U.S. patent application number 09/725430 was filed with the patent office on 2001-12-13 for dental composition system and method.
Invention is credited to Hammesfahr, Paul D., Lu, Kewang.
Application Number | 20010051671 09/725430 |
Document ID | / |
Family ID | 26996997 |
Filed Date | 2001-12-13 |
United States Patent
Application |
20010051671 |
Kind Code |
A1 |
Lu, Kewang ; et al. |
December 13, 2001 |
Dental composition system and method
Abstract
The invention provides dental composition system having curable
liquid which is useful alone as a light curable composition and
which is useful by mixing with a powder in preselected proportions
to form dual cure compositions. The composition system is useful as
bonding agent, cement, liner, base, restorative, pit and fissure
sealants, and/or core build-up material, having improved adhesion
to dentin. After storing the powder and the liquid in separate
containers for at least two weeks and then mixing a portion of the
powder and a portion of the liquid to form a mixture, the
polymerizable compound polymerizes within 20 minutes of the mixing
to form a first polymeric material having a flexural strength of at
least 50 MPa, and an expansion in water at 37.degree. C. after 90
days of less than 1 percent by volume.
Inventors: |
Lu, Kewang; (Dover, DE)
; Hammesfahr, Paul D.; (Wyoming, DE) |
Correspondence
Address: |
DALE R. LOVERCHECK
DENTSPLY INTERNATIONAL INC.
570 West College Avenue
York
PA
17405-0872
US
|
Family ID: |
26996997 |
Appl. No.: |
09/725430 |
Filed: |
November 29, 2000 |
Related U.S. Patent Documents
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Application
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Filing Date |
Patent Number |
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09725430 |
Nov 29, 2000 |
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09351231 |
Jul 12, 1999 |
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6211264 |
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09351231 |
Jul 12, 1999 |
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08742019 |
Nov 1, 1996 |
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5973022 |
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Current U.S.
Class: |
523/116 |
Current CPC
Class: |
A61K 6/893 20200101;
A61K 6/889 20200101; A61K 6/889 20200101; A61K 6/30 20200101; A61K
6/30 20200101; A61K 6/893 20200101; A61K 6/20 20200101; A61K 6/20
20200101; A61K 6/30 20200101; A61K 6/20 20200101; A61K 6/889
20200101; A61K 6/30 20200101; A61K 6/30 20200101; A61K 6/893
20200101; A61K 6/20 20200101; C08L 33/00 20130101; A61K 6/20
20200101; C08L 75/16 20130101; C08L 75/16 20130101; C08L 75/16
20130101; C08L 75/16 20130101; C08L 33/00 20130101; C08L 75/16
20130101; C08L 33/00 20130101; C08L 33/00 20130101; C08L 33/00
20130101; C08L 75/16 20130101; C08L 33/00 20130101 |
Class at
Publication: |
523/116 |
International
Class: |
C08L 001/00; C08J
003/00; C08K 003/00; A61K 006/08 |
Claims
What is claimed is:
1. A dental composition system, comprising: a liquid composition in
a first container and a powder composition in a second container,
said liquid composition comprising a polymerizable compound, a
photoinitiator, and a first part of a redox polymerization catalyst
system, said powder composition comprising filler powder and a
second part of said redox polymerization catalyst system, said
powder being stored in said first container and said liquid being
stored in said second container for at least two weeks and a first
portion of said powder being mixed with a first portion of said
liquid to form a first polymerizable mixture, said polymerizable
compound in said first polymerizable mixture polymerizing within 20
minutes of said mixing to form a first polymeric material having a
flexural strength of at least 50 MPa, a second portion of said
liquid being exposed to actinic light and polymerizing within 40
seconds of said exposing to form a second polymeric material having
an expansion in water at 37.degree. C. after 7 days of less than 1
percent by volume.
2. The composition of claim 1 further comprising exposing said
first polymerizable mixture to actinic light.
3. The composition of claim 1 wherein said liquid further comprises
an ethylenically unsaturated organic phosphate ester or
phosphonate.
4. The composition of claim 1 wherein said liquid further comprises
ethylenically unsaturated organic phosphoric acid ester and said
acid ester is from about 20 to about 40 equivalent weight percent
neutralized.
5. The composition of claim 1 wherein said first polymeric material
has an expansion in water at 37.degree. C. after 90 days of less
than 1 percent by volume, and said powder comprises glass having
elutable strontium ions.
6. The composition according to claim 1 wherein said second
polymeric material has a flexural strength of at least 50 MPa.
7. The composition of claim 1 wherein said liquid further
comprising an acid ester is of the general formula: 8wherein
R.sub.1 is hydrogen, lower alkyl of from 1 to 5 carbons, halogen or
CN radical; n and m are independently integers of 1 or greater, Z
is an aliphatic, cycloaliphatic or aryl radical, having a carbon
chain comprising at least 2 carbon atoms and 0 or more oxygen or
sulfur atoms and having a valency of m+n and containing at least 2
carbon atoms.
