Polymerizable compositions with high polymerization depth

Patent metadata

Field	Value
Publication number	US-9532930-B2
Application number	US-201314391759-A
Country	US
Kind code	B2
Filing date	Apr 11, 2013
Priority date	Apr 11, 2012
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

The invention relates to a composition with at least one polymerizable binder, wherein the composition contains a photoinitiator mixture which contains (a) at least one diacylgermanium compound of general formula (I)

in which R 1 , R 2 independently of each other are a linear C 1-4 -alkyl, or C 2-4 -alkenyl radical, which can be substituted by one or more polymerizable groups; R 3 , R 4 independently of each other are in each case H, halogen, a branched or linear C 1-4 -alkyl or —O—C 1-4 -alkyl radical; R 5 , R 6 , R 7 independently of each other are in each case H, halogen, a linear C 1-20 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical, which can be interrupted by one or more —O—, —S— or —NR 8 — radicals and substituted by one or more polymerizable groups; and R 8 independently is in each case H, a C 1-20 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical, (b) at least one α-diketone and (c) at least one accelerator, as well as the use of the composition for example for producing a filling composite.

First claim

The invention claimed is:

1. A composition with at least one polymerizable binder, in which it contains a photoinitiator mixture which contains
(a) at least one diacylgermanium compound of Formula (I),
(b) at least one α-diketone,
(c) at least one accelerator and
(d) at least one acyl- or bisacylphosphine oxide which is selected from the group consisting of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and mixtures thereof;

wherein
R 1 , R 2 independently of each other are a linear C 1-4 -alkyl, or C 2-4 -alkenyl radical, which can be substituted by one or more polymerizable groups;
R 3 , R 4 independently of each other are in each case H, halogen, a branched or linear C 1-4 -alkyl or —O—C 1-4 -alkyl radical;
R 5 , R 6 independently of each other are in each case H, halogen, a linear C 1-20 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical which can be interrupted by one or more —O—, —S— or —NR 8 -radicals and substituted by one or more polymerizable groups;
R 7 independently of each other is in each case H, halogen, a linear C 1-20 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical which can be interrupted by one or more —O—, —S— or NR 8 — radicals and substituted by one or more polymerizable groups; and
R 8 independently is in each case H, a C 1-20 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical.

2. A composition according to claim 1 , in which the photoinitiator mixture contains, relative to the polymerizable binder
(a) 0.05 to 1.1 wt.-% o diacylgermanium compound,
(b) 0.1 to 1.1 wt.-% α-diketone,
(c) 0.1 to 2.1 wt.-% accelerator and
(d) 0 to 2.1 wt.-% bisacylphosphine oxide.

3. A composition according to claim 2 , in which the photoinitiator mixture contains, relative to the polymerizable binder
(a) 0.1 to 0.5 wt.-% diacylgermanium compound,
(b) 0.2 to 0.6 wt.-% α-diketone,
(c) 0.3 to 1.5 wt.-% accelerator and
(d) 0 to 1.5 wt.-% acyl- or bisacylphosphine oxide.

4. A composition according to claim 3 , in which the photoinitiator mixture contains, relative to the polymerizable binder
(a) 0.2 to 0.5 wt.-% diacylgermanium compound,
(b) 0.2 to 0.5 wt.-% α-diketone,
(c) 0.4 to 0.8 wt.-% accelerator and
(d) 0.1 to 0.6 wt.-% acyl- or bisacylphosphine oxide.

5. A composition according to claim 1 , in which the diacylgermanium compound is a compound of Formula (II)

wherein
R 1 , R 2 independently of each other are a linear C 1-4 -alkyl radical;
R 3 , R 4 are in each case H;
R 5 , R 6 are in each case H; and
R 7 independently of each other are in each case H, a linear C 1-6 -alkyl or -alkoxy radical.

6. A composition according to claim 5 , in which the diacylgermanium compound is selected from the group consisting of bis(4-methoxybenzoyl)diethylgermanium, dibenzoyl diethylgermanium and mixtures thereof.

7. A composition according to claim 1 , in which the α-diketone is selected from the group consisting of camphorquinone, 1-phenylpropane-1,2-dione and mixtures thereof.

8. A composition according to claim 1 , in which the accelerator is an amine accelerator which is selected from the group consisting of p-(dimethylamino)-benzoic acid ethyl ester, dimethylaminoethyl methacrylate, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, triethanolamine and mixtures thereof.

9. A composition according to claim 1 , which contains as polymerizable binder at least one radically polymerizable monomer and/or prepolymer.

10. A composition according to claim 9 , which contains as binder a mono- or multifunctional (meth)acrylate, an N-mono- or -disubstituted acrylamide, a bisacrylamide, a radically ring-opening polymerizable monomer, a cyclic allyl sulphide, a polysiloxane based on methacryl silanes or a mixture thereof or a mixture of at least one of the binders with a radically polymerizable, acid-group-containing monomer.

11. A composition according to claim 9 , which contains as binder a mono- or multifunctional (meth)acrylate or a mixture thereof.

12. A composition according to claim 1 which additionally contains filler.

13. A composition according to claim 1 , which additionally contains at least one additive selected from stabilizers, dyes, microbiocidal active ingredients, fluoride-ion-releasing additives, optical brighteners, plasticizers, UV absorbers and mixtures thereof.

14. A composition according to claim 12 , which contains 0.002 to 5 wt.-% photoinitiator mixture, 9 to 59.8 wt.-% polymerizable binder and 30 to 90 wt.-% filler, relative in each case to the total mass of the composition.

15. A process for producing a composite, in which the composition according to claim 1 is produced and then completely or partially cured.

16. The process according to claim 15 producing adhesives, coatings, cements, composites, shaped parts or dental materials.

17. A composition according to claim 1 , in which the accelerator is an amine accelerator.

Assignees

• Ivoclar Vivadent Ag

Inventors

• Burtscher Peter
• Moszner Norbert
• Rheinberger Volker

Classifications

• A61K6/62 Primary

  Photochemical radical initiators · CPC title

• A61K6/889 Primary

  Polycarboxylate cements; Glass ionomer cements · CPC title

• A61K6/0052

  Human Necessities · mapped topic

• A61K6/0835 Primary

  Human Necessities · mapped topic