obtained organic layer, stirred, and then filtered. The obtained organic layer was concentrated to obtain UA-PTMG65.

[0362] The proton nuclear magnetic resonance spectrum of the obtained concentrate was measured, and as a result, a peak of about 36H based on tetramethyleneoxy was shown around δ 1.0 - 2.0 ppm, a peak of about 44H based on tetramethyleneoxy and ethyleneoxy was shown around δ 3.0 - 4.5 ppm, and a peak of 6H of protons based on acryloyl was shown around δ 5.5 - 6.5 ppm.

[0363] (Manufacture of photochromic curable composition)

[0364] First, each component was prepared according to the following formulation.

[0365] (Component (A))

[0366] (Component (UA)): 63 parts by mass of UA-PTMG65.

[0367] (Component (A-2)): 31.4 parts by mass of TMPT.

[0368] (Component (A-3)): 5.6 parts by mass of TSL.

[0369] (Component (B)): 1.6 parts by mass of PC1.

[0370] (Other compounding agents)

[0371] (Polymerization initiator): 0.3 parts by mass of PI.

[0372] (Stabilizer): 1 part by mass of HP. 3 parts by mass of HALS.

[0373] After all the compounds corresponding to component (A) were mixed, component (B) and other additives were mixed therein to obtain a mixture. 1000 ppm of a leveling agent L7001 manufactured by Dow Corning Toray Co., Ltd. was added to the obtained mixture and mixed to obtain a photochromic curable composition.

[0374] (Manufacture of optical article)

[0375] Using the photochromic curable composition, a photochromic laminate is obtained by a lamination method of polymerization as follows.

[0376] First, as an optical substrate, a thiocarbamate-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 is prepared. It should be noted that the thiocarbamate-based plastic lens is previously subjected to alkali etching with a 5% aqueous sodium hydroxide solution at 50 °C for 5 minutes, and then thoroughly washed with distilled water.

[0377] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curable primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) is coated on the surface of the above plastic lens at a rotational speed of 70 rpm for 15 seconds, and then coated at 700 rpm for 10 seconds. Then, about 1 g of the above-obtained photochromic curable composition is spin-coated to make the film thickness of the photochromic coating 40 μm.

[0378] In a nitrogen atmosphere, using a metal halide lamp with an output power of 200 mW / cm 2 The lens having the photochromic curable composition (photochromic coating) coated on its surface is irradiated with light for 90 seconds to cure the coating film. Then, it is further heated at 90 °C for 1 hour to produce a photochromic laminate having a photochromic layer.

[0379] Evaluation is carried out according to the following evaluation method, and the results are shown in Table 5.

[0380] <Evaluation method>

[0381] The obtained photochromic laminate is evaluated by the method shown below.

[0382] (1) Photochromic properties

[0383] [1] Maximum absorption wavelength (λmax):

[0384] The maximum absorption wavelength after color development obtained by a spectrophotometer (instantaneous multi-channel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd. is used as an index of the hue at the time of color development.

[0385] [2] Color development concentration at 23 °C (A 23 ):

[0386] It is the difference between the absorbance {ε(240)} after 240 seconds of light irradiation at 23 °C and the absorbance ε(0) without light irradiation at the above maximum absorption wavelength, and is used as an index of the color development concentration. The higher this value, the more excellent the photochromic property can be said to be.

[0387] [3]Half-life of fading at 23 °C [τ1 / 2 (sec.)]:

[0388] (3) After irradiating the sample with light for 300 seconds at 23 °C and then stopping the light irradiation, the time required for the absorbance of the sample at the aforementioned maximum absorption wavelength to decrease to 1 / 2 of {ε(300) - ε(0)} is used as an index of the fading rate. The shorter this time, the faster the fading rate.

[0389] (2) Vickers hardness

[0390] The Vickers hardness was measured using a micro-Vickers hardness tester PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A tetrahedral diamond indenter was used, and the measurement was carried out under the conditions of a load of 10 gf and a holding time of the indenter of 30 seconds. The measurement results were measured a total of 4 times, and the average value of a total of 3 times after removing the first value with a large measurement error was used to represent.

[0391] (3) Crack evaluation

[0392] Twenty photochromic laminates were produced, and the presence or absence of cracks was visually confirmed, and the cracks were evaluated according to the following criteria.

