Optical material compound, curable composition, cured product, and optical article

Abstract

Provided are: a novel compound for an optical material; and a curable composition, a cured body, and an optical article that contain the compound for an optical material. According to an embodiment, there is provided a compound for an optical material represented by formula (Ia). In formula (Ia), X1 and X2 each are NH, S, or O. R1 is a 1- to 30-valent organic residue. R3 is a group formed from: a polymer of repeating units selected from –(CH2)mO–, –(CH2CH2O)–, –(CH(CH3)CH2O)–, –(CH2CH(CH3)O)–, and the group consisting of –(C(=O)–CH2CH2CH2CH2CH2O)–, –(C(=O)–O–CH2CH2CH2CH2CH2O)–, and –(C(=O)–O–CH2CH2CH2CH2CH2CH2O)–; a random copolymer of at least two repeating units selected from said group; or a block copolymer of at least two repeating units selected from said group.

Description

[Technical Field]

[0001] The present invention relates to a compound for optical materials, a curable composition, a cured product, and an optical article. [Background technology]

[0002] Demand for photochromic glasses, which have photochromic properties, is expanding worldwide. Photochromic glasses change their lens transmittance depending on the ambient brightness (amount of ultraviolet light), allowing for adjustable anti-glare properties.

[0003] In recent years, the development of plastic lenses with photochromic properties has progressed. Such photochromic lenses can be obtained, for example, by curing a polymerizable composition containing a photochromic compound whose structure changes depending on the amount of ultraviolet light. As a technique for improving photochromic performance, a technique for suppressing aggregation of the photochromic compound in the cured product and improving dispersibility has been proposed (Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. WO2014 / 007154 [Patent Document 2] Special Publication No. 2008-506031 [Patent Document 3] Japanese Patent Application Publication No. 1-152182 [Non-patent literature]

[0005] [Non-Patent Document 1] Chem.Mater.,2014, 26, 724-744 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a novel compound for optical materials, as well as a curable composition, a cured product, and an optical article each containing the compound for optical materials. [Means for solving the problem]

[0007] The present invention includes the following inventions. 1. A compound for optical materials represented by the following formula (Ia): [ka] In the formula (Ia), X 1 and X 2 are NH, S, or O, respectively; R 1 is a 1-30 valent organic residue, R 2 is H or CH3, R 3 teeth, -(CH2) m O-, -(CH2CH2O)-, -(CH(CH3)CH2O)-, -(CH2CH(CH3)O)-, -(C(=O)-CH2CH2CH2CH2CH2O)-, -(C(=O)-O-CH2CH2CH2CH2CH2O)-, and -(C(=O)-O-CH2CH2CH2CH2CH2CH2O)- A polymer of repeating units selected from the group consisting of: A random copolymer of at least two types of repeating units selected from the above group, or a group consisting of a block copolymer of at least two types of repeating units selected from the above group, R 4 teeth, H, H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, H2C=CH-C(=O)-OCH2CH2NHC(=O)-, HS-CH2-CH2-C(=O)-, or is a glycidyl group, a is an integer of 0 to 29, b is 0 or 1, c is 0 or 1, d is an integer of 1 to 30, a+d is an integer of 1 to 30, and m is an integer of 3 to 20.

[0008] 2. The above R 1 3. The compound for optical materials according to item 1 above, wherein is a monovalent, divalent, trivalent, tetravalent or hexavalent organic residue.

[0009] 3. The above R 1 2. The compound for optical materials according to item 1 above, wherein is an organic residue represented by the following formula (IIIa), (IIIb), (IIIc) or (IIId): C(CH2) e (CH2CH3) f (IIIa) In the formula (IIIa), e is 1 to 4, f is 0 to 3, and e+f is 4, C(CH2OC(=O)CH2CH2) g (CH2CH3) h (IIIb) In the formula (IIIb), g is 1 to 4, h is 0 to 3, and g+h is 4, C(CH2O-C(=O)CH2CH2) α (CH2CH3) β -CH2OCH2-C(CH2O-C(=O)CH2CH2) γ (CH2CH3) δ (IIIc) In the formula (IIIc), α is 0 to 3, β is 0 to 3, α+β is 3, γ is 0 to 3, δ is 0 to 3, γ+δ is 3, and α+γ is 1 to 6, C(CHO) ε (CH2CH3) ζ -CH2OCH2-C(CH2O) η (CH2CH3) ι (IIId) In the formula (IIId), ε is 0 to 3, ζ is 0 to 3, ε+ζ is 3, η is 0 to 3, ι is 0 to 3, η+ι is 3, and ε+η is 1 to 6.

[0010] 4. The above R 1 is an organic residue selected from the group consisting of formulas (4c), (4b), (5d), (5a), (6h), (6a), and (6e) described below. 5. The above R 3 is a group consisting of a block copolymer of a polymer having a repeating unit of -(CH2CH2O)- and a polymer having a repeating unit of (CH2CH(CH3)O)-.

[0011] 6. The above R 3 6. The compound for optical materials according to any one of items 1 to 5 above, wherein is a group consisting of a block copolymer represented by the following formula (IIa): -(CH2CH2O) x -(CH2CH(CH3)O) y -(CH2CH2O) z - (IIa) In the formula (IIa), x is an integer of 0 to 20, y is an integer of 5 to 40, and z is an integer of 1 to 20.

[0012] 7. A curable composition comprising the compound for optical materials (component D) according to any one of items 1 to 6 above, and at least one compound (component B) selected from the group consisting of polyisocyanate compounds and polyisothiocyanate compounds. 8. R in formula (Ia) 4 8. A curable composition comprising the compound for optical materials (component D) according to item 7 above, wherein H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, or H2C=CH-C(=O)-OCH2CH2NHC(=O)-. 9. The curable composition according to item 7 or 8 above, further comprising a photochromic compound (component A). 10. A cured product obtained by curing the curable composition according to any one of items 7 to 9 above. 11. An optical article comprising the cured product according to item 10 above. [Effects of the Invention]

[0013] According to the present invention, there are provided a novel compound for optical materials, as well as a curable composition, a cured product, and an optical article each containing the compound for optical materials. The photochromic cured product and optical article containing the compound for optical materials of the present invention have a maximum absorption wavelength (λmax), coloring density, and fading half-life [τ 1 / 2 (sec)] and has excellent photochromic properties, and the coloring is also durable. DETAILED DESCRIPTION OF THE INVENTION

[0014] [Compound for optical materials] The compound for optical materials according to this embodiment is represented by the following formula (Ia).

[0015] [ka]

[0016] In formula (Ia), X 1 and X 2 are NH, S, or O, respectively. 1 and X 2 are preferably NH or S. 1 and X 2 When an amine compound where X is NH and a thiol compound where X is S are used as materials, a cured product with high durability and photochromic properties tends to be obtained. 1 and X 2 and are each more preferably S.

[0017] a is an integer of 0 to 29. a is preferably 0, 1, or 2, and more preferably 0. b is 0 or 1. b is preferably 0. That is, when a compound having no S or NH is used, a cured product having high durability and photochromic properties tends to be obtained.

[0018] R 1 is an organic residue having a valence of 1 to 30. 1 is preferably a monovalent, divalent, trivalent, tetravalent, pentavalent, hexavalent, heptavalent, or decavalent organic residue, and more preferably a divalent, trivalent, tetravalent, or hexavalent organic residue. When a compound with a high valence of the organic residue is used, a cured product with excellent photochromic properties tends to be obtained. Details of the organic residue will be described later.

[0019] R 2 is H or CH3. 2 is preferably H.

[0020] c is 0 or 1. When c is 1, i.e., when a compound for optical materials having a structure with the subscript c is used, the durability of the cured product tends to be enhanced. When c is 0, i.e., when a compound for optical materials having no structure with the subscript c is used, a cured product that has both durability and photochromic properties tends to be obtained.

[0021] R 3 teeth, -(CH2) m O-, -(CH2CH2O)-, -(CH(CH3)CH2O)-, -(CH2CH(CH3)O)-, -(C(=O)-CH2CH2CH2CH2CH2O)-, -(C(=O)-O-CH2CH2CH2CH2CH2O)-, and -(C(=O)-O-CH2CH2CH2CH2CH2CH2O)- A polymer of repeating units selected from the group consisting of: A random copolymer of at least two types of repeating units selected from the above group, or It is a group consisting of a block copolymer of at least two types of repeating units selected from the above group. m is an integer of 3 to 20. It is more preferable that m is an integer of 4 or more. R 3is a homopolymer of one type of repeating unit selected from the above group, a random copolymer of at least two types of repeating units selected from the above group, or a block copolymer of at least two types of repeating units selected from the above group.

[0022] R 3 is a group consisting of a polymer and is a flexible chain with a relatively flexible structure. In the cured product, the flexible chain R 3 The region around the flexible chain R tends to be more flexible. 3 Compounds that undergo structural changes, such as photochromic compounds, located in the vicinity of the flexible chain R are unlikely to be hindered from undergoing structural changes. 3 When the compound for optical materials according to the embodiment having the flexible chain R is used, the photochromic performance of the cured product can be improved. 3 is the organic residue R 1 is connected to the structure with optional subscripts c and b, so this flexible chain R 3 This makes it easier to increase the flexibility of the area around the area, thereby increasing durability over a long period of time.

[0023] R 3 are -(CH2CH2O)-, -(CH2CH(CH3)O)-, and -(CH2) m Preferably, the group is a polymer of a repeating unit selected from the group consisting of -(CH2CH2O)-, a random copolymer of at least two repeating units selected from the group consisting of -(CH2CH2O)-, or a block copolymer of at least two repeating units selected from the group consisting of -(CH2CH2O)-. When an optical material compound containing a polymer having a repeating unit of -(CH2CH(CH3)O)- is used, a cured product with excellent durability tends to be obtained. When an optical material compound containing a polymer having a repeating unit of -(CH2CH(CH3)O)- is used, a cured product with excellent photochromic properties tends to be obtained. -(CH2) m When an optical material compound containing a polymer having O- repeating units is used, a cured product with excellent durability tends to be obtained.

[0024] R 3is preferably a group consisting of a block copolymer of a polymer having a repeating unit of -(CH2CHO)- and a polymer having a repeating unit of -(CH2CH(CH3)O)-. In this block copolymer, the polymer having a repeating unit of -(CH2CHO)- is bonded to the organic residue R via the polymer having a repeating unit of -(CH2CH(CH3)O)-. 1 In other words, it is preferable that the compound for optical materials is positioned so as to face the compound for optical materials, and positioned on the outer side in the structural formula of the compound for optical materials. When a compound for optical materials having such a structure is used, the durability of the cured product tends to be further increased.

[0025] The number of repeating units of each repeating unit is, for example, 2 or more and 30 or less, preferably 5 or more and 20 or less, more preferably 7 to 16, and even more preferably 7, 9, 10, 11, 12, 15, or 16. When a compound for optical materials having a large number of repeating units is used, a cured product with high photochromic properties tends to be obtained. On the other hand, if the number of repeating units is excessively large, the durability and photochromic properties of the cured product may be reduced.

[0026] R 3 is more preferably a group consisting of a block copolymer represented by the following formula (IIa): When a compound for optical materials containing such a structure is used, the durability and photochromic properties of the cured product tend to be improved.

[0027] -(CH2CH2O) x -(CH2CH(CH3)O) y -(CH2CH2O) z - (IIa) In formula (IIa), x is an integer of 0 to 20, y is an integer of 5 to 40, and z is an integer of 1 to 20.

[0028] R 4 teeth, H, H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, H2C=CH-C(=O)-OCH2CH2NHC(=O)-, HS-CH2-CH2-C(=O)-, or It is a glycidyl group. R 4 The compound for optical materials in which is H is suitable as a material for polyurethane-based resins. R 4 is H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, or The compound for optical materials, H2C=CH-C(=O)-OCH2CH2NHC(=O)-, is suitable as a material for (meth)acrylic resins. R 4 The compound for optical material in which is HS-CH2-CH2-C(=O)- is suitable as a material for polyurethane resin. R 4 The compound for optical materials in which is a glycidyl group is suitable as a material for epoxy resin or acrylic resin.

[0029] d is an integer of 1 to 30. a+d is an integer of 1 to 30. d is, for example, 1, 2, 3, 4, 5, 6, or 7. d and the organic residue R 1 The ratio of the valence of the organic residue R to the valence of the organic residue R (d / valence) is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 1. 1 It is preferable that the ratio of bonds between the bond of and the structure with the subscript d is high. 3 By increasing the proportion of the compound, a cured product having high durability and photochromic properties tends to be obtained.

[0030] In the compound for optical materials according to the embodiment, an organic residue R having a valence of 1 or more 1 In order to use one or more flexible chains R 3 Therefore, when this compound for optical materials is used, a cured product having excellent durability can be obtained.

[0031] 〈Organic residue R 1 〉 organic residue R 1The structure of the following will be explained using specific examples. In the structural formulas shown, the portion marked with a wavy line represents a bond that bonds to other structures. 1 Specific examples of the group include groups represented by the following formulas: Specific examples of the monovalent organic residue include an alkyl group having 1 to 20 carbon atoms, a polyoxyethylene monomethyl ether group, and a propionic acid derivative group represented by the following formula (2a).

[0032] [ka]

[0033] In formula (2a), R 6 is an alkyl group having 1 to 20 carbon atoms or a polyoxyethylene monomethyl ether group.

