Photochromic compound, photochromic composition, photochromic article, and eyeglasses

Abstract

Provided is a photochromic compound that is represented by general formula 1 and has no perfluoromethyl groups or perfluoromethylene groups. (In general formula 1, Ar represents a fluorinated aryl group, L represents a divalent linking group, R1 to R6, B, and B' each independently represent a hydrogen atom or a substituent, m represents 0 or 1, and n represents an integer in the range of 1 to 4.)

Description

Photochromic compounds, photochromic compositions, photochromic articles and eyeglasses

[0001] The present invention relates to photochromic compounds, photochromic compositions, photochromic articles and eyeglasses.

[0002] A photochromic compound is a compound that exhibits a property of coloring when irradiated with light in a photoresponsive wavelength range and fading in the absence of light (photochromic property). For example, Patent Document 1 discloses a naphthopyran-based compound having photochromic property.

[0003] EP2078006B1

[0004] Methods for imparting photochromic properties to articles such as eyeglass lenses include a method of incorporating a photochromic compound into a substrate and a method of forming a layer containing a photochromic compound. A desired performance of an article imparted with photochromic properties in this way is to exhibit a fast color fading rate after coloring by light irradiation. Therefore, it is desirable for the photochromic compound to exhibit a fast color fading rate after coloring.

[0005] In recent years, a proposal has been made to restrict organic fluorine compounds (PFAS) containing perfluoromethyl and / or perfluoromethylene groups under the European REACH regulation (PFAS regulation). Therefore, it is desirable that photochromic compounds are exempt from the PFAS regulation.

[0006] An object of one aspect of the present invention is to provide a photochromic compound that does not have a perfluoromethyl group or a perfluoromethylene group and that fades quickly after coloring.

[0007] One aspect of the present invention relates to a photochromic compound represented by the following general formula 1, which does not have a perfluoromethyl group or a perfluoromethylene group.

[0008] Another aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by the following general formula 1 and having no perfluoromethyl group or perfluoromethylene group:

[0009] Another aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by the following general formula 1 and having no perfluoromethyl group or perfluoromethylene group:

[0010]

[0011] In General Formula 1, Ar represents a fluorinated aryl group, L represents a divalent linking group, and R １ ~R ６ , B and B' each independently represent a hydrogen atom or a substituent; m represents 0 or 1; and n represents an integer ranging from 1 to 4.

[0012] The compound represented by general formula 1 does not have a perfluoromethyl group or a perfluoromethylene group and can exhibit a fast fading rate after coloring. The compound represented by general formula 1 makes it possible to provide a photochromic article that exhibits a fast fading rate after coloring.

[0013] For example, a photochromic compound undergoes an excited state upon irradiation with light such as sunlight, and then undergoes structural transformation into a colored form. The structure after structural transformation via light irradiation can be called a "colored form." In contrast, the structure before light irradiation can be called a "colorless form." However, the term "colorless" in relation to the colorless form does not necessarily mean complete colorlessness, but also includes cases where the color is lighter than that of the colored form. The structure of general formula 1 is the structure of a colorless form.

[0014] In the present invention and this specification, the term "photochromic article" refers to an article containing a photochromic compound. A photochromic article according to one embodiment of the present invention contains at least one photochromic compound represented by General Formula 1 as a photochromic compound. The photochromic compound can be contained in the substrate of the photochromic article, and / or in the photochromic layer of a photochromic article having a substrate and a photochromic layer. The term "photochromic layer" refers to a layer containing a photochromic compound.

[0015] In the present invention and this specification, the term "photochromic composition" refers to a composition containing a photochromic compound. The photochromic composition according to one aspect of the present invention contains at least one photochromic compound represented by General Formula 1 as the photochromic compound, and can be used to produce the photochromic article according to one aspect of the present invention.

[0016] In the present invention and this specification, substituents in various general formulae described in detail later, and further, substituents on each group described later when it has a substituent, each independently include: a linear or branched alkyl group having 1 to 18 carbon atoms such as a hydroxy group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.; a monocyclic or polycyclic (e.g., bicyclic) aliphatic alkyl group having 5 to 18 carbon atoms such as a cyclopentyl group, a cyclohexyl group, etc.; a linear or branched alkoxy group having 1 to 24 constituent atoms such as a methoxy group, an ethoxy group, a butoxy group, etc.; a non-aromatic cyclic substituent having 1 to 24 constituent atoms; a linear or branched perfluoroalkyl group having 2 to 18 carbon atoms; a linear or branched perfluoroalkoxy group (excluding perfluoromethoxy group), etc.; a linear or branched alkyl group having 1 to 24 constituent atoms such as a methyl sulfide group, an ethyl sulfide group, a butyl sulfide group, etc. or branched alkyl sulfide groups, aryl groups such as a phenyl group, a naphthyl group, an anthracenyl group, a fluoranthenyl group, a phenanthryl group, a pyranyl group, a perylenyl group, a styryl group, or a fluorenyl group, aryloxy groups such as a phenyloxy group, aryl sulfide groups such as a phenyl sulfide group, heteroaryl groups such as a pyridyl group, a furanyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothiophenyl group, an indolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a diazolyl group, a triazolyl group, a quinolinyl group, a phenothiazinyl group, a phenoxazinyl group, a phenazinyl group, a thianthryl group, or an acridinyl group, amino groups (-NH ２a substituent R selected from the group consisting of a monoalkylamino group such as a monomethylamino group, a dialkylamino group such as a dimethylamino group, a monoarylamino group such as a monophenylamino group, a diarylamino group such as a diphenylamino group, a cyclic amino group such as a piperidino group, a morpholino group, a thiomorpholino group, a tetrahydroquinolino group, or a tetrahydroisoquinolino group, an ethynyl group, a mercapto group, a silyl group, a sulfonic acid group, an alkylsulfonyl group, a formyl group, a carboxy group, a cyano group, and a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; ｍ or R ｍ and one or more identical or different R ｍ The substituent may be substituted with ;

[0017] The above R ｍ and one or more of the same or different R ｍ An example of a substituent substituted with R is a structure in which an alkoxy group is further substituted on the terminal carbon atom of an alkoxy group, and another alkoxy group is further substituted on the terminal carbon atom of this alkoxy group. ｍ and one or more of the same or different R ｍ Another example of a substituent substituted with R is a substituent substituted with the same or different R at two or more of the five substitutable positions of the phenyl group. ｍ However, the present invention is not limited to such examples.

[0018] In the present invention and this specification, unless otherwise specified, the groups described are substituted or unsubstituted groups. In the present invention and this specification, "substituted or unsubstituted" has the same meaning as "having one or more substituents or being unsubstituted." The "number of carbon atoms" and "number of constituent atoms" refer to the numbers including the number of carbon atoms or atoms of the substituent in a group having a substituent, unless otherwise specified.