[0393] A: No cracks were observed in all 20 photochromic laminates.

[0394] B: One photochromic laminate with cracks was observed among the 20 photochromic laminates.

[0395] C: Among the 20 photochromic laminates, there were 1 to more than 3 photochromic laminates with cracks observed.

[0396] D: Among the 20 photochromic laminates, there were more than 5 photochromic laminates with cracks observed in a part of the surface.

[0397] Comparative Examples 1 to 4, Examples 2 to 30

[0398] Except for using the photochromic curable compositions described in Tables 1 to 4, photochromic cured products were produced in the same manner as in Example 1 and evaluated according to the same evaluation items. The results are shown in Tables 5 to 8.

[0399] The urethane (meth)acrylate used in Tables 1 to 4 was synthesized by the following method.

[0400] (Synthesis of UMA-PTMG100)

[0401] Referring to the method of Reference Example 1, polytetramethylene glycol with a molecular weight of 1001 was used instead of polytetramethylene glycol with a molecular weight of 650, and 2-methylacryloyloxyethyl isocyanate was used instead of 2-acryloyloxyethyl isocyanate. Otherwise, the reaction was carried out in the same manner to synthesize UMA-PTMG100. The proton nuclear magnetic resonance spectrum of the obtained UMA-PTMG100 was measured, and as a result, peaks of about 61H based on tetramethyleneoxy and methyl were shown near δ1.0 to 2.0 ppm, peaks of about 63H based on tetramethyleneoxy and ethyleneoxy were shown near δ3.0 to 4.5 ppm, and peaks of 4H of protons based on methacryloyl were shown near δ5.5 to 6.5 ppm.

[0402] (Synthesis of UMA-EG-PTMG65)

[0403] Referring to the method of Reference Example 1, 2-(2-methylacryloyloxyethyloxy)ethyl isocyanate was used instead of 2-acryloyloxyethyl isocyanate. Otherwise, the reaction was carried out in the same manner to synthesize UMA-EG-PTMG65.

[0404] The proton nuclear magnetic resonance spectrum of the obtained UMA-EG-PTMG65 was measured, and as a result, peaks of about 42H based on tetramethyleneoxy and methyl were shown near δ1.0 to 2.0 ppm, peaks of about 52H based on tetramethyleneoxy were shown near δ3.0 to 4.5 ppm, and peaks of 4H of protons based on methacryloyl were shown near δ5.5 to 6.5 ppm.

[0405] (Synthesis of UMA-PEGTMG160)

[0406] Instead of polytetramethylene glycol with a molecular weight of 1000, the polyol represented by the following formula was used, and otherwise, the reaction was carried out in the same manner as UMA-PTMG100 to synthesize UMA-PEGTMG160.

[0407]

[0408] The proton nuclear magnetic resonance spectrum of the obtained UMA-PEGTMG160 was measured, and as a result, peaks of about 62H based on tetramethyleneoxy and methyl were shown near δ1.0 to 2.0 ppm, peaks of about 120H based on tetramethyleneoxy and ethyleneoxy were shown near δ3.0 to 4.5 ppm, and peaks of 4H of protons based on methacryloyl were shown near δ5.5 to 6.5 ppm.

[0409] (Synthesis of UMA-PEGPGTMG80)

[0410] Instead of polytetramethylene glycol with a molecular weight of 1000, a polyol represented by the following formula was used, and the reaction was carried out in the same manner as UMA-PTMG100 to synthesize UMA-PEGPGTMG80.

[0411]

[0412] (In the formula, d + h = 7, e + g = 4)

[0413] The proton nuclear magnetic resonance spectrum of the obtained UMA-PEGPGTMG80 showed peaks of about 30H based on tetramethyleneoxy and methyl near δ 1.0 - 2.0 ppm, peaks of about 60H based on tetramethyleneoxy, ethyleneoxy, and propyleneoxy near δ 3.0 - 4.5 ppm, and peaks of 4H of protons based on methacryloyl near δ 5.5 - 6.5 ppm.

