Dental materials based on low-odour thiols

Patent metadata

Field	Value
Publication number	US-9877898-B2
Application number	US-201515113202-A
Country	US
Kind code	B2
Filing date	Feb 24, 2015
Priority date	Feb 24, 2014
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

Dental material, which contains an ene compound with two or more C—C multiple bonds and a thiol according to general Formula (1) or an oligomer based on such a thiol,

wherein n, p and m are chosen such that the thiol has a total of at least 3 SH groups.

First claim

The invention claimed is:

1. Dental material, which contains at least one thiol and at least one ene compound with two or more C—C multiple bonds, characterized in that it contains at least one thiol according to general Formula (1),

in which
R is —SO 2 —, a linear or branched aliphatic C 1-20 radical, an aromatic C 6-20 radical, a cycloaliphatic C 3-18 radical or a heterocyclic radical with 3 to 17 C atoms and 1 to 3 heteroatoms which are selected from N, O and S;
R 1 is absent or is a linear or branched aliphatic C 1-12 radical, an aromatic C 6-20 radical, a cycloaliphatic C 3-18 radical or a heterocyclic radical with 3 to 17 C atoms and 1 to 3 heteroatoms which are selected from N, O and S;
R 2 is absent or is a linear or branched aliphatic C 1-20 radical which can be interrupted by O or S, an aromatic C 6-10 radical which can be substituted by CH 3 , CH 2 CH 3 , OH, OCH 3 or —O—CO—CH 3 ;
R 3 is absent or is a linear or branched aliphatic C 1-20 radical which can be interrupted by O or S, an aromatic C 6-10 radical which can be substituted by CH 3 , CH 2 CH 3 , OH, OCH 3 or —O—CO—CH 3 ;
R 4 is a C 1-6 alkyl radical;
X, Y independently of each other are O, S, CO—NH, O—CO—NH or NH—CO—NH or are absent;
Z is O, S, CO—NH, O—CO—NH or NH—CO—NH or is absent;
m is an integer from 1 to 4;
n is an integer from 1 to 4;
p is an integer from 1 to 6;
q is an integer from 0 to 4,
wherein n, p and m are chosen such that the thiol has a total of at least 3 SH groups.

2. Dental material according to claim 1 , in which the variables of Formula 1 have the following meanings:
R is —SO 2 —, a linear or branched aliphatic C 1-12 radical, an aromatic C 6-18 radical, a cycloaliphatic C 5-8 radical or a heterocyclic radical with 3 to 5 C atoms, 1 to 3 heteroatoms and a total of 5-8 ring atoms, wherein the heteroatoms are selected from N, O and S;
R 1 is absent, a linear or branched aliphatic C 1-10 radical or an aromatic C 6-10 radical;
R 2 is absent or is a linear or branched aliphatic C 1-10 radical or a phenyl radical;
R 3 is a linear or branched aliphatic C 1-10 radical or a phenyl radical;
R 4 is a C 1-4 alkyl radical;
X is O or is absent;
Y is O or is absent;
Z is O or is absent;
m is 1, 2 or 3;
n is 1 or 2;
p is 1, 2 or 3;
q is 0, 1 or 2.

3. Dental material according to claim 2 , in which the variables of Formula 1 have the following meanings:
R is —SO 2 —, a linear or branched aliphatic C 1-6 radical, an aromatic C 6 radical, a cycloaliphatic C 5-8 radical or a 1,3,5-triazine-2,4,6-trione radical;
R 1 is absent, a linear or branched aliphatic C 1-6 radical or a phenyl radical;
R 2 is absent or is a linear or branched aliphatic C 1-3 radical;
R 3 is a linear or branched aliphatic C 2-6 radical;
R 4 is a C 1-3 alkyl radical;
X is O or is absent;
Y is O or is absent;
Z is O or is absent;
m is 2 or 3;
n is 1;
p is 1 or 2;
q is 0 or 1.

4. Dental material according to claim 3 , in which the thiol of general Formula (1) is present as reaction product with a di- or multi-functional acrylate or acrylamide or with a di- or multi-functional isocyanate.

5. Dental material according to claim 4 , which contains a vinyl, allyl or norbornene compound or an alkyne as ene compound.

