Photochromic compound, photochromic composition, photochromic article, and eyeglasses

Abstract

The present invention provides a photochromic compound expressed by general formula 1. In general formula 1: R1 and R2 bond to each other to form a ring structure; the ring structure is spiro fused with an indeno-fused naphthopyran or R1 and R2 each independently represent a substituted or unsubstituted C1 or more straight-chain or branched alkyl group, a substituted or unsubstituted C3 or more cyclic alkyl group, or a substituted or unsubstituted group represented by –R100)nR101; R100 represents an alkyleneoxy group; R101 represents an alkyl group; n represents an integer of at least 1; there are at least a total of 2 carbon atoms in the n alkyleneoxy groups represented by R100 and alkyl groups represented by R101; R3-R6 each independently represent a hydrogen atom or a nonconjugated substituent; R7-R10 each independently represent a hydrogen atom or a substituent; and R11-R20 each independently represent a hydrogen atom or a substituent, where one or more of R11-R20 represents an amino group represented by general formula 2. In general formula 2: n represents 0 or 1; Ar, when n is 0, represents a substituted or unsubstituted aryl group having 5 or more ring constituent atoms or a substituted or unsubstituted heteroaryl group having 5 or more ring constituent atoms, or, when n is 1, a substituted or unsubstituted arylene group having 5 or more ring constituent atoms or a substituted or unsubstituted heteroarylene group having 5 or more ring constituent atoms; R, when n is 0, represents a monovalent substituent, and, when n is 1, represents a divalent substituent; L represents a single bond or a divalent linking group selected from the group consisting of C1-10 substituted or unsubstituted straight-chain, branched, or cyclic alkylene groups, C1-20 substituted or unsubstituted arylene groups, C1-20 substituted or unsubstituted alkyl arylene groups, ether groups, sulfide groups, sulfone groups, sulfoxide groups, –NR200– (R200 represents a hydrogen atom or a substituent), or –SiRaRb– (Ra and Rb each independently represent a substituted or unsubstituted alkyl group); and "*" represents a bonding site with a benzene ring.

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 the property of coloring when irradiated with light in a photoresponsive wavelength range and fading in the absence of light (photochromic property). For example, Patent Documents 1 to 3 disclose naphthopyran-based compounds having photochromic properties.

[0003] WO2001 / 60811A1 WO1996 / 014596A1 U.S. Pat. No. 6,296,785

[0004] Methods for imparting photochromic properties to various articles include a method of incorporating a photochromic compound into a substrate and a method of forming a layer containing a photochromic compound. For example, articles imparted with photochromic properties in this way (photochromic articles) are useful as optical articles such as eyeglass lenses.

[0005] For example, when irradiated with light such as sunlight, a photochromic compound undergoes an excited state and undergoes structural transformation into a colored body. The structure after structural transformation via light irradiation can be called a "colored body." In contrast, the structure before light irradiation can be called a "colorless body." Note that "colorless" in the colorless body does not necessarily mean completely colorless, but also includes cases where the color is lighter than that of the colored body. Photochromic compounds that have low absorption of short-wavelength visible light around 400 nm in the colorless state are preferred for providing photochromic articles with little coloring (e.g., yellowish tinge) in usage environments such as indoors.

[0006] In recent years, studies have been conducted to achieve a desired color tone when coloring a photochromic article by combining multiple photochromic compounds with different absorption characteristics. Photochromic compounds with a large absorption peak on the long wavelength side (e.g., wavelengths of 580 nm or longer) are useful as such photochromic compounds. However, in photochromic compounds in which the colored form has a large absorption peak on the long wavelength side, not only the colored form but also the uncolored form tends to easily absorb light on the long wavelength side, and in the colorless form, absorption of short-wavelength visible light around 400 nm tends to be large.

[0007] An object of one aspect of the present invention is to provide a photochromic compound that has a large absorption peak on the long wavelength side and absorbs little short wavelength visible light in a colorless state.

[0008] As a result of extensive research, the present inventors have newly discovered that a photochromic compound represented by general formula 1 having the structure shown below has a peak wavelength on the long wavelength side and exhibits little absorption of short wavelength visible light in a colorless state.

[0009] That is, one aspect of the present invention relates to a photochromic compound represented by the following general formula 1:

[0010] The structure of general formula 1 is the structure of a colorless body.

[0011] Another aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by the following general formula 1:

[0012] Another aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by the following general formula 1:

[0013]

[0014] In general formula 1, R １ and R ２ are bonded to each other to form a ring structure, and this ring structure is a ring structure that is spiro-fused with the indeno-fused naphthopyran, or R １ and R ２are each independently a substituted or unsubstituted linear or branched alkyl group having 1 or more carbon atoms; a substituted or unsubstituted cyclic alkyl group having 3 or more carbon atoms; or a substituted or unsubstituted -(R １００ ) ｎ R １０１ R represents a group represented by １００ represents an alkyleneoxy group, and R １０１ represents an alkyl group, n represents an integer of 1 or more, and n R １００ and an alkyleneoxy group represented by R １０１ The total number of carbon atoms in the alkyl group represented by R is 2 or more, ３ ~R ６ each independently represents a hydrogen atom or a non-conjugated substituent, R ７ ~R １０ each independently represents a hydrogen atom or a substituent, R １１ ~R ２０ each independently represents a hydrogen atom or a substituent, provided that R １１ ~R ２０ At least one of represents an amino group represented by the following general formula 2.