[0019] Furthermore, in the present invention and this specification, the substituents in the various general formulas described in detail below, and further, when each group described below has a substituent, the substituents can each independently be a solubilizing group. In the present invention and this specification, the term "solubilizing group" refers to a substituent that can contribute to improving compatibility with any liquid or a specific liquid. Suitable solubilizing groups include alkyl groups having a linear, branched, or cyclic structure with 4 to 50 carbon atoms, linear, branched, or cyclic alkoxy groups having 4 to 50 constituent atoms, linear, branched, or cyclic silyl groups having 4 to 50 constituent atoms, groups in which a portion of the above groups is replaced with a silicon atom, sulfur atom, nitrogen atom, phosphorus atom, or the like, and combinations of two or more of the above groups, and other substituents whose presence can contribute to promoting the thermal motion of the compound's molecules. Compounds having a solubilizing group as a substituent can prevent the solute from solidifying by inhibiting the distance between solute molecules from narrowing, or can create a molecular aggregation state similar to that of a liquid by lowering the melting point and / or glass transition temperature of the solute. Thus, the solubilizing group can liquefy a solute or increase the solubility of a compound having this substituent in a liquid. In one embodiment, the solubilizing group is preferably a linear alkyl group such as an n-butyl group, an n-pentyl group, an n-hexyl group, or an n-octyl group, a branched alkyl group such as a tert-butyl group, or a cyclic alkyl group such as a cyclopentyl group or a cyclohexyl group.

[0020] The substituent may be preferably a substituent selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group, a methyl sulfide group, an ethyl sulfide group, a phenyl sulfide group, a phenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a phenothiazinyl group, a phenoxazinyl group, a phenazinyl group, an acridinyl group, a dimethylamino group, a diphenylamino group, a piperidino group, a morpholino group, a thiomorpholino group, a cyano group, and a solubilizing group, and more preferably a substituent selected from the group consisting of a methoxy group, a phenoxy group, a methyl sulfide group, a phenyl sulfide group, a phenyl group, a dimethylamino group, a diphenylamino group, a piperidino group, a morpholino group, a thiomorpholino group, a cyano group, and a solubilizing group.

[0021] In the present invention and this specification, the term "electron-donating group" refers to a substituent that more easily donates electrons to the atom to which it is bonded compared to a hydrogen atom. The electron-donating group can be a substituent that more easily donates electrons as a sum of inductive effect, mesomeric effect (or resonance effect), etc. Specific examples of the electron-donating group include a hydroxy group: -OH, a thiol group: -SH, an alkoxy group: -OR (R is an alkyl group), an alkylsulfide group: -SR (R is an alkyl group), an arylsulfide group, and an acetyl group: -OCOCH ３ , amino group: —NH ２ , alkylamide group: —NHCOCH ３ , dialkylamino group: —N(R) ２ (wherein the two R's are the same or different alkyl groups), a morpholino group, a piperidino group, a methyl group, etc. Suitable electron donating groups include those having a substituent constant σ at the para position based on Hammett's rule. ｐ can be exemplified by electron donating groups in which the value of

[0022] Para-position substituent constant σ based on Hammett's rule ｐ (Source: Hide Iwamura, Ryoji Noyori, Takeshi Nakai, Isao Kitagawa, Graduate School Organic Chemistry (Vol. 1) (1988)) Specific examples of -N(CH ３ ) ２ :-0.83 -OCH ３ :-0.27 -t-C ４ H ９ : -0.20 -CH ３ : -0.17 -C ２ H ５ : -0.15 -C ６ H ５ :-0.01 (-H:0) -F:+0.06 -Cl:+0.27 -Br:+0.23 -CO ２ C ２ H ５ : +0.45 -CF ３ :+0.54 -CN:+0.66 -SO ２ CH ３ : +0.72 -NO ２ : +0.78

[0023] [Photochromic Compound] A photochromic compound according to one embodiment of the present invention is a photochromic compound represented by General Formula 1 and having neither a perfluoromethyl group nor a perfluoromethylene group. Such a photochromic compound has neither a perfluoromethyl group nor a perfluoromethylene group.

[0024] General formula 1 will be explained in more detail below.

[0025]

[0026] In General Formula 1, Ar represents a fluorinated aryl group. A "fluorinated aryl group" is an aryl group substituted with one or more fluorine atoms. Examples of the aryl group include aryl groups having 6 to 10 carbon atoms, such as a phenyl group, a biphenyl group, a tolyl group, or a naphthyl group, with a phenyl group being preferred. That is, in one embodiment, Ar can be a fluorinated phenyl group.

[0027] The number of fluorine atoms substituting the aryl group in the fluorinated aryl group is 1 or more, and may be 2 or more, or 3 or more. In one embodiment, the fluorinated aryl group represented by Ar may be an aryl group in which all positions substitutable with fluorine atoms are substituted with fluorine atoms, i.e., a perfluoroaryl group.

[0028] In one embodiment, Ar is preferably a fluorinated phenyl group substituted with three or more fluorine atoms, more preferably a fluorinated phenyl group substituted with four or more fluorine atoms, and even more preferably a perfluorophenyl group.

[0029] In General Formula 1, n represents an integer ranging from 1 to 4. When n represents an integer ranging from 2 to 4, there are multiple Ars in General Formula 1. These multiple Ars may be the same or different.

[0030] The substitution positions of the phenyl groups are as follows:

[0031]

[0032] Specific examples of the fluorinated phenyl group include the following.

[0033]

[0034] In one embodiment, Ar is preferably a phenyl group substituted with fluorine atoms at least at the 3- and 5-positions.

[0035] In one embodiment, when Ar is a fluorinated phenyl group, the present inventors speculate that, from the viewpoint of the orientation of the substituent effect, the fluorine atoms are preferably substituted at the para-position (4-position) and the ortho-position (2-position), and more preferably at the para-position (4-position). From the viewpoint of the inductive effect, the present inventors speculate that the fluorine atoms are preferably substituted at positions away from the indeno-fused naphthopyran substituted by Ar. That is, the present inventors speculate that, in the case of monosubstitution, the fluorine atoms are preferably substituted at the para-position (4-position), in the case of disubstitution, the fluorine atoms are preferably substituted at the meta-position (3-position) and the para-position (4-position), and in the case of trisubstitution, the fluorine atoms are preferably substituted at the meta-position (3-position), the para-position (4-position), and the meta-position (5-position). However, the present invention is not limited by the speculations described in this specification.

[0036] In one embodiment, when the fluorinated aryl group represented by Ar is a trifluorophenyl group, the substitution positions of the three fluorine atoms can be, for example, the ortho-, ortho-, or para-positions (i.e., 2-, 4-, and 6-positions) relative to the carbon atom of the indeno-fused naphthopyran substituted by Ar.

[0037] In general formula 1, the fluorinated aryl group represented by Ar is directly bonded to one or more carbon atoms at any one of the 9th, 10th, 11th, and 12th positions of the indeno-fused naphthopyran or is substituted via L. When n is 1, the fluorinated aryl group represented by Ar is preferably directly bonded to the carbon atom at the 11th position of the indeno-fused naphthopyran or is substituted via L. When n is 2, the fluorinated aryl group represented by Ar is preferably directly bonded to the carbon atoms at the 10th and 12th positions of the indeno-fused naphthopyran or is substituted via L.

[0038] In General Formula 1, L represents a divalent linking group, and m represents 0 or 1. When m represents 0, Ar is directly bonded to a carbon atom of the indeno-fused naphthopyran. When n represents an integer ranging from 2 to 4, multiple Ls can be present in General Formula 1. These multiple Ls can be the same or different. Furthermore, when n represents a range of from 2 to 4, multiple partial structures represented by "Ar-(L)m-" are present in General Formula 1. In this case, m may be 0 and L may be absent in one or more of the multiple "Ar-(L)m-", and m may be 1 and L may be present in one or more others, or m may be 0 and L may be absent in all of the "Ar-(L)m-". In one embodiment, n can represent 1 or 2, and m can represent 0.

