Self-adhesive dental composite cement with good transparency

1 . A radically polymerizable composition comprising

at least one acidic radically polymerizable monomer,

at least one fluoroaluminosilicate glass filler, and/or radiopaque glass filler, and

at least one masking agent, characterized in that the masking agent is in solid form and in that the composition comprises a catalyst paste as a first component and a base paste as a second component, wherein the masking agent is added in an amount of 1.0 to 12 wt. %, based on the total mass of the paste, to the paste containing the acidic radically polymerizable monomer and the fluoroaluminosilicate glass filler and/or radiopaque glass filler.

2 . The composition according to claim 1 ,

wherein the masking agent comprises ethylenediaminetetraacetic acid (EDTA) and its disodium salt (disodium ethylenediaminetetraacetate), nitrilotriacetic acid, diethy-lenetriaminepentaacetic acid, tetrasodium iminodisuccinate, and the trisodium salt of methylglycinediacetic acid.

3 . The composition according to claim 1 ,

wherein the masking agent is in particulate form and has a volume average particle size (D50 value) in a range selected from 300 to 350 μm, 200 to 250 μm, and 100 to 170 μm, and also has a D10 value in a range selected from 130 to 150 μm, 80 to 100 μm, and 70 to 55 μm.

4 . The composition according to claim 1 , which comprises

5 to 60 wt. % of at least one radically polymerizable monomer without an acid group,

1 to 15 wt. % of at least one radically polymerizable monomer containing an acid group,

25 to 80 wt. % of at least one fluoroaluminosilicate glass filler and/or radiopaque glass filler,

0.1 to 8 wt. % of at least one initiator for radical polymerization, and

0.5 to 6.0 wt. % of at least one masking agent, in each case based on the total mass of the composition.

5 . The composition according to claim 4 , which comprises

a) 0.5 to 6 wt. % of at least one solid masking agent,

b) 5 to 40 wt. % of at least one polyfunctional monomer without an acid group,

c) 1 to 15 wt. % of at least one monomer containing an acid group,

d) 0 to 10 wt. % of one or more oligomeric carboxylic acids,

e) 1 to 20 wt. % of one or more monofunctional monomers without an acid group,

f) 25 to 80 wt. % of at least one fluoroaluminosilicate glass filler and/or radiopaque glass filler,

g) 0.1 to 25 wt. % of one or more additional fillers,

h) 0.1 to 8 wt. % of an initiator for radical polymerization,

i) 0 to 20 wt. % of water, and

j) 0.001 to 5 wt. % of additives, in each case based on the total mass of the composition.

6 . The composition according to claim 5 ,

wherein the polyfunctional monomer (b) comprises at least one monomer selected from bisphenol A dimethacrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxy- or propoxylated bisphenol A dimethacrylates, urethanes of 2-(hydroxymethyl)acrylic acid and diisocyanates, UDMA (an addition product of 2hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene,1,6-diisocyanate),tetramethylxylylene diurethane ethylene glycol di(meth)acrylate or tetramethylxylylene diurethane-2-methylethylene glycol diurethane di(meth)acrylate (V380), di-, tri-or tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, glycerol di-methacrylate, glycerol trimethacrylate, 1,4-butanediol dimethacrylate, 1,10-decanediol dimethacrylate (D 3 MA), bis(methacryloyloxymethyl)tricyclo-[5.2.1.0 2,6 ]decane (DCP), polyethylene glycol dimethacrylates, polypropylene glycol dimethacrylates, 1,12-dodecanediol dimethacrylate, radically polymerizable pyrrolidones, bisacrylamides, bis(meth)acrylamides, and mixtures thereof.

7 . The composition according to claim 5 ,

wherein the at least one monomer containing an acid group (c) comprises at least one monomer selected from monomers containing a phosphoric ester group or phosphonic acid group,.

8 . The composition according to claim 5 ,

wherein the oligomeric carboxylic acid (d) comprises polyacrylic acid with a number average molecular weight less than 7,200 g/mol.

9 . The composition according to claim 5 ,

wherein the monofunctional monomer (e) comprises at least one monomer selected from benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, p-cumyl phenoxyethylene glycol methacrylate (CMP-1E), 2-([1,1′-biphenyl]-2-oxy)ethyl methacrylate (MA-836), tricyclodecane methyl (meth)acrylate, 2-(2-biphenyloxy)ethyl (meth)acrylate, 2-hydroxyethyl (methacrylate), hydroxyethylpropyl (methacrylate), 2-acetoxyethyl methacrylate, and mixtures thereof.

