Patent Application
20230340318
The present disclosure relates to a photochromic compound, a photochromic composition, a photochromic article and eyeglasses.
A photochromic compound is a compound having a property of coloring under emission of light in a wavelength range having photoresponsivity and fading without light emission (photochromic properties). For example, WO 2000/15631, which is expressly incorporated by reference, in its entirety, discloses a naphthopyran compound having photochromic properties.
Examples of methods of imparting photochromic properties to optical 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. Examples of properties desired for optical articles to which photochromic properties are imparted in this manner include exhibiting a high coloring concentration in a visible range (a wavelength of 380 to 780 nm) during coloring and exhibiting a fast fade rate after coloring by light emission.
One aspect of the present disclosure provides for a photochromic article with a high coloring concentration in a visible range during coloring and a high fade rate.
One aspect of the present disclosure relates to a photochromic compound represented by the following General Formula 1.
In addition, one aspect of the present disclosure relates to a photochromic article containing one or more compounds represented by the following General Formula 1.
In addition, one aspect of the present disclosure relates to a photochromic composition contained one or more compounds represented by the following General Formula 1.
In General Formula 1, R30 and R31 each independently represent a linear or branched alkyl group having 2 or more carbon atoms, which is unsubstituted or has one or more substituents; a cyclic alkyl group having 3 or more carbon atoms which is unsubstituted or has one or more substituents; or represents a group represented by - (R100) nR101 which is unsubstituted or has one or more substituents, R100 represents an alkyleneoxy group, R101 represents an alkyl group, n represents an integer of 1 or more, a total number of carbon atoms of n alkyleneoxy groups represented by R100 and alkyl groups represented by R101 is 2 or more, R32 to R35 each independently represent a hydrogen atom or a substituent other than an electron-attracting group, and R36, R37, B7 and B8 each independently represent a hydrogen atom or a substituent.
The compound represented by General Formula 1 can be colored with a high concentration in a visible range during coloring by light emission and can exhibit a fast fade rate. The inventors speculate that having R31 and R32 in General Formula 1 may contribute to these points. However, the present disclosure is not limited by the speculation described in this specification. According to the compound represented by General Formula 1, it is possible to provide a photochromic article with a high coloring concentration in a visible range during coloring and a high fade rate.
According to one aspect of the present disclosure, it is possible to provide a photochromic article with a high coloring concentration in a visible range during coloring and a high fade rate.
As an example, a photochromic compound undergoes structural conversion into a colored component through an excited state when it receives light such as sunlight. The structure after structural conversion via light emission may be called a “colored component”. On the other hand, the structure before light emission may be called a “colorless component”. However, regarding the colorless component, “colorless” is not limited to being completely colorless, and includes a case in which the color is lighter than that of the colored component. The structure of General Formula 1 and the structures of general formulae of various photochromic compounds to be described below are structures of respective colorless components.
In the present disclosure and this specification, the term “photochromic article” refers to an article containing a photochromic compound. The photochromic article according to one aspect of the present disclosure contains at least one or more compounds represented by General Formula 1 as a photochromic compound. The photochromic compound can be incorporated into a substrate of a photochromic article and/or can be incorporated into a photochromic layer in a photochromic article having a substrate and a photochromic layer. The term “photochromic layer” is a layer containing a photochromic compound.
In the present disclosure and this specification, the term “photochromic composition” refers to a composition containing a photochromic compound. The photochromic composition according to one aspect of the present disclosure contains at least one or more compounds represented by General Formula 1 as a photochromic compound, and can be used for producing a photochromic article according to one aspect of the present disclosure.
In the present disclosure and this specification, substituents in various general formulae whose details will be described below, and substituents when respective groups to be described below have substituents may each independently
As an example of the substituent in which the above Rm is additionally substituted with one or more of the same or different Rm’s, a structure in which the terminal carbon atom of an alkoxy group is additionally substituted with an alkoxy group, and the terminal carbon atom of the alkoxy group is additionally substituted with an alkoxy group may be exemplified. In addition, as another example of the substituent in which the above Rm is additionally substituted with one or more of the same or different Rm’s, a structure in which two or more positions among five substitutable positions of a phenyl group are substituted with the same or different Rm’s may be exemplified. However, the present disclosure is not limited to such examples.
In the present disclosure and this specification, unless otherwise specified, the terms “number of carbon atoms” and “number of constituent atoms” refer to the numbers including the number of carbon atoms or the number of atoms of the substituent with respect to a group having a substituent. In addition, in the present disclosure and this specification, “unsubstituted or having one or more substituents” is synonymous with “substituted or unsubstituted”.
In addition, in the present disclosure and this specification, substituents in various general formulae whose details will be described below, and substituents when respective groups to be described below have substituents may each independently a solubilizing group. In the present disclosure and this specification, the “solubilizing group” refers to a substituent that can contribute to increasing the compatibility with any liquid or a specific liquid. Examples of solubilizing groups include alkyl groups containing a linear, branched or cyclic structure having 4 to 50 carbon atoms, linear, branched or cyclic alkoxy groups having 4 to 50 constituent atoms, linear, branched or cyclic silyl groups having 4 to 50 constituent atoms, those in which some of the above groups are substituted with a silicon atom, sulfur atom, nitrogen atom, phosphorus atom or the like, and those obtained by combining two or more of the above groups, and the solubilizing group may be a substituent that can contribute to promoting thermal motion of molecules of the compound according to inclusion of this substituent. A compound having a solubilizing group as a substituent can inhibit the distance between solute molecules from decreasing and prevent the solute from solidifying, and can lower the melting point and/or glass transition temperature of the solute and create a molecule aggregation state close to that of a liquid. Therefore, the solubilizing group can liquefy a solute or increase the solubility of the compound having this substituent in a liquid. In one aspect, the solubilizing group may be an n-butyl group, n-pentyl group, n-hexyl group, and n-octyl group which are a linear alkyl group, a tert-butyl group which is a branched alkyl group, or a cyclopentyl group and a cyclohexyl group which are a cyclic alkyl group.
The substituent may be a substituent selected from the group consisting of a methoxy group, ethoxy group, phenoxy group, methylsulfide group, ethylsulfide group, phenylsulfide group, trifluoromethyl group, phenyl group, naphthyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, phenothiazinyl group, phenoxazinyl group, phenazinyl group, acridinyl group, dimethylamino group, diphenylamino group, piperidino group, morpholino group, thiomorpholino group, cyano group and solubilizing group, and may be a substituent selected from the group consisting of a methoxy group, phenoxy group, methylsulfide group, phenylsulfide group, trifluoromethyl group, phenyl group, dimethylamino group, diphenylamino group, piperidino group, morpholino group, thiomorpholino group, cyano group and solubilizing group.
