Photochromic compound, photochromic composition, photochromic article and glasses

Abstract

A photochromic compound represented by general formula 1. In general formula 1, R1 and R2 bond with one another and form a ring structure along with a carbon atom at the 13 position of an indeno-fused naphthopyran, R3 to R6 each independently represent a hydrogen atom or an electron-withdrawing group, one or more of R3 to R6 represent an electron-withdrawing group, R8 and R9 each independently represent a hydrogen atom or an electron-donating group, one or more of R8 and R9 represent an electron-donating group, and R7, R10, A and A' each independently represent a hydrogen atom or a substituent group.

Description

Technical Field

[0001] The present invention relates to a photochromic compound, a photochromic composition, a photochromic article, and glasses.

Background Art

[0002] A photochromic compound is a compound having a property (photochromic property) of coloring under irradiation with light in a wavelength range having photoreactivity and fading in the absence of irradiation. For example, Patent Document 1 discloses a naphthopyran-based compound having photochromic properties.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] As a method for imparting photochromic properties to an article such as a spectacle lens, there are a method of incorporating a photochromic compound into a substrate and a method of forming a layer containing a photochromic compound. Desirable performances for an article thus imparted with photochromic properties include a high coloring density during coloring in the visible region (wavelength 380 to 780 nm) and a fast fading rate after coloring by light irradiation.

[0005] One aspect of the present invention aims to provide a photochromic article having a high coloring density during coloring in the visible region and a fast fading rate.

Means for Solving the Problems

[0006] One aspect of the present invention relates to a photochromic compound represented by the following general formula 1.

[0007] Another aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by the following general formula 1.

[0008] Another aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by the following general formula 1.

[0009] [Chemical formula]

[0010] In general formula 1, R 1 and R 2 are bonded to each other to form a ring structure together with the carbon atom at the 13th position of indeno-fused naphthopyran, R 3 ~R 6 each independently represents a hydrogen atom or an electron-withdrawing group, and one or more of R 3 ~R 6 represent an electron-withdrawing group, R 8 and R 9 each independently represents a hydrogen atom or an electron-donating group, and at least one of R 8 and R 9 represents an electron-donating group, R 7 , R 10 , A and A' each independently represent a hydrogen atom or a substituent. [Advantages of the Invention]

[0011] When the compound represented by general formula 1 is colored by light irradiation, it can be colored at a high concentration in the visible region and can also exhibit a fast fading rate. In these respects, in general formula 1, R 1 and R 2 are bonded to each other to form a ring structure together with the carbon atom at the 13th position of indeno-fused naphthopyran, R 8 and R 9The inventors speculate that at least one of them representing an electron-donating group or the like may contribute. However, the present invention is not limited to the speculation described in this specification. According to the compound represented by General Formula 1, it becomes possible to provide a photochromic article having a high coloring density and a high fading rate when coloring in the visible region.

Embodiments for Carrying Out the Invention

[0012] As an example, a photochromic compound is irradiated with light such as sunlight and undergoes a structural conversion to a colored form through an excited state. The structure after the structural conversion through light irradiation can be referred to as the "colored form". In contrast, the structure before light irradiation can be referred to as the "colorless form". However, the "colorless" of the colorless form is not limited to completely colorless, but also includes cases where the color is lighter than that of the colored form. The structure of General Formula 1 is the structure of the colorless form.

[0013] In the present invention and this specification, the "photochromic article" refers to an article containing a photochromic compound. The photochromic article according to one aspect of the present invention contains at least one or more photochromic compounds represented by General Formula 1 as the photochromic compound. The photochromic compound can be contained in the base material of the photochromic article and / or can be contained in the photochromic layer in a photochromic article having a base material and a photochromic layer. The "photochromic layer" is a layer containing a photochromic compound.

[0014] In the present invention and this specification, the "photochromic composition" refers to a composition containing a photochromic compound. The photochromic composition according to one aspect of the present invention contains at least one or more photochromic compounds represented by General Formula 1 as the photochromic compound and can be used for the production of the photochromic article according to one aspect of the present invention.

[0015] In the present invention and in this specification, the substituents in various general formulas described in detail below, and further, the substituents when each of the groups described below has a substituent, are each independently, a hydroxyl group, a linear or branched alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclic aliphatic alkyl group having 5 to 18 carbon atoms such as a monocyclic or bicyclic group such as a cyclopentyl group, a cyclohexyl group, a linear or branched alkoxy group having 1 to 24 constituent atoms such as a methoxy group, an ethoxy group, a butoxy group, a non-aromatic cyclic substituent having 1 to 24 constituent atoms, a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms such as a trifluoromethyl group, a linear or branched perfluoroalkoxy group such as a trifluoromethoxy group, a linear or branched alkyl sulfide group having 1 to 24 constituent atoms such as a methyl sulfide group, an ethyl sulfide group, a butyl sulfide group, an aryl group such as a phenyl group, a naphthyl group, an anthracenyl group, a fluoranthenyl group, a phenanthryl group, a pyranyl group, a perylenyl group, a styryl group, a fluorenyl group, an aryloxy group such as a phenyloxy group, an aryl sulfide group such as a phenyl sulfide group, a heteroaryl group such as a pyridyl group, a furanyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothiophenyl group, an indolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a diazolyl group, a triazolyl group, a quinolinyl group, a phenothiazinyl group, a phenoxazinyl group, a phenazinyl group, a thianthrenyl group, an acridinyl group, an amino group (-NH2), a monoalkylamino group such as a monomethylamino group, a dialkylamino group such as a dimethylamino group, a monoarylamino group such as a monophenylamino group, a diarylamino group such as a diphenylamino group, a cyclic amino group such as a piperidino group, a morpholino group, a thiomorpholino group, a tetrahydroquinolino group, a tetrahydroisoquinolino group, an ethynyl group, a mercapto group, a silyl group, a sulfonic acid group, an alkylsulfonyl group, a formyl group, a carboxy group, a cyano group, and a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a substituent R m ; or, R m is further substituted with one or more identical or different R ma substituted group that has been replaced; can be.

[0016] the above R m with one or more identical or different R m as an example of a substituted group in which an alkoxy group is further substituted at the terminal carbon atom of the alkoxy group, and an alkoxy group is further substituted at the terminal carbon atom of this alkoxy group can be cited. Also, the above R m with one or more identical or different R m as another example of a substituted group in which an alkoxy group is further substituted at the terminal carbon atom of the alkoxy group, and an alkoxy group is further substituted at the terminal carbon atom of this alkoxy group can be cited. Also, the above R m as another example of a substituted group in which the same or different R

[0017] In the present invention and this specification, unless otherwise specified, the groups described are substituted or unsubstituted groups. In the present invention and this specification, "substituted or unsubstituted" is synonymous with "having one or more substituents or unsubstituted". "Number of carbon atoms" and "number of constituent atoms" refer to the number including the number of carbon atoms or atoms of the substituent for a group having a substituent, unless otherwise specified.

