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
  • C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
• • 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
  • C07D311/78—Ring systems having three or more relevant 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
  • 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
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/23—Photochromic filters
• • 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
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
  • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
• • 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 spectacles.
• a photochromic compound is a compound that has a property (photochromic property) of coloring under irradiation with light in a wavelength region having photoresponsiveness and fading under non-irradiation.
• Patent Document 1 discloses a naphthopyran-based compound having photochromic properties.
• Methods for imparting photochromic properties to articles such as spectacle lenses include a method of incorporating a photochromic compound into a substrate and a method of forming a layer containing a photochromic compound.
• the properties desired for such articles to which photochromic properties are imparted include a high coloring density during coloring in the visible region (wavelength of 380 to 780 nm), and a fast fading rate after being colored by light irradiation. mentioned.
• An object of one aspect of the present invention is to provide a photochromic article that has a high color density when colored in the visible region and a fast color fading rate.
• One aspect of the present invention relates to a photochromic compound represented by general formula 1 below.
• one aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by general formula 1 below.
• one aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by general formula 1 below.
• R 1 and R 2 are bonded to each other to form a ring structure with the carbon atom at position 13 of the indeno-fused naphthopyran;
• R 3 to R 6 each independently represent a hydrogen atom or an electron-withdrawing group, one or more of R 3 to R 6 represents an electron-withdrawing group,
• R 8 and R 9 each independently represent a hydrogen atom or an electron donating group, at least one of R 8 and R 9 represents an electron donating group,
• R7 , R10 , A and A' each independently represent a hydrogen atom or a substituent.
• the compound represented by the general formula 1 can be colored with high density in the visible region when it is colored by light irradiation, and can also exhibit a fast color fading rate.
• R 1 and R 2 are bonded together to form a ring structure with the 13-position carbon atom of the indeno-fused naphthopyran, and at least one of R 8 and R 9 is an electron-donating
• the present inventor speculates that representing a group or the like may contribute.
• the invention is not limited to the speculations described herein. According to the compound represented by the general formula 1, it is possible to provide a photochromic article having a high coloring density in the visible range and a high fading rate.
• a photochromic compound undergoes structural transformation into a colored body through an excited state upon irradiation with light such as sunlight.
• the structure after structural conversion via light irradiation can be called a "color body”.
• the structure before light irradiation can be called a "colorless body”.
• colorless with respect to a colorless body is not limited to a completely colorless body, but also includes a case where the color is lighter than that of a colored body.
• the structure of general formula 1 is a colorless structure.
• 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 included in the substrate of the photochromic article and/or can be included in the photochromic layer in a photochromic article having a substrate and a photochromic layer.
• a "photochromic layer” is a layer containing a photochromic compound.
• 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 a photochromic compound, and is used for producing the photochromic article according to one aspect of the present invention. can be done.
• the substituents in various general formulas whose details will be described later, and the substituents when each group described later has a substituent are each independently Linear or branched alkyl groups having 1 to 18 carbon atoms such as hydroxy group, methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; cyclic or bicyclic cyclic aliphatic alkyl groups, linear or branched alkoxy groups having 1 to 24 atoms such as methoxy, ethoxy, butoxy, non-aromatic groups having 1 to 24 atoms a cyclic substituent, 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 methylsulfide group, an ethylsulfide group, Line
• aryl group aryloxy group such as phenyloxy group, arylsulfide group such as phenylsulfide group, pyridyl group, furanyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, Dibenzothiophenyl group, carbazolyl group, diazolyl group, triazolyl group, quinolinyl group, phenothiazinyl group, phenoxazinyl group, phenazinyl group, thianthryl group, heteroaryl group such as acridinyl group, amino group (-NH 2 ), monomethylamino group, etc.
• R m selected from the group consisting of halogen atoms; or a substituent in which R m is further substituted with one or more identical or different R m ; can be
• R m is further substituted with one or more identical or different R m is a terminal carbon atom of the alkoxy group further substituted with an alkoxy group, and a terminal carbon atom of the alkoxy group is further substituted with A structure in which an alkoxy group is substituted can be mentioned.
