Photochromic compounds, photochromic compositions, photochromic articles and eyeglasses

Abstract

This invention relates to photochromic compounds represented by the following general formula 1, in which Az represents an unsubstituted or substituent monovalent azazine cyclogroup, L represents a divalent or higher linking group, D represents a photochromic pigment structure, a and c each independently represent an integer of 1 or more, and b represents an integer of 0 or 1 or more. When general formula 1 contains multiple Az groups, the multiple Az groups may be the same or different; similarly, when general formula 1 contains multiple L groups, the multiple L groups may be the same or different.

Description

Technical Field

[0001] This invention relates to photochromic compounds, 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 (photochromic properties). For example, Naphthalopyran compounds with photochromic properties are disclosed in Patent Documents 1 and 2.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: WO2000 / 15631

[0006] Patent Document 2: WO1996 / 14596 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] For example, by methods such as containing photochromic compounds in a substrate or forming a layer containing photochromic compounds, photochromic properties can be imparted to optical articles such as eyeglass lenses.

[0009] 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 light exposure can be called a "chromophore." Conversely, the structure before light exposure can be called a "colorless body." 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 the chromophore. A desirable property of photochromic compounds is the ability to exhibit a rapid fading rate after being chromated by light.

[0010] One objective of this invention is to provide photochromic compounds that fade rapidly.

[0011] Problem Solving Methods

[0012] One aspect of the present invention relates to a photochromic compound, which is represented by the following general formula 1.

[0013] [Chemical Formula 1]

[0014] (General Formula 1)

[0015]

[0016] In General Formula 1, Az represents an unsubstituted or substituent monovalent azazine cyclogroup, L represents a divalent or higher linking group, D represents a photochromic pigment structure (also known as a "light-tuning pigment structure"), a and c each independently represent an integer of 1 or higher, and b represents an integer of 0 or higher. When General Formula 1 contains multiple Az groups, the Az groups can be the same or different. Similarly, when General Formula 1 contains multiple L groups, the L groups can be the same or different.

[0017] Additionally, one aspect of the present invention relates to a photochromic composition comprising a photochromic compound represented by general formula 1.

[0018] Additionally, one aspect of the present invention relates to a photochromic article comprising a photochromic compound represented by general formula 1.

[0019] The photochromic compound represented by general formula 1 has the above-mentioned azazine cyclic group directly in the photochromic pigment structure, or has the above-mentioned azazine cyclic group substituted by a linking group. As a result of the inventors' in-depth research, it has been newly discovered that the above-mentioned photochromic compound can exhibit a fast fading rate.

[0020] The effects of the invention

[0021] According to one aspect of the present invention, a photochromic compound with a rapid fading rate can be provided. Detailed Implementation

[0022] 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 1 and the general formulas described below represent the structures of colorless bodies.

[0023] 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 1 as the photochromic compound. 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.

[0024] In this invention and specification, "photochromic composition" refers to a composition comprising a photochromic compound. One aspect of the photochromic composition of this invention comprises one or more compounds represented by general formula 1 as photochromic compounds, which can be used in the manufacture of photochromic articles according to one aspect of this invention.

[0025] [Photochromic compounds]

[0026] In this invention and this specification, the substituents contained in the compounds represented by general formula 1 and the various substituents contained in the compounds represented by the various general formulas described below can each be independently a 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] Two or more substituents can bond together to form a ring structure.

[0029] 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. mAnother 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.

[0030] 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.

[0031] Furthermore, in this invention and this specification, the substituents contained in the compounds represented by General Formula 1 and the various substituents contained in the compounds represented by the various general formulas described below can each be independently a solubilizing group. In this invention and this specification, a "solubilizing group" refers to a substituent that can help improve compatibility with any liquid or a specific liquid. As a solubilizing group, preferred substituents 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 comprising a straight-chain, branched, or cyclic structure; groups formed by replacing a portion of the above groups with silicon atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, 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 molecular aggregate state close to that of a liquid 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.

[0032] 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.

[0033] The compounds represented by general formula 1 will now be described in more detail. For the partial structures described below, "*" indicates the position where the partial structure is bonded to adjacent atoms.

[0034] [Chemical Formula 2]

[0035] (General Formula 1)

[0036]

[0037] In general formula 1, Az represents an unsubstituted or substituent monovalent azazine cyclogroup, L represents a divalent or higher linking group, D represents a photochromic pigment structure, a and c each independently represent an integer of 1 or higher, and b represents an integer of 0 or 1 or higher. When general formula 1 contains multiple Az groups, the Az groups can be the same or different. Similarly, when general formula 1 contains multiple L groups, the L groups can be the same or different.

[0038] Az represents a monovalent azine cyclogroup, either unsubstituted or with substituents. For the case of substituents, refer to the above description related to substituents. The aforementioned azine cyclogroup may have one or more substituents. In the case of having two or more substituents, the substituents may be the same or different. The azine ring is an aromatic heterocycle containing one or more nitrogen atoms in a six-membered ring, or a fused ring containing an aromatic heterocycle containing one or more nitrogen atoms in a six-membered ring as part thereof. The inventors have deduced that including Az in general formula 1 contributes to the photochromic compound represented by general formula 1 exhibiting a rapid fading rate after light irradiation, but the present invention is not limited to the deductions described in this specification.