[0015]

[0016] In general formula 2, n represents 0 or 1; when n is 0, Ar represents a substituted or unsubstituted aryl group having 5 or more ring atoms or a substituted or unsubstituted heteroaryl group having 5 or more ring atoms, when n is 1, Ar represents a substituted or unsubstituted arylene group having 5 or more ring atoms or a substituted or unsubstituted heteroarylene group having 5 or more ring atoms; when n is 0, R represents a monovalent substituent; when n is 1, R represents a divalent substituent; L represents a single bond, a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted arylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylarylene group having 1 to 20 carbon atoms, an ether group, a sulfide group, a sulfone group, a sulfoxide group, -NR １００ - (R １００represents a hydrogen atom or a substituent) or a divalent linking group selected from the group consisting of -SiRaRb- (Ra and Rb each independently represent a substituted or unsubstituted alkyl group), and * represents the bonding position to the benzene ring.

[0017] According to one aspect of the present invention, it is possible to provide a photochromic compound that has a large absorption peak on the long wavelength side and that absorbs little short wavelength visible light in a colorless state, and a photochromic article containing such a photochromic compound.

[0018] 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.

[0019] 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.

[0020] In the present invention and this specification, the substituents in the various general formulae described in detail later, and further the substituents when each group described later 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 (bicyclic or other) 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 1 to 18 carbon atoms such as a trifluoromethyl group; a linear or branched perfluoroalkoxy group such as a trifluoromethoxy group; linear or branched alkyl sulfide groups, aryl groups such as phenyl group, naphthyl group, anthracenyl group, fluoranthenyl group, phenanthryl group, pyranyl group, perylenyl group, styryl group, and fluorenyl group, aryloxy groups such as phenoxy group, aryl sulfide groups such as phenyl sulfide group, heteroaryl groups such as pyridyl group, furanyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, diazolyl group, triazolyl group, quinolinyl group, phenothiazinyl group, phenoxazinyl group, phenazinyl group, thianthryl group, and acridinyl group, amino groups (-NH ２ a 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 ｍThe substituent may be substituted with ;

[0021] 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 at the terminal carbon atom of the alkoxy group, and another alkoxy group is further substituted at 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.

[0022] In the present invention and this specification, the terms "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. Furthermore, in the present invention and this specification, "substituted or (or) unsubstituted" is synonymous with "unsubstituted or (or) having one or more substituents."

[0023] 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.

[0024] 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 trifluoromethyl 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 trifluoromethyl 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.

[0025] In the present invention and this specification, the term "electron-withdrawing group" refers to a substituent that more easily attracts electrons from the atom to which it is bonded compared to a hydrogen atom. The electron-withdrawing group can attract electrons as a result of substituent effects such as the inductive effect and the mesomeric effect (or resonance effect). Specific examples of the electron-withdrawing group include halogen atoms (fluorine atom: -F, chlorine atom: -Cl, bromine atom: -Br, iodine atom: -I), trifluoromethyl group: -CF ３ , nitro group: —NO ２ , cyano group: —CN, formyl group: —CHO, acyl group: —COR (R is a substituent), alkoxycarbonyl group: —COOR, carboxy group: —COOH, substituted sulfonyl group: —SO ２ R (R is a substituent), sulfo group: —SO ３ Suitable electron-withdrawing groups include a fluorine atom, which is an electron-withdrawing group with high electronegativity, and a substituent group having a para-substituent constant σ based on Hammett's rule. ｐ can be exemplified by electron-withdrawing groups in which the value of is positive.

[0026] 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 , alkylamino group: -NHR (R is an alkyl group), acetamide group: -NHCOCH ３ , dialkylamino group: —N(R) ２ (wherein the two R's are the same or different alkyl groups), 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

[0027] 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

[0028] [Photochromic Compound Represented by General Formula 1] The photochromic compound represented by General Formula 1 will be described in more detail below.

[0029]

[0030] In general formula 1, R １ and R ２ are bonded to each other to form a ring structure, and this ring structure is a ring structure that is spiro-fused with the indeno-fused naphthopyran, or R １ and R ２ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 or more carbon atoms; a substituted or unsubstituted cyclic alkyl group having 3 or more carbon atoms; or a substituted or unsubstituted -(R １００ ) ｎ R １０１ R represents a group represented by １００ represents an alkyleneoxy group, and R １０１ represents an alkyl group, n represents an integer of 1 or more, and n R １００ and an alkyleneoxy group represented by R １０１ The total number of carbon atoms in the alkyl group represented by the formula (I) is 1 or more.

