CN116745383A

CN116745383A - Photochromic composition, photochromic article and glasses

Info

Publication number: CN116745383A
Application number: CN202180086095.1A
Authority: CN
Inventors: 川上宏典; 小林敬; 松江葵; 岛田拓哉; 山下照夫
Original assignee: Hoya Lens Thailand Ltd
Current assignee: Hoya Lens Thailand Ltd
Priority date: 2020-12-24
Filing date: 2021-12-24
Publication date: 2023-09-12
Also published as: CN116783174A

Abstract

The present invention provides a photochromic composition comprising, in a given combination, one or more photochromic compounds represented by formula 1, and one or more photochromic compounds selected from the group consisting of photochromic compounds represented by formula A, photochromic compounds represented by formula B, and photochromic compounds represented by formula C. In the general formula 1, R ³⁰ R is R ³¹ All represent ethyl, R ³² ～R ³⁵ Each independently represents a hydrogen atom or an electron withdrawing group, wherein R ³² ～R ³⁵ More than one of them represents an electron withdrawing group, R ³⁶ 、R ³⁷ 、B ⁷ B (B) ⁸ Each independently represents a hydrogen atom or a substituent. In the general formula A, R ¹ ～R ⁶ 、B ¹ B (B) ² Each independently represents a hydrogen atom or a substituent. In the general formula B, R ⁷ ～R ¹² 、B ³ B (B) ⁴ Each independently represents a hydrogen atom or a substituent, R ¹³ R is R ¹⁴ Each independently represents an electron donating group. In the general formula C, R ¹⁵ ～R ²⁰ 、B ⁵ B (B) ⁶ Each independently represents a hydrogen atom or a substituent, R ²¹ R is R ²² One of them represents a hydrogen atom and the other represents an electron donating group.

Description

Photochromic composition, photochromic article and glasses

Technical Field

The present invention relates to a photochromic composition, a photochromic article and glasses.

Background

Photochromic compounds are compounds having the following properties: coloring (coloring) under irradiation of light having a wavelength range of photoreactivity, and fading (photochromic) under no irradiation. For example, patent document 1 discloses naphthopyrans having photochromic properties.

Prior art literature

Patent literature

Patent document 1: WO2000/15631

Disclosure of Invention

Problems to be solved by the invention

Examples of the method for imparting photochromic properties to an optical article such as an ophthalmic lens include a method in which a base material is made to contain a photochromic compound and a method in which a layer containing a photochromic compound is formed. The desired properties of the optical article to which photochromic properties are imparted in this way include a high coloring density in the visible light region (wavelength 380 to 780 nm).

An object of one embodiment of the present invention is to provide a photochromic article having a high coloring concentration when coloring in the visible light range.

Means for solving the problems

One embodiment of the present invention relates to a photochromic article comprising a photochromic compound represented by the following general formula 1 and one or more selected from a photochromic compound represented by the following general formula a, a photochromic compound represented by the following general formula B, and a photochromic compound represented by the following general formula C, in any combination of the following (a) to (g).

The present invention also relates to a photochromic composition comprising, in any combination of the following (a) to (g), a photochromic compound represented by the following general formula 1, and at least one selected from the group consisting of a photochromic compound represented by the following general formula A, a photochromic compound represented by the following general formula B, and a photochromic compound represented by the following general formula C,

[ chemical formula 1]

(general formula 1)

In the general formula 1, R ³⁰ R is R ³¹ All represent ethyl, R ³² ～R ³⁵ Each independently represents a hydrogen atom or an electron withdrawing group, wherein R ³² ～R ³⁵ More than one of them represents an electron withdrawing group, R ³⁶ 、R ³⁷ 、B ⁷ B (B) ⁸ Each independently represents a hydrogen atom or a substituent.

[ chemical formula 2]

(general formula A)

In the general formula A, R ¹ ～R ⁶ 、B ¹ B (B) ² Each independently represents a hydrogen atom or a substituent.

[ chemical formula 3]

(general formula B)

In the general formula B, R ⁷ ～R ¹² 、B ³ B (B) ⁴ Each independently represents a hydrogen atom or a substituent, R ¹³ R is R ¹⁴ Each independently represents an electron donating group.

[ chemical formula 4]

(general formula C)

In the general formula C, R ¹⁵ ～R ²⁰ 、B ⁵ B (B) ⁶ Each independently represents a hydrogen atom or a substituent, R ²¹ R is R ²² One of them represents a hydrogen atom and the other represents an electron donating group.

(a) Comprises one or more photochromic compounds selected from the photochromic compounds represented by the general formula B and the photochromic compounds represented by the general formula C, and one or more R ³⁰ R is R ³¹ All represent ethyl, R ³⁶ R is R ³⁷ All represent a hydrogen atom, R ³³ The compound representing an electron withdrawing group is used as the photochromic compound represented by the general formula 1.

(b) Comprises one or more photochromic compounds selected from the photochromic compounds represented by the general formula B and the photochromic compounds represented by the general formula C, and one or more R ³⁰ R is R ³¹ All represent ethyl, R ³⁶ R is R ³⁷ All represent a hydrogen atom, R ³² R is R ³⁴ The compound each independently representing an electron withdrawing group is used as the photochromic compound represented by formula 1.

(c) Comprises an orderThe above is selected from photochromic compounds represented by the general formula B and photochromic compounds represented by the general formula C, and contains more than one R ³⁰ R is R ³¹ All represent ethyl, R ³³ R is R ³⁷ The compound each independently representing an electron withdrawing group is used as the photochromic compound represented by formula 1.

(d) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl, R ³³ Represents an electron withdrawing group, R ³⁷ The compound representing an electron donating group is used as the photochromic compound represented by the general formula 1.

(e) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl and R ³² R is R ³⁴ Each independently represents an electron withdrawing group, R ³⁷ The compound representing an electron donating group is used as the photochromic compound represented by the general formula 1.

(f) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl, R ³³ Represents an electron withdrawing group, R ³⁶ R is R ³⁷ The compound each independently representing an electron donating group is used as the photochromic compound represented by formula 1.

(g) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl, R ³² R is R ³⁴ Each independently represents an electron withdrawing group, R ³⁶ R is R ³⁷ The compound each independently representing an electron donating group is used as the photochromic compound represented by formula 1.

The present inventors have repeatedly conducted intensive studies and have newly found the following results: by combining a plurality of photochromic compounds in accordance with the combination of (a) to (g) above, a photochromic article capable of being colored at a high concentration in the visible light region can be provided. It is assumed that this is because the absorption peak position and/or peak intensity of the plurality of compounds to be combined are different in the visible light region, and therefore, by combining these compounds, it is possible to color at a high concentration in a wide wavelength region. However, the present invention is not limited to the estimation described in the present specification. In addition, it was also ascertained that by combining the photochromic compounds in accordance with the above combinations, a photochromic article exhibiting a rapid fading rate can be provided.

ADVANTAGEOUS EFFECTS OF INVENTION

According to one embodiment of the present invention, a photochromic article having a high coloring density when colored in the visible light range can be provided.

Detailed Description

As an example, a photochromic compound is irradiated with light such as sunlight, and is converted into a colored body by the excitation state. The structure after the structure conversion by the illumination may be referred to as a "coloring body". In contrast, the structure before illumination may be referred to as "leuco". However, it should be noted that the term "colorless" is not limited to a completely colorless body, and includes a case where the color is lighter than that of a colored body. The general structures of the various photochromic compounds in the present invention and the present specification are each colorless structures.

In the present invention and in the present description, "photochromic article" refers to an article comprising a photochromic compound. The photochromic article according to one embodiment of the present invention contains a plurality of photochromic compounds in accordance with the combination of (a) to (g) above. The photochromic compound may be included in a substrate of the photochromic article and/or may be included in a photochromic layer of the photochromic article having the substrate and the photochromic layer. "photochromic layer" refers to a layer comprising a photochromic compound.

In the present invention and in the present specification, "photochromic composition" means a composition comprising a photochromic compound. The photochromic composition according to one embodiment of the present invention contains a plurality of photochromic compounds according to the combination of (a) to (g), and can be used for manufacturing the photochromic article according to one embodiment of the present invention.

