Photochromic compound, phenol derivative, curable composition, optical article, lens, and eyeglass

Abstract

The purpose of the present disclosure is to provide: a photochromic compound having excellent temperature dependency and an excellent color fading rate; a phenol derivative that can be an intermediate for the photochromic compound; and a curable composition, an optical article, a lens, and an eyeglass, each containing the photochromic compound. An embodiment of the present invention provides a photochromic compound having a backbone represented by formula (1). In formula (1), M represents C, Si, or Ge. Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring obtained through fusing, to either of said rings, an aromatic ring or an aromatic heterocyclic ring. Z1 represents a group represented by formula (1a) or a group represented by formula (1b).

Description

Photochromic compound, phenol derivative, curable composition, optical article, lens, and eyeglasses

[0001] The present invention relates to a photochromic compound, a phenol derivative, a curable composition, an optical article, a lens, and eyeglasses.

[0002] Photochromic compounds are compounds that can reversibly convert into two isomers with different absorption spectra when irradiated with ultraviolet light, such as sunlight or light from a mercury lamp. Generally, when a colorless, bleached compound is irradiated with ultraviolet light, it quickly changes color and undergoes isomerization (coloring reaction) to a colored state. Photochromic compounds are being researched and developed as materials for photochromic lenses.

[0003] In such applications for photochromic lenses, the photochromic compound may be required to have the following properties: (I) A low degree of coloration in the visible light region before ultraviolet irradiation (hereinafter referred to as initial coloration); (II) A high rate at which the color density (hereinafter referred to as color density) reaches saturation after ultraviolet irradiation begins (hereinafter also referred to as high color sensitivity); (III) A high rate at which the compound returns to its original state after ultraviolet irradiation is stopped (hereinafter referred to as fading rate); (IV) A high durability against repeated reversible action; and (V) A high solubility in the material that forms the lens matrix and a high dispersibility in the cured product.

[0004] Known photochromic compounds that can satisfy these requirements include chromene compounds having an indeno(2,1-f)naphtho(1,2-b)pyran structure as a basic skeleton, such as the chromene compound represented by the following formula (A) (Patent Document 1), the chromene compound represented by the following formula (B) (Patent Document 2), and the chromene compound represented by the following formula (C) (Patent Document 3).

[0005]

[0006]

[0007]

[0008] In recent years, the performance required of photochromic compounds has become more sophisticated, and in addition to the above characteristics (I) to (V), the ability to exhibit high color density even at high temperatures such as those in summer is also required. Hereinafter, such a characteristic may also be referred to as "low temperature dependency." Generally, by improving the thermal stability of the colored state, high color density can be exhibited even at high temperatures, but the color fading rate decreases, so there is a trade-off between color density and color fading rate at high temperatures. There is a demand for photochromic compounds that can achieve both high color density and high color fading rate at high temperatures.

[0009] Japanese Patent Publication No. 2018-062496, International Publication No. WO 2005 / 090327, U.S. Patent Application Publication No. 2012 / 0053341, International Publication No. WO 2018 / 215371, International Publication No. 2013 / 042800, International Publication No. 2015 / 035325, International Publication No. 2018 / 235771, International Publication No. 2012 / 102410, International Publication No. 2011 / 053615, International Publication No. 2007 / 078529, International Publication No. 2019 / 013249, International Publication No. 2016 / 143910

[0010] An object of the present invention is to provide a photochromic compound having excellent temperature dependency and fading speed, a phenol derivative that can serve as an intermediate for this photochromic compound, and a curable composition, optical article, lens, and eyeglasses that contain this photochromic compound.

[0011] According to the present disclosure, there is provided a photochromic compound having a skeleton represented by the following formula (1):

[0012]

[0013] In formula (1), M is C, Si, or Ge. Ring A is an aromatic ring, a heteroaromatic ring, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or a heteroaromatic ring is fused to the above ring.

[0014] Z １ is a group represented by the following formula (1a) or a group represented by the following formula (1b):

[0015]

[0016]

[0017] In formula (1a), R １ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the above substituent.

[0018] R ２ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a):

[0019] -Q １ -(X １ Q ２ ) a-X ２ Q ３ (2a) In formula (2a), Q １ is an alkylene group or a haloalkylene group, ２ is an alkylene group or a haloalkylene group, and Q ３ is an alkyl group or a haloalkyl group. １ , and X ２ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O). ７００ and R ７０１ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and a is 0 or 1 to 3.

[0020] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings.

[0021] Y １ is a substituted or unsubstituted methylene group. ２represents a substituted or unsubstituted methylene group, O, S, SO ２ , N.R. ６００ , R ６０１ C=CR ６０２ , or CC. R ６００ , R ６０１ , and R ６０２ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ３ is a substituted or unsubstituted methylene group, m is an integer of 1 to 4, n is an integer of 0 to 4, and m+n is an integer of 1 or more.

[0022] R ３ , and R ４ are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3):

[0023] L １ -R ４００ (X3) In formula (X3), R ４００ is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent, and L １ is a group represented by the following formula (X2).

[0024]

[0025] In formula (X2), R ３０ is a group represented by the following formula (X2a).

[0026]

[0027] In formula (X2) and formula (X2a), J represents a divalent group, each independently representing a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, and R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, and R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group; h, j, k, and l are each independently an integer of 0 or 1; i is an integer of 1 to 200; and when i is 2 or more, a plurality of R ３０ may be the same or different, and the dashed line represents R ４００ Represents a bond with

[0028] R ３ and R ４ may, together with M, form a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to the heterocycle.

[0029] R ５ and R ６ are each independently a hydrogen atom or a substituent, and R ７ and R ８ are each independently a substituent, b is an integer of 0 to 3, and c is an integer of 0 to 4.

[0030] According to the present disclosure, there is provided a curable composition, which includes a photochromic compound according to an embodiment and at least one selected from the group consisting of a radical polymerizable monomer, a cationically polymerizable monomer, a compound having a polymerization reactive group, and a (thio)urethane (urea) polymer.

[0031] According to another embodiment, an optical article is provided, the optical article comprising a cured form of the curable composition.

[0032] According to the present disclosure, a lens is provided, the lens including a photochromic compound according to an embodiment.

[0033] According to the present disclosure, eyeglasses are provided, the eyeglasses including lenses according to an embodiment.

[0034] According to the present disclosure, there is provided a phenol derivative, which has a skeleton represented by the following formula (5):

[0035]

[0036] In formula (5), M, ring A, Z １ , R ３ , and R ４ are each independently defined as in the above formula (1).

[0037] According to the present invention, there are provided a photochromic compound having excellent temperature dependency and fading speed, a phenol derivative that can serve as an intermediate for this photochromic compound, and a curable composition, optical article, lens, and eyeglasses that contain this photochromic compound.

[0038] 1 is a graph showing an example of the relationship between the 23° C. color fading half-life and the high-temperature color development rate of photochromic laminates according to Examples and Comparative Examples.

[0039] [Photochromic Compound] According to an embodiment, there is provided a photochromic compound represented by the following formula (1):

[0040]

[0041] In formula (1), M is C, Si, or Ge. Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the ring. Z １ is a group represented by the following formula (1a) or a group represented by the following formula (1b):

[0042]

[0043] In formula (1a), R １ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. ２ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a):

[0044] -Q １ -(X １ Q ２ ) a-X ２ Q ３ (2a) In formula (2a), Q １ is an alkylene group or a haloalkylene group. ２ is an alkylene group or a haloalkylene group. ３ is an alkyl group or a haloalkyl group. １ , and X ２ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O). ７００ and R ７０１ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. a is 0 or 1 to 3.

[0045]

[0046] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring. １ is a substituted or unsubstituted methylene group. ２ represents a substituted or unsubstituted methylene group, O, S, SO ２ , N.R. ６００ , R ６０１ C=CR ６０２ , or CC. R６００ , R ６０１ , and R ６０２ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ３ is a substituted or unsubstituted methylene group or an oxygen atom, m is an integer of 1 to 4, n is an integer of 1 to 4, and m+n is an integer of 1 or more.

[0047] R ３ , and R ４ are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3):

[0048] R ３ and R ４ may, together with M, form a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to the heterocycle.

[0049] L １ -R ４００ (X3) In formula (X3), R ４００ is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent.

[0050] L １is a group represented by the following formula (X2).

[0051]

[0052] In formula (X2), R ３０ is a group represented by the following formula (X2a).

[0053]

[0054] In formula (X2) and formula (X2a), J represents a divalent group, each independently representing a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group.

[0055] L is an oxygen atom or a sulfur atom. ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent.

[0056] R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group. h, j, k, and l are each independently an integer of 0 or 1. i is an integer of 1 to 200, and when i is 2 or greater, multiple R ３０ may be the same or different, and the dashed line represents R ４００ represents a bond with ５ and R ６ are each independently a hydrogen atom or a substituent. ７ and R ８ are each independently a substituent. b is an integer of 0 to 3. c is an integer of 0 to 4.

[0057] This photochromic compound has excellent temperature dependency and fading speed. The reason for this is not clear, but the present inventors believe it to be as follows.

[0058] Substituent Z of the photochromic compound according to the embodiment １The above formula (1a) or (1b) is used in the above formula (1a) or (1b). In the above formula (1a) and formula (1b), an aryl group or a heteroaryl group is directly bonded to a nitrogen atom, and thus the skeleton shown in formula (1) and the substituent Z are bonded via a p orbital on the nitrogen atom. １ It is believed that the compound having such a structure has an extended conjugation compared to a compound in which the above formula (1a) and the above formula (1b) are not substituted. This extension increases the amount of light absorbed in the bleached state, and therefore it is believed that the color density can be improved even at high temperatures.

[0059] In addition, the substituent Z １ When the substitution position to which the substituent Z is bonded is substituted with a substituent having high electron donating property, the fading rate of the photochromic compound tends to decrease. １ In the formula, an aryl group or heteroaryl group is bonded to the nitrogen atom, and the electron donating property is thought to be reduced by conjugation. １ It is believed that the photochromic compound having the formula (I) exhibits a suppressed decrease in the fading rate.

[0060] From the above, by using the photochromic compound according to the embodiment, a cured product excellent in both temperature dependency and fading speed can be realized. Therefore, such a photochromic compound is suitable for optical articles used in environments with large temperature changes, such as sunglasses.

[0061] The photochromic compound represented by formula (1) will be described in detail below.

[0062] <M> In formula (1), M is C, Si, or Ge. M is preferably C.

[0063] <Ring A> In formula (1), ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring.

[0064] Examples of the aromatic hydrocarbon ring include a benzene ring and a cyclotetradecaheptaene ring.

[0065] Examples of the aromatic heterocycle include a furan ring, a thiophene ring, and a pyridine ring.

[0066] Examples of the fused polycyclic ring include a naphthalene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a perylene ring, a benzofuran ring, a benzothiophene ring, a quinoline ring, an isoquinoline ring, an indole ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a cinnoline ring, a phthalazine ring, a 1,2,3-, 1,2,4-, or 1,3,5-triazine ring, a carbazole ring, a benzoxazole ring, and an isothiazole ring.

[0067] Among these, a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a pyrene ring, a furan ring, a thiophene ring, or a pyridine ring is preferred, a benzene ring, a naphthalene ring, a fluorene ring, or a phenanthrene ring is more preferred, and a benzene ring is most preferred.

[0068] <Z １ In formula (1), Z １ is a group represented by the following formula (1a) or a group represented by the following formula (1b): The dashed lines in formula (1a) and formula (1b) represent the bond to the carbon atom at the 11th position of the naphthopyran skeleton of formula (1).

[0069] <Formula (1a)>

[0070]

[0071] <Formula (1b)>

[0072]

[0073] (R １ ) R １ R is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the above substituent. １ The substituents that may be possessed by the group will be described later.

[0074] The number of carbon atoms in the substituted or unsubstituted aryl group is, for example, 5 to 12, preferably 6 to 10. Examples of heteroatoms in the substituted or unsubstituted heteroaryl group include at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. The number of heteroatoms in the substituted or unsubstituted heteroaryl group is, for example, 1 to 3, preferably 1 or 2. The number of carbon atoms in the substituted or unsubstituted heteroaryl group is, for example, 4 to 11, preferably 5 to 9.

[0075] R １ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted 1-naphthyl group, a substituted or unsubstituted 2-naphthyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyrrolinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzofuranyl group, or a substituted or unsubstituted benzopyrrolinyl group, more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted 1-naphthyl group, or a substituted or unsubstituted 2-naphthyl group, and particularly preferably a substituted or unsubstituted phenyl group.

[0076] R １ The substituent that may be possessed by is preferably at least one selected from the group consisting of a linear or branched alkyl group having from 1 to 6 carbon atoms, a linear or branched haloalkyl group having from 1 to 6 carbon atoms, a linear or branched alkoxy group having from 1 to 6 carbon atoms, and a halogen atom. The number of substituents is, for example, from 1 to 3.

[0077] (R ２ ) R ２ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a):

[0078] R ２is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a), more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a group represented by the following formula (2a), and particularly preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, or a group represented by the following formula (2a).

[0079] The alkyl group is preferably an unsubstituted alkyl group having from 1 to 10 carbon atoms, and more preferably an unsubstituted alkyl group having from 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0080] The haloalkyl group is preferably a haloalkyl group having 1 to 6 carbon atoms. The number of halogen atoms is preferably 1 to 10, and more preferably 2 to 5. The haloalkyl group having 1 to 6 carbon atoms is preferably an alkyl group substituted with a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group preferably has a terminal perfluoromethyl group. Examples of suitable haloalkyl groups include a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, a tetrafluoroethyl group, a chloromethyl group, a 2-chloroethyl group, and a bromomethyl group.

[0081] The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms (a cycloalkyl group having 3 to 8 carbon atoms forming a ring). Examples of cycloalkyl groups having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The cycloalkyl group may have a substituent, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms of the substituent.

[0082] The alkoxy group is preferably an alkoxy group having from 1 to 6 carbon atoms. Examples of suitable alkoxy groups having from 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0083] The aryl group is R １ The aryl group is preferably a phenyl group or a naphthyl group.

[0084] The heteroaryl group is R １ The same groups as those exemplified in the above can be used.

[0085] R ２ The substituent that may be possessed by is preferably at least one selected from the group consisting of a linear or branched alkyl group having from 1 to 6 carbon atoms, a linear or branched haloalkyl group having from 1 to 6 carbon atoms, a linear or branched alkoxy group having from 1 to 6 carbon atoms, and a halogen atom. The number of substituents is, for example, from 1 to 3.

[0086] R ２ is preferably any one of an alkyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a phenyl group, or a phenyl group having a substituent. The fluoroalkyl group having 1 to 5 carbon atoms preferably has a perfluoromethyl group at the end.

[0087] (Group represented by formula (2a)) -Q １ -(X １ Q ２ ) a-X ２ Q ３ (2a) In formula (2a), Q １ is an alkylene group or a haloalkylene group.

[0088] The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 12, even more preferably 1 to 7, and most preferably 2 to 6. As the halogen atom of the haloalkylene group, at least one selected from the group consisting of I, Cl, Br, and F can be used. The halogen atom is preferably at least one of C1 and F, more preferably F. In the haloalkylene group, a halogen atom is preferably bonded to a terminal carbon, and the terminal is more preferably a perfluoromethyl group.

[0089] Q ２ is an alkylene group or a haloalkylene group. A preferred embodiment of the alkylene group or the haloalkylene group is １ It is the same as: ２ The number of carbon atoms in the alkylene group or haloalkylene group is １ The number of carbon atoms in the alkylene group or haloalkylene group may be the same as or different from that of the alkylene group or haloalkylene group.

[0090] Q ３ is an alkyl group or a haloalkyl group, which may be linear or branched, but is preferably linear.

[0091] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and most preferably 1 to 7. The halogen atom in the haloalkyl group can be at least one selected from the group consisting of I, Cl, Br, and F. The halogen atom is preferably at least one of C1 and F, and more preferably F.

[0092] Q ３ is preferably a straight chain alkyl group.

[0093] X １ , and X ２ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O). X １ , and X ２ is O, S, or NR ７００is preferred, and O is most preferred.

[0094] R ７００ and R ７０１ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0095] R ７００ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. The aryl group is preferably a phenyl group or a naphthyl group.

[0096] R ７０１ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group. The aryl group is preferably a phenyl group or a naphthyl group.

[0097] a is 0 or 1 or more and 3 or less;

[0098] Formula (2a) is preferably an alkylenealkoxy group, an alkylenethioalkyl group, or an alkyleneoxyalkylenealkoxy group.

[0099] Specific examples of the group represented by formula (2a) include —CH ２ OCH ３ , -CH ２ SCH ３ , -CH ２ CH ２ OCH ３ , -CH ２ CH ２ OCH ２ CH ３ , -CH ２ CH ２ SCH ３ , -CH ２ CH ２ CH ２ OCH ３ , -CH ２ CH ２ CH２ SCH ３、 -CH ２ CH ２ OCH ２ CH ２ OCH ３、 and -CH ２ CH ２ OCH ２ CH ２ OCH ２ CH ３ Examples include:

[0100] The group represented by formula (2a) is —CH ２ OCH ３ , -CH ２ CH ２ OCH ３ , -CH ２ CH ２ OCH ２ CH ３ , -CH ２ CH ２ CH ２ OCH ３ , -CH ２ CH ２ OCH ２ CH ２ OCH ３、 Or, -CH ２ CH ２ OCH ２ CH ２ OCH ２ CH ３ is preferred.

