Photochromic compound, propargyl alcohol compound, curable composition, optical article, lens, and glasses

Abstract

The purpose of the present invention is to provide: a photochromic compound having excellent fading speed and durability; an propargyl alcohol compound which 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), R3 represents an aryl group or a heteroaryl group substituted with a group represented by formula (1a). In formula (1a), R1 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted fused polycyclic group in which an aromatic ring or an aromatic heterocyclic ring is fused to the substituted or unsubstituted aryl group, the substituted or unsubstituted heteroaryl group, or the substituted or unsubstituted fused polycyclic group. R2 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a group represented by formula (2a), or the like.

Description

Technical Field

[0001] This invention relates to photochromic compounds, propargyl alcohol compounds, 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) The speed from the start of ultraviolet irradiation to the saturation of color development concentration (hereinafter referred to as color development concentration) is high.

[0006] (III) High speed from the start of ultraviolet irradiation to the saturation of colorimetric concentration (hereinafter also referred to as high colorimetric sensitivity).

[0007] (IV) The rate at which the irradiation stops and the color returns to its original state (hereinafter referred to as the fading rate) is high.

[0008] (V) The reversible effects described above have high durability.

[0009] (VI) It has high solubility in the matrix material of the lens and high dispersibility in the cured product.

[0010] As photochromic compounds that satisfy these properties, a large number of chromene compounds have been studied. 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.

[0011]

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: International Publication No. 1996 / 014596; Patent Document 2: International Publication No. 2004 / 085568; Patent Document 3: International Publication No. 2001 / 060811; Patent Document 4: International Publication No. 2015 / 035325

[0015] Patent Document 5: International Publication No. 2007 / 078529

[0016] Patent Document 6: International Publication No. 2021 / 075456

[0017] Patent Document 7: International Publication No. 2018 / 235771

[0018] Patent Document 8: International Publication No. 2012 / 102410

[0019] Patent Document 9: International Publication No. 2011 / 053615

[0020] Patent Document 10: International Publication No. 2013 / 042800

[0021] Patent Document 11: International Publication No. 2019 / 228604

[0022] Patent Document 12: International Publication No. 2019 / 013249

[0023] Patent Document 13: International Publication No. 2016 / 143910

[0024] Non-patent literature

[0025] Non-patent literature 1: Journal of Organic Chemistry 69(10)3282-3293; 2004

[0026] Non-patent literature 2: Synthetic Communications 23(16)2241-2249(1993)

[0027] Non-patent literature 3: J.Am.Chem.Soc.132(41)14324-14326(2010)

[0028] Non-patent literature 4: Org. Lett. 16, 6492-6495 (2014) Summary of the Invention

[0029] The problem the invention aims to solve

[0030] The object of the present invention is to provide a photochromic compound with excellent fading speed and durability, a propargyl alcohol compound that can be an intermediate of the photochromic compound, a curable composition containing the photochromic compound, optical articles, lenses and eyeglasses.

[0031] Solution for solving the problem

[0032] This disclosure relates to photochromic compounds having a skeleton as shown in formula (1).

[0033]

[0034] In the aforementioned formula (1), M is C, Si, or Ge.

[0035] R 3 It is an aryl or heteroaryl group substituted with the group shown in formula (1a) below.

[0036]

[0037] In the aforementioned equation (1a), R 1 For substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, or substituted or unsubstituted fused polycyclic groups with aromatic rings or aromatic heterocycles fused to these substituents. R 2 It is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below.

[0038] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[0039] In the aforementioned 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 Independently defined as O, S, NR 700 PR 701 Or P (=O). R 700 and R 701 Each of the following 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 an integer greater than or equal to 1 and less than or equal to 3.

[0040] R 4 It can be a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0041] Ring A and ring B are independently 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.

[0042] In addition, this disclosure relates to curable compositions. The curable compositions comprise the aforementioned photochromic compounds and include at least one selected from the group consisting of free radical polymerizable monomers, cationic polymerizable monomers, compounds having condensation reactive groups, and (thio)carbamate (urea) polymers.

[0043] Furthermore, this disclosure relates to optical articles. These optical articles comprise cured products of the aforementioned curable composition.

[0044] In addition, this disclosure relates to lenses. The lenses contain the aforementioned photochromic compounds.

[0045] Furthermore, this disclosure relates to eyeglasses. Eyeglasses include the aforementioned lenses.

[0046] Furthermore, this disclosure relates to propargyl alcohol compounds. Proargyl alcohol compounds have the skeleton shown in the following formula (9).

[0047]

[0048] In equation (9), R 3 and R 4 They are independently equivalent to the meaning in equation (1) above.

[0049] The effects of the invention

[0050] According to the present invention, a photochromic compound with excellent fading speed and durability is provided, a propargyl alcohol compound that can be an intermediate of the photochromic compound, a curable composition comprising the photochromic compound, optical articles, lenses, and eyeglasses are provided. Detailed Implementation

[0051] [Photochromic compounds]

[0052] According to an embodiment, a photochromic compound having a skeleton as shown in the following formula (1) is provided.

[0053]

[0054] In equation (1), M is C, Si or Ge.

[0055] R 3It is an aryl or heteroaryl group substituted with a group represented by formula (1a) below. 4 It is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Ring A and ring B are independently 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.

[0056]

[0057] In the aforementioned 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.

[0058] R 2 It is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below.

[0059] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[0060] In the aforementioned equation (2a),

[0061] Q 1 It is an alkylene or haloalkylene.

[0062] Q 2 It is an alkylene or haloalkylene.

[0063] Q 3 It is an alkyl or haloalkyl group.

[0064] X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O),

[0065] R 700 and R 701 Each of the following 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.

[0066] a is an integer that is 0, or greater than 1 and less than 3.

[0067] This photochromic compound exhibits excellent fading speed and durability. The reason for this is not yet clear, but the inventors believe it to be as follows.

[0068] First, in photochromic compounds having the framework shown in formula (1), R 3 To replace aryl or heteroaryl groups. The inventors have discovered that this substituent has a significant impact on the fading rate. That is, from R 3 The stronger the electron supply, the lower the thermal stability of the chromogenic structure of the photochromic compound during photoisomerization, thus making fading easier and resulting in a faster fading rate. However, organic compounds with electron-donating substituents typically have abundant electrons within their molecules, making them prone to oxidation. This is especially true for photochromic compounds; oxidation easily reduces their durability. For example, photochromic compounds with highly electron-donating substituents such as substituted amino groups or nitrogen-containing heterocycles exhibit excellent fading rates but low durability, making it difficult to balance fading speed and durability to date.

[0069] Substituent R of the photochromic compound in the embodiments 3 The compound has the above formula (1a) as a substituent. Formula (1a) has a substituted amino structure in which an aryl or heteroaryl group is directly bonded to one linker bond of the nitrogen atom, and a group other than an aryl or heteroaryl group or a hydrogen atom is bonded to the other linker bond. It is believed that since the aryl or heteroaryl group is directly bonded to one linker bond of the nitrogen atom, it can be conjugated with the aryl or heteroaryl group substituted by formula (1a) via the p orbital on the nitrogen atom. It is believed that the conjugation of compounds with such a structure is extended compared to compounds without an amino group substituted by an aryl or heteroaryl group. It is believed that through this extension, electrons are delocalized in the chromophore due to the resonance structure, making it difficult to be oxidized and improving the durability of repeated use. In addition, it is believed that such compounds are compatible with R 3 Compared to cases where amino groups with diaryl groups are used as substituents, the conjugation does not extend excessively, resulting in superior fading speed and repeated durability.

[0070] As can be seen from the above, when using the photochromic compound of the embodiment, a cured product with excellent fading speed and thus excellent repeated durability can be achieved. Therefore, such a photochromic compound is suitable for optical articles used for a long time, such as photochromic glasses.

[0071] The following is a detailed description of photochromic compounds having the framework shown in formula (1).

[0072]

[0073] <m>

[0074] In equation (1), M is C, Si, or Ge. M is preferably C.

[0075] <Ring A and Ring B>

[0076] In formula (1), ring A and ring B are independently 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.

[0077] Examples of aromatic hydrocarbon rings include the benzene ring and the cyclotetradecane-7-ene ring.

[0078] Examples of aromatic heterocyclic rings include furan rings, thiophene rings, and pyridine rings.

[0079] Examples of fused polycyclic rings include naphthalene rings, fluorene rings, anthracene rings, phenanthrene rings, tetraphenylene rings, pentaphenylene rings, and benzo[a]pyrene rings. Rings, including 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, isothiazazole rings, etc.

[0080] 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.

[0081] <R 3 >

[0082] In equation (1), R 3 The aryl or heteroaryl group is substituted with the group shown in formula (1a) below. The dashed line indicates the bond to the carbon atom of the aryl or heteroaryl group. R 3 Preferably, it is an aryl group substituted with one group represented by formula (1a) below, more preferably a phenyl group substituted with one group represented by formula (1a) below.

[0083]

[0084] (R 1 )

[0085] R 1 For 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 the possibility of becoming R... 1 The groups that may have substituents will be described later.

[0086] 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.

[0087] 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 if ease of manufacture is taken into consideration.

[0088] R 1 Details regarding the substituents that the group may have are described later. As R 1 The group may have substituents, preferably at least one of the following groups: a straight-chain or branched alkyl group having 1 or more and 6 or less carbon atoms; a straight-chain or branched haloalkyl group having 1 or more and 6 or less carbon atoms; a straight-chain or branched alkoxy group having 1 or more and 6 or less carbon atoms; and a halogen atom. The number of substituents is, for example, 1 or more and 3 or less.

[0089] (R 2 )

[0090] R 2 It is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below.

[0091] R 2 Preferably, it is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below.

[0092] From the perspective of accelerating the fading process, R 2 Further preferred are substituted or unsubstituted alkyl groups, substituted or unsubstituted haloalkyl groups, substituted or unsubstituted cycloalkyl groups, or groups represented by formula (2a) below.

[0093] The halogen atom is preferably a fluorine atom or a chlorine atom.

[0094] The alkyl group is preferably an unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0095] The haloalkyl group is preferably a haloalkyl group having 1 to 20 carbon atoms. The number of halogen atoms is preferably 1 to 20, more preferably 2 to 10. As a haloalkyl group having 1 to 20 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, and bromomethyl.

[0096] The cycloalkyl group is preferably a cycloalkyl group with 3 to 10 carbon atoms (a cycloalkyl group with 3 to 8 carbon atoms forming the ring). Examples of cycloalkyl groups with 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. It should be noted that the cycloalkyl group may have substituents, but the number of carbon atoms (3 to 10) does not include the number of carbon atoms of the substituents.

[0097] The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. Examples of suitable alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0098] The aryloxy group is preferably an aryloxy group with 6 to 12 carbon atoms. Examples of aryloxy groups with 6 to 12 carbon atoms include phenoxy and naphthoxy groups.

[0099] The alkylthio group is preferably an alkylthio group with 1 to 6 carbon atoms. Examples of alkylthio groups with 1 to 6 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, and tert-butylthio.

[0100] The aryl thio group is preferably an aryl thio group with 6 to 10 carbon atoms. Examples of aryl thio groups with 6 to 10 carbon atoms include phenylthio, 1-naphthio, and 2-naphthio.

[0101] The aralkyl group is preferably an aralkyl group with 7 to 11 carbon atoms. Examples of aralkyl groups with 7 to 11 carbon atoms include benzyl, phenylethyl, phenylpropyl, phenylbutyl, and naphthylmethyl.

[0102] R 2 Details regarding the substituents that the group may have are described later. As R 2 The substituents that may be present in the group 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 carbon atoms; a straight-chain or branched haloalkyl group having 1 or more and 6 or less carbon atoms; a straight-chain or branched alkoxy group having 1 or more and 6 or less carbon atoms; a cycloalkyl group having 4 or more and 8 or less carbon atoms; and a halogen atom. The number of substituents is, for example, 1 or more and 3 or less.

[0103] R 2 Preferably, it is an alkyl group with 1 to 20 carbon atoms, a haloalkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkoxyalkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, or a fluorine atom; more preferably, it is an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, or a cycloalkyl group with 5 to 8 carbon atoms.

[0104] The alkyl halogroup having 1 to 10 carbon atoms is preferably a fluoroalkyl group, and particularly preferably a perfluoromethyl group at the end.

[0105] (The group shown in formula (2a))

[0106] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[0107] In equation (2a), Q 1 It is an alkylene or haloalkylene.

[0108] 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 haloside 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 haloside, the terminal carbon atom is preferably bonded to the halogen atom, more preferably the terminal carbon is a perfluoromethyl group.

[0109] 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.

[0110] Q 3 It can be an alkyl or haloalkyl group, and can be straight-chain or branched, preferably straight-chain.

[0111] 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, 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.

[0112] Q 3 Preferably, it is a straight-chain alkyl group.

[0113] X 1 and X 2 Independently defined as 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.

[0114] R 700 and R 701 Each of the following 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.

[0115] 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.

[0116] 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.

[0117] a is 0, or an integer greater than 1 and less than 3.

[0118] Formula (2a) is preferably alkylene alkoxy, alkylene thioalkyl or alkylene oxyalkylene alkoxy.

[0119] Specific examples of equation (2a) include -CH2OCH3, -CH2SCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2SCH3, -CH2CH2CH2OCH3, -CH2CH2CH2SCH3, -CH2CH2OCH2CH2OCH3, and -CH2CH2OCH2CH2OCH2CH3.

[0120] The group represented by formula (2a) is preferably -CH2OCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2CH2OCH3, -CH2CH2OCH2CH2OCH3, or -CH2CH2OCH2CH2OCH2CH3.

[0121] (Specific examples of formula (1a))

[0122] If a suitable equation (1a) is exemplified, then it is as follows.

[0123]

[0124] <R 4 >

[0125] In equation (1), R 4 It can be a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0126] 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.

[0127] R 4 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 phenyl.

[0128] <The skeleton shown in equation (2)>

[0129] The photochromic compound of the embodiment preferably has a naphthylpyran skeleton as shown in formula (2) below. In formula (2) below, M, R 3 and R 4 The meanings are the same as those in equation (1).

[0130]

[0131] <The skeleton shown in formula (3)>

[0132] The photochromic compound used in the embodiments is preferably a compound having the framework shown in the following formula (3). In the following formula (3), M and R 3 and R 4 The meanings are the same as those in equation (1).

[0133]

[0134] <R 5 and R 6 >

[0135] R 5 and R 6 Each of the following is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a) above, the group represented by formula (X) below, or the group represented by formula (X3) below.

[0136] As substituted or unsubstituted alkyl, haloalkyl, group shown in formula (2a), substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted arylthio, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, can be used with R 1 Or R 2 The groups shown in the example are the same groups.

[0137] 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. The amino group can be the group shown in formula (1a) above. Examples of substituents for substituted amino groups include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms. Suitable examples of amino groups include amino, methylamino, dimethylamino, ethylamino, diethylamino, methylphenylamino, and diphenylamino.

[0138] As a heterocyclic group, a heterocyclic group having 3 to 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 and 5 or less, 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 indole. The heterocyclic group can be 2,6-dimethylmorpholino, 2,6-dimethylpiperridinyl, and 2,2,6,6-tetramethylpiperridinyl.

[0139] The alkyl carbonyl group is preferably an alkyl carbonyl group with 2 to 7 carbon atoms. Examples of alkyl carbonyl groups with 2 to 7 carbon atoms include acetyl and ethyl carbonyl.

[0140] The preferred alkoxycarbonyl group is one with 2 to 7 carbon atoms. Examples of alkoxycarbonyl groups with 2 to 7 carbon atoms include methoxycarbonyl and ethoxycarbonyl.

