Photochromic compositions, photochromic articles and eyewear

Abstract

The present application provides a photochromic composition comprising one or more compounds represented by General Formula A and one or more compounds represented by General Formula B. In General Formula A, R 1 , R 2 , B 1 , and B 2 each independently represent a hydrogen atom or a substituent, R 3 to R 6 each independently represent a hydrogen atom or an electron-withdrawing group, wherein one or more of R 3 to R 6 represent an electron-withdrawing group. In General Formula B, R 7 to R 12 , B 3 , and B 4 each independently represent a hydrogen atom or a substituent, R 13 and R 14 each independently represent a hydrogen atom or an electron-donating group, wherein one or more of R 13 and R 14 represent an electron-donating group.

Description

Technical Field

[0001] This invention relates to photochromic compositions, photochromic articles, and eyeglasses. Background Technology

[0002] Photochromic compounds are compounds that possess the property of coloring under irradiation with light in a photoresponsive wavelength range and fading under no irradiation (photochromism). For example, patent document 1 discloses a naphthopyran compound with photochromic properties.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: WO2000 / 15631 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] Examples of methods for imparting photochromic properties to optical articles such as eyeglass lenses include methods of containing a photochromic compound in a substrate and methods of forming a layer containing a photochromic compound. Desired properties of such photochromic optical articles include high coloring concentration when colored in the visible light region (wavelength 380–780 nm) and a rapid fading rate after being colored by light.

[0008] One objective of this invention is to provide photochromic articles that have high color concentration when colored in the visible light region and fast fading speed.

[0009] Problem Solving Methods

[0010] One aspect of the present invention relates to a photochromic article comprising a compound represented by one or more general formulas A and B.

[0011] Additionally, one aspect of the present invention relates to a photochromic composition comprising a compound represented by one or more general formulas A and B.

[0012] [Chemical Formula 1]

[0013] (General Formula A)

[0014]

[0015] In general formula A, R 1 R 2 B 1 and B 2 Each independently represents a hydrogen atom or a substituent, R3 ~R 6 Each can independently represent a hydrogen atom or an electron-withdrawing group, where R 3 ~R 6 One or more of them represent electron-withdrawing groups.

[0016] [Chemical Formula 2]

[0017] (General Formula B)

[0018]

[0019] 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 can independently represent a hydrogen atom or an electron-donating group, where R 13 and R 14 One or more of them represent electron-donating groups.

[0020] Through repeated and in-depth research, the inventors have made the following new discovery: by combining compounds represented by general formula A with compounds represented by general formula B, photochromic articles capable of high-concentration coloring in the visible light region can be provided. This is presumably because compounds represented by general formula A and compounds represented by general formula B have different absorption peak positions in the visible light region; therefore, by combining these compounds, high-concentration coloring can be achieved over a wide wavelength range. However, the present invention is not limited to the presumptions described in this specification. Furthermore, the inventors have also made the following new discovery: by combining compounds represented by general formula A with compounds represented by general formula B, photochromic articles exhibiting a fast fading rate can be provided.

[0021] The effects of the invention

[0022] According to one aspect of the present invention, it is possible to provide photochromic articles with high color concentration and fast fading rate when colored in the visible light region. Detailed Implementation

[0023] As an example, photochromic compounds, when exposed to light such as sunlight, undergo a structural transformation into a chromophore after being excited. The structure that has undergone this structural transformation after illumination can be called a "chromophore." Conversely, the structure before illumination can be called a "colorless body." However, it should be noted that "colorless" in the context of a colorless body is not limited to complete colorlessness; it also includes cases where the color is lighter than that of a chromophore. The structures of general formula A and general formula B are respectively the structures of colorless bodies.

[0024] In this invention and specification, "photochromic article" refers to an article containing a photochromic compound. One aspect of the photochromic article of this invention comprises one or more compounds represented by general formula A and one or more compounds represented by general formula B as photochromic compounds. The photochromic compound may be contained in the substrate of the photochromic article, and / or may be contained in the photochromic layer of the photochromic article having a substrate and a photochromic layer. "Photochromic layer" refers to a layer containing the photochromic compound.

[0025] In this invention and specification, "photochromic composition" refers to a composition containing a photochromic compound. One aspect of the photochromic composition of this invention comprises one or more compounds represented by general formula A and one or more compounds represented by general formula B as photochromic compounds, which can be used in the manufacture of photochromic articles according to one aspect of this invention.

[0026] In this invention and this specification, various substituents, i.e., those that can be derived from R in general formula A, are used. 1 R 2 B 1 B 2 R in general formula B 7 ~R 12 B 3 and B 4 Substituents represented by any of the groups mentioned above, as well as substituents in cases where substituents are present in the groups described later, can each be independently represented as substituent R. m , or in R m The next step is to replace one or more identical or different Rs. m The substituent R m Selected from:

[0027] The following are listed as examples of cyclic aliphatic alkyl groups with 1-18 carbon atoms (such as hydroxyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.), monocyclic or bicyclic alkyl groups with 5-18 carbon atoms (such as cyclopentyl, cyclohexyl, etc.), alkoxy groups with 1-24 carbon atoms (such as methoxy, ethoxy, butoxy, etc.), non-aromatic cyclic substituents with 1-24 carbon atoms, perfluoroalkyl groups with 1-18 carbon atoms (such as trifluoromethyl, etc.), and straight-chain or branched perfluoroalkyl groups with 1-18 carbon atoms (such as trifluoromethoxy, etc.). Or branched perfluoroalkoxy, methylthio, ethylthio, butylthio, etc., constituting straight-chain or branched alkylthio, phenyl, naphthyl, anthracene, fluoranyl, phenanthryl, pyranyl, perylene, styryl, fluorenyl, etc., aryl, phenoxy, etc., arylthio, phenylthio, etc., with 1 to 24 atoms, pyridyl, furanyl, thiophene, pyrrole, benzofuranyl, benzothiophene, indolyl, dibenzofuranyl, dibenzothiophene, carbazole, diazolyl, triazolyl, quinolinyl, phenothiazine, phenanthrene, etc. The group includes heteroaryl groups such as azinoyl, phenazinyl, thianzyl, and acridineyl; amino (-NH2); monoalkylamino groups such as monomethylamino; dialkylamino groups such as dimethylamino; monoarylamino groups such as monophenylamino; diarylamino groups such as diphenylamino; piperidinyl; morpholinyl; thiomorpholinyl; tetrahydroquinolinyl; tetrahydroisoquinolinyl; cyclic amino groups such as ethynyl; mercapto; silyl; sulfonic acid; alkylsulfonyl; formyl; carboxyl; cyano; and halogen atoms such as fluorine, chlorine, bromine, and iodine.

[0028] As mentioned above in R m The next step is to replace one or more identical or different Rs. m One example of a substituent is a structure in which an alkoxy group is further substituted on the terminal carbon atom of the alkoxy group, and further substituted on the terminal carbon atom of the alkoxy group. Additionally, as described above, in R... m The next step is to replace one or more identical or different Rs. m Another example of a substituent is when two or more of the five substituted positions of the phenyl group have the same or different R groups. m The structure is not limited to such examples.