8. The composition of claim 1 wherein said liquid further comprises
an acid ester mixture of compounds of the general formulas:
9wherein R.sub.1 is hydrogen, lower alkyl of from 1 to 5 carbons,
halogen or CN radical; n and m are independently integers of 1 or
greater, Z is an aliphatic, cycloaliphatic or aryl radical having a
carbon chain comprising at least 2 carbon atoms and 0 or more
oxygen or sulfur atoms and having a valency of m+n and M, M.sub.1
and M.sub.2 each is independently a cation.
9. The composition of claim 1 wherein said filler comprises from
about 20 to 90 percent by weight of said composition.
10. The method of claim 1 wherein said photoinitiator is a
phosphine oxide.
11. The method of claim 1 wherein said photoinitiator is
2,4,6-trimethyl benzoyl phosphine oxide.
12. A method of using a dental composition system comprising:
providing a liquid composition and a powder composition, said
liquid composition being enclosed by a first container and
comprising a polymerizable compound, a photoinitiator, and a first
part of a redox polymerization catalyst system, said powder
composition being enclosed by a second container and comprising
filler powder and a second part of said polymerization redox
catalyst system, storing said powder in said second container and
storing said liquid in said first container for at least two weeks,
mixing a first portion of said liquid with a first portion of said
powder to form a first mixture, applying said first mixture to a
first tooth surface, said polymerizable compound in said first
mixture polymerizes within 20 minutes of said mixing to form a
first polymeric material having a flexural strength of at least 50
MPa, applying a second portion of said liquid to a second tooth
surface and exposing said second portion of said liquid to light,
said polymerizable compound in said second portion of said liquid
polymerizes within 40 seconds of said exposing to form a second
polymeric material having an expansion in water at 37.degree. C.
after 90 days of less than 1 percent by volume.
13. The method of claim 12 wherein said first tooth surface is in a
first patient's mouth.
14. The method of claim 12 wherein said first tooth surface is in a
first patient's mouth and said second tooth surface is in a second
patient's mouth.
15. The method of claim 14 further comprising treating said first
tooth surface.
16. The method of claim 15 wherein said treating comprises etching
said first tooth surface.
17. The method of claim 15 wherein said treating comprises
drilling.
18. The method of claim 12 wherein said second portion of said
liquid and said first portion of said powder are mixed in a weight
ratio of between 1 to 5 and 4 to 1.
19. The method of claim 12 wherein said second portion of said
liquid and said first portion of said powder are mixed in a weight
ratio of between 1 to 3.4 and 1 to 4.5.
20. The method of claim 15 further comprising applied a bracket to
said first tooth.
21. The method of claim 12 further comprising mixing a third
portion of said liquid with a second portion of said powder to form
a second mixture, and applying said second mixture to a third tooth
surface.
22. The method of claim 12 wherein said powder further comprises
fluoride elutable glass.
23. The method of claim 12 wherein said powder comprises about
70-99 percent by weight strontium fluoroaluminosilicate glass.
24. The method of claim 12 wherein said powder comprises about 5 to
0.1 percent by weight benzoyl peroxide.
25. The method of claim 12 wherein said powder comprises about 5 to
0.1 percent by weight ascorbyl palmitate.
26. The method of claim 12 wherein said liquid comprises about 90
to 10 percent by weight alkylacrylate.
27. The method of claim 26 wherein said powder further comprising
about 30 to 0.1 percent by weight dipentaerythritol pentacrylate
phosphoric acid.
28. The method of claim 27 wherein said powder further comprising
about 25 to 0.1 percent by weight (2,4,6-trimethyl benzoyl)
phosphine oxide.
29. The method of claim 28 wherein said powder further comprising
about 5 to 0.1 percent by weight tert-butyl peroxybenzoate.
30. The method of claim 23 wherein said powder comprises a
glass-containing elutable cations of valence of 2 or more.
31. The method of claim 23 wherein said second tooth is a cleaned
tooth.
32. The method of claim 23 wherein said powder and liquid are mixed
in a ratio of from 0.5 to 6 parts by weight powder to 1 part by
weight liquid.
33. The method of claim 12 wherein said photoinitiator is a
phosphine oxide.
34. The method of claim 12 wherein said photoinitiator is
2,4,6-trimethyl benzoyl phosphine oxide.
35. The method of claim 12 wherein said first polymeric material
has an expansion in water at 37.degree. C. after 90 days of less
than 1 percent by volume.
36. The method of claim 15 wherein said treating comprises
excavating carie dentin.
37. The method of claim 12 wherein said liquid polymerizes within
10 minutes.
38. The method of claim 12 wherein said first polymeric material
adheres to said first tooth with a bond strength of at least 700
psi.
39. The method of claim 12 further comprising mixing a third
portion of said liquid and a second portion of said powder to form
a second polymerizable mixture and applying said second
polymerizable mixture to a metal substrate selected from the group
consisting of a amalgam, bracket or a crown.
40. The method of claim 39 wherein said second polymerizable
mixture forms a third polymeric material and said third polymeric
material adheres to said metal substrate with a bond strength of at
least 500 psi.