[0034] Specific examples of the divalent organic residue include an alkylene group having 1 to 20 carbon atoms, a polyoxyethylene glycol group, a divalent propionic acid derivative group represented by the following formula (3a), and a polyoxyethylene-block-polyoxypropylene-block-polyoxyethylene glycol group represented by the following formula (3b).

[0035] [ka]

[0036] In formula (3a), R 5 is an alkylene group having 1 to 20 carbon atoms or a polyoxyethylene group.

[0037] [ka]

[0038] In the formula (3b), q is 1 to 20, and r is 5 to 40.

[0039] Specific examples of the trivalent organic residue include a trimethylolpropane tripropionate derivative group represented by the following formula (4c), a glycerol derivative group represented by the following formula (4a), and a trimethylolpropane derivative group represented by the following formula (4b).

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] Examples of the tetravalent organic residue include a ditrimethylolpropane tetrapropionate derivative group, a pentaerythritol tetrapropionate derivative group represented by the following formula (5d), a pentaerythritol group represented by the following formula (5a), a diglycerol derivative group represented by the following formula (5b), and an erythritol derivative group represented by the following formula (5c).

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] An example of the pentavalent organic residue is a D-glucopyranose group represented by the following formula (6d).

[0049] [ka]

[0050] Examples of the hexavalent organic residue include a dipentaerythritol hexapropionate derivative group represented by the following formula (6h), a dipentaerythritol group represented by the following formula (6a), a sorbitol group represented by the following formula (6b), and a mannitol group represented by the following formula (6c). Note that mannitol is a stereoisomer of sorbitol.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] An example of an organic residue having a valence of 1 to 21 is a β-cyclodextrin group represented by the following formula (6e): When the valence of the β-cyclodextrin group is less than 21, the bond positions are selected at random. The non-bond positions are modified with, for example, OH or CH.

[0056] [ka]

[0057] An example of an organic residue having a valence of 1 to 18 is an α-cyclodextrin group represented by the following formula (6f): When the valence of the α-cyclodextrin group is less than 18, the bond positions are selected at random. The non-bond positions are modified with, for example, OH or CH.

[0058] [ka]

[0059] An example of a monovalent to 24-valent organic residue is a γ-cyclodextrin group represented by the following formula (6g): In the γ-cyclodextrin group, when the valence is less than 24, the bond positions are selected at random. The non-bond positions are modified with, for example, OH or CH3.

[0060] [ka]

[0061] organic residue R 1 is preferably an organic residue of a compound represented by the following formula (IIIa), (IIIb), (IIIc), or (IIId). The organic residue represented by formula (IIIa) is a mono- to tetravalent pentaerythritol derivative group. The organic residue represented by formula (IIIb) is a mono- to tetravalent pentaerythritol propionate derivative group. The organic residue represented by formula (IIIc) is a mono- to hexavalent dipentaerythritol propionate derivative group. The organic residue represented by formula (IIId) is a mono- to hexavalent dipentaerythritol derivative group. When a compound for optical materials having these organic residues is used, the durability and photochromic properties of the cured product tend to be high. In terms of excellent handleability, it is preferable to use an organic residue represented by formula (IIIa) or (IIIb).

[0062] C(CH2) e (CH2CH3) f (IIIa) In formula (IIIa), e is 1 to 4, f is 0 to 3, and e+f is 4.

[0063] C(CH2OC(=O)CH2CH2) g (CH2CH3) h (IIIb) In formula (IIIb), g is 1 to 4, h is 0 to 3, and g+h is 4.

[0064] C(CH2O-C(=O)CH2CH2) α (CH2CH3) β -CH2OCH2-C(CH2O-C(=O)CH2CH2) γ (CH2CH3) δ (IIIc) In the formula (IIIc), α is 0 to 3, β is 0 to 3, α+β is 3, γ is 0 to 3, δ is 0 to 3, γ+δ is 3, and α+γ is 1 to 6.

[0065] C(CHO) ε (CH2CH3) ζ -CH2OCH2-C(CH2O) η (CH2CH3) ι (IIId) In formula (IIId), ε is 0 to 3, ζ is 0 to 3, and ε+ζ is 3. η is 0 to 3, ι is 0 to 3, η+ι is 3, and ε+η is 1 to 6.

[0066] <Examples of compounds for optical materials> Compounds (7a) to (25a) are listed below as specific examples of the compound for optical materials according to the embodiment.

[0067] [ka]

[0068] [ka]

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080] [ka]

[0081] In formula (22a), ten Rs selected at random are molecular chains shown below. -R = -(CH2CH2O)7-(CH2CH(CH3)O) 16 -(CH2CH2O)7-H

[0082] [ka]

[0083] Compounds (24a) and (25a) are described below as further specific examples of the compound for optical materials according to the embodiment. [ka]

[0084] [ka]

[0085] [Method for producing compounds for optical materials] <Michael addition reaction> The method for synthesizing the compound for optical materials is not particularly limited. For example, the compound for optical materials according to the embodiment can be obtained by a Michael addition reaction. The Michael addition reaction is, for example, a reaction shown in the following reaction formula 1, and known reaction conditions can be used (Non-Patent Document 1).

[0086] [ka]

[0087] Specifically, the organic residue R acts as a nucleophile. 1and a polymeric group R activated against nucleophilic attack. 3 After mixing with a compound having the structure, the mixture is stirred for a certain period of time under a nitrogen atmosphere, whereby the compound for optical materials according to the embodiment can be synthesized.

[0088] Organic residue R acts as a nucleophile 1 Examples of compounds having the structure include the above-mentioned organic residue R 1 A compound in which the bond is modified with OH, SH or NH2 is used. Organic residue R acts as a nucleophile 1 Specific examples of compounds having the structure include tridecyl(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0089] Polymer group R 3 Specific examples of compounds having the structure include polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol polyethylene glycol, and the like. polymeric group R activated towards nucleophilic attack 3 The compound having the structure is, for example, a polymeric group R 3 It can be obtained by treating a compound having the structure with an acrylate. <Nucleophilic substitution reaction> The compound for optical materials according to the embodiment can also be synthesized by, for example, a nucleophilic substitution reaction, such as the reaction shown in the following reaction formula 2, and known reaction conditions can be used. [ka] Specifically, the polymer group R acts as a nucleophile. 3 A compound having the structure is anionized with a base, and an organic residue R having a leaving group L activated against nucleophilic attack is obtained. 1After mixing, the mixture is stirred for a certain period of time under a nitrogen atmosphere, whereby the compound for optical materials according to the embodiment can be synthesized. Polymer group R acting as a nucleophile 3 Specific examples of compounds having the structure include polyethylene glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol, polytetramethylene glycol, polyethylene glycol, and the like. Examples of the base used in the nucleophilic substitution reaction include metal hydroxides, sodium hydride, and potassium tert-butoxide. In the reaction formula 2, L is a leaving group, and is not particularly limited as long as it forms an ether bond as a result of the nucleophilic substitution reaction. Examples thereof include a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, and a trifluoromethanesulfonyloxy group. an organic residue R bearing a leaving group L activated for nucleophilic attack; 1 Specific examples include pentaerythrityl tetrabromide. The nucleophilic substitution reaction can be carried out in a solvent. The solvent is not particularly limited as long as it does not interfere with the nucleophilic substitution reaction, and examples thereof include aprotic polar solvents such as tetrahydrofuran, acetonitrile, and dimethylformamide.

[0090] [Curable composition] The compound for optical materials (component D) represented by formula (Ia) can be used as a constituent component of a curable composition. A cured product is obtained by curing the curable composition. The curable composition may contain a polyisocyanate compound and a polyisothiocyanate compound (component B) in addition to the compound for optical materials represented by formula (Ia) (component D). The curable composition may also contain at least one selected from the group consisting of an active hydrogen-containing compound (component C), a photochromic compound (component A), a curing accelerator (component E), and other additives.

[0091] <Urethane-based curable composition> The compound for optical materials (component D) can be used as a component of a urethane-based curable composition. The urethane-based curable composition contains, in addition to the compound for optical materials (component D), at least one of a polyisocyanate compound and a polyisothiocyanate compound, i.e., a polyiso(thio)cyanate compound (component B). It is preferable to add an active hydrogen-containing compound (component C) to the urethane-based curable composition immediately before curing it.

[0092] The content of the compound for optical materials (component D) in the urethane-based curable composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 8% by mass or more. When the content of the compound for optical materials (component D) is high, the photochromic properties of the cured product tend to be enhanced. On the other hand, from the viewpoint of improving the durability of the cured product, the content of the compound for optical materials (component D) is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0093] The blending amount of the compound for optical materials (component D) relative to a total of 100 parts by mass of the polyiso(thio)cyanate compound (component B) and the active hydrogen-containing compound (component C) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less, and even more preferably 10 parts by mass or more and 25 parts by mass or less.

[0094] <Polyiso(thio)cyanate compound (Component B)> The "polyiso(thio)cyanate compound (component B)" is a compound having two or more isocyanate groups, a compound having two or more isothiocyanate groups, or a compound having one or more isocyanate groups and one or more isothiocyanate groups.

[0095] Examples of the polyisocyanate compound (component B) include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, sulfur-containing heterocyclic isocyanate compounds, sulfur-containing aliphatic isocyanate compounds, aliphatic sulfide-based isocyanate compounds, aromatic sulfide-based isocyanate compounds, aliphatic sulfone-based isocyanate compounds, aromatic sulfone-based isocyanate compounds, sulfonate ester-based isocyanate compounds, and aromatic sulfonic acid amide-based isocyanate compounds.

[0096] The polyisocyanate compound (component B) also includes blocked isocyanate compounds in which the isocyanate group of the above-mentioned isocyanate compound is blocked with at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds, and acetoacetic acid ester compounds.

[0097] The amount of the polyiso(thio)cyanate compound (component B) in the urethane-based curable composition is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 50 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of the active hydrogen-containing compound (component C).

[0098] Among polyisocyanate compounds (component B), compounds suitable for forming optical articles excellent in transparency and mechanical strength, particularly compounds suitable for producing optical articles containing a photochromic compound (component A), include compounds represented by the following formulas (I) to (VIII).

[0099] Preferred aliphatic isocyanate compounds are those represented by the following formula:

[0100] [ka]

[0101] (In the formula, R 100is an alkylene group having 1 to 10 carbon atoms, and may be a group in which some of the methylene groups in the alkylene group chain have been substituted with sulfur atoms. Examples of compounds include those represented by the following formula:

[0102] R 100 is an alkylene group having 1 to 10 carbon atoms, and may be a linear or branched group. Among these, linear groups such as pentamethylene, hexamethylene, heptamethylene, or octamethylene groups, or branched groups in which some of the hydrogen atoms of the pentamethylene, hexamethylene, heptamethylene, or octamethylene groups have been substituted with methyl groups are preferred. Furthermore, the alkylene group in which some of the methylene groups have been substituted with sulfur atoms is preferably a —CH2CH2SCH2CH2SCH2CH2— group.

[0103] Specific examples of the compound represented by formula (I) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexanemethylene diisocyanate, 1,2-bis(2-isocyanatoethylthio)ethane, etc. These compounds can be used alone or in combination of two or more.

[0104] Preferable alicyclic isocyanate compounds and aromatic isocyanate compounds include those represented by the following formula (II) and the following formula (III):

[0105] [ka]

[0106] [ka]

[0107] (In the formula, R 101 are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups, R 102 is an alkyl group having 1 to 4 carbon atoms, and when a plurality of groups are present, they may be the same or different groups, a 100 is an integer 2 or 3, and b 100 is an integer between 0 and 4, and c 100 is an integer of 0 to 4. The difference between the compound represented by formula (II) and the compound represented by formula (III) is that the compound represented by formula (II) has a phenyl group, while the compound represented by formula (III) has a cyclohexane group.

[0108] R 101 In the formula, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. 101 is particularly preferably a hydrogen atom, a methyl group, or an ethyl group. 102 In the formula, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. 102 is particularly preferably a methyl group or an ethyl group.

[0109] Specific examples of the compound represented by formula (II) or formula (III) include isophorone diisocyanate, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, etc. These compounds can be used alone or in combination of two or more types.

[0110] Preferred alicyclic isocyanate compounds and aromatic isocyanate compounds include those represented by the following formula (IV) and the following formula (V):

[0111] [ka]

[0112] [ka]

[0113] (In the formula, R 103 are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups; d 100 is an integer of 0 to 4. The difference between the compound represented by formula (IV) and the compound represented by formula (V) is that the compound represented by formula (IV) has two phenyl groups, while the compound represented by formula (V) has two cyclohexane groups.

[0114] R 103 In the formula, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. 103 is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0115] Specific examples of the compound represented by formula (IV) or formula (V) include 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, etc. These compounds can be used alone or in combination of two or more types.

[0116] Furthermore, preferred alicyclic isocyanate compounds include those represented by the following formula (VI):

[0117] [ka]

[0118] (In the formula, R 104 are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups; e 100 is an integer of 0 to 4.

[0119] R 104In the formula, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. 104 is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0120] Specific examples of the compound represented by formula (VI) include norbornane diisocyanate, 2,5-bis(isocyanatemethyl)-bicyclo[2,2,1]-heptane, and 2,6-bis(isocyanatemethyl)-bicyclo[2,2,1]-heptane.

