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

Abstract

The purpose of the present invention is to provide: a photochromic compound having excellent temperature dependence and fading speed; a phenol derivative that can be used as an intermediate of the photochromic compound; a curable composition containing the photochromic compound; an optical article; according to one embodiment, a photochromic compound having a skeleton represented by formula (1) is provided. In formula (1), M is 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 fused polyring in which an aromatic ring or an aromatic heterocyclic ring is fused to these rings. Z1 represents a group represented by formula (1a) or a group represented by formula (1b).

Description

Technical Field

[0001] This invention relates to photochromic compounds, phenolic derivatives, curable compositions, optical articles, lenses, and eyeglasses. Background Technology

[0002] Photochromic compounds are compounds that can reversibly acquire two isomers with different absorption spectra when exposed to ultraviolet light, such as sunlight or mercury lamp light. Generally, by irradiating a colorless, achromatic compound with ultraviolet light, its color changes rapidly, isomerizing into a colored, chromogenic state (a colorimetric reaction). Photochromic compounds have been researched and developed as materials for photochromic lenses.

[0003] In the application of such photochromic lenses, photochromic compounds sometimes require the following properties.

[0004] (I) The chromaticity (hereinafter referred to as initial chromaticity) in the visible light region before ultraviolet irradiation is small.

[0005] (II) High speed from the start of ultraviolet irradiation to the saturation of color development concentration (hereinafter referred to as color development concentration) (hereinafter also referred to as high color development sensitivity).

[0006] (III) The rate at which the irradiation of ultraviolet light stops and the color returns to its original state (hereinafter referred to as the fading rate) is high.

[0007] (IV) The reversible effects described above have high durability.

[0008] (V) It has high solubility in the matrix material of the lens and high dispersibility in the cured product.

[0009] As photochromic compounds capable of meeting such requirements, chromene compounds having an inden(2,1-f)naphtho(1,2-b)pyran structure as the basic framework are known. For example, chromene compounds represented by the following formula (A) (Patent Document 1), chromene compounds represented by the following formula (B) (Patent Document 2), and chromene compounds represented by the following formula (C) (Patent Document 3) are known.

[0010]

[0011]

[0012]

[0013] In recent years, the performance requirements for photochromic compounds have become increasingly sophisticated. In addition to the properties mentioned above (I) to (V), high color concentration is also required even at high temperatures, such as in summer. This characteristic is sometimes referred to as "low temperature dependence." Generally, by improving the thermal stability of the color-developing state, high color concentration can be maintained even at high temperatures. However, due to the reduced fading rate, there is a tradeoff between color concentration and fading rate at high temperatures. Therefore, photochromic compounds that can balance high color concentration and high fading rate at high temperatures are desired.

[0014] Existing technical documents

[0015] Patent documents

[0016] Patent Document 1: Japanese Patent Application Publication No. 2018-062496

[0017] Patent Document 2: International Publication No. 2005 / 090327

[0018] Patent Document 3: U.S. Patent Application Publication No. 2012 / 0053341

[0019] Patent Document 4: International Publication No. 2018 / 215371

[0020] Patent Document 5: International Publication No. 2013 / 042800

[0021] Patent Document 6: International Publication No. 2015 / 035325

[0022] Patent Document 7: International Publication No. 2018 / 235771

[0023] Patent Document 8: International Publication No. 2012 / 102410

[0024] Patent Document 9: International Publication No. 2011 / 053615

[0025] Patent Document 10: International Publication No. 2007 / 078529

[0026] Patent Document 11: International Publication No. 2019 / 013249

[0027] Patent Document 12: International Publication No. 2016 / 143910 Summary of the Invention

[0028] The problem the invention aims to solve

[0029] The purpose of this invention is to provide a photochromic compound with excellent temperature dependence and fading rate, a phenolic derivative that can serve as an intermediate of the photochromic compound, a curable composition comprising the photochromic compound, optical articles, lenses and eyeglasses.

[0030] Solution for solving the problem

[0031] According to this disclosure, a photochromic compound having a skeleton as shown in formula (1) is provided.

[0032]

[0033] In formula (1), M is C, Si, or Ge. Ring A is an aromatic ring, an aromatic heterocyclic ring, or a fused polycyclic ring with substituted or unsubstituted aromatic rings or aromatic heterocyclic rings fused together.

[0034] Z 1 It is a group represented by formula (1a) or formula (1b) below.

[0035]

[0036]

[0037] In equation (1a), R 1 It is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted fused polycyclic group with an aromatic ring or aromatic heterocycle fused to these substituents.

[0038] R 2 It 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 formula (2a) below.

[0039] -Q 1 -(X) 1 Q 2 )aX 2 Q 3 (2a)

[0040] In equation (2a), Q 1 It is an alkylene or haloalkylene.

[0041] Q 2 It is an alkylene or haloalkylene, Q 3 It is an alkyl or haloalkyl group. X 1 and X 2 Each is independently O, S, NR 700 PR 701 Or P (=O). R700 and R 701 Each is 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, where a is 0, or more than 1 and less than 3.

[0042] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[0043] Y 1 The substituted or unsubstituted methylene group. 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C=CR 602 Or CC. R 600 R 601 and R 602 Each of these elements is 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 The m group is either substituted or unsubstituted. m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than or equal to 1.

[0044] R 3 and R 4 Each of the following is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the aforementioned 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 aroxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3).

[0045] L 1 -R 400 (X3)

[0046] In equation (X3), R 400 It is a silyl group consisting of a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or having alkyl, alkoxy, or aryl substituents, L 1 It is the group represented by the following formula (X2).

[0047]

[0048] In equation (X2), R 30It is a group represented by the following formula (X2a).

[0049]

[0050] In formula (X2) and the aforementioned formula (X2a), J is a divalent group, which is independently a directly bonded, substituted or unsubstituted methylene, oxygen atom, sulfur atom, or NR. 301 R 301 For hydrogen atoms or alkyl groups, L is an oxygen atom or a sulfur atom, and R is a hydrogen atom or an alkyl group. 300 R is an alkylene group or a silylene group having alkyl or aryl substituents. 302 R 303 and R 304 Each is independently an alkylene group, h, j, k, and l are each independently an integer of 0 or 1, i is an integer from 1 to 200, and when i is 2 or higher, multiple R... 30 Choose either the same or different; the dashed line indicates the same as R. 400 The bond.

[0051] R 3 and R 4 The following can be selected together with M to form a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocycle fused to the aforementioned aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 cyclic atoms, or a substituted or unsubstituted fused polycyclic ring having an aromatic ring or an aromatic heterocycle fused to the aforementioned heterocycle.

[0052] R 5 and R 6 Each is an independent hydrogen atom or substituent, R 7 and R 8 Each is an independent substituent, b is an integer from 0 to 3, and c is an integer from 0 to 4.

[0053] According to this disclosure, a curable composition is provided. The curable composition comprises the photochromic compound of the embodiments, and at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerizable reactive group, and a (thio)carbamate (urea) polymer.

[0054] According to yet another embodiment, an optical article is provided. The optical article comprises a cured product of a curable composition.

[0055] According to this disclosure, a lens is provided. The lens comprises a photochromic compound according to an embodiment.

[0056] According to this disclosure, eyeglasses are provided. The eyeglasses include lenses according to embodiments.

[0057] According to this disclosure, a phenolic derivative is provided. The phenolic derivative has the skeleton shown in the following formula (5).

[0058]

[0059] In equation (5), M, ring A, and Z 1 R 3 and R 4 Each has the same meaning as in the above formula (1) independently.

[0060] The effects of the invention

[0061] According to the present invention, photochromic compounds with excellent temperature dependence and fading speed, phenolic derivatives that can serve as intermediates of the photochromic compounds, curable compositions comprising the photochromic compounds, optical articles, lenses and eyeglasses can be provided. Attached Figure Description

[0062] Figure 1 This is a graph illustrating the relationship between the 23°C fading half-life and the high-temperature color development rate of the photochromic laminates of the embodiments and comparative examples. Detailed Implementation

[0063] [Photochromic compounds]

[0064] According to an embodiment, a photochromic compound represented by the following formula (1) is provided.

[0065]

[0066] 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 polycyclic aromatic ring or aromatic heterocycle fused to these rings. Z 1 It is a group represented by formula (1a) or formula (1b) below.

[0067]

[0068] In equation (1a), R 1 It can be a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 2 It 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 formula (2a) below.

[0069] -Q 1 -(X) 1 Q 2 )aX 2 Q3 (2a)

[0070] In equation (2a), Q 1 It is an alkylene or haloalkylene. Q 2 It is an alkylene or haloalkylene. Q 3 It is an alkyl or haloalkyl group. X 1 and X 2 Each is independently O, S, NR 700 PR 701 Or P (=O). R 700 and R 701 Each is 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 more than 1 and less than 3.

[0071]

[0072] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. 1 The substituted or unsubstituted methylene group. 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C=CR 602 Or CC. R 600 R 601 and R 602 Each of these elements is 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 The substituted or unsubstituted methylene group or oxygen atom. m is an integer from 1 to 4, n is an integer from 1 to 4, and m+n is an integer greater than or equal to 1.

[0073] R 3 and R 4 Each of the following is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by the aforementioned 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 aroxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3).

[0074] R 3 and R 4The following can be selected together with M to form a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocycle fused to the aforementioned aliphatic ring, a substituted or unsubstituted heterocycle having 3 to 20 cyclic atoms, or a substituted or unsubstituted fused polycyclic ring having an aromatic ring or an aromatic heterocycle fused to the aforementioned heterocycle.

[0075] L 1 -R 400 (X3)

[0076] In equation (X3), R 400 It is a silyl group that is a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or has alkyl, alkoxy or aryl substituents.

[0077] L 1 It is the group represented by the following formula (X2).

[0078]

[0079] In equation (X2), R 30 It is a group represented by the following formula (X2a).

[0080]

[0081] In formula (X2) and the aforementioned formula (X2a), J is a divalent group, which is independently a directly bonded, substituted or unsubstituted methylene, oxygen atom, sulfur atom, or NR. 301 R 301 It can be a hydrogen atom or an alkyl group.

[0082] L represents an oxygen atom or a sulfur atom. R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents.

[0083] R 302 R 303 and R 304 Each is independently an alkylene group. h, j, k, and l are each independently an integer of 0 or 1. i is an integer from 1 to 200; when i is 2 or higher, multiple R... 30 Choose either the same or different; the dashed line indicates the same as R. 400 The bond.

[0084] R 5 and R 6 Each can be an independent hydrogen atom or a substituent.

[0085] R 7 and R 8 Each is an independent substituent.

[0086] b is an integer from 0 to 3. c is an integer from 0 to 4.

[0087] This photochromic compound exhibits excellent temperature dependence and fading rate. The reason for this is not yet clear, but the inventors believe it to be as follows.

[0088] Substituent Z of the photochromic compound in the embodiments 1 Using formula (1a) or formula (1b) above. It is believed that formula (1a) and formula (1b) above, through the structure with aryl or heteroaryl groups directly bonded to the nitrogen atom, can, via the p orbital on the nitrogen atom, the skeleton shown in formula (1) and the substituent Z 1 Conjugation. It is believed that the conjugation of compounds with such a structure is extended compared to unsubstituted compounds of formulas (1a) and (1b) above. It is believed that through this extension, the absorbance in the achromatic state increases, thus enabling an increase in colorimetric concentration even at high temperatures.

[0089] Additionally, if the substituent Z 1 When the bonded substitution site is replaced by a substituent with high electron-donating capacity, the fading rate of the photochromic compound tends to decrease. As mentioned above, due to substituent Z... 1 The presence of aryl or heteroaryl groups bonded to the nitrogen atom suggests that electron-donating ability is reduced due to conjugation. Therefore, the presence of substituent Z is considered... 1 The rate of fading of the photochromic compound was suppressed.

[0090] As can be seen from the above, when using the photochromic compound of the embodiment, a cured product with excellent temperature dependence and fading rate can be achieved. Therefore, such a photochromic compound is suitable for optical articles used in environments with large temperature variations, such as sunglasses.

[0091] The following is a detailed description of the photochromic compound shown in formula (1).

[0092] <m>

[0093] In equation (1), M is C, Si, or Ge. M is preferably C.

[0094] <Ring A>

[0095] In formula (1), ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[0096] Examples of aromatic hydrocarbon rings include the benzene ring and the cyclotetradecane-7-ene ring.

[0097] Examples of aromatic heterocyclic rings include furan rings, thiophene rings, and pyridine rings.

[0098] Examples of fused polycyclic rings include naphthyl rings, fluorene rings, anthracene rings, phenanthrene rings, tetraphenyl rings, pentaphenyl rings, benzo[a]pyrene rings, cyclopentadiene rings, pyrene rings, triphenylene rings, perylene rings, benzofuran rings, benzothiophene rings, quinoline rings, isoquinoline rings, indole rings, pyrimidine rings, quinazoline rings, pyridazine rings, cyclophosphine rings, phthalazine rings, 1,2,3-, 1,2,4- or 1,3,5-triazine rings, carbazole rings, benzoxazole rings, and isothiazole rings.

[0099] Preferably, the rings are benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, pyrene ring, furan ring, thiophene ring, or pyridine ring; more preferably, benzene ring, naphthalene ring, fluorene ring, or phenanthrene ring; and most preferably, benzene ring.

[0100] <Z 1 >

[0101] In equation (1), Z 1 It is a group represented by formula (1a) or formula (1b) below. The dashed lines in formula (1a) and formula (1b) refer to the bonds bonded to the carbon atom at position 11 of the naphthopyran skeleton of formula (1).

[0102] <Formula (1a)>

[0103]

[0104] <Formula (1b)>

[0105]

[0106] (R) 1 )

[0107] R 1 It refers to substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, or substituted or unsubstituted fused polycyclic compounds with aromatic rings or aromatic heterocycles fused to these substituents. Regarding R... 1 The substituents that may be present will be described later.

[0108] The substituted or unsubstituted aryl group has, for example, 5 or more and 12 or less carbon atoms, preferably 6 or more and 10 or less. The heteroatom of the substituted or unsubstituted heteroaryl group can be at least one selected from the group consisting of oxygen, sulfur, nitrogen, and phosphorus atoms. The substituted or unsubstituted heteroaryl group has, for example, 1 or more and 3 or less heteroatoms, preferably 1 or 2. The substituted or unsubstituted heteroaryl group has, for example, 4 or more and 11 or less carbon atoms, preferably 5 or more and 9 or less.

[0109] R 1 Preferably, it is a substituted or unsubstituted phenyl, a substituted or unsubstituted 1-naphthyl, a substituted or unsubstituted 2-naphthyl, a substituted or unsubstituted thiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted pyrrolinyl, a substituted or unsubstituted pyridinyl, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted benzofuranyl, or a substituted or unsubstituted benzopyrrolinyl, more preferably a substituted or unsubstituted phenyl, a substituted or unsubstituted 1-naphthyl, or a substituted or unsubstituted 2-naphthyl, and particularly preferably a substituted or unsubstituted phenyl.

[0110] As R 1 The substituents that may be present are preferably selected from at least one of the following groups: a straight-chain or branched alkyl group having 1 or more and 6 or less free carbon atoms; a straight-chain or branched haloalkyl group having 1 or more and 6 or less free carbon atoms; a straight-chain or branched alkoxy group having 1 or more and 6 or less free carbon atoms; and a halogen atom. The number of substituents is, for example, 1 or more and 3 or less.

[0111] (R) 2 )

[0112] R 2 It 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 formula (2a) below.

[0113] R 2 Preferably, it 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 formula (2a) below, 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 formula (2a) below, particularly preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, or a group represented by formula (2a) below.

[0114] The alkyl group is preferably an alkyl group with 1 or more and 10 or less unsubstituted carbon atoms, and more preferably an alkyl group with 1 or more and 6 or less unsubstituted carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl or hexyl.

[0115] The haloalkyl group is preferably a haloalkyl group having 1 or more and 6 or less carbon atoms. The number of halogen atoms is preferably 1 or more and 10 or less, more preferably 2 or more and 5 or less. As a haloalkyl group having 1 or more and 6 or less carbon atoms, it is preferably an alkyl group substituted with a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group is preferably terminally perfluoromethyl. Examples of preferred haloalkyl groups include trifluoromethyl, trifluoroethyl, trifluoropropyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl, bromomethyl, etc.

[0116] The cycloalkyl group is preferably a cycloalkyl group with 3 or more but less than 8 carbon atoms (a cycloalkyl group forming a ring with 3 or more but less than 8 carbon atoms). Examples of cycloalkyl groups with 3 or more but less than 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. It should be noted that cycloalkyl groups may have substituents, but the number of carbon atoms (3 or more but less than 8 carbon atoms) does not include the number of carbon atoms of the substituents.

[0117] The preferred alkoxy group is one with 1 or more carbon atoms and 6 or fewer carbon atoms. Examples of suitable alkoxy groups with 1 or more carbon atoms and 6 or fewer carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, etc.

[0118] Aryl groups can be used with R 1 The same group as the one illustrated. The aryl group is preferably phenyl or naphthyl.

[0119] Heteroaryl groups can be used with R 1 The groups shown in the example are the same groups.

[0120] As R 2 The substituents that may be present are preferably selected from at least one of the following groups: a straight-chain or branched alkyl group having 1 or more and 6 or less free carbon atoms; a straight-chain or branched haloalkyl group having 1 or more and 6 or less free carbon atoms; a straight-chain or branched alkoxy group having 1 or more and 6 or less free carbon atoms; and a halogen atom. The number of substituents is, for example, 1 or more and 3 or less.