[0141] The preferred arylalkoxy group is one with 7 to 11 carbon atoms. Examples of arylalkoxy groups with 7 to 11 carbon atoms include benzyloxy and naphthylmethoxy.

[0142] The preferred alkoxyalkylthio group is one with 2 to 9 carbon atoms. Examples of alkoxyalkylthio groups with 2 to 9 carbon atoms include methoxymethylthio, methoxyethylthio, methoxyn-propylthio, methoxyn-butylthio, ethoxyethylthio, and n-propoxypropylthio.

[0143] The haloalkylthio group is preferably a haloalkylthio group with 1 to 6 carbon atoms. Examples of haloalkylthio groups with 1 to 6 carbon atoms include trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio, and bromomethylthio.

[0144] The cycloalkyl thio group is preferably a cycloalkyl thio group with 3 to 8 carbon atoms. Examples of cycloalkyl thio groups with 3 to 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 to 8) does not include the number of carbon atoms of the substituents.

[0145] Silyyl groups may have substituents. There are no particular restrictions on the substituents that can be present in substituted silyl groups, and examples include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms.

[0146] 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 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms.

[0147] It should be noted that cycloalkyl, arylthio, arylalkyl, arylalkoxy, aryloxy, aryl, heteroaryl, and cycloalkylthio 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 with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, amino, substituted amino, heterocyclic group with 3 to 8 atoms, cyano, nitro, and halogen atoms.

[0148] R 5 and R 6 It may be a hydrogen atom, 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 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 aryl group, a substituted or unsubstituted heteroaryl group, or the following formula (X3).

[0149] R 5 and R 6 Together with M, they can form substituted or unsubstituted aliphatic rings with 3 to 20 carbon atoms, substituted or unsubstituted fused polycyclic rings with aromatic hydrocarbon rings or aromatic heterocycles fused to an aliphatic ring, substituted or unsubstituted heterocycles with 3 to 20 cyclic atoms, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to a heterocycle.

[0150] R 5 and R 6 Preferably, the ring is formed by a substituted or unsubstituted aliphatic ring with 3 to 20 carbon atoms, a fused polycyclic ring with an aromatic hydrocarbon ring or aromatic heterocycle fused to the aliphatic ring, or a substituted or unsubstituted heterocycle with 3 to 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 with 1 to 5 carbon atoms or cycloalkyl groups with 5 to 7 carbon atoms as substituents, and the cycloalkyl groups with 5 to 7 carbon atoms may be fused.

[0151] Specifically, it is more preferable to form the ring shown below.

[0152]

[0153] R 5 and R 6 Details of the substituents that the group may have are described later. As substituents that may be present in these groups, straight-chain or branched alkyl groups having 1 or more and 6 or fewer carbon atoms are preferred.

[0154] <Group represented by formula (X)>

[0155]

[0156] In formula (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.

[0157] F can be an oxygen atom or a sulfur atom. F is preferably an oxygen atom.

[0158] 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.

[0159] g is 0 or 1.

[0160] 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 having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0161] The suitable group represented by formula (X) is shown below.

[0162]

[0163] <The group shown in formula (X3)>

[0164] L 1 -R 400 (X3)

[0165] In equation (X3),

[0166] 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.

[0167] L 1 It is the group represented by the following formula (X2).

[0168]

[0169] In equation (X2), R 30 It is a group represented by the following formula (X2a).

[0170]

[0171] In formulas (X2) and (X2a), J is a divalent group. Multiple Js can be independently directly attached, substituted, or unsubstituted methylene, oxygen, sulfur, or NR atoms. 301 R 301 It can be a hydrogen atom or an alkyl group. R 301 Preferably, it is an alkyl group having 1 to 20 carbon atoms. The alkyl group preferably has a silyl group, polymeric group or photochromic group having 1 to 10 carbon atoms as a substituent.

[0172] 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 consisting of (meth)acryloyl, 2-(methacryloyloxy)ethylcarbamoyl, 2-(methacryloyloxy)ethoxycarbonyl, epoxy, OH, SH, NH2, and COOH groups.

[0173] A photochromic group is a group that contains a photochromic site. Examples of photochromic groups include naphthopyran, spiroxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene. From the perspective of exhibiting excellent photochromic properties, indene-naphthopyran is preferred, and indene[2,1-f]naphtho[1,2-b]pyran is particularly preferred.

[0174] The indo[2,1-f]naphtho[1,2-b]pyran is preferably represented by the group shown in the following formula (X4).

[0175]

[0176] In equation (X4), R 401 and R 402 It can be the same as the above R 5 and R 6 The same groups are used.

[0177] R 403 and R 404 They can be used independently as R as described above. 5 and R 6 The same groups are used.

[0178] 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 the same as the above R 4 The same groups are used.

[0179] In equation (X4), o is an integer from 0 to 4.

[0180] n is an integer from 0 to 4.

[0181] When o is 2 to 4, multiple R 403 Choose either the same or different from each other.

[0182] When n is 2 to 4, multiple R 404 Choose either the same or different from each other.

[0183] 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.

[0184] The group represented by the particularly preferred formula (X2) is represented by the following formula.

[0185]

[0186] In formulas (X2) and (X2a), L represents an oxygen atom or a sulfur atom.

[0187] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents. R 300 Preferably, it is a alkylene group having 1 to 6 carbon atoms or a silylene group having 1 to 6 carbon atoms as a substituent.

[0188] R 302 R 303 and R 304 Each is an alkylene group, independently. R 302 Preferably, it is an alkylene group having 1 to 6 carbon atoms. 303 Preferably, it is an alkylene group having 1 to 6 carbon atoms. 304 Preferably, it is an alkylene group having 1 to 6 carbon atoms.

[0189] h, j, k, and l are each an independent integer of 0 or 1.

[0190] In equation (X2a), i is an integer from 1 to 200. When i is 2 or higher, multiple R... 30 The structures can be chosen to 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.

[0191] The dashed line indicates the relationship with R. 400 . bond.

[0192] <The photochromic compound shown in formula (4)>

[0193] The photochromic compound used in the embodiments is preferably a compound represented by the following formula (4).

[0194]

[0195] In equation (4), R 3 R 4 R 5 R 6 M and M have the same meaning as in equation (3).

[0196] <R 7 and R 8 >

[0197] R 7 and R 8 Each of the following can be independently a hydroxyl group, 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 haloalkoxy 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 aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkoxythio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, a group represented by formula (X) above, or a group represented by formula (X3) above. As these groups, they can be used with R 1 ~R 6 The groups shown in the example are the same groups.

[0198] b is an integer between 0 and 4, and c is an integer between 0 and 4.

[0199] When b is 2 to 4, multiple R 7 Choose either the same or different.

[0200] When c is 2 to 4, multiple R 8 Choose either the same or different.

[0201] In R where b is 2 to 4 and there are adjacent values 7 In the case of two adjacent R 7 Choose to bond together with 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 is the 5 and 6 positions, or the 6 and 7 positions, or the 7 and 8 positions of the chromene compound.

[0202] When c is 2 to 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 Choose to bond together with 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 9th and 10th positions, or the 10th and 11th positions, or the 11th and 12th positions of the chromene compound.

[0203] It can also contain R 7 Or R 8 The bonded carbon atoms form a ring with 5 to 8 atoms. Furthermore, this ring may have substituents, such as those selected from hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen atoms. Specific examples of these substituents will be described later.

[0204] As a suitable ring, the ring shown in the following formula (X5) can be cited.

[0205]

[0206] In formula (X5), Q and T are independently sulfur atoms, substituted or unsubstituted methylene groups, oxygen atoms, or NR atoms, respectively. 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).

[0207] R 305 and R 306 Each of the following is preferably hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic, cyano, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, halogen atom, substituted or unsubstituted aralkyl, substituted or unsubstituted aralkoxy, substituted or unsubstituted aryl, thiol, alkathio, alkoxyalkathio, haloalkathio, cycloalkylthio, or substituted or unsubstituted arthio.

[0208] 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.

[0209] In equation (X5), m is an integer from 1 to 4.

[0210] <The photochromic compound shown in formula (5)>

[0211] Suitable chromene compounds include those shown in formula (5) below.

[0212]

[0213] In equation (5),

[0214] R 3 R 4 R 5 R 6 R 7 R 8 b and c have the same meaning as in equation (4) independently.

[0215] <The photochromic compound shown in formula (6)>

[0216] As a more preferred photochromic compound, the compound shown in the following formula (6) can be cited.

[0217]

[0218] In equation (6), R 5 R 6 R 7 R 8 b and c have the same meaning as in equation (5) independently.

[0219] <R 9a >

[0220] R 9a The group can be any of the following: a group represented by formula (1a), a hydrogen atom, 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 aryl group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, or a group represented by formula (X3) above. As these groups, groups related to R can be used. 1 ~R 8 The groups shown in the example are the same groups.

[0221] d1 represents R 9a The number of elements is an integer from 1 to 5.

[0222] When d1 is 1, R 9a The group is the one shown in the aforementioned formula (1a).

[0223] When d1 is 2 to 5, R 9a At least one of them is a group represented by the aforementioned formula (1a), and the plurality of R 9a The groups can be either the same or different from each other.

[0224] In the presence of adjacent R groups other than those shown in formula (1a) above. 9a In the case of two adjacent R 9a Choose to bond together with these R 9a 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. R 9a Two adjacent atoms can be combined to form a cycloalloy, optionally comprising at least one atom selected from the group consisting of oxygen, sulfur, carbon, and nitrogen atoms. This cycloalloy is not particularly limited, but preferably contains R. 9a The bonded carbon atoms form a ring with 5 to 8 atoms. Furthermore, this ring may also have substituents. Examples of such substituents include hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen groups. Specific examples of these substituents are groups identical to those described above. Preferably, the ring is formed together with the ring shown in formula (X5). However, as mentioned above, for the group shown in formula (1a) above, even if other adjacent R atoms are present... 9a And the aforementioned ring will not be formed.

[0225] <R 10a >

[0226] R 10a The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group shown in formula (2a) above, or the group shown in formula (X3) above. As these groups, R can be used. 1 ~R 8 The groups shown in the example are the same groups.

[0227] e1 represents R 10a The number of elements is an integer from 0 to 5.

[0228] When e1 is 2 or higher, R 10a Choose either the same or different from each other.

[0229] In R where e1 is 2 to 5 and there are adjacent values... 10a In the case of two adjacent R 10a Choose to bond together with these R 10a 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.

[0230] R 10a Two adjacent atoms can be used together to form a cycloalloy, optionally comprising at least one atom selected from the group consisting of oxygen, sulfur, carbon, and nitrogen atoms. This cycloalloy is not particularly limited, but preferably contains R. 10a The bonded carbon atoms form a ring with 5 to 8 atoms. Furthermore, this ring may also have substituents. Examples of such substituents include hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen groups. Specific examples of these substituents are groups identical to those described above. Preferably, the ring is formed together with the ring shown in formula (X5).

[0231] <The photochromic compound shown in formula (7)>

[0232] As a photochromic compound with superior fading speed and repeated durability, the compound shown in the following formula (7) can be cited.

[0233]

[0234] In equation (7), R 5 R 6 R 7 R 8 R 10a b, c, and e1 have the same meaning as in equation (6), R 9 The group is the one shown in the aforementioned formula (1a).

[0235] <R 9b >

[0236] R 9b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group shown in formula (2a) above, or the group shown in formula (X3) above. As these groups, R can be used. 1 ~R 8 The groups shown in the example are the same groups.

[0237] d2 represents R 9b The number of elements is an integer from 0 to 4.

[0238] When d2 is greater than 2, R 9b Choose either the same or different from each other.

[0239] In R where d2 is 2 to 4 and there are adjacent values 9b In the case of two adjacent R 9b Optional and bonded to these R 9b 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.

[0240] R 9b Two adjacent atoms can be used together to form a cycloalloy, optionally comprising at least one atom selected from the group consisting of oxygen, sulfur, carbon, and nitrogen atoms. This cycloalloy is not particularly limited, but preferably contains R. 9b The bonded carbon atoms form a ring with 5 to 8 atoms. Furthermore, this ring may also have substituents. Examples of such substituents include hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen groups. Specific examples of these substituents are groups identical to those described above. Preferably, the ring is formed together with the ring shown in formula (X5).

[0241] <The photochromic compound shown in formula (8)>

[0242] Examples of photochromic compounds that exhibit particularly excellent fading speed and repeated durability include compounds represented by the following formula (8).

[0243]

[0244] In equation (8), R 5 R 6 R 7 R 8 R 9 R 9b b, c and d2 have the same meaning as in equation (7).

[0245] <R 10 >

[0246] R 10 The group can be 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 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 substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, or a group represented by formula (X3) above. As these groups, R can be used. 1 ~R 8 The groups shown in the example are the same groups.

[0247] <R 10b >

[0248] R 10b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group shown in formula (2a) above, or the group shown in formula (X3) above. As these groups, R can be used. 1 ~R 8 The groups shown in the example are the same groups.

[0249] e2 represents R 10b The number of elements is an integer from 0 to 4.

[0250] When e2 is greater than 2, R 10b Choose either the same or different from each other.

[0251] In R where e2 is 2 to 4 and there are adjacent values... 10b In the case of two adjacent R 10b Choose to bond together with these R 10b 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.

[0252] R 10b Two adjacent atoms can be used together to form a cycloalloy, optionally comprising at least one atom selected from the group consisting of oxygen, sulfur, carbon, and nitrogen atoms. This cycloalloy is not particularly limited, but preferably contains R. 10b The bonded carbon atoms form a ring with 5 to 8 atoms. Furthermore, this ring may also have substituents. Examples of such substituents include hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen groups. Specific examples of these substituents are groups identical to those described above. Preferably, the ring is formed together with the ring shown in formula (X5).

[0253] <Detailed explanation of substituents, etc.>

[0254] As in the above R 1 ~R 10b 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 8 The same group as the group detailed in the text.

[0255] <Specific examples of suitable photochromic compounds>

[0256] If a particularly suitable photochromic compound is to be specifically exemplified, the photochromic compound shown in the following formula can be cited.

[0257]

[0258] [Propylene alcohol compound]

[0259] The propargyl alcohol compound of the embodiment has the skeleton shown in formula (9) below. This propargyl alcohol compound can be used as an intermediate for synthesizing photochromic compounds having the skeletons shown in formulas (1), (2), (3), (4) and (5) above.

[0260]

[0261] In equation (9), R 3 R 4 They are independently equivalent to the meaning in equation (1) above.

[0262] <The propargyl alcohol compound shown in formula (10)>

[0263] The propargyl alcohol compound shown in formula (10) can be used as an intermediate for the synthesis of the photochromic compound shown in formula (6) above.

[0264]

[0265] In equation (10), R 9a R 10a d1 and e1 have the same meaning as in equation (6) above.

[0266] <The propargyl alcohol compound shown in formula (11)>

[0267] The propargyl alcohol compound shown in formula (11) can be used as an intermediate for the synthesis of the photochromic compound shown in formula (7) above.

[0268]

[0269] In equation (10), R 10a R 9 R 9b e1 and d2 are independently equivalent to the meanings in equation (7) above.

[0270] <The propargyl alcohol compound shown in formula (12)>

[0271] The propargyl alcohol compound shown in formula (12) can be used as an intermediate for the synthesis of the photochromic compound shown in formula (8) above.

[0272]

[0273] In equation (10), R 9 R 9b R 10 R 10b d2 and e2 have the same meaning as in equation (8) above.

[0274] <Specific examples of naphthol derivatives>

[0275] Specific examples of naphthol derivatives used in implementation methods include compounds represented by the following formulas.

[0276]

[0277] [Methods for manufacturing photochromic compounds]

[0278] 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 denote the meanings explained above.