[0414] (Synthesis of UMA-PPG90)

[0415] Instead of polytetramethylene glycol with a molecular weight of 1000, polypropylene glycol with a molecular weight of 900 was used, and the reaction was carried out in the same manner as UMA-PTMG100 to synthesize UMA-PPG900. The proton nuclear magnetic resonance spectrum of the obtained UMA-PPG90 showed peaks of about 37H based on propyleneoxy and methyl near δ 1.0 - 2.0 ppm, peaks of about 70H based on propyleneoxy and ethyleneoxy near δ 3.0 - 4.5 ppm, and peaks of 4H of protons based on methacryloyl near δ 5.5 - 6.5 ppm.

[0416] (Synthesis of UMA-BioPTMG100)

[0417] Instead of polytetramethylene glycol with a molecular weight of 1000, polytetramethylene glycol with a biomass content of 95% by mass and a molecular weight of 1035 was used, and the reaction was carried out in the same manner as UMA-PTMG100 to synthesize UMA-BioPTMG100 (biomass content 76.1% by mass). The proton nuclear magnetic resonance spectrum of the obtained UMA-BioPTMG100 showed peaks of about 62H based on tetramethyleneoxy and methyl near δ 1.0 - 2.0 ppm, peaks of about 64H based on tetramethyleneoxy and ethyleneoxy near δ 3.0 - 4.5 ppm, and peaks of 4H of protons based on methacryloyl near δ 5.5 - 6.5 ppm.

[0418] (Synthesis of UMA-PTMG130)

[0419] UMA-PTMG130 was synthesized by reacting in the same manner as UMA-PTMG100, except that polytetramethylene glycol with a molecular weight of 1302 was used instead of polytetramethylene glycol with a molecular weight of 1000. The proton nuclear magnetic resonance spectrum of the resulting UMA-PTMG130 showed a peak at approximately 77H at around δ1.0-2.0 ppm, attributed to tetramethyleneoxy groups and methyl groups; a peak at approximately 79H at around δ3.0-4.5 ppm, attributed to tetramethyleneoxy groups and ethyleneoxy groups; and a peak at approximately 4H at around δ5.5-6.5 ppm, attributed to the protons of the methacryloyl group.

[0420] (Synthesis of UMA-BioPTMG200)

[0421] UMA-BioPTMG200 (biomass 82.3% by mass) was synthesized by the same reaction as for UMA-PTMG100, except that polytetramethylene glycol with a biomass content of 95% by mass and a molecular weight of 2015 was used instead of polytetramethylene glycol with a molecular weight of 1000. The proton nuclear magnetic resonance spectrum of the resulting UMA-BioPTMG200 showed a peak at approximately 117H at δ1.0-2.0 ppm, a peak at approximately 119H at δ3.0-4.5 ppm, and a peak at approximately 4H at δ5.5-6.5 ppm, attributed to the protons of the methacryloyl group.

[0422] (Synthesis of UMA-PTMG65)

[0423] UMA-PTMG65 was synthesized by the same reaction as in Example 1, except that 2-methacryloyloxyethyl isocyanate was used instead of 2-acryloyloxyethyl isocyanate. The proton nuclear magnetic resonance spectrum of the resulting UMA-PTMG65 showed a peak at approximately 42H at around δ1.0-2.0 ppm, attributed to tetramethyleneoxy and methyl groups; a peak at approximately 44H at around δ3.0-4.5 ppm, attributed to tetramethyleneoxy and ethyleneoxy groups; and a peak at approximately 4H at around δ5.5-6.5 ppm, attributed to the protons of the methacryloyl group.

[0424] [Table 1]

[0425]

[0426] [Table 2]

[0427]

[0428] [Table 3]

[0429]

[0430] [Table 4]

[0431]

[0432] [Table 5]

[0433]

[0434] [Table 6]

[0435]

[0436] [Table 7]

[0437]

[0438] [Table 8]

[0439]

[0440] As can be seen from Table 1, when the curable composition of Example 1 is used, a cured product with particularly excellent color development concentration at 23°C can be obtained.

[0441] Hereinafter, preferred embodiments of the present invention are described. [1]

[0443] A urethane (meth) acrylate represented by the following formula (1):

[0444]

[0445] In the above formula (1),

[0446] Q 1 and Q 5 are each independently a hydrogen atom or a methyl group,

[0447] Q 2 and Q 4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0448] Q 3 is a divalent group represented by the following formula (1a),

[0449] a and b are each independently 0 or more and 10 or less,

[0450]

[0451] In the above formula (1a),

[0452] Q 6 and Q 10 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0453] Q 7 and Q 9 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is different from Q 6 and Q 10 which are different groups from each other.