In the present disclosure and this specification, “electron-attracting group” refers to a substituent that attracts electrons from the side of atoms bonded more easily than hydrogen atoms. Electron-attracting groups can attract electrons as a result of substituent effects such as an inductive effect, a mesomeric effect (or a resonance effect). Specific examples of electron-attracting groups include halogen atoms (fluorine atom: —F, chlorine atom: —Cl, bromine atom: —Br, iodine atom: —I), trifluoromethyl group: —CF3, nitro group: —NO2, cyano group: —CN, formyl group: —CHO, acyl group: —COR (R is a substituent), alkoxycarbonyl group: —COOR, carboxy group: —COOH, substituted sulfonyl group: —SO2R (R is a substituent), and sulfo group: —SO3H. Examples of electron-attracting groups include a fluorine atom which is an electron-attracting group having high electronegativity and an electron-attracting group having a positive value for the substituent constant σp at the para position based on Hammett’s rule.
In the present disclosure and this specification, “electron-donating group” refers to a substituent that donates electrons to the side of atoms bonded more easily than hydrogen atoms. Electron-donating groups can be substituents that tend to donate electrons as a summation of an inductive effect, a mesomeric effect (or a resonance effect) and the like. Specific examples of electron-donating groups include hydroxy group: —OH, thiol group: —SH, alkoxy group: —OR (R is an alkyl group), alkylsulfide group: —SR (R is an alkyl group), arylsulfide group, acetyl group: —OCOCH3, amino group: —NH2, alkylamide group: —NHCOCH3, dialkylamino group: —N(R)2 (two R’s are the same or different alkyl groups), and methyl group. Examples of electron-donating groups include electron-donating groups having a negative value for the substituent constant σp at the para position based on Hammett’s rule.
Specific examples of the substituent constant σp at the para position based on Hammett’s rule (source: edited by Shu Iwamura, Ryoji Noyori, Takeshi Nakai, and Isao Kitagawa, Graduate School of Organic Chemistry (Part 1) (1988)) are shown below.
Hereinafter, compounds represented by General Formula 1 will be described in more detail.
In General Formula 1, R30 and R31 each independently represent a linear or branched alkyl group having 2 or more carbon atoms, which is unsubstituted or has one or more substituents; a cyclic alkyl group having 3 or more carbon atoms which is unsubstituted or has one or more substituents; or represents a group represented by - (R100) nR101 which is unsubstituted or has one or more substituents, R100 represents an alkyleneoxy group, R101 represents an alkyl group, n represents an integer of 1 or more, a total number of carbon atoms of n alkyleneoxy groups represented by R100 and alkyl groups represented by R101 is 2 or more.
In General Formula 1, R30 and R31 each independently represent a linear or branched alkyl group which is unsubstituted or has one or more substituents and has 2 or more carbon atoms (for example, 2 or more and 20 or less, and may be 2 or more and 10 or less); a cyclic alkyl group which is unsubstituted and has one or more substituents and has 3 or more carbon atoms (for example, 3 or more and 20 or less); or a group represented by - (R100) nR101 which is unsubstituted or has one or more substituents, R100 represents an alkyleneoxy group, R101 represents an alkyl group, n represents an integer of 1 or more, and a total number of carbon atoms of n alkyleneoxy groups represented by R100 and alkyl groups represented by R101 is 2 or more (for example, 2 or more and 50 or less). When the linear or branched alkyl group having 2 or more carbon atoms has a substituent, the number of carbon atoms of the alkyl group refers to the number of carbon atoms in a moiety containing no substituent. When the cyclic alkyl group having 3 or more carbon atoms has a substituent, the number of carbon atoms of the alkyl group refers to the number of carbon atoms in a moiety containing no substituent. When the group represented by “- (R100) nR101” has a substituent, a total number of carbon atoms of n alkyleneoxy groups represented by R100 and alkyl groups represented by R101 refers to the number of carbon atoms in a moiety containing no substituent.
R30 and R31 each independently may represent an ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group or t-butyl group. R30 and R31 both may represent an ethyl group.
In General Formula 1, R32 to R35 each independently represent a hydrogen atom or a substituent other than an electron-attracting group. Two or more substituents may be bonded to form a ring.
In one aspect, R32 to R35 all may represent a hydrogen atom. In another aspect, R32 to R35 may each independently represent a hydrogen atom, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkoxy group. For such aryl groups and alkoxy groups, the above description regarding the substituent Rm can be referred to. In one aspect, R32 to R35 may each independently represent a hydrogen atom, a substituted or unsubstituted phenyl group or a methoxy group.
In one aspect, in R32 to R35, R33 may represent a substituent other than an electron-attracting group, and R32, R34 and R35 may represent a hydrogen atom. In this case, R33 may be a substituted or unsubstituted aryl group or a substituted or unsubstituted alkoxy group, and may be, for example, a substituted or unsubstituted phenyl group or a methoxy group.
In General Formula 1, R36, R37, B7 and B8 each independently represent a hydrogen atom or a substituent.
In one aspect, R36 and R37 both may represent a hydrogen atom. In another aspect, R36 and R37 may each independently represent a hydrogen atom or an electron-donating group, and R36 may represent a hydrogen atom and R37 may represent an electron-donating group, and also R36 and R37 may represent the same or different electron-donating groups. The electron-donating group that may be represented by R36 and/or R37 may be an electron-donating group selected from the group consisting of a methoxy group, ethoxy group, phenoxy group, methylsulfide group, phenylsulfide group, dimethylamino group, pyrrolidino group, piperidino group, morpholino group and thiomorpholino group.
In General Formula 1, B7 and B8 each independently may represent a substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted benzofluorenyl group, substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted dibenzofuranyl group or substituted or unsubstituted dibenzothiophenyl group. B7 and B8 each independently may represent a substituted phenyl group. Such substituted phenyl groups may include one or more substituents selected from the group consisting of a methoxy group, methylsulfide group, amino group, dimethylamino group, piperidino group, morpholino group, thiomorpholino group, phenyl group, fluorine, chlorine, bromine, iodine, a trifluoromethyl group and a cyano group.
Examples of compounds represented by General Formula 1 include the following compounds. However, the present disclosure is not limited to the compounds exemplified below.
The compound represented by General Formula 1 and the photochromic compounds represented by various general formulae to be described below can be synthesized by a known method. For the synthesis method, for example, the following documents can be referred to. Japanese Patent No. 4884578, US 2006/0226402A1, US 2006/0228557A1, US 2008/0103301A1, US 2011/0108781A1, US 2011/0108781A1, U.S. Pat. No. 7527754, U.S. Pat. No. 7556751, WO 2001/60811A1, WO 2013/086248A1, WO 1996/014596A1 and WO 2001/019813A1.
One aspect of the present disclosure relates to a photochromic composition containing one or more photochromic compounds represented by General Formula 1.