[0279] The photochromic compound can be prepared by reacting a naphthol derivative of formula (13) with a propargyl alcohol compound of formula (9) in the presence of an acid catalyst.

[0280]

[0281] The reaction ratio of the naphthol compound to the propargyl alcohol compound is preferably selected from the range of 1:10 to 10:1 (molar ratio). As an acid catalyst, for example, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina, etc., can be used. 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 amount of naphthol compound and 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, toluene, etc. The purification method for the product obtained by this reaction is not particularly limited. For example, purification can be performed by silica gel column chromatography followed by recrystallization, thereby purifying the product.

[0282] <Synthetic methods of naphthol derivatives>

[0283] Naphthol derivatives can be synthesized, for example, based on the reaction methods described in Non-Patent Literature 1, Non-Patent Literature 2, Patent Literature 3, etc. As an example, the synthesis method of the naphthol derivative shown in formula (14) is not particularly limited; for example, when M is a carbon atom, it can be synthesized as follows. It should be noted that in formula (14), R... 5 R 6 R 7 R 8 b and c have the same meaning as in the aforementioned equation (4).

[0284]

[0285] First, the benzophenone compound shown in formula (15) was synthesized using a benzene compound and an acyl chloride via a Friedel-Crafts reaction.

[0286]

[0287] It should be noted that in equation (15), R 7 R 8 b and c have the same meaning as in formula (4). Furthermore, the benzophenone compound shown in formula (15) 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 the carboxylic acid with hydroxyl groups protected by benzyl (Bn) as shown in formula (16).

[0288]

[0289] Next, the benzyl-protected carboxylic acid shown in formula (16) 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 then converted into halides such as bromides and iodides by the Sandmeyer reaction, etc., to obtain the halide shown in formula (17) below (where Hal represents halogen).

[0290]

[0291] The obtained halide is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then reacted with the following formula (18) (where R...). 5 and R 6 The ketone (with the same meaning as in formula (4)) is reacted in an organic solvent at -100 to 70°C to give the compound shown in formula (19) below.

[0292]

[0293]

[0294] After debenzylation of the obtained compound (19), the alcohol is spirocyclized under neutral to acidic conditions at 10–120 °C for 10 minutes to 2 hours, thereby synthesizing the naphthol derivative of formula (14) as the target. In this reaction, the reaction ratio of the organometallic reagent to the ketone shown in formula (19) 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.

[0295] <Synthetic methods for naphthol derivatives containing Si and Ge>

[0296] The following describes an example of a method for manufacturing a naphthol derivative in formula (14) where M is Si or Ge.

[0297] First, the halide shown in formula (17) is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then reacted with the following formula (20) (where R... 5 and R 6 The monohalides (with the same meaning as in formula (4)) are reacted in an organic solvent at -100 to 70°C to give the compound shown in formula (21) below.

[0298]

[0299] The obtained compound (21) was subjected to a reaction method described in Non-Patent Literature 3, Non-Patent Literature 4, Patent Literature 4, etc., to obtain the cyclized body shown in the following formula (22).

[0300]

[0301] By debenzylation of the obtained cyclized body, the naphthol derivative of the above formula (14) can be obtained.

[0302] <Synthetic methods of propargyl alcohol compounds>

[0303] Propylene alcohol compounds can be synthesized, for example, based on the reaction methods described in Patent Documents 5 and 6. As an example, in the case of the propylene alcohol compound shown in formula (11) above, it can be synthesized as follows. First, by reacting the benzene compound shown in formula (23) below with the acyl chloride compound shown in formula (24) below, the following formula (25) is obtained (where R is a benzene compound shown in formula (23) below). 9 The benzophenone compound shown in formula (1a) above has the same meaning.

[0304]

[0305] As another method, as shown in formula (26) below (where Hal represents a halogen atom), after synthesizing halogen-substituted benzophenone, the halogen atom is replaced by an amino compound as shown in formula (27) below, thereby synthesizing the aforementioned benzophenone compound of formula (25).

[0306]

[0307] By reacting the obtained benzophenone compound with metal acetylene such as sodium acetylene or lithium acetylene, or with acetylene Grignard reagents or other acetylene derivatives, the propargyl alcohol compound shown in formula (11) above can be synthesized.

[0308] Alternatively, as another synthetic method, by reacting propargyl alcohol of formula (28) synthesized from benzophenone compound of formula (26) with naphthol derivative of formula (14) to synthesize photochromic compound of formula (29) having halogen atoms, and then replacing the halogen atoms with amino compound of formula (27), the photochromic compound of the present invention can also be obtained.

[0309]

[0310] <Identification of Photochromic Compounds>

[0311] The photochromic compound in the embodiments is, for example, a solid or a viscous liquid at room temperature and pressure. In this solid or liquid state, the photochromic compound can be separated by separation operations such as thin-layer chromatography, silica gel column chromatography, high-performance liquid chromatography, and gas chromatography. Furthermore, in addition to the photochromic compound, it can be confirmed that there are no byproducts such as starting material compounds and coloring components.

[0312] 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 compound.

[0313] 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.

[0314] <Photochromic Composition>

[0315] The photochromic compound of the embodiment can be dissolved in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the photochromic compound having the skeleton shown in formula (1) is dissolved in such a solvent, a colorless and transparent solution is obtained. It exhibits a good photochromic effect, rapidly developing color when exposed to sunlight or ultraviolet light, and reversibly and rapidly returning to its original colorless state when sunlight or the like is blocked.

[0316] 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 high color development concentration at high temperatures and fast fading rate, as well as excellent durability, it is preferable to use multiple photochromic compounds to adjust the hue.

[0317] 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.

[0318] <Photochromic Curable Composition>

[0319] The photochromic curable composition, as an embodiment, comprises the photochromic compound of the embodiment and includes at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a condensation reactive group, and a (thio)carbamate (urea) polymer. Here, the (thio)carbamate (urea) polymer includes at least one selected from the group consisting of carbamate polymers, thiocarbamate polymers, carbamate urea polymers, and thiocarbamate urea polymers.

[0320] The photochromic compounds and photochromic compositions of the embodiments are preferably combined with polymeric compounds to be used as photochromic curable compositions.

[0321] For photochromic curable compositions, since the color rendering intensity of the photochromic compound, the selected lens material, and the lens thickness are all factors, a general rule cannot be applied. It is preferable to use 0.001 to 10 parts by weight of the photochromic compound (or photochromic composition) 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 the case where the photochromic curable composition is used as a thin film optical article and as a thick film optical article.

[0322] (Used as a thin-film optical article)

[0323] For example, when the photochromic curable composition is made into a thin film (a polymer film polymerized from the photochromic curable composition) with a thickness of 10 μm or more and less than 1000 μm, for example, about 100 μm, the hue can be adjusted by using 0.001 to 10 parts by mass of the photochromic compound (or photochromic composition) relative to 100 parts by mass of other polymeric monomers.

[0324] (Use as a thick-film optical material)

[0325] 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 using 0.001 to 1 part by mass of the photochromic compound (or photochromic composition) of the present invention relative to 100 parts by mass of the thick cured material or other polymeric monomers that provide the thick cured material.

[0326] <Polymerizing compounds>

[0327] 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 condensation-reactive groups; free radical polymeric compounds; and epoxy polymeric compounds. These polymeric compounds are not particularly limited; for example, the polymeric compound described in Patent Document 7 is preferred.

[0328] Among them, the following polymeric compounds are particularly preferred.

[0329] <Compounds with condensation-reactive groups>

[0330] Compounds having condensation-reactive groups include those having isocyanate groups. Isocyanate compounds are compounds having either isocyanate or isothiocyanate groups, and may contain both. 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 isocyanate compounds.

[0331] (polyisocyanate)

[0332] Polyisocyanates are compounds having at least two isocyanate groups in a single molecule. Examples of polyisocyanates include aromatic polyisocyanates with aromatic rings such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate, as well as aliphatic polyisocyanates such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

[0333] (Compounds containing active hydrogen)

[0334] The compound having active hydrogen is 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.

[0335] (Free radical polymeric compounds)

[0336] 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.).

[0337] Polyfunctional radical polymerizable compounds are compounds having 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.

[0338] 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.

[0339] (Polyfunctional (meth)acrylate compounds)

[0340] 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.

[0341] (Multifunctional allyl compounds)

[0342] 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 carbonate.

[0343] (Polyfunctional thio(meth)acrylate compounds)

[0344] 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl) ether, 1,4-bis(methacryloylthiomethyl)benzene.

[0345] (Vinyl compounds)

[0346] Divinylbenzene.

[0347] 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.

[0348] In addition, a monofunctional free radical polymerizable compound is a compound having one 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.

[0349] (Unsaturated carboxylic acids)

[0350] Acrylic acid, methacrylic acid, maleic anhydride.

[0351] ((meth)acrylate)

[0352] Methyl methacrylate, benzyl methacrylate, phenyl methacrylate.

[0353] 2-Hydroxyethyl methacrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-epoxypropoxymethacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl methacrylate, 3-(epoxypropoxy-1-isopropyloxy)-2-hydroxypropyl acrylate, 3-epoxypropoxy-2-hydroxypropoxy)-2-hydroxypropyl acrylate.

[0354] (Fumarate)

[0355] Diethyl fumarate, diphenyl fumarate.

[0356] (Thio(meth)acrylic acid)

[0357] Methyl thioacrylate, benzyl thioacrylate, benzyl thiomethacrylate.

[0358] (Vinyl compounds)

[0359] Styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene.

[0360] 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.

[0361] (Various compounding agents)

[0362] In curable compositions, various known compounding agents can be formulated 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 formulated. Thiols such as tert-dodecyl mercaptan can be formulated as polymerization modifiers.

[0363] 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.

[0364] 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 ADEKACORPORATION, 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.

[0365] 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.

[0366] <Instructions for use of photochromic curable compositions; optical articles>

[0367] Photochromic cured materials are obtained by curing the photochromic curable composition. The polymerization and curing used to produce photochromic cured materials are carried out as follows: free radical polymerization, ring-opening polymerization, anionic polymerization, or polycondensation is performed by irradiation with 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.

[0368] When a curable composition containing polymerizable compounds is thermally polymerized, the temperature affects the properties of the resulting photochromic cured product.

[0369] The temperature conditions are affected by the type and amount of the thermal polymerization initiator and the type of polymerizable compound, and therefore 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 a 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.

[0370] 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.

[0371] [Optical Items]

[0372] 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, light meters, decorative materials, fabrics, threads, and other materials.

[0373] 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.

[0374] 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.

[0375] 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.

[0376] Alternatively, by placing an optical substrate, such as a lens substrate, facing a glass mold with 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, which is performed by using UV irradiation, heating, etc. (cast polymerization method).

[0377] 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 pre-treating the surface of the optical substrate with 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.

[0378] Furthermore, in the case of exhibiting photochromic properties through an adhesive method, a photochromic sheet is prepared by sheet forming 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 adhesive sheet with a photochromic layer as the adhesive layer.

[0379] In this case, a coating method using a coating liquid prepared by dissolving the curable composition in an organic solvent can also be used in the fabrication of the photochromic film. Alternatively, an adhesive layer can be provided between the photochromic film and the optical film.

[0380] For example, an adhesive sheet made in this way can be installed in a mold, and then an optical substrate such as a lens can be obtained by injection molding with a thermoplastic resin (e.g., polycarbonate) to give it a prescribed shape and impart photochromic properties.

[0381] Alternatively, the adhesive sheet can also be bonded to the surface of an optical substrate using an adhesive or similar bonding agent, thereby obtaining a photochromic lens.

[0382] In addition, the photochromic layer and photochromic cured product formed by the curable composition can also 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, anti-reflective treatment using thin films coated with organic polymers, antistatic treatment, protective coating treatment with urethane resins, etc., and other post-processing.

[0383] Example

[0384] The invention will be described in more 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.

[0385] (Example 1)

[0386] First process

[0387] Add 95.4 g (500 mmol) of p-toluenesulfonic acid monohydrate and 1000 mL of toluene, and perform azeotropic dehydration. The water content was confirmed to be 202 ppm.

[0388] Referring to the method described in Patent Document 8, 37.3 g (100.0 mmol) of a carboxylic acid compound of formula (30) synthesized from 3-bromo-4-methoxybenzophenone was added, and the reaction was carried out while undergoing azeotropic dehydration. After confirming that the raw material was consumed, the mixture was cooled to room temperature, and then the resulting solid was filtered to obtain a carbonyl compound of formula (31) in 90% yield.

[0389]

[0390] Second process

[0391] Referring to the method described in Patent Document 9, the carbonyl compound represented by the aforementioned formula (31) was reacted to obtain the naphthol derivative represented by the following formula (32) in a yield of 83%.

[0392]

[0393] Third process

[0394] 17.1 g (49.9 mmol) of the naphthol derivative shown in formula (32) was mixed with 11.2 g (54.3 mmol) of 4-morpholinophenylboronic acid, 11.5 g (108.7 mmol) of sodium carbonate, 103.5 mL of water, 121.5 mL of 1,2-dimethoxyethane, and 12.2 mL of ethanol, and stirred while bubbling with nitrogen. After bubbling with nitrogen for about 20 minutes, 142.7 mg (0.1 mmol) of Pd(PPh3)4 was added, and the mixture was reacted at 75 °C for 2 hours. After the reaction, the mixture was cooled to room temperature, 650 mL of THF was added, and the mixture was cooled to 0-5 °C. Concentrated hydrochloric acid was added until the pH reached 1, and the mixture was separated. The solvent was removed by washing twice with 500 mL of water. The mixture was then purified by re-slurrying with 300 mL of methanol to obtain the naphthol derivative shown in formula (33) in 96% yield.

[0395]

[0396] Fourth process

[0397] 2.91 g (10.0 mmol) of 4-bromo-4'-methoxybenzophenone, 1.50 g (14.0 mmol) of N-methylaniline, and 0.29 g (30.0 mol) of sodium tert-butoxide were added to 50 mL of toluene, and the mixture was bubbled under nitrogen for 20 minutes. 46 mg (0.05 mmol) of tris(dibenzylacetone)dipalladium(O) and 95 mg (0.20 mmol) of 2-dicyclohexylphosphino-triisopropylbiphenyl were added, and the mixture was reacted at 80 °C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and 30 mL of THF was added, followed by filtration. The mixture was cooled at 0–5 °C, and 10% hydrochloric acid was added until the pH reached 6–7. The mixture was separated and washed three times with 100 mL of water. The solvent of the resulting organic layer was removed, and the mixture was purified by silica gel-based chromatography to obtain benzophenone as shown in formula (34) in 92% yield.

[0398]

[0399] Using the obtained benzophenone, propargyl alcohol as shown in the following formula (35) was obtained in a yield of 86% by referring to the method described in Patent Document 6.

[0400]

[0401] Fifth process

[0402] 2.80 g (6.6 mol) of the naphthol derivative of formula (33) above, 5.60 g of Wakogel C300, and 80 mL of toluene were added, and the mixture was heated to 100 °C. 2.71 g (7.9 mmol) of propargyl alcohol of formula (35) above, dissolved in 20 mL of toluene, was added, and the mixture was heated to 100 °C. After the naphthol derivative of the starting 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 resulting organic layer was removed, and the mixture was purified by silica gel-based chromatography, thereby obtaining the photochromic compound of formula (36) below in 87% yield.

[0403]

[0404] Sixth process

[0405] Add 4.1 g (5.5 mmol) of the photochromic compound of formula (36), 3.9 g (27.5 mmol) of iodomethane, and 60 mL of THF, and chill. While maintaining the temperature at 0–5°C, add 1.8 g (16.5 mmol) of tBuOK in four portions. After the raw material is consumed, neutralize with 10% hydrochloric acid, add 30 mL of toluene, and separate the layers. After removing the solvent from the obtained organic layer, purify by silica gel-based chromatography to obtain the photochromic compound of formula (37) in 89% yield.

