Dental materials based on compounds having debonding-on-demand properties

Patent metadata

Field	Value
Publication number	US-9320686-B2
Application number	US-201214343300-A
Country	US
Kind code	B2
Filing date	Sep 10, 2012
Priority date	Sep 8, 2011
Publication date	Apr 26, 2016
Grant date	Apr 26, 2016

Abstract

The invention relates to a dental restorative material which comprises a thermolabile compound of Formula I:

[(Z 1 ) m -Q 1 -X)] k -T-[Y-Q 2 -(Z 2 ) n ] l   Formula I,

in which T represents a thermolabile unit which contains at least one thermolabile group based on non-covalent interactions, Z 1 and Z 2 in each case independently represent a polymerizable group selected from vinyl groups, CH 2 ═CR 1 —CO—O— and CH 2 ═CR 1 —CO—NR 2 — or an adhesive group selected from —Si(OR) 3 , —COOH, —O—PO(OH) 2 , —PO(OH) 2 , —SO 2 OH and —SH, Q 1 in each case independently is missing or represents an (m+1)-valent linear or branched aliphatic C 1 -C 20 radical which can be interrupted by —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 —, —NR 3 —CO—, —O—CO—NR 3 —, —NR 3 —CO—O— or —NR 3 —CO—NR 3 —, Q 2 in each case independently is missing or represents an (n+1)-valent linear or branched aliphatic C 1 -C 20 radical which can be interrupted by —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 —, —NR 3 —CO—, —O—CO—NR 3 —, —NR 3 —CO—O— or —NR 3 —CO—NR 3 —, X and Y in each case independently are missing or represent —O—, —S—, CO—O—, —O—CO—, —CO—NR 3 — or —NR 3 —CO—, R, R 1 , R 2 and R 3 in each case independently represent H or a C 1 -C 7 alkyl radical, k and l in each case independently are 0, 1, 2 or 3 and m and n in each case independently are 1, 2 or 3.

First claim

The invention claimed is:

1. Dental restorative material which comprises a thermolabile polymerizable compound of Formula II:
[(Z 1 ) m -Q 1 -X)] k -T-[Y-Q 2 -(Z 2 ) n ] l   Formula II,

in which
T represents a thermolabile group,
Z 1 and Z 2 in each case independently represent a polymerizable group selected from vinyl groups, CH 2 ═CR 1 —CO—O— and CH 2 ═CR 1 —CO—NR 2 - or an acid group selected from —O—PO(OH) 2 , —PO(OH) 2 and —SO 2 OH, wherein at least one Z 1 or Z 2 is a polymerizable group and at least one Z 1 or Z 2 is an acid group,
Q 1 in each case independently is missing or represents an (m+1)-valent linear or branched aliphatic C 1 -C 10 radical which can be interrupted by —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 - or —NR 3 —CO—,
Q 2 in each case independently is missing or represents an (n+1)-valent linear or branched aliphatic C 1 -C 10 radical which can be interrupted by —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 - or —NR 3 —CO—,
X and Y in each case independently are missing or represent —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 - or —NR 3 —CO—,
R 1 , R 2 and R 3 in each case independently represent H or a C 1 -C 7 alkyl radical and
k, l, m and n in each case independently are 1, 2 or 3.

2. Dental restorative material according to claim 1 , in which the thermolabile unit T is a thermolabile group and has the formula -T 1 • • T 2 -, in which T 1 and T 2 represent complementary groups which are connected to each other by thermolabile non-covalent interactions.

3. Dental restorative material according to claim 1 in which the thermolabile unit T is an oligomeric or polymeric unit which contains at least one thermolabile group and at least one oligomeric, homopolymeric or heteropolymeric chain P.

4. Dental restorative material according to claim 3 , in which the chain P is selected from the group consisting of vinyl, diene, polycondensation and polyaddition oligomers and polymers, copolymers and mixtures thereof.

5. Dental restorative material according to claim 3 , in which the chain P has a number average molar mass of from 200 to 20000 g/mol.

6. Dental restorative material according to claim 3 , in which the thermolabile unit T has the Formula III or IV:
[—P—(X 1 -Q-Y 1 -T 1 • • T 2 -Y 2 -Q-X 2 —) q ] p   Formula III,

[—P—(X 1 -Q-Y 1 -T 1 -Y 2 -Q-X 2 —) q ] p

[(—X 2 -Q-Y 2 -T 2 -Y 1 -Q-X 1 ) q —P—] p   Formula IV,

in which
P in each case independently represents an oligomeric, homopolymeric or heteropolymeric chain which preferably has a number average molar mass of from 200 to 20000 g/mol,
T 1 and T 2 represent groups which are connected to each other by thermolabile non-covalent interactions,
Q in each case independently is missing or represents a divalent linear, branched and/or cyclic C 1 -C 20 radical which can be fully or partly unsaturated and/or aromatic and can be interrupted by —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 —, —NR 3 —CO—, —O—CO—NR 3 —, —NR 3 —CO—O—or —NR 3 —CO—NR 3 —,
X 1 and X 2 in each case independently are missing or represent —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 —, —NR 3 —CO—, —O—CO—NR 3 —, —NR 3 —CO—O—or —NR 3 —CO—NR 3 —,
Y 1 and Y 2 in each case independently are missing or represent —O—, —S—, —CO—O—, —O—CO—, —CO—NR 3 —, —NR 3 —CO—, —O—CO—NR 3 —, —NR 3 —CO—O—or —NR 3 —CO—NR 3 —,
p in each case independently is 1 to 100 and
q in each case independently is 1, 2, 3 or 4.