In addition, one aspect of the present disclosure relates to a photochromic article containing one or more photochromic compounds represented by General Formula 1.
The photochromic composition and the photochromic article may contain only one photochromic compound represented by General Formula 1 or two or more (for example, two or more and four or less) thereof. In addition, examples of the photochromic compound that can be included in the photochromic composition and the photochromic article together with the photochromic compounds represented by General Formula 1 include compounds represented by the following General Formula A, compounds represented by the following General Formula B and compounds represented by the following General Formula C. Only one, two or three of compounds represented by the following General Formula A, compounds represented by the following General Formula B and compounds represented by the following General Formula C may be included.
In order to further improve the coloring concentration in a visible range during coloring, as a compound represented by General Formula 1 which may be combined with a compound represented by General Formula B and/or a compound represented by General Formula C, (a) a compound in which, in General Formula 1, R30 and R31 both represent an ethyl group, and R36 and R37 both represent a hydrogen atom may be exemplified.
In order to further improve the coloring concentration in a visible range during coloring, as a compound represented by General Formula 1 which may be combined with a compound represented by General Formula A, one or more compounds selected from the group consisting of (b) a compound in which, in General Formula 1, R30 and R31 both represent an ethyl group, and R36 and R37 each independently represent an electron-donating group, and (c) a compound in which, in General Formula 1, R30 and R31 both represent an ethyl group, one of R36 and R37 represents a hydrogen atom and the other represents an electron-donating group may be exemplified.
In the above (c), R36 may represent a hydrogen atom and R37 may represent an electron-donating group.
Hereinafter, among compounds represented by General Formula 1, the compound satisfying the above (a) is called “Compound 1-a”, the compound satisfying the above (b) is called “Compound 1-b”, and the compound satisfying the above (c) is called “Compound 1-c”. In addition, the compound represented by General Formula A is called “Compound A”, the compound represented by General Formula B is called “Compound B”, and the compound represented by General Formula C is called “Compound C”. Compound A and Compound 1-a are collectively referred to a “group A compound”, Compound B and Compound 1-b are collectively referred to a “group B compound”, and Compound C and Compound 1-c are collectively referred to a “group C compound”.
A photochromic article according to one aspect of the present disclosure and a photochromic composition according to one aspect of the present disclosure may contain one or more group A compounds, one or more group B compounds, and one or more group C compounds.
The group A compound contained in the photochromic article and the photochromic composition may be of only one type or two or more types (for example, two or more and four or less).
The group B compound contained in the photochromic article and the photochromic composition may be of only one type or two or more types (for example, two or more and four or less).
The group C compound contained in the photochromic article and the photochromic composition may be of only one type or two or more types (for example, two or more and four or less).
In the photochromic article and the photochromic composition, on a mass basis, a total content of the group B compound and the group C compound may be larger than the content of the group A compound. Based on a total content of 100 mass% of the group A compound, the group B compound and the group C compound, a total content of the group B compound and the group C compound may be more than 50 mass%, may be 60 mass% or more, may be 70 mass% or more, may be 80 mass% or more, and may be 90 mass% or more. Based on a total content (100 mass%) of the group A compound, the group B compound and the group C compound, a total content of the group B compound and the group C compound may be less than 100 mass%, 99 mass% or less, 98 mass% or less, 97 mass% or less, 96 mass% or less or 95 mass% or less.
Regarding the mixing ratio between the group B compound and the group C compound, based on a total content of 100 mass% of the group B compound and the group C compound, the content of the group B compound may be 1 mass% or more or 99 mass% or more and may be 25 mass% or less or 75 mass% or less. When the photochromic article and the photochromic composition contain two or more group B compounds, the content of the group B compounds is a total content thereof. The same applies to the contents of various components in the present disclosure and this specification.
The photochromic article and the photochromic composition based on a total amount of 100 mass% thereof may contain a total content of, for example, about 0.1 to 15.0 mass% of the group A compound, the group B compound and the group C compound. The photochromic article and the photochromic composition can contain, for example, about 0.1 to 15.0 mass% of the compound represented by General Formula 1 with respect to a total amount of 100 mass% thereof. However, the present disclosure is not limited to the above range.
Hereinafter, compounds represented by General Formula A, compounds represented by General Formula B and compounds represented by General Formula C will be described in more detail.
In General Formula A, R1 to R6, B1 and B2 each independently represent a hydrogen atom or a substituent.
R1 and R2 each independently may represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and may represent a methyl group, ethyl group, propyl group, butyl group, pentyl group or hexyl group. R1 and R2 each independently may represent a methyl group or ethyl group, and R1 and R2 both may represent a methyl group or both may represent an ethyl group.
B1 and B2 each independently may represent a substituted or unsubstituted phenyl group. When the phenyl group has a plurality of substituents, two or more of these substituents may be bonded to form a ring. Specific examples of the formed rings include rings included in exemplary compounds listed below. The substitution position of the substituent in the substituted phenyl group may be a position that is a para position with respect to a carbon atom to which B3 and B2 are bonded. Specific examples of substituents of substituted phenyl groups include a morpholino group, piperidino group, halogen atom, alkoxy group, and substituents included in exemplary compounds listed below such as the following substituents. In the present disclosure and this specification, “*” for a partial structure of a compound indicates a bonding position with an atom to which such a partial structure is bonded.
In General Formula A, R3 to R6 each independently represent a hydrogen atom or a substituent. In one aspect, R3 to R6 all may be hydrogen atoms. In another aspect, R3 to R6 each independently represent a hydrogen atom or an electron-attracting group, provided that one or more of R3 to R6 represent an electron-attracting group. The electron-attracting group may be a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group or a cyano group. The halogen atom may be a fluorine atom. The perfluoroalkyl group having 1 to 6 carbon atoms may be a trifluoromethyl group.
In one aspect, the compound represented by General Formula A may be the following compound.
A compound in which, among R3 to R6, only R4 is an electron-attracting group, and R3, R5 and R6 are a hydrogen atom.
A compound in which, among R3 to R6, R4 and R6 are the same or different electron-attracting groups, and R3 and R5 are a hydrogen atom.
A compound in which, among R3 to R6, R3 and R5 are the same or different electron-attracting groups, and R4 and R6 are a hydrogen atom.
Examples of compounds represented by General Formula A include the following compounds. However, the present disclosure is not limited to the compounds exemplified below.
[0066]
[0068]
[0074]
In General Formula B, R7 to R12, B3 and B4 each independently represent a hydrogen atom or a substituent.
R7 and R8 each independently may represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and may represent a methyl group, ethyl group, propyl group, butyl group, pentyl group or hexyl group. R7 and R8 each independently may represent a methyl group or ethyl group, and R7 and R8 both may represent a methyl group or both represent an ethyl group.