[0406]

[0407] The elemental analysis values ​​of the photochromic compound shown in formula (37) are C: 81.93%, H: 6.21%, and N: 3.62%, which are similar to C. 53 H 48 The calculated values ​​of N2O4, namely C: 81.93%, H: 6.23%, and N: 3.61%, are largely consistent.

[0408] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl and morpholino groups of 13H in the vicinity of δ0.5–3.0 ppm, peaks based on methoxy and morpholino groups of 10H in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons of 25H in the vicinity of δ5.0–9.0 ppm.

[0409] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0410] (Example 2)

[0411] First process

[0412] Referring to the method described in Patent Document 8, 31.8 g (68.6 mmol) of the compound shown in Formula (38) synthesized from the carboxylic acid compound of Formula (30) above, 550 mL of toluene, 14.79 g (87.4 mmol) of diphenylamine, and 30.8 g (274.6 mmol) of sodium tert-butoxide were added to the reaction solution, 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 degrees Celsius. Heating continued until the starting material disappeared. After the reaction was completed, the mixture was cooled to room temperature and filtered. 500 mL of tetrahydrofuran and 10% hydrochloric acid were added to the filtrate for neutralization, and the mixture was separated. The resulting organic layer was concentrated and then slurried with 200 mL of methanol for purification, yielding the carboxylic acid compound shown in Formula (39) in 87% yield.

[0413]

[0414] Second process

[0415] In addition to using the carboxylic acid compound obtained in the first step, the iodine compound shown in the following formula (40) was obtained in a yield of 75% by referring to the method of Patent Document 8.

[0416]

[0417] Third process

[0418] 28.4 g (44.8 mmol) of the compound of formula (40) obtained in the second step was added to 400 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 33.6 mL of n-BuLi (1.6 mol / L hexane solution) was slowly added dropwise while maintaining the temperature at -15 to -20 °C. After confirming that the raw material had been consumed, 8.64 g (56.0 mmol) of 4,4-diethylcyclohexanone was slowly added dropwise while maintaining the temperature at -5 to -20 °C. After the addition, the temperature was slowly raised to room temperature. After the temperature was raised, 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, thereby obtaining the compound of formula (41) in 86% yield.

[0419]

[0420] Fourth process

[0421] 25.5 g (38.5 mmol) of the compound of formula (41) was dissolved in 500 mL of THF, and then 7.6 g of 5% Pd / C (50% aqueous) was added. The reaction was carried out with hydrogen gas at a pressure of 0.05–0.1 MPa. After confirming that the starting material was consumed, Pd / C was filtered off, and the solvent of the obtained organic layer was removed to obtain the compound of formula (42) in 100% yield.

[0422]

[0423] Fifth process

[0424] 750 mL of toluene was added to 14.7 g (77.0 mmol) of p-toluenesulfonic acid monohydrate, and azeotropic dehydration was carried out until the water content in the toluene was below 150 ppm. Then, 100 mL of a toluene solution of 22.0 g (38.5 mmol) of the aforementioned formula (42) 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, 500 mL of water was added, and the mixture was separated. This operation was repeated 3 times to remove the solvent from the obtained organic layer, and the mixture was purified by silica gel-based chromatography, thereby obtaining the naphthol derivative shown in the following formula (43) in 83% yield.

[0425]

[0426] Fifth process

[0427] In the fourth step of Example 1, 4-bromo-4'-methylbenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and 4-(methylamino)toluene was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (44) in 89% yield.

[0428]

[0429] Sixth process

[0430] Add 3.05 g (5.5 mmol) of the naphthol derivative of formula (43), 6.00 g of Wakogel C300, and 60 mL of toluene, and heat to 100 °C. While maintaining an internal temperature of 95-100 °C, add dropwise a 10 mL toluene solution of 2.26 g (6.6 mmol) of propargyl alcohol of formula (44). After confirming the consumption of the raw materials, filter to remove the solvent from the resulting organic layer, and purify by silica gel-based chromatography to obtain the photochromic compound of formula (45) in 77% yield.

[0431]

[0432] The elemental analysis values ​​of the photochromic compound shown in formula (45) are C: 86.29%, H: 6.87%, and N: 3.21%, which are similar to C. 63 H 60 The calculated values ​​of N2O2, namely C: 86.26%, H: 6.89%, and N: 3.19%, are largely consistent.

[0433] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 27H based on methyl and 4,4-diethylcyclohexyl cyclogroups in the vicinity of δ0.5–3.0 ppm, a peak of 3H based on methoxy group in the vicinity of δ3.0–5.0 ppm, and a peak of 30H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0434] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0435] (Example 3)

[0436] In the first step of Example 1, 4,4'-dimethoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone, and in the sixth step, iodopropane was used instead of iodomethane. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (46) in 82% yield.

[0437]

[0438] The elemental analysis values ​​of the photochromic compound shown in formula (46) are C: 82.11%, H: 6.76%, and N: 2.01%, which are similar to C. 48 H 47 The calculated values ​​for NO4, namely C: 82.14%, H: 6.75%, and N: 2.00%, are largely consistent.

[0439] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 17H peak based on methyl and propyl groups in the vicinity of δ0.5–3.0 ppm, a 9H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0440] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0441] (Example 4)

[0442] First process

[0443] In the fourth step of Example 1, 4-bromo-4'-fluorobenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and N-ethylaniline was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (47) in 91% yield.

[0444]

[0445] Second process

[0446] In the first step of Example 1, 4-methoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone, and in the sixth step, iodohexane was used instead of iodomethane. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (48) in 79% yield.

[0447]

[0448] The elemental analysis values ​​of the photochromic compound shown in formula (48) are C: 83.96%, H: 7.43%, and N: 1.84%, which are similar to C. 53 H 56 The calculated values ​​of FNO4, namely C: 83.98%, H: 7.45%, and N: 1.85%, are largely consistent.

[0449] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 31H peak based on ethyl and hexyl groups in the vicinity of δ0.5–3.0 ppm, a 3H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 22H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0450] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0451] (Example 5)

[0452] First process

[0453] In the fourth step of Example 1, 4-bromo-4'-propylbenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (49) in 92% yield.

[0454]

[0455] Second process

[0456] In the fifth step of Example 2, instead of the naphthol derivative of the aforementioned formula (43), a naphthol derivative of the following formula (50) synthesized by the method described in Patent Document 10 was used. Instead of the propargyl alcohol of the aforementioned formula (44), propargyl alcohol of the aforementioned formula (49) was used. The reaction was carried out in the same manner to obtain the photochromic compound of the following formula (51) in a yield of 82%.

[0457]

[0458]

[0459] The elemental analysis values ​​of the photochromic compound shown in formula (51) are C: 83.77%, H: 7.15%, N: 1.64%, S: 3.75%, which are similar to C. 60 H 61 The calculated values ​​for NO2S, namely C: 83.78%, H: 7.15%, N: 1.63%, and S: 3.73%, are largely consistent.

[0460] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 34H of methyl, propyl, and 3,3,5,5-tetramethylcyclohexyl cyclogroups in the vicinity of δ0.5–3.0 ppm, peaks based on 3H of methoxy group in the vicinity of δ3.0–5.0 ppm, and peaks based on 24H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0461] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0462] (Example 6)

[0463] First process

[0464] In the fourth step of Example 1, N-cyclohexylaniline was used instead of N-methylaniline, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (52) in 89% yield.

[0465]

[0466] Second process

[0467] In the first step of Example 1, 3,4-dimethoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the fifth step, propargyl alcohol of the aforementioned formula (52) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, 1-bromo-4-fluorobutane was used instead of iodomethane. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (53) in a yield of 69%.

[0468]

[0469] The elemental analysis values ​​of the photochromic compound shown in formula (53) are C: 79.18%, H: 6.88%, and N: 1.66%, which are similar to C. 55 H 57 The calculated values ​​of F2NO4, namely C: 79.20%, H: 6.89%, and N: 1.68%, are largely consistent.

[0470] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on cyclohexyl and 4-fluorobutyl 27H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy 9H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 21H in the vicinity of δ5.0–9.0 ppm.

[0471] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0472] (Example 7)

[0473] First process

[0474] In the fourth step of Example 1, 4-bromo-3'-fluoro-4'-methoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (54) in 91% yield.

[0475]

[0476] Second process

[0477] In the third step of Example 1, 2,4-dimethoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid; in the fifth step, propargyl alcohol of the aforementioned formula (54) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, iodopropane was used instead of iodomethane. The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (55) was obtained in a yield of 73%.

[0478]

[0479] The elemental analysis values ​​of the photochromic compound shown in formula (55) are C: 79.95%, H: 6.34%, and N: 1.69%, which are similar to C. 55 H 52 The calculated values ​​of FNO5, namely C: 79.97%, H: 6.35%, and N: 1.70%, are largely consistent.

[0480] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 17H peak based on methyl and propyl groups in the vicinity of δ0.5–3.0 ppm, a 12H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 23H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0481] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0482] (Example 8)

[0483] First process

[0484] In the fourth step of Example 1, 4-bromo-3',4'-dimethoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and 4-fluoro-N-methylaniline was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (56) in 91% yield.

[0485]

[0486] Second process

[0487] In the first step of Example 1, 4,4'-dimethylbenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the fifth step, propargyl alcohol of the aforementioned formula (56) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, 1-bromo-2-(2-methoxyethoxy)ethane was used instead of iodomethane. The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (57) was obtained in a yield of 68%.

[0488]

[0489] The elemental analysis values ​​of the photochromic compound shown in formula (57) are C: 75.95%, H: 6.74%, and N: 1.69%, which are similar to C. 53 H 56 The calculated values ​​of FNO7, namely C: 75.96%, H: 6.74%, and N: 1.67%, are largely consistent.

[0490] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on methyl and 2-(2-methoxyethoxy)ethyl 13H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy 24H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 19H in the vicinity of δ5.0–9.0 ppm.

[0491] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0492] (Example 9)

[0493] First process

[0494] In the fourth step of Example 1, 4-bromo-4'-propoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and N-(2,2,2-trifluoroethyl)aniline was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (58) in 87% yield.

[0495]

[0496] In the fifth step of Example 2, the naphthol derivative shown in the following formula (59) was used instead of the naphthol derivative of the aforementioned formula (43), and the propargyl alcohol of the aforementioned formula (58) was used instead of the propargyl alcohol of the aforementioned formula (44). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (60) in a yield of 74%.

[0497]

[0498] The elemental analysis values ​​of the photochromic compound shown in formula (60) are C: 80.09%, H: 6.16%, and N: 1.85%, which are similar to C. 50 H 46 The calculated values ​​of F3NO2, namely C: 80.08%, H: 6.18%, and N: 1.87%, are largely consistent.

[0499] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 21H based on cyclooctane cyclogroup, (2,2,2-trifluoroethyl, propoxy) near δ0.5–3.0 ppm, a peak of 2H based on propoxy near δ3.0–5.0 ppm, and a peak of 23H based on aromatic protons and alkene protons near δ5.0–9.0 ppm.

[0500] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0501] (Example 10)

[0502] First process

[0503] In the fifth step of Example 2, N-butylaniline was used instead of 4-(methylamino)toluene, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (61) in 91% yield.

[0504]

[0505] Second process

[0506] In the first step of Example 2, morpholine was used instead of diphenylamine; in the third step, diethyl ketone was used instead of 4,4-diethylcyclohexanone; and in the fifth step, propargyl alcohol of the aforementioned formula (61) was used instead of propargyl alcohol of the aforementioned formula (44), thereby obtaining the photochromic compound of the following formula (62) in a yield of 77%.

[0507]

[0508] The elemental analysis values ​​of the photochromic compound shown in formula (62) are C: 82.74%, H: 7.19%, and N: 3.72%, which are similar to C. 52 H 54 The calculated values ​​of N2O3, namely C: 82.72%, H: 7.21%, and N: 3.71%, are largely consistent.

[0509] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks of 26H based on methyl, ethyl, butyl, and morpholino groups in the vicinity of δ0.5–3.0 ppm, peaks of 7H based on methoxy and morpholino groups in the vicinity of δ3.0–5.0 ppm, and peaks of 21H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0510] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0511] (Example 11)

[0512] First process

[0513] In the fourth step of Example 1, 4-methoxy-N-methylaniline was used instead of N-methylaniline, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (63) in 93% yield.

[0514]

[0515] Second process

[0516] In the first step of Example 1, 4-bromo-4'-methoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the fifth step, propargyl alcohol of the aforementioned formula (63) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, 1-bromo-4-methoxybutane was used instead of iodomethane. All other steps were carried out in the same manner to synthesize the photochromic compound shown in the following formula (64).

[0517]

[0518] Third process

[0519] Referring to the method described in Patent Document 10, the photochromic compound of the aforementioned formula (64) was reacted with 2,6-dimethylbenzenethiol to obtain the photochromic compound of the following formula (65) in a yield of 86%.

[0520]

[0521] The elemental analysis values ​​of the photochromic compound shown in formula (65) are C: 77.83%, H: 6.86%, N: 1.50%, S: 3.44%, which are similar to C. 60 H 63 The calculated values ​​of NO6S, namely C: 77.81%, H: 6.86%, N: 1.51%, and S: 3.46%, are largely consistent.

[0522] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 21H based on methyl and 4-methoxybutyl in the vicinity of δ0.5–3.0 ppm, a peak of 19H based on methoxy and 4-methoxybutyl in the vicinity of δ3.0–5.0 ppm, and a peak of 23H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0523] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0524] (Example 12)

[0525] First process

[0526] In the first step of Example 1, 3-bromo-4-methoxy-4'-methylbenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the third step, 2,4,6-trimethoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid; and in the sixth step, 1-bromo-3-methylthiopropane was used instead of iodomethane. All other steps were carried out in the same manner to obtain the photochromic compound shown in the following formula (66) in 74% yield.

[0527]

[0528] The elemental analysis values ​​of the photochromic compound shown in formula (66) are C: 75.07%, H: 6.50%, N: 1.48%, S: 6.80%, which are similar to C. 59 H 61 The calculated values ​​of NO6S2, namely C: 75.05%, H: 6.51%, N: 1.48%, and S: 6.79%, are largely consistent.

[0529] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on methyl and 3-methylthiopropyl 24H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy 15H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 22H in the vicinity of δ5.0–9.0 ppm.

[0530] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0531] (Example 13)

[0532] First process

[0533] In the fourth step of Example 1, 4-bromo-4'-phenoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (67) in 86% yield.

[0534]

[0535] Second process

[0536] In the second step of Example 6, 4-bromo-3',4'-dimethoxybenzophenone was used instead of 3,4-dimethoxybenzophenone, 1,1,1-trifluoro-4-iodobutane was used instead of 1-bromo-4-fluorobutane, and propargyl alcohol of the aforementioned formula (67) was used instead of propargyl alcohol of the aforementioned formula (52). The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (68) was obtained in a yield of 82%.

[0537]

[0538] Third process

[0539] In the third step of Example 1, the photochromic compound of the aforementioned formula (68) was used instead of the naphthol derivative of the aforementioned formula (32), and 4-trifluoromethylphenylboronic acid was used instead of 4-morpholinophenylboronic acid. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (69) in a yield of 89%.

[0540]

[0541] The elemental analysis values ​​of the photochromic compound shown in formula (69) are C: 71.30%, H: 4.80%, N: 1.32%, which are similar to C. 62 H 50 The calculated values ​​of F9NO4, namely C: 71.32%, H: 4.83%, and N: 1.34%, are largely consistent.

