Dental materials based on monofunctional vinylcyclopropane derivatives

Patent metadata

Field	Value
Publication number	US-10512593-B2
Application number	US-201715661359-A
Country	US
Kind code	B2
Filing date	Jul 27, 2017
Priority date	Aug 3, 2016
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

Dental material which contains at least one vinylcyclopropane of the general formulae I,

in which A, B independently of each other are in each case OH or COOH; X, Y independently of each other are in each case O or NH; R 1 , R 2 independently of each other are in each case H or an aliphatic linear or branched C 1 -C 10 hydrocarbon radical which can be interrupted by O, S or an ester group; and n, m independently of each other are in each case 0, 1 or 2, wherein, if X═Y═O, R 1 ≠H and R 2 ≠H, n+m≥1. The vinylcyclopropanes are characterized by a low shrinkage and a high reactivity on radical polymerization and are suitable in particular for the preparation of dental materials.

First claim

The invention claimed is:

1. Dental material which contains at least one vinylcyclopropane of the general formulae I,

in which
A, B are COOH,
X, Y independently of each other are in each case O or NH,
R 1 , R 2 independently of each other are in each case an aliphatic linear or branched C 1 -C 10 hydrocarbon radical which can be interrupted by O, S or an ester group, an alicyclic or aromatic C 6 -C 14 radical or an aromatic or non-aromatic heterocyclic radical which can contain 4 to 14 carbon atoms and 1 to 6 heteroatoms which are selected from N, O and/or S atoms, and
n, m independently of each other are in each case 0, 1 or 2,
wherein, if X═O and Y═O, then n+m≥1,
at least one further radically polymerizable monomer and
at least one initiator for the radical polymerization.

2. Dental material which contains 2 to 95 wt.-% vinylcyclopropane(s) according to claim 1 , relative to the total mass of the material.

3. Dental material according to claim 2 , which contains 5 to 85 wt.-% vinylcyclopropane(s).

4. Dental material according to claim 2 , which contains 5 to to 70 wt.-% vinylcyclopropane(s).

5. Dental material according to claim 2 , which contains 10 to 50 wt.-% vinylcyclopropane(s).

6. Dental material according to claim 1 , wherein the at least one further radically polymerizable monomer is selected from 1,1-di(ethoxycarbonyl)- or 1,1-di(methoxycarbonyl)-2-vinylcyclopropane, bis(2-vinylcyclopropane-1-carboxylic acid ethyl ester-1-carbonamido)-2,2-dimethyl-4-methylhexane, 1,8-bis(2-vinylcyclopropane-1-carboxylic acid ethyl ester-1-carbonyloxy)-3,6-dioxaoctane or the esters of 1-ethoxycarbonyl- or 1-methoxycarbonyl-2-vinylcyclopropanecarboxylic acid with ethylene glycol, 1,1,1-trimethylolpropane, 1,4-cyclohexanediol or resorcinol, bis-(2-vinyl-1,1-dicarboxylic acid monoethylester)resorcinylester, 2-(bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl esters or disubstitution products thereof in the 3 position, (3,3-bis(ethoxycarbonyl)bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl ester, or a mixture thereof.

7. Dental material according to claim 1 , wherein the at least one further radically polymerizable is selected from methyl, ethyl, 2-hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E), bisphenol A di(meth)acrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxylated or propoxylated bisphenol A dimethacrylate, bisphenol A dimethacrylate 2-[4-(3-methacryloyloxyethoxyethyl)phenyl]-2-[4-(3-methacryloyloxyethyl)phenyl]-propane) (SR-348c) with 3 ethoxy groups, 2,2-bis[4-(2-(meth)acryloxypropoxy)phenyl]propane, UDMA (an addition product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethylhexamethylene diisocyanate), TMX-UDMA (an addition product of a mixture of HEMA and hydroxypropyl methacrylate (HPMA) with α,α,α′,α′-tetramethyl-m-xylylene diisocyanate (TMXDI)), di-, tri- or tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di- and trimethacrylate, 1,4-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate (D 3 MA), 1,12-dodecanediol di(meth)acrylate and acid group-containing monomers, or a mixture thereof.