B3 and B4 each independently may represent a substituted or unsubstituted phenyl group. When the phenyl group has a plurality of substituents, two or more of these substituents may be bonded to form a ring. Specific examples of the formed rings include rings included in exemplary compounds listed below. The substitution position of the substituent in the substituted phenyl group may be a position that is a para position with respect to a carbon atom to which B3 and B4 are bonded. Specific examples of substituents of substituted phenyl groups include a morpholino group, piperidino group, halogen atom, alkoxy group, and substituents included in exemplary compounds listed below such as the following substituents.
R9 to R12 each independently represent a hydrogen atom or a substituent. In one aspect, R9 to R12 all may be hydrogen atoms. In another aspect, R10 may be an electron-attracting group, and R9, R11 and R12 all may be hydrogen atoms. In addition, in another aspect, R9 and R11 may each independently represent an electron-attracting group, and R10 and R12 may be hydrogen atoms. The electron-attracting group may be a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group or a cyano group. The halogen atom may be a fluorine atom. The perfluoroalkyl group having 1 to 6 carbon atoms may be a trifluoromethyl group.
In one aspect, R10 may be a substituted or unsubstituted phenyl group, and R10 may be a substituted or unsubstituted phenyl group and R9, R11 and R12 may be hydrogen atoms. Specific examples of such substituted phenyl groups include phenyl groups substituted with one or more halogen atoms and/or one or more cyano groups are, for example, phenyl groups substituted with halogen atoms (for example, fluorine atoms) at all five substitution positions of the phenyl group, and monosubstituted phenyl groups substituted with a cyano group at a position that is a para position with respect to a carbon atom to which R10 is bonded.
R13 and R14 each independently represent an electron-donating group. That is, R13 and R14 represent the same or different electron-donating groups. R13 and R14 each independently may represent an electron-donating group selected from the group consisting of a methoxy group, ethoxy group, phenoxy group, methylsulfide group, phenylsulfide group, dimethylamino group, pyrrolidino group, piperidino group, morpholino group and thiomorpholino group. Among these, for R13 and R14, R13 may be a morpholino group and R14 may be an alkoxy group (for example, a methoxy group), R13 may be a morpholino group and R14 may be a methylsulfide group (-S-CH3), R13 and R14 both may be an alkoxy group (for example, a methoxy group), and R13 and R14 both may be a methylsulfide group.
Examples of compounds represented by General Formula B include the following compounds. However, the present disclosure is not limited to the compounds exemplified below.
In General Formula C, R15 to R20, B5 and B6 each independently represent a hydrogen atom or a substituent,
one of R21 and R22 represents a hydrogen atom, and the other represents an electron-donating group.
In General Formula C, R15 and R16 each independently may represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and may represent a methyl group, ethyl group, propyl group, butyl group, pentyl group or hexyl group. R15 and E16 each independently may represent a methyl group or ethyl group, and R15 and R16 both may represent a methyl group or both may represent an ethyl group.
B8 and B6 each independently may represent a substituted or unsubstituted phenyl group. When the phenyl group has a plurality of substituents, two or more of these substituents may be bonded to form a ring. Specific examples of the formed rings include rings included in exemplary compounds listed below. The substitution position of the substituent in the substituted phenyl group may be a position that is a para position with respect to a carbon atom to which B5 and B6 are bonded. Specific examples of substituents of substituted phenyl groups a morpholino group, piperidino group, halogen atom, alkoxy group, and the following substituents.
R17 to R20 each independently represent a hydrogen atom or a substituent. In one aspect, R17 to R20 all may be hydrogen atoms. In another aspect, R18 may be an electron-attracting group and R17, R19 and R20 all may be hydrogen atoms. In addition, in another aspect, R17 and R19 may each independently represent an electron-attracting group, and R18 and R20 may be hydrogen atoms. The electron-attracting group may be a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group or a cyano group. The halogen atom may be a fluorine atom. The perfluoroalkyl group having 1 to 6 carbon atoms may be a trifluoromethyl group.
In one aspect, R18 may be a substituted or unsubstituted phenyl group, and R18 may be a substituted or unsubstituted phenyl group, and R17, R19 and R20 may be hydrogen atoms. Specific examples of such substituted phenyl groups include phenyl groups substituted with one or more halogen atoms and/or one or more cyano groups are, for example, phenyl groups substituted with halogen atoms (for example, fluorine atoms) at all five substitution positions of the phenyl group, and monosubstituted phenyl groups substituted with a cyano group at a position that is a para position with respect to a carbon atom to which R10 is bonded.
One of R21 and R22 represents a hydrogen atom, and the other represents an electron-donating group. R21 may be a hydrogen atom, and R22 may be an electron-donating group. The electron-donating group represented by R21 or R22 (for example, R22) may represent an electron-donating group selected from the group consisting of a methoxy group, ethoxy group, phenoxy group, methylsulfide group, phenylsulfide group, dimethylamino group, pyrrolidino group, piperidino group, morpholino group and thiomorpholino group.
Examples of compounds represented by General Formula C include the following compounds. However, the present disclosure is not limited to the compounds exemplified below.
The photochromic article can have at least a substrate. In one aspect, the photochromic compound can be included in the substrate of the photochromic article. The photochromic article can have a substrate and a photochromic layer, and the substrate and/or photochromic layer can contain one or more compounds represented by General Formula 1 and additionally contain one or more selected from the group consisting of compounds represented by General Formula A, compounds represented by General Formula B and compounds represented by General Formula C. In the substrate and the photochromic layer, in one aspect, the photochromic compound can be contained only in the substrate, in another aspect, the photochromic compound can be contained only in the photochromic layer, and in still another aspect, the photochromic compound can be contained in the substrate and the photochromic layer. In addition, the substrate and the photochromic layer can contain, as a photochromic compound, only the above compound or one or more other photochromic compounds. Examples of other photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaallylbisimidazoles, donor-acceptor Stenhouse adducts (DASA), salicylidene anilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, and stilbenes.
The photochromic article can contain a substrate selected according to the type of the photochromic article. Examples of substrates include spectacle lens substrates such as a plastic lens substrate and a glass lens substrate. The glass lens substrate can be, for example, a lens substrate made of inorganic glass. Examples of plastic lens substrates include styrene resins such as (meth)acrylic resins, allyl carbonate resins such as a polycarbonate resin, allyl resin, and diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, polyether resins, urethane resins obtained by reacting an isocyanate compound and a hydroxy compound such as diethylene glycol, thiourethane resins obtained by reacting an isocyanate compound and a polythiol compound, and a cured product obtained by curing a curable composition containing a (thio)epoxy compound having one or more disulfide bonds in the molecule (generally referred to as a transparent resin). As the lens substrate, an undyed substrate (colorless lens) may be used or a dyed substrate (dyed lens) may be used. The refractive index of the lens substrate may be, for example, about 1.50 to 1.75. However, the refractive index of the lens substrate is not limited to the above range, and may be within the above range or may be above or below outside the above range. Here, the refractive index refers to a refractive index for light having a wavelength of 500 nm. In addition, the lens substrate may be a lens having refractive power (so-called prescription lens) or a lens having no refractive power (so-called non-prescription lens) .