[0542] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 15H based on methyl and 1,1,1-trifluorobutyl in the vicinity of δ0.5–3.0 ppm, a peak of 6H based on methoxy in the vicinity of δ3.0–5.0 ppm, and a peak of 29H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0543] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0544] (Example 14)

[0545] First process

[0546] In the fourth step of Example 1, 4-bromo-3',4'-ethylidene dioxane was used instead of 4-bromo-4'-methoxybenzophenone, and N-(2-methoxyethyl)aniline was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (70) in 86% yield.

[0547]

[0548] Second process

[0549] In the fifth step of Example 1, the naphthol derivative of Formula (71) was used instead of the naphthol derivative of Formula (33), and the propargyl alcohol of Formula (70) was used instead of the propargyl alcohol of Formula (35). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of Formula (72) in a yield of 84%.

[0550]

[0551] The elemental analysis values ​​of the photochromic compound shown in formula (72) are C: 78.77%, H: 6.48%, N: 1.63%, S: 3.76%, which are similar to C. 56 H 55 The calculated values ​​of NO5S, namely C: 78.75%, H: 6.49%, N: 1.64%, and S: 3.75%, are largely consistent.

[0552] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 26H based on methyl, 2-methoxyethyl, and spiro[5,5]undecane cycloyl groups in the vicinity of δ0.5–3.0 ppm, a peak of 9H based on 2-methoxyethyl and ethylenedioxy groups in the vicinity of δ3.0–5.0 ppm, and a peak of 20H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0553] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0554] (Example 15)

[0555] First process

[0556] In the fifth step of Example 2, N-methylaniline was used instead of 4-(methylamino)toluene, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (73) in 90% yield.

[0557]

[0558] Second process

[0559] In the second step of Example 6, 4-bromo-3'-methyl-4'-methoxybenzophenone was used instead of 3,4-dimethoxybenzophenone, iodobutane was used instead of 1-bromo-4-fluorobutane, and propargyl alcohol of the aforementioned formula (73) was used instead of propargyl alcohol of the aforementioned formula (52). The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (74) was obtained in a yield of 76%.

[0560]

[0561] Third process

[0562] 3.34 g (4.3 mmol) of the aforementioned formula (74) was dissolved in 35 mL of THF and cooled to an internal temperature of -78 °C. While maintaining below -70 °C, 3.3 mL of n-BuLi (1.6 mol / L hexane solution) was slowly added dropwise. After confirming that the raw material was consumed, 1.5 g (6.5 mmol) of diphenylmethylchlorosilane dissolved in 10 mL of THF was slowly added dropwise while maintaining below -70 °C. After the addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, 50 mL of water and 50 mL of toluene were added, and the mixture was separated. The water was washed repeatedly 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, thereby obtaining the photochromic compound shown in the following formula (75) in 48% yield.

[0563]

[0564] The elemental analysis values ​​of the photochromic compound shown in formula (75) are C: 84.59%, H: 7.11%, and N: 1.55%, which are similar to C. 63 H 63 The calculated values ​​of NO2Si, namely C: 84.61%, H: 7.10%, and N: 1.57%, are largely consistent.

[0565] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl and butyl 30H in the vicinity of δ0.5–3.0 ppm, peaks based on methoxy 30H in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0566] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0567] (Example 16)

[0568] First process

[0569] In the fourth step of Example 1, 4-bromo-3'-methyl-4'-methoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner otherwise, to obtain propargyl alcohol as shown in the following formula (76) in 88% yield.

[0570]

[0571] Second process

[0572] In the first step of Example 2, (4-methoxyphenyl)[(4-trifluoromethoxy)phenyl] methyl ketone was used instead of 4-bromo-4'-methoxybenzophenone, and in the fifth step, propargyl alcohol of the aforementioned formula (76) was used instead of propargyl alcohol of the aforementioned formula (44). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (77) in 78% yield.

[0573]

[0574] The elemental analysis values ​​of the photochromic compound shown in formula (77) are C: 77.08%, H: 6.21%, and N: 1.71%, which are similar to C. 52 H 50 The calculated values ​​of F3NO4, namely C: 77.11%, H: 6.22%, and N: 1.73%, are largely consistent.

[0575] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on 24H of methyl and 4,4-diethylcyclohexyl groups in the vicinity of δ0.5–3.0 ppm, a peak based on 6H of methoxy groups in the vicinity of δ3.0–5.0 ppm, and a peak based on 20H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0576] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0577] (Example 17)

[0578] First process

[0579] In the first step of Example 1, 3-bromo-4-methyl-4'-methylbenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the third step, 4-methoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid; in the fifth step, propargyl alcohol of the aforementioned formula (58) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, iodoethane was used instead of iodomethane. All other steps were carried out in the same manner to obtain the photochromic compound shown in the following formula (78) in a yield of 70%.

[0580]

[0581] The elemental analysis values ​​of the photochromic compound shown in formula (78) are C: 79.66%, H: 6.20%, N: 1.66%, which are similar to C. 56 H 52 The calculated values ​​of F3NO3, namely C: 79.69%, H: 6.21%, and N: 1.66%, are largely consistent.

[0582] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 23H of methyl, ethyl, 1,1,1-trifluoroethyl, and propoxy in the vicinity of δ0.5–3.0 ppm, peaks based on 5H of methoxy and propoxy in the vicinity of δ3.0–5.0 ppm, and peaks based on 24H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

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

[0584] (Example 18)

[0585] First process

[0586] In the first step of Example 1, 3-bromo-4-methylbenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the third step, 4-methylphenylboronic acid was used instead of 4-morpholinophenylboronic acid; in the fifth step, propargyl alcohol of the aforementioned formula (49) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, 1-iodo-2-methoxyethane was used instead of iodomethane. All other steps were carried out in the same manner to obtain the photochromic compound shown in the following formula (79) in a yield of 76%.

[0587]

[0588] The elemental analysis values ​​of the photochromic compound shown in formula (79) are C: 85.12%, H: 7.04%, and N: 1.77%, which are similar to C. 56 H 55 The calculated values ​​for NO3, namely C: 85.13%, H: 7.02%, and N: 1.77%, are largely consistent.

[0589] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on 20H of methyl, propyl, and 2-methoxyethyl protons in the vicinity of δ0.5–3.0 ppm, a peak based on 10H of 2-methoxyethyl protons in the vicinity of δ3.0–5.0 ppm, and a peak based on 25H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0590] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0591] (Example 19)

[0592] In the third step of Example 1, 2,4-dimethoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid; in the fifth step, propargyl alcohol of the aforementioned formula (73) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, iodopropane was used instead of iodomethane. All other steps were carried out in the same manner to obtain the photochromic compound shown in the following formula (80) in a yield of 72%.

[0593]

[0594] The elemental analysis values ​​of the photochromic compound shown in formula (80) are C: 83.39%, H: 6.75%, and N: 1.78%, which are similar to C. 55 H 53 The calculated values ​​for NO4, namely C: 83.41%, H: 6.74%, and N: 1.77%, are largely consistent.

[0595] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on methyl and propyl 20H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy 9H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 24H in the vicinity of δ5.0–9.0 ppm.

[0596] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0597] (Example 20)

[0598] In the second step of Example 13, 1-iodo-3-methoxypropane was used instead of 1,1,1-trifluoro-4-iodobutane, propargyl alcohol of the aforementioned formula (70) was used instead of propargyl alcohol of the aforementioned formula (67), and 4-tert-butylphenylboronic acid was used instead of 4-trifluoromethylphenylboronic acid in the third step. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (81) in 75% yield.

[0599]

[0600] The elemental analysis values ​​of the photochromic compound shown in formula (81) are C: 78.32%, H: 7.00%, and N: 1.44%, which are similar to C. 63 H 67 The calculated values ​​for NO8, namely C: 78.31%, H: 6.99%, and N: 1.45%, are largely consistent.

[0601] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on 19H of tert-butyl, 3-methoxypropyl, and 2-methoxyethyl in the vicinity of δ0.5–3.0 ppm, a peak based on 25H of methoxy, 3-methoxypropyl, 2-methoxyethyl, and ethylenedioxy in the vicinity of δ3.0–5.0 ppm, and a peak based on 23H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0602] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0603] (Example 21)

[0604] First process

[0605] In the second step of Example 11, propargyl alcohol of the aforementioned formula (54) was used instead of propargyl alcohol of the aforementioned formula (63), and iodobutane was used instead of 1-bromo-4-methoxybutane. Otherwise, the reaction was carried out in the same manner to synthesize the photochromic compound shown in the following formula (82).

[0606]

[0607] Second process

[0608] In the third step of Example 1, the photochromic compound of the aforementioned formula (82) was used instead of the naphthol derivative of the aforementioned formula (32), and 4-isopropoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (83) in a yield of 89%.

[0609]

[0610] The elemental analysis values ​​of the photochromic compound shown in formula (83) are C: 81.77%, H: 6.85%, and N: 1.64%, which are similar to C. 58 H 58 The calculated values ​​of FNO4, namely C: 81.75%, H: 6.86%, and N: 1.64%, are largely consistent.

[0611] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 27H based on butyl, methyl, and isopropoxy in the vicinity of δ0.5–3.0 ppm, a peak of 7H based on methoxy and isopropoxy in the vicinity of δ3.0–5.0 ppm, and a peak of 24H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0612] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0613] (Example 22)

[0614] First process

[0615] In the third step of Example 2, 4-heptanone was used instead of 4,4-diethylcyclohexanone, and in the sixth step, propargyl alcohol of the aforementioned formula (73) was used instead of propargyl alcohol of the aforementioned formula (44). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (84) in a yield of 86%.

[0616]

[0617] The elemental analysis values ​​of the photochromic compound shown in formula (84) are C: 86.08%, H: 6.61%, and N: 3.41%, which are similar to C. 59 H 54 The calculated values ​​of N2O2, namely C: 86.10%, H: 6.61%, and N: 3.40%, are largely consistent.

[0618] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on methyl and propyl 20H in the vicinity of δ0.5–3.0 ppm, a peak based on methoxy 3H in the vicinity of δ3.0–5.0 ppm, and a peak based on aromatic protons and olefin protons 31H in the vicinity of δ5.0–9.0 ppm.

[0619] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0620] (Example 23)

[0621] In the third step of Example 1, 4-diphenylaminophenylboronic acid was used instead of 4-morpholinophenylboronic acid; in the fifth step, propargyl alcohol of the aforementioned formula (67) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, 1-iodo-2-methoxyethane was used instead of iodomethane. The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (85) was obtained in a yield of 71%.

[0622]

[0623] The elemental analysis values ​​of the photochromic compound shown in formula (85) are C: 83.33%, H: 5.98%, and N: 2.76%, which are similar to C. 70 H 60 The calculated values ​​of N2O5, namely C: 83.31%, H: 5.99%, and N: 2.78%, are largely consistent.

[0624] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak based on 7H of methyl and 2-methoxyethyl in the vicinity of δ0.5–3.0 ppm, a peak based on 13H of methoxy and 2-methoxyethyl in the vicinity of δ3.0–5.0 ppm, and a peak based on 40H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0625] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0626] (Example 24)

[0627] In the third step of Example 1, 4-methylphenylaminophenylboronic acid was used instead of 4-morpholinophenylboronic acid; in the fifth step, propargyl alcohol of the aforementioned formula (73) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, iodopropane was used instead of iodomethane. All other steps were carried out in the same manner to obtain the photochromic compound shown in the following formula (86) in a yield of 77%.

[0628]

[0629] The elemental analysis values ​​of the photochromic compound shown in formula (86) are C: 86.09%, H: 6.75%, and N: 3.33%, which are similar to C. 60 H 56 The calculated values ​​of N2O2, namely C: 86.09%, H: 6.74%, and N: 3.35%, are largely consistent.

[0630] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 23H peak based on methyl and propyl groups in the vicinity of δ0.5–3.0 ppm, a 3H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 30H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0631] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0632] (Example 25)

[0633] First process

[0634] In the fourth step of Example 1, N-ethyl-4-methoxyaniline was used instead of N-methylaniline, and the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (87) in 89% yield.

[0635]

[0636] Second process

[0637] In the fifth step of Example 1, propargyl alcohol of formula (87) was used instead of propargyl alcohol of formula (35), and the reaction was carried out in the same manner to obtain the photochromic compound of formula (88) in 81% yield.

[0638]

[0639] The elemental analysis values ​​of the photochromic compound shown in formula (88) are C: 80.44%, H: 6.38%, and N: 3.42%, which are similar to C. 55 H 52 The calculated values ​​of N2O5, namely C: 80.46%, H: 6.38%, and N: 3.41%, are largely consistent.

[0640] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on methyl, ethyl, and morpholino groups of 15H in the vicinity of δ0.5–3.0 ppm, peaks based on methoxy and morpholino groups of 13H in the vicinity of δ3.0–5.0 ppm, and peaks based on aromatic protons and olefin protons of 24H in the vicinity of δ5.0–9.0 ppm.

[0641] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0642] (Physical property evaluation of photochromic plastic lenses produced by coating method)

[0643] (Example 26)

[0644] (Preparation of Curable Compositions)

[0645] First, the photochromic compound, photopolymerization initiator, and polymerizable compound obtained in Example 1 above are mixed to obtain a curable composition.

[0646] As a polymerizable compound, a polymerizable compound is used that is formulated by combining the following free radical polymerizable monomers.

[0647] Polyethylene glycol dimethacrylate (average molecular weight 736): 42 parts by weight

[0648] Polyethylene glycol dimethacrylate (average molecular weight 536): 12 parts by weight

[0649] Trimethylolpropane trimethacrylate: 38 parts by weight

[0650] γ-Methacryloxypropyltrimethoxysilane: 2 parts by weight

[0651] Glycidyl methacrylate: 1 part by weight

[0652] It should be noted that when the total amount of free radical polymerizable monomers in the curable composition is set to 100g, the photochromic compound is added in a manner that results in 0.25mmol.

[0653] The following additives are used as additives.

[0654] Phenylenol bis(2,4,6-trimethylbenzoyl)phosphine oxide (photopolymerization initiator: Omnirad 819): 0.3 parts by weight

[0655] Ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (stabilizer, Irganox 245): 1 part by weight

[0656] bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate: 3 parts by weight

[0657] Dow-Toray Corporation Leveling agent (L7001): 0.1 parts by weight

[0658] 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.

[0659] (Manufacturing of optical items)

[0660] Using this curable composition, polymerization is carried out as follows to obtain a photochromic laminate based on a lamination method.

[0661] 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.

[0662] 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 application at 1000 rpm for 10 seconds. Then, approximately 2 g of the aforementioned photochromic curing composition was spin-coated at a speed of 60 rpm for 40 seconds, followed by application at 600 rpm for 10–20 seconds, to achieve a photochromic coating thickness of 40 μm.

[0663] 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.

[0664] (Examples 27-50)

[0665] Photochromic laminates were prepared using the photochromic compounds obtained in Examples 2-25, following the same method as in Example 26.

[0666] (Comparative Examples 1-8)

[0667] Using the photochromic compounds shown in formulas (A) to (H) below, each photochromic laminate was obtained in the same manner as in Example 26.

[0668]

[0669]

[0670]

[0671]

[0672] (Synthesis of compound A)

[0673] In Example 1, 4-dimethylamino-4'-methoxybenzophenone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0674] (Synthesis of compound B)

[0675] In Example 1, 4-diphenylamino-4'-methoxybenzophenone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0676] (Synthesis of compound C)

[0677] In Example 1, [4-(9H-carbazole-9-yl)phenyl]-(4-methoxyphenyl)methyl ketone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0678] (Synthesis of compound D)

[0679] In Example 1, 4-phenoxy-4'-methoxybenzophenone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0680] (Synthesis of compound E)

[0681] In Example 1, (4-methoxyphenyl)-(4-phenylthiophenyl) methyl ketone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0682] (Synthesis of compound F)

[0683] In Example 1, (4-methoxyphenyl)-[(4-morpholin-1-yl)phenyl] ketone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0684] (Synthesis of compound G)

[0685] In Example 1, (4-methoxyphenyl)-[(4-piperidin-1-yl)phenyl] ketone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0686] (Synthesis of compound H)

[0687] In Example 1, 4-methoxy-4'-methylbenzophenone was used instead of the benzophenone of the aforementioned formula (34), and the reaction was carried out in the same manner otherwise.