[0121] R 2 Preferably, it is any one of the following: alkyl group having 1 or more but less than 5 carbon atoms, fluoroalkyl group having 1 or more but less than 5 carbon atoms, alkoxy group having 1 or more but less than 5 carbon atoms, alkoxyalkyl group having 2 or more but less than 6 carbon atoms, phenyl group, or phenyl group having a substituent. Fluoroalkyl group having 1 or more but less than 5 carbon atoms preferably has a perfluoromethyl terminal.

[0122] (The group shown in formula (2a))

[0123] -Q 1 -(X) 1 Q 2 )aX 2 Q 3 (2a)

[0124] In equation (2a), Q 1 It is an alkylene or haloalkylene.

[0125] The alkylene group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 12 or less, even more preferably 1 or more and 7 or less, and most preferably 2 or more and 6 or less. The halogen atom used as the alkylene haloide 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 Cl and F, more preferably F. In the alkylene haloide, the halogen atom is preferably bonded to the terminal carbon, more preferably a perfluoromethyl group.

[0126] Q 2 It is an alkylene or haloalkylene. The preferred method for alkylene or haloalkylene is related to Q. 1 Same. Q 2 The number of carbon atoms in the alkylene or haloalkylene group can be related to Q. 1 The number of carbon atoms in alkylene or haloalkylene compounds can be the same or different.

[0127] Q 3 It can be an alkyl or haloalkyl group, and can be straight-chain or branched, preferably straight-chain.

[0128] The alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 12 or less, and most preferably 1 or more and 7 or less. The halogen atom used as 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 Cl and F, more preferably F.

[0129] Q 3 Preferably, it is a straight-chain alkyl group.

[0130] X 1 and X 2 Each is independently O, S, NR 700 PR 701 Or P (=O). X 1 and X 2 Preferably O, S, or NR 700 The optimal choice is O.

[0131] R 700 and R 701 Each of them is 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.

[0132] R 700 Preferably, it consists of a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably methyl, ethyl, propyl, butyl, or pentyl. The aryl group is preferably phenyl or naphthyl.

[0133] R 701 Preferably, it consists of a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably methyl, ethyl, propyl, butyl, or pentyl. The aryl group is preferably phenyl or naphthyl.

[0134] a is 0, or 1 or more but less than 3.

[0135] Formula (2a) is preferably alkylene alkoxy, alkylene thioalkyl or alkylene oxyalkylene alkoxy.

[0136] Among the specific examples of the groups shown in formula (2a) are -CH2OCH3, -CH2SCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2SCH3, -CH2CH2CH2OCH3, and -CH2CH2CH2SCH. 3、 -CH2CH2OCH2CH2OCH 3、 And -CH2CH2OCH2CH2OCH2CH3.

[0137] The group represented by formula (2a) is preferably -CH2OCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2CH2OCH3, -CH2CH2OCH2CH2OCH3, or -CH2CH2OCH2CH2OCH2CH3.

[0138] (Specific examples of formula (1a))

[0139] If a suitable equation (1a) is exemplified, then it is as follows.

[0140]

[0141] <Formula (1b)>

[0142]

[0143] In formula (1b), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings. The meaning of suitable ring B is the same as that exemplified in ring A.

[0144] Y 1 The substituted or unsubstituted methylene group. In Y 1 When substituents are present, the substituents are preferably halogen atoms, haloalkyl groups having 1 or more but 3 or fewer carbon atoms, or alkyl groups having 1 or more but 3 or fewer carbon atoms, and more preferably fluorine atoms or methyl groups. In Y 1 When substituents are present, the number of substituents is 1 or 2.

[0145] Y 1 More preferably, it is a methylene group substituted with a methyl or fluorine atom or an unsubstituted methylene group, and particularly preferably an unsubstituted methylene group.

[0146] Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C=CR 602 Or CC.

[0147] R 600 R 601 and R 602 Each of the following is 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, preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.

[0148] Y 2 Preferably, it contains substituted or unsubstituted methylene, O, S, SO2, or NR. 600 More preferably, it is an unsubstituted methylene, O, S or SO2.

[0149] Y 3 For substituted or unsubstituted methylene, regarding the suitable Y 3 , with Y 1 The examples in the text have the same meaning.

[0150] m is an integer from 1 to 4. m is preferably 1 or 2. n is an integer from 0 to 4. n is preferably 0 or 1. m+n is an integer greater than or equal to 1. m+n is preferably greater than or equal to 1 and less than or equal to 4, more preferably 1 or 2. When n is 0, Y 2 Bonded to ring B.

[0151] If a suitable equation (1b) is exemplified, then it is as follows.

[0152]

[0153] <R 3 and R 4 >

[0154] R 3 and R 4 Each of the following groups is independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted arylalkyl, substituted or unsubstituted arylalkoxy, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, or the group represented by formula (X3) below. R 3 and R 4 It is a group other than substituted or unsubstituted phenyl groups.

[0155] As substituted or unsubstituted alkyl, haloalkyl, group shown in formula (2a), substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted heteroaryl, it can be used with R 1 or R 2 The groups shown in the example are the same groups.

[0156] The amino group can be a primary amino group (-NH2) or a secondary or tertiary amino group in which one or two hydrogen atoms are substituted. Examples of substituents for substituted amino groups include alkyl groups with 1 or more but less than 6 carbon atoms, haloalkyl groups with 1 or more but less than 6 carbon atoms, alkoxy groups with 1 or more but less than 6 carbon atoms, cycloalkyl groups with 3 or more but less than 7 carbon atoms, aryl groups with 6 or more but less than 14 carbon atoms, and heteroaryl groups with 4 or more but less than 14 carbon atoms. Suitable examples of amino groups include amino, methylamino, dimethylamino, ethylamino, diethylamino, methylphenylamino, and diphenylamino.

[0157] As a heterocyclic group, a heterocyclic group having 3 or more but less than 10 atoms is preferred. The heteroatom in the heterocyclic group is preferably at least one selected from the group consisting of oxygen, nitrogen, sulfur, and phosphorus atoms. The number of heteroatoms is, for example, 1 or more but less than 5, preferably 1 or 2. Specifically, examples include aliphatic heterocyclic groups such as morpholino, piperidinyl, pyrrolyl, piperazine, and N-methylpiperazine, or aromatic heterocyclic groups such as dihydroindolyl. The heterocyclic group can be 2,6-dimethylmorpholino, 2,6-dimethylpiperidinyl, or 2,2,6,6-tetramethylpiperidinyl.

[0158] The alkylthio group is preferably an alkylthio group with 1 or more but 6 or fewer carbon atoms. Examples of alkylthio groups with 1 or more but 6 or fewer carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, etc.

[0159] The aryl thio group is preferably an aryl thio group with 6 or more but less than 10 carbon atoms. Examples of aryl thio groups with 6 to 10 carbon atoms include phenylthio, 1-naphthio, and 2-naphthio.

[0160] The alkyl carbonyl group is preferably an alkyl carbonyl group with 2 or more but less than 7 carbon atoms. Examples of alkyl carbonyl groups with 2 to 7 carbon atoms include acetyl and ethyl carbonyl.

[0161] The preferred alkoxycarbonyl group is one with 2 or more but less than 7 carbon atoms. Examples of alkoxycarbonyl groups with 2 to 7 carbon atoms include methoxycarbonyl and ethoxycarbonyl.

[0162] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0163] The aralkyl group is preferably an aralkyl group with 7 or more but less than 11 carbon atoms. Examples of aralkyl groups with 7 to 11 carbon atoms include benzyl, phenylethyl, phenylpropyl, phenylbutyl, and naphthylmethyl.

[0164] The arylalkoxy group is preferably an arylalkoxy group with 7 or more but less than 11 carbon atoms. Examples of arylalkoxy groups with 7 to 11 carbon atoms include benzyloxy and naphthylmethoxy.

[0165] The aryloxy group is preferably an aryloxy group with 6 or more but less than 12 carbon atoms. Examples of aryloxy groups with 6 to 12 carbon atoms include phenoxy and naphthoxy groups.

[0166] The preferred alkoxyalkylthio group is one with 2 or more but 9 or fewer carbon atoms. Examples of alkoxyalkylthio groups with 2 or more but 9 or fewer carbon atoms include methoxymethylthio, methoxyethylthio, methoxyn-propylthio, methoxyn-butylthio, ethoxyethylthio, and n-propoxypropylthio.

[0167] The haloalkylthio group is preferably a haloalkylthio group with 1 or more and 6 or less carbon atoms. Examples of haloalkylthio groups with 1 or more and 6 or less carbon atoms include trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio, and bromomethylthio.

[0168] The cycloalkyl thio group is preferably a cycloalkyl thio group with 3 or more but less than 8 carbon atoms. Examples of cycloalkyl thio groups with 3 or more but less than 8 carbon atoms include cyclopropyl thio, cyclobutyl thio, cyclopentyl thio, and cyclohexyl thio. It should be noted that the cycloalkyl thio group may have substituents, but the number of carbon atoms (3 or more but less than 8 carbon atoms) does not include the number of carbon atoms of the substituents.

[0169] Silyyl groups may have substituents. There are no particular limitations on the substituents that can be present in substituted silyl groups, and examples include alkyl groups with 1 or more and 6 or less carbon atoms, haloalkyl groups with 1 or more and 6 or less carbon atoms, alkoxy groups with 1 or more and 6 or less carbon atoms, cycloalkyl groups with 3 or more and 7 or less carbon atoms, aryl groups with 6 or more and 14 or less carbon atoms, and heteroaryl groups with 4 or more and 14 or less carbon atoms.

[0170] Oxymethylsilyl groups may have substituents. There are no particular limitations on the substituents that can be present in substituted oxymethylsilyl groups, and examples include alkyl groups with 1 or more but less than 6 carbon atoms, haloalkyl groups with 1 or more but less than 6 carbon atoms, alkoxy groups with 1 or more but less than 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 or more but less than 14 carbon atoms, and heteroaryl groups with 4 or more but less than 14 carbon atoms.

[0171] It should be noted that cycloalkyl, arylthio, arylalkyl, arylalkoxy, aryloxy, aryl, heteroaryl, and cycloalkylthio groups can be unsubstituted. Where substituents are present, preferably 1 to 8 hydrogen atoms, and particularly preferably 1 to 4 hydrogen atoms, in the group forming the ring are substituted with a substituent selected from hydroxyl, alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups having 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen atoms. Specific examples of these substituents are described later.

[0172] R 3 and R 4 It may 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 aroxy group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (X3) below.

[0173] R 3 and R 4 Preferably, it is a substituted or unsubstituted alkyl group, a haloalkyl group, a group represented by formula (2a), or a group represented by formula (X3). If R 3 and R 4 For these groups, there is a tendency for photochromic compounds to fade at a faster rate.

[0174] R 3 and R 4 The following can be selected together with M to form a substituted or unsubstituted aliphatic ring having 3 or more but less than 20 cyclic carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocycle fused to an aliphatic ring, a substituted or unsubstituted heterocycle having 3 or more but less cyclic carbon atoms, or a substituted or unsubstituted fused polycyclic ring having an aromatic ring or an aromatic heterocycle fused to a heterocycle.

[0175] R 3 and R 4 Preferably, the ring is formed with a substituted or unsubstituted aliphatic ring having 3 or more but less than 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or aromatic heterocycle fused to the aliphatic ring, or a substituted or unsubstituted heterocyclic ring having 3 or more but less than 20 cyclic atoms. More preferably, it is formed together with M into a ring selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and spirobicyclohexane. Furthermore, the ring may have 1 to 10 alkyl groups having 1 or more but less than 5 carbon atoms, or cycloalkyl groups having 5 or more but less than 7 carbon atoms as substituents, and the cycloalkyl groups having 5 or more but less than 7 carbon atoms may be fused. Specifically, the ring shown below is more preferably formed.

[0176]

[0177] As R 3 and R 4 The substituents that may be present are preferably straight-chain or branched alkyl groups with 1 or more and 6 or fewer carbon atoms.

[0178] <The group shown in formula (X3)>

[0179] L 1 -R 400 (X3)

[0180] In equation (X3), R 400 It is a silyl group that is a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or has alkyl, alkoxy or aryl substituents.

[0181] L 1 It is the group represented by the following formula (X2).

[0182]

[0183] In formula (X2), J is a divalent group. Each J can independently be a directly bonded, substituted, or unsubstituted methylene group, oxygen atom, sulfur atom, or NR. 301 R 301 It can be a hydrogen atom or an alkyl group. R 301 Preferably, the alkyl group has 1 or more but less than 20 carbon atoms. This alkyl group preferably has a silyl group, a polymeric group, or a photochromic group as a substituent, having an alkyl group with 1 or more but less than 10 carbon atoms.

[0184] Examples of polymerizable groups include vinyl, 1-chlorovinyl, allyl, styryl, (meth)acryloyl, 2-(methacryloyloxy)ethylcarbamoyl, 2-(methacryloyloxy)ethoxycarbonyl, and crotonyl. In addition, epoxy, cyclosulfide, thiocyclobutyl, OH, SH, NH2, COOH, NCO, or NCS groups can also be listed. Preferably, the polymerizable group is selected from at least one group formed by (meth)acryloyl, 2-(methacryloyloxy)ethylcarbamoyl, 2-(methacryloyloxy)ethoxycarbonyl, epoxy, OH, SH, NH2, and COOH groups.

[0185] A photochromic group is a group that contains a photochromic site. Examples of representative photochromic groups include naphthopyran, spirooxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene. From the perspective of exhibiting excellent photochromic properties, indene-naphthopyran is preferred, and particularly indene[2,1-f]naphtho[1,2-b]pyran is preferred.

[0186] The indo[2,1-f]naphtho[1,2-b]pyran is preferably represented by the group shown in the following formula (X4).

[0187]

[0188] In equation (X4), R 401 and R 402 It can be the same as the above R 3 and R 4 The same groups are used.

[0189] R 403 and R 404 Each can be independently associated with the aforementioned R. 3 and R 4 The same groups are used.

[0190] R 405 and R 406 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 405 and R 406 It can be used in conjunction with R described later. 5 and R 6 The same groups are used.

[0191] o is an integer from 0 to 4.

[0192] n is an integer between 0 and 4.

[0193] When o is 2~4, multiple R 403 Choose either the same or different from each other.

[0194] When n is 2~4, multiple R 404 Choose either the same or different from each other.

[0195] In R 401 R 402 R 403 R 404 and R 405 At least one of the substituents on the aryl or heteroaryl group is associated with L 1 Bonding.

[0196] The group represented by the particularly preferred formula (X2) is represented by the following formula.

[0197]

[0198] In formula (X2), L is an oxygen atom or a sulfur atom.

[0199] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents. R 300 Preferably, it is an alkylene group having 1 or more but less than 6 carbon atoms, or a silylene group having 1 or more but less than 6 carbon atoms as a substituent.

[0200] R 302 R 303 and R 304 Each is an alkylene group independently. R 302 Preferably, it is an alkylene group having 1 or more but less than 6 carbon atoms. 303 Preferably, it is an alkylene group having 1 or more but less than 6 carbon atoms. 304 Preferably, it is an alkylene group with 1 or more but less than 6 carbon atoms.

[0201] h, j, k, and l are each an independent integer of 0 or 1.

[0202] i is an integer from 1 to 200. The structures with multiple i added can be the same or different. i is preferably 5 to 100, more preferably 8 to 75, and most preferably a number in the range of 10 to 70.

[0203] The dashed line in equation (X2) represents the relationship with R. 400 The bond.

[0204] <R 5 and R 6 >

[0205] In equation (1), R 5 and R 6 Each can be an independent hydrogen atom or a substituent. R 5 and R 6 Each group is preferably a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. These groups can be used with R 1 The groups shown in the example are the same groups.

[0206] R 5 and R 6 More preferably, each is a substituted or unsubstituted phenyl, a substituted or unsubstituted 1-naphthyl, a substituted or unsubstituted 2-naphthyl, a substituted or unsubstituted thiophene, a substituted or unsubstituted furanyl, a substituted or unsubstituted pyrrolinyl, a substituted or unsubstituted pyridinyl, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted benzofuranyl, or a substituted or unsubstituted benzopyrrolinyl. Furthermore, R is preferred. 5 and R 6 At least one of them is a substituted or unsubstituted phenyl group, with R being more preferred. 5 and R 6 All are substituted phenyl groups.

[0207] The substituents of the phenyl group are preferably groups represented by formula (2a), hydroxyl, alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or groups represented by formula (X3). As a substituent, it is more preferably an alkyl, haloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or a group represented by formula (X3).

[0208] <R 7 and R 8 >

[0209] In equation (1), R 5 and R 6 Each is an independent substituent. R 7 and R 8 Each of these groups is preferably hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group shown in formula (2a), the group shown in formula (X) below, or the group shown in formula (X3). As these groups, groups with R can be used. 1 ~R 4 The groups shown in the example are the same groups.

[0210] b is an integer from 0 to 3. c is an integer from 0 to 4. When b is 2 to 3, multiple R... 7 Choose either the same or different. In R where b is 2~3 and there are adjacent pairs... 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 7 The combination represents the 9th and 10th positions of this chromene compound.

[0211] When c is 2~4, multiple R 8 Choose either the same or different. In R where c is 2~4 and there are adjacent pairs... 8 In the case of two adjacent R 8 Optional and bonded to R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 8 The combination is the 5 and 6 positions, or the 6 and 7 positions, or the 7 and 8 positions of the chromene compound.

[0212] It can also contain R 7 or R 8 The bonded carbon atoms form a ring with 5 or more but 8 or fewer atoms. Furthermore, this ring may have substituents, such as those selected from hydroxyl groups, alkyl groups with 1 or more but 6 or fewer carbon atoms, haloalkyl groups with 1 or more but 6 or fewer carbon atoms, cycloalkyl groups with 3 or more but 8 or fewer carbon atoms, alkoxy groups with 1 or more but 6 or fewer carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 or more but 8 or fewer carbon atoms, cyano groups, nitro groups, and halogen groups. Specific examples of these substituents will be described later.