For example, the photochromic composition can be a polymerizable composition. In the present disclosure and this specification, the “polymerizable composition” is a composition containing one or more polymerizable compounds. A polymerizable composition containing at least one or more photochromic compounds and one or more polymerizable compounds can be molded by a known molding method to produce a cured product of such a polymerizable composition. 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 emission and/or a heat treatment. The polymerizable compound is a compound having a polymerizable group, and as the polymerization reaction of the polymerizable compound proceeds, the polymerizable composition can be cured to form a cured product. The polymerizable composition can further contain one or more additives (for example, a polymerization initiator).
The spectacle lens may include various lenses such as a single focus lens, a multifocal lens, and a progressive power lens. The type of the lens is determined by the surface shape of both sides of the lens substrate. In addition, the surface of the lens substrate may be a convex surface, a concave surface, or a flat surface. In a general lens substrate and spectacle lens, the object-side surface is a convex surface and the eyeball-side surface is a concave surface. However, the present disclosure is not limited thereto. The photochromic layer may be generally provided on the object-side surface of the lens substrate, or may be provided on the eyeball-side surface.
The photochromic layer can be a layer that is directly provided on the surface of the substrate or indirectly provided 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 and one or more polymerizable compounds. For example, when such a polymerizable composition is directly applied to the surface of the substrate or applied to the surface of the layer provided on the substrate, and a curing treatment is performed on the applied polymerizable composition, a photochromic layer can be formed as a cured layer containing one or more photochromic compounds. As the coating method, known coating methods such as a spin coating method, a dip coating method, a spray coating method, an inkjet method, a nozzle coating method, and a slit coating method can be used. The curing treatment can be light emission and/or a heat treatment. The polymerizable composition can further contain one or more additives (for example, a polymerization initiator) in addition to one or more polymerizable compounds. As the polymerization reaction of the polymerizable compound proceeds, the polymerizable composition can be cured to form a cured layer.
The thickness of the photochromic layer may be, for example, 5 µm or more, 10 µm or more or 20 µm or more, and may be, for example, 80 µm or less, 70 µm or less or 50 µm or less.
In the present disclosure and this specification, the term polymerizable compound refers to a compound having one or more polymerizable groups in one molecule, and the term “polymerizable group” refers to a reactive group that can undergo a polymerization reaction. Examples of polymerizable groups include an acryloyl group, methacryloyl group, vinyl group, vinyl ether group, epoxy group, thiol group, oxetane group, hydroxy group, carboxy group, amino group, and isocyanate group.
Examples of polymerizable compounds that can be used to form the above substrate and the above photochromic layer include the following compounds.
The episulfide compound is a compound having two or more episulfide groups in one molecule. The episulfide group is a polymerizable group that can undergo ring-opening polymerization. Specific examples of episulfide compounds include bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide, bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropylthio)methane, bis(2,3-epithiopropyl)disulfide, bis(2,3-epithiopropyldithio)methane, bis(2,3-epithiopropyldithio)ethane, bis(6,7-epithio-3,4-dithiaheptyl)sulfide, bis(6,7-epithio-3,4-dithiaheptyl)disulfide, 1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl), 1,3-bis(2,3-epithiopropyldithiomethyl(benzene, 1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane, 1,2,3-tris(2,3-epithiopropyldithio)propane, 1,1,1,1-tetrakis(2,3-epithiopropyldithiomethyl)methane, 1,3-bis(2,3-epithiopropyldithio)-2-thiapropane, 1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane, 1,1,1-tris(2,3-epithiopropyldithio)methane, 1,1,1-tris(2,3-epithiopropyldithiomethylthio)methane, 1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane, 1,1,2,2-tetrakis(2,3-epithiopropyldithiomethylthio)ethane, 1,1,3,3-tetrakis(2,3-epithiopropyldithio)propane, 1,1,3,3-tetrakis(2,3-epithiopropyldithiomethylthio)propane, 2-[1,1-bis(2,3-epithiopropyldithio)methyl]-1,3-dithietane, and 2-[1,1-bis(2,3-epithiopropyldithiomethylthio)methyl]-1,3-dithietane.
The thietanyl compound is a thietane compound having two or more thietanyl groups in one molecule. The thietanyl group is a polymerizable group that can undergo ring-opening polymerization. Some thietanyl compounds have an episulfide group together with a plurality of thietanyl groups. Such compounds are listed as examples in the above episulfide compound. Other thietanyl compounds include metal-containing thietane compounds having metal atoms in the molecule and non-metallic thietane compounds which contain no metal.
Specific examples of non-metallic thietane compounds include bis(3-thietanyl)disulfide, bis(3-thietanyl)sulfide, bis(3-thietanyl)trisulfide, bis(3-thietanyl)tetrasulfide, 1,4-bis(3-thietanyl)-1,3,4-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-thietanylthio)methane, 1,2-bis(3-thietanylthio)ethane, 1,2,3-tris(3-thietanylthio)propane, 1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane, 1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiundecane, 2,5-bis(3-thietanylthiomethyl)-1,4-dithiane, 2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane, 2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, bis-thietanylsulfide, bis(thietanylthio)methane, 3-[<(thietanylthio)methylthio>methylthio]thietane, bis-thietanyl disulfide, bis-thietanyl trisulfide, bis-thietanyl tetrasulfide, bis-thietanyl pentasulfide, 1,4-bis(3-thietanyldithio)-2,3-dithibutane, 1,1,1-tris(3-thietanyldithio)methane, 1,1,1-tris(3-thietanyldithiomethylthio)methane, 1,1,2,2-tetrakis(3-thietanyldithio)ethane, and 1,1,2,2-tetrakis(3-thietanyldithiomethylthio)ethane.
Examples of metal-containing thietane compounds include those containing 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 13 atoms such as Al atoms, and Group 12 atoms such as Zn atoms, as metal atoms in the molecule. Specific examples thereof include alkylthio(thietanylthio)tin, bis(alkylthio)bis(thietanylthio)tin, alkylthio(alkylthio)bis(thietanylthio)tin, bis(thietanylthio)cyclic dithiotin compounds, and alkyl(thietanylthio)tin compounds.
Specific examples of alkylthio(thietanylthio)tin include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, and isopropylthiotris(thietanylthio)tin.
Specific examples of 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.
Specific examples of alkylthio(alkylthio)bis(thietanylthio)tin 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.