41. The method of claim 12 wherein said liquid composition further
comprises a polymerizable acrylate compound having at least one
carboxylic acid containing moiety.
42. The method of claim 12 wherein said liquid and said powder are
in a ratio between 2.0:1 to 6.0:1 in said mixture.
43. A shelf stable polymerizable liquid comprising a thermally
stable peroxide, said peroxide decays by a percentage less than or
about equal to the percentage that TBPO decays within one week at
23.degree. C., and a polymerizable compound within the scope of the
general formula: 10wherein R.sub.1 is hydrogen, lower alkyl of from
1 to 5 carbons, halogen or CN radical; n and m are independently
integers of 1 or greater, Z is an aliphatic, cycloaliphatic or aryl
radical having a carbon chain comprising at least 2 carbon atoms
and 0 or more oxygen or sulfur atoms and having a valency of
m+n.
44. A shelf stable polymerizable liquid comprising a thermally
stable peroxide, said peroxide decomposing by a percentage less
than or about equal to the percentage that TBPO decays within one
week at 23.degree. C. and a polymerizable compound within the scope
of the general formula: 11wherein M, M.sub.1 and M.sub.2 each is
independently a cation, such as K, Li, Na, NH.sub.4 or an amine
wherein after storage for two weeks said liquid polymerizes within
40 seconds from exposing the liquid to light to form a polymeric
material having an expansion of less than 1 percent by volume after
7 days in water at 37.degree. C.
45. The composition of claim 43 wherein said peroxide is tert-Butyl
peroxybenzoate (TBPO).
46. A storage stable polymerizable liquid composition which
includes a polymerizable phosphoric acid compound and a peroxide
compound, said peroxide compound decomposing less than or about
equal to the percent of decomposition of TBPO within one week at
23.degree. C., after storage of said liquid for 2 weeks said liquid
polymerizes within 40 seconds of exposing said liquid to light to
form a polymeric material having an expansion of less than 1
percent by volume after 7 days in water at 37.degree. C.
47. The composition of claim 46 wherein said peroxide is TBPO.
48. The composition of claim 46 wherein said peroxide is stable for
at least one month and then polymerizes within 20 minutes after
exposure to light.
49. A storage stable polymerizable liquid composition which
includes a polymerizable phosphoric acid compound and a peroxide
compound, said peroxide compound decomposing by less than or about
equal to the percent of decomposition of TBPO within one week at
23.degree. C., after storage of said liquid for 2 weeks said liquid
polymerizes within 40 seconds of exposing said liquid to light to
form a polymeric material having an expansion of less than 1
percent by volume after 7 days in water at 37.degree. C.
50. The composition of claim 49 further comprising a compound
within the scope of the general formula: 12wherein X, is O, S,
13wherein R.sub.1 and R.sub.2 each independently is a polymerizable
unsaturated moiety having from 2 to 13 carbon atoms, R.sub.3,
R.sub.4, R.sub.5, and R.sub.6 each independently is hydrogen,
halogen, alkyl having from 1 to 10 carbon atoms or halogenated
alkyl of from 1 to 10 carbon atoms, R.sub.9, R.sub.10, R.sub.11,
R.sub.12, R.sub.13 and R.sub.14 each independently is hydrogen,
alkyl having from 1 to 10 carbon atoms or aryl having from 6 to 10
carbon atoms. Z.sub.1 and Z.sub.2 each independently is a moiety
including an acid group or a reactive acid derivative, a, m and n
each independently is 0 or 1, b and p each independently is an
integer from 1 to 10.
Description
[0001] The invention relates to dental compositions. In particular
the invention provides dental composition system which polymerizes
in-situ by reaction between polymerizable monomers and/or
prepolymers. Dental composition systems in accordance with the
invention are useful as dental cement, liner, base, restorative,
core build-up material and pit and fissure sealants. A liquid
composition is useful alone as a sealant. The liquid is also useful
by mixing the liquid in preselected proportions with a powder
containing glass.
[0002] It is the object of the invention to provide a method of
using a dental composition system having a liquid composition and a
powder composition. The liquid composition is enclosed by a first
container and includes a polymerizable compound, a photoinitiator,
and a first part of a redox polymerization catalyst system. The
powder composition is enclosed by a second container and includes
filler powder and a second part of the polymerization redox
catalyst system. A first tooth surface is cleaned and then a first
portion of the liquid is applied to the first tooth surface. A
second portion of the liquid is mixed with a first portion of the
powder to form a first mixture, which is applied to a second tooth
surface.
[0003] Huang et al in U.S. Pat. No. 5,367,002 disclose a light
curable dental composition and method which includes a powder in
combination with a liquid. Lu et al in U.S. Pat. No. 5,338,773
disclose dental composition and method which includes a powder in
combination with a liquid. The prior art does not disclose a dual
cure dental composition and method which includes a powder in
combination with a liquid, which after storing the powder and
liquid in separate containers for at least two weeks, polymerizes
within 20 minutes of mixing the powder and liquid to form a
polymeric material having a flexural strength of at least 50 MPa as
is provided by the invention.