[0213] As R 7 and R 8 A suitable ring that can be formed is the ring shown in the following formula (X5).

[0214]

[0215] In formula (X5), Q and T are each independently a sulfur atom, a substituted or unsubstituted methylene group, an oxygen atom, or NR. 307 The group shown. R 307 It is a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, or a group represented by formula (2a).

[0216] R 305 and R 306 Each of the following is preferably an independent hydroxyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, substituted amino group, substituted or unsubstituted heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkoxy group, substituted or unsubstituted aryl group, thiol group, alkoxyalkoxy group, haloalkoxy group, cycloalkylthio group, or substituted or unsubstituted arthio group.

[0217] Additionally, R 305 and R 306 The carbon atoms bonded to them can be optionally combined to form substituted or unsubstituted aliphatic rings. Examples of specific aliphatic rings include cyclopentane rings and cyclohexane rings. Furthermore, in this aliphatic ring, 1 to 8 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, can be substituted with at least one group selected from hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, heterocyclic, cyano, nitro, and halogen atoms. Specific examples of these substituents are described later.

[0218] In the formula, m is an integer from 1 to 4.

[0219] <Group represented by formula (X)>

[0220]

[0221] In equation (X), E is an oxygen atom or NR. 101 R 101 It can be a hydrogen atom or an alkyl group. E is preferably NR. 101 R 101 Preferably, it is an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0222] F can be an oxygen atom or a sulfur atom. F is preferably an oxygen atom.

[0223] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. G is preferably NH.

[0224] g is 0 or 1.

[0225] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. When G is an oxygen atom or a sulfur atom, R... 201 It is a group other than a hydrogen atom. R 201 Preferably, it is an alkyl group with 1 or more but less than 6 carbon atoms, an alkoxy group with 1 or more but less than 6 carbon atoms, or an aryl group with 6 or more but less than 12 carbon atoms.

[0226] The suitable group represented by formula (X) is shown below.

[0227]

[0228] <The skeleton shown in equation (2)>

[0229] The photochromic compound of the embodiment preferably has a naphthopyran skeleton as shown in formula (2) below. In formula (2) below, Z 1 R 3 R 4 M and M each have the same meaning as in equation (1).

[0230]

[0231] <Compounds shown in formula (3)>

[0232] The photochromic compound used in 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 The meanings of , b, a and M are the same as those in equation (1).

[0233]

[0234] <The photochromic compound shown in formula (4)>

[0235] As particularly suitable chromene compounds, compounds represented by the following formula (4) can be listed.

[0236]

[0237] In equation (4), R 3 R 4 R 7 R 8 Z 1 M, b and c each have the same meaning as in equation (3).

[0238] <R 9 and R 10 >

[0239] R 9 and R 10 Each of the following is independently a hydroxyl group, an alkyl group having 1 or more and 6 or less carbon atoms, a haloalkyl group having 1 or more and 6 or less carbon atoms, a cycloalkyl group having 3 or more and 8 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, a substituted or unsubstituted amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 or more and 6 or less carbon atoms, a substituted or unsubstituted arylthio 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).

[0240] d represents R 9 The number of elements is an integer from 0 to 5. When d is greater than 2, R... 9 The groups can be either the same or different from each other.

[0241] In R where d is between 2 and 5 and there are adjacent pairs 9 In the case of two adjacent R 9 Optional and bonded to R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0242] e represents R 10 The number of elements is an integer between 0 and 5. When e is greater than 2, R... 10 The groups can be either the same or different from each other.

[0243] In R where e is 2~5 and there are adjacent values 10 In the case of two adjacent R 10 Optional and bonded to R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0244] R 9 and R 10 Two adjacent rings can be independently joined to form a cyclic group optionally comprising at least one of the following groups: oxygen, sulfur, carbon, and nitrogen atoms. The cyclic group is not particularly limited, but preferably contains R. 9 and R 10 The bonded carbon atoms form a ring with 5 or more but 8 or fewer atoms. Furthermore, this ring may also have substituents. Examples of such substituents include hydroxyl groups, alkyl groups with 1 or more but 6 or fewer carbon atoms, haloalkyl groups with 1 or more but 6 or fewer carbon atoms, cycloalkyl groups with 3 or more but 8 or fewer carbon atoms, alkoxy groups with 1 or more but 6 or fewer carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 or more but 8 or fewer carbon atoms, cyano groups, nitro groups, and halogen groups. Specific examples of these substituents can be listed in R... 1 ~R 4 The groups illustrated in the example are the same as the groups described in the example. As R 9 and R 10 The resulting ring is preferably formed together with the ring shown in formula (X5).

[0245] <Detailed explanation of substituents, etc.>

[0246] As in the above R 1 ~R 10 Substituents that may be present on the group include hydroxyl, cyano, halogen atom, nitro, formyl, hydroxycarbonyl, thiol, group shown in formula (2a), group shown in formula (X), group shown in formula (X3), alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, heterocyclic, halogen atom, alkylthio, arylthio, alkylcarbonyl, alkoxycarbonyl, arylalkyl, arylalkoxy, aryl, heteroaryl, alkoxyalkylthio, haloalkylthio, cycloalkylthio, silyl, or oxysilyl. As these groups, R can be used... 1 ~R 4 The same group as the group detailed in the text.

[0247] <Specific examples of suitable photochromic compounds>

[0248] If a particularly suitable photochromic compound is to be specifically exemplified, the photochromic compound shown in the following formula can be cited.

[0249]

[0250] [Phenol derivatives]

[0251] The phenolic derivative of the embodiment is represented by the following formula (5). This phenolic derivative can be used as an intermediate for synthesizing the photochromic compound shown in formula (1) above.

[0252]

[0253] In equation (5), M and R 3 R 4 R 7 R 8 Z 1 The rings A, b, and c each have the same meaning as in equation (1) above.

[0254] <Phenolic derivatives shown in formula (6)>

[0255] The phenolic derivative of the embodiment may have the skeleton shown in formula (6) below. This phenolic derivative can be used as an intermediate for synthesizing photochromic compounds having the skeleton shown in formula (2) above.

[0256]

[0257] In equation (6), M and R 3 R 4 and Z 1 Each has the same meaning as in equation (2) above.

[0258] <Phenolic derivatives shown in formula (7)>

[0259] The phenolic derivative of the embodiment is represented by the following formula (7). This phenolic derivative can be used as an intermediate for synthesizing the photochromic compound shown in formula (3) and the photochromic compound shown in formula (4).

[0260]

[0261] In equation (7), M and R 3 R 4 R 7 R 8 Z 1 b and c each have the same meaning as in equation (4) above.

[0262] <Specific examples of phenolic derivatives>

[0263] Specific examples of phenolic derivatives used in implementation include compounds represented by the following formulas.

[0264]

[0265] [Methods for manufacturing photochromic compounds]

[0266] The photochromic compounds of the embodiments can be manufactured by any synthetic method. Representative examples of methods for manufacturing photochromic compounds are described, but the method is not limited to these. It should be noted that, in the following description, unless otherwise specified, the symbols in the formulas have the meanings explained in the above formulas.

[0267] The photochromic compound can be produced by reacting the phenolic derivative shown in formula (7) above with the propargyl alcohol compound shown in formula (8) below in the presence of an acid catalyst.

[0268]

[0269] The reaction ratio of the phenolic derivative to the propargyl alcohol compound is preferably selected from the range of 1:10 to 10:1 (molar ratio). As an acid catalyst, examples include sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, and acidic alumina. The acid catalyst is preferably used in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the total mixture of the phenolic derivative and the propargyl alcohol compound. The reaction temperature is preferably 0 to 200°C. As a solvent, aprotic organic solvents are preferably used, such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, and toluene. The purification method for the product obtained by this reaction is not particularly limited. For example, silica gel column purification can be performed, followed by purification by recrystallization.

[0270] <Synthetic methods of phenolic derivatives>

[0271] Phenolic derivatives can be synthesized using known methods.

[0272] The synthesis method of the phenolic derivative shown in formula (7) is not particularly limited. For example, when M is a carbon atom, it can be synthesized as follows.

[0273] First, by reacting the benzene compound shown in formula (9) with the acyl chloride compound shown in formula (10), the benzophenone compound shown in formula (11) is obtained. It should be noted that in formula (11), Z... 1 R 7 R 8 b and c have the same meaning as in equation (3).

[0274]

[0275]

[0276]

[0277] It should be noted that, depending on the structure and substituents of the desired photochromic compound, the substituents of the acyl chloride compound and the benzene compound can be interchanged. That is, it is possible to make the acyl chloride compound with Z... 1 R 7 Acyl chloride compounds with R 8 The reaction of benzene compounds.

[0278] Furthermore, benzophenone compound (11) is subjected to the Stobbe reaction, cyclization reaction, hydrolysis reaction using a base or acid, benzyl protection, or debenzylation based on hydrolysis reaction using a base or acid to obtain a carboxylic acid with a hydroxyl group protected by a benzyl (Bn) as shown in formula (12). Next, the benzyl-protected carboxylic acid shown in formula (12) is converted into an amine by methods such as the Curtius rearrangement, Hofmann rearrangement, and Lossen rearrangement, and a diazonium salt is prepared therefrom. The diazonium salt is converted into a halide such as a bromide or iodide by the Sandmeyer reaction, etc., to obtain a halide shown in formula (13) (where Hal represents a halogen).

[0279]

[0280]

[0281] The obtained halide is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then reacted with the following formula (14) (where R... 3 and R 4 The ketone (with the same meaning as in formula (3)) is reacted in an organic solvent at -100~70℃ to give the compound shown in formula (15) below.

[0282]

[0283]

[0284] After debenzylation of the compound shown in formula (15), the alcohol is spirocyclized under neutral to acidic conditions at 10 to 120 °C for 10 minutes to 2 hours, thereby synthesizing the target phenolic derivative of formula (7). In this reaction, the reaction ratio of the organometallic reagent to the ketone shown in formula (14) is adopted in a wide range, preferably from 1:10 to 10:1 (molar ratio). The reaction temperature is preferably -100 to 70 °C. As a solvent, an aprotic organic solvent, such as diethyl ether, tetrahydrofuran, benzene, or toluene, is preferred. The spirocyclization of the alcohol under neutral to acidic conditions is preferably carried out in the presence of an acid catalyst. As an acid catalyst, acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, or acidic alumina are used, for example. Such an acid catalyst is preferably used in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the alcohol. During spirocyclization, it is preferably carried out in the presence of solvents such as tetrahydrofuran, benzene, or toluene.

[0285] The above method demonstrates the use of a substituent Z. 1 This is one example of a method using raw materials, but it is also possible, for example, to use Z after synthesizing a precursor having halogen atoms. 1 Substituents Z can be introduced through methods such as the introduction of -H-structured amines and the Buchwald reaction with Pd catalysts. 1 .

[0286] Importing substituent Z 1 The reaction is not particularly limited; for example, it can be introduced after the synthesis of a photochromic compound having halogen atoms. One example is shown below.

[0287] First, replace the substituent Z with a compound containing a halogen atom. 1 The reaction is carried out in the same manner as in the example above, but with a benzophenone compound having halogen atoms instead of Z. 1 The carboxylic acid compound of formula (16) obtained by Stobbe reaction, cyclization reaction, or hydrolysis reaction using base or acid is subjected to spirocyclization under neutral to acidic conditions and reduction reaction using hydrogen, hydrazine, etc., thereby obtaining the phenolic derivative of formula (17).

[0288]

[0289]

[0290] In addition to the methods described above, the compound of formula (17) can also be synthesized by intramolecular cyclization of the halogen compound of formula (13) in the presence of a palladium catalyst.

[0291] Using the obtained phenolic derivative, a photochromic compound of the following formula (18) was obtained.

[0292]

[0293] By reacting the obtained photochromic compound with R under alkaline conditions 3 The halide reaction yields a photochromic compound precursor of the following formula (19).

[0294]

[0295] By reacting the halogen atoms of the obtained precursor with Z 1 The photochromic compound of this invention can be obtained by performing the Buchwald reaction using a Pd catalyst on an amine with a -H structure.

[0296] <Synthetic methods for phenolic derivatives containing Si and Ge>

[0297] Hereinafter, an example of a method for manufacturing a phenolic derivative in formula (7) where M is Si or Ge will be described.

[0298] First, the halide shown in formula (13) is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then used in the following formula (20) (where R... 3 and R 4 The monohalides shown in formula (7) are reacted in an organic solvent at -100 to 70°C to give the compound shown in formula (21) below.

[0299]

[0300]

[0301] By using a known method of the compound shown in formula (21), the cyclized body shown in formula (22) is obtained.

[0302]

[0303] By debenzylation of the obtained cyclized body, the phenolic derivative of formula (7) can be obtained.

[0304] Identification of Photochromic Compounds

[0305] The photochromic compounds in the embodiments are, for example, solids or viscous liquids at room temperature and pressure. In these solids or liquids, the photochromic compounds can be separated using separation techniques such as thin-layer chromatography, silica gel column chromatography, high-performance liquid chromatography, and gas chromatography. Furthermore, in addition to the photochromic compounds, no byproducts such as starting materials or coloring components have been identified.

[0306] By using proton nuclear magnetic resonance spectroscopy ( 1 Photochromic compounds, as determined by ¹H-NMR, exhibit peaks based on aromatic and alkene protons in the δ range of 5.0–9.0 ppm, and peaks based on alkyl and alkylene protons in the δ range of 1.0–4.0 ppm. Furthermore, by comparing the relative spectral intensities, the number of protons in each bonding group can be determined. This allows for the identification of the skeleton and substituents of the photochromic compounds.

[0307] Furthermore, when the photochromic compound is contained in a cured material such as a resin, the photochromic compound can be separated by dissolving the resin and using the separation method described above.

[0308] <Photochromic Composition>

[0309] The photochromic compound of the embodiment can be dissolved in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the photochromic compound of formula (1) is dissolved in such a solvent, a colorless and transparent solution is obtained. It exhibits a good photochromic effect, which rapidly develops color when exposed to sunlight or ultraviolet light, and reversibly and rapidly returns to its original colorless state when sunlight or the like is blocked.

[0310] Furthermore, the photochromic compounds in the embodiments can be used in combination with photochromic compounds having other structures, depending on the intended use. For example, to obtain various hues required for photochromic lenses, they can also be used in combination with other photochromic compounds. Known compounds can be used without any limitations when combining them. Examples include indene-naphthopyran, naphthopyran, spiroxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene. Among these, indene-naphthopyran compounds are particularly preferred from the viewpoint of uniformly maintaining the hue during color development and fading, suppressing color deviation during color development accompanied by degradation of photochromic properties, and thus reducing initial coloration. In particular, from the perspective of balancing color development concentration at high temperatures and rapid fading rate, as well as excellent durability, it is preferable to use multiple photochromic compounds to adjust the hue.

[0311] When preparing a photochromic composition containing the photochromic compound of the embodiment and other photochromic compounds, the mixing ratio of each photochromic compound can be appropriately determined according to the desired hue.

[0312] <Photochromic Curable Composition>

[0313] The curable composition of the embodiments comprises the photochromic compound of the embodiments, and at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerization reactive group, and a (thio)carbamate (urea) polymer. Here, the (thio)carbamate (urea) polymer comprises at least one selected from the group consisting of carbamate polymers, thiocarbamate polymers, carbamate urea polymers, and thiocarbamate urea polymers.

[0314] The photochromic compounds and photochromic compositions of the embodiments are preferably combined with polymeric compounds to be used as photochromic curable compositions.

[0315] The photochromic curable composition depends on the color intensity of the photochromic compound, the selected lens material, and the lens thickness; therefore, it cannot be generalized. It is preferable to use the photochromic compound (or photochromic composition) in an amount of 0.001 to 10 parts by weight relative to 100 parts by weight of the polymeric compound. The optimal mixing amount varies depending on the intended use. For example, the following applies to both the use of the photochromic curable composition as a thin film optical article and as a thick film optical article.

[0316] (Use as a thin-film optical product)

[0317] For example, when the photochromic curable composition is made into a film of 10 μm or more and less than 1000 μm, for example, about 100 μm (a polymer film polymerized from the photochromic curable composition), the hue can be adjusted by mixing 0.001 to 10 parts by mass of the photochromic compound (or photochromic composition) of the above embodiment with 100 parts by mass relative to other polymeric monomers.

[0318] (Use as a thick-film optical material)

[0319] In the case of a thick cured material (a polymer molded body formed by polymerizing the photochromic curing composition), for example, a cured material with a thickness of 1 mm or more, the hue can be adjusted by mixing the photochromic compound (or photochromic composition) of the above embodiment in 0.001 to 1 part by mass relative to 100 parts by mass of the thick cured material or other polymeric monomers that provide the thick cured material.

[0320] <Polymerizing compounds>

[0321] As described above, the photochromic compound is preferably used in combination with a polymerizable compound as a photochromic curable composition. Examples of polymerizable compounds include urethane or urea-based polymeric compounds capable of forming urethane bonds, urea bonds, etc., compounds having polymerizable reactive groups, free radical polymeric compounds, epoxy polymeric compounds, etc. These polymeric compounds are not particularly limited; for example, the polymeric compound described in Patent Document 7 is preferred.

[0322] Among them, compounds with polymerization reactive groups as shown below are particularly preferred.

