Photoinitiators for light-curable compositions

Patent metadata

Field	Value
Publication number	US-11518823-B2
Application number	US-201816633385-A
Country	US
Kind code	B2
Filing date	Jul 27, 2018
Priority date	Jul 27, 2017
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

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 —ORs— 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;
n is ≥1, wherein
i) if n=1, Z and Y are not present and X represents —OR 3 ; and
ii) if n is >1, Z represents —OR 4 —, Y represents —OR 5 — and X represents —H or —OH;

wherein
R 3 represents —H or one of the options mentioned for R 1 ; 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;
wherein the compound of formula (I) is used in photopolymerizable compositions as a photoinitiator in combination with one or more co-initiators comprising one or more mono- or polyhydric alcohols selected from sugars, glycerol, thiols, polyethylene glycol and polypropylene glycol; and/or
wherein the compound of formula (I) is used in a photoinitiator or photosensitizer composition to be cured inside the human body or in curable compositions from the food sector.

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
b1) n=1 and X represents —OR 3 , wherein R 3 independently represents —H or one of the options described for R 1 ; or
b2) 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 photoinitiator or photosensitizer 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 the one or more compounds is/are used as co-initiator/s further comprise(s) a compound selected from 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 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.

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

8. A photopolymerizable composition comprising at least one compound of formula (I) as a photoinitiator or photosensitizer, at least one photopolymerizable monomer,

wherein in formula (I):
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;
n is ≥1, wherein
i) if n =1, Z and Y are not present and X represents —OR 3; and
ii) if n is >1, Z represents —OR4—, Y represents —OR 5 — and X represents —H or —OH;

wherein
R 3 represents —H or one of the options mentioned for R 1 ; 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 Ri are selected from polymerizable double or triple bonds as well as lactam, lactone and epoxide moieties, which are subjectable to ring-opening polymerization;
wherein any two of R 1 to R 5 may be optionally linked to one another to form a ring or a dimer;
wherein the photopolymerizable composition additionally comprises one or more co-initiators comprising mono- or polyhydric alcohols selected from sugars, glycerol, thiols, polyethylene glycol and polypropylene glycol; and/or
wherein the photopolymerizable composition is to be cured inside the human body or in curable compositions from the food sector.

Assignees

• Univ Wien Tech

Inventors

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

Classifications

• C08F222/102

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

• C08F2/50 Primary

  with sensitising agents · CPC title

• C07C327/02

  Monothiocarboxylic acids · CPC title

• C07C69/716

  Esters of keto-carboxylic acids {or aldehydo-carboxylic acids} · CPC title

• C07C327/20

  Esters of monothiocarboxylic acids · CPC title