• R m is further substituted with one or more of the same or different R m is the same or different Structures in which R m is substituted can be mentioned.
• the groups described are substituted or unsubstituted groups.
• substituted or unsubstituted is synonymous with “having one or more substituents or unsubstituted.”
• carbon number and “constituent atom number” refer to the numbers including the carbon number or the atom number of the substituents for a group having a substituent.
• solubilizing group refers to a substituent that can contribute to enhancing compatibility with any liquid or a specific liquid.
• solubilizing groups include alkyl groups containing linear, branched or cyclic structures having 4 to 50 carbon atoms, linear, branched or cyclic alkoxy groups having 4 to 50 atoms, and straight chains having 4 to 50 atoms.
• a branched or cyclic silyl group a silicon atom, a sulfur atom, a nitrogen atom, a phosphorus atom, or the like in part of the above groups, or a combination of two or more of the above groups.
• Substituents that can contribute to promoting thermal motion of the molecules of the compound are preferred.
• a compound having a solubilizing group as a substituent prevents the solute from solidifying by inhibiting the distance between the solute molecules from approaching each other. state can be created.
• a solubilizing group can liquefy a solute or increase the solubility of a compound bearing this substituent in a liquid.
• the solubilizing group includes linear alkyl groups such as n-butyl, n-pentyl, n-hexyl, and n-octyl, branched alkyl groups such as tert-butyl, and cyclic alkyl groups. Certain cyclopentyl and cyclohexyl groups are preferred.
• substituents are preferably methoxy, ethoxy, phenoxy, methylsulfide, ethylsulfide, phenylsulfide, trifluoromethyl, phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, a substituent selected from the group consisting of 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 morpholylno group, a thiomorpholino group, a cyano group and a solubilizing group; more preferably methoxy group, phenoxy group, methylsulfide group, phenylsulfide group, trifluoromethyl group, phenyl group, dimethylamino group,
• Electron-withdrawing group refers to a substituent that more easily attracts electrons from the bonding atom side than a hydrogen atom. Electron withdrawing groups can attract electrons as a result of substituent effects such as inductive effects, mesomeric effects (or resonance effects).
• electron-withdrawing groups include halogen atoms (fluorine atom: -F, chlorine atom: -Cl, bromine atom: -Br, iodine atom: -I), trifluoromethyl group: -CF 3 , nitro group: -NO 2 , cyano group: -CN, formyl group: -CHO, acyl group: -COR (R is a substituent), alkoxycarbonyl group: -COOR, carboxy group: -COOH, substituted sulfonyl group: -SO 2 R ( R is a substituent), a sulfo group: —SO 3 H, and the like.
• halogen atoms fluorine atom: -F, chlorine atom: -Cl, bromine atom: -Br, iodine atom: -I
• trifluoromethyl group -CF 3
• nitro group: -NO 2 cyano group:
• Suitable electron-withdrawing groups include a fluorine atom which is an electron-withdrawing group with high electronegativity, and an electron-withdrawing group having a positive substituent constant ⁇ p at the para position based on Hammett's rule. can.
• Electron-donating group refers to a substituent group that readily donates electrons to a bonding atom side compared to a hydrogen atom. Electron-donating groups can be substituents that tend to donate electrons as the sum of inductive effects, mesomeric effects (or resonance effects), and the like. Specific examples of the electron-donating group 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), and an arylsulfide group.
• Suitable electron-donating groups include electron-donating groups having a negative value for the substituent constant ⁇ p at the para-position based on Hammett's rule.
• Photochromic compound represented by general formula 1 The photochromic compound represented by Formula 1 will be described in more detail below.
• the 13-position carbon atom of the indeno-fused naphthopyran can be a spiro atom shared by the above ring structure and the indeno-fused naphthopyran. That is, the ring structure can be a ring structure spiro-fused with an indeno-fused naphthopyran.
• R 1 and R 2 are bonded together to form a ring structure together with the 13-position carbon atom of the indeno-fused naphthopyran.
