SOLIDIFYING PREPARATIONS, SOLIDIFYING OBJECTS, MULTILAYER SHEETS, OPTICAL INSTRUMENTS, LENSES, EYEGLASSES, AND OPTICAL-CHROMATIC INSTRUMENTS

Abstract

The invention proposes a curable composition capable of producing a cured object with superior functional and formal dyeing performance, and also proposes a cured object, a multilayer plate, an optical instrument, a lens, eyeglasses, and an optically colored instrument. The invention proposes a curable composition. The curable composition consists of a functional dye, first (met)acrylate, and second (met)acrylate. First (met)acrylate has an average molecular weight of 850 to 3000, and has three or more (met)acryloyl groups. Second (met)acrylate has an average molecular weight of 850 or greater, and has two (met)acryloyl groups.

Description

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

[0001] The present invention relates to a curable composition, a cured product, a laminate, an optical article, a lens, eyeglasses, and a photochromic optical article.

[0002] Photochromic compounds, such as naphthopyran compounds, fulgide compounds, and spirooxazine compounds, are compounds that can reversibly convert into two isomers with different absorption spectra upon irradiation with ultraviolet light, such as sunlight or light from a mercury lamp. Photochromic compounds have the property that when a colorless, bleached compound is irradiated with ultraviolet light, it isomerizes to a colored state and returns to its original color when the light irradiation is stopped and the compound is placed in a dark place. Taking advantage of this property, they are used in a variety of applications, particularly optical materials. For example, photochromic eyeglass lenses, which are imparted with photochromic properties by the use of a photochromic compound, quickly color and function as sunglasses outdoors where they are irradiated with ultraviolet light, such as sunlight, and fade and function as transparent, ordinary eyeglasses indoors where they are not irradiated with such light. Demand for such lenses has been increasing in recent years. Photochromic eyeglass lenses can be obtained, for example, by applying a photochromic curable composition to a plastic lens by spin coating or the like, followed by photocuring to form a photochromic coating layer.

[0003] Japanese Patent Laid-Open No. 10-338869 Japanese Patent Laid-Open No. 2015-025063 Japanese Patent Laid-Open No. 2017-052869 International Publication No. 2009 / 075388 International Publication No. 2021 / 241596

[0004] An object of the present invention is to provide a curable composition capable of realizing a cured product having excellent functional dye performance and appearance, and to provide a cured product, a laminate, an optical article, a lens, eyeglasses, and a photochromic optical article.

[0005] According to the present disclosure, there is provided a curable composition. The curable composition includes a functional dye, a first (meth)acrylate, and a second (meth)acrylate. The first (meth)acrylate has a number average molecular weight of 850 or more and 3,000 or less and has three or more (meth)acryloyl groups. The second (meth)acrylate has a number average molecular weight of 850 or more and has two (meth)acryloyl groups.

[0006] According to the present disclosure, a cured product is provided. The cured product is obtained by curing the curable composition according to an embodiment.

[0007] According to the present disclosure, there is provided a laminate, which includes an optical substrate and a resin layer including a cured body according to an embodiment.

[0008] According to the present disclosure, there is provided a laminate including an optical substrate, a primer layer including a urethane resin, and a resin layer including a cured body according to an embodiment laminated on the primer layer.

[0009] According to the present disclosure, an optical article is provided. The optical article includes a cured body according to an embodiment.

[0010] According to the present disclosure, a lens is provided, which includes a lens substrate and a cured body according to an embodiment located on a surface of the optical substrate.

[0011] According to the present disclosure, eyeglasses are provided, the eyeglasses including lenses according to an embodiment.

[0012] According to the present disclosure, there is provided a photochromic optical article, which, when measured according to a method in accordance with Japanese Industrial Standards T7333, has a luminous transmittance of 12% or less when colored in an atmosphere at 23°C, a difference in luminous transmittance between 23°C and 35°C when colored in an atmosphere at 23°C and 35°C being within 12%, and takes 400 seconds or less to reach a luminous transmittance of 70% when faded.

[0013] According to the present invention, there are provided a curable composition capable of realizing a cured product having excellent functional dye performance and appearance, as well as a cured product, a laminate, an optical article, a lens, eyeglasses, and a photochromic optical article.

[0014] FIG. 1 is a cross-sectional view schematically illustrating an example of a laminate according to an embodiment.

[0015] The curable composition according to the embodiment includes a functional dye, a first (meth)acrylate, and a second (meth)acrylate. The first (meth)acrylate has a number-average molecular weight of 850 or more and 3,000 or less, and has three or more (meth)acryloyl groups. The second (meth)acrylate has a number-average molecular weight of 850 or more and has two (meth)acryloyl groups. Here, the (meth)acryloyl group refers to at least one of an acryloyl group and a methacryloyl group. The (meth)acrylate refers to a compound having at least one of an acryloyl group and a methacryloyl group. By using such a curable composition, a cured product having excellent performance and appearance of the functional dye can be realized. The reason for this has not been clearly elucidated, but the present inventors believe it to be as follows.

[0016] First, functional dyes such as photochromic compounds include compounds that undergo structural changes due to energy such as light, resulting in color development, fading, or discoloration. For such functional dyes to easily undergo structural changes in a polymer solid matrix, it is important that sufficient soft segments are present in the polymer solid matrix. The second (meth)acrylate is thought to contribute to the formation of these soft segments because of its relatively high number-average molecular weight. However, as the proportion of di(meth)acrylate increases, the number of crosslinking points decreases, which can reduce the curability of the polymer solid matrix. Reduced curability can lead to poor appearance of the cured product obtained by curing this curable composition. Specifically, when a curable composition is applied to a substrate by spin coating or the like, a thick coating film may form a puddle around the periphery of the substrate. When a substrate having a relatively thin coating film in a central region and a peripheral region around the central region where a puddle is formed is cured, the coating film may not cure sufficiently in the peripheral region where the puddle is formed, resulting in wrinkled, poor appearance of the cured product. The curable composition according to the embodiment contains a first (meth)acrylate having a relatively high number average molecular weight and a functionality of three or more. Therefore, a polymer solid matrix with high crosslink density can be formed without impeding the formation of soft segments. Therefore, the cured product obtained by curing this curable composition can fully exhibit the performance of the functional dye and can achieve minimal appearance defects.

[0017] The curable composition according to the embodiment will be described in detail below.

[0018] <First (meth)acrylate> The first (meth)acrylate has a number average molecular weight of 850 or more and 3000 or less, and has three or more (meth)acryloyl groups. The number of (meth)acryloyl groups may be 3, 4, 5, 6, 7, or 8. The number average molecular weight of the first (meth)acrylate can be measured, for example, by gel permeation chromatography (GPC). From the viewpoint of enhancing the functionality of the cured body, the number average molecular weight of the first (meth)acrylate is preferably 950 or more, more preferably 1000 or more, and even more preferably 1100 or more. On the other hand, if the number average molecular weight of the first (meth)acrylate is excessively high, the fluidity of the first (meth)acrylate may decrease, which may result in deterioration in handling and coating properties. From this viewpoint, the number average molecular weight of the first (meth)acrylate is preferably 2500 or less, more preferably 2000 or less, and even more preferably 1500 or less.

[0019] In the curable composition, the proportion of the first (meth)acrylate is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more, from the viewpoint of improving the appearance of the cured body. In terms of improving the functionality of the cured body, the proportion of the first (meth)acrylate is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the first (meth)acrylate separated by silica gel column chromatography.

[0020] The first (meth)acrylate preferably has one or more methacryloyl groups, more preferably has two or more methacryloyl groups, and even more preferably has three or more methacryloyl groups. The presence of methacryloyl groups can suppress deterioration of the functional dye and tends to improve the appearance of the cured product.

[0021] The first (meth)acrylate preferably includes an alkylene oxide chain. Use of such a first (meth)acrylate tends to enhance the functionality of the cured body. The number of carbon atoms in the alkylene oxide chain is, for example, 1 or more and 10 or less, preferably 2 or more and 4 or less.

[0022] The raw material of the first (meth)acrylate may be a compound derived from a biological resource or a compound derived from a fossil resource. The first (meth)acrylate containing an alkylene oxide chain can be obtained by using, for example, a plant-derived polyol compound.

[0023] The first (meth)acrylate is preferably an acyclic (meth)acrylate that does not contain a cyclic structure such as an aromatic ring or an aliphatic ring. Use of such a first (meth)acrylate tends to enhance the functionality of the cured body.

[0024] The first (meth)acrylate may contain at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, and a carbonyl group. Preferably, the first (meth)acrylate does not contain any of the structures of an ester bond, a urethane bond, a urea bond, and a carbonyl group.

[0025] The first (meth)acrylate preferably contains a tri- to hexa-functional (meth)acrylate represented by the following formula (I):

[0026]

[0027] In formula (I), Q １０ is a linear or branched alkylene group having 1 to 3 carbon atoms. １０ is preferably a methylene group. a1 is 0 or 1.

[0028] Q １１ is a linear or branched alkylene group having 1 to 10 carbon atoms. １１ is preferably a linear alkylene group. １１ is preferably an alkylene group having 2 to 5 carbon atoms. １１is more preferably an ethylene group, an n-propylene group, or an n-butylene group.

[0029] a2 is a number of 3 or more and 15 or less. a2 is preferably a number of 5 or more and 10 or less.

[0030] Q １２ is a hydrogen atom or a methyl group. １２ is preferably a methyl group.

[0031] Q １３ is a trivalent to hexavalent organic group having 1 to 10 carbon atoms. １３ Examples of the organic group represented by Q include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and an organic group containing a trivalent to hexavalent urethane bond. １３ is preferably a tetravalent hydrocarbon group or a hexavalent hydrocarbon group. １３ may be a group derived from trimethylolpropane, a group derived from glycerin, a group derived from pentaerythritol, a group derived from ditrimethylolpropane, or a group derived from dipentaerythritol.