[0018] Also, in the present invention and this specification, the substituents in various general formulas described later in detail, and further, the substituents when each of the groups described later has a substituent can each independently be solubilizing groups. In the present invention and this specification, the "solubilizing group" refers to a substituent that can contribute to enhancing the compatibility with any liquid or a specific liquid. Examples of the solubilizing group include an alkyl group having a linear, branched or cyclic structure with 4 to 50 carbon atoms, a linear, branched or cyclic alkoxy group having 4 to 50 constituent atoms, a linear, branched or cyclic silyl group having 4 to 50 constituent atoms, a group in which a part of the above groups is replaced with a silicon atom, a sulfur atom, a nitrogen atom, a phosphorus atom, etc., a combination of two or more of the above groups, etc. Substituents having such a substituent are preferably those that can contribute to promoting the thermal motion of the molecules of the compound. A compound having a solubilizing group as a substituent can prevent solidification of the solute by inhibiting the approach of the distances between solute molecules, or can create a molecular aggregation state close to a liquid by lowering the melting point and / or glass transition temperature of the solute. Thus, the solubilizing group can liquefy the solute or enhance the solubility of the compound having this substituent in a liquid. In one form, preferred solubilizing groups include the n-butyl group, n-pentyl group, n-hexyl group, n-octyl group which are linear alkyl groups, the tert-butyl group which is a branched alkyl group, and the cyclopentyl group and cyclohexyl group which are cyclic alkyl groups.

[0019] The above substituents can preferably be substituents selected from the group consisting of a methoxy group, an ethoxy group, a phenoxy group, a methyl sulfide group, an ethyl sulfide group, a phenyl sulfide group, a trifluoromethyl group, a phenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a phenothiazinyl group, a phenoxazinyl group, a phenazinyl group, an acridinyl group, a dimethylamino group, a diphenylamino group, a piperidino group, a morpholinyl group, a thiomorpholinyl group, a cyano group and a solubilizing group, and more preferably can be substituents selected from the group consisting of a methoxy group, a phenoxy group, a methyl sulfide group, a phenyl sulfide group, a trifluoromethyl group, a phenyl group, a dimethylamino group, a diphenylamino group, a piperidino group, a morpholinyl group, a thiomorpholinyl group, a cyano group and a solubilizing group.

[0020] In the present invention and this specification, the "electron-withdrawing group" refers to a substituent that is more likely to attract electrons from the bonded atom side compared to a hydrogen atom. Due to substituent effects such as the inductive effect and the mesomeric effect (or resonance effect), the electron-withdrawing group can attract electrons. Specific examples of the electron-withdrawing group include a halogen atom (fluorine atom: -F, chlorine atom: -Cl, bromine atom: -Br, iodine atom: -I), trifluoromethyl group: -CF3, nitro group: -NO2, cyano group: -CN, formyl group: -CHO, acyl group: -COR (R is a substituent), alkoxycarbonyl group: -COOR, carboxy group: -COOH, substituted sulfonyl group: -SO2R (R is a substituent), sulfo group: -SO3H, etc. Preferred electron-withdrawing groups include a fluorine atom, which is an electron-withdrawing group with a high electronegativity, and an electron-withdrawing group having a positive value for the para-position substituent constant σ p based on the Hammett rule, etc. can be mentioned.

[0021] In the present invention and this specification, the "electron-donating group" refers to a substituent that is more likely to donate electrons to the bonded atom side compared to a hydrogen atom. Due to the sum of substituent effects such as the inductive effect and the mesomeric effect (or resonance effect), the electron-donating group can be a substituent that is more likely to donate electrons. Specific examples of the electron-donating group include a hydroxy group: -OH, thiol group: -SH, alkoxy group: -OR (R is an alkyl group), alkyl sulfide group: -SR (R is an alkyl group), aryl sulfide group, acetyl group: -OCOCH3, amino group: -NH2, alkylamide group: -NHCOCH3, dialkylamino group: -N(R)2 (two Rs are the same or different alkyl groups), morpholino group, piperidino group, methyl group, etc. Preferred electron-donating groups include an electron-donating group having a negative value for the para-position substituent constant σ p based on the Hammett rule, etc. can be mentioned.

[0022] The para-position substituent constant σ p (Source: Edited by Hideaki Iwamura, Ryoji Noyori, Takeshi Nakai, Isao Kitagawa, Graduate School Organic Chemistry (Part 1) (1988)) Specific examples are shown below. -N(CH3)2: -0.83 -OCH3: -0.27 -t-C4H9: -0.20 -CH3: -0.17 -C2H5: -0.15 -C6H5: -0.01 (-H: 0) -F: +0.06 -Cl: +0.27 -Br: +0.23 -CO2C2H5: +0.45 -CF3: +0.54 -CN: +0.66 -SO2CH3: +0.72 -NO2: +0.78

[0023] [The photochromic compound represented by General Formula 1] The photochromic compound represented by General Formula 1 will be described in more detail below.

[0024] [Chemical formula]

[0025] The 13th carbon atom of indeno-fused naphthopyran can be a spiro atom shared by the above ring structure and indeno-fused naphthopyran. That is, the above ring structure can be a ring structure that spiro-fuses with indeno-fused naphthopyran.

[0026] In General Formula 1, R 1 and R 2 are bonded to each other to form a ring structure together with the 13th carbon atom of indeno-fused naphthopyran. Regarding such a ring structure, the number of carbon atoms constituting the ring shall mean the number of carbon atoms including the 13th carbon atom of indeno-fused naphthopyran.

[0027] The above ring structure can be a monocyclic structure, or can be a condensed polycyclic structure such as bicyclic or tricyclic, or can be a bridged ring structure such as bicyclic, or can be a spiro ring structure such as bicyclic.

[0028] Examples of the above ring structure include an aliphatic ring. Such an aliphatic ring can be unsubstituted or can have a substituent. For the substituent, reference can be made to the previous description regarding the substituent.

[0029] Examples of the above aliphatic ring include an aliphatic ring having 3 or more and 20 or less carbon atoms constituting the ring including the 13th carbon atom of indeno-fused naphthopyran. Specific examples thereof include monocyclics such as cyclohexane ring, cyclooctane ring, and cycloheptane ring, bicyclics such as norbornane ring and bicyclononane ring, and tricyclics such as adamantane ring. The above "number of carbon atoms constituting the ring" means that for an aliphatic ring having a substituent, the number of carbon atoms contained in the substituent is also included. Also, the "number of atoms constituting the ring including the 13th carbon atom of indeno-fused naphthopyran" described later means that for a ring structure having a substituent, the number of atoms contained in the substituent is also included.

[0030] R 1 and R 2 When the ring structure formed by bonding to each other together with the 13th carbon atom of indeno-fused naphthopyran is an aliphatic ring, in one form, the number of carbon atoms constituting the ring of such an aliphatic ring is preferably 3 or more and 6 or less, can be 3, 4, 5, or 6, and more preferably 6. Also, in another form, the number of carbon atoms constituting the ring of such an aliphatic ring is preferably 7 or more and 20 or less, can be 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, and more preferably 7 or 10.