[0029] In this invention and this specification, "number of carbon atoms" and "number of constituent atoms" refer to the number of carbon atoms or atoms in a group having substituents, including the number of substituents.

[0030] Furthermore, in this invention and this specification, various substituents, i.e., those derived from R in general formula A, are used. 1 R 2 B 1 B 2 R in general formula B 7 ~R 12 B 3 and B 4Substituents represented by any of the following, as well as substituents in cases where substituents are present in the groups described below, can also be independently solubilizing groups. In this invention and this specification, a "solubilizing group" refers to a substituent that contributes to improving compatibility with any liquid or a specific liquid. Preferably, solubilizing groups include alkyl groups with 4 to 50 carbon atoms comprising a straight-chain, branched, or cyclic structure; alkoxy groups comprising 4 to 50 carbon atoms comprising a straight-chain, branched, or cyclic structure; silyl groups comprising 4 to 50 carbon atoms; groups formed by replacing a portion of the above groups with silicon, sulfur, nitrogen, phosphorus, etc.; and groups formed by combining two or more of the above groups. Substituents having a solubilizing group as a substituent can prevent the solute from solidifying by hindering the proximity of solute molecules, or can form a near-liquid molecular aggregate state by lowering the melting point and / or glass transition temperature of the solute. In this way, the solubilizing group can liquefy the solute or improve the solubility of the compound having the substituent in a liquid. In one embodiment, the solubilizing group is preferably n-butyl, n-pentyl, n-hexyl, n-octyl as a straight-chain alkyl group, tert-butyl as a branched alkyl group, and cyclopentyl and cyclohexyl as cyclic alkyl groups.

[0031] The substituents mentioned above are preferably selected from methoxy, ethoxy, phenoxy, methylthio, ethylthio, phenylthio, trifluoromethyl, phenyl, naphthyl, dibenzofuranyl, dibenzothiophene, carbazole, phenothiazinyl, and phenanthrene. Substituents selected from azino, phenazinyl, acridine, dimethylamino, diphenylamino, piperidinyl, morpholinyl, thiomorpholinyl, cyano, and solubilizing groups, and more preferably substituents selected from methoxy, phenoxy, methylthio, phenylthio, trifluoromethyl, phenyl, dimethylamino, diphenylamino, piperidinyl, morpholinyl, thiomorpholinyl, cyano, and solubilizing groups.

[0032] In this invention and specification, "electron-withdrawing group" refers to a substituent that, compared to a hydrogen atom, readily attracts electrons from the bonded atom. Electron-withdrawing groups attract electrons through substituent effects such as inductive effects, mediating effects (or resonance effects). Specific examples of electron-withdrawing groups include: halogen atoms (fluorine: -F, chlorine: -Cl, bromine: -Br, iodine: -I), trifluoromethyl: -CF3, nitro: -NO2, cyano: -CN, formyl: -CHO, acyl: -COR (R is a substituent), alkoxycarbonyl: -COOR, carboxyl: -COOH, substituted sulfonyl: -SO2R (R is a substituent), sulfonyl: -SO3H, etc. Suitable electron-withdrawing groups include fluorine atoms as highly electronegative electron-withdrawing groups, and the para-substituent constant σ based on the Hammett equation. pElectron-withdrawing groups with positive values, etc.

[0033] In this invention and specification, "electron-donating group" refers to a substituent that readily donates electrons to the bonded atom compared to a hydrogen atom. The electron-donating group can be a substituent that readily donates electrons based on a combination of inductive effects, mediating effects (or resonance effects), etc. Specific examples of electron-donating groups include: hydroxyl: -OH, thiohydroxyl: -SH, alkoxy: -OR (R is alkyl), alkylthiol: -SR (R is alkyl), arylthiol, acetyl: -OCOCH3, amino: -NH2, alkylamide: -NHCOCH3, dialkylamino: -N(R)2 (the two Rs are the same or different alkyl or aryl groups, and the Rs can bond together to form a ring structure), methyl, etc. Suitable electron-donating groups include the para-substituent constant σ based on the Hammett equation. p Electron-donating groups with negative values, etc.

[0034] The following shows the substituent constant σ at the para site based on the Hammett equation. p (Source: Hideo Iwamura, Ryoji Noyori, Takeshi Nakai, Isao Kitagawa, eds., Graduate School Organic Chemistry (Vol. 1) (1988)) Specific examples.

[0035] -N(CH3)2: -0.83

[0036] -OCH3: -0.27

[0037] -t-C4H9: -0.20

[0038] -CH3: -0.17

[0039] -C2H5: -0.15

[0040] -C6H5: -0.01

[0041] (-H: 0)

[0042] -F: +0.06

[0043] -Cl: +0.27

[0044] -Br: +0.23

[0045] -CO2C2H5: +0.45

[0046] -CF3: +0.54

[0047] -CN: +0.66

[0048] -SO2CH3: +0.72

[0049] -NO2: +0.78

[0050] The compounds represented by general formula A and general formula B will be described in more detail below.

[0051] <Compounds represented by general formula A>

[0052] [Chemical Formula 3]

[0053] (General Formula A)

[0054]

[0055] In general formula A, R 1 R 2 B 1 and B 2 Each can independently represent a hydrogen atom or a substituent.

[0056] Preferred R 1 and R 2 Each alkyl group independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl. R is even more preferred. 1 and R 2 Each can be independently represented as methyl or ethyl, with R being even more preferred. 1 and R 2 Both indicate methyl or both indicate ethyl.

[0057] Preferred option B 1 and B 2 Each can be independently represented as a substituted or unsubstituted phenyl group. In cases where the phenyl group has multiple substituents, two or more of these substituents can also bond together to form a ring. Specific examples of the formed rings can be found in the example compounds described later. The substitution positions of the substituents in a substituted phenyl group are preferably relative to B. 1 With B 2 The bonded carbon atom is in the para position. Specific examples of substituents for substituted phenyl groups include morpholino, piperidinyl, halogen, alkoxy, and the substituents included in the example compounds described below. In this invention and this specification, an asterisk (*) related to a portion of the compound's structure indicates the bonding position of an atom bonded to such a portion of the structure.

[0058] [Chemical Formula 4]

[0059]

[0060] In general formula A, R 3 ~R 6 Each can independently represent a hydrogen atom or an electron-withdrawing group. Among them, R... 3 ~R 6One or more of these groups represent electron-withdrawing groups. Preferred electron-withdrawing groups are halogen atoms, perfluoroalkyl groups with 1 to 6 carbon atoms, perfluorophenyl groups, perfluoroalkylphenyl groups, or cyano groups. Preferred halogen atoms are fluorine atoms. Preferred perfluoroalkyl groups with 1 to 6 carbon atoms are trifluoromethyl groups.

[0061] In one approach, the compound represented by general formula A can be one of the following compounds.

[0062] R 3 ~R 6 Only R in China 4 It is an electron-withdrawing group, and R 3 R 5 and R 6 Compounds containing hydrogen atoms.

[0063] R 3 ~R 6 Chinese R 4 and R 6 For the same or different electron-withdrawing groups, and R 3 and R 5 Compounds containing hydrogen atoms.

[0064] R 3 ~R 6 Chinese R 3 and R 5 For the same or different electron-withdrawing groups, and R 4 and R 6 Compounds containing hydrogen atoms.

