Dental composites with improved storage stability

Patent metadata

Field	Value
Publication number	US-11357708-B2
Application number	US-201615541257-A
Country	US
Kind code	B2
Filing date	Jan 8, 2016
Priority date	Jan 9, 2015
Publication date	Jun 14, 2022
Grant date	Jun 14, 2022

Abstract

Dental material which contains (a) at least one mono- or multifunctional radically polymerizable monomer, (b) at least one organic halogen compound as initiator for the radical polymerization, (c) at least one transition metal compound as catalyst and (d) at least one reducing agent. The material is characterized by a high storage stability at room temperature and does not have the disadvantages associated with peroxides.

First claim

The invention claimed is:

1. Dental material comprising
(a) a mixture of at least one mono- and at least one polyfunctional methacrylate as radically polymerizable monomer,
(b) at least one organic halogen compound,
(c) at least one transition metal compound, and
(d) at least one reducing agent,
wherein said dental material does not comprise peroxides or solvents, wherein the transition metal compound is a compound of copper, iron, ruthenium, nickel or palladium and wherein the at least one halogen compound (b) is selected from halogenated alkyl aromatics, benzyl halides, benzyl chloride, benzyl bromide, 1-phenylethyl chloride, benzotrichloride, benzhydryl chloride, benzhydryl bromide; α-halogen carboxylic acid esters, C 1 -C 6 -alkyl esters of an α-halogen-C 1 -C 6 -carboxylic acid, α-chloropropionic acid, α-bromopropionic acid, α-chloro-isobutanoic acid, α-bromo-iso-butanoic acid, α-bromophenylacetic acid, esters of α-bromo-isobutanoic acid, α-bromo-isobutanoic acid methylester, α-bromo-isobutanoic acid ethylester, α-bromo-iso-butyryl bromide, 2-(2-bromoisobutyryloxy)ethyl methacrylate, tert-butyl α-bromoisobutyrate, 3-butynyl-2-bromo-iso-butyrate, dipentaerythritol hexakis(2-bromoisobutyrate), 1,1,1-tris(2-bromoisobutyryloxymethyl)ethane, ethyl α-bromophenylacetate; α-halogenketones, 1,1,1-trichloropropan-2-one, dichloromethyl phenyl ketone; α-halogen nitriles, 2-bromopropionitrile, trichloroacetonitrile; sulphonyl halides, methylsulphonyl chloride, trichloromethylsulphonyl chloride, p-toluenesulphonyl chloride and 4-methoxyphenylsulphonyl chloride.

2. Dental material according to claim 1 further comprising at least one organic and/or inorganic filler as constituent (e).

3. Dental material according to claim 1 comprising as monomer (a) a mixture of mono- and difunctional methacrylates.

4. Dental material according to claim 1 comprising as component (c) at least one transition metal complex compound which is selected from the complexes of the metals copper, iron, ruthenium, nickel and palladium; copper complexes with the ligands phenanthroline, 1,10-phenanthroline (Phen), terpyridine, bipyridine, 2,2′-bipyridine (Bipy), 4,4′-dimethyl-2,2′-bipyridine, 6,6′-dimethyl-2,2′-bipyridine, pyridinimine, aliphatic amines, 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), N,N,N′,N″,N″-penta-methyldiethylenetriamine (PMDETA) and tris[2-(dimethylamino)ethyl]amine (Me 6 TREN); iron complexes with the ligands triphenylphosphine, 4,4′-di(5-nonyl)-2,2′-bipyridine (dNbpy) or 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (PriIm), FeCl 2 (PPh 3 ) 2 , FeBR 2 -dNbpy (dNbpy: 4,4′-di(5-nonyl)-2,2′-bipyridine), FeC 2 (PriIm) 2 and FeBr 2 (PriIm) 2 (PriIm: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene); the ruthenium complexes RuCl 2 (PPh 3 ) 4 and RuH 2 (PPh 3 ) 4 ; or the nickel complexes Ni[o,o′(CH 2 NMe 2 )C 6 H 3 ]Br and NiBr 2 (PPh 3 ) 2 .