[0101] (Specific Examples of Formula (1a)) Suitable examples of formula (1a) are as follows.

[0102]

[0103] <Formula (1b)>

[0104]

[0105] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring. Suitable ring B has the same meaning as that exemplified for ring A.

[0106] Y１ is a substituted or unsubstituted methylene group. １ When Y has a substituent, the substituent is preferably a halogen atom, a haloalkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and more preferably a fluorine atom or a methyl group. １ When has a substituent, the number of the substituents is one or two.

[0107] Y １ is more preferably a methylene group substituted with a methyl group or a fluorine atom, or an unsubstituted methylene group, and particularly preferably an unsubstituted methylene group.

[0108] Y ２ represents a substituted or unsubstituted methylene group, O, S, SO ２ , N.R. ６００ , R ６０１ C=CR ６０２ , or CC.

[0109] R ６００ , R ６０１ , and R ６０２ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.

[0110] Y ２ represents a substituted or unsubstituted methylene group, O, S, SO ２ , or NR ６００ is preferably an unsubstituted methylene group, O, S, or SO ２ It is more preferable that:

[0111] Y ３ is a substituted or unsubstituted methylene group, and preferred Y ３ Regarding Y １ This has the same meaning as the example given above.

[0112] m is an integer of 1 to 4. m is preferably 1 or 2. n is an integer of 0 to 4. n is preferably 0 or 1. m+n is an integer of 1 or more. m+n is preferably 1 or more and 4 or less, more preferably 1 or 2. When n is 0, ring B does not contain Y ２ are combined.

[0113] A preferred example of formula (1b) is as follows:

[0114]

[0115] <R ３ and R ４ > R ３ , and R ４ are each independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the formula (2a), or a group represented by the following formula (X3). ３ , and R ４ is a group other than a substituted or unsubstituted phenyl group.

[0116] Examples of the substituted or unsubstituted alkyl group, haloalkyl group, group represented by formula (2a), substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, and substituted or unsubstituted heteroaryl group include R １ or R ２ The same groups as those exemplified in the above can be used.

[0117] The amino group is a primary amino group (-NH ２ ) or a secondary or tertiary amino group in which one or two hydrogen atoms have been substituted. Examples of the substituent on the substituted amino group include an alkyl group having from 1 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 7 carbon atoms, an aryl group having from 6 to 14 carbon atoms, and a heteroaryl group having from 4 to 14 carbon atoms. Examples of suitable amino groups include an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a methylphenylamino group, and a diphenylamino group.

[0118] The heterocyclic group is preferably a heterocyclic group having 3 to 10 atoms. The heteroatom of the heterocyclic group is preferably at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. The number of heteroatoms is, for example, 1 to 5, preferably 1 or 2. Specific examples include aliphatic heterocyclic groups such as a morpholino group, a piperidino group, a pyrrolidinyl group, a piperazino group, and an N-methylpiperazino group, and aromatic heterocyclic groups such as an indolinyl group. The heterocyclic group may be a 2,6-dimethylmorpholino group, a 2,6-dimethylpiperidino group, or a 2,2,6,6-tetramethylpiperidino group.

[0119] The alkylthio group is preferably an alkylthio group having from 1 to 6 carbon atoms. Examples of the alkylthio group having from 1 to 6 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group, and a t-butylthio group.

[0120] The arylthio group is preferably an arylthio group having from 6 to 10 carbon atoms. Examples of the arylthio group having from 6 to 10 carbon atoms include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

[0121] The alkylcarbonyl group is preferably an alkylcarbonyl group having from 2 to 7 carbon atoms. Examples of the alkylcarbonyl group having from 2 to 7 carbon atoms include an acetyl group and an ethylcarbonyl group.

[0122] The alkoxycarbonyl group is preferably an alkoxycarbonyl group having from 2 to 7 carbon atoms. Examples of the alkoxycarbonyl group having from 2 to 7 carbon atoms include a methoxycarbonyl group and an ethoxycarbonyl group.

[0123] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0124] The aralkyl group is preferably an aralkyl group having from 7 to 11 carbon atoms. Examples of the aralkyl group having from 7 to 11 carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a naphthylmethyl group.

[0125] The aralkoxy group is preferably an aralkoxy group having from 7 to 11 carbon atoms. Examples of the aralkoxy group having from 7 to 11 carbon atoms include a benzyloxy group and a naphthylmethoxy group.

[0126] The aryloxy group is preferably an aryloxy group having from 6 to 12 carbon atoms. Examples of the aryloxy group having from 6 to 12 carbon atoms include a phenyloxy group and a naphthyloxy group.

[0127] The alkoxyalkylthio group is preferably an alkoxyalkylthio group having from 2 to 9 carbon atoms. Examples of the alkoxyalkylthio group having from 2 to 9 carbon atoms include a methoxymethylthio group, a methoxyethylthio group, a methoxy n-propylthio group, a methoxy n-butylthio group, an ethoxyethylthio group, and an n-propoxypropylthio group.

[0128] The haloalkylthio group is preferably a haloalkylthio group having from 1 to 6 carbon atoms. Examples of the haloalkylthio group having from 1 to 6 carbon atoms include a trifluoromethylthio group, a tetrafluoroethylthio group, a chloromethylthio group, a 2-chloroethylthio group, and a bromomethylthio group.

[0129] The cycloalkylthio group is preferably a cycloalkylthio group having 3 to 8 carbon atoms. Examples of the cycloalkylthio group having 3 to 8 carbon atoms include a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, and a cyclohexylthio group. The cycloalkylthio group may have a substituent, but the number of carbon atoms in the substituent is not included in the number of carbon atoms (3 to 8 carbon atoms).

[0130] The silyl group may have a substituent. The substituent of the substituted silyl group is not particularly limited, and examples thereof include an alkyl group having from 1 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 7 carbon atoms, an aryl group having from 6 to 14 carbon atoms, and a heteroaryl group having from 4 to 14 carbon atoms.

[0131] The oxysilyl group may have a substituent. The substituent of the substituted oxysilyl group is not particularly limited, and examples thereof include an alkyl group having from 1 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 7 carbon atoms, an aryl group having from 6 to 14 carbon atoms, and a heteroaryl group having from 4 to 14 carbon atoms.

[0132] The cycloalkyl group, arylthio group, aralkyl group, aralkoxy group, aryloxy group, aryl group, heteroaryl group, and cycloalkylthio group may be unsubstituted. However, when they have a substituent, it is preferable that 1 to 8 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, in the group forming the ring are substituted with a substituent selected from a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group having 3 to 8 atoms, a cyano group, a nitro group, and a halogen atom. Specific examples of these substituents will be described later.

[0133] R ３ and R ４may be a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3):

[0134] R ３ and R ４ is preferably a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), or a group represented by formula (X3). ３ and R ４ When is one of these groups, the fading rate of the photochromic compound tends to increase.

[0135] R ３ and R ４ may, together with M, form a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to an aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocycle is fused to a heterocycle.

[0136] R ３ and R ４preferably forms a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to an aliphatic ring, or a substituted or unsubstituted heterocyclic ring having 3 to 20 ring atoms, and more preferably forms a ring selected from a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a spirodicyclohexane ring. Furthermore, the ring may have 1 to 10 alkyl groups having 1 to 5 carbon atoms or cycloalkyl groups having 5 to 7 carbon atoms as substituents, or may be fused with cycloalkyl groups having 5 to 7 carbon atoms. Specifically, it is more preferable that the rings shown below be formed.

[0137]

[0138] R ３ and R ４ The substituent that may be possessed by is preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

[0139] <Group represented by formula (X3)> L １ -R ４００ (X3) In formula (X3), R ４００ is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent.

[0140] L １ is a group represented by the following formula (X2).

[0141]

[0142] In formula (X2), J is a divalent group. Each of the plurality of Js independently represents a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR ３０１ It is. ３０１ is a hydrogen atom or an alkyl group. ３０１is preferably an alkyl group having 1 to 20 carbon atoms. This alkyl group preferably has, as a substituent, a silyl group, a polymerizable group, or a photochromic group having an alkyl group having 1 to 10 carbon atoms.

[0143] Examples of the polymerizable group include radically polymerizable groups such as vinyl group, 1-chlorovinyl group, allyl group, styryl group, (meth)acrylic group, 2-(methacryloxy)ethylcarbamyl group, 2-(methacryloxy)ethoxycarbonyl group, and crotyl group. In addition to these, other radically polymerizable groups include epoxy group, episulfide group, thietanyl group, OH group, SH group, and NH ２ Examples of the polymerizable group include a (meth)acrylic group, a 2-(methacryloxy)ethylcarbamyl group, a 2-(methacryloxy)ethoxycarbonyl group, an epoxy group, an OH group, an SH group, an NH ２ At least one selected from the group consisting of a group and a COOH group is preferred.

[0144] The photochromic group is a group containing a photochromic moiety. Representative examples of the photochromic group include naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, and diarylethene. In terms of being able to exhibit excellent photochromic properties, indenonaphthopyran is preferred, and among these, indeno[2,1-f]naphtho[1,2-b]pyran is particularly preferred.

[0145] The indeno[2,1-f]naphtho[1,2-b]pyran is preferably a group represented by the following formula (X4).

[0146]

[0147] In formula (X4), R ４０１ and R ４０２ is the above-mentioned R ３ and R ４ The group may be the same as the group used in

[0148] R ４０３ and R ４０４ are each independently the above-mentioned R ３ and R ４The group may be the same as the group used in

[0149] R ４０５ and R ４０６ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. ４０５ and R ４０６ is R ５ and R ６ The group may be the same as the group used in

[0150] o is an integer of 0 to 4. n is an integer of 0 to 4. When o is 2 to 4, multiple R ４０３ may be the same or different. When n is 2 to 4, multiple R ４０４ may be the same or different from each other.

[0151] R ４０１ , R ４０２ , R ４０３ , R ４０４ , and R ４０５ At least one of the substituents on the aryl or heteroaryl group of L １ and combine.

[0152] A particularly preferred group represented by formula (X2) is represented by the following formula:

[0153]

[0154] In formula (X2), L is an oxygen atom or a sulfur atom.

[0155] R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent. ３００ is preferably an alkylene group having 1 to 6 carbon atoms, or a silylene group having an alkyl group having 1 to 6 carbon atoms as a substituent.

[0156] R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group. ３０２ is preferably an alkylene group having 1 to 6 carbon atoms. ３０３is preferably an alkylene group having 1 to 6 carbon atoms. ３０４ is preferably an alkylene group having 1 to 6 carbon atoms.

[0157] h, j, k, and l each independently represent an integer of 0 or 1;

[0158] "i" is an integer of 1 to 200. The structures of groups to which multiple "i"s are attached may be the same or different. "i" is preferably a number in the range of 5 to 100, more preferably 8 to 75, and most preferably 10 to 70.

[0159] The dashed line in formula (X2) represents R ４００ represents a bond with ５ and R ６ In formula (1), R ５ and R ６ are each independently a hydrogen atom or a substituent. ５ and R ６ are each preferably independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. １ The same groups as those exemplified in the above can be used.

[0160] R ５ and R ６ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted 1-naphthyl group, a substituted or unsubstituted 2-naphthyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyrrolinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzofuranyl group, or a substituted or unsubstituted benzopyrrolinyl group. ５ and R ６ Preferably, at least one of R is a substituted or unsubstituted phenyl group. ５ and R ６ More preferably, both are substituted phenyl groups.

[0161] The substituent on the phenyl group is preferably a group represented by formula (2a), a hydroxyl group, an alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (X3). The substituent is more preferably an alkyl group, a haloalkyl group, an alkoxy group, an amino group, a substituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, an alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, or a group represented by formula (X3).

[0162] <R ７ and R ８ In formula (1), R ５ and R ６ are each independently a substituent. ７ and R ８are each independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), a group represented by the following formula (X), or a group represented by formula (X3) is preferred. These groups include R １ ~R ４ The same groups as those exemplified in the above can be used.

[0163] b is an integer of 0 to 3. c is an integer of 0 to 4. When b is 2 or 3, multiple R ７ may be the same or different from each other. ７ If there is a ７ is R ７ and the carbon atom bonded thereto may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings. ７ The combination of these is at the 9th and 10th positions of the chromene compound.

[0164] When c is 2 to 4, multiple R ８ may be the same or different from each other. ８ If there is a ８ is R ８and the carbon atom bonded thereto may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings. ８ The combinations are the 5th and 6th positions, the 6th and 7th positions, and the 7th and 8th positions of the chromene compound.

[0165] R ７ or R ８ may form a ring having 5 to 8 atoms, including the carbon atom to which is bonded. The ring may have a substituent, and examples of the substituent include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group having 3 to 8 atoms, a cyano group, a nitro group, and a halogen atom. Specific examples of these substituents will be described later.

[0166] R ７ or R ８ A preferred ring formed by the formula (X5) is a ring represented by the following formula (X5).

[0167]

[0168] In formula (X5), Q and T each independently represent a sulfur atom, a substituted or unsubstituted methylene group, an oxygen atom, or NR ３０７ R is a group represented by the formula: ３０７ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (2a).

[0169] R ３０５ and R ３０６are each independently a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryl group, a thiol group, an alkylthio group, an alkoxyalkylthio group, a haloalkylthio group, a cycloalkylthio group, or a substituted or unsubstituted arylthio group.

[0170] Also, R ３０５ and R ３０６ may form a substituted or unsubstituted aliphatic ring together with the carbon atom to which they are bonded. Specific examples of the aliphatic ring include a cyclopentane ring and a cyclohexane ring. In addition, in the aliphatic ring, 1 to 8 hydrogen atoms, and particularly preferably 1 to 4 hydrogen atoms, may be substituted with at least one group selected from the group consisting of a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group, a cyano group, a nitro group, and a halogen atom. Specific examples of these substituents will be described later.

[0171] In the formula, m is an integer of 1 to 4.

[0172] <Group represented by formula (X)>

[0173]

[0174] In formula (X), E is an oxygen atom or NR １０１ It is. １０１ is a hydrogen atom or an alkyl group. １０１ and R １０１ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0175] F is an oxygen atom or a sulfur atom, and preferably an oxygen atom.

[0176] G is an oxygen atom, a sulfur atom, or NR ２０２ It is. ２０２is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. G is preferably NH.

[0177] g is 0 or 1.

[0178] R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. When G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom. ２０１ is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0179] Suitable groups of formula (X) are as follows:

[0180]

[0181] <Skeleton Represented by Formula (2)> The photochromic compound according to the embodiment preferably has a naphthopyran skeleton represented by the following formula (2). In the following formula (2), Z １ , R ３ , R ４ and M have the same meanings as in formula (1).

[0182]

[0183] <Compound Represented by Formula (3)> The photochromic compound according to the embodiment is preferably a compound represented by the following formula (3). In the following formula (3), Z １ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , b, a, and M have the same meanings as in formula (1).

[0184]

[0185] <Photochromic Compound Represented by Formula (4)> Particularly suitable chromene compounds include compounds represented by the following formula (4).

[0186]

[0187] In formula (4), R ３ , R ４ , R ７ , R ８ , Z １ , M, b, and c each independently have the same meaning as in formula (3).

[0188] <R ９ and R １０ > R ９ and R １０ are each independently a hydroxyl group, an alkyl group having from 1 to 6 carbon atoms, a haloalkyl group having from 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having from 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3).

[0189] d is R ９ and is an integer of 0 to 5. When d is 2 or more, R ９ may be the same or different groups.

[0190] d is 2 to 5, and adjacent R ９ If there is a ９ is R ９ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings.

[0191] e is R １０ and is an integer of 0 to 5. When e is 2 or more, R １０ may be the same or different groups.

[0192] e is 2 to 5, and adjacent R １０ If there is a １０ is R １０ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings.

[0193] R ９ and R １０ are each independently, and two adjacent ones can join together to form a cyclic group which may contain at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom. This cyclic group is not particularly limited, but ９ and R １０ It is preferable that the ring has 5 to 8 atoms, including the carbon atom to which R is bonded. The ring may have a substituent. Examples of the substituent include a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group having 3 to 8 atoms, a cyano group, a nitro group, and a halogen atom. Specific examples of these substituents include R １ ~R ４ The same groups as those exemplified in the group R ９ and R １０ The ring formed by these preferably forms a ring represented by formula (X5) together.