[0065] The following compounds can be exemplified as compounds represented by general formula A. However, the present invention is not limited to the compounds exemplified below.

[0066] [Chemical Formula 5]

[0067]

[0068] [Chemical Formula 6]

[0069]

[0070] [Chemical Formula 7]

[0071]

[0072] [Chemical Formula 8]

[0073]

[0074] [Chemical Formula 9]

[0075]

[0076] [Chemical Formula 10]

[0077]

[0078] [Chemical Formula 11]

[0079]

[0080] [Chemical Formula 12]

[0081]

[0082] [Chemical Formula 13]

[0083]

[0084] [Chemical Formula 14]

[0085]

[0086] [Chemical Formula 15]

[0087]

[0088] [Chemical Formula 16]

[0089]

[0090] [Chemical Formula 17]

[0091]

[0092] [Chemical Formula 18]

[0093]

[0094] [Chemical Formula 19]

[0095]

[0096] [Chemical Formula 20]

[0097]

[0098] [Chemical Formula 21]

[0099]

[0100] [Chemical Formula 22]

[0101]

[0102] [Chemical Formula 23]

[0103]

[0104] [Chemical Formula 24]

[0105]

[0106] [Chemical Formula 25]

[0107]

[0108] [Chemical Formula 26]

[0109]

[0110] [Chemical Formula 27]

[0111]

[0112] [Chemical Formula 28]

[0113]

[0114] <Compounds represented by general formula B>

[0115] [Chemical Formula 29]

[0116] (General Formula B)

[0117]

[0118] In general formula B, R 7 ~R 12 B 3 and B 4 Each can independently represent a hydrogen atom or a substituent.

[0119] Preferred R 7 and R 8 Each alkyl group independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl. R is even more preferred. 7 and R 8 Each can be independently represented as methyl or ethyl, with R being even more preferred. 7 and R 8 Both indicate methyl or both indicate ethyl.

[0120] Preferred option B 3 and B 4 Each can be independently represented as a substituted or unsubstituted phenyl group. In cases where the phenyl group has multiple substituents, two or more of these substituents can also bond together to form a ring. Specific examples of the formed rings can be found in the example compounds described later. The substitution positions of the substituents in a substituted phenyl group are preferably relative to B. 3 With B 4The bonded carbon atom is in the para position. Specific examples of substituents for substituted phenyl groups include morpholino, piperidinyl, halogen, alkoxy, and the substituents included in the example compounds described below.

[0121] [Chemical Formula 30]

[0122]

[0123] R 9 ~R 12 Each can independently represent a hydrogen atom or a substituent. In one manner, R 9 ~R 12 It can be all hydrogen atoms. In other cases, it can be R. 10 It is an electron-withdrawing group, and R 9 R 11 and R 12 All are hydrogen atoms. Alternatively, in other configurations, it could be R. 9 and R 11 Each is an electron-withdrawing group independently, and R 10 and R 12 It is a hydrogen atom. As an electron-withdrawing group, it is preferably a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group. As a halogen atom, it is preferably a fluorine atom. As a perfluoroalkyl group having 1 to 6 carbon atoms, it is preferably a trifluoromethyl group.

[0124] In one approach, R 10 It can be a substituted or unsubstituted phenyl group, with R being preferred. 10 For substituted or unsubstituted phenyl, and R 9 R 11 and R 12 The hydrogen atom is present. Specific examples of such substituted phenyl groups include phenyl groups substituted with one or more halogen atoms and / or one or more cyano groups, phenyl groups in which all five substitution positions of the phenyl group are substituted with halogen atoms (preferably fluorine atoms), and phenyl groups in which the hydrogen atom is substituted with respect to R. 10 The bonded carbon atom becomes a monosubstituted phenyl group with a cyano group at the para position.

[0125] R 13 and R 14 Each can independently represent a hydrogen atom or an electron-donating group. Among them, R... 13 and R 14 One or more of them represent electron-donating groups. R is preferred. 13 and R 14 Each of these groups independently represents an electron-donating group selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolyl, piperidinyl, morpholinyl, and thiomorpholinyl.

[0126] In one approach, it could be R 13 and R 14 One of them is a hydrogen atom and the other is an electron-donating group; in another embodiment, both can be electron-donating groups independently. R is preferred. 13 and R 14 Both are electron-donating groups. In this case, R 13 and R 14 These can be the same or different electron-donating groups. Specifically, for R... 13 and R 14 In this regard, R is preferred 13 It is morpholino and R 14 It is an alkoxy group (preferably a methoxy group), R 13 It is morpholino and R 14 It is a methylthio (-S-CH3), R 13 and R 14 All are alkoxy (preferably methoxy), and R 13 and R 14 All of them are methylthio (-S-CH3).

[0127] The following compounds can be exemplified as compounds represented by general formula B. However, the present invention is not limited to the compounds exemplified below.

[0128] [Chemical Formula 31]

[0129]

[0130] [Chemical Formula 32]

[0131]

[0132] [Chemical Formula 33]

[0133]

[0134] [Chemical Formula 34]

[0135]

[0136] [Chemical Formula 35]

[0137]

[0138] [Chemical Formula 36]

[0139]

[0140] [Chemical Formula 37]

[0141]

[0142] [Chemical Formula 38]

[0143]

[0144] [Chemical Formula 39]

[0145]

[0146] [Chemical Formula 40]

[0147]

[0148] [Chemical Formula 41]

[0149]

[0150] [Chemical Formula 42]

[0151]

[0152] [Chemical Formula 43]

[0153]

[0154] [Chemical Formula 44]

[0155]

[0156] [Chemical Formula 45]

[0157]

[0158] [Chemical Formula 46]

[0159]

[0160] [Chemical Formula 47]

[0161]

[0162] [Chemical Formula 48]

[0163]

[0164] Compounds represented by general formula A and compounds represented by general formula B can be synthesized by known methods. For synthetic methods, please refer to the following documents, for example: Japanese Patent No. 4884578, US2006 / 0226402A1, US2006 / 0228557A1, US2008 / 0103301A1, US2011 / 0108781A1, US2011 / 0108781A1, US Patent No. 7527754, US Patent No. 7556751, WO2001 / 60811A1, WO2013 / 086248A1, WO1996 / 014596A1, and WO2001 / 019813A1.

[0165] A photochromic article of one aspect of the present invention and a photochromic composition of one aspect of the present invention comprise one or more compounds represented by general formula A and one or more compounds represented by general formula B.

[0166] The compound represented by general formula A contained in the above-mentioned photochromic articles and photochromic compositions may be only one or more (e.g., more than two but less than four).

[0167] The compound represented by general formula B contained in the above-mentioned photochromic articles and photochromic compositions may be only one, or may be two or more, preferably two or more, and may also be four or less or three or less.

[0168] Preferably, the photochromic articles and photochromic compositions described above contain more compounds represented by general formula B than compounds represented by general formula A, based on a mass basis. The total amount of compounds represented by general formula A and compounds represented by general formula B is set at 100% by mass. The content of compounds represented by general formula B is preferably more than 50% by mass, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, and still more preferably 90% by mass or more. The content of compounds represented by general formula B may be less than 100% by mass relative to the total amount of compounds represented by general formula A and compounds represented by general formula B (100% by mass), and may be 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, or 95% by mass or less. When the photochromic articles and photochromic compositions described above contain two compounds represented by general formula B, the content of the compounds represented by general formula B is their combined content. This also applies to the content of various components in this invention and this specification.

