US-12624048-B2 - Photochromic cyclic compound and curable composition containing the photochromic cyclic compound

US12624048B2US 12624048 B2US12624048 B2US 12624048B2US-12624048-B2

Abstract

The photochromic cyclic compound of the present invention is represented by Formula (1) below: in the formula, L is a divalent bridging group and PC is a divalent T-type photochromic basic structural group having a naphthopyran structure, where one end of the bridging group L is bonded to at least the 3-position of the naphthopyran structure.

Inventors

Masayuki Miyazaki
Junji Takenaka
Junji Momoda
Srinivas VENU
Katsuhiro Mori

Assignees

TOKUYAMA CORPORATION

Dates

Publication Date: 20260512
Application Date: 20210218
Priority Date: 20200218

Claims (12)

1 . A photochromic cyclic compound represented by Formula (1) below: in the formula, PC denotes a divalent T-type photochromic basic structural group, L denotes a divalent bridging group, and n is an integer of 1 or more, the PC to denote the T-type photochromic basic structural group is a naphthopyran structural group represented by Formula (2) below: in Formula (2), provided that at least one of R 3 and R 4 is a bonding hand to the divalent bridging group L or a group having the bonding hand, R 1 and R 2 are each a group having a bonding hand to the divalent bridging group L or a group having the bonding hand, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group, an aralkoxy group, an aryloxy group, an aryl group, a heteroaryl group, a thiol group, an alkoxyalkylthio group, a cycloalkylthio group, a group represented by Formula (X) below, or a group represented by Formula (Y) below: in the Formula (X), E is an oxygen atom or NR 101 , and R 101 is a hydrogen atom or an alkyl group, F is an oxygen atom or a sulfur atom, G is an oxygen atom, a sulfur atom or a NR 202 , and R 202 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, g is an integer of 0 or 1, R 201 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, in a case where G is an oxygen atom or a sulfur atom, R 201 is a group other than a hydrogen atom; in the Formula (Y), R 300 is an alkylene group, or a silylene group having as a substituent an alkyl group or an aryl group, R 301 is an alkyl group or an aryl group, R 302 , R 303 and R 304 are alkylene groups, h, j, k and l are integers of 0 or 1, i is an integer of 2 to 200, and the plural units of i may be expressed in the same or different units, or R 1 and R 2 may together form a ring that may have a heteroatom, a is an integer of 0 to 2, and b is an integer of 0 to 4, when a is 2, two R 1 may be different from each other, and in a case where a is 2 and two R 1 are present adjacent to each other, the two R 1 may together form a ring that may have a heteroatom, in a case where b is 2 to 4, a plurality of R 2 may be different from each other, and in a case where b is 2 to 4 and two R 2 are present adjacent to each other, the adjacent two R 2 may together form a ring that may have a heteroatom, R 3 and R 4 are each a bonding hand to the divalent bridging group L or a group having the bonding hand, an aryl group or a heteroaryl group, and the divalent bridging group L is a group represented by Formula (3) below: —R 8 —R 9 —R 10 — (3) in Formula (3), provided that not all of R 8 , R 9 and R 10 become direct bonds at the same time, R 8 and R 10 are each either a direct bonding hand or a divalent aromatic ring group having 6 to 30 carbon atoms, and at least either R 8 or R 10 is a p-phenylene group, and R 9 is a direct bonding hand or a divalent organic group.
2 . The photochromic cyclic compound according to claim 1 , wherein n in Formula (1) is an integer of 2 or more.
3 . The photochromic cyclic compound according to claim 1 , wherein the naphthopyran structural group is an indenonaphthopyran structural group represented by Formula (4) below: in the formula, R 2 , R 3 , R 4 and b are as described above as defined in claim 1 , a structural moiety in which (R 5 ) c, R 6 and R 7 are present is a cyclic moiety formed with two R 1 in Formula (2), R 5 is a bonding hand to a divalent bridging group L, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group, an aralkoxy group, an aryloxy group, an aryl group, a heteroaryl group, a thiol group, an alkoxyalkylthio group, a cycloalkylthio group, the Formula (X), or the Formula (Y), c is an integer of 0 to 4, in a case where c is 2 to 4, a plurality of R 5 may be different from each other, and in a case where c is 2 to 4 and two R 5 are present adjacent to each other, the two R 5 may together form a ring that may contain a heteroatom, R 6 and R 7 are each a bonding hand to the divalent bridging group L, a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aralkoxy group, an aryloxy group, an aryl group, a heterocyclic group, the Formula (X), or the Formula (Y), or R 6 and R 7 may together form an aliphatic ring having 3 to 20 membered carbon atoms, a fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused with the aliphatic ring, a heterocyclic ring having 3 to 20 membered carbon atoms, or a fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused with the heterocyclic ring.
4 . The photochromic cyclic compound according to claim 3 , wherein in the indenonaphthopyran structural group represented by Formula (4), a combination of R 6 and R 7 form a ring selected from the group consisting of: an aliphatic ring having 3 to 20 membered carbon atoms; a fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused with the aliphatic ring; a heterocyclic ring having 3 to 20 membered carbon atoms; or a fused polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is fused with the heterocyclic ring.
5 . The photochromic cyclic compound according to claim 4 , wherein in the ring formed of the combination of R 6 and R 7 , the aliphatic ring having 3 to 20 carbon atoms is selected from the group consisting of a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and a spirodicyclohexane ring.
6 . The photochromic cyclic compound according to claim 5 , wherein the aliphatic ring has 1 to 10 substituents, the substituent being an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, or the aliphatic ring is a ring with which a cycloalkyl group having 5 to 7 carbon atoms is fused.
7 . The photochromic cyclic compound according to claim 1 , wherein R 3 and R 4 in the Formula (2) are bonded to the divalent bridging group L.
8 . The photochromic cyclic compound according to claim 1 , wherein the divalent bridging group L has a molecular weight of less than 1000.
9 . A photochromic curable composition comprising the photochromic cyclic compound according to claim 1 and a polymerizable compound.
10 . A photochromic optical article formed by polymerizing the photochromic curable composition according to claim 9 .
11 . A polymer molded body in which the photochromic cyclic compound according to claim 1 is dispersed inside.
12 . An optical article coated with a polymer film in which the photochromic cyclic compound according to claim 1 is dispersed.