[0194] <Detailed Description of Substituents, etc.> The above-mentioned R １ ~R １０Examples of the substituent that may be possessed by the group include a hydroxyl group, a cyano group, a halogen atom, a nitro group, a formyl group, a hydroxycarbonyl group, a thiol group, a group represented by formula (2a), a group represented by formula (X), a group represented by formula (X3), an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group, a halogen atom, an alkylthio group, an arylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl, an aralkoxy group, an aryloxy group, an aryl group, a heteroaryl group, an alkoxyalkylthio group, a haloalkylthio group, a cycloalkylthio group, a silyl group, or an oxysilyl group. １ ~R ４ The same as those detailed in 1. can be used.

[0195] <Specific Examples of Suitable Photochromic Compounds> Specific examples of particularly suitable photochromic compounds include photochromic compounds represented by the following formulas.

[0196]

[0197] [Phenol Derivative] The phenol derivative according to this embodiment is represented by the following formula (5): This phenol derivative can be used as an intermediate for synthesizing the photochromic compound represented by the above formula (1).

[0198]

[0199] In formula (5), M and R ３ , R ４ , R ７ , R ８ , Z １ , ring A, b, and c each independently have the same meaning as in the above formula (1).

[0200] <Phenol derivative represented by formula (6)> The phenol derivative according to this embodiment may have a skeleton represented by the following formula (6): This phenol derivative can be used as an intermediate for synthesizing a photochromic compound having the skeleton represented by the above formula (2).

[0201]

[0202] In formula (6), M and R ３ , R ４ , and Z １ are each independently defined as in the above formula (2).

[0203] <Phenol derivative represented by formula (7)> ​​The phenol derivative according to this embodiment is represented by the following formula (7): This phenol derivative can be used as an intermediate for synthesizing the photochromic compound represented by the above formula (3) and the photochromic compound represented by the above formula (4).

[0204]

[0205] In formula (7), M and R ３ , R ４ , R ７ , R ８ , Z １ , b, and c each independently have the same meaning as in the above formula (4).

[0206] <Specific Examples of Phenol Derivatives> Specific examples of phenol derivatives according to the embodiment include compounds represented by the following formulas.

[0207]

[0208] [Method for producing photochromic compound] The photochromic compound according to the embodiment may be produced by any synthesis method. A typical example of a method for producing a photochromic compound will be described, but the method is not limited to this method. In the following description, the symbols in each formula have the same meaning as those described for the formula above, unless otherwise specified.

[0209] The photochromic compound can be produced by reacting the phenol derivative represented by the above formula (7) with a propargyl alcohol compound represented by the following formula (8) in the presence of an acid catalyst.

[0210]

[0211] The reaction ratio of the phenol derivative to the propargyl alcohol compound is preferably selected from the range of 1:10 to 10:1 (molar ratio). Examples of acid catalysts that can be used include sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, and acidic alumina. The acid catalyst is used in an amount of preferably 0.1 to 10 parts by weight per 100 parts by weight of the total of the phenol derivative and the propargyl alcohol compound. The reaction temperature is preferably 0 to 200°C. The solvent is preferably an aprotic organic solvent, such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, or toluene. The purification method for the product obtained by this reaction is not particularly limited. For example, the product can be purified by silica gel column purification followed by recrystallization.

[0212] <Method for synthesizing phenol derivative> The phenol derivative represented by formula (7) can be synthesized by a known method. The method for synthesizing the phenol derivative represented by formula (7) is not particularly limited, but for example, when M is a carbon atom, it can be synthesized as follows.

[0213] First, a benzene compound represented by the following formula (9) is reacted with an acid chloride compound represented by the following formula (10) to obtain a benzophenone compound represented by the following formula (11). １ , R ７ , R ８ , b and c have the same meanings as in formula (3).

[0214]

[0215]

[0216]

[0217] Depending on the structure and substituents of the photochromic compound to be synthesized, the substituents of the acid chloride compound and the benzene compound may be interchanged. １ , R ７ and an acid chloride compound having R ８ The compound may be reacted with a benzene compound having the formula:

[0218] Furthermore, benzophenone compound (11) is subjected to a Stobbe reaction, a cyclization reaction, a hydrolysis reaction using an alkali or an acid, benzyl protection, or debenzylation by hydrolysis reaction using an alkali or an acid to obtain a carboxylic acid represented by the following formula (12) in which the hydroxyl group is protected with benzyl (Bn). Next, the benzyl-protected carboxylic acid represented by formula (12) is converted to an amine by a method such as Curtius rearrangement, Hofmann rearrangement, or Lossen rearrangement, and a diazonium salt is prepared from the amine. This diazonium salt is converted to a halide such as bromide or iodide by a Sandmeyer reaction or the like to obtain a halide represented by the following formula (13) (wherein Hal represents a halogen).

[0219]

[0220]

[0221] The obtained halide is reacted with magnesium, lithium, or the like to prepare an organometallic reagent. This organometallic reagent is represented by the following formula (14) (wherein R ３ and R ４ has the same meaning as in formula (3)) in an organic solvent at −100 to 70° C. to obtain a compound represented by the following formula (15).

[0222]

[0223]

[0224] The resulting compound represented by formula (15) is debenzylated, followed by reaction under neutral to acidic conditions at 10 to 120°C for 10 minutes to 2 hours to spirate the alcohol, thereby synthesizing the desired phenol derivative represented by formula (7). In this reaction, the reaction ratio of the organometallic reagent to the ketone represented by formula (14) can be varied over a wide range, but is preferably selected from a molar ratio of 1:10 to 10:1. The reaction temperature is preferably −100 to 70°C. Preferred solvents include aprotic organic solvents such as diethyl ether, tetrahydrofuran, benzene, and toluene. Spiration of the alcohol under neutral to acidic conditions is preferably carried out in the presence of an acid catalyst. Examples of acid catalysts that can be used include acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, and acidic alumina. Such acid catalysts are preferably used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the alcohol. The spiro reaction is preferably carried out in the presence of a solvent such as tetrahydrofuran, benzene, or toluene.

[0225] In the above method, the substituent Z １ This shows an example of a method using a raw material having Z. For example, after synthesizing a precursor having a halogen atom, １ By using a Buchwald reaction using an amine having a -H structure and a Pd catalyst, a substituent Z １ can also be introduced.

[0226] Substituent Z １ The reaction for introducing is not particularly limited, and for example, after synthesizing a photochromic compound having a halogen atom, the halogen atom can be introduced. An example is shown below.

[0227] First, the substituent Z １ Instead of Z, a compound having a halogen atom is used, and the reaction is carried out in the same manner as in the above example, to obtain Z １Instead of the above, a benzophenone compound having a halogen atom is used, and a carboxylic acid compound represented by the following formula (16) obtained by a Stobbe reaction, a cyclization reaction, or a hydrolysis reaction using an alkali or an acid is subjected to spiro reaction under neutral to acidic conditions, or a reduction reaction using hydrogen, hydrazine, or the like, to obtain a phenol derivative represented by the following formula (17).

[0228]

[0229]

[0230] Alternatively, the compound of formula (17) can be synthesized by intramolecular cyclization of the halogen compound of formula (13) in the presence of a palladium catalyst.

[0231] The resulting phenol derivative is used to obtain a photochromic compound of the following formula (18).

[0232]

[0233] The resulting photochromic compound was reacted with R ３ By reacting the compound with a halide of the formula (19), a photochromic compound precursor of the formula (19) is obtained.

[0234]

[0235] The halogen atoms of the obtained precursor and Z １ The photochromic compound of the present invention can be obtained by subjecting an amine having a —H structure to a Buchwald reaction using a Pd catalyst.

[0236] <Method for synthesizing phenol derivative containing Si or Ge> An example of a method for producing a phenol derivative in which M in formula (7) is Si or Ge will be described below.

[0237] First, the halide represented by formula (13) is reacted with magnesium, lithium, or the like to prepare an organometallic reagent. This organometallic reagent is then converted into a compound represented by the following formula (20) (wherein R ３ and R ４has the same meaning as in formula (7)) in an organic solvent at −100 to 70° C. to obtain a compound represented by the following formula (21).

[0238]

[0239]

[0240] The resulting compound represented by formula (21) is used to obtain a cyclized product represented by formula (22) below by a known method.

[0241]

[0242] The resulting cyclized product is debenzylated to give a phenol derivative of formula (7).

[0243] <Identification of Photochromic Compound> The photochromic compound according to the embodiment is, for example, a solid or a viscous liquid at room temperature and normal pressure. From this solid or liquid, the photochromic compound can be isolated by a separation procedure such as thin layer chromatography, silica gel column chromatography, high performance liquid chromatography, or gas chromatography. In addition, it is confirmed that there are no by-products such as raw material compounds and coloring matters other than the photochromic compound.

[0244] The obtained photochromic compound was analyzed by proton nuclear magnetic resonance spectroscopy ( １ By measuring the photochromic compound by H-NMR, peaks due to aromatic protons and alkene protons appear around δ: 5.0 to 9.0 ppm, and peaks due to alkyl and alkylene protons appear around δ: 1.0 to 4.0 ppm. Furthermore, by comparing the respective spectral intensities relatively, the number of protons in each bonding group can be determined. This allows the skeleton and substituents of the photochromic compound to be identified.

[0245] Furthermore, when the photochromic compound is contained in a cured product such as a resin, the photochromic compound can be isolated by dissolving the resin and using the above-mentioned separation means.

[0246] <Photochromic Composition> The photochromic compound according to the embodiment can be dissolved in a common organic solvent such as toluene, chloroform, or tetrahydrofuran. When the photochromic compound represented by formula (1) is dissolved in such a solvent, a colorless, transparent solution is obtained. When this solution is irradiated with sunlight or ultraviolet light, it rapidly develops color, and when the sunlight or the like is blocked, it reversibly and rapidly returns to its original colorless state, exhibiting good photochromic properties.

[0247] The photochromic compound according to the embodiment can be used in combination with photochromic compounds having other structures depending on the intended application. For example, it can be used in combination with other photochromic compounds to obtain various color tones required for a photochromic lens. Known photochromic compounds can be used without any limitations as the photochromic compound to be combined. Examples include indenonaphthopyran, naphthopyran, spirooxazine, spiropyran, fulgide, fulgimide, and diarylethene. Among these, indenonaphthopyran compounds are particularly preferred because they can maintain a uniform color tone during color development and fading, suppress color shift during color development due to deterioration of photochromic properties, and further reduce initial coloring. It is preferable to use multiple photochromic compounds to adjust the color tone, particularly because they can achieve both high color density and fast fading speed at high temperatures and also have excellent durability.

[0248] When a photochromic composition containing the photochromic compound according to the embodiment and other photochromic compounds is prepared, the blending ratio of each photochromic compound is appropriately determined depending on the desired color tone.

[0249] <Photochromic Curable Composition> The curable composition according to the embodiment includes the photochromic compound according to the embodiment and at least one selected from the group consisting of a radical polymerizable monomer, a cationically polymerizable monomer, a compound having a polymerization reactive group, and a (thio)urethane (urea) polymer. Here, the (thio)urethane (urea) polymer includes at least one selected from the group consisting of a urethane polymer, a thiourethane polymer, a urethane urea polymer, and a thiourethane urea polymer.

[0250] The photochromic compound and photochromic composition according to the embodiment are preferably used in combination with a polymerizable compound as a photochromic curable composition.

[0251] The amount of the photochromic curable composition used depends on the color intensity of the photochromic compound, the selected lens material, and the lens thickness, and cannot be generalized; however, it is preferable to use the photochromic compound (or photochromic composition) in an amount of 0.001 to 10 parts by mass per 100 parts by mass of the polymerizable compound. The optimal amount varies depending on the intended use. For example, the amounts are as follows when the photochromic curable composition is used as a thin-film optical article and when it is used as a thick-film optical article.

[0252] (Use as Thin Film Optical Article) For example, when the photochromic curable composition is made into a thin film (a polymer film obtained by polymerizing the photochromic curable composition) having a thickness of 10 μm or more and less than 1000 μm, for example, about 100 μm, it is preferable to adjust the color tone by blending 0.001 to 10 parts by mass of the photochromic compound (or photochromic composition) of the above embodiment with 100 parts by mass of other polymerizable monomers.

[0253] (Use as a thick-film optical article) In the case of a thick cured body (a polymer molded body obtained by polymerizing the photochromic curable composition), for example, a cured body having a thickness of 1 mm or more, it is preferable to adjust the color tone by blending 0.001 to 1 part by mass of the photochromic compound (or photochromic composition) of the above embodiment with 100 parts by mass of the thick cured body or another polymerizable monomer that gives a thick cured body.

[0254] <Polymerizable Compound> As described above, the photochromic compound is preferably used in combination with a polymerizable compound to form a photochromic curable composition. Examples of the polymerizable compound include urethane or urea-based polymerizable compounds capable of forming a urethane bond, a urea bond, etc., compounds having a polymerization reactive group, radical polymerizable compounds, and epoxy-based polymerizable compounds. These polymerizable compounds are not particularly limited, but for example, the polymerizable compounds described in Patent Document 7 can be suitably used.

[0255] Among these, the compounds having the following polymerizable reactive groups are particularly preferably used.

[0256] <Compound Having a Polymerization Reactive Group> Examples of compounds having a polymerization reactive group include compounds having an iso(thio)cyanate group (iso(thio)cyanate compound). The iso(thio)cyanate compound is a compound having an isocyanate group or an isothiocyanate group, and may contain both an isocyanate group and an isothiocyanate group. This compound is preferably used in combination with a compound containing active hydrogen, which will be described later. Examples of such iso(thio)cyanate compounds include, but are not limited to, the following compounds:

[0257] (Polyiso(thio)cyanate) Polyiso(thio)cyanate is a compound having at least two iso(thio)cyanate groups in one molecule. Examples of polyiso(thio)cyanates include aromatic polyiso(thio)cyanates having an aromatic ring, such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and aliphatic polyiso(thio)cyanates, such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

[0258] (Compound Having Active Hydrogen) The compound having active hydrogen is not limited thereto, but is preferably a compound having a hydroxyl group and / or a thiol group, and particularly preferably a polyfunctional compound having two or more active hydrogens in one molecule. Specific examples of the compound having active hydrogen include polyfunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate) and 4-mercaptomethyl-3,6-dithia-octanedithiol; and polyfunctional alcohols such as trimethylolpropane and pentaerythritol.

[0259] (Radical Polymerizable Compound) The radical polymerizable compound includes a polyfunctional radical polymerizable compound and a monofunctional radical polymerizable compound. These can be used alone or in combination. The radical polymerizable substituent includes a group having an unsaturated double bond, i.e., a vinyl group (including a styryl group, a (meth)acrylic group, an allyl group, etc.).

[0260] The polyfunctional radical polymerizable compound is a compound having two or more radical polymerizable substituents in the molecule, and includes a first polyfunctional radical polymerizable compound having 2 to 10 radical polymerizable substituents and a second polyfunctional radical polymerizable compound having more than 10 radical polymerizable substituents.

[0261] The first polyfunctional radically polymerizable compound is not particularly limited, but it is more preferable that the number of radically polymerizable substituents is 2 to 6. Specific examples thereof are as follows:

[0262] (Polyfunctional (meth)acrylic acid ester compounds) Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane.

[0263] (Polyfunctional allyl compounds) Diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate.

[0264] (Polyfunctional thio(meth)acrylic acid ester compounds) 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl)ether, 1,4-bis(methacryloylthiomethyl)benzene.

[0265] (Radical Polymerizable Compound) Examples of the second polyfunctional radically polymerizable compound having more than 10 radically polymerizable substituents include compounds with relatively large molecular weights, such as silsesquioxane compounds having radically polymerizable substituents and polyrotaxane compounds having radically polymerizable substituents.

[0266] Furthermore, the monofunctional radically polymerizable compound is a compound having one radically polymerizable substituent in the molecule, and specific examples thereof include, but are not limited to, the following compounds.

[0267] (Unsaturated carboxylic acids) acrylic acid, methacrylic acid, maleic anhydride.

[0268] ((Meth)acrylic acid esters) Methyl (meth)acrylate, benzyl methacrylate, phenyl methacrylate.

[0269] 2-hydroxyethyl methacrylate, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, bisphenol A monoglycidyl ether methacrylate, 4-glycidyloxy methacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 3-(glycidyloxy-1-isopropyloxy)-2-hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy)-2-hydroxypropyl acrylate.

[0270] (Fumaric acid esters) Diethyl fumarate, diphenyl fumarate.

[0271] (Thio(meth)acrylic acid) methyl thioacrylate, benzyl thioacrylate, benzyl thiomethacrylate.

[0272] (Vinyl Compounds) Divinylbenzene, styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene.