[0169] For the above-mentioned photochromic articles and photochromic compositions, their total amount is set to 100% by mass, and may include, for example, about 0.1 to 15.0% by mass of compounds represented by general formula A and compounds represented by general formula B, but is not limited to this range.

[0170] [Photochromic items, photochromic compositions]

[0171] The aforementioned photochromic article may at least have a substrate. In one embodiment, the compound represented by general formula A and the compound represented by general formula B may be included in the substrate of the aforementioned photochromic article. The aforementioned photochromic article may have a substrate and a photochromic layer, and the compound represented by general formula A and the compound represented by general formula B may be included in the substrate and / or the photochromic layer. In the substrate and the photochromic layer, the compound represented by general formula A and the compound represented by general formula B may be included only in the substrate in one embodiment, only in the photochromic layer in another embodiment, and in yet another embodiment, both in the substrate and the photochromic layer. Furthermore, the substrate and the photochromic layer may contain only the compound represented by general formula A and the compound represented by general formula B as photochromic compounds, or they may contain one or more other photochromic compounds. Examples of other photochromic compounds include: azobenzenes, spiropyrans, and spiropyrans. Azides, naphthopyrans, indo-naphthopyrans, phenanthrenepyrans, hexallyl diimidazoles, donor-acceptor Steinhaus adducts (DASA), salicylaniline derivatives, dihydropyrene derivatives, anthracene dimers, styric anhydrides, diarylethylene derivatives, phenoxynaphthoquinone derivatives, stilbenes, etc.

[0172] <Substrate>

[0173] The aforementioned photochromic articles may include a substrate selected according to the type of photochromic article. As an example of a substrate, for eyeglass lens substrates, plastic lens substrates or glass lens substrates may be cited. Glass lens substrates may, for example, be lens substrates made of inorganic glass. As plastic lens substrates, examples include allyl carbonate resins such as (meth)acrylic resin (represented by styrene resin), polycarbonate resin, allyl resin, diethylene glycol dielyl carbonate resin (CR-39), vinyl resin, polyester resin, polyether resin, urethane resin obtained by reacting isocyanate compounds with hydroxyl compounds such as diethylene glycol, thiourethane resin obtained by reacting isocyanate compounds with polythiols, and cured products (generally referred to as transparent resins) formed by curing a curable composition containing a (thio)epoxide compound having one or more disulfide bonds within its molecule. As lens substrates, undyed substrates (colorless lenses) or dyed substrates (dyed lenses) may be used. The refractive index of the lens substrate can be, for example, around 1.50 to 1.75, but it is not limited to this range; it can be within the range or deviate slightly above or below it. Here, refractive index refers to the refractive index relative to light with a wavelength of 500 nm. Furthermore, the lens substrate can be a lens with refractive power (so-called a prescription lens) or a lens without refractive power (so-called a non-prescription lens).

[0174] For example, the aforementioned photochromic composition can be a polymeric composition. In this invention and specification, "polymeric composition" refers to a composition containing one or more polymeric compounds. A cured product of the polymeric composition can be produced by molding a polymeric composition containing at least one compound represented by general formula A, one or more compounds represented by general formula B, and one or more polymeric compounds using a known molding method. This cured product can be included as a substrate in the aforementioned photochromic article, and / or as a photochromic layer in the aforementioned photochromic article. The curing process can be light exposure and / or heat treatment. A polymeric compound refers to a compound having polymeric groups, and a cured product can be formed by curing the polymeric composition through a polymerization reaction of the polymeric compound. The polymeric composition may further contain one or more additives (e.g., polymerization initiators, etc.).

[0175] Eyeglass lenses can be various types, including single-focal lenses, multifocal lenses, and progressive refractive lenses. The type of lens is determined by the shape of the two surfaces of the lens substrate. Furthermore, the surface of the lens substrate can be any surface, including convex, concave, and flat surfaces. For typical lens substrates and eyeglass lenses, the object-side surface is convex and the eye-side surface is concave, but this is not a limitation. The photochromic layer can typically be applied to the object-side surface of the lens substrate, but it can also be applied to the eye-side surface.

[0176] <Photochromic layer>

[0177] The photochromic layer can be a layer directly disposed on the surface of a substrate, or a layer indirectly disposed on the surface of a substrate through one or more other layers. For example, the photochromic layer can be a cured layer formed by curing a polymeric composition. A cured layer can be formed by curing a polymeric composition containing at least one compound represented by general formula A, one or more compounds represented by general formula B, and one or more polymeric compounds, thereby forming a photochromic layer. For example, such a polymeric composition can be directly coated onto the surface of a substrate, or coated onto the surface of a layer disposed on a substrate, and the coated polymeric composition can be cured to form a cured layer containing one or more compounds represented by general formula A and one or more compounds represented by general formula B, thereby forming a photochromic layer. Known coating methods such as spin coating, dip coating, spray coating, inkjet coating, nozzle coating, and slot coating can be used as coating methods. The curing treatment can be light exposure and / or heat treatment. In addition to one or more polymeric compounds, the polymeric composition may further contain one or more additives (e.g., polymerization initiators). By allowing the polymerization reaction of polymeric compounds to proceed, the polymeric composition can be cured to form a cured layer.

[0178] The thickness of the photochromic layer can be, for example, 5 μm or more, 10 μm or more, or 20 μm or more, or, for example, 80 μm or less, 70 μm or less, or 50 μm or less.

[0179] <Polymerizing compounds>

[0180] In this invention and 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 polymerizable groups include: acryloyl, methacryloyl, vinyl, vinyl ether, epoxy, thiohydroxy, oxetyl, hydroxyl, carboxyl, amino, isocyanate, etc.

[0181] Examples of polymerizable compounds that can be used to form the aforementioned substrate and photochromic layer include the following compounds.

[0182] (Cyclic sulfide compounds)

[0183] Cyclic sulfides are compounds containing two or more cyclic sulfide groups per molecule. Cyclic sulfide groups are polymerizable groups capable of ring-opening polymerization. Specific examples of cyclic sulfides include: bis(1,2-cyclothioethyl) sulfide, bis(1,2-cyclothioethyl) disulfide, bis(2,3-cyclothiopropyl) sulfide, bis(2,3-cyclothiopropylthio)methane, bis(2,3-cyclothiopropyl) disulfide, bis(2,3-cyclothiopropyldithio)methane, bis(2,3-cyclothiopropyldithio)ethane, bis(6,7-cyclothio-3,4-dithionyl) sulfide, bis( 6,7-Cyclothio-3,4-dithioheptyl) disulfide, 1,4-dithiane-2,5-bis(2,3-cyclothiopropyldithiomethyl), 1,3-bis(2,3-cyclothiopropyldithiomethyl)benzene, 1,6-bis(2,3-cyclothiopropyldithiomethyl)-2-(2,3-cyclothiopropyldithioethylthio)-4-thiahexane, 1,2,3-tris(2,3-cyclothiopropyldithio)propane, 1,1,1,1-tetra(2 3-Cyclothiopropyldithiomethyl)methane, 1,3-bis(2,3-cyclothiopropyldithio)-2-thiapropane, 1,4-bis(2,3-cyclothiopropyldithio)-2,3-dithiabutane, 1,1,1-tris(2,3-cyclothiopropyldithio)methane, 1,1,1-tris(2,3-cyclothiopropyldithiomethylthio)methane, 1,1,2,2-tetra(2,3-cyclothiopropyldithio)ethane, 1,1,2, 2-Tetra(2,3-cyclothiopropyldithiomethylthio)ethane, 1,1,3,3-tetra(2,3-cyclothiopropyldithio)propane, 1,1,3,3-tetra(2,3-cyclothiopropyldithiomethylthio)propane, 2-[1,1-bis(2,3-cyclothiopropyldithio)methyl]-1,3-dithionecyclobutane, 2-[1,1-bis(2,3-cyclothiopropyldithiomethylthio)methyl]-1,3-dithionecyclobutane, etc.

