Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
  • C09K9/02—Organic tenebrescent materials
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
  • G02C7/102—Photochromic filters

Definitions

• the present invention relates to photochromic compounds, photochromic compositions, photochromic articles, and eyeglasses.
• Photochromic compounds are compounds that have the property of coloring when irradiated with light in a wavelength range that has photoresponsiveness, and fading when not irradiated (photochromic properties).
• Patent Document 1 discloses naphthopyran-based compounds that have photochromic properties.
• Methods for imparting photochromic properties to articles such as eyeglass lenses include a method of incorporating a photochromic compound into a substrate and a method of forming a layer containing a photochromic compound.
• the desired performance of an article imparted with photochromic properties in this way includes a small molar absorption coefficient at at least one wavelength in the visible range (wavelengths 380 to 780 nm) when not irradiated with light (i.e., high transparency in the visible range), and a fast fading rate after coloring by irradiation with light.
• One aspect of the present invention aims to provide a photochromic article that has high transparency in the visible range when uncolored and exhibits a fast fading rate after coloring.
• One aspect of the present invention relates to a photochromic compound represented by the following general formula 1:
• Another aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by the following general formula 1:
• Another aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by the following general formula 1:
• A represents a ring structure having 3 or more carbon atoms constituting the ring, including the carbon atom at the 13th position of the indeno-fused naphthopyran;
• R 1 and R 4 to R 8 each independently represent a hydrogen atom or a substituent;
• R2 represents an electron donating group (excluding sulfur-containing electron donating groups);
• R3 represents a hydrogen atom or an electron-donating group (excluding sulfur-containing electron-donating groups);
• B and B' each independently represent a substituent.
• the compound represented by general formula 1 can exhibit high transparency in the visible range when uncolored, and can also exhibit a fast fading rate after coloring.
• the compound represented by general formula 1 makes it possible to provide a photochromic article that has high transparency in the visible range when uncolored, and a fast fading rate after coloring.
• a photochromic compound When a photochromic compound is irradiated with light such as sunlight, it goes through an excited state and undergoes a structural transformation into a colored body.
• the structure after structural transformation through light irradiation can be called the "colored body.”
• the structure before light irradiation can be called the “colorless body.”
• colorless when referring to a colorless body, "colorless” does not mean that it is completely colorless, but also includes cases where the color is lighter than that of the colored body.
• the structure of general formula 1 is the structure of a colorless body.
• photochromic article refers to an article that contains a photochromic compound.
• a photochromic article according to one embodiment of the present invention contains at least one type of photochromic compound represented by general formula 1 as a photochromic compound.
• the photochromic compound can be contained in the substrate of the photochromic article, and/or in a photochromic article having a substrate and a photochromic layer, the photochromic compound can be contained in the photochromic layer.
• a “photochromic layer” is a layer that contains a photochromic compound.
• photochromic composition refers to a composition containing a photochromic compound.
• the photochromic composition according to one embodiment of the present invention contains at least one photochromic compound represented by general formula 1 as a photochromic compound, and can be used for producing the photochromic article according to one embodiment of the present invention.
• substituents in various general formulae described in detail below each independently represent: linear or branched alkyl groups having 1 to 18 carbon atoms, such as a hydroxy group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group; a monocyclic or polycyclic aliphatic alkyl group having 5 to 18 carbon atoms, such as a cyclopentyl group or a cyclohexyl group; linear or branched alkoxy groups having 1 to 24 constituent atoms, such as a methoxy group, an ethoxy group, or a butoxy group; a non-aromatic cyclic substituent having 1 to 24 constituent atoms; linear or branched perfluoroalkyl groups having 1 to 18 carbon atoms, such as
• An example of a substituent in which the above R m is further substituted with one or more identical or different R m can be a structure in which an alkoxy group is further substituted at the terminal carbon atom of an alkoxy group, and an alkoxy group is further substituted at the terminal carbon atom of this alkoxy group.
• Another example of a substituent in which the above R m is further substituted with one or more identical or different R m can be a structure in which the same or different R m is substituted at two or more positions among the five substitutable positions of a phenyl group.
• the present invention is not limited to such examples.
• the groups described are substituted or unsubstituted groups.
• substituted or unsubstituted is synonymous with “having one or more substituents or being unsubstituted.”
• Numberer of carbon atoms and “number of constituent atoms” refer to numbers including the number of carbon atoms or atoms of the substituent in groups having a substituent, unless otherwise specified.