[0688] <Evaluation Methods>

[0689] The obtained photochromic laminate was evaluated using the method shown below.

[0690] (1) Photochromic properties

[0691] [1] Maximum absorption wavelength (λmax):

[0692] The maximum absorption wavelength after color development, determined by a spectrophotometer (MCPD3000 instantaneous multichannel photodetector) manufactured by OTSUKAELECTRONICS CO.,LTD, is set as the index of hue during color development.

[0693] [2] Colorimetric concentration at 23℃ (A) 23 ):

[0694] The difference between the absorbance {ε(300)} after 300 seconds of light irradiation at 23°C at the maximum absorption wavelength and the absorbance ε(0) before irradiation is set as an index of colorimetric concentration. The higher this value, the better the photochromic property.

[0695] [3] Fading half-life at 23℃ [τ1 / 2(sec.)]:

[0696] The time required for the absorbance of the sample at its maximum absorption wavelength to decrease to half of {ε(300)-ε(0)} after 300 seconds of light irradiation at 23°C and then stopping the light irradiation is defined as the fading rate. The shorter this time, the faster the fading rate.

[0697] [4] Survival rate (A 120 / A0×100):

[0698] The obtained photochromic plastic lenses were subjected to 120 hours of accelerated degradation using a Suga Test Instruments Co., Ltd. X25 xenon weathering apparatus. Then, the colorimetric concentration was evaluated before and after the test, measuring the colorimetric concentration before the test (A0) and the colorimetric concentration after the test (A...). 120 ), and the ratio (A) 120 / A0) is used as the retention rate, which is set as an indicator of color development durability. The higher the retention rate, the higher the color development durability.

[0699] The results of Examples 26, 50, and Comparative Examples 1 to 8 are summarized in Table 1, and the results of Examples 27 to 49 are summarized in Tables 2 to 3.

[0700] [Table 1]

[0701] Table 1

[0702]

[0703] [Table 2]

[0704] Table 2

[0705]

[0706] [Table 3]

[0707] Table 3

[0708]

[0709] Example 51

[0710] First process

[0711] In the first step of Example 1, (3,4-dimethoxyphenyl)-[4-(trifluoromethyl)phenyl] ketone was used instead of 3-bromo-4-methoxybenzophenone, and in the sixth step, 13-bromo-2,5,8,11-tetraoxatridecane was used instead of iodomethane. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (89) in 61% yield.

[0712]

[0713] The elemental analysis values ​​of the photochromic compound shown in formula (89) are C: 68.70%, H: 6.61%, and N: 1.31%, which are similar to C. 61 H 70 F3NO 12 The calculated values, namely C: 68.72%, H: 6.62%, and N: 1.31%, are largely consistent.

[0714] In addition, proton NMR spectra were measured, and the results showed a 7H peak based on methyl, 2,5,8,11-tetraoxatridecyl in the vicinity of δ0.5–3.0 ppm, a 43H peak based on methoxy, 2,5,8,11-tetraoxatridecyl in the vicinity of δ3.0–5.0 ppm, and a 20H peak based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0715] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0716] Example 52

[0717] First process

[0718] Using the method described in Patent Document 8, benzophenone of the following formula (90) was obtained by reacting 4-bromobenzoyl chloride with 2,2-dimethyl-1,3-benzenedithiol, except that the reaction was carried out in the same manner as in Example 2 to synthesize a carboxylic acid compound of the following formula (91).

[0719]

[0720] Second process

[0721] In the third step of Example 1, the compound of the aforementioned formula (91) was used instead of the compound of the aforementioned formula (32), and (2,3,4-trifluorophenyl)boronic acid was used instead of 4-morpholinophenylboronic acid. Otherwise, the reaction was carried out in the same manner to synthesize the carboxylic acid compound of the following formula (92) in 91% yield.

[0722]

[0723] Third process

[0724] In the second step of Example 2, the compound of the aforementioned formula (92) was used instead of the compound of the aforementioned formula (39). In the third step, cyclododecane was used instead of 4,4-diethylcyclohexanone. In the fifth step, propargyl alcohol of the aforementioned formula (35) was used instead of propargyl alcohol of the aforementioned formula (44). The reaction was carried out in the same manner otherwise, and the photochromic compound of the following formula (93) was obtained in a yield of 56%.

[0725]

[0726] The elemental analysis values ​​of the photochromic compound shown in formula (93) are C: 76.30%, H: 5.96%, N: 1.47%, S: 6.80%, which are similar to C. 60 H 56 The calculated values ​​of F3NO2S2, namely C: 76.32%, H: 5.98%, N: 1.48%, and S: 6.79%, are largely consistent.

[0727] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 31H peak based on methyl and cyclododecane ring groups in the vicinity of δ0.5–3.0 ppm, a 3H peak based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a 22H peak based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[0728] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0729] Example 53

[0730] First process

[0731] In the fifth step of Example 1, the naphthol compound of formula (32) was used instead of the naphthol compound of formula (33), and the propargyl alcohol of formula (54) was used instead of the propargyl alcohol of formula (35). Otherwise, the reaction was carried out in the same manner. In the sixth step, 1-(2-iodoethoxy)butane was used instead of iodomethane. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of formula (94) in 64% yield.

[0732]

[0733] Second process

[0734] Referring to the method described in Patent Document 11, the photochromic compound of the aforementioned formula (94) was reacted with benzamide. After the reaction, the compound was purified by silica gel-based chromatography, thereby obtaining the photochromic compound of the following formula (95) in 64% yield.

[0735]

[0736] The elemental analysis values ​​of the photochromic compound shown in formula (95) are C: 77.88%, H: 6.65%, and N: 3.02%, which are similar to C. 60 H 61 The calculated values ​​of FN2O6, namely C: 77.90%, H: 6.65%, and N: 3.03%, are largely consistent.

[0737] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 21H based on methyl and ethyl butoxy groups in the vicinity of δ0.5–3.0 ppm, a peak of 15H based on methoxy, ethyl butoxy, and amide groups in the vicinity of δ3.0–5.0 ppm, and a peak of 25H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0738] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0739] Example 54

[0740] First process

[0741] In the first step of Example 12, 3-bromo-4-methoxy-4'-methoxybenzophenone was used instead of 3-bromo-4-methoxy-4'-methylbenzophenone, 4-thiomorpholinophenylboronic acid was used instead of 2,4,6-trimethoxyphenylboronic acid, and 1,1,1-trifluoro-3-iodopropane was used instead of 1-bromo-3-methylthiopropane. The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (96) was obtained in 55% yield.

[0742]

[0743] The elemental analysis values ​​of the photochromic compound shown in formula (96) are C: 70.55%, H: 5.30%, N: 2.85%, S: 3.24%, which are similar to C. 58 H 52 The calculated values ​​of F6N2O4S, namely C: 70.57%, H: 5.31%, N: 2.84%, and S: 3.25%, are largely consistent.

[0744] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 19H of methyl, 1,1,1-trifluoropropyl, and thiomorpholino groups in the vicinity of δ0.5–3.0 ppm, peaks based on 9H of methoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks based on 24H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0745] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0746] Example 55

[0747] First process

[0748] 27.7 g (100.1 mmol) of (4-chlorophenyl)[4-(2-hydroxyethoxy)phenyl] ketone and 15.0 g (220.2 mmol) of imidazole were dissolved in 200 mL of dimethylformamide, and the internal temperature was cooled to 2°C. While maintaining the internal temperature below 5°C, 80 mL of dimethylformamide containing 16.6 g (110.1 mmol) of tert-butyldimethylchlorosilane was added dropwise. After stirring below 5°C until the raw materials were consumed, 300 mL of toluene and 150 mL of water were added, and the mixture was separated. 300 mL of water was added, and the separation was repeated twice. The resulting organic layer was concentrated and purified by silica gel-based chromatography, thereby giving the benzophenone compound shown in formula (97) in 94% yield.

[0749]

[0750] Second process

[0751] In the fourth step of Example 1, the compound of the aforementioned formula (97) was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner to obtain propargyl alcohol of the following formula (98) in 80% yield.

[0752]

[0753] Third process

[0754] In the first step of Example 2, 3-bromo-4-methoxy-4'-methylbenzophenone was used instead of 3-bromo-4-methoxybenzophenone, and benzomorpholine was used instead of diphenylamine. In the third step, diethyl ketone was used instead of diethylcyclohexanone. In the fifth step, propargyl alcohol of the aforementioned formula (98) was used instead of propargyl alcohol of the aforementioned formula (44). The reaction was carried out in the same manner otherwise, and the compound shown in the following formula (99) was obtained in a yield of 58%.

[0755]

[0756] Fourth process

[0757] 4.88 g (5.3 mmol) of the compound of formula (99) was dissolved in 25 mL of THF, and the internal temperature was cooled to 3 degrees Celsius. 6 mL of tetrabutylammonium fluoride (1.0 mol / L THF solution) was added dropwise. The mixture was stirred at an internal temperature below 5 degrees Celsius. After confirming that the raw material was consumed, 20 mL of water and 20 mL of toluene were added, and the mixture was separated. This separation process was repeated until the pH of the aqueous layer reached approximately 7. The resulting organic layer was concentrated and purified by silica gel-based chromatography, thereby yielding the compound of formula (100) in 97% yield.

[0758]

[0759] Fifth process

[0760] Referring to the method described in Patent Document 12, a compound of formula (101) synthesized from polytetramethylene glycol with a number average molecular weight of 1000 is reacted with a compound of formula (100) to obtain a photochromic compound of formula (102) in a yield of 79%.

[0761]

[0762]

[0763] The proton nuclear magnetic resonance spectrum of the photochromic compound represented by the aforementioned formula (102) was measured. The results showed a peak of about 100H based on methyl, ethyl, benzomorpholino, succinic acid, and polytetramethylene glycol chain groups in the vicinity of δ0.5 to 3.0 ppm, a peak of about 74H based on methoxy, ethylene glycol, polytetramethylene glycol chain groups, and benzomorpholino in the vicinity of δ3.0 to 5.0 ppm, and a peak of 48H based on aromatic protons and olefin protons in the vicinity of δ5.0 to 9.0 ppm.

[0764] Example 56

[0765] First process

[0766] In the first step of Example 55, (4-chlorophenyl)[4-(2-hydroxyethyl)phenyl] methyl ketone was used instead of (4-chlorophenyl)[4-(2-hydroxyethoxy)phenyl] methyl ketone, and in the second step, 4-methoxy-N-methylaniline was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to obtain propargyl alcohol as shown in the following formula (103).

[0767]

[0768] Second process

[0769] In Example 3, (4-methoxyphenyl)(4-phenoxyphenyl) methyl ketone was used instead of 4,4'-dimethoxybenzophenone, 1-iodo-3-methoxypropane was used instead of iodopropane, and propargyl alcohol of the aforementioned formula (103) was used instead of propargyl alcohol of the aforementioned formula (35). The reaction was carried out in the same manner otherwise, and the compound shown in the following formula (104) was obtained in 75% yield.

[0770]

[0771] Third process

[0772] In the fourth step of Example 55, the compound of the aforementioned formula (104) was used instead of the compound of the aforementioned formula (99). In the fifth step, polypropylene glycol monobutyl ether with a number average molecular weight of 1250 was used instead of polytetramethylene glycol with a number average molecular weight of 1000. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (105) in a yield of 81%.

[0773]

[0774] The proton nuclear magnetic resonance spectrum of the photochromic compound represented by the aforementioned formula (105) was measured. The results showed a peak of about 84H based on methyl, 3-methoxypropyl, ethyl, succinic acid group, polypropylene glycol chain group, and butyl group in the vicinity of δ0.5 to 3.0 ppm, a peak of about 80H based on methoxy, 3-methoxypropyl, ethoxy, polypropylene glycol chain group, and butoxy group in the vicinity of δ3.0 to 5.0 ppm, and a peak of 25H based on aromatic protons and olefin protons in the vicinity of δ5.0 to 9.0 ppm.

[0775] Example 57

[0776] First process

[0777] The following formula (106) was obtained by reacting 2-bromoanisole with 4-trifluoromethoxybenzoyl chloride using the method described in Reference Patent Document 8. Otherwise, the reaction was carried out in the same manner as in Example 1 to synthesize the naphthol derivative shown in the following formula (107).

[0778]

[0779] Second process

[0780] In the fifth step of Example 1, the compound of formula (107) was used instead of the compound of formula (33), and propargyl alcohol of formula (108) was used instead of propargyl alcohol of formula (35). In the sixth step of Example 1, iodopropane was used instead of iodomethane. Otherwise, the reaction was carried out in the same manner to obtain the compound of formula (109) in a yield of 54%.

[0781]

[0782]

[0783] Third process

[0784] By referring to the method described in Patent Document 10, the compound of the aforementioned formula (109) was reacted with 2,6-dimethylbenzenethiol to obtain the compound of the following formula (110) in 88% yield.

[0785]

[0786] The elemental analysis values ​​of the photochromic compound shown in formula (110) are C: 74.25%, H: 5.88%, N: 1.51%, S: 3.46%, which are similar to C. 57 H 54 The calculated values ​​of F3NO5S, namely C: 74.24%, H: 5.90%, N: 1.52%, and S: 3.48%, are largely consistent.

[0787] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 23H based on methyl and propyl groups in the vicinity of δ0.5–3.0 ppm, a peak of 9H based on methoxy groups in the vicinity of δ3.0–5.0 ppm, and a peak of 22H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0788] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0789] Example 58

[0790] First process

[0791] In the first step of Example 57, 4-phenylbenzoyl chloride was used instead of 4-trifluoromethoxybenzoyl chloride, and the reaction was carried out in the same manner to synthesize the naphthol derivative shown in the following formula (111).

[0792]

[0793] Second process

[0794] In the fourth step of Example 1, (4-bromophenyl)[4-[2-(2-methoxyethoxy)ethoxy]phenyl]methyl ketone was used instead of 4-bromo-4'-methoxybenzophenone, propargyl alcohol of the synthesized formula (112) was used instead of propargyl alcohol of the aforementioned formula (108), and 1-bromo-4-methoxybutane was used instead of iodopropane. Otherwise, the reaction was carried out in the same manner, and the compound shown in formula (113) was obtained in a yield of 59%.

[0795]

[0796]

[0797] Third process

[0798] In the first step of Example 2, the compound of the aforementioned formula (113) was used instead of the compound of the aforementioned formula (38), and thiomorpholine 1,1-dioxide was used instead of diphenylamine. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (114) in a yield of 72%.

[0799]

[0800] The elemental analysis values ​​of the photochromic compound shown in formula (114) are C: 73.85%, H: 6.84%, N: 2.66%, S: 3.01%, which are similar to C. 65 H 72 The calculated values ​​of N2O9S, namely C: 73.84%, H: 6.86%, N: 2.65%, and S: 3.03%, are largely consistent.

[0801] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 19H based on methyl, 4-methoxybutyl, and thiomorpholine 1,1-dioxide in the vicinity of δ0.5–3.0 ppm, a peak of 28H based on methoxy, 4-methoxybutyl, thiomorpholine 1,1-dioxide, and 2-(2-methoxyethoxy)ethoxy in the vicinity of δ3.0–5.0 ppm, and a peak of 25H based on aromatic protons and alkene protons in the vicinity of δ5.0–9.0 ppm.