[0273] The radical polymerizable compounds can be used alone or in combination. In this case, the amount of the polyfunctional radical polymerizable compound is preferably 80 to 100 parts by mass and the amount of the monofunctional radical polymerizable compound is preferably 0 to 20 parts by mass, and more preferably 90 to 100 parts by mass of the polyfunctional radical polymerizable compound and 0 to 10 parts by mass of the monofunctional radical polymerizable compound, per 100 parts by mass of the total of the radical polymerizable compounds. Furthermore, the amount of the first polyfunctional radical polymerizable compound is preferably 80 to 100 parts by mass, the amount of the second polyfunctional radical polymerizable compound is 0 to 20 parts by mass, and the amount of the monofunctional radical polymerizable compound is preferably 0 to 20 parts by mass, and more preferably 85 to 100 parts by mass of the first polyfunctional radical polymerizable compound, the amount of the second polyfunctional radical polymerizable compound is 0 to 10 parts by mass, and the amount of the monofunctional radical polymerizable compound is 0 to 10 parts by mass, per 100 parts by mass of the total of the radical polymerizable compounds.

[0274] (Various Compounding Agents) Various known compounding agents can be compounded into the curable composition as long as the effects are not impaired. Examples of compounding agents include various stabilizers such as release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances. Solvents and leveling agents can also be compounded. Thiols such as t-dodecyl mercaptan can also be compounded as polymerization regulators.

[0275] Among the above-mentioned compounding ingredients, ultraviolet stabilizers are preferred because they can improve the durability of the photochromic moiety. Known examples of such ultraviolet stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. Particularly preferred ultraviolet stabilizers are as follows:

[0276] Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Adeka STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87 manufactured by Adeka Corporation, 2,6-di-tert-butyl-4-methyl-phenol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565 manufactured by BASF Japan Ltd. The amount of such an ultraviolet stabilizer used is not particularly limited as long as the effect is not impaired, but is usually in the range of 0.001 to 10 parts by mass, particularly 0.01 to 1 part by mass, per 100 parts by mass of the photochromic curable composition.

[0277] In addition to the ultraviolet stabilizer, an ultraviolet absorber can also be used. Known ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, triazine-based compounds, and benzoate-based compounds can be used as the ultraviolet absorber, with cyanoacrylate-based compounds and benzophenone-based compounds being particularly preferred. The ultraviolet stabilizer is preferably used in an amount of 0.001 to 5 parts by mass relative to 100 parts by mass of the photochromic curable composition containing the photochromic compound and the polymerizable compound.

[0278] <Method of using photochromic curable composition; optical article> A photochromic cured product is obtained by curing the photochromic curable composition. Polymerization and curing for producing the photochromic cured product is carried out by 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. That is, an appropriate polymerization method may be adopted depending on the types of polymerizable compound and polymerization and curing accelerator and the form of the photochromic cured product to be formed.

[0279] When a curable composition containing a polymerizable compound is thermally polymerized, the temperature affects the properties of the resulting photochromic cured product.

[0280] The temperature conditions cannot be unconditionally limited because they are affected by the type and amount of the thermal polymerization initiator and the type of polymerizable compound, but a generally preferred method is to start the polymerization at a relatively low temperature and slowly increase the temperature. 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. Generally, however, it is preferable to select conditions so that the polymerization is completed within 2 to 48 hours. When obtaining a photochromic laminate sheet, it is preferable to carry out the polymerization at a temperature at which the reaction between polymerizable functional groups proceeds, and to determine the optimal temperature and time to achieve the desired molecular weight.

[0281] Furthermore, when photopolymerizing a curable composition, among the polymerization conditions, UV intensity in particular affects the properties of the resulting photochromic cured product. The illuminance conditions cannot be generally limited because they are affected by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, but generally range from 50 to 500 mW / cm at a wavelength of 365 nm. ２ It is preferable to select the conditions so that the UV light is irradiated for 0.5 to 5 minutes.

[0282] [Optical Articles] The photochromic compound according to the embodiment can be used in a wide range of applications as a photochromic material, and can be used as various memory materials, such as various memory materials replacing silver halide photosensitive materials, copying materials, printing photoreceptors, memory materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, etc. The photochromic material can also be used as a photochromic lens material, optical filter material, display material, actinometer, decoration material, etc.

[0283] The photochromic compound according to the embodiment is particularly suitable for use in photochromic lenses. The photochromic lenses are suitable as lenses for spectacles such as sunglasses. Any known method can be used to manufacture the photochromic lenses, as long as it can provide uniform photochromic performance.

[0284] When photochromic properties are expressed by the kneading method, the above-mentioned curable composition is injected between glass molds held by elastomer gaskets or spacers, and depending on the types of polymerizable compound and polymerization curing accelerator, a photochromic cured product molded into the shape of an optical material such as a lens can be obtained by casting polymerization using heating in an air oven or irradiation with active energy rays such as ultraviolet rays.

[0285] When photochromic properties are expressed by a lamination method, a coating liquid is prepared by dissolving a curable composition in an appropriate organic solvent, and the coating liquid is applied to the surface of an optical substrate such as a lens substrate by spin coating, dipping, or the like, and then dried to remove the organic solvent. Subsequently, polymerization and curing are carried out by UV irradiation or heating in an inert gas such as nitrogen, thereby forming a photochromic layer made of a photochromic cured product on the surface of the optical substrate (coating method).

[0286] Alternatively, a photochromic layer made of a photochromic cured product can be formed on the surface of an optical substrate by cast polymerization using an inner mold in which an optical substrate such as a lens substrate is placed facing a glass mold so that a predetermined gap is formed, a curable composition is injected into this gap, and polymerization and curing are carried out in this state by UV irradiation, heating, etc. (cast polymerization method).

[0287] When a photochromic layer is formed on the surface of an optical substrate by the above-mentioned lamination methods (coating method and cast polymerization method), the adhesion between the photochromic layer and the optical substrate can be improved by previously subjecting the surface of the optical substrate to a chemical treatment using an alkaline solution, an acid solution, etc., or a physical treatment using corona discharge, plasma discharge, polishing, etc. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0288] Furthermore, when photochromic properties are expressed by a binder method, a photochromic sheet is produced by sheet molding using a curable composition, and this is sandwiched between two transparent sheets (optical sheets), and the aforementioned polymerization and curing is carried out to obtain a photochromic laminate in which the photochromic layer serves as an adhesive layer.

[0289] In this case, the photochromic sheet can also be produced by coating with a coating liquid prepared by dissolving the curable composition in an organic solvent.

[0290] The photochromic laminate produced in this manner is, for example, placed in a mold, and then a thermoplastic resin (e.g., polycarbonate) for optical substrates such as lenses is injection molded to obtain optical substrates such as lenses of a predetermined shape to which photochromic properties have been imparted.

[0291] This photochromic laminate can also be adhered to the surface of an optical substrate with an adhesive or the like, thereby obtaining a photochromic lens.

[0292] When preparing a photochromic laminate as described above, it is preferable to use a urethane or urea-based polymerizable compound, particularly a urethane-based polymerizable compound, as the polymerizable compound, and adjust it so that polyurethane is formed, in order to obtain particularly high adhesion to the optical substrate.

[0293] The above-described curable composition can exhibit photochromic properties with excellent color density at high temperatures.

[0294] Furthermore, the photochromic layer or photochromic cured product formed from the curable composition can be dyed using a dye such as a disperse dye, or a hard coat film can be formed using a hard coat agent whose main component is a sol of a silane coupling agent or silicon, zirconium, antimony, aluminum, tin, tungsten, or the like, depending on the application. ２ , TiO ２ , ZrO ２ It is also possible to carry out post-processing such as forming a thin film by vapor deposition of a metal oxide such as ZnO, applying an organic polymer to form a thin film to prevent reflection, or performing antistatic treatment.

[0295] The present invention will be described in more detail by the following examples, which are merely illustrative of the present invention and are not intended to limit the scope and spirit of the present invention.

[0296] (Example 1) First Step: 28.9 g (62.4 mmol) of the compound represented by the following formula (1-1) synthesized from 4-bromo-4'-methoxybenzophenone with reference to the method described in Patent Document 8, 550 mL of toluene, 9.36 g (87.4 mmol) of N-methylaniline, and 24.0 g (249.6 mmol) of sodium tert-butoxide were added, and the mixture was stirred under reduced pressure to remove dissolved oxygen. ２ (dba) ３ 0.57 g (0.6 mmol) of HCl and 1.19 g (2.5 mmol) of X-phos were added, and the mixture was heated to 80°C.

[0297]

[0298] Heating was continued until the raw materials were consumed. After the reaction was completed, the mixture was cooled to room temperature and then filtered. 500 mL of tetrahydrofuran and 10% hydrochloric acid were added to the obtained filtrate, neutralized, and then the layers were separated. The obtained organic layer was concentrated and purified by reslurrying in 100 mL of methanol, yielding a carboxylic acid compound represented by the following formula (1-2) in a yield of 92%.

[0299]

[0300] Second Step: An iodine compound represented by the following formula (1-3) was obtained in a yield of 86% by referring to the method of Patent Document 8, except that the carboxylic acid compound obtained in Example 1 was used.

[0301]

[0302] Step 3: 360 mL of toluene was added to 22.5 g (41.5 mmol) of the compound of formula (1-3) obtained in Step 2, and azeotropic dehydration was performed until the water content in the toluene was 100 ppm or less. After azeotropic dehydration, the mixture was slowly cooled to -20°C, and 31.2 mL of n-BuLi (1.6 mol / L hexane solution) was slowly added dropwise while maintaining the temperature at -15 to -20°C. After confirming that the raw materials had been consumed, 4.5 g of dehydrated acetone was added dropwise. After the addition, the mixture was slowly heated to room temperature. After heating, 200 mL of water was added and the mixture was separated. Water washing was repeated until the pH of the aqueous layer reached 7-8. The solvent from the resulting organic layer was removed, and the mixture was purified by silica gel chromatography to obtain the compound represented by the following formula (1-4) in an 80% yield.

[0303]

[0304] Step 4: 750 mL of toluene was added to 28.4 g (150.0 mmol) of p-toluenesulfonic acid monohydrate, and azeotropic dehydration was performed until the water content in the toluene was 300 ppm or less. Subsequently, a toluene solution prepared by dissolving 17.7 g (35.0 mmol) of the formula (1-4) in 100 mL of toluene was slowly added while maintaining the temperature at 85-100°C, and the mixture was refluxed after dropwise addition. After confirming the consumption of raw materials, the mixture was cooled to room temperature, and 500 mL of water was added and the mixture was separated. This procedure was repeated five times, and the solvent in the resulting organic layer was removed. The residue was purified by silica gel chromatography to obtain the phenol derivative represented by the following formula (1-5) in a yield of 78%.

[0305]

[0306] Fifth Step: 2.38 g (6.0 mmol) of the phenol derivative of the formula (1-5) and 1.92 g (7.2 mmol) of propargyl alcohol represented by the following formula (1-6) were dissolved in 40 mL of toluene, and 0.15 g (0.6 mmol) of pyridinium p-toluenesulfonate was further added thereto, followed by stirring at 85° C. for 2 hours.

[0307]

[0308] After the raw material phenol derivative was consumed, the mixture was cooled to room temperature, 40 mL of water was added, and the layers were separated. The solvent in the resulting organic layer was removed, and the residue was purified by silica gel chromatography to obtain a photochromic compound represented by the following formula (1-7) in a yield of 80%.

[0309]

[0310] The elemental analysis results of the photochromic compound represented by the formula (1-7) were C: 81.82%, H: 6.06%, and N: 2.16%. ４４ H ４９ NO ４ The results were in good agreement with the calculated values ​​of C: 81.83%, H: 6.09%, and N: 2.17%.

[0311] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 9H peak due to a methyl group at around δ0.5 to 3.5 ppm, a 9H peak due to a methoxy group at around δ3.5 to 5.0 ppm, and a 21H peak due to aromatic protons and alkene protons at around δ5.0 to 9.0 ppm.

[0312] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0313] Example 2 Step 1 A reaction was carried out in the same manner as in Step 1 of Example 1, except that 4-bromo-3',4'-dimethoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, to obtain a carboxylic acid represented by the following formula (2-1) in a yield of 92%.

[0314]

[0315] Step 2: 10.4 g (20.0 mmol) of the compound of formula (2-1) was dissolved in 400 mL of THF, 3 g of 5% Pd / C (50% water content) was added, and the mixture was stirred for 19 hours under hydrogen pressure. After completion of the reaction, the mixture was filtered, and THF was removed from the filtrate. The resulting mixture was purified by silica gel chromatography to obtain a debenzylated product represented by the following formula (2-2) in a 100% yield.

[0316]

[0317] Step 3: 7.6 g (40.0 mmol) of p-toluenesulfonic acid monohydrate and 400 mL of toluene were added, and azeotropic dehydration was carried out until the water content in the toluene was 100 ppm or less. After azeotropic dehydration, the compound of formula (2-2) was added at an internal temperature of 80°C, and the temperature was raised to the azeotropic temperature, and the reaction was carried out while azeotropic dehydration was carried out. After confirming the consumption of the raw materials, the mixture was cooled to room temperature, and the resulting solid was filtered, yielding the carbonyl compound represented by the following formula (2-3) in a yield of 96%.

[0318]

[0319] Fourth Step: With reference to the method described in Patent Document 9, a reaction was carried out using the carbonyl compound represented by the formula (2-3) to obtain a phenol derivative represented by the following formula (2-4) in a yield of 91%.

[0320]

[0321] Step 5: 6.9 g (17.4 mmol) of the phenol derivative represented by the formula (2-4) and 2.7 g (21.3 mmol) of benzyl chloride were dissolved in 100 ml of DMF. 3.6 g (26.1 mmol) of potassium carbonate was added to this solution, and the mixture was stirred at 80°C. After the raw materials were consumed, the mixture was cooled to room temperature, and water was added and washed until neutral. The solvent was removed from the resulting organic layer, and the mixture was purified by silica gel chromatography to obtain the benzyl compound represented by the following formula (2-5) in a yield of 97%.

[0322]

[0323] Step 6: 4.9 g (10.0 mmol) of the benzyl compound of formula (2-5), 8.4 g (50.0 mmol) of 1-bromo-4-methoxybutane, and 60 mL of THF were added and cooled on ice. While maintaining the temperature at 0-5°C, 3.4 g (30.0 mmol) of tBuOK was added in four portions. After the raw materials were consumed, the mixture was neutralized with 10% hydrochloric acid, and 30 mL of toluene was added and the mixture was separated. After removing the solvent from the resulting organic layer, a debenzylation reaction was carried out in the same manner as in Step 2. The product was purified by silica gel chromatography to obtain the phenol derivative represented by the following formula (2-6) in an 88% yield.

[0324]

[0325] Step 7: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (2-6) was used instead of the compound of formula (1-5), to obtain a photochromic compound represented by the following formula (2-7) in a yield of 76%.

[0326]

[0327] The elemental analysis results of the photochromic compound represented by the formula (2-7) were C: 77.62%, H: 7.00%, and N: 1.72%, ５３ H ５７ NO ７ These results were in good agreement with the calculated values ​​of C: 77.63%, H: 7.01%, and N: 1.71%.

[0328] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 15H peak due to a methyl group and a 4-methoxybutyl group around δ 0.5 to 3.5 ppm, a 22H peak due to a methoxy group and a 4-methoxybutyl group around δ 3.5 to 5.0 ppm, and a 20H peak due to an aromatic proton and an alkene proton around δ 5.0 to 9.0 ppm.

[0329] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0330] Example 3 Step 1 A phenol derivative represented by the following formula (3-1) was synthesized by carrying out the reaction in the same manner as in Example 2, except that in Step 1, 4-bromo-3',4'-dimethoxybenzophenone was replaced with 4-bromo-4'-methylbenzophenone, benzomorpholine was replaced with N-methylaniline, and in Step 6, 1,1,1-trifluoro-4-iodobutane was replaced with 1-bromo-4-methoxybutane.

[0331]

[0332] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (3-1) was used instead of the compound of formula (1-5) and the compound of formula (3-2) below was used instead of the compound of formula (1-6) above, to obtain a photochromic compound represented by formula (3-3) below in a yield of 75%.

[0333]

[0334]

[0335] The elemental analysis results of the photochromic compound represented by formula (3-3) were C: 72.73%, H: 5.75%, and N: 1.55%. ５４ H ５１ F ６ NO ４These results were in good agreement with the calculated values ​​of C: 72.71%, H: 5.76%, and N: 1.57%.

[0336] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 24H peaks due to methyl groups, 1,1,1-trifluorobutyl groups, butoxy groups, and benzmorpholino groups were observed around δ0.5 to 3.5 ppm, 7H peaks due to methoxy groups, butoxy groups, and benzmorpholino groups were observed around δ3.5 to 5.0 ppm, and 20H peaks due to aromatic protons and alkene protons were observed around δ5.0 to 9.0 ppm.

[0337] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0338] Example 4 First Step The reaction was carried out in the same manner as in the third step of Example 1, except that cyclooctanone was used instead of acetone, to obtain naphthol of the following formula (4-1) in a yield of 42%.

[0339]

[0340] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (4-1) was used instead of the compound of formula (1-5) and the compound of formula (4-2) below was used instead of the compound of formula (1-6) above, to obtain a photochromic compound represented by formula (4-3) below in a yield of 75%.