• substituents in various general formulas described in detail below, and further, the substituents in the case where each group described below has a substituent can each independently be a solubilizing group.
• solubilizing group refers to a substituent that can contribute to increasing compatibility with any liquid or a specific liquid.
• a substituent that can contribute to promoting the thermal motion of the molecules of the compound by having this substituent such as 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, or the like, or a combination of two or more of the above groups, is suitable.
• a compound having a solubilizing group as a substituent can prevent the solute from solidifying by inhibiting the distance between solute molecules from approaching each other, or can create a molecular aggregation state close to a liquid by lowering the melting point and/or glass transition temperature of the solute.
• the solubilizing group can liquefy the solute or increase the solubility of the compound having this substituent in the liquid.
• the solubilizing group is preferably a linear alkyl group such as n-butyl, n-pentyl, n-hexyl, or n-octyl, a branched alkyl group such as tert-butyl, or a cyclic alkyl group such as cyclopentyl or cyclohexyl.
• substituents may preferably be selected from the group consisting of methoxy, ethoxy, phenoxy, methyl sulfide, ethyl sulfide, phenyl sulfide, trifluoromethyl, phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenothiazinyl, phenoxazinyl, phenazinyl, acridinyl, dimethylamino, diphenylamino, piperidino, morpholino, thiomorpholino, cyano, and solubilizing groups, and more preferably be selected from the group consisting of methoxy, phenoxy, methyl sulfide, phenyl sulfide, trifluoromethyl, phenyl, dimethylamino, diphenylamino, piperidino, morpholino, thiomorpholino, cyano, and solubil
• the term "electron-donating group” refers to a substituent that is more likely to donate electrons to the atom to which it is bonded than a hydrogen atom.
• the electron-donating group can be a substituent that is more likely to donate electrons as a sum of induction effect, mesomeric effect (or resonance effect), and the like.
• the electron-donating group examples include a hydroxy group: -OH, a thiol group: -SH, an alkoxy group: -OR (R is an alkyl group), an alkylsulfide group: -SR (R is an alkyl group), an arylsulfide group, an acetyl group: -OCOCH 3 , an amino group: -NH 2 , an alkylamide group: -NHCOCH 3 , a dialkylamino group: -N(R) 2 (two R are the same or different alkyl groups), a morpholino group, a piperidino group, and a methyl group.
• Suitable electron-donating groups include an electron-donating group in which the substituent constant ⁇ p at the para position based on the Hammett rule is a negative value.
• the carbon atom at the 13th position of the indeno-fused naphthopyran can be a spiro atom shared by the ring structure represented by A and the indeno-fused naphthopyran.
• the ring structure represented by A can be a ring structure that is spiro-condensed with the indeno-fused naphthopyran.
• A represents a ring structure having three or more carbon atoms, including the carbon atom at the 13th position of the indeno-fused naphthopyran.
• the inventors speculate that the presence of such a ring structure may contribute to the photochromic compound represented by general formula 1 being able to exhibit a fast fading rate after coloring.
• the present invention is not limited to the speculations described in this specification.
• the ring structure may be a monocyclic structure, a condensed polycyclic structure such as a bicyclic or tricyclic structure, a bridged ring structure such as a bicyclic structure, or a spiro ring structure such as a bicyclic structure.
• the ring structure may be an aliphatic ring.
• Such an aliphatic ring may be unsubstituted or may have a substituent.
• substituent please refer to the above description of the substituent.
• the above aliphatic ring can be an aliphatic ring having 3 to 20 carbon atoms constituting the ring, including the carbon atom at position 13 of the indeno-condensed naphthopyran.
• Specific examples include monocyclic rings such as a cyclohexane ring, a cyclooctane ring, and a cycloheptane ring; bicyclic rings such as a norbornane ring and a bicyclononane ring; and tricyclic rings such as an adamantane ring.
• the above "number of carbon atoms constituting the ring" includes the number of carbon atoms contained in the substituent for an aliphatic ring having a substituent.
• the "number of atoms constituting the ring, including the carbon atom at position 13 of the indeno-condensed naphthopyran" described below includes the number of atoms contained in the substituent for a ring structure having a substituent.
• the number of carbon atoms constituting the ring of the aliphatic ring is preferably 3 or more and 6 or less, and can be 3, 4, 5, or 6, and more preferably 6.
