Photochromic articles and glasses

Abstract

To provide a photochromic composition that gives a photochromic article having a high coloring density when coloring in the visible range, and to provide a photochromic article.SOLUTION: A photochromic composition comprises three photochromic compounds each having a specific fused structure of benzo[h]chromene and indene, two of them having electron-donating substituents.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] A photochromic compound is a compound that exhibits a property (photochromic property) of coloring when irradiated with light in a wavelength range that has photoresponsiveness and fading when not irradiated with light. For example, Patent Document 1 discloses a naphthopyran-based compound having photochromic property. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2000 / 15631 Summary of the Invention [Problem to be solved by the invention]

[0004] Methods for imparting photochromic properties to optical 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 optical article imparted with photochromic properties in this way is a high color density in the visible range (wavelength 380 to 780 nm) when colored.

[0005] An object of one aspect of the present invention is to provide a photochromic article that exhibits high color density when colored in the visible range. [Means for solving the problem]

[0006] One aspect of the present invention relates to a photochromic article comprising one or more compounds represented by the following general formula A, one or more compounds represented by the following general formula B, and one or more compounds represented by the following general formula C:

[0007] Another aspect of the present invention relates to a photochromic composition containing one or more compounds represented by the following general formula A and one or more compounds represented by the following general formula B:

[0008] [ka]

[0009] In general formula A, R 1 ~R 6 , B 1 and B 2 each independently represents a hydrogen atom or a substituent.

[0010] [ka]

[0011] In general formula B, R 7 ~R 12 , B 3 and B 4 each independently represents a hydrogen atom or a substituent, R 13 and R 14 each independently represents an electron-donating group.

[0012] [ka]

[0013] In general formula C, R 15 ~R 20 , B 5 and B 6 each independently represents a hydrogen atom or a substituent, R 21 and R 22 represents a hydrogen atom and the other represents an electron-donating group.

[0014] As a result of extensive research, the present inventors have newly discovered that combining a compound represented by general formula A, a compound represented by general formula B, and a compound represented by general formula C makes it possible to provide a photochromic article that can be colored at a high concentration in the visible range. This is presumably because the compound represented by general formula A, the compound represented by general formula B, and the compound represented by general formula C have different absorption peak positions and / or peak intensities in the visible range, and therefore combining these compounds makes it possible to color at a high concentration over a wide wavelength range. However, the present invention is not limited by the conjecture described herein. Furthermore, it has also been found that combining a compound represented by general formula A, a compound represented by general formula B, and a compound represented by general formula C makes it possible to provide a photochromic article that exhibits a fast fading rate. [Effects of the Invention]

[0015] According to one aspect of the present invention, a photochromic article having a high color density in the visible range when colored can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0016] 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 upon irradiation with light can be called a "colored form." In contrast, the structure before irradiation with light can be called a "colorless form." However, the term "colorless" in the colorless form does not necessarily mean completely colorless, but also includes cases where the color is lighter than that of the colored form. The structures of general formula A, general formula B, and general formula C are each structures of a colorless form.

[0017] 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, as photochromic compounds, one or more compounds represented by general formula A, one or more compounds represented by general formula B, and one or more compounds represented by general formula C. 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 "photochromic layer" is a layer containing a photochromic compound.

[0018] 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 embodiment of the present invention contains, as photochromic compounds, one or more compounds represented by general formula A, one or more compounds represented by general formula B, and one or more compounds represented by general formula C, and can be used to produce a photochromic article according to one embodiment of the present invention.

[0019] In the present invention and the present specification, various substituents, i.e., R 1 , R 2 , B 1 , B 2 , R in general formula B 7 ~R 12 , B 3 and B 4 R in general formula C 15 ~R 20 , R 5 and R 6 and when each group described later has a substituent, the substituent can be each independently represented by: linear or branched alkyl groups 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, or a hexyl group; a monocyclic or polycyclic aliphatic alkyl group having 5 to 18 carbon atoms, such as a cyclopentyl group or a cyclohexyl group; a linear or branched alkoxy group having 1 to 24 constituent atoms, such as a methoxy group, an ethoxy group, or a butoxy group; a non-aromatic cyclic substituent having 1 to 24 constituent atoms; a linear or branched alkoxy group having 1 to 18 carbon atoms, such as a trifluoromethyl group; perfluoroalkyl groups such as the above, linear or branched perfluoroalkoxy groups such as trifluoromethoxy groups, linear or branched alkylsulfide groups having 1 to 24 constituent atoms such as methyl sulfide group, ethyl sulfide group, and butyl sulfide group, 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 phenyloxy group, and 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, and an acridinyl group; an amino group (-NH2), a monoalkylamino group such as a monomethylamino group, and a dimethylamino group; a substituent R selected from the group consisting of dialkylamino groups such as monophenylamino groups, monoarylamino groups such as monophenylamino groups, diarylamino groups such as diphenylamino groups, cyclic amino groups such as piperidino groups, morpholino groups, thiomorpholino groups, tetrahydroquinolino groups, and tetrahydroisoquinolino groups, ethynyl groups, mercapto groups, silyl groups, sulfonic acid groups, alkylsulfonyl groups, formyl groups, carboxy groups, cyano groups, and halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; m or R m and one or more identical or different R m Substituents substituted with; It can be.