[0032] a3 is 3, 4, 5, or 6. a3 is preferably 3 or 4.

[0033] The first (meth)acrylate more preferably contains a tri- or tetrafunctional (meth)acrylate represented by the following formula (II):

[0034]

[0035] In formula (II), Q ２０ , Q ２１ , Q ２２ , and Q ２３ are each independently an alkylene group having 1 to 3 carbon atoms. ２０ , Q ２１ , Q ２２ , and Q ２３ is preferably a methylene group. a4, a5, a6, and a7 each independently represent 0 or 1.

[0036] Q ２４ , Q ２５ , and Q ２６are each independently a monovalent group represented by the following formula (III):

[0037]

[0038] In formula (III), Q １１ , Q １２ , a2 have the same meanings as in formula (I).

[0039] Q ２４ , Q ２５ , and Q ２６ may have different structures from each other or may have the same structure. ２４ , Q ２５ , and Q ２６ Preferably, the structures of the two compounds are the same.

[0040] Q ２７ Q is a hydrogen atom, a linear or branched alkyl group having from 1 to 5 carbon atoms, a linear or branched alkoxy group having from 1 to 5 carbon atoms, or a monovalent group represented by formula (III). ２７ is preferably a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a monovalent group represented by formula (III).

[0041] Specific examples of the polyfunctional (meth)acrylate represented by the above formula (I) include at least one selected from the group consisting of alkoxylated trimethylolpropane tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, alkoxylated ditrimethylolpropane (meth)acrylate, and alkoxylated dipentaerythritol (meth)acrylate.

[0042] The alkoxylated trimethylolpropane tri(meth)acrylate includes at least one selected from the group consisting of ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, butoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and butoxylated trimethylolpropane triacrylate.

[0043] The alkoxylated glycerin tri(meth)acrylate includes at least one selected from the group consisting of ethoxylated glycerin trimethacrylate, propoxylated glycerin trimethacrylate, butoxylated glycerin trimethacrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, and butoxylated glycerin triacrylate.

[0044] The alkoxylated pentaerythritol tetra(meth)acrylate includes at least one selected from the group consisting of ethoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetramethacrylate, butoxylated pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, and butoxylated pentaerythritol tetraacrylate.

[0045] The polyfunctional (meth)acrylate represented by formula (I) more preferably includes at least one selected from the group consisting of ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

[0046] The first (meth)acrylate may contain a polyfunctional (meth)acrylate having a urethane bond. The polyfunctional (meth)acrylate having a urethane bond is obtained by reacting a polyol compound having three or more hydroxyl groups in the molecule with a (meth)acrylate having one isocyanate group in the molecule. Alternatively, it can also be obtained by reacting a polyol compound having a urethane bond and three or more hydroxyl groups in the molecule with a (meth)acrylate. The polyfunctional (meth)acrylate having a urethane bond preferably has four or more (meth)acryloyl groups in the molecule. Commercially available products include U-6HA (molecular weight 1,019, manufactured by Shin-Nakamura Chemical Co., Ltd., functional group number 6) and U-15HA (molecular weight 2,300, manufactured by Shin-Nakamura Chemical Co., Ltd., functional group number 15).

[0047] The first (meth)acrylate may include a polyester (meth)acrylate compound obtained by modifying the end of a polyester compound with a (meth)acryloyl group. Various polyester (meth)acrylate compounds with different molecular weights of the raw polyester compound and different amounts of (meth)acryloyl group modification are commercially available, and these can be used. Specific examples include tetrafunctional polyester oligomers (molecular weight 2,500 to 3,500, Daicel-Allnex Corporation, EB80, etc.), hexafunctional polyester oligomers (molecular weight 6,000 to 8,000, Daicel-Allnex Corporation, EB450, etc.), hexafunctional polyester oligomers (molecular weight 45,000 to 55,000, Daicel-Allnex Corporation, EB1830, etc.), and tetrafunctional polyester oligomers (e.g., GX8488B, Dai-ichi Kogyo Seiyaku Co., Ltd., molecular weight 10,000).

[0048] <Second (meth)acrylate> The second (meth)acrylate has a number average molecular weight of 850 or more and is a di(meth)acrylate having two (meth)acryloyl groups. The number average molecular weight of the second (meth)acrylate can be measured, for example, by gel permeation chromatography (GPC). From the viewpoint of enhancing the functionality of the cured product, the number average molecular weight of the second (meth)acrylate is preferably 950 or more, more preferably 1000 or more, and even more preferably 1100 or more. On the other hand, if the number average molecular weight of the second (meth)acrylate is excessively high, the fluidity of the second (meth)acrylate may decrease, leading to solidification or deterioration in handling and coating properties. From this viewpoint, the number average molecular weight of the second (meth)acrylate is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2000 or less.

[0049] In the curable composition, the proportion of the second (meth)acrylate is preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more, from the viewpoint of improving the functionality of the cured body. In terms of improving the appearance of the cured body, the proportion of the second (meth)acrylate is preferably 75% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 55% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the second (meth)acrylate separated by silica gel column chromatography.

[0050] The ratio M1 / M2 of the mass M1 of the first (meth)acrylate to the mass M2 of the second (meth)acrylate is, for example, 0.1 or more and 2.0 or less. From the viewpoint of improving the appearance of the cured body, the ratio M1 / M2 is preferably 0.25 or more, more preferably 0.30 or more, even more preferably 0.40 or more, and particularly preferably 0.65 or more. From the viewpoint of improving the functionality of the cured body, the ratio M1 / M2 is preferably 1.7 or less, more preferably 1.50 or less, even more preferably 1.20 or less, and particularly preferably 1.00 or less.

[0051] The second (meth)acrylate preferably has one or more methacryloyl groups, and more preferably has two methacryloyl groups. The presence of methacryloyl groups tends to suppress deterioration of the functional dye and improve the appearance of the cured product.

[0052] The second (meth)acrylate preferably includes an alkylene oxide chain. Use of such a second (meth)acrylate tends to enhance the functionality of the cured product. The number of carbon atoms in the alkylene oxide chain is, for example, 1 or more and 10 or less, preferably 2 or more and 4 or less.

[0053] The raw material for the second (meth)acrylate may be a compound derived from a biological resource or a compound derived from a fossil resource. The second (meth)acrylate containing an alkylene oxide chain can be obtained, for example, from a plant-derived polyol compound. The biomass degree of the second (meth)acrylate is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The upper limit of the biomass degree is, for example, 100% by mass or less, or 98% by mass or less.

[0054] The second (meth)acrylate is preferably an acyclic (meth)acrylate that does not contain a cyclic structure such as an aromatic ring or an aliphatic ring. Use of such a second (meth)acrylate tends to enhance the functionality of the cured body.

[0055] The second (meth)acrylate may contain at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, and a carbonyl group. Preferably, the second (meth)acrylate does not contain any of the structures of an ester bond, a urethane bond, a urea bond, and a carbonyl group.

[0056] The second (meth)acrylate preferably contains a di(meth)acrylate represented by the following formula (1).

[0057]

[0058] In formula (1), R １ and R ７ are each independently a hydrogen atom or a methyl group. That is, the compound represented by formula (1) may be a diacrylate, a dimethacrylate, or a methacrylate acrylate. １ and R ７ is preferably a methyl group.

[0059] R ４ is a linear or branched alkylene group having 3 to 10 carbon atoms which may have a substituent. c is 2 to 100. c is a number larger than a, b, d, and e.

[0060] That is, the repeating unit -(OR ４ )- is a first alkylene oxide unit. The polymer portion formed by this repeating unit can form the soft segment of the cured product. ４ is preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 3 or more and 6 or less, and more preferably 4 or more and 5 or less. The greater the number of carbon atoms in the alkylene group, the greater the functionality of the cured body. On the other hand, if the number of carbon atoms in the alkylene group is too large, the amount of soft segments per unit mass decreases, which may reduce the functionality of the cured body.

[0061] From the viewpoint of achieving both functionality and hardness, c is preferably 5 to 85, more preferably 7 to 70, even more preferably 10 to 50, and particularly preferably 13 to 20.

[0062] 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. ２ , R ３ , R ５ , and R ６ are each independently preferably a hydrogen atom or a methyl group. ２ and R ３ are different groups. ５ and R ６ are different groups. ２ and R ６ may be the same group. ３ and R ５ may be the same group.

[0063] a and e each independently represent an integer of 0 to 10. From the viewpoint of achieving both functionality and hardness, a and e preferably represent an integer of 0 to 5, more preferably an integer of 0 to 2, even more preferably 0 or 1, and most preferably 0.

[0064] b and d each independently represent an integer of 0 to 20. From the viewpoint of achieving both functionality and hardness, b and d are preferably an integer of 0 to 15, more preferably an integer of 0 to 10, even more preferably an integer of 0 to 5, and most preferably 0.

[0065] In other words, the di(meth)acrylate represented by formula (1) may be a monomer further comprising at least one of a second alkylene oxide unit, which is a repeating unit having b and d attached thereto, and a third alkylene oxide unit, which is a repeating unit having a and e attached thereto.

[0066] The di(meth)acrylate represented by formula (1) preferably contains only first alkylene oxide units, where a, b, d, and e are all 0. The hardness of the cured product tends to increase when such a di(meth)acrylate represented by formula (1) is used. c may be 4 or more and 20 or less, or 6 or more and 15 or less.

[0067] Such a compound is represented, for example, by the following formula (3).

[0068]

[0069] In the above formula (3), R １ , R ７ , c has the same meaning as in formula (1).