• the number of carbon atoms constituting the ring of the aliphatic ring is preferably 7 or more and 20 or less, and can be 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, and more preferably 7, 8, or 10.
• a photochromic article As described above, it is desirable for a photochromic article to exhibit a fast fading rate after being colored by irradiation with light. On the other hand, there are cases where a photochromic article exhibiting a moderately fast fading rate is desired compared to a photochromic article exhibiting an extremely fast fading rate. From the viewpoint of providing a photochromic article exhibiting a moderately fast fading rate, when the ring structure represented by A 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.
• the ring structure represented by A is, a condensed polycyclic ring in which one or more ring structures selected from the group consisting of an aromatic ring and an aromatic heterocyclic ring are condensed to an aliphatic ring having 3 to 20 carbon atoms constituting the ring, including the carbon atom at position 13 of an indeno-condensed naphthopyran; A heterocycle having 3 to 20 ring atoms including the carbon atom at position 13 of the indeno-fused naphthopyran; and a condensed polycyclic ring in which one or more ring structures selected from the group consisting of an aromatic ring and an aromatic heterocycle are condensed to the heterocycle;
• Other examples include:
• heterocyclic rings having 3 to 20 atoms constituting the ring, including the carbon atom at the 13th position of the indeno-fused naphthopyran include a thiophene ring, a furan ring, and a pyridine ring.
• Examples of the condensed polycyclic ring in which one or more ring structures selected from the group consisting of aromatic rings and aromatic heterocycles are condensed to the heterocycle include a phenylfuran ring, a biphenylthiophene ring, etc.
• ring structure represented by A include the ring structures below.
• the carbon atom at the position indicated by 13 is the carbon atom at the 13th position of the indeno-fused naphthopyran in general formula 1.
• Specific examples of the ring structure represented by A include the ring structures contained in the example compounds shown below.
• the ring structure represented by A is preferably the following ring structure:
• R 1 and R 4 to R 8 each independently represent a hydrogen atom or a substituent.
• R 1 and one or more of R 4 to R 8 represent a substituent
• the substituent is as described above.
• R 1 and R 4 to R 8 may all represent a hydrogen atom.
• R7 can represent an aryl group.
• R7 represents an aryl group and R1 , R4 , R5 , R6 and R8 may all represent hydrogen atoms.
• aryl group represented by R7 examples include aryl groups 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, and a fluorenyl group, with a phenyl group being preferred.
• the aryl group may be a substituted or unsubstituted aryl group.
• substituents include the various substituents described above.
• the substituted aryl group can have one or more substituents selected from the group consisting of alkyl groups, alkoxy groups, and amino groups.
• such an alkyl group can be 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, or a hexyl group, and is preferably an alkyl group selected from the group consisting of a methyl group, an isopropyl group, and a tert-butyl group.
• the alkoxy group may be a straight-chain or branched alkoxy group having 1 to 24 constituent atoms, such as a methoxy group, an ethoxy group, or a butoxy group, with a methoxy group being preferred.
• the substituted aryl group has an amino group as a substituent, the amino group may be an unsubstituted amino group (-NH 2 ) or a substituted amino group, preferably a dialkylamino group such as a dimethylamino group.
• the substituted aryl group may be, for example, a mono- or di-substituted aryl group.
• the substitution position of the substituent is preferably the para-position and/or the ortho-position relative to the carbon atom at the 11th position of the indeno-fused naphthopyran to which the aryl group represented by R7 is bonded.
• R2 represents an electron donating group (excluding sulfur-containing electron donating groups)
• R3 represents a hydrogen atom or an electron donating group (excluding sulfur-containing electron donating groups).
• the electron donating group is as described above.
• the inventors speculate that at least R2 being an electron donating group (excluding sulfur-containing electron donating groups) can contribute to the compound represented by general formula 1 being able to exhibit high visible transparency when not irradiated.
• the electron-donating group that may be represented by R2 and/or R3 include alkoxy groups having 1 to 10 carbon atoms (e.g., methoxy, ethoxy, etc.), oxoaryl groups (e.g., phenoxy, etc.), amino groups (e.g., dimethylamino, piperidino, morpholino, etc.), etc. As described above, each of the above groups and each of the following groups may be substituted or unsubstituted.
• R2 and R3 can each independently represent an electron donating group (excluding sulfur-containing electron donating groups).
• the electron donating group represented by R2 can be an alkoxy group (e.g., an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group or an ethoxy group) or a phenoxy group
• the electron donating group represented by R3 can be an amino group.