[0039] In one embodiment, the azine cyclogroup described above can be exemplified by the following azine cyclogroups. In the following descriptions, X represents a nitrogen atom or an unsubstituted or substituent carbon atom. Since the following structures represent azine cyclogroups, one or more of the plurality of X's contained in each of the following structures represent a nitrogen atom. The plurality of X's contained in each azine cyclogroup may be the same or different. * indicates the bonding position with L (when b is an integer greater than or equal to 1) or D (when b is 0 (in the above case, Az and D are bonded by a single bond)).

[0040] [Chemical Formula 3]

[0041]

[0042] Specific examples of the azine ring contained in the aforementioned azine ring group include: pyridine ring, o-diazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, and quinoline ring. Phosphine ring, benzoquinazoline ring, azafluoranthracene ring, etc.

[0043] When the carbon atom represented by X has a substituent, the above description of the substituent can be referred to in relation to the substituent.

[0044] In one embodiment, the azine cyclogroup described above may be one of the following azine cyclogroups.

[0045] [Chemical Formula 4]

[0046]

[0047] In the above, R 1 ~R 8 Each can be used independently to represent a hydrogen atom or a substituent. For information on substituents, please refer to the above description related to substituents. Two or more substituents can bond together to form a ring structure. *When b is an integer greater than or equal to 1, it indicates the bonding position with L; when b is 0, it indicates the bonding position with D.

[0048] From the viewpoint of further accelerating the fading speed, the azine cyclogroup represented by Az in general formula 1 is preferably an azine cyclogroup in which one or both of the constituent atoms of the azine ring are nitrogen atoms at one or both of the two positions adjacent to the carbon atom of the linking group L (when b is an integer of 1 or more) or the photochromic pigment structure D (when b is 0). More preferably, it is an azine cyclogroup in which the nitrogen atom is located at both of the above two positions.

[0049] Among the above, preferred azine cyclo groups include the following azine cyclo groups (a), (b) and (c), with the following azine cyclo groups (b) and (c) being more preferred.

[0050] [Chemical Formula 5]

[0051]

[0052] Preferably, R in the azine cyclogroup (b) above 1 and R 2 Each can independently represent phenyl or methoxy, more preferably phenyl. Furthermore, R in the azazine cyclogroup (b) described above is preferred. 3 It represents a hydrogen atom.

[0053] The preferred R in the azine cyclogroup (c) above 1 and R 2 Each can be independently represented as phenyl or methoxy, more preferably as phenyl.

[0054] In general formula 1, L represents a linking group with a valence of 2 or higher. Specific examples of the linking groups include alkylene, alkenylene, arylene, heteroarylene, polyoxyethylene oligomer chains, polyester oligomer chains, polysiloxane chains, and polyester polyether oligomer chains, with arylene and heteroarylenes being preferred. A preferred example is phenylene. Each of the groups listed above as linking groups may be unsubstituted or may have substituents. Regarding substituents, please refer to the above description related to substituents.

[0055] In general formula 1, D represents a photochromic pigment structure. A "photochromic pigment structure" refers to a structure that imparts photochromic properties to the compound represented by general formula 1. Compounds represented by general formula 1, by including a photochromic pigment structure, can reversibly change their structure depending on the presence or absence of light, as described above. Examples of photochromic pigment structures represented by D include azobenzene and its derivatives, spiropyran and its derivatives, and spiropyran. Azides and their derivatives, benzo[a]pyran and their derivatives, naphtho[a]pyran and their derivatives, indene-fused naphtho[a]pyran and their derivatives, fluoranthenopyran and their derivatives, phenanthrene[a]pyran and their derivatives, triphenylenopyran and their derivatives, diimidazole and their derivatives, donor-acceptor Steinhaus adduct (DASA) and its derivatives, salicylaniline and its derivatives, dihydropyrene and its derivatives, anthracene dimer and its derivatives, fentanyl anhydride and its derivatives, diaryleneethylene and its derivatives, phenoxynaphthoquinone and its derivatives, stilbene and its derivatives, etc.

[0056] In one embodiment, the photochromic pigment structure represented by D can be selected from naphthopyran and its derivatives, as well as indene-fused naphthopyran and its derivatives. Examples of compounds represented by the general formula 1 having the aforementioned photochromic pigment structure include compounds represented by the following general formula.

[0057] [Chemical Formula 6]

[0058]

[0059] [Chemical Formula 7]

[0060]

[0061] [Chemical Formula 8]

[0062]

[0063] R in general formula 3 10 ~R 15 B and B'

[0064] R in general formula 4 10 ~R 15 B and B'

[0065] R in general formula 5 10 ~R 17 B and B'

[0066] R in Formula 6 10 ~R 17 B and B'

[0067] R in general formula 710 ~R 19 B and B'

[0068] R in Formula 8 10 ~R 21 B and B'

[0069] R in Formula 9 10 ~R 19 B and B'

[0070] R in Formula 10 10 ~R 20 B and B'

[0071] R in general formula 11 10 ~R 19 B and B'

[0072] Each can independently represent a hydrogen atom or a substituent.

