# US 9,040,602 B2 · Dental materials on the basis of highly acidic polymerizable bisphosphonic acids

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- Number: US 9,040,602 B2
- Document ID: US9040602B2
- Status: Granted
- Kind: B2
- Application number: 13/981,971
- Filed: 2012-12-06
- Published: 2014-10-02
- Granted: 2015-05-26
- Earliest claimed: 2011-12-06
- Assignees: Ivoclar Vivadent AG
- Applicants: Ivoclar Vivadent AG
- Inventors: Norbert Moszner; Yohann Catel; Jörg Angermann; Thorsten Bock; Volker Rheinberger
- Web page: https://patentgrep.com/patent/US9040602B2

## CPC

- A61K 6/889: Polycarboxylate cements; Glass ionomer cements
- A61K 6/30: Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
- A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- 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)

## Abstract

The invention relates to a dental material which comprises a polymerizable bisphosphonic acid of Formula I: The invention also relates to the use of a polymerizable bisphosphonic acid of Formula I for the preparation of a dental material and in particular for the preparation of an adhesive, cement or composite.

## Claims

### Claim 1

Dental material comprising a polymerizable bisphosphonic acid of Formula III:
wherein
PG independently represents a polymerizable group selected from CH2═CR2—CO—O—, CH2═CR2—CO—NR3—,
R2 independently represents H or CH3,
R3 independently represents H or a C1-C10 alkyl radical.

### Claim 2

Dental material comprising a polymerizable bisphosphonic acid of Formula V:
wherein
PG represents a polymerizable group selected from CH2═CR2—CO—O—, CH2═CR2—CO—NR3— and R4O—CO—C(═CH2)—CH2—O—,
R2 represents H or CH3,
R3 represents H or a C1-C10 alkyl radical,
R4 represents H, a C1-C10 alkyl radical, phenyl or mesityl.

### Claim 3 (depends on 2)

Dental material according to claim 2, wherein:
PG represents a polymerizable group selected from CH2═CR2—CO—O— and CH2═CR2—CO—NR3—,
R2 represents H or CH3—,
R3 represents H or a C1-C10 alkyl radical.

### Claim 4 (depends on 1)

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

### Claim 5 (depends on 4)

Dental material according to claim 4, which comprises
methyl, ethyl, hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, bisphenol-A-di(meth)acrylate, bis-GMA, UDMA, di-, tri- or tetra-ethylene 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, N-methyl-N-(2-hydroxyethyl)acrylamide, one or more N-monosubstituted 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 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.

### Claim 6 (depends on 1)

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

### Claim 7 (depends on 6)

Dental material according to claim 6, which comprises
maleic acid, acrylic acid, methacrylic acid, 2-(hydroxy-methyl)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-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-methacryloyloxyethylphenyl hydrogen phosphate, dipentaerythritol-pentamethacryloyloxyphosphate, 10-methacryloyl-oxydecyl 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-(meth-acrylamido)propyl sulphonic acid,
or a mixture thereof.

### Claim 8 (depends on 1)

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

### Claim 9 (depends on 1)

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

### Claim 10 (depends on 1)

Dental material according to claim 1, which comprises
a) 0.1 to 50 wt.-%, polymerizable bisphosphonic acid of 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 and
f) 0 to 70 wt.-%, solvent.

### Claim 11 (depends on 10)

A method of using the dental material according to claim 10 as an adhesive which comprises adding 0 to 20 wt.-% filler to the dental material.

### Claim 12 (depends on 10)

A method of using the dental material according to claim 10 as a composite which comprises adding 20 to 80 wt.-% filler to the dental material.

### Claim 13 (depends on 1)

A method of using the polymerizable bisphosphonic acid of Formula III as defined in claim 1 for the preparation of a dental material.

### Claim 14 (depends on 13)

A method of using the polymerizable bisphosphonic acid of Formula III according to claim 13 for the preparation of an adhesive, cement or composite.

### Claim 15 (depends on 14)

A method of using the polymerizable bisphosphonic acid of Formula III according to claim 14, wherein the adhesive is self-etching.

### Claim 16 (depends on 14)

A method of using the polymerizable bisphosphonic acid of Formula III according to claim 14, wherein the cement is self-etching.

### Claim 17 (depends on 1)

Dental material according to claim 1, wherein
PG represents particular CH2═CR2—CO—O—,
R2 represents CH3.

### Claim 18 (depends on 1)

Dental material according to claim 1, wherein
R3 represents a C1-C7 radical, a C1-C5 radical, or a C1-C3.

### Claim 19 (depends on 18)

Dental material according to claim 18, wherein
R3 represents CH3 or C2H5.

### Claim 20 (depends on 2)

Dental material according to claim 2, wherein
R3 represents a C1-C7 radical, a C1-C5 radical, or a C1-C3 radical.

### Claim 21 (depends on 20)

Dental material according to claim 20, wherein
R3 represents CH3 or C2H5.