[0341]

[0342]

[0343] The elemental analysis results of the photochromic compound represented by the formula (4-3) were C: 81.24%, H: 6.81%, and N: 3.64%, ５２ H ５２ N ２ O ４ The results were in good agreement with the calculated values ​​of C: 81.22%, H: 6.82%, and N: 3.64%.

[0344] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 21H peaks due to methyl groups, cyclooctyl groups, and morpholino groups were observed around δ 0.5 to 3.5 ppm, 10H peaks due to methoxy groups and morpholino groups were observed around δ 3.5 to 5.0 ppm, and 21H peaks due to aromatic protons and alkene protons were observed around δ 5.0 to 9.0 ppm.

[0345] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0346] Example 5 First Step With reference to the method described in Patent Document 5, 4-bromobenzoyl chloride was reacted with 2,4-dimethoxy-1,1-biphenyl to obtain the compound represented by the following formula (5-1) in a yield of 83%.

[0347]

[0348] Step 2: The reaction was carried out in the same manner as in Example 1, except that in Step 1, the compound of formula (5-1) was used instead of 4-bromo-4'-methoxybenzophenone, 4-fluoro-N-methylaniline was used instead of N-methylaniline, and in Step 3, diethyl ketone was used instead of acetone, to synthesize a phenol derivative represented by the following formula (5-2).

[0349]

[0350] Step 3: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (5-2) was used instead of the compound of formula (1-5) and the compound of formula (1-6) was used instead of the compound of formula (5-3) below, to obtain a photochromic compound represented by formula (5-4) below in a yield of 71%.

[0351]

[0352]

[0353] The elemental analysis results of the photochromic compound represented by the formula (5-4) were C: 80.14%, H: 6.59%, and N: 1.65%, ５７ H ５６ FNO ５ The results were in good agreement with the calculated values ​​of C: 80.16%, H: 6.61%, and N: 1.64%.

[0354] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 23H peaks due to methyl groups, ethyl groups, and propyloxy groups were observed around δ0.5 to 3.5 ppm, 10H peaks due to methoxy groups and propyloxy groups were observed around δ3.5 to 5.0 ppm, and 23H peaks due to aromatic protons and alkene protons were observed around δ5.0 to 9.0 ppm.

[0355] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0356] Example 6 First Step The reaction was carried out in the same manner as in Example 1, except that in Step 1, 4-bromo-4'-methoxybenzophenone was replaced with 4-bromo-4'-trifluoromethoxybenzophenone, and 4-(trifluoromethyl)-N-methylaniline was replaced with N-methylaniline, and in Step 3, acetone was replaced with 4,4-diethylcyclohexanone, to synthesize a phenol derivative represented by the following formula (6-1).

[0357]

[0358] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (6-1) was used instead of the compound of formula (1-5) and the compound of formula (1-6) was used instead of the compound of formula (6-2) below, to obtain a photochromic compound represented by formula (6-3) below in a yield of 67%.

[0359]

[0360]

[0361] The elemental analysis results of the photochromic compound represented by the formula (6-3) were C: 74.13%, H: 6.72%, and N: 1.40%. ６２ H ６７ F ６ NO ４ The results were in good agreement with the calculated values ​​of C: 74.16%, H: 6.73%, and N: 1.39%.

[0362] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 43H peaks due to methyl groups, diethylcyclohexyl groups, and hexyloxy groups around δ 0.5 to 3.5 ppm, 4H peaks due to hexyloxy groups around δ 3.5 to 5.0 ppm, and 20H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm.

[0363] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0364] Example 7 Step 1 The reaction was carried out in the same manner as in Step 1 of Example 5, except that 2,2-dimethyl-1,3-benzoxathiol was used instead of 2,4-dimethoxy-1,1-biphenyl, to obtain a compound represented by the following formula (7-1) in a yield of 71%.

[0365]

[0366] Step 2: The reaction was carried out in the same manner as in Example 2, except that in Step 1, the compound of formula (7-1) was used instead of 4-bromo-3',4'-dimethoxybenzophenone, 1,2,3,4-tetrahydroquinoline was used instead of N-methylaniline, and in Step 6, 1-bromo-3-methoxypropane was used instead of 1-bromo-4-methoxybutane, to synthesize a phenol derivative represented by the following formula (7-2).

[0367]

[0368] Step 3: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (7-2) was used instead of the compound of formula (1-5) and the compound of formula (1-6) was used instead of the compound of formula (7-3) below, to obtain a photochromic compound represented by formula (7-4) below in a yield of 77%.

[0369]

[0370]

[0371] The elemental analysis results of the photochromic compound represented by the formula (7-4) were C: 76.95%, H: 6.81%, N: 1.59%, and S: 3.67%, ５６ H ５９ NO ６ The calculated values ​​of S were C: 76.94%, H: 6.80%, N: 1.60%, and S: 3.67%, which were in good agreement with the calculated values.

[0372] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 25H peaks due to methyl groups, 3-methoxypropyl groups, propoxy groups, and 1,2,3,4-tetrahydroquinoline ring groups were observed around δ0.5 to 3.5 ppm, 15H peaks due to methoxy groups, 3-methoxypropyl groups, and propoxy groups were observed around δ3.5 to 5.0 ppm, and 19H peaks due to aromatic protons and alkene protons were observed around δ5.0 to 9.0 ppm.

[0373] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0374] Example 8 First Step The reaction was carried out in the same manner as in Example 2, except that in Step 1, 4-bromo-3',4'-dimethoxybenzophenone was replaced with 4-bromo-4'-phenoxybenzophenone, diphenylamine was replaced with N-methylaniline, and in Step 6, 1-bromo-4-fluorobutane was replaced with 1-bromo-4-methoxybutane, to synthesize a phenol derivative represented by the following formula (8-1).

[0375]

[0376] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (8-1) was used instead of the compound of formula (1-5), to obtain a photochromic compound represented by the following formula (8-2) in a yield of 71%.

[0377]

[0378] The elemental analysis results of the photochromic compound represented by the formula (8-2) were C: 80.95%, H: 5.98%, and N: 1.57%, ６０ H ５３ F ２ NO ４ The results were in good agreement with the calculated values ​​of C: 80.97%, H: 6.00%, and N: 1.57%.

[0379] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 16H peak due to a 4-fluorobutyl group at around δ 0.5 to 3.5 ppm, a 6H peak due to a methoxy group at around δ 3.5 to 5.0 ppm, and a 31H peak due to aromatic protons and alkene protons at around δ 5.0 to 9.0 ppm.

[0380] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0381] Example 9 First Step The reaction was carried out in the same manner as in Example 2, except that in Step 1, 4-bromo-3',4'-dimethoxybenzophenone was used instead of 4-bromo-4'-methoxy-3'-methylbenzophenone, benzothiomorpholine was used instead of N-methylaniline, and in Step 6, iodopropane was used instead of 1-bromo-4-methoxybutane, to synthesize a phenol derivative represented by the following formula (9-1).

[0382]

[0383] Step 2: The reaction was carried out in the same manner as in Step 3 of Example 7, except that the compound of formula (9-1) was used instead of the compound of formula (7-2), to obtain a photochromic compound represented by the following formula (9-2) in a yield of 76%.

[0384]

[0385] The elemental analysis results of the photochromic compound represented by the formula (9-2) were C: 79.26%, H: 6.80%, N: 1.78%, and S: 4.09%, and C ５２ H ５３ NO ４ The calculated values ​​of S were C: 79.25%, H: 6.78%, N: 1.78%, and S: 4.07%, which were in good agreement.

[0386] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 24H peaks due to methyl groups, propyl groups, propoxy groups, and benzothiomorpholine ring groups were observed around δ0.5 to 3.5 ppm, 10H peaks due to methoxy groups, propoxy groups, and benzothiomorpholine ring groups were observed around δ3.5 to 5.0 ppm, and 19H peaks due to aromatic protons and alkene protons were observed around δ5.0 to 9.0 ppm.

[0387] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0388] Example 10 First Step A reaction was carried out using 4-bromo-3'-fluoro-4'-methylbenzophenone with reference to the method described in Patent Document 10, to obtain a compound represented by the following formula (10-1) in a yield of 83%.

[0389]

[0390] The reaction was carried out in the same manner as in Example 2, except that in Step 1, the compound represented by the formula (10-1) was used instead of 4-bromo-3',4'-dimethoxybenzophenone, N-(2-methoxyethyl)aniline was used instead of N-methylaniline, and in Step 6, 1-bromo-2-methoxyethane was used instead of 1-bromo-4-methoxybutane, to synthesize a phenol derivative represented by the following formula (10-2).

[0391]

[0392] Step 3: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (10-2) was used instead of the compound of formula (1-5), to obtain a photochromic compound represented by the following formula (10-3) in a yield of 65%.

[0393]

[0394] The elemental analysis results of the photochromic compound represented by the formula (10-3) were C: 76.59%, H: 6.89%, and N: 3.32%, ５４ H ５８ N ２ O ７ The results were in good agreement with the calculated values ​​of C: 76.57%, H: 6.90%, and N: 3.31%.

[0395] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 13H peaks due to methyl groups, 2-methoxyethyl groups, and morpholino groups were observed around δ 0.5 to 3.5 ppm, 25H peaks due to methoxy groups, 2-methoxyethyl groups, and morpholino groups were observed around δ 3.5 to 5.0 ppm, and 20H peaks due to aromatic protons and alkene protons were observed around δ 5.0 to 9.0 ppm.

[0396] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0397] Example 11 First Step With reference to the method described in Patent Document 5, 2-bromoanisole and 2,6-dimethylbenzenethiol were reacted to obtain a compound represented by the following formula (11-1) in a yield of 89%.

[0398]

[0399] Second Step: With reference to the method described in Patent Document 5, the compound of formula (11-1) was reacted with 4-bromobenzoyl chloride to obtain a compound represented by the following formula (11-2) in a yield of 91%.

[0400]

[0401] Step 3: The naphthol represented by the following formula (11-3) was synthesized in the same manner as in Example 1, except that in Step 1, the compound of formula (11-2) was used instead of 4-bromo-4'-methoxybenzophenone, and 3,4-dihydro-7-fluoro-2H-1,4-benzoxazine was used instead of N-methylaniline, and in Step 3, 3,3,5,5-tetramethylcyclohexanone was used instead of acetone.

[0402]

[0403] Step 4: The reaction was carried out in the same manner as in Step 2 of Example 4, except that the compound represented by the formula (11-3) was used instead of the compound represented by the formula (4-1), to obtain a photochromic compound represented by the following formula (11-4) in a yield of 71%.

[0404]

[0405] The elemental analysis results of the photochromic compound represented by the formula (11-4) were C: 77.25%, H: 6.48%, N: 2.85%, and S: 3.25%, and C ６３ H ６３ FN ２ O ５ The calculated values ​​of S were C: 77.27%, H: 6.48%, N: 2.86%, and S: 3.27%, which were in good agreement.

[0406] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 30H peaks due to methyl groups, tetramethylcyclohexyl groups, morpholino groups, and benzmorpholino groups were observed around δ0.5 to 3.5 ppm, 12H peaks due to methoxy groups, morpholino groups, and benzmorpholino groups were observed around δ3.5 to 5.0 ppm, and 21H peaks due to aromatic protons and alkene protons were observed around δ5.0 to 9.0 ppm.

[0407] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0408] Example 12 Step 1: 7.2 g (15.0 mmol) of the compound of the following formula (12-1) synthesized from 3-bromo-4-methyl-4'-chlorobenzophenone with reference to the method described in Patent Document 8, 40 mL of 1,2-dimethoxyethane, 4 mL of ethanol, 3.5 g (33.0 mmol) of sodium carbonate, 66 mL of water, and 2.6 g (17.3 mmol) of 4-methoxyphenylboronic acid were added, and the mixture was purged with nitrogen under reduced pressure. 86.6 mg of tetrakis(triphenylphosphine)palladium was added, and the reaction was carried out under reflux. After the raw materials were consumed, 100 mL of THF and 50 mL of toluene were added, and 10% hydrochloric acid was added until the pH of the aqueous layer reached 1, and the layers were separated. 20 mL of water was added, the layers were separated, and the solvent in the organic layer was concentrated. 50 mL of methanol was added, and the mixture was heated. The mixture was heated under reflux for 1 hour, and then cooled. After stirring at 0 to 5° C. for 3 hours, the resulting solid was filtered to obtain a carboxylic acid represented by the following formula (12-2) in a yield of 95%.

[0409]

[0410]

[0411] Second Step: The reaction was carried out in the same manner as in Example 1, except that in Step 1, the compound represented by the formula (1-1) was replaced with the compound represented by the formula (12-2), and N-ethylaniline was used instead of N-methylaniline, and in Step 3, dibutyl ketone was used instead of acetone, to synthesize a phenol derivative represented by the following formula (12-3).

[0412]

[0413] Step 3: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound represented by the formula (12-3) was used instead of the compound represented by the formula (1-5) and the compound represented by the formula (12-4) below was used instead of the compound represented by the formula (1-6) above, to obtain a photochromic compound represented by the formula (12-5) below in a yield of 67%.

[0414]

[0415]

[0416] The elemental analysis results of the photochromic compound represented by the formula (12-5) were C: 86.08%, H: 7.21%, and N: 3.15%. ６４ H ６４ N ２ O ２ The results were in good agreement with the calculated values ​​of C: 86.06%, H: 7.22%, and N: 3.14%.

[0417] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 32H peaks due to methyl groups, ethyl groups, and butyl groups around δ 0.5 to 3.5 ppm, a 3H peak due to methoxy groups around δ 3.5 to 5.0 ppm, and a 29H peak due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm.

[0418] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0419] Example 13 First Step The reaction was carried out in the same manner as in Example 1, except that benzmorpholine was used instead of N-methylaniline, to synthesize a phenol derivative represented by the following formula (13-1).

[0420]

[0421] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (1-5) was replaced with the compound of formula (13-1), to obtain a photochromic compound represented by the following formula (13-2) in a yield of 76%.

[0422]

[0423] The elemental analysis results of the photochromic compound represented by the formula (13-2) were C: 80.21%, H: 5.85%, and N: 2.06%, ４５ H ３９ NO ５ The results were in good agreement with the calculated values ​​of C: 80.21%, H: 5.83%, and N: 2.08%.

[0424] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed an 8H peak due to a methyl group and a benzmorpholino group around δ 0.5 to 3.5 ppm, an 11H peak due to a methoxy group and a benzmorpholino group around δ 3.5 to 5.0 ppm, and a 20H peak due to an aromatic proton and an alkene proton around δ 5.0 to 9.0 ppm.

[0425] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0426] Example 14 First Step The reaction was carried out in the same manner as in Example 2, except that in Step 1, 4-bromo-3',4'-dimethoxybenzophenone was replaced with 4-bromo-4'-methoxybenzophenone, and N-methyl-p-toluidine was replaced with N-methylaniline, and in Step 6, 1,1,1-trifluoromethyl-3-iodopropane was replaced with 1-bromo-4-methoxybutane, to synthesize a phenol derivative represented by the following formula (14-1).

[0427]

[0428] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (14-1) was used instead of the compound of formula (1-5) and the compound of formula (14-2) below was used instead of the compound of formula (1-6) above, to obtain a photochromic compound represented by formula (14-3) below in a yield of 68%.

[0429]

[0430]

[0431] The elemental analysis results of the photochromic compound represented by the formula (14-3) were C: 70.63%, H: 5.21%, and N: 3.22%, ５１ H ４５ F ７ N ２ O ３ The results were in good agreement with the calculated values ​​of C: 70.66%, H: 5.23%, and N: 3.23%.

[0432] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 18H peaks due to methyl groups, 1,1,1-trifluoropropyl groups, and morpholino groups around δ 0.5 to 3.5 ppm, 7H peaks due to methoxy groups and morpholino groups around δ 3.5 to 5.0 ppm, and 20H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm.

[0433] moreover １３Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0434] Example 15 First Step The reaction was carried out in the same manner as in Example 1, except that diphenylamine was used instead of N-methylaniline, to synthesize a phenol derivative represented by the following formula (15-1).

[0435]

[0436] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (1-5) was replaced with the compound of formula (15-1), to obtain a photochromic compound represented by the following formula (15-2) in a yield of 82%.

[0437]

[0438] The elemental analysis results of the photochromic compound represented by the formula (15-2) were C: 83.15%, H: 5.85%, and N: 2.00%, ４９ H ４１ NO ４ The results were in good agreement with the calculated values ​​of C: 83.14%, H: 5.84%, and N: 1.98%.

[0439] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 6H peak due to a methyl group at around δ0.5 to 3.5 ppm, a 9H peak due to a methoxy group at around δ3.5 to 5.0 ppm, and a 26H peak due to aromatic protons and alkene protons at around δ5.0 to 9.0 ppm.

[0440] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0441] Example 16 First Step The reaction was carried out in the same manner as in Example 1, except that in Step 1, 4-bromobenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and in Step 2, dimethoxyacetone was used instead of acetone, to synthesize a phenol derivative represented by the following formula (16-1).