[0073] in,

[0074] R in general formula 3 10 ~R 15 Any of B and B' represents a partial structure shown in the following general formula 2.

[0075] R in general formula 4 10 ~R 15 Any of B and B' represents a partial structure shown in the following general formula 2.

[0076] R in general formula 5 10 ~R 17 Any of B and B' represents a partial structure shown in the following general formula 2.

[0077] R in Formula 6 10 ~R 17 Any of B and B' represents a partial structure shown in the following general formula 2.

[0078] R in general formula 7 10 ~R 19 Any of B and B' represents a partial structure shown in the following general formula 2.

[0079] R in Formula 8 10 ~R 21 Any of B and B' represents a partial structure shown in the following general formula 2.

[0080] R in Formula 9 10 ~R 19 Any of B and B' represents a partial structure shown in the following general formula 2.

[0081] R in Formula 1010 ~R 20 Any of B and B' represents a partial structure shown in the following general formula 2.

[0082] R in general formula 11 10 ~R 19 Any of B and B' represents a partial structure shown in the following general formula 2.

[0083] In general formula 2, a is 1, and Az, L, b, and c have the same meanings as in general formula 1. * indicates the bonding position with an adjacent atom (e.g., a carbon atom). For more information on general formula 2, please refer to the preceding and following descriptions related to general formula 1.

[0084] [Chemical Formula 9]

[0085] (General Formula 2)

[0086]

[0087] In one approach, in each of the above general formulas, either B or B' can represent a portion of the structure shown in general formula 2.

[0088] Alternatively, in another approach, regarding R in general formula 3 10 ~R 15 R in general formula 4 10 ~R 15 R in general formula 5 10 ~R 17 R in general formula 6 10 ~R 17 R in general formula 7 10 ~R 19 R in general formula 8 10 ~R 21 R in general formula 9 10 ~R 19 R in Formula 10 10 ~R 20 R in general formula 11 10 ~R 19 (Hereafter, they will also be referred to as “R part”). Any one of the R parts in the above general formulas can represent the partial structure shown in general formula 2.

[0089] For compounds represented by the above general formulas, if they contain one or more substituents in addition to the partial structure represented by general formula 2, the substituents can be referred to the preceding descriptions related to substituents.

[0090] In the compounds represented by the above general formulas, where either B or B' represents a portion of the structure represented by general formula 2, the other is preferably a substituent. The substituent preferably represents a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted benzo[a]fluorenyl, a substituted or unsubstituted fluoranyl, a substituted or unsubstituted dibenzofuranyl, or a substituted or unsubstituted dibenzothiopheneyl, and more preferably a substituted phenyl. The substituted phenyl may contain one or more substituents selected from alkoxy, methylthio, amino, dimethylamino, piperidinyl, morpholinyl, thiomorpholinyl, phenyl, fluorine, chlorine, bromine, iodine, trifluoromethyl, and cyano groups having 1 to 6 carbon atoms. When either B or B' is a substituted phenyl, it is preferable that the substituent in the substituted phenyl is substituted at a para position relative to the position where B or B' is bonded to the carbon atom of the pyran ring constituting the indene-fused naphthanopyran. Furthermore, regarding B and B', where any of the R parts of the compounds represented by the above general formulas represent a partial structure represented by general formula 2, please refer to the above description.

[0091] For example, the compound represented by general formula 1 can be the compound represented by general formula 7 above.

[0092] In one embodiment, either B or B' in general formula 7 can represent a portion of the structure shown in general formula 2. In another embodiment, in general formula 7, R... 10 ~R 19 Any of these can represent a portion of the structure shown in general formula 2. In the above case, for example, R... 13 It can represent part of the structure shown in general formula 2.

[0093] In one approach, in general formula 7, R 12 ~R 15 Both can represent hydrogen atoms.

[0094] In the case where either B or B' in general formula 7 represents a portion of the structure shown in general formula 2, the compound represented by general formula 7 may be, for example, the following compounds.

[0095] Formula 7 is R 10 and R 11 Each can independently represent a methyl or ethyl compound. For example, R 10 and R 11 Both can represent methyl groups. Additionally, for example, R... 10 and R 11 All can represent ethyl. In the above compounds, for example, it could be R. 13 Indicates phenyl or trifluoromethyl, R 17 and R 18 Both represent methoxy groups, or can be R. 17Represents a hydrogen atom, and R 18 The methoxy group and other R groups all represent hydrogen atoms. Alternatively, for example, it could be R... 13 The R radical indicates phenyl or trifluoromethyl; other R radicals represent hydrogen atoms. Additionally, for example, R... 13 ~R 19 Both can represent hydrogen atoms.

[0096] Formula 7 is R 10 With R 11 Compounds that form a ring structure by bonding with indene-fused naphthopyran. In the above compounds, the carbon atom at position 13 of the indene-fused naphthopyran (i.e., in general formula 7, is bonded to R...) 10 and R 11 The bonded carbon atom is a spiro atom common to indene-fused naphthylpyran and the above-mentioned ring structure.