• R2 can represent an alkoxy group and R3 can represent an amino group.
• R2 can represent a methoxy group and R3 can represent an amino group.
• R7 can represent an aryl group, for example, a phenyl group.
• the amino group represented by R3 can be, for example, a morpholino group or a piperidino group.
• R2 can represent a methoxy group and R3 can represent a morpholino group or a piperidino group.
• R7 can represent an aryl group, for example a phenyl group.
• the electron donating group represented by R2 and the electron donating group represented by R3 can each independently be an alkoxy group (e.g., an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group or an ethoxy group).
• R2 and R3 can both represent a methoxy group.
• R7 can represent an aryl group, such as a phenyl group.
• R2 may represent an electron donating group (excluding sulfur-containing electron donating groups) and R3 may represent a hydrogen atom.
• the electron donating group represented by R2 may be an alkoxy group (e.g., an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group or an ethoxy group).
• B and B' each independently represent a substituent.
• B and B' can each independently be a substituted or unsubstituted phenyl group.
• the phenyl group having a substituent can be a mono- to penta-substituted phenyl group.
• the substituents can be the same or different, and two or more of the substituents can be bonded to form a ring structure.
• the above description of the substituents can be referred to.
• At least one of B and B' can represent a phenyl group having a substituent at the para-position relative to the carbon atom bonded to the pyran ring of the indeno-condensed naphthopyran.
• only one of B and B' can represent a phenyl group having a substituent at the para-position relative to the carbon atom bonded to the pyran ring of the indeno-condensed naphthopyran.
• both B and B' can independently represent a phenyl group having a substituent at the para-position relative to the carbon atom bonded to the pyran ring of the indeno-condensed naphthopyran.
• the substituent at the para-position can be, for example, an electron-donating group.
• electron-donating groups the above description of the electron-donating group can be referred to.
• Specific examples of the electron-donating group at the para-position can include, for example, an alkoxy group such as a methoxy group, and an amino group such as a dimethylamino group, a morpholino group, or a piperidino group.
• At least one of B and B' may be a phenyl group having a nitrogen atom-containing substituent at the para-position relative to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• only one of B and B' may be a phenyl group having a nitrogen atom-containing substituent at the para-position relative to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• both B and B' may be phenyl groups each independently having a nitrogen atom-containing substituent at the para-position relative to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• the nitrogen atom-containing substituent include an unsubstituted amino group (-NH 2 ), 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, and a diarylamino group such as a diphenylamino group), and a cyclic amino group (for example, a piperidino group, a morpholino group, a thiomorpholino group, a tetrahydroquinolino group, a tetrahydroisoquinolino group, etc.).
• the photochromic compound represented by general formula 1 can be synthesized by known methods.
• the following documents can be referred to: Japanese Patent No. 4884578, JP 2011-57581 A, US 2006/0226402 A1, US 2006/0228557 A1, US 2008/0103301 A1, US 2011/0108781 A1, US 2011/0108781 A1, US 7,527,754, US 7,556,751, WO 2001/60811 A 1, WO2013/086248A1, WO1996/014596A1, WO2001/019813A1, WO2001/60811, WO2009/136668, WO2010/150905, WO2011/010744, WO2011/016582, WO2011/025056, WO2011/034202 and WO2012/102409.
• Photochromic Compositions and Photochromic Articles 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 comprising one or more photochromic compounds represented by general formula 1.
• the photochromic composition and the photochromic article may contain only one type of photochromic compound represented by general formula 1, or may contain two or more types (e.g., two or more and four or less types).
• the photochromic article and the photochromic composition may contain, for example, about 0.1 to 15.0% by mass of the photochromic compound represented by general formula 1, with the total amount of the photochromic article and the photochromic composition being 100% by mass. However, they are not limited to the above range.
• the photochromic composition and the photochromic article may contain one or more photochromic compounds represented by general formula 1 and one or more other photochromic compounds.
• the other photochromic compounds will be described later.
• the photochromic article may have at least a substrate.
• the photochromic compound represented by general formula 1 may be included in the substrate of the photochromic article.
• the photochromic article may have a substrate and a photochromic layer, and the substrate and/or photochromic layer may contain one or more photochromic compounds represented by general formula 1.
• the photochromic compound represented by general formula 1 may be included only in the substrate, in another embodiment, or in the photochromic layer, or in both the substrate and the photochromic layer.
