Long-afterglow luminescent material

Patent metadata

Field	Value
Publication number	US-2022204838-A1
Application number	US-201917600929-A
Country	US
Kind code	A1
Filing date	Apr 4, 2019
Priority date	Apr 4, 2019
Publication date	Jun 30, 2022
Grant date	—

Abstract

Disclosed is a long-afterglow luminescent material, comprising A) at least one light-absorbing agent, B) at least one luminescent agent, and C) at least one photochemical cache agent. The light-absorbing agent and the luminescent agent are compounds having different structures, and the cache agent is selected from one or more compounds of formula (I), (II) and/or (III).The material has luminescent intensity reaching the level of commercialized inorganic long-afterglow powder SrAl2O4:Eu2+, Dy3+, and can emit light when the exciting light is turned off with a light emitting time up to 100 ms to 3600 s.

First claim

1 . A long-afterglow luminescent material, comprising
A) at least one light-absorbing agent, B) at least one luminescent agent, and C) at least one photochemical cache agent; wherein, the light-absorbing agent and the luminescent agent are compounds having different structures, and the cache agent is selected from one or more compounds of formula (I), (II) and/or (III):

wherein

part forms a divalent aromatic ring or a heteroaromatic ring having 5 to 24, preferably 6 to 14 ring carbon atoms, wherein one or more ring carbon atoms other than carbon atoms in a C═C bond connected with R x and R y may be replaced by a heteroatom selected from N, S, Se or O, and the aromatic ring or the heteroaromatic ring optionally has one or more substituents L,
R x and R y are mutually independently selected from H, hydroxyl, carboxyl, amino, mercapto, ester groups, nitro, sulfo, halogen, acylamino, or alkyl having 1 to 50, preferably 1 to 24, for example 2 to 14 carbon atoms, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, aryl, aralkyl, heteroaryl with N, O, or S or heteroaryl alkyl, or a combination thereof, wherein aryl, aralkyl, heteroaryl or heteroaryl alkyl optionally has one or more substituents L; or
R x and R y together form alkylene or alkenylene having 2 to 20, preferably 3 to 15 C atoms, and optionally having one or more substituents L; and
L is selected from hydroxyl, carboxyl, amino, mercapto, ester groups, nitro, sulfo, halogen, acylamino, or alkyl having 1 to 50, preferably 1 to 24, for example 2 to 14 or 6 to 12 carbon atoms, alkenyl, alkynyl, alkoxy, alkylamino, or a combination thereof.

wherein

part represents phenyl substituted or unsubstituted by one or more L or represents a heterocyclic ring formed by replacing one or more ring carbon atoms other than carbon atoms connected with groups R c′ and R d′ in a five-membered or six-membered olefinic unsaturated carbocyclic ring with N, S, Se, or O, wherein the heterocyclic ring is only allowed to be condensed with at most one phenyl substituted or unsubstituted by one or more L and may be substituted by one or more groups L or one or more aryl or heteroaryl having 4 to 24, preferably 5 to 14, more preferably 6 to 10 ring carbon atoms,
R c′ and R d′ each independently has a definition given for R x and R y in formula (I), but not together form a divalent group, and at least one of R c′ and R d′ is aryl or heteroaryl; and
L is as defined in formula (I);
a premise is that when the

part is phenyl substituted or unsubstituted by one or more L, then the groups R c′ and R d′ together form a divalent group —C(═O)—NH—NH—C(═O)—, optionally substituted by L.
Ar—CR a ═CR b R c   (III)

wherein
Ar represents aryl or heteroaryl having 5 to 24, preferably 6 to 14 ring carbon atoms, wherein one or more ring carbon atoms may be replaced by heteroatoms selected from N, S, Se or O, preferably phenyl, and aryl or heteroaryl optionally has one or more substituents L;
R a , R b and R c each independently have the definition given for R x and R y in formula (I), provided that at most one of R a , R b and R c is H; and
L is as defined in formula (I).