[0070] R １１ is a linear alkylene group having 1 to 10 carbon atoms. １１ is preferably a linear alkylene group having 2 to 7 carbon atoms, more preferably a linear alkylene group having 3 to 5 carbon atoms, and most preferably a linear alkylene group having 4 carbon atoms.

[0071] 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, and polyhexamethylene glycol di(meth)acrylate.

[0072] When a di(meth)acrylate represented by formula (1) in which a and e are 0 and b and d are 1 or greater is used, i.e., a di(meth)acrylate represented by formula (1) further containing a second alkylene oxide unit, a cured product with high functionality of the functional dye tends to be obtained. b and d may be 2 or greater and 15 or less, or 4 or greater and 10 or less.

[0073] Specific examples of such di(meth)acrylates represented by formula (1) are as follows:

[0074]

[0075]

[0076] The di(meth)acrylate represented by formula (1) may be a monomer in which a, b, d, and e are each 1 or more, i.e., further comprising both a second alkylene oxide unit and a third alkylene oxide unit, wherein the second alkylene oxide unit and the third alkylene oxide unit have different structures.

[0077] Specific examples of such di(meth)acrylates represented by formula (1) are as follows:

[0078]

[0079] The di(meth)acrylate represented by formula (1) can be produced, for example, by the following method.

[0080] The diacrylate represented by formula (1) having an acryloyl group can be synthesized by esterification of a polyol compound represented by the following formula with acrylic acid. ２ , R ３ , R ４ , R ５ , R ６ , a, b, c, d and e have the same meanings as in formula (1).

[0081]

[0082] Specifically, the polyol compound and acrylic acid dissolved in a solvent such as toluene are stirred in the presence of a mineral 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 ether, while heating as necessary, and the resulting water is removed by azeotropy to cause the reaction. Examples of methods for removing water in the esterification reaction include a method using a drying agent such as anhydrous magnesium sulfate or molecular sieves, and a method in which water is removed in the presence of a dehydrating agent typified by dicyclohexylcarbodiimide.

[0083] Alternatively, the compound can be synthesized by esterification using an acrylic acid halide. Specifically, the polyol compound and acrylic acid dissolved in an ether solvent such as tetrahydrofuran are stirred in the presence of a base such as pyridine or dimethylaniline, with heating as necessary, and the resulting hydrogen halide is removed.

[0084] Furthermore, it can also be synthesized by a transesterification reaction with an ester compound such as acrylic anhydride or methyl acrylate. Specifically, a method can be employed in which the polyol compound and acrylic acid are dissolved in a solvent such as toluene in the presence of an acidic catalyst such as an aromatic sulfonic acid or a basic catalyst such as sodium acetate or pyridine, and then stirred while heating as necessary.

[0085] The compound represented by formula (1) having a methacryloyl group can be synthesized in the same manner as above, for example, by using methacrylic acid instead of acrylic acid.

[0086] Among the above polyol compounds, a polyol compound in which a and e are 0 and b and d are 1 or more, that is, a polyol having a second alkylene oxide unit, can be synthesized, for example, by the following method.

[0087] H-(OR ４A polyol having a second alkylene oxide unit can be synthesized by reacting c-OH with a cyclic ether compound such as ethylene oxide or propylene oxide. The polyol compound having a second alkylene oxide unit can be synthesized, for example, by carrying out the reaction in a nitrogen-substituted autoclave at high temperature and pressure in the presence of a catalyst such as an alkali metal hydroxide, e.g., potassium hydroxide.

[0088] Among the above polyol compounds, a polyol compound in which a, b, d, and e are 1 or more, i.e., a di(meth)acrylate represented by formula (1) further containing second and third alkylene oxide units, can be synthesized, for example, by the following method.

[0089] A polyol compound having a second alkylene oxide unit is reacted with a cyclic ether compound to synthesize a polyol compound having a third alkylene oxide unit, and the resulting polyol compound further having a third alkylene oxide unit is reacted with acrylic acid or methacrylic acid in the same manner as described above to synthesize a di(meth)acrylate represented by formula (1) further containing second and third alkylene oxide units.

[0090] The second (meth)acrylate may contain a di(meth)acrylate represented by the following formula (4).

[0091]

[0092] In the above formula (4), R １２ and R １３ are each independently a hydrogen atom or a methyl group. j and k are each independently an integer of 0 or greater, and j + k is an integer of 2 or greater. In addition, the di(meth)acrylate represented by formula (4) is often obtained as a mixture in production. Therefore, j + k is an integer of 2 or greater, and preferably an integer of 2 or greater and 50 or less, on average.

[0093] Specific examples of the compound represented by the above formula (4) are as follows:

[0094] Polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, dimethacrylate obtained from a polyol consisting of a copolymer of polyethylene glycol and polypropylene glycol, and diacrylate obtained from a polyol consisting of a copolymer of polyethylene glycol and polypropylene glycol.

[0095] The second (meth)acrylate may contain a di(meth)acrylate represented by the following formula (4').

[0096]

[0097] In the above formula (4′), R １２１ and R １３１ are each independently a hydrogen atom or a methyl group. j1, j2, and k1 are each independently an integer of 1 or greater. Furthermore, the di(meth)acrylate represented by formula (4') is often obtained as a mixture during production. Therefore, j1 + j2 + k1 has an average value of 3 or greater, and preferably an integer of 3 or greater and 50 or less on average. Specific examples of the bifunctional (meth)acrylate represented by formula (4') above include a dimethacrylate obtained from a polyol composed of a triblock copolymer having a polyethylene glycol structure at both ends of polypropylene glycol, and a diacrylate obtained from a polyol composed of a triblock copolymer having a polyethylene glycol structure at both ends of polypropylene glycol. The second (meth)acrylate may contain a di(meth)acrylate represented by formula (5) below.

[0098]

[0099] In the above formula (5), R １４ and R １５ are each a hydrogen atom or a methyl group. １６ and R １７ are each a hydrogen atom or a methyl group.

[0100] A is a divalent organic group, which is a linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group which may have 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:

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] In the above formula, R １８Ａ , R １８Ｂ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. xx and xy each represent an integer of 0 to 4 or 0 to 10. Ring X represents a benzene ring or a cyclohexane ring. YY represents -O-, -S-, -(SO ２ )-,-CO-,-CH ２ -, -CH=CH-, -C(CH ３ ) ２ -, -C(CH ３ ) (C ６ H ５ )—, or a group represented by any of the following formulae:

[0107]

[0108]

[0109] In the above formula (5), l and m are each an integer of 0 or 1 or more, and l+m is an average value of 2 or more and 30 or less.

[0110] Specific examples of the bifunctional (meth)acrylate represented by the above formula (5) include alkoxylated bisphenol A diacrylate and alkoxylated bisphenol A dimethacrylate.

[0111] The second (meth)acrylate may contain a di(meth)acrylate represented by the following formula (6).

[0112]

[0113] In the above formula (6), R １９ and R ２０ are each a hydrogen atom or a methyl group.

[0114] n is a number between 1 and 20 on average.

[0115] 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. When there are multiple Bs, the multiple Bs may be the same or different groups.

[0116] The bifunctional (meth)acrylate represented by the above formula (6) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0117] Examples of the polycarbonate diol to be used here include the following: Specifically, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of trimethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of tetramethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of pentamethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of hexamethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of octamethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation with nonamethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation with triethylene glycol and tetramethylene glycol, Examples thereof include recarbonate diol (number average molecular weight 750 to 2000), polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of tetramethylene glycol and octamethylene glycol, polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and polycarbonate diol (number average molecular weight 750 to 2000) obtained by phosgenation of 1-methyltrimethylene glycol.

[0118] The second (meth)acrylate may include a di(meth)acrylate having a urethane bond, i.e., a urethane di(meth)acrylate, which is obtained by reacting a polyisocyanate compound having two isocyanate groups in the molecule, a polyol compound having two hydroxyl groups in the molecule, and a hydroxyl group-containing (meth)acrylate.

[0119] Suitable examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, and methylcyclohexane diisocyanate.

[0120] Examples of polyols include polyalkylene glycols having 2 to 4 carbon atoms and having repeating units of ethylene oxide, propylene oxide, or hexamethylene oxide, and polyester diols such as polycaprolactone diol. Further examples include polycarbonate diol, polybutadiene diol, pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, and trimethylolpropane.

[0121] In addition, a reaction mixture obtained by further reacting a urethane prepolymer having an isocyanate group at its terminal by the reaction of such a polyisocyanate and a polyol with 2-hydroxy(meth)acrylate, or a reaction mixture obtained by directly reacting the diisocyanate with 2-hydroxy(meth)acrylate, such as a urethane(meth)acrylate monomer, can also be used.

[0122] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0123] As the bifunctional (meth)acrylate having a urethane bond, commercially available products can be used without any limitation, and examples thereof include UA-122P (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 1,100) and U-122P (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 1,100).

[0124] <Third (meth)acrylate> The curable composition according to this embodiment preferably further contains a third (meth)acrylate. When the curable composition contains a third (meth)acrylate, the appearance of the cured product tends to be improved.

[0125] The third (meth)acrylate has a number average molecular weight of less than 850 and has three or more (meth)acryloyl groups. The number of (meth)acryloyl groups may be 3, 4, 5, 6, 7, or 8. The number average molecular weight of the third (meth)acrylate can be measured, for example, by gel permeation chromatography (GPC). From the viewpoint of improving the functionality of the cured body, the number average molecular weight of the third (meth)acrylate is preferably 250 or more, and more preferably 300 or more. From the viewpoint of improving the appearance of the cured body, the number average molecular weight of the third (meth)acrylate is preferably 800 or less, more preferably 700 or less, and even more preferably 600 or less.