In the present invention and the present specification, the substituents in the various formulae described later and the cases where each group described later has a substituent are described in detailIn which case the substituents may each independently be substituents R ^m Or at R ^m Further substituted by more than one R, which may be identical or different ^m Is a substituent of (2), the substituent R ^m Selected from:

straight-chain or branched alkyl groups having 1 to 18 carbon atoms such as hydroxyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc., monocyclic or bicyclic or other polycyclic aliphatic alkyl groups having 5 to 18 carbon atoms such as cyclopentyl group, cyclohexyl group, etc., straight-chain or branched alkoxy groups having 1 to 24 carbon atoms such as methoxy group, ethoxy group, butoxy group, etc., non-aromatic cyclic substituent groups having 1 to 24 carbon atoms such as non-aromatic cyclic substituent groups, straight-chain or branched perfluoroalkyl groups having 1 to 18 carbon atoms such as trifluoromethyl group, straight-chain or branched perfluoroalkoxy groups such as trifluoromethoxy group, methylthio group, ethylthio group, butylthio group, etc., straight-chain or branched alkylthio groups having 1 to 24 carbon atoms such as alkylthio group, phenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyranyl group, perylene group, styryl group, fluorenyl group, etc., aryloxy groups such as phenoxy group, etc., arylthio groups, pyridyl group, furyl group, thienyl group, pyrrolyl group, benzothienyl group, indolyl group, dibenzofuranyl group, dibenzothienyl, diazolyl, triazolyl, quinolyl, phenothiazine, etc Heteroaryl groups such as oxazinyl, phenazinyl, thianthrene, and acridinyl, and amino groups (-NH) ₂ ) Monoalkylamino groups such as monomethylamino groups, dialkylamino groups such as dimethylamino groups, monoarylamino groups such as monoarylamino groups, diarylamino groups such as diphenylamino groups, cyclic amino groups such as piperidinyl groups, morpholinyl groups, thiomorpholinyl groups, tetrahydroquinolinyl groups, tetrahydroisoquinolinyl groups, ethynyl groups, mercapto groups, silyl groups, sulfonic acid groups, alkylsulfonyl groups, formyl groups, carboxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and other halogen atoms.

As described above at R ^m Further substituted by more than one R, which may be identical or different ^m Examples of the substituent(s) include an alkoxy group further substituted at the terminal carbon atom of the alkoxy group and a substituent at the terminal carbon atom of the alkoxy groupStructure with further alkoxy groups on the atoms. In addition, as described above, at R ^m Further substituted by more than one R, which may be identical or different ^m Another example of the substituent(s) of (C) may be mentioned a phenyl group wherein 2 or more of the 5 substitutable positions are substituted with the same or different R ^m Is a structure of (a). However, the present invention is not limited to such examples.

In the present invention and the present specification, unless otherwise specified, "the number of carbon atoms" and "the number of constituent atoms" refer to the number including the number of carbon atoms or the number of atoms of a substituent in a group having a substituent. In the present invention and the present specification, the term "unsubstituted or having one or more substituents" means the same as "substituted or unsubstituted".

In the present invention and the present specification, the substituents in the various general formulae described below and the substituents in the case where each group described below has a substituent may be each independently a solubilizing group. In the present invention and in the present specification, a "solubilizing group" refers to a substituent that can contribute to improving compatibility with any liquid or a specific liquid. The solubilizing group is preferably a substituent having a substituent which can contribute to promotion of thermal movement of the compound molecule, such as an alkyl group having 4 to 50 carbon atoms and containing a linear, branched or cyclic structure, a linear, branched or cyclic alkoxy group having 4 to 50 atoms, a linear, branched or cyclic silyl group having 4 to 50 atoms, a group in which a part of the above groups is replaced with a silicon atom, a sulfur atom, a nitrogen atom, a phosphorus atom or the like, a group in which 2 or more of the above groups are combined, or the like. Compounds having a solubilizing group as a substituent may form a molecular assembly state close to that of a liquid by preventing solidification of a solute by blocking proximity of a distance between solute molecules, or by lowering a melting point and/or glass transition temperature of a solute. Thus, the solubilizing group can liquefy a solute or enhance the solubility of the compound having the substituent in a liquid. In one embodiment, the solubilizing group is preferably n-butyl, n-pentyl, n-hexyl, n-octyl, t-butyl, which is a branched alkyl group, and cyclopentyl and cyclohexyl, which are cyclic alkyl groups.

The above substituent may preferably be selected from methoxy, ethoxy, phenoxy, methylthio, ethylthio, phenylthio, trifluoromethyl, phenyl, naphthyl, dibenzofuranyl, dibenzothienyl, carbazolyl, phenothiazinyl, phenoneThe substituent selected from the group consisting of an oxazinyl group, a phenazinyl group, an acridinyl group, a dimethylamino group, a diphenylamino group, a piperidinyl group, a morpholinyl group, a thiomorpholinyl group, a cyano group, and a solubilizing group may be more preferably a substituent selected from the group consisting of a methoxy group, a phenoxy group, a methylthio group, a phenylthio group, a trifluoromethyl group, a phenyl group, a dimethylamino group, a diphenylamino group, a piperidinyl group, a morpholinyl group, a thiomorpholinyl group, a cyano group, and a solubilizing group.

In the present invention and in the present specification, the "electron withdrawing group" means a substituent which attracts electrons more easily from the bonded atom side than from the hydrogen atom. The electron withdrawing group can attract electrons as a result of a substituent effect such as an induction effect, a mediator effect (or a resonance effect). Specific examples of the electron withdrawing group include: halogen atom (fluorine atom: -F, chlorine atom: -Cl, bromine atom: -Br, iodine atom: -I), trifluoromethyl: -CF ₃ And (3) nitro: -NO ₂ Cyano group: -CN, formyl: CHO, acyl: -COR (R is a substituent), alkoxycarbonyl: -COOR, carboxyl: -COOH, substituted sulfonyl: -SO ₂ R (R is a substituent), sulfo: -SO ₃ H, etc. Examples of suitable electron-withdrawing groups include fluorine atoms as electron-withdrawing groups having high electronegativity and a substituent constant σ at the para position based on the Hammett equation _p An electron withdrawing group having a positive value, and the like.

In the present invention and the present specification, the "electron donating group" means a substituent which is easier to supply electrons to the bonded atom side than to the hydrogen atom. The electron donating group may be a substituent that easily donates electrons based on the sum of an induction effect, an intermediate effect (or a resonance effect), and the like. Specific examples of the electron donating group include: hydroxyl group: -OH, thiol: -SH, alkoxy:-OR (R is alkyl), alkylthio: -SR (R is alkyl), arylthio, acetyl: -OCOCH ₃ Amino: -NH ₂ Alkylamide group: NHCOCH ₃ Dialkylamino group: -N (R) ₂ (2R are the same or different alkyl groups), methyl, and the like. Examples of suitable electron donating groups include the para-substituent constant σ based on the Hammett equation _p Electron donating groups that are negative, and the like.

The substituent constant σ of para-position based on Hammett equation is shown below _p Specific examples of (Yuan, ye Liang Zhi, zhongjing Wu, north Chuan Xun, university college organic chemistry (top) (1988)).

-N(CH ₃ ) ₂ ：-0.83

-OCH3：-0.27

-t-C ₄ H ₉ ：-0.20

-CH ₃ ：-0.17

-C ₂ H ₅ ：-0.15

-C ₆ H ₅ ：-0.01

(-H：0)

-F：+0.06

-Cl：+0.27

-Br：+0.23

-CO ₂ C ₂ H ₅ ：+0.45

-CF ₃ ：+0.54

-CN：+0.66

-SO ₂ CH ₃ ：+0.72

-NO ₂ ：+0.78

[ photochromic Compound represented by the general formula 1 ]

The compound represented by the general formula 1 will be described in more detail below.

[ chemical formula 5]

(general formula 1)

In the general formula 1, R ³⁰ R is R ³¹ All represent ethyl groups.

In the general formula 1, R ³² ～R ³⁵ Each independently represents a substituent other than a hydrogen atom or an electron withdrawing group, and 2 or more substituents may be bonded to form a ring.

In the general formula A, R ³² ～R ³⁵ Each independently represents a hydrogen atom or an electron withdrawing group, wherein R ³² ～R ³⁵ More than one of them represents an electron withdrawing group. The electron withdrawing group is preferably a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group. As the halogen atom, a fluorine atom is preferable. As the perfluoroalkyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferable.

In one embodiment, the compound represented by formula 1 may be the following compound.

R ³² ～R ³⁵ Of only R ³³ Is an electron withdrawing group, R ³² 、R ³⁴ R is R ³⁵ A compound which is a hydrogen atom.