[0031] In one embodiment, in general formula 1, R １ and R ２ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 or more carbon atoms; a substituted or unsubstituted cyclic alkyl group having 3 or more carbon atoms; or a substituted or unsubstituted -(R １００ ) ｎ R １０１ R represents a group represented by １００ represents an alkyleneoxy group, and R １０１ represents an alkyl group, n represents an integer of 1 or more, and n R １００ and an alkyleneoxy group represented by R １０１ The total number of carbon atoms in the alkyl group represented by the formula (I) is 2 or more.

[0032] In general formula 1, R １ and R ２ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 or more carbon atoms (for example, 1 to 20, preferably 1 to 10); a substituted or unsubstituted cyclic alkyl group having 3 or more carbon atoms (for example, 3 to 20); or a substituted or unsubstituted -(R １００ ) ｎ R １０１ R represents a group represented by １００ represents an alkyleneoxy group, and R １０１ represents an alkyl group, n represents an integer of 1 or more, and n R １００ and an alkyleneoxy group represented by R １０１ The total number of carbon atoms in the alkyl group represented by the formula (I) is 2 or more (for example, 2 or more and 50 or less). When the linear or branched alkyl group having 1 or more carbon atoms has a substituent, the number of carbon atoms in the alkyl group refers to the number of carbon atoms in the portion excluding the substituent. When the cyclic alkyl group having 3 or more carbon atoms has a substituent, the number of carbon atoms in the alkyl group refers to the number of carbon atoms in the portion excluding the substituent. １００ ) ｎ R １０１ " has a substituent, n R １００ and an alkyleneoxy group represented by R １０１ The total number of carbon atoms in the alkyl group represented by the formula (I) refers to the number of carbon atoms in the portion excluding the substituents.

[0033] R １ and R ２ Preferably, R each independently represents a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, or a t-butyl group. ３０ and R ３１ More preferably, each of R represents an ethyl group. １ and R ２ may each independently be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, or a substituted or unsubstituted propyl group. １ and R ２ may each independently be an unsubstituted methyl group, an unsubstituted ethyl group, or an unsubstituted propyl group. １ and R ２ can all be unsubstituted methyl groups, can all be unsubstituted ethyl groups, or can all be unsubstituted propyl groups.

[0034] R １ and R ２ can be the same group or different groups.

[0035] In one form, R １ and R ２ are bonded to each other to form a ring structure, and this ring structure is a ring structure that is spiro-fused with the indeno-fused naphthopyran. Such a ring structure can be unsubstituted or can have a substituent. When the ring structure has a substituent, the number of carbon atoms mentioned above refers to the number of carbon atoms including the number of carbon atoms of the substituent. The number of carbon atoms in the ring structure (including the carbon atom at position 13 of the indeno-fused naphthopyran) can be, for example, 3 or more, 4 or more, 5 or more, 6 or more, or 7 or more. Furthermore, the number of carbon atoms in the ring structure (including the carbon atom at position 13 of the indeno-fused naphthopyran) can be, for example, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, or 15 or less.

[0036] The ring structure may be a substituted or unsubstituted alicyclic structure. Such an alicyclic structure may be a monocyclic structure, a fused polycyclic structure such as a bicyclic or tricyclic structure, or a bridged ring structure such as a bicyclic structure.

[0037] In general formula 1, the following partial structure: Specific examples of the partial structure include the following partial structures and partial structures contained in the exemplified compounds shown below. In the present invention and this specification, an "*" regarding a partial structure of a compound indicates the bonding position of the atom to which the partial structure is bonded.

[0038]

[0039] R ３ ~R ６ each independently represents a hydrogen atom or a non-conjugated substituent. ３ ~R ６ (Especially R ４ When a substituent other than a conjugated substituent is substituted on the group (B), the absorption of short wavelength visible light by the photochromic compound tends to increase.

[0040] In the present invention and this specification, the term "non-conjugated substituent" refers to a substituent that does not form a conjugated system with the aromatic ring when substituted into an aromatic ring. The non-conjugated substituent preferably satisfies one or more of the following (i) to (iii), more preferably satisfies two or more, and even more preferably satisfies all three. (i) The atoms constituting this substituent are all sp3 hybridized atoms. (ii) The atoms constituting this substituent do not have lone pairs. (iii) This substituent does not have an empty p orbital.

[0041] Specific examples of the non-conjugated substituent include substituted or unsubstituted alkyl groups such as a substituted or unsubstituted methyl group, an ethyl group, and a propyl group; a substituted or unsubstituted silyl group; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; and a perfluoroalkyl group such as a trifluoromethyl group. From the viewpoint that the photochromic compound can exhibit a fast fading rate after being colored by light irradiation, a fluorine atom or a trifluoromethyl group, which are electron-withdrawing groups, are preferred, and R ４is more preferably a fluorine atom or a trifluoromethyl group.

