Long-wave absorbing photoinitiators
Compounds according to general formula (I) in which M is Ge or Sn, RAr is R 1 , R 2 , R 3 , R 4 , R 5 , independently of one another in each case, are —H, —F, —Cl, —OR 6 , —SR 6 , —N(R 6 ) 2 , —CF 3 , —CN, —NO 2 , —COOR 6 , —CONHR 6 , a branched, cyclic or preferably linear C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkyloxy or a C 2-20 alkenoxy radical, which can be interrupted one or more times by O, S or —NR 6 — and substituted by one or more polymerizable groups and/or radicals R 6 , R 6 is H, a branched, cyclic or preferably linear C 1-20 alkyl or C 2-20 alkenyl radical, R 7 is a chemical bond, an n-valent aromatic radical or a branched, cyclic or preferably linear C 1-20 alkylene radical, which can be interrupted one or more times by O, S or —NR 6 — and substituted by one or more polymerizable groups, ═O and/or radicals R 6 , n is 2 or 3 and m is 0 or 1. The compounds are particularly suitable as photoinitiators for radical polymerization and in particular for the production of dental materials.
1. A compound according to general formula (I)
in which the variables have the following meanings:
M Ge or Sn,
RAr
R 1 , R 2 , R 3 , R 4 , R 5 independently of one another in each case —H, —F, —Cl, —OR 6 , —SR 6 , —N(R 6 ) 2 , —CF 3 , —CN, —NO 2 , —COOR 6 , —CONHR 6 , a branched, cyclic or linear C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkyloxy or a C 2-20 alkenoxy radical, which can be interrupted one or more times by O, S or —NR 6 — and which can be substituted by one or more polymerizable groups and/or radicals R 6 ,
R 6 in each case independently of one another H, a branched, cyclic or linear C 1-20 alkyl or C 2-20 alkenyl radical,
R 7 an n-valent aromatic radical or a branched, cyclic or linear C 2-20 alkylene radical, which can be interrupted one or more times by O, S or —NR 6 — and which can be substituted by one or more polymerizable groups, ═O and/or radicals R 6 ,
n 2 or 3,
m 0 or 1.
2. The compound according to claim 1 , wherein the variables of formula (I) have the following meanings:
M Ge or Sn,
RAr
R 1 , R 2 , R 3 , R 4 , R 5 independently of one another in each case —H, —F, —Cl, —OR 6 , —CF 3 , —CN, —COOR 6 , —CONHR 6 , a linear C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkyloxy or a C 2-20 alkenoxy radical, which can be interrupted one or more times by O or S and which can be substituted by one or more polymerizable groups and/or radicals R 6 ;
R 6 H, an aromatic radical or a linear C 1-10 alkyl radical, C 2-10 alkenyl radical,
R 7 a branched or linear n-valent C 2-10 alkylene radical, which can be interrupted one or more times by O or S and which can be substituted by one or more polymerizable groups, ═O and/or radicals R 6 ,
n 2,
m 0 or 1.
3. The compound according to claim 1 , wherein the variables of formula (I) have the following meanings:
M Ge or Sn,
RAr
R 1 , R 2 , R 3 , R 4 , R 5 independently of one another in each case —H or a C 1-3 alkyl radical,
R 7 an n-valent benzene radical or an n-valent, linear C 2-8 alkyl radical,
n 2,
m 0 or 1.
4. The compound according to claim 1 , wherein the variables of formula (I) have the following meanings:
M Ge or Sn,
RAr
R 1 , R 2 , R 3 , R 4 , R 5 independently of one another in each case —H or methyl,
R 7 an n-valent benzene radical or an n-valent, linear C 2-6 alkyl radical,
n 2,
m 0 or 1.
5. The compound according to claim 1 , wherein the variables of formula (I) have the following meanings:
M Ge or Sn
RAr
R 7
n 2
m 1.
6. The compound according to claim 1 , wherein the variables of formula (I) have the following meanings:
M Ge
RAr
R 7
n 3
m 1.
7. The compound according to claim 1 , wherein the variables of formula (I) have the following meanings:
M Ge
RAr
R 7 C 2 -C 8 alkylene, particularly preferably —C 4 H 8 —
n 2
m 0.