10 . The composition according to claim 4 ,

wherein the a radiopaque glass filler comprises the composition (wt. %): SiO 2 : 20-80; B 2 O 3 : 2-15, BaO or SrO: 0-40; Al 2 O 3 : 2-20; CaO and/or MgO: 0-20; Na 2 O, K 2 O, Cs 2 O: 0-10 each; WO 3 : 0-20; ZnO: 0-20; La 2 O 3 : 0-10; ZrO 2 : 0-15; P 2 O 5 : 0-30; Ta 2 O 5 , Nb 2 O 5 or Yb 2 O 3 : 0-5; and CaF 2 and/or SrF 2 0-10; and/or

wherein the fluoroaluminosilicate glass filler comprises the composition (wt. %): SiO 2 : 20-35; Al 2 O 3 : 15-35; BaO or SrO: 10-25; CaO: 0-20; ZnO: 0-15; P 2 O 5 : 5-20; Na 2 O, K 2 O, Cs 2 O: 0-10 each; and CaF 2 : 0.5-20 wt. %; with all figures being based on the total mass of the glass and all components except fluorine being calculated as oxides.

11 . The composition according to claim 1 , comprising

at least one redox initiator or

at least one redox initiator and at least one photoinitiator.

12 . The composition according to claim 1 , wherein the catalyst paste comprises

a) 1.0 to 12 wt. % of at least one solid masking agent,

b) 5 to 40 wt. % of at least one polyfunctional monomer without an acid group,

c) 2 to 30 wt. % of at least one monomer containing an acid group,

d) 0.1 to 20 wt. % of one or more oligomeric carboxylic acids,

e) 1 to 20 wt. % of one or more monofunctional monomers without an acid group,

f) 25 to 80 wt. % of at least one fluoroaluminosilicate glass filler and/or glass filler,

g) 0.1 to 25 wt. % of one or more additional fillers,

h) 0.01 to 16 wt. % of at least one peroxide and/or hydroperoxide and optionally at least one photoinitiator,

i) 0 to 20 wt. % of water, and

j) 0.001 to 5 wt. % of additives, in each case based on the total mass of the catalyst paste,

and wherein the base paste comprises

a) not applicable,

b) 5 to 40 wt. % of at least one polyfunctional monomer without an acid group,

c) not applicable,

d) not applicable,

e) 1 to 20 wt. % of one or more monofunctional monomers without an acid group,

f) 25 to 80 wt. % of at least one fluoroaluminosilicate glass filler and/or glass filler,

g) 0.1 to 25 wt. % of one or more additional fillers,

h) 0.01 to 16 wt. % of at least one suitable reducing agent and optionally a photoinitiator,

i) 0 to 20 wt. % of water, and

j) 0.001 to 5 wt. % of additives, in each case based on the total mass of the base paste.

13 . The composition of claim 12 ,

wherein the catalyst paste and the base paste are each contained in different chambers of a dual-push syringe.

14 . The composition according to claim 1 for therapeutic use as a dental material comprising a dental cement, coating or veneering material, restorative composite or luting cement.

15 . The composition according to claim 1 for non-therapeutic use for the manufacture or repair of dental restorations comprising inlays, onlays, crowns or bridges.

16 . The composition according to claim 6 ,

wherein the at least one ethoxy- or propoxylated bisphenol A dimethacrylate is selected from bisphenol A dimethacrylate with 3 ethoxy groups or 2,2-bis [4-(2-methacry-loyloxypropoxy)phenyl]propane, and/or

wherein the diisocyanate of the at least one urethane of 2-(hydroxymethyl)acrylic acid and diisocyanate is selected from 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate, and/or

wherein the at least one radically polymerizable pyrrolidone is 1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, and/or

wherein the at least one bisacrylamide is selected from methylene or ethylene bisacrylamide, and/or

wherein the at least one bis(meth)acrylamide is selected from N,N′-diethyl-1,3-bis(acrylamido)propane, 1,3-bis(methacrylamido)propane, 1,4-bis(acrylamido)butane or 1,4-bis(acryloyl)piperazine.

17 . The composition according to claim 7 ,

wherein the at least one monomer containing a phosphoric ester group or phosphonic acid group is selected from 2-methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), glycerol dimethacrylate dihydrogen phosphate, dipentaerythritol pentamethacryloyloxy phosphate, 4-vinylbenzylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid and/or 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid-2,4,6-trimethylphenyl ester, and/or

wherein the at least one monomer containing a carboxy group is selected from 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy3-methacryloyloxypropyl)-N-phenylglycine and/or 4-vinylbenzoic acid.