[0031] As described above, it is desirable that the photochromic article exhibits a fast fading rate after being colored by light irradiation. On the other hand, a photochromic article exhibiting a moderately fast fading rate may be desired as compared with a photochromic article exhibiting an extremely fast fading rate. From the viewpoint of providing a photochromic article exhibiting a moderately fast fading rate, R 1 and R 2 When the ring structure formed together with the 13th carbon atom of indeno-fused naphthopyran by bonding to each other is an aliphatic ring, the number of carbon atoms constituting the ring of such an aliphatic ring is preferably 3 or more and 6 or less, and more preferably 6.

[0032] Also, as the ring structure formed by R 1 and R 2 bonding to each other and together with the 13th carbon atom of indeno-fused naphthopyran, a condensed polycycle in which one or more ring structures selected from the group consisting of an aromatic ring and an aromatic heterocyclic ring are condensed with an aliphatic ring having 3 or more and 20 or less carbon atoms constituting the ring including the 13th carbon atom of indeno-fused naphthopyran; a heterocyclic ring having 3 or more and 20 or less atoms constituting the ring including the 13th carbon atom of indeno-fused naphthopyran; and a condensed polycycle in which one or more ring structures selected from the group consisting of an aromatic ring and an aromatic heterocyclic ring are condensed with the above heterocyclic ring, can also be mentioned.

[0033] Specific examples of the condensed polycycle in which one or more ring structures selected from the group consisting of an aromatic ring and an aromatic heterocyclic ring are condensed with an aliphatic ring having 3 or more and 20 or less carbon atoms constituting the ring including the 13th carbon atom of indeno-fused naphthopyran include a fluorene ring.

[0034] Specific examples of the heterocyclic ring having 3 or more and 20 or less atoms constituting the ring including the 13th carbon atom of indeno-fused naphthopyran include a thiophene ring, a furan ring, a pyridine ring, and the like.

[0035] Examples of the condensed polycycle in which one or more ring structures selected from the group consisting of an aromatic ring and an aromatic heterocyclic ring are condensed with the above complex ring include a phenylfuran ring, a biphenylthiophene ring, and the like.

[0036] R 1 and R 2 Specific examples of the ring structure formed by bonding to each other and together with the 13th carbon atom of the indenocondensed naphthopyran include the following ring structures. In the following, the carbon atom at the position indicated by 13 is the 13th carbon atom of the indenocondensed naphthopyran in General Formula 1. Also, R 1 and R 2 Specific examples of the ring structure formed by bonding to each other and together with the 13th carbon atom of the indenocondensed naphthopyran include the ring structures included in the exemplified compounds described later.

[0037]

Chemical formula

[0038]

Chemical formula

[0039] In General Formula 1, R 3 ~R 6 each independently represents a hydrogen atom or an electron-withdrawing group, and one or more of R 3 ~R 6 represent an electron-withdrawing group. Specific examples of the electron-withdrawing group include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a perfluoroalkyl group having 1 to 10 carbon atoms (for example, a trifluoromethyl group, etc.), and a cyano group. In one embodiment, the electron-withdrawing group can be an electron-withdrawing group selected from the group consisting of a fluorine atom and a trifluoromethyl group. In one embodiment, R 4 can be a trifluoromethyl group. Also, in one embodiment, R 3 and R 5 can both be fluorine atoms. The inventor has found that R 3 ~R6 It is speculated that the fact that one or more of them are electron-withdrawing groups contributes to the compound represented by General Formula 1 showing a fast fading rate after light irradiation.

[0040] In General Formula 1, R 3 ~R 6 One or more of them are electron-withdrawing groups. That is, the total number of electron-withdrawing groups contained in R 3 ~R 6 is 1 or more and 4 or less. The total number can be 4 or less, 3 or less, 2 or less, or 1. In one form, in R 3 ~R 6 , one or more of R 3 ~R 5 can be electron-withdrawing groups. As a specific form, only R 4 is an electron-withdrawing group and R 3 , R 5 and R 6 are hydrogen atoms, a form where R 3 and R 5 are electron-withdrawing groups and R 4 and R 6 are hydrogen atoms, etc. can be cited. As a more specific form, only R 4 is a trifluoromethyl group and R 3 , R 5 and R 6 are hydrogen atoms, a form where R 3 and R 5 are fluorine atoms and R 4 and R 6 are hydrogen atoms, etc. can be cited.

[0041] R 8 and R 9 each independently represent a hydrogen atom or an electron-donating group, and at least one of R 8 and R 9 represents an electron-donating group. In one form, R 8 and R 9 each independently represent a hydrogen atom or an electron-donating group (excluding sulfur atoms), and R 8 and R 9At least one of R can represent an electron donating group. 8 and / or R 9 Specific examples of the electron-donating group represented by the formula (I) include an alkoxy group having 1 to 10 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an oxoaryl group (e.g., a phenoxy group, etc.), and an amino group (e.g., a dimethylamino group, a piperidino group, a morpholino group, etc.).

[0042] R 8 and R 9 In one form, R 8 represents a hydrogen atom and R 9 can represent an electron donating group. 8 represents an electron donating group and R 9 can represent a hydrogen atom. 8 and R 9 may represent the same or different electron donating groups. In one embodiment, the compound represented by the general formula 1 may have two absorption peaks in the visible range. The visible range refers to a wavelength range of 380 to 780 nm. The present inventors have 8 and R 9 are both electron-donating groups, which is believed to contribute to the compound represented by formula 1 exhibiting absorption characteristics with two absorption peaks in the visible range.

[0043] R 7 , R 10 Each of A and A' independently represents a hydrogen atom or a substituent. For such a substituent, the above description of the substituent can be referred to.

[0044] In one embodiment, A and A' may each independently be a substituted or unsubstituted phenyl group. The phenyl group having a substituent may be a mono- to penta-substituted phenyl group. In a phenyl group having two or more substituents, the substituents may be the same or different, and two or more of the substituents may be bonded to form a ring structure. For the substituents of the phenyl group, the above description of the substituents can be referred to.

[0045] In one embodiment, at least one of A and A' can represent a phenyl group having a substituent at the para-position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran. In this case, only one of A and A' can represent a phenyl group having a substituent at the para-position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran. Alternatively, both A and A' can each independently represent a phenyl group having a substituent at the para-position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran. The substituent substituting at the para-position can be, for example, an electron-donating group. Regarding such an electron-donating group, reference can be made to the previous description regarding the electron-donating group. Specific examples of the electron-donating group substituting at the para-position include, for example, an alkoxy group such as a methoxy group, a morpholino group, and the like.