8. A composition which comprises at least one compound according to general formula (I)
in which the variables have the following meanings:
M Ge or Sn,
RAr
R 1 , R 2 , R 3 , R 4 , R 5 independently of one another in each case —H, —F, —Cl, —OR 6 , —SR 6 , —N(R 6 ) 2 , —CF 3 , —CN, —NO 2 , —COOR 6 , —CONHR 6 , a branched, cyclic or linear C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkyloxy or a C 2-20 alkenoxy radical, which can be interrupted one or more times by O, S or —NR 6 — and which can be substituted by one or more polymerizable groups and/or radicals R 6 ,
R 6 in each case independently of one another H, a branched, cyclic or linear C 1-20 alkyl or C 2-20 alkenyl radical,
R 7 an n-valent aromatic radical or a branched, cyclic or linear C 2-20 alkylene radical, which can be interrupted one or more times by O, S or —NR 6 — and which can be substituted by one or more polymerizable groups, ═O and/or radicals R 6 ,
n 2 or 3,
m 0 or 1; and
at least one polymerizable monomer.
9. The composition which comprises at least one compound according to general formula (I)
in which the variables have the following meanings:
M Ge or Sn,
RAr
R 1 , R 2 , R 3 , R 4 , R 5 independently of one another in each case —H, —F, —Cl, —OR 6 , —SR 6 , —N(R 6 ) 2 , —CF 3 , —CN, —NO 2 , —COOR 6 , —CONHR 6 , a branched, cyclic or linear C 1-20 alkyl, C 2-20 alkenyl, C 1-20 alkyloxy or a C 2-20 alkenoxy radical, which can be interrupted one or more times by O, S or —NR 6 — and which can be substituted by one or more polymerizable groups and/or radicals R 6 ,
R 6 in each case independently of one another H, a branched, cyclic or linear C 1-20 alkyl or C 2-20 alkenyl radical,
R 7 an n-valent aromatic radical or a branched, cyclic or linear C 2-20 alkylene radical, which can be interrupted one or more times by O, S or —NR 6 — and which can be substituted by one or more polymerizable groups, ═O and/or radicals R 6 ,
n 2 or 3,
m 0 or 1; and
at least one radically polymerizable monomer.
10. The composition according to claim 9 , which comprises 0.001 to 3 wt.-% of the at least one compound according to general formula (I), relative to the total mass of the composition.
11. The composition according to claim 10 , which comprises 0.001 to 1 wt.-% of the at least one compound according to general formula (I), relative to the total mass of the composition.
12. The composition according to claim 10 , which comprises 0.005 to 0.5 wt.-% of the at least one compound according to general formula (I), relative to the total mass of the composition.
13. The composition according to claim 9 , which comprises at least one mono- or multifunctional (meth)acrylate or a mixture thereof as the at least one radically polymerizable monomer.
14. The composition according to claim 9 , which comprises
(a) 0.001 to 3 wt.-% of at least one compound of general formula (I),
(b) 1 to 99.9 wt.-% of at least one radically polymerizable monomer,
(c) 0 to 85 wt.-% of at least one filler and
(d) 0 to 70 wt.-% of one or more additives,
in each case relative to the total mass of the composition.
15. The composition according to claim 14 , which comprises
(a) 0.001 to 1.0 wt.-% of at least one compound of general formula (I),
(b) 5 to 95 wt.-% of at least one radically polymerizable monomer,
(c) 5 to 80 wt.-% of at least one filler and
(d) 0.1 to 60 wt.-% of one or more additives,
in each case relative to the total mass of the composition.
16. The composition according to claim 14 , which comprises
(a) 0.005 to 0.5 wt.-% of at least one compound of general formula (I),
(b) 10 to 90 wt.-% of at least one radically polymerizable monomer,
(c) 10 to 75 wt.-% of at least one filler and
(d) 0.1 to 50 wt.-% of one or more additives,
in each case relative to the total mass of the composition.
17. The composition according to claim 8 for therapeutic use as a dental material, preferably as a dental cement, filling composite or veneering material.
18. The compound according to claim 1 for use as a photoinitiator.