[0184] (Thioheterocyclic butyl compounds)

[0185] Thiohecyclic butyl compounds are thioheterocyclic butane compounds having two or more thioheterocyclic butyl groups within a single molecule. Thiohecyclic butyl groups are polymerizable groups capable of ring-opening polymerization. Thiohecyclic butyl compounds include compounds that possess multiple thioheterocyclic butyl groups along with cyclic sulfide groups. Such compounds have been listed in the examples of cyclic sulfides above. Other thioheterocyclic butyl compounds include metal-containing thioheterocyclic butane compounds with metal atoms within the molecule, and non-metal-containing thioheterocyclic butane compounds.

[0186] Specific examples of non-metallic thiocyclic butane compounds include: bis(3-thiocyclic butyl) disulfide, bis(3-thiocyclic butyl) sulfide, bis(3-thiocyclic butyl) trisulfide, bis(3-thiocyclic butyl) tetrasulfide, 1,4-bis(3-thiocyclic butyl)-1,3,4-trithiobutane, 1,5-bis(3-thiocyclic butyl)-1,2,4,5-tetrathiapentane, 1,6-bis(3-thiocyclic butyl)-1,3,4,6-tetrathiahexane, 1,6-bis(3-thiocyclic butyl)-1,3,5,6-tetrathiahexane, 1,7-bis(3-thiocyclic butyl) 1,7-bis(3-thionecyclobutylthio)-1,2,4,6,7-pentathione, 1,1-bis(3-thionecyclobutylthio)methane, 1,2-bis(3-thionecyclobutylthio)ethane, 1,2,3-tris(3-thionecyclobutylthio)propane, 1,8-bis(3-thionecyclobutylthio)-4-(3-thionecyclobutylthiomethyl)-3,6-dithiaoctane, 1,11-bis(3-thionecyclobutylthio)-4,8-bis(3-thionecyclobutylthiomethyl)-3,6,9-trithiaundecane, 1, 11-bis(3-thiocyclobutylthio)-4,7-bis(3-thiocyclobutylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(3-thiocyclobutylthio)-5,7-bis(3-thiocyclobutylthiomethyl)-3,6,9-trithiaundecane, 2,5-bis(3-thiocyclobutylthiomethyl)-1,4-dithiaane, 2,5-bis[[2-(3-thiocyclobutylthio)ethyl]thiomethyl]-1,4-dithiaane, 2,5-bis(3-thiocyclobutylthiomethyl)-2,5-dimethyl-1,4-dithiaane, dithiacyclobutyl sulfide, bis(thiocyclobutylthiomethyl)-4,7-bis(3-thiocyclobutylthiomethyl)-3,6,9-trithiaundecane, 2,5-bis(3-thiocyclobutylthiomethyl)-1,4-dithiaane, dithiacyclobutyl sulfide, bis(thiacyclobutylthiomethyl)-4,7-bis(3-thiocyclobutylthiomethyl)-3,6,9-trithiaundecane, 2,5-bis(3-thiocyclobutylthiomethyl)-2,5-dimethyl ...4,7-bis(3-thiocyclobutylthiomethyl)-3,6,9-trithiaundecane, 2,5 Heterocyclic butylthio)methane, 3-[<(thiocyclic butylthio)methylthio>methylthio]thiocyclic butane, dithiocyclic butyl disulfide, dithiocyclic butyl trisulfide, dithiocyclic butyl tetrasulfide, dithiocyclic butyl pentasulfide, 1,4-bis(3-thiocyclic butyl disulfide)-2,3-dithiobutane, 1,1,1-tris(3-thiocyclic butyl disulfide)methane, 1,1,1-tris(3-thiocyclic butyl disulfide methylthio)methane, 1,1,2,2-tetra(3-thiocyclic butyl disulfide)ethane, 1,1,2,2-tetra(3-thiocyclic butyl disulfide methylthio)ethane, etc.

[0187] Examples of metal-sulfur heterocyclic butane compounds include those containing metal atoms such as Sn, Si, Ge, Pb (Group 14 atoms), Zr, Ti (Group 4 elements), Al (Group 13 atoms), and Zn (Group 12 atoms). Specific examples include alkylthio(thiocyclic butylthio)tin, bis(alkylthio)bis(thiocyclic butylthio)tin, alkylthio(alkylthio)bis(thiocyclic butylthio)tin, bis(thiocyclic butylthio)cyclic disulfotin compounds, and alkyl(thiocyclic butylthio)tin compounds.

[0188] Specific examples of alkylthio (thioheterobutylthio)tin include: methylthiotris(thioheterobutylthio)tin, ethylthiotris(thioheterobutylthio)tin, propylthiotris(thioheterobutylthio)tin, isopropylthiotris(thioheterobutylthio)tin, etc.

[0189] Specific examples of bis(alkylthio)bis(thioheterobutylthio)tin include: bis(methylthio)bis(thioheterobutylthio)tin, bis(ethylthio)bis(thioheterobutylthio)tin, bis(propylthio)bis(thioheterobutylthio)tin, bis(isopropylthio)bis(thioheterobutylthio)tin, etc.

[0190] Specific examples of alkylthiobis(thioheterocyclic butylthio)tin include: ethylthiobis(thioheterocyclic butylthio)tin, methylthiobis(thioheterocyclic butylthio)tin, isopropylthiobis(thioheterocyclic butylthio)tin, ethylthiobis(thioheterocyclic butylthio)tin, ethylthiobis(thioheterocyclic butylthio)tin, isopropylthiobis(thioheterocyclic butylthio)tin, etc.

[0191] Specific examples of bis(thiohexacyclic butylthio) cyclic dithiotin compounds include: bis(thiohexacyclic butylthio) dithiotin heterocyclic butyl ring, bis(thiohexacyclic butylthio) dithiotin heterocyclic pentane ring, bis(thiohexacyclic butylthio) dithiotin heterocyclic hexane ring, bis(thiohexacyclic butylthio) trithiotin heterocyclic heptane ring, etc.

[0192] Specific examples of alkyl(thiocyclobutylthio)tin compounds include: methyltri(thiocyclobutylthio)tin, dimethylbis(thiocyclobutylthio)tin, butyltri(thiocyclobutylthio)tin, tetra(thiocyclobutylthio)tin, tetra(thiocyclobutylthio)germanium, tri(thiocyclobutylthio)bismuth, etc.