[0802] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0803] Example 59

[0804] First process

[0805] In the second step of Example 57, propargyl alcohol of the aforementioned formula (98) was used instead of propargyl alcohol of the aforementioned formula (108), and 1,1,1-trifluoro-3-iodopropane was used instead of iodopropane. Otherwise, the reaction was carried out in the same manner to obtain the compound shown in the following formula (115) in a yield of 63%.

[0806]

[0807] Second process

[0808] In the third step of Example 1, the compound of the aforementioned formula (32) was used instead of the compound of the aforementioned formula (115), and 2,4-dimethoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid. Otherwise, the reaction was carried out in the same manner to obtain the compound of the following formula (116) in 91% yield.

[0809]

[0810] Third process

[0811] In the fourth step of Example 55, the compound of the aforementioned formula (99) was used instead of the compound of the aforementioned formula (116), and in the fifth step, sebacate chloride was used instead of the compound of the aforementioned formula (101). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (117) in a yield of 89%.

[0812]

[0813] The elemental analysis values ​​of the photochromic compound shown in formula (117) are C: 66.88%, H: 4.96%, and N: 1.25%, which are similar to C. 124 H 110 F 18 N2O 16 The calculated values, namely C: 66.90%, H: 4.98%, and N: 1.26%, are largely consistent.

[0814] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 38H based on methyl, 1,1,1-trifluoropropyl, and sebacate groups in the vicinity of δ0.5–3.0 ppm, a peak of 26H based on methoxy and ethylene glycol groups in the vicinity of δ3.0–5.0 ppm, and a peak of 46H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0815] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0816] Example 60

[0817] First process

[0818] In the first step of Example 57, 4-trifluoromethylbenzoyl chloride was used instead of 4-trifluoromethoxybenzoyl chloride, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (118) in 86% yield.

[0819]

[0820] Second process

[0821] In the first step of Example 2, the compound of formula (118) was used instead of 3-bromo-4-methoxybenzophenone, and N-methylaniline was used instead of diphenylamine. In the third step, 4,4-dimethylcyclohexanone was used instead of 4,4-diethylcyclohexanone, and propargyl alcohol of formula (103) was used instead of propargyl alcohol of formula (44). Otherwise, the reaction was carried out in the same manner to synthesize the compound shown in formula (119).

[0822]

[0823] Third process

[0824] In the fourth step of Example 55, the compound of the aforementioned formula (119) was used instead of the compound of the aforementioned formula (99), and the reaction was carried out in the same manner to synthesize the compound of the following formula (120) in 92% yield.

[0825]

[0826] Fourth process

[0827] In the first step of Example 55, the compound of the aforementioned formula (120) was used instead of (4-chlorophenyl)[4-(2-hydroxyethoxy)phenyl] methyl ketone, and [tris(trimethylsiloxy)silylethyl]dimethylchlorosilane was used instead of tert-butyldimethylchlorosilane. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound of the following formula (121) in 92% yield.

[0828]

[0829] The elemental analysis values ​​of the photochromic compound shown in formula (121) are C: 66.50%, H: 7.17%, and N: 2.22%, which are similar to C. 71 H 91 The calculated values ​​of F3N2O7Si5, namely C: 66.52%, H: 7.16%, and N: 2.19%, are largely consistent.

[0830] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a 59H peak based on methyl, [tris(trimethylsiloxy)silylethyl]silyl, and 4,4-dimethylcyclohexyl groups near δ0.5–3.0 ppm, an 8H peak based on methoxy and ethoxysilyl groups near δ3.0–5.0 ppm, and a 24H peak based on aromatic protons and olefin protons near δ5.0–9.0 ppm.

[0831] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0832] Example 61

[0833] In the first step of Example 2, 3-methoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the third step, 3,3,5,5,-tetramethylcyclohexanone was used instead of 4,4-diethylcyclohexanone; and in the fifth step, propargyl alcohol of the aforementioned formula (49) was used instead of propargyl alcohol of the aforementioned formula (44). The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (122) was obtained in a yield of 67%.

[0834]

[0835] The elemental analysis values ​​of the photochromic compound shown in formula (122) are C: 86.27%, H: 7.08%, and N: 2.03%, which are similar to C. 50 H 49 The calculated values ​​for NO2, namely C: 86.29%, H: 7.10%, and N: 2.01%, are largely consistent.

[0836] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed peaks based on 24H of methyl, propyl, and cyclooctyl groups in the vicinity of δ0.5–3.0 ppm, peaks based on 3H of methoxy groups in the vicinity of δ3.0–5.0 ppm, and peaks based on 22H of aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0837] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0838] Example 62

[0839] First process

[0840] In the fourth step of Example 1, (4-bromophenyl)(2,3-dihydro-5-benzofuranyl) methyl ketone was used instead of 4-bromo-4'-methoxybenzophenone, and the reaction was carried out in the same manner to give propargyl alcohol as shown in the following formula (123) in 79% yield.

[0841]

[0842] Second process

[0843] In the first step of Example 1, 4-bromo-3-methoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone; in the third step, 2,4-dimethoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid; in the fifth step, propargyl alcohol of the aforementioned formula (123) was used instead of propargyl alcohol of the aforementioned formula (35); and in the sixth step, 1-bromo-4-methoxybutane was used instead of iodomethane. The reaction was carried out in the same manner otherwise, and the photochromic compound shown in the following formula (124) was obtained in a yield of 52%.

[0844]

[0845] The elemental analysis values ​​of the photochromic compound shown in formula (124) are C: 79.36%, H: 6.77%, and N: 1.52%, which are similar to C. 60 H 61 The calculated values ​​for NO7, namely C: 79.35%, H: 6.77%, and N: 1.54%, are largely consistent.

[0846] In addition, proton nuclear magnetic resonance spectra were measured, and the results showed a peak of 17H based on methyl, 4-methoxybutyl, and dihydrobenzofuranyl in the vicinity of δ0.5–3.0 ppm, a peak of 21H based on methoxy, 4-methoxybutyl, and dihydrobenzofuranyl in the vicinity of δ3.0–5.0 ppm, and a peak of 23H based on aromatic protons and olefin protons in the vicinity of δ5.0–9.0 ppm.

[0847] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons in the vicinity of δ110–160 ppm, peaks for olefin-based carbons in the vicinity of δ80–140 ppm, and peaks for alkyl-based carbons in the vicinity of δ20–60 ppm.

[0848] (Examples 63-74)

[0849] Property Evaluation of Photochromic Plastic Lenses Fabricated by Coating Method

[0850] Using the same method as in Example 26, the photochromic composites of Examples 51-62 were prepared to produce the photochromic laminates of Examples 63-74.

[0851] It should be noted that in Examples 67 and 71, which used Example 55 (the compound of formula (101) above) and Example 59 (the compound of formula (117) above), when the total amount of free radical polymerizable monomer was set to 100 g, the photochromic compound was added in a manner that resulted in 0.125 mmol. The results are shown in Table 4.

[0852] [Table 4]

[0853] Table 4

[0854]

[0855] <Property Evaluation of Photochromic Layers Fabricated Using Adhesive Method>

[0856] (Example 75)

[0857] The adhesive sheet is fabricated using the following method. The adhesive sheet comprises, in sequence, a first optical sheet, a first adhesive layer, a photochromic layer, a second adhesive layer, and a second optical sheet. A polycarbonate sheet with a thickness of 400 μm is used as both the first and second optical sheets.

[0858] (Preparation of the composition for forming a photochromic layer)

[0859] In a 2L four-necked flask equipped with a stirring blade, condenser, thermometer, and nitrogen inlet, 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 approximately 0°C and dissolved in 205 parts by mass of tert-butanol and 382 parts by mass of diethyl ketone, and the solution 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 continued 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.

[0860] 100 parts by weight of the obtained terminal non-reactive urethane resin solution, 6.3 parts by weight of the photochromic compound of Example 1 (formula (28) 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 DOW CORNING TORAY L-7001 as a surfactant were added and stirred and mixed at room temperature to obtain a composition for forming a photochromic layer.

[0861] In addition, a photochromic compound is added in a manner that yields 0.25 mmol per 100 parts by weight of terminal non-reactive urethane resin.

[0862] (Preparation of the adhesive layer composition)

[0863] A 5L separable flask (4-necked) equipped with a stirrer, condenser, thermometer, and nitrogen inlet 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 mixture was reacted at 110°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer with isocyanate-terminated ends. After the urethane prepolymer reaction was complete, the reaction solution was cooled to approximately 20°C and dissolved in 2500 parts by mass of propylene glycol-monomethyl ether, maintaining the temperature at 20°C. Next, 60 parts by mass of isophorone diamine, acting as a chain extender, were added dropwise, and the reaction was continued at 20°C for 1 hour. Then, 3 parts by mass of n-butylamine were further added dropwise, and the reaction was continued at 20°C for 1 hour, thereby obtaining a propylene glycol-monomethyl ether solution of a terminally non-reactive urethane urea resin.

[0864] Add 0.2 parts by mass of DOW CORNING TORAY 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.

[0865] (Manufacturing of adhesive sheets)

[0866] 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.

[0867] 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 26. The results are shown in Table 4.

[0868] (Examples 76-83, Comparative Examples 9-13)

[0869] Adhesive sheets were prepared using the photochromic compounds shown in Table 5, following the same method as in Example 50.

[0870] [Table 5]

[0871] Table 5

[0872]

[0873] <Physical Property Evaluation of Photochromic Cured Products Produced by Mixing Method>

[0874] (Example 84)

[0875] (Preparation of Curable Compositions)

[0876] First, the photochromic compound, additive, and polymerizable compound obtained in Example 1 are mixed to obtain a curable composition.

[0877] As a polymerizable compound, a polymerizable compound prepared by combining and mixing the following polymerizable monomers is used.

[0878] 1,3-Bis(isocyanate methyl)cyclohexane: 36.7 parts by weight

[0879] Pentaerythritol tetra(3-mercaptopropionate): 39.4 parts by weight

[0880] Polyoxyethylene polyoxypropylene lauryl ether (manufactured by AOKIOIL INDUSTRIAL Co., Ltd., WANDERSURF140): 17.4 parts by weight

[0881] 1-Decanethiol: 2.8 parts by weight

[0882] RX-1 prepared using the method described in Patent Document 13: 3.8 parts by weight

[0883] 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.

[0884] The following additives are used as additives.

[0885] Dimethyltin dichloride: 0.05 parts by weight

[0886] Irganox 245: 0.1 parts by weight

[0887] 2-Ethylhexyl 4-methoxycinnamic acid: 0.6 parts by weight

[0888] (Manufacturing of solidified products)

[0889] 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 26. The results are shown in Table 6.

[0890] (Examples 85-99, Comparative Examples 14-18)

[0891] Photochromic cured products were prepared using the photochromic compounds shown in Tables 6 and 7, in the same manner as in Example 84.

[0892] The results of Examples 84, 85 and Comparative Examples 14-18 are summarized in Table 6, and the results of Examples 86-99 are summarized in Table 7.

[0893] [Table 6]

[0894] Table 6

[0895] [Table 7]

[0896] Table 7

[0897] [1]

[0899] A photochromic compound having the framework shown in formula (1):

[0900]

[0901] In the aforementioned formula (1),

[0902] M is C, Si, or Ge.

[0903] R 3 For aryl or heteroaryl groups substituted with the group shown in formula (1a) below,

[0904]

[0905] In the aforementioned equation (1a),

[0906] 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,

[0907] R 2 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below.

[0908] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[0909] In the aforementioned equation (2a),

[0910] Q 1 It is an alkylene or haloalkylene.

[0911] Q 2 It is an alkylene or haloalkylene.

[0912] Q 3 It is an alkyl or haloalkyl group.

[0913] X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O),

[0914] R 700 and R 701 Each of the following 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.

[0915] a is an integer that is 0, or greater than 1 and less than 3.

[0916] R 4 For substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups,

[0917] Ring A and ring B are independently 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. [2]

[0919] The photochromic compound according to [1] has the skeleton shown in the following formula (2):

[0920]

[0921] In the aforementioned equation (2), M and R 3 and R 4 They have the same meaning as in the aforementioned formula (1). [3]

[0923] The photochromic compound according to [1] or [2] has the skeleton shown in the following formula (3):

[0924]

[0925] In the aforementioned equation (3), M and R 3 and R 4 They have the same meaning as in the aforementioned equation (1),

[0926] R 5 and R 6 Each of the following groups can be independently represented as a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a) above, the group represented by formula (X) below, or the group represented by formula (X3) below.

[0927]

[0928] In formula (X),

[0929] E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group.

[0930] F represents an oxygen atom or a sulfur atom.

[0931] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[0932] g is 0 or 1.

[0933] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[0934] When G is an oxygen atom or a sulfur atom, R 201 Groups other than hydrogen atoms

[0935] L 1 -R 400 (X3)

[0936] In the aforementioned formula (X3),

[0937] 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.

[0938] L 1 The group represented by the following formula (X2)

[0939]

[0940] In the aforementioned equation (X2), R 30 The group is represented by the following formula (X2a).

[0941]

[0942] In the aforementioned equations (X2) and (X2a),

[0943] J is a divalent group, which can be independently a directly attached, substituted, or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group.

[0944] L represents an oxygen atom or a sulfur atom.

[0945] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents.

[0946] R 302 R 303 and R 304 Each is independently an alkylene group.

[0947] h, j, k, and l are each an independent integer of 0 or 1.

[0948] 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,

[0949] R 5 and R 6 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 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 aforementioned heterocyclic ring. [4]

[0951] According to the photochromic compound described in [3], R 5 and R 6 Each of the following is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (X) above, or group represented by formula (X3) above. [5]

[0953] The photochromic compound described in [3] is represented by the following formula (4):

[0954]

[0955] In the aforementioned equation (4), R 3 R 4 R 5 R 6 M and M have the same meaning as in the aforementioned equation (3),

[0956] R 7 and R 8 Each of the following can be independently a hydroxyl group, 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 haloalkoxy 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 aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkoxythio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, a group represented by formula (X) above, or a group represented by formula (X3) above.

[0957] b is an integer between 0 and 4, and c is an integer between 0 and 4.

[0958] When b is 2 to 4, multiple R 7 Choose either the same or different.

[0959] When c is 2 to 4, multiple R 8 Choose either the same or different.

[0960] In R where b is 2 to 4 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.

[0961] In R where c is 2 to 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. [6]

[0963] The photochromic compound described in [5] is represented by the following formula (5):

[0964]

[0965] In the aforementioned equation (5), R 3 R 4 R 5 R 6 R 7 R 8 b and c have the same meaning as in the aforementioned equation (4). [7]

[0967] The photochromic compound according to [6] is represented by the following formula (6):

[0968]

[0969] In the aforementioned equation (6), R 5 R 6 R 7 R 8 b and c have the same meaning as in the aforementioned equation (5).

[0970] R 9a The group represented by formula (1a), hydrogen atom, hydroxyl group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, alkylthio group having 1 to 6 carbon atoms, substituted or unsubstituted arylthio group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a) above, or the group represented by formula (X3) above.

[0971] d1 is an integer from 1 to 5. When d1 is 1, R 9a The group represented by formula (1a) above,

[0972] When d1 is 2 to 5, R 9a At least one of them is a group represented by the aforementioned formula (1a), and the plurality of R 9a The groups can be chosen to be the same or different from each other.

[0973] In the presence of adjacent R groups other than those shown in formula (1a) above. 9a In the case of two adjacent R 9a Optional and bonded to R 9a 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.

[0974] R 10a The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, or the group represented by formula (X3) above.

[0975] e1 is an integer from 0 to 5.