[0097] The aforementioned ring structure can be an unsubstituted ring structure or a ring structure with substituents. When R represents a ring structure with substituents, the number of carbon atoms mentioned above refers to the number of carbon atoms including the carbon atoms of the substituents. The number of carbon atoms in the ring structure represented by R (including the carbon atom at the 13th position of the indene-fused naphthopyran) is 3 or more, and can be 4 or more, 5 or more, 6 or more, or 7 or more. Alternatively, the number of carbon atoms in the ring structure represented by R (including the carbon atom at the 13th position of the indene-fused naphthopyran) is 20 or less, and can be 19 or less, 18 or less, 17 or less, 16 or less, or 15 or less.

[0098] The aforementioned ring structure can be an unsubstituted or substituent alicyclic structure. The aforementioned alicyclic structure can be a monocyclic structure, a fused polycyclic structure such as a bicyclic or tricyclic structure, a bridged ring structure such as a bicyclic structure, or a spirocyclic structure such as a bicyclic structure.

[0099] In general formula 7, R 10 With R 11 In compounds that form a ring structure through spirofusion with indene-fused naphthopyran, the following partial structure is included:

[0100] [Chemical Formula 10]

[0101] Specific examples can be given in the following partial structures:

[0102] [Chemical Formula 11]

[0103]

[0104] In general formula 7, R 10 With R 11 In compounds that form a cyclic structure through spirocyclic fusion with indene-fused naphthylpyran, for example, R 12 ~R19 Both can represent hydrogen atoms. Alternatively, for example, it could be R. 13 Represents a fluorine atom or trifluoromethyl group, R 12 and R 14 ~R 19 Both represent hydrogen atoms.

[0105] In General Formula 1, a and c each independently represent integers greater than or equal to 1. In General Formula 1, b represents an integer greater than or equal to 0 or 1. When General Formula 1 contains multiple Az, the multiple Az can be the same or different. When General Formula 1 contains multiple L, the multiple L can be the same or different.

[0106] In one approach, in general formula 1, b can represent 0 or 1. In another approach, in general formula 1, both a and c can represent 1.

[0107] In one embodiment, in general formula 1, b can represent 1, and L can represent an unsubstituted or substituted arylene or an unsubstituted or substituted heteroarylene. Preferably, L is an unsubstituted or substituted arylene, more preferably an unsubstituted or substituted phenylene, and even more preferably an unsubstituted phenylene. For example, the unsubstituted or substituted phenylene may have an azazine cyclogroup at the para-position relative to the L-D bond.

[0108] The photochromic compound represented by Formula 1 can be used in the manufacture of photochromic articles. Specific examples of photochromic compounds represented by Formula 1 include the following compounds. However, the present invention is not limited to the following example compounds.

[0109] [Chemical Formula 12]

[0110]

[0111] [Chemical Formula 13]

[0112]

[0113] [Chemical Formula 14]

[0114]

[0115] [Chemical Formula 15]

[0116]

[0117] [Chemical Formula 16]

[0118]

[0119] [Chemical Formula 17]

[0120]

[0121] [Chemical Formula 18]

[0122]

[0123] [Chemical Formula 19]

[0124]

[0125] [Chemical Formula 20]

[0126]

[0127] [Chemical Formula 21]

[0128]

[0129] [Chemical Formula 22]

[0130]

[0131] [Chemical Formula 23]

[0132]

[0133] [Chemical Formula 24]

[0134]

[0135] [Chemical Formula 25]

[0136]

[0137] [Chemical Formula 26]

[0138]

[0139] [Chemical Formula 27]

[0140]

[0141] [Chemical Formula 28]

[0142]

[0143] [Chemical Formula 29]

[0144]

[0145] [Chemical Formula 30]

[0146]

[0147] [Chemical Formula 31]

[0148]

[0149] [Chemical Formula 32]

[0150]

[0151] [Chemical Formula 33]

[0152]

[0153] [Chemical Formula 34]

[0154]

[0155] [Chemical Formula 35]

[0156]

[0157] [Chemical Formula 36]

[0158]

[0159] [Chemical Formula 37]

[0160]

[0161] [Chemical Formula 38]

[0162]

[0163] The photochromic compounds represented by general formula 1 can be synthesized by known methods. For example, the following documents can be consulted regarding synthetic methods: 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, WO2001 / 019813A1, WO1995 / 16215A1, US Patent No. 5656206, and WO2011 / 016582A1. In addition, for the introduction reaction of the azine cyclo group, please refer to the following literature: (1) Journal of Industrial and Engineering Chemistry, 102, 226-232 (2021), (2) Heterocycles, 26(11), 2853-2856 (1987). As an example, the synthetic routes of reactant 2 in Example 1 described below and reactant 1 in Example 16 described below are shown below. In step 1 below, you can refer to (1) above in particular. After step 2, you can refer to the literature shown above.

[0164] [Chemical Formula 39]

[0165]

[0166] [Photochromic compositions, photochromic articles]

[0167] One aspect of the present invention relates to a photochromic composition comprising one or more photochromic compounds represented by general formula 1.

[0168] Additionally, one aspect of the present invention relates to a photochromic article comprising one or more photochromic compounds represented by general formula 1.