• the number of carbon atoms constituting the ring means the number of carbon atoms including the 13-position carbon atom of the indeno-fused naphthopyran.
• the ring structure can be a monocyclic structure, can be a condensed polycyclic structure such as bicyclic or tricyclic, or can be a bridged ring structure such as bicyclic. It can also be a spiro ring structure such as formula.
• An aliphatic ring can be mentioned as the ring structure. Such aliphatic rings can be unsubstituted or can have substituents. For substituents, reference can be made to the above description of substituents.
• the aliphatic ring examples include an aliphatic ring having 3 or more and 20 or less carbon atoms, including the carbon atom at the 13th position of the indeno-fused naphthopyran. Specific examples thereof include monocyclic rings such as cyclohexane ring, cyclooctane ring and cycloheptane ring, bicyclo rings such as norbornane ring and bicyclononane ring, and tricyclo rings such as adamantane ring.
• the above-mentioned "the number of carbon atoms constituting the ring" includes the number of carbon atoms contained in the substituent in the case of an aliphatic ring having a substituent.
• the "number of atoms forming a ring including the carbon atom at the 13th position of the indeno-fused naphthopyran" described later includes the number of atoms contained in the substituents 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, can be 3, 4, 5 or 6, and is more preferably 6. Further, in another embodiment, the number of carbon atoms constituting the ring of such an aliphatic ring is preferably 7 or more and 20 or less. , 16, 17, 18, 19 or 20, more preferably 7 or 10.
• photochromic articles it is desirable for photochromic articles to exhibit fast fading rates after being colored by photoirradiation.
• the ring structure formed by bonding R 1 and R 2 together with the carbon atom at the 13th position of the indeno-fused naphthopyran is an aliphatic ring, such an aliphatic ring
• the number of carbon atoms constituting the ring of the tricyclic ring is preferably 3 or more and 6 or less, more preferably 6.
• ring structure formed by bonding R 1 and R 2 together with the carbon atom at the 13th position of the indeno-fused naphthopyran One of the ring structures selected from the group consisting of an aliphatic ring, an aromatic ring and an aromatic heterocyclic ring having 3 or more and 20 or less carbon atoms constituting the ring including the carbon atom at the 13th position of the indeno-fused naphthopyran
• 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 the above heterocycle; can also be mentioned.
• One of the ring structures selected from the group consisting of an aliphatic ring, an aromatic ring and an aromatic heterocyclic ring having 3 or more and 20 or less carbon atoms constituting the ring including the carbon atom at the 13th position of the indeno-fused naphthopyran
• a specific example of the condensed polycyclic ring obtained by condensing the above is a fluorene ring.
• heterocyclic ring in which the number of atoms forming the ring including the carbon atom at the 13th position of the indeno-fused naphthopyran is 3 or more and 20 or less include a thiophene ring, a furan ring, a pyridine ring, and the like.
• condensed polycyclic rings in which one or more ring structures selected from the group consisting of aromatic rings and aromatic heterocycles are condensed to the above heterocycles include phenylfuran rings and biphenylthiophene rings.
• Specific examples of the ring structure formed by combining R 1 and R 2 together with the carbon atom at the 13th position of the indeno-fused naphthopyran include the following ring structures.
• the carbon atom at position 13 is the carbon atom at position 13 of the indeno-fused naphthopyran in general formula 1.
• specific examples of the ring structure formed by bonding R 1 and R 2 together with the carbon atom at the 13th position of the indeno-fused naphthopyran include ring structures included in the exemplified compounds shown below.
• R 3 to R 6 each independently represent a hydrogen atom or an electron-withdrawing group, and one or more of R 3 to R 6 represents an electron-withdrawing group.
• electron-withdrawing groups include halogen atoms such as fluorine, chlorine, bromine and iodine atoms, perfluoroalkyl groups having 1 to 10 carbon atoms (eg, trifluoromethyl group), and cyano groups. be able to.