Specific examples of bis(thietanylthio)cyclic dithiotin compounds include bis(thietanylthio)dithiastannetane, bis(thietanylthio)dithiastannolane, bis(thietanylthio)dithiastannolane, and bis(thietanylthio)trithiastannocane.
Specific examples of alkyl(thietanylthio)tin compounds include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, tetrakis(thietanylthio)tin, tetrakis(thietanylthio)germanium, and tris(thietanylthio)bismuth.
The polyamine compound is a compound having two or more NH2 groups in one molecule, and can form a urea bond according to a reaction with a polyisocyanate and can form a thiourea bond according to a reaction with a polyisothiocyanate. Specific examples of polyamine compounds 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.
The epoxy compound is a compound having an epoxy group in the molecule. The epoxy group is a polymerizable group that can undergo ring-opening polymerization. The epoxy compounds are generally classified into aliphatic epoxy compounds, alicyclic epoxy compounds and aromatic epoxy compounds.
Specific examples of 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 triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, and tris(2-hydroxyethyl)isocyanurate triglycidyl ether.
Specific examples of alicyclic epoxy compounds include isophoronediol diglycidyl ether and bis-2,2-hydroxycyclohexylpropane diglycidyl ether.
Specific examples of aromatic epoxy compounds include resole syndiglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl orthophthalate, phenol novolac polyglycidyl ether, and cresol novolac polyglycidyl ether.
In addition, in addition to the above examples, an epoxy compound having a sulfur atom in the molecule together with an epoxy group can be used. Such epoxy compounds containing sulfur atoms include linear aliphatic compounds and cycloaliphatic compounds.
Specific examples of linear aliphatic epoxy compounds containing sulfur atoms include bis(2,3-epoxypropyl)sulfide, bis(2,3-epoxypropyl)disulfide, bis(2,3-epoxypropylthio)methane, 1,2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio)butane, 1,4-bis(2,3-epoxypropylthio)-2-methylbutane, 1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio)pentane, 1,5-bis(2,3-epoxypropylthio)-2-methylpentane, 1,5-bis(2,3-epoxypropylthio)-3-thiapentane, 1,6-bis(2,3-epoxypropylthio)hexane, 1,6-bis(2,3-epoxypropylthio)-2-methylhexane, 3,8-bis(2,3-epoxypropylthio)-3,6-dithia octane, 1,2,3-tris(2,3-epoxypropylthio)propane, 2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane, and 2,2-bis(2,3-epoxypropylthiomethyl)-1-(2,3-epoxypropylthio)butane.
Specific examples of cycloaliphatic epoxy compounds containing sulfur atoms 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 compound having a radically polymerizable group has a polymerizable group that can undergo radical polymerization. Examples of radically polymerizable groups include an acryloyl group, methacryloyl group, allyl group, and vinyl group.
In the following, a compound having a polymerizable group selected from the group consisting of acryloyl groups and methacryloyl groups will be referred to as a “(meth)acrylate compound”. Specific examples of (meth)acrylate compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol bisglycidyl(meth)acrylate), bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, bisphenol F di(meth)acrylate, 1,1-bis(4-(meth)acryloxyethoxyphenyl)methane, 1,1-bis(4-(meth)acryloxydiethoxyphenyl)methane, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, methylthio(meth)acrylate, phenylthio(meth)acrylate, benzylthio(meth)acrylate, xylylene dithiol di(meth)acrylate, mercaptoethylsulfide di(meth)acrylate, and difunctional urethane (meth)acrylate.
Specific examples of compounds having an allyl group (allyl compound) include allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxy polyethylene glycol allyl ether, polyethylene glycol allyl ether, methoxy polyethylene glycol-polypropylene glycol allyl ether, butoxy polyethylene glycol-polypropylene glycol allyl ether, methacryloyloxy polyethylene glycol-polypropylene glycol allyl ether, phenoxy polyethylene glycol allyl ether, and methacryloyloxy polyethylene glycol allyl ether.
Examples of compounds having a vinyl group (vinyl compound) include α-methylstyrene, α-methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobi (m-dioxane).
The photochromic article can include one or more layers known as functional layers of the photochromic article such as a protective layer for improving the durability of the photochromic article, an antireflection layer, a water-repellent or hydrophilic antifouling layer, a defogging layer, and a primer layer for improving adhesion between layers at any position.
The photochromic article can be an optical article. One form of the optical article is a spectacle lens. Such a spectacle lens can also be called a photochromic lens or a photochromic spectacle lens. In addition, as one form of the optical article, a goggle lens, a visor (cap) part of a sun visor, a shield member of a helmet and the like may be exemplified. The photochromic composition which is a polymerizable composition is applied to the substrate for these optical articles, a curing treatment is performed on the applied composition, a photochromic layer is formed, and thereby an optical article having an anti-glare function can be obtained.
One aspect of the present disclosure relates to eyeglasses having a spectacle lens that is one form of the photochromic article. Details of the spectacle lens included in the eyeglasses are as described above. By providing such a spectacle lens, for example, the eyeglasses can exhibit an anti-glare effect like sunglasses when the photochromic compound is colored upon receiving sunlight outdoors, and the photochromic compound can fade upon returning indoors, and thus the transmittance can be recovered. For the eyeglasses, a known technique can be applied to the configuration of the frame or the like.
Hereinafter, the present disclosure will be described in more detail with reference to examples. However, the present disclosure is not limited to embodiments shown in examples.
In the following, the molecular structure was identified using a nuclear magnetic resonance device (NMR). Proton NMR of ECS-400 (commercially available from JEOL Ltd.) was used as NMR. As a measurement solvent, deuterated chloroform was mainly used, and heavy dimethylsulfoxide, heavy acetone, heavy acetonitrile, heavy benzene, heavy methanol, heavy pyridine or the like was appropriately used only when it was poorly soluble in deuterated chloroform.
The purity was analyzed using high-performance liquid chromatography (HPLC). LC-2040C (commercially available from Shimadzu Corporation) was used as HPLC. YMC-Triart C18 was used for the column, and the measurement temperature was set to 40° C. For the mobile phase, a mixed solvent containing water containing 0.1% of trifluoroacetic acid and acetonitrile was used and the flow rate was 0.4 mL/min.
For mass spectrometry, a device including SQD2 was used as a mass spectrometry unit in ACQUITY UPLC H-Class system (UPLC) (commercially available from Nihon Waters K.K.). ACQUITY UPLC BEH C18 was used as the column, and the measurement temperature was set to 40° C. For the mobile phase, a mixed solvent containing water to which formic acid was added and acetonitrile was used, a concentration gradient was applied and the flow rate was set to 0.61 mL/min for flowing. An electrospray ionization (ESI) method was used for ionization.
CHN (carbonhydrogennitrogen) elemental analysis was performed by a combustion method.