[0193] (Polyamine compounds)

[0194] Polyamine compounds are compounds having two or more NH2 groups in one molecule. They can form urea bonds through reactions with polyisocyanates or thiourea bonds through reactions with polyisothiocyanates. Specific examples of polyamine compounds include: ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undemoethylenediamine, dodemoethylenediamine, m-phenylenediamine, 1,3-propanediamine, 1,4-butanediamine, 2-(2-aminoethylamino)ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, and 1,3,5-phenyltriamine.

[0195] (Epoxy compounds)

[0196] Epoxides are compounds that contain epoxy groups within their molecules. Epoxy groups are polymerizable groups capable of ring-opening polymerization. Epoxides can generally be classified into aliphatic epoxides, alicyclic epoxides, and aromatic epoxides.

[0197] Specific examples of aliphatic epoxy compounds include: ethylene oxide, 2-ethyl ethylene oxide, butyl glycidyl ether, phenyl glycidyl ether, 2,2'-methylenebis(ethylene oxide), 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 tri(2-hydroxyethyl)isocyanurate, etc.

[0198] Specific examples of alicyclic epoxides include isophorone diol diglycidyl ether and bis-2,2-hydroxycyclohexylpropane diglycidyl ether.

[0199] Specific examples of aromatic epoxy compounds include: resorcinol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, phthalic acid diglycidyl ester, phenolic varnish polyglycidyl ether, cresol phenolic varnish polyglycidyl ether, etc.

[0200] In addition to the above, epoxy compounds that have both epoxy groups and sulfur atoms in the molecule can also be used. Such sulfur-containing epoxy compounds include both chain-like aliphatic sulfur-containing epoxy compounds and cyclic aliphatic sulfur-containing epoxy compounds.

[0201] Specific examples of chain-like aliphatic sulfur-containing epoxide 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)butane, and 1,3-bis(2,3-epoxypropylthio)butane. 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, etc.

[0202] Specific examples of cyclic aliphatic sulfur-containing epoxy compounds 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, 2,5-bis(2,3-epoxypropylthiomethyl)-2,5-dimethyl-1,4-dithiane, etc.

[0203] (Compounds with free radical polymerizable groups)

[0204] Compounds containing free radical polymerizable groups are polymerizable groups capable of undergoing free radical polymerization. Examples of free radical polymerizable groups include: acryloyl, methacryloyl, allyl, vinyl, etc.

[0205] Hereinafter, compounds having polymerizable groups selected from acryloyl and methacryloyl groups will be referred to as "(meth)acrylate compounds". Specific examples of (meth)acrylate compounds 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 diglycidyl(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(methyl)propane, and 2,2-bis(3,5-dibromo-4-(meth)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, and 2,2-bis(3,5-dibromo-4-(meth)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, dihydroxymethyltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methyl thio(meth)acrylate, phenyl thio(meth)acrylate, benzyl thio(meth)acrylate, diphenyl dimethyl dithiol di(meth)acrylate, mercaptoethyl sulfide di(meth)acrylate, difunctional carbamate (meth)acrylate, etc.

[0206] Specific examples of compounds containing an allyl group (allyl compounds) include: allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol dielyl carbonate, methoxy polyethylene glycol allyl ether, polyethylene glycol allyl ether, methoxy polyethylene glycol-polypropylene glycol allyl ether, butoxy polyethylene glycol-polypropylene glycol allyl ether, methacryloyloxy polyethylene glycol-polypropylene glycol allyl ether, phenoxy polyethylene glycol allyl ether, methacryloyloxy polyethylene glycol allyl ether, etc.

[0207] Examples of compounds containing vinyl groups (vinyl compounds) include: α-methylstyrene, α-methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobis(m-dioxane), etc.

[0208] The aforementioned photochromic articles may include, at any location, one or more layers known as functional layers of the photochromic articles, such as a protective layer, an anti-reflective layer, a water-repellent or hydrophilic antifouling layer, an anti-fog layer, or a base layer for improving interlayer adhesion.

[0209] The aforementioned photochromic articles can be optical articles. One type of optical article is an eyeglass lens. Such an eyeglass lens can also be called a photochromic lens or photochromic eyeglass lens. Other examples of optical articles include: lenses for safety goggles, the brim (visor) of a sun hat, and the visor of a helmet. By coating the aforementioned photochromic composition, which is a polymeric composition, onto a substrate for these optical articles and then curing the coated composition to form a photochromic layer, an optical article with anti-glare functionality can be obtained.

[0210] [Glasses]

[0211] One aspect of the present invention relates to eyeglasses comprising spectacle lenses as described above for photochromic articles. Details regarding the spectacle lenses included in these eyeglasses are as described previously. By comprising such spectacle lenses, these eyeglasses, for example, can, when outdoors, exhibit an anti-glare effect similar to sunglasses by coloring upon exposure to sunlight using a photochromic compound, and upon returning indoors, can restore transmittance by fading through the photochromic compound. The construction of the frames, etc., for these eyeglasses can be made using known techniques.

[0212] Example

[0213] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to the embodiments shown. "%" in the following description represents mass%.

[0214] [Compound Synthesis]

[0215] Compounds 1 to 15, shown below, were synthesized according to the methods described in the preceding references. The compounds were identified using the same methods as described in the reference publications, confirming the synthesis of the compounds shown below. Compounds 1 to 7 are compounds represented by general formula A, and compounds 8 to 15 are compounds represented by general formula B.

[0216] [Chemical Formula 49]

[0217]

[0218] [Chemical Formula 50]

[0219]

[0220] [Examples 1-28, Comparative Examples 1-3]

[0221] <Preparation of Photochromic Compositions (Polymerizable Compositions)>

[0222] In a plastic container, a (meth)acrylate mixture was prepared by mixing 68 parts by mass of polyethylene glycol diacrylate, 12 parts by mass of trimethylolpropane trimethacrylate, and 20 parts by mass of neopentyl glycol dimethacrylate, relative to a total of 100 parts by mass of (meth)acrylate. A photochromic compound was then mixed relative to 100 parts by mass of this (meth)acrylate mixture, bringing the total to 2.5 parts by mass. For compositions containing multiple photochromic compounds, Table 2 shows the mass ratios of the individual photochromic compounds when the total amount of the photochromic compound is set to 10. Then, the photopolymerization initiator (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), antioxidant [bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid] [ethylene bis(ethylene oxide)] ester], and light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate) were mixed and stirred thoroughly. Then, a silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane) was added dropwise while stirring. Finally, degassing was performed using a rotation-revolution stirring and degassing device.

[0223] The photochromic composition was prepared using the above method.

[0224] The comparative compounds used in Comparative Example 3 are the following compounds.