[0046] In one embodiment, at least one of A and A' can be a phenyl group having a nitrogen atom-containing substituent at the para-position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran. In this case, only one of A and A' can be a phenyl group having a nitrogen atom-containing substituent at the para-position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran. Alternatively, both A and A' can each independently be a phenyl group having a nitrogen atom-containing substituent at the para-position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran. Examples of the nitrogen atom-containing substituent include an unsubstituted amino group (-NH2), a substituted amino group (for example, a monoalkylamino group such as a monomethylamino group, a dialkylamino group such as a dimethylamino group, a monoarylamino group such as a monophenylamino group, a diarylamino group such as a diphenylamino group, etc.), a cyclic amino group (for example, a piperidino group, a morpholino group, a thiomorpholino group, a tetrahydroquinolino group, a tetrahydroisoquinolino group, etc.).

[0047] In one embodiment, in General Formula 1, R 8represents a hydrogen atom, and R 9 represents an electron-donating group, and at least one of A and A’ can represent a phenyl group having a nitrogen atom-containing substituent at the para-substituted position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran.

[0048] Examples of the compound represented by General Formula 1 include the following compounds. Specific examples of each part in General Formula 1 also include those contained in the following exemplified compounds. However, the present invention is not limited to the following exemplified compounds.

[0049] [Chemical formula]

[0050] [Chemical formula]

[0051] [Chemical formula]

[0052] [Chemical formula]

[0053] [Chemical formula]

[0054] [Chemical formula]

[0055] [Chemical formula]

[0056] [Chemical formula]

[0057]

Chem.

[0058]

Chem.

[0059]

Chem.

[0060]

Chem.

[0061]

Chem.

[0062]

Chem.

[0063]

Chem.

[0064]

Chem.

[0065]

Chem.

[0066]

Chem.

[0067] [Chemical]

[0068] [Chemical]

[0069] [Chemical]

[0070] [Chemical]

[0071] The photochromic compound represented by General Formula 1 can be synthesized by a known method. For the synthesis method, for example, the following documents can be referred to. 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, and WO2011 / 016582A1.

[0072] [Photochromic Composition, Photochromic Article] One aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by General Formula 1. Another aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by General Formula 1.

[0073] The above photochromic composition and the above photochromic article can contain only one kind of photochromic compound represented by General Formula 1, or can contain two or more kinds (for example, two or more and four or less kinds). The above photochromic article and the above photochromic composition can contain the photochromic compound represented by General Formula 1 in an amount of, for example, about 0.1 to 15.0% by mass, with the total amount thereof being 100% by mass. However, it is not limited to the above range.

[0074] The above photochromic article can have at least a substrate. In one form, the photochromic compound represented by General Formula 1 can be contained in the substrate of the above photochromic article. The above photochromic article can have a substrate and a photochromic layer, and can contain one or more kinds of the photochromic compounds represented by General Formula 1 in the substrate and / or the photochromic layer. The photochromic compound represented by General Formula 1 can be contained only in the substrate in one form, only in the photochromic layer in another form, or in both the substrate and the photochromic layer in still another form. Further, the substrate and the photochromic layer can contain only the photochromic compound represented by General Formula 1 as the photochromic compound, or can also contain one or more other photochromic compounds. Examples of the other photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaaryl bisimidazoles, donor-acceptor Stenhouse adducts (DASAs), salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, stilbenes, and the like.

[0075] <substrate> The above photochromic article can include a substrate selected according to the type of the photochromic article. As an example of the substrate, as a spectacle lens substrate, a plastic lens substrate or a glass lens substrate can be mentioned. The glass lens substrate can be, for example, a lens substrate made of inorganic glass. Examples of the plastic lens substrate include styrene resins such as (meth)acrylic resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, polyether resins, urethane resins obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, thiourethane resins obtained by reacting an isocyanate compound with a polythiol compound, and cured products of curable compositions containing a (thio)epoxy compound having one or more disulfide bonds in the molecule (generally called transparent resins). As the lens substrate, an undyed one (colorless lens) may be used, or a dyed one (dyed lens) may be used. The refractive index of the lens substrate can be, for example, about 1.50 to 1.75. However, the refractive index of the lens substrate is not limited to the above range, and it may be within or outside the above range. Here, the refractive index refers to the refractive index with respect to light having a wavelength of 500 nm. Further, the lens substrate may be a lens having a refractive power (so-called powered lens), or a lens having no refractive power (so-called non-powered lens).

[0076] For example, the above photochromic composition can be a polymerizable composition. In the present invention and this specification, the "polymerizable composition" is a composition containing one or more polymerizable compounds. By molding a polymerizable composition containing at least one photochromic compound represented by General Formula 1 and one or more polymerizable compounds by a known molding method, a cured product of such a polymerizable composition can be produced. Such a cured product can be included as a base material in the above photochromic article and / or can be included as a photochromic layer. The curing treatment can be light irradiation and / or heat treatment. The polymerizable compound is a compound having a polymerizable group, and when the polymerization reaction of the polymerizable compound proceeds, the polymerizable composition can be cured to form a cured product. The polymerizable composition can further contain one or more additives (such as a polymerization initiator, etc.).

[0077] The spectacle lens can be various lenses such as a single-focus lens, a multi-focus lens, and a progressive power lens. The type of the lens is determined by the surface shape of both surfaces of the lens base material. Also, the surface of the lens base material can be any of a convex surface, a concave surface, and a flat surface. In a normal lens base material and spectacle lens, the object-side surface is convex and the eyeball-side surface is concave. However, it is not limited thereto. The photochromic layer can usually be provided on the object-side surface of the lens base material, but can also be provided on the eyeball-side surface.

[0078] <Photochromic layer> The photochromic layer can be a layer provided directly on the surface of the substrate or indirectly via one or more other layers. The photochromic layer can be, for example, a cured layer obtained by curing a polymerizable composition. The photochromic layer can be formed as a cured layer obtained by curing a polymerizable composition containing at least one photochromic compound represented by General Formula 1 and at least one polymerizable compound. For example, such a polymerizable composition is directly applied onto the surface of the substrate or applied onto the surface of a layer provided on the substrate, and the applied polymerizable composition is subjected to a curing treatment, whereby the photochromic layer can be formed as a cured layer containing at least one photochromic compound represented by General Formula 1. As the coating method, known coating methods such as spin coating method, dip coating method, spray coating method, inkjet method, nozzle coating method, slit coating method, etc. can be adopted. The curing treatment can be light irradiation and / or heat treatment. The polymerizable composition can further contain one or more additives (such as a polymerization initiator, etc.) in addition to one or more polymerizable compounds. The polymerizable composition can be cured and a cured layer can be formed by the progress of the polymerization reaction of the polymerizable compound.

[0079] The thickness of the photochromic layer can be, for example, 5 μm or more, 10 μm or more, or 20 μm or more, and can also be, for example, 80 μm or less, 70 μm or less, or 50 μm or less.

[0080] <Polymerizable compound> In the present invention and this specification, the polymerizable compound refers to a compound having one or more polymerizable groups in one molecule, and the "polymerizable group" refers to a reactive group capable of undergoing a polymerization reaction. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, a vinyl ether group, an epoxy group, a thiol group, an oxetane group, a hydroxy group, a carboxy group, an amino group, an isocyanate group, etc.

[0081] Examples of the polymerizable compounds that can be used for forming the above substrate and the above photochromic layer include the following compounds.