[0039] Examples of the divalent linking group represented by L include an alkylene group and an arylene group. Examples of the alkylene group include a linear or branched alkyl group having 1 to 18 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, pentylene group, or hexylene group; a monocyclic or polycyclic (e.g., bicyclic) aliphatic alkylene group having 5 to 18 carbon atoms, such as a cyclopentylene group or cyclohexylene group; and an arylene group having 6 to 10 carbon atoms, such as a phenylene group, biphenylene group, tolylene group, or naphthylene group.

[0040] In general formula 1, R １ ~R ６ R each independently represents a hydrogen atom or a substituent. １ ~R ６ may be bonded to form a ring structure.

[0041] In one form, R １ and R ２ R each independently represents a substituted or unsubstituted alkyl group. １ and R ２When represents a substituted or unsubstituted alkyl group, the alkyl groups may be the same or different. Examples of the alkyl group include substituted or unsubstituted linear or branched alkyl groups having 1 to 18 carbon atoms, preferably substituted or unsubstituted linear or branched alkyl groups having 1 to 6 carbon atoms, more preferably substituted or unsubstituted linear alkyl groups having 1 to 6 carbon atoms, even more preferably substituted or unsubstituted linear alkyl groups having 1 to 3 carbon atoms (substituted or unsubstituted methyl groups, ethyl groups, and propyl groups), and even more preferably substituted or unsubstituted methyl groups or ethyl groups. Examples of the substituent include alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.).

[0042] In another embodiment, R １ and R ２ are bonded to each other to form a ring structure having three or more carbon atoms constituting the ring, including the carbon atom at position 13 of the indeno-fused naphthopyran. In this case, the carbon atom at position 13 of the indeno-fused naphthopyran can be a spiro atom shared by the ring structure and the indeno-fused naphthopyran. That is, the ring structure can be a ring structure that is spiro-fused with the indeno-fused naphthopyran.

[0043] The ring structure may be a monocyclic structure, a fused polycyclic structure such as a bicyclic or tricyclic structure, a bridged ring structure such as a bicyclic structure, or a spiro ring structure such as a bicyclic structure.

[0044] The ring structure may be an aliphatic ring. Such an aliphatic ring may be unsubstituted or may have a substituent. For the substituent, the above description of the substituent may be referred to.

[0045] Examples of the aliphatic ring include an aliphatic ring having 3 to 20 carbon atoms constituting the ring, including the carbon atom at position 13 of the indeno-fused naphthopyran. Specific examples include monocyclic rings such as a cyclohexane ring, a cyclooctane ring, and a cycloheptane ring; bicyclic rings such as a norbornane ring and a bicyclononane ring; and tricyclic rings such as an adamantane ring. The above-mentioned "number of carbon atoms constituting the ring" also includes the number of carbon atoms contained in the substituent in the case of a substituted aliphatic ring. Furthermore, the "number of atoms constituting the ring, including the carbon atom at position 13 of the indeno-fused naphthopyran" described below also includes the number of atoms contained in the substituent in the case of a substituted ring structure.

[0046] When the ring structure is an aliphatic ring, in one embodiment, the number of carbon atoms constituting the ring of the aliphatic ring is preferably 3 or more and 6 or less, and can be 3, 4, 5, or 6, and more preferably 6. In another embodiment, the number of carbon atoms constituting the ring of the aliphatic ring is preferably 7 or more and 20 or less, and can be 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, and more preferably 7, 8, or 10.

[0047] Examples of the ring structure include: a fused polycyclic ring in which one or more ring structures selected from the group consisting of aromatic rings and aromatic heterocycles are fused to an aliphatic ring having 3 to 20 carbon atoms constituting the ring, including the carbon atom at position 13 of the indeno-fused naphthopyran; a heterocyclic ring in which the number of atoms constituting the ring, including the carbon atom at position 13 of the indeno-fused naphthopyran, is 3 to 20; and a fused polycyclic ring in which one or more ring structures selected from the group consisting of aromatic rings and aromatic heterocycles are fused to the above-mentioned heterocyclic ring.

[0048] A specific example of a fused polycycle in which one or more ring structures selected from the group consisting of aromatic rings and aromatic heterocycles are fused to an aliphatic ring having 3 to 20 carbon atoms constituting the ring, including the carbon atom at position 13 of the indeno-fused naphthopyran, is a fluorene ring.

[0049] Specific examples of heterocyclic rings having 3 to 20 atoms constituting the ring, including the carbon atom at the 13th position of the indeno-fused naphthopyran, include a thiophene ring, a furan ring, and a pyridine ring.

[0050] Examples of the fused polycyclic ring in which one or more ring structures selected from the group consisting of aromatic rings and aromatic heterocycles are fused to the heterocycle include a phenylfuran ring and a biphenylthiophene ring.

[0051] Specific examples of the ring structure include the following ring structures: In the following, the carbon atom at the position indicated by 13 is the carbon atom at the 13th position of the indeno-fused naphthopyran in general formula 1.

[0052]

[0053]

[0054] In one embodiment, the ring structure is preferably the following ring structure.

[0055]

[0056] In one form, R ４ and R ５ At least one of R may represent an electron-donating group. In the present invention and this specification, "at least one" is synonymous with "only one or both." ４ and R ５ may each independently represent an electron-donating group. ４ and R ５ represents electron donating groups, the electron donating groups may be the same or different.

[0057] R ４ and R ５ When at least one of R represents an electron-donating group, one may represent an electron-donating group and the other may represent a hydrogen atom. ４ represents an electron-donating group, and R ５ can represent a hydrogen atom, and in another embodiment, R ４ represents a hydrogen atom and R ５ can represent an electron donating group.

[0058] R４ and / or R ５ The electron-donating group represented by the formula (I) is preferably an electron-donating group selected from the group consisting of an alkoxy group, a morpholino group, and a piperidino group, and more preferably an electron-donating group selected from the group consisting of a methoxy group, a morpholino group, and a piperidino group.

[0059] In another embodiment, R ４ and R ５ can all represent a hydrogen atom.

[0060] In another embodiment, R ５ may represent a fluorinated aryl group. ５ For the fluorinated aryl group represented by, the above description of the fluorinated aryl group represented by Ar can be referred to. ５ can represent a perfluoroaryl group, and preferably represents a perfluorophenyl group.

[0061] R ３ and R ６ each independently represents a hydrogen atom or a substituent, and preferably all represent a hydrogen atom.

[0062] In general formula 1, B and B' each independently represent a hydrogen atom or a substituent, and preferably each independently represent a substituent. When B and B' represent a substituent, the substituents may be the same or different.

[0063] In one embodiment, B and B' can each independently be a substituted or unsubstituted phenyl group. The phenyl group having a substituent can be a mono- to penta-substituted phenyl group. In a phenyl group having two or more substituents, the substituents can be the same or different, and two or more of the substituents may be bonded to form a ring structure. For the substituents of the phenyl group, the above description of the substituents can be referred to.

