Liquid arylbenzoyl benzoic acid ester derivatives for energy curable compositions

Patent metadata

Field	Value
Publication number	US-9938231-B2
Application number	US-201515302683-A
Country	US
Kind code	B2
Filing date	Apr 17, 2015
Priority date	Apr 23, 2014
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

4-Arylbenzoyl benzoic acid esters, such as the ethylhexyl esters and amyl esters of 4-phenylbenzoyl benzoic acid, are described, which are liquid and show excellent solubility in acrylic or methacrylic monomers. Compounds of Formula 1, wherein R 1 , R 2 , and A are as defined herein, are disclosed. They are suitable as components for radical photoinitiator systems for UV-curable compositions.

First claim

What is claimed is:

1. A compound of Formula 1:

wherein:
A is C 6 -C 22 aryl or a (6- to 22-membered) heteroaryl;
R 1 is selected from the group consisting of H, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 3 -C 22 cycloalkyl, a (3- to 22-membered) unsaturated or partially unsaturated heterocycle, C 6 -C 22 aryl, a (6- to 22-membered) heteroaryl, and NR 3 R 4 ;
R 3 and R 4 are each independently selected from H or C 1 -C 8 alkyl; or R 3 and R 4 , together with the nitrogen atom to which they are attached, form a five or six membered ring;
R 2 is selected from the group consisting of C 4 -C 22 alkyl, C 7 -C 22 alkaryl, C 7 -C 22 aralkyl, a glycol ether residue comprising a total of between five and twenty two carbon and oxygen atoms, a C 4 -C 22 aminoalkyl, and NR 3 R 4 optionally substituted with C 1 -C 8 alkyl;
provided that when A is phenyl and R 2 is a glycol ether residue, methyl, ethyl, ethylhexyl, methylheptyl, benzyl, t-butylbenzyl, or methylnaphthyl, then R 1 is not H; and
provided that when A is phenyl and R 2 is t-butyl, then R 1 is not methyl.

2. The compound of claim 1 , wherein A is phenyl.

3. The compound of claim 1 , wherein the compound is a C 9 -C 22 alkyl or aralkyl ester.

4. The compound of claim 1 , wherein the compound is a glycol ether ester; provided that if A is phenyl, then R 1 is not H.

5. The compound of claim 1 , wherein the compound is an alicyclic ester.

6. The compound of claim 1 , wherein the compound is a dialkylaminoalkyl ester.

7. A UV-curable ink or coating comprising as a component for radical photoinitiator systems a compound of claim 1 .

8. A UV-curable ink or coating, comprising as a component for radical photoinitiator systems a compound of claim 1 and a C 5 -C 8 ester of said compound.

9. A composition comprising at least one compound of claim 1 and at least one hydrogen radical donor; wherein the composition is liquid at 25° C.

10. The composition of claim 9 , comprising at least one C 5 -C 8 ester of a compound of Formula 1:

wherein:
A is C 6 -C 22 aryl or a (6- to 22-membered) heteroaryl;
R 1 is selected from the group consisting of H, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 3 -C 22 cycloalkyl, a (3- to 22-membered) unsaturated or partially unsaturated heterocycle, C 6 -C 22 aryl, a (6- to 22-membered) heteroaryl, and NR 3 R 4 ;
R 3 and R 4 are each independently selected from H or C 1 -C 8 alkyl; or R 3 and R 4 , together with the nitrogen atom to which they are attached, form a five or six membered ring;
R 2 is selected from the group consisting of C 4 -C 22 alkyl, C 7 -C 22 alkaryl, C 7 -C 22 aralkyl, a glycol ether residue comprising a total of between five and twenty two carbon and oxygen atoms, a C 4 -C 22 aminoalkyl, and NR 3 R 4 optionally substituted with C 1 -C 8 alkyl;
provided that when A is phenyl and R 2 is a glycol ether residue, methyl, ethyl, ethylhexyl, methylheptyl, benzyl, t-butylbenzyl, or methylnaphthyl, then R 1 is not H; and
provided that when A is phenyl and R 2 is t-butyl, then R 1 is not methyl.

11. The composition of claim 10 , wherein the concentration of the C 5 -C 8 ester compound of Formula I is greater than 10 weight %.