[0082] (Episulfide compound) An episulfide compound is a compound having two or more episulfide groups in one molecule. An episulfide group is a polymerizable group capable of ring-opening polymerization. Specific examples of episulfide compounds include bis(1,2-epithioethyl) sulfide, bis(1,2-epithioethyl) disulfide, bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropylthio) methane, bis(2,3-epithiopropyl) disulfide, bis(2,3-epithiopropyldithio) methane, bis(2,3-epithiopropyldithio) ethane, bis(6,7-epithio-3,4-dithiaheptyl) sulfide, bis(6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl), 1,3-bis(2,3-epithiopropyldithiomethyl) benzene, 1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane, 1,2,3-tris(2,3-epithiopropyldithio) propane, 1,1,1,1-tetrakis(2,3-epithiopropyldithiomethyl) methane, 1,3-bis(2,3-epithiopropyldithio)-2-thiapropane, 1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane, 1,1,1-tris(2,3-epithiopropyldithio) methane, 1,1,1-tris(2,3-epithiopropyldithiomethylthio) methane, 1,1,2,2-tetrakis(2,3-epithiopropyldithio) ethane, 1,1,2,2-tetrakis(2,3-epithiopropyldithiomethylthio) ethane, 1,1,3,3-tetrakis(2,3-epithiopropyldithio) propane, 1,1,3,3-tetrakis(2,3-epithiopropyldithiomethylthio) propane, 2-[1,1-bis(2,3-epithiopropyldithio) methyl]-1,3-dithiane, 2-[1,1-bis(2,3-epithiopropyldithiomethylthio) methyl]-1,3-dithiane, etc.

[0083] (Thietanyl compound) A thietanyl compound is a thiethane compound having two or more thietanyl groups in one molecule. A thietanyl group is a polymerizable group capable of ring-opening polymerization. Among thietanyl compounds, some have an episulfide group together with a plurality of thietanyl groups. Such compounds are listed as examples of the above episulfide compounds. Other thietanyl compounds include a metal-containing thiethane compound having a metal atom in the molecule and a non-metal thiethane compound not containing a metal.

[0084] Specific examples of non-metallic thietane compounds include bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide, bis(3-thietanyl) trisulfide, bis(3-thietanyl) tetrasulfide, 1,4-bis(3-thietanyl)-1,3,4-trithia butane, 1,5-bis(3-thietanyl)-1,2,4,5-tetrathia pentane, 1,6-bis(3-thietanyl)-1,3,4,6-tetrathia hexane, 1,6-bis(3-thietanyl)-1,3,5,6-tetrathia hexane, 1,7-bis(3-thietanyl)-1,2,4,5,7-pentathia heptane, 1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathia heptane, 1,1-bis(3-thietanylthio) methane, 1,2-bis(3-thietanylthio) ethane, 1,2,3-tris(3-thietanylthio) propane, 1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithia octane, 1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithia undecane, 1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trithia undecane, 1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithia undecane, 2,5-bis(3-thietanylthiomethyl)-1,4-dithiane, 2,5-bis[[2-(3-thietanylthio) ethyl] thiomethyl]-1,4-dithiane, 2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, bisthietanyl sulfide, bis(thietanylthio) methane, 3-[<(thietanylthio) methylthio> methylthio] thietane, bisthietanyl disulfide, bisthietanyl trisulfide, bisthietanyl tetrasulfide, bisthietanyl pentasulfide, 1,4-bis(3-thietanyldithio)-2,3-dithia butane, 1,1,1-tris(3-thietanyldithio) methane, 1,1,1-tris(3-thietanyldithiomethylthio) methane, 1,1,2,2-tetrakis(3-thietanyldithio) ethane, 1,1,2,2-tetrakis(3-thietanyldithiomethylthio) ethane, and the like.

[0085] Examples of the metal-containing thietane compounds include those containing, within the molecule, as the metal atom, a Group 14 atom such as Sn, Si, Ge, or Pb atoms, a Group 4 element such as Zr or Ti atoms, a Group 13 atom such as Al atoms, a Group 12 atom such as Zn atoms, and the like. Specific examples include alkylthio(thietanythio)tin, bis(alkylthio)bis(thietanythio)tin, alkylthio(alkylthio)bis(thietanythio)tin, bis(thietanythio)cyclic dithiostannane compounds, alkyl(thietanythio)tin compounds, and the like.

[0086] Specific examples of alkylthio(thietanythio)tin include methylthiotris(thietanythio)tin, ethylthiotris(thietanythio)tin, propylthiotris(thietanythio)tin, isopropylthiotris(thietanythio)tin, and the like.

[0087] Specific examples of bis(alkylthio)bis(thietanythio)tin include bis(methylthio)bis(thietanythio)tin, bis(ethylthio)bis(thietanythio)tin, bis(propylthio)bis(thietanythio)tin, bis(isopropylthio)bis(thietanythio)tin, and the like.

[0088] Specific examples of alkylthio(alkylthio)bis(thietanythio)tin include ethylthio(methylthio)bis(thietanythio)tin, methylthio(propylthio)bis(thietanythio)tin, isopropylthio(methylthio)bis(thietanythio)tin, ethylthio(propylthio)bis(thietanythio)tin, ethylthio(isopropylthio)bis(thietanythio)tin, isopropylthio(propylthio)bis(thietanythio)tin, and the like.

[0089] Specific examples of bis(thietanythio)cyclic dithiostannane compounds include bis(thietanythio)dithiastanetane, bis(thietanythio)dithiastanonane, bis(thietanythio)dithianonanane, bis(thietanythio)trithiastanonane, and the like.

[0090] Specific examples of the alkyl(thietanylthio)tin compound include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, tetrakis(thietanylthio)tin, etc.

[0091] (Polyamine compound) The polyamine compound is a compound having two or more NH2 groups in one molecule, and can form a urea bond by reacting with a polyisocyanate and can form a thiourea bond by reacting with a polyisothiocyanate. Specific examples of the polyamine compound include ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine, 1,3-propanediamine, putrescine, 2-(2-aminoethylamino)ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3,5-benzenetriamine, etc.

[0092] (Epoxy compound) The epoxy compound is a compound having an epoxy group in the molecule. The epoxy group is a polymerizable group capable of ring-opening polymerization. The epoxy compound is generally classified into an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound.

[0093] Specific examples of the aliphatic epoxy compound include ethylene oxide, 2-ethyloxirane, butyl glycidyl ether, phenyl glycidyl ether, 2,2'-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl ether of tris(2-hydroxyethyl)isocyanurate, and the like.

[0094] Specific examples of the alicyclic epoxy compound include isophorone diol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like.

[0095] Specific examples of the aromatic epoxy compound include resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolak polyglycidyl ether, cresol novolak polyglycidyl ether, and the like.

[0096] In addition to the above, epoxy compounds having a sulfur atom in the molecule together with an epoxy group can also be used. Such sulfur atom-containing epoxy compounds include chain aliphatic ones and cyclic aliphatic ones.

