Polycyclic glyoxylates as photoinitiators
The present invention relates to photoinitiator compounds of the formula (1) wherein X is O, S or a direct bond; Y is O, S or CR 9 R 10 ; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently of each other are hydrogen, halogen, C 1 -C 18 alkyl, C 5 -C 10 cycloalkyl, C 2 -C 18 alkenyl, phenyl, C 1 -C 4 alkoxy, C 5 -C 7 cycloalkoxy, phenoxy, C 1 -C 4 -alkylthio, C 5 -C 7 cycloalkylthio, phenylthio, di(C 1 -C 4 alkyl)amino, di(C 5 -C 7 cycloalkyl)amino, N-morpholinyl, N-piperidinyl or a group of formula (2) provided that one or more than one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 is a group of formula (2); R 9 , R 10 independently of each other are hydrogen, C 1 -C 18 alkyl, C 2 -C 12 alkenyl, C 5 -C 10 cycloalkyl, phenyl-C 1 -C 4 alkyl, phenyl or together with the C atom to which they are attached form a 5-membered, 6-membered or 7-membered ring; and R 11 is hydrogen, C 1 -C 18 alkyl, C 5 -C 10 cycloalkyl, C 2 -C 12 alkenyl, phenyl-C 1 -C 4 alkyl or phenyl.
1. A photopolymerizable composition comprising:
(A) at least one ethylenically unsaturated photopolymerizable compound and
(B) at least one photoinitiator compound of formula (1)
wherein
X is O, S or a direct bond;
Y is O, S or CR 9 R 10 ;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently of each other are hydrogen, halogen, C 1 -C 18 alkyl, C 5 -C 10 cycloalkyl, C 2 -C 18 alkenyl, phenyl, C 1 -C 4 alkoxy, C 5 -C 7 cycloalkoxy, phenoxy, C 1 -C 4 -alkylthio, C 5 -C 7 cycloalkylthio, phenylthio, di(C 1 -C 4 alkyl)amino, di(C 5 -C 7 cycloalkyl)amino, N-morpholinyl, N-piperidinyl or a group of formula (2)
provided that one or more than one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 is a group of formula (2);
R 9 , R 10 independently of each other are hydrogen, C 1 -C 18 alkyl, C 2 -C 12 alkenyl, C 5 -C 10 cycloalkyl, phenyl-C 1 -C 4 alkyl, phenyl or together with the C atom to which they are attached form a 5-membered, 6-membered or 7-membered ring; and
R 11 is hydrogen, C 1 -C 18 alkyl, C 5 -C 10 cycloalkyl, C 2 -C 12 alkenyl, phenyl, or phenyl-C 1 -C 4 alkyl.
2. The photopolymerizable composition according to claim 1 , wherein the photoinitiator of formula (1) is a compound of formula (3):
wherein;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are as defined in claim 1 .
3. The photopolymerizable composition according to claim 1 , wherein:
(i) one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 is a group of formula (2);
or
(ii) one of R 1 , R 2 , R 3 or R 4 is a group of formula (2) and one of R 5 , R 6 , R 7 or R 8 is a group of formula (2).
4. The photopolymerizable composition according to claim 1 , wherein R 1 to R 4 and R 5 to R 8 are independently of each other hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, N-morpholinyl or N-piperidinyl or a group of formula (2).
5. The photopolymerizable composition according to claim 1 , which additionally to the component (B) comprises:
(x) at least one further photoinitiator (C);
(xi) at least one further coinitiator (D);
(xii) at least one other additive (E); or
(xiii) a combination of (x) and (xi) or a combination of (x) and (xii) or a combination of (x) and (xi) and (xii).
6. The photopolymerizable composition according to claim 1 , which comprises 0.05 to 15% by weight, of the photoinitiator compound of formula (1), based on the total composition.
7. A process for the photopolymerization of monomeric, oligomeric or polymeric compounds containing at least one ethylenically unsaturated double bond, which comprises:
adding to the monomeric, oligomeric or polymeric compounds at least one photoinitiator of formula (1);
wherein;
X is O, S or a direct bond;
Y is O, S or CR 9 R 10 ;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently of each other are hydrogen, halogen, C 1 -C 18 alkyl, C 5 -C 10 cycloalkyl, C 2 -C 18 alkenyl, phenyl, C 1 -C 4 alkoxy, C 5 -C 7 cycloalkoxy, phenoxy, C 1 -C 4 -alkylthio, C 5 -C 7 cycloalkylthio, phenylthio, di(C 1 -C 4 alkyl)amino, di(C 5 -C 7 cycloalkyl)amino, N-morpholinyl, N-piperidinyl or a group of formula (2)
provided that one or more than one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 is a group of formula (2);
R 9 , R 10 independently are hydrogen, C 1 -C 18 alkyl, C 2 -C 12 alkenyl, C 5 -C 10 cycloalkyl, phenyl-C 1 -C 4 alkyl, phenyl or together with the C atom to which they are attached form a 5-membered, 6-membered or 7-membered ring; and
R 11 is hydrogen, C 1 -C 18 alkyl, C 5 -C 10 cycloalkyl, C 2 -C 12 alkenyl, phenyl, or phenyl-C 1 -C 4 alkyl; and
irradiating the resulting composition with electromagnetic or particulate radiation.
8. The process according to claim 7 , wherein the at least one photoinitiator of formula (1) is a compound of formula (3):
wherein;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are as defined in claim 7 .
9. The process according to claim 7 , wherein the monomeric, oligomeric or polymeric compounds and the at least one photoinitiator are provided in a preparation of pigmented and nonpigmented paints and varnishes, powder coatings, printing inks, screen printing inks, inks for offset-, flexo- or inkjet printing, printing plates, adhesives, sealings, potting components, dental compositions, foams, moulding compounds, composite compositions, glass fibre cable coatings, screen printing stencils, compositions for producing three-dimensional objects by means of stereolithography, image recording material, photoresist compositions, decolorizing materials, decolorizing materials for image recording materials, or image recording materials using microcapsules.
10. A coated substrate coated on at least one surface with a composition according to claim 1 .
11. Article comprising a polymerized or crosslinked composition obtained by curing a polymerizable composition according to claim 1 .
12. The photopolymerizable composition according to claim 2 , wherein
R 9 , and R 10 independently are hydrogen, C 1 -C 18 alkyl or together with the C atom to which they are attached form a 5-membered, 6-membered or 7-membered ring; and
R 11 is C 1 -C 18 alkyl.
13. The photopolymerizable composition according to claim 2 , wherein;
R 9 , R 10 independently are hydrogen or methyl; and
R 11 is methyl or ethyl.
14. The photopolymerizable composition according to claim 3 , wherein;
R 1 to R 4 and R 5 to R 8 are independently a group of formula (2) or hydrogen.
15. The photopolymerizable composition according to claim 6 , which comprises 0.1 to 10% by weight of the photoinitiator compound of formula (1).
16. The process according to claim 8 , wherein;
(i) one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 is a group of formula (2); or
(ii) one of R 1 , R 2 , R 3 or R 4 is a group of formula (2) and one of R 5 , R 6 , R 7 or R 8 is a group of formula (2).
17. The process according to claim 8 , wherein R 1 to R 4 and R 5 to R 8 are independently of each other hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, N-morpholinyl or N-piperidinyl or a group of formula (2).