Transparent, fracture-tough polymerization resins for the production of dental shaped bodies

Patent metadata

Field	Value
Publication number	US-11998621-B2
Application number	US-202217736166-A
Country	US
Kind code	B2
Filing date	May 4, 2022
Priority date	May 7, 2021
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

Abstract

Radically polymerizable dental material, which contains at least one ABA or AB block copolymer, preferably at least one monofunctional, radically polymerizable monomer (a) and preferably at least one radically polymerizable urethane di(meth)acrylate telechel (b).

First claim

The invention claimed is:

1. A radically polymerizable dental material, which comprises
at least one ABA or AB block copolymer (d),
at least one monofunctional, radically polymerizable monomer (a) and
at least one radically polymerizable urethane di(meth)acrylate telechel (b) with a number-average molar mass of from 750 to 2000 g/mol in accordance with general formula (II),

in which the variables have the following meanings:
R 1 , R 2 independently of each other in each case H or methyl,
R 3 , R 4 independently of each other in each case H or methyl,
x, y independently of each other in each case an integer from 1 to 11,
n 1, 2 or 3,
Z

DA a structural element, which is derived from a diol HO-DA-OH by cleaving the hydrogen atoms from the hydroxyl groups, wherein the diol HO-DA-OH is selected from the following compounds: ethoxylated or propoxylated bisphenol A, o-diphenyl or p-diphenyl with 2 to 6 ethoxy or propoxy groups, C 2 -C 18 alkanediols, which can contain 1 to 4 O or S atoms in the carbon chain, ethoxylated or propoxylated bisphenol A with 2, 3 or 4 ethoxy or propoxy groups, hexane-1,6-diol, octane-1,8-diol, nonane-1,9-diol, decane-1,10-diol, undecanediol or dodecane-1,12-diol, tetra- or pentaethylene glycol, cyclic or polycyclic aliphatic diols, cyclohexanediol, norbornanediol, tricyclodecanediol and tricyclodecanedimethanol (octahydro-4,7-methano-1H-indenedimethanol).

2. The radically polymerizable dental material according to claim 1 , which comprises
(a) 30 to 70 wt.-% of at least one aromatic, bicyclic or tricyclic mono(meth)acrylate,
(b) 20 to 60 wt.-% of at least one urethane di(meth)acrylate telechel with a number-average molar mass of from 750 to 2000 g/mol,
(c) 0 to 30 wt.-% of di(meth)acrylate monomer(s),
(d) 1 to 12 wt.-% of at least one ABA and/or AB block copolymer, wherein the A block or blocks are homogeneously miscible with the mixture of components (a) to (c) and the B block is not homogeneously miscible with the mixture of components (a) to (c), and
(e) 0.1 to 5.0 wt.-% of at least one initiator for the radical polymerization,
in each case relative to the total mass of the material.

3. The radically polymerizable dental material according to claim 1 , which comprises as component (a) at least one aromatic, bicyclic or tricyclic monomethacrylate of Formula (I)

in which the variables have the following meanings:
A an aromatic group with 6 to 15 carbon atoms or a bicyclic or tricyclic aliphatic group with 7 to 10 carbon atoms, wherein A can be unsubstituted or substituted by one or more C 1 -C 5 alkyl groups, C 1 -C 5 alkoxy groups and/or chlorine atoms;
R hydrogen or methyl;
X 1 , X 2 independently of each other is in each case absent or an ether, ester or urethane group, wherein X 1 is absent if Y 1 is absent and wherein X 2 is absent if Y 2 is absent;
Y 1 , Y 2 independently of each other is in each case absent or a branched or linear aliphatic hydrocarbon radical with 1 to 10 carbon atoms, which can be interrupted by 1 to 3 oxygen atoms.

4. The radically polymerizable dental material according to claim 3 , which comprises as component (a) 2-phenoxyethyl (meth)acrylate, 2-(o-biphenyloxy)ethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenethyl (meth)acrylate, 2-[(benzyloxycarbonyl)-amino]-ethyl (meth)acrylate, 2-[(benzylcarbamoyl)-oxy]-ethyl (meth)acrylate, 1-phenoxypropan-2-yl (meth)acrylate and 2-(p-cumylphenoxy)-ethyl (meth)acrylate, 2-(benzyloxy)ethyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, phenoxypropyl (meth)acrylate, 2-benzyloxyethyl (meth)acrylate, 2-benzoyloxyethyl (meth)acrylate, 2-(meth)acryloyloxybenzoic acid methyl ester, tricyclodecane (meth)acrylate, tricyclodecane methyl (meth)acrylate, 2-(p-cumylphenoxy)ethyl (meth)acrylate, 4,7,7-trimethylbicyclo[2.2.1]heptanyl (meth)acrylate, octahydro-1H-4,7-methanoinden-5-yl (meth)acrylate or a mixture thereof.