[0064] In one embodiment, at least one of B and B' may represent a phenyl group having a substituent at the para-position relative to the carbon atom bonding to the pyran ring of the indeno-fused naphthopyran. In this case, only one of B and B' may represent a phenyl group having a substituent at the para-position relative to the carbon atom bonding to the pyran ring of the indeno-fused naphthopyran. Alternatively, both B and B' may independently represent phenyl groups having a substituent at the para-position relative to the carbon atom bonding to the pyran ring of the indeno-fused naphthopyran. The substituent at the para-position may be, for example, an electron-donating group. For details about such electron-donating groups, the above description of electron-donating groups may be referred to. Specific examples of the electron-donating group at the para-position include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, and amino groups such as dimethylamino, morpholino, and piperidino. Further examples include alkoxy groups substituted with an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, or the alkoxy group may be further substituted with an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

[0065] In one embodiment, at least one of B and B' may be a phenyl group having a nitrogen atom-containing substituent at the para-position relative to the carbon atom bonding to the pyran ring of the indeno-fused naphthopyran. In this case, only one of B and B' may be a phenyl group having a nitrogen atom-containing substituent at the para-position relative to the carbon atom bonding to the pyran ring of the indeno-fused naphthopyran. Alternatively, both B and B' may each independently be a phenyl group having a nitrogen atom-containing substituent at the para-position relative to the carbon atom bonding to the pyran ring of the indeno-fused naphthopyran. Examples of the nitrogen atom-containing substituent include an unsubstituted amino group (-NH ２), substituted amino groups (for example, monoalkylamino groups such as monomethylamino group, dialkylamino groups such as dimethylamino group, monoarylamino groups such as monophenylamino group, diarylamino groups such as diphenylamino group, etc.), cyclic amino groups (for example, piperidino group, morpholino group, thiomorpholino group, tetrahydroquinolino group, tetrahydroisoquinolino group, etc.).

[0066] In one embodiment, at least one of B and B′ can be a phenyl group having a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom at a para-substitution position relative to the carbon atom bonding to the pyran ring of the indeno-fused naphthopyran.

[0067] Examples of compounds represented by general formula 1 include the following: (1) R １ and R ２ each independently represents a substituted or unsubstituted alkyl group having two or more carbon atoms, and B and B' each independently represent an unsubstituted phenyl group or a phenyl group substituted with a methoxy group. １ and R ２ each independently represents a substituted or unsubstituted alkyl group having two or more carbon atoms, and at least one of B and B' represents a phenyl group substituted with an amino group. (3) R １ and R ２ represents a methyl group, and at least one of B and B' represents a phenyl group substituted with an amino group. １ and R ２ represents a methyl group, and B and B' each independently represent an unsubstituted phenyl group or a phenyl group substituted with a methoxy group.

[0068] In the above (1) to (4), the substitution position of the methoxy group or amino group on the phenyl group can be, for example, the 4-position.

[0069] In the above (1) to (4), examples of the substituent of the substituted alkyl group having two or more carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy.

[0070] In one embodiment, in the above (2) and (3), one of B and B' may be a phenyl group substituted with an amino group, and the other may be an unsubstituted phenyl group or a substituted or unsubstituted alkoxy group. The alkoxy group may be an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Examples of the substituent in the substituted alkoxy group include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

[0071] In one embodiment, the molecular weight of the compound represented by general formula 1 can be 1,500 or less. The compound represented by general formula 1 can be a dimer in which two structures represented by general formula 1 are linked together, or a polymer in which three or more structures are linked together. From the viewpoint of photochromic properties, it is preferable that the number of units that exhibit photochromic properties in one molecule is small. From this point of view, it is preferable that the compound represented by general formula 1 is a monomer.

[0072] Examples of compounds represented by general formula 1 include the following compounds. Specific examples of each moiety in general formula 1 include those included in the exemplary compounds shown below. However, the present invention is not limited to the exemplary compounds shown below.

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089] The photochromic compound represented by general formula 1 can be synthesized by a known method. For the synthesis method, reference can be made to the following documents, for example: Japanese Patent No. 4884578, JP 2011-57581 A, US 2006 / 0226402 A1, US 2006 / 0228557 A1, US 2008 / 0103301 A1, US 2011 / 0108781 A1, US 2011 / 0108781 A1, US 7,527,754, US 7,556,751, WO 2001 / 60811 A1, WO 2013 / 0862 48A1, WO1996 / 014596A1, WO2001 / 019813A1, WO2001 / 60811, WO2006 / 110221, WO2009 / 136668, WO2010 / 150905, WO2011 / 010744, WO2011 / 016582, WO2011 / 025056, WO2011 / 034202, WO2012 / 102409 and WO2023 / 136213.

[0090] [Photochromic Composition, Photochromic Article] One aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by general formula 1. Another aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by general formula 1.

[0091] The photochromic composition and the photochromic article may contain only one type of photochromic compound represented by General Formula 1, or may contain two or more types (for example, two or more and four or less types). The photochromic article and the photochromic composition may contain, for example, about 0.1 to 15.0% by mass of the photochromic compound represented by General Formula 1, with the total amount of the photochromic composition and the photochromic article being 100% by mass. However, the amount is not limited to the above range.

[0092] The photochromic composition and the photochromic article can contain one or more photochromic compounds represented by General Formula 1 and one or more other photochromic compounds. The other photochromic compounds will be described later.

[0093] The photochromic article may have at least a substrate. In one embodiment, the photochromic compound represented by General Formula 1 may be contained in the substrate of the photochromic article. The photochromic article may have a substrate and a photochromic layer, and the substrate and / or photochromic layer may contain one or more photochromic compounds represented by General Formula 1. In one embodiment, the photochromic compound represented by General Formula 1 may be contained only in the substrate, in another embodiment, or in the photochromic layer, or in both the substrate and the photochromic layer. Furthermore, the substrate and the photochromic layer may contain only the photochromic compound represented by General Formula 1 as the photochromic compound, or may contain one or more other photochromic compounds. Examples of other photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaarylbisimidazoles, donor-acceptor Stenhouse adducts (DASA), salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, stilbenes, etc. Examples of other photochromic compounds include one or more compounds selected from the group consisting of photochromic compounds represented by general formula A, photochromic compounds represented by general formula B, and photochromic compounds represented by general formula C, which are described in WO2022 / 138966.

[0094] <Substrate> The photochromic article may include a substrate selected depending on the type of photochromic article. Examples of substrates include spectacle lens substrates, such as plastic lens substrates or glass lens substrates. The glass lens substrate may be, for example, a lens substrate made of inorganic glass. Examples of plastic lens substrates include (meth)acrylic resins, styrene resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, polyether resins, urethane resins obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, thiourethane resins obtained by reacting an isocyanate compound with a polythiol compound, and cured products (commonly referred to as transparent resins) obtained by curing a curable composition containing a (thio)epoxy compound having one or more disulfide bonds in the molecule. The lens substrate may be either undyed (colorless lenses) or dyed (dyed lenses). The refractive index of the lens substrate may be, for example, approximately 1.50 to 1.75. However, the refractive index of the lens substrate is not limited to the above range, and may be within the above range or may deviate above or below the above range. Here, the refractive index refers to the refractive index for light with a wavelength of 500 nm. Furthermore, the lens substrate may be a lens with refractive power (a so-called prescription lens) or a lens without refractive power (a so-called non-prescription lens).