[0442]

[0443] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (16-1) was used instead of the compound of formula (1-5) and the compound of formula (16-2) below was used instead of the compound of formula (1-6) above, to obtain a photochromic compound represented by formula (16-3) below in a yield of 69%.

[0444]

[0445]

[0446] The elemental analysis results of the photochromic compound represented by the formula (16-3) were C: 77.92%, H: 5.82%, and N: 2.04%, ４５ H ４０ FNO ５ The results were in good agreement with the calculated values ​​of C: 77.90%, H: 5.81%, and N: 2.02%.

[0447] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 3H peak due to a methyl group around δ 0.5 to 3.5 ppm, a 16H peak due to a methoxy group and a methoxymethyl group around δ 3.5 to 5.0 ppm, and a 21H peak due to an aromatic proton and an alkene proton around δ 5.0 to 9.0 ppm.

[0448] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0449] Example 17 First Step The reaction was carried out in the same manner as in Example 1, except that in Step 1, 1,2,3,4-tetrahydroquinoline was used instead of N-methylaniline, and in Step 2, dipropyl ketone was used instead of acetone, to synthesize a phenol derivative represented by the following formula (17-1).

[0450]

[0451] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (17-1) was used instead of the compound of formula (1-5) and the compound of formula (1-6) was used instead of the compound of formula (17-2) below, to obtain a photochromic compound represented by formula (17-3) below in a yield of 66%.

[0452]

[0453]

[0454] Step 3: 3.8 g (5.0 mmol) of the photochromic compound of formula (17-3) and 0.75 g (11.0 mmol) of imidazole were dissolved in 50 mL of dimethylformamide. After cooling the internal temperature to 5°C or below, a 10 mL dimethylformamide solution of 2.3 g (5.5 mmol) of [tris(trimethylsiloxy)silylethyl]dimethylchlorosilane was slowly added dropwise while maintaining the internal temperature at 5°C or below. After the dropwise addition, the mixture was stirred for 12 hours while slowly warming to room temperature. After completion of the reaction, 50 mL of water and 100 mL of toluene were added, and the mixture was separated. The solvent in the resulting organic layer was removed, and the residue was purified by silica gel chromatography to obtain the photochromic compound represented by formula (17-4) in a yield of 91%.

[0455]

[0456] The elemental analysis results of the photochromic compound represented by the formula (17-4) were C: 67.74%, H: 7.77%, and N: 1.22%, and ６５ H ８９ NO ８ Si ５ These results were in good agreement with the calculated values ​​of C: 67.72%, H: 7.78%, and N: 1.21%.

[0457] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 59H peaks at around δ0.5 to 3.5 ppm due to propyl groups, 1,2,3,4-tetrahydroquinoline ring groups, propyloxy groups, and [tris(trimethylsiloxy)silylethyl]silyl groups, 10H peaks at around δ3.5 to 5.0 ppm due to methoxy groups and propyloxy groups, and 20H peaks at around δ5.0 to 9.0 ppm due to aromatic protons and alkene protons.

[0458] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0459] Example 18 Step 1 The reaction was carried out in the same manner as in Step 1 of Example 1, except that benzothiomorpholine was used instead of N-methylaniline and cyclododecanone was used instead of acetone, to synthesize a phenol derivative represented by the following formula (18-1).

[0460]

[0461] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (18-1) was used instead of the compound of formula (1-5) and the compound of formula (1-6) was used instead of the compound of formula (18-2) below, to obtain a photochromic compound represented by formula (18-3) below in a yield of 61%.

[0462]

[0463]

[0464] Third Step: A compound represented by the following formula (18-4), which was synthesized from polyethylene glycol monomethyl ether having a number average molecular weight of 1,000 with reference to the method described in Patent Document 11, was reacted with the photochromic compound of the formula (18-3), to obtain a photochromic compound represented by the following formula (18-5) in a yield of 67%.

[0465]

[0466]

[0467] The proton nuclear magnetic resonance spectrum of the photochromic compound represented by the formula (18-5) was measured, and it showed 32H peaks due to a cyclododecyl group, a succinic acid moiety, a morpholine group, and a benzothiomorpholino group around δ 0.5 to 3.5 ppm, 104H peaks due to a methoxy group, an ethylenedioxy group, a polyethylene glycol chain group, a morpholino group, and a thiomorpholino group around δ 3.5 to 5.0 ppm, and 20H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm.

[0468] Example 19 Step 1 The reaction was carried out in the same manner as in Step 1 of Example 17, except that benzomorpholine was used instead of 1,2,3,4-tetrahydroquinoline and diethyl ketone was used instead of dipropyl ketone, to synthesize a phenol derivative represented by the following formula (19-1).

[0469]

[0470] Step 2: The reaction was carried out in the same manner as in Step 2 of Example 18, except that the compound of formula (19-1) was used instead of the compound of formula (18-1), to obtain a photochromic compound represented by the following formula (19-2) in a yield of 67%.

[0471]

[0472] Step 3 The reaction was carried out in the same manner as in Step 3 of Example 18, except that sebacoyl chloride was used instead of the compound of formula (18-4), to obtain a photochromic compound represented by the following formula (19-3) in a yield of 85%.

[0473]

[0474] The elemental analysis results of the photochromic compound represented by the formula (19-3) were C: 77.33%, H: 6.59%, and N: 3.22%, １１２ H １１４ N ４ O１４ The results were in good agreement with the calculated values ​​of C: 77.30%, H: 6.60%, and N: 3.22%.

[0475] Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 48H peaks due to ethyl groups, sebacic acid groups, morpholino groups, and benzmorpholino groups around δ 0.5 to 3.5 ppm, 26H peaks due to methoxy groups, morpholino groups, benzmorpholino groups, and ethylenedioxy groups around δ 3.5 to 5.0 ppm, and 40H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm.

[0476] moreover １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0477] (Analysis Results of Phenol Derivatives) Tables 1 and 2 summarize the analysis results of the phenol derivatives used in Examples 1 to 19.

[0478]

[0479]

[0480] (Evaluation of physical properties of photochromic plastic lens produced by coating method) (Example 20) (Preparation of curable composition) First, the photochromic compound obtained in Example 1 above, a photopolymerization initiator, and a polymerizable compound were mixed to obtain a curable composition.

[0481] As the polymerizable compound, a mixture of the following radical polymerizable monomers was used.

[0482] Polyethylene glycol dimethacrylate (average molecular weight 736): 42 parts by mass Polyethylene glycol dimethacrylate (average molecular weight 536): 12 parts by mass Trimethylolpropane trimethacrylate: 38 parts by mass γ-methacryloyloxypropyltrimethoxysilane: 2 parts by mass Glycidyl methacrylate: 1 part by mass

[0483] In the curable composition, the photochromic compound obtained in Example 1 was added in an amount of 0.25 mmol when the total amount of the radical polymerizable monomers was 100 g. The following additives were used.

[0484] Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photopolymerization initiator: Omnirad 819): 0.3 parts by mass Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (stabilizer, Irganox 245): 1 part by mass Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate: 3 parts by mass Leveling agent (L7001) manufactured by DuPont Toray Specialty Materials Co., Ltd.: 0.1 parts by mass.

[0485] The additives are blended in proportions based on 100 parts by mass of the total amount of radical polymerizable monomers.

[0486] (Production of Optical Article) Using this curable composition, polymerization was carried out as follows, and a photochromic laminate was obtained by the following lamination method.

[0487] First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 10% aqueous solution of sodium hydroxide at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0488] Using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the above plastic lens was coated with a moisture-curable primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds. Thereafter, approximately 2 g of the above obtained photochromic curable composition was spin coated at a rotation speed of 60 rpm for 40 seconds, followed by 600 rpm for 10 to 20 seconds, so as to form a photochromic coating layer with a thickness of 40 μm.

[0489] The lens having the photochromic curable composition (photochromic coating layer) applied to its surface was heated in a nitrogen gas atmosphere at an output of 200 mW / cm ２ The coating was cured by irradiating it with light for 90 seconds using a metal halide lamp, and then heated at 110°C for 1 hour to prepare a photochromic laminate having a photochromic layer.

[0490] Examples 21 to 38 In the same manner as in Example 20, photochromic laminates were prepared using the photochromic compounds obtained in Examples 2 to 19.

[0491] In Example 38 using Compound 19-3, the photochromic compound was added in an amount of 0.25 mmol when the total amount of the radical polymerizable monomers was 200 g.

[0492] Comparative Examples 1 to 6 Photochromic laminates were obtained in the same manner as in Example 20 using photochromic compounds represented by the following formulae (A) to (F).

[0493]

[0494]

[0495]

[0496]

[0497]

[0498]

[0499] <Evaluation Method> The obtained photochromic laminate was evaluated by the following method. Photochromic Properties [1] Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development measured using a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., and was used as an index of the color tone during color development. [2] Color density at 23°C (A ２３[3] 35°C color density (A): The difference between the absorbance {ε(240)} after irradiating light for 240 seconds at 23°C and the absorbance ε(0) before irradiation at the maximum absorption wavelength, and is used as an index of color density. The higher this value, the better the photochromic properties. ３５ [4] High-temperature color development rate (A): The difference between the absorbance {ε(240)} after irradiating light for 240 seconds at 35°C and the absorbance ε(0) before irradiation at the first and second absorption wavelengths, and is used as an index of color development density. The higher this value, the better the photochromic properties. ３５ / A ２３ × 100): 35°C color density (A ３５ ) / 23℃ color density (A ２３ ) x 100 (%). A high value indicates a small difference in color density between high and low temperatures, and low temperature dependency. [5] 23°C fading half-life [τ1 / 2 (sec.)]: This is the time required for the absorbance at the maximum absorption wavelength of a sample to decrease to half of {ε(240) - ε(0)} when the light irradiation is stopped after 240 seconds of light irradiation at 23°C, and is used as an index of the fading rate. The shorter this time, the faster the fading rate.

[0500] The results of Examples 20, 32, and 34 and Comparative Examples 1 to 6 are summarized in Table 3, and the results of Examples 21 to 31, 33, and 35 to 38 are summarized in Table 4. The relationship between the 23°C color fading half-life and high-temperature color development rate of the photochromic laminates according to the Examples and Comparative Examples is shown in the graph of Figure 1.

[0501]

[0502]

[0503] <Evaluation of physical properties of photochromic layer prepared by binder method> (Example 39) A binder sheet was prepared by the following method. The binder sheet used was a laminate of a first optical sheet, a first adhesive layer (first coating), a photochromic layer (third coating), a second adhesive layer (second coating), and a second optical sheet in this order. Polycarbonate sheets with a thickness of 400 μm were used as the first optical sheet and the second optical sheet.

[0504] (Preparation of Photochromic Layer-Forming Composition) A 2 L four-neck flask equipped with a stirring blade, a cooling tube, a thermometer, and a nitrogen gas inlet tube was charged with 315 parts by mass of polycarbonate diol having a number average molecular weight of 1,000, 100 parts by mass of isophorone diisocyanate, and 72 parts by mass of toluene, and the mixture was allowed to react at 100°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer having an isocyanate group at its terminal. After completion of the urethane prepolymer reaction, the reaction solution was cooled to around 0°C and dissolved in 205 parts by mass of tertiary butyl alcohol and 382 parts by mass of diethyl ketone, and the liquid temperature was maintained at 0°C. Next, a mixed solution of 21.3 parts by mass of bis-(4-aminocyclohexyl)methane and 20 parts by mass of diethyl ketone, which served as a chain extender, was added dropwise within 30 minutes, and the mixture was allowed to react at 0°C for 1 hour. Thereafter, 8.1 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine was further added dropwise, and the mixture was allowed to react at 0° C. for 1 hour to obtain a diethyl ketone solution of a terminally unreactive urethane urea resin.

[0505] 100 parts by mass of the obtained terminally non-reactive urethane urea resin solution, the photochromic compound of Example 1 (the above formula (1-7)), 6.3 parts by mass of a mixture of isomers of 4,4'-methylenebis(cyclohexyl isocyanate) (polyisocyanate compound), 0.4 parts by mass of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] as an antioxidant, and 0.06 parts by mass of L-7001 manufactured by DuPont-Toray Specialty Materials Co., Ltd. as a surfactant were added, and the mixture was stirred and mixed at room temperature to obtain a photochromic layer-forming composition.

[0506] The photochromic compound was added in an amount of 0.25 mmol per 100 parts by mass of the terminally non-reactive urethane urea resin.

[0507] (Preparation of Adhesive Layer Composition) A 5 L separable flask (four necks) equipped with a stirring blade, a cooling tube, a thermometer, and a nitrogen gas inlet tube was prepared. 400 parts by mass of polycarbonate diol having a number average molecular weight of 1000, 175 parts by mass of isophorone diisocyanate, and 120 parts by mass of toluene were charged into this container and reacted for 7 hours at 110°C under a nitrogen atmosphere to synthesize a urethane prepolymer having an isocyanate group at the end. After completion of the urethane prepolymer reaction, the reaction solution was cooled to around 20°C and dissolved in 2500 parts by mass of propylene glycol-monomethyl ether, and the liquid temperature was maintained at 20°C. Next, 60 parts by mass of isophorone diamine, a chain extender, was added dropwise, and the mixture was allowed to react for 1 hour at 20°C. Thereafter, 3 parts by mass of n-butylamine was added dropwise, and the mixture was allowed to react for 1 hour at 20°C to obtain a propylene glycol-monomethyl ether solution of a terminally non-reactive urethane urea resin.

[0508] To 500 parts by mass of the obtained terminally non-reactive urethane urea resin solution, 0.2 parts by mass of L-7001 manufactured by DuPont Toray Specialty Materials Co., Ltd. was added as a surfactant, and the mixture was stirred and mixed at room temperature to obtain a composition for adhesive layer.

[0509] (Production of binder sheet) Using a coater (manufactured by Tester Sangyo Co., Ltd.), the adhesive layer composition was applied to one main surface of the first optical sheet at a coating speed of 0.5 m / min, and the resulting sheet was dried for 3 minutes at a drying temperature of 110° C., thereby obtaining a first optical sheet having a first coating film with a thickness of 5 μm. In the same manner, the adhesive layer composition was applied to one main surface of the second optical sheet, thereby obtaining a second optical sheet having a second coating film.

[0510] Next, using a coater (manufactured by Tester Sangyo Co., Ltd.), the photochromic layer-forming composition was applied to a 50 μm-thick OPP film (stretched polypropylene film) at a coating speed of 0.3 m / min and dried at a drying temperature of 100°C for 5 minutes. This resulted in a third coating film. The third coating film was then bonded to a first optical sheet so that the third coating film and the first coating film were in contact with each other. The OPP film was peeled off from this structure, and the second optical sheet was bonded to the third coating film so that the other main surface of the exposed third coating film was in contact with the second coating film. The resulting laminate was then left to stand at 40°C under vacuum for 24 hours, then heat-treated at 110°C for 60 minutes, then humidified at 60°C and 100% RH for 24 hours, and finally left to stand at 40°C under vacuum for 24 hours to obtain a binder sheet. The resulting binder sheet was evaluated in the same manner as in Example 23. The results are shown in Table 5.

[0511] Examples 40 to 49, Comparative Examples 7 to 10 Binder sheets were prepared using the photochromic compounds shown in Table 5 in the same manner as in Example 39.

[0512]

[0513] Evaluation of Physical Properties of Photochromic Cured Material Prepared by Kneading Method Example 50 Preparation of Curable Composition First, the photochromic compound obtained in Example 1, additives, and polymerizable compound were mixed to obtain a curable composition. The polymerizable compound used was a combination of the following polymerizable monomers: 1,3-bis(isocyanatomethyl)cyclohexane: 36.7 parts by mass Pentaerythritol tetrakis(3-mercaptopropionate): 39.4 parts by mass Polyoxyethylene polyoxypropylene lauryl ether (Wondersurf 140 manufactured by Aoki Oil & Fats Industries Co., Ltd.): 17.4 parts by mass 1-Decanethiol: 2.8 parts by mass RX-1 prepared by the method described in Patent Document 12: 3.8 parts by mass In the curable composition, the photochromic compound was added so that the amount was 0.106 mmol per 100 g of the total amount of polymerizable monomers.

[0514] The following additives were used: dimethyltin dichloride: 0.05 parts by mass; Irganox 245 manufactured by BASF Japan Ltd.: 0.1 parts by mass; 2-ethylhexyl 4-methoxycinnamate: 0.6 parts by mass.

[0515] (Production of Cured Product) The prepared curable composition was thoroughly degassed and then poured into a glass mold with a 1 mm gap, and the curable composition was polymerized by cast polymerization. The polymerization was carried out in an air oven over 18 hours while gradually increasing the temperature from 27°C to 120°C. After polymerization, the cured product was removed from the glass mold to obtain a photochromic cured product with a thickness of 1 mm. The obtained photochromic cured product was evaluated in the same manner as in Example 23. The results are shown in Table 6.

[0516] (Examples 51 to 60, Comparative Examples 11 to 14) Photochromic cured products were prepared using the photochromic compounds shown in Table 6 in the same manner as in Example 50. The results are summarized in Table 6.

