UV curable inkjet inks and inkjet printing methods

Patent metadata

Field	Value
Publication number	US-12448533-B2
Application number	US-202118253235-A
Country	US
Kind code	B2
Filing date	Sep 23, 2021
Priority date	Nov 19, 2020
Publication date	Oct 21, 2025
Grant date	Oct 21, 2025

Abstract

A UV curable inkjet ink including a free radical polymerizable compound and an acyl phosphine oxide initiator wherein the acyl phosphine oxide initiator includes an acyl group selected from the group consisting of a benzoyl group substituted by an urea group or an oxalylamide group; a 2,6-dimethyl benzoyl group substituted in position 3 by an urea group or an oxalylamide group; a 2,6-dimethoxy benzoyl group substituted in position 3 by an urea group or an oxalylamide group; a 2,4,6-trimethyl benzoyl group substituted in position 3 by an urea group or an oxalylamide group; and a 2,4,6-trimethoxybenzoyl group substituted in position 3 by an urea group or an oxalylamide group wherein the urea group and the oxalylamide group include a tertiary amine group positioning a phosphorus atom of the acylphosphine oxide initiator in a 1 to Z position, where position 1 is defined as that of the phosphorus atom and position Z is defined as the nitrogen atom of the tertiary amine group with Z representing an integer of at least 11; and that the acyl phosphine oxide initiator contains no more than two photoinitiating moieties having a phosphine oxide group.

First claim

The invention claimed is:

1. A UV curable inkjet ink including a free radical polymerizable compound and an acyl phosphine oxide initiator, wherein the acyl phosphine oxide initiator includes an acyl group selected from the group consisting of a benzoyl group substituted by an urea group or an oxalylamide group; a 2,6-dimethyl benzoyl group substituted in position 3 by an urea group or an oxalylamide group; a 2,6-dimethoxy benzoyl group substituted in position 3 by an urea group or an oxalylamide group; a 2,4,6-trimethyl benzoyl group substituted in position 3 by an urea group or an oxalylamide group; and a 2,4,6-trimethoxybenzoyl group substituted in position 3 by an urea group or an oxalylamide group,
wherein the urea group and the oxalylamide group include a tertiary amine group positioning a phosphorus atom of the acylphosphine oxide initiator in a 1 to Z position, where position 1 is defined as that of the phosphorus atom and position Z is defined as the nitrogen atom of the tertiary amine group with Z representing an integer of at least 11; and
wherein the acyl phosphine oxide initiator contains no more than two photoinitiating moieties having a phosphine oxide group.

2. The UV curable inkjet ink of claim 1 , where position 1 is defined as that of the phosphorus atom and position Z is defined as the nitrogen atom of the tertiary amine group with Z representing an integer selected from 12 to 16.

3. The UV curable inkjet ink of claim 1 , wherein the acyl phosphine oxide initiator is represented by formula I:

wherein
R 1 is a group according to formula II, with the dotted line representing the point of attachment to the phosphorus atom in formula I,

R 2 is selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and OR 7 ;
R 3 is selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and an acyl group;
R 4 , R 5 , and R 6 are independently selected from the group consisting of hydrogen, a methyl group, and a methoxy group;
R 7 is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group; and a substituted or unsubstituted aryl or heteroaryl group;
x is an integer having a value of 0 or 1;
L is a divalent linking group having no more than 5 carbon atoms; and
A is an aliphatic tertiary amine.

4. The UV curable inkjet ink of claim 3 , wherein acyl group R 3 is a group R 1 according to formula II.

5. The UV curable inkjet ink of claim 3 , wherein the aliphatic tertiary amine A is substituted by alkyl groups independently selected from methyl, ethyl, propyl, and butyl.

6. The UV curable inkjet ink of claim 1 , wherein the acyl phosphine oxide initiator is represented by formula III:

wherein
R4, R5, and R6 are independently selected from the group consisting of hydrogen, a methyl group, and a methoxy group;
R8 is selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and OR12;
R9 is selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and an acyl group;
R10 is a substituted or unsubstituted alkyl group;
each R11 independently is selected from the group consisting of a hydrogen and a methyl group;
Y is selected from the group consisting of an oxygen and NR13;
R12 and R13 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, and a substituted or unsubstituted aryl or heteroaryl group;
L1 is a substituted or unsubstituted C 2 to C 6 alkylene group;
L2 is a divalent linking group comprising no more than 10 carbon atoms;
n is an integer 1 or 2;
m is an integer from 0 to 3; and
M is hydrogen if m=0; a covalent bond if n=m=1 or an n+m-valent moiety if n>1 and m>0.

7. The UV curable inkjet ink of claim 6 , wherein R9 is an acyl group selected from the group consisting of a benzoyl group, a 2,6-dimethyl benzoyl group, a 2,6-dimethoxy benzoyl group, a 2,4,6-trimethyl benzoyl group, and a 2,4,6-trimethoxy benzoyl group.

8. The UV curable inkjet ink of claim 7 , wherein the n+m-valent moiety M is an aliphatic moiety comprising 1 to 10 carbon atoms.

9. The UV curable inkjet ink of claim 1 , wherein the acyl phosphine oxide initiator is selected from the group consisting of:

10. The UV curable inkjet ink of claim 1 , wherein the acyl phosphine oxide initiator is a compound obtainable by the synthesis scheme:

wherein R 1 is OEt or phenyl; R 2 is a C 1 to C 8 alkyl group; and L is a divalent linking group having no more than 20 carbon atoms being not further functionalized with acrylates; and wherein the difunctional acrylate Acr is selected from the compounds Acr-1 to Acr-15:

11. The UV curable inkjet ink of claim 10 , wherein R 2 is a C 1 to an ethyl or a methyl group.

12. The UV curable inkjet ink of claim 1 , further comprising a colour pigment.

13. The UV curable inkjet ink of claim 1 , wherein the acyl phosphine oxide initiator is present in an amount between 1 and 25 wt % based on the total weight of the UV curable inkjet ink.

14. A UV curable inkjet ink set containing a plurality of UV curable inkjet inks as defined in claim 13 .

15. The UV curable inkjet ink set of claim 14 , wherein the ink set includes:
a cyan UV curable inkjet ink containing a beta-copper phthalocyanine pigment;
a red UV curable inkjet ink containing a pigment selected from the group consisting of C.I. Pigment Red 57/1, C.I. Pigment Red 122, C.I. Pigment Red 170, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 187, C.I. Pigment Red 188, C.I. Pigment Red 207, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 272, and mixed crystals thereof;
a yellow UV curable inkjet ink containing a pigment selected from C.I. Pigment Yellow 74 C.I. Pigment Yellow 83, C.I. Pigment Yellow 97, C.I. Pigment Yellow 110, C.I. Pigment Yellow 120, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 175, C.I. Pigment Yellow 180, C.I. Pigment Yellow 181, C.I. Pigment Yellow 194, C.I. Pigment Yellow 213, C.I. Pigment

Assignees

• Agfa Nv

Inventors

• Loccufier Johan

Classifications

• C09D11/322

  Pigment inks · CPC title

• C09D11/101 Primary

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

• C09D11/037

  characterised by the pigment · CPC title

• B41M7/0081

  using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams · CPC title

• B41J2/2107

  characterised by the ink properties (supplying ink in a solid state B41J2/17593) · CPC title