[0454] Q 8 is an optionally substituted linear or branched alkylene group having 1 to 7 carbon atoms.

[0455] d and h are 0 or more and 10 or less.

[0456] e and g are 0 or more and 20 or less.

[0457] f is 2 or more and 100 or less. [2]

[0459] The urethane (meth) acrylate according to [1] is represented by the following formula (1b):

[0460]

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

[0462] Q 1 、Q 2 、Q 4 、Q 5 、Q 8 and f have the same meanings as in the aforementioned formula (1). [3]

[0464] A curable composition comprising the urethane (meth) acrylate according to [1] or [2] and a functional pigment. [4]

[0466] In the curable composition according to [3], the ratio M10 / M2 of the mass M10 of the aforementioned urethane (meth) acrylate to the mass M2 of the aforementioned functional pigment is 10 or more and 10,000 or less. [5]

[0468] In the curable composition according to [3] or [4], the content of the aforementioned urethane (meth) acrylate is 10% by mass or more and 99% by mass or less. [6]

[0470] The curable composition according to any one of [3] to [5] further comprises a first radically polymerizable monomer represented by the following formula (I).

[0471]

[0472] In the aforementioned formula (I),

[0473] R 1 and R 7 are each independently a hydrogen atom or a methyl group,

[0474] R 2 and R 6 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,

[0475] R 3 and R 5 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and are groups different from R 2 and R 6 respectively,

[0476] R 4 is a linear or branched alkylene group having 1 to 7 carbon atoms which may optionally have a substituent,

[0477] a1 and e1 are 0 or more and 10 or less,

[0478] b1 and d1 are 0 or more and 20 or less,

[0479] c1 is 2 to 100, and is a number larger than each of a1, b1, d1, and e1. [7]

[0481] The curable composition according to any one of [3] to [6] further contains a second radically polymerizable monomer having 3 or more (meth)acryloyl groups in one molecule. [8]

[0483] In the curable composition according to [7], the aforementioned second radically polymerizable monomer contains a polyfunctional (meth)acrylate represented by the following formula (Ia),

[0484]

[0485] In the aforementioned formula (Ia),

[0486] R 8 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,

[0487] R 9 is a hydrogen atom or a methyl group,

[0488] R 10 is a 3- to 6-valent organic group having 1 to 10 carbon atoms,

[0489] i1 is 0 to 3,

[0490] h1 is 3 to 6. [9]

[0492] The curable composition according to [7] or [8], wherein the content of the aforementioned second radically polymerizable monomer is 1% by mass or more and 85% by mass or less.

[10]

[0494] The curable composition according to any one of [7] to [9], wherein the ratio M10 / M3 of the mass M10 of the aforementioned urethane (meth)acrylate to the mass M3 of the aforementioned second radically polymerizable monomer is 0.1 or more and 20 or less.

[11]

[0496] The curable composition according to any one of [3] to

[10] , further comprising a third radically polymerizable monomer having 1 (meth)acryloyl group in one molecule.

[12]

[0498] The curable composition according to

[11] , wherein the content of the aforementioned third radically polymerizable monomer is 0.1% by mass or more and 20% by mass or less.

[13]

[0500] The curable composition according to

[11] or

[12] , wherein the ratio M10 / M4 of the mass M10 of the aforementioned urethane (meth)acrylate to the mass M4 of the aforementioned third radically polymerizable monomer is 0.1 or more and 50 or less.

[14]

[0502] The curable composition according to any one of [3] to

[13] , wherein the content of (poly)ethylene glycol di(meth)acrylate is 30% by mass or less.

[15]

[0504] The curable composition according to any one of [3] to

[14] , wherein the aforementioned functional pigment contains at least 1 compound selected from the group consisting of chromene compounds and spirooxazine compounds.

[16]

[0506] A cured product obtained by curing the curable composition according to any one of [3] to

[15] .

[17]

[0508] A laminate comprising an optical substrate and the cured product according to

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

[18]

[0510] An optical article comprising the cured product according to

[16] .

[19]

[0512] A lens, which contains the cured product described in

[16] .

[20]

[0514] A pair of glasses, which contains the lens described in

[19] .