[0976] When e1 is 2 to 5, multiple R 10a The groups can be chosen to be the same or different from each other, in the presence of adjacent R 10a In the case of two adjacent R 10a Optional and bonded to R 10a 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. [8]

[0978] The photochromic compound described in [7] is represented by the following formula (7):

[0979]

[0980] In the aforementioned equation (7), R 5 R 6 R 7 R 8 R 10a b, c, and e1 have the same meaning as in the aforementioned equation (6).

[0981] R 9 The group represented by formula (1a) above,

[0982] R 9b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, or the group represented by formula (X3) above.

[0983] d2 is an integer from 0 to 4.

[0984] When d2 is 2 to 4, multiple R 9b The groups can be chosen to be the same or different from each other.

[0985] In the case of adjacent R 9b In the case of two adjacent R 9b Optional and bonded to R 9b 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. [9]

[0987] The photochromic compound described in [8] is represented by the following formula (8):

[0988]

[0989] In the aforementioned equation (8), R 5 R 6 R 7 R 8 R 9 R 9b b, c, and d2 have the same meanings as in the aforementioned equation (7).

[0990] R 10 It can be 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 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 substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, or a group represented by formula (X3) above.

[0991] R 10b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, or the group represented by formula (X3) above.

[0992] e2 is an integer between 0 and 4.

[0993] When e2 is 2 to 4, multiple R 10b The groups can be chosen to be the same or different from each other.

[0994] In the case of adjacent R 10b In the case of two adjacent R 10b Optional and bonded to R 10b 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.

[10]

[0996] According to any one of [1] to [9], the photochromic compound, wherein R 1 The phenyl group can be substituted or unsubstituted.

[11]

[0998] According to any one of [1] to

[10] , the photochromic compound, wherein R 2 It is an alkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, a cycloalkyl group with 5 or more but less than 10 carbon atoms that is substituted or unsubstituted, a haloalkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, or a group represented by the aforementioned formula (2a).

[12]

[1000] A curable composition comprising any one of the photochromic compounds described in [1] to

[11] , and comprising at least one of the groups selected from free radical polymerizable monomers, cationic polymerizable monomers, compounds having condensation reactive groups, and (thio)carbamate (urea) polymers.

[13]

[1002] A cured product, which is a cured product of the curable composition described in

[12] .

[14]

[1004] An optical article comprising the cured material described in

[13] .

[15]

[1006] A lens comprising any one of the photochromic compounds described in [1] to

[11] .

[16]

[1008] A pair of eyeglasses comprising the lens described in

[15] .

[17]

[1010] A propargyl alcohol compound, represented by the following formula (9):

[1011]

[1012] In the aforementioned equation (9),

[1013] R 3 For aryl or heteroaryl groups substituted with the group shown in formula (1a) below,

[1014]

[1015] In the aforementioned equation (1a),

[1016] 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,

[1017] R 2 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below.

[1018] -Q 1 -(X 1 Q 2 )aX 2 Q 3 (2a)

[1019] In the aforementioned equation (2a),

[1020] Q 1 It is an alkylene or haloalkylene.

[1021] Q 2 It is an alkylene or haloalkylene.

[1022] Q 3 It is an alkyl or haloalkyl group.

[1023] X 1 and X 2 Independently defined as O, S, NR 700 PR 701 Or P (=O),

[1024] R 700 and R 701 Each of the following 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.

[1025] a is an integer that is 0, or greater than 1 and less than 3.

[1026] R 4 It can be a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[18]

[1028] The propargyl alcohol compound according to

[17] is represented by the following formula (10):

[1029]

[1030] In the aforementioned formula (10),

[1031] R 9a The group represented by formula (1a) above, hydrogen atom, hydroxyl group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, alkylthio group having 1 to 6 carbon atoms, substituted or unsubstituted arylthio group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a) above, or the group represented by formula (X3) below.

[1032] L 1 -R 400 (X3)

[1033] In the aforementioned formula (X3),

[1034] 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.

[1035] L 1 The group represented by the following formula (X2)

[1036]

[1037] In the aforementioned equation (X2), R 30 The group is represented by the following formula (X2a).

[1038]

[1039] In the aforementioned equations (X2) and (X2a),

[1040] J is a divalent group, which can be independently a directly bonded, substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group.

[1041] L represents an oxygen atom or a sulfur atom.

[1042] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents.

[1043] R 302 R 303 and R 304 Each is independently an alkylene group.

[1044] h, j, k, and l are each an independent integer of 0 or 1.

[1045] 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,

[1046] d1 is an integer from 1 to 5. When d1 is 1, R 9a The group represented by formula (1a) above,

[1047] When d1 is 2 to 5, R 9a At least one of them is a group represented by the aforementioned formula (1a), and the plurality of R 9a The groups can be chosen to be the same or different from each other.

[1048] In the presence of adjacent R groups other than those shown in formula (1a) above. 9a In the case of two adjacent R 9a Optional and bonded to R 9a 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.

[1049] R 10a The group is a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, a haloalkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 8 carbon atoms, an alkoxy group with 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 with 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) above, or a group represented by formula (X3) above, where e1 is an integer from 0 to 5.

[1050] When e1 is 2 to 5, multiple R 10a The groups can be chosen to be the same or different from each other, in the presence of adjacent R 10a In the case of two adjacent R 10a Optional and bonded to R 10a 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.

[19]

[1052] The propargyl alcohol compound according to

[18] is represented by the following formula (11):

[1053]

[1054] In the aforementioned equation (11), R 10a e1 has the same meaning as in the aforementioned equation (10).

[1055] R 9 The group represented by formula (1a) above,

[1056] R 9b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, or the group represented by formula (X3) above.

[1057] d2 is an integer from 0 to 4.

[1058] When d2 is 2 to 4, multiple R 9b The groups can be chosen to be the same or different from each other, in the presence of adjacent R 9b In the case of two adjacent R 9b Optional and bonded to R 9b 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.

[20]

[1060] According to

[19] , the propargyl alcohol compound is represented by the following formula (12):

[1061]

[1062] In the aforementioned equation (12), R 9 R 9b d2 has the same meaning as in the aforementioned equation (11).

[1063] R 10 It can be 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 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 substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a) above, or a group represented by formula (X3) above.

[1064] R 10b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a) above, or the group represented by formula (X3) above.

[1065] e2 is an integer between 0 and 4.

[1066] When e2 is 2 to 4, multiple R 10b The groups can be chosen to be the same or different from each other.

[1067] In the case of adjacent R 10b In the case of two adjacent R 10b Optional and bonded to R 10b 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. [twenty one]

[1069] According to any one of

[17] to

[21] , the propargyl alcohol compound, wherein R 1 For substituted or unsubstituted phenyl groups, R 2 It is an alkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, a cycloalkyl group with 5 or more but less than 1 carbon atoms that is substituted or unsubstituted, a haloalkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, or a group represented by formula (2a).< / m>

Claims

1. A photochromic compound having the framework shown in formula (1): In the above formula (1), M is C, Si, or Ge. R 3 For aryl or heteroaryl groups substituted with the group shown in formula (1a) below, In the aforementioned formula (1a), 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, R 2 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below. -Q 1 -(X 1 Q 2 )a-X 2 Q 3 (2a) In the aforementioned formula (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 Independently defined as O, S, NR 700 PR 701 Or P (=O), R 700 and R 701 Each of the following 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 an integer that is 0, or greater than 1 and less than 3. R 4 For substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups, Ring A and ring B are independently 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.

2. The photochromic compound according to claim 1, having the skeleton shown in formula (2): In equation (2), M and R 3 and R 4 They have the same meaning as in equation (1).

3. The photochromic compound according to claim 1 or 2, having the skeleton shown in formula (3): In the above formula (3), M and R 3 and R 4 They have the same meaning as in equation (1). R 5 and R 6 Each of the following groups is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X) below, or group represented by formula (X3) below. In formula (X), E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group. F represents an oxygen atom or a sulfur atom. 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 0 or 1. 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 Groups other than hydrogen atoms L 1 -R 400 (X3) In the aforementioned formula (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. L 1 The group is represented by the following formula (X2). In the formula (X2), R 30 The group is represented by the following formula (X2a). In equations (X2) and (X2a), J is a divalent group, which can be independently a directly attached, substituted, or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group. 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. R 302 R 303 and R 304 Each is independently an alkylene group. h, j, k, and l are each an independent 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, R 5 and R 6 The substituted or unsubstituted aliphatic ring having 3 to 20 carbon atoms fused together with M, the substituted or unsubstituted fused polycyclic ring having an aromatic hydrocarbon ring or an aromatic heterocycle fused to the aliphatic ring, the substituted or unsubstituted heterocycle having 3 to 20 cyclic atoms, or the substituted or unsubstituted fused polycyclic ring having an aromatic ring or an aromatic heterocycle fused to the heterocycle.

4. The photochromic compound according to claim 3, wherein, R 5 and R 6 Each of the following is independently represented as a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (X), or group represented by formula (X3).

5. The photochromic compound according to claim 3, which is represented by the following formula (4), In equation (4), R 3 R 4 R 5 R 6 M and M have the same meaning as in equation (3). R 7 and R 8 Each of the following can be independently a hydroxyl group, 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 haloalkoxy 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 aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkoxythio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), a group represented by formula (X), or a group represented by formula (X3). b is an integer between 0 and 4, and c is an integer between 0 and 4. When b is 2 to 4, multiple R 7 Choose either the same or different. When c is 2 to 4, multiple R 8 Choose either the same or different. In R where b is 2 to 4 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 R where c is 2 to 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.

6. The photochromic compound according to claim 5, which is represented by the following formula (5), In equation (5), R 3 R 4 R 5 R 6 R 7 R 8 b and c have the same meaning as in equation (4).

7. The photochromic compound according to claim 6, which is represented by the following formula (6), In equation (6), R 5 R 6 R 7 R 8 b and c have the same meaning as in equation (5). R 9a The group represented by formula (1a), hydrogen atom, hydroxyl group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, alkylthio group having 1 to 6 carbon atoms, substituted or unsubstituted arylthio group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a), or the group represented by formula (X3). d1 is an integer from 1 to 5. When d1 is 1, R 9a The group represented by formula (1a), When d1 is 2 to 5, R 9a At least one of them is a group represented by formula (1a), and the plurality of R 9a The groups can be chosen to be the same or different from each other. In the presence of adjacent R groups other than those shown in formula (1a) 9a In the case of two adjacent R 9a Optional and bonded to R 9a 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. R 10a The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), or the group represented by formula (X3). e1 is an integer from 0 to 5. When e1 is 2 to 5, multiple R 10a The groups can be chosen to be the same or different from each other, in the presence of adjacent R 10a In the case of two adjacent R 10a Optional and bonded to R 10a 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.

8. The photochromic compound according to claim 7, which is represented by the following formula (7), In equation (7), R 5 R 6 R 7 R 8 R 10a b, c, and e1 have the same meaning as in equation (6). R 9 The group represented by formula (1a), R 9b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), or the group represented by formula (X3). d2 is an integer from 0 to 4. When d2 is 2 to 4, multiple R 9b The groups can be chosen to be the same or different from each other. In the case of adjacent R 9b In the case of two adjacent R 9b Optional and bonded to R 9b 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.

9. The photochromic compound according to claim 8, which is represented by the following formula (8), In equation (8), R 5 R 6 R 7 R 8 R 9 R 9b b, c, and d2 have the same meaning as in equation (7). R 10 The group can be 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 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 substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3). R 10b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), or the group represented by formula (X3). e2 is an integer between 0 and 4. When e2 is 2 to 4, multiple R 10b The groups can be chosen to be the same or different from each other. In the case of adjacent R 10b In the case of two adjacent R 10b Optional and bonded to R 10b 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.

10. The photochromic compound according to claim 1, wherein, R 1 The phenyl group can be substituted or unsubstituted.

11. The photochromic compound according to claim 1, wherein, R 2 It is an alkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, a cycloalkyl group with 5 or more but less than 10 carbon atoms that is substituted or unsubstituted, a haloalkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, or a group represented by formula (2a).

12. A curable composition comprising the photochromic compound of claim 1, and comprising 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.

13. A cured product, which is a cured product of the curable composition of claim 12.

14. An optical article comprising the cured material of claim 13.

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

16. A pair of eyeglasses comprising the lens of claim 15.

17. A propargyl alcohol compound represented by the following formula (9): In the aforementioned formula (9), R 3 For aryl or heteroaryl groups substituted with the group shown in formula (1a) below, In the aforementioned formula (1a), 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, R 2 It can be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkyl group, or a group represented by formula (2a) below. -Q 1 -(X 1 Q 2 )a-X 2 Q 3 (2a) In the aforementioned formula (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 Independently defined as O, S, NR 700 PR 701 Or P (=O), R 700 and R 701 Each of the following 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 an integer that is 0, or greater than 1 and less than 3. R 4 It can be a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

18. The propargyl alcohol compound according to claim 17, which is represented by the following formula (10): In the aforementioned formula (10), R 9a The group represented by formula (1a), hydrogen atom, hydroxyl group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, alkylthio group having 1 to 6 carbon atoms, substituted or unsubstituted arylthio group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, nitro group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a), or the group represented by formula (X3) below. L 1 -R 400 (X3) In the aforementioned formula (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. L 1 The group is represented by the following formula (X2). In the formula (X2), R 30 The group is represented by the following formula (X2a). In equations (X2) and (X2a), J is a divalent group, which can be independently a directly bonded, substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group. 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. R 302 R 303 and R 304 Each is independently an alkylene group. h, j, k, and l are each an independent 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, d1 is an integer from 1 to 5. When d1 is 1, R 9a The group represented by formula (1a), When d1 is 2 to 5, at least one is a group represented by formula (1a), and multiple R 9a The groups can be chosen to be the same or different from each other. In the presence of adjacent R groups other than those shown in formula (1a) 9a In the case of two adjacent R 9a Optional and bonded to R 9a 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. R 10a The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), or the group represented by formula (X3). e1 is an integer from 0 to 5. When e1 is 2 to 5, multiple R 10a The groups can be chosen to be the same or different from each other. In the case of adjacent R 10a In the case of two adjacent R 10a Optional and bonded to R 10a 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.

19. The propargyl alcohol compound according to claim 18, which is represented by the following formula (11): In equation (11), R 10a e1 has the same meaning as in equation (10). R 9 The group represented by formula (1a), R 9b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), or the group represented by formula (X3). d2 is an integer from 0 to 4. When d2 is 2 to 4, multiple R 9b The groups can be chosen to be the same or different from each other, in the presence of adjacent R 9b In the case of two adjacent R 9b Optional and bonded to R 9b 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.

20. The propargyl alcohol compound according to claim 19, which is represented by the following formula (12): In equation (12), R 9 R 9b d2 has the same meaning as in equation (11). R 10 The group can be 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 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 substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3). R 10b The group can be hydroxyl, alkyl with 1 to 6 carbon atoms, haloalkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, alkoxy with 1 to 6 carbon atoms, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic group, cyano, halogen atom, alkylthio with 1 to 6 carbon atoms, substituted or unsubstituted arylthio, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, nitro, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, the group represented by formula (2a), or the group represented by formula (X3). e2 is an integer between 0 and 4. When e2 is 2 to 4, multiple R 10b The groups can be chosen to be the same or different from each other. In the case of adjacent R 10b In the case of two adjacent R 10b Optional and bonded to R 10b 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.

21. The propargyl alcohol compound according to claim 17, wherein, R 1 For substituted or unsubstituted phenyl groups, R 2 It is an alkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, a cycloalkyl group with 5 or more but less than 1 carbon atoms that is substituted or unsubstituted, a haloalkyl group with 1 or more but less than 10 carbon atoms that is substituted or unsubstituted, or a group represented by formula (2a).

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