8. Dental material according to claim 1 which additionally contains at least one particulate filler.

9. Dental material according claim 1 which additionally contains at least one additive which is selected from solvents, water, ethanol or a mixture thereof, stabilizers, polymerization stabilizers, flavourings, dyes, microbiocidal active ingredients, fluoride-ion-releasing additives, optical brighteners, plasticizers and/or UV-absorbers.

10. Dental material according claim 1 which contains
a) 2 to 95 wt.-% of the at least one vinylcyclopropane of general formula I,
b) 0.01 to 5 wt.-% of the at least one initiator for the radical polymerization,
c) greater than 0 and up to 80 wt.-% of the at least one further radically polymerizable monomer and optionally
d) 0 to 85 wt.-% filler(s),
in each case relative to the total mass of the material.

11. Dental material according claim 1 which contains
a) 2 to 90 wt.-% of the at least one vinylcyclopropane of general formula I,
b) 0.1 to 3.0 wt.-% of the at least one initiator for the radical polymerization,
c) greater than 0 and up to 60 wt.-% of the at least one further radically polymerizable monomer and optionally
d) 0 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.

12. Dental material according claim 1 which contains
a) 10 to 85 wt.-% of the at least one vinylcyclopropane of general formula I,
b) 0.2 to 2 wt.-% of the at least one initiator for the radical polymerization,
c) greater than 0 and up to 50 wt.-% of the at least one further radically polymerizable monomer and optionally
d) 0 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.

13. Dental material according to claim 10 which contains 0 to 40 wt.-% filler(s), for use as coating material, or which contains 10-70 wt.-% filler(s), for use as cement, or which contains 10-85 wt.-% filler(s), for use as filling material.

14. Dental material according to claim 13 for use as filling material which contains
a) 2 to 50 wt.-% of the at least one vinylcyclopropane of general formula I,
b) 0.1 to 3 wt.-% of the at least one initiator or 0.1 to 3 wt.-% of the at least one initiator being a photoinitiator for the radical polymerization,
c) greater than 0 and up to to 50 wt.-% of the at least one further radically polymerizable monomer, and
d) 40 to 85 wt.-% filler(s),
in each case relative to the total mass of the material.

15. Dental material according to claim 13 for use as filling material which contains
a) 5 to 50 wt.-% of the at least one vinylcyclopropane of general formula I,
b) 0.2 to 3.0 wt.-% of the at least one initiator for the radical polymerization,
c) greater than 0 and up to 40 wt.-% of the at least one further radically polymerizable monomer, and
d) 40 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.

16. Dental material according to claim 13 for use as filling material which contains
a) 10 to 50 wt.-% of the at least one vinylcyclopropane of general formula I,
b) 0.2 to 1 wt.-% of the at least one initiator for the radical polymerization,
c) greater than 0 and up to 30 wt.-% of the at least one further radically polymerizable monomer, and
d) 40 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.

17. Method of using the dental material according to claim 1 for the production or repair of dental restorations, prostheses, artificial teeth, inlays, onlays, crowns or bridges.

18. Method of using the dental material according to claim 1 for the production of a shaped body by a stereolithographic process.

19. Method of using at least one vinylcyclopropane of the general formulae I,

in which
A, B are COOH,
X, Y independently of each other are in each case 0 or NH,
R 1 , R 2 independently of each other are in each case an aliphatic linear or branched C 1 -C 10 hydrocarbon radical which can be interrupted by O, S or an ester group, an alicyclic or aromatic C 6 -C 14 radical o

Assignees

• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Catel Yohann
• Fischer Urs Karl
• Tauscher Sven

Classifications

• C08F22/1006

  of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate · CPC title

• C07C2601/02

  with a three-membered ring · CPC title

• A61K6/30

  Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives · CPC title

• C07C233/58

  having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals · CPC title

• C08F222/36

  Amides or imides · CPC title