Surface-modified fillers
A filler which is surface-modified with a compound of the formula [(PG)-R 1 —Z] n —SP—[Y—R 2 -(AG)] m is particularly suitable for use in dental materials, for the preparation of adhesives, coatings and composites.
1. Dental material comprising
(a) 5 to 90 wt.-% filler that is based on an inorganic filler and that is surface-modified with a compound of the formula (I),
[(PG)-R 1 —Z] n —SP—[—R 2 -(AG)] m (I)
in which
AG is —SiR 3 R 4 X,
R 1 is a C 1 -C 3 alkylene group or cyclopropylene group or is absent,
R 2 is a C 1 -C 10 alkylene group or is absent,
R 3 is a C 1 -C 8 alkyl group, chlorine or OR 5 ,
R 4 is a C 1 -C 8 alkyl group, phenyl, chlorine or OR 5 ,
R 5 is a C 1 -C 6 alkyl group,
X is OR 5 or chlorine,
Z is CO—NR 6 , in which R 6 is H or C 1 -C 6 alkyl,
PG is an allyl group, a styryl group, a vinyl cyclopropyl group or a radically polymerizable group of the formula
in which
R 9 is H, C 1 -C 3 alkyl, C 1 -C 3 hydroxyalkyl or COOR 10 ,
R 10 is H, C 1 -C 10 alkyl, 1,6-dimethylphenyl or mesityl,
R 11 is H or phenyl,
m is 1 or 2,
n is 1, 2, 3 or 4,
SP is absent or an (n+m)-valent linear or branched aliphatic C 1 -C 30 radical in which the carbon chain can be interrupted by O, S, CO—NH, O—CO—NH or NH—CO—NH, an (n+m)-valent aromatic C 6 -C 18 radical, an (n+m)-valent cycloaliphatic C 3 -C 18 radical or an (n+m)-valent heterocyclic C 3 -C 18 radical, wherein the radicals can be substituted with a C 1 -C 5 alkyl, Cl, Br and/or OH or unsubstituted,
(b) 9.9 to 90 wt.-% radically polymerizable monomer,
(c) 0.1 to 5.0 wt.-% initiator for the radical polymerization, and
(d) 0 to 70 wt.-% solvent,
each relative to the total mass of the dental material.
2. Dental material according to claim 1 , in which PG is a vinyl group of the formula H 2 C═C(—R 9 )—, an acrylic acid group of the formula H 2 C═C(—COOR 10 )—, an allyl, a styryl and/or a vinyl cyclopropyl.
3. Dental material according to claim 1 , in which at least one of the variables has one of the following meanings:
R 1 is a methylene group, cyclopropylene group or is absent,
R 2 is a C 1 -C 3 alkylene group or is absent,
R 3 is a C 1 -C 3 alkyl group, chlorine or OR 5 ,
R 4 is a C 1 -C 3 alkyl group, phenyl, chlorine or OR 5 ,
R 5 is a C 1 -C 2 alkyl group,
X is OR 5 or chlorine,
PG is a vinyl group H 2 C═C(—R 9 )— in which R 9 is H or CH 3 ,
m is 1 or 2,
n is 1 or 2,
SP is absent or an (n+m)-valent linear or branched aliphatic C 1 -C 6 radical, an (n+m)-valent aromatic C 6 -C 10 radical, an (n+m)-valent cycloaliphatic C 3 -C 10 radical or an (n+m)-valent heterocyclic C 3 -C 10 radical.
4. Dental material according to claim 1 , wherein the filler is based on an inorganic, particulate filler with a particle size of 0.01 to 5 μm.
5. Dental material according to claim 4 , wherein the filler is an amorphous filler based on one or more metal oxides and/or silicon oxide.
6. Dental material according to claim 4 , wherein the filler is based on quartz, glass ceramic or glass powder.
7. Dental material according to claim 1 , wherein the filler is based on an inorganic, particulate filler with a specific surface area of more than 20 m 2 /g.
8. Dental material according to claim 1 , wherein the filler is obtained by chemically reacting an inorganic particulate filler with a compound of the formula (I).
