Dental materials with improved hydrolysis stability based on phthalic acid monomers

Patent metadata

Field	Value
Publication number	US-9393181-B2
Application number	US-201213630491-A
Country	US
Kind code	B2
Filing date	Sep 28, 2012
Priority date	Oct 6, 2011
Publication date	Jul 19, 2016
Grant date	Jul 19, 2016

Abstract

Dental material which contains a polymerizable phthalic acid derivative of the general Formula I:

with R 1 =H, methyl or a C 1 -C 5 alkyl residue; R 2 =H, a phenyl, benzyl or C 1 -C 8 alkyl residue; Q 1 =is absent or is a C 1 -C 15 alkylene residue, wherein the carbon chain can be interrupted by O or S; Q 2 =is absent or a (n+1)-valent aliphatic C 1 -C 20 residue, wherein the carbon chain can be interrupted by O or S and wherein Q 1 and Q 2 cannot be absent simultaneously; X=is absent, is O, S or (—CO—NR 4 —)—, wherein R 4 is H, CH 3 or C 2 H 5 ; Y=is absent, is O, S or (—CO—NR 5 —)—, wherein R 5 is H, CH 3 or C 2 H 5 ; n, m=independently of one another in each case mean 1, 2 or 3; R 3 =H, CH 3 , C 2 H 5 , Cl, Br or OCH 3 , and wherein the two carboxyl groups of the benzene ring can together form an anhydride group.

First claim

The invention claimed is:

1. Dental material, comprising a polymerizable phthalic acid derivative of the general Formula I:

in which
R 1 =H, methyl,
R 2 =a C 1 -C 4 alkyl residue,
Q 1 =is absent or is a C 2 -C 12 alkylene residue, wherein the carbon chain can be interrupted by O,
Q 2 =is absent or is a (n+1)-valent aliphatic C 1 -C 10 residue, wherein the carbon chain can be interrupted by O and wherein Q 1 and Q 2 cannot be absent simultaneously,
X=is absent, is O, S or (—CO—NR 4 —), wherein R 4 is H, CH 3 or C 2 H 5 ,
Y=O,
n, m=independently of one another in each case mean 1or 2,
R 3 =is H, CH 3 , C 2 H 5 or OCH 3 , and
wherein the two carboxyl groups of the benzene ring can together form an anhydride group.

2. Dental material according to claim 1 , wherein at least one of the variables has one of the following meanings:
R 1 =H or methyl,
R 2 =methyl or ethyl,
Q 1 =a C 2 -C 12 alkylene residue, wherein the chain can be interrupted by O,
Q 2 =is absent or is a (n+1)-valent aliphatic C 1 -C 8 residue, wherein the chain can be interrupted by O and wherein Q 1 and Q 2 cannot be absent simultaneously,
X=is absent,
Y=O,
n, m=independently of one another are 1 or 2,
R 3 =H, CH 3 ,or OCH 3 .

3. Dental material according to claim 1 , comprising one or more additional radically polymerizable monomers as co-monomers.

4. Dental material according to claim 3 , comprising
methyl, ethyl, hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, bisphenol-A-di(meth)acrylate, bis-GMA, which is an addition product of methacrylic acid and bisphenol-A-diglycidyl ether, UDMA, which is an addition product of 2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene diisocyanate, 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-dodecanediol di(meth)acrylate,
and/or
one or more N-mono- or disubstituted acrylamides, N-ethylacrylamide, N,N-dimethacrylamide, N-(2-hydroxyethyl)acrylamide or N-methyl-N-(2-hydroxyethyl)acrylamide, one or more N-monosubstituted methacrylamides, N-ethyl-methacrylamide, 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 bisacrylamides, 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, or a mixture thereof.

5. Dental material according to claim 1 , comprising one or more radically polymerizable, acid-group-containing monomers as adhesive monomers.