[0323] <Compounds with polymerizable reactive groups>

[0324] Examples of compounds having polymerization-reactive groups include compounds having an isocyanate group (isocyanate compounds). An isocyanate compound is a compound having an isocyanate group or an isothiocyanate group, or may contain both an isocyanate group and an isothiocyanate group. This compound is preferably used in combination with compounds containing active hydrogen, as described later. However, this is not a limitation; the following compounds are examples of such isocyanate compounds.

[0325] (Polyisocyanate)

[0326] Polyisocyanates are compounds having at least two isocyanate groups in a single molecule. Examples of polyisocyanates include aromatic polyisocyanates with aromatic rings such as isophthalimide diisocyanate and 4,4'-diphenylmethane diisocyanate, as well as aliphatic polyisocyanates such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

[0327] (Compounds containing active hydrogen)

[0328] The compounds having active hydrogen are not limited to this, but compounds having hydroxyl and / or thiol groups are preferred, and polyfunctional compounds having two or more active hydrogens in one molecule are particularly preferred. Specifically, examples of compounds having active hydrogen include polyfunctional thiols such as pentaerythritol tetra(3-mercaptopropionate), 4-mercaptomethyl-3,6-dithiooctanedithiol; and polyfunctional alcohols such as trimethylolpropane and pentaerythritol.

[0329] (Free radical polymerizable compounds)

[0330] Radical polymerizable compounds include polyfunctional and monofunctional radical polymerizable compounds. They can be used individually or in combination. Examples of radical polymerizable substituents include groups with unsaturated double bonds, namely vinyl groups (including styryl, (meth)acryloyl, allyl, etc.).

[0331] Polyfunctional radical polymerizable compounds are compounds with two or more radical polymerizable substituents within their molecules. These polyfunctional radical polymerizable compounds include first polyfunctional radical polymerizable compounds with 2 to 10 radical polymerizable substituents and second polyfunctional radical polymerizable compounds with more than 10 radical polymerizable substituents.

[0332] There are no particular limitations on the first type of polyfunctional radical polymerizable compound, but the number of radical polymerizable substituents is more preferably 2 to 6. Specific examples are described below.

[0333] (Polyfunctional (meth)acrylate compounds)

[0334] Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol diglycidyl(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane.

[0335] (Multifunctional allyl compounds)

[0336] Diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chloramphenicol, diallyl hexahydrophthalate, diallyl carbonate, allyl diethylene glycol carbonate, and trimethylolpropane triallyl ester.

[0337] (Polyfunctional thio(meth)acrylate compounds)

[0338] 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl) ether, 1,4-bis(methacryloylthiomethyl)benzene.

[0339] (Free radical polymerizable compounds)

[0340] Examples of highly functional free radical polymerizable compounds with more than 10 free radical polymerizable substituents include silsesquioxane compounds and polyrotaxane compounds with relatively large molecular weights.

[0341] In addition, a monofunctional free radical polymerizable compound is a compound having a free radical polymerizable substituent in the molecule. However, it is not limited to this specific example, and the following compounds can be cited as examples.

[0342] (Unsaturated carboxylic acids)

[0343] Acrylic acid, methacrylic acid, maleic anhydride.

[0344] ((meth)acrylate)

[0345] Methyl methacrylate, benzyl methacrylate, phenyl methacrylate.

[0346] 2-Hydroxyethyl methacrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyl etheroxymethacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl acrylate, 3-(glycidyl etheroxy-1-isopropyloxy)-2-hydroxypropyl acrylate, 3-glycidyl etheroxy-2-hydroxypropyloxy)-2-hydroxypropyl acrylate.

[0347] (Fumarate)

[0348] Diethyl fumarate, diphenyl fumarate.

[0349] (Thio(meth)acrylic acid)

[0350] Methyl thioacrylate, benzyl thioacrylate, benzyl thiomethacrylate.

[0351] (Vinyl compounds)

[0352] Divinylbenzene, styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene.

[0353] The free radical polymerizable compound can be used alone or in mixtures of several compounds. In this case, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set the polyfunctional free radical polymerizable compound to 80-100 parts by mass and the monofunctional free radical polymerizable compound to 0-20 parts by mass; more preferably, the polyfunctional free radical polymerizable compound to 90-100 parts by mass and the monofunctional free radical polymerizable compound to 0-10 parts by mass. Furthermore, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set the first polyfunctional free radical polymerizable compound to 80-100 parts by mass, the second polyfunctional free radical polymerizable compound to 0-20 parts by mass, and the monofunctional free radical polymerizable compound to 0-20 parts by mass; even more preferably, the first polyfunctional free radical polymerizable compound to 85-100 parts by mass, the second polyfunctional free radical polymerizable compound to 0-10 parts by mass, and the monofunctional free radical polymerizable compound to 0-10 parts by mass.

[0354] (Various compounding agents)

[0355] In curable compositions, various known compounding agents can be incorporated without impairing the effect. These compounding agents include, for example, release agents, UV absorbers, infrared absorbers, UV stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and various other stabilizers. Additionally, solvents and leveling agents can also be incorporated. Thiols such as tert-dodecyl mercaptan can also be incorporated as polymerization modifiers.

[0356] Among the above-mentioned compounding agents, ultraviolet (UV) stabilizers are preferred from the perspective of improving the durability of photochromic sites. Such UV stabilizers include hindered amine light stabilizers, hindered phenolic antioxidants, and sulfur-based antioxidants. Particularly preferred UV stabilizers are described below.

[0357] Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, ADK 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-methylphenol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] manufactured by BASF Japan Ltd., IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565 manufactured by BASF Japan Ltd. There are no particular restrictions on the amount of such UV stabilizer used, as long as it does not impair the effect. It is usually in the range of 0.001 to 10 parts by weight, especially 0.01 to 1 part by weight, relative to 100 parts by weight of the photochromic curing composition.

[0358] In addition to UV stabilizers, UV absorbers can also be used. Known UV absorbers such as benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, and benzoate compounds can be used as UV absorbers, with cyanoacrylate compounds and benzophenone compounds being particularly preferred. The UV stabilizer is preferably used in the range of 0.001 to 5 parts by weight relative to 100 parts by weight of the photochromic curable composition containing the photochromic compound and the polymerizable compound.

[0359] <Instructions for use of photochromic curable compositions; optical articles>

[0360] Photochromic cured materials are obtained by curing photochromic curable compositions. The polymerization and curing of photochromic cured materials are carried out through free radical polymerization, ring-opening polymerization, anionic polymerization, or polycondensation using active energy rays such as ultraviolet light, alpha rays, beta rays, and gamma rays, heat, or a combination of both. In other words, appropriate polymerization methods are employed depending on the type of polymerizable compound, the type of polymerization accelerator, and the morphology of the resulting photochromic cured material.

[0361] When a curable composition containing polymerizable compounds is thermally polymerized, the temperature affects the properties of the resulting photochromic cured product.

[0362] The temperature conditions are affected by the type and amount of the thermal polymerization initiator and the type of polymerizable compound, so they cannot be generalized. Generally, it is preferable to start polymerization at a relatively low temperature and then slowly increase the temperature. The polymerization time, like the temperature, varies for various reasons, so it is preferable to predetermine the optimal time corresponding to these conditions, but it is generally preferred to select conditions in a way that completes polymerization in 2 to 48 hours. In the case of obtaining photochromic laminates, polymerization is preferably carried out at the temperature at which the polymerizable functional groups react with each other. In this case, the optimal temperature and time are determined in a manner that achieves the target molecular weight.

[0363] Furthermore, during photopolymerization of the curable composition, the polymerization conditions, particularly the UV intensity, affect the properties of the resulting photochromic cured product. These irradiation conditions are influenced by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, and therefore cannot be generalized. Generally, irradiation at a wavelength of 365 nm for 0.5 to 5 minutes at a rate of 50 to 500 mW / cm² is preferred. 2 The selection criteria for UV light mode.

[0364] [Optical Items]

[0365] The photochromic compounds described in this embodiment can be widely used as photochromic materials. For example, they can be used as various storage materials, photocopying materials, photoreceptors for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, and other storage materials, replacing silver halide photosensitive materials. Photochromic materials can also be used as photochromic lens materials, optical filter materials, display materials, photometers, decorative materials, etc.

[0366] The photochromic compound described in this embodiment is particularly suitable for use in photochromic lenses. Photochromic lenses are suitable for use as lenses in eyeglasses such as sunglasses. Known methods can be used to manufacture photochromic lenses as long as they achieve uniform light-adjusting performance.

[0367] When photochromism is manifested by a mixing method, the above-mentioned curing composition is injected into a glass mold held by an elastomer gasket or spacer. Depending on the type of polymerizable compound and polymerization curing accelerator, a photochromic cured product in the form of an optical material such as a lens can be obtained by casting polymerization based on heating in an air furnace and irradiation by active energy rays such as ultraviolet light.

[0368] In the case of developing photochromic properties through a lamination method, a coating liquid is prepared by appropriately dissolving a curable composition in an organic solvent. The coating liquid is then applied to the surface of an optical substrate such as a lens substrate by spin coating or dipping. After drying to remove the organic solvent, the coating liquid is polymerized and cured by UV irradiation in an inactive gas such as nitrogen or by heating, thereby forming a photochromic layer (coating method) on the surface of the optical substrate.

[0369] Alternatively, by placing an optical substrate such as a lens substrate facing a glass mold in a manner that forms a predetermined gap, and injecting a curable composition into the gap, a photochromic layer formed by the photochromic cured material can be formed on the surface of the optical substrate through casting polymerization based on an inner mold by using UV irradiation, heating, etc. (cast polymerization method).

[0370] When a photochromic layer is formed on the surface of an optical substrate using the lamination method (coating method and casting polymerization method) as described above, the adhesion between the photochromic layer and the optical substrate can be improved by performing pre-treatment on the surface of the optical substrate using chemical treatment based on alkaline solutions, acid solutions, etc., or physical treatment based on corona discharge, plasma discharge, grinding, etc. Alternatively, a transparent adhesive resin layer can be pre-formed on the surface of the optical substrate.

[0371] Furthermore, in the case of exhibiting photochromic properties through an adhesive method, a photochromic sheet is prepared by sheet molding of a curable composition, and then sandwiched between two transparent sheets (optical sheets) and subjected to the aforementioned polymerization and curing, thereby obtaining a photochromic laminate with a photochromic layer as the adhesive layer.

[0372] In this case, the photochromic film can also be produced by coating with a coating solution made by dissolving the curable composition in an organic solvent.

[0373] The photochromic laminate produced in this way is, for example, installed in a mold, and then the optical substrate such as a lens is injection molded with a thermoplastic resin (e.g., polycarbonate) to obtain an optical substrate such as a lens with a specified shape that is endowed with photochromic properties.

[0374] In addition, the photochromic laminate can also be bonded to the surface of an optical substrate using an adhesive or similar agent, thereby obtaining a photochromic lens.

[0375] It should be noted that, when fabricating photochromic laminates as described above, especially from the viewpoint of high adhesion to optical substrates, urethane-based or urea-based polymeric compounds, particularly urethane-based polymeric compounds, are preferably used as polymeric compounds to form polyurethane.

[0376] The above-mentioned curable composition exhibits excellent photochromic properties at high temperature.

[0377] In addition, the photochromic layer and photochromic cured product formed by the curable composition can be dyed with dyes such as disperse dyes, made into hard coating films using hard coating agents with sols as the main components of silane coupling agents, silicon, zirconium, antimony, aluminum, tin, tungsten, etc., formed into thin films based on the vapor deposition of metal oxides such as SiO2, TiO2, ZrO2, and subjected to anti-reflective treatment and antistatic treatment using thin films coated with organic polymers, etc., depending on their application.

[0378] Example

[0379] The present invention will be further described in detail through the following examples. These examples are for illustrative purposes only, and the spirit and scope of the invention are not limited to these examples.

[0380] [Example 1]

[0381] First process

[0382] Referring to the method described in Patent Document 8, 28.9 g (62.4 mmol) of the compound of formula (1-1) synthesized from 4-bromo-4'-methoxybenzophenone, 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. Then, 30.57 g (0.6 mmol) of Pd2(dba) and 1.19 g (2.5 mmol) of X-phos were added to the reaction solution, and the mixture was heated to 80 °C.

[0383]

[0384] Continue heating until the reactants disappear. After the reaction is complete, cool to room temperature and filter. Add 500 mL of tetrahydrofuran and 10% hydrochloric acid to the filtrate, neutralize, and separate. Concentrate the organic layer and then slurry it with 100 mL of methanol for purification, yielding the carboxylic acid compound shown in formula (1-2) in 92% yield.

[0385]

[0386] Second process

[0387] Using the carboxylic acid compound obtained in Example 1, and in addition, referring to the method of Patent Document 8, the iodine compound shown in the following formula (1-3) was obtained in a yield of 86%.

[0388]

[0389] Third process

[0390] 22.5 g (41.5 mmol) of the compound of formula (1-3) obtained in the second step was added to 360 mL of toluene, and azeotropic dehydration was performed until the water content in the toluene was below 100 ppm. 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 starting material had been consumed, 4.5 g of dehydrated acetone was added dropwise. After the addition, the temperature was slowly raised to room temperature. After warming, 200 mL of water was added, and the mixture was separated. The water washing was repeated until the pH of the aqueous layer reached 7-8. The solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography to obtain the compound of formula (1-4) in 80% yield.

[0391]

[0392] Fourth process

[0393] 28.4 g (150.0 mmol) of p-toluenesulfonic acid monohydrate was added to 750 mL of toluene, and azeotropic dehydration was carried out until the water content in the toluene was below 300 ppm. Then, a toluene solution obtained by dissolving 17.7 g (35.0 mmol) of the aforementioned formula (1-4) in 100 mL of toluene was slowly added while maintaining 85-100 °C, and refluxed after dropwise addition. After confirming that the raw material was consumed, the mixture was cooled to room temperature, and 500 mL of water was added, followed by separation. This operation was repeated 5 times to remove the solvent from the obtained organic layer, and the solution was purified by silica gel-based chromatography, thereby obtaining the phenolic derivative shown in the following formula (1-5) in 78% yield.

[0394]

[0395] Fifth process

[0396] Dissolve 2.38 g (6.0 mmol) of the phenolic derivative of formula (1-5) and 1.92 g (7.2 mmol) of propargyl alcohol of formula (1-6) in 40 mL of toluene, and further add 0.15 g (0.6 mmol) of p-toluenesulfonic acid pyridinium, and stir at 85 °C for 2 hours.

[0397]

[0398] After the phenolic derivative of the raw material was consumed, the mixture was cooled to room temperature, 40 mL of water was added, and the mixture was separated. The solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography to obtain the photochromic compound shown in the following formula (1-7) in 80% yield.

[0399]

[0400] The elemental analysis values ​​of the photochromic compound shown in formulas (1-7) are C: 81.82%, H: 6.06%, and N: 2.16%, which are similar to C. 44 H 49 The calculated values ​​of NO4, namely C: 81.83%, H: 6.09%, and N: 2.17%, are in good agreement.

[0401] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 9H peak based on methyl groups in the vicinity of δ0.5~3.5ppm, a 9H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0402] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0403] (Example 2)

[0404] First process

[0405] In the first step of Example 1, 4-bromo-3',4'-dimethoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner otherwise, to obtain the carboxylic acid shown in the following formula (2-1) in 92% yield.

[0406]

[0407] Second process

[0408] 10.4 g (20.0 mmol) of the compound of formula (2-1) was dissolved in 400 mL of THF, and 3 g of 5% Pd / C (50% water content) was added. The mixture was stirred under hydrogen pressure for 19 hours. After the reaction was completed, the mixture was filtered, and the THF was removed from the filtrate. The filtrate was then purified by silica gel-based chromatography to give the debenzylated matrix of formula (2-2) in 100% yield.

[0409]

[0410] Third process

[0411] 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 below 100 ppm. 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 to carry out the reaction while simultaneously carrying out azeotropic dehydration. After confirming that the starting material was consumed, the mixture was cooled to room temperature, and the resulting solid was filtered to obtain the carbonyl compound shown in formula (2-3) in 96% yield.

[0412]

[0413] Fourth process

[0414] Referring to the method described in Patent Document 9, the carbonyl compound shown in the aforementioned formula (2-3) was reacted to obtain the phenolic derivative shown in the following formula (2-4) in a yield of 91%.

[0415]

[0416] Fifth process

[0417] 6.9 g (17.4 mmol) of the phenolic derivative shown in 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 the solution, and the mixture was stirred at 80 °C. After the starting material was consumed, the mixture was cooled to room temperature, and water was added to wash until neutral. The solvent was removed from the resulting organic layer, and the mixture was purified by silica gel-based chromatography to give the benzyl compound shown in formula (2-5) in 97% yield.

[0418]

[0419] Sixth process

[0420] Add 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, and chill. While maintaining the temperature at 0-5°C, add 3.4 g (30.0 mmol) of tBuOK in four portions. After the starting material is consumed, neutralize with 10% hydrochloric acid, add 30 mL of toluene, and separate the layers. After removing the solvent from the resulting organic layer, perform the debenzylation reaction in the same manner as in the second step, and purify by silica gel-based chromatography to obtain the phenolic derivative shown in formula (2-6) in 88% yield.

[0421]

[0422] Seventh process

[0423] In the fifth step of Example 1, the compounds of the aforementioned formulas (2-6) were used instead of the compounds of the aforementioned formulas (1-5), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compounds shown in the following formulas (2-7) in a yield of 76%.

[0424]

[0425] The elemental analysis values ​​of the photochromic compound shown in formula (2-7) are C: 77.62%, H: 7.00%, N: 1.72%, which are similar to C. 53 H 57 The calculated values ​​of NO7, namely C: 77.63%, H: 7.01%, and N: 1.71%, are in good agreement.