[0042] In one form, R ３ ~R ６ can all represent hydrogen atoms. ４ represents a non-conjugated substituent and R ３ , R ５ and R ６ can represent a hydrogen atom, and preferably R ４ represents the non-conjugated substituents listed as specific examples above, and R ３ , R ５ and R ６ can represent a hydrogen atom, and more preferably R ４ represents a fluorine atom or a trifluoromethyl group, and R ３ , R ５ and R ６ can represent a hydrogen atom.

[0043] R ７ ~R １０ each independently represents a hydrogen atom or a substituent. For the substituent, see the above description.

[0044] R ７ and R １０ are preferably all hydrogen atoms.

[0045] In one form, R ８ and R ９ may each independently represent a hydrogen atom or an electron-donating group. From the viewpoint of further suppressing absorption of short-wavelength visible light, R ８ represents an electron-donating group and R ９ represents a hydrogen atom, or R ８ and R ９ Preferably, each independently represents an electron-donating group. ８ and an electron-donating group represented by R ９ The electron donating groups represented by the following formula may be bonded to form a ring structure. Examples of such ring structures include the following ring structures in which alkyl sulfide groups or alkoxy groups are bonded to each other, and the following ring structures in which alkyl sulfide groups and alkoxy groups are bonded to each other. ｍis the substituent R ｍ and is preferably a substituted or unsubstituted methyl group or ethyl group, more preferably an unsubstituted methyl group or ethyl group.

[0046]

[0047] In one form, R ８ and R ９ can represent a hydrogen atom. ８ and R ９ In another embodiment, one of R represents an electron-donating group and the other represents a hydrogen atom. ８ and R ９ R may represent the same or different electron donating groups. ８ and / or R ９ The electron-donating group represented by the formula (I) is preferably an alkoxy group, more preferably a methoxy group.

[0048] In another embodiment, R ８ and R ９ R can each independently represent a hydrogen atom or an electron-withdrawing group. ８ and R ９ Each of R independently represents a hydrogen atom or an electron-withdrawing group, from the viewpoint of further suppressing absorption of short-wavelength visible light. ８ and an electron-withdrawing group represented by R ９ may be bonded to form a ring structure. For example, R ８ and R ９ In another embodiment, one of R represents an electron-withdrawing group and the other represents a hydrogen atom. ８ and R ９ R may represent the same or different electron-withdrawing groups. ８ and / or R ９ The electron-withdrawing group represented by is preferably a halogen atom, more preferably a fluorine atom. More preferably, R ９ and R ４ can represent a fluorine atom, and more preferably R ９ and R ４ represents a fluorine atom and R ３ ~R ８ and R１０ can represent a hydrogen atom.

[0049] R １１ ~R ２０ each independently represents a hydrogen atom or a substituent. １１ ~R ２０ One or more of the following represent an amino group represented by the following general formula 2. By having such a structure in which the π-conjugated system of the molecular skeleton is extended, the photochromic compound represented by general formula 1 can have a large absorption peak on the long wavelength side. On the other hand, if the conjugated system of the photochromic compound is simply extended, not only the colored form but also the uncolored form will tend to absorb light on the long wavelength side, and in the colorless state, absorption of short wavelength visible light with a wavelength of around 400 nm tends to be large. In contrast, the photochromic compound represented by general formula 1, having the structure described above, can contribute to suppressing absorption of short wavelength visible light with a wavelength of around 400 nm in the colorless state.

[0050]

[0051] In general formula 2, * represents the bonding position to the benzene ring.

[0052] In general formula 2, n represents 0 or 1. When n is 0, Ar represents a substituted or unsubstituted aryl group having 5 or more ring atoms or a substituted or unsubstituted heteroaryl group having 5 or more ring atoms, and when n is 1, Ar represents a substituted or unsubstituted arylene group having 5 or more ring atoms or a substituted or unsubstituted heteroarylene group having 5 or more ring atoms.

[0053] The substituted or unsubstituted aryl group having 5 or more ring atoms can be, for example, a substituted or unsubstituted aryl group having 5 to 10 ring atoms, and specific examples thereof include a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group. When the aryl group is a substituted aryl group, examples of the substituent include the substituents described above, and specific examples thereof include alkyl groups (e.g., methyl groups), alkoxy groups (e.g., methoxy groups, ethoxy groups, butoxy groups), aryl groups (e.g., phenoxy groups), heteroaryl groups (e.g., pyridyl groups), and aryloxy groups (e.g., phenoxy groups). The above substituents can also have a substituent. Examples of such substituents include the substituents described above. In addition, the substituent of the substituted aryl group may form a ring structure such as a fused ring together with the aryl group substituted by this substituent. Specific examples of such ring structures include the ring structures contained in the exemplary compounds shown below.

[0054] The substitution position of the substituent in the substituted phenyl group can be the ortho-position, meta-position or para-position relative to the nitrogen atom (N) shown in General Formula 2, and the para-position is preferred.