6. Dental material according to claim 5 , comprising
maleic acid, acrylic acid, methacrylic acid, 2-(hydroxymethyl)acrylic acid, 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine, 4-vinylbenzoic acid,
and/or
vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-meth-acrylamido-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-methacryloyloxyethylphenyl hydrogen phosphate, dipentaerythritol-pentamethacryloyloxyphosphate, 10-meth-acryloyloxydecyl dihydrogen phosphate, phosphoric acid mono-(1 -acryloyl-piperidine-4-yl)-ester, 6-(methacrylamido)hexyl dihydrogen phosphate, 1,3-bis-(N-acryloyl-N-propyl-amino)-propane-2-yl-dihydrogen phosphate,
and/or
vinylsulphonic acid, 4-vinylphenylsulphonic acid, 3-(methacrylamido)propyl sulphonic acid,
or a mixture thereof.

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

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

9. Dental material according to claim 1 , which comprises solvents, stabilizers, flavourings, dyes, microbiocidal active ingredients, fluoride-ion-releasing additives, optical brighteners, plasticizers and/or UV absorbers.

10. Dental material according to claim 1 , which comprises
a) 0.1 to 50 wt.-% polymerizable phthalic acid derivative of the general Formula I,
b) 0.01 to 10 wt.-% initiator,
c) 0 to 80 wt.-% co-monomer,
d) 0 to 30 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler,
f) 0 to 70 wt.-% solvent.

11. Dental material according to claim 10 for use as an adhesive which contains 0 to 20 wt.-% filler.

12. Dental material according to claim 10 for use as a composite which contains 20 to 80 wt.-% filler.

13. Dental material according to claim 1 , which comprises
a) 1 to 40 wt.-% polymerizable phthalic acid derivative of the general Formula I,
b) 0.1 to 3.0 wt.-% initiator,
c) 0 to 60 wt.-% co-monomer,
d) 0 to 15 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler,
f) 0 to 60 wt.-% solvent.

14. Dental material according to claim 13 for use as an adhesive which contains 0 to 20 wt.-% filler.

15. Dental material according to claim 13 for use as a composite which contains 20 to 80 wt.-% filler.

16. Dental material according to claim 1 , which comprises
a) 2 to 30 wt.-% polymerizable phthalic acid derivative of the general Formula I,
b) 0.01 to 10 wt.-% initiator,
c) 5 to 50 wt.-% co-monomer,
d) 0 to 30 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler,
f) 0 to 50 wt.-% solvent.

17. Dental material according to claim 16 for use as an adhesive which contains 0 to 20 wt.-% filler.

18. Dental material according to claim 16 for use as a composite which contains 20 to 80 wt.-% filler.

19. A method of using a compound of Formula I for the preparation of a dental material, wherein Formula I comprises

in which
R 1 =H or methyl,
R 2 =a C 1 -C 4 alkyl residue,
Q 1 =is absent or is a C 2 -C 12 alkylene residue, wherein the carbon chain can be interrupted by O,
Q 2 =is absent or is a (n+1)-valent aliphatic C 1 -C 10 residue, wherein the carbon chain can be interrupted by O and wherein Q 1 and Q 2 cannot be absent simultaneously,
X=is absent, is O, S or (—CO—NR 4 —), wherein R 4 is H, CH 3 or C 2 H 5 ,
Y=O,
n, m=independently of one another in each case mean 1 or 2,
R 3 =is H, CH 3 , C 2 H 5 or OCH 3 , and wherein the two carboxyl groups of the benzene ring can together form an anhydride group,
the method comprising preparing the compound of Formula I and mixing it with one or more of an initiator, a co-monomer, an adhesive monomer, a filler and a solvent.

20. The method of claim 19 , wherein the method comprises preparing an adhesive or a cement or a self-etching adhesive or a self-etching cement.

21. Dental material according to claim 1 , wherein at least one of the variables has one of the following meanings:
R 1 =H,
R 2 =methyl,
Q 1 =a linear C 2

Assignees

• Bock Thorsten
• Fischer Urs Karl
• Lamparth Iris
• Moszner Norbert
• Rheinberger Volker
• Ivoclar Vivadent Ag

Inventors

• Bock Thorsten
• Fischer Urs Karl
• Lamparth Iris
• Moszner Norbert
• Rheinberger Volker

Classifications

• A61K6/30 Primary

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

• A61K6/887

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

• A61K6/083

  Human Necessities · mapped topic

• A61K6/0023 Primary

  Human Necessities · mapped topic

• C08L33/24

  Homopolymers or copolymers of amides or imides · CPC title