Composite with reduced polymerization shrinkage stress

1. A radically polymerizable dental material, which comprises at least one compound of Formulae I to III:

in which the variables have the following meanings:

R 1 hydrogen, an aliphatic linear or branched C 1 -C 15 alkyl radical, which can be interrupted by one or more O or S and which can be substituted or unsubstituted, benzyl or phenyl;

R 2 hydrogen, an aliphatic linear or branched C 1 -C 15 alkyl radical, which can be interrupted by one or more O or S and which can be substituted or unsubstituted, benzyl, an aromatic C 6 -C 18 radical, which can be substituted or unsubstituted, or a (meth)acryloyloxy group;

R 3 an aliphatic linear or branched C 1 -C 15 alkyl radical, which can be interrupted by one or more O and which can be substituted or unsubstituted, benzyl, or an aromatic C 6 -C 18 radical, which can be substituted or unsubstituted;

X 1 a linear or branched aliphatic C 1 -C 15 alkylene radical, which can be interrupted by one or more O or S, or a cycloaliphatic C 6 -C 16 radical;

X 2 an (n+1)-valent organic C 1 -C 20 radical, which can be interrupted by one or more O or S, a cycloaliphatic C 5 -C 20 radical, an aromatic C 6 -C 20 radical or an isocyanuric acid radical according to the following formula:

X 3 a 3-valent linear or branched aliphatic C 3 -C 20 radical;

X 4 a 2-valent organic C 2 -C 30 radical, which can be substituted by one or more methyl groups or is unsubstituted;

Y is absent or an ether (—O—), ester (—COO— or —OOC—), urethane (—NR 4 —CO—O— or —O—CO—NR 4 —) or amide group (—CONR 4 — or —NR 4 —CO—), wherein R 4 in each case represents H or a C 1 -C 3 alkyl radical;

Z is absent or an ether (—O—), ester (—COO— or —OOC—), or amide group (—CONR 5 — or —NR 5 —CO—), wherein R 5 represents H or a C 1 -C 3 alkyl radical;

W an oligomeric polyester, polyether or polythioether group;

m 1, 2, 3, 4, 5 or 6;

n 1, 2, 3 or 4,

wherein, if X 2 is an isocyanuric acid radical, then Y and R 2 are absent and n is 3.

2. The dental material according to claim 1 , which comprises at least one additional radically polymerizable monomer and at least one initiator for the radical polymerization.

3. The dental material according to claim 1 , wherein the variables have the following meanings:

R 1 hydrogen, an aliphatic linear or branched C 1 -C 10 alkyl radical, which can be interrupted by one or more O and which can carry one or more substituents, which are selected from —CH 3 , —C 2 H 5 and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, benzyl or phenyl;

R 2 hydrogen, an aliphatic linear or branched C 1 -C 10 alkyl radical, which can be interrupted by one or more O and which can carry one or more substituents, which are selected from —CH 3 , —C 2 H 5 and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, benzyl, or an aromatic C 6 -C 12 radical, which can carry one or more substituents, which are selected from —CH 3 , —C 2 H 5 , and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, or a (meth)acryloyloxy group;

R 3 an aliphatic linear or branched C 1 -C 10 alkyl radical, which can carry one or more substituents, which are selected from —CH 3 , —C 2 H 5 , halogen and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, benzyl, or an aromatic C 6 -C 18 radical, which can carry one or more substituents, which are selected from —CH 3 , —C 2 H 5 , polymerizable vinyl and/or (meth)acryloyloxy groups, or is unsubstituted;

X 1 a linear or branched aliphatic C 1 -C 10 alkylene radical, which can be interrupted by one or more O, or a cycloaliphatic C 6 -C 12 radical;

X 2 an (n+1)-valent organic C 1 -C 15 radical, which can be interrupted by one or more O, a cycloaliphatic radical or an aromatic C 6 -C 14 radical;

X 3 a 3-valent linear or branched aliphatic C 3 -C 10 radical;

X 4 a 2-valent organic C 2 -C 20 radical, a cycloaliphatic C 5 -C 10 radical or a combination thereof, which can carry one or more methyl groups as substituents, or is unsubstituted;

Y is absent or an ester or urethane group;

Z is absent or an ether or ester group;

W an oligomeric polyester or polyether group and

n 1, 2 or 3.

