Acylphosphine oxide photoinitiators

Patent metadata

Field	Value
Publication number	US-11053404-B2
Application number	US-201716096702-A
Country	US
Kind code	B2
Filing date	Apr 28, 2017
Priority date	May 4, 2016
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

Thiol modified acylphosphine oxide photoinitiators exhibiting improved smell and extractability are disclosed. Also disclosed is a UV curable inkjet ink containing an acylphosphine oxide photoinitiator and a polymerizable compound, wherein the acylphosphine oxide photoinitiator includes one or more acyl groups substituted by a thiol.

First claim

The invention claimed is:

1. An acylphosphine oxide photoinitiator selected from the group consisting of:

or
the acylphosphine oxide photoinitiator is a compound according to Formula (I) or (IV):

wherein
n represents an integer having a value of 0 or 1;
R2 is selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, a group according to Formula (I-a), a —NH—C(═O)—R26 group, a —NH—C(═O)—O—R27 group, and a —NH—C(═)O—NH—R28 group;
R26 to R28 are independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkaryl group, an aralkyl group, and a heteroaryl group;
R1, R3, R4, and R5 are independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, and a group according to Formula (I-a);
at least one of R1 to R5 is a group substituted by a thiol or a group according to Formula (I-a):

wherein
Q is a z-valent linking group containing 6 to 30 carbon atoms in which z=k+p+m and z≤6, k=1 to z-p-m, p=0 to 2, and m=1 to 5;
A is a group according to Formula (I-b):

wherein
R1 to R5 have a same meaning as a meaning in Formula (I) in which Q is coupled to the aromatic ring of A in any one of positions occupied by R1 to R5;
R8 and R9 are independently selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, and an aryloxy group;
R10 represents an alkyl group substituted by a thiol or an aryl group substituted by a thiol;
R6 is selected from an alkyl group, an aryl group, an alkoxy group, and an aryloxy group if n=0, and if n=1 R6 represents an alkyl group substituted by a thiol or an aryl group substituted by a thiol;
R7 is selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a group according to Formula (I-c):

wherein
R1 to R6 and n have a same meaning as a meaning in Formula (I);
s is an integer having a value of 0 to 4;
t is an integer having a value of 1 to 5;
u=s+t+1; and
L represents a u-valent linking group having 2 to 16 carbon atoms;
R16 and R21 are independently selected from the group consisting of hydrogen, an alkyl group, an alkoxy group, a group according to Formula (I-a), a —NH—C(═O)—R26 group, a —NH—C(═O)—O—R27 group, and a —NH—C(═)O—NH—R28 group;
R26 to R28 are independently selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkaryl group, an aralkyl group, and a heteroaryl group;
R15, R17 to R20, and R22 to R24 are independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group;
at least one of R15 to R19 is a group substituted by a thiol and at least one of R20 to R24 is a group substituted by a thiol; and
R25 is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkaryl group, an aralkyl group, an aryl group, a heteroaryl group, an alkoxy group, and an aryloxy group;
wherein
one or more of the groups R5, R6, R10, and R15 to R24 are substituted by a thiol represented by Formula (II):

wherein
* represents a point of attachment;
X is selected from the group consisting of O, S, and NR11;
L represents a divalent linking group including no more than 15 carbon atoms;
n represents 0 or 1;
R11 is selected from the group consisting of a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkaryl group, an aralkyl group, an aryl or heteroaryl group, and NR12R13;
R12 and R13 are independently selected from the group consisting of a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkaryl group, an aralkyl group, an aryl, a heteroaryl group, and an acyl group;

or
one of the groups R3, R4, R5, R6, R10, and R15 to R24 are substituted by a thiol represented by Formula (III):

wherein
* represents a point of attachment;
o represents an integer selected from 0 and 1;
m and n independently represent an integer selected from 1 to 5;
L represents an n+m-valent linking group including no more than 15 carbon atoms; and
R14 is selected from the group consisting of a hydrogen and an alkyl group.

2. The acylphosphine oxide photoinitiator according to claim 1 , wherein the at least one of the R1 to R5 groups substituted by a thiol is R3.

3. The acylphosphine oxide photoinitiator according to claim 2 , wherein R1 and R5 represent methyl.

4. The acylphosphine oxide photoinitiator according to claim 1 , wherein R2 and R4 represent hydrogen.

5. The acylphosphine oxide photoinitiator according to claim 1 , wherein R14 is selected from the group consisting of a hydrogen and a methyl group; and
in Formula (III), n and m are represented by an integer selected from 1 to 3, and L represents a tri- or tetra-valent linking group.

6. A UV curable inkjet ink comprising:
an acylphosphine oxide photoinitiator; and
a polymerizable compound; wherein
the acylphosphine oxide photoinitiator includes one or more acyl groups substituted by a thiol according to claim 1 .

7. The UV curable inkjet ink according to claim 6 , wherein the polymerizable compound includes one or more polymerizable groups selected from the group consisting of an acrylamide, a methacrylamide, a vinyl ether group, a vinyl ester group, an allyl ether group, an allyl ester group, a vinyl carbonate group, and an alkyne group.

8. The UV curable inkjet ink according to claim 6 , further comprising a color pigment and/or a polymerizable or polymeric thioxanthone photoinitiator.

9. A printed article comprising:
a substrate; and
the UV curable inkjet ink according to claim 6 ; wherein
the substrate is selected from the group consisting of polyethylene terephthalate, aluminum, and glass.

10. An inkjet printing method comprising the steps of:
jetting a UV curable inkjet ink according to claim 6 on a substrate; and
at least partially UV curing the UV curable inkjet ink jetted on the substrate with UV LEDs.

Assignees

• Agfa Nv

Inventors

• Loccufier Johan

Classifications

• C08K5/5397

  Phosphine oxides · CPC title

• C07F9/65583

  each of the hetero rings containing nitrogen as ring hetero atom · CPC title

• C07F9/65586

  at least one of the hetero rings does not contain nitrogen as ring hetero atom · CPC title

• C07F9/5337

  Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se) · CPC title

• C07F9/6518

  Five-membered rings · CPC title