5. The radically polymerizable dental material according to claim 2 , which comprises as component (d) at least one ABA and/or AB block copolymer, in which the A block is an oligomer which is made up of one or more of the following monomers: cyclic, aliphatic esters or ethers, arylene oxide, alkylene oxide, radically polymerizable monomers, α,β-unsaturated acids and α,β-unsaturated acid esters; and the B block is a polysiloxane oligomer and/or a polyvinyl oligomer and/or a polyalkene oligomer and/or a polydiene oligomer.

6. The radically polymerizable dental material according to claim 5 , which comprises as component (d) at least one ABA and/or AB block copolymer, in which the A block is an oligomeric polycaprolactone (PCL), poly(2,6-dimethyl-1,4-phenylene oxide), poly(ethylene oxide), poly(propylene oxide) or poly(meth)acrylate building block and the B block is an oligomeric poly(dimethylsiloxane) (PDMS), poly(isoprene), poly(vinyl acetate), poly(isobutene), cis-poly(butadiene) or poly(ethylene) building block.

7. The radically polymerizable dental material according to claim 6 , which comprises as component (d) at least one ABA triblock copolymer of the PCL-b-PDMS-b-PCL and/or PMMA-b-PDMS-b-PMMA type with a molar ratio of A:B of from 0.1 to 5 and with a molar mass of from 3 to 25 kDa, 4 to 20 kDa or 5 to 10 kDa.

8. The radically polymerizable dental material according to claim 2 , which comprises as component (e) at least one photoinitiator, which is selected from benzophenone, benzoin or a derivative thereof, an α-diketone or a derivative thereof, 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl or 4,4′-dichlorobenzil, camphorquinone (CQ), 2,2-dimethoxy-2-phenylacetophenone or an α-diketone in combination with an amine as reducing agent, 4-(dimethylamino)-benzoic acid ester (EDMAB), N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym-xylidine or triethanolamine, monoacyltrialkyl-, diacyldialkyl-, tetraacylgermanium, a tetraacylstannane, benzoyltrimethylgermanium, dibenzoyldiethylgermanium, bis(4-methoxybenzoyl)diethylgermanium, tetrakis(2-methylbenzoyl)germane or tetrakis(mesitoyl)stannane or a mixture thereof,
a Norrish type I photoinitiator comprising acetophenones, 2,2-diethoxy-1-phenylethanone, benzoin ethers, Irgacure 651 (benzil dimethyl ketal), hydroxyalkylphenylacetophenones, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), an acyl- or bisacylphosphine oxide, Irgacure TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Irgacure 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone (Irgacure 369) and/or 1-butanone-2-(dimethylamino)-2-(4-methylphenyl)methyl-1-4-(4-morpholinyl)phenyl (Irgacure 379).

9. The radically polymerizable dental material according to claim 1 , with the following composition:
(a) 30 to 70 wt.-% of at least one aromatic, bicyclic or tricyclic mono(meth)acrylate,
(b) 20 to 60 wt.-% of at least one urethane di(meth)acrylate telechel with a number-average molar mass of from 750 to 2000 g/mol,
(c) 0 to 30 wt.-% of di(meth)acrylate monomer(s),
(d) 1 to 12 wt.-% of at least one ABA or AB block copolymer,
(e) 0.1 to 5.0 wt.-% of at least one initiator for the radical polymerization,
(f) 0 to 15 wt.-% of core-shell polymer particles,
(g) 0 to 20 wt.-% % of filler,
(h) 0 to 1.0 wt.-% of UV absorber,
(i) 0 to 0.5 wt.-% of optical brightener and
(j) 0 to 15 wt.-% of further additives,
in ea

Assignees

• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Angermann Jörg
• Lamparth Iris
• Catel Yohann
• Rist Kai

Classifications

• A61K6/889 Primary

  Polycarboxylate cements; Glass ionomer cements · CPC title

• A61C9/004

  Means or methods for taking digitized impressions · CPC title

• A61C13/34

  Making or working of models, e.g. preliminary castings, trial dentures; Dowel pins [4] · CPC title

• A61K6/15

  Compositions characterised by their physical properties · CPC title

• A61K6/62

  Photochemical radical initiators · CPC title