US 11,673,980 B2
Photopolymerizable dental composites with rapid curing and low shrinkage stress
Benjamin Gebhardt, Grabs (CH); and Norbert Moszner, Triesen (LI)
Assigned to Ivoclar Vivadent AG, Schaan (LI)
Filed by Ivoclar Vivadent AG, Schaan (LI)
Filed on Oct. 15, 2019, as Appl. No. 16/653,119.
Claims priority of application No. 18208916 (EP), filed on Nov. 28, 2018.
Prior Publication US 2020/0165363 A1, May 28, 2020
Int. Cl. C08F 20/18 (2006.01); C08K 3/013 (2018.01); A61K 6/20 (2020.01); A61K 6/62 (2020.01); C08F 2/38 (2006.01); C08K 5/07 (2006.01); C08K 5/18 (2006.01); C08K 5/41 (2006.01)
CPC C08F 20/18 (2013.01) [A61K 6/20 (2020.01); A61K 6/62 (2020.01); C08F 2/38 (2013.01); C08K 3/013 (2018.01); C08K 5/07 (2013.01); C08K 5/18 (2013.01); C08K 5/41 (2013.01)] 19 Claims
 
1. A radically polymerizable material consisting of
(a) 0.01 to 5 wt.-% of at least one transfer reagent,
(b) 10 to 40 wt.-% of at least one multifunctional (meth)acrylate selected from bi-sphenol A dimethacrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), 2-[4-(2-(meth)acryloyloxyethoxyethoxy)phenyl]-2-[4-(2-methacryloyloxy-ethoxy)phenyl]propane), 2,2-bis[4-(2-methacryloxypropoxy)phenyl]propane (bis-PMA), UDMA (an addition product of 2-hydroxyethyl methacrylate and 2,2,4- or 2,4,4-trimethylhexa-methylene-1,6-diisocyanate), bismethacryloyloxymethyltricyclo[5.2.1.]decane (TCDMA) and mixtures thereof,
(c) 0.01 to 2.0 wt.-% of a mixture of
at least one monomolecular photoinitiator selected from a diacyldialkylgermanium, tetraacylgermanium and tetraacylstannane compound, a mono- or bisacylphosphine oxide or a mixture thereof, and
at least one bimolecular photoinitiator selected from camphorquinone (CQ), 9,10-phenanthrenequinone, 1-phenylpropane-1,2-dione, 2,2-dimethoxy-2-phenylacetophenone, diacetyl, 4,4′-dichlorobenzil or a combination of at least one of camphorquinone (CQ), 9,10-phenanthrenequinone, 1-phenylpropane-1,2-dione, 2,2-dimethoxy-2-phenylacetophenone, diacetyl, 4,4′-dichlorobenzil with an amine selected from with 4-(dimethylamino)-benzoic acid ester (EDMAB), N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine, triethanolamine or a mixture thereof,
(d) 50 to 85 wt.-% of at least one filler selected from mixed oxides of SiO2 and ZrO2, glass powders, radiopaque fillers, ground prepolymers and mixtures thereof, and
(e) 0 to 3 wt.-% additive(s), in each case relative to the total mass of the material,
wherein the material comprises as transfer reagent (a) at least one allyl sulfone of Formula I

OG Complex Work Unit Chemistry
in which the variables have the following meanings:
A H; —CN; a phenyl radical, which can bear one or more substituents, such as —CH3, —C2H5, —OH, —OCH3, —O—COCH3, a polymerizable vinyl, (meth)acryloyloxy or (meth)acrylamide group, or an aliphatic linear or branched C1—C20 alkylene or C1—C20 alkyl radical, which can be interrupted by one or more 1,4-phenylene groups, urethane groups, O or S, which can bear one or more substituents, such as —OH or —OCH3, and which can bear a tri-C1-C4 alkoxysilyl group or a polymerizable vinyl, (meth)acryloyloxy or (meth)acrylamide group terminally;
R1 in each case independently of one another H, an aliphatic linear or branched C1-C9 alkyl radical, tolyl or phenyl;
R2 in each case independently of one another a phenyl radical, which can bear one or more substituents, such as —CH3, —C2H5, —OH, —OCH3, —O—COCH3, a polymerizable vinyl, (meth)acryloyloxy or (meth)acrylamide group, —C(═CH2)—COOR3 or —C(═CH2)—CO—NR4R5; or an aliphatic linear or branched C1—C20 alkyl radical, which can be interrupted by O or S and which can bear a polymerizable vinyl, (meth)acryloyloxy or (meth)acrylamide group, —C(═CH2)—COOR3 or —C(═CH2)—CO—NR4R5 terminally, wherein R3-5 independently of one another are in each case a linear or branched C1-6 alkyl radical;
X —COO—, —CON(R6)— or is absent, wherein the bonding to A is effected via O or N and wherein
R6 is H; or an aliphatic linear or branched C1-C20 alkyl radical, which can be interrupted by one or more O or S and which can bear a polymerizable vinyl, (meth)acryloyloxy or (meth)acrylamide group, —C(═CH2)—COOR3 or —C(═CH2)—CO—NR4R5 terminally, wherein R3-5 independently of one another are in each case a linear or branched C1-6 alkyl radical;
n an integer from 1 to 6,
and/or
a vinyl sulfone ester of Formula II,

OG Complex Work Unit Chemistry
in which the variables have the following meanings:
B H, CN, a cycloaliphatic, linear or branched aliphatic C1-C30 hydrocarbon radical, which can be substituted by one or more substituents, which can be interrupted by one or more urethane groups, ester groups, O and/or S and which can contain 1 to 4 benzene groups,
an aromatic C6-C30 hydrocarbon radical, which can be substituted by one or more substituents;
Y —COO—, —CON(R7)— or is absent, wherein the bonding to B is effected via O or N;
C a cycloaliphatic, linear or branched aliphatic C1-C30 hydrocarbon radical, which can be substituted by one or more substituents, which can be interrupted by one or more urethane groups, ester groups, O and/or S and which can contain 1 to 4 benzene groups,
an aromatic C6-C30 hydrocarbon radical, which can be substituted by one or more substituents;
R7 hydrogen, a cycloaliphatic, linear or branched aliphatic C1-C10 hydrocarbon radical, which can be interrupted by one or more oxygen atoms and which can be substituted by one or more OH groups, or
an aromatic C6-C10 hydrocarbon radical, which can be substituted by one or more OH groups;
p an integer from 1 to 6;
k an integer from 1 to 6;
q an integer from 1 to 6; wherein
p and q cannot be greater than 1 at the same time and wherein if p=1, q=k, and if q=1, p=k.