Photoinitiators for light-curable compositions

Patent metadata

Field	Value
Publication number	US-11655314-B2
Application number	US-202217719757-A
Country	US
Kind code	B2
Filing date	Apr 13, 2022
Priority date	Jul 27, 2017
Publication date	May 23, 2023
Grant date	May 23, 2023

Abstract

Compounds of formula (I) are photoinitiators or photosensitizers in a photopolymerizable composition:R1 represents a monovalent, linear, branched or cyclic, aliphatic hydrocarbon group having 1 to 20 carbon atoms, optionally substituted with substituent(s) selected from —Cl, —Br, —OH, ═O, —NH—CO—OR2, —NH—CO—R2 or free-radically or ionically polymerizable groups. Each R2 is independently —H or C1-6 alkyl; n is ≥1. If n=1, Z and Y are absent and X represents —OR3; if n is >1, Z represents —OR4—, Y represents —OR5— and X represents —H or —OH. R3 represents —H or R1; and R4 and R5 each independently represent a bivalent hydrocarbon group. The polymerizable moieties as optional substituents of R1 are polymerizable double or triple bonds, lactam, lactone and epoxide moieties, which are subjectable to ring-opening polymerization; and two of R1 to R5 may be linked to one another to form a ring or a dimer.

First claim

The invention claimed is:

1. A photoinitiator or photosensitizer of the following formula (I) for use in a photopolymerizable composition:

wherein
R 1 represents a monovalent, linear, branched or cyclic, aliphatic hydrocarbon group having 1 to 20 carbon atoms, which is optionally substituted with one or more substituents selected from —Cl, —Br, —OH, ═O, —NH—CO—OR 2 , —NH—CO—R 2 or free-radically or ionically polymerizable groups, wherein each R 2 radical is independently selected from —H or C 1-6 alkyl;
wherein n is >1; Z represents —OR 4 —; Y represents —OR 5 —; X represents —H or —OH; and R 4 and R 5 each independently represent a bivalent hydrocarbon group for which otherwise the same options as mentioned for R 1 apply;
wherein the polymerizable moieties as optional substituents of R 1 are selected from polymerizable double or triple bonds as well as lactam, lactone and epoxide moieties, which are subjectable to ring-opening polymerization;
and wherein any two of R 1 to R 5 may be optionally linked to one another to form a ring or a dimer.

2. The photoinitiator or photosensitizer according to claim 1 , wherein, in formula (I):
a) R 1 represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, in which one or more carbon atoms may have been replaced by oxygen atoms and which is optionally substituted with one or more substituents selected from —Cl, —Br, —OH and —SH; and/or
n is >1 and is selected from the range from 2 to 100 or from 2 to 50 or from 2 to 20, Z represents —OR 4 —, Y represents —OR 5 —, and X represents —OH.

3. The use according to claim 1 , wherein the compound of formula (I) is used as a type I or type II photoinitiator.

4. The photoinitiator or photosensitizer according to claim 1 , wherein the compound of formula (I) is used in photopolymerizable compositions as a photoinitiator in combination with one or more co-initiators.

5. The photoinitiator or photosensitizer according to claim 4 , wherein one or more compounds is/are used as co-initiator/s selected from mono- or polyhydric alcohols (—OH), thiols (—SH), amines (—NR—), silanes (═SiH—), germanes (═GeH—), phosphines (—PRR′R″—), ethers (>CH—O—CH<), iodonium (—I + —) and sulfonium (═S + —) salts and compounds based on derivatives thereof.

6. The photoinitiator or photosensitizer according to claim 5 , wherein one or more mono- or polyhydric alcohols selected from sugars, glycerol, thiols, polyethylene glycol and polypropylene glycol are used as co-initiators.

7. The photoinitiator or photosensitizer according to claim 1 , wherein the compound of formula (I) is used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of polymerizable monomers.

8. The photoinitiator or photosensitizer according to claim 1 , wherein the compound of formula (I) is used for curing acrylate or methacrylate monomers.

9. The photoinitiator or photosensitizer according to claim 1 , wherein the compound of formula (I) is used as a photoinitiator or photosensitizer in compositions to be cured inside the human body or in curable compositions from the food sector.

10. A photopolymerizable composition comprising at least one compound of formula (I) as a photoinitiator or photosensitizer, at least one photopolymerizable monomer and optionally at least one co-initiator, fillers, solvents, further initiators or sensitizers, plasticizers and/or flow enhancers:

wherein:
R 1 represents a monovalent, linear, branched or cyclic, aliphatic hydrocarbon group having 1 to 20 carbon atoms, which is optionally substituted with one or more substituents selected from —Cl, —Br, —OH, ═O, —NH—CO—OR 2 , —NH—CO—R 2 or free-radically or ionically polymerizable groups, wherein each R 2 radical is independently selected from —H or C 1-6 alkyl;
wherein n is >1; Z represents —OR 4 —; Y represents —OR 5 —; X represents —H or —OH; and R 4 and R 5 each independently represent a bivalent hydrocarbon group for which otherwise the same options as mentioned for R 1 apply;
wherein the polymerizable moieties as optional substituents of R 1 are selected from polymerizable double or triple bonds as well as lactam, lactone and epoxide moieties, which are subjectable to ring-opening polymerization;
and wherein any two of R 1 to R 5 may be optionally linked to one another to form a ring or a dimer.

11. The photoinitiator or photosensitizer according to claim 1 , wherein n is selected from the range from 2 to 100.

12. The photoinitiator or photosensitizer according to claim 11 , wherein n is selected from the range from 2 to 50.

13. The photoinitiator or photosensitizer according to claim 12 , wherein n is selected from the range from 2 to 20.

Assignees

• Univ Wien Tech

Inventors

• Liska Robert
• Knaack Patrick
• Gauss Paul
• Taschner Roland

Classifications

• C08F2/50 Primary

  with sensitising agents · CPC title

• C08F22/22

  Esters containing nitrogen · CPC title

• C08F222/102

  of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate · CPC title

• C08G18/4238

  derived from dicarboxylic acids and dialcohols · CPC title

• C08F22/20

  Esters containing oxygen in addition to the carboxy oxygen · CPC title