[0517]

[0518] Example 61, Step 1: 86 g (645.0 mmol) of aluminum chloride and 500 mL of dichloromethane were placed in a 1 L four-neck flask and cooled with ice. 121.5 g (663.0 mmol) of N-methyldiphenylamine dissolved in 100 mL of dichloromethane was slowly added dropwise, and the mixture was stirred for 2 hours. 80.6 g (323.0 mmol) of 3-bromo-4-methoxybenzoyl chloride was slowly added dropwise while maintaining the internal temperature at 5°C or below. After stirring for 3 hours at an internal temperature of 0-5°C, the mixture was added to 2000 mL of ice water and warmed to room temperature. The layers were separated, and 2000 mL of water was added, followed by washing with water. Washing with water was repeated until the pH of the aqueous layer reached 6-7. The resulting organic layer was concentrated and recrystallized from 780 mL of methanol to obtain the compound represented by the following formula (61-1) in a 70% yield.

[0519]

[0520] Step 2: The reaction was carried out in the same manner as in Step 1 of Example 1, except that the compound of formula (61-1) was used instead of 4-bromo-4'-methoxybenzophenone, to obtain a carboxylic acid compound of formula (61-2) below.

[0521]

[0522] Step 3: The reaction was carried out in the same manner as in Step 2 of Example 2, except that the compound of formula (61-2) was used instead of the compound of formula (2-1), and the reaction was carried out in the same manner as in Step 6 of Example 2, except that iodopropane was used instead of 1-bromo-4-methoxybutane, to obtain a compound represented by the following formula (61-3).

[0523]

[0524] Step 4: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (61-3) was used instead of the compound of formula (1-5) and the compound of formula (5-3) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (61-4) in a yield of 72%.

[0525]

[0526] The elemental analysis results of the photochromic compound represented by the formula (61-4) were C: 82.12%, H: 7.26%, and N: 3.23%, and ５９ H ６２ N ２ O ４ The results were in good agreement with the calculated values ​​of C: 82.10%, H: 7.24%, and N: 3.25%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 30H peaks due to methyl groups, propyl groups, and propyloxy groups around δ 0.5 to 3.5 ppm, 7H peaks due to propyloxy groups and methoxy groups around δ 3.5 to 5.0 ppm, and 25H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm. １３Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0527] Example 62, Step 1 The reaction was carried out in the same manner as in Step 1 of Example 61, except that triphenylamine was used instead of N-methyldiphenylamine, to obtain a compound represented by the following formula (62-1).

[0528]

[0529] Step 2 A reaction was carried out in the same manner as in Step 2 of Example 61, except that the compound of formula (62-1) was used instead of the compound of formula (61-1), to obtain a carboxylic acid compound represented by the following formula (62-2).

[0530]

[0531] Step 3 The reaction was carried out in the same manner as in Step 1 of Example 12, except that the compound of formula (62-2) was used instead of the compound of formula (12-1) and 2,4,6-trimethoxyphenylboronic acid was used instead of 4-methoxyphenylboronic acid, to obtain a compound of formula (62-3) below.

[0532]

[0533] Step 4: The reaction was carried out in the same manner as in Example 2, except that in Step 1, the compound of formula (62-3) was used instead of the compound of formula (2-1), and in Step 6, 1-bromo-2-[2-(2-methoxyethoxy)ethoxy]ethane was used instead of 1-bromo-4-methoxybutane, to obtain a phenol derivative represented by the following formula (62-4).

[0534]

[0535] Step 5 In the same manner as in Step 5 of Example 1, except that the compound of formula (1-5) was replaced with the compound of formula (62-4), a photochromic compound represented by the following formula (62-5) was obtained in a yield of 62%.

[0536]

[0537] The elemental analysis results of the photochromic compound represented by the formula (62-5) were C: 73.88%, H: 6.62%, and N: 1.22%, and ７１ H ７７ NO １３ These results were in good agreement with the calculated values ​​of C: 73.86%, H: 6.64%, and N: 1.23%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 4H peak due to the 2-[2-(2-methoxyethoxy)ethoxy]ethyloxy group at around δ 0.5 to 3.5 ppm, a 44H peak due to the 2-[2-(2-methoxyethoxy)ethoxy]ethyloxy group and methoxy group at around δ 3.5 to 5.0 ppm, and a 27H peak due to aromatic protons and alkene protons at around δ 5.0 to 9.0 ppm. １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0538] Example 63 Step 1 The reaction was carried out in the same manner as in Example 62, except that in Step 2, the compound of formula (62-1) was replaced with the compound of formula (61-1), in Step 3, 4-trifluoromethylphenylboronic acid was replaced with 2,4,6-trimethoxyphenylboronic acid, and in Step 4, iodopropane was replaced with 1-bromo-2-[2-(2-methoxyethoxy)ethoxy]ethane, to obtain a phenol derivative represented by the following formula (63-1).

[0539]

[0540] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (63-1) was used instead of the compound of formula (1-5) and the compound of formula (3-2) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (63-2) in a yield of 69%.

[0541]

[0542] The elemental analysis results of the photochromic compound represented by the formula (63-2) were C: 78.41%, H: 6.34%, and N: 1.59%, ５８ H ５６ F ３ NO ４ The results were in good agreement with the calculated values ​​of C: 78.44%, H: 6.36%, and N: 1.58%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 24H peaks due to propyl groups, butyloxy groups, and methyl groups were observed around δ 0.5 to 3.5 ppm, 8H peaks due to butyloxy groups and methoxy groups were observed around δ 3.5 to 5.0 ppm, and 24H peaks due to aromatic protons and alkene protons were observed around δ 5.0 to 9.0 ppm. １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0543] Example 64, Step 1 The compound represented by the following formula (64-1) was synthesized in the same manner as in Step 1 of Example 1, except that the compound of formula (62-2) was used instead of the compound of formula (1-1) and 4-trifluoromethylpiperidine was used instead of N-methylaniline.

[0544]

[0545] Step 2 The reaction was carried out in the same manner as in Example 2, except that the compound of formula (64-1) was used instead of the compound of formula (1-2) and spiro[5.5]undecan-3-one was used instead of acetone in Step 3, to synthesize a compound represented by the following formula (64-2).

[0546]

[0547] Step 3: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (64-2) was used instead of the compound of formula (1-5) and the compound of formula (6-2) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (64-3) in a yield of 61%.

[0548]

[0549] The elemental analysis results of the photochromic compound represented by the formula (64-3) were C: 79.16%, H: 7.34%, and N: 2.52%, ７３ H ８１ F ３ N ２ O ４ These values ​​were in good agreement with the calculated values ​​of C: 79.17%, H: 7.37%, and N: 2.53%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 49H peaks due to the spiro[5.5]undecane ring group, hexyloxy group, and 4-trifluoropiperidine group were observed around δ 0.5 to 3.5 ppm, 7H peaks due to the hexyloxy group and methoxy group were observed around δ 3.5 to 5.0 ppm, and 25H peaks due to aromatic protons and alkene protons were observed around δ 5.0 to 9.0 ppm. １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0550] Example 65, Step 1 The reaction was carried out in the same manner as in Example 61, except that in Step 1, the compound of formula (61-1) was replaced with the compound of formula (62-1), and N-methyl-4-(trifluoromethyl)aniline was replaced with N-methylaniline, and in Step 3, 1-butoxy-2-bromoethane was replaced with iodopropane, to obtain a phenol derivative represented by the following formula (65-1).

[0551]

[0552] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (65-1) was used instead of the compound of formula (1-5) and the compound of formula (7-3) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (65-2) in a yield of 68%.

[0553]

[0554] The elemental analysis results of the photochromic compound represented by the formula (65-2) were C: 76.61%, H: 6.58%, and N: 2.57%, ６９ H ７１ F ３ N ２ O ６ These values ​​were in good agreement with the calculated values ​​of C: 76.64%, H: 6.62%, and N: 2.59%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 26H peaks due to 2-butoxyethyl groups, propyloxy groups, and methyl groups around δ 0.5 to 3.5 ppm, 16H peaks due to 2-butoxyethyl groups, propyloxy groups, and methoxy groups around δ 3.5 to 5.0 ppm, and 29H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm. １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0555] Example 66, Step 1 In Step 1 of Example 5, except that 1-bromo-4-(2-methoxyphenyl)benzene was used instead of 2,4-dimethoxy-1,1-biphenyl, the compound represented by the following formula (66-1) was obtained in a yield of 68%.

[0556]

[0557] Second Step The reaction was carried out in the same manner as in the first step of Example 1, except that the compound of the formula (66-1) was used instead of 4-bromo-4'-methoxybenzophenone, to synthesize a compound of the following formula (66-2).

[0558]

[0559] Instead of the compound of formula (1-1), the compound of formula (66-2) was used, and instead of N-methylaniline, benzomorpholine was used. Furthermore, benzomorpholine, tert-butoxy sodium, Pd ２ (dba) ３ The reaction was carried out in the same manner except that the molar equivalent of X-phos was doubled, to synthesize a compound represented by the following formula (66-3).

[0560]

[0561] Step 3 The reaction was carried out in the same manner as in Step 2 of Example 1, except that the compound of formula (66-3) was used instead of the compound of formula (1-2) and 6-undecanone was used instead of acetone in Step 3, to obtain a phenol derivative represented by the following formula (66-4).

[0562]

[0563] Step 4: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (66-4) was used instead of the compound of formula (1-5), to obtain a photochromic compound represented by the following formula (66-5) in a yield of 65%.

[0564]

[0565] The elemental analysis results of the photochromic compound represented by the formula (66-5) were C: 80.85%, H: 6.70%, and N: 2.82%, ６７ H ６６ N ２ O ６ The results were in good agreement with the calculated values ​​of C: 80.86%, H: 6.68%, and N: 2.81%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 26H peak due to a pentyl group and a benzmorpholino group around δ 0.5 to 3.5 ppm, a 13H peak due to a benzmorpholino group and a methoxy group around δ 3.5 to 5.0 ppm, and a 27H peak due to an aromatic proton and an alkene proton around δ 5.0 to 9.0 ppm. １３Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0566] Example 67 Step 1 The reaction was carried out in the same manner as in Example 62, except that in Step 2, the compound of formula (62-1) was replaced with the compound of formula (61-1), in Step 3, 2,4,6-trimethoxyphenylboronic acid was replaced with 2,4-dimethoxyphenylboronic acid, and in Step 4, iodoethane was replaced with 1-bromo-2-[2-(2-methoxyethoxy)ethoxy]ethane, to obtain a phenol derivative represented by the following formula (67-1).

[0567]

[0568] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (67-1) was used instead of the compound of formula (1-5) and the compound of formula (4-2) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (67-2) in a yield of 71%.

[0569]

[0570] The elemental analysis results of the photochromic compound represented by the formula (67-2) were C: 79.16%, H: 6.52%, and N: 3.23%, and ５７ H ５６ N ２ O ６ The results were in good agreement with the calculated values ​​of C: 79.14%, H: 6.52%, and N: 3.24%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 17H peaks due to methyl groups, ethyl groups, and morpholino groups around δ 0.5 to 3.5 ppm, 16H peaks due to morpholino groups and methoxy groups around δ 3.5 to 5.0 ppm, and 23H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm. １３Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0571] Example 68, Step 1 The reaction was carried out in the same manner as in Example 2, except that in Step 1, 4-methyldiphenylamine was used instead of N-methylaniline, and in Step 6, 1-butoxy-2-bromoethane was used instead of 1-bromo-4-methoxybutane, to obtain a phenol derivative represented by the following formula (68-1).

[0572]

[0573] Step 2: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (68-1) was used instead of the compound of formula (1-5) and the compound of formula (4-2) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (68-2) in a yield of 75%.

[0574]

[0575] The elemental analysis results of the photochromic compound represented by the formula (68-2) were C: 78.51%, H: 7.19%, and N: 2.86%, ６４ H ７０ N ２ O ７ These values ​​were in good agreement with the calculated values ​​of C: 78.50%, H: 7.21%, and N: 2.86%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, 25H peaks due to methyl groups, 2-butoxyethyl groups, and morpholino groups were observed around δ 0.5 to 3.5 ppm, 21H peaks due to 2-butoxyethyl groups, morpholino groups, and methoxy groups were observed around δ 3.5 to 5.0 ppm, and 24H peaks due to aromatic protons and alkene protons were observed around δ 5.0 to 9.0 ppm. １３Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0576] Example 69, Step 1 The reaction was carried out in the same manner as in Example 65, except that in Step 1, morpholine was used instead of N-methyl-4-(trifluoromethyl)aniline, and in Step 2, 1-bromo-3-methoxypropane was used instead of 1-butoxy-2-bromoethane, to synthesize a phenol derivative represented by the following formula (69-1).

[0577]

[0578] Step 2 The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (69-1) was used instead of the compound of formula (1-5) and the compound of formula (12-4) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (69-2) in a yield of 75%.

[0579]

[0580] The elemental analysis results of the photochromic compound represented by the formula (69-2) were C: 80.61%, H: 6.76%, and N: 4.35%, ６５ H ６５ N ３ O ５ These values ​​were in good agreement with the calculated values ​​of C: 80.63%, H: 6.77%, and N: 4.34%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 18H peaks due to methyl groups, methoxypropyl groups, and morpholino groups around δ 0.5 to 3.5 ppm, 17H peaks due to methoxypropyl groups, morpholino groups, and methoxy groups around δ 3.5 to 5.0 ppm, and 30H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm. １３Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0581] Example 70, Step 1 The reaction was carried out in the same manner as in Step 1 of Example 12, except that the compound of formula (62-2) was used instead of the compound of formula (12-1) and 2-chlorophenylboronic acid was used instead of 4-methoxyphenylboronic acid, to obtain a compound represented by the following formula (70-1).

[0582]

[0583] Step 2 A reaction was carried out in the same manner as in Step 1 of Example 1, except that the compound of formula (70-1) was used instead of the compound of formula (1-1) and morpholine was used instead of N-methylaniline, to obtain a compound represented by the following formula (70-2).

[0584]

[0585] The reaction was carried out in the same manner as in Example 1, except that in Step 3, the compound of formula (70-2) was used instead of the compound of formula (1-3), and in Step 4, dihexyl ketone was used instead of acetone, to synthesize a phenol derivative represented by the following formula (70-3).

[0586]

[0587] Step 4: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (70-3) was used instead of the compound of formula (1-5) and the compound of formula (16-2) was used instead of the compound of formula (1-6), to obtain a photochromic compound represented by the following formula (70-4) in a yield of 68%.

[0588]

[0589] The elemental analysis results of the photochromic compound represented by the formula (70-4) were C: 80.64%, H: 6.96%, and N: 2.72%, ６９ H ７１FN ２ O ５ These values ​​were in good agreement with the calculated values ​​of C: 80.67%, H: 6.97%, and N: 2.73%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed a 30H peak due to a hexyl group and a morpholino group in the vicinity of δ 0.5 to 3.5 ppm, a 13H peak due to a morpholino group and a methoxy group in the vicinity of δ 3.5 to 5.0 ppm, and a 28H peak due to an aromatic proton and an alkene proton in the vicinity of δ 5.0 to 9.0 ppm. １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0590] Example 71 Step 1 A reaction was carried out in the same manner as in Example 62, except that in Step 2, the compound of formula (62-1) was replaced with the compound of formula (61-1), and in Step 3, 4-chlorophenylboronic acid was replaced with 2,4,6-trimethoxyphenylboronic acid, to obtain a compound represented by the following formula (71-1).

[0591]

[0592] Step 2 A reaction was carried out in the same manner as in Step 1 of Example 1, except that the compound of formula (71-1) was used instead of the compound of formula (1-1) and 3,5-dimethylmorpholine was used instead of N-methylaniline, to obtain a compound represented by the following formula (71-2).

[0593]

[0594] The reaction was carried out in the same manner as in Example 1, except that in Step 3, the compound of formula (71-2) was used instead of the compound of formula (1-3), and in Step 4, dipropyl ketone was used instead of acetone, to synthesize a phenol derivative represented by the following formula (71-3).

[0595]

[0596] Step 4: The reaction was carried out in the same manner as in Step 5 of Example 1, except that the compound of formula (71-3) was used instead of the compound of formula (1-5) and the compound of formula (1-6) was used instead of the compound of formula (71-4) below, to obtain a photochromic compound represented by formula (71-5) below in a yield of 71%.

[0597]

[0598]

[0599] The elemental analysis values ​​of the photochromic compound represented by the formula (71-5) were C: 78.72%, H: 7.13%, and N: 4.30%, ６４ H ６９ N ３ O ６ The results were in good agreement with the calculated values ​​of C: 78.74%, H: 7.12%, and N: 4.30%. Furthermore, when the proton nuclear magnetic resonance spectrum was measured, it showed 31H peaks due to propyl groups, morpholino groups, and methyl groups around δ 0.5 to 3.5 ppm, 15H peaks due to morpholino groups and methoxy groups around δ 3.5 to 5.0 ppm, and 23H peaks due to aromatic protons and alkene protons around δ 5.0 to 9.0 ppm. １３ Measurement of the C-nuclear magnetic resonance spectrum showed a peak due to aromatic ring carbon at around δ 110 to 160 ppm, a peak due to alkene carbon at around δ 80 to 140 ppm, and a peak due to alkyl carbon at δ 20 to 60 ppm.