Description

TECHNICAL FIELD The present invention relates to a novel photochromic cyclic compound. More specifically, the present invention relates to novel photochromic cyclic compound with improved temperature dependence. BACKGROUND ART Photochromic compounds are compounds that can undergo a reversible transformation between two isomers with different absorption spectra when irradiated with ultraviolet-containing light such as sunlight or light from a mercury lamp. Usually, when a colorless compound in a decolored state is irradiated with ultraviolet rays, it rapidly undergoes isomerization (color development reaction) involving a color change to a colored compound in a color developed state. Upon isomerization from the color developed state to the decolored state (fading reaction), some photochromic compounds return to the original colorless state not only by light with a specific wavelength but also by heat. Such photochromic compounds are referred to as T-type photochromic compounds, which have been well studied and developed especially as a photochromic lens material. Such a T-type photochromic compound to be used for a photochromic lens is usually required to possess the following properties. (1) The degree of coloration (initial coloration) in a visible light region before ultraviolet irradiation is low.(2) The color optical density is saturated quickly after the start of ultraviolet irradiation, that is, color development sensitivity is high.(3) The speed (fading rate) of return to the original state after the stop of ultraviolet irradiation is high.(4) The durability against the repetition of this reversible action is favorable.(5) The dissolubility in a monomer composition that will serve as a host material after curing is high to achieve high dispersibility in the host material to be used. A number of chromene compounds including naphthopyran have been studied as T-type photochromic compounds satisfying these properties. Furthermore, since the demand for the T-type photochromic compounds has been increasing in recent years, the T-type photochromic compounds are expected to satisfy further properties that have not been requested. In general, T-type photochromic compounds are known to have a trade-off relationship between the fading rate and the color optical density. As a result, for instance, when a T-type photochromic compound is used under high temperature as in summer with the hot sun, it is subject to fading and declines in color optical density. In other words, the compounds are easily affected by ambient environmental temperature (have large temperature dependence). In order to prevent decrease in the color optical density, a larger amount of T-type photochromic compound may be blended, so that the color optical density is increased, thereby obtaining a photochromic lens having high color optical density even under high temperature. However, as the blending amount increases, a proportional relationship between the blending amount and the color optical density usually collapses. And this countermeasure can cause other problems in cost and the dissolubility of the T-type photochromic compound itself due to the increased blending amount. That is, there is a limit to enhance the color optical density by increasing the blending amount. As described above, a sufficient improvement has not yet been made in T-type photochromic compounds for use under high temperature as in summer by merely increasing the blending amount thereof. Under the circumstances, there has been a growing demand especially for the development of a T-type photochromic compound having high color optical density (that is, a small temperature dependence) even under high temperature as in summer. In order to achieve a T-type photochromic compound having a high color optical density under high temperature, it is necessary to improve the thermal stability in the colored state. However, this causes a decrease in the fading rate because of the trade-off relationship between the fading rate and the color optical density. In conclusion, it is usually difficult to achieve both a fast fading rate and small temperature dependence. In order to solve this problem, the present inventors propose a chromene compound having substituents at specific positions (see Patent Document 1). This compound has relatively small temperature dependence. PRIOR ART DOCUMENTS Patent Documents Patent Document 1: JP 2018-062496 SUMMARY OF THE INVENTION Problem to be Solved by the Invention However, the chromene compound described in Patent Document 1 still needs improvement since the compound has a substituent at a specific position, namely, the color tone may be limited. In general, chromene compounds are designed to satisfy desired photochromic properties for their purposes by various substituents. Though it is possible to achieve a chromene compound with smaller temperature dependence by limiting the substituents according to the technique of Patent Document 1, it is dif