[0020] The above Rm and one or more identical 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 identical 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.

[0021] In the present invention and this specification, 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.

[0022] In the present invention and this specification, various substituents, i.e., R 1 , R 2 , B 1 , B 2 , R in general formula B 7 ~R 12 , B 3 and B 4 R in general formula C 15 ~R 20 , R 5 and R 6or a substituent that can be represented by any of the following formulas; and further, when each group described below has a substituent, the substituent 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 groups in which two or more of the above groups are combined, and other substituents that can contribute to promoting the thermal motion of the compound's molecules. Compounds having solubilizing groups as substituents can prevent the solute from solidifying by inhibiting the solute molecules from narrowing in distance, 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 n-butyl, n-pentyl, n-hexyl, or n-octyl, a branched alkyl group such as tert-butyl, or a cyclic alkyl group such as cyclopentyl or cyclohexyl.

[0023] 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 morpholyl 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 morpholyl group, a thiomorpholino group, a cyano group, and a solubilizing group.

[0024] 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 than 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 electron-withdrawing groups include halogen atoms (fluorine atom: -F, chlorine atom: -Cl, bromine atom: -Br, iodine atom: -I), trifluoromethyl group: -CF3, nitro group: -NO2, cyano group: -CN, formyl group: -CHO, acyl group: -COR (R is a substituent), alkoxycarbonyl group: -COOR, carboxy group: -COOH, substituted sulfonyl group: -S02R (R is a substituent), and sulfo group: -S03H. Suitable electron-withdrawing groups include a fluorine atom, which is a highly electronegative electron-withdrawing group, and a group having a para-position substituent constant σ based on Hammett's rule. p can be exemplified by electron-withdrawing groups in which the value of is positive.

[0025] 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 result of the sum of inductive effect, mesomeric effect (or resonance effect), etc. Specific examples of electron-donating groups include a hydroxy group (-OH), a thiol group (-SH), an alkoxy group (-OR) (where R is an alkyl group), an alkylsulfide group (-SR) (where R is an alkyl group), an arylsulfide group, an acetyl group (-OCOCH3), an amino group (-NH2), an alkylamide group (-NHCOCH3), a dialkylamino group (-N(R)2) (where the two Rs are the same or different alkyl groups), and a methyl group. Suitable electron-donating groups include those having a para-position substituent constant σ based on Hammett's rule. p can be exemplified by electron donating groups in which the value of

[0026] Para-position substituent constant σ based on Hammett's rule p (Source: Graduate School Organic Chemistry (Vol. 1) (1988), edited by Iwamura Hide, Noyori Ryoji, Nakai Takeshi, and Kitagawa Isao) A specific example is shown below. -N(CH3)2:-0.83 -OCH3:-0.27 -t-C4H9:-0.20 -CH3:-0.17 -C2H5:-0.15 -C6H5:-0.01 (-H:0) -F:+0.06 -Cl:+0.27 -Br:+0.23 -CO2C2H5:+0.45 -CF3:+0.54 -CN:+0.66 -SO2CH3:+0.72 -NO2:+0.78

[0027] The compounds represented by general formula A, the compounds represented by general formula B, and the compounds represented by general formula C will be explained in more detail below.

[0028] <Compound represented by general formula A> [ka]

[0029] In general formula A, R 1 ~R 6 , B 1 and B 2 each independently represents a hydrogen atom or a substituent.

[0030] R 1 and R 2 R preferably each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably represent a methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group. 1 and R 2 more preferably, each independently represents a methyl group or an ethyl group, and R 1 and R 2 More preferably, both represent a methyl group or both represent an ethyl group.