[0600] The analytical results of the phenol derivatives synthesized in Examples 61 to 71 are shown in Table 7.

[0601]

[0602] (Examples 72 to 81) Photochromic laminates were produced using the photochromic compounds obtained in Examples 61 to 71 in the same manner as in Example 20. The results are shown in Table 8.

[0603]

[0604] Preferred embodiments of the present invention are described below.

[0605] [1] A photochromic compound represented by the following formula (1):

[0606]

[0607] In the formula (1), M is C, Si, or Ge, ring A is an aromatic ring, a heteroaromatic ring, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or a heteroaromatic ring is fused to the ring, and Z １ is a group represented by the following formula (1a) or a group represented by the following formula (1b):

[0608]

[0609] In the formula (1a), R １ is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the above substituent, R ２ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a): １ -(X １ Q ２ ) a-X ２ Q ３ (2a) In the formula (2a), Q １ is an alkylene group or a haloalkylene group, ２ is an alkylene group or a haloalkylene group, ３ is an alkyl group or a haloalkyl group, １ , and X ２ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O), R ７００ , and R ７０１are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or substituted aryl group, or a substituted or unsubstituted heteroaryl group, a is 0 or 1 to 3,

[0610]

[0611] In the formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the ring, and Y １ is a substituted or unsubstituted methylene group, Y ２ represents a substituted or unsubstituted methylene group, O, S, SO ２ , N.R. ６００ , R ６０１ C=CR ６０２ , or CC, and R ６００ , R ６０１ , and R ６０２ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; ３ is a substituted or unsubstituted methylene group, m is an integer of 1 to 4, n is an integer of 0 to 4, and m+n is an integer of 1 or more, R ３ , and R ４ each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3): １ -R ４００(X3) In the formula (X3), R ４００ is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent; １ is a group represented by the following formula (X2):

[0612]

[0613] In the formula (X2), R ３０ is a group represented by the following formula (X2a):

[0614]

[0615] In the formula (X2) and the formula (X2a), J represents a divalent group, each of which independently represents a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, and R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group; h, j, k, and l are each independently an integer of 0 or 1; i is an integer of 1 to 200, and when i is 2 or greater, a plurality of R ３０ may be the same or different, and the dashed line represents R ４００ represents a bond with ３ and R ４ may form, together with M, a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the aliphatic ring, a substituted or unsubstituted heterocyclic ring having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the heterocyclic ring, ５ and R ６ are each independently a hydrogen atom or a substituent, R ７ and R ８are each independently a substituent, b is an integer of 0 to 3, and c is an integer of 0 to 4.

[0616] [2] The photochromic compound according to [1], represented by the following formula (3):

[0617]

[0618] In the formula (3), R ３ , R ４ , Z １ , M, b, and c are each defined as in the formula (1), ５ and R ６ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, ７ , and R ８ are each independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the formula (2a), a group represented by the following formula (X), or a group represented by the formula (X3), When b is 2 or 3, multiple R ７ may be the same or different, and when c is 2 to 4, a plurality of R ８ may be the same or different, b is 2 to 3, and adjacent R ７ If there is a ７ is R ７and may form, together with the carbon atom bonded to it, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, ８ If there is a ８ is R ８ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings,

[0619]

[0620] In the formula (X), E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom or NR ２０２ and R ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; g is 0 or 1; R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, and when G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom.

[0621] [3] The photochromic compound according to [2], represented by the following formula (4):

[0622]

[0623] In the formula (4), R ３ , R ４ , R ７ , R ８ , Z １ , M, b, and c each independently have the same meaning as in the formula (3), ９ and R １０are each independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3), d is an integer of 0 to 5, and when d is 2 to 5, a plurality of R ９ may be the same or different groups, and adjacent R ９ If there is a ９ is R ９ may form, together with the carbon atom bonded to R, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, e is an integer of 0 to 5, and when e is 2 to 5, a plurality of R １０ may be the same or different groups, and adjacent R １０ If there is a １０ is R １０ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings.

[0624] [4] The photochromic compound according to any one of [1] to [3], wherein M in the formula (1) is C.

[0625] [5] R in the formula (1) ３ , and R ４is a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), a substituted or unsubstituted alkoxy group, a group represented by formula (X3), a substituted or unsubstituted aliphatic ring formed together with M and having 3 to 20 ring carbon atoms, or a substituted or unsubstituted heterocycle formed together with M and having 3 to 20 ring atoms.

[0626] [6] Z in the formula (1) １ has a group represented by the formula (1a), and R １ is a substituted or unsubstituted phenyl group.

[0627] [7] Z in the formula (1) １ has a group represented by the formula (1a), and R ２ is a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted haloalkyl group having from 1 to 10 carbon atoms, or a group represented by formula (2a).

[0628] [8] Z in the formula (1) １ has a group represented by the formula (1b), and ring B is a substituted or unsubstituted phenyl group.

[0629] [9] Z in the formula (1) １ has a group represented by the formula (1b), and Y ２ is a substituted or unsubstituted methylene group, O, or S. [1] The photochromic compound according to any one of [1] to [8].

[0630]

[10] Z in the formula (1) １ The photochromic compound according to any one of [1] to [9], wherein m+n is an integer of 1 to 3, and m+n is a group represented by the formula (1b).

[0631]

[11] A curable composition comprising the photochromic compound according to any one of [1] to

[10] and at least one selected from the group consisting of a radically polymerizable monomer, a cationically polymerizable monomer, a compound having a polymerization reactive group, and a (thio)urethane (urea) polymer.

[0632]

[12] A cured product of the curable composition according to

[11] .

[0633]

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

[12] .

[0634]

[14] A lens containing the photochromic compound according to any one of [1] to

[10] .

[0635]

[15] Eyeglasses including the lens according to

[14] .

[0636]

[16] A phenol derivative represented by the following formula (5):

[0637]

[0638] In the formula (5), M is C, Si, or Ge, ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the ring, and Z １ is a group represented by the following formula (1a) or a group represented by the following formula (1b):

[0639]

[0640] In the formula (1a), R １ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ２ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a): １ -(X １ Q ２ ) a-X ２ Q ３(2a) In the formula (2a), Q １ is an alkylene group or a haloalkylene group, ２ is an alkylene group or a haloalkylene group, ３ is an alkyl group or a haloalkyl group, １ , and X ２ are each independently O, S, or NR ７００ R ７０１ , P.R. ７０２ R ７０３ , or P(=O)R ７０４ and R ７００ , R ７０１ , R ７０２ , R ７０３ and R ７０４ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, a is 0 or an integer of 1 to 3,

[0641]

[0642] In the formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the ring, and Y １ is a substituted or unsubstituted methylene group, Y ２ represents a substituted or unsubstituted methylene group, O, S, SO ２ , N.R. ６００ , R ６０１ C=CR ６０２ , or CC, and R ６００ , R ６０１ , and R ６０２ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; ３is a substituted or unsubstituted methylene group, m is an integer of 1 to 4, n is an integer of 0 to 4, and m+n is an integer of 1 or more, R ３ , and R ４ each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3): １ -R ４００ (X3) In the formula (X3), R ４００ is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent; L １ is a group represented by the following formula (X2):

[0643]

[0644] In the formula (X2), R ３０ is a group represented by the following formula (X2a):

[0645] In the formula (X2) and the formula (X2a), J represents a divalent group, each of which independently represents a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, and R ３０２ , R ３０３ , and R ３０４are each independently an alkylene group; h, j, k, and l are each independently an integer of 0 or 1; i is an integer of 1 to 200, and when i is 2 or greater, a plurality of R ３０ may be the same or different, and the dashed line represents R ４００ represents a bond with ３ and R ４ may form, together with M, a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted fused polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the aliphatic ring, a substituted or unsubstituted heterocyclic ring having 3 to 20 ring atoms, or a substituted or unsubstituted fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused to the heterocyclic ring, ７ and R ８ are each independently a substituent, b is an integer of 0 to 3, and c is an integer of 0 to 4.

[0646]

[17] A phenol derivative according to

[16] , represented by the following formula (7):

[0647]

[0648] In the formula (7), Z １ , R ３ , R ４ , M, b, and c are the same as those in formula (6), ７ , and R ８are each independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the formula (2a), a group represented by the following formula (X), or a group represented by the formula (X3), When b is 2 or 3, multiple R ７ may be the same or different, and when c is 2 to 4, a plurality of R ８ may be the same or different, b is 2 to 3, and adjacent R ７ If there is a ７ is R ７ and may form, together with the carbon atom bonded to it, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings, ８ If there is a ８ is R ８ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to any of these rings,

[0649]

[0650] In the formula (X), E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom or NR ２０２ and R ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; g is 0 or 1; R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, and when G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom.

Claims

1. A photochromic compound represented by the following formula (1): In the formula (1), M is C, Si, or Ge, ring A is an aromatic ring, an aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the ring, Z １ is a group represented by the following formula (1a) or a group represented by the following formula (1b): In the formula (1a), R １ R is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the above substituent, ２ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a): １ - (X １ Q ２ ) a-X ２ Q ３ (2a) In the formula (2a), Q １ is an alkylene group or a haloalkylene group; Q ２ is an alkylene group or a haloalkylene group; Q ３ is an alkyl group or a haloalkyl group; X １ , and X ２ are each independently O, S, or NR ７００ , P.R. ７０１ or P(=O), R ７００ , and R ７０１ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; a represents 0 or an integer between 1 and 3; In the formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the ring, and Y １ is a substituted or unsubstituted methylene group; Y ２ represents a substituted or unsubstituted methylene group, O, S, SO ２ , N.R. ６００ , R ６０１ C=CR ６０２ , or CC, R ６００ , R ６０１ , and R ６０２ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; ３ is a substituted or unsubstituted methylene group, m is an integer of 1 to 4, n is an integer of 0 to 4, and m+n is an integer of 1 or more; R ３ , and R ４ each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3): １ -R ４００ (X3) In the formula (X3), R ４００ is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent; L １ is a group represented by the following formula (X2): In the formula (X2), R ３０ is a group represented by the following formula (X2a): In the formula (X2) and the formula (X2a), J is a divalent group, each of which independently represents a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group; h, j, k, and l are each independently an integer of 0 or 1; i is an integer of 1 to 200, and when i is 2 or more, a plurality of R ３０ may be the same or different, and the dashed line represents R ４００ represents a bond with ３ and R ４ may form, together with M, a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted condensed polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle; ５ and R ６ are each independently a hydrogen atom or a substituent; R ７ and R ８ are each independently a substituent, b is an integer of 0 to 3, and c is an integer of 0 to 4.

2. The photochromic compound according to claim 1, represented by the following formula (3): In the formula (3), R ３ , R ４ , Z １ , M, b, and c are the same as those in the formula (1), ５ and R ６ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; R ７ , and R ８ are each independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the formula (2a), a group represented by the following formula (X), or a group represented by the formula (X3), When b is 2 to 3, multiple R ７ may be the same or different, and when c is 2 to 4, a plurality of R ８ may be the same or different, b is 2 to 3, and adjacent R ７ If there is a pair of adjacent R ７ is R ７ and may form, together with the carbon atom bonded to the ring, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to any of these rings; ８ If there is a pair of adjacent R ８ is R ８ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to any of these rings, In the formula (X), E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom, or NR ２０２ and R ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; g is 0 or 1; R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; when G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom.

3. The photochromic compound according to claim 2, represented by the following formula (4): In the formula (4), R ３ , R ４ , R ７ , R ８ , Z １ , M, b, and c each independently have the same meaning as in formula (3); ９ and R １０ each independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, or a group represented by formula (X3) above, d represents an integer of 0 to 5, and when d is 2 to 5, a plurality of R ９ may be the same or different groups, and adjacent R ９ If there is a pair of adjacent R ９ is R ９ and a carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the ring, e is an integer of 0 to 5, and when e is 2 to 5, a plurality of R １０ may be the same or different groups, and adjacent R １０ If there is a pair of adjacent R １０ is R １０ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to these rings.

4. The photochromic compound according to claim 1, wherein M in formula (1) is C.

5. R in the above formula (1) ３ , and R ４ is a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), a substituted or unsubstituted alkoxy group, a group represented by formula (X3), a substituted or unsubstituted aliphatic ring formed together with M and having 3 to 20 ring carbon atoms, or a substituted or unsubstituted heterocycle formed together with M and having 3 to 20 ring atoms.

6. Z in the formula (1) １ has a group represented by the formula (1a), and R １ The photochromic compound according to claim 1 , wherein is a substituted or unsubstituted phenyl group.

7. Z in the formula (1) １ has a group represented by the formula (1a), and R ２ is a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted haloalkyl group having from 1 to 10 carbon atoms, or a group represented by formula (2a).

8. Z in the formula (1) １ The photochromic compound according to claim 1 , wherein R 1 has a group represented by formula (1b), and ring B is a substituted or unsubstituted phenyl group.

9. Z in the formula (1) １ has a group represented by the formula (1b), and Y ２ The photochromic compound according to claim 1 , wherein is a substituted or unsubstituted methylene group, O, or S.

10. Z in the formula (1) １ The photochromic compound according to claim 1, wherein m+n is an integer of 1 to 3, and m+n is a group represented by formula (1b).

11. A curable composition comprising the photochromic compound according to claim 1 and at least one member selected from the group consisting of radically polymerizable monomers, cationic polymerizable monomers, compounds having a polymerization reactive group, and (thio)urethane (urea) polymers.

12. A cured product of the curable composition according to claim 11.

13. An optical article comprising the cured product according to claim 12.

14. A lens comprising the photochromic compound of claim 1.

15. Eyeglasses comprising the lens of claim 14.

16. A phenol derivative represented by the following formula (5): In the formula (5), M is C, Si, or Ge, ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the ring, Z １ is a group represented by the following formula (1a) or a group represented by the following formula (1b): In the formula (1a), R １ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; R ２ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (2a): １ - (X １ Q ２ ) a-X ２ Q ３ (2a) In the formula (2a), Q １ is an alkylene group or a haloalkylene group; Q ２ is an alkylene group or a haloalkylene group; Q ３ is an alkyl group or a haloalkyl group; X １ , and X ２ are each independently O, S, or NR ７００ R ７０１ , P.R. ７０２ R ７０３ , or P(=O)R ７０４ And R ７００ , R ７０１ , R ７０２ , R ７０３ And R ７０４ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; a represents 0 or an integer of 1 to 3; In the formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the ring, and Y １ is a substituted or unsubstituted methylene group; Y ２ represents a substituted or unsubstituted methylene group, O, S, SO ２ , N.R. ６００ , R ６０１ C=CR ６０２ , or CC, R ６００ , R ６０１ , and R ６０２ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloalkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; ３ is a substituted or unsubstituted methylene group, m is an integer of 1 to 4, n is an integer of 0 to 4, and m+n is an integer of 1 or more; R ３ , and R ４ each independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the formula (2a), a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3): １ -R ４００ (X3) In the formula (X3), R ４００ is a hydrogen atom, an alkyl group, an aryl group, a polymerizable group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent; L １ is a group represented by the following formula (X2): In the formula (X2), R ３０ is a group represented by the following formula (X2a): In the formula (X2) and the formula (X2a), J is a divalent group, each of which independently represents a direct bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ and R ３０１ is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent, R ３０２ , R ３０３ , and R ３０４ are each independently an alkylene group; h, j, k, and l are each independently an integer of 0 or 1; i is an integer of 1 to 200, and when i is 2 or more, a plurality of R ３０ may be the same or different, and the dashed line represents R ４００ represents a bond with ３ and R ４ may form, together with M, a substituted or unsubstituted aliphatic ring having 3 to 20 ring carbon atoms, a substituted or unsubstituted condensed polycyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 ring atoms, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle; ７ and R ８ are each independently a substituent, b is an integer of 0 to 3, and c is an integer of 0 to 4.

17. The phenol derivative according to claim 16, represented by the following formula (7): In the formula (7), Z １ , R ３ , R ４ , M, b and c are the same as those in formula (6); ７ , and R ８ are each independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by the formula (2a), a group represented by the following formula (X), or a group represented by the formula (X3), When b is 2 to 3, multiple R ７ may be the same or different, and when c is 2 to 4, a plurality of R ８ may be the same or different, b is 2 to 3, and adjacent R ７ If there is a pair of adjacent R ７ is R ７ and may form, together with the carbon atom bonded to the ring, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to any of these rings; ８ If there is a pair of adjacent R ８ is R ８ and the carbon atom bonded to the ring may form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocycle, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to any of these rings, In the formula (X), E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom, or NR ２０２ and R ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; g is 0 or 1; R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group; when G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom.

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