• the electron withdrawing group can be an electron withdrawing group selected from the group consisting of fluorine atoms and trifluoromethyl groups.
• R 4 can be a trifluoromethyl group.
• both R 3 and R 5 can be fluorine atoms.
• the present inventor presumes that the fact that one or more of R 3 to R 6 is an electron-withdrawing group contributes to the ability of the compound represented by general formula 1 to exhibit a fast discoloration rate after light irradiation. ing.
• one or more of R 3 to R 6 is an electron-withdrawing group. That is, the total number of electron-withdrawing groups contained in R 3 to 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.
• one or more of R 3 to R 5 can be an electron withdrawing group. Specific forms include a form in which only R 4 is an electron - withdrawing group and R 3 , R 5 and R 6 are hydrogen atoms; Examples include a form in which 6 is a hydrogen atom. More specifically, R 4 alone is a trifluoromethyl group and R 3 , R 5 and R 6 are hydrogen atoms, R 3 and R 5 are fluorine atoms, R 4 and R Examples include a form in which 6 is a hydrogen atom.
• R8 and R9 each independently represent a hydrogen atom or an electron donating group, and at least one of R8 and R9 represents an electron donating group.
• R 8 and R 9 each independently represent a hydrogen atom or an electron-donating group (excluding a sulfur atom), and at least one of R 8 and R 9 can represent an electron-donating group.
• Specific examples of electron-donating groups represented by R 8 and/or R 9 include alkoxy groups having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.), oxoaryl groups (eg, phenoxy group, etc.), amino groups (eg, dimethylamino group, piperidino group, morpholino group, etc.) and the like.
• R8 and R9 in one aspect, R8 can represent a hydrogen atom and R9 can represent an electron donating group. In another form, R8 can represent an electron donating group and R9 can represent a hydrogen atom. Also, in another aspect, R 8 and R 9 can represent the same or different electron-donating groups.
• the compound represented by General Formula 1 can have two absorption peaks in the visible region. The visible range shall mean the wavelength range of 380 to 780 nm. The present inventor presumes that the fact that both R 8 and R 9 are electron-donating groups contributes to the fact that the compound represented by general formula 1 exhibits absorption characteristics having two absorption peaks in the visible region. ing.
• R7 , R10 , A and A' each independently represent a hydrogen atom or a substituent.
• substituents reference can be made to the above description of substituents.
• a and A' can each independently be a substituted or unsubstituted phenyl group.
• a substituted phenyl group can be a mono- to penta-substituted phenyl group.
• those substituents may be the same or different substituents, and two or more of those substituents may combine to form a ring structure.
• substituents of the phenyl group the above description of substituents can be referred to.
• At least one of A and A' can represent a phenyl group having a substituent at a substitution position para to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• only one of A and A' can represent a phenyl group having a substituent at the substitution position para to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• both A and A' can each independently represent a phenyl group having a substituent at a substitution position para to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• the substituent substituting at the above para-substitution position can be, for example, an electron-donating group.
• electron-donating groups reference can be made to the above description of electron-donating groups.
• Specific examples of the electron-donating group to be substituted at the para-position include an alkoxy group such as a methoxy group, and a morpholino group.
• At least one of A and A' is a phenyl group having a nitrogen atom-containing substituent at a substitution position para to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• only one of A and A' can be a phenyl group having a nitrogen atom-containing substituent at the substitution position para to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran.
• both A and A' can each independently be a phenyl group having a nitrogen atom-containing substituent at the substitution position para 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 monophenylamino group, and the like).
• cyclic amino group eg, piperidino group, morpholino group, thiomorpholino group, tetrahydroquinolino group, tetrahydroisoquinolino group, etc.
• R 8 represents a hydrogen atom
• R 9 represents an electron-donating group
• at least one of A and A' is the carbon at the position bonded to the pyran ring of the indeno-fused naphthopyran.
• a phenyl group may be represented having a nitrogen atom-containing substituent at the substitution position para to the atom.
• the photochromic compound represented by general formula 1 can be synthesized by a known method.