[0126] In the curable composition, the proportion of the third (meth)acrylate is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, from the viewpoint of improving the appearance of the cured body. In terms of improving the functionality of the cured body, the proportion of the third (meth)acrylate is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the third (meth)acrylate separated by silica gel column chromatography.

[0127] The ratio M1 / M3 of the mass M1 of the first (meth)acrylate to the mass M3 of the third (meth)acrylate is preferably 0.1 or more and 10.0 or less, more preferably 0.2 or more and 5.0 or less, and even more preferably 0.5 or more and 3.0 or less.

[0128] The ratio M2 / M3 of the mass M2 of the second (meth)acrylate to the mass M3 of the third (meth)acrylate is preferably 0.1 or more and 20.0 or less, more preferably 0.2 or more and 10.0 or less, and even more preferably 0.5 or more and 2.0 or less.

[0129] In the curable composition, when the (meth)acrylate component consists solely of first to third (meth)acrylates, the proportion of the first (meth)acrylate in the (meth)acrylate component is, for example, 20% by mass to 50% by mass, and preferably 25% by mass to 40% by mass. The proportion of the second (meth)acrylate in the (meth)acrylate component is, for example, 20% by mass to 70% by mass, and preferably 25% by mass to 60% by mass, and more preferably 35% by mass to 50% by mass. The proportion of the third (meth)acrylate in the (meth)acrylate component is the remainder, and is, for example, 5% by mass to 40% by mass, and preferably 10% by mass to 35% by mass, and more preferably 25% by mass to 30% by mass.

[0130] The third (meth)acrylate is preferably an acyclic (meth)acrylate that does not contain a cyclic structure such as an aromatic ring or an aliphatic ring. Use of such a third (meth)acrylate tends to enhance the functionality of the cured body.

[0131] The third (meth)acrylate may contain at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, and a carbonyl group. Preferably, the third (meth)acrylate does not contain any of the structures of an ester bond, a urethane bond, a urea bond, and a carbonyl group.

[0132] The raw material for the third (meth)acrylate may be a compound derived from a biological resource or a compound derived from a fossil resource.

[0133] As the third (meth)acrylate, a compound represented by the above formula (I) and having a number average molecular weight of less than 850 can be suitably used. Specifically, it is preferable to use one represented by the following formula (Ia):

[0134]

[0135] In formula (Ia), Q １０ , Q １１ , Q １２ , Q １３ , a1, and a3 have the same meanings as in formula (I). b1 is 0, 1, 2, or 3.

[0136] The third (meth)acrylate more preferably contains a tri- or tetrafunctional (meth)acrylate represented by the following formula (IIa):

[0137]

[0138] In formula (IIa), Q ２０ , Q ２１ , Q ２２ , Q ２３ , a4, a5, a6, and a7 have the same meanings as in formula (II).

[0139] Q ３０ , Q ３１ , and Q ３２ are each independently a monovalent group represented by the following formula (IIIa):

[0140]

[0141] In formula (IIIa), Q １１ , Q １２ and b1 have the same meanings as in formula (Ia).

[0142] Q ３０ , Q ３１ , and Q ３２ may have different structures from each other or may have the same structure. ３０ , Q ３１ , and Q３２ Preferably, the structures of the two compounds are the same.

[0143] Q ３３ Q is a hydrogen atom, a linear or branched alkyl group having from 1 to 5 carbon atoms, a linear or branched alkoxy group having from 1 to 5 carbon atoms, or a monovalent group represented by formula (IIIa). ３３ is preferably a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a monovalent group represented by formula (IIIa).

[0144] 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, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, and the like.

[0145] The third (meth)acrylate may contain a polyfunctional (meth)acrylate having a urethane bond. Commercially available products include U-4HA (molecular weight 596, number of functional groups 4) and U-6LPA (molecular weight 818, number of functional groups 6) manufactured by Shin-Nakamura Chemical Co., Ltd.

[0146] <Fourth (meth)acrylate> The curable composition according to this embodiment preferably further contains a fourth (meth)acrylate. When the curable composition contains a fourth (meth)acrylate, the appearance of the cured product tends to be improved.

[0147] The fourth (meth)acrylate has a number average molecular weight of less than 850 and is a di(meth)acrylate having two (meth)acryloyl groups. The number average molecular weight of the fourth (meth)acrylate can be measured, for example, by gel permeation chromatography (GPC). From the viewpoint of improving the functionality of the cured body, the number average molecular weight of the fourth (meth)acrylate is preferably 300 or more, more preferably 400 or more, and even more preferably 500 or more. From the viewpoint of improving the appearance of the cured body, the number average molecular weight of the fourth (meth)acrylate is preferably 800 or less, more preferably 750 or less, and even more preferably 700 or less.

[0148] In the curable composition, the proportion of the quaternary (meth)acrylate is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of improving the appearance of the cured body. In terms of improving the functionality of the cured body, the proportion of the quaternary (meth)acrylate is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the quaternary (meth)acrylate separated by silica gel column chromatography.

[0149] The ratio M1 / M4 of the mass M1 of the first (meth)acrylate to the mass M4 of the fourth (meth)acrylate is preferably 0.1 or more and 20.0 or less, more preferably 0.5 or more and 10.0 or less, and even more preferably 1.0 or more and 5.0 or less.

[0150] The ratio M2 / M4 of the mass M2 of the second (meth)acrylate to the mass M4 of the fourth (meth)acrylate is preferably 0.1 or more and 20.0 or less, more preferably 0.5 or more and 10.0 or less, and even more preferably 1.0 or more and 5.0 or less.

[0151] The ratio M3 / M4 of the mass M3 of the third (meth)acrylate to the mass M4 of the fourth (meth)acrylate is preferably 0.1 or more and 20.0 or less, more preferably 0.5 or more and 10.0 or less, and even more preferably 1.0 or more and 5.0 or less.

[0152] The fourth (meth)acrylate preferably contains one or more acryloyl groups, and more preferably is a diacrylate having two acryloyl groups. Use of a fourth (meth)acrylate containing an acryloyl group tends to increase the polymerizability of the curable composition and improve the appearance of the cured product.

[0153] The quaternary (meth)acrylate preferably contains a polycarbonate structure. Use of such a quaternary (meth)acrylate tends to improve the appearance of the cured product.

[0154] The fourth (meth)acrylate is preferably an acyclic (meth)acrylate that does not contain a cyclic structure such as an aromatic ring or an aliphatic ring. Use of such a fourth (meth)acrylate tends to enhance the functionality of the cured body.

[0155] The fourth (meth)acrylate may contain at least one structure selected from the group consisting of a urethane bond and a urea bond. It is preferable that the fourth (meth)acrylate does not contain either a urethane bond or a urea bond.

[0156] The raw material of the quaternary (meth)acrylate may be a compound derived from a biological resource or a compound derived from a fossil resource.

[0157] In the curable composition, when the (meth)acrylate component consists solely of the first to fourth (meth)acrylates, the proportion of the first (meth)acrylate in the (meth)acrylate component is, for example, 20% by mass to 40% by mass, and preferably 25% by mass to 30% by mass. The proportion of the second (meth)acrylate in the (meth)acrylate component is, for example, 20% by mass to 50% by mass, and preferably 25% by mass to 45% by mass, and more preferably 35% by mass to 40% by mass. The proportion of the third (meth)acrylate in the (meth)acrylate component is, for example, 5% by mass to 40% by mass, and preferably 10% by mass to 35% by mass, and more preferably 25% by mass to 30% by mass. The proportion of the third (meth)acrylate in the (meth)acrylate component is the remainder, and is, for example, 1% by mass or more and 30% by mass or less, preferably 5% by mass or more and 25% by mass or less, and more preferably 10% by mass or more and 20% by mass or less.

[0158] As the quaternary (meth)acrylate, a compound represented by the above formula (1), formula (3), formula (4), formula (4'), formula (5), or formula (6), which has a number average molecular weight of less than 850, can be suitably used. A compound represented by the above formula (1), formula (3), formula (5), or formula (6) can be particularly suitably used. When a compound represented by formula (1) or formula (3) is contained, the functionality of the cured body can be improved. When a compound represented by formula (5) or formula (6) is contained, the appearance of the cured body can be improved.

[0159] Specific examples of the quaternary (meth)acrylate represented by formula (1) include polypropylene glycol di(meth)acrylate. Specific examples of the quaternary (meth)acrylate represented by formula (3) include polyethylene glycol di(meth)acrylate, polytrimethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polypentamethylene glycol di(meth)acrylate, and polyhexamethylene glycol di(meth)acrylate.

[0160] A specific example of the quaternary (meth)acrylate represented by formula (5) is neopentyl glycol di(meth)acrylate.

[0161] Specific examples of the fourth (meth)acrylate represented by formula (6) include those obtained by reacting the following polycarbonate diols with (meth)acrylic acid: polycarbonate diol (number average molecular weight 500-700) obtained by phosgenation of trimethylene glycol, polycarbonate diol (number average molecular weight 500-700) obtained by phosgenation of tetramethylene glycol, polycarbonate diol (number average molecular weight 500-700) obtained by phosgenation of pentamethylene glycol, polycarbonate diol (number average molecular weight 500-700) obtained by phosgenation of hexamethylene glycol, polycarbonate diol (number average molecular weight 500-700) obtained by phosgenation of octamethylene glycol, polycarbonate diol (number average molecular weight 500-700) obtained by phosgenation with nonamethylene glycol, and polycarbonate diol (number average molecular weight 500-700) obtained by phosgenation with triethylene glycol and tetramethylene glycol. Examples of the polycarbonate diol include polycarbonate diol (number average molecular weight 500 to 700) obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol, polycarbonate diol (number average molecular weight 500 to 700) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol, polycarbonate diol (number average molecular weight 500 to 700) obtained by phosgenation of tetramethylene glycol and octamethylene glycol, polycarbonate diol (number average molecular weight 500 to 700) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and polycarbonate diol (number average molecular weight 500 to 700) obtained by phosgenation of 1-methyltrimethylene glycol.