[0097] Specific examples of the chain aliphatic sulfur atom-containing epoxy compounds include bis(2,3-epoxypropyl) sulfide, bis(2,3-epoxypropyl) disulfide, bis(2,3-epoxypropylthio) methane, 1,2-bis(2,3-epoxypropylthio) ethane, 1,2-bis(2,3-epoxypropylthio) propane, 1,3-bis(2,3-epoxypropylthio) propane, 1,3-bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio) butane, 1,4-bis(2,3-epoxypropylthio)-2-methylbutane, 1,3-bis(2,3-epoxypropylthio) butane, 1,5-bis(2,3-epoxypropylthio) pentane, 1,5-bis(2,3-epoxypropylthio)-2-methylpentane, 1,5-bis(2,3-epoxypropylthio)-3-thiapentane, 1,6-bis(2,3-epoxypropylthio) hexane, 1,6-bis(2,3-epoxypropylthio)-2-methylhexane, 3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane, 1,2,3-tris(2,3-epoxypropylthio) propane, 2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl) propane, 2,2-bis(2,3-epoxypropylthiomethyl)-1-(2,3-epoxypropylthio) butane, and the like.

[0098] Specific examples of the cyclic aliphatic sulfur atom-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, and the like.

[0099] (Compound having a radically polymerizable group) A radically polymerizable group is a polymerizable group capable of radical polymerization. Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, and the like.

[0100] Hereinafter, a compound having a polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group is referred to as a “(meth)acrylate compound”. Specific examples of the (meth)acrylate compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, bisphenol F di(meth)acrylate, 1,1-bis(4-(meth)acryloxyethoxyphenyl)methane, 1,1-bis(4-(meth)acryloxydiethoxyphenyl)methane, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methylthio (meth)acrylate, phenylthio (meth)acrylate, benzylthio (meth)acrylate, xylylene dithiol di(meth)acrylate, mercaptoethyl sulfide di(meth)acrylate, bifunctional urethane (meth)acrylate, and the like.

[0101] Specific examples of the compound having an allyl group (allyl compound) include allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether, polyethylene glycol allyl ether, methoxypolyethylene glycol - polypropylene glycol allyl ether, butoxypolyethylene glycol - polypropylene glycol allyl ether, methacryloyloxy polyethylene glycol - polypropylene glycol allyl ether, phenoxypolyethylene glycol allyl ether, methacryloyloxy polyethylene glycol allyl ether, and the like.

[0102] Examples of the compound having a vinyl group (vinyl compound) include α - methylstyrene, α - methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9 - divinylspirobi(m - dioxane), and the like.

[0103] The above - mentioned photochromic article can include, at an arbitrary position, one or more layers known as functional layers of a photochromic article, such as a protective layer for improving the durability of the photochromic article, an antireflection layer, a water - repellent or hydrophilic antifouling layer, an anti - fogging layer, a primer layer for improving the adhesion between layers.

[0104] The above - mentioned photochromic article can be an optical article. One form of the optical article is an eyeglass lens. Such an eyeglass lens can also be called a photochromic lens or a photochromic eyeglass lens. Also, as one form of the optical article, a lens for goggles, the visor part of a visor, a shield member of a helmet, etc. can be mentioned. By applying the above - mentioned photochromic composition, which is a polymerizable composition, onto a substrate for these optical articles and subjecting the applied composition to a curing treatment to form a photochromic layer, an optical article having an antiglare function can be obtained.

[0105] [Glasses] One aspect of the present invention relates to glasses provided with spectacle lenses, which are one form of the above photochromic article. Details of the spectacle lenses included in the glasses are as described above. By providing such spectacle lenses, the glasses can exhibit an anti-glare effect like sunglasses, for example, when outdoors, the photochromic compound is irradiated with sunlight and colored, and when returning indoors, the photochromic compound can fade to restore transparency. Regarding the configuration such as the frame of the glasses, known techniques can be applied.

Example

[0106] Hereinafter, the present invention will be further described with reference to examples. However, the present invention is not limited to the embodiments shown in the examples.

[0107] In the following, a nuclear magnetic resonance apparatus (NMR) was used for the identification of the molecular structure. As the NMR, a proton NMR of JNM-ECS400 manufactured by JEOL Ltd. was used. As the measurement solvent, mainly deuterated chloroform was used, and deuterated dimethyl sulfoxide, deuterated acetone, deuterated acetonitrile, deuterated benzene, deuterated methanol, deuterated pyridine, etc. were appropriately used only when it was hardly soluble in deuterated chloroform. High performance liquid chromatography (HPLC) was used for the purity analysis. As the HPLC, LC-2040C manufactured by Shimadzu Corporation was used. YMC-Triart C18 was used for the column, and the measurement temperature was set at 40 °C. The mobile phase was a mixed solvent of water containing 0.1% trifluoroacetic acid and acetonitrile, and the flow rate was 0.4 mL / min. For mass spectrometry, an apparatus equipped with SQD2 as a mass spectrometry unit for an ACQUITY UPLC H-Class system (UPLC) manufactured by Waters Japan was used. ACQUITY UPLC BEH C18 was used for the column, and the measurement temperature was set at 40 °C. The mobile phase was a mixed solvent of water added with formic acid and acetonitrile, and it was flowed at a flow rate of 0.61 mL / min with a concentration gradient. Electrospray ionization (ESI) method was used for ionization. CHN (carbon, hydrogen, nitrogen) elemental analysis was carried out by the combustion method.

[0108] [Example 1] From the reactants shown in Table 2, the products shown in Table 2 were obtained by the following method. Under an argon atmosphere, p-toluenesulfonic acid monohydrate (0.15 g, 0.80 mmol) was added to a toluene solution (36 mL) of Reactant 1 (1.9 g, 4 mmol) and Reactant 2 (2.1 g, 8 mmol) shown in Table 2, and the mixture was stirred overnight at room temperature. An aqueous sodium hydroxide solution (1.0 M, 37 mL) was added, and the mixture was stirred for about 20 minutes. Impurities were removed by filtration, and after extraction with toluene (30 mL × 2), the combined organic layers were washed with water (20 mL × 2) and concentrated. The obtained residue was purified by column chromatography (SiO2: 200 g, heptane / chloroform (volume basis) = 70 / 30 to 60 / 40) (1.2 g, brown solid). The obtained solid was suspended in heptane / ethyl acetate (2 / 1 (volume basis), 90 mL), sonicated for about 30 minutes, filtered, and dried to obtain the product shown in Table 2 as a pale yellow-green solid (0.9 g).

[0109] The analysis of the obtained product was carried out by the following method. The structure was identified using a nuclear magnetic resonance apparatus (NMR). When the purity was analyzed by HPLC, the value shown in Table 2 was obtained in terms of the area ratio. As a result of mass spectrometry, the measured value shown in Table 2 ([M+H] + , relative intensity 100) was obtained with respect to the calculated value of the exact mass shown in Table 2. As a result of CHN elemental analysis by combustion method, the measured value was the value shown in Table 2 with respect to the calculated value shown in Table 2. Based on the above analysis results, it was confirmed that the compound shown in Table 2, which is the target compound, was obtained.