• the following documents can be referred to, for example. ⁇ 4884578 ⁇ US2006/0226402A1 ⁇ US2006/0228557A1 ⁇ US2008/0103301A1 ⁇ US2011/0108781A1 ⁇ US2011/0108781A1 ⁇ 7527754 ⁇ 7556751 ⁇ WO2001/60811A1 ⁇ WO2013/086248A1 , WO1996/014596A1, WO2001/019813A1 and WO2011/016582A1.
• Photochromic composition, photochromic article One aspect of the present invention relates to a photochromic composition containing one or more photochromic compounds represented by Formula 1. In addition, one aspect of the present invention relates to a photochromic article containing one or more photochromic compounds represented by general formula (1).
• the photochromic composition and the photochromic article can contain only one type of photochromic compound represented by general formula 1, or can contain two or more types (for example, two to four types).
• the photochromic article and the photochromic composition can contain, for example, about 0.1 to 15.0% by mass of the photochromic compound represented by the general formula 1 based on the total amount of 100% by mass. However, it is not limited to the above range.
• the photochromic article can have at least a base material.
• the photochromic compound represented by General Formula 1 can be included in the base material of the photochromic article.
• the photochromic article can have a substrate and a photochromic layer, and the substrate and/or the photochromic layer can contain one or more photochromic compounds represented by the general formula (1).
• the photochromic compound represented by the general formula 1, in the substrate and the photochromic layer can be contained only in the substrate in one form, can be contained only in the photochromic layer in another form, or can be contained only in the photochromic layer in another form.
• the form can be included in the substrate and the photochromic layer.
• the substrate and the photochromic layer can contain only the photochromic compound represented by General Formula 1 as the photochromic compound, or can contain one or more other photochromic compounds.
• Other photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaarylbisimidazoles, donor-acceptor Stenhaus adducts (DASA). , salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, stilbenes and the like.
• the photochromic article can contain a substrate selected according to the type of photochromic article.
• substrates include spectacle lens substrates such as plastic lens substrates and glass lens substrates.
• the glass lens substrate can be, for example, a lens substrate made of inorganic glass.
• Plastic lens substrates include styrene resins such as (meth)acrylic resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, and polyether resins.
• a urethane resin obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol a thiourethane resin obtained by reacting an isocyanate compound with a polythiol compound, and a (thio)epoxy compound having one or more disulfide bonds in the molecule.
• a cured product (generally called a transparent resin) obtained by curing the curable composition contained therein can be mentioned.
• 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.
• the refractive index of the lens substrate is not limited to the above range, and may be within the above range or vertically separated from 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 having refractive power (so-called prescription lens) or a lens without refractive power (so-called non-prescription lens).
• the photochromic composition can be a polymerizable composition.
• a "polymerizable composition” is a composition containing one or more polymerizable compounds.
• a cured product of the polymerizable composition can be made.
• Such a cured product can be included as a substrate in the photochromic article and/or can be included as a photochromic layer.
• the curing treatment can be light irradiation and/or heat treatment.
• a polymerizable compound is a compound having a polymerizable group, and the polymerizable composition can be cured to form a cured product as the polymerization reaction of the polymerizable compound proceeds.
• the polymerizable composition can further include one or more additives (eg, polymerization initiators, etc.).
• Spectacle lenses can be various lenses such as monofocal lenses, multifocal lenses, and progressive power lenses.
• the type of lens is determined by the surface shape of both surfaces of the lens substrate.
• the surface of the lens substrate may be convex, concave, or flat.
• the object-side surface is convex and the eyeball-side surface is concave.
• the photochromic layer can usually be provided on the object-side surface of the lens substrate, but may 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.
• a photochromic layer can be formed as a cured layer obtained by curing a polymerizable composition containing at least one or more photochromic compounds represented by Formula 1 and one or more polymerizable compounds.
• a photochromic layer can be formed as a cured layer containing one or more of the photochromic compounds represented by Formula 1.