[0095] For example, the photochromic composition may be a polymerizable composition. In the present invention and this specification, a "polymerizable composition" refers to a composition containing one or more polymerizable compounds. A cured product of the polymerizable composition can be produced by molding a polymerizable composition containing at least one photochromic compound represented by General Formula 1 and one or more polymerizable compounds using a known molding method. Such a cured product can be included as a substrate and / or a photochromic layer in the photochromic article. The curing treatment can be light irradiation and / or heat treatment. The polymerizable compound is a compound having a polymerizable group, and the polymerization reaction of the polymerizable compound progresses, causing the polymerizable composition to harden and form a cured product. The polymerizable composition may further contain one or more additives (e.g., a polymerization initiator, etc.).

[0096] The spectacle lens can be any of various lenses, such as a single-vision lens, a multifocal lens, or a progressive-power lens. The type of lens is determined by the surface shapes of both sides of the lens substrate. The surface of the lens substrate may be convex, concave, or flat. In typical lens substrates and spectacle lenses, the object-side surface is convex and the eyeball-side surface is concave. However, this is not limited to this. The photochromic layer can usually be provided on the object-side surface of the lens substrate, but it may also be provided on the eyeball-side surface.

[0097] <Photochromic Layer> The photochromic layer can be a layer formed directly on the surface of the substrate or indirectly via one or more other layers. The photochromic layer can be, for example, a cured layer formed by curing a polymerizable composition. A photochromic layer can be formed by curing a polymerizable composition containing at least one photochromic compound represented by General Formula 1 and one or more polymerizable compounds. For example, the polymerizable composition can be applied directly to the surface of the substrate or to the surface of a layer formed on the substrate, and the applied polymerizable composition can be cured to form a photochromic layer as a cured layer containing one or more photochromic compounds represented by General Formula 1. Examples of coating methods include known coating methods such as spin coating, dip coating, spray coating, inkjet coating, nozzle coating, and slit coating. The curing treatment can be light irradiation and / or heat treatment. The polymerizable composition can further contain one or more additives (e.g., polymerization initiators) in addition to one or more polymerizable compounds. As the polymerization reaction of the polymerizable compound progresses, the polymerizable composition hardens, and a hardened layer can be formed.

[0098] The thickness of the photochromic layer can be, for example, 5 μm or more, 10 μm or more, or 20 μm or more, and can be, for example, 80 μm or less, 70 μm or less, or 50 μm or less.

[0099] <Polymerizable Compound> In the present invention and this specification, a polymerizable compound refers to a compound having one or more polymerizable groups in one molecule, and a "polymerizable group" refers to a reactive group capable of undergoing a polymerization reaction. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, a vinyl ether group, an epoxy group, a thiol group, an oxetane group, a hydroxy group, a carboxy group, an amino group, and an isocyanate group.

[0100] Examples of polymerizable compounds that can be used to form the substrate and the photochromic layer include the following compounds.

[0101] (Episulfide Compound) An episulfide compound is a compound having two or more episulfide groups in one molecule. The episulfide group is a polymerizable group capable of ring-opening polymerization. Specific examples of episulfide compounds include bis(1,2-epithioethyl) sulfide, bis(1,2-epithioethyl) disulfide, bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropylthio)methane, bis(2,3-epithiopropyl) disulfide, bis(2,3-epithiopropyldithio)methane, bis(2,3-epithiopropyldithio)ethane, bis(6,7-epithio-3,4-dithiaheptyl) sulfide, bis(6,7-epithio-3,4-dithiaheptyl)disulfide, 1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl), 1,3-bis(2,3-epithiopropyldithiomethyl)benzene, 1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane, 1,2,3-tris(2,3-epithiopropyldithio)propane, 1,1,1,1-tetramethyl- tetrakis(2,3-epithiopropyldithiomethyl)methane, 1,3-bis(2,3-epithiopropyldithio)-2-thiapropane, 1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane, 1,1,1-tris(2,3-epithiopropyldithio)methane, 1,1,1-tris(2,3-epithiopropyldithiomethylthio)methane, 1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane, 1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane, Examples include tetrakis(2,3-epithiopropyldithiomethylthio)ethane, 1,1,3,3-tetrakis(2,3-epithiopropyldithio)propane, 1,1,3,3-tetrakis(2,3-epithiopropyldithiomethylthio)propane, 2-[1,1-bis(2,3-epithiopropyldithio)methyl]-1,3-dithietane, and 2-[1,1-bis(2,3-epithiopropyldithiomethylthio)methyl]-1,3-dithietane.

[0102] (Thietanyl Compounds) Thietanyl compounds are thietanyl compounds having two or more thietanyl groups in one molecule. The thietanyl group is a polymerizable group capable of ring-opening polymerization. Some thietanyl compounds have episulfide groups in addition to multiple thietanyl groups. Such compounds are listed above as examples of episulfide compounds. Other thietanyl compounds include metal-containing thietanyl compounds having a metal atom in the molecule and non-metal thietanyl compounds that do not contain a metal.

[0103] Specific examples of non-metallic thietane compounds include bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide, bis(3-thietanyl) trisulfide, bis(3-thietanyl) tetrasulfide, 1,4-bis(3-thietanyl)-1,3,4-trithiabutane, 1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane, 1,6-bis(3-thietanyl)-1,3,4,6-tetrathiahexane, 1,6-bis(3-thietanyl)-1,3,5,6-tetrathiahexane, 1,7-bis(3-thietanyl)- 1,2,4,5,7-pentathiaheptane, 1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathiaheptane, 1,1-bis(3-thietanylthio)methane, 1,2-bis(3-thietanylthio)ethane, 1,2,3-tris(3-thietanylthio)propane, 1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane, 1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(3-thietanyl 1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane, 2,5-bis(3-thietanylthiomethyl)-1,4-dithiane, 2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane, 2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, bisthietanyl sulfide, bis(thietanylthio)methane, 3-[<(thietanylthio)methyl]-1,4-dithiane,

[0033] bisthietanyl disulfide, bisthietanyl trisulfide, bisthietanyl tetrasulfide, bisthietanyl pentasulfide, 1,4-bis(3-thietanyldithio)-2,3-dithiabutane, 1,1,1-tris(3-thietanyldithio)methane, 1,1,1-tris(3-thietanyldithiomethylthio)methane, 1,1,2,2-tetrakis(3-thietanyldithio)ethane, 1,1,2,2-tetrakis(3-thietanyldithiomethylthio)ethane, and the like can be mentioned.

[0104] Examples of metal-containing thietane compounds include those containing, as metal atoms in the molecule, atoms of Group 14 such as Sn, Si, Ge, and Pb, elements of Group 4 such as Zr and Ti, atoms of Group 13 such as Al, and atoms of Group 12 such as Zn. Specific examples include alkylthio(thietanylthio)tin, bis(alkylthio)bis(thietanylthio)tin, alkylthio(alkylthio)bis(thietanylthio)tin, bis(thietanylthio)cyclic dithiotin compounds, and alkyl(thietanylthio)tin compounds.

[0105] Specific examples of alkylthio(thietanylthio)tin include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, and isopropylthiotris(thietanylthio)tin.

[0106] Specific examples of bis(alkylthio)bis(thietanylthio)tin include bis(methylthio)bis(thietanylthio)tin, bis(ethylthio)bis(thietanylthio)tin, bis(propylthio)bis(thietanylthio)tin, and bis(isopropylthio)bis(thietanylthio)tin.