• 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.
• photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaarylbisimidazoles, donor-acceptor Stenhouse adducts (DASA), salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, stilbenes, etc.
• other photochromic compounds include one or more selected from the group consisting of photochromic compounds represented by general formula A, photochromic compounds represented by general formula B, and photochromic compounds represented by general formula C described in WO2022/138966.
• the photochromic article may include a substrate selected according to the type of the photochromic article.
• a spectacle lens substrate may include a plastic lens substrate or a glass lens substrate.
• the glass lens substrate may be, for example, a lens substrate made of inorganic glass.
• plastic lens substrate examples 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 a cured product (generally called a transparent resin) obtained by curing a curable composition containing a (thio)epoxy compound having one or more disulfide bonds in the molecule.
• 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 resin
• the lens substrate a non-dyed one (colorless lens) or a dyed one (dyed lens) may be used.
• the refractive index of the lens substrate may be, for example, about 1.50 to 1.75.
• the refractive index of the lens substrate is not limited to the above range, and may be within the above range or may be above or below the above range.
• the refractive index refers to the refractive index for light with a wavelength of 500 nm.
• the lens substrate may be a lens with refractive power (so-called prescription lens) or a lens without refractive power (so-called non-prescription lens).
• the photochromic composition may be a polymerizable composition.
• a "polymerizable composition” is a composition containing one or more polymerizable compounds.
• a polymerizable composition containing at least one photochromic compound represented by general formula 1 and one or more polymerizable compounds is molded by a known molding method to produce a cured product of the polymerizable composition.
• Such a cured product may be included as a substrate in the photochromic article and/or as a photochromic layer.
• the curing treatment may be light irradiation and/or heat treatment.
• a polymerizable compound is a compound having a polymerizable group, and the polymerizable composition may be cured to form a cured product by the progress of a polymerization reaction of the polymerizable compound.
• the polymerizable composition may further contain one or more additives (e.g., a polymerization initiator, etc.).
• the spectacle lenses can be various lenses such as single-focus lenses, multifocal lenses, and progressive power lenses.
• the type of lens is determined by the surface shapes of both sides of the lens substrate.
• the surface of the lens substrate can be convex, concave, or flat. In normal lens substrates and spectacle lenses, the object side surface is convex and the eyeball side surface is concave. However, this is not limited to this.
• the photochromic layer can usually be provided on the object side surface of the lens substrate, but it may also be provided on the eyeball side surface.
• 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 one or more polymerizable compounds.
• the photochromic layer can be formed as a cured layer containing one or more photochromic compounds represented by general formula 1 by directly applying the polymerizable composition onto the surface of the substrate or applying the polymerizable composition onto the surface of a layer provided on the substrate and subjecting the applied polymerizable composition to a curing treatment.
• a curing treatment known coating methods such as spin coating, dip coating, spray coating, inkjet, nozzle coating, and slit coating can be adopted.
• the curing treatment can be light irradiation and/or heat treatment.
• the polymerizable composition can further contain one or more additives (e.g., polymerization initiators, etc.) in addition to one or more polymerizable compounds. As the polymerization reaction of the polymerizable compound progresses, the polymerizable composition can be cured to form a cured layer.
• the thickness of the photochromic layer can be, for example, 5 ⁇ m or more, 10 ⁇ m or more, or 20 ⁇ m or more, and can be, for example, 80 ⁇ m or less, 70 ⁇ m or less, or 50 ⁇ m or less.
• a polymerizable compound refers to a compound having one or more polymerizable groups in one molecule
• a "polymerizable group” refers to a reactive group capable of undergoing a polymerization reaction.
• the polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, a vinyl ether group, an epoxy group, a thiol group, an oxetane group, a hydroxy group, a carboxy group, an amino group, and an isocyanate group.
• polymerizable compounds that can be used to form the substrate and the photochromic layer include the following compounds:
• An episulfide compound is a compound having two or more episulfide groups in one molecule.
• the episulfide group is a polymerizable group capable of undergoing ring-opening polymerization.
• Specific examples of episulfide compounds include bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide, bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropylthio)methane, bis(2,3-epithiopropyl)disulfide, bis(2,3-epithiopropyldithio)methane, bis(2,3-epithiopropyldithio)ethane, bis(6,7-epithio-3,4-dithiaheptyl)sulfide, bis(6,7-epithio-3,4-di
• a thietanyl compound is a thietanyl compound having two or more thietanyl groups in one molecule.