[0055] The substituted or unsubstituted heteroaryl group having 5 or more ring atoms can be, for example, a substituted or unsubstituted heteroaryl group having 5 to 10 ring atoms, and specific examples include a substituted or unsubstituted pyridyl group. When the heteroaryl group is a substituted heteroaryl group, the above description of the substituents that the aryl group may have can be referenced for the substituents.

[0056] When n is 1, with respect to a substituted or unsubstituted arylene group having 5 or more ring-constituting atoms or a substituted or unsubstituted heteroarylene group having 5 or more ring-constituting atoms represented by Ar, the above descriptions regarding the aryl group and the heteroaryl group for Ar when n is 0 can be applied by replacing the descriptions regarding the aryl group with the descriptions regarding the arylene group, and the descriptions regarding the heteroaryl group with the descriptions regarding the heteroarylene group.

[0057] When n is 0, L is absent and R represents a monovalent substituent.

[0058] For the monovalent substituent, the above description regarding substituents can be referenced. In one embodiment, the monovalent substituent can represent a substituted or unsubstituted aryl group having 5 or more ring atoms or a substituted or unsubstituted heteroaryl group having 5 or more ring atoms. For such aryl groups and heteroaryl groups, the above description regarding Ar can be referenced. When R represents a substituted or unsubstituted aryl group having 5 or more ring atoms or a substituted or unsubstituted heteroaryl group having 5 or more ring atoms, R can be the same as or different from Ar.

[0059] When n is 1, L is present, and R represents a divalent substituent. In this case, R is bonded to Ar via L. In one embodiment, the divalent substituent can represent a substituted or unsubstituted arylene group having 5 or more ring-constituting atoms or a substituted or unsubstituted heteroarylene group having 5 or more ring-constituting atoms. With regard to such arylene groups and heteroarylene groups, the above description regarding the aryl group and heteroaryl group for Ar can be applied by replacing the description regarding the aryl group with the description regarding the arylene group, and the description regarding the heteroaryl group with the description regarding the heteroarylene group.

[0060] L is a single bond, a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted arylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylarylene group having 1 to 20 carbon atoms, an ether group (—O—), a sulfide group (—S—), a sulfone group (—S(═O) ２ -), sulfoxide group (-S(=O)-), -NR １００ - (R ２００ represents a hydrogen atom or a substituent) or a divalent linking group selected from the group consisting of -SiRaRb- (Ra and Rb each independently represent a substituted or unsubstituted alkyl group). R ２００When represents a substituent, such a substituent can be, for example, an alkyl group, and preferably a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms (preferably 1 or 2). Ra and Rb can each preferably independently represent a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms (preferably 1 or 2). When n represents 1 and L is present, the amino group represented by general formula 2 can be an amino group having a fused ring structure. Specific examples of such amino groups include the amino groups contained in the exemplified compounds shown below.

[0061] In general formula 1, R １１ ~R ２０ One or more of R represents an amino group represented by general formula 2. １１ ~R ２０ In the photochromic compound represented by general formula 1, when two or more amino groups represented by general formula 2 are contained, the amino groups may be the same or different. １１ ~R ２０ The total number of amino groups represented by general formula 2 contained as one or more of R １１ ~R ２０ Among them, R １８ represents an amino group represented by general formula 2, and R １２ and R １３ may each independently represent a hydrogen atom or a substituent, and the others may each represent a hydrogen atom. More preferably, R １１ ~R ２０ Among them, R １８ represents an amino group represented by general formula 2, and R １３ represents a substituent, and the others may represent a hydrogen atom. １２ and / or R １３When R represents a substituent, examples of the substituent include a halogen atom (e.g., a fluorine atom), an alkoxy group (e.g., a methoxy group, an ethoxy group, a butoxy group), an alkyl sulfide group (e.g., a methyl sulfide group), a dialkylamino group (e.g., a dimethylamino group), an aryloxy group (e.g., a phenoxy group), a cyclic amino group (e.g., a piperidino group, a morpholino group), and the like. １３ may preferably represent an alkoxy group, a dialkylamino group, an aryloxy group, or a cyclic amino group, and more preferably represent an alkoxy group, a dimethylamino group, a phenoxy group, a piperidino group, or a morpholino group.

[0062] In one form, R １８ represents an amino group represented by general formula 2, in which n represents 0 and Ar represents a substituted aryl group having 5 or more ring atoms. Preferably, R represents a substituted aryl group having 5 or more ring atoms. More preferably, Ar and R each independently represent a mono-substituted phenyl group substituted with an alkoxy group. Even more preferably, Ar and R represent a mono-substituted phenyl group substituted with a methoxy group. The substitution position of the alkoxy group or methoxy group is preferably the para position relative to the nitrogen atom (N) shown in general formula 2.