R ³² ～R ³⁵ R in (B) ³² R is R ³⁴ Are identical or different electron withdrawing groups, R ³³ R is R ³⁵ A compound which is a hydrogen atom.

In the general formula 1, R ³⁶ 、R ³⁷ 、B ⁷ B (B) ⁸ Each independently represents a hydrogen atom or a substituent.

In one embodiment, R ³⁶ R is R ³⁷ May each represent a hydrogen atom. In another embodiment, R ³⁶ R is R ³⁷ Can each independently represent a hydrogen atom or an electron donating group, preferably R ³⁶ Represents a hydrogen atom, R ³⁷ Represents an electron donating group, preferably R ³⁶ R is R ³⁷ Representing the same or different electron donating groups. As a result of R ³⁶ And/or R ³⁷ The electron donating group represented is preferably an electron donating group selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolidinyl, piperidinyl, morpholinyl and thiomorpholinyl.

In formula 1, B is preferred ⁷ B (B) ⁸ Each independently represents substitution orUnsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl. More preferably B ⁷ B (B) ⁸ Each independently represents a substituted phenyl group. The substituted phenyl group may contain one or more substituents selected from methoxy, methylthio, amino, dimethylamino, piperidinyl, morpholinyl, thiomorpholinyl, phenyl, fluoro, chloro, bromo, iodo, trifluoromethyl and cyano.

As the compound represented by the general formula 1, the following compounds can be exemplified. However, the present invention is not limited to the compounds exemplified below.

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

[ chemical formula 29]

[ chemical formula 30]

[ chemical formula 31]

[ chemical formula 32]

[ chemical formula 33]

[ chemical formula 34]

[ chemical formula 35]

[ chemical formula 36]

[ chemical formula 37]

[ chemical formula 38]

[ chemical formula 39]

[ chemical formula 40]

[ chemical formula 41]

[ chemical formula 42]

[ chemical formula 43]

< combination of photochromic Compounds >

The photochromic article according to one embodiment of the present invention and the photochromic composition according to one embodiment of the present invention contain a plurality of photochromic compounds in any combination of the following (a) to (g). The photochromic article and the photochromic composition may contain compounds satisfying 2 or more of the general formulae described in the present specification.

In the combinations (a) to (g), the combination of the compound represented by the general formula 1 and the compound represented by the general formula a may include only one kind of compound represented by the general formula 1, may include 2 or more (for example, 2 or more and 4 or less) kinds of compounds represented by the general formula 1, may include only one kind of compound represented by the general formula a, and may include 2 or more (for example, 2 or more and 4 or less) kinds of compounds represented by the general formula a.

In the combinations (a) to (g), the combination of the compound represented by the general formula 1 and the compound represented by the general formula B and/or the compound represented by the general formula C may include only one kind of compound represented by the general formula 1, may include 2 or more (for example, 2 or more and 4 or less) kinds of compounds represented by the general formula 1, may include only one kind of compound represented by the general formula B, may include 2 or more (for example, 2 or more and 4 or less) kinds of compounds represented by the general formula B, may include only one kind of compound represented by the general formula C, and may include 2 or more (for example, 2 or more and 4 or less) kinds of compounds represented by the general formula C. In the above combination, only one of the compound represented by the general formula B and the compound represented by the general formula C may be contained, or both may be contained.

(combination (a))

The combination (a) is a combination of at least one photochromic compound selected from the photochromic compounds represented by the general formula B and the photochromic compounds represented by the general formula C and at least one photochromic compound represented by the general formula 1, and the photochromic compound represented by the general formula 1 is R ³⁰ R is R ³¹ All represent ethyl, R ³⁶ R is R ³⁷ All represent a hydrogen atom, R ³³ A compound representing an electron withdrawing group (hereinafter, also referred to as "compound a 1"). With respect to R in compound a1 ³³ Details of the electron withdrawing group represented by formula 1 can be referred to in the foregoing description. In addition, for other details of the compound a1, the foregoing description related to the general formula 1 may be referred to. In one embodiment, R in combination (a) ³² ～R ³⁷ In the above, hydrogen atoms may be used.

(combination (b))

The combination (b) is a slaveA combination of at least one photochromic compound selected from the photochromic compounds represented by the formula B and the photochromic compounds represented by the formula C and at least one photochromic compound represented by the formula 1, wherein R is in the photochromic compounds represented by the formula 1 ³⁰ R is R ³¹ All represent ethyl, R ³⁶ R is R ³⁷ All represent a hydrogen atom, R ³² R is R ³⁴ Each independently represents an electron withdrawing group (hereinafter, also referred to as "compound a 2"). R is R ³² R is R ³⁴ May be the same or different electron withdrawing groups. With respect to R in compound a2 ³² Represented electron withdrawing group and R ³⁴ Details of the electron withdrawing group represented by formula 1 can be referred to in the foregoing description. In addition, for other details of the compound a2, the foregoing description related to the general formula 1 may be referred to. In one embodiment, R in combination (b) ³² ～R ³⁷ In the above, hydrogen atoms may be used.

(combination (c))

The combination (C) is a combination of at least one photochromic compound selected from the photochromic compounds represented by the general formula B and the photochromic compounds represented by the general formula C and at least one photochromic compound represented by the general formula 1, wherein R is a group of at least one photochromic compound selected from the photochromic compounds represented by the general formula 1 ³⁰ R is R ³¹ All represent ethyl, R ³³ R is R ³⁷ Each independently represents an electron withdrawing group (hereinafter, also referred to as "compound a 3"). R is R ³³ R is R ³⁷ May be the same or different electron withdrawing groups. With respect to R in compound a3 ³³ Represented electron withdrawing group and R ³⁷ Details of the electron withdrawing group represented by formula 1 can be referred to in the foregoing description. In addition, for other details of the compound a3, the foregoing description related to the general formula 1 may be referred to. In one embodiment, R in combination (c) ³² ～R ³⁷ In the above, hydrogen atoms may be used.

(combination (d))

The combination (d) is a photochromic compound represented by the above formula A, and a photochromic compound represented by the above formula 1A combination of photochromic compounds represented by the general formula 1, wherein R ³⁰ R is R ³¹ All represent ethyl, R ³³ Represents an electron withdrawing group, R ³⁷ A compound (hereinafter, also referred to as "compound c 1") representing an electron donating group. With respect to R in compound c1 ³³ Represented electron withdrawing group and R ³⁷ The details of the electron donating group represented by formula 1 can be referred to in the foregoing description. In addition, for other details of the compound c1, the foregoing description related to the general formula 1 may be referred to. In one embodiment, R in combination (d) ³² ～R ³⁷ In the above, hydrogen atoms may be used.

(combination (e))

The combination (e) is a combination of one photochromic compound represented by the above general formula A and one photochromic compound represented by the above general formula 1, wherein R in the photochromic compound represented by the general formula 1 ³⁰ R is R ³¹ All represent ethyl, R ³² R is R ³⁴ Each independently represents an electron withdrawing group, R ³⁷ A compound representing an electron donating group (hereinafter, also referred to as "compound c 2"). R is R ³² R is R ³⁴ May be the same or different electron withdrawing groups. With respect to R in compound c2 ³² Represented electron withdrawing group, R ³⁴ Represented electron withdrawing group and R ³⁷ The details of the electron donating group represented by formula 1 can be referred to in the foregoing description. In addition, for other details of the compound c2, the above description related to the general formula 1 may be referred to. In one embodiment, R in combination (e) ³² ～R ³⁷ In the above, hydrogen atoms may be used.

(combination (f))

The combination (f) is a combination of one photochromic compound represented by the above general formula A and one photochromic compound represented by the above general formula 1, wherein R in the photochromic compound represented by the general formula 1 ³⁰ R is R ³¹ All represent ethyl, R ³³ Represents an electron withdrawing group, R ³⁶ R is R ³⁷ A compound (hereinafter, also referred to as "Compound b") each independently representing an electron donating group1"). In the compound b1, R ³⁶ R is R ³⁷ And may be the same or different electron donating groups. With respect to R in compound b1 ³³ Represented electron withdrawing group, R ³⁶ Represented electron donating group and R ³⁷ The details of the electron donating group represented by formula 1 can be referred to in the foregoing description. In addition, for other details of the compound b1, the foregoing description related to the general formula 1 may be referred to. In one embodiment, R in combination (f) ³² ～R ³⁷ In the above, hydrogen atoms may be used.