From the reaction product shown in Table 1, a product shown in Table 1 was obtained by the following method.
Under an argon atmosphere, p-toluenesulfonic acid monohydrate (0.15 g, 0.80 mmol) was added to a toluene solution (36 mL) containing Reaction Product 1 (1.4 g, 4 mmol) and Reaction Product 2 (2.1 g, 8 mmol) shown in Table 1, and the mixture was stirred at room temperature overnight. A sodium hydroxide aqueous solution (1.0 M, 37 mL) was added thereto and the mixture was stirred for about 20 minutes. Impurities were removed by filtration, extraction with toluene (30 mL×2) was performed, and the combined organic layer was then washed with water (20 mL×2) and concentrated. The obtained residue was purified through column chromatography (SiO2: 200 g, heptane/chloroform (volume basis)=70/30 to 60/40) (1.2 g, brown solid). The obtained solid was suspended in heptane/ethyl acetate (2/1 (volume basis), 90 mL), subjected to an ultrasonic treatment for about 30 minutes, and filtered and dried, and thereby, as the final product, a product shown in Table 1 was obtained as a light yellow-green solid (0.9 g).
The obtained products were analyzed by the following method.
The structure was identified by a nuclear magnetic resonance device (NMR).
The purity was analyzed by HPLC and was 98% in terms of area ratio. s a result of mass spectrometry, the measured value was 598.8 (M+, a relative intensity of 100) for the calculated value of the exact mass of 598.272.
As a result of CHN elemental analysis by a combustion method, C: 80.0%, H: 6.6%, N: 0% for the calculated values C: 80.2%, H: 6.4%, and N: 0%.
It was confirmed based on the above analysis results that a product shown in Table 1 as a desired compound was produced comprehensively.
Products shown in Table 1 were obtained by the same operation except that reaction products shown in Table 1 were used as Reaction Product 1 and Reaction Product 2 used to synthesize the compound represented by General Formula 1. The obtained products were analyzed by the method described above. The analysis results are shown in Table 1.
Compounds of Example 3 and comparative examples were dissolved in chloroform containing no stabilizer to prepare a chloroform solution containing the compound.
A 1 cm square quartz spectroscopic cell containing the prepared solution was covered, and ultraviolet rays were emitted using UV-LED (commercially available from Hamamatsu Photonics K.K.) (a combination of LIGHTNINGCURE LC-L1V5 and L14310-120, an output of 70%) as an ultraviolet light source for 15 seconds. The solution was stirred with a small stirrer during UV emission. Within 10 seconds after UV emission was completed, the absorbance was measured using a UV-visible spectrophotometer (UV-1900i, commercially available from Shimadzu Corporation, a measurement wavelength of 700 to 400 nm, wavelength increments of 2 nm, survey mode). The absorbance was measured at room temperature (23 to 28° C.). Here, the concentration of the solution was adjusted so that the absorbance at the first absorption wavelength (the peak of the absorption intensity observed at the longest wavelength) was 0.95 to 1.05. In addition, the absorbance was measured every 10 seconds, and the attenuation of the absorbance was measured. Normalization was performed so that the peak of the first absorption wavelength in the first absorbance measurement became 1, the attenuation of the absorbance was then measured, data of fading for an initial 100 seconds (11 absorbance measurements) from the change in absorbance over time was analyzed with a first - order reaction model, and thus the reaction rate constant was obtained. If [A0] is the initial concentration of the colored component, that is, the normalized absorbance value of 1, [A] is the concentration of the colored component after a certain time, that is, the normalized absorbance value, t is time (seconds), and k is a rate constant, the first - order reaction can be expressed as in the following formula. This formula is called an integral rate formula.
As an example,
Based on the results shown in
The same measurement was performed for Examples 1, 2, and 4 to 11. It was confirmed that compounds of all examples exhibited photochromic properties of structural transition to a molecular structure with strong absorption in a visible range upon irradiation with ultraviolet rays and exhibited a fast fade rate as in Example 3.
Table 1 (Table 1-1 to Table 1-3) shows the reaction rate constants obtained for Examples 1 to 11 and comparative examples.
indicates text missing or illegible when filed
Compounds 1 to 16 shown below were synthesized by the above synthesis method or with reference to the documents shown above regarding the compound synthesis method. Compounds 1 to 8 were compounds represented by General Formula 1. Compound 9 was a compound represented by General Formula A, Compound 13 was a compound represented by General Formula C, and Compounds 10 to 12 and 14 to 16 were compounds represented by General Formula B. Compounds 9 to 16 were identified in the same method as described in the above reference publication, and it was confirmed that the compounds were synthesized.
In a plastic container, with respect to a total amount of 100 parts by mass of (meth)acrylates, 68 parts by mass of polyethylene glycol diacrylate, 12 parts by mass of trimethylolpropane trimethacrylate, and 20 parts by mass of neopentyl glycol dimethacrylate were mixed to prepare a (meth)acrylate mixture. 2.5 parts by mass of a photochromic compound was mixed with respect to 100 parts by mass of the (meth)acrylate mixture. For a composition containing a plurality of photochromic compounds, Table 2 (Table 2-1 and Table 2-2) shows the mass ratio of respective photochromic compounds based on a total amount of 10 of the photochromic compounds. In addition, a photopolymerization initiator (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), an antioxidant [bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid)] [ethylene bis (oxyethylene) and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) were mixed and sufficiently stirred and a silane coupling agent (γ-methacryloxypropyltrimethoxysilane) was then added dropwise with stirring. Then, defoaming was performed using an automatic revolution type stirring and defoaming device.
A photochromic composition was prepared by the above method.
The comparative compound used in Comparative Example 3 was the following compound.
A plastic lens substrate (commercially available from HOYA, product name EYAS: a center thickness of 2.5 mm, a diameter of 75 mm, and a spherical lens power of -4.00) was immersed in a sodium hydroxide aqueous solution having a concentration of 10 mass% (a liquid temperature of 60° C.) for 5 minutes, washed with an alkali and additionally washed with pure water and dried. Then, a water-based polyurethane resin liquid (polycarbonate polyol-based polyurethane emulsion, a viscosity of 100 cPs, and a solid content concentration of 38 mass%) was applied to the convex surface of the plastic lens substrate in an environment of room temperature and a relative humidity of 40 to 60% using a spin coater MS-B150 (commercially available from Mikasa Corporation) at a rotational speed of 1,500 rpm for 1 minute according to a spin coating method and then dried naturally for 15 minutes, and thereby a primer layer having a thickness of 5.5 µm was formed.