[0063] Examples of photochromic compounds represented by general formula 1 include the following compounds. Specific examples of each moiety in general formula 1 include those included in the exemplified compounds shown below. However, the present invention is not limited to the exemplified compounds shown below.

[0064]

[0065]

[0066]

[0067] 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, US 2006 / 0226402 A1, US 2006 / 0228557 A1, US 2008 / 0103301 A1, US 2011 / 0108781 A1, US 2012 / 0145973 A1, U.S. Patent No. 7,527,754, U.S. Patent No. 7,556,751, WO 2001 / 60811 A1, WO 2013 / 086248 A1, WO 1996 / 014596 A1, and WO 2001 / 019813 A1.

[0068] [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.

[0069] 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.

[0070] 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. Other photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaarylbisimidazoles, donor-acceptor Stenhouse adducts (DASA), salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, and stilbenes.

[0071] <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 be higher or lower than 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).

[0072] 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.).

[0073] 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.

[0074] <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.

[0075] 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.

[0076] <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.

[0077] Examples of polymerizable compounds that can be used to form the substrate and the photochromic layer include the following compounds.

[0078] (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.

[0079] (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.

[0080] 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.

[0081] 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.

[0082] Specific examples of alkylthio(thietanylthio)tin include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, and isopropylthiotris(thietanylthio)tin.

[0083] 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.

[0084] 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.

[0085] Specific examples of the bis(thietanylthio)cyclic dithiotin compound include bis(thietanylthio)dithiastannetane, bis(thietanylthio)dithiastannolane, bis(thietanylthio)dithiastanninane, and bis(thietanylthio)trithiastannocane.

[0086] Specific examples of the alkyl(thietanylthio)tin compound include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, and tetrakis(thietanylthio)tin.

[0087] (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.

[0088] (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.

[0089] 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.

[0090] Specific examples of the alicyclic epoxy compound include isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] (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.

[0096] 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.

[0097] 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.

[0098] 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).

[0099] 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.

[0100] 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.

[0101] [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.

[0102] 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.

[0103] [Example 1] The product shown in Table 1 was obtained from raw material compound A and raw material compound B shown in Table 1 by the following method. Under an argon atmosphere, raw material compound A (125 g, 243 mmol), dipalladium-tris(dibenzylideneacetone) chloroform complex (Pd ２ dba ３ CHCl ３ , 2.52 g, 2.43 mmol), XPhos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) (2.52 g, 2.43 mmol), sodium tert-butoxide (32.7 g, 341 mmol), and a toluene solution (300 mL) of diphenylamine (61.8 g, 365 mmol) as raw material compound B were stirred at an external temperature of 105°C for 2 hours. After cooling, the mixture was filtered through Celite, and the insoluble matter was washed with chloroform (500 mL). The concentrate of the filtrate was subjected to silica gel column chromatography (SiO ２ The product (120 g) was obtained as a dark blue solid by purifying with 2 kg of hexane / ethyl acetate (volume basis) = 90 / 10 to 75 / 25).

[0104] The molecular structure of the product was identified by nuclear magnetic resonance (proton NMR), accurate mass analysis, and CHN elemental analysis. The nuclear magnetic resonance spectrometer used was an ECS-400 manufactured by JEOL Ltd., and deuterated chloroform or deuterated dimethyl sulfoxide was used as the measurement solvent. For accurate mass analysis, a Shimadzu Corporation high-performance liquid chromatography LC-30A system equipped with a Thermo Fisher Scientific K.K. Q Exactive mass spectrometer was used. The combustion method was used for CHN elemental analysis. High-performance liquid chromatography (HPLC) was used for purity analysis. The LC-2040C manufactured by Shimadzu Corporation was used for purity analysis. The above analytical results comprehensively confirmed that the target compound, the product shown in Table 1, was obtained.

[0105] [Examples 2 to 6, Comparative Examples 1 and 2] The products shown in Table 1 were obtained by the same procedures as above, except that the compounds shown in Table 1 were used as raw material compound A and raw material compound B used in the synthesis of the compounds. The obtained products were analyzed by the methods described above. The analytical results comprehensively confirmed that the target compounds, the products shown in Table 1, were obtained.

[0106] [Evaluation Method] <Evaluation of Transparency in Short Wavelength Visible Region of Uncolored Material> Each compound of the Examples and Comparative Examples was dissolved in chloroform containing no stabilizer, and the chloroform solution of the compound (concentration: 2.8×10 －３ The prepared solution was placed in a 1 cm square quartz spectroscopic cell, which was then covered and left to stand in a UV-visible spectrophotometer (i.e., under light-shielded conditions) for 30 minutes, after which the absorbance was measured using a UV-visible spectrophotometer (Shimadzu UV-1900i, measurement wavelength: 800-250 nm, wavelength increments of 2 nm, high-speed mode). The absorbance was measured at room temperature (20-25°C). The molar extinction coefficient ε (mol －１ Lcm －１ The molar extinction coefficient ε was 6,000 mol －１ Lcm －１ If it is less than 6,000 mol, it is considered "passed" －１ Lcm －１The compounds of Examples 1 to 6 and Comparative Example 2 all had a molar absorption coefficient ε of 6000 mol at a wavelength of 400 nm. －１ Lcm －１ The molar absorption coefficient ε of the compound of Comparative Example 2 at a wavelength of 400 nm was 2900 mol －１ Lcm －１ The compound of Comparative Example 1 had a molar absorption coefficient ε of 6200 mol at a wavelength of 400 nm. －１ Lcm －１ The result was a "fail" rating.