[0121] These compounds can be used alone or in combination of two or more.

[0122] (Sulfur-containing heterocyclic isocyanate compound) Preferred sulfur-containing heterocyclic isocyanate compounds include those represented by the following formula (VII) and the following formula (VIII):

[0123] [ka]

[0124] [ka]

[0125] (In the formula, R 105 are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and may be the same group or different groups, R 106 is a methylene group or a sulfur atom, and R 107 is an alkylene group having 1 to 6 carbon atoms or a group in which some of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms have been substituted with sulfur atoms, and f 100 is an integer of 0 to 2.

[0126] Specific examples of the compound represented by formula (VII) or formula (VIII) include 2,5-bis(isocyanatomethyl)thiophene, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, etc. These compounds can be used alone or in combination of two or more.

[0127] Furthermore, halogen-substituted, alkyl-substituted, alkoxy-substituted, and nitro-substituted products of the above polyisocyanates, prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimerization reaction products, etc. can also be used.

[0128] The polyisothiocyanate compound may be a compound in which the isocyanate group in the polyisocyanate compounds represented by formulas (I) to (VIII) is replaced with an isothiocyanate group. More specific examples include aliphatic isothiocyanate compounds, alicyclic isothiocyanate compounds, aromatic isothiocyanate compounds, sulfur-containing heterocyclic isothiocyanate compounds, heterocyclic isothiocyanate compounds, sulfur-containing aliphatic isothiocyanate compounds, and sulfur-containing aromatic isothiocyanate compounds.

[0129] Specific examples of suitable isothiocyanate compounds include aliphatic isothiocyanate compounds such as hexamethylene diisothiocyanate, 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, 2,4,4-trimethylhexanemethylene diisothiocyanate, thiobis(3-isothiocyanate propane), thiobis(2-isothiocyanate ethane), and dithiobis(2-isothiocyanate ethane).

[0130] Examples of alicyclic isothiocyanate compounds and aromatic isothiocyanate compounds include p-phenylenediisopropylidenediisothiocyanate, 1,2-diisothiocyanate benzene, 1,3-diisothiocyanate benzene, 1,4-diisothiocyanate benzene, 2,4-diisothiocyanate toluene, isophorone diisothiocyanate, xylene diisothiocyanate (o-, m-, p-), 2,4-tolylene diisothiocyanate, 2,6-tolylene diisothiocyanate, and cyclohexane diisothiocyanate. Further examples include 1,1'-methylenebis(4-isothiocyanate benzene), 1,1'-methylenebis(4-isothiocyanate 2-methylbenzene), and 1,1'-methylenebis(4-isothiocyanate 3-methylbenzene).

[0131] Furthermore, preferred alicyclic isothiocyanate compounds include 2,4-bis(isothiocyanatomethyl)norbornane, 2,5-bis(isothiocyanatomethyl)norbornane, 2,6-bis(isothiocyanatomethyl)norbornane, 3,5-bis(isothiocyanatomethyl)norbornane, and norbornane diisocyanate.

[0132] Preferred sulfur-containing heterocyclic isothiocyanate compounds include thiophene-2,5-diisothiocyanate, 1,4-dithiane-2,5-diisothiocyanate, 2,5-bis(isothiocyanatomethyl)-1,4-dithiane, and 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane.

[0133] Examples of compounds having both an isocyanate group and an isothiocyanate group include the following compounds. For example, among the polyisocyanate compounds specifically exemplified above, there are compounds in which at least one isocyanate group is an isothiocyanate group. Also, among the polyisothiocyanate compounds specifically exemplified above, there are compounds in which at least one isothiocyanate group is an isocyanate group.

[0134] A compound having an iso(thio)cyanate group blocked with a blocking agent (hereinafter also referred to as a blocked iso(thio)cyanate compound) can be obtained by reacting the iso(thio)cyanate group of the polyiso(thio)cyanate compound with at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds, and acetoacetic acid ester compounds. The conditions for reacting the iso(thio)cyanate group with the blocking agent vary depending on the type of blocking agent, and can be determined appropriately depending on the blocking agent selected. Protection of the iso(thio)cyanate group by the blocking agent can be confirmed by Fourier transform infrared spectroscopy (FT-IR).

[0135] By using a blocked iso(thio)cyanate compound, the usable time of the urethane-based curable composition can be further extended.

[0136] Preferred examples of the isocyanate compound include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, norbornane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 1,2-bis(2-isocyanatoethylthio)ethane, xylene diisocyanate (o-, m-, p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate, which may be used alone or as a mixture thereof.

[0137] <Active hydrogen-containing compound (component C)> Examples of the active hydrogen-containing compound (component C) include aliphatic poly(thiol) compounds and aromatic poly(thiol) compounds. Aliphatic poly(thiol) compounds include aliphatic polyol compounds and aliphatic polythiol compounds. Aromatic poly(thiol) compounds include aromatic polyol compounds and aromatic polythiol compounds.

[0138] The amount of the active hydrogen-containing compound (component C) in the urethane-based curable composition is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 80 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of the polyiso(thio)cyanate compound (component B).

[0139] Among poly(thiol) compounds, compounds suitable for forming optical articles having excellent transparency and heat resistance, particularly compounds suitable for producing optical articles containing a photochromic compound (component A), include compounds represented by the following formulas (IX) to (XVII).

[0140] (Aliphatic poly(thiol) compounds) A preferred aliphatic poly(thiol) compound is a compound represented by the following formula (IX): [ka]

[0141] {In the formula, R 108 is a hydrogen atom or the following formula (X)

[0142] [ka]

[0143] (In the formula, R 111 is an alkylene group having 1 to 6 carbon atoms. and may be the same or different, R 109are each a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different, R 110 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are a plurality of groups, they may be the same or different, o 100 is 0 to 2, and p 100 is 1 to 6, and q 100 is 0 to 10, and r 100 is 2 to 4, and 100 +r 100 is 4.} Examples of compounds include those represented by the following formula:

[0144] R 111 is an alkylene group having 1 to 6 carbon atoms, and may be a linear or branched group. 111 is particularly preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group.

[0145] Specific examples of the compound represented by formula (IX) include trimethylolpropane, pentaerythritol, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and the like.

[0146] Among the preferred aliphatic poly(thio)ol compounds, the polyfunctional poly(thio)ol compound having an ether bond is a compound represented by the following formula (XI):

[0147] [ka]

[0148] {In the formula, F 100 are each an alkyl group having 1 to 6 carbon atoms, or a group represented by the following formula (XII):

[0149] [ka]

[0150] (In the formula, R 112 represents a hydrogen atom or a group having the same meaning as that of formula (X) above, and may be the same group or different groups, R 113 are each a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different groups; s 100 is 1 to 6, and t 100 is 0 to 10. Examples of compounds include those represented by the following formula:

[0151] F 100 At least two of the groups are groups represented by formula (XII). The other groups include alkyl groups having 1 to 6 carbon atoms, which may be linear or branched. Among these, F 100 is particularly preferably a methyl group, an ethyl group, a trimethyl group, or a propyl group. 100 and may be the same or different groups as long as two or more of them are groups represented by formula (XII). Specific examples of compounds represented by formula (XI) include ditrimethylolpropane, dipentaerythritol, ditrimethylolpropane tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), etc.

[0152] Among the preferred aliphatic poly(thiol) compounds, the polyfunctional polythiol compound is a compound represented by the following formula (XIII):

[0153] [ka]

[0154] (In the formula, R 114 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group in which a methylene group of the alkyl group having 1 to 6 carbon atoms has been partially substituted with a sulfur atom, and R 114When a plurality of groups are present, they may be the same group or different groups,

[0155] R 115 is an alkylene group having 1 to 10 carbon atoms, in which some of the methylene groups in the chain of the alkylene group having 1 to 10 carbon atoms have been substituted with sulfur atoms, or a group in which some of the hydrogen atoms of the alkylene group having 1 to 10 carbon atoms have been substituted with thiol groups, and R 115 When a plurality of groups are present, they may be the same group or different groups, u 100 is an integer between 2 and 4, and v 100 is an integer between 0 and 2, and u 100 +v 100 is 4.) It is preferred to use a compound represented by the formula:

[0156] R 114 In the formula, the alkyl group having 1 to 6 carbon atoms may be a linear or branched group, and among these, R 114 is preferably a hydrogen atom, a methyl group, or an ethyl group. Specific examples of groups in which some of the methylene groups in the chain of an alkyl group having 1 to 6 carbon atoms have been substituted with sulfur atoms include -CH2SCH3.

[0157] R 115 In the above, the alkylene group having 1 to 10 carbon atoms may be a linear or branched group. 115 Particularly preferred are a methylene group, an ethylene group, a trimethylene group, and a propylene group. Specific examples of groups in which some of the methylene groups in the chain of an alkylene group having 1 to 10 carbon atoms have been substituted with sulfur atoms include -CHS-, -CHCHS-, and -CHCHCHS-. Examples of groups in which some of the hydrogen atoms in an alkyl group having 1 to 6 carbon atoms have been substituted with thiol groups include groups such as -CHSCH(SCHSH)-.

[0158] Specific examples of the compound represented by formula (XIII) include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,7-bismercaptomethyl-3,6,9-trithio-1,11-undecanedithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0159] Among the preferred aromatic poly(thiol) compounds, the phenyl group-containing polythiol compound is a compound represented by the following formula (XIV):

[0160] [ka]

[0161] (In the formula, R 116 is an alkylene group having 1 to 6 carbon atoms, or a group in which some of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms have been substituted with sulfur atoms, and w 100 is 3.) Examples of compounds include those represented by the following formula:

[0162] R 116 In the above, the alkylene group having 1 to 6 carbon atoms may be a linear or branched group. 116 is preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Specific examples of groups in which some of the methylene groups in the chain of an alkylene group having 1 to 6 carbon atoms have been substituted with sulfur atoms include -CH2CH2CH2SCH2-, -CH2CH2SCH2-, and -CH2SCH2-. Specific examples of compounds represented by formula (XIV) include 1,3,5-tris(mercaptopropylthiomethyl)benzene.

[0163] Among the preferred poly(thiol) compounds other than those mentioned above, the poly(thiol) compound having a triazine ring is a compound represented by the following formula (XV):

[0164] [ka]

[0165] {In the formula, R 117 are each an alkyl group having 1 to 6 carbon atoms, or a group represented by the following formula (XVI):

[0166] [ka]

[0167] (In the formula, R 118 , and R 119 is an alkylene group having 1 to 6 carbon atoms, R 120 is an oxygen atom or a sulfur atom) wherein R 117 at least two of the R 117 may be the same group or different groups. Examples of compounds include those represented by the following formula:

[0168] R 118 , and R 119 In the above, the alkylene group having 1 to 6 carbon atoms may be a linear or branched group. 118 , and R 119 is preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Specific examples of the compound represented by formula (XV) include 2-mercaptomethanol and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate.

[0169] Among the preferred poly(thiol) compounds other than those mentioned above, compounds having a silsesquioxane structure can be used. Compounds having a silsesquioxane structure have various molecular structures such as cage-like, ladder-like, and random-like structures, and are compounds represented by the following formula (XVII):

[0170] [ka]

[0171] (In the formula, there are multiple R 500 may be the same or different and are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, and an organic group containing at least two hydroxyl groups and / or thiol groups in at least one molecule, and n 100 is an integer between 3 and 100.) The poly(thio)ol compounds can be used without particular limitations, and a combination of multiple compounds can be used in consideration of the photochromic properties and mechanical properties of the resulting cured product. Among them, in order to produce a photochromic optical article with excellent properties and to provide a curable composition with excellent moldability and ease of handling, it is preferable to use a poly(thio)ol compound having 3 to 6 active hydrogen-containing groups per molecule.

[0172] Preferred poly(thio)ol compounds include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate. Of these, it is more preferable to use at least one of trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate).

[0173] Among these, dipentaerythritol hexakis(3-mercaptopropionate) is most preferred because it can improve the photochromic properties and mechanical properties of the resulting cured product. From the viewpoint of photochromic properties, it is preferable to use dipentaerythritol hexakis(3-mercaptopropionate) alone as the poly(thio)ol compound, but dipentaerythritol hexakis(3-mercaptopropionate) has a high viscosity, so when a cured product is obtained by cast polymerization, it can be mixed with other poly(thio)ol compounds to adjust the viscosity. Other poly(thio)ol compounds include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 2,5-bis(mercaptomethyl)-1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and 1,1,1,1- Tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate are preferred, and trimethylolpropane tris(3-mercaptopropionate) is particularly preferred when used in combination, as this improves handling while maintaining excellent photochromic properties.

[0174] <Photochromic compound (component A)> The photochromic compound (component A) can be used without any particular limitation as long as it is a compound that exhibits photochromic properties, and these can be used alone or in combination of two or more types.

[0175] Typical examples of such photochromic compounds (component A) include known photochromic compounds such as chromene compounds, fulgimide compounds, spirooxazine compounds, and spiropyran compounds, and can be used without any restrictions.

[0176] Examples of the above-mentioned fulgimide compounds, spirooxazine compounds, spiropyran compounds and chromene compounds include compounds described in, for example, JP-A-2-28154, JP-A-62-288830, WO94 / 22850, WO96 / 14596, etc.