• a known coating method such as a spin coating method, a dip coating method, a spray coating method, an inkjet method, a nozzle coating method, a slit coating method, or the like can be employed.
• the curing treatment can be light irradiation and/or heat treatment.
• the polymerizable composition can further comprise one or more additives (eg, polymerization initiators, etc.) in addition to one or more polymerizable compounds. As the polymerization reaction of the polymerizable compound proceeds, the polymerizable composition may be cured to form a cured layer.
• additives eg, polymerization initiators, etc.
• 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
• the term "polymerizable group” refers to a reactive group capable of undergoing a polymerization reaction. do.
• Examples of polymerizable groups include acryloyl groups, methacryloyl groups, vinyl groups, vinyl ether groups, epoxy groups, thiol groups, oxetane groups, hydroxy groups, carboxy groups, amino groups, isocyanate groups, and the like.
• Examples of polymerizable compounds that can be used for forming 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.
• 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-epithiopropyl) thio)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-epithioo
• a thietanyl-based compound is a thietane compound having two or more thietanyl groups in one molecule.
• a thietanyl group is a polymerizable group capable of ring-opening polymerization.
• Some thietanyl-based compounds have an episulfide group along with multiple thietanyl groups. Such compounds are listed as examples of episulfide compounds above.
• Other thietanyl-based compounds include metal-containing thietane compounds having metal atoms in the molecule and non-metallic thietane compounds containing no metal.
• nonmetallic 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-trithibutane, 1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane, 1,6-bis(3-thietanyl)-1, 3,4,6-tetrathiahexane, 1,6-bis(3-thietanyl)-1,3,5,6-tetrathiahexane, 1,7-bis(3-thietanyl)-1,2,4, 5,7-pentathiaheptane, 1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathiaheptane, 1,1-bis((3
• metal-containing thietane compounds metal atoms such as Sn atoms, Si atoms, Ge atoms and Pb atoms, Group 14 atoms such as Sn atoms, Si atoms, Ge atoms and Pb atoms; Group 4 elements such as Zr atoms and Ti atoms; group atoms, group 12 atoms such as Zn atoms, and the like.
• 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)tin. Examples include 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, and ethylthio(propylthio)tin.
• Examples include bis(thietanylthio)tin, ethylthio(isopropylthio)bis(thietanylthio)tin, isopropylthio(propylthio)bis(thietanylthio)tin and the like.
• bis(thietanylthio)cyclic dithiotin compounds include bis(thietanylthio)dithiastanetan, bis(thietanylthio)dithiastanenolan, bis(thietanylthio)dithiastanninan, bis(thietanylthio)trithiastanocane, and the like. can be exemplified.
• alkyl(thietanylthio)tin compounds include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, and tetrakis(thietanylthio)tin.
• a 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. .
• polyamine compounds include ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2-(2-aminoethyl amino) ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3,5-benzenetriamine and the like.
• Epoxy compound An epoxy-based compound is a compound having an epoxy group in its molecule.
• An 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 Glycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether
• alicyclic epoxy compounds include isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like.
• aromatic epoxy compounds include resole syndiglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolak polyglycidyl ether, cresol novolac poly glycidyl ether and the like.
• an epoxy-based compound having a sulfur atom in the molecule can also be used along with the epoxy group.
• Such sulfur-containing epoxy compounds include linear aliphatic compounds and cycloaliphatic compounds.
• chain aliphatic sulfur-containing atom epoxy compounds include bis(2,3-epoxypropyl) sulfide, bis(2,3-epoxypropyl) disulfide, and 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-e
• cycloaliphatic sulfur-containing atom 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.
• a radically polymerizable group is a polymerizable group capable of undergoing radical polymerization.
• examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, allyl groups, and vinyl groups.
• a compound having a polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group is hereinafter referred to as a "(meth)acrylate compound".
• (meth)acrylate compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene.
• allyl compounds include allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether, and polyethylene glycol allyl ether.