[0162] The fourth (meth)acrylate may contain a sulfur atom. The sulfur atom preferably forms part of the molecular chain as a sulfide group. Specific examples include bis(2-methacryloyloxyethylthioethyl)sulfide, bis(methacryloyloxyethyl)sulfide, bis(acryloyloxyethyl)sulfide, 1,2-bis(methacryloyloxyethylthio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2-bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyethylthioisopropyl)sulfide, and 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide.

[0163] <Fifth (meth)acrylate> The curable composition according to this embodiment may further contain a fifth (meth)acrylate. The fifth (meth)acrylate is a monofunctional (meth)acrylate having one (meth)acryloyl group.

[0164] In the curable composition, the proportion of the fifth (meth)acrylate is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of improving the appearance of the cured body. In terms of improving the functionality of the cured body, the proportion of the fifth (meth)acrylate is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. Alternatively, it may be 5% by mass or more or 15% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the fifth (meth)acrylate separated by silica gel column chromatography.

[0165] In the curable composition, when the (meth)acrylate component consists solely of the first to fifth (meth)acrylates, the proportion of the first (meth)acrylate in the (meth)acrylate component is, for example, 20% by mass to 40% by mass, and preferably 25% by mass to 30% by mass. The proportion of the second (meth)acrylate in the (meth)acrylate component is, for example, 20% by mass to 50% by mass, and preferably 25% by mass to 45% by mass, and more preferably 35% by mass to 40% by mass. The proportion of the third (meth)acrylate in the (meth)acrylate component is, for example, 5% by mass to 40% by mass, and preferably 10% by mass to 35% by mass, and more preferably 25% by mass to 30% by mass. The proportion of the fourth (meth)acrylate in the (meth)acrylate component is, for example, 1% by mass to 30% by mass, preferably 5% by mass to 25% by mass, and more preferably 10% by mass to 20% by mass. The proportion of the fifth (meth)acrylate in the (meth)acrylate component is the remainder, and is, for example, 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and more preferably 5% by mass to 10% by mass.

[0166] The raw material of the fifth (meth)acrylate may be a compound derived from a biological resource or a compound derived from a fossil resource.

[0167] As the fifth (meth)acrylate, a monofunctional (meth)acrylate represented by the following formula (7) can be used.

[0168]

[0169] In formula (7), R ２１ R is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, a glycidyl group, a 1,2,2,6,6-pentamethylpiperidino group, or a 2,2,6,6-tetramethylpiperidino group. ２２ is a hydrogen atom or a methyl group. o is 0 or an integer of 1 to 10. p is 0 or an integer of 1 to 20.

[0170] R２１ is preferably a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group. When a monofunctional acrylate having such a functional group is contained, the adhesion between the cured product and the substrate, or between the cured product and a hard coat film to be processed later, tends to be improved.

[0171] In terms of increasing the durability of the hardened body, R ２１ is preferably a 1,2,2,6,6-pentamethylpiperidino group or a 2,2,6,6-tetramethylpiperidino group. Such a monofunctional acrylate can function as a light stabilizer (HALS). In the curable composition according to the embodiment, the HALS tends to bleed out easily. By blending a HALS having a (meth)acryloyl group, it is possible to suppress the bleed-out of the HALS.

[0172] Specific examples of the monofunctional (meth)acrylate represented by the above formula (7) 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 (meth)acrylate, and 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate.

[0173] <Other radical polymerizable compounds> The curable composition according to the embodiment may further contain another radical polymerizable monomer. The other radical polymerizable monomer may be one selected from the group consisting of (meth)acrylates having a number average molecular weight of more than 3,000, compounds having an allyl group, and compounds having a vinyl group.

[0174] The (meth)acrylate having a number average molecular weight of more than 3000 includes those having the structural formula given for the first (meth)acrylate or the second (meth)acrylate and having a number average molecular weight of more than 3000. The (meth)acrylate having a number average molecular weight of more than 3000 includes polyrotaxanes and silsesquioxanes having a plurality of radically polymerizable groups.

[0175] Polyrotaxanes have a composite molecular structure consisting of an axis molecule and multiple cyclic molecules that encapsulate the axis molecule. Bulky terminal groups are formed at both ends of the axis molecule, preventing the cyclic molecules from detaching from the axis molecule. Radical-polymerizable polyrotaxanes are polyrotaxanes in which radically polymerizable groups have been introduced into the side chains of the cyclic molecules. The radically polymerizable groups are introduced, for example, by modifying 1 mol % or more but less than 100 mol % of the hydroxyl groups of the cyclic molecules with radically polymerizable groups. Cyclic molecules are preferably cyclodextrin rings, crown ether rings, benzocrown rings, dibenzocrown rings, or dicyclohexanocrown rings, with cyclodextrin rings and crown ether rings being particularly preferred, and cyclodextrin rings being most preferred.

[0176] Silsesquioxanes having radical polymerizable groups have various molecular structures such as cage-like, ladder-like, and random structures, and have radical polymerizable groups such as (meth)acrylic groups.

[0177] An example of such a silsesquioxane polymerizable compound is one represented by the following formula (8).

[0178]

[0179] In formula (8), q is the degree of polymerization and is an integer of 3 to 100.

[0180] Multiple R ２３ may be the same or different and are a radical polymerizable group, an organic group containing a radical polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, and at least one R ２３ is a radically polymerizable group or an organic group containing a radically polymerizable group.

[0181] Here, R ２３ Examples of the radically polymerizable group represented by the formula (I) or an organic group containing a radically polymerizable group include a (meth)acrylic group; an organic group having a (meth)acrylic group such as a (meth)acryloyloxypropyl group or a (3-(meth)acryloyloxypropyl)dimethylsiloxy group; an allyl group; an organic group having an allyl group such as an allylpropyl group or an allylpropyldimethylsiloxy group; a vinyl group; and an organic group having a vinyl group such as a vinylpropyl group or a vinyldimethylsiloxy group.

[0182] Examples of allyl-based polymerizable compounds having an allyl group include the following: diethylene glycol bisallyl 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, and methoxypolyethylene thioglycol allyl thioether.

[0183] Examples of vinyl-based polymerizable compounds 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 persulfide, dimethyldivinylsilane, 1,2,4-trivinylcyclohexane, methyltrivinylsilane, α-methylstyrene, and α-methylstyrene dimer.

[0184] <Functional Dyes> Functional dyes include compounds capable of selectively absorbing visible light, as well as compounds that develop, lose, or change color in response to energy such as light, heat, an electric field, or pressure. Such functional dyes can exhibit specific functions by undergoing a structural change under specific conditions. The functional dye 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.

[0185] The content of the functional dye in the curable composition is, for example, 0.01% by mass to 20% by mass, preferably 0.1% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass.

[0186] <Photochromic Compound> The photochromic compound is not limited to any particular one, and known compounds can be used. These compounds can be used alone or in combination of two or more. Typical examples of such photochromic compounds include chromene compounds, fulgide compounds, fulgimide compounds, and spirooxazine compounds. Among these photochromic compounds, it is preferable to use chromene compounds and spirooxazine compounds. Chromene compounds are particularly preferable. Chromene compounds include compounds having a 1-benzopyran skeleton, spiropyran compounds containing a spiropyran skeleton, and naphthopyran compounds having a naphthopyran skeleton.

[0187] The naphthopyran compound preferably contains at least one of the compounds represented by the following formula (9), (10), (11), (12), (13), and (14):

[0188]

[0189] In formula (9), ring AA is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring. Ring AA may not be present.

[0190] Ring AB is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring.

[0191] 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.

[0192] The substituent 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 which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, an arylthio group which may have a substituent, an aryl group which may have a substituent, an amino group, a substituted amino group, or a heterocyclic group which may have a substituent, and is preferably at least one selected from the group consisting of a haloalkylthio group, a cycloalkylthio group which may have a substituent, an oligomer group, and a group represented by the following formula (15):

[0193] -Q １ - (P １ Q ２ ) ａａ -P ２ Q ３ (15) Q １ is an alkylene group which may contain a halogen atom as a substituent. ２ is an alkylene group which may contain a halogen atom as a substituent. ３ is an alkyl group which may contain a halogen atom as a substituent. １ , and P ２ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O). ７００ R is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ７０１represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. aa is 0 or 1 to 10.

[0194] In equation (9), M is CR ２６ R ２７ , SiR ２６ R ２７ , GeR ２６ R ２７ , or NR ２６ It is. ２６ and R ２７ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure.

[0195] The substituent 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 which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, an arylthio group which may have a substituent, an aryl group which may have a substituent, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, and a group represented by the above formula (15).

[0196] Also, R ２６ and R ２７ When two of these are taken together to form a ring structure, it is preferable that they form an aliphatic ring having 3 to 20 ring carbon atoms, a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to an aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to a heterocycle.

[0197]

[0198] In formula (10), R １０００ , R １００１ and R １００２are 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 those described in formula (9). mm is 1 to 10.

[0199]

[0200] 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 those described in formula (9). nn is 1 to 10.

[0201]

[0202] 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 those described in formula (9). oo is 1 to 12.

[0203]

[0204] In formula (13), R １００９ , R １０１０ and R １０１１ 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 those described in formula (9). pp is 1 to 12.

[0205]

[0206] In formula (14), R １０１２ , R １０１３ and R １０１４ 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 those described in formula (9). qq is 1 to 12.