The photochromic composition prepared above was added dropwise to the primer layer, and applied by a spin coating method using a program in which the rotational speed was changed in a slope mode from a rotational speed of 500 rpm to 1,500 rpm over 1 minute, and rotation was additionally performed at 1,500 rpm for 5 seconds using MS-B150 (commercially available from Mikasa Corporation). Then, ultraviolet rays (with a dominant wavelength of 405 nm) were emitted to the photochromic composition applied on the primer layer formed on the plastic lens substrate in a nitrogen atmosphere (with an oxygen concentration of 500 ppm or less) for 40 seconds, and the composition was cured to form a photochromic layer. The thickness of the formed photochromic layer was 45 µm.
Accordingly, a photochromic article (spectacle lens) was produced.
The luminous reflectance was obtained by the following method according to JIS T 7333: 2005.
Light was emitted to the convex surface of each spectacle lens of examples and comparative examples using a xenon lamp as a light source through an air mass filter for 15 minutes, and the photochromic layer was colored. Light emission was performed so that the irradiance and irradiance tolerance were values shown in Table 2 as specified in JIS T 7333: 2005. The transmittance during the coloring was measured with a spectrophotometer (commercially available from Otsuka Electronics Co., Ltd.). Table 3 shows the luminous transmittance T(%) obtained from the measurement results in a wavelength range of 380 nm to 780 nm. A smaller value of T(%) means that the photochromic compound is colored at a higher concentration.
The fade rate was evaluated by the following method.
The transmittance (measurement wavelength: 550 nm) of each spectacle lens of the examples and comparative example before light emission (uncolored state) was measured with a spectrophotometer (commercially available from Otsuka Electronics Co., Ltd.). The transmittance measured here is called an “initial transmittance”.
Light was emitted to each spectacle lens using a xenon lamp as a light source through an air mass filter for 15 minutes, and the photochromic layer was colored. Light emission was performed sot that the irradiance and irradiance tolerance were values shown in Table 1 as specified in JIS T 7333: 2005. The transmittance during the coloring was measured in the same manner as the initial transmittance. The transmittance measured here is called a “transmittance during coloring”.
Then, the time required for the transmittance to reach [(initial transmittance-transmittance during coloring)/2] from the time when light emission was stopped was measured. This time is called a “half-life time”. It can be said that the shorter the half-life time, the higher the fade rate. Table 3 shows the obtained half-life time.
Based on the results shown in Table 3, it was confirmed that each spectacle lens of the examples was a photochromic article that was colored at a high concentration in a visible range and exhibited a fast fade rate.
Finally, the above aspects are summarized.
According to one aspect, there is provided a photochromic compound represented by General Formula 1.
In one aspect, in General Formula 1, R36 and R37 both may represent a hydrogen atom.
In one aspect, in General Formula 1, R36 and R37 may each independently represent an electron-donating group.
In one aspect, the compound represented by General Formula 1 may be a compound in which R36 represents a hydrogen atom, and R37 represents an electron-donating group.
In one aspect, the electron-donating group may be an electron-donating group selected from the group consisting of a methoxy group, ethoxy group, phenoxy group, methylsulfide group, phenylsulfide group, dimethylamino group, pyrrolidino group, piperidino group, morpholino group and thiomorpholino group.
In one aspect, in General Formula 1, R30 and R31 may each independently represent an ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group or t-butyl group.
In one aspect, in General Formula 1, R30 and R31 both may represent an ethyl group.
In one aspect, in General Formula 1, B7 and B3 may each independently represent a substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted benzofluorenyl group, substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted dibenzofuranyl group or substituted or unsubstituted dibenzothiophenyl group.
In one aspect, in General Formula 1, B7 and B8 may each independently represent a substituted phenyl group. Such substituted phenyl groups may include one or more substituents selected from the group consisting of a methoxy group, methylsulfide group, amino group, dimethylamino group, piperidino group, morpholino group, thiomorpholino group, phenyl group, fluorine, chlorine, bromine, iodine, a trifluoromethyl group and a cyano group.
In one aspect, R32 to R35 all may represent a hydrogen atom.
In one aspect, R32 to R35 may each independently represent a hydrogen atom, a phenyl group or a methoxy group.
According to one aspect, there is provided a photochromic composition containing one or more photochromic compounds represented by General Formula 1.
In one aspect, the photochromic composition may be a photochromic composition containing, as photochromic compounds represented by General Formula 1, one or more compounds in which, in General Formula 1, R30 and R31 both represent an ethyl group, and R36 and R37 both represent a hydrogen atom, and one or more photochromic compounds selected from the group consisting of photochromic compounds represented by General Formula B and photochromic compounds represented by General Formula C.
In one aspect, the photochromic composition may be a photochromic composition containing, as photochromic compounds represented by General Formula 1, one or more compounds in which, in General Formula 1, R30 and R31 both represent an ethyl group, and R36 and R37 each independently represent an electron-donating group, and one or more photochromic compounds represented by General Formula A.
In one aspect, the photochromic composition may be a photochromic composition containing, as photochromic compounds represented by General Formula 1, one or more compounds in which, in General Formula 1, R30 and R31 both represent an ethyl group, one of R36 and R37 represents a hydrogen atom and the other represents an electron-donating group, and one or more photochromic compounds represented by General Formula A.
In one aspect, the photochromic composition may further include a polymerizable compound.
According to one aspect, there is provided a photochromic article including a cured product obtained by curing the photochromic composition.
In one aspect, the photochromic article may include a substrate and a photochromic layer which is the cured product.
In one aspect, the photochromic article may be a spectacle lens.
In one aspect, the photochromic article may be a goggle lens.
In one aspect, the photochromic article may be a visor part of a sun visor.
In one aspect, the photochromic article may be a shield member of a helmet.
According to one aspect, there is provided eyeglasses including the spectacle lens.
Two or more of various aspects and various forms described in this specification can be combined in arbitrary combinations.
The embodiments disclosed herein are only examples in all respects and should not be considered as restrictive. The scope of the present disclosure is not limited to the above description, but is defined by the scope of claims, and is intended to encompass equivalents to the scope of claims and all modifications within the scope of the claims.
One aspect of the present disclosure is beneficial in the technical fields of eyeglasses, goggles, sun visors, helmets and the like.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-215158 | Dec 2020 | JP | national |
| 2020-215159 | Dec 2020 | JP | national |
| 2021-018610 | Feb 2021 | JP | national |
This application is a Continuation of PCT International Application No. PCT/JP2021/048400 filed on Dec. 24, 2021, which was published under PCT Article 21(2) in Japanese and claims priority under 35 U.S.C. §119(a) to Japanese Patent Application No. 2020-215158 filed on Dec. 24, 2020, Japanese Patent Application No.2020-215159 filed on Dec. 24, 2020, and Japanese Patent Application No.2021-018610 filed on Feb. 8, 2021. Each of the above applications is hereby expressly incorporated by reference, in its entirety, into the present application.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2021/048400 | Dec 2021 | WO |
| Child | 18122935 | US |
