# US 11,998,621 B2 · Transparent, fracture-tough polymerization resins for the production of dental shaped bodies

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- Number: US 11,998,621 B2
- Document ID: US11998621B2
- Status: Granted
- Kind: B2
- Application number: 17/736,166
- Filed: 2022-05-04
- Published: 2022-11-24
- Granted: 2024-06-04
- Earliest claimed: 2021-05-07
- Assignees: Ivoclar Vivadent AG
- Applicants: Ivoclar Vivadent AG
- Inventors: Norbert Moszner; Jörg Angermann; Iris Lamparth; Yohann Catel; Kai Rist
- Web page: https://patentgrep.com/patent/US11998621B2

## CPC

- A61K 6/60: comprising organic or organo-metallic additives
- A61K 6/889: Polycarboxylate cements; Glass ionomer cements
- A61C 9/004: {Means or methods for taking digitized impressions}
- A61C 13/087: Artificial resin teeth {(A61C13/081 takes precedence; preparations A61K6/80)}
- A61C 13/34: Making or working of models, e.g. preliminary castings, trial dentures; Dowel pins [4]
- A61K 6/15: Compositions characterised by their physical properties
- A61K 6/62: Photochemical radical initiators
- A61K 6/893: Polyurethanes
- B29C 64/386: Data acquisition or data processing for additive manufacturing
- B33Y 10/00: Processes of additive manufacturing
- B33Y 50/00: Data acquisition or data processing for additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08F 222/10: Esters
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08L 51/08: grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L 53/00: Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- B29C 64/124: using layers of liquid which are selectively solidified
- B29K 2096/04: Block polymers
- B29K 2105/0085: {Copolymers}
- B29L 2031/753: {Medical equipment; Accessories therefor (bloodbags, medical bags B29L2031/7148; artificial eyes B29L2011/0008)}
- C08F 2438/01: Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61C: DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE (non-driven toothbrushes A46B; {tongue scrapers A61B17/24;} preparations for dentistry A61K6/00; preparations for cleaning the teeth or mouth A61K8/00, A61Q11/00)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29L: INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES

## 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).

## Claims

### Claim 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:
R1, R2 independently of each other in each case H or methyl,
R3, R4 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, C2-C18 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).

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 1)

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 C1-C5 alkyl groups, C1-C5 alkoxy groups and/or chlorine atoms;
R hydrogen or methyl;
X1, X2 independently of each other is in each case absent or an ether, ester or urethane group, wherein X1 is absent if Y1 is absent and wherein X2 is absent if Y2 is absent;
Y1, Y2 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.

### Claim 4 (depends on 3)

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.

### Claim 5 (depends on 2)

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.

### Claim 6 (depends on 5)

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.

### Claim 7 (depends on 6)

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.

### Claim 8 (depends on 2)

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).

### Claim 9 (depends on 1)

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 each case relative to the total mass of the material.

### Claim 10 (depends on 9)

Dental material according to claim 9, which comprises
(a) 40 to 61 wt.-% of 2-phenoxyethyl (meth)acrylate, 2-(o-biphenyloxy)ethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-[(benzyloxycarbonyl)amino]ethyl (meth)acrylate, 1-phenoxypropan-2-yl (meth)acrylate, 2-(benzyloxy)-ethyl (meth)acrylate, 2-(methacryloyloxy)ethyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, phenoxypropyl (meth)acrylate, 2-benzyloxyethyl (meth)acrylate, 2-benzoyloxyethyl (meth)acrylate, 2-(meth)acryloyloxybenzoic acid methyl ester, 2-phenylethyl (meth)acrylate, tricyclodecane (meth)acrylate, tricyclodecane methyl (meth)acrylate and/or 2-(p-cumylphenoxy)ethyl methacrylate,
(b) 33 to 55 wt.-% of at least one urethane di(meth)acrylate telechel with a number-average molar mass of 750-2000 g/mol and with at least 4 urethane groups, prepared by reacting 1 mol ethoxylated or propoxylated bisphenol A, decanediol or dodecanediol with 2 mol isophorone diisocyanate (IPDI) and then reacting with 2 mol 2-hydroxyethyl methacrylate (HEMA) or hydroxypropyl methacrylate (HPMA),
(d) 2 to 10 wt.-% of at least one ABA or AB block copolymer, wherein the A block is made up of oligomeric polycaprolactone, poly(2,6-dimethyl-1,4-phenylene oxide), poly(ethylene oxide), poly(propylene oxide) or poly(meth)acrylate building blocks and the B block is made up of poly(dimethylsiloxane), poly(isoprene), poly(vinyl acetate), poly(isobutene), cis-poly(butadiene) or poly(ethylene) building blocks,
(e) 0.1 to 5.0 wt.-% of at least one photoinitiator and
(g) 0.2 to 5 wt.-% of one or more further additives,
in each case relative to the total mass of the material, and which is substantially free of di(meth)acrylate monomers and core-shell polymer particles.

### Claim 11 (depends on 1)

The radically polymerizable dental material according to claim 1, which has a transparency of ≥60% and a viscosity of ≤10.0 Pas at 25° C.

### Claim 12 (depends on 1)

The radically polymerizable dental material according to claim 1, which has a crosslinking density after curing of from 300 to 5000 mol/m3.