[0177] In particular, in addition to the chromene compounds described in the above patent documents, chromene compounds having excellent photochromic properties are known, and such chromene compounds can be suitably used as Component A.Examples of such chromene compounds include those disclosed in JP-A Nos. 2001-031670, 2001-011067, 2001-011066, 2000-344761, 2000-327675, 2000-256347, 2000-229976, 2000-229975, 2000-229974, 2000-229973, 2000-229972, 2000-219678, 2000-219686, JP-A Nos. 11-322739, 11-28 6484, JP 11-279171, JP 09-218301, JP 09-124645, JP 08-295690, JP 08-176139, JP 08-157467, U.S. Patent No. 5645767, U.S. Patent No. 5658501, U.S. Patent No. 5961892, U.S. Patent No. 6296785, Japanese Patent No. 4424981, Japanese Patent No. 4424962, WO2009 / 136668 pamphlet, WO2008 / 023828 pamphlet, Japanese Patent No. 43 69754, Japanese Patent No. 4301621, Japanese Patent No. 4256985, WO2007 / 086532 pamphlet, JP-A-2009-120536, JP-A-2009-67754, JP-A-2009-67680, JP-A-2009-57300, Japanese Patent No. 4195615, Japanese Patent No. 4158881, Japanese Patent No. 4157245, Japanese Patent No. 4157239, Japanese Patent No. 4157227, Japanese Patent No. 4118458, JP-A-2008-74832, These are disclosed in Japanese Patent No. 3982770, Japanese Patent No. 3801386, WO2005 / 028465 pamphlet, WO2003 / 042203 pamphlet, JP 2005-289812, JP 2005-289807, JP 2005-112772, Japanese Patent No. 3522189, WO2002 / 090342 pamphlet, Japanese Patent No. 3471073, JP 2003-277381, WO2001 / 060811 pamphlet, WO00 / 71544 pamphlet, and the like.Fulgide compounds, chromene compounds and spirooxazine compounds are disclosed in many documents, such as Japanese Patent Application Laid-Open Nos. 2-28154, 62-288830, WO94 / 22850 and WO96 / 14596.

[0178] Among known photochromic compounds, it is more preferable to use a chromene compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton from the viewpoint of photochromic properties such as color density, initial coloring, durability, and fading speed. In addition to the above, photochromic compounds having an oligomer chain group in the molecule can also be suitably used. Such photochromic compounds having an oligomer chain group are disclosed in many documents, such as WO2000 / 015630 pamphlet, WO2004 / 041961 pamphlet, WO2009 / 146509 pamphlet, WO2012 / 149599 pamphlet, WO2012 / 162725 pamphlet, WO2013 / 078086 pamphlet, WO2019 / 013249 pamphlet, and WO2019 / 203205 pamphlet. Among these photochromic compounds having an oligomer chain group in the molecule, it is preferable to use photochromic compounds having an oligomer chain group described in WO2019 / 013249 pamphlet and WO2019 / 203205 pamphlet, as they exhibit better photochromic properties and durability.

[0179] The photochromic compound (component A) is preferably a compound represented by the following formula: [ka]

[0180] The above-mentioned various photochromic compounds (component A) can be used either alone or in combination of two or more kinds, and the amount used can be small, for example, in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, per 100 parts by mass of the total of the polyiso(thio)cyanate compound (component B) and the active hydrogen-containing compound (component C). In the urethane-based curable composition according to the present embodiment, the weight ratios of the polyiso(thio)cyanate compound (component B), the active hydrogen-containing compound (component C), and the compound for optical materials (component D) are not particularly limited, but are preferably in the ranges of 20 to 75 parts by weight of the polyiso(thio)cyanate compound (component B), 20 to 75 parts by weight of the active hydrogen-containing compound (component C), and 5 to 40 parts by weight of the compound for optical materials (component D) per 100 parts by weight of the polyiso(thio)cyanate compound (component B), the active hydrogen-containing compound (component C), and the compound for optical materials (component D) combined. This range tends to enhance the photochromic properties and durability of the cured product. The proportions are more preferably in the range of 25 to 70 parts by mass of the polyiso(thio)cyanate compound (component B), 25 to 70 parts by mass of the active hydrogen-containing compound (component C), and 5 to 35 parts by mass of the compound for optical materials (component D), and even more preferably in the range of 30 to 60 parts by mass of the polyiso(thio)cyanate compound (component B), 30 to 60 parts by mass of the active hydrogen-containing compound (component C), and 10 to 25 parts by mass of the compound for optical materials (component D).

[0181] <Curing accelerator (component E)> The urethane-based curable composition may further contain various curing accelerators (component E) to rapidly accelerate the polymerization and curing depending on the types of the above-mentioned components. The curing accelerator (component E) is a urethane or urea reaction catalyst or condensing agent used in the reaction of hydroxyl groups and thiol groups with isocyanate groups and isocyanate groups.

[0182] (Urethane or urea reaction catalyst) This urethane or urea reaction catalyst is used in the production of poly(thio)urethane bonds by the reaction of polyiso(thio)cyanate with polyol or polythiol. Examples of these urethane or urea reaction catalysts include tertiary amines and their corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids, and organic sulfonic acids. Specific examples include the following: Furthermore, if the catalytic activity is too high due to the type of compound selected, the catalytic activity can be suppressed by mixing a tertiary amine and a Lewis acid. Tertiary amines: triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, triethylamine, hexamethylenetetramine, N,N-dimethyloctylamine, N,N,N',N'-tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis(1-methylpiperidine), 1,8-diazabicyclo-(5,4,0)-7-undecene. Phosphines: trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(dimethylphosphino)ethane. Quaternary ammonium salts: tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide. Quaternary phosphonium salts: tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide. Lewis acid; triphenylaluminum, dimethyltin dichloride, dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinoleate, dibutyltin bis(dodecyl mercaptide), dibutyltin bis(isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin bis(butyl maleate), dioctyltin dilaurate, dioctyltin diricinoleate, dioctyltin dioleate, dioctyltin di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate), didodecyltin diricinoleate. Organic sulfonic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid.

[0183] (Condensing agent) Specific examples of the condensing agent include the following. Inorganic acids; hydrogen chloride, hydrogen bromide, sulfuric acid, phosphoric acid, etc. Organic acids: p-toluenesulfonic acid, camphorsulfonic acid, etc. Acidic ion exchange resins; Amberlite, Amberlyst, etc. Carbodiimides; dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopyrrolyl)-carbodiimide.

[0184] The various curing accelerators (component E) described above can be used either alone or in combination of two or more. The amount used may be a so-called catalytic amount, for example, a small amount in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, per 100 parts by mass of the total of the polyiso(thio)cyanate compound (component B) and the active hydrogen-containing compound (component C).

[0185] <Other additives> The curable composition may contain various known additives, such as ultraviolet absorbers, antistatic agents, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances, as well as solvents, leveling agents, internal mold release agents, and polymerization regulators such as thiols, such as t-dodecyl mercaptan, as needed, within the range that does not impair the effects of the composition.

[0186] (stabilizer) In particular, in consideration of improving the durability of the photochromic compound (component A), it is preferable to use an ultraviolet stabilizer, such as a hindered amine light stabilizer, a hindered phenol antioxidant, or a sulfur-based antioxidant. Particularly suitable UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 2,6-di-t-butyl-4-methyl-phenol, ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], and the like. Commercially available products include ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, and LA-87 manufactured by Asahi Denka Kogyo Co., Ltd., and IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565 manufactured by Ciba Specialty Chemicals.

[0187] (ultraviolet absorber) In addition, in consideration of improving the durability and photochromic properties of the photochromic compound (component A), it is preferable to use an ultraviolet absorber. Examples of such ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, diphenylacrylate-based ultraviolet absorbers, phenol-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and cinnamic acid ester-based ultraviolet absorbers.

[0188] Among these, it is preferable to use a cyanoacrylate-based UV absorber, a diphenylacrylate-based UV absorber, a phenol-based UV absorber, an oxanilide-based UV absorber, a malonate ester-based UV absorber, or a cinnamate ester-based UV absorber, and it is particularly preferable to use a cinnamate ester-based UV absorber, from the viewpoint that durability can be improved without impairing photochromic properties (particularly color density) compared to when no UV absorber is used.

[0189] (mold release agent) Furthermore, if the optical article has poor releasability, an internal release agent can be used. Any internal release agent can be used as long as it has releasability and does not impair the resin's physical properties, such as transparency. Surfactants are preferred. Among these, phosphate ester surfactants are preferred. The internal release agent referred to here includes those catalysts that exhibit release effects, such as quaternary ammonium salts and quaternary phosphonium salts. These internal release agents are appropriately selected based on the combination with the monomer, polymerization conditions, economic efficiency, and ease of handling. Specific examples of phosphate ester internal release agents are as follows:

[0190] Alkyl acid phosphate; mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, bis(2-ethylhexyl) phosphate, di(2-ethylhexyl) phosphate, di-n-octyl phosphate, di-n-butyl phosphate, butyl acid phosphate (mono- and di-mixture), ethyl acid phosphate (mono- and di-mixture), butoxyethyl acid phosphate (mono- and di-mixture), 2-ethylhexyl acid phosphate (mono- and di-mixture), isotridene acid phosphate (mono- and di-mixture), tetracosyl acid phosphate (mono- and di-mixture), stearyl acid phosphate (mono- and di-mixture), Other examples of phosphate esters include oleyl acid phosphate (mono- and di-mixture), dibutyl pyrophosphate, ethylene glycol acid phosphate (mono- and di-mixture), and butoxyethyl acid phosphate (mono- and di-mixture).

[0191] Furthermore, to impart desired properties to the photochromic optical article, such as blue light blocking ability, fendering properties, and high contrast, a specific wavelength absorber that absorbs light in a specific wavelength range can be blended as needed. For example, blending a blue light absorber with an absorption peak in the range of 400 nm to 450 nm can block blue light that is harmful to the eyes. Furthermore, blending an organic dye with an absorption peak in the range of 550 nm to 600 nm can enhance contrast and improve visibility.

[0192] (blue light absorber) Considering the need to cut off blue light that is harmful to eyes, it is preferable to use a blue light absorber.Such a blue light absorber can be used without any particular limitation as long as it is a compound that has an absorption peak in the range of 400 nm to 450 nm, and commercially available compounds can also be used.Such a blue light absorber can include perylene compounds, porphyrin compounds, carotenoids, cyanine compounds, etc. Among these, it is preferable to use a porphyrin compound. Also, a porphyrin metal complex having a metal atom at the center can be used. Commercially available porphyrin metal complexes can be used. For example, FDB-001 and FDB-002 manufactured by Yamada Chemical Industry Co., Ltd. and products manufactured by Tokyo Chemical Industry Co., Ltd. can be used. Among these, it is particularly preferable to use a porphyrin compound represented by the following formula (XVIII).

[0193] [ka]

[0194] In the formula (XVIII), Y 11 ~Y 81 are hydrogen atoms, halogen atoms, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkyloxy group, substituted or unsubstituted acyl groups, a linear, branched or cyclic halogenoalkyl group, a linear, branched or cyclic halogenoalkoxy group, linear, branched or cyclic alkoxyalkyl groups, linear, branched or cyclic alkoxyalkoxyalkyl groups, substituted or unsubstituted aryloxyalkyl groups, substituted or unsubstituted aralkyloxyalkyl groups, linear, branched or cyclic halogenoalkoxyalkyl groups; is a substituent selected from Also, Y 11 ~Y 81 Adjacent groups selected from may be bonded to each other to form a substituted or unsubstituted aromatic ring together with the substituting carbon atoms. Z 1 ~Z 4 are each a substituted or unsubstituted aryl group, M is two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide.

[0195] In order to achieve the greatest effect, Y 11 ~Y 81are each preferably a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, Z 1 ~Z 4 are each preferably a substituted or unsubstituted aryl group, Preferably, M is copper, magnesium, zinc, cobalt, titanium, iron, vanadium, or vanadium oxide. Specific examples of suitable porphyrin compounds include copper porphyrin complexes, vanadium porphyrin complexes, magnesium porphyrin complexes, and zinc porphyrin complexes.

[0196] (Organic dye with an absorption peak in the range of 550nm to 600nm) Considering the improvement of visibility, it is preferable to use an organic dye having an absorption peak in the range of 550 nm to 600 nm. Examples of such organic dyes include nitro compounds, azo compounds, anthraquinone compounds, threne compounds, porphyrin compounds, and rare earth metal compounds. Among these, porphyrin compounds and rare earth compounds are preferred. Furthermore, from the viewpoint of compatibility with the curable composition, porphyrin compounds are most preferred.

[0197] The porphyrin compound may have various substituents on the porphyrin skeleton. For example, compounds described in JP-A-5-194616, JP-A-5-195446, JP-A-2003-105218, JP-A-2008-134618, JP-A-2013-61653, JP-A-2015-180942, WO2012 / 020570, Japanese Patent No. 5626081, Japanese Patent No. 5619472, Japanese Patent No. 5778109, etc. can be suitably used. Commercially available products can also be used. For example, FDG-005, FDG-006, FDG-007, FDR-001 manufactured by Yamada Chemical Industry Co., Ltd., PD-320 manufactured by Yamamoto Chemical Industry Co., Ltd., etc. can be used. Among them, a particularly suitable porphyrin compound is a tetraazaporphyrin compound represented by the following formula (XIX).