7. Dental restorative material according to claim 1 , in which the thermolabile group is selected from the group consisting of:

wherein:
R 4 is H or a C 1 -C 10 alkyl radical,
M is a transition metal or lanthanoid.

8. Dental restorative material according to claim 1 , which comprises one or more radically polymerizable monomers.

9. Dental restorative material according to claim 8 , which comprises
methyl, ethyl, hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth) acrylate, bisphenol-A-di(meth)acrylate, bis-GMA, UDMA, di-, tri- or tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra-(meth)acrylate, glycerol di(meth)acrylate, 1,4-butanediol di-(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecane-diol di(meth)acrylate,
and/or
one or more N-mono- or disubstituted acrylamides, N-ethyl-acrylamide, N,N-dimethacrylamide, N-(2-hydroxyethyl)acrylamide, N-methyl-N-(2-hydroxyethyl)acrylamide, one or more N-mono-substituted methacrylamides, N-ethylmethacrylamide, N-(2-hydroxyethyl)methacrylamide, N-vinylpyrrolidone, one or more cross-linking allyl ethers,
and/or
one or more cross-linking pyrrolidones, 1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, one or more cross-linking bisacryl-amides, methylene or ethylene bisacrylamide, one or more cross-linking bis(meth)acrylamides, N,NT-diethyl-1,3-bis(acrylamido)-propane, 1,3-bis(methacrylamido)-propane, 1,4-bis(acrylamido)-butane, 1,4-bis(acryloyl)-piperazine,
and/or
one or more thermolabile cross-linking monomers
or a mixture thereof.

10. Dental restorative material according to claim 1 , which comprises one or more radically polymerizable, acid-group-containing monomers.

11. Dental restorative material according to claim 10 , which comprises maleic acid, acrylic acid, methacrylic acid, 2-(hydroxymethyl)-acrylic acid, 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy- 3 -methacryl-oyloxypropyl)-N-phenylglycine, 4-vinylbenzoic acid,
and/or
vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinyl-benzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacrylamido-4-methyl-pentyl-phosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid ethyl- or -2,4,6-trimethylphenyl ester
and/or
2-methacryloyloxypropyl mono- or dihydrogen phosphate, 2-meth-acryloyloxyethylphenyl hydrogen phosphate, dipentaerythritol-pentamethacryloyloxyphosphate, 10-methacryloyloxydecyl dihydrogen phosphate, phosphoric acid mono-(1-acryloyl-piperidin-4-yl) -ester, 6-(methacrylamido)hexyl dihydrogen phosphate, 1,3-bis-(N-acryloyl-N-propyl-amino)-propan-2-yl-dihydrogen phosphate,
and/or
vinylsulphonic acid, 4-vinylphenylsulphonic acid, 3-(methacryl-amido)propylsulphonic acid,
or a mixture thereof.

12. Dental restorative material according to claim 1 , which comprises an initiator for radical polymerization.

13. Dental restorative material according to claim 1 , which comprises a thermally gas-releasing additive.

14. Dental restorative material according to claim 1 , which comprises an additive which can convert radiated electromagnetic radiation into heat.

15. Dental restorative material according to claim 1 , which comprises organic and/or inorganic filler.

16. Dental restorative material according to claim 1 , which comprises
a) 0.1 to 50 wt.-% compound of Formula I,
b) 0.01 to 10 wt.-% initiator,
c) 0 to 80 wt.-% comonomer,
d) 0 to 30 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler,
f) 0 to 70 wt.-% solvent.

17. Dental restorative material according to claim 15 for use as adhesive, which comprises 0 to 20 wt.-% filler.

18. Dental restorative material according to claim 15 for use as composite, which comprises 20 to 80 wt.- % filler.

19. Method of using a compound comprising a thermolabile compound of Formula I:
[(Z 1 ) m -Q 1 -X)] k -T-[Y-Q 2 -(Z 2 ) n ] l   Formula I,

in which
T represents a ther

Assignees

• Moszner Norbert
• Hirt Thomas
• Rist Kai
• Salz Ulrich
• Weder Christoph
• Fiore Gina
• Heinzmann Christian
• Rheinberger Volker
• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Hirt Thomas
• Rist Kai
• Salz Ulrich
• Weder Christoph
• Fiore Gina
• Heinzmann Christian
• Rheinberger Volker

Classifications

• A61K6/30

  Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives · CPC title

• A61K6/15

  Compositions characterised by their physical properties · CPC title

• A61K6/889 Primary

  Polycarboxylate cements; Glass ionomer cements · CPC title

• C07D239/47 Primary

  One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine · CPC title

• A61K6/887

  Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title