[0207] The naphthopyran compound includes an indenonaphthopyran compound having an indenonaphthopyran skeleton, and the indenonaphthopyran compound preferably has an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.

[0208] In addition to the above, photochromic compounds having an oligomer chain group in the molecule can also be suitably used.

[0209] The indenonaphthopyran compound preferably includes a compound represented by the following formula (16).

[0210]

[0211] In formula (16), R ２４ , R ２５ , R ２６ and R ２７ is the same as above.

[0212] r is an integer of 0 to 4. s is an integer of 0 to 4. When r is 2 to 4, multiple R ２８ may be the same or different. When s is 2 to 4, multiple R ２９ may be the same or different. ２８ If there is a ２８ Together they ２８ and the carbon atom bonded to the adjacent R may form a ring which may contain at least one heteroatom selected from the group consisting of an oxygen atom, a carbon atom, a sulfur atom, and a nitrogen atom, and the ring may further have a substituent. ２９ If there is a ２９ Together they ２９ and the carbon atom bonded to the aryl group may form a ring which may contain at least one heteroatom selected from the group consisting of an oxygen atom, a carbon atom, a sulfur atom, or a nitrogen atom, and the ring may further have a substituent.

[0213] R ２８ , and R ２９are each independently a group represented by formula (15), a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group which may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group which may have a substituent, a silyl group which may have a substituent, an oxysilyl group which may have a substituent, a group represented by formula (17) below, or L-R ４００ It is a group represented by:

[0214]

[0215] In formula (17), E is an oxygen atom or NR １０１ and 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 It is. 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.

[0216] R ４００ is a hydrogen atom, an alkyl group, an aryl group, a silyl group having a substituent, a polymerizable group, or a photochromic group. The substituent of the silyl group is an alkyl group, an alkoxyl group, or an aryl group. L is a group represented by the following formula (X2):

[0217]

[0218] In formula (X2), R ３０is a group represented by the following formula (X2a).

[0219]

[0220] In formulas (X2) and (X2a), J is a divalent group, each independently representing a direct bond, a substituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ And. R ３０１ is a hydrogen atom or an alkyl group. In formulas (X2) and (X2a), L is an oxygen atom or a sulfur atom. ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent. ３０２ , R ３０３ and R ３０４ is an alkylene group. h, j, k, and l are 0 or 1. i is an integer from 1 to 200. When i is 2 or more, multiple R ３０ may be the same or different. The dashed line indicates R ４００ Represents a bond with.

[0221] <Other Additives> The curable composition may contain various known additives. Examples of additives include various stabilizers such as release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances. Solvents and leveling agents may also be added. Thiols such as t-dodecyl mercaptan may be added as polymerization regulators.

[0222] As the ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, or a sulfur-based antioxidant can be suitably used. The hindered amine light stabilizer is not particularly limited, but bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is preferred, particularly from the viewpoint of preventing deterioration of the photochromic compound. Furthermore, hindered amine light stabilizers commercially available from ADEKA Corporation under the trade names Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-87, and the like can also be suitably used.

[0223] Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methyl-phenol, IRGANOX 245 (ethylene bis(oxyethylene)bis[3,5-tert-butyl-4-hydroxy-m-toluyl]propionate) manufactured by BASF Japan Ltd., and IRGANOX 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) manufactured by BASF Japan Ltd. IRGANOX 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] manufactured by BASF Japan Ltd., and other products such as IRGANOX 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565 manufactured by BASF Japan Ltd.

[0224] The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator, and specific examples thereof are as follows:

[0225] Examples of the thermal polymerization initiator include diacyl peroxides; benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide; peroxy esters; t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate; percarbonates; diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate; azo compounds; azobisisobutyronitrile; and the like.

[0226] Examples of the photopolymerization initiator include acetophenone compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; α-dicarbonyl compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; and acylphosphine oxide compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine oxide.

[0227] When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine may be used in combination.

[0228] Examples of surfactants include known surfactants such as silicone surfactants having a silicone chain (polyalkylsiloxane unit) as a hydrophobic group, fluorine surfactants having a fluorocarbon chain, etc. When using surfactants, two or more types may be mixed and used.

[0229] Specific examples of silicone surfactants and fluorosurfactants that can be suitably used include L-7001, L-7002, L-7604, FZ-2123, and FZ-2110 manufactured by Dow Toray Co., Ltd.; Megafac F-470, Megafac F-1405, and Megafac F-479 manufactured by DIC Corporation; FLORAD FC-430 manufactured by 3M Japan; TEGORAD 2100 and TEGORAD 2300 manufactured by Evonik Japan Co., Ltd.; and BYK-UV3505 and B Examples of such vinyl acrylates include YK-UV3505, BYK-UV3510, BYK-UV3530, BYK-3550, BYK-3560, BYK-UV3565, BYK-3566, BYK-UV3500, BYK-UV3535, BYK-UV3570, BYK-UV3575, BYK-UV3576, and KR-513, X-22-2445, X-40-9296, X-22-164, X-22-164A, X-22-164B, X-22-164C, and X-22-164E manufactured by Shin-Etsu Chemical Co., Ltd.

[0230] As the ultraviolet absorber, known ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, triazine-based compounds, benzoate-based compounds, cinnamic acid ester-based compounds, and oxanilide-based compounds can be used, and cyanoacrylate-based compounds, benzophenone-based compounds, benzotriazole-based compounds, and cinnamic acid ester-based compounds are particularly preferred.

[0231] <Cured Product> A cured product is obtained by curing a curable composition. The curable composition is cured by inducing a radical polymerization reaction by irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, γ-rays, or LED, heat, or a combination of both. That is, an appropriate curing method may be adopted depending on the type of polymerizable monomer and polymerization curing accelerator used and the form of the cured product to be formed. When forming a laminate by the coating method described below, it is preferable to adopt photopolymerization because a uniform film thickness can be obtained.

[0232] When thermally polymerizing a curable composition containing a polymerizable compound, the thermal polymerization temperature affects the properties of the resulting cured product. While temperature conditions cannot be generally defined because they are influenced by the type and amount of thermal polymerization initiator and the type of polymerizable compound, a generally preferred method is to initiate polymerization at a relatively low temperature and slowly increase the temperature. Like temperature, polymerization time also varies depending on various factors, so it is best to determine the optimal time based on these conditions in advance. Generally, however, it is preferable to select conditions so that polymerization is complete within 2 to 48 hours. When obtaining a photochromic laminate sheet, polymerization is preferably carried out at a temperature at which the reaction between polymerizable functional groups proceeds, and the optimal temperature and time are determined to achieve the desired molecular weight.

[0233] Furthermore, when photopolymerizing a curable composition, among the polymerization conditions, UV intensity in particular affects the properties of the resulting photochromic cured product. The illuminance conditions cannot be generally limited because they are affected by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, but generally range from 50 to 500 mW / cm at a wavelength of 365 nm. ２ It is preferable to select the conditions so that the UV light is irradiated for 0.5 to 5 minutes.

[0234] The biomass plastic degree of the cured body is preferably 25% by mass or more. The biomass plastic degree can be calculated by a method in accordance with ISO standard 16620-3. The biomass plastic degree of the cured body is preferably 30% by mass or more, and more preferably 40% by mass or more. There is no particular upper limit to this biomass plastic degree, but in one example, it is 100% by mass or less.

[0235] <Laminate> The laminate according to the embodiment includes an optical substrate and a resin layer including the cured product according to the embodiment. The laminate according to the embodiment may include an optical substrate, a primer layer including a urethane resin, and a resin layer including the cured product according to the embodiment laminated on the primer layer.

[0236] The optical substrate contains a resin such as a diallyl carbonate resin, a urethane resin, or a thiourethane resin. The optical substrate may be derived from a plant material or a petroleum material. The optical substrate may be a lens substrate. A primer layer may be provided between the laminate and the cured body. The primer layer contains a urethane resin.

[0237] The biomass plastic content of the optical substrate is preferably 25% by mass or more. The biomass plastic content can be calculated using a method in accordance with ISO standard 16620-3. The biomass plastic content of the optical substrate is preferably 30% by mass or more, and more preferably 40% by mass or more. There is no particular upper limit to this biomass plastic content, but in one example, it is 100% by mass or less.

[0238] Fig. 1 is a cross-sectional view schematically illustrating an example of a laminate according to an embodiment. The laminate 10 shown in Fig. 1 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 includes a cured product according to an embodiment. The optical substrate 11 is a convex meniscus lens having an uneven shape.

[0239] <Optical Articles> The cured product according to the embodiment can be used in a wide range of applications as an optical article, including, for example, various memory materials such as various memory materials replacing silver halide photosensitive materials, copying materials, printing photosensitive materials, memory materials for cathode ray tubes, photosensitive materials for lasers, and photosensitive materials for holography, as well as lenses. Lenses are suitable for eyeglasses. Photochromic cured products containing a photochromic compound can also be used as photochromic lens materials, optical filter materials, display materials, actinometers, decorative materials, and the like.

[0240] The cured product according to the embodiment is particularly suitable for use in photochromic lenses. Photochromic lenses are suitable as lenses for spectacles such as sunglasses. Any known method can be used to manufacture photochromic lenses, as long as it can provide uniform photochromic performance.

[0241] When photochromic properties are expressed by the kneading method, the above-mentioned curable composition is injected between glass molds held by elastomer gaskets or spacers, and depending on the types of polymerizable compound and polymerization curing accelerator, a photochromic cured product molded into the shape of an optical material such as a lens can be obtained by casting polymerization using heating in an air oven or irradiation with active energy rays such as ultraviolet rays.