(combination (g))

The combination (g) is a combination of one photochromic compound represented by the above general formula A and one photochromic compound represented by the above general formula 1, wherein R in the photochromic compound represented by the general formula 1 ³⁰ R is R ³¹ All represent ethyl, R ³² R is R ³⁴ Each independently represents an electron withdrawing group, R ³⁶ R is R ³⁷ Each independently represents an electron donating group (hereinafter, also referred to as "compound b 2"). R is R ³² R is R ³⁴ May be the same or different electron withdrawing groups. R is R ³⁶ R is R ³⁷ And may be the same or different electron donating groups. With respect to R in compound b2 ³² Represented electron withdrawing group, R ³⁴ Represented electron withdrawing group, R ³⁶ Represented electron donating group and R ³⁷ The details of the electron donating group represented by formula 1 can be referred to in the foregoing description. In addition, for other details of the compound b2, the foregoing description related to the general formula 1 may be referred to. In one embodiment, R in combination (g) ³² ～R ³⁷ In the above, hydrogen atoms may be used.

The compound represented by the general formula a, the compound represented by the general formula B, and the compound represented by the general formula C will be described in more detail below.

[ photochromic Compound represented by the general formula A ]

[ chemical formula 44]

(general formula A)

Preferably R ¹ R is R ² Each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. Further preferably R ¹ R is R ² Each independently represents methyl or ethyl, more preferably R ¹ R is R ² All represent methyl or all represent ethyl.

Preferably B ¹ B (B) ² Each independently represents a substituted or unsubstituted phenyl group. In the case where a phenyl group has a plurality of substituents, 2 or more of these substituents may be bonded to form a ring. Specific examples of the formed ring include rings contained in example compounds described later. The substitution position of the substituent in the substituted phenyl group is preferably relative to B ¹ And B is connected with ² The bonded carbon atoms become para-positions. Specific examples of the substituent for the substituted phenyl group include substituents contained in the below-described exemplary compounds, such as morpholino group, piperidyl group, halogen atom, alkoxy group, and the following substituents. In the present invention and in the present specification, "related to a partial structure of a compound" means a bonding position of an atom bonded to such a partial structure.

[ chemical formula 45]

In the general formula A, R ³ ～R ⁶ Each independently represents a hydrogen atom or a substituent. In one embodiment, R ³ ～R ⁶ All hydrogen atoms are possible. In other aspects, R ³ ～R ⁶ Each independently represents a hydrogen atom or an electron withdrawing group, and R ³ ～R ⁶ More than one of them represents an electron withdrawing group. As electron withdrawing groups, preference is given toHalogen atom, perfluoroalkyl group having 1 to 6 carbon atoms, perfluorophenyl group, perfluoroalkylphenyl group or cyano group. As the halogen atom, a fluorine atom is preferable. As the perfluoroalkyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferable.

In one embodiment, the compound represented by the general formula a may be the following compound.

R ³ ～R ⁶ Of only R ⁴ Is an electron withdrawing group, and R ³ 、R ⁵ R is R ⁶ A compound which is a hydrogen atom.

R ³ ～R ⁶ R in (B) ⁴ R is R ⁶ Are identical or different electron-withdrawing groups, and R ³ R is R ⁵ A compound which is a hydrogen atom.

R ³ ～R ⁶ R in (B) ³ R is R ⁵ Are identical or different electron-withdrawing groups, and R ⁴ R is R ⁶ A compound which is a hydrogen atom.

As the compound represented by the general formula a, the following compounds can be exemplified. However, the present invention is not limited to the compounds exemplified below.

[ chemical formula 46]

[ chemical formula 47]

[ chemical formula 48]

[ chemical formula 49]

[ chemical formula 50]

[ chemical formula 51]

[ chemical formula 52]

[ chemical formula 53]

[ chemical formula 54]

[ chemical formula 55]

[ chemical formula 56]

[ chemical formula 57]

[ chemical formula 58]

[ chemical formula 59]

[ chemical formula 60]

[ chemical formula 61]

[ chemical formula 62]

[ chemical formula 63]

[ chemical formula 64]

[ chemical formula 65]

[ chemical formula 66]

[ chemical formula 67]

[ chemical formula 68]

[ chemical formula 69]

[ chemical formula 70]

[ chemical formula 71]

[ chemical formula 72]

[ chemical formula 73]

[ chemical formula 74]

[ chemical formula 75]

[ chemical formula 76]

[ photochromic Compound represented by the general formula B ]

[ chemical formula 77]

(general formula B)

In the general formula B, R ⁷ ～R ¹² 、B ³ B (B) ⁴ Each independently represents a hydrogen atom or a substituent.

Preferably R ⁷ R is R ⁸ Each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. Further preferably R ⁷ R is R ⁸ Each independently represents methyl or ethyl, more preferably R ⁷ R is R ⁸ All represent methyl or all represent ethyl.

Preferably B ³ B (B) ⁴ Each independently represents a substituted or unsubstituted phenyl group. In the case where a phenyl group has a plurality of substituents, 2 or more of these substituents may be bonded to form a ring. Specific examples of the formed ring include rings contained in example compounds described later. The substitution position of the substituent in the substituted phenyl group is preferably relative to B ³ And B is connected with ⁴ The bonded carbon atoms become para-positions. Specific examples of the substituent for the substituted phenyl group include substituents contained in the below-described exemplary compounds, such as morpholino group, piperidyl group, halogen atom, alkoxy group, and the following substituents.

[ chemical formula 78]

R ⁹ ～R ¹² Each independently represents a hydrogen atom or a substituent. In one embodiment, R ⁹ ～R ¹² All hydrogen atoms are possible. In other modes, can be R ¹⁰ Is an electron withdrawing group, and R ⁹ 、R ¹¹ R is R ¹² Are all hydrogen atoms. In other embodiments, R may be ⁹ R is R ¹¹ Each independently is an electron withdrawing group, and R ¹⁰ R is R ¹² Is a hydrogen atom. The electron withdrawing group is preferably a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group. As the halogen atom, a fluorine atom is preferable. As the perfluoroalkyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferable.

In one embodiment, R ¹⁰ May be a substituted or unsubstituted phenyl group, R may be preferred ¹⁰ Is a substituted or unsubstituted phenyl group, and R ⁹ 、R ¹¹ R is R ¹² Is a hydrogen atom. Specific examples of such a substituted phenyl group include a phenyl group substituted with one or more halogen atoms and/or one or more cyano groups, a phenyl group in which halogen atoms (preferably fluorine atoms) are substituted at all 5 substitution positions of the phenyl group, and a phenyl group in which R is a substituent ¹⁰ The bonded carbon atom becomes a monosubstituted phenyl group substituted with a cyano group at the para position.

R ¹³ R is R ¹⁴ Each independently represents an electron donating group. Namely, R ¹³ R is R ¹⁴ Representing the same or different electron donating groups. Preferably R ¹³ R is R ¹⁴ Each independently represents an electron donating group selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolidinyl, piperidinyl, morpholinyl, and thiomorpholinyl. Wherein for R ¹³ R is R ¹⁴ In terms of, R is preferred ¹³ Is morpholinyl and R ¹⁴ Is alkoxy (preferably methoxy), R ¹³ Is morpholinyl and R ¹⁴ Is methylthio (-S-CH) ₃ )、R ¹³ R is R ¹⁴ Are all alkoxy groups (preferably methoxy groups), and R ¹³ R is R ¹⁴ Are methylthio groups.

As the compound represented by the general formula B, the following compounds can be exemplified. However, the present invention is not limited to the compounds exemplified below.

[ chemical formula 79]

[ chemical formula 80]

[ chemical formula 81]

[ chemical formula 82]

[ chemical formula 83]

[ chemical formula 84]

[ chemical formula 85]

[ chemical formula 86]

[ chemical formula 87]

[ chemical formula 88]

[ chemical formula 89]

[ chemical formula 90]

[ chemical formula 91]

[ chemical formula 92]

[ chemical formula 93]

[ chemical formula 94]

[ chemical formula 95]

[ chemical formula 96]

[ photochromic Compound represented by the general formula C ]

[ chemical formula 97]

(general formula C)

In the general formula C, R is preferable ¹⁵ R is R ¹⁶ Each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. Further preferably R ¹⁵ R is R ¹⁶ Each independently represents methyl or ethyl, more preferably R ¹⁵ R is R ¹⁶ All represent methyl or all represent ethyl.