• the thietanyl group is a polymerizable group capable of ring-opening polymerization.
• Some thietanyl compounds have episulfide groups in addition to multiple thietanyl groups. Such compounds are listed as examples of episulfide compounds above.
• Other thietanyl compounds include metal-containing thietanyl compounds having metal atoms in the molecule and non-metal thietanyl compounds not containing metals.
• non-metallic thietanyl compounds include bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide, bis(3-thietanyl) trisulfide, bis(3-thietanyl) tetrasulfide, 1,4-bis(3-thietanyl)-1,3,4-trithiabutane, 1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane, 1,6-bis(3-thietanyl)-1,3,4,6-tetrathiahexane, 1,6-bis(3-thietanyl)-1,3,5,6-tetrathiahexane, and 1,7-bis(3-thietanyl).
• metal-containing thietane compounds include those that contain, as metal atoms in the molecule, atoms of group 14 such as Sn, Si, Ge, and Pb atoms, elements of group 4 such as Zr and Ti atoms, atoms of group 13 such as Al atoms, and atoms of group 12 such as Zn atoms.
• alkylthio(thietanylthio)tin bis(alkylthio)bis(thietanylthio)tin
• alkylthio(alkylthio)bis(thietanylthio)tin bis(thietanylthio)cyclic dithiotin compounds
• alkyl(thietanylthio)tin compounds include alkylthio(thietanylthio)tin, bis(alkylthio)bis(thietanylthio)tin, alkylthio(alkylthio)bis(thietanylthio)tin, bis(thietanylthio)cyclic dithiotin compounds, and alkyl(thietanylthio)tin compounds.
• alkylthio(thietanylthio)tin examples include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, and isopropylthiotris(thietanylthio)tin.
• bis(alkylthio)bis(thietanylthio)tin include bis(methylthio)bis(thietanylthio)tin, bis(ethylthio)bis(thietanylthio)tin, bis(propylthio)bis(thietanylthio)tin, and bis(isopropylthio)bis(thietanylthio)tin.
• alkylthio(alkylthio)bis(thietanylthio)tin examples include ethylthio(methylthio)bis(thietanylthio)tin, methylthio(propylthio)bis(thietanylthio)tin, isopropylthio(methylthio)bis(thietanylthio)tin, ethylthio(propylthio)bis(thietanylthio)tin, ethylthio(isopropylthio)bis(thietanylthio)tin, and isopropylthio(propylthio)bis(thietanylthio)tin.
• bis(thietanylthio)cyclic dithiotin compounds include bis(thietanylthio)dithiastannetane, bis(thietanylthio)dithiastannolane, bis(thietanylthio)dithiastanninane, and bis(thietanylthio)trithiastannocane.
• alkyl(thietanylthio)tin compounds include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, and tetrakis(thietanylthio)tin.
• the polyamine compound is a compound having two or more NH2 groups in one molecule, and can form a urea bond by reaction with a polyisocyanate, and can form a thiourea bond by reaction with a polyisothiocyanate.
• polyamine compound examples include ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2-(2-aminoethylamino)ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, and 1,3,5-benzenetriamine.
• Epoxy compounds are compounds having an epoxy group in the molecule.
• the epoxy group is a polymerizable group capable of ring-opening polymerization.
• Epoxy compounds are generally classified into aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds.
• aliphatic epoxy compounds 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
• alicyclic epoxy compounds include isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, etc.
• aromatic epoxy compounds include resorcinol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ether, and cresol novolac polyglycidyl ether.
• epoxy compounds that contain sulfur atoms in the molecule as well as epoxy groups can also be used.
• sulfur-containing epoxy compounds include linear aliphatic and cyclic aliphatic compounds.
• chain aliphatic sulfur-containing epoxy compounds include bis(2,3-epoxypropyl)sulfide, bis(2,3-epoxypropyl)disulfide, bis(2,3-epoxypropylthio)methane, 1,2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio)butane, 1,4-bis(2,3-epoxypropylthio)-2-methylbutane, 1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio) 1,5-bis(2,3-epoxypropylthio)pentane,
• 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, and 2,5-bis(2,3-epoxypropylthiomethyl)-2,5-dimethyl-1,4-dithiane.
• the radical polymerizable group is a polymerizable group that can undergo radical polymerization.