[0107] Specific examples of alkylthio(alkylthio)bis(thietanylthio)tin include ethylthio(methylthio)bis(thietanylthio)tin, methylthio(propylthio)bis(thietanylthio)tin, isopropylthio(methylthio)bis(thietanylthio)tin, ethylthio(propylthio)bis(thietanylthio)tin, ethylthio(isopropylthio)bis(thietanylthio)tin, and isopropylthio(propylthio)bis(thietanylthio)tin.

[0108] Specific examples of the bis(thietanylthio)cyclic dithiotin compound include bis(thietanylthio)dithiastannetane, bis(thietanylthio)dithiastannolane, bis(thietanylthio)dithiastanninane, and bis(thietanylthio)trithiastannocane.

[0109] Specific examples of the alkyl(thietanylthio)tin compound include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, and tetrakis(thietanylthio)tin.

[0110] (Polyamine Compound) A polyamine compound has NH ２ It is a compound having two or more groups, which can form a urea bond by reaction with a polyisocyanate, and can form a thiourea bond by reaction with a polyisothiocyanate. Specific examples of the polyamine compound include ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2-(2-aminoethylamino)ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, and 1,3,5-benzenetriamine.

[0111] (Epoxy Compound) Epoxy compounds are compounds having an epoxy group in the molecule. The epoxy group is a polymerizable group capable of ring-opening polymerization. Epoxy compounds are generally classified into aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds.

[0112] Specific examples of the aliphatic epoxy compound include ethylene oxide, 2-ethyloxirane, butyl glycidyl ether, phenyl glycidyl ether, 2,2'-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, and triglycidyl ether of tris(2-hydroxyethyl)isocyanurate.

[0113] Specific examples of the alicyclic epoxy compound include isophoronediol diglycidyl ether and bis-2,2-hydroxycyclohexylpropane diglycidyl ether.

[0114] Specific examples of aromatic epoxy compounds include resorcinol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ether, and cresol novolac polyglycidyl ether.

[0115] In addition to the above, epoxy compounds containing sulfur atoms in the molecule as well as epoxy groups can also be used. Such sulfur-containing epoxy compounds include linear aliphatic and cyclic aliphatic compounds.

[0116] Specific examples of the chain aliphatic sulfur atom-containing epoxy compound include bis(2,3-epoxypropyl) sulfide, bis(2,3-epoxypropyl) disulfide, bis(2,3-epoxypropylthio)methane, 1,2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio)butane, 1,4-bis(2,3-epoxypropylthio)-2-methylbutane, 1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio) 1,5-bis(2,3-epoxypropylthio)pentane, 1,5-bis(2,3-epoxypropylthio)-2-methylpentane, 1,5-bis(2,3-epoxypropylthio)-3-thiapentane, 1,6-bis(2,3-epoxypropylthio)hexane, 1,6-bis(2,3-epoxypropylthio)-2-methylhexane, 3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane, 1,2,3-tris(2,3-epoxypropylthio)propane, 2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane, 2,2-bis(2,3-epoxypropylthiomethyl)-1-(2,3-epoxypropylthio)butane, and the like.

[0117] Specific examples of the cyclic aliphatic sulfur atom-containing epoxy compound include 1,3-bis(2,3-epoxypropylthio)cyclohexane, 1,4-bis(2,3-epoxypropylthio)cyclohexane, 1,3-bis(2,3-epoxypropylthiomethyl)cyclohexane, 1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane, 2,5-bis(2,3-epoxypropylthiomethyl)-1,4-dithiane, 2,5-bis[<2-(2,3-epoxypropylthio)ethyl>thiomethyl]-1,4-dithiane, and 2,5-bis(2,3-epoxypropylthiomethyl)-2,5-dimethyl-1,4-dithiane.

[0118] (Compound Having a Radically Polymerizable Group) The radically polymerizable group is a polymerizable group that can undergo radical polymerization. Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group.

[0119] Hereinafter, a compound having a polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group will be referred to as a "(meth)acrylate compound." Specific examples of the (meth)acrylate compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo 1,1-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, bisphenol F di(meth)acrylate, 1,1-bis(4-(meth)acryloyloxyethoxyphenyl)methane, 1,1-bis(4-(meth)acryloyloxydiethoxyphenyl)methane, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylol Examples of the methylthio(meth)acrylate include methylpropane tetra(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methylthio(meth)acrylate, phenylthio(meth)acrylate, benzylthio(meth)acrylate, xylylenedithiol di(meth)acrylate, mercaptoethyl sulfide di(meth)acrylate, and bifunctional urethane (meth)acrylate.

[0120] Specific examples of compounds having an allyl group (allyl compounds) include allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether, polyethylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether, methacryloyloxypolyethylene glycol-polypropylene glycol allyl ether, phenoxypolyethylene glycol allyl ether, and methacryloyloxypolyethylene glycol allyl ether.

[0121] Examples of compounds having a vinyl group (vinyl compounds) include α-methylstyrene, α-methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobi(m-dioxane).

[0122] The photochromic article may include, at any position, one or more layers known as functional layers for photochromic articles, such as a protective layer for improving the durability of the photochromic article, an antireflection layer, a water-repellent or hydrophilic antifouling layer, an antifogging layer, and a primer layer for improving adhesion between layers.

[0123] The photochromic article can be an optical article. One type of optical article is a spectacle lens. Such spectacle lenses can also be called photochromic lenses or photochromic spectacle lenses. Other examples of optical articles include lenses for goggles, the visor portion of a sun visor, and the shielding member of a helmet. An optical article having anti-glare function can be obtained by applying the photochromic composition, which is a polymerizable composition, onto a substrate for such an optical article and then subjecting the applied composition to a curing treatment to form a photochromic layer.

[0124] [Eyeglasses] One aspect of the present invention relates to eyeglasses equipped with eyeglass lenses, which are one form of the photochromic article. Details of the eyeglass lenses included in the eyeglasses are as described above. By including such eyeglass lenses, the eyeglasses can, for example, exhibit an anti-glare effect like sunglasses outdoors by coloring the photochromic compound when irradiated with sunlight, and regain their transparency when returning indoors by fading the photochromic compound. Known technologies can be applied to the construction of the frames and other components of the eyeglasses.

[0125] The present invention will be further described below with reference to examples, but the present invention is not limited to the embodiments shown in the examples.

[0126] In the following, a nuclear magnetic resonance (NMR) spectrometer was used to identify molecular structures. A JEOL ECS-400 proton NMR spectrometer was used. Deuterated chloroform was primarily used as the measurement solvent, with deuterated dimethyl sulfoxide, deuterated acetone, deuterated acetonitrile, deuterated benzene, deuterated methanol, deuterated pyridine, and other solvents being used as appropriate only when the solvent was poorly soluble in deuterated chloroform. High-performance liquid chromatography (HPLC) was used to analyze purity. A Shimadzu LC-2040C HPLC was used. A YMC-Triart C18 column was used, and the measurement temperature was set to 40°C. The mobile phase was a mixed solvent of water and acetonitrile containing 0.1% trifluoroacetic acid, with a flow rate of 0.4 mL / min. Mass spectrometry was performed using a Nihon Waters ACQUITY UPLC H-Class system (UPLC) equipped with an SQD2 mass spectrometry unit. The column used was an ACQUITY UPLC BEH C18, and the measurement temperature was set to 40°C. The mobile phase was a mixed solvent of water with added formic acid and acetonitrile, with a concentration gradient applied at a flow rate of 0.61 mL / min. Electrospray ionization (ESI) was used for ionization. CHN (carbon, hydrogen, nitrogen) elemental analysis was performed by combustion. An Elementar Vario MICRO Cube was used as the measurement device, with temperatures set to 1150°C for the combustion furnace and 850°C for the reduction furnace. The helium flow rate was 200 mL / min, and the oxygen flow rate was 25-30 mL / min.