6. Dental material according to claim 5 , which contains as ene compound
a vinyl ether, vinyl ester or an N-vinyl amide;
and/or
an allyl ether of tri- or higher-functionalized alcohols or a reaction product of tri- or higher-functionalized carboxylic acids with allyl alcohol or allyl amine, a triallyl amine or triallyl-1,3,5-triazine-2,4,6-trione (TATATO);
and/or
an ester of 5-norbornene-2-carboxylic acid with tri- or higher-functionalized alcohols or an ester of 5-norbornene-2-methanol with tri- or higher-functionalized carboxylic acids;
and/or
an ester of propargyl alcohol with tri- or higher-functionalized carboxylic acids or an ether of propargyl alcohol with tri- or higher-functionalized alcohols.

7. Dental material according to claim 6 , which additionally contains at least one mono- or multi-functional methacrylate or a mixture thereof.

8. Dental material according to claim 7 , which additionally contains an initiator for the radical polymerization.

9. Dental material according to claim 8 , which additionally contains organic or inorganic particulate filler.

10. Dental material according to claim 9 , which contains the following components:
a) 5 to 40 wt.-% of at least one thiol of general Formula I or an oligomer thereof,
b) 5 to 40 wt.-% of at least one ene component,
c) 0 to 40 wt.-% methacrylate(s),
d) 0.01 to 10 wt.-% initiator(s),
e) 10 to 85 wt.-% filler(s), and
f) 0 to 10 wt.-% additive(s).

11. Dental material according to claim 1 for intraoral use as dental cement, filling composite or veneering material.

12. Process of using the dental material according to claim 1 for preparing an inlay, onlay, crown or bridge comprising forming the inlay, onlay, crown or bridge with the dental material and curing the dental material.

13. Process for preparing an oligomeric thiol, in which a thiol of Formula (I) in a stoichiometric excess is reacted with a di- or multi-functional ene compound or with a di- or multi-functional isocyanate wherein Formula (I) comprises

in which
R is —SO 2 —, a linear or branched aliphatic C 1-20 radical, an aromatic C 6-20 radical, a cycloaliphatic C 3-18 radical or a heterocyclic radical with 3 to 17 C atoms and 1 to 3 heteroatoms which are selected from N, O and S;
R 1 is absent or is a linear or branched aliphatic C 1-12 radical, an aromatic C 6-20 radical, a cycloaliphatic C 3-18 radical or a heterocyclic radical with 3 to 17 C atoms and 1 to 3 heteroatoms which are selected from N, O and S;
R 2 is absent or is a linear or branched aliphatic C 1-20 radical which can be interrupted by O or S, an aromatic C 6-10 radical which can be substituted by CH 3 , CH 2 CH 3 , OH, OCH 3 or —O—CO—CH 3 ;
R 3 is absent or is a linear or branched aliphatic C 1-20 radical which can be interrupted by O or S, an aromatic C 6-10 radical which can be substituted by CH 3 , CH 2 CH 3 , OH, OCH 3 or —O—CO—CH 3 ;
R 4 is a C 1-6 alkyl radical;
X, Y independently of each other are O, S, CO—NH, O—CO—NH or NH—CO—NH or are absent;
Z is O, S, CO—NH, O—CO—NH or NH—CO—NH or is absent;
m is an integer from 1 to 4;
n is an integer from 1 to 4;
p is an integer from 1 to 6;
q is an integer from 0 to 4,
wherein n, p and m are chosen such that the thiol has a total of at least 3 SH groups.

14. Process according to claim 13 , in which the thiol of Formula (I) is reacted with a di- or multi-functional acrylate, di- or multi-functional acrylamide or di- or multi-functional isocyanate in a molar ratio of SH to acryl or NCO groups of from 1.5:1 to 15:1.

15. Oligomeric thiol, which is obtainable using a process comprising reacting a thiol of Formula (I) in a stoichiometric excess with a di- or multi-functional ene compound or with a di- or multi-functional isocyanate wherein Formula (I) comprises

in which
R

Assignees

• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Burtscher Peter
• Fischer Urs-Karl
• Ritter Helmut
• Tabatabai Monir
• Utterodt Andreas

Classifications

• A61K6/62

  Photochemical radical initiators · CPC title

• A61K6/887

  Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• A61K6/891 Primary

  Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• A61K6/71

  Fillers · CPC title

• A61K6/77

  Glass · CPC title