### Claim 22 (depends on 3)

Dental material according to claim 3, wherein
R3 represents a C1-C7 radical, a C1-C5 radical, or a C1-C3 radical.

### Claim 23 (depends on 22)

Dental material according to claim 22, wherein
R3 represents CH3 or C2H5.

### Claim 24 (depends on 10)

Dental material according to claim 10, which comprises
a) 1 to 40 wt.-%, polymerizable bisphosphonic acid of Formula I,
b) 0.1 to 3 wt.-% initiator,
c) 0 to 60 wt.-% co-monomer,
d) preferably 0.5 to 15 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler and
f) 0 to 60 wt.-% solvent.

### Claim 25 (depends on 10)

Dental material according to claim 10, which comprises
a) 2 to 30 wt.-% polymerizable bisphosphonic acid of Formula I,
b) 0.2 to 2 wt.-% initiator,
c) 5 to 50 wt.-% co-monomer,
d) 1 to 5 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler and
f) 0 to 50 wt.-% solvent.

### Claim 26 (depends on 10)

Dental material according to claim 10, which comprises
a) 5 to 20 wt.-% polymerizable bisphosphonic acid of Formula I,
b) 0.2 to 2 wt.-% initiator,
c) 5 to 50 wt.-% co-monomer,
d) 1 to 5 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler and
f) 0 to 50 wt.-% solvent.

### Claim 27 (depends on 2)

Dental material according to claim 2, wherein
PG represents a polymerizable group selected from CH2═CR2—CO—O— and CH2═CR2—CO—NR3—.

### Claim 28 (depends on 2)

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

### Claim 29 (depends on 28)

Dental material according to claim 28, which comprises methyl, ethyl, hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, bisphenol-A-di(meth)acrylate, bis-GMA, UDMA, di-, tri- or tetra-ethylene 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, N-methyl-N-(2-hydroxyethyl)acrylamide, one or more N-monosubstituted 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,
or a mixture thereof.

### Claim 30 (depends on 2)

Dental material according to claim 2, which comprises one or more additional radically polymerizable, acid group-containing monomers.

### Claim 31 (depends on 30)

Dental material according to claim 30, which comprises
maleic acid, acrylic acid, methacrylic acid, 2-(hydroxy-methyl)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-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-methacryloyloxyethylphenyl hydrogen phosphate, dipenta-erythritol-pentamethacryloyloxyphosphate, 10-methacryloyl-oxydecyl 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.

### Claim 32 (depends on 2)

Dental material according to claim 2, which comprises an initiator for radical polymerization.

### Claim 33 (depends on 2)

Dental material according to claim 2, which comprises organic and/or inorganic filler.

### Claim 34 (depends on 2)

Dental material according to claim 2, which comprises
a) 0.1 to 50 wt.-%, polymerizable bisphosphonic acid of 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 and
f) 0 to 70 wt.-%, solvent.

### Claim 35 (depends on 34)

A method of using the dental material according to claim 34 as an adhesive which comprises adding 0 to 20 wt.-% filler to the dental material.

### Claim 36 (depends on 34)

A method of using the dental material according to claim 34 as a composite which comprises adding 20 to 80 wt.-% filler to the dental material.

### Claim 37 (depends on 2)

A method of using the polymerizable bisphosphonic acid of Formula V as defined in claim 2 for the preparation of a dental material.

### Claim 38 (depends on 37)

A method of using the polymerizable bisphosphonic acid of Formula V according to claim 37 for the preparation of an adhesive, cement or composite.

### Claim 39 (depends on 38)

A method of using the polymerizable bisphosphonic acid of Formula V according to claim 38, wherein the adhesive is self-etching.

### Claim 40 (depends on 38)

A method of using the polymerizable bisphosphonic acid of Formula V according to claim 38, wherein the cement is self-etching.

### Claim 41 (depends on 34)

Dental material according to claim 34, which comprises
a) 1 to 40 wt.-%, polymerizable bisphosphonic acid of Formula I,
b) 0.1 to 3 wt.-% initiator,
c) 0 to 60 wt.-% co-monomer,
d) preferably 0.5 to 15 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler and
f) 0 to 60 wt.-% solvent.

### Claim 42 (depends on 34)

Dental material according to claim 34, which comprises
a) 2 to 30 wt.-% polymerizable bisphosphonic acid of Formula I,
b) 0.2 to 2 wt.-% initiator,
c) 5 to 50 wt.-% co-monomer,
d) 1 to 5 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler and
f) 0 to 50 wt.-% solvent.

### Claim 43 (depends on 34)

Dental material according to claim 34, which comprises
a) 5 to 20 wt.-% polymerizable bisphosphonic acid of Formula I,
b) 0.2 to 2 wt.-% initiator,
c) 5 to 50 wt.-% co-monomer,
d) 1 to 5 wt.-% adhesive monomer,
e) 0 to 80 wt.-% filler and
f) 0 to 50 wt.-% solvent.