Fluorescent compounds

Patent metadata

Field	Value
Publication number	US-9701840-B2
Application number	US-201615360266-A
Country	US
Kind code	B2
Filing date	Nov 23, 2016
Priority date	Jan 13, 2011
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

The present invention relates to fluorescent compounds with large Stokes-shift and a process for their preparation. More particularly, the present invention relates to fluorescent compounds that are colorless. The compounds may be used in compositions for inks, paints and plastics, especially in a wide variety of printing systems and are particularly well-suited for security applications.

First claim

The invention claimed is:

1. A method of security printing, the method comprising:
contacting a compound with a substrate;
wherein said compound has a formula (I)

 wherein
R 1 and R 1′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy;
R 2 and R 2′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy,
R 3 and R 3′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 8 alkoxy,
R 4 and R 4′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy, or
one or more pairs of two substituents selected from the group consisting of R 1 and R 2 , R 1′ and R 2′ , R 3 and R 4 , and R 3′ and R 4′ together form a group

 wherein
R 105 , R 106 , R 107 and R 108 are each independently H, C 1 -C 18 alkyl, C 1 -C 18 alkyl interrupted by —O—, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy interrupted by —O—, and
Y is a group of formula —(Y 1 ) n1 —(Y 2 ) n2 —(Y 3 ) n3 —,
wherein Y 1 and Y 3 are independently of each other a substituted, or unsubstituted arylene group having 6 to 10 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 9 ring carbon atoms,
Y 2 is —O—, —S—, —NR 12 —, —SO 2 —, —C(═O)—, —(CR 8 R 9 ) n4 —, —O—(CR 10 R 11 ) n5 —O—, R 8 and R 9 are independently of each other H, or a C 1 -C 8 alkyl group,
R 10 and R 11 are independently of each other H, or a C 1 -C 8 alkyl group,
R 12 is H, or a C 1 -C 8 alkyl group, or a C 6 -C 10 aryl group,
n1 is 1, or 2, n2 is 0, or 1, n3 is 1, or 2, n4 is an integer of 1 to 4 and n5 is an integer of 1 to 4.

2. A method of improving a fastness property of a print, the method comprising:
contacting a printing ink formulation comprising a compound with a substrate;
wherein said compound has a formula (I)

 wherein
R 1 and R 1′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy;
R 2 and R 2′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy,
R 3 and R 3′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy,
R 4 and R 4′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy, or
one or more pairs of two substituents selected from the group consisting of R 1 and R 2 , R 1′ and R 2′ , R 3 and R 4 , and R 3′ and R 4′ together form a group

 wherein
R 105 , R 106 , R 107 and R 108 are each independently H, C 1 -C 18 alkyl, C 1 -C 18 alkyl interrupted by —O—, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy interrupted by —O—, and
Y is a group of formula —(Y 1 ) n1 —(Y 2 ) n2 —(Y 3 ) n3 —,
wherein Y 1 and Y 3 are independently of each other a substituted, or unsubstituted arylene group having 6 to 10 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 9 ring carbon atoms,
Y 2 is —O—, —S—, —NR 12 —, —SO 2 —, —C(═O)—, —(CR 8 R 9 ) n4 —, —O—(CR 10 R 11 ) n5 —O—, R 8 and R 9 are independently of each other H, or a C 1 -C 8 alkyl group,
R 10 and R 11 are independently of each other H, or a C 1 -C 8 alkyl group,
R 12 is H, or a C 1 -C 8 alkyl group, or a C 6 -C 10 aryl group,
n1 is 1, or 2, n2 is 0, or 1, n3 is 1, or 2, n4 is an integer of 1 to 4 and n5 is an integer of 1 to 4.

3. A printing ink formulation, comprising:
a) at least one compound,
b) a polymeric binder,
c) a solvent,
d) optionally a colorant, and
e) optionally a further additive;
wherein said compound has a formula (I)

 wherein
R 1 and R 1′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy;
R 2 and R 2′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy,
R 3 and R 3′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy,
R 4 and R 4′ are each independently hydrogen, C 1 -C 18 alkyl, substituted C 1 -C 18 alkyl, C 6 -C 24 aryl, substituted C 6 -C 24 aryl, C 6 -C 24 heteroaryl, substituted C 6 -C 24 heteroaryl, halogen, or C 1 -C 18 alkoxy, or
one or more pairs of two substituents selected from the group consisting of R 1 and R 2 , R 1′ and R 2′ , R 3 and R 4 , and R 3′ and R 4′ together form a group

 wherein
R 105 , R 106 , R 107 and R 108 are each independently H, C 1 -C 18 alkyl, C 1 -C 18 alkyl interrupted by —O—, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy interrupted by —O—, and
Y is a group of formula —(Y 1 ) n1 —(Y 2 ) n2 —(Y 3 ) n3 —,
wherein Y 1 and Y 3 are independently of each other a substituted, or unsubstituted arylene group having 6 to 10 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 9 ring carbon atoms,
Y 2 is —O—, —S—, —NR 12 —, —SO 2 —, —C(═O)—, —(CR 8 R 9 ) n4 —, —O—(CR 10 R 11 ) n5 —O—, R 8 and R 9 are independently of each other H, or a C 1 -C 8 alkyl group,
R 10 and R 11 are independently of each other H, or a C 1 -C 8 alkyl group,
R 12 is H, or a C 1 -C 8 alkyl group, or a C 6 -C 10 aryl group,
n1 is 1, or 2, n2 is 0, or 1, n3 is 1, or 2, n4 is an integer of 1 to 4 and n5 is an integer of 1 to 4.

4. The printing ink formulation of claim 3 , comprising
a) 0.0001 to 25% by weight of the compound,
b) 5 to 74% by weight of the polymeric binder,
c) 1 to 94.9999% by weight of the solvent,
d) 0 to 25% by weight of the colorant, and
e) 0 to 25% by weight of the further additive,
wherein the sum of components a) to e) is 100%.

5. A security document, comprising:
a substrate and a compound of
fo

Assignees

• Basf Se

Inventors

• Eberius Karin
• Huegin Max

Classifications

• C09D11/037

  characterised by the pigment · CPC title

• C09D11/50

  Sympathetic, colour changing or similar inks · CPC title

• D21H21/40

  Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper (watermarking B41M3/10, D21F1/44; security printing B41M3/14; securities or banknotes characterised by colour effects B42D25/29, B42D25/30; testing paper currency or valuable papers for genuineness G07D7/00) · CPC title

• B42D25/24

  Passports · CPC title

• C09K11/06

  containing organic luminescent materials · CPC title