[0031] B1 and B 2 Preferably, each independently represents a substituted or unsubstituted phenyl group. When the phenyl group has a plurality of substituents, two or more of these substituents may be bonded to form a ring. Specific examples of the ring formed include rings contained in the exemplary compounds shown below. The substitution position of the substituent in the substituted phenyl group is 1 and B 2 and preferably in the para position relative to the carbon atom to which they are bonded. Specific examples of the substituent of the substituted phenyl group include a morpholino group, a piperidino group, a halogen atom, an alkoxy group, and the substituents contained in the exemplified compounds shown below, such as the following substituents. In the present invention and this specification, an "*" associated with a partial structure of a compound indicates the bonding position of the atom to which such partial structure is bonded.

[0032] [ka]

[0033] In general formula A, R 3 ~R 6 each independently represents a hydrogen atom or a substituent. 3 ~R 6 In another embodiment, R 3 ~R 6 each independently represents a hydrogen atom or an electron-withdrawing group, provided that R 3 ~R 6 At least one of the groups represents an electron-withdrawing group. As the electron-withdrawing group, a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group is preferred. As the halogen atom, a fluorine atom is preferred. As the perfluoroalkyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferred.

[0034] In one embodiment, the compound represented by formula A can be the following compound: R 3 ~R 6 Among them, R 4is the only electron-withdrawing group, and R 3 , R 5 and R 6 is a compound in which the atom is hydrogen. R 3 ~R 6 Among them, R 4 and R 6 are the same or different electron-withdrawing groups, and R 3 and R 5 is a compound in which the atom is hydrogen. R 3 ~R 6 Among them, R 3 and R 5 are the same or different electron-withdrawing groups, and R 4 and R 6 is a compound in which the atom is hydrogen.

[0035] Examples of compounds represented by general formula A include the following compounds, however, the present invention is not limited to the compounds exemplified below.

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[0067] <Compound represented by general formula B> [ka]

[0068] In general formula B, R 7 ~R 12 , B 3 and B 4 each independently represents a hydrogen atom or a substituent.

[0069] R 7 and R 8 R preferably each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably represent a methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group. 7 and R 8 more preferably, each independently represents a methyl group or an ethyl group, and R 7 and R 8 More preferably, both represent a methyl group or both represent an ethyl group.

[0070] B 3 and B 4Preferably, each independently represents a substituted or unsubstituted phenyl group. When the phenyl group has a plurality of substituents, two or more of these substituents may be bonded to form a ring. Specific examples of the ring formed include rings contained in the exemplary compounds shown below. The substitution position of the substituent in the substituted phenyl group is 3 and B 4 Specific examples of the substituent of the substituted phenyl group include a morpholino group, a piperidino group, a halogen atom, an alkoxy group, and the substituents contained in the exemplified compounds shown below, such as the following substituents:

[0071] [ka]

[0072] R 9 ~R 12 each independently represents a hydrogen atom or a substituent. 9 ~R 12 In another embodiment, R 10 is an electron-withdrawing group, and R 9 , R 11 and R 12 In another embodiment, R 9 and R 11 are each independently an electron-withdrawing group, and R 10 and R 12 can be a hydrogen atom. As the electron-withdrawing group, a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group is preferred. As the halogen atom, a fluorine atom is preferred. As the perfluoroalkyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferred.

[0073] In one form, R 10 can be a substituted or unsubstituted phenyl group, preferably R 10 is a substituted or unsubstituted phenyl group, and R 9 , R11 and R 12 can be a hydrogen atom. Specific examples of such a substituted phenyl group include a phenyl group substituted with one or more halogen atoms and / or one or more cyano groups, for example, a phenyl group in which halogen atoms (preferably fluorine atoms) are substituted at all five substitution positions of the phenyl group, and 10 and a monosubstituted phenyl group in which a cyano group is substituted at the para position relative to the carbon atom to which the group is bonded.

[0074] R 13 and R 14 each independently represents an electron-donating group. 13 and R 14 R represents the same or different electron-donating groups. 13 and R 14 are preferably each independently an electron-donating group selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group, a methyl sulfide group, a phenyl sulfide group, a dimethylamino group, a pyrrolidino group, a piperidino group, a morpholino group, and a thiomorpholino group. 13 and R 14 About R 13 is a morpholino group and R 14 is an alkoxy group (preferably a methoxy group), R 13 is a morpholino group and R 14 is a methyl sulfide group (-S-CH3), R 13 and R 14 are both alkoxy groups (preferably methoxy groups), and R 13 and R 14 are preferably all methyl sulfide groups.