[0242] When photochromic properties are expressed by a lamination method, a coating solution is prepared by dissolving the curable composition in an appropriate organic solvent, and the coating solution is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and then dried to remove the organic solvent, followed by polymerization and curing by UV irradiation or heating in an inert gas such as nitrogen, thereby forming a photochromic layer made of a photochromic cured product on the surface of the optical substrate (coating method). The curable composition according to the embodiment is particularly suitable for the coating method.

[0243] Alternatively, a photochromic layer made of a photochromic cured product can be formed on the surface of an optical substrate by cast polymerization using an inner mold in which an optical substrate such as a lens substrate is placed facing a glass mold so that a predetermined gap is formed, a curable composition is injected into this gap, and polymerization and curing are carried out in this state by UV irradiation, heating, etc. (cast polymerization method).

[0244] When a photochromic layer is formed on the surface of an optical substrate by the above-mentioned lamination methods (coating method and cast polymerization method), the adhesion between the photochromic layer and the optical substrate can be improved by previously subjecting the surface of the optical substrate to a chemical treatment using an alkaline solution, an acid solution, etc., or a physical treatment using corona discharge, plasma discharge, polishing, etc. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0245] If necessary, a protective layer can be laminated on the surface of the formed photochromic layer. The protective layer can be made of a common resin such as a urethane resin, an epoxy resin, a (meth)acrylic resin, or a polyvinyl alcohol, without any particular limitations. The provision of the protective layer can improve the weather resistance and hardness of the photochromic layer.

[0246] The cured product formed from the curable composition may be subjected to post-processing depending on its intended use. Examples of post-processing include dyeing using a dye such as a disperse dye, forming a hard coat film using a hard coat agent mainly composed of a sol of a silane coupling agent or silicon, zirconium, antimony, aluminum, tin, tungsten, or the like, and forming a SiO ２ , TiO ２ , ZrO ２ Examples of such methods include forming a thin film by vapor deposition of a metal oxide such as the above, anti-reflection treatment using a thin film by coating an organic polymer, and anti-static treatment.

[0247] <Photochromic Optical Article> When measured according to a method in accordance with Japanese Industrial Standards T7333, the photochromic optical article according to the embodiment has a luminous transmittance of 12% or less when colored in a 23°C atmosphere, a difference in luminous transmittance between 23°C and 35°C atmospheres when colored is within 12%, and a time required for the luminous transmittance to reach 70% when faded is within 400 seconds.

[0248] The luminous transmittance during color development in an atmosphere of 23° C. is preferably 11% or less, and more preferably 10% or less. The lower limit of this luminous transmittance is preferably 8% or more from the viewpoint of visibility.

[0249] The difference in luminous transmittance during color development between an atmosphere at 23° C. and an atmosphere at 35° C. is preferably 10% or less, and more preferably 8% or less. There is no particular lower limit to this luminous transmittance, but in one example it is 0% or more, and in another example it is 5% or more.

[0250] The time required for the luminous transmittance to reach 70% upon fading is preferably within 300 seconds, more preferably within 200 seconds. There is no particular lower limit to this time, but from the viewpoint of visibility, it is, for example, 50 seconds or more, and in another example, 100 seconds or more.

[0251] The photochromic optical article may be, for example, a laminate or an optical article according to the embodiment.

[0252] EXAMPLES Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. The notation of each component and the evaluation methods are as follows.

[0253] <Components> First (meth)acrylates TMPT-20E: ethoxylated trimethylolpropane trimethacrylate (number average molecular weight 1218) Gly-20E: ethoxylated glycerin trimethacrylate (number average molecular weight 1176) TMMT-35E: ethoxylated pentaerythritol tetramethacrylate (number average molecular weight 1948) Second (meth)acrylates M-PTMG85: polytetramethylene glycol dimethacrylate (number average molecular weight 986) M-PTMG100: polytetramethylene glycol dimethacrylate (number average molecular weight 1136) M-PTMG130: polytetramethylene glycol dimethacrylate (number average molecular weight 1436) M-EGTME: dimethacrylate of the following formula (number average molecular weight 1762)

[0254]

[0255] M-PTMG100-B: Polytetramethylene glycol dimethacrylate obtained from plant-derived polytetramethylene glycol with a biomass content of 95% by mass (number average molecular weight 1136, biomass content 83.6% by mass) M-EGPG: Dimethacrylate of the following formula (number average molecular weight 1120)

[0256]

[0257] Tertiary (meth)acrylate TMPT: trimethylolpropane trimethacrylate (molecular weight 338) Quaternary (meth)acrylate 14G: polyethylene glycol dimethacrylate (number average molecular weight 770) APC56: diacrylate obtained by acrylating polycarbonatediol obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (number average molecular weight 606) M-PTMG65: polytetramethylene glycol dimethacrylate (number average molecular weight 786) M-NPG: neopentyl glycol dimethacrylate A-PPG12: polypropylene glycol diacrylate (number average molecular weight 822) Quinary (meth)acrylate TSL: γ-methacryloyloxypropyltrimethoxysilane LA82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate

[0258] Photochromic compound PC1: A compound represented by the following formula.

[0259]

[0260] PC2: A compound represented by the following formula: In the formula, "Me" represents a methyl group.

[0261]

[0262] PC3: A compound represented by the following formula: In the formula, "Me" represents a methyl group, and "Pr" represents a normal propyl group.

[0263]

[0264] PC4: A compound represented by the following formula:

[0265]

[0266] PC5: A compound represented by the following formula:

[0267]

[0268] PC6: A compound represented by the following formula:

[0269]

[0270] Other compounding agents (stabilizers) HALS: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate HP: ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (manufactured by BASF Japan Ltd., Irganox 245).

[0271] (Photopolymerization initiator) PI: phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (Omnirad 819, manufactured by IGM) (Leveling agent) L-7001, manufactured by Dow Toray Industries, Inc.

[0272] Example 1 (Production of Photochromic Curable Composition) First and second methacrylates were mixed uniformly according to the following formulation.

[0273] First methacrylate: TMPT-20E 1.0 g Second methacrylate: M-PTMG100 9.0 g The following components were further added to the resulting mixture, and the mixture was stirred at 60° C. for 1 hour to obtain a uniform solution.

[0274] Photochromic compounds: PC1 0.04 g / PC2 0.11 g / PC3 0.17 g / PC4 0.08 g / PC5 0.03 g / PC6 0.02 g Polymerization initiator: PI1 0.03 g Stabilizer: HP 0.05 g / HALS: 0.3 g Fifth methacrylate: TSL 0.6 g 1000 ppm of leveling agent L-7001 was added to the solution and mixed to obtain a photochromic curable composition.

[0275] (Production of Optical Article) Using the obtained photochromic curable composition, a photochromic laminate was obtained by the following lamination method.

[0276] First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 5% aqueous solution of sodium hydroxide at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0277] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curable primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) was applied to the surface of the above-mentioned plastic lens at a rotation speed of 200 rpm for 10 seconds, then at 1000 rpm for 5 seconds, and dried at 23°C for 10 minutes to obtain a primer layer of 7.5 μm. Thereafter, using the same spin coater, 2 g of the photochromic curable composition obtained above was supplied onto the lens on which the primer layer had been formed, and the spin coater was rotated at 100 rpm for 20 seconds to spread the photochromic curable composition, and then the spin coater was rotated at 800 rpm for 5 seconds. Next, the lens on whose surface the photochromic curable composition had been applied was subjected to a spin coater at an output of 200 mW / cm in a nitrogen gas atmosphere. ２ The coating was cured by irradiating the coating with light for 40 seconds using a metal halide lamp, to obtain a 40 μm thick photochromic layer, which was then further heated at 90° C. for 1 hour to obtain a photochromic laminate having a photochromic layer.

[0278] (Examples 2 to 28 and Comparative Examples 1 to 7) As shown in Table 1, photochromic cured products were prepared in the same manner as in Example 1, except that the types and amounts of the first to fifth (meth)acrylates were changed, and evaluations were performed according to the same evaluation items.

[0279] Example 29 A photochromic cured product was prepared in the same manner as in Example 1, except that the second (meth)acrylate was changed to M-PTMG100-B, and evaluated according to the same evaluation items. The biomass plastic content of the obtained cured product was calculated based on ISO Standard 16620-3 and was found to be 65.8% by mass. Calculation: [M-PTMG100-B (9 g) × biomass content 0.836)] / total amount of curable composition (11.43 g) × 100 = 65.8% by mass

[0280] (Examples 30 to 38) Photochromic cured products were prepared in the same manner as in Example 1, except that HALS as a stabilizer was not used and the types and amounts of the first to fifth (meth)acrylates were changed as shown in Table 2, and evaluations were performed according to the same evaluation items.

[0281] <Evaluation Method> The obtained photochromic laminate was evaluated by the following method.

[0282] (1) Photochromic Properties [1] Maximum absorption wavelength (λmax (nm)): This is the maximum absorption wavelength after color development measured using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., and was used as an index of the color tone during color development.

[0283] [2] 23 ° C color density (A ２３ ) is the difference between the absorbance {ε(300)} after 300 seconds of light irradiation at 23°C and the absorbance ε(0) before light irradiation at the maximum absorption wavelength, and is used as an index of color density. The higher this value, the better the photochromic properties.

[0284] [3] 23°C fading half-life (τ1 / 2 (sec.)): This is the time required for the absorbance of the sample at the maximum absorption wavelength to decrease to 1 / 2 of {ε(300) - ε(0)} when the light irradiation is stopped after 300 seconds of light irradiation at 23°C, and is used as an index of the fading rate. The shorter this time, the faster the fading rate.

[0285] [4] Luminous transmittance at 23°C (T ２３ (%)) This is the luminous transmittance after irradiating light for 300 seconds at 23°C, as determined using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd. The lower this value, the better the photochromic properties.