[0110] [Example 2 , Reference Examples 3 and 4, Example 5, Reference Example 6, Examples 7 to 18, Reference Example 19, Comparative Examples 1, 2] The compound shown in Table 2 was obtained by the same operation as above, except that the reactants shown in Table 2 were used as Reactant 1 and Reactant 2 used in the synthesis of the compound represented by General Formula 1. The analysis of the obtained product was carried out by the method described above. The analysis results are shown in Table 2.

[0111] [Production of spectacle lenses (photochromic articles)] [Preparation of photochromic composition (polymerizable composition)] In a plastic container, 68 parts by mass of polyethylene glycol diacrylate, 12 parts by mass of trimethylolpropane trimethacrylate, and 20 parts by mass of neopentyl glycol dimethacrylate were mixed with respect to a total of 100 parts by mass of (meth)acrylate to prepare a (meth)acrylate mixture. A photochromic compound was mixed so as to be 2.5 parts by mass with respect to 100 parts by mass of this (meth)acrylate mixture. Further, a photopolymerization initiator (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), an antioxidant [bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)] and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) were mixed and stirred well, and then a silane coupling agent (γ-methacryloxypropyltrimethoxysilane) was added dropwise while stirring. Thereafter, defoaming was carried out using an automatic revolution type stirring defoaming device. A photochromic composition was prepared by the above method.

[0112] [Formation of primer layer] A plastic lens substrate (product name EYAS manufactured by HOYA: center thickness 2.5 mm, diameter 75 mm, spherical lens power -4.00) was alkali-washed by immersing it in an aqueous sodium hydroxide solution with a concentration of 10% by mass (liquid temperature 60 °C) for 5 minutes, and then washed with pure water and dried. Thereafter, with respect to the convex surface of this plastic lens substrate, an aqueous polyurethane resin solution (a polycarbonate polyol-based polyurethane emulsion, viscosity 100 cPs, solid content concentration 38% by mass) was applied by spin coating at a rotation speed of 1500 rpm for 1 minute using a spin coater MS-B150 manufactured by Mikasa Co., Ltd. in an environment at room temperature and a relative humidity of 40 to 60%, and then naturally dried for 15 minutes to form a primer layer with a thickness of 5.5 μm.

[0113] <Formation of Photochromic Layer> The prepared photochromic composition was dropped onto the primer layer, and using MS-B150 manufactured by Mikasa Co., Ltd., the rotation speed was changed in slope mode from 500 rpm to 1500 rpm over 1 minute, and then it was rotated at 1500 rpm for 5 seconds, and it was applied by spin coating method using this program. Then, the photochromic composition applied on the primer layer formed on the plastic lens substrate was irradiated with ultraviolet rays (main wavelength 405 nm) for 40 seconds in a nitrogen atmosphere (oxygen concentration 500 ppm or less), and this composition was cured to form a photochromic layer. The thickness of the formed photochromic layer was 45 μm. Thus, a photochromic article (eyeglass lens) was produced.

[0114] [Evaluation Method] <Evaluation of Coloring Concentration> The visual transmittance was determined by the following method in accordance with JIS T7333:2005. Example , Reference Example For the convex surfaces of the eyeglass lenses of the examples and comparative examples, light passing through an aerosol mass filter was irradiated for 15 minutes using a xenon lamp as a light source to color the photochromic layer. This irradiated light was carried out so that the irradiance and the tolerance of the irradiance were the values shown in Table 1 as defined in JIS T7333:2005. The transmittance at the time of this coloring was measured with a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. Table 2 shows the visual transmittance T (%) obtained from the measurement results in the wavelength range of 380 nm to 780 nm. The smaller the value of T (%), the more highly concentrated the photochromic compound is colored.

[0115]

Table 1

[0116] <Evaluation of Fading Rate> The fading rate was evaluated by the following method. Example , Reference ExampleThe transmittance (measurement wavelength: 550 nm) of each spectacle lens before light irradiation (uncolored state) in the examples and comparative examples was measured using a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The transmittance measured here is referred to as the "initial transmittance". Each spectacle lens was irradiated with light passing through an aero-mass filter for 15 minutes using a xenon lamp as a light source to color the photochromic layer. This irradiation light was carried out so that the irradiance and the tolerance of the irradiance were the values shown in Table 2 as defined in JIS T7333:2005. The transmittance at the time of this coloring was measured in the same manner as the initial transmittance. The transmittance measured here is referred to as the "transmittance at the time of coloring". Thereafter, the time required for the transmittance to reach [(initial transmittance - transmittance at the time of coloring) / 2] was measured from the time when the light irradiation was stopped. This time is defined as the "half-life time". It can be said that the shorter the half-life time, the faster the fading rate. The obtained half-life times are shown in Table 2.

[0117] The above results are shown in Table 2 (Tables 2-1 to 2-6).

[0118]

Table 2-1

[0119]

Table 2-2

[0120]

Table 2-3

[0121]

Table 2-4

[0122]

Table 2-5

[0123]

Table 2-6

[0124] From the results shown in Table 2, it can be confirmed that each spectacle lens of the examples is a photochromic article that is highly colored in the visible region and exhibits a fast fading rate.

[0125] Finally, the above aspects are summarized.

[0126] [1] A photochromic compound represented by the following general formula 1. [Chemical formula] (In general formula 1, R 1 and R 2 are bonded to each other to form a ring structure together with the 13th carbon atom of indeno-fused naphthopyran, R 3 ~R 6 each independently represents a hydrogen atom or an electron-withdrawing group, and one or more of R 3 ~R 6 represent an electron-withdrawing group, R 8 and R 9 each independently represents a hydrogen atom or an electron-donating group, and at least one of R 8 and R 9 represents an electron-donating group, R 7 , R 10 , A and A' each independently represent a hydrogen atom or a substituent.) [2] The photochromic compound according to [1], wherein both R 7 and R 10 represent hydrogen atoms. [3] The photochromic compound according to [1] or [2], wherein the ring structure formed by R 1 and R 2 being bonded to each other together with the 13th carbon atom of indeno-fused naphthopyran is an aliphatic ring. [4] The photochromic compound according to [3], wherein the number of carbon atoms constituting the ring of the aliphatic ring is 3 or more and 6 or less. [5] The number of carbon atoms constituting the ring of the above aliphatic ring is 6, the photochromic compound according to [3]. [6] The number of carbon atoms constituting the ring of the above aliphatic ring is 7 or more and 20 or less, the photochromic compound according to [3]. [7] R 8 and R 9 each independently represents a hydrogen atom or an electron-donating group (excluding a sulfur atom), and at least one of R 8 and R 9 represents an electron-donating group, the photochromic compound according to any one of [1] to [6]. [8] The above electron-withdrawing group is selected from the group consisting of a fluorine atom and a trifluoromethyl group, the photochromic compound according to any one of [1] to [7]. [9] In General Formula 1, R 4 represents a trifluoromethyl group, the photochromic compound according to any one of [1] to [8].