[0075] Examples of compounds represented by general formula B include the following compounds, but the present invention is not limited to the compounds exemplified below.

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[0094] <Compound represented by general formula C> [ka]

[0095] In general formula C, R 15 ~R 20 , B 5 and B 6 each independently represents a hydrogen atom or a substituent, R 21 and R 22 represents a hydrogen atom and the other represents an electron-donating group.

[0096] In general formula C, R 15 and R 16R preferably each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably represent a methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group. 15 and R 16 more preferably, each independently represents a methyl group or an ethyl group, and R 15 and R 16 More preferably, both represent a methyl group or both represent an ethyl group.

[0097] B 5 and B 6 Preferably, each independently represents a substituted or unsubstituted phenyl group. When the phenyl group has a plurality of substituents, two or more of these substituents may be bonded to form a ring. Specific examples of the ring formed include rings contained in the exemplary compounds shown below. The substitution position of the substituent in the substituted phenyl group is 5 and B 6 It is preferable that the substituent be in the para position relative to the carbon atom to which the carbon atom is bonded. Specific examples of the substituent of the substituted phenyl group include a morpholino group, a piperidino group, a halogen atom, an alkoxy group, and the following substituents.

[0098] [ka]

[0099] R 17 ~R 20 each independently represents a hydrogen atom or a substituent. 17 ~R 20 In another embodiment, R 18 is an electron-withdrawing group, and R 17 , R 19 and R 20 In another embodiment, R 17 and R 19 are each independently an electron-withdrawing group, and R 18 and R 20can be a hydrogen atom. As the electron-withdrawing group, a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group is preferred. As the halogen atom, a fluorine atom is preferred. As the perfluoroalkyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferred.

[0100] In one form, R 18 can be a substituted or unsubstituted phenyl group, preferably R 18 is a substituted or unsubstituted phenyl group, and R 17 , R 19 and R 20 can be a hydrogen atom. Specific examples of such a substituted phenyl group include a phenyl group substituted with one or more halogen atoms and / or one or more cyano groups, for example, a phenyl group in which halogen atoms (preferably fluorine atoms) are substituted at all five substitution positions of the phenyl group, and 10 and a monosubstituted phenyl group in which a cyano group is substituted at the para position relative to the carbon atom to which the group is bonded.

[0101] R 21 and R 22 One represents a hydrogen atom and the other represents an electron-donating group. 21 is a hydrogen atom, and R 22 is preferably an electron donating group. 21 or R 22 (preferably R 22 ) more preferably represents an electron donating group selected from the group consisting of methoxy, ethoxy, phenoxy, methylsulfide, phenylsulfide, dimethylamino, pyrrolidino, piperidino, morpholino, and thiomorpholino.

[0102] Examples of compounds represented by general formula C include the following compounds, but the present invention is not limited to the compounds exemplified below.

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[0111] The compounds represented by general formula A, B, and C can be synthesized by known methods. For the synthesis methods, reference can be made to the following documents, for example: Japanese Patent No. 4884578, US2006 / 0226402A1, US2006 / 0228557A1, US2008 / 0103301A1, US2011 / 0108781A1, US2011 / 0108781A1, US7527754, US7556751, WO2001 / 60811A1, WO2013 / 086248A1, WO1996 / 014596A1, and WO2001 / 019813A1.

[0112] A photochromic article according to one embodiment of the present invention and a photochromic composition according to one embodiment of the present invention contain one or more compounds represented by general formula A, one or more compounds represented by general formula B, and one or more compounds represented by general formula C. The compound represented by general formula A contained in the photochromic article and the photochromic composition may be one kind or two or more kinds (for example, two or more and four or less kinds). The compound represented by general formula B contained in the photochromic article and the photochromic composition may be one kind or two or more kinds (for example, two or more and four or less kinds). The compound represented by general formula C contained in the photochromic article and the photochromic composition may be one kind or two or more kinds (for example, two or more and four or less kinds). In the photochromic article and the photochromic composition, the total content of the compound represented by general formula B and the compound represented by general formula C is preferably greater than the content of the compound represented by general formula A, on a mass basis. When the total of the compounds represented by general formula A, the compounds represented by general formula B, and the compounds represented by general formula C is taken as 100 mass%, the total content of the compounds represented by general formula B and the compounds represented by general formula C is preferably greater than 50 mass%, more preferably 60 mass% or more, even more preferably 70 mass% or more, even more preferably 80 mass% or more, and even more preferably 90 mass% or more. With respect to the total (100 mass%) of the compounds represented by general formula A, the compounds represented by general formula B, and the compounds represented by general formula C, the total content of the compounds represented by general formula B and the compounds represented by general formula C can be less than 100 mass%, and can be 99 mass% or less, 98 mass% or less, 97 mass% or less, 96 mass% or less, or 95 mass% or less. Regarding the mixing ratio of the compound represented by general formula B and the compound represented by general formula C, the content of the compound represented by general formula B can be 1% by mass or more or 99% by mass or more, and 25% by mass or less or 75% by mass or less, where the total of the compound represented by general formula B and the compound represented by general formula C is 100% by mass. When the photochromic article and the photochromic composition contain two or more compounds represented by general formula B, the content of the compound represented by general formula B is the total content of those compounds. This also applies to the contents of various components in the present invention and this specification. The photochromic article and the photochromic composition may contain, for example, about 0.1 to 15.0 mass % of the compound represented by general formula A, the compound represented by general formula B, and the compound represented by general formula C in total, with the total amount taken as 100 mass %, although the amount is not limited to this range.