[0225] [Chemical Formula 51]

[0226] Comparison of compounds

[0227]

[0228] <Film Formation of the Primer>

[0229] The plastic lens substrate (HOYA Co., Ltd., trade name EYAS: center thickness 2.5 mm, diameter 75 mm, spherical lens power -4.00) was subjected to alkaline cleaning by immersing it in a 10% by mass sodium hydroxide aqueous solution (liquid temperature 60°C) for 5 minutes, followed by rinsing with pure water and drying. Then, in an environment with room temperature and relative humidity of 40-60%, an aqueous polyurethane resin liquid (polycarbonate polyol polyurethane emulsion, viscosity 100 cPs, solid content concentration 38% by mass) was applied to the convex surface of the plastic lens substrate for 1 minute using a MIKASA Co., Ltd. MS-B150 spin coater at a speed of 1500 rpm for 1 minute, and then allowed to air dry for 15 minutes, thereby forming a base coating with a thickness of 5.5 μm.

[0230] <Film Formation of Photochromic Layers>

[0231] The photochromic composition prepared above was drop-added onto the aforementioned base coating layer. Using an MS-B150 spin coater manufactured by MIKASA Co., Ltd., the coating was applied via a spin coating method employing a procedure of rotating the spindle speed from 500 rpm to 1500 rpm over one minute in tilt mode, followed by a further rotation at 1500 rpm for 5 seconds. Then, the photochromic composition coated on the base coating layer formed on the plastic lens substrate was irradiated with ultraviolet light (dominant wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration ≤ 500 ppm) for 40 seconds to cure the composition, forming a photochromic layer. The thickness of the formed photochromic layer was 45 μm.

[0232] Photochromic items (eyeglass lenses) were thus produced.

[0233] [Evaluation Method]

[0234] <Evaluation of coloring density>

[0235] The light reflectance was determined using the following method based on JIS T7333:2005.

[0236] Using a xenon lamp as the light source, the convex surfaces of the spectacle lenses of the examples and comparative examples were irradiated with light filtered through an air quality filter for 15 minutes to color the photochromic layer. This irradiation was performed in accordance with JIS T7333:2005, ensuring that the irradiance and the permissible difference in irradiance met the values ​​shown in Table 1. The transmittance during coloring was measured using an Otsuka Electronics spectrophotometer. The light transmittance T (%), calculated based on measurements within the wavelength range of 380 nm to 780 nm, is shown in Table 2. A smaller T (%) value indicates a higher concentration of the photochromic compound.

[0237] [Table 1]

[0238] 300～340 ＜2.5 - 340～380 5.6 ±1.5 380～420 12 ±3.0 420～460 12 ±3.0 460～500 26 ±2.6

[0239] <Evaluation of fading speed>

[0240] The fading rate was evaluated using the following method.

[0241] The transmittance (measurement wavelength: 550 nm) of each spectacle lens of the Examples and Comparative Examples before illumination (uncolored state) was measured using an Otsuka Electronics spectrophotometer. Here, the measured transmittance is referred to as "initial transmittance".

[0242] For each spectacle lens, a xenon lamp was used as the light source, and the lens was irradiated for 15 minutes with light filtered through an air quality filter to color the photochromic layer. This irradiation was performed in accordance with JIS T7333:2005 to ensure that the irradiance and the permissible difference in irradiance met the values ​​shown in Table 1. The transmittance at this coloring stage was measured in the same manner as the initial transmittance. Here, the measured transmittance is referred to as the "transmittance at coloring stage".

[0243] Then, the time required from the time the light exposure stops until the transmittance reaches [(initial transmittance - transmittance at color) / 2] is measured. This time is designated as the "halving time". It can be assumed that the shorter the halving time, the faster the fading rate. The calculated halving times are shown in Table 2.

[0244] [Table 2]

[0245]

[0246] The results shown in Table 2 confirm that by combining the compound represented by general formula A with the compound represented by general formula B, it is possible to provide photochromic articles that exhibit high concentration coloration in the visible light region and fast fading rate.

[0247] Finally, let's summarize the methods mentioned above.

[0248] According to one method, a photochromic article and a photochromic composition may be provided, comprising one or more compounds represented by general formula A and one or more compounds represented by general formula B.

[0249] In one approach, in general formula A, R 1 and R 2 Each can independently represent a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms.

[0250] In one approach, in general formula A, R 1 and R 2 Each can independently represent methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0251] In one approach, B in general formula A 1 and B 2 And B in the general formula B 3 and B 4 Each can independently represent a substituted or unsubstituted phenyl group. In the case of a phenyl group having multiple substituents, these substituents can bond together to form a ring.

[0252] In one embodiment, the electron-withdrawing group in general formula A may be a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group.

[0253] In one embodiment, the aforementioned halogen atom can be a fluorine atom.

[0254] In one embodiment, the perfluoroalkyl group can be trifluoromethyl.

[0255] In one approach, R is selected from general formula A. 1 R 2 B 1 B 2 R in general formula B 7 ~R 12 B 3 and B 4 One or more of them represent substituents, and the substituent can be substituent R. m , or in R m The next step is to replace one or more identical or different Rs. m The substituent, or a solubilizing group, wherein the substituent R m Selected from:

[0256] Hydroxyl groups, straight-chain or branched alkyl groups with 1 to 18 carbon atoms, polycyclic cyclic aliphatic alkyl groups with 5 to 18 carbon atoms (monocyclic or bicyclic), straight-chain or branched alkoxy groups with 1 to 24 carbon atoms, non-aromatic cyclic substituents with 1 to 24 carbon atoms, straight-chain or branched perfluoroalkyl groups with 1 to 18 carbon atoms, straight-chain or branched perfluoroalkoxy groups, straight-chain or branched alkylthio groups with 1 to 24 carbon atoms, aryl, aryloxy, arylthio, heteroaryl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, piperidinyl, morpholinyl, thiomorpholinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl and other cyclic amino groups, ethynyl, mercapto, silyl, sulfonic acid, alkylsulfonyl, formyl, carboxyl, cyano and halogen atoms.

[0257] In one approach, in general formula B, R 7 and R 8 Each can independently represent a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms.

[0258] In one approach, in general formula B, R 7 and R 8 Each can independently represent methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0259] In one approach, in general formula B, R 13 and R 14 Each can independently represent an electron-donating group selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolyl, piperidinyl, morpholinyl, and thiomorpholinyl.

[0260] In one embodiment, the aforementioned photochromic article and the aforementioned photochromic composition may contain, on a mass basis, more compounds represented by general formula B than compounds represented by general formula A.

[0261] In one embodiment, the aforementioned photochromic article and the aforementioned photochromic composition may contain only one compound represented by general formula A and two compounds represented by general formula B.

[0262] In one embodiment, the aforementioned photochromic article may have a substrate and a photochromic layer, and the photochromic layer may contain one or more compounds represented by general formula A and one or more compounds represented by general formula B.

[0263] In one embodiment, the photochromic layer may be a cured layer formed by curing a polymeric composition.

[0264] In one embodiment, the photochromic composition described above may contain a polymeric compound.

[0265] In one embodiment, the aforementioned photochromic article can be an eyeglass lens.

[0266] In one embodiment, the aforementioned photochromic article can be a lens for goggles.

[0267] In one embodiment, the aforementioned photochromic item can be the brim of a sun hat.

[0268] In one embodiment, the aforementioned photochromic article can be a visor component of a helmet.

[0269] According to one method, eyeglasses having the aforementioned spectacle lenses can be provided.

