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

Patent metadata

Field	Value
Publication number	US-9668946-B2
Application number	US-201214343297-A
Country	US
Kind code	B2
Filing date	Sep 10, 2012
Priority date	Sep 8, 2011
Publication date	Jun 6, 2017
Grant date	Jun 6, 2017

Abstract

The invention relates to a dental restorative material which comprises a thermolabile or photolabile polymerizable 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 or photolabile 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 adhesive group selected from —Si(OR) 3 , —COOH, —O—PO(OH) 2 , —PO(OH) 2 , —SO 2 OH and —SH, wherein at least one Z 1 or Z 2 is a polymerizable group, 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 —, —NR 3 —CO—, —O—CO—NR 3 —, —NR 3 —CO—O— or —NR 3 —CO—NR 3 —, R, 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.

First claim

The invention claimed is:

1. Dental restorative material which comprises a thermolabile polymerizable compound of Formula II:

in which in each case independently of each other
one of Z 1 and Z 2 in each case independently represents a polymerizable group selected from CH 2 ═CR 1 —CO—O— and CH 2 ═CR 1 —CO—NR 2 — and the other of Z 1 and Z 2 in each case independently represents an adhesive group selected from —Si(OR)3, —COOH, —O—PO(OH)2, —PO(OH)2, SO2OH and —SH,
Q 1 in each case independently is missing or represents a C 1 -C 10 radical,
Q 2 in each case independently is missing or represents a C 1 -C 10 radical,
R in each case independently is CH 3 or C 2 H 5 ,
R 1 in each case independently is H or CH 3 ,
R 2 in each case independently is H, CH 3 or C 2 H 5 ,
R 3 in each case independently is H, CH 3 or C 2 H 5 ,
R 4 is H, CH 3 or C 2 H 5 ,
R 5 is H,
R 6 is H and/or
m and n in each case independently are 1 or 2.

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

3. Dental restorative material according to claim 2 , 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,N′-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.

4. Dental restorative material according to claim 1 , which comprises one or more thermolabile cross-linking monomers.

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

6. Dental restorative material according to claim 5 , 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, 2meth-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.

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

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

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

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

11. Dental restorative material according to claim 1 , which comprises
a) 1 to 40 wt.-% compound of Formula II,
b) 0.1 to 3.0 wt.-% initiator,
c) 1 to 60 wt.-% comonomer,
d) 0.5 to 15 wt.-% adhesive monomer,
e) up to 80 wt.-% filler,
f) 0 to 70 wt.-% solvent.

12. Dental restorative material according to claim 1 , which comprises
a) 2 to 30 wt.-% compound of Formula II,
b) 0.2 to 2 wt.-% initiator,
c) 5 to 50 wt.-% comonomer,
d) 1 to 5 wt.-% adhesive monomer,
e) up to 80 wt.-% filler,
f) 0 to 70 wt.-% solvent.

13. Dental restorative material according to claim 1 , which comprises
a) 5 to 30 wt.-% compound of Formula II,
b) 0.01 to 10 wt.-% initiator,
c) 0 to 80 wt.-% comonomer,
d) 0 to 30 wt.-% adhesive monomer,
e) up to 80 wt.-% filler,
f) 0 to 70 wt.-% solvent.

14. Dental restorative material according to claim 1 , in which in each case independently of each other
Q 1 in each case independently is missing or represents a C 1 -C 8 radical, and/or Q 2 in each case independently is missing or represents C 1 -C 8 radical.

15. Dental restorative material according to claim 1 , in which in each case independently of each other
Q 1 in each case independently is missing or represents a C 2 -C 6 radical, and/or
Q 2 in each case independently is missing or represents a C 2 -C 6 radical.

16. Dental restorative material according to claim 1 , in which in each case independently of each other
Q 1 in each case independently is missing or represents C 1 -C 2 radical, which can be interrupted by —O—, —CO—O—, —O—CO—, —CO—NR3-, —NR3-CO—, —O—CO—NR3-, —NR3-CO—O— or —NR3-CO—NR3-, and/or
Q 2 in each case independently is missing or represents a C 2 -C 3 radical, which can be interrupted by —O—, —CO—O—, —O—CO—, —CO—NR 3 —, —NR 3 —CO—, —O—CO—NR 3 —, —NR 3 —CO—O— or —NR 3 —CO—NR 3 —.

Assignees

• Moszner Norbert
• Lamparth Iris
• Bock Thorsten
• Fischer Urs Karl
• Salz Ulrich
• Rheinberger Volker
• Liska Robert
• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Lamparth Iris
• Bock Thorsten
• Fischer Urs Karl
• Salz Ulrich
• Rheinberger Volker
• Liska Robert

Classifications

• A61K6/30

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

• C07D239/47 Primary

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

• A61K6/15

  Compositions characterised by their physical properties · CPC title

• A61K6/887

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

• A61K6/889 Primary

  Polycarboxylate cements; Glass ionomer cements · CPC title