[0286] [5] 35°C luminous transmittance (T ３５ (%)) This is the luminous transmittance after irradiating light for 300 seconds at 35°C, as determined using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd. The lower this value, the better the photochromic properties.

[0287] [6] Luminous transmittance difference This is the difference between the 23°C luminous transmittance value obtained by the measurement in [4] and the 35°C luminous transmittance value obtained by the measurement in [5]. The smaller this difference is, the less susceptible the film is to the effects of temperature and the more excellent its photochromic properties are.

[0288] [7] Fading rate at 23°C (T70% (sec.)) This is the time required for the luminous transmittance of a sample to reach 70% after 300 seconds of light irradiation at 23°C and then stopping the light irradiation. The shorter this time, the faster the fading rate, and the more excellent the photochromic properties.

[0289] (2) Appearance Evaluation The photochromic laminate was exposed to fluorescent light in a black box, and the appearance was evaluated according to the following criteria. A: No appearance defects were observed. B: Wrinkle defects due to uneven shrinkage occurred in one or two lenses out of ten. C: Wrinkle defects due to uneven shrinkage occurred in five or more lenses out of ten. D: Wrinkle defects due to uneven shrinkage occurred around the entire periphery of the lens. E: Wrinkle defects due to uneven shrinkage occurred in the periphery of the lens, and partial peeling of the photochromic layer occurred. F: Wrinkle defects occurred all over the lens.

[0290] (3) Storage stability of photochromic curable composition The time and temperature at which the obtained photochromic curable composition can be stably stored in a homogeneous state were evaluated. A: A homogeneous state can be maintained for one month or more at a storage temperature of 25°C. A homogeneous state can be maintained even when frozen at -20°C and thawed. B: A homogeneous state can be maintained for one month or more at a storage temperature of 25°C. When frozen at -20°C and thawed, partial turbidity occurs. C: A homogeneous state can be maintained for one month or more at a storage temperature of 25°C. When frozen at -20°C and thawed, layer separation occurs. D: Layer separation occurs within one month at a storage temperature of 25°C.

[0291]

[0292]

[0293] In Tables 1 and 2, the numbers in parentheses indicate parts by mass of each (meth)acrylate.

[0294]

[0295]

[0296] Preferred aspects of the present invention are described below. [1] A curable composition comprising: a functional dye; a first (meth)acrylate having a number average molecular weight of 850 to 3,000 and having three or more (meth)acryloyl groups; and a second (meth)acrylate having a number average molecular weight of 850 or more and having two (meth)acryloyl groups. [2] The curable composition according to [1], wherein the first (meth)acrylate accounts for 20% by mass to 60% by mass. [3] The curable composition according to [1] or [2], wherein the second (meth)acrylate accounts for 15% by mass to 75% by mass. [4] The curable composition according to any one of [1] to [3], wherein the ratio M1 / M2 of the mass M1 of the first (meth)acrylate to the mass M2 of the second (meth)acrylate is 0.1 to 2.0. [5] The curable composition according to any one of [1] to [4], wherein the functional dye contains a photochromic compound. [6] The curable composition according to any one of [1] to [5], wherein the first (meth)acrylate does not contain a cyclic structure. [7] The curable composition according to any one of [1] to [6], wherein the first (meth)acrylate contains a (meth)acrylate represented by the following formula (I):

[0297]

[0298] In the formula (I), Q １０ is a linear or branched alkylene group having 1 to 3 carbon atoms, １１ is a linear or branched alkylene group having from 1 to 10 carbon atoms, １２ is a hydrogen atom or a methyl group, and Q １３ is a trivalent to hexavalent organic group having 1 to 10 carbon atoms, a1 is 0 or 1, a2 is 3 to 15, and a3 is 3, 4, 5, or 6. [8] The curable composition according to any one of [1] to [7], wherein the second (meth)acrylate does not contain a cyclic structure. [9] The curable composition according to any one of [1] to [8], wherein the second (meth)acrylate contains a (meth)acrylate represented by the following formula (1):

[0299]

[0300] In the formula (1), R １ and R ７ are each independently a hydrogen atom or a methyl group, R ２ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, ３ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, ４is a linear or branched alkylene group having 3 to 10 carbon atoms, which may have a substituent; a and e each independently represent 0 to 10; b and d each independently represent 0 to 20; and c is a number from 2 to 100, and is greater than each of a, b, d, and e.

[10] The curable composition according to any one of [1] to [9], further comprising a third (meth)acrylate having a number average molecular weight of less than 850 and having three or more (meth)acryloyl groups.

[11] The curable composition according to

[10] , wherein a proportion of the third (meth)acrylate in the curable composition is 5% by mass or more and 50% by mass or less.

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

[11] , further comprising a fourth (meth)acrylate having a number average molecular weight of less than 850 and having two (meth)acryloyl groups.

[13] The curable composition according to

[12] , wherein the proportion of the fourth (meth)acrylate in the curable composition is 1% by mass or more and 30% by mass or less.

[14] A cured product obtained by curing the curable composition according to any one of [1] to

[13] .

[15] A laminate comprising an optical substrate and a resin layer comprising the cured product according to

[14] .

[16] A laminate comprising an optical substrate, a primer layer comprising a urethane resin, and a resin layer comprising the cured product according to

[14] laminated on the primer layer.

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

[14] .

[18] A lens comprising the cured product according to

[14] .

[19] Eyeglasses comprising the lens according to

[18] .

[20] The cured product according to

[14] , having a biomass plastic content of 25% by mass or more as measured by a method in accordance with ISO Standard 16620-3.

[21] The laminate according to

[15] or

[16] , wherein the biomass plastic content of the optical substrate is 25% by mass or more as measured by a method in accordance with ISO Standard 16620-3.

[22] A photochromic optical article, which, when measured by a method in accordance with Japanese Industrial Standard T7333, has a luminous transmittance of 12% or less when colored in a 23°C atmosphere, a difference in luminous transmittance when colored between 23°C and 35°C atmospheres is within 12%, and a time required for the luminous transmittance to reach 70% when faded is within 400 seconds.

Claims

1. A curable composition comprising: a functional dye; a first (meth)acrylate having a number average molecular weight of 850 or more and 3,000 or less and having three or more (meth)acryloyl groups; and a second (meth)acrylate having a number average molecular weight of 850 or more and having two (meth)acryloyl groups.

2. The curable composition according to claim 1, wherein the proportion of the first (meth)acrylate in the curable composition is 20% by mass or more and 60% by mass or less.

3. The curable composition according to claim 1, wherein the proportion of the second (meth)acrylate in the curable composition is 15% by mass or more and 75% by mass or less.

4. The curable composition according to claim 1, wherein the ratio M1 / M2 of the mass M1 of the first (meth)acrylate to the mass M2 of the second (meth)acrylate is 0.1 or more and 2.0 or less.

5. The curable composition of claim 1, wherein the functional dye comprises a photochromic compound.

6. The curable composition according to claim 1, wherein the first (meth)acrylate does not contain a cyclic structure.

7. The curable composition according to claim 1, wherein the first (meth)acrylate comprises a (meth)acrylate represented by the following formula (I): In the formula (I), Q １０ is a linear or branched alkylene group having 1 to 3 carbon atoms; １１ is a linear or branched alkylene group having 1 to 10 carbon atoms; １２ is a hydrogen atom or a methyl group, Q １３ represents a trivalent to hexavalent organic group having 1 to 10 carbon atoms; a1 is 0 or 1; a2 is 3 to 15; and a3 is 3, 4, 5, or 6.

8. The curable composition according to claim 1, wherein the second (meth)acrylate does not contain a cyclic structure.

9. The curable composition according to claim 1, wherein the second (meth)acrylate comprises a (meth)acrylate represented by the following formula (1): In the formula (1), R １ and R ７ are each independently a hydrogen atom or a methyl group; R ２ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ３ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ４ represents a linear or branched alkylene group having 3 to 10 carbon atoms which may have a substituent; a and e each independently represent a number from 0 to 10; b and d each independently represent a number from 0 to 20; and c is a number from 2 to 100 and is greater than each of a, b, d, and e.

10. The curable composition of claim 1, further comprising a tertiary (meth)acrylate having a number average molecular weight of less than 850 and having three or more (meth)acryloyl groups.

11. The curable composition according to claim 10, wherein the proportion of the third (meth)acrylate in the curable composition is 5% by mass or more and 50% by mass or less.

12. The curable composition of claim 1, further comprising a quaternary (meth)acrylate having a number average molecular weight of less than 850 and having two (meth)acryloyl groups.

13. The curable composition according to claim 12, wherein the proportion of the fourth (meth)acrylate in the curable composition is 1% by mass or more and 30% by mass or less.

14. A cured product obtained by curing the curable composition according to claim 1.

15. A laminate comprising an optical substrate and a resin layer containing the cured product according to claim 14.

16. A laminate comprising: an optical substrate; a primer layer containing a urethane resin; and a resin layer containing the cured product according to claim 14 laminated on the primer layer.

17. An optical article comprising the cured product according to claim 14.

18. A lens comprising the cured product according to claim 14.

19. Eyeglasses comprising the lens of claim 18.

20. The hardened body according to claim 14, having a biomass plastic content of 25% by mass or more as measured according to a method in accordance with ISO standard 16620-3.

21. The laminate according to claim 15, wherein the biomass plastic content of the optical substrate is 25% by mass or more, as determined by a method in accordance with ISO standard 16620-3.

22. A photochromic optical article, which, when measured according to a method conforming to Japanese Industrial Standard T7333, has a visual transmittance of 12% or less when colored in an atmosphere at 23°C, a difference in visual transmittance of 12% or less when colored in atmospheres at 23°C and 35°C, and a time required for the visual transmittance to reach 70% when faded is within 400 seconds.

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