5. Dental material comprising
(a) a mixture of at least one mono- and at least one polyfunctional methacrylate as radically polymerizable monomer,
(b) at least one organic halogen compound,
(c) at least one transition metal compound, and
(d) at least one reducing agent,
wherein said dental material does not comprise peroxides or solvents, wherein the at least one transition metal compound is a
transition metal salt which is selected from the salts of the metals copper, iron, ruthenium, nickel and palladium, CuCl, CuBr, CuCl 2 , CuBr 2 , CuI 2 , Cu(II) carboxylates, Cu(II) acetate, Cu(II)-2-ethylhexanoate, FeCl 3 , FeBr 2 , FeCl 2 , RuCl 2 , NiBr 2 , NiCl 2 , Pd(OAc) 2 and wherein the dental material additionally comprises at least one
complexing organic compound which is selected from P- and N-containing ligands, phosphines, triphenylphosphine; ethylenediaminetetraacetic acid (EDTA); phenanthrolines, 1,10-phenanthroline (Phen); bipyridines, 2,2′-bipyridine (Bipy), 4,4′-dimethyl-2,2′-bipyridine, 6,6′-dimethyl-2,2′-bipyridine and 4,4′-di(5-nonyl)-2,2′-bipyridine (dNbpy); terpyridines, 2′:6′,2″-terpyridine (tpy), 4,4′,4″-tris(5-nonyl)-2,2′:6′,2″-terpyridine; pyridinimines, N-octyl-2-pyridylmethanimine; alkylated imidazoles, 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (PriIm); alkylamino-substituted benzenes, o,o′(CH 2 NMe 2 ) 2 C 6 H 3 ; aliphatic amines, 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me 6 TREN), N,N,N′,N′-tetramethylethylenediamine (TMEDA), 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane (Me4CYCLAM), diethylenetriamine (DETA), triethylenetetramine (TETA) and 1,4,8,11-tetraazacyclotetradecane (CYCLAM)); pyridine-containing ligands, N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN), N,N-bis(2-pyridylmethyl)amine (BPMA) and N,N-bis(2-pyridylmethyl)octylamine (BPMOA), alkyl-substituted 2-(1H-1,2,3-triazol-4-yl)pyridines, 2,6-bis(1H-1,2,3-triazol-4-yl)-pyridine and alkyl-substituted 2,6-bis(1H-1,2,3-triazol-4-yl)pyridines.

6. Dental material according to claim 1 comprising as reducing agent (d) at least one compound which is selected from ascorbic acid and derivatives thereof, tin compounds, Sn(II) octoate, Sn(II)-2-ethylhexanoate, reducing sugars, glucose, fructose, antioxidants, β-carotenoids, vitamin A, α-tocopherol (vitamin E), phenolic reducing agents, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), propyl gallate, octyl gallate, pyrogallol, sulphites, bisulphites, thiosulphates, hydroxylamine, hydrazine and derivatives thereof.

7. Dental material according to claim 1 further comprising a photoinitiator.

8. Dental material according to claim 1 comprising no plasticizers/phlegmatizing agents.

9. Dental material comprising
(a) 5 to 80 wt.-% of a mixture of at least one mono- and at least one polyfunctional methacrylate as radically polymerizable monomer,
(b) 0.1 to 6.0 wt.-% of at least one organic halogen compound,
(c) 0.0001 to 1.0 wt.-% of at least one transition metal compound,
(d) 0.01 to 5.0 wt.-% of at least one reducing agent and
(e) 10 to 85 wt.-% filler(s),
wherein said dental material does not comprise peroxides or solvents, wherein the transition metal compound is a compound of copper, iron, ruthenium, nickel or palladium and wherein, if constituent (c) is a non-complex transition metal salt, then the dental material additionally contains 0.0001 to 1.0 wt.-% of at least one complexing organic compound.

10. Dental material according to claim 9 , which additionally comprises
(f) 0.01 to 3.0 wt.-% photoinitiator, and/or
(g) 0.001 to 5.0 wt.-% additive(s).

11. Dental material according to claim 10 which is present in the form of at least two separate components which are mixed with each other before use.

12. Dental material according to claim 11 which comprises a first component and a second component, wherein the first component contains the constituents (a), (c) and optionally one or more of the constituents (f)-(g) and the second component contains the constituents (a), (b), (d), (e) and optionally one or more of the constituents (f)-(g).

13. Dental material according to claim 1 for use as cement or filling material.

14. Dental material according to claim 1 manufactured into dental restorations, inlays, onlays, crowns or bridges.

15. Dental material according to claim 9 comprising
(a) 10 to 70 wt.-% mono- and polyfunctional (meth)acrylates,
(b) 0.2 to 4.0 wt.-% of at least one organic halogen compound,
(c) 0.001 to 1.0 wt.-% of at least one transition metal compound,
(d) 0.01 to 3.0 wt.-% reducing agent and
(e) 22 to 82 wt.-% filler(s),
wherein, if constituent (c) is a non-complex transition metal salt, then the d

Assignees

• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Fischer Urs Karl
• Schubert Ulrich S
• Hager Martin

Classifications

• A61K6/61 Primary

  Cationic, anionic or redox initiators · CPC title

• A61K6/887 Primary

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

• A61K6/62

  Photochemical radical initiators · CPC title