[0113] [Photochromic Articles and Photochromic Compositions] The photochromic article may have at least a substrate. In one embodiment, the compound represented by general formula A, the compound represented by general formula B, and the compound represented by general formula C 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 the compound represented by general formula A, the compound represented by general formula B, and the compound represented by general formula C. In one embodiment, the compound represented by general formula A, the compound represented by general formula B, and the compound represented by general formula C 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 compound represented by general formula A, the compound represented by general formula B, and the compound represented by general formula C as photochromic compounds, 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.

[0114] <Base material> 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 styrene resins such as (meth)acrylic 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 (generally 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).

[0115] 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 compound represented by general formula A, one or more compounds represented by general formula B, one or more compounds represented by general formula C, and one or more polymerizable compounds using a known molding method. The 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.).

[0116] 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.

[0117] <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 as a cured layer formed by curing a polymerizable composition containing at least one compound represented by general formula A, one or more compounds represented by general formula B, one or more compounds represented by general formula C, 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 compounds represented by general formula A, one or more compounds represented by general formula B, and one or more compounds represented by general formula C. Examples of coating methods that can be used 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 may 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 compounds progresses, the polymerizable composition hardens to form a hardened layer.

[0118] 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.

[0119] <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.

[0120] Examples of polymerizable compounds that can be used to form the substrate and the photochromic layer include the following compounds.

[0121] (episulfide compounds) An episulfide compound is a compound having two or more episulfide groups in one molecule. The episulfide group is a polymerizable group capable of undergoing 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.

[0122] (Thietanyl compounds) A thietanyl compound is a thietanyl compound 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 that have a metal atom in the molecule and non-metal-containing thietanyl compounds that do not contain a metal.

[0123] 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-thietanylthio) thio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane, 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]

[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.

[0124] 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.

[0125] Specific examples of alkylthio(thietanylthio)tin include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, and isopropylthiotris(thietanylthio)tin.

[0126] 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.

[0127] 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.

[0128] Specific examples of the bis(thietanylthio)cyclic dithiotin compound include bis(thietanylthio)dithiastannetane, bis(thietanylthio)dithiastannolane, bis(thietanylthio)dithiastanninane, and bis(thietanylthio)trithiastannocane.

[0129] Specific examples of the alkyl(thietanylthio)tin compound include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, tetrakis(thietanylthio)tin, tetrakis(thietanylthio)germanium, and tris(thietanylthio)bismuth.

[0130] (Polyamine compounds) A polyamine compound is a compound having two or more NH groups in one molecule, and can form a urea bond by reacting with a polyisocyanate, and can form a thiourea bond by reacting with a polyisothiocyanate. Specific examples of polyamine compounds 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.

[0131] (epoxy compounds) Epoxy compounds are compounds that contain an epoxy group in the molecule. The epoxy group is a polymerizable group that can undergo ring-opening polymerization. Epoxy compounds are generally classified into aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds.

[0132] 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.

[0133] Specific examples of the alicyclic epoxy compound include isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like.

[0134] 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.

[0135] 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.

[0136] Specific examples of the chain aliphatic sulfur atom-containing epoxy compounds 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.

[0137] Specific examples of the alicyclic sulfur-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.

[0138] (Compound having a radical polymerizable group) The compound having a radical polymerizable group is a polymerizable group that can undergo radical polymerization. Examples of the radical polymerizable group include an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group.