Preferably B ⁵ B (B) ⁶ Each independently represents a substituted or unsubstituted phenyl group. In the case where a phenyl group has a plurality of substituents, 2 or more of these substituents may be bonded to form a ring. Specific examples of the formed ring include rings contained in example compounds described later. The substitution position of the substituent in the substituted phenyl group is preferably relative to B ⁵ And B is connected with ⁶ The bonded carbon atoms become para-positions. Specific examples of the substituent for the substituted phenyl group include morpholinyl, piperidinyl, halogen, alkoxy, and the following substituents.

[ chemical formula 98]

R ¹⁷ ～R ²⁰ Each independently represents a hydrogen atom or a substituent. In one embodiment, R ¹⁷ ～R ²⁰ All hydrogen atoms are possible. In another mode, can be R ¹⁸ Is an electron withdrawing group, R ¹⁷ 、R ¹⁹ R is R ²⁰ Are all hydrogen atoms. In other embodiments, R may be ¹⁷ R is R ¹⁹ Each independently is an electron withdrawing group, R ¹⁸ R is R ²⁰ Is a hydrogen atom. The electron withdrawing group is preferably a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group. As the halogen atom, a fluorine atom is preferable. As the perfluoroalkyl group having 1 to 6 carbon atoms, a trifluoromethyl group is preferable.

In one embodiment, R ¹⁸ May be a substituted or unsubstituted phenyl group, R being preferred ¹⁸ Is a substituted or unsubstituted phenyl group, R ¹⁷ 、R ¹⁹ R is R ²⁰ Is a hydrogen atom. Specific examples of such a substituted phenyl group include a phenyl group substituted with one or more halogen atoms and/or one or more cyano groups, for example, a phenyl group in which all of the 5 substitution positions of the phenyl group are substituted with halogen atoms (preferably fluorine atoms), and a phenyl group in which R is a group opposite to R ¹⁰ The bonded carbon atom becomes a monosubstituted phenyl group substituted with a cyano group at the para position.

R ²¹ R is R ²² One of them represents a hydrogen atom and the other represents an electron donating group. Preferably R ²¹ Is a hydrogen atom, R ²² Is an electron donating group. More preferably from R ²¹ Or R is ²² (preferably R) ²² ) The electron donating group represented by the formula (I) represents an electron donating group selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolidinyl, piperidinyl, morpholinyl and thiomorpholinyl.

As the compound represented by the general formula C, the following compounds can be exemplified. However, the present invention is not limited to the compounds exemplified below.

[ chemical formula 99]

[ chemical formula 100]

[ chemical formula 101]

[ chemical formula 102]

[ chemical formula 103]

[ chemical formula 104]

[ chemical formula 105]

[ chemical formula 106]

The photochromic compounds represented by the above general formulae can be synthesized by a known method. For the synthesis method, for example, the following references can be referred to. Japanese patent No. 4884578 specification, US2006/0226402A1, US2006/0228557A1, US2008/0103301A1, US2011/0108781A1, US 7527754 specification, US 7556751 specification, WO2001/60811A1, WO2013/086248A1, WO1996/014596A1 and WO2001/019813A1.

[ photochromic composition, photochromic article ]

One embodiment of the present invention relates to a photochromic composition comprising a plurality of photochromic compounds according to any combination of the above (a) to (g).

The present invention also relates to a photochromic article comprising one or more photochromic compounds in any combination of the above (a) to (g).

Hereinafter, the compound represented by the general formula a is referred to as "compound a", the compound represented by the general formula B is referred to as "compound B", and the compound represented by the general formula C is referred to as "compound C". The compound a and the above-described compounds a1, a2 and a3 are collectively referred to as "group a compounds". The compound B and the above-described compounds B1 and B2 are collectively referred to as "group B compound". The compound C and the above-described compounds C1 and C2 are collectively referred to as "group C compound".

The photochromic article according to one embodiment of the present invention and the photochromic composition according to one embodiment of the present invention 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 one or more (for example, 2 or more and 4 or less).

The group B compound contained in the photochromic article and the photochromic composition may be one or more (for example, 2 or more and 4 or less).

The group C compound contained in the photochromic article and the photochromic composition may be one or more (for example, 2 or more and 4 or less).

In the photochromic article and the photochromic composition, the total content of the group B compound and the group C compound is preferably higher than the content of the group a compound on a mass basis. The total content of the group a compound, the group B compound, and the group C compound is preferably more than 50 mass%, more preferably 60 mass% or more, still more preferably 70 mass% or more, still more preferably 80 mass% or more, still more preferably 90 mass% or more, based on 100 mass% of the total. The total content of the group B compound and the group C compound may be less than 100% by mass, or 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, or 95% by mass, based on the total (100% by mass) of the group a compound, the group B compound, and the group C compound.

The mixing ratio of the group B compound and the group C compound is 100% by mass of the total of the group B compound and the group C compound, and the content of the group B compound may be 1% by mass or more and 99% by mass or more, and may be 25% by mass or less and 75% by mass or less. When two or more B group compounds are contained in the photochromic article and the photochromic composition, the content of the B group compounds is the total content of the B group compounds. The same applies to the content of each component in the present invention and the present specification.

The photochromic article and the photochromic composition may contain, for example, about 0.1 to 15.0 mass% of a group a compound, a group B compound, and a group C compound in total, based on 100 mass% of the total amount of the photochromic article and the photochromic composition. The photochromic article and the photochromic composition may contain, for example, about 0.1 to 15.0% by mass of the compound represented by the general formula 1, with the total amount of the photochromic article and the photochromic composition being 100% by mass. But is not limited to the above range.

The photochromic article may have at least a base material. In one embodiment, the photochromic compound may be contained in a base material of the photochromic article. The photochromic article may have a substrate and a photochromic layer, and may contain a plurality of photochromic elements in the substrate and/or the photochromic layer according to any combination of the above (a) to (g) And (3) a compound. In the substrate and the photochromic layer, the plurality of photochromic compounds according to any combination of the above (a) to (g) may be contained only in the substrate in one embodiment, may be contained only in the photochromic layer in another embodiment, and may be contained in the substrate and the photochromic layer in yet another embodiment. The base material and the photochromic layer may contain only the photochromic compound of any combination of the above (a) to (g) as the photochromic compound, or may contain one or more other photochromic compounds. Examples of other photochromic compounds include: azobenzenes, spiropyrans and spirosOxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaallylbisimidazoles, donor-acceptor Stanhaus adducts (DASA) s, salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthonaphthaquinones, stilbenes, and the like.

< substrate >

The photochromic article may include a base material selected corresponding to the type of the photochromic article. As an example of the substrate, a plastic lens substrate or a glass lens substrate is given as an eyeglass lens substrate. The glass lens substrate may be, for example, a lens substrate made of inorganic glass. Examples of the plastic lens base material include an allyl carbonate resin such as a styrene resin, a polycarbonate resin, an allyl resin, and a diethylene glycol bis allyl carbonate resin (CR-39), a vinyl resin, a polyester resin, a polyether resin, a urethane resin obtained by reacting an isocyanate compound with a hydroxyl compound such as diethylene glycol, a thiocarbamate resin obtained by reacting an isocyanate compound with a polythiol compound, and a cured product (generally referred to as a transparent resin) obtained by curing a curable composition containing a (thio) epoxy compound having one or more disulfide bonds in the molecule. 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 base material may be, for example, about 1.50 to 1.75, but the refractive index of the lens base material is not limited to the above range, and may be within the above range or may be deviated up and down from the above range. Here, the refractive index refers to a refractive index with respect to light having a wavelength of 500 nm. The lens base material may be a lens having refractive power (so-called "power-added lens"), or may be a lens having no refractive power (so-called "power-free lens").

For example, the photochromic composition may be a polymerizable composition. In the present invention and the present specification, "polymerizable composition" means a composition comprising one or more polymerizable compounds. The curable 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 the polymerizable composition. The cured product may be contained in the photochromic article as a base material and/or may be contained in the photochromic article as a photochromic layer. The curing treatment may be a light and/or heat treatment. The polymerizable compound is a compound having a polymerizable group, and the polymerizable composition can be cured by allowing the polymerization reaction of the polymerizable compound to proceed, thereby forming a cured product. The polymerizable composition may further contain one or more additives (for example, a polymerization initiator, etc.).

The spectacle lenses may be various lenses such as single focal lens, multi focal lens, progressive power lens, and the like. The type of lens can be determined by the shape of the surfaces on both sides of the lens substrate. In addition, the surface of the lens substrate may be any of convex, concave, and planar. The lens base material and the spectacle lens are generally not limited to those having a convex object side surface and a concave eyeball side surface. The photochromic layer may be generally disposed on the object-side surface of the lens substrate, but may also be disposed on the eyeball-side surface.