[21]

[0516] The cured product described in

[16] , whose bioplastic degree obtained by the method according to ISO standard 16620-3 is 10% by mass or more.

[22]

[0518] The laminate described in

[17] or

[18] , whose bioplastic degree of the aforementioned optical substrate obtained by the method according to ISO standard 16620-3 is 25% by mass or more.

Claims

1. A urethane (meth)acrylate represented by the following formula (1): In the formula (1), Q 1 and Q 5 each independently represents a hydrogen atom or a methyl group, Q 2 and Q 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 3 is a divalent group represented by the following formula (1a): a and b are each independently 0 or more and 10 or less, In the formula (1a), Q 6 、Q 7 、Q 9 and Q 10 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Q 6 and Q 7 are different groups from each other, Q 9 and Q 10 are different groups from each other, Q 8 is an optionally substituted linear or branched alkylene group having 1 to 7 carbon atoms, d and h are 0 or more and 10 or less, e and g are 0 or more and 20 or less, f is 2 or more and 100 or less.

2. The urethane (meth)acrylate according to claim 1, represented by the following formula (1b): In the formula (1b), Q 1 and Q 2 and Q 4 and Q 5 and Q 8 and f have the same meanings as in the foregoing formula (1).

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

4. The curable composition according to claim 3, wherein, The ratio M10 / M2 of the mass M10 of the urethane (meth)acrylate to the mass M2 of the functional pigment is 10 or more and 10,000 or less.

5. The curable composition according to claim 3, wherein, The content of the urethane (meth)acrylate is 10% by mass or more and 99% by mass or less.

6. The curable composition according to claim 3, further comprising a first radically polymerizable monomer represented by the following formula (I), In the formula (I), R 1 and R 7 each independently represents 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, and is different from R 2 and R 6 are different groups from each other, R 4 is an optionally substituted linear or branched alkylene group having 1 to 7 carbon atoms, a1 and e1 are 0 or more and 10 or less, b1 and d1 are 0 or more and 20 or less, c1 is 2 to 100 and is a number larger than each of a1, b1, d1, and e1.

7. The curable composition according to claim 3, further comprising a second radically polymerizable monomer having three or more (meth)acryloyl groups in one molecule.

8. The curable composition according to claim 7, wherein, The second radically polymerizable monomer includes a polyfunctional (meth)acrylate represented by the following formula (Ia), In the formula (Ia), Q 10 is methylene, Q 11 is a linear or branched alkylene group having 1 to 3 carbon atoms, Q 12 is a hydrogen atom or a methyl group, Q 13 is an organic group with a valence of 3 to 6 and 1 to 10 carbon atoms, a1 is 0 or 1, a2 is 0, 1, 2, or 3, a3 is 3, 4, 5, or 6.

9. The curable composition according to claim 7, wherein, The content of the second radically polymerizable monomer is 1% by mass or more and 85% by mass or less.

10. The curable composition according to claim 7, wherein, The ratio M10 / M3 of the mass M10 of the urethane (meth)acrylate to the mass M3 of the second radically polymerizable monomer is 0.1 or more and 20 or less.

11. The curable composition according to claim 3, further comprising a third radically polymerizable monomer having one (meth)acryloyl group in one molecule.

12. The curable composition according to claim 11, wherein, The content of the third radically polymerizable monomer is 0.1% by mass or more and 20% by mass or less.

13. The curable composition according to claim 11, wherein, The ratio M10 / M4 of the mass M10 of the urethane (meth)acrylate to the mass M4 of the third radically polymerizable monomer is 0.1 or more and 50 or less.

14. The curable composition according to claim 3, wherein, The content of (poly)ethylene glycol di(meth)acrylate is 30% by mass or less.

15. The curable composition according to claim 3, wherein, The functional pigment includes at least one compound selected from the group consisting of chromene compounds and spirooxazine compounds.

16. A cured product obtained by curing the curable composition according to claim 3.

17. A laminate comprising an optical substrate and the cured product according to claim 16 on the 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.

20. A pair of glasses comprising the lens according to claim 19.

21. The cured product according to claim 16, wherein the bioplastic degree obtained by the method based on ISO standard 16620-3 is 10% by mass or more.

22. The laminate according to claim 17, wherein the bioplastic degree of the optical substrate obtained by the method based on ISO standard 16620-3 is 25% by mass or more.

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