[0426] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 15H peak based on methyl and 4-methoxybutyl in the vicinity of δ0.5~3.5ppm, a 22H peak based on methoxy and 4-methoxybutyl in the vicinity of δ3.5~5.0ppm, and a 20H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0427] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0428] (Example 3)

[0429] First process

[0430] In the first step of Example 2, 4-bromo-4'-methylbenzophenone was used instead of 4-bromo-3',4'-dimethoxybenzophenone, and benzomorpholine was used instead of N-methylaniline. In the sixth step, 1,1,1-trifluoro-4-iodobutane was used instead of 1-bromo-4-methoxybutane. All other reactions were carried out in the same manner to synthesize the phenolic derivative shown in the following formula (3-1).

[0431]

[0432] Second process

[0433] In the fifth step of Example 1, the compound of formula (3-1) 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). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (3-3) in 75% yield.

[0434]

[0435]

[0436] The elemental analysis values ​​of the photochromic compound shown in formula (3-3) are C: 72.73%, H: 5.75%, N: 1.55%, which are similar to C. 54 H 51 The calculated values ​​of F6NO4, namely C: 72.71%, H: 5.76%, and N: 1.57%, are in good agreement.

[0437] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on 24H of methyl, 1,1,1-trifluorobutyl, butoxy, and benzyl morpholino groups in the vicinity of δ0.5~3.5 ppm, peaks based on 7H of methoxy, butoxy, and benzyl morpholino groups in the vicinity of δ3.5~5.0 ppm, and peaks based on 20H of aromatic protons and alkene protons in the vicinity of δ5.0~9.0 ppm.

[0438] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0439] (Example 4)

[0440] First process

[0441] In the third step of Example 1, cyclooctanone was used instead of acetone, and the reaction was carried out in the same manner otherwise, to obtain naphthol of the following formula (4-1) in a yield of 42%.

[0442]

[0443] Second process

[0444] In the fifth step of Example 1, the compound of formula (4-1) 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). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (4-3) in 75% yield.

[0445]

[0446]

[0447] The elemental analysis values ​​of the photochromic compound shown in formula (4-3) are C: 81.24%, H: 6.81%, and N: 3.64%, which are similar to C. 52 H 52 The calculated values ​​of N2O4, namely C: 81.22%, H: 6.82%, and N: 3.64%, are in good agreement.

[0448] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl, cyclooctyl, and morpholino groups in the vicinity of δ0.5~3.5 ppm, peaks based on methoxy and morpholino groups in the vicinity of δ3.5~5.0 ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0 ppm.

[0449] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0450] (Example 5)

[0451] First process

[0452] Referring to the method described in Patent Document 5, 4-bromobenzoyl chloride was reacted with 2,4-dimethoxy-1,1-biphenyl to obtain the compound shown in the following formula (5-1) in 83% yield.

[0453]

[0454] Second process

[0455] In the first step of Example 1, the compound of the aforementioned formula (5-1) was used instead of 4-bromo-4'-methoxybenzophenone, and 4-fluoro-N-methylaniline was used instead of N-methylaniline. In the third step, diethyl ketone was used instead of acetone. The reaction was carried out in the same manner otherwise to synthesize the phenolic derivative shown in the following formula (5-2).

[0456]

[0457] Third process

[0458] In the fifth step of Example 1, the compound of formula (5-2) 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). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (5-4) in 71% yield.

[0459]

[0460]

[0461] The elemental analysis values ​​of the photochromic compound shown in formula (5-4) are C: 80.14%, H: 6.59%, N: 1.65%, which are similar to C. 57 H 56 The calculated values ​​of FNO5, namely C: 80.16%, H: 6.61%, and N: 1.64%, are in good agreement.

[0462] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks of 23H based on methyl, ethyl, and propoxy groups in the vicinity of δ0.5~3.5ppm, peaks of 10H based on methoxy and propoxy groups in the vicinity of δ3.5~5.0ppm, and peaks of 23H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0463] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0464] (Example 6)

[0465] First process

[0466] In the first step of Example 1, 4-bromo-4'-trifluoromethoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and 4-(trifluoromethyl)-N-methylaniline was used instead of N-methylaniline. In the third step, 4,4-diethylcyclohexanone was used instead of acetone. The reaction was carried out in the same manner otherwise to synthesize the phenolic derivative shown in the following formula (6-1).

[0467]

[0468] Second process

[0469] In the fifth step of Example 1, the compound of formula (6-1) 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). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (6-3) in a yield of 67%.

[0470]

[0471]

[0472] The elemental analysis values ​​of the photochromic compound shown in formula (6-3) are C: 74.13%, H: 6.72%, N: 1.40%, which are similar to C. 62 H 67 The calculated values ​​of F6NO4, namely C: 74.16%, H: 6.73%, and N: 1.39%, are in good agreement.

[0473] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 43H based on methyl, diethylcyclohexyl, and hexoxy groups in the vicinity of δ0.5~3.5ppm, a peak of 4H based on hexoxy groups in the vicinity of δ3.5~5.0ppm, and a peak of 20H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0474] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0475] (Example 7)

[0476] First process

[0477] In the first step of Example 5, 2,2-Dimethyl-1,3-benzooxathiole was used instead of 2,4-dimethoxy-1,1-biphenyl, and the reaction was carried out in the same manner to give the compound shown in the following formula (7-1) in 71% yield.

[0478]

[0479] Second process

[0480] In the first step of Example 2, the compound of the aforementioned formula (7-1) was used instead of 4-bromo-3',4'-dimethoxybenzophenone, and 1,2,3,4-tetrahydroquinoline was used instead of N-methylaniline. In the sixth step, 1-bromo-3-methoxypropane was used instead of 1-bromo-4-methoxybutane. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (7-2).

[0481]

[0482] Third process

[0483] In the fifth step of Example 1, the compound of formula (7-2) 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). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (7-4) in 77% yield.

[0484]

[0485]

[0486] The elemental analysis values ​​of the photochromic compound shown in formula (7-4) are C: 76.95%, H: 6.81%, N: 1.59%, S: 3.67%, which are similar to C. 56 H 59 The calculated values ​​of NO6S, namely C: 76.94%, H: 6.80%, N: 1.60%, and S: 3.67%, are in good agreement.

[0487] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 25H based on methyl, 3-methoxypropyl, propoxy, and 1,2,3,4-tetrahydroquinoline cyclogroups in the vicinity of δ0.5~3.5ppm, a peak of 15H based on methoxy, 3-methoxypropyl, and propoxy in the vicinity of δ3.5~5.0ppm, and a peak of 19H based on aromatic protons and alkene protons in the vicinity of δ5.0~9.0ppm.

[0488] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0489] (Example 8)

[0490] First process

[0491] In the first step of Example 2, 4-bromo-4'-phenoxybenzophenone was used instead of 4-bromo-3',4'-dimethoxybenzophenone, and diphenylamine was used instead of N-methylaniline. In the sixth step, 1-bromo-4-fluorobutane was used instead of 1-bromo-4-methoxybutane. The reaction was carried out in the same manner otherwise to synthesize the phenolic derivative shown in the following formula (8-1).

[0492]

[0493] Second process

[0494] In the fifth step of Example 1, the compound of formula (8-1) was used instead of the compound of formula (1-5), and the reaction was carried out in the same manner to obtain the photochromic compound of formula (8-2) in 71% yield.

[0495]

[0496] The elemental analysis values ​​of the photochromic compound shown in formula (8-2) are C: 80.95%, H: 5.98%, N: 1.57%, which are similar to C. 60 H 53 The calculated values ​​of F2NO4, namely C: 80.97%, H: 6.00%, and N: 1.57%, are in good agreement.

[0497] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 16H peak based on 4-fluorobutyl in the vicinity of δ0.5~3.5ppm, a 6H peak based on methoxy in the vicinity of δ3.5~5.0ppm, and a 31H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0498] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0499] (Example 9)

[0500] First process

[0501] In the first step of Example 2, 4-bromo-4'-methoxy-3'-methylbenzophenone was used instead of 4-bromo-3',4'-dimethoxybenzophenone, and benzothiomorpholine was used instead of N-methylaniline. In the sixth step, iodopropane was used instead of 1-bromo-4-methoxybutane. All other reactions were carried out in the same manner to synthesize the phenolic derivative shown in the following formula (9-1).

[0502]

[0503] Second process

[0504] In the third step of Example 7, the compound of formula (9-1) was used instead of the compound of formula (7-2), and the reaction was carried out in the same manner to obtain the photochromic compound of formula (9-2) in 76% yield.

[0505]

[0506] The elemental analysis values ​​of the photochromic compound shown in formula (9-2) are C: 79.26%, H: 6.80%, N: 1.78%, S: 4.09%, which are similar to C. 52 H 53 The calculated values ​​of NO4S, namely C: 79.25%, H: 6.78%, N: 1.78%, and S: 4.07%, are in good agreement.

[0507] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 24H peak based on methyl, propyl, propoxy, and benzothiomorpholine ring groups in the vicinity of δ0.5~3.5ppm, a 10H peak based on methoxy, propoxy, and benzothiomorpholine ring groups in the vicinity of δ3.5~5.0ppm, and a 19H peak based on aromatic protons and alkene protons in the vicinity of δ5.0~9.0ppm.

[0508] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0509] (Example 10)

[0510] First process

[0511] Referring to the method described in Patent Document 10, the reaction was carried out using 4-bromo-3'-fluoro-4'-methylbenzophenone to obtain the compound shown in the following formula (10-1) in 83% yield.

[0512]

[0513] Second process

[0514] In the first step of Example 2, the compound shown in formula (10-1) above was used instead of 4-bromo-3',4'-dimethoxybenzophenone, and N-(2-methoxyethyl)aniline was used instead of N-methylaniline. In the sixth step, 1-bromo-2-methoxyethane was used instead of 1-bromo-4-methoxybutane. The reaction was carried out in the same manner otherwise to synthesize the phenolic derivative shown in formula (10-2).

[0515]

[0516] Third process

[0517] In the fifth step of Example 1, the compound of the aforementioned formula (10-2) was used instead of the compound of the aforementioned formula (1-5), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (10-3) in a yield of 65%.

[0518]

[0519] The elemental analysis values ​​of the photochromic compound shown in formula (10-3) are C: 76.59%, H: 6.89%, N: 3.32%, which are similar to C. 54 H 58 The calculated values ​​of N2O7, namely C: 76.57%, H: 6.90%, and N: 3.31%, are in good agreement.

[0520] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 13H based on methyl, 2-methoxyethyl, and morpholino groups in the vicinity of δ0.5~3.5ppm, a peak of 25H based on methoxy, 2-methoxyethyl, and morpholino groups in the vicinity of δ3.5~5.0ppm, and a peak of 20H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0521] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0522] (Example 11)

[0523] First process

[0524] Referring to the method described in Patent Document 5, 2-bromoanisole was reacted with 2,6-dimethylbenzylthiophenol to obtain the compound shown in the following formula (11-1) in 89% yield.

[0525]

[0526] Second process

[0527] Referring to the method described in Patent Document 5, the compound of the aforementioned formula (11-1) was reacted with 4-bromobenzoyl chloride to obtain the compound of the following formula (11-2) in 91% yield.

[0528]

[0529] Third process

[0530] In the first step of Example 1, the compound of the aforementioned 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. In the third step, 3,3,5,5-tetramethylcyclohexanone was used instead of acetone. All other reactions were carried out in the same manner to synthesize naphthol as shown in the following formula (11-3).

[0531]

[0532] Fourth process

[0533] In the second step of Example 4, the compound shown in Formula (11-3) was used instead of the compound shown in Formula (4-1), and the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (11-4) in a yield of 71%.

[0534]

[0535] The elemental analysis values ​​of the photochromic compound shown in formula (11-4) are C: 77.25%, H: 6.48%, N: 2.85%, S: 3.25%, which are similar to C. 63 H 63 The calculated values ​​of FN2O5S, namely C: 77.27%, H: 6.48%, N: 2.86%, and S: 3.27%, are well consistent.

[0536] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl, tetramethylcyclohexyl, morpholino, and benzomorpholino groups in the vicinity of δ0.5~3.5 ppm, peaks based on methoxy, morpholino, and benzomorpholino groups in the vicinity of δ3.5~5.0 ppm, and peaks based on aromatic protons and alkene protons in the vicinity of δ5.0~9.0 ppm.

[0537] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0538] (Example 12)

[0539] First process

[0540] Referring to the method described in Patent Document 8, 7.2 g (15.0 mmol) of a compound of formula (12-1) synthesized from 3-bromo-4-methyl-4'-chlorobenzophenone, 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 starting material was consumed, 100 mL of THF and 50 mL of toluene were added, followed by the addition of 10% hydrochloric acid until the pH of the aqueous layer reached 1, and the mixture was separated. 20 mL of water was added, and the mixture was separated again. The solvent in the organic layer was concentrated, and 50 mL of methanol was added, followed by heating. After heating under reflux for 1 hour, the mixture was cooled. After stirring at 0–5 °C for 3 hours, the resulting solid was filtered, yielding a carboxylic acid of formula (12-2) in 95% yield.

[0541]

[0542]

[0543] Second process

[0544] In the first step of Example 1, the compound shown in Formula (12-2) was used instead of the compound shown in Formula (1-1), and N-ethylaniline was used instead of N-methylaniline. In the third step, dibutyl ketone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in Formula (12-3).

[0545]

[0546] Third process

[0547] In the fifth step of Example 1, the compound shown in Formula (12-3) was used instead of the compound shown in Formula (1-5), and the compound shown in Formula (12-4) was used instead of the compound shown in Formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (12-5) in a yield of 67%.

[0548]

[0549]

[0550] The elemental analysis values ​​of the photochromic compound shown in formula (12-5) are C: 86.08%, H: 7.21%, N: 3.15%, which are similar to C. 64 H 64 The calculated values ​​of N2O2, namely C: 86.06%, H: 7.22%, and N: 3.14%, are in good agreement.

[0551] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 32H peak based on methyl, ethyl, and butyl protons in the vicinity of δ0.5~3.5ppm, a 3H peak based on methoxy protons in the vicinity of δ3.5~5.0ppm, and a 29H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0552] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0553] (Example 13)

[0554] First process

[0555] In Example 1, benzomorpholine was used instead of N-methylaniline, and the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (13-1).

[0556]

[0557] Second process

[0558] In the fifth step of Example 1, the compound of the aforementioned formula (13-1) was used instead of the compound of the aforementioned formula (1-5), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (13-2) in a yield of 76%.

[0559]

[0560] The elemental analysis values ​​of the photochromic compound shown in formula (13-2) are C: 80.21%, H: 5.85%, N: 2.06%, which are similar to C. 45 H 39 The calculated values ​​of NO5, namely C: 80.21%, H: 5.83%, and N: 2.08%, are in good agreement.

[0561] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed an 8H peak based on methyl and benzomorpholino groups in the vicinity of δ0.5~3.5ppm, an 11H peak based on methoxy and benzomorpholino groups in the vicinity of δ3.5~5.0ppm, and a 20H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0562] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0563] (Example 14)

[0564] First process

[0565] In the first step of Example 2, 4-bromo-4'-methoxybenzophenone was used instead of 4-bromo-3',4'-dimethoxybenzophenone, and N-methyl-p-toluidine was used instead of N-methylaniline. In the sixth step, 1,1,1-trifluoromethyl-3-iodopropane was used instead of 1-bromo-4-methoxybutane. All other reactions were carried out in the same manner to synthesize the phenolic derivative shown in the following formula (14-1).

[0566]

[0567] Second process

[0568] In the fifth step of Example 1, the compound of formula (14-1) was used instead of the compound of formula (1-5), and the compound of formula (14-2) was used instead of the compound of formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (14-3) in a yield of 68%.

[0569]

[0570]

[0571] The elemental analysis values ​​of the photochromic compound shown in formula (14-3) are C: 70.63%, H: 5.21%, N: 3.22%, which are similar to C. 51 H 45 The calculated values ​​of F7N2O3, namely C: 70.66%, H: 5.23%, and N: 3.23%, are in good agreement.

[0572] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on 18H of methyl, 1,1,1-trifluoropropyl, and morpholino groups in the vicinity of δ0.5~3.5 ppm, peaks based on 7H of methoxy and morpholino groups in the vicinity of δ3.5~5.0 ppm, and peaks based on 20H of aromatic protons and olefin protons in the vicinity of δ5.0~9.0 ppm.

[0573] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0574] (Example 15)

[0575] First process

[0576] In Example 1, diphenylamine was used instead of N-methylaniline, and the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (15-1).

[0577]

[0578] Second process

[0579] In the fifth step of Example 1, the compound of the aforementioned formula (15-1) was used instead of the compound of the aforementioned formula (1-5), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (15-2) in a yield of 82%.

[0580]

[0581] The elemental analysis values ​​of the photochromic compound shown in formula (15-2) are C: 83.15%, H: 5.85%, N: 2.00%, which are similar to C. 49 H 41 The calculated values ​​of NO4, namely C: 83.14%, H: 5.84%, and N: 1.98%, are in good agreement.

[0582] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 6H peak based on methyl groups in the vicinity of δ0.5~3.5ppm, a 9H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 26H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0583] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0584] (Example 16)

[0585] First process

[0586] In the first step of Example 1, 4-bromobenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and in the second step, dimethoxyacetone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (16-1).

[0587]

[0588] Second process

[0589] In the fifth step of Example 1, the compound of formula (16-1) 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). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (16-3) in a yield of 69%.

[0590]

[0591]

[0592] The elemental analysis values ​​of the photochromic compound shown in formula (16-3) are C: 77.92%, H: 5.82%, N: 2.04%, which are similar to C. 45 H 40 The calculated values ​​of FNO5, namely C: 77.90%, H: 5.81%, and N: 2.02%, are in good agreement.