[0198] [ka]

[0199] In the formula (XIX), Y 12 , Y 32 , Y 52 , and Y 72 is a hydrogen atom, Y 22 , Y 42 , Y 62 , and Y 82 are each a linear or branched alkyl group having 1 to 6 carbon atoms, M is a divalent metal atom or metal oxide atom. Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1,2-dimethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, an n-hexyl group, a 2-methylpentyl group, a 4-methylpentyl group, a 4-methyl-2-pentyl group, a 1,2-dimethylbutyl group, a 2,3-dimethylbutyl group, and a 2-ethylbutyl group. Examples of divalent metal atoms include Cu, Zn, Fe, Co, Ni, Ru, Pd, Pt, Mn, Mg, Ti, Ba, Cd, Hg, and Sn. Examples of oxidized metal atoms include VO, MnO, and TiO.

[0200] The other compounding agents can be used either alone or in combination of two or more. The amount used can be small, for example, 0.0001 to 10 parts by mass, preferably 0.001 to 10 parts by mass, per 100 parts by mass of the polyiso(thio)cyanate compound (component B) and polyol compound combined.

[0201] <Acrylic Curable Composition> The acrylic curable composition contains a polymerizable monomer component. The acrylic curable composition may contain a photochromic compound (component A), a curing accelerator (component E), and additives. Examples of additives include stabilizers. The compound for optical materials (component D) can be used as a polymerizable monomer component of the acrylic curable composition. The acrylic curable composition may contain at least one of an acrylate compound and a methacrylate compound, i.e., a (meth)acrylate compound, in addition to the compound for optical materials (component D) according to the embodiment.

[0202] The content of the compound for optical materials (component D) in the acrylic curable composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. When the content of the compound for optical materials (component D) is high, the photochromic properties of the cured product tend to be enhanced. On the other hand, from the viewpoint of enhancing the durability of the cured product, the content of the compound for optical materials is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0203] The blending amount of the compound for optical materials (component D) per 100 parts by mass of the (meth)acrylate compound is preferably 1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 35 parts by mass.

[0204] R in formula (Ia) 4 However, the compound for optical materials (component D) having the structure H2C=CH-C(=O)-, H2C=C(CH3)-C(=O)-, or H2C=CH-C(=O)-OCH2CH2NHC(=O)- can itself function as a (meth)acrylate compound, and is therefore particularly suitable as a material for acrylic curable compositions.

[0205] Such an R 4 The content of the compound for optical materials (component D) in which is a (meth)acrylic group is, for example, 90% by mass or more and 100% by mass or less, and may account for the majority of the acrylic curable composition.

[0206] <(Meth)acrylate compounds> As the (meth)acrylate compound, for example, a bifunctional (meth)acrylic polymerizable compound, a polyfunctional (meth)acrylic polymerizable compound, a monofunctional (meth)acrylic polymerizable compound, etc. can be used, and it is preferable to include a bifunctional (meth)acrylic polymerizable compound.

[0207] (Bifunctional (meth)acrylic polymerizable compound) Examples of the bifunctional (meth)acrylic polymerizable compound include compounds represented by the following formulas (5), (6) and (7).

[0208] [ka]

[0209] In the formula, R 14 and R 15 are each a hydrogen atom or a methyl group, j and k are each independently an integer of 0 or more, and j+k is an average value of 2 or more and 50 or less.

[0210] The polymerizable compound represented by the formula (5) is usually obtained in the form of a mixture of molecules with different molecular weights, and therefore j and k are shown as average values.

[0211] Specific examples of the compound represented by the above formula (5) are as follows. Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate consisting of a mixture of polypropylene glycol and polyethylene glycol (having two polyethylene and two polypropylene repeating units), polyethylene glycol Cholesterol dimethacrylate (especially average molecular weight 330), polyethylene glycol dimethacrylate (especially average molecular weight 536), polyethylene glycol dimethacrylate (especially average molecular weight 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (especially average molecular weight 536), polyethylene glycol diacrylate (especially average molecular weight 258), polyethylene glycol diacrylate (especially average molecular weight 308), polyethylene glycol diacrylate (especially average molecular weight 508), polyethylene glycol diacrylate (especially average molecular weight 708), polyethylene glycol methacrylate acrylate (especially average molecular weight 536).

[0212] [ka]

[0213] In the formula, R 16 and R 17 are each a hydrogen atom or a methyl group, R 18 and R 19 are each a hydrogen atom or a methyl group, R 20 is a hydrogen atom or a halogen atom, B is any one of -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, and -C(CH3)(C6H5)-; l and m are each an integer of 1 or more, and l+m has an average value of 2 or more and 30 or less. The polymerizable compound represented by the formula (6) is usually obtained in the form of a mixture of molecules with different molecular weights, and therefore, l and m are shown as average values.

[0214] A specific example of the compound represented by the above formula (6) is bisphenol A di(meth)acrylate shown below.

[0215] 2,2-Bis[4-methacryloyloxyethoxy)phenyl]propane(l+m=2), 2,2-Bis[4-methacryloyloxydiethoxy)phenyl]propane(l+m=4), 2,2-Bis[4-methacryloyloxypolyethoxy)phenyl]propane(l+m=7), 2,2-Bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane(l+m=2), 2,2-Bis(4-methacryloyloxydipropoxyphenyl)propane(l+m=4), 2,2-Bis[4-acryloyloxydiethoxy)phenyl]propane(l+m=4), 2,2-Bis[4-acryloyloxypolyethoxy]phenyl]propane 2,2-bis[4-acryloyloxy(polyethoxy)phenyl]propane (l + m = 3), 2,2-bis[4-acryloyloxy-polyethoxy)phenyl]propane (l + m = 7), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane (l + m = 10), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane (l + m = 17), 2,2-bis[4-methacryloyloxy(polyethoxy)phenyl]propane (l + m = 30), 2,2-bis[4-acryloyloxy(polyethoxy)phenyl]propane (l + m = 10), 2,2-bis[4-acryloyloxy(polyethoxy)phenyl]propane (l + m = 20).

[0216] [ka]

[0217] In the formula, R 21 and R 22 are each a hydrogen atom or a methyl group, n is an average number between 1 and 20, A and A' may be the same or different and each represents a linear or branched alkylene group having 2 to 15 carbon atoms, and when there are multiple As, the multiple As may be the same or different groups.

[0218] The compound represented by the above formula (7) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0219] Examples of the polycarbonate diol that can be used here include the following: polycarbonate diols (having a number average molecular weight of 500 to 2,000) obtained by phosgenation of polyalkylene glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, and nonamethylene glycol; Polycarbonate diols (number average molecular weight 500 to 2,000) obtained by phosgenation of mixtures of two or more polyalkylene glycols (for example, a mixture of trimethylene glycol and tetramethylene glycol, a mixture of tetramethylene glycol and hexamethylene glycol, a mixture of pentamethylene glycol and hexamethylene glycol, a mixture of tetramethylene glycol and octamethylene glycol, a mixture of hexamethylene glycol and octamethylene glycol, etc.); Polycarbonate diol (number average molecular weight 500-2,000) obtained by phosgenation of 1-methyltrimethylene glycol;

[0220] As the (meth)acrylate compound, a bifunctional (meth)acrylic polymerizable compound having a urethane bond may be used.

[0221] The bifunctional (meth)acrylic polymerizable compound having a urethane bond is, for example, a reaction product of a polyol and a polyisocyanate. 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, norbornenemethane diisocyanate, and methylcyclohexane diisocyanate.

[0222] On the other hand, 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, 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, and 1,4-cyclohexanedimethanol.

[0223] In addition, a reaction mixture obtained by further reacting a urethane prepolymer obtained by the reaction of these polyisocyanates and polyols with 2-hydroxy(meth)acrylate, or a reaction mixture obtained by directly reacting the diisocyanates with 2-hydroxy(meth)acrylate, such as a urethane(meth)acrylate, can also be used.

[0224] Examples of bifunctional (meth)acrylic polymerizable compounds having a urethane bond include U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), U-122P (molecular weight 1,100), U-108A, U-200PA, UA-511, U-412A, UA-4100, UA-4200, UA-4400, UA-2235PE, UA-160™, UA-6100, UA-6200, U-108, UA-4000, and UA-512, all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.; EB4858 (molecular weight 454), all of which are manufactured by Daicel-UCB Ltd.; and UX-2201, UX3204, UX4101, 6101, 7101, and 8101, all of which are manufactured by Nippon Kayaku Co., Ltd.

[0225] As the (meth)acrylate compound, bifunctional (meth)acrylic polymerizable compounds other than those mentioned above may also be used. Examples of such (meth)acrylate compounds include compounds having (meth)acrylic groups at both ends of an alkylene group which may have a substituent. Preferred (meth)acrylate compounds include those having an alkylene group having 6 to 20 carbon atoms. Specific examples include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, and 1,10-decanediol dimethacrylate.

[0226] Other (meth)acrylate compounds include bifunctional (meth)acrylate monomers containing sulfur atoms. The sulfur atom is preferably a sulfide group that forms part of the molecular chain. 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.

[0227] In the above (meth)acrylate compounds, each component may be used alone, or a plurality of the above-described types may be used.

[0228] (Polyfunctional (meth)acrylic polymerizable compound) Next, the polyfunctional (meth)acrylic polymerizable compound will be described.

[0229] Examples of the polyfunctional (meth)acrylic polymerizable compound include compounds represented by the following formula (8).

[0230] [ka]

[0231] In the formula, R 23 is a hydrogen atom or a methyl group, R 24 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R 25 is a trivalent to hexavalent organic group having 1 to 10 carbon atoms, o is a number between 0 and 3 on average, and p is a number between 3 and 6.

[0232] R 24 The alkyl group having 1 to 2 carbon atoms represented by R is preferably a methyl group. 25 Examples of the organic group represented by the formula (I) include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and an organic group containing a trivalent to hexavalent urethane bond.

[0233] Specific examples of the compound represented by the above formula (8) are as follows: trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, and ditrimethylolpropane tetraacrylate.

[0234] Furthermore, examples of the polyfunctional (meth)acrylic polymerizable compound include polyfunctional (meth)acrylic polymerizable compounds having a urethane bond.

[0235] Polyfunctional (meth)acrylic polymerizable compounds having urethane bonds are obtained by reacting the polyisocyanate compounds described above for the bifunctional (meth)acrylic polymerizable compounds having urethane bonds with polyol compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol, and are compounds having three or more (meth)acrylate groups in the molecule. Commercially available products include U-4HA (molecular weight 596, number of functional groups 4), U-6HA (molecular weight 1,019, number of functional groups 6), U-6LPA (molecular weight 818, number of functional groups 6), and U-15HA (molecular weight 2,300, number of functional groups 15), all manufactured by Shin-Nakamura Chemical Co., Ltd.

[0236] In addition, compounds other than those mentioned above may also be used as the polyfunctional (meth)acrylic polymerizable compound. Examples of such polyfunctional (meth)acrylic polymerizable compounds include compounds in which the terminals of polyester compounds are modified with (meth)acrylic groups. Various commercially available polyester (meth)acrylate compounds can be used depending on the molecular weight of the raw polyester compound and the amount of modification with the (meth)acrylic group. Specific examples include tetrafunctional polyester oligomers (molecular weight 2,500 to 3,500, Daicel-UCB, EB80, etc.), hexafunctional polyester oligomers (molecular weight 6,000 to 8,000, Daicel-UCB, EB450, etc.), hexafunctional polyester oligomers (molecular weight 45,000 to 55,000, Daicel-UCB, EB1830, etc.), and tetrafunctional polyester oligomers (e.g., molecular weight 10,000, Dai-ichi Kogyo Seiyaku, GX8488B, etc.).

[0237] By using the polyfunctional (meth)acrylic polymerizable compounds exemplified above, the crosslink density can be improved by polymerization, and the surface hardness of the resulting cured product can be increased. Therefore, it is preferable to use a polyfunctional (meth)acrylic polymerizable compound, particularly when a photochromic cured product (laminate) obtained by a coating method is to be obtained.

[0238] The above polyfunctional (meth)acrylic polymerizable compounds may be used as a single component of each component, or may be used in combination with a plurality of the above-described components.

[0239] (Monofunctional (meth)acrylic polymerizable compound) Next, the monofunctional (meth)acrylic polymerizable compound will be described.

[0240] The monofunctional (meth)acrylic polymerizable compound includes a compound represented by the following formula (9).

[0241] [ka]

[0242] In the formula, R 26 is a hydrogen atom or a methyl group, R 27 is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group, q is an integer from 0 to 10, r is an integer of 0 to 20.

[0243] Specific examples of the compound represented by the above formula (9) are as follows: Methoxypolyethylene glycol methacrylate (especially average molecular weight 293), methoxypolyethylene glycol methacrylate (especially average molecular weight 468), methoxypolyethylene glycol acrylate (especially average molecular weight 218), methoxypolyethylene glycol acrylate (especially average molecular weight 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate.

[0244] <Curing accelerator (component E)> As the curing accelerator (component E), at least one of a thermal polymerization initiator and a photopolymerization initiator can be used. Examples of the thermal polymerization initiator include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide.