[0107] <Evaluation of Absorption Properties of Colored Materials> For each of the Examples and Comparative Examples shown in Table 1, 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. Within 10 seconds after the end of UV irradiation, the absorbance was measured using a UV-visible spectrophotometer (Shimadzu UV-1900i, measurement wavelength 700-400 nm, wavelength increments of 2 nm, survey mode) to obtain an absorption spectrum. 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. The wavelength of the first absorption wavelength (the peak of absorption intensity observed at the longest wavelength) of the absorption spectrum thus obtained was read and shown as the maximum absorption peak wavelength in Table 1. From the viewpoint of usefulness as a photochromic compound having a large absorption peak on the long wavelength side, the maximum absorption peak wavelength thus obtained is preferably 580 nm or longer, and more preferably 600 nm or longer.

[0108] The results are shown in Table 1 (Table 1-1 to Table 1-3).

[0109]

[0110]

[0111]

[0112] Finally, the above-mentioned aspects will be summarized.

[0113] [1] A photochromic compound represented by the following general formula 1: (In general formula 1, R １ and R ２ are bonded to each other to form a ring structure, and this ring structure is a ring structure that is spiro-fused with the indeno-fused naphthopyran, or R １ and R ２ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 or more carbon atoms; a substituted or unsubstituted cyclic alkyl group having 3 or more carbon atoms; or a substituted or unsubstituted -(R １００ ) ｎ R １０１ R represents a group represented by １００ represents an alkyleneoxy group, and R １０１ represents an alkyl group, n represents an integer of 1 or more, and n R １００ and an alkyleneoxy group represented by R １０１ The total number of carbon atoms in the alkyl group represented by R is 2 or more, ３ ~R ６ each independently represents a hydrogen atom or a non-conjugated substituent, ７ ~R １０ each independently represents a hydrogen atom or a substituent, R １１ ~R ２０ each independently represents a hydrogen atom or a substituent, provided that R １１ ~R ２０ At least one of represents an amino group represented by the following general formula 2: (In General Formula 2, n represents 0 or 1; when n is 0, Ar represents a substituted or unsubstituted aryl group having 5 or more ring atoms or a substituted or unsubstituted heteroaryl group having 5 or more ring atoms, when n is 1, Ar represents a substituted or unsubstituted arylene group having 5 or more ring atoms or a substituted or unsubstituted heteroarylene group having 5 or more ring atoms; when n is 0, R represents a monovalent substituent; when n is 1, R represents a divalent substituent; L represents a single bond, a substituted or unsubstituted linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted arylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylarylene group having 1 to 20 carbon atoms, an ether group, a sulfide group, a sulfone group, a sulfoxide group, -NR ２００ - (R ２００ represents a hydrogen atom or a substituent) or a divalent linking group selected from the group consisting of -SiRaRb- (Ra and Rb each independently represent a substituted or unsubstituted alkyl group), and * represents a bonding position with the benzene ring. [2] In general formula 2, n represents 0, and R represents a substituted or unsubstituted aryl group having 5 or more ring atoms or a substituted or unsubstituted heteroaryl group having 5 or more ring atoms. [3] In general formula 2, n represents 1, and R represents a substituted or unsubstituted arylene group having 5 or more ring atoms or a substituted or unsubstituted heteroarylene group having 5 or more ring atoms. [4] In general formula 1, R １１ ~R ２０ Among them, R １８ represents an amino group represented by general formula 2, R １２ and R １３ [5] The photochromic compound according to any one of [1] to [3], wherein R each independently represents a hydrogen atom or a substituent, and the others each represent a hydrogen atom. １１ ~R ２０ Among them, R １８ represents an amino group represented by general formula 2, R １３ [6] The photochromic compound according to any one of [1] to [3], wherein R represents a substituent, and the others represent hydrogen atoms. １３[7] The photochromic compound according to [5], wherein R represents an alkoxy group, a dimethylamino group, a phenoxy group, a piperidino group, or a morpholino group. １８ represents an amino group represented by general formula 2, and in general formula 2, n represents 0, and Ar represents a substituted aryl group having 5 or more ring atoms. [8] The photochromic compound according to [7], wherein in general formula 2, R represents a substituted aryl group having 5 or more ring atoms. [9] The photochromic compound according to general formula 1, wherein R ８ and R ９

[10] In the general formula 1, R ４ and R ９

[14] The photochromic article according to

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

[15] The photochromic article according to

[13] or

[14] , which is a spectacle lens.