9. Dental material according to claim 1 , which contains at least one acidic monomer.
10. Dental material according to claim 4 , wherein the filler is based on ytterbium trifluoride.
11. Dental material according to claim 7 , wherein the surface area is more than 40 m 2 /g.
12. Dental material according to claim 1 ,
wherein
AG is —SiR 3 R 4 X,
R 1 is a methylene group or cyclopropylene group,
R 2 is a C 1 -C 10 alkylene group or is absent,
R 3 is a C 1 -C 8 alkyl group, chlorine or OR 5 ,
R 4 is a C 1 -C 8 alkyl group, phenyl, chlorine or OR 5 ,
R 5 is a C 1 -C 6 alkyl group,
X is OR 5 or chlorine,
Z is CO—NR 6 , in which R 6 is H or C 1 -C 6 alkyl,
PG is a vinyl group of the formula H 2 C═CH—,
m is 1 or 2,
n is 1, 2, 3 or 4,
SP is absent or an (n+m)-valent linear or branched aliphatic C 1 -C 30 radical in which the carbon chain can be interrupted by O, S, CO—NH, O—CO—NH or NH—CO—NH, an (n+m)-valent aromatic C 6 -C 18 radical, an (n+m)-valent cycloaliphatic C 3 -C 18 radical or an (n+m)-valent heterocyclic C 3 -C 18 radical.
13. Dental material according to claim 1 ,
wherein
AG is —SiR 3 R 4 X,
R 1 is a methylene group, cyclopropylene group, or is absent,
R 2 is a C 1 -C 10 alkylene group or is absent,
R 3 is a C 1 -C 8 alkyl group, chlorine or OR 5 ,
R 4 is a C 1 -C 8 alkyl group, phenyl, chlorine or OR 5 ,
R 5 is a C 1 -C 6 alkyl group,
X is OR 5 or chlorine,
Z is CO—NR 6 , in which R 6 is H or C 1 -C 6 alkyl,
PG is a vinyl group of the formula H 2 C═C(—R 9 )—
in which
R 9 is H or CH 3 ,
m is 1 or 2,
n is 1, 2, 3 or 4,
SP is absent or an (n+m)-valent linear or branched aliphatic C 1 -C 30 radical in which the carbon chain can be interrupted by O, S, CO—NH, O—CO—NH or NH—CO—NH, an (n+m)-valent aromatic C 6 -C 18 radical, an (n+m)-valent cycloaliphatic C 3 -C 18 radical or an (n+m)-valent heterocyclic C 3 -C 18 radical.
14. Dental material which contains
(a) 5 to 90 wt. % filler that is surface-modified with a compound of the formula (I),
[(PG)-R 1 Z] n —SP—[—R 2 -(AG)] m (I)
in which
AG is —SiR 3 R 4 X,
R 1 is a C 1 -C 3 alkylene group or cyclopropylene group or is absent,
R 2 is a C 1 -C 10 alkylene group or is absent,
R 3 is a C 1 -C 8 alkyl group, chlorine or OR 5 ,
R 4 is a C 1 -C 8 alkyl group, phenyl, chlorine or OR 5 ,
R 5 is a C 1 -C 6 alkyl group,
X is OR 5 or chlorine,
Z is CO—NR 6 , in which R 6 is H or C 1 -C 6 alkyl,
PG is an allyl group, a styryl group, a vinyl cyclopropyl group or a radically polymerizable group of the formula
in which
R 9 is H, C 1 -C 3 alkyl, C 1 -C 3 hydroxyalkyl or COOR 10 ,
R 10 is H, C 1 -C 10 alkyl, 1,6-dimethylphenyl or mesityl,
R 11 is H or phenyl,
m is 1 or 2,
n is 1, 2, 3 or 4,
SP is absent or an (n+m)-valent linear or branched aliphatic C 1 -C 30 radical in which the carbon chain can be interrupted by O, S, CO—NH, O—CO—NH or NH—CO—NH, an (n+m)-valent aromatic C 6 -C 18 radical, an (n+m)-valent cycloaliphatic C 3 -C 18 radical or an (n+m)-valent heterocyclic C 3 -C 18 radical, wherein the radicals can be substituted with a C 1 -C 5 alkyl, Cl, Br and/or OH or unsubstituted,
(b) 9.9 to 90 wt.-% radically polymerizable monomer, and
(c) 0.1 to 5.0 wt.-% an initiator for the radical polymerization,
(d) 0 to 70 wt.-% solvent,
each relative to the total mass of the dental material.
15. Dental material according to claim 14 , which contains at least one acidic monomer.
16. Dental material according to claim 14 , wherein the dental material is an adhesive, filling composite, fixing cement, fissure sealer or coating material.