[0127] [Example 1] The products shown in the table below were obtained from the reactants shown in the table below by the following method. Under an argon atmosphere, p-toluenesulfonic acid monohydrate (0.15 g, 0.80 mmol) was added to a toluene solution (36 mL) of reactant A (1.9 g, 4 mmol) and reactant B (2.6 g, 8 mmol) shown in the table below, and the mixture was stirred at room temperature overnight. An aqueous sodium hydroxide solution (1.0 M, 37 mL) was added, and the mixture was stirred for about 20 minutes. Impurities were removed by filtration, and the mixture was extracted with toluene (30 mL x 2), after which the combined organic layers were washed with water (20 mL x 2) and concentrated. The resulting residue was purified by column chromatography (SiO ２The resulting solid was purified in a solvent (200 g, heptane / chloroform (volume basis) = 70 / 30 to 60 / 40) (1.0 g, brown solid). The resulting solid was suspended in heptane / ethyl acetate (2 / 1 (volume basis), 90 mL), ultrasonicated for about 30 minutes, and filtered. The filtered solid was dried in a vacuum oven at 105°C for 8 hours to obtain the final product shown in the table below as a light blue solid (0.8 g).

[0128] The resulting product was analyzed by the following method. The structure was identified by nuclear magnetic resonance (NMR). The purity was analyzed by HPLC, and the area ratio was the value shown in the table below. As a result of mass analysis, the calculated value of the exact mass shown in the table below was different from the measured value ([M+H] ＋ , relative intensity 100). As a result of CHN elemental analysis by combustion method, the calculated values ​​shown in the table below were compared with the measured values ​​shown in the table below. From the above analysis results, it was confirmed that the target compound, the compound shown in the table below, was obtained.

[0129] [Examples 2 to 20, Comparative Examples 1 to 3] The compounds shown in the tables below were obtained by the same procedures as above, except that the reactants A and B used in the synthesis of the compound represented by general formula 1 were replaced with the reactants shown in the tables below. The products obtained were analyzed by the methods described above. The analytical results are shown in the tables below.

[0130] [Fabrication of Eyeglass Lenses (Photochromic Articles)] <Preparation of Photochromic Composition (Polymerizable Composition)> In a plastic container, 68 parts by mass of polyethylene glycol diacrylate, 12 parts by mass of trimethylolpropane trimethacrylate, and 20 parts by mass of neopentyl glycol dimethacrylate were mixed with 100 parts by mass of (meth)acrylates in total to prepare a (meth)acrylate mixture. Each of the photochromic compounds of Examples 1 to 20 was mixed with 100 parts by mass of this (meth)acrylate mixture so that the amount was 2.5 parts by mass. Furthermore, a photopolymerization initiator (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), an antioxidant [bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid)] [ethylenebis(oxyethylene) and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) were mixed and thoroughly stirred, and then a silane coupling agent (γ-methacryloxypropyltrimethoxysilane) was added dropwise with stirring. The mixture was then degassed using an automatic revolution type stirring and degassing device. A photochromic composition was prepared by the above method.

[0131] <Formation of Primer Layer> A plastic lens substrate (manufactured by HOYA Corporation under the trade name EYAS: center thickness 2.5 mm, diameter 75 mm, spherical lens power -4.00) was subjected to alkaline cleaning by immersion in a 10% by mass aqueous sodium hydroxide solution (liquid temperature 60°C) for 5 minutes, followed by rinsing with pure water and drying. Thereafter, a water-based polyurethane resin liquid (polycarbonate polyol-based polyurethane emulsion, viscosity 100 cPs, solids concentration 38% by mass) was applied to the convex surface of the plastic lens substrate by spin coating at 1500 rpm for 1 minute using a Mikasa spin coater MS-B150 in an environment of room temperature and a relative humidity of 40 to 60%, and then allowed to air dry for 15 minutes to form a 5.5 μm-thick primer layer.

[0132] <Photochromic Layer Formation> The photochromic composition prepared above was dropped onto the primer layer and applied by spin coating using a MIKASA MS-B150 spin coater, with a program that ramped the rotational speed from 500 rpm to 1500 rpm over 1 minute in a slope mode, followed by 5 seconds at 1500 rpm. The photochromic composition coated on the primer layer formed on the plastic lens substrate was then irradiated with ultraviolet light (dominant wavelength 405 nm) for 40 seconds in a nitrogen atmosphere (oxygen concentration 500 ppm or less) to harden the composition and form a photochromic layer. The formed photochromic layer had a thickness of 45 μm. In this way, photochromic articles (eyeglass lenses) containing each of the photochromic compounds of Examples 1 to 20 were prepared. It was confirmed that all eyeglass lenses were colored upon UV irradiation and returned to their pre-UV state when UV irradiation was stopped.

[0133] [Evaluation of Fading Rate] For each of the Examples and Comparative Examples shown in the tables below, each compound was dissolved in stabilizer-free chloroform to prepare a chloroform solution of this compound. A 1 cm square quartz spectroscopic cell containing the prepared solution was covered, and the cell was irradiated with ultraviolet light for 15 seconds using a Hamamatsu Photonics UV-LED (a combination of LIGHTNINGCURE LC-L1V5 and L14310-120, output 70%) as the ultraviolet light source. The solution was stirred with a small stirrer during UV irradiation. The absorbance was measured within 10 seconds after the end of UV irradiation using a UV-visible spectrophotometer (Shimadzu UV-1900i, measurement wavelength 700-400 nm, wavelength in 2 nm increments, survey mode). The absorbance was measured at room temperature (23-28°C). The concentration of the solution was adjusted so that the absorbance at the first absorption wavelength (the peak of absorption intensity observed at the longest wavelength) was 0.95 to 1.05. Furthermore, the absorbance was measured every 10 seconds, and the attenuation of the absorbance was measured. The first absorbance measurement was normalized so that the peak at the first absorption wavelength was 1, and the subsequent attenuation of the absorbance was measured. The data for the first 100 seconds of fading (11 absorbance measurements) was analyzed using a first-order reaction model from the change in absorbance over time, and the reaction rate constant was determined. [A ０[A] is the concentration of the colored substance after a certain time, i.e., the normalized absorbance value, t is time (seconds), and k is the rate constant. The first-order reaction can be expressed by the following equation:

[0134]

[0135] The table below shows the reaction rate constants determined for each of the Examples and Comparative Examples. The photochromic compounds of Comparative Example 1 and Comparative Example 2 contain perfluoromethyl groups and are therefore subject to PFAS regulations. In contrast, the photochromic compounds of Examples 1 to 20 contain neither perfluoromethyl nor perfluoromethylene groups and are therefore exempt from PFAS regulations. The results shown in the table below confirm that the photochromic compounds of Examples 1 to 20 are exempt from PFAS regulations and exhibit a fast fading rate equivalent to that of the photochromic compounds of Comparative Example 1 and Comparative Example 2. Furthermore, the above measurements confirmed that the photochromic compounds of Examples 1 to 20 exhibit photochromic performance, in which they undergo structural transition to a molecular structure with strong visible absorption upon irradiation with ultraviolet light.