[0139] 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 -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.

[0140] 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.

[0141] 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).

[0142] 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.

[0143] 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 properties 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.

[0144] [glasses] 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 anti-glare effects similar to 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. [Example]

[0145] The present invention will be further described below with reference to examples, although the present invention is not limited to the embodiments shown in the examples.

[0146] [Compound synthesis] Compounds 1 to 15 shown below were synthesized with reference to the reference documents listed above regarding compound synthesis methods. The compounds were identified in the same manner as in the reference publications, and it was confirmed that the compounds shown below had been synthesized. Compounds 1 to 7 are compounds represented by general formula A, compounds 8 to 15 are compounds represented by general formula B, and compounds 16 to 23 are compounds represented by general formula C.

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] [Examples 1 to 48, Comparative Examples 1 to 3] <Preparation of Photochromic Composition (Polymerizable Composition)> In a plastic container, 68 parts by weight of polyethylene glycol diacrylate, 12 parts by weight of trimethylolpropane trimethacrylate, and 20 parts by weight of neopentyl glycol dimethacrylate were mixed with 100 parts by weight of (meth)acrylates to prepare a (meth)acrylate mixture. A photochromic compound was added to this (meth)acrylate mixture at a ratio of 2.5 parts by weight. For compositions containing multiple photochromic compounds, the mass ratio of each photochromic compound, assuming the total amount of photochromic compounds to be 10, is shown in Table 2 (Table 2-1 and Table 2-2). Furthermore, a photopolymerization initiator (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), an antioxidant [bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid] [ethylene bis(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.

[0151] <Deposition 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 weight aqueous sodium hydroxide solution (liquid temperature 60°C) for 5 minutes, followed by rinsing with pure water and drying. A water-based polyurethane resin solution (polycarbonate polyol-based polyurethane emulsion, viscosity 100 cPs, solids concentration 38% by weight) was then 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 at room temperature and a relative humidity of 40-60%, followed by air drying for 15 minutes to form a 5.5 μm-thick primer layer.

[0152] <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 rotation speed from 500 rpm to 1500 rpm over 1 minute, then rotated at 1500 rpm for 5 seconds. The photochromic composition applied to 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), curing the composition to form a photochromic layer. The resulting photochromic layer had a thickness of 45 μm. In this way, a photochromic article (eyeglass lens) was produced.

[0153] [Evaluation method] <Evaluation of color density> The luminous reflectance was determined by the following method in accordance with JIS T7333:2005. The convex surface of each eyeglass lens in the Examples and Comparative Examples was irradiated for 15 minutes with light from a xenon lamp through an aeromass filter, thereby coloring the photochromic layer. The irradiance and irradiance tolerance, as specified in JIS T7333:2005, were measured to obtain the values ​​shown in Table 1. The transmittance after coloring was measured using a spectrophotometer manufactured by Otsuka Electronics. The luminous transmittance T (%) calculated from the measurement results in the wavelength range of 380 nm to 780 nm is shown in Table 2. The smaller the T (%) value, the higher the concentration of coloration of the photochromic compound.

[0154] [Table 1]

[0155] <Evaluation of fading speed> The fading rate was evaluated by the following method. The transmittance (measurement wavelength: 550 nm) of each spectacle lens of the Examples and Comparative Examples before light irradiation (uncolored state) was measured using a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The transmittance measured here is referred to as the "initial transmittance." Each spectacle lens was irradiated with light from a xenon lamp through an aeromass filter for 15 minutes to tint the photochromic layer. This irradiation light was set so that the irradiance and irradiance tolerance were the values ​​shown in Table 1, as specified in JIS T7333:2005. The transmittance after this tinting was measured in the same manner as the initial transmittance. The transmittance measured here is referred to as the "transmittance after tinting." The time required from the time when the light irradiation was stopped until the transmittance reached [(initial transmittance - transmittance after coloring) / 2] was measured. This time is called the "half-life." The shorter the half-life, the faster the fading rate. The calculated half-life is shown in Table 2.

[0156] [Table 2-1]

[0157] [Table 2-2]

[0158] The results shown in Table 2 confirm that it is possible to provide a photochromic article that is highly colored in the visible range by combining a compound represented by general formula A, a compound represented by general formula B, and a compound represented by general formula C. Furthermore, the results shown in Table 2 also confirm that each of the spectacle lenses of the examples exhibits a fast fading rate.

[0159] Finally, the above-mentioned aspects will be summarized.