12. The composition of claim 10 , wherein the C 5 -C 8 ester compound of Formula I is an amyl ester or an ethylhexyl ester.

13. The composition of claim 9 , wherein the hydrogen donor is a tertiary amine or a thioether.

14. A composition comprising at least two compounds of claim 1 , wherein the at least two compounds are not liquid at 25° C. in a pure form.

15. The composition of claim 9 further comprising one or more C 1 -C 4 esters of 4-arylbenzoylbenzoic acid.

16. A coating or printing ink, curable with actinic light, comprising one or more acrylates or methacrylates, a tertiary amine and at least one compound of claim 1 .

17. A coating or printing ink, curable with actinic light, comprising one or more acrylates or methacrylates, a tertiary amine and the composition of claim 9 .

18. A The coating or printing ink of claim 16 , comprising at least one C 5 -C 8 ester of a compound of Formula I:

wherein:
A is C 6 -C 22 aryl or a (6- to 22-membered) heteroaryl;
le is selected from the group consisting of H, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 3 -C 22 cycloalkyl, a (3- to 22-membered) unsaturated or partially unsaturated heterocycle, C 6 -C 22 aryl, a (6- to 22-membered) heteroaryl, and NR 3 R 4 ;
R 3 and R 4 are each independently selected from H or C 1 -C 8 alkyl; or R 3 and R 4 , together with the nitrogen atom to which they are attached, form a five or six membered ring;
R 2 is selected from the group consisting of C 4 -C 22 alkyl, C 7 -C 22 alkaryl, C 7 -C 22 aralkyl, a glycol ether residue comprising a total of between five and twenty two carbon and oxygen atoms, a C 4 -C 22 aminoalkyl, and NR 3 R 4 optionally substituted with C 1 -C 8 alkyl;
provided that when A is phenyl and R 2 is a glycol ether residue, methyl, ethyl, ethylhexyl, methylheptyl, benzyl, t-butylbenzyl, or methylnaphthyl, then R 1 is not H; and
provided that when A is phenyl and R 2 is t-butyl, then R 1 is not methyl.

19. The coating or printing ink of claim 18 , wherein the at least one C 5 -C 8 ester compound of Formula I is an ethylhexyl ester or an amyl ester.

20. The coating or printing ink of claim 16 , wherein the acrylates or methacrylates are present at a concentration of 20-98 weight %.

21. A process for preparation of a 4-phenylbenzoic acid compound of formula (1) comprising the steps of:
a) dispersing or dissolving biphenyl and phthalic anhydride in a molar ratio of 0.95:1 to 1.05:1 in an inert solvent;
b) feeding aluminum trichloride in molar excess to phthalic anhydride, so that the temperature does not exceed 20° C.;
c) stirring at 25° C. or above for at least 6 hours;
d) pouring the reaction mixture in acidified water having a pH<1; and
e) filtering off the solid precipitate, washing with water, and drying.

22. A composition comprising a 4-phenylbenzoylbenzoic acid amyl ester of formula (1), wherein the composition is liquid at 25° C.

23. A composition comprising a 4-phenylbenzoylbenzoic acid ethylhexyl ester of formula (1), wherein the composition is liquid at 25° C.

24. The coating or printing ink of claim 17 , comprising at least one C 5 -C 8 ester of a compound of Formula 1:

wherein:
A is C 6 -C 22 aryl or a (6- to 22-membered) heteroaryl;
R 1 is selected from the group consisting of H, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 3 -C 22 cycloalkyl, a (3- to 22-membered) unsaturated or partially unsaturated heterocycle, C 6 -C 22 aryl, a (6- to 22-membered) heteroaryl, and NR 3 R 4 ;
R 3 and R 4 are each independently selected from H or C 1 -C 8 alkyl; or R 3 and R 4 , together with the nitrogen atom to which they are attached, form a five or six membered ring;

Assignees

• Sun Chemical Corp

Inventors

• Gaudl Kai-Uwe W
• Dieker Juergen

Classifications

• C07C69/76 Primary

  Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring · CPC title

• C09D11/03

  characterised by features other than the chemical nature of the binder · CPC title

• C07C63/06

  Benzoic acid · CPC title

• C09D11/101

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title

• C07C51/083

  from carboxylic acid anhydrides · CPC title