[0593] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 3H peak based on methyl groups in the vicinity of δ0.5~3.5ppm, a 16H peak based on methoxy and methoxymethyl groups in the vicinity of δ3.5~5.0ppm, and a 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0594] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0595] (Example 17)

[0596] First process

[0597] In the first step of Example 1, 1,2,3,4-tetrahydroquinoline was used instead of N-methylaniline, and in the second step, dipropyl ketone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (17-1).

[0598]

[0599] Second process

[0600] In the fifth step of Example 1, the compound of formula (17-1) was used instead of the compound of formula (1-5), and the compound of formula (17-2) was used instead of the compound of formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (17-3) in a yield of 66%.

[0601]

[0602]

[0603] Third process

[0604] 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. The internal temperature was cooled to below 5°C, and while maintaining the internal temperature below 5°C, 2.3 g (5.5 mmol) of [tris(trimethylsiloxy)silylethyl]dimethylchlorosilane in 10 mL of dimethylformamide solution was slowly added dropwise. After the addition, the mixture was stirred while slowly warming to room temperature for 12 hours. After the reaction was complete, 50 mL of water and 100 mL of toluene were added, and the mixture was separated. The solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography to obtain the photochromic compound of formula (17-4) in 91% yield.

[0605]

[0606] The elemental analysis values ​​of the photochromic compound shown in formula (17-4) are C: 67.74%, H: 7.77%, N: 1.22%, which are similar to C. 65 H 89 The calculated values ​​of NO8Si5, namely C: 67.72%, H: 7.78%, and N: 1.21%, are in good agreement.

[0607] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 59H peak based on propyl, 1,2,3,4-tetrahydroquinoline cycloyl, propoxy, and [tris(trimethylsiloxy)silylethyl]silyl groups in the δ 0.5–3.5 ppm range, a 10H peak based on methoxy and propoxy groups in the δ 3.5–5.0 ppm range, and a 20H peak based on aromatic protons and olefin protons in the δ 5.0–9.0 ppm range.

[0608] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0609] (Example 18)

[0610] First process

[0611] In the first step of Example 1, benzothiomorpholine was used instead of N-methylaniline, and cyclododecyl ketone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (18-1).

[0612]

[0613] Second process

[0614] In the fifth step of Example 1, the compound of formula (18-1) was used instead of the compound of formula (1-5), and the compound of formula (18-2) was used instead of the compound of formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (18-3) in a yield of 61%.

[0615]

[0616]

[0617] Third process

[0618] Referring to the method described in Patent Document 11, a compound of formula (18-4) synthesized from polyethylene glycol monomethyl ether with a number average molecular weight of 1000 was reacted with a photochromic compound of formula (18-3) to obtain a photochromic compound of formula (18-5) in a yield of 67%.

[0619]

[0620]

[0621] The proton nuclear magnetic resonance spectra of the photochromic compound represented by the aforementioned formula (18-5) were measured. The results showed a 32H peak based on cyclododecyl, succinic acid, morpholino, and benzothiomorpholino groups in the vicinity of δ0.5~3.5ppm, a 104H peak based on methoxy, ethylenedioxy, polyethylene glycol chain, morpholino, and thiomorpholino groups in the vicinity of δ3.5~5.0ppm, and a 20H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0622] (Example 19)

[0623] First process

[0624] In the first step of Example 17, benzomorpholine was used instead of 1,2,3,4-tetrahydroquinoline, and diethyl ketone was used instead of dipropyl ketone. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (19-1).

[0625]

[0626] Second process

[0627] In the second step of Example 18, the compound of the aforementioned formula (18-1) was replaced with the aforementioned formula (19-1), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (19-2) in a yield of 67%.

[0628]

[0629] Third process

[0630] In the third step of Example 18, sebacate chloride was used instead of the compound of the aforementioned formula (18-4), and the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (19-3) in 85% yield.

[0631]

[0632] The elemental analysis values ​​of the photochromic compound shown in formula (19-3) are C: 77.33%, H: 6.59%, N: 3.22%, which are similar to C. 112 H 114 N4O 14 The calculated values ​​of C: 77.30%, H: 6.60%, and N: 3.22% are in good agreement.

[0633] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 48H peak based on ethyl, sebacate, morpholino, and benzomorpholino groups in the vicinity of δ0.5–3.5 ppm, a 26H peak based on methoxy, morpholino, benzomorpholino, and ethylenedioxy groups in the vicinity of δ3.5–5.0 ppm, and a 40H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0634] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0635] (Analysis results of phenol derivatives)

[0636] Tables 1 and 2 summarize the analytical results of the phenolic derivatives used in Examples 1-19.

[0637] [Table 1]

[0638]

[0639] [Table 2]

[0640]

[0641] (Evaluation of the physical properties of photochromic plastic lenses produced by coating method)

[0642] (Example 20)

[0643] (Preparation of curable composition)

[0644] First, the photochromic compound, photopolymerization initiator, and polymerizable compound obtained in Example 1 above are mixed to obtain a curable composition.

[0645] As a polymerizable compound, a polymerizable compound is used that is formulated by combining the following free radical polymerizable monomers.

[0646] Polyethylene glycol dimethacrylate (average molecular weight 736): 42 parts by weight

[0647] Polyethylene glycol dimethacrylate (average molecular weight 536): 12 parts by weight

[0648] Trimethylolpropane trimethacrylate: 38 parts by weight

[0649] γ-Methacryloxypropyltrimethoxysilane: 2 parts by weight

[0650] Glycidyl methacrylate: 1 part by weight.

[0651] It should be noted that when the total amount of the free radical polymerizable monomer in the curable composition is set to 100g, the photochromic compound obtained in Example 1 above is added in a manner that yields 0.25mmol. The following additives are used as additives.

[0652] Phenylacetic bis(2,4,6-trimethylbenzoyl)phosphine oxide (photopolymerization initiator: Omnirad 819): 0.3 parts by weight)

[0653] Ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (stabilizer, Irganox 245: 1 part by weight)

[0654] bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate: 3 parts by weight

[0655] DuPont Toray Specialty Materials KK leveling agent (L7001): 0.1 parts by weight.

[0656] It should be noted that the above additives are the mixing ratio when the total amount of free radical polymerizable monomers is set to 100 parts by mass.

[0657] (Manufacturing of optical items)

[0658] Using this curable composition, polymerization is carried out as follows to obtain a photochromic laminate based on the following lamination method.

[0659] First, a thiocarbamate-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as the optical substrate. It should be noted that the thiocarbamate-based plastic lens was first subjected to alkaline etching at 50°C for 5 minutes using a 10% sodium hydroxide aqueous solution, and then thoroughly cleaned with distilled water.

[0660] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) was applied to the surface of the aforementioned plastic lens at a speed of 70 rpm for 15 seconds, followed by a 10-second application at 1000 rpm. Then, approximately 2 g of the aforementioned photochromic curing composition was spin-coated at 60 rpm for 40 seconds, followed by a 10-20 second application at 600 rpm, resulting in a photochromic coating layer thickness of 40 μm.

[0661] A lens with a photochromic curable composition (photochromic coating) coated on its surface was used in a nitrogen atmosphere with an output power of 200mW / cm. 2 The coating is cured by irradiating it with a metal halide lamp for 90 seconds. Then, it is further heated at 110°C for 1 hour to produce a photochromic laminate with a photochromic layer.

[0662] (Examples 21-38)

[0663] Photochromic laminates were fabricated using the photochromic compounds obtained in Examples 2-19, following the same method as in Example 20.

[0664] It should be noted that in Example 38, which used compound 19-3, the photochromic compound was added in a manner that yielded 0.25 mmol when the total amount of the free radical polymerizable monomer was set to 200 g.

[0665] (Comparative Examples 1-6)

[0666] Using the photochromic compounds shown in formulas (A) to (F) below, each photochromic laminate was obtained in the same manner as in Example 20.

[0667]

[0668]

[0669]

[0670]

[0671]

[0672]

[0673] <Evaluation Methods>

[0674] The obtained photochromic laminate was evaluated using the method shown below.

[0675] Photochromic properties

[0676] [1] Maximum absorption wavelength (λmax):

[0677] The maximum absorption wavelength after color development, determined by the spectrophotometer (instantaneous multichannel photodetector MCPD3000) manufactured by OTSUKA ELECTRONICS CO.,LTD, is used as an indicator of the hue during color development.

[0678] [2] Colorimetric concentration at 23℃ (A) 23 ):

[0679] The difference between the absorbance {ε(240)} after 240 seconds of light irradiation at 23°C at the maximum absorption wavelength and the absorbance ε(0) before irradiation is used as an indicator of colorimetric concentration. The higher this value, the better the photochromic property.

[0680] [3] Colorimetric concentration at 35℃ (A) 35 ):

[0681] The difference between the absorbance {ε(240)} after irradiation at 35°C for 240 seconds at the first and second absorption wavelengths and the absorbance ε(0) before irradiation is used as an indicator of colorimetric concentration. The higher this value, the better the photochromic property.

[0682] [4] High temperature colorimetric rate (A) 35 / A 23 ×100):

[0683] 35℃ colorimetric concentration (A) 35 ) / 23℃ colorimetric concentration (A) 23 (%) × 100 (%). If this value is high, the difference in colorimetric concentration between high and low temperatures is small, which can be described as low temperature dependence.

[0684] [5] Fading half-life at 23℃ [τ1 / 2 (sec.)]:

[0685] The time required for the absorbance of the sample at its maximum absorption wavelength to decrease to half of {ε(240)-ε(0)} after 240 seconds of light irradiation at 23°C and then stopping the light irradiation is used as an indicator of the fading rate. The shorter this time, the faster the fading rate.

[0686] The results of Examples 20, 32, 34, and Comparative Examples 1-6 are summarized in Table 3, and the results of Examples 21-31, 33, and 35-38 are summarized in Table 4. The relationship between the 23°C fading half-life and high-temperature color development rate of the photochromic laminates of the Examples and Comparative Examples is shown in Table 4. Figure 1 The image.

[0687] [Table 3]

[0688]

[0689] [Table 4]

[0690]

[0691] <Property Evaluation of Photochromic Layers Fabricated Using Adhesive Method>

[0692] (Example 39)

[0693] The adhesive sheet is manufactured using the following method. The adhesive sheet comprises, in sequence, 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. A polycarbonate sheet with a thickness of 400 μm is used as both the first and second optical sheets.

[0694] (Preparation of the composition for forming a photochromic layer)

[0695] In a 2L four-necked flask equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe, 315 parts by mass of polycarbonate diol with a number average molecular weight of 1000, 100 parts by mass of isophorone diisocyanate, and 72 parts by mass of toluene were added. The mixture was reacted at 100°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was complete, the reaction solution was cooled to near 0°C and dissolved in 205 parts by mass of tert-butanol and 382 parts by mass of diethyl ketone, and the liquid temperature was maintained at 0°C. Then, a mixed solution of 21.3 parts by mass of bis(4-aminocyclohexyl)methane and 20 parts by mass of diethyl ketone as a chain extender was added dropwise over 30 minutes, and the reaction was carried out at 0°C for 1 hour. Then, 8.1 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine were added dropwise, and the mixture was reacted at 0°C for 1 hour to obtain a diethyl ketone solution of terminal non-reactive carbamate urea resin.

[0696] 100 parts by weight of the obtained terminal non-reactive carbamate urea resin solution, 6.3 parts by weight of the photochromic compound of Example 1 (formula (1-7) above), a mixture of isomers of 4,4'-methylenebis(cyclohexyl isocyanate) (polyisocyanate compound), 0.4 parts by weight of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] as an antioxidant, and 0.06 parts by weight of DuPont Toray Specialty Materials KK L-7001 as a surfactant were added and stirred and mixed at room temperature to obtain a composition for forming a photochromic layer.

[0697] It should be noted that the photochromic compound is added in a manner that yields 0.25 mmol per 100 parts by weight of the terminal non-reactive urethane resin.

[0698] (Preparation of the adhesive layer composition)

[0699] A 5L separable flask (4-necked) equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe was prepared. 400 parts by mass of polycarbonate diol (number average molecular weight 1000), 175 parts by mass of isophorone diisocyanate, and 120 parts by mass of toluene were added to the flask. The reaction was carried out under a nitrogen atmosphere at 110°C for 7 hours to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was completed, the reaction solution was cooled to approximately 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 as a chain extender were added dropwise, and the reaction was carried out at 20°C for 1 hour. Then, 3 parts by mass of n-butylamine were further added dropwise, and the reaction was carried out at 20°C for 1 hour, thereby obtaining a propylene glycol-monomethyl ether solution of a terminally non-reactive urethane urea resin.

[0700] Add 0.2 parts by mass of DuPont Toray Specialty Materials KK L-7001 as a surfactant to 500 parts by mass of the obtained terminal non-reactive urethane resin solution, and stir and mix at room temperature to obtain a composition for adhesive layer.

[0701] (Manufacturing of adhesive sheets)

[0702] Using a coating machine (manufactured by TESTER SANGYO CO,. LTD.), the adhesive layer composition was coated onto one main surface of the first optical film at a coating speed of 0.5 m / min, and dried at a drying temperature of 110°C for 3 minutes, thereby obtaining a first optical film with a first coating film thickness of 5 μm. Using the same method, the adhesive layer composition was coated onto one main surface of the second optical film to obtain a second optical film with a second coating film.

[0703] Next, using a coating machine (manufactured by TESTER SANGYO CO,. LTD.), the photochromic layer forming composition was coated onto 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 yielded a third coating. Then, the third coating was bonded to the first optical sheet in contact with the first coating. The OPP film was peeled off from this structure, and the second optical sheet and the third coating were bonded together with the exposed main surface of the third coating in contact with the second coating. The resulting laminate was then left to stand at 40°C under vacuum for 24 hours, followed by heat treatment 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 an adhesive sheet. The obtained adhesive sheet was evaluated in the same manner as in Example 23. The results are shown in Table 5.

[0704] (Examples 40-49, Comparative Examples 7-10)

[0705] Adhesive sheets were prepared using the photochromic compounds shown in Table 5, following the same method as in Example 39.

[0706] [Table 5]

[0707]

[0708] <Physical Property Evaluation of Photochromic Cured Products Produced by Mixing Method>

[0709] (Example 50)

[0710] (Preparation of curable composition)

[0711] First, the photochromic compound, additive, and polymerizable compound obtained in Example 1 are mixed to obtain a curable composition. As the polymerizable compound, a polymerizable compound formulated by combining the following polymerizable monomers is used.

[0712] 1,3-Bis(isocyanate methyl)cyclohexane: 36.7 parts by weight

[0713] Pentaerythritol tetra(3-mercaptopropionate): 39.4 parts by weight

[0714] Polyoxyethylene polyoxypropylene lauryl ether (manufactured by AOKI OIL INDUSTRIAL Co., Ltd. WONDERSURF140): 17.4 parts by weight

[0715] 1-Decanethiol: 2.8 parts by weight

[0716] RX-1 prepared using the method described in Patent Document 12: 3.8 parts by mass

[0717] It should be noted that when the total amount of polymerizable monomers in the curable composition is set to 100g, the photochromic compound is added in a manner that results in 0.106mmol.

[0718] The following additives are used as additives.

[0719] Dimethyltin dichloride: 0.05 parts by weight

[0720] Irganox 245 manufactured by BASF Japan Ltd.: 0.1 parts by weight

[0721] 2-Ethylhexyl 4-methoxycinnamic acid: 0.6 parts by weight

[0722] (Manufacturing of solidified products)

[0723] After thorough degassing, the prepared curable composition was injected into a glass mold with a 1 mm gap, and polymerization was carried out by casting. Polymerization was performed in an air furnace, gradually increasing the temperature from 27°C to 120°C over 18 hours. After polymerization, the cured material was removed from the glass mold, yielding a 1 mm thick photochromic cured product. The obtained photochromic cured product was evaluated in the same manner as in Example 23. The results are shown in Table 6.

[0724] (Examples 51-60, Comparative Examples 11-14)

[0725] Photochromic cured products were prepared using the photochromic compounds shown in Table 6, following the same method as in Example 50. The results are summarized in Table 6.

[0726] [Table 6]

[0727]

[0728] Example 61

[0729] First process

[0730] In a 1L four-necked flask, 86g (645.0mmol) of aluminum chloride and 500mL of dichloromethane were added and the flask was chilled. 121.5g (663.0mmol) of N-methyldiphenylamine dissolved in 100mL of dichloromethane was slowly added dropwise, and the mixture was stirred for 2 hours. While maintaining an internal temperature below 5°C, 80.6g (323.0mmol) of 3-bromo-4-methoxybenzoyl chloride was slowly added dropwise. After stirring for 3 hours at an internal temperature of 0-5°C, the mixture was added to 2000mL of ice water and the temperature was raised to room temperature. The mixture was separated, and 2000mL of water was added for washing. Washing with water was repeated until the pH of the aqueous layer reached 6-7. The resulting organic layer was concentrated and recrystallized from 780mL of methanol to give the compound shown in formula (61-1) in 70% yield.

[0731]

[0732] Second process

[0733] In the first step of Example 1, the compound of the aforementioned formula (61-1) was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner to obtain the carboxylic acid compound shown in the following formula (61-2).

[0734]

[0735] Third process

[0736] In the second step of Example 2, the compound of the aforementioned formula (61-2) was used instead of the compound of the aforementioned formula (2-1), and the reaction was carried out in the same manner. In the sixth step of Example 2, iodopropane was used instead of 1-bromo-4-methoxybutane, and the reaction was carried out in the same manner to obtain the compound shown in the following formula (61-3).