< photochromic layer >)

The photochromic layer may be a layer directly provided on the surface of the substrate or a layer indirectly provided on the surface of the substrate with one or more other layers interposed therebetween. The photochromic layer may be, for example, a cured layer obtained by curing the polymerizable composition. The photochromic layer can be formed by preparing a cured layer obtained by curing a polymerizable composition containing at least one or more of the above-mentioned photochromic compounds and one or more polymerizable compounds. For example, the photochromic layer may be formed by directly coating the polymerizable composition on the surface of the substrate or on the surface of a layer provided on the substrate, and curing the applied polymerizable composition to prepare a cured layer containing one or more photochromic compounds. As the coating method, a known coating method such as spin coating, dip coating, spray coating, inkjet coating, nozzle coating, and slit coating can be used. The curing treatment may be a light and/or heat treatment. The polymerizable composition may further contain one or more additives (for example, a polymerization initiator) in addition to one or more polymerizable compounds. By allowing the polymerization reaction of the polymerizable compound to proceed, 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.

< polymerizable Compound >)

In the present invention and the present specification, a polymerizable compound means a compound having one or more polymerizable groups in 1 molecule, and a "polymerizable group" means a reactive group capable of undergoing a polymerization reaction. Examples of the polymerizable group include: acryl, methacryl, vinyl ether, epoxy, thiol, oxetane, hydroxyl, carboxyl, amino, isocyanate, and the like.

As the polymerizable compound that can be used for forming the base material and the photochromic layer, the following compounds can be exemplified.

(episulfide Compound)

The episulfide compound is a compound having 2 or more cyclic thioether groups in 1 molecule. The cyclic thioether group is a polymerizable group capable of undergoing ring-opening polymerization. Specific examples of the episulfide compound include: bis (1, 2-cyclosulfanyl) sulfide, bis (1, 2-cyclosulfanyl) disulfide, bis (2, 3-cyclosulfanyl) sulfide, bis (2, 3-cyclosulfanyl) methane, bis (2, 3-cyclosulfanyl) disulfide, bis (2, 3-cyclosulfanyl) dithio-methane, bis (2, 3-cyclosulfanyl) dithio-ethane, bis (6, 7-cyclosulfanyl-3, 4-dithioheptyl) sulfide, bis (6, 7-cyclosulfanyl-3, 4-dithioheptyl) disulfide, 1, 4-dithiane-2, 5-bis (2, 3-cyclosulfanyl dithiomethyl), 1, 3-bis (2, 3-cyclosulfanyl dithiomethyl) benzene 1, 6-bis (2, 3-Cyclothiopropyldithiomethyl) -2- (2, 3-Cyclothiopropyldithioethylthio) -4-thiahexane, 1,2, 3-tris (2, 3-Cyclothiopropyldithio) propane, 1-tetrakis (2, 3-Cyclothiopropyldithiomethyl) methane, 1, 3-bis (2, 3-Cyclothiopropyldithio) -2-thiapropane 1, 4-bis (2, 3-cyclopropyldithio) -2, 3-dithiobutane, 1-tris (2, 3-cyclopropyldithio) methane, 1, 2-tetrakis (2, 3-cyclopropyldithio) ethane, 1, 2-tetra (2, 3-Cyclothiopropyldithiomethylsulfanyl) ethane, 1, 3-tetra (2, 3-Cyclothiopropyldithio) propane 1, 3-tetra (2, 3-Cyclothiopropyldithiomethylsulfanyl) propane 2- [1, 1-bis (2, 3-cyclopropyldithio) methyl ] -1, 3-dithiine, and the like.

(thietane-based compounds)

The thietane compound is a thietane compound having at least 2 thietanes in 1 molecule. Thietane is a polymerizable group capable of ring-opening polymerization. The thietane compound includes a compound having a plurality of thietanes and a cyclic thioether group. Such compounds are exemplified by the episulfide compounds mentioned above. Other thietane-based compounds include a metal-containing thietane compound having a metal atom in the molecule and a metal-free nonmetallic thietane-based compound.

Specific examples of the nonmetallic thietane compound 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-trityl, 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-thietanylthio) -3, 6-dithiaoctane, 1, 11-bis (3-thietanylthio) -4, 8-bis (3-thietanylthio) -3,6, 9-trithiaundecane, 1, 11-bis (3-thietanylthio) -4, 7-bis (3-thietanylthio) -3,6, 9-trithiaundecane, 1, 11-bis (3-thietanylthio) -5, 7-bis (3-thietanylthio) -3,6, 9-trithioundecane, 2, 5-bis (3-thietanylthio) -1, 4-dithiane, 2, 5-bis [ [2- (3-thietanylthio) ethyl ] thiomethyl ] -1, 4-dithiane, 2, 5-bis (3-thietanylthio) -2, 5-dimethyl-1, 4-dithiane, dithian-yl sulfide, bis (thietanylthio) methane, 3- [ < (thietanylthio) methylthio ] thietane, dithian-trithio, dithian-tetrasulfide, dithian-pentasulfide, 1, 4-bis (3-thietanylthio) -2, 3-dithian-e, 1-tris (3-thietanylthio) methane, 1, 3-thietanylthio-methane, 1, 2-tetrathian-e and the like.

Examples of the metal-containing thietane compound include metal-containing thietane compounds having, as metal atoms, atoms of group 14 such as Sn, si, ge, and Pb, group 4 such as Zr and Ti, group 13 such as Al, and group 12 such as Zn. Specific examples include: alkylthio (thietanylthio) tin, bis (alkylthio) bis (thietanylthio) tin, alkylthio (alkylthio) bis (thietanylthio) tin, bis (thietanylthio) cyclic dithiotin compounds, alkyl (thietanylthio) tin compounds, and the like.

As a specific example of alkylthio (thietanylthio) tin, there can be exemplified: methylthio-tris (thietanylthio) tin, ethylthio-tris (thietanylthio) tin, propylthio-tris (thietanylthio) tin, isopropylthio-tris (thietanylthio) tin, and the like.

As a specific example of bis (alkylthio) bis (thietanylthio) tin, there can be exemplified: bis (methylthio) bis (thietanylthio) tin, bis (ethylthio) bis (thietanylthio) tin, bis (propylthio) bis (thietanylthio) tin, bis (isopropylthio) bis (thietanylthio) tin, and the like.

As a specific example of alkylthio (alkylthio) bis (thietanylthio) tin, there can be exemplified: 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, isopropylthio (propylthio) bis (thietanylthio) tin and the like.

As specific examples of the bis (thietanylthio) cyclic dithiotin compound, there can be exemplified: bis (thietanylthio) dithiatin heterocycles, bis (thietanylthio) trithiatin heterocycles, and the like.

As specific examples of the alkyl (thietanylthio) tin compound, there can be exemplified: methyltri (thietanylthio) tin, dimethylbis (thietanylthio) tin, butyltris (thietanylthio) tin, tetrakis (thietanylthio) germanium, tris (thietanylthio) bismuth, and the like.

(polyamine Compound)

The polyamine compound has more than 2 NH in 1 molecule ₂ Radical compounds, which can form urea bonds by reaction with polyisocyanates, or by reaction with polyisocyanatesThe reaction of thiocyanates forms thiourea linkages. Specific examples of the polyamine compound include: ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecylenediamine, dodecamethylenediamine, m-xylylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 2- (2-aminoethylamino) ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3, 5-benzenetriamine, and the like.

(epoxy compound)

The epoxy compound is a compound having an epoxy group in a molecule. The epoxy group is a polymerizable group capable of undergoing ring-opening polymerization. The epoxy compounds can be generally classified into aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds.

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

Specific examples of the alicyclic epoxy compound include: isophorone glycol diglycidyl ether, bis-2, 2-hydroxycyclohexyl propane diglycidyl ether, and the like.

Specific examples of the aromatic epoxy compound include: resorcinol diglycidyl ether, bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl phthalate, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, and the like.

In addition to the above, an epoxy compound having an epoxy group and a sulfur atom in the molecule may be used. Such sulfur atom-containing epoxy compounds include chain aliphatic sulfur atom-containing epoxy compounds and cyclic aliphatic sulfur atom-containing epoxy compounds.