• methoxypolyethyleneglycol-polypropyleneglycol allyl ether methoxypolyethyleneglycol-polypropyleneglycol allyl ether, butoxypolyethyleneglycol-polypropyleneglycol allyl ether, methacryloyloxypolyethyleneglycol-polypropyleneglycol allyl ether, phenoxypolyethyleneglycol allyl ether, methacryloyloxypolyethyleneglycol allyl ether and the like.
• Vinyl compounds include ⁇ -methylstyrene, ⁇ -methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane). etc.
• the photochromic article includes a protective layer for improving the durability of the photochromic article, an antireflection layer, a water-repellent or hydrophilic antifouling layer, an antifogging layer, and a primer layer for improving adhesion between layers.
• a protective layer for improving the durability of the photochromic article, an antireflection layer, a water-repellent or hydrophilic antifouling layer, an antifogging layer, and a primer layer for improving adhesion between layers.
• One or more of the layers known as functional layers can be included at any location.
• 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.
• a lens for goggles, a visor (eaves) portion of a sun visor, a shield member of a helmet, and the like can be mentioned.
• Optical articles having an antiglare function by coating the photochromic composition, which is a polymerizable composition, on a substrate for these optical articles, and subjecting the coated composition to a curing treatment to form a photochromic layer. can be obtained.
• One aspect of the present invention relates to spectacles having a spectacle lens that is one form of the photochromic article.
• the details of the spectacle lenses included in these spectacles are as described above.
• the above spectacles can exhibit an anti-glare effect like sunglasses when the photochromic compound is colored by being irradiated with sunlight outdoors, and the photochromic compound can be colored when returned indoors. Transmittance can be recovered by fading.
• a known technique can be applied to the configuration of the frame and the like.
• NMR nuclear magnetic resonance spectroscopy
• YMC-Triart C18 was used for the column, and the measurement temperature was set to 40°C.
• a mixed solvent of water and acetonitrile containing 0.1% trifluoroacetic acid was used as the mobile phase, and the flow rate was 0.4 mL/min.
• ACQUITY UPLC H-Class system UPLC
• ACQUITY UPLC BEH C18 was used as the column, and the measurement temperature was set to 40°C.
• a mixed solvent of water and acetonitrile to which formic acid was added was used as the mobile phase, and the flow rate was 0.61 mL/min. It was flushed with Electrospray ionization (ESI) method was used for ionization.
• CHN carbon, hydrogen, nitrogen elemental analysis was performed by a combustion method.
• 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 and stirred overnight at room temperature. Aqueous sodium hydroxide (1.0 M, 37 mL) was added and stirred for about 20 minutes. Impurities were removed by filtration, and after extraction with toluene (30 mL ⁇ 2), the combined organic layer was washed with water (20 mL ⁇ 2) and concentrated.
• p-toluenesulfonic acid monohydrate (0.15 g , 0.80 mmol
• Aqueous sodium hydroxide 1.0 M, 37 mL
• Impurities were removed by filtration, and after extraction with toluene (30 mL ⁇ 2), the combined organic layer was washed with water (20 mL ⁇ 2) and concentrated.
• the resulting solid was suspended in heptane/ethyl acetate (2/1 (by volume), 90 mL), sonicated for about 30 minutes, filtered and dried to give the final product shown in Table 2.
• the product was obtained as a pale yellow-green solid (0.9 g).
• a photopolymerization initiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide
• an antioxidant bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid)
• ethylene Bis(oxyethylene) and a light stabilizer bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate
• a silane coupling agent ⁇ -methacrylic oxypropyltrimethoxysilane
• a plastic lens substrate (manufactured by HOYA under the trade name EYAS: center thickness 2.5 mm, diameter 75 mm, spherical lens power -4.00) is immersed in an aqueous sodium hydroxide solution having a concentration of 10% by mass (liquid temperature 60°C) for 5 minutes. By doing so, it was washed with alkali, further washed with pure water, and dried. After that, a water-based polyurethane resin liquid (polycarbonate polyol-based polyurethane emulsion, viscosity of 100 cPs, solid content concentration of 38% by mass) was applied to the convex surface of the plastic lens substrate in an environment of room temperature and relative humidity of 40 to 60%. Using a spin coater MS-B150, a primer layer having a thickness of 5.5 ⁇ m was formed by spin coating at a rotation speed of 1500 rpm for 1 minute and air drying for 15 minutes.