[0737]

[0738] Fourth process

[0739] In the fifth step of Example 1, the compound of the aforementioned formula (61-3) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (5-3) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (61-4) in a yield of 72%.

[0740]

[0741] The elemental analysis values ​​of the photochromic compound shown in formula (61-4) are C: 82.12%, H: 7.26%, N: 3.23%, which are similar to C. 59 H 62 The calculated values ​​of N2O4, namely C: 82.10%, H: 7.24%, and N: 3.25%, are in good agreement.

[0742] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 30H peak based on methyl, propyl, and propoxy groups in the vicinity of δ0.5~3.5ppm, a 7H peak based on propoxy and methoxy groups in the vicinity of δ3.5~5.0ppm, and a 25H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0743] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0744] Example 62

[0745] First process

[0746] In the first step of Example 61, triphenylamine was used instead of N-methyldiphenylamine, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (62-1).

[0747]

[0748] Second process

[0749] In the second step of Example 61, the compound of the aforementioned formula (62-1) was used instead of the compound of the aforementioned formula (61-1), and the reaction was carried out in the same manner otherwise, to obtain the carboxylic acid compound shown in the following formula (62-2).

[0750]

[0751] Third process

[0752] In the first step of Example 12, the compound of the aforementioned formula (62-2) was used instead of the compound of the aforementioned formula (12-1), and 2,4,6-trimethoxyphenylboronic acid was used instead of 4-methoxyphenylboronic acid. Otherwise, the reaction was carried out in the same manner to obtain the compound of the following formula (62-3).

[0753]

[0754] Fourth process

[0755] In the first step of Example 2, the compound of the aforementioned formula (62-3) was used instead of the compound of the aforementioned formula (2-1). In the sixth step, 1-bromo-2-[2-(2-methoxyethoxy)ethoxy]ethane was used instead of 1-bromo-4-methoxybutane. Otherwise, the reaction was carried out in the same manner to obtain the phenolic derivative shown in the following formula (62-4).

[0756]

[0757] Fifth process

[0758] In the fifth step of Example 1, the compound of the aforementioned formula (62-4) was used instead of the compound of the aforementioned formula (1-5), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (62-5) in a yield of 62%.

[0759]

[0760] The elemental analysis values ​​of the photochromic compound shown in formula (62-5) are C: 73.88%, H: 6.62%, N: 1.22%, which are similar to C. 71 H 77 NO 13 The calculated values ​​of C: 73.86%, H: 6.64%, and N: 1.23% are in good agreement.

[0761] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak based on 4H of 2-[2-(2-methoxyethoxy)ethoxy]ethoxy in the vicinity of δ0.5~3.5ppm, a peak based on 44H of 2-[2-(2-methoxyethoxy)ethoxy]ethoxy and methoxy in the vicinity of δ3.5~5.0ppm, and a peak based on 27H of aromatic protons and alkene protons in the vicinity of δ5.0~9.0ppm.

[0762] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0763] Example 63

[0764] First process

[0765] In the second step of Example 62, the compound of the aforementioned formula (61-1) was used instead of the compound of the aforementioned formula (62-1). In the third step, 4-trifluoromethylphenylboronic acid was used instead of 2,4,6-trimethoxyphenylboronic acid. In the fourth step, iodopropane was used instead of 1-bromo-2-[2-(2-methoxyethoxy)ethoxy]ethane. The reaction was carried out in the same manner otherwise to obtain the phenolic derivative shown in the following formula (63-1).

[0766]

[0767] Second process

[0768] In the fifth step of Example 1, the compound of the aforementioned formula (63-1) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (3-2) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (63-2) in a yield of 69%.

[0769]

[0770] The elemental analysis values ​​of the photochromic compound shown in formula (63-2) are C: 78.41%, H: 6.34%, N: 1.59%, which are similar to C. 58 H 56 The calculated values ​​of F3NO4, namely C: 78.44%, H: 6.36%, and N: 1.58%, are in good agreement.

[0771] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on propyl, butoxy, and methyl 24H in the vicinity of δ0.5~3.5ppm, peaks based on butoxy and methoxy 8H in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons 24H in the vicinity of δ5.0~9.0ppm.

[0772] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0773] Example 64

[0774] First process

[0775] In the first step of Example 1, the compound of the aforementioned formula (62-2) was used instead of the compound of the aforementioned formula (1-1), and 4-trifluoromethylpiperidine was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to synthesize the compound shown in the following formula (64-1).

[0776]

[0777] Second process

[0778] In the second step of the example, the compound of the aforementioned formula (64-1) was used instead of the compound of the aforementioned formula (1-2), and in the third step, spiro[5.5]undecane-3-one was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the compound shown in the following formula (64-2).

[0779]

[0780] Third process

[0781] In the fifth step of Example 1, the compound of the aforementioned formula (64-2) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (6-2) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (64-3) in a yield of 61%.

[0782]

[0783] The elemental analysis values ​​of the photochromic compound shown in formula (64-3) are C: 79.16%, H: 7.34%, N: 2.52%, which are similar to C. 73 H 81 The calculated values ​​of F3N2O4, namely C: 79.17%, H: 7.37%, and N: 2.53%, are in good agreement.

[0784] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 49H peak based on spiro[5.5]undecanecycloyl, hexoxy, and 4-trifluoropiperidinyl in the vicinity of δ0.5~3.5ppm, a 7H peak based on hexoxy and methoxy in the vicinity of δ3.5~5.0ppm, and a 25H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0785] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0786] Example 65

[0787] First process

[0788] In the first step of Example 61, the compound of the aforementioned formula (62-1) was used instead of the compound of the aforementioned formula (61-1), and N-methyl-4-(trifluoromethyl)aniline was used instead of N-methylaniline. In the third step, 1-butoxy-2-bromoethane was used instead of iodopropane. The reaction was carried out in the same manner otherwise to obtain the phenolic derivative shown in the following formula (65-1).

[0789]

[0790] Second process

[0791] In the fifth step of Example 1, the compound of the aforementioned formula (65-1) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (7-3) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (65-2) in a yield of 68%.

[0792]

[0793] The elemental analysis values ​​of the photochromic compound shown in formula (65-2) are C: 76.61%, H: 6.58%, N: 2.57%, which are similar to C. 69 H 71 The calculated values ​​of F3N2O6, namely C: 76.64%, H: 6.62%, and N: 2.59%, are in good agreement.

[0794] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 26H based on 2-butoxyethyl, propoxy, and methyl in the vicinity of δ0.5~3.5ppm, a peak of 16H based on 2-butoxyethyl, propoxy, and methoxy in the vicinity of δ3.5~5.0ppm, and a peak of 29H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0795] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0796] Example 66

[0797] First process

[0798] In the first step of Example 5, 1-bromo-4-(2-methoxyphenyl)benzene was used instead of 2,4-dimethoxy-1,1-biphenyl to obtain the compound shown in the following formula (66-1) in 68% yield.

[0799]

[0800] Second process

[0801] In the first step of Example 1, 4-bromo-4'-methoxybenzophenone was replaced with the aforementioned formula (66-1), and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (66-2).

[0802]

[0803] The compound of formula (66-2) was used instead of the compound of formula (1-1), and benzmorpholine was used instead of N-methylaniline. The molar equivalents of benzmorpholine, sodium tert-butoxide, Pd2(dba)3, and X-phos were further increased by 2 times. Otherwise, the reaction was carried out in the same manner to synthesize the compound shown in formula (66-3).

[0804]

[0805] Third process

[0806] In the second step of Example 1, the compound of the aforementioned formula (66-3) was used instead of the compound of the aforementioned formula (1-2), and in the third step, 6-undecylone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to obtain the phenolic derivative shown in the following formula (66-4).

[0807]

[0808] Fourth process

[0809] In the fifth step of Example 1, the compound of the aforementioned formula (66-4) was used instead of the compound of the aforementioned formula (1-5), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound of the following formula (66-5) in a yield of 65%.

[0810]

[0811] The elemental analysis values ​​of the photochromic compound shown in formula (66-5) are C: 80.85%, H: 6.70%, N: 2.82%, which are similar to C. 67 H 66 The calculated values ​​of N2O6, namely C: 80.86%, H: 6.68%, and N: 2.81%, are in good agreement.

[0812] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak based on pentyl and benzomorpholino groups of 26H in the vicinity of δ0.5~3.5ppm, a peak based on benzomorpholino groups of 13H and methoxy groups in the vicinity of δ3.5~5.0ppm, and a peak based on aromatic protons and olefin protons of 27H in the vicinity of δ5.0~9.0ppm.

[0813] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0814] Example 67

[0815] First process

[0816] In the second step of Example 62, the compound of the aforementioned formula (62-1) was replaced by the aforementioned formula (61-1). In the third step, 2,4-dimethoxyphenylboronic acid was replaced by 2,4,6-trimethoxyphenylboronic acid. In the fourth step, iodoethane was replaced by 1-bromo-2-[2-(2-methoxyethoxy)ethoxy]ethane. The reaction was carried out in the same manner otherwise to obtain the phenolic derivative shown in the following formula (67-1).

[0817]

[0818] Second process

[0819] In the fifth step of Example 1, the compound of the aforementioned formula (67-1) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (4-2) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (67-2) in a yield of 71%.

[0820]

[0821] The elemental analysis values ​​of the photochromic compound shown in formula (67-2) are C: 79.16%, H: 6.52%, N: 3.23%, which are similar to C. 57 H 56 The calculated values ​​of N2O6, namely C: 79.14%, H: 6.52%, and N: 3.24%, are in good agreement.

[0822] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 17H peak based on methyl, ethyl, and morpholino groups in the vicinity of δ0.5~3.5ppm, a 16H peak based on morpholino and methoxy groups in the vicinity of δ3.5~5.0ppm, and a 23H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0823] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0824] Example 68

[0825] First process

[0826] In the first step of Example 2, 4-methyldiphenylamine was used instead of N-methylaniline, and in the sixth step, 1-butoxy-2-bromoethane was used instead of 1-bromo-4-methoxybutane. Otherwise, the reaction was carried out in the same manner to obtain the phenolic derivative shown in the following formula (68-1).

[0827]

[0828] Second process

[0829] In the fifth step of Example 1, the compound of the aforementioned formula (68-1) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (4-2) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (68-2) in a yield of 75%.

[0830]

[0831] The elemental analysis values ​​of the photochromic compound shown in the aforementioned formula (68-2) are C: 78.51%, H: 7.19%, N: 2.86%, which are similar to C. 64 H 70 The calculated values ​​of N2O7, namely C: 78.50%, H: 7.21%, and N: 2.86%, are in good agreement.

[0832] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 25H based on methyl, 2-butoxyethyl, and morpholino groups in the vicinity of δ0.5~3.5ppm, a peak of 21H based on 2-butoxyethyl, morpholino, and methoxy groups in the vicinity of δ3.5~5.0ppm, and a peak of 24H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0833] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0834] Example 69

[0835] First process

[0836] In the first step of Example 65, morpholine was used instead of N-methyl-4-(trifluoromethyl)aniline, and in the second step, 1-bromo-3-methoxypropane was used instead of 1-butoxy-2-bromoethane. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (69-1).

[0837]

[0838] Second process

[0839] In the fifth step of Example 1, the compound of the aforementioned formula (69-1) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (12-4) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (69-2) in a yield of 75%.

[0840]

[0841] The elemental analysis values ​​of the photochromic compound shown in formula (69-2) are C: 80.61%, H: 6.76%, N: 4.35%, which are similar to C. 65 H 65 The calculated values ​​of N3O5, namely C: 80.63%, H: 6.77%, and N: 4.34%, are in good agreement.

[0842] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl, methoxypropyl, and morpholino groups of 18H in the vicinity of δ0.5~3.5ppm, peaks based on methoxypropyl, morpholino, and methoxy groups of 17H in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons of 30H in the vicinity of δ5.0~9.0ppm.

[0843] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0844] Example 70

[0845] First process

[0846] In the first step of Example 12, the compound of the aforementioned formula (62-2) was used instead of the compound of the aforementioned formula (12-1), and 2-chlorophenylboronic acid was used instead of 4-methoxyphenylboronic acid. Otherwise, the reaction was carried out in the same manner to obtain the compound shown in the following formula (70-1).

[0847]

[0848] Second process

[0849] In the first step of Example 1, the compound of the aforementioned formula (70-1) was used instead of the compound of the aforementioned formula (1-1), and morpholine was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to synthesize the compound shown in the following formula (70-2).

[0850]

[0851] Third process

[0852] In the second step of Example 1, the compound of the aforementioned formula (70-2) was used instead of the compound of the aforementioned formula (1-3), and in the fourth step, dihexyl ketone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (70-3).

[0853]

[0854] Fourth process

[0855] In the fifth step of Example 1, the compound of the aforementioned formula (70-3) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (16-2) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (70-4) in a yield of 68%.

[0856]

[0857] The elemental analysis values ​​of the photochromic compound shown in formula (70-4) are C: 80.64%, H: 6.96%, N: 2.72%, which are similar to C. 69 H 71 The calculated values ​​of FN2O5, namely C: 80.67%, H: 6.97%, and N: 2.73%, are in good agreement.

[0858] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 30H peak based on hexyl and morpholino groups in the vicinity of δ0.5~3.5ppm, a 13H peak based on morpholino and methoxy groups in the vicinity of δ3.5~5.0ppm, and a 28H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0859] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0860] Example 71

[0861] First process

[0862] In the second step of Example 62, the compound of the aforementioned formula (62-1) was replaced with the compound of the aforementioned formula (61-1). In the third step, 4-chlorophenylboronic acid was replaced with 2,4,6-trimethoxyphenylboronic acid. Otherwise, the reaction was carried out in the same manner to obtain the compound shown in the following formula (71-1).

[0863]

[0864] Second process

[0865] In the first step of Example 1, the compound of the aforementioned formula (71-1) was used instead of the compound of the aforementioned formula (1-1), and 3,5-dimethylmorpholine was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain the compound shown in the following formula (71-2).

[0866]

[0867] Third process

[0868] In the second step of Example 1, the compound of the aforementioned formula (71-2) was used instead of the compound of the aforementioned formula (1-3), and in the fourth step, dipropyl ketone was used instead of acetone. Otherwise, the reaction was carried out in the same manner to synthesize the phenolic derivative shown in the following formula (71-3).

[0869]

[0870] Fourth process

[0871] In the fifth step of Example 1, the compound of the aforementioned formula (71-3) was used instead of the compound of the aforementioned formula (1-5), and the compound of the aforementioned formula (71-4) was used instead of the compound of the aforementioned formula (1-6). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (71-5) in a yield of 71%.

[0872]

[0873]

[0874] The elemental analysis values ​​of the photochromic compound shown in formula (71-5) are C: 78.72%, H: 7.13%, N: 4.30%, which are similar to C. 64 H 69 The calculated values ​​of N3O6, namely C: 78.74%, H: 7.12%, and N: 4.30%, are in good agreement.

[0875] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak based on propyl, morpholino, and methyl 31H in the vicinity of δ0.5~3.5ppm, a peak based on morpholino and methoxy 15H in the vicinity of δ3.5~5.0ppm, and a peak based on aromatic protons and olefin protons 23H in the vicinity of δ5.0~9.0ppm.

[0876] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0877] The analytical results of the phenolic derivatives synthesized in Examples 61-71 are shown in Table 7.

[0878] [Table 7]

[0879]

[0880] (Examples 72-81)

[0881] Photochromic laminates were fabricated using the photochromic compounds obtained in Examples 61-71, following the same method as in Example 20. The results are shown in Table 8.

[0882] [Table 8]

[0883]

[0884] The preferred embodiments of the present invention are described below. [1]

[0886] A photochromic compound represented by the following formula (1),

[0887]

[0888] In the above formula (1),

[0889] M is C, Si, or Ge.

[0890] Ring A is an aromatic ring, an aromatic heterocyclic ring, or a fused polycyclic ring with substituted or unsubstituted aromatic rings or aromatic heterocyclic rings fused to it.

[0891] Z 1 It is a group represented by formula (1a) or a group represented by formula (1b) below.

[0892]

[0893] In the above formula (1a),

[0894] R 1 The substituted or unsubstituted aryl group, the substituted or unsubstituted heteroaryl group, or the substituted or unsubstituted fused polycyclic aromatic rings fused with aromatic rings or aromatic heterocyclic rings on these substituents,

[0895] R 2 It 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 formula (2a) below.

[0896] -Q 1 -(X) 1 Q 2 )aX 2 Q 3 (2a)

[0897] In the above formula (2a),

[0898] Q 1 It is an alkylene or haloalkylene.

[0899] Q 2 It is an alkylene or haloalkylene.

[0900] Q 3 It is an alkyl or haloalkyl group.

[0901] X 1 and X 2 Each is independently O, S, NR 700 PR 701 Or P (=O),

[0902] R 700 and R 701 Each of these can be 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.

[0903] a is 0, or 1 or more but less than 3.

[0904]

[0905] In the above equation (1b),

[0906] Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[0907] Y 1 For substituted or unsubstituted methylene,

[0908] Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C=CR 602 Or CC,

[0909] R 600 R 601 and R 602 Each of these elements is 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.

[0910] Y 3 For substituted or unsubstituted methylene,

[0911] m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than or equal to 1.

[0912] R 3 and R 4 Each of the following groups is independently 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, 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 aroxy group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (X3) below.

[0913] L 1 -R 400 (X3)

[0914] In the above formula (X3),

[0915] R 400 It is a silyl group consisting of a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or having alkyl, alkoxy, or aryl substituents.

[0916] L 1 The group is represented by the following formula (X2).

[0917]

[0918] In the above formula (X2), R 30 The group is represented by the following formula (X2a).