2 . The long-afterglow luminescent material according to claim 1 , wherein in formula (I):

part is an acridine ring or an anthracene ring substituted or unsubstituted by the group L;
R x and R y are mutually independently selected from alkyl having 1 to 18, preferably 2 to 12 carbon atoms, alkoxy, alkylthio (alkyl-S—), alkylamino or aryl, or preferably together form alkylene having 2 to 20, preferably 3 to 15 C atoms, and optionally having one or more substituents L, or a combination thereof; and more preferably, the groups R x and R y are mutually independently selected from alkyl having 1 to 8 carbon atoms, alkoxy, alkylthio, sulfo alkoxy, sulfo alkylthio, phenyl or alkylene having 3 to 12 C atoms, such as adamantylene;
L is selected from hydroxyl, sulfo, linear or branched alkyl having 1 to 12, more preferably 1 to 6 carbon atoms, alkoxy, alkylamino, amino, or a combination thereof; and
aryl is preferably phenyl, biphenyl or naphthyl substituted or unsubstituted by L, and more preferably phenyl or naphthyl.

3 . The long-afterglow luminescent material according to claim 1 , wherein in formula (II):

part is a thiophene ring, a phenylthiophene ring, a benzene ring, a naphthalene ring,

substituted or unsubstituted by one or more groups L, or a combination thereof;
R c′ and R d′ are each independently selected from alkyl having 1 to 18, preferably 1 to 12 carbon atoms, alkoxy, alkylamino or aryl, or a combination thereof, wherein aryl may be substituted by one or more groups L and preferably is phenyl or naphthyl substituted or unsubstituted by L; or R c′ and R d′ together form —CO—NH—NH—CO— groups;
and/or
L is selected from hydroxyl, sulfo, halogen, nitro, linear or branched alkyl having 1 to 12, more preferably 1 to 6 carbon atoms, alkoxy, alkylamino, amino, or a combination thereof.

4 . The long-afterglow luminescent material according to claim 1 , wherein in formula (III):
R a , R b and R c are each independently and preferably selected from H, hydroxyl, linear or branched alkyl having 1 to 18, preferably 1 to 12 carbon atoms, alkoxy, alkylamino or aryl such as phenyl, or a combination thereof; preferably, R b and R c together form alkylene having 2 to 20, preferably 3 to 15 C atoms, such as adamantylene; L is selected from hydroxyl, sulfo, C1-C6 alkyl ester vinyl (C 1-6 alkyl-O—C(═O)—C═C—), linear or branched alkyl having 1 to 12, more preferably 1 to 6 carbon atoms, alkoxy, alkylamino, or a combination thereof; and/or aryl is preferably phenyl or naphthyl substituted or unsubstituted by L.

5 . The long-afterglow luminescent material according to claim 1 , wherein the photochemical cache agent is selected from one or more of phenylthiophene compounds of the following formula (IV), a compound of the following formula (V), acridine compounds of the following formula (VI), a compound of the following formula (VII), a compound of the following formula (VIII), luminol compounds of the following formula (IX), phenylimidazole compounds of the following formula (X), and derivatives of these compounds:

wherein
G and T are a single bond, C or heteroatoms selected from O, S, Se and N, provided that G and T are not single bond or C at the same time;
groups R 1-11 represent H, hydroxyl, carboxyl, amino, mercapto, ester, nitro, sulfo, halogen, acylamino, or alkyl having 1 to 50, preferably 1 to 24, for example 2 to 14 carbon atoms, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, aryl, aralkyl, heteroaryl with N, O, or S or heteroaryl alkyl, or a combination thereof, wherein aryl, aralkyl, heteroaryl or heteroaryl alkyl optionally have one or more substituents L; and
L is selected from hyd

Assignees

• Univ Fudan

Inventors

• Li Fuyou
• Xu Ming

Classifications

• C09K11/06 Primary

  containing organic luminescent materials · CPC title

• C09K11/02

  Use of particular materials as binders, particle coatings or suspension media therefor · CPC title

• C09K11/025 Primary

  non-luminescent particle coatings or suspension media · CPC title

• C09K11/65

  containing carbon (in organic compounds C09K11/06) · CPC title

• C09K2211/1092

  containing sulfur as the only heteroatom · CPC title