[0169] The aforementioned photochromic composition and photochromic article may contain only one photochromic compound represented by General Formula 1, or may contain two or more (e.g., two or more but no more than four) photochromic compounds represented by General Formula 1. For the aforementioned photochromic article and the aforementioned photochromic composition, if their total amount is set to 100% by mass, they may contain, for example, about 0.1 to 15.0% by mass of the photochromic compound represented by General Formula 1. However, they are not limited to the above range.

[0170] The aforementioned photochromic article may have at least a substrate. In one embodiment, the photochromic compound represented by General Formula 1 may be contained in the substrate of the aforementioned photochromic article. The aforementioned photochromic article may have a substrate and a photochromic layer, and may contain one or more photochromic compounds represented by General Formula 1 in the substrate and / or the photochromic layer. In the substrate and the photochromic layer, the photochromic compound represented by General Formula 1 may be contained only in the substrate in one embodiment, only in the photochromic layer in another embodiment, and in yet another embodiment, in both the substrate and the photochromic layer. Alternatively, the substrate and the photochromic layer may contain only the photochromic compound represented by General Formula 1 as the photochromic compound, or may contain one or more other photochromic compounds. Examples of other photochromic compounds include: azobenzene and its derivatives, spiropyran and its derivatives, and spiropyran. Phosphines and their derivatives, benzo[a]pyrans and their derivatives, naphtho[a]pyrans and their derivatives, indene-fused naphtho[a]pyrans and their derivatives, fluoranthene[a]pyrans and their derivatives, phenanthrene[a]pyrans and their derivatives, benzo[a]phenanthrene[a]pyrans and their derivatives, diimidazoles and their derivatives, donor-acceptor Steinhaus adduct (DASA) and its derivatives, salicylaniline and its derivatives, dihydropyrene and its derivatives, anthracene dimers and their derivatives, fenanoic anhydrides and their derivatives, diarylethenes and their derivatives, phenoxynaphthoquinones and their derivatives, stilbenes and their derivatives, etc. Among these, naphtho[a]pyrans and their derivatives, indene-fused naphtho[a]pyrans and their derivatives, fluoranthene[a]pyrans and their derivatives, and benzo[a]phenanthrene[a]pyrans and their derivatives are preferred.

[0171] <Substrate>

[0172] The aforementioned photochromic articles may include a substrate selected according to the type of photochromic article. As an example of a substrate, for eyeglass lenses, plastic or glass lens substrates may be used. Glass lens substrates may, for example, be lens substrates made of inorganic glass. Plastic lens substrates may include styrene resins (represented by (meth)acrylic resin), polycarbonate resins, allyl resins, diethylene glycol dielyl carbonate resins (CR-39), vinyl resins, polyester resins, polyether resins, urethane resins obtained by reacting isocyanate compounds with hydroxyl compounds such as diethylene glycol, thiourethane resins 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 a lens substrate, an undyed substrate (colorless lens) or a dyed substrate (dyed lens) may be used. The refractive index of the lens substrate may, for example, be around 1.50 to 1.75. However, the refractive index of the lens substrate is not limited to the above range; it can be within the above 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).

[0173] 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 photochromic compound represented by general formula 1 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 irradiation 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.).

[0174] 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.

[0175] <Photochromic layer>

[0176] 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 photochromic compound represented by General Formula 1 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 photochromic compounds represented by General Formula 1, thereby forming a photochromic layer. As a coating method, known coating methods such as spin coating, dip coating, spray coating, inkjet coating, nozzle coating, and slot coating can be used. The curing treatment can be light irradiation 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.

[0177] 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.

[0178] <Polymerizing compounds>

[0179] 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.

[0180] Examples of polymerizable compounds that can be used to form the aforementioned substrate and photochromic layer include the following compounds.

[0181] (Cyclic sulfide compounds)

[0182] 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.

[0183] (Thioheterocyclic butyl compounds)

[0184] 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.

[0185] 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.

[0186] Examples of metal-sulfur heterocyclic butane compounds include those containing elements from Group 14 (Sn, Si, Ge, Pb, etc.), Group 4 (Zr, Ti, etc.), Group 13 (Al, etc.), and Group 12 (Zn, etc.) as metal atoms within the molecule. 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.

[0187] Specific examples of alkylthio (thioheterobutylthio)tin include: methylthiotris(thioheterobutylthio)tin, ethylthiotris(thioheterobutylthio)tin, propylthiotris(thioheterobutylthio)tin, isopropylthiotris(thioheterobutylthio)tin, etc.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] (Polyamine compounds)

[0193] 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.

[0194] (Epoxy compounds)

[0195] 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.

[0196] 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.

[0197] Specific examples of alicyclic epoxides include isophorone diol diglycidyl ether and bis-2,2-hydroxycyclohexylpropane diglycidyl ether.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] (Compounds with free radical polymerizable groups)

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] [Glasses]

[0210] 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.

[0211] Example

[0212] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to the implementation methods shown in the embodiments.