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146] Finally, the above-mentioned aspects will be summarized.

[0147] [1] A photochromic compound represented by the following general formula 1, which does not have a perfluoromethyl group or a perfluoromethylene group. (In General Formula 1, Ar represents a fluorinated aryl group, L represents a divalent linking group, R １ ~R ６ , B and B' each independently represent a hydrogen atom or a substituent, m represents 0 or 1, and n represents an integer ranging from 1 to 4. [2] The photochromic compound according to [1], wherein Ar represents a fluorinated phenyl group. [3] The photochromic compound according to [2], wherein Ar represents a fluorinated phenyl group substituted with three or more fluorine atoms. [4] The photochromic compound according to [3], wherein Ar represents a perfluorophenyl group. [5] R ４ and R ５ and R represent an electron-donating group. [6] The photochromic compound according to any one of [1] to [4]. ４ and R ５ [7] The photochromic compound according to [5], wherein R each independently represents an electron-donating group. [8] The photochromic compound according to [5] or [6], wherein the electron-donating group is an electron-donating group selected from the group consisting of an alkoxy group, a morpholino group, and a piperidino group. ４ and R ５ [9] The photochromic compound according to any one of [1] to [4], wherein R represents a hydrogen atom. ５

[10] The photochromic compound according to any one of [1] to [4], wherein R represents a fluorinated aryl group. ５

[11] The photochromic compound according to any one of [1] to

[10] , wherein B and B' each independently represent a substituted or unsubstituted phenyl group.

[12] R １ and R ２

[13] The photochromic compound according to any one of [1] to

[11] , wherein R each independently represents a substituted or unsubstituted alkyl group. １ and R ２

[14] The photochromic compound according to any one of [1] to

[12] , wherein R each independently represents a substituted or unsubstituted alkyl group having two or more carbon atoms, and B and B' each independently represent an unsubstituted phenyl group or a phenyl group substituted with a methoxy group. １ and R ２

[15] The photochromic compound according to any one of [1] to

[12] , wherein R each independently represents a substituted or unsubstituted alkyl group having two or more carbon atoms, and at least one of B and B' represents a phenyl group substituted with an amino group. １ and R ２

[16] The photochromic compound according to any one of [1] to

[12] , wherein R represents a methyl group, and at least one of B and B' represents a phenyl group substituted with an amino group. １ and R ２

[17] The photochromic compound according to any one of [1] to

[12] , wherein R represents a methyl group, and B and B' each independently represent an unsubstituted phenyl group or a phenyl group substituted with a methoxy group. １ and R ２ The photochromic compound according to any one of [1] to

[11] , wherein R are bonded to each other to form a ring structure having three or more carbon atoms constituting the ring, including the carbon atom at the 13th position of the indeno-fused naphthopyran.

[18] R ３ and R ６and m each represent a hydrogen atom.

[19] The photochromic compound according to any one of [1] to

[18] , wherein n represents 1 or 2 and m represents 0.

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

[19] .

[21] The photochromic composition according to

[20] , further comprising a polymerizable compound.

[22] A photochromic article comprising a cured product obtained by curing the photochromic composition according to

[21] .

[23] The photochromic article according to

[22] , which has a substrate and a photochromic layer that is the cured product.

[24] The photochromic article according to

[22] or

[23] , which is a spectacle lens.

[25] The photochromic article according to

[22] or

[23] , which is a goggle lens, a visor portion of a sun visor, or a helmet shield member.

[26] Eyeglasses equipped with the spectacle lens according to

[24] .

[0148] Two or more of the various aspects and configurations described herein may be combined in any combination.

[0149] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims, not by the above description, and is intended to include all modifications within the meaning and scope of the claims.

[0150] One aspect of the present invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets, and the like.

Claims

1. A photochromic compound represented by the following general formula 1 and having no perfluoromethyl group and perfluoromethylene group. (In general formula 1, Ar represents a fluorinated aryl group, L represents a divalent linking group, and R １ ~R ６ , B and B' each independently represent a hydrogen atom or a substituent, m represents 0 or 1, and n represents an integer in the range of 1 to 4.) 2. The photochromic compound according to claim 1, wherein Ar represents a fluorinated phenyl group.

3. The photochromic compound according to claim 2, wherein Ar represents a fluorinated phenyl group substituted by three or more fluorine atoms.

4. The photochromic compound according to claim 3, wherein Ar represents a perfluorophenyl group.

5. R ４ and R ５ is a photochromic compound according to any one of claims 1 to 4, wherein at least one of them represents an electron-donating group.

6. R ４ and R ５ each independently represents an electron-donating group, the photochromic compound according to claim 5.

7. The photochromic compound according to claim 5 or 6, wherein the electron-donating group is an electron-donating group selected from the group consisting of an alkoxy group, a morpholino group, and a piperidino group.

8. R ４ and R ５ The photochromic compound according to any one of claims 1 to 4, wherein both represent a hydrogen atom.

9. R ５ The photochromic compound according to any one of claims 1 to 4, wherein R represents a fluorinated aryl group.

10. R ５ The fluorinated aryl group represented by is a perfluoroaryl group, and the photochromic compound according to claim 9.

11. The photochromic compound according to any one of claims 1 to 10, wherein B and B' each independently represent a substituted or unsubstituted phenyl group.

12. R １ and R ２ each independently represents a substituted or unsubstituted alkyl group, the photochromic compound according to any one of claims 1 to 11.

13. R １ and R ２ each independently represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, and B and B' each independently represent an unsubstituted phenyl group or a phenyl group substituted with a methoxy group. The photochromic compound according to any one of claims 1 to 12.

14. R １ and R ２ each independently represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, and at least one of B and B' represents a phenyl group substituted with an amino group. The photochromic compound according to any one of claims 1 to 12.

15. R １ and R ２ each represents a methyl group, and at least one of B and B' represents a phenyl group substituted with an amino group, the photochromic compound according to any one of claims 1 to 12.

16. R １ and R ２ each represents a methyl group, and B and B' each independently represent an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, the photochromic compound according to any one of claims 1 to 12.

17. R １ and R ２ are bonded to each other to form a ring structure having 3 or more carbon atoms including the carbon atom at the 13-position of the indeno-fused naphthopyran, the photochromic compound according to any one of claims 1 to 11.

18. R ３ and R ６ The photochromic compound according to any one of claims 1 to 17, wherein both represent a hydrogen atom.

19. The photochromic compound according to any one of claims 1 to 18, wherein n represents 1 or 2 and m represents 0.

20. A photochromic composition comprising the photochromic compound according to any one of claims 1 to 19.

21. The photochromic composition according to claim 20, further comprising a polymerizable compound.

22. A photochromic article comprising a cured product obtained by curing the photochromic composition according to claim 21.

23. The photochromic article according to claim 22, having a substrate and the photochromic layer which is the cured product.

24. The photochromic article according to claim 22 or 23, which is an eyeglass lens.

25. The photochromic article according to claim 22 or 23, which is a lens for goggles, a visor portion of a sun visor, or a shield member of a helmet.

26. A pair of glasses provided with the eyeglass lens according to claim 24.

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