[0245] Examples of peroxyesters include t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, and t-butylperoxybenzoate.

[0246] Examples of peroxydicarbonates include diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate.

[0247] Examples of the azo compound include azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile).

[0248] Examples of the photopolymerization initiator include acetophenone-based 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.

[0249] Examples of α-dicarbonyl compounds include 1,2-diphenylethanedione and methylphenylglycoxylate.

[0250] Examples of the acylphosphine oxide compound include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. When a photopolymerization initiator is used, a known polymerization hardening accelerator such as a tertiary amine can be used in combination.

[0251] The acrylic polymerizable composition may further contain the photochromic compound (component A), the curing accelerator (component E), other additives, and the like, which are described in the urethane polymerizable composition, in the proportions mentioned above.

[0252] [Method for producing curable composition] The curable composition is obtained by mixing a compound for optical materials (component D) with a polyiso(thio)cyanate compound (component B) by a known method. The curable composition may contain a photochromic compound (component A), an active hydrogen-containing compound (component C), a curing accelerator (component E), and other additives.

[0253] For example, a urethane-based curable composition can be obtained by mixing a polyiso(thio)cyanate compound (component B) with a compound for optical materials (component D), then adding an active hydrogen-containing compound (component C) and stirring. The stirring temperature can be adjusted to 0 to 100°C, and the stirring time can be adjusted appropriately within the range of 0.1 to 48 hours. To prevent moisture contamination, the composition is preferably produced in an inert gas atmosphere such as argon or nitrogen.

[0254] In the urethane-based curable composition, when the polyiso(thio)cyanate compound (component B) and the active hydrogen-containing compound (component C) are mixed, a polymerization reaction can immediately begin to produce a cured product. Therefore, the urethane-based curable composition is preferably prepared immediately before obtaining the cured product. The urethane-based curable composition may be prepared, for example, using a preparation kit including a first container containing the polyiso(thio)cyanate compound (component B) and a second container containing a mixture of the active hydrogen-containing compound (component C), a compound for optical materials (component D), and other optional components. Using such a preparation kit, the contents of the first container and the second container can be mixed and stirred at the desired timing to prepare the urethane-based curable composition. The acrylic curable composition can be obtained by mixing polymerizable monomer components containing a compound for optical materials (component D) by a known method. The acrylic curable composition may also contain a photochromic compound (component A), a curing accelerator (component E), additives, etc.

[0255] [Hardened body] The curable composition can be cured to obtain a cured product. Examples of the curing method include radical polymerization, ring-opening polymerization, anionic polymerization, or condensation polymerization, using irradiation with active energy rays such as ultraviolet rays, α-rays, β-rays, or γ-rays, heat, or a combination of both.

[0256] A cured product can be obtained, for example, by thermal polymerization of a curable composition. When thermally polymerizing a curable composition, the temperature in particular can affect the properties of the resulting cured product. The temperature conditions cannot be generally limited because they are affected by the type and amount of the thermal polymerization initiator and the type of compound, but a method in which polymerization is initiated at a relatively low temperature and the temperature is slowly increased is generally preferred. Like the temperature, the polymerization time also varies depending on various factors, so it is preferable to determine the optimal time in advance based on these conditions, but it is generally preferable to select conditions so that polymerization is completed within 2 to 48 hours.

[0257] [Method for manufacturing optical articles] Optical articles such as lenses include a cured product of the curable composition. The cured product according to the embodiment is particularly suitable for use in photochromic optical articles. The photochromic optical article includes a cured product of a curable composition containing a photochromic compound (component A). Examples of photochromic optical articles include photochromic lenses. Photochromic lenses can be produced by known methods such as a kneading method, a cast polymerization method, a glass lamination method, or a binder method.

[0258] Photochromic optical articles produced by the kneading method can be produced, for example, by injecting a photochromic compound-containing curable composition between glass molds held together by elastomer gaskets or spacers, thoroughly degassing the composition, and then subjecting the composition to cast polymerization by heating in an air oven or in water to produce a photochromic cured product (photochromic optical article) molded into the shape of an optical material such as a lens.

[0259] Optical articles produced by the cast polymerization method can be manufactured by, for example, arranging an optical substrate such as a lens substrate so that a predetermined gap is formed, injecting a photochromic compound-containing curable composition into this gap, and then performing cast polymerization in an inner mold in which polymerization is carried out by heating, thereby producing a photochromic lens (a laminate in which photochromic optical articles are laminated) in which a photochromic layer is formed on the surface of the optical substrate. The optical substrate is not particularly limited, and any known plastic optical substrate can be used, such as (meth)acrylic resin, polycarbonate resin, allyl resin, thiourethane resin, urethane resin, and thioepoxy resin.

[0260] When forming a photochromic layer on the surface of an optical substrate by the above-mentioned 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.

[0261] A photochromic optical article produced by the glass lamination method can be obtained, for example, by applying a required amount of a photochromic compound-containing curable composition onto one optical substrate such as glass on which a spacer is disposed, placing the other optical substrate such as glass on the coating film, and then curing the coating film to bond the pair of optical substrates such as glass.

[0262] When manufacturing a photochromic lens using the binder method, first, a photochromic curable composition is applied to a substrate, and the coating is dried to form an adhesive layer sheet. The resulting photochromic sheet is sandwiched between two optical sheets, which are then pressed together to bond them. In this way, a photochromic laminate is obtained in which two optical sheets are bonded together via an adhesive layer containing a photochromic compound.

[0263] The adhesive layer sheet may be prepared using a coating liquid prepared by dissolving the photochromic curable composition in an organic solvent.

[0264] The photochromic laminate thus produced can be placed in a mold, and then a thermoplastic resin (e.g., polycarbonate) for optical substrates such as lenses can be injection molded to obtain a photochromic lens of a predetermined shape in which the photochromic laminate is laminated on a lens. The photochromic laminate can also be adhered to the surface of an optical substrate such as a lens with an adhesive or the like, thereby obtaining a photochromic lens.

[0265] When producing a photochromic lens as described above, it is preferable to use a polyurethane adhesive as the adhesive. The adhesive preferably contains a urethane or urea polymerizable compound, and more preferably a urethane polymerizable compound. Use of a polyurethane adhesive can improve adhesion to the optical substrate.

[0266] The obtained photochromic cured body / laminate can exhibit photochromic properties excellent in color density, fading speed, etc., and is effectively used for producing optical substrates imparted with photochromic properties, such as photochromic lenses (photochromic optical articles).

[0267] Furthermore, the photochromic cured product can be laminated with other functional layers or dyed with dyes such as disperse dyes depending on its intended use, as long as the effects of the present invention are not impaired. A hard coating film can be formed thereon using a hard coating agent whose main component is a silane coupling agent or a sol such as silicon, zirconium, antimony, aluminum, tin, or tungsten. Thin films can also be formed by vapor deposition of metal oxides such as SiO2, TiO2, and ZrO2. Antireflection treatment can be performed using a thin film coated with an organic polymer. Antistatic treatment can also be performed.

[0268] Furthermore, as an example of lamination with the above-mentioned other functional layer, a polarizing film may be laminated to impart polarization properties to the obtained photochromic cured body. The position of the polarizing film is not particularly limited, and it may be laminated on the outside of the photochromic cured body, between the photochromic cured body and another layer, or within an adhesive layer when an adhesive layer is used. However, from the viewpoint of adhesiveness, it is preferable to embed the polarizing film within an adhesive layer when an adhesive layer is used.

[0269] The lamination method of the polarizing film is not particularly limited, and any known method may be employed. For example, in the case of the above-mentioned cast polymerization method, when the photochromic curable composition is poured into a glass mold, a polarizing film is placed between the front or rear mold and the photochromic curable composition, or within the photochromic composition, and then the photochromic curable composition is polymerized to laminate the polarizing film. In the case of the glass lamination method, it is preferable to laminate a polarizing film in advance on one side of an optical substrate made of inorganic glass. When laminating the polarizing film, a known heat-curing adhesive or ultraviolet (UV)-curing adhesive may be used to bond the optical substrate made of inorganic glass and the polarizing film.

[0270] The polarizing film is not particularly limited, and commercially available polarizing films can be used.

[0271] The polarizing film preferably has a thickness of 20 to 100 μm. The polarizing film is made, for example, by stretching polyvinyl alcohol dyed with a dichroic substance such as iodine or a dichroic dye.

[0272] The dichroic dye contained in the polarizing film may be any commercially available dichroic dye without limitation, such as azo-based or anthraquinone-based dyes. Specific examples include Chloranthine Fast Red (CI 28160), Congo Red (CI 22120), Brilliant Blue B (CI 24410), Benzopurpurine (CI 23500), Chlorazol Black BH (CI 22590), Direct Blue 2B (CI 22610), Diamine Green (CI 30295), Chrysophenine (CI 24895), Sirius Yellow (CI 29000), Direct Fast Red (CI 23630), Acid Black (CI 20470), Direct Sky Blue (CI 24400), Solophenyl Blue 4GL (CI 34200), Direct Copper Blue 2B (CI 24185), Nippon Brilliant Violet BKconc (CI 27885), etc. Two or more colors of dyes can be selected from these dichroic dyes depending on the purpose. The numbers in parentheses indicate the color index numbers listed in "New Edition Dye Handbook" compiled by the Organic Synthesis Association (Maruzen Co., Ltd., 1970).

[0273] By using the photochromic curable composition described above, it is possible to firmly bond even polarizing films with a luminous transmittance of 10 to 60% and a polarization degree of 70.0 to 99.9, which are usually difficult to bond.

[0274] The polarizing film may have a cellulose triacetate film laminated on both sides thereof to enhance its functionality and adhesiveness. The thickness of the cellulose triacetate film is preferably 20 to 200 μm, and more preferably 20 to 100 μm.

[0275] In order to adjust the amount of moisture contained in the polarizing film and to improve the dimensional stability of the polarizing film, the polarizing film may be subjected to a heat treatment at 40 to 100°C for about 5 seconds to 30 minutes before producing the photochromic cured product of the present invention. [Example]

[0276] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. [Synthesis of compounds (7a) to (23a) for optical materials] The raw materials used in the synthesis are as follows:

[0277] TDMP: Tridecyl (3-mercaptopropionate) represented by the following formula (10) (manufactured by Yodo Chemical Co., Ltd.) PEMP: pentaerythritol tetrakis(3-mercaptopropionate) represented by the following formula (11) (manufactured by SC Organic Chemical Co., Ltd.) BLEMMAR-AE-400: polyethylene glycol monoacrylate represented by the following formula (12) (manufactured by NOF Corporation) TMMP: Trimethylolpropane tris(3-mercaptopropionate) Neutral alumina: MP Alumina N-Super I (sold by Fujifilm Wako Pure Chemical Industries, Ltd.) Pluronic (registered trademark) L31: polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 1100) Pluronic (registered trademark) L34: polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 1600) Pluronic (registered trademark) L35: polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 1900) Pluronic (registered trademark) L44: polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 2000) Pluronic (registered trademark) L64: polyethylene glycol, polypropylene glycol, polyethylene glycol (Aldrich, weight average molecular weight 2900) Me-β-CD: Methylation degree 1.5 / glucose unit, molecular weight 1282 (sold by Junsei Chemical) The obtained compound was dissolved in deuterated chloroform and then 1 Identification was performed using a H-nuclear magnetic resonance spectrometer (JNM-ECA400II, 400 MHz, JEOL Ltd., reference material: TMS).

[0278] [ka]

[0279] (Example 1) Synthesis of compound (7a) TDMP (6.9 g, 23.9 mmol) and AE-400 (12.2 g, 23.9 mmol) were mixed uniformly, and then 15 g of neutral alumina was added and stirred at room temperature under a nitrogen atmosphere for 5 hours. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was removed by distillation under reduced pressure to obtain compound (7a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (7a) was measured, the following peaks were observed. δ0.85(m,9H),1.26(br-m,14H),1.61(m,2H),1.63(t,1H),2.65-2.78(m,8H),3.60-3.679(m,38H),4.11(m,2H),4.31(m,2H).

[0280] (Example 2) Synthesis of compound (8a) PEMP (5.8 g, 12.0 mmol) and AE-400 (12.2 g, 23.9 mmol) were mixed uniformly, and then 15 g of neutral alumina was added and stirred at room temperature under a nitrogen atmosphere for 5 hours. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was removed by distillation under reduced pressure to obtain compound (8a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (8a) was measured, the following peaks were observed. δ1.63(t,4H),2.68-2.78(m,24H),3.60-3.79(m,76H),4.19(s,8H),4.31(m,4H).

[0281] (Example 3) Synthesis of compound (9a) PEMP (2.9 g, 6.0 mmol) and AE-400 (12.2 g, 23.9 mmol) were mixed uniformly, and then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was removed by distillation under reduced pressure to obtain compound (9a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (9a) was measured, the following peaks were observed. δ1.63(t,4H),2.68-2.78(m,32H),3.60-3.79(m,152H),4.19(s,8H),4.31(m,8H).