[0160] According to one aspect, photochromic articles and compositions are provided that include one or more compounds represented by general formula A, one or more compounds represented by general formula B, and one or more compounds represented by general formula C.

[0161] In one embodiment, in general formula A, R 1 and R 2 may each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0162] In one embodiment, in general formula A, R 1 and R 2 can each independently represent a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

[0163] In one embodiment, B in general formula A 1 and B 2 , B in general formula B 3 and B 4 and B in general formula C 5 and B 6 may each independently represent a substituted or unsubstituted phenyl group. When such a phenyl group has a plurality of substituents, the substituents may be bonded to form a ring.

[0164] In one embodiment, in general formula A, R 3 ~R 6 each independently represents a hydrogen atom or an electron-withdrawing group (provided that R 3 ~R 6 one or more of may represent an electron-withdrawing group).

[0165] In one embodiment, the electron-withdrawing group can be a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group.

[0166] In one embodiment, the halogen atom can be a fluorine atom.

[0167] In one embodiment, the perfluoroalkyl group can be a trifluoromethyl group.

[0168] In one embodiment, R in general formula A 1 ~R 6 , B 1 , B 2 , R in general formula B 7 ~R 12 , B 3 , B 4 , R in general formula C 15 ~R20 , B 5 and B 6 may represent a substituent, and such substituent may be one or more selected from the group consisting of: a substituent R selected from the group consisting of a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, a monocyclic or polycyclic aliphatic alkyl group having 5 to 18 carbon atoms such as a bicyclic ring, a linear or branched alkoxy group having 1 to 24 constituent atoms, a non-aromatic cyclic substituent having 1 to 24 constituent atoms, a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms, a linear or branched perfluoroalkoxy group, a linear or branched alkylsulfide group having 1 to 24 constituent atoms, an aryl group, an aryloxy group, an arylsulfide group, a heteroaryl group, an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino 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; m ; R m and one or more identical or different R m a substituent substituted with; or solubilizing group It can be.

[0169] In one embodiment, in general formula B, R 7 and R 8 may each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0170] In one embodiment, in general formula B, R 7 and R 8 can each independently represent a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

[0171] In one embodiment, in general formula B, R 13 and R 14may each independently represent an electron-donating group selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group, a methyl sulfide group, a phenyl sulfide group, a dimethylamino group, a pyrrolidino group, a piperidino group, a morpholino group, and a thiomorpholino group.

[0172] In one embodiment, in general formula C, R 15 and R 16 may each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0173] In one embodiment, in general formula C, R 15 and R 16 can each independently represent a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

[0174] In one embodiment, in general formula C, R 21 or R 22 The electron donating group represented by the formula (I) can be an electron donating group selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group, a methyl sulfide group, a phenyl sulfide group, a dimethylamino group, a pyrrolidino group, a piperidino group, a morpholino group, and a thiomorpholino group.

[0175] In one embodiment, in the photochromic article and the photochromic composition, the total content of the compound represented by general formula B and the compound represented by general formula C can exceed the content of the compound represented by general formula A by mass.

[0176] In one embodiment, the photochromic article can be a photochromic article having a substrate and a photochromic layer, the photochromic layer containing one or more compounds represented by general formula A, one or more compounds represented by general formula B, and one or more compounds represented by general formula C.

[0177] In one embodiment, the photochromic layer can be a cured layer obtained by curing a polymerizable composition.

[0178] In one embodiment, the photochromic composition can include a polymerizable compound.

[0179] In one form, the photochromic article can be an eyeglass lens.

[0180] In one form, the photochromic article can be a lens for goggles.

[0181] In one form, the photochromic article can be the visor portion of a sun visor.

[0182] In one form, the photochromic article can be a shield member of a helmet.

[0183] According to one aspect, eyeglasses are provided that include the above-described eyeglass lenses.

[0184] Two or more of the various aspects and configurations described herein may be combined in any combination.

[0185] 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. [Industrial Applicability]

[0186] One aspect of the present invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets, and the like.

