3-ketocoumarines for LED photocuring

Patent metadata

Field	Value
Publication number	US-9951034-B2
Application number	US-201314437779-A
Country	US
Kind code	B2
Filing date	Oct 17, 2013
Priority date	Oct 22, 2012
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

The present invention relates to 3-ketocoumarines which can be used as photoinitiators in LED photocuring and to a process for curing compositions comprising said 3-ketocoumarines.

First claim

The invention claimed is:

1. A process for LED photocuring photopolymerizable compositions comprising:
I) preparing a photopolymerizable composition comprising:
a) from about 50 to about 99.9% by weight of at least one ethylenically unsaturated compound; and
b) from about 0.1 to about 35% by weight by weight of at least one 3-ketocoumarine having a general formula I:

wherein:
R 1 is a substituted or unsubstituted C 2 -C 12 alkyl group;
Cou is a coumarine group of formula:

wherein:
at least one of R 2 R 3 , R 4 and R 5 is —S—R 7 ,
wherein R 7 is hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkenyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C 5 -C 6 cycloalkyl, C 1 -C 12 alkyl which is substituted with SH, —N(C 1 -C 6 alkyl) 2 , piperidino, morpholino, piperazine, —OH, —O(C 1 -C 12 alkyi), —COOH, and

R 6 is hydrogen, a hydroxyl group or an alkyl group having from 1 to 4 carbon atoms;
and

II) photopolymerizing the photopolymerizable composition so obtained with a LED light source emitting at wavelengths ranging from 365 nm to 420 nm.

2. The process for photocuring photopolymerizable compositions of claim 1 , wherein the photopolymerizable composition comprises:
a) from about 70 to about 98.9% by weight of at least one ethylenically unsaturated compound;
b) from about 0.1 to about 20% by weight of at least one 3-ketocoumarine of formula I.

3. The process for photocuring photopolymerizable compositions according to claim 1 , wherein the photopolymerizable composition further comprises from about 0.2 to about 15% by weight of at least one co-initiator and/or from about 0.5 to about 15% by weight of at least one additional photoinitiator.

4. The process for photocuring photopolymerizable compositions of claim 3 , wherein the photopolymerizable composition comprises from about 70 to about 98.9% by weight of at least one photopolymerizable compound, from about 0.1 to about 10% by weight of at least one 3-ketocoumarine of formula I, from about 1 to about 15% by weight at least one sensitizable photoinitiator and, optionally, from about 0.2 to about 8% by weight of a co-initiator.

5. The process for photocuring photopolymerizable compositions of claim 1 , wherein the photopolymerizable composition further comprises: c) from 0.01 to 30% by weight of colorants.

6. The process for photocuring photopolymerizable compositions of claim 5 , wherein the photopolymerizable composition comprises:
a) from about 70 to about 98.9% by weight of at least one ethylenically unsaturated compound;
b) from about 0.1 to about 20% by weight of at least one 3-ketocoumarine of formula I.

7. The process for photocuring photopolymerizable compositions according to claim 5 , wherein the photopolymerizable composition further comprises from about 0.2 to about 15% by weight of at least one co-initiator and/or from about 0.5 to about 15% by weight of at least one additional photoinitiator.

8. The process for photocuring photopolymerizable compositions of claim 7 , wherein the photopolymerizable composition comprises from about 70 to about 98.9% by weight of at least one photopolymerizable compound, from about 0.1 to about 10% by weight of at least one 3-ketocoumarine of formula I, from about 1 to about 15% by weight at least one sensitizable photoinitiator and, optionally, from about 0.2 to about 8% by weight of a co-initiator.

9. The process for photocuring photopolymerizable compositions of claim 5 , wherein the colorants are colorants for ink-jet printing.

10. A composition comprising 3-ketocoumarines having a general formula I:

wherein:
R 1 is a substituted or unsubstituted C 2 -C 12 alkyl group;
Cou is a coumarine group of formula:

wherein
at least one of R 2 R 3 , R 4 and R 5 is —S—R 7 ,
wherein R 7 is hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkenyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C 5 -C 6 cycloalkyl, C 1 -C 12 alkyl which is substituted with SH, —N(C 1 -C 6 alkyl) 2 , piperidino, morpholino, piperazine, —OH, —O(C 1 -C 12 alkyi), —COOH, and

R 6 is hydrogen, a hydroxyl group or an alkyl group having from 1 to 4 carbon atoms.

11. The composition of claim 10 wherein R 7 is an alkyl group having from 1 to 6 carbon atoms.

12. A composition comprising 3-ketocoumarines having a general formula I:

wherein:
R 1 is a substituted or unsubstituted C 2 -C 12 alkyl group; and
Cou is a coumarine group of formula:

wherein
at least one of R 2 R 3 , R 4 and R 5 is an alkoxy group having from 1 to 6 carbon atoms and R 6 is hydrogen, a hydroxyl group or an alkyl group having from 1 to 4 carbon atoms;

or Cou is a substituted or unsubstituted naphtho-coumarine having a general formula selected from the group consisting of:

13. A process for LED photocuring photopolymerizable compositions comprising:
I) preparing a photopolymerizable composition comprising:
a) from about 50 to about 99.9% by weight of at least one ethylenically unsaturated compound; and
b) from about 0.1 to about 35% by weight by weight of at least one 3-ketocoumarine having a general formula I:

wherein:
R 1 is a substituted or unsubstituted C 2 -C 12 alkyl group;
Cou is a coumarine group of formula:

wherein:
R 2 , R 3 , R 4 and R 5 are, independently of one another, hydrogen; or —S—R 7 , wherein R 7 is hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkenyl, substituted or unsubstituted phenyl, aryl or heteroaryl, C 5 -C 6 cycloalkyl, C 1 -C 12 alkyl which is substituted with SH, —N(C 1 -C 6 alkyl) piperidino, morpholino, piperazino, —OH, —O(C 1 -C 12 alkyl), —COOH;
or C 1 -C 12 alkoxy;
R 6 is hydrogen, a hydroxyl group, an alkyl group having from 1 to 4 carbon atoms;

or Cou is a substituted or unsubstituted naphtho-coumarine group having a general formula selected from the group consisting of:

wherein at least one of R 2 , R 3 , R 4 and R 5 is different from H and that, when Cou is (a) and at least one of R 2 , R 3 , R 4 and R 5 is C 1 -C 12 alkoxy or when Cou is (b), (c) or (d), R 1 is a substituted or an unsubstituted C 1 -C 12 alkyl group; and

II) photopolymerizing the photopolymerizable composition so obtained with a LED light source emitting at wavelengths ranging from 365 nm to 420 nm; and
wherein:
in the 3-ketocoumarine of fo

Assignees

• Lamberti Spa
• Igm Resins Italia Srl

Inventors

• Morone Marika
• Bernini Freddi Andrea
• Norcini Gabriele
• Floridi Giovanni
• Li Bassi Giuseppe

Classifications

• A61K6/62

  Photochemical radical initiators · CPC title

• C07D311/16

  substituted in position 7 · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C07D311/78 Primary

  Ring systems having three or more relevant rings · CPC title

• A61K6/0052

  Human Necessities · mapped topic