[0919]

[0920] In equations (X2) and (X2a),

[0921] J is a divalent group, which can be independently a directly bonded, substituted, or unsubstituted methylene group, oxygen atom, sulfur atom, or NR group. 301 R 301 It is a hydrogen atom or an alkyl group.

[0922] L represents an oxygen atom or a sulfur atom.

[0923] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents.

[0924] R 302 R 303 and R 304 Each is independently an alkylene group.

[0925] h, j, k, and l are each an independent integer of 0 or 1.

[0926] i is an integer from 1 to 200. When i is 2 or higher, multiple R 30 Choose either the same or different; the dashed line indicates the same as R. 400 The bond,

[0927] R 3 and R 4 The following can be selected together with M to form a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocycle fused to the aliphatic ring, a substituted or unsubstituted heterocyclic ring having 3 to 20 cyclic atoms, or a substituted or unsubstituted fused polycyclic ring having an aromatic ring or an aromatic heterocycle fused to the heterocycle.

[0928] R 5 and R 6 Each can be an independent hydrogen atom or a substituent.

[0929] R 7 and R 8 Each is an independent substituent.

[0930] b is an integer between 0 and 3.

[0931] c is an integer between 0 and 4. [2]

[0933] The photochromic compound described in [1] is represented by the following formula (3):

[0934]

[0935] In the above equation (3), R 3 R 4 Z 1 M, b, and c each have the same meaning as in equation (1).

[0936] R 5 and R 6 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0937] R 7 and R 8 Each of the following groups is independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), the group represented by formula (X) below, or the group represented by formula (X3).

[0938] When b is 2~3, multiple R 7 Choose either the same or different.

[0939] When c is 2~4, multiple R 8 Choose either the same or different.

[0940] In R where b is 2~3 and there are adjacent values 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0941] In R where c is 2~4 and there are adjacent values 8 In the case of two adjacent R 8 Optional and bonded to R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0942]

[0943] In the above formula (X),

[0944] E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group.

[0945] F represents an oxygen atom or a sulfur atom.

[0946] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[0947] g is 0 or 1.

[0948] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[0949] When G is an oxygen atom or a sulfur atom, R 201 It refers to groups other than hydrogen atoms. [3]

[0951] According to [2], the photochromic compound is represented by the following formula (4):

[0952]

[0953] In the above equation (4),

[0954] R 3 R 4 R 7 R 8 Z 1 M, b, and c each have the same meaning as in equation (3).

[0955] R 9 and R 10 Each of the following groups is 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 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).

[0956] d is an integer between 0 and 5.

[0957] When d is 2~5, multiple R 9 Choose either the same or different.

[0958] In the case of adjacent R 9 In the case of two adjacent R 9 Optional and bonded to R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0959] e is an integer between 0 and 5.

[0960] When e is 2~5, multiple R 10 Choose either the same or different.

[0961] In the case of adjacent R 10 In the case of two adjacent R 10 Optional and bonded to R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. [4]

[0963] The photochromic compound according to any one of [1] to [3], wherein M in the formula (1) is C. [5]

[0965] The photochromic compound according to any one of [1] to [4], wherein R in formula (1) is... 3 and R 4 The group may be 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 with 3 to 20 carbon atoms formed together with M, or a substituted or unsubstituted heterocycle with 3 to 20 carbon atoms formed together with M. [6]

[0967] The photochromic compound according to any one of [1] to [5], wherein Z in formula (1) is... 1 Having the group shown in formula (1a), R 1 The phenyl group can be substituted or unsubstituted. [7]

[0969] The photochromic compound according to any one of [1] to [6], wherein Z in formula (1) is... 1 Having the group shown in formula (1a), R 2 It is an alkyl group with 1 or more but less than 10 carbon atoms, a haloalkyl group with 1 or more but less than 10 carbon atoms, or a group represented by formula (2a). [8]

[0971] The photochromic compound according to any one of [1] to [7], wherein Z in formula (1) is... 1 It has the group shown in formula (1b), where ring B is a substituted or unsubstituted phenyl group. [9]

[0973] The photochromic compound according to any one of [1] to [8], wherein Z in formula (1) is... 1 Having the group shown in formula (1b), Y 2 The substituted or unsubstituted methylene, O, or S.

[10]

[0975] The photochromic compound according to any one of [1] to [9], wherein Z in formula (1) is... 1 It has the group shown in formula (1b), where m+n is an integer from 1 to 3.

[11]

[0977] A curable composition comprising:

[0978] The photochromic compound described in any one of [1] to

[10] ; and

[0979] Select at least one from the group consisting of free radical polymerizable monomers, cationic polymerizable monomers, compounds having polymerizable reactive groups, and (thio)carbamate (urea) polymers.

[12]

[0981] A cured product, which is a cured product of the curable composition described in

[11] .

[13]

[0983] An optical article comprising the cured material described in

[12] .

[14]

[0985] A lens comprising any one of the photochromic compounds described in [1] to

[10] .

[15]

[0987] A pair of eyeglasses comprising the lens described in

[14] .

[16]

[0989] A phenolic derivative, represented by the following formula (5):

[0990]

[0991] In the above equation (5),

[0992] M is C, Si, or Ge.

[0993] Ring A is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[0994] Z 1 It is a group represented by formula (1a) or a group represented by formula (1b) below.

[0995]

[0996] In the above formula (1a),

[0997] R 1 For substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups,

[0998] R 2 It 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 formula (2a) below.

[0999] -Q 1 -(X) 1 Q 2 )aX 2 Q 3 (2a)

[1000] In the above formula (2a),

[1001] Q 1 It is an alkylene or haloalkylene.

[1002] Q 2 It is an alkylene or haloalkylene.

[1003] Q 3 It is an alkyl or haloalkyl group.

[1004] X 1 and X 2 Each is independently O, S, NR 700 R 701 PR 702 R 703 Or P(=O)R 704 ,

[1005] R 700 R 701 R 702 R 703 and R 704 Each of these can be 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.

[1006] a is an integer that is 0, or greater than 1 and less than 3.

[1007]

[1008] In the above equation (1b),

[1009] Ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycyclic ring with an aromatic ring or aromatic heterocycle fused to these rings.

[1010] Y 1 For substituted or unsubstituted methylene,

[1011] Y 2 For substituted or unsubstituted methylene, O, S, SO2, NR 600 R 601 C=CR 602 Or CC,

[1012] R 600 R 601 and R 602 Each of these elements is 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.

[1013] Y 3 For substituted or unsubstituted methylene,

[1014] m is an integer from 1 to 4, n is an integer from 0 to 4, and m+n is an integer greater than or equal to 1.

[1015] R 3 and R 4 Each of the following groups is independently 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, 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 aroxy group, a substituted or unsubstituted heteroaryl group, or a group represented by formula (X3) below.

[1016] L 1 -R 400 (X3)

[1017] In the above formula (X3),

[1018] R 400 It is a silyl group consisting of a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or having alkyl, alkoxy, or aryl substituents.

[1019] L 1 The group is represented by the following formula (X2).

[1020]

[1021] In the above formula (X2), R 30 The group is represented by the following formula (X2a).

[1022]

[1023] In equations (X2) and (X2a),

[1024] J is a divalent group, which can be independently a directly bonded, substituted, or unsubstituted methylene group, oxygen atom, sulfur atom, or NR group. 301 R 301 It is a hydrogen atom or an alkyl group.

[1025] L represents an oxygen atom or a sulfur atom.

[1026] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents.

[1027] R 302 R 303 and R 304 Each is independently an alkylene group.

[1028] h, j, k, and l are each an independent integer of 0 or 1.

[1029] i is an integer from 1 to 200. When i is 2 or higher, multiple R 30 Choose either the same or different; the dashed line indicates the same as R. 400 The bond,

[1030] R 3 and R 4 The following can be selected together with M to form a substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms, a substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocycle fused to the aliphatic ring, a substituted or unsubstituted heterocyclic ring having 3 to 20 cyclic atoms, or a substituted or unsubstituted fused polycyclic ring having an aromatic ring or an aromatic heterocycle fused to the heterocycle.

[1031] R 7 and R 8 Each is an independent substituent.

[1032] b is an integer between 0 and 3.

[1033] c is an integer between 0 and 4.

[17]

[1035] According to

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

[1036]

[1037] In the above equation (7), Z 1 R 3 R 4 M, b, and c have the same meaning as in equation (6).

[1038] R 7 and R 8 Each of the following groups is independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), the group represented by formula (X) below, or the group represented by formula (X3).

[1039] When b is 2~3, multiple R 7 Choose either the same or different.

[1040] When c is 2~4, multiple R 8 Choose either the same or different.

[1041] In R where b is 2~3 and there are adjacent values 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[1042] In R where c is 2~4 and there are adjacent values 8 In the case of two adjacent R 8 Optional and bonded to R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[1043]

[1044] In the above formula (X),

[1045] E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group.

[1046] F represents an oxygen atom or a sulfur atom.

[1047] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[1048] g is 0 or 1.

[1049] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[1050] When G is an oxygen atom or a sulfur atom, R 201 It refers to groups other than hydrogen atoms.< / m>

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 heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on these rings, Z 1 a group represented by the following formula (1a), or a group represented by the following formula (1b), in the formula (la), R 1 substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted condensed polycyclic group having an aromatic ring or an aromatic heterocyclic ring condensed on these substituents, 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), Q 1 - (X 1 Q 2 ) a-X 2 Q 3 (2a) in the formula (2a), Q 1 alkylene or haloalkylene, Q 2 alkylene or haloalkylene, Q 3 R is H, alkyl, or haloalkyl, X 1 and X 2 each independently O, S, NR 700 , PR 701 or P(=O), R 700 and R 701 each independently is 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 or more and 3 or less, in the formula (lb), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on these rings, Y 1 substituted or unsubstituted methylene, Y 2 is substituted or unsubstituted methylene, O, S, SO2, NR 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, Y 3 substituted or unsubstituted methylene, 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 is 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 hydroxylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3), L 1 -R 400 (X3) in the formula (X3), R 400 is a hydrogen atom, an alkyl group, an aryl group, a polymeric group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent, L 1 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 independently a direct bond, substituted or unsubstituted methylene, an oxygen atom, a sulfur atom, or NR 301 , R 301 is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R 300 is alkylene or silyl ene with alkyl or aryl as substituents, R 302 , R 303 , and R 304 are each independently alkylene, h, j, k, and 1 are each independently an integer of 0 or 1, i is an integer from 1 to 200, in case i is 2 or more, a plurality of R 30 optionally same or different, dotted line represents a bond to R 400 , R 3 and R 4 optionally forms, together with M, a substituted or unsubstituted aliphatic ring having 3 to 20 ring-forming carbon atoms, a substituted or unsubstituted condensed polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocyclic ring condensed on the aliphatic ring, a substituted or unsubstituted heterocyclic ring having 3 to 20 ring-forming atoms, or a substituted or unsubstituted condensed polycyclic ring having an aromatic ring or an aromatic heterocyclic ring condensed on the heterocyclic ring, R 5 and R 6 each independently is a hydrogen atom or a substituent, R 7 and R 8 each independently is a substituent, b is an integer of 0 to 3, c is an integer of 0 to 4.

2. The photochromic compound according to claim 1, which is represented by the following formula (3), In the formula (3), R 3 , R 4 , Z 1 , M, b and c each have the same meaning as in the formula (1), R 5 and R 6 each independently is substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, R 7 and R 8 each independently is 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 aralkyloxy 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, the group represented by the formula (2a), the group represented by the formula (X) described below, or the group represented by the formula (X3), In case b is 2 to 3, the plurality of R 7 optionally the same as or different from each other, in case c is 2 to 4, a plurality of R 8 optionally the same or different from each other, In R where b is 2~3 and there are adjacent values 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. in case that c is 2 to 4 and adjacent R 8 groups are present, 8 optionally forms, together with the carbon atom to which R 8 is bound, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocyclic ring, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring condensed with an aromatic ring or an aromatic heterocyclic ring on these rings, in the formula (X), E is an oxygen atom or NR 101 , R 101 is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom or NR 202 , R 202 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, g is 0 or 1, R 201 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, In the case where G is an oxygen atom or a sulfur atom, R 201 is a group other than a hydrogen atom.

3. The photochromic compound according to claim 2, which is represented by the following formula (4), in the formula (4), R 3 , R 4 , R 7 , R 8 , Z 1 , M, b and c are each independently of the meanings in formula (3), R 9 and R 10 each independently is 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, the group represented by the formula (2a), or the group represented by the formula (X3), d is an integer of 0 to 5, in case that d is 2 to 5, a plurality of R 9 optionally the same as or different from each other, In the case where the adjacent R 9 , the two adjacent R 9 optionally form, together with the carbon atom to which R 9 is bound, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocyclic ring, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring condensed with an aromatic ring or an aromatic heterocyclic ring on these rings, e is an integer of 0 to 5, In case e is 2 to 5, the plurality of R 10 optionally the same or different from each other, In the case where the adjacent R 10 , the two adjacent R 10 optionally form, together with the carbon atom to which R 10 is bound, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocyclic ring, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring condensed with an aromatic ring or an aromatic heterocyclic ring on these rings.

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

5. The photochromic compound of claim 1, wherein, R 3 and R 4 is a substituted or unsubstituted alkyl group, a halogenated alkyl group, a group represented by the formula (2a), a substituted or unsubstituted alkoxy group, a group represented by the formula (X3), a substituted or unsubstituted aliphatic ring having 3 to 20 ring-forming carbon atoms together with M, or a substituted or unsubstituted heterocyclic ring having 3 to 20 ring-forming atoms together with M.

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

7. The photochromic compound of claim 1, wherein, Z in the formula (1) is 1 having the group represented by the formula (1a), R 2 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 10 carbon atoms, or a group represented by the formula (2a).

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

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

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

11. A curable composition comprising: the photochromic compound according to claim 1; and at least one selected from the group consisting of a radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerization reactive group, and a (thio)urethane (urea) polymer.

12. A cured product which is 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 according to claim 1.

15. Eyeglasses comprising the lens according to 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 heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on these rings, Z 1 a group represented by the following formula (1a), or a group represented by the following formula (1b), in the formula (la), R 1 substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, 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), - Q 1 - (X 1 Q 2 ) a-X 2 Q 3 (2a) in the formula (2a), Q 1 alkylene or haloalkylene, Q 2 alkylene or haloalkylene, Q 3 R is H, alkyl, or haloalkyl, X 1 and X 2 each independently O, S, NR 700 R 701 , PR 702 R 703 or P(=O)R 704 , 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 or more and 3 or less, in the formula (lb), ring B is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed on these rings, Y 1 substituted or unsubstituted methylene, Y 2 is substituted or unsubstituted methylene, O, S, SO2, NR 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, Y 3 substituted or unsubstituted methylene, 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 is 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 hydroxylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a group represented by the following formula (X3), L 1 -R 400 (X3) in the formula (X3), R 400 is a hydrogen atom, an alkyl group, an aryl group, a polymeric group, a photochromic group, or a silyl group having an alkyl group, an alkoxy group, or an aryl group as a substituent, L 1 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 independently a direct bond, substituted or unsubstituted methylene, an oxygen atom, a sulfur atom, or NR 301 , R 301 is a hydrogen atom or an alkyl group, L is an oxygen atom or a sulfur atom, R 300 is alkylene or silyl ene with alkyl or aryl as substituents, R 302 , R 303 , and R 304 are each independently alkylene, h, j, k, and 1 are each independently an integer of 0 or 1, i is an integer from 1 to 200, in case i is 2 or more, a plurality of R 30 optionally same or different, dotted line represents a bond to R 400 , R 3 and R 4 optionally forms, together with M, a substituted or unsubstituted aliphatic ring having 3 to 20 ring-forming carbon atoms, a substituted or unsubstituted condensed polycyclic ring having a condensed aromatic hydrocarbon ring or a condensed aromatic heterocyclic ring on the aliphatic ring, a substituted or unsubstituted heterocyclic ring having 3 to 20 ring-forming atoms, or a substituted or unsubstituted condensed polycyclic ring having a condensed aromatic ring or a condensed aromatic heterocyclic ring on the heterocyclic ring, R 7 and R 8 each independently is a substituent, b is an integer of 0 to 3, c is an integer of 0 to 4.

17. The phenol derivative according to claim 16, which is represented by the following formula (7), In the formula (7), Z 1 , R 3 , R 4 , M, b and c have the same meanings as in the formula (6), R 7 and R 8 each independently is a hydroxyl group, a substituted or unsubstituted alkyl group, a halogenated alkyl 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 aralkyloxy 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 halogenated alkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, the group represented by the formula (2a), the group represented by the formula (X) described below, or the group represented by the formula (X3), In case b is 2 to 3, the plurality of R 7 optionally the same as or different from each other, in case c is 2 to 4, a plurality of R 8 optionally the same or different from each other, In R where b is 2~3 and there are adjacent values 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. in case c is 2 to 4 and there is an adjacent R 8 , the two adjacent R 8 , are optionally taken together with the carbon atom to which they are bound to form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocyclic ring, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polycyclic ring fused with an aromatic ring or an aromatic heterocyclic ring on these rings, 8 , are optionally taken together with the carbon atom to which they are bound to form a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aliphatic heterocyclic ring, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted aromatic heterocyclic ring, or a substituted or unsubstituted fused polycyclic ring fused with an aromatic ring or an aromatic heterocyclic ring on these rings, in the formula (X), E is an oxygen atom or NR 101 , R 101 is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom or NR 202 , R 202 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, g is 0 or 1, R 201 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, In the case where G is an oxygen atom or a sulfur atom, R 201 is a group other than a hydrogen atom.

Images