[0270] The various methods and forms described in this specification can be combined in any way, and two or more combinations can be made.

[0271] It should be understood that the embodiments disclosed herein are merely illustrative in all respects and are not intended to be restrictive. The scope of the invention is as set forth in the claims and is not limited to the foregoing description, and is intended to include all modifications in the equivalent sense and scope of the claims.

[0272] Industrial applicability

[0273] One aspect of the present invention is useful in the technical fields of eyeglasses, goggles, sun hats, helmets, etc.

Claims

1. A photochromic composition comprising one or more compounds represented by general formula A and one or more compounds represented by general formula B. General Formula A: In general formula A, R 1 R 2 B 1 and B 2 Each can independently represent a hydrogen atom or a substituent. R 4 R represents an electron-withdrawing group. 3 R 5 and R 6 Each represents a hydrogen atom independently. General formula B: In general formula B, R 7 ~R 12 B 3 and B 4 Each can independently represent a hydrogen atom or a substituent. R 13 and R 14 Each can independently represent a hydrogen atom or an electron-donating group, among which, R 13 and R 14 One or more of them represent electron-donating groups. R selected from general formula A 1 R 2 B 1 B 2 R in general formula B 7 ~R 12 B 3 and B 4 One or more of them represent substituents, and the substituent is substituent R. m , or in R m The next step is to replace one or more identical or different Rs. m The substituents, or solubilizing groups, are present. The substituent R m Selected from: Hydroxyl group, straight-chain or branched alkyl group with 1 to 18 carbon atoms, monocyclic or polycyclic cyclic aliphatic alkyl group with 5 to 18 carbon atoms, straight-chain or branched alkoxy group with 1 to 24 carbon atoms, non-aromatic cyclic substituent with 1 to 24 carbon atoms, straight-chain or branched perfluoroalkyl group with 1 to 18 carbon atoms, straight-chain or branched perfluoroalkoxy group, straight-chain or branched alkylthio group with 1 to 24 carbon atoms, aryl group, aryloxy group, arylthio group, heteroaryl group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group, piperidinyl group, morpholinyl group, thiomorpholinyl group, tetrahydroquinolinyl group, tetrahydroisoquinolinyl group, ethynyl group, mercaptoyl group, silyl group, sulfonic acid group, alkylsulfonyl group, formyl group, carboxyl group, cyano group and halogen atom.

2. A photochromic composition comprising one or more compounds represented by general formula A and one or more compounds represented by general formula B. General Formula A: In general formula A, R 1 R 2 B 1 and B 2 Each can independently represent a hydrogen atom or a substituent. R 3 ~R 6 Each can independently represent a hydrogen atom or an electron-withdrawing group, among which, R 3 ~R 6 One or more of them represent electron-withdrawing groups. General formula B: In general formula B, R 7 R 8 B 3 and B 4 Each can independently represent a hydrogen atom or a substituent. R 10 Indicates a hydrogen atom, a substituted or unsubstituted phenyl group. R 9 R 11 and R 12 Represents a hydrogen atom. R 13 and R 14 Each can independently represent a hydrogen atom or an electron-donating group, where R 13 and R 14 One or more of them represent electron-donating groups. R selected from general formula A 1 R 2 B 1 B 2 R in general formula B 7 R 8 B 3 and B 4 One or more of them represent substituents, and the substituent is substituent R. m , or in R m The next step is to replace one or more identical or different Rs. m The substituents, or solubilizing groups, are present. The substituent R m Selected from: Hydroxyl group, straight-chain or branched alkyl group with 1 to 18 carbon atoms, monocyclic or polycyclic cyclic aliphatic alkyl group with 5 to 18 carbon atoms, straight-chain or branched alkoxy group with 1 to 24 carbon atoms, non-aromatic cyclic substituent with 1 to 24 carbon atoms, straight-chain or branched perfluoroalkyl group with 1 to 18 carbon atoms, straight-chain or branched perfluoroalkoxy group, straight-chain or branched alkylthio group with 1 to 24 carbon atoms, aryl group, aryloxy group, arylthio group, heteroaryl group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group, piperidinyl group, morpholinyl group, thiomorpholinyl group, tetrahydroquinolinyl group, tetrahydroisoquinolinyl group, ethynyl group, mercaptoyl group, silyl group, sulfonic acid group, alkylsulfonyl group, formyl group, carboxyl group, cyano group and halogen atom.

3. The photochromic composition according to claim 1 or 2, wherein, In general formula A, R 1 and R 2 Each can be used independently to represent a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms.

4. The photochromic composition according to claim 1 or 2, wherein, In general formula A, R 1 and R 2 Each can be independently represented as methyl, ethyl, propyl, butyl, pentyl, or hexyl.

5. The photochromic composition according to claim 1 or 2, wherein, In general formula A, R 1 and R 2 Each can be used independently to represent either methyl or ethyl.

6. The photochromic composition according to claim 1 or 2, wherein, B in general formula A 1 and B 2 and B in the general formula B 3 and B 4 Each can be independently represented as a substituted or unsubstituted phenyl group, where, in the case of a phenyl group having multiple substituents, the substituents may be optionally bonded to form a ring.

7. The photochromic composition according to claim 6, wherein, The substitution position of the substituent in a substituted phenyl group is relative to B. 1 With B 2 The bonded carbon atom or B 3 With B 4 The bonded carbon atom becomes the para position.

8. The photochromic composition according to claim 1 or 2, wherein, The electron-withdrawing group is a halogen atom, a perfluoroalkyl group with 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group.

9. The photochromic composition according to claim 8, wherein, The halogen atom is a fluorine atom.

10. The photochromic composition according to claim 8, wherein, The perfluoroalkyl group is trifluoromethyl.

11. The photochromic composition according to claim 1 or 2, wherein, In general formula B, R 7 and R 8 Each can be used independently to represent a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms.

12. The photochromic composition according to claim 1 or 2, wherein, In general formula B, R 7 and R 8 Each can be independently represented as methyl, ethyl, propyl, butyl, pentyl, or hexyl.

13. The photochromic composition according to claim 1 or 2, wherein, In general formula B, R 7 and R 8 Each can be used independently to represent either methyl or ethyl.

14. The photochromic composition according to claim 1 or 2, wherein, In general formula B, R 13 and R 14 Each of these groups independently represents an electron-donating group selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolyl, piperidinyl, morpholinyl, and thiomorpholinyl.

15. The photochromic composition according to claim 1 or 2, wherein, On a mass basis, it contains more compounds represented by general formula B than compounds represented by general formula A.

16. The photochromic composition according to claim 1 or 2, further comprising a polymeric compound.

17. A photochromic article comprising a cured product formed by curing the photochromic composition of claim 16.

18. The photochromic article according to claim 17, comprising a substrate and a photochromic layer, wherein the photochromic layer is the cured product.

19. The photochromic article according to claim 17 or 18, wherein it is an eyeglass lens.

20. The photochromic article according to claim 17 or 18, wherein it is a lens for goggles.

21. The photochromic article according to claim 17 or 18, wherein it is the brim portion of a sun hat.

22. The photochromic article according to claim 17 or 18, which is a visor component of a helmet.

23. A pair of eyeglasses having the eyeglass lens as described in claim 19.

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