Specific examples of the chain aliphatic sulfur atom-containing epoxy compound 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) -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) -3-thiapentane, 1, 6-bis (2, 3-epoxypropylthio) -2-methylpropane, 1, 6-bis (2, 3-epoxypropylthio) -2-epoxypropane, 1, 3-bis (2, 3-epoxypropylthio) -2, 3-epoxypropane, 1, 3-bis (2, 3-epoxypropylthio) propane, 1, 5-bis (2, 3-epoxypropylthio) propane 2, 2-bis (2, 3-glycidoxylthiomethyl) -1- (2, 3-glycidoxylthio) butane, and the like.

Specific examples of the cyclic aliphatic sulfur atom-containing epoxy compound include: 1, 3-bis (2, 3-epoxypropylthio) cyclohexane, 1, 4-bis (2, 3-epoxypropylthio) cyclohexane, 1, 3-bis (2, 3-epoxypropylthio methyl) cyclohexane, 1, 4-bis (2, 3-epoxypropylthio methyl) cyclohexane, 2, 5-bis (2, 3-epoxypropylthio methyl) -1, 4-dithiane, 2, 5-bis [ <2- (2, 3-epoxypropylthio) ethyl > thiomethyl ] -1, 4-dithiane, 2, 5-bis (2, 3-epoxypropylthio methyl) -2, 5-dimethyl-1, 4-dithiane and the like.

(Compound having radical polymerizable group)

The compound having a radical polymerizable group is a polymerizable group capable of undergoing radical polymerization. Examples of the radical polymerizable group include: acryl, methacryl, allyl, vinyl, and the like.

Hereinafter, a compound having a polymerizable group selected from an acryl group and a methacryl group is referred to as a "(meth) acrylate compound". Specific examples of the (meth) acrylate compound include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol diglycidyl (meth) acrylate, bisphenol A di (meth) acrylate, 2-bis (4- (meth) acryloyloxyethoxyphenyl) propane 2, 2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2-bis (3, 5-dibromo-4- (meth) acryloyloxyethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, bisphenol F di (meth) acrylate, 1-bis (4- (meth) acryloyloxyethoxyphenyl) methane, 1-bis (4- (meth) acryloyloxydiethoxyphenyl) methane, dimethyloltricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, methylthio (meth) acrylate, phenylthio (meth) acrylate, benzylthio (meth) acrylate, xylylene dithiol di (meth) acrylate, mercaptoethyl sulfide di (meth) acrylate, difunctional urethane (meth) acrylate, and the like.

Specific examples of the compound having an allyl group (allyl compound) include: allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bis allyl carbonate, methoxypolyethylene glycol allyl ether, polyethylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether, methacryloxypolyethylene glycol-polypropylene glycol allyl ether, phenoxypolyethylene glycol allyl ether, methacryloxypolyethylene glycol allyl ether, and the like.

Examples of the compound having a vinyl group (vinyl compound) include: alpha-methylstyrene, alpha-methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3, 9-divinylbenzene, spirobis (m-dioxane), and the like.

The photochromic article may include at least one layer known as a functional layer of the photochromic article, such as a protective layer for improving durability of the photochromic article, an antireflection layer, a water repellent or hydrophilic antifouling layer, an antifogging layer, and an undercoat layer for improving adhesion between layers, at any positions.

The photochromic article may be an optical article. One way of optical article is an eyeglass lens. Such ophthalmic lenses may also be referred to as photochromic lenses or photochromic ophthalmic lenses. As an embodiment of the optical article, there is also mentioned: a lens for goggles, a visor (peak) portion of a visor cap, a shield member of a helmet, and the like. The above-mentioned photochromic composition as a polymerizable composition is applied to a substrate for an optical article, and the applied composition is cured to form a photochromic layer, whereby an optical article having an antiglare function can be obtained.

Glasses (glasses)

One embodiment of the present invention relates to an eyeglass comprising an eyeglass lens as one embodiment of the photochromic article. The details of the spectacle lenses included in the spectacles are as described above. By providing such a spectacle lens, for example, the photochromic compound can be colored by irradiation of sunlight when outdoors to exert an antiglare effect like a sunglass, and can be discolored when returned indoors to restore transmittance. The above-described glasses, frame, and the like can be configured by known techniques.

Examples

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

[ Synthesis of Compound ]

Compounds 1 to 15 shown below were synthesized with reference to the references shown above for the synthetic methods of compounds. The identification of the compounds was performed in the same manner as described in the reference publication, and it was confirmed that the compounds shown below were synthesized.

[ chemical formula 107]

[ chemical formula 108]

Examples 1 to 28 and comparative examples 1 and 2

Preparation of photochromic composition (polymerizable composition)

A (meth) acrylate mixture was prepared by mixing 68 parts by mass of polyethylene glycol diacrylate, 12 parts by mass of trimethylolpropane trimethacrylate, and 20 parts by mass of neopentyl glycol dimethacrylate with 100 parts by mass of the total of the (meth) acrylates in a plastic container. The photochromic compound was mixed to 100 parts by mass of the (meth) acrylate mixture to 2.5 parts by mass. For a composition containing a plurality of photochromic compounds, the mass ratio of each photochromic compound in the case where the total amount of the photochromic compounds is 10 is shown in table 2. Then, a photopolymerization initiator (phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide), an antioxidant [ bis (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid) ] [ ethylenebis (ethyleneoxide) ] ester and a light stabilizer (bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate) were mixed, and after stirring thoroughly, a silane coupling agent (. Gamma. -methacryloxypropyl trimethoxysilane) was added dropwise while stirring. Then, the deaeration was performed by stirring the deaeration apparatus in an automatic revolution manner.

The photochromic composition was prepared by the above method.

< film formation of undercoat layer >

A plastic lens base material (product name EYAS: center thickness 2.5mm, diameter 75mm, spherical lens power-4.00 manufactured by HOYA Co., ltd.) was subjected to an alkali cleaning by immersing it in a 10% strength by mass aqueous sodium hydroxide solution (liquid temperature 60 ℃ C.) for 5 minutes, and further washed with pure water and dried. Then, an aqueous polyurethane resin solution (polycarbonate polyol polyurethane emulsion, viscosity 100cPs, solid content 38 mass%) was applied to the convex surface of the plastic lens base material by spin coating at 1500rpm for 1 minute using a spin coater MS-B150 manufactured by MIKASA corporation at room temperature and a relative humidity of 40 to 60%, and then naturally dried for 15 minutes, thereby forming an undercoat layer having a thickness of 5.5 μm.

< film formation of photochromic layer >)

The photochromic composition prepared above was applied dropwise to the primer layer, and the composition was applied by spin coating using a procedure of changing the rotation speed from 500rpm to 1500rpm and further rotating at 1500rpm for 5 seconds in a tilt mode using MS-B150 manufactured by MIKASA corporation. Then, the photochromic composition coated on the primer layer formed on the plastic lens substrate was irradiated with ultraviolet light (dominant wavelength 405 nm) for 40 seconds in a nitrogen atmosphere (oxygen concentration 500ppm or less) to cure the composition, thereby forming a photochromic layer. The thickness of the formed photochromic layer was 45 μm.

Photochromic articles (spectacle lenses) were thus produced.

[ evaluation method ]

< evaluation of coloring concentration >

By following JIS T7333: the light reflectance was obtained by the following method 2005.

The photochromic layer was colored by irradiating the convex surface of each of the spectacle lenses of examples and comparative examples with light passing through an air quality filter for 15 minutes using a xenon lamp as a light source. The irradiation light was in accordance with JIS T7333:2005 is performed so that the allowable difference between the illuminance and the illuminance reaches the value shown in table 1. The transmittance at the time of coloring was measured by using an Otsuka electron spectrometer. Table 2 shows the light transmittance T (%) obtained from the measurement results in the wavelength range of 380nm to 780 nm. The smaller the value of T (%) is, the more the photochromic compound is colored at a high concentration.

TABLE 1

Wavelength region (nm)	Irradiance (W/m) ² )	Allowable difference of irradiance (W/m) ² )
			300～340	＜2.5	-
340～380	5.6	±1.5
			380～420	12	±3.0
420～460	12	±3.0
			460～500	26	±2.6

< evaluation of fading Rate >

The fading speed was evaluated by the following method.

The transmittance (measurement wavelength: 550 nm) before illumination (uncolored state) of each of the spectacle lenses of examples and comparative examples was measured by using an Otsuka electron spectrometer. Here, the measured transmittance is referred to as "initial transmittance".