4. The dental material according to claim 3 , wherein the variables have the following meanings:

R 1 an aliphatic linear or branched C 1 -C 4 alkyl radical or benzyl (Ph-CH 2 —);

R 2 hydrogen or a (meth)acryloyloxy group;

R 3 a linear C 1 -C 3 alkyl radical, benzyl (Ph-CH 2 —), phenyl (Ph-) or p-tolyl (H 3 C-Ph-), wherein these radicals can be substituted in each case by a (meth)acryloyloxy group;

X 1 a linear C 1 -C 3 alkylene radical;

X 2 an (n+1)-valent linear or branched aliphatic C 2 -C 12 radical, which can be interrupted by 1 to 3O, or an aromatic C 6 -C 12 radical;

X 3 a 3-valent linear or branched aliphatic C 3 -C 4 radical;

X 4 a 2-valent aliphatic C 2 -C 10 radical or a cycloaliphatic C 6 radical, which can be substituted with 1 to 3 methyl groups;

Y is absent or an ester or urethane group;

Z is absent;

W an oligomeric polyester or polyether group and

n 1, 2 or 3.

5. The dental material according to claim 1 , wherein the substituents present in the case of the individual radicals are selected in each case from C 1 -C 3 alkyl groups, halogen, OH, OCH 3 or —O—COCH 3 , polymerizable vinyl, (meth)acryloyloxy and/or (meth)acrylamide groups.

6. The dental material according to claim 1 , which contains at least one multifunctional (meth)acrylate or a mixture of mono- and multifunctional (meth)acrylates.

7. The dental material according to claim 1 , which comprises at least one filler.

8. The dental material according to claim 1 , which additionally comprises at least one photoinitiator for the radical polymerization.

9. The dental material according to claim 1 , which comprises

(a) 0.1 to 30 wt.-% of at least one compound of general formula I, II or III,

(b) 5 to 99.1 wt.-% of at least one further radically polymerizable monomer,

(c) 0.01 to 5.0 wt.-% of at least one initiator for the radical polymerization,

(d) 0 to 90 wt.-% of at least one filler, and

(e) 0 to 70 wt.-% of one or more additives,

in each case relative to the total mass of the dental material.

10. The dental material according to claim 9 , which has the following composition:

(a) 0.1 to 20 wt.-% of at least one urethane allyl sulfide of general formula I, II and/or III,

(b) 5 to 50 wt.-% of at least one further radically polymerizable monomer,

(c) 0.01 to 5.0 wt.-% of at least one initiator for the radical polymerization,

(d) 10 to 70 wt.-% of at least one filler and

(e) 0 to 5 wt.-% of one or more additives,

in each case relative to the total mass of the dental material.

11. The dental material according to claim 9 , which has the following composition:

(a) 0.1 to 20 wt.-% of at least one urethane allyl sulfide of general formula I, II and/or III,

(b) 10 to 50 wt.-% of at least one further radically polymerizable monomer,

(c) 0.01 to 5.0 wt.-% of at least one initiator for the radical polymerization,

(d) 10 to 85 wt.-% of at least one filler and

(e) 0 to 5 wt.-% of one or more additives,

in each case relative to the total mass of the dental material.

12. The dental material according to claim 1 , which, apart from one or more compounds of Formulae I, II and III, comprises no volatile mercaptans.

13. The dental material according to claim 1 for intraoral use for the restoration of damaged teeth.

14. The dental material according to claim 1 , wherein the variables have the following meanings:

R 1 hydrogen, an aliphatic linear or branched C 1 -C 10 alkyl radical, which can be interrupted by one or two O and which can carry 1 to 3 substituents, which are selected from —CH 3 , —C 2 H 5 and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, benzyl or phenyl;

R 2 hydrogen, an aliphatic linear or branched C 1 -C 10 alkyl radical, which can be interrupted by one or two O and which can carry 1 to 3 substituents, which are selected from —CH 3 , —C 2 H 5 and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, benzyl, or an aromatic C 6 -C 12 radical, which can carry 1 to 3 substituents, which are selected from —CH 3 , —C 2 H 5 , and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, or a (meth)acryloyloxy group;

R 3 an aliphatic linear or branched C 1 -C 10 alkyl radical, which can carry 1 to 3 substituents, which are selected from —CH 3 , —C 2 H 5 , halogen and/or polymerizable (meth)acryloyloxy groups, or is unsubstituted, benzyl, or an aromatic C 6 -C 18 radical, which can carry 1 to 3 substituents, which are selected from —CH 3 , —C 2 H 5 , polymerizable vinyl and/or (meth)acryloyloxy groups, or is unsubstituted;