[0282] (Example 4) Synthesis of compound (10a) Pluronic® L-31 (14.3 g, 13.0 mmol) and toluenesulfonic acid monohydrate (0.74 g, 3.9 mmol) were dissolved in 120 mL of toluene, and then 3-mercaptopropionic acid (4.1 g, 39.0 mmol) was added. The mixture was heated to reflux at 130°C for 10 hours to carry out dehydration condensation. After the reaction, the solvent was removed by distillation under reduced pressure, and the mixture was dissolved in dichloromethane. The organic layer was then washed with 1% aqueous ammonia. After washing three times with ion-exchanged water, the organic layer was dried over magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain the 3-mercaptopropionic acid ester of Pluronic® L-31 (yield: 95%).

[0283] Next, the resulting Pluronic® L-31 3-mercaptopropionic acid ester (15.3 g, 12.0 mmol) and AE-400 (12.2 g, 23.9 mmol) were uniformly mixed, and then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was evaporated under reduced pressure to obtain compound (10a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (10a) was measured, the following peaks were observed. δ1.14 (m, 48H), 2.68-2.81 (m, 16H), 3.40-3.70 (m, 128H), 4.10-4.30 (m, 8H).

[0284] (Example 5) Synthesis of compound (11a) Pluronic® L-34 (64.0 g, 40.0 mmol) and sodium hydroxide (0.8 g, 20.0 mmol) were dissolved in 150 mL of a tetrahydrofuran / water (2:1) mixed solvent, and then acrylic acid chloride (1.8 g, 20.0 mmol) was added and stirred at room temperature for 15 hours. After the reaction, the mixture was extracted with chloroform, and the organic layer was washed three times with water. The organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain Pluronic® L-34 monoacrylate (yield: 85%).

[0285] TMMP (3.19 g, 8.0 mmol) and Pluronic® L-34 monoacrylate (39.5 g, 23.9 mmol) were uniformly mixed, and then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was evaporated under reduced pressure to obtain compound (11a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (11a) was measured, the following peaks were observed. δ0.91(t,J=8Hz,3H),1.14(m,144H),1.50(q,J=8Hz,2H),2.68-2.81(m,24H),3.40-3.70(m,306H),4.08(s,6H),4.31(m,6H).

[0286] (Example 6) Synthesis of compound (12a) Pluronic® L-34 monoacrylate was prepared in the same manner as described in Example 5. PEMP (2.9 g, 6.0 mmol) and Pluronic® L-34 monoacrylate (39.5 g, 23.9 mmol) were uniformly mixed, and then 15 g of neutral alumina was added and stirred at room temperature under a nitrogen atmosphere for 5 hours. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was removed by distillation under reduced pressure to obtain compound (12a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (12a) was measured, the following peaks were observed. δ1.14 (m, 192H), 2.68-2.78 (m, 32H), 3.40-3.70 (m, 408H), 4.19 (s, 8H), 4.31 (m, 8H).

[0287] (Example 7) Synthesis of compound (13a) Pluronic® L-34 monoacrylate was prepared in the same manner as in Example 5. DPMP (3.15 g, 4.0 mmol) and Pluronic® L-34 monoacrylate (39.5 g, 23.9 mmol) were uniformly mixed, and then 15 g of neutral alumina was added and stirred at room temperature under a nitrogen atmosphere for 5 hours. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was removed by distillation under reduced pressure to obtain compound (13a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (13a) was measured, the following peaks were observed. δ1.14(m,288H),2.68-2.78(m,48H),3.40-3.70(m,636H),4.16(s,12H),4.31(m,12H).

[0288] (Example 8) Synthesis of compound (14a) Sodium hydride (0.57 g, 23.9 mmol) was dispersed in dry THF (150 mL), and Pluronic® L-34 (38.2 g, 23.9 mmol) was added and stirred at room temperature for 30 minutes. Pentaerythrityl tetrabromide (2.33 g, 6.0 mmol) was then added and stirred at room temperature for 2 hours under a nitrogen atmosphere. After completion of the reaction, ion-exchanged water was added to quench the reaction, followed by extraction with dichloromethane. The organic layer was washed three times with water, and the solvent was removed by distillation under reduced pressure to obtain compound (14a) (yield: 85%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (14a) was measured, the following peaks were observed. δ1.14(m,192H),3.40-3.70(m,424H).

[0289] (Example 9) Synthesis of compound (15a) Compound (15a) was obtained in a yield of 82% in the same manner as in Example 8, except that Pluronic (registered trademark) L-35 (45.4 g, 23.9 mmol) was used instead of Pluronic (registered trademark) L-34. Furthermore, when the proton nuclear magnetic resonance spectrum of compound (15a) was measured, the following peaks were observed. δ1.14(m,192H),3.40-3.70(m,520H).

[0290] (Example 10) Synthesis of compound (16a) Compound (16a) was obtained in a yield of 82% in the same manner as in Example 8, except that Pluronic (registered trademark) L-44 (47.8 g, 23.9 mmol) was used instead of Pluronic (registered trademark) L-34. Furthermore, when the proton nuclear magnetic resonance spectrum of compound (16a) was measured, the following peaks were observed. δ1.14(m,252H),3.40-3.70(m,548H).

[0291] (Example 11) Synthesis of compound (17a) Compound (17a) was obtained in a yield of 80% by the same method as in Example 8, except that Pluronic (registered trademark) L-64 (69.3 g, 23.9 mmol) was used instead of Pluronic (registered trademark) L-34. Furthermore, when the proton nuclear magnetic resonance spectrum of compound (17a) was measured, the following peaks were observed. δ1.14(m,360H),3.40-3.70(m,784H).

[0292] (Example 12) Synthesis of compound (18a) Sodium hydride (0.57 g, 23.9 mmol) was dispersed in dry THF (150 mL), and then pentaerythritol (0.82 g, 6.0 mmol) was added and stirred at room temperature for 30 minutes. Propylene oxide (11.1 g, 192 mmol) was then added and stirred at room temperature for 2 hours under a nitrogen atmosphere. After the reaction was completed, polyethylene glycol monotosylate (average number of oxyethylene units: 7, 11.3 g, 23.9 mmol) was added and stirred at room temperature for 18 hours. The reaction was then stopped by adding ion-exchanged water, followed by extraction with dichloromethane. The organic layer was washed three times with water, and the solvent was removed under reduced pressure to obtain compound (18a) (yield: 85%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (18a) was measured, the following peaks were observed. δ1.14(m,96H),3.40-3.70(m,216H).

[0293] (Example 13) Synthesis of compound (19a) Sodium hydride (0.57 g, 23.9 mmol) was dispersed in dry THF (150 mL), and then pentaerythritol (0.82 g, 6.0 mmol) was added and stirred at room temperature for 30 minutes. Propylene oxide (22.2 g, 384 mmol) was then added and stirred at room temperature for 2 hours under a nitrogen atmosphere. After the reaction was completed, polyethylene glycol monotosylate (average number of oxyethylene units: 10, 14.2 g, 23.9 mmol) was added and stirred at room temperature for 18 hours. The reaction was then terminated by adding ion-exchanged water, followed by extraction with dichloromethane. The organic layer was washed three times with water, and the solvent was removed by distillation under reduced pressure to obtain compound (19a) (yield: 82%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (19a) was measured, the following peaks were observed. δ1.14(m,192H),3.40-3.70(m,360H).

[0294] (Example 14) Synthesis of compound (20a) PE-4A (2.9 g, 6.0 mmol) and 11-mercapto-1-undecanol (4.9 g, 23.9 mmol) were mixed uniformly, and then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was removed by distillation under reduced pressure to obtain compound (20a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (20a) was measured, the following peaks were observed. δ1.20-1.58(m,72H),2.68-2.78(m,24H),3.60(t,8H),4.19(s,8H).

[0295] (Example 15) Synthesis of compound (21a) PE-4A (2.9 g, 6.0 mmol) and 12-amino-1-dodecanol (4.8 g, 23.9 mmol) were mixed uniformly, and then 15 g of neutral alumina was added and stirred at room temperature under a nitrogen atmosphere for 5 hours. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was removed by distillation under reduced pressure to obtain compound (21a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (21a) was measured, the following peaks were observed. δ1.20-1.58(m,80H),2.05(br-s,4H),2.68-2.78(m,24H),3.60(t,8H),4.19(s,8H).

[0296] (Example 16) Synthesis of compound (22a) Me-β-CD (16.7 g, 13.0 mmol) and toluenesulfonic acid monohydrate (0.74 g, 3.9 mmol) were dissolved in 120 mL of toluene, followed by the addition of 3-mercaptopropionic acid (4.1 g, 39.0 mmol). The mixture was heated to reflux at 130°C for 10 hours to carry out dehydration condensation. After the reaction, the solvent was removed by distillation under reduced pressure, and the residue was dissolved in dichloromethane. The organic layer was then washed with 1% aqueous ammonia. After washing three times with ion-exchanged water, the organic layer was dried over magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain Me-β-CD in which 95% of the total hydroxyl groups were esterified with 3-mercaptopropionic acid. Pluronic® L-34 monoacrylate was also prepared using the same method as described in Example 5.

[0297] Next, the resulting 3-mercaptopropionic acid ester of Me-β-CD (25.4 g, 12.0 mmol) and Pluronic® L-34 monoacrylate (39.5 g, 23.9 mmol) were uniformly mixed, and then 15 g of neutral alumina was added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was completed, 150 mL of toluene was added and stirred for 5 minutes. The neutral alumina was then filtered off (PTFE, 0.5 μm), and the solvent was evaporated under reduced pressure to obtain compound (22a) (yield: 99%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (22a) was measured, the following peaks were observed. 1.14(m,480H),2.68-2.78(m,80H),3.10-3.71(m,1100H),4.31(m,20H).

[0298] (Example 17) Synthesis of compound (23a) Compound (14a) (6.5 g, 1.0 mmol) synthesized in Synthesis Example 8 was dissolved in 50 mL of dry toluene, and 5 mg of dibutylhydroxytoluene (polymerization inhibitor) was added. Then, 0.73 g (5.1 mmol) of 2-acryloyloxyethyl isocyanate was added dropwise. 10 mg of dibutyltin dilaurate was added as a catalyst, and the mixture was heated and stirred at 70°C for 4 hours. This solution was added dropwise to hexane and vigorously stirred. The phase-separated hexane layer was decanted to obtain compound (23a) (yield 95%).

[0299] Furthermore, when the proton nuclear magnetic resonance spectrum of compound (23a) was measured, the following peaks were observed. δ1.14(m,192H),3.40-3.70(m,424H),4.15(m,8H),4.31(m,8H),5.84(d,J=10Hz,4H),6.16(dd,J=10Hz,17Hz,4H),6.43(d,J=17Hz,4H).

[0300] [Curable composition and cured product] <Production of urethane-based curable composition and cured product> Next, photochromic optical articles were produced using the compounds (7a) to (23a) obtained by the methods of Examples 1 to 17. The materials and evaluation methods used were as follows.

[0301] <Photochromic compound (component A)> PC1: A compound represented by the following formula: [ka]

[0302] <Polyisocyanate compound (Component B)> H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane (mixture of isomers) NBDI: Norbornane diisocyanate IPDI: Isophorone diisocyanate XDI: m-xylylene diisocyanate

[0303] <Active hydrogen-containing compound (component C): polythiol compound> TMMP: Trimethylolpropane tris(3-mercaptopropionate) PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) DPMP: Dipentaerythritol hexakis(3-mercaptopropionate)

[0304] <Compound for optical materials (D component)> Compounds (7a)~(22a)

[0305] <Curing accelerator (component E)> E1: Dimethyldichlorotin

[0306] <Other ingredients> HP: Stabilizer ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] Dye 1: tetraazaporphyrin compound FDG-006 (absorption wavelength: 585 nm, Yamada Chemical Industry). Dye 2: Blue light absorber FDB-002 (absorption wavelength: 431 nm, Yamada Chemical Industry)

[0307] [Evaluation method] <Photochromic properties> The photochromic cured products obtained in the Examples and Comparative Examples were evaluated by the following methods. The following values were measured using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd. Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development. Color density: absorbance (A) at the maximum absorption wavelength after irradiating light at 23°C for 300 seconds 300 ) and the absorbance (A0) when not irradiated with light. Fading half-life [τ 1 / 2 (sec)]: the absorbance at the maximum absorption wavelength of the sample when the light irradiation is stopped after 300 seconds of light irradiation at 23°C. 300 -A0}.

[0308] <Durability> Survival rate (%) = [(A 96 ) / (A0) x 100) The photochromic cured body was subjected to accelerated aging for 96 hours using a Xenon Weather Meter X25 manufactured by Suga Test Instruments Co., Ltd. The color density was evaluated before and after the accelerated aging test, and the color density of the photochromic cured body before the test (A0) and after the test (A 96 ) ratio (A 96 / A0) was taken as the residual rate and was used as an index of color durability. A higher residual rate means higher color durability.

[0309] Example 18 Photochromic curable compositions were prepared by mixing the components shown in Table 1. The prepared photochromic curable composition was thoroughly degassed and then poured into a glass mold with a 2 mm gap, and the photochromic curable composition was polymerized by cast polymerization. The polymerization was carried out in an air oven over 18 hours, gradually increasing the temperature from 27°C to 120°C. After polymerization, the cured product was removed from the glass mold to obtain a 2 mm thick photochromic cured product (photochromic optical article). The evaluation results of the photochromic cured product are shown in Tables 1 to 4.

[0310] (Examples 19 to 48, Comparative Example 1) A photochromic cured product was produced and evaluated in the same manner as in Example 18, except that the formulation was changed to those shown in Tables 1 to 4. The evaluation results are shown in Tables 1 to 4, as in Example 18.