For each spectacle lens, a xenon lamp was used as a light source, and the photochromic layer was colored by irradiating light having passed through an air quality filter for 15 minutes. The irradiation light was in accordance with JIS T7333:2005, the difference between the illuminance and the allowable difference between the illuminance is set to the value shown in table l. The transmittance at the time of coloring was measured in the same manner as the initial transmittance. The measured transmittance is referred to herein as "transmittance at coloring".

Then, the time required from the time when the light was stopped until the transmittance reached [ (initial transmittance-transmittance at coloring)/2 ] was measured. This time is set to "halving time". It is considered that the shorter the halving time, the faster the fading speed. The halving time obtained is shown in table 2.

TABLE 2

From the results shown in table 2, it was confirmed that by combining the photochromic compounds in accordance with the combinations described above, a photochromic article colored at a high concentration in the visible light region can be provided. Further, from the results shown in table 2, it was also confirmed that each of the eyeglass lenses of the examples exhibited a fast fading speed.

Finally, the above modes are summarized.

According to one embodiment, there can be provided a photochromic composition and a photochromic article, each of which comprises one or more photochromic compounds represented by the above general formula 1, and one or more selected from the group consisting of a photochromic compound represented by the general formula a, a photochromic compound represented by the general formula B, and a photochromic compound represented by the general formula C, in any combination of the above (a) to (g).

In one embodiment, the electron donating group in formula 1 may be an electron donating group selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolidinyl, piperidinyl, morpholinyl, and thiomorpholinyl.

In one embodiment, the electron withdrawing group in the general formula 1 may be a halogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluorophenyl group, a perfluoroalkylphenyl group, or a cyano group.

In one embodiment, the halogen atom may be a fluorine atom.

In one embodiment, the perfluoroalkyl group may be a trifluoromethyl group.

In one embodiment, B in formula 1 ⁷ B (B) ⁸ May each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

In one embodiment, B in formula 1 ⁷ B (B) ⁸ Each independently represents a substituted phenyl group, and the substituted phenyl group may contain one or more substituents selected from methoxy, methylthio, amino, dimethylamino, piperidinyl, morpholinyl, thiomorpholinyl, phenyl, fluoro, chloro, bromo, iodo, trifluoromethyl and cyano.

In one embodiment, the photochromic composition may further include a polymerizable compound.

According to one embodiment, there is provided a photochromic article comprising a cured product obtained by curing the photochromic composition.

In one embodiment, the photochromic article may include a base material and a photochromic layer, and the photochromic layer may be the cured product.

In one embodiment, the photochromic article may be an ophthalmic lens.

In one embodiment, the photochromic article may be a lens for goggles.

In one embodiment, the photochromic article may be a visor portion of a visor cap.

In one embodiment, the photochromic article may be a shielding member of a helmet.

According to one embodiment, there is provided glasses including the above-described glasses lenses.

The various aspects and various forms described in the present specification may be combined in any combination of two or more kinds, and two or more kinds may be combined in any combination.

It should be understood that the embodiments disclosed herein are merely examples in all respects and are not to be interpreted as limiting. The scope of the present invention is defined by the appended claims, and is not limited to the description above, but is intended to include all modifications within the meaning and scope equivalent to the claims.

Industrial applicability

One embodiment of the present invention is useful in the technical field of eyeglasses, goggles, suncaps, helmets, and the like.

Claims

1. A photochromic composition comprising a photochromic compound represented by the following general formula 1 and at least one selected from the group consisting of a photochromic compound represented by the following general formula A, a photochromic compound represented by the following general formula B and a photochromic compound represented by the following general formula C in any combination of the following (a) to (g),

general formula 1:

in the general formula 1, the components of the compound,

R ³⁰ r is R ³¹ All of which represent an ethyl group,

R ³² ～R ³⁵ each independently represents a hydrogen atom or an electron withdrawing group, wherein R ³² ～R ³⁵ More than one of them represents an electron withdrawing group,

R ³⁶ 、R ³⁷ 、B ⁷ b (B) ⁸ Each independently represents a hydrogen atom or a substituent,

general formula A:

in the general formula A, R ¹ ～R ⁶ 、B ¹ B (B) ² Each independently represents a hydrogen atom or a substituent,

the general formula B:

in the general formula B, the components of the compound,

R ⁷ ～R ¹² 、B ³ b (B) ⁴ Each independently represents a hydrogen atom or a substituent,

R ¹³ r is R ¹⁴ Each independently represents an electron donating group,

the general formula C:

in the general formula C, the components of the compound,

R ¹⁵ ～R ²⁰ 、B ⁵ b (B) ⁶ Each independently represents a hydrogen atom or a substituent,

R ²¹ r is R ²² One of which represents a hydrogen atom and the other represents an electron donating group,

(a) Comprises one or more photochromic compounds selected from the photochromic compounds represented by the general formula B and the photochromic compounds represented by the general formula C, and one or more R ³⁰ R is R ³¹ All represent ethyl, R ³⁶ R is R ³⁷ All represent a hydrogen atom, R ³³ A compound representing an electron withdrawing group as a photochromic compound represented by formula 1;

(b) Comprises one or more photochromic compounds selected from the photochromic compounds represented by the general formula B and the photochromic compounds represented by the general formula C, and one or more R ³⁰ R is R ³¹ All represent ethyl, R ³⁶ R is R ³⁷ All represent a hydrogen atom, R ³² R is R ³⁴ A compound each independently representing an electron withdrawing group as a photochromic compound represented by formula 1;

(c) Comprises one or more photochromic compounds selected from the photochromic compounds represented by the general formula B and the photochromic compounds represented by the general formula C, and one or more R ³⁰ R is R ³¹ All represent ethyl, R ³³ R is R ³⁷ A compound each independently representing an electron withdrawing group as a photochromic compound represented by formula 1;

(d) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl, R ³³ Represents an electron withdrawing group, R ³⁷ A compound representing an electron donating group as a photochromic compound represented by the general formula 1;

(e) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl, R ³² R is R ³⁴ Each independently represents an electron withdrawing group, R ³⁷ A compound representing an electron donating group as a photochromic compound represented by the general formula 1;

(f) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl, R ³³ Represents an electron withdrawing group, R ³⁶ R is R ³⁷ A compound each independently representing an electron donating group as a photochromic compound represented by formula 1;

(g) Comprises one photochromic compound represented by the general formula A and more than one R ³⁰ R is R ³¹ All represent ethyl group,R ³² R is R ³⁴ Each independently represents an electron withdrawing group, R ³⁶ R is R ³⁷ The compound each independently representing an electron donating group is used as the photochromic compound represented by formula 1.

2. The photochromic composition of claim 1 wherein,

the electron donating group is selected from methoxy, ethoxy, phenoxy, methylthio, phenylthio, dimethylamino, pyrrolidinyl, piperidinyl, morpholinyl and thiomorpholinyl.

3. The photochromic composition according to claim 1 or 2, wherein,

the electron withdrawing group is halogen atom, perfluoroalkyl group with 1-6 carbon atoms, perfluorophenyl group, perfluoroalkyl phenyl group or cyano group.

4. The photochromic composition of claim 3 wherein,

the halogen atom is a fluorine atom.

5. The photochromic composition of claim 3 wherein,

the perfluoroalkyl group is trifluoromethyl.

6. The photochromic composition according to any one of claims 1 to 7, wherein,

in the general formula 1, B ⁷ B (B) ⁸ Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.

7. The photochromic composition according to any one of claims 1 to 7, wherein,

in the general formula 1, B ⁷ B (B) ⁸ Each independently represents a substituted phenyl group comprising one or more substituents selected from methoxy, methylthio, amino, dimethylamino, piperidinyl, morpholinyl, thiomorpholinyl, phenyl, fluoro, chloro, bromo, iodo, trifluoromethyl and cyano.

8. The photochromic composition of any one of claims 1-7, further comprising a polymerizable compound.

9. A photochromic article comprising a cured product obtained by curing the photochromic composition of claim 8.

10. The photochromic article of claim 9 having a substrate and a photochromic layer, the photochromic layer being the cured product.

11. The photochromic article of claim 9 or 10, which is an ophthalmic lens.

12. The photochromic article of claim 9 or 10, which is a lens for goggles.

13. The photochromic article of claim 9 or 10, which is a visor portion of a visor cap.

14. The photochromic article of claim 9 or 10, which is a shade member of a helmet.

15. An eyeglass comprising the eyeglass lens of claim 11.