[16] The photochromic article according to

[13] or

[14] , which is a spectacle lens.

[17] The photochromic article according to

[13] or

[14] , which is a goggle lens, a sun visor visor, or a helmet shield member.

[18] The photochromic article according to

[13] or

[14] , which is a goggle lens, a sun visor visor, or a helmet shield member.

[19] Eyeglasses equipped with the spectacle lens according to

[15] .

[20] The photochromic article according to

[21] or

[22] , which is a goggle lens, a sun visor visor, or a helmet shield member.

[21] Eyeglasses equipped with the spectacle lens according to

[22] .

[0114] Two or more of the various aspects and configurations described herein may be combined in any combination.

[0115] 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.

[0116] 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. 【Chemistry 1】 (In general formula 1, R １ and R ２ They bond to each other to form a ring structure, and this ring structure is a ring structure that spirocondenses with indeno-condensed naphthopyran, or R １ and R ２ each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 or more carbon atoms; a substituted or unsubstituted cyclic alkyl group having 3 or more carbon atoms; or a substituted or unsubstituted -(R １００ ) ｎ R １０１ group represented by, R １００ represents an alkyleneoxy group, R １０１ represents an alkyl group, n represents an integer of 1 or more, and the total number of carbon atoms of the alkyleneoxy group represented by n R １００ and the alkyl group represented by R １０１ is 2 or more, R ３ ~R ６ Each of these independently represents a hydrogen atom or a non-conjugated substituent. R ７ ~R １０ Each of these independently represents a hydrogen atom or a substituent. R １１ ~R ２０ Each of these independently represents a hydrogen atom or a substituent, except R １１ ~R ２０ One or more of these represent an amino group represented by the general formula 2 below. 【Chemistry 2】 (In general formula 2, n represents 0 or 1, Ar represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group with 5 or more ring constituent atoms when n is 0, and a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group with 5 or more ring constituent atoms when n is 1. R represents a monovalent substituent when n is 0, and a divalent substituent when n is 1. L is a single bond, or a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted arylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylarylene group having 1 to 20 carbon atoms, an ether group, a sulfide group, a sulfone group, a sulfoxide group, or -NR ２００ - (R ２００ represents a divalent linking group selected from the group consisting of a hydrogen atom or substituent, or -SiRaRb- (where Ra and Rb each independently represent a substituted or unsubstituted alkyl group), * indicates the bond position with the benzene ring.

2. The photochromic compound according to claim 1, wherein in general formula 2, n represents 0, and R represents a substituted or unsubstituted aryl group with 5 or more ring constituent atoms, or a substituted or unsubstituted heteroaryl group with 5 or more ring constituent atoms.

3. The photochromic compound according to claim 1, wherein in general formula 2, n represents 1, and R represents a substituted or unsubstituted arylene group having 5 or more ring constituent atoms, or a substituted or unsubstituted heteroarylene group having 5 or more ring constituent atoms.

4. In general formula 1, R １１ ~R ２０ Of these, R １８ This represents the amino group represented by general formula 2, R １２ and R １３ Each of these independently represents a hydrogen atom or a substituent. The photochromic compound according to claim 1, wherein the other atoms represent hydrogen atoms.

5. In general formula 1, R １１ ~R ２０ Of these, R １８ This represents the amino group represented by general formula 2, R １３ represents a substituent, The photochromic compound according to claim 1, wherein the other atoms represent hydrogen atoms.

6. R １３ The photochromic compound according to claim 5, wherein represents an alkoxy group, a dimethylamino group, a phenoxy group, a piperidino group, or a morpholino group.

7. R １８ represents an amino group represented by general formula 2, and The photochromic compound according to claim 6, wherein in general formula 2, n represents 0 and Ar represents a substituted aryl group having 5 or more ring constituent atoms.

8. The photochromic compound according to claim 7, wherein in general formula 2, R represents a substituted aryl group having 5 or more ring constituent atoms.

9. In general formula 1, R ８ and R ９ The photochromic compound according to claim 1, wherein each of the groups independently represents a hydrogen atom or an electron-donating group.

10. In general formula 1, R ４ and R ９ The photochromic compound according to claim 1, wherein each of these represents a fluorine atom.

11. A photochromic composition comprising the photochromic compound described in any one of claims 1 to 10.

12. The photochromic composition according to claim 11, further comprising a polymerizable compound.

13. A photochromic article comprising a cured product obtained by curing the photochromic composition according to claim 12.

14. A photochromic article according to claim 13, comprising a base material and a photochromic layer which is a cured product.

15. A photochromic article according to claim 13, which is an eyeglass lens.

16. The photochromic article according to claim 13, which is a lens for goggles, a visor portion of a sun visor, or a shield member of a helmet.

17. Eyeglasses equipped with the eyeglass lenses described in claim 15.

Images