[0311] Example 49 Photochromic curable compositions were prepared by mixing the components shown in Table 4. The prepared photochromic curable composition was then thoroughly degassed and poured into a mold consisting of a glass plate with a 1 mm gap and a thiourethane-based plastic lens with a refractive index of 1.60, and the photochromic composition was polymerized by cast polymerization. Polymerization was performed using an air oven, and the composition was cured over 18 hours while gradually increasing the temperature from 27°C to 120°C. After polymerization, the glass plate was removed, and a laminated photochromic optical article was obtained in which a 1 mm-thick cured photochromic body was laminated on the surface of the thiourethane-based plastic lens with a refractive index of 1.60. The photochromic properties and durability of the obtained photochromic optical article were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 4.

[0312] Example 50 Photochromic curable compositions were prepared by mixing the components shown in Table 4. Next, a photochromic optical article was produced by bonding a pair of glass plates for optical articles using the prepared photochromic curable composition as an adhesive. First, the photochromic curable composition was applied to one of the glass plates for optical articles, on which a 0.1 mm thick spacer was placed, and the other glass plate for optical articles was then placed on top of it. The photochromic curable composition was then polymerized. The polymerization was carried out in an air oven, and the temperature was gradually increased from 27 ° C to 120 ° C over 18 hours while the composition was cured. By bonding the pair of optical article plates, a glass-laminated photochromic optical article having a 0.1 mm thick photochromic layer was obtained. The photochromic properties and durability of the obtained photochromic optical article were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 4.

[0313] [Table 1]

[0314] [Table 2]

[0315] [Table 3]

[0316] [Table 4]

[0317] <Production of acrylic curable composition and cured product>

[0318] <Photochromic compound (component A)> PC1

[0319] <Polymerizable monomer component> Compound (23a) Polyethylene glycol dimethacrylate (average molecular weight 736) Polyethylene glycol dimethacrylate (average molecular weight 536) Trimethylolpropane trimethacrylate γ-Methacryloyloxypropyltrimethoxysilane Glycidyl methacrylate pr2: A polyrotaxane synthesized by the method described in WO 2018 / 235771. The axial molecule is formed of polyethylene glycol with a molecular weight of 11,000, the bulky groups at both ends are adamantyl groups, the cyclic molecule is α-cyclodextrin, and an average of 3.5 molecules of ε-caprolactone are ring-opening polymerized via oxypropylene groups.

[0320] The characteristics of pr2 are shown below. Inclusion amount of α-cyclodextrin: 0.25. Side chain modification degree: 0.5. Side chain molecular weight: Average of about 100. Molecular weight of chains containing polymerizable groups (acrylic groups): Average of about 650 (excluding polymerizable groups). Weight average molecular weight: 200000. From these results, it can be seen that pr2 has a structure in which acrylic groups are introduced as polymerizable groups in 50% of the side chains, and 50% of the side chains have OH groups at their terminals. 1 H-NMR measurements revealed that chains having an average of approximately 140 polymerizable groups (acrylic groups) were introduced per molecule.

[0321] <Curing accelerator (component E)> Irgacure 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (polymerization initiator manufactured by BASF)

[0322] <Other ingredients> Stabilizer HP: Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]

[0323] (Examples 51 to 52, Comparative Example 2) A photochromic curable composition was prepared by mixing the components according to the formulation shown in Table 5. Next, 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 10% aqueous sodium hydroxide solution at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0324] The surface of the plastic lens was coated with a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) using a spin coater (1H-DX2, manufactured by MIKASA) at 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds. Approximately 2 g of the photochromic composition obtained above was then spin coated at 60 rpm for 40 seconds, followed by 600 rpm for 10 to 20 seconds, to form a photochromic coating layer with a thickness of 40 μm.

[0325] The lens with the coating applied to its surface was placed in a nitrogen gas atmosphere with an output of 200mW / cm 2 The coating was cured by irradiating the coating with light for 90 seconds using a metal halide lamp, and then heated at 110°C for an additional hour to obtain a photochromic optical article in which the surface of the plastic lens was coated with a photochromic cured product.

[0326] The photochromic properties and durability of the obtained photochromic optical article were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 5.

[0327] [Table 5]

[0328] (Example 53) Synthesis of compound (24a) Compound (14a) (6.5 g, 1.0 mmol) synthesized in Example 8 and toluenesulfonic acid monohydrate (0.076 g, 0.4 mmol) were dissolved in 50 mL of dry toluene, and then 3-mercaptopropionic acid (0.47 g, 4.4 mmol) was added. The mixture was heated to reflux at 130°C for 10 hours to carry out dehydration condensation. After the reaction, the solvent was removed by distillation under reduced pressure, and the resulting mixture was dissolved in dichloromethane. The organic layer was then washed with 1% aqueous ammonia. After washing three times with ion-exchanged water, the organic layer was dried over magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain compound (24a) (yield: 92%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (24a) was measured, the following peaks were observed. δ1.14 (m, 192H), 2.68-2.81 (m, 16H), 3.40-3.70 (m, 416H), 4.10 (m, 8H).

[0329] (Example 54) Synthesis of compound (25a) Compound (14a) (6.5 g, 1.0 mmol) synthesized in Example 8 was dissolved in 50 mL of dry tetrahydrofuran, and then 60% sodium hydride (0.24 g, 6.0 mmol) was added to the solution and stirred at room temperature for 1 hour. Epichlorohydrin (0.56 g, 6.0 mmol) was added to the stirred solution and stirred at room temperature for 15 hours. After the reaction, the solvent was evaporated under reduced pressure, and the residue was dissolved in dichloromethane. The organic layer was washed three times with ion-exchanged water. The organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain compound (25a). Proton nuclear magnetic resonance spectroscopy analysis revealed that the introduction rate of glycidyl groups was 70%.

[0330] Example 55 The components were mixed according to the formulation shown in Table 6 to prepare photochromic curable compositions. Next, the prepared photochromic curable composition was thoroughly degassed, and then this composition was used as an adhesive to produce a photochromic optical article having a polarizing film layer and a photochromic layer by a glass lamination method. Specifically, a pair of glass plates for optical articles was first prepared. An acrylic adhesive was applied to one side of one of the glass plates for optical articles by spin coating to form a coating film. A polarizing film (thickness 27 μm, luminous transmittance 42.5%, polarization degree 99.2%, gray color, polyvinyl alcohol base) was laminated on this coating film. Next, the coating film was cured by irradiating it with UV light through the glass plate. This resulted in a first laminate in which one of the glass plates and the polarizing film were bonded via the acrylic adhesive layer.

[0331] Next, the photochromic curable composition was applied to the other glass plate for optical articles, which had 0.1 mm thick spacers on its edge, to form a coating film. The first laminate obtained by the above method was laminated on this coating film so that the polarizing film was in contact with the coating film. The coating was then cured to obtain a photochromic optical article in which the other glass plate and the polarizing film were bonded via the photochromic resin layer. The photochromic curable composition was polymerized in an air oven by gradually increasing the temperature from 27°C to 120°C over 18 hours. The photochromic resin layer had a thickness of 0.1 mm. The photochromic properties and durability of the obtained photochromic optical article were evaluated in the same manner as in Example 18, and the evaluation results are shown in Table 6.

[0332] Example 56 A photochromic cured product was prepared and evaluated in the same manner as in Example 18, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0333] Example 57 A photochromic cured product was prepared and evaluated in the same manner as in Example 49, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0334] Example 58 A photochromic cured product was prepared and evaluated in the same manner as in Example 50, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0335] Example 59 A photochromic cured product was prepared and evaluated in the same manner as in Example 55, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0336] (Example 60) Synthesis of compound (26a)

[0337] [ka]

[0338] Polyethylene glycol 400 (Fujifilm Wako Pure Chemical Industries, Ltd., 16.0 g, 40.0 mmol) and imidazole (2.72 g, 40.0 mmol) were dissolved in 150 mL of dichloromethane, and then t-butyldimethylsilyl chloride (Aldrich, Ltd., 6.03 g, 40.0 mmol) was added and stirred at room temperature for 15 hours. After the reaction, the organic layer was washed three times with water. After drying the organic layer over magnesium sulfate, the solvent was removed under reduced pressure. Next, the obtained compound and triethylamine (4.05 g, 40.0 mmol) were dissolved in 150 mL of dichloromethane, and then p-toluenesulfonic acid chloride (Tokyo Chemical Industry, 7.63 g, 40.0 mmol) was added and stirred at room temperature for 15 hours. After the reaction, the organic layer was washed three times with water. After drying the organic layer over magnesium sulfate, the solvent was evaporated under reduced pressure (yield: 70%).

[0339] Next, sodium hydride (0.60 g, 25.0 mmol) was dispersed in dry THF (150 mL), and polytetramethylene oxide 1000 (Fujifilm Wako Pure Chemical Industries, 12.5 g, 12.5 mmol) was added and stirred at room temperature for 30 minutes. The compound obtained above (17.1 g, 25.0 mmol) was then added and stirred at room temperature for 5 hours under a nitrogen atmosphere. After the reaction was completed, ion-exchanged water was added to terminate the reaction, followed by extraction with dichloromethane. The organic layer was washed three times with water, and the solvent was removed under reduced pressure. Next, the obtained compound was dissolved in THF, and a 1 mol tetrabutylammonium fluoride / LTHF solution (Tokyo Chemical Industry, 25.0 mL, 25.0 mmol) was added and stirred at room temperature for 15 hours. After the reaction, the organic layer was washed three times with water. The organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure to obtain compound (26a) (yield: 85%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (26a) was measured, the following peaks were observed. δ1.55-1.70(m,56H),3.40-3.70(m,128H).

[0340] (Example 61) Synthesis of compound (27a) [ka]

[0341] Sodium hydride (0.60 g, 25.0 mmol) was dispersed in dry THF (150 mL), and then compound (26a) (45.0 g, 25.0 mmol) synthesized by the method described in Example 60 was added and stirred at room temperature for 30 minutes. Pentaerythrityl tetrabromide (2.33 g, 6.0 mmol) was then added and stirred at room temperature for 4 hours under a nitrogen atmosphere. After completion of the reaction, ion-exchanged water was added to quench the reaction, followed by extraction with dichloromethane. The organic layer was washed three times with water, and the solvent was evaporated under reduced pressure to obtain compound (27a) (yield: 75%). Furthermore, when the proton nuclear magnetic resonance spectrum of compound (27a) was measured, the following peaks were observed. δ1.55-1.70(m,224H),3.40-3.70(m,520H).

[0342] (Examples 62 to 63) A photochromic cured product was prepared and evaluated in the same manner as in Example 18, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0343] Example 64 A photochromic cured product was prepared and evaluated in the same manner as in Example 49, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0344] Example 65 A photochromic cured product was prepared and evaluated in the same manner as in Example 50, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0345] Example 66 A photochromic cured product was prepared and evaluated in the same manner as in Example 55, except that the formulation was changed as shown in Table 6. The evaluation results are shown in Table 6.

[0346] (Comparative Example 3) As shown in Table 6, a photochromic cured product was prepared and evaluated in the same manner as in Comparative Example 1, except that the amount of TDMP was increased and the amounts of H6XDI and TMMP were decreased. The evaluation results are shown in Table 6.

[0347] Comparative Example 4 As shown in Table 6, a photochromic cured product was prepared and evaluated in the same manner as in Example 18, except that compound 7a was omitted and the amounts of H6XDI and TMMP were increased. The evaluation results are shown in Table 6.

[0348] [Table 6] [Industrial Applicability]

[0349] The compound for optical materials, the curable composition and the cured product of the present invention can be used for optical articles having photochromic properties, such as plastic lenses.

Claims

1. A compound for optical materials represented by the following formula (Ia): 【Chemical 1】 In the formula (Ia), X １ and X ２ are each NH, S, or O, R １ is the following formula (4c), (4a), (4b), (5d), (5a), (5b), (6h), or (6a), 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 R ２ is H or CH ３ and R ３ is a group consisting of a block copolymer represented by the following formula (IIa): -(CH 2 CH 2 O) x - (CH 2 CH (CH 3 ) O) y - (CH 2 CH 2 O) z - (IIa) In the formula (IIa), x is an integer of 5 to 20, y is an integer of 5 to 40, and z is an integer of 1 to 20. R ４ teeth, H. H ２ C=CH-C(=O)-, or H ２ C=C(CH ３ )-C(=O)-、 and a is 0, b is 1, c is 0 or 1, and d is 3, 4, or 6.

2. The R １ is an organic residue selected from the group consisting of the following formulae (4c), (4b), (5d), (5a), (6h), and (6a): 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】

3. A curable composition comprising the compound for optical materials (component D) according to claim 1 or 2, and at least one compound (component B) selected from the group consisting of polyisocyanate compounds and polyisothiocyanate compounds.

4. R in formula (Ia) ４ But, H ２ C=CH-C(=O)-, or H ２ C=C(CH ３ )-C(=O)- A curable composition comprising the compound for optical materials (component D) according to claim 3, wherein

5. The curable composition according to claim 3 or 4, further comprising a photochromic compound (component A).

6. A cured product obtained by curing the curable composition according to any one of claims 3 to 5.

7. An optical article comprising the cured product according to claim 6.

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