• examples of the radical polymerizable group include an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group.
• 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.”
• 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-
• allyl compounds include allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether, polyethylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether, methacryloyloxypolyethylene glycol-polypropylene glycol allyl ether, phenoxypolyethylene glycol allyl ether, methacryloyloxypolyethylene glycol allyl ether, etc.
• Examples of compounds having a vinyl group include ⁇ -methylstyrene, ⁇ -methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobis (m-dioxane).
• the photochromic article may include, at any position, one or more layers known as functional layers for photochromic articles, such as a protective layer for improving the durability of the photochromic article, an anti-reflection layer, a water-repellent or hydrophilic anti-fouling layer, an anti-fogging layer, and a primer layer for improving adhesion between layers.
• a protective layer for improving the durability of the photochromic article
• an anti-reflection layer such as a water-repellent or hydrophilic anti-fouling layer
• an anti-fogging layer such as a primer layer for improving adhesion between layers.
• the photochromic article can be an optical article.
• One form of optical article is a spectacle lens.
• Such spectacle lenses can also be called photochromic lenses or photochromic spectacle lenses.
• Other examples of optical articles include lenses for goggles, the visor portion of a sun visor, and the shielding member of a helmet.
• An optical article having an anti-glare function can be obtained by applying the photochromic composition, which is a polymerizable composition, onto a substrate for such optical articles and then subjecting the applied composition to a curing treatment to form a photochromic layer.
• One aspect of the present invention relates to glasses having a spectacle lens which is one form of the photochromic article. Details of the spectacle lens included in the glasses are as described above. By including such a spectacle lens, the glasses can exhibit an anti-glare effect like sunglasses, for example, outdoors, when the photochromic compound is irradiated with sunlight and colored, and when returning indoors, the photochromic compound fades, thereby recovering transparency. For the configuration of the frame, etc. of the glasses, known techniques can be applied.
• NMR nuclear magnetic resonance
• a proton NMR ECS-400 manufactured by JEOL Ltd. was used as the NMR.
• Deuterated chloroform was mainly used as the measurement solvent, and deuterated dimethyl sulfoxide, deuterated acetone, deuterated acetonitrile, deuterated benzene, deuterated methanol, deuterated pyridine, etc. were used appropriately only when the substance was poorly soluble in deuterated chloroform.
• High performance liquid chromatography (HPLC) was used for the analysis of purity. Shimadzu Corporation's LC-2040C was used as the HPLC.
• a YMC-Triart C18 was used as the column, and the measurement temperature was set to 40°C.
• a mixed solvent of water containing 0.1% trifluoroacetic acid and acetonitrile was used as the mobile phase, and the flow rate was 0.4 mL/min.
• UPLC Nippon Waters ACQUITY UPLC H-Class system
• the column used was an ACQUITY UPLC BEH C18, and the measurement temperature was set to 40°C.
• the mobile phase was a mixed solvent of water and acetonitrile to which formic acid had been added, and was run at a flow rate of 0.61 mL/min. with a concentration gradient.
• Electrospray ionization (ESI) was used for ionization.
• CHN carbon, hydrogen, nitrogen elemental analysis was carried out by the combustion method.
• Example 1 The products shown in the following table were obtained from the reactants shown in the following table 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 (1.5 g, 4 mmol) and reactant 2 (2.3 g, 8 mmol) shown in the table below, and the mixture was stirred at room temperature overnight. Aqueous sodium hydroxide solution (1.0 M, 37 mL) was added, and the mixture was stirred for about 20 minutes.
• the resulting product was analyzed by the following methods.
• the structure was identified by nuclear magnetic resonance (NMR) spectroscopy.
• the purity was analyzed by HPLC, and the area ratio was the value shown in the table below.
• mass spectrometry the calculated accurate mass shown in the table below was compared with the measured value ([M+H] + , relative intensity 100) shown in the table below.
• CHN elemental analysis by the combustion method the calculated values shown in the table below were compared with the measured values shown in the table below. From the above analytical results, it was confirmed that the target compounds, which are shown in the table below, were obtained.