17. Dental material according to claim 1 , wherein the filler is based on ZrO 2 , Ta 2 O 3 , TiO 2 , a mixed oxide of SiO 2 , ZrO 2 and/or TiO 2 , Yb 2 O 3 , Y 2 O 3 , YbF 3 , Al 2 O 3 and AlO(OH), boehmite, silicon oxide, glass ceramic or glass powder.
18. Dental material according to claim 5 , wherein the filler is based on ZrO 2 , Ta 2 O 3 , TiO 2 , a mixed oxide of SiO 2 , ZrO 2 and/or TiO 2 , Yb 2 O 3 , Y 2 O 3 , YbF 3 , Al 2 O 3 and AlO(OH), boehmite, pyrogenic silica or precipitated silica.
19. Dental material according to claim 4 , wherein the filler is based on an X-ray opaque metal compound.
20. Dental material according to claim 1 , wherein the dental material is an adhesive, filling composite, fixing cement, fissure sealer or coating material.
21. Method of applying the dental material according to claim 1 to a patient's tooth or teeth for restoring the tooth or teeth.
22. Dental material comprising a filler that is based on Ta 2 O 3 , Yb 2 O 3 , Y 2 O 3 , YbF 3 , silicon oxide, glass ceramic or glass powder and that is surface-modified with a compound of the formula (I),
[(PG)-R 1 —Z] n —SP—[—R 2 -(AG)] m (I)
in which
AG is —SiR 3 R 4 X,
R 1 is a C 1 -C 3 alkylene group or cyclopropylene group or is absent,
R 2 is a C 1 -C 10 alkylene group or is absent,
R 3 is a C 1 -C 8 alkyl group, chlorine or OR 5 ,
R 4 is a C 1 -C 8 alkyl group, phenyl, chlorine or OR 5 ,
R 5 is a C 1 -C 6 alkyl group,
X is OR 5 or chlorine,
Z is CO—NR 6 , in which R 6 is H or C 1 -C 6 alkyl,
PG is an allyl group, a styryl group, a vinyl cyclopropyl group or a radically polymerizable group of the formula
in which
R 9 is H, C 1 -C 3 alkyl, C 1 -C 3 -hydroxyalkyl or COOR 10 ,
R 10 is H, C 1 -C 10 alkyl, 1,6-dimethylphenyl or mesityl,
R 11 is H or phenyl,
m is 1 or 2,
n is 1, 2, 3 or 4,
SP is absent or an (n+m)-valent linear or branched aliphatic C 1 -C 30 radical in which the carbon chain can be interrupted by O, S, CO—NH, O—CO—NH or NH—CO—NH, an (n+m)-valent aromatic C 6 -C 18 radical, an (n+m)-valent cycloaliphatic C 3 -C 18 radical or an (n+m)-valent heterocyclic C 3 -C 18 radical, wherein the radicals can be substituted with a C 1 -C 5 alkyl, Cl, Br and/or OH or unsubstituted.
23. Dental material according to claim 22 , wherein the filler is based on silicon oxide, glass ceramic or glass powder.
24. Dental material according to claim 1 , which contains 5 to 50 wt.-% filler that is based on an inorganic filler and that is surface-modified with a compound of the formula (I) relative to the total mass of the dental material.
25. Dental material according to claim 1 , which contains 9.9 to 40 wt.-% radically polymerizable monomer relative to the total mass of the dental material.
26. Dental material according to claim 1 , which contains 0.2 to 2.0 wt.-% initiator for the radical polymerization relative to the total mass of the dental material.
27. Dental material according to claim 1 , which contains 0 to 50 wt.-% solvent relative to the total mass of the dental material.
28. Dental material according to claim 1 , which contains
(a) 5 to 50 wt.-% filler that is based on an inorganic filler and that is surface-modified with a compound of the formula (I),
(b) 9.9 to 40 wt.-% radically polymerizable monomer,
(c) 0.2 to 2.0 wt.-% initiator for the radical polymerization, and
(d) 0 to 50 wt.-% solvent,
each relative to the total mass of the dental material.
29. Dental material according to claim 9 , wherein the acidic monomer is selected from the group consisting of 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid ethyl ester, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid-2,4,6-trimethylphenylester, 6-(N-acryloylamino)hexyldihydrogen phosphate, 6-(N-methacryloylamino)hexyldihydrogen phosphate, 1,3-bis-(N-acryloylamino)-propan-2-yl-dihydrogen phosphate and 1,3-bis-(N-methacryloylamino)-propan-2-yl-dihydrogen phosphate.