Claims

1. A substrate, a photochromic layer; one or more additional layers other than the photochromic layer; 1. A photochromic article comprising: The photochromic layer comprises: a polymerizable compound; One or more compounds represented by the following general formula A; One or more compounds represented by the following general formula B; One or more compounds represented by the following general formula C, The photochromic article is a cured product obtained by curing a photochromic composition comprising the above. 【Chemical 1】 (In general formula A, R 1 to R 3 , R 5 , B 1 and B 2 each independently represent a hydrogen atom or a substituent; R 4 represents a hydrogen atom, a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group or a cyano group; and R 6 represents a hydrogen atom or an electron-withdrawing group.) 【Chemistry 2】 (In general formula B, R ７ ~R １２ , B ３ and B ４ each independently represents a hydrogen atom or a substituent, R １３ and R １４ each independently represents an electron-donating group. 【Chemistry 3】 (In general formula C, R 15 and R 16 each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; R 17 to R 20 , B 5 and B 6 each independently represent a hydrogen atom or a substituent; R ２１ and R ２２ One represents a hydrogen atom and the other represents an electron-donating group.)

2. In general formula A, R １ and R ２ and each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

3. In general formula A, R １ and R ２ The photochromic article of claim 1 or 2, wherein each independently represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

4. B in general formula A １ and B ２ , B in general formula B ３ and B ４ and B in general formula C ５ and B ６ each independently represent a substituted or unsubstituted phenyl group, and when the phenyl group has a plurality of substituents, the substituents may be bonded to form a ring. The photochromic article according to any one of claims 1 to 3.

5. In general formula A, among R 3 to R 6 , R 4 represents a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group or a cyano group; R 3 , R 5 and R 6 represent hydrogen atoms; R 4 represents a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group or a cyano group; R 6 represents an electron-withdrawing group; R 3 and R 5 each represent a hydrogen atom; or The photochromic article according to any one of claims 1 to 4, wherein R 3 and R 5 are the same or different electron-withdrawing groups, and R 4 and R 6 are hydrogen atoms.

6. 6. The photochromic article according to claim 5, wherein the electron-withdrawing group is a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group.

7. 7. The photochromic article of claim 6, wherein said halogen atoms are fluorine atoms.

8. 7. The photochromic article of claim 6, wherein said perfluoroalkyl group is a trifluoromethyl group.

9. R in General Formula A １ to R 3 , R 5 , B 1 , B 2 , R 7 to R 12 in general formula B, B 3 , B 4 , R 17 to R in general formula C ２０ , B ５ and B ６ and one or more selected from the group consisting of: a substituent R selected from the group consisting of a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, a monocyclic or polycyclic aliphatic alkyl group having 5 to 18 carbon atoms such as a bicyclic ring, a linear or branched alkoxy group having 1 to 24 constituent atoms, a non-aromatic cyclic substituent having 1 to 24 constituent atoms, a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms, a linear or branched perfluoroalkoxy group, a linear or branched alkylsulfide group having 1 to 24 constituent atoms, an aryl group, an aryloxy group, an arylsulfide group, a heteroaryl group, an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino 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; ｍ ; R ｍ and one or more identical or different R ｍ a substituent substituted with; or solubilizing group 9. The photochromic article according to claim 1, wherein

10. In general formula B, R ７ and R ８ The photochromic article according to any one of claims 1 to 9, wherein each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

11. In general formula B, R ７ and R ８ The photochromic article according to any one of claims 1 to 10, wherein each independently represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

12. In general formula B, R １３ and R １４ each independently represent an electron-donating group selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group, a methylsulfide group, a phenylsulfide group, a dimethylamino group, a pyrrolidino group, a piperidino group, a morpholino group, and a thiomorpholino group.

13. In general formula C, R １５ and R １６ The photochromic article of any one of claims 1 to 12, wherein each independently represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group.

14. In general formula C, R ２１ or R ２２ The photochromic article according to any one of claims 1 to 13, wherein the electron-donating group represented by the formula (I) is an electron-donating group selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group, a methyl sulfide group, a phenyl sulfide group, a dimethylamino group, a pyrrolidino group, a piperidino group, a morpholino group, and a thiomorpholino group.

15. A photochromic article described in any one of claims 1 to 14, wherein the photochromic composition has a total content, by mass, of the compound represented by general formula B and the compound represented by general formula C that is greater than the content of the compound represented by general formula A.

16. A photochromic article described in any one of claims 1 to 15, wherein the one or more further layers are selected from the group consisting of a protective layer, an anti-reflective layer, a water-repellent anti-fouling layer, a hydrophilic anti-fouling layer, an anti-fog layer and a primer layer.

17. The photochromic article of any one of claims 1 to 16, which is a spectacle lens.

18. The photochromic article according to any one of claims 1 to 16, which is a lens for goggles, a visor portion of a sun visor, or a shield member for a helmet.

19. Eyeglasses comprising the eyeglass lens according to claim 17.

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