• 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
• a silane coupling agent ⁇ -methacryloxypropyltrimethoxysilane
• a plastic lens substrate manufactured by HOYA Corporation under the trade name EYAS: center thickness 2.5 mm, diameter 75 mm, spherical lens power -4.00
• EYAS center thickness 2.5 mm, diameter 75 mm, spherical lens power -4.00
• a water-based polyurethane resin liquid (polycarbonate polyol polyurethane emulsion, viscosity 100 cPs, solid content concentration 38% by mass) was applied to the convex surface of this plastic lens substrate by spin coating at 1500 rpm for 1 minute using a Mikasa spin coater MS-B150 in an environment of room temperature and relative humidity of 40 to 60%, and then naturally dried for 15 minutes to form a primer layer having a thickness of 5.5 ⁇ m.
• the photochromic composition prepared above was dropped onto the primer layer, and coated by spin coating using a program in which the rotation speed was changed from 500 rpm to 1500 rpm in a slope mode over 1 minute, and then rotated at 1500 rpm for 5 seconds using MS-B150 manufactured by Mikasa Co., Ltd. Then, the photochromic composition coated on the primer layer formed on the plastic lens substrate was irradiated with ultraviolet light (dominant wavelength 405 nm) for 40 seconds in a nitrogen atmosphere (oxygen concentration 500 ppm or less), and the composition was cured to form a photochromic layer. The thickness of the formed photochromic layer was 45 ⁇ m.
• photochromic articles eyeglass lenses
• photochromic compounds of Examples 1 to 6 were produced containing the photochromic compounds of Examples 1 to 6. It was confirmed that all of the eyeglass lenses were colored when irradiated with ultraviolet light, and returned to their original state before ultraviolet light irradiation when the irradiation was stopped.
• the absorbance was measured with a UV-visible spectrophotometer (Shimadzu UV-1900i, measurement wavelength 700-400 nm, wavelength 2 nm interval, survey mode) within 10 seconds after the end of ultraviolet irradiation.
• the absorbance was measured at room temperature (23-28°C).
• the concentration of the solution was adjusted so that the absorbance of the first absorption wavelength (the peak of absorption intensity observed at the longest wavelength) was 0.95-1.05.
• the absorbance was further measured every 10 seconds to measure the attenuation of the absorbance.
• the peak of the first absorption wavelength in the first absorbance measurement was normalized to 1, and the subsequent attenuation of absorbance was measured.
• the data for the first 100 seconds of fading was analyzed from the change in absorbance over time using a first-order reaction model to determine the reaction rate constant. If [A 0 ] is the initial concentration of the colored body, i.e., 1, which is the normalized value of absorbance, [A] is the concentration of the colored body after a certain time, i.e., the normalized absorbance value, t is time (seconds), and k is the rate constant, the first-order reaction can be expressed by the following formula.
• the molar extinction coefficient ⁇ (mol ⁇ 1 Lcm ⁇ 1 ) at a wavelength of 400 nm was read. A molar extinction coefficient ⁇ of less than 8,000 mol ⁇ 1 Lcm ⁇ 1 was judged as “pass”, and a molar extinction coefficient ⁇ of 8,000 mol ⁇ 1 Lcm ⁇ 1 or more was judged as “fail”.
• the following table shows the reaction rate constant and the visible region transparency evaluation results obtained for each of the examples and comparative examples. From the results shown in the table, it can be confirmed that each compound of the examples shown in the table has a faster fading rate than the compound of Comparative Example 2 and has a better visible region transparency than the compound of Comparative Example 1. In addition, in the above measurements, it was confirmed that the compounds of all the Examples exhibited photochromic properties, in which the compounds were irradiated with ultraviolet light to undergo structural transition to a molecular structure having strong absorption in the visible range.
• a photochromic compound represented by the following general formula 1 (In General Formula 1, A represents a ring structure having 3 or more carbon atoms constituting the ring, including the carbon atom at the 13th position of the indeno-fused naphthopyran; R 1 and R 4 to R 8 each independently represent a hydrogen atom or a substituent; R2 represents an electron donating group (excluding sulfur-containing electron donating groups); R3 represents a hydrogen atom or an electron-donating group (excluding sulfur-containing electron-donating groups); B and B' each independently represent a substituent. [2] The photochromic compound according to [1], wherein R 2 represents an alkoxy group and R 3 represents a hydrogen atom.
• B and B' each independently represent a phenyl group having an electron-donating group as a substituent at the para-position relative to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• a photochromic composition comprising the photochromic compound according to any one of [1] to [18].
• a photochromic article comprising a cured product obtained by curing the photochromic composition according to [21].
• One aspect of the present invention is useful in the technical fields of glasses, goggles, sun visors, helmets, and the like.

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