X 1 a linear or branched aliphatic C 1 -C 10 alkylene radical, which can be interrupted by one or two 0, or a cycloaliphatic C 6 -C 12 radical;

X 2 an (n+1)-valent an aliphatic C 1 -C 15 radical, which can be interrupted by one or two 0, a cycloaliphatic radical or an aromatic C 6 -C 14 radical;

X 3 a 3-valent linear or branched aliphatic C 3 -C 10 radical;

X 4 a 2-valent aliphatic C 2 -C 20 radical, a cycloaliphatic C 5 -C 10 radical or a combination thereof, which can carry one or two methyl groups as substituents, or is unsubstituted;

Y is absent or an ester or urethane group;

Z is absent or an ether or ester group;

W an oligomeric polyester or polyether group and

n 1, 2 or 3.

15. The dental material according to claim 3 , wherein the variables have the following meanings:

R 1 methyl or ethyl;

R 2 hydrogen or a (meth)acryloyloxy group;

R 3 a linear C 1 -C 3 alkyl radical, benzyl (Ph-CH 2 —), phenyl (Ph-) or p-tolyl (H 3 C-Ph-), wherein these radicals can be substituted in each case by a (meth)acryloyloxy group;

X 1 a linear C 1 -C 3 alkylene radical;

X 2 an (n+1)-valent linear or branched aliphatic C 2 -C 12 radical, which can be interrupted by 1 to 3O, or an aromatic C 6 -C 12 radical;

X 3 —CH 2 —CH (−)—CH 2 —;

X 4 a 2-valent aliphatic C 2 -C 10 radical or a cycloaliphatic C 6 radical, which can be substituted with 1 to 3 methyl groups;

Y is absent or an ester or urethane group;

Z is absent;

W an oligomeric polyester or polyether group and

n 1 or 2.

16. The dental material according to claim 1 , which comprises

(a) 0.5 to 20 wt.-% of at least one compound of general formula I,

(b) 15 to 95 wt.-% of at least one multifunctional (meth)acrylate,

(c) 0.1 to 3.0 wt.-% of at least one initiator for the radical polymerization,

(d) 0 to 82 wt.-% of at least one filler, and

(e) 0.1 to 60 wt.-% of one or more additives,

in each case relative to the total mass of the dental material.

17. The dental material according to claim 9 , which has the following composition:

(a) 0.5 to 10 wt.-% of at least one urethane allyl sulfide of general formula I,

(b) 20 to 40 wt.-% of at least one further radically polymerizable monomer,

(c) 0.2 to 3.0 wt.-% of at least one initiator for the radical polymerization,

(d) 30 to 70 wt.-% of at least one filler and

(e) 0.2 to 4.0 wt.-% of one or more additives,

in each case relative to the total mass of the dental material.

18. The dental material according to claim 9 , which has the following composition:

(a) 0.5 to 8 wt.-% of at least one urethane allyl sulfide of general formula I,

(b) 15 to 30 wt.-% of at least one further radically polymerizable monomer,

(c) 0.1 to 0.3 wt.-% of at least one initiator for the radical polymerization,

(d) 30 to 85 wt.-% of at least one filler and

(e) 0.2 to 3.0 wt.-% of one or more additives,

in each case relative to the total mass of the dental material.

19. A method of using a dental material comprising extraorally producing a dental restoration or repairing a dental restoration with the dental material of claim 1 .

20. The method according to claim 14 , wherein the dental restoration is selected from the group consisting of dental cement, filling composite, inlay, onlay, crown, bridge, dental prosthesis, artificial teeth, and veneering material.

21. A method of using a dental material comprising producing a curable dental material comprising a compound of Formula I, II or III, in which the variables are as defined in claim 1 ; and

thermally curing and/or light-curing the curable dental material, thereby reducing the polymerization shrinkage stress (PSS) of the dental material.

22. A method of producing a dental material comprising the steps of mixing a compound of Formula I, II or III, in which the variables are as defined in claim 1 with one or more of a radically polymerizable monomer, one or more initiator for the polymerization, one or more filler, and optionally one or more additives; and

thermally curing and/or light-curing the above obtained mixture.