• EYAS center thickness 2.5 mm, diameter 75 mm, spherical
• ⁇ Deposition of photochromic layer> The photochromic composition prepared above is dropped on the primer layer, and using Mikasa's MS-B150, the rotation speed is changed in slope mode from 500 rpm to 1500 rpm over 1 minute, and further 5 times at 1500 rpm. It was applied by a spin coating method using a program to rotate for 1 second. After that, the photochromic composition coated 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 was cured to form a photochromic layer. The thickness of the formed photochromic layer was 45 ⁇ m. Thus, a photochromic article (spectacle lens) was produced.
• Luminous transmittance was obtained by the following method according to JIS T7333:2005.
• a xenon lamp was used as a light source and light passed through an aeromass filter was irradiated for 15 minutes toward the convex surface of each spectacle lens of Examples and Comparative Examples to color the photochromic layer.
• This irradiation light was applied so that the irradiance and the tolerance of the irradiance were the values shown in Table 1 as specified in JIS T7333:2005.
• the transmittance at the time of coloring was measured with a spectrophotometer manufactured by Otsuka Electronics.
• Table 2 shows the luminous transmittance T (%) obtained from the measurement results in the wavelength range of 380 nm to 780 nm. A smaller value of T (%) means that the photochromic compound is highly colored.
• the fading speed was evaluated by the following method.
• the transmittance (measurement wavelength: 550 nm) of each spectacle lens of Examples and Comparative Examples before light irradiation (uncolored state) was measured with a spectrophotometer manufactured by Otsuka Electronics. The transmittance measured here is called "initial transmittance".
• Each spectacle lens was irradiated with light for 15 minutes through an aeromass filter using a xenon lamp as a light source to color the photochromic layer. This irradiation light was applied so that the irradiance and the tolerance of the irradiance were the values shown in Table 2 as specified in JIS T7333:2005.
• the transmittance during this coloring was measured in the same manner as the initial transmittance.
• the transmittance measured here is called “coloring transmittance”.
• the time required for the transmittance to reach [(initial transmittance ⁇ transmittance when colored)/2] from the time when light irradiation was stopped was measured. This time is called “half-life time”. It can be said that the shorter the half-life time, the faster the fading speed. Table 2 shows the obtained half-life time.
• each spectacle lens of the example is a photochromic article that is highly densely colored in the visible region and exhibits a fast discoloration rate.
• R 1 and R 2 are bonded to each other to form a ring structure with the carbon atom at position 13 of the indeno-fused naphthopyran;
• R 3 to R 6 each independently represent a hydrogen atom or an electron-withdrawing group, one or more of R 3 to R 6 represents an electron-withdrawing group,
• R 8 and R 9 each independently represent a hydrogen atom or an electron donating group, at least one of R 8 and R 9 represents an electron donating group,
• R7 , R10 , A and A' each independently represent a hydrogen atom or a substituent.
• a and A′ each independently represent a phenyl group having a substituent at a substitution position para to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran, [ 1] The photochromic compound according to any one of [11].
• a and A′ are each independently a phenyl having an electron-donating group as a substituent at the substitution position para to the carbon atom bonded to the pyran ring of the indeno-fused naphthopyran
• a photochromic article comprising a cured product obtained by curing the photochromic composition according to [17].
• the photochromic article according to [18] which has a substrate and a photochromic layer that is the cured product.
• the photochromic article according to [18] or [19] which is a spectacle lens.
• the photochromic article according to [18] or [19] which is a lens for goggles.
• the photochromic article according to [18] or [19] which is a visor portion of a sun visor.
• Spectacles comprising the spectacle lens according to [20].
• One aspect of the present invention is useful in technical fields such as eyeglasses, goggles, sun visors, and helmets.

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