[10] In General Formula 1, R 3 and R 5 both represent a fluorine atom, the photochromic compound according to any one of [1] to [8].

[11] In General Formula 1, at least one of A and A' represents a phenyl group having a substituent at the para-position substitution position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran, the photochromic compound according to any one of [1] to

[10] .

[12] In General Formula 1, A and A' each independently represent a phenyl group having a substituent at the para-position substitution position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran, the photochromic compound according to any one of [1] to

[11] .

[13] In General Formula 1, A and A' each independently represent a phenyl group having an electron-donating group as a substituent at the para-position substitution position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran, the photochromic compound according to any one of [1] to

[11] .

[14] In General Formula 1, R 8 represents a hydrogen atom, the photochromic compound according to any one of [1] to

[13] .

[15] In general formula 1, R 8 represents a hydrogen atom, and R 9 represents an electron-donating group, and at least one of A and A' represents a phenyl group having a nitrogen atom-containing substituent at the para-substituted position with respect to the carbon atom at the position where it is bonded to the pyran ring of the indeno-fused naphthopyran, the photochromic compound according to any one of [1] to

[10] .

[16] A photochromic composition containing the photochromic compound according to any one of [1] to

[15] .

[17] The photochromic composition according to

[16] , further containing a polymerizable compound.

[18] A photochromic article containing a cured product obtained by curing the photochromic composition according to

[17] .

[19] The photochromic article according to

[18] , having a substrate and the photochromic layer which is the cured product.

[20] The photochromic article according to

[18] or

[19] , which is an eyeglass lens.

[21] The photochromic article according to

[18] or

[19] , which is a lens for goggles.

[22] The photochromic article according to

[18] or

[19] , which is the visor portion of a sun visor.

[23] The photochromic article according to

[18] or

[19] , which is a shield member of a helmet.

[24] Eyeglasses provided with the eyeglass lens according to

[20] .

[0127] The various aspects and various forms described in this specification can be combined in any combination of two or more.

[0128] The embodiments disclosed this time should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and it is intended that all modifications within the meaning and scope equivalent to the claims are included.

Industrial Applicability

[0129] One aspect of the present invention is useful in the technical fields of glasses, goggles, visors, helmets, and the like.

Claims

1. A photochromic compound represented by the following general formula 1. 【Chemical Formula 1】 (In general formula 1, R １ and R ２ are bonded to each other to form a ring structure together with the 13th carbon atom of indeno-fused naphthopyran, R3 represents a hydrogen atom, R4 to R ６ each independently represents a hydrogen atom or an electron-withdrawing group, and one or more of R4 to R ６ represent an electron-withdrawing group, R8 represents a hydrogen atom, R ９ represents an electron-donating group, R ７ and R １０ and A and A' each independently represent a hydrogen atom or a substituent. )

2. R ７ and R １０ both represent hydrogen atoms, the photochromic compound according to Claim 1.

3. R １ and R ２ are bonded to each other to form a ring structure together with the 13th carbon atom of indeno-fused naphthopyran, which is an aliphatic ring, the photochromic compound according to Claim 1.

4. The number of carbon atoms constituting the ring of the aliphatic ring is 3 or more and 6 or less, the photochromic compound according to Claim 3.

5. The number of carbon atoms constituting the ring of the aliphatic ring is 6, the photochromic compound according to Claim 3.

6. The number of carbon atoms constituting the ring of the aliphatic ring is 7 or more and 20 or less, the photochromic compound according to Claim 3.

7. The photochromic compound according to claim 1, wherein the electron-withdrawing group is selected from the group consisting of a fluorine atom and a trifluoromethyl group.

8. In General Formula 1, R ４ represents a trifluoromethyl group, and the photochromic compound according to claim 1.

9. In General Formula 1, at least one of A and A' represents a phenyl group having a substituent at a para-substitution position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran, and the photochromic compound according to claim 1.

10. In General Formula 1, A and A' each independently represent a phenyl group having a substituent at a para-substitution position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran, and the photochromic compound according to claim 1.

11. In General Formula 1, A and A' each independently represent a phenyl group having an electron-donating group as a substituent at a para-substitution position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran, and the photochromic compound according to claim 1.

12. A photochromic compound represented by the following General Formula 1. 【Chemical Formula 2】 (In General Formula 1, R1 and R2 are bonded to each other to form a ring structure together with the 13th carbon atom of indeno-fused naphthopyran, R3 represents a hydrogen atom, R4 to R6 each independently represent a hydrogen atom or an electron-withdrawing group, and one or more of R4 to R6 represent an electron-withdrawing group, R8 and R9 each independently represent a hydrogen atom or an electron-donating group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an oxoaryl group, and an amino group, and at least one of R8 and R9 represents the electron-donating group, R7, R10, A and A' each independently represent a hydrogen atom or a substituent.

13. The photochromic compound according to claim 12, wherein both R7 and R10 represent a hydrogen atom.

14. The photochromic compound according to claim 12, wherein the ring structure formed by R1 and R2 bonding to each other together with the carbon atom at the 13th position of indeno-fused naphthopyran is an aliphatic ring.

15. The photochromic compound according to claim 14, wherein the number of carbon atoms constituting the aliphatic ring is 3 or more and 6 or less.

16. The photochromic compound according to claim 14, wherein the number of carbon atoms constituting the aliphatic ring is 6.

17. The photochromic compound according to claim 14, wherein the number of carbon atoms constituting the aliphatic ring is 7 or more and 20 or less.

18. The photochromic compound according to claim 12, wherein the electron-withdrawing group is selected from the group consisting of a fluorine atom and a trifluoromethyl group.

19. The photochromic compound according to claim 12, wherein in General Formula 1, R4 represents a trifluoromethyl group.

20. The photochromic compound according to claim 12, wherein in General Formula 1, at least one of A and A' represents a phenyl group having a substituent at the para-substituted position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran.

21. The photochromic compound according to claim 12, wherein in General Formula 1, A and A' each independently represent a phenyl group having a substituent at the para-substituted position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran.

22. The photochromic compound according to claim 12, wherein in General Formula 1, A and A' each independently represent a phenyl group having an electron-donating group as a substituent at the para-substituted position with respect to the carbon atom at the position where it is bonded to the pyran ring of indeno-fused naphthopyran.

23. A photochromic composition comprising the photochromic compound according to any one of claims 1 to 22.

24. The photochromic composition according to claim 23, further comprising a polymerizable compound.

25. A photochromic article comprising a cured product obtained by curing the photochromic composition according to claim 24.

26. The photochromic article according to claim 25, having a substrate and the photochromic layer which is the cured product.

27. The photochromic article according to claim 26, which is an eyeglass lens.

28. The photochromic article according to claim 26, which is a lens for goggles, a visor portion of a sun visor or a shield member of a helmet.

29. Glasses provided with the eyeglass lens according to claim 27.

Images