[0213] The molecular structure was identified using nuclear magnetic resonance (NMR). For NMR, a proton NMR spectrometer from the ECS-400 manufactured by NEC Corporation was used. Deuterated chloroform was primarily used as the solvent; for those poorly soluble in deuterated chloroform, deuterated dimethyl sulfoxide, deuterated acetone, deuterated acetonitrile, deuterated benzene, deuterated methanol, and deuterated pyridine were used as appropriate.

[0214] Purity analysis was performed using high-performance liquid chromatography (HPLC). A Shimadzu LC-2040C HPLC system was used. A YMC-Triart C18 column was employed, and the measurement temperature was set to 40°C. The mobile phase consisted of a mixture of water and acetonitrile containing 0.1% trifluoroacetic acid, and the flow rate was set to 0.4 mL / min.

[0215] Mass spectrometry analysis was performed using an ACQUITY UPLC H-Class system (UPLC) manufactured by Waters, Japan, equipped with an SQD2 mass analysis unit. An ACQUITY UPLC BEH C18 column was used, and the measurement temperature was set to 40°C. The mobile phase consisted of a mixture of water and acetonitrile with added formic acid, providing a concentration gradient to allow flow at a rate of 0.61 mL / min. Ionization was performed using electrospray ionization (ESI).

[0216] CHN (carbon / hydrogen / nitrogen) elemental analysis was performed by combustion.

[0217] [Example 1]

[0218] The following example compound 1 was obtained from the reactants shown in Table 1 using the following method.

[0219] In an argon atmosphere, p-toluenesulfonic acid monohydrate (0.15 g, 0.80 mmol) was added to a toluene solution (36 mL) of reactant 1 (1.0 g, 4 mmol) and reactant 2 (3.5 g, 8 mmol) as shown in Table 1, and the mixture was stirred overnight at room temperature. Sodium hydroxide aqueous solution (1.0 M, 37 mL) was added, and the mixture was stirred for approximately 20 minutes. Impurities were removed by filtration, and the mixture was extracted with toluene (30 mL × 2). The combined organic layers were washed with water (20 mL × 2) and concentrated. The residue obtained was purified by column chromatography (SiO2: 200 g, heptane / chloroform (volume basis) = 70 / 30–60 / 40) (1.2 g, brown solid). The obtained solid was suspended in heptane / ethyl acetate (2 / 1 (volume basis), 90 mL), sonicated for approximately 30 minutes, filtered, and dried to obtain example compound 1 as a pale purple solid (0.8 g) as the final product. Hereinafter, Example Compound 1 represents the product of Example 1 in Table 1. The same applies to the other examples. Comparative Compound 1 represents the purified product of Comparative Example 1 in Table 1. The same applies to the other comparative examples.

[0220] The resulting products were analyzed using the following methods.

[0221] The structure was identified using nuclear magnetic resonance (NMR).

[0222] Purity was analyzed by HPLC, and the results are shown in Table 1 as area ratios.

[0223] The results of the mass spectrometry analysis are the measured values ​​(M+, relative intensity 100) shown in Table 1, relative to the calculated values ​​of the precision mass shown in Table 1.

[0224] The results of CHN elemental analysis based on the combustion method are shown in Table 1, and the measured values ​​are the values ​​shown in Table 1, relative to the calculated values.

[0225] Based on the above analytical results, example compound 1 was generated as the target compound.

[0226] [Examples 2-16, Comparative Examples 1-3]

[0227] Reactants 1 and 2 used in the synthesis of the compounds were the reactants shown in Table 1. Otherwise, example compounds 2 to 16 and comparative compounds 1 to 3 were obtained by the same operation as described above.

[0228] The products obtained were analyzed using the methods described above. The analytical results are shown in Table 1 (Tables 1-1 to 1-5).

[0229]

[0230]

[0231]

[0232]

[0233]

[0234] [Evaluation Method]

[0235] <Determination of solution spectroscopy and evaluation of fading rate>

[0236] The compounds of Examples 1-16 and Comparative Examples 1-3 were dissolved in chloroform without stabilizers to prepare chloroform solutions of the compounds.

[0237] A 1 cm square quartz spectrophotometer lid containing the prepared solution was irradiated with ultraviolet light for 15 seconds using a Hamamatsu Photonics UV-LED (a combination of a Lightning Cure LC-L1V5 and an L14310-120, with 70% output) as the ultraviolet light source. The solution was stirred with a small stirrer during the irradiation. Absorbance was measured within 10 seconds of the end of the irradiation using a UV-Vis spectrophotometer (Shimadzu UV-1900i, measurement wavelength 700–400 nm, wavelength interval 2 nm, survey mode). Absorbance measurements were performed at room temperature (20–30 °C). It should be noted that the solution concentration was prepared such that the absorbance at the first absorption wavelength (the peak of absorption intensity observed at the longest wavelength) reached 0.95–1.05. Furthermore, absorbance measurements were performed every 10 seconds to measure the attenuation of absorbance. Standardization was performed with the peak of the first absorption wavelength from the first absorbance measurement as 1. The absorbance decay was then measured, and the rate constant was determined by analyzing the data from the initial 100 seconds (11 absorbance measurements) of fading based on the absorbance change over time and using a first-order reaction model. With [A0] set as the initial concentration of the pigment, i.e., the value obtained by standardizing the absorbance (i.e., 1), and [A] set as the concentration of the pigment after a certain time, i.e., the value of the standardized absorbance, and t set as time (seconds), and k set as the rate constant, the first-order reaction can be expressed by the following formula.

[0238] [Mathematical Expression 1]

[0239]

[0240] Regarding examples 1-16, new absorption peaks appeared in the visible light region after ultraviolet irradiation, thus confirming that these compounds exhibit photochromic properties. Compounds exhibiting photochromic properties can be used in the manufacture of various photochromic articles, such as eyeglass lenses.

[0241] Table 1 shows the reaction rate constants obtained for Examples 1-16 and Comparative Examples 1-3, respectively. Based on the results shown in Table 1, it can be confirmed that the fading rate of each compound in Examples 1-16 is faster than that of Comparative Compounds 1-3 in Comparative Examples 1-3.

[0242] [Eyeglass Lens Manufacturing and Evaluation]

[0243] <Preparation of Photochromic Compositions (Polymerizable Compositions)>

[0244] 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. Example compound 1 was mixed with 100 parts by mass of this (meth)acrylate mixture to a final mass of 3 parts by mass. Then, a photopolymerization initiator (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), an antioxidant [bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid] [ethylene bis(ethylene oxide)] ester, and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacic acid ester) were mixed and stirred thoroughly. Simultaneously, a silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane) was added dropwise while stirring. Degassing was then performed using a rotation-revolution stirring and degassing apparatus.

[0245] The photochromic composition was prepared using the above method.

[0246] <Film Formation of the Primer>

[0247] 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.

[0248] <Film Formation of Photochromic Layer>

[0249] 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.

[0250] Photochromic items (eyeglass lenses) were thus produced.

[0251] <Evaluation of coloring concentration>

[0252] The light transmittance was determined using the following method based on JIS T7333:2005.

[0253] A xenon lamp was used as the light source, and the convex surface of the aforementioned spectacle lenses was irradiated with air-filtered light for 15 minutes to color the photochromic layer. The irradiation was performed in accordance with JIS T7333:2005, ensuring that the irradiance and permissible difference in irradiance met the values ​​shown in Table 2. The transmittance during coloring was measured using a Daizoku electronic spectrophotometer.

[0254] [Table 2]

[0255] Wavelength region (nm) <![CDATA[Irradiance (W / m 2 )]]> <![CDATA[Permissible difference of irradiance (W / m 2 )]]> 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

[0256] <Evaluation of fading speed>

[0257] The fading rate was evaluated using the following method.

[0258] The transmittance (measurement wavelength: 550 nm) of the above-mentioned spectacle lenses before illumination (uncolored state) was measured using a Daizo electronic spectrophotometer. Here, the measured transmittance is referred to as "initial transmittance".

[0259] 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, ensuring that the irradiance and the permissible difference in irradiance met the values ​​shown in Table 2. 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".

[0260] Then, the time required from the time the illumination stops until the transmittance reaches [(initial transmittance - transmittance at color) / 2] is measured.

[0261] The light transmittance T% of the above-mentioned spectacle lens containing Example Compound 1 is 36% when tinted, and the halving time is 245 seconds.

[0262] Based on the above results, it was confirmed that the light transmittance of the aforementioned spectacle lenses changed before and after ultraviolet irradiation, and that the spectacle lenses exhibited photochromic properties, returning to their original state after a period of time if ultraviolet irradiation was stopped (photochromic lenses).

[0263] Finally, let's summarize the methods mentioned above.

[0264] According to one method, a photochromic compound can be provided, which is represented by general formula 1.

[0265] In one embodiment, the azine cyclogroup described above may be one of the following azine cyclogroups.

[0266] [Chemical Formula 40]

[0267]

[0268] (In the above, X represents a nitrogen atom or an unsubstituted or substituent carbon atom. The multiple Xs contained in each azazine cycloalgide group can be the same or different. One or more of the multiple Xs contained in each azazine cycloalgide group represent a nitrogen atom. *When b is an integer greater than or equal to 1, it represents the bonding position with L. When b is 0, it represents the bonding position with D.)

[0269] In one embodiment, in the azaz cycloalgide represented by Az in general formula 1, when b is an integer greater than or equal to 1, one or both of the constituent atoms at the two positions adjacent to the carbon atom bonded to the linking group L can be nitrogen atoms; when b is 0, one or both of the constituent atoms at the two positions adjacent to the carbon atom bonded to the photochromic pigment structure D can be nitrogen atoms.

[0270] In one embodiment, the azine cyclogroup described above may be one of the following azine cyclogroups.

[0271] [Chemical Formula 41]

[0272]

[0273] (In the above, R) 1 ~R 8 Each symbol independently represents a hydrogen atom or substituent. *When b is an integer greater than or equal to 1, it represents the bonding position with L; when b is 0, it represents the bonding position with D.

[0274] In one embodiment, the azine cyclogroup described above may be one of the following azine cyclogroups.

[0275] [Chemical Formula 42]

[0276]

[0277] (In the above, R) 1 ~R 3 Each symbol independently represents a hydrogen atom or substituent. *When b is an integer greater than or equal to 1, it represents the bonding position with L; when b is 0, it represents the bonding position with D.

[0278] In one embodiment, the photochromic pigment structure represented by D can be selected from naphthopyran and its derivatives, as well as indene-fused naphthopyran and its derivatives.

[0279] In one approach, b can be 0.

[0280] In one embodiment, b can be 1, and L can represent an unsubstituted or substituent-containing aryl group or an unsubstituted or substituent-containing heteroaryl group.

[0281] In one embodiment, the photochromic compound represented by Formula 1 can be any photochromic compound represented by any of the formulas 3 to 11 described above.

[0282] In one approach, in general formulas 3 to 11, either B or B' can represent a portion of the structure shown in general formula 2.

[0283] In one embodiment, the photochromic compound represented by general formula 1 can be the photochromic compound represented by general formula 7 above.

[0284] In one approach, either B or B' in general formula 7 can represent a portion of the structure shown in general formula 2.

[0285] In one approach, in general formula 7, R 12 ~R 15 Both can represent hydrogen atoms.

[0286] According to one method, a photochromic composition comprising the aforementioned photochromic compound can be provided.

[0287] In one embodiment, the above-described photochromic composition may further comprise a polymeric compound.

[0288] According to one method, a photochromic article may be provided, comprising a cured product formed by curing the aforementioned photochromic composition.

[0289] In one embodiment, the photochromic article may have a substrate and a photochromic layer, wherein the photochromic layer is the cured product.

[0290] In one embodiment, the aforementioned photochromic article can be an eyeglass lens.

[0291] In one embodiment, the aforementioned photochromic article can be a lens for goggles.

[0292] In one embodiment, the aforementioned photochromic item can be the brim of a sun hat.

[0293] In one embodiment, the aforementioned photochromic article can be a visor component of a helmet.

[0294] According to one method, eyeglasses having the aforementioned spectacle lenses can be provided.

[0295] The various methods and forms described in this specification can be combined in any way, and two or more combinations can be combined in any way.

[0296] 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.

[0297] Industrial applicability

[0298] This invention is useful in the fields of eyeglasses, goggles, sun hats, helmets, etc.

Claims

1. A photochromic compound, represented by a general formula selected from general formulas 3 to 11 below, R in the above general formulas 3 to 11 10 ~R 21 Each of these elements independently represents a hydrogen atom or a substituent, which is selected from straight-chain or branched alkyl groups having 1 to 18 carbon atoms, monocyclic or bicyclic cyclic aliphatic alkyl groups having 5 to 18 carbon atoms, methoxy, ethoxy, and butoxy groups. Either B or B' represents a portion of the structure represented by general formula 2, and the other is a substituent selected from the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted fluoranyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiopheneyl, wherein the substituent is selected from straight-chain or branched alkyl groups having 1 to 18 carbon atoms, monocyclic or bicyclic cyclic aliphatic alkyl groups having 5 to 18 carbon atoms, methoxy, ethoxy, and butoxy. General Formula 2: In general formula 2, a is 1, Az represents the azazine cycloyl group represented by (b) or (c) below, L represents an unsubstituted or substituted phenylene group, wherein the substituent is selected from straight-chain or branched alkyl groups having 1 to 18 carbon atoms, monocyclic or bicyclic cyclic aliphatic alkyl groups having 5 to 18 carbon atoms, methoxy, ethoxy, and butoxy groups, c represents an integer of 1 or more, and b represents an integer of 0 or more. When General Formula 2 contains multiple Az atoms, the multiple Az atoms may be chosen to be the same or different. When General Formula 2 contains multiple L atoms, the multiple L atoms may be chosen to be the same or different. * indicates the bonding position with adjacent atoms. In (b) above, R 1 and R 2 Each independently represents either phenyl or methoxy, R 3 Representing a hydrogen atom, in (c) above, R 1 and R 2 Each can be represented independently as either phenyl or methoxy.

2. The photochromic compound according to claim 1, represented by general formula 7, and R 12 ~R 15 Both represent hydrogen atoms.

3. The photochromic compound according to claim 1 or 2, wherein, In the case where either B or B' is a substituted phenyl group, the substitution position of the substituent in the substituted phenyl group is a para position relative to the position where B or B' is bonded to the carbon atom of the pyran ring constituting indene-fused naphthopyran.

4. A photochromic composition comprising the photochromic compound according to any one of claims 1 to 3.

5. The photochromic composition according to claim 4, further comprising a polymeric compound.

6. A photochromic article comprising a cured product formed by curing the photochromic composition of claim 5.

7. The photochromic article according to claim 6, comprising a substrate and a photochromic layer, wherein the photochromic layer is the cured product.

8. The photochromic article according to claim 6 or 7, wherein it is an eyeglass lens.

9. The photochromic article according to claim 6 or 7, wherein it is a lens for goggles.

10. The photochromic article according to claim 6 or 7, wherein it is the brim portion of a sun hat.

11. The photochromic article according to claim 6 or 7, which is a helmet shading component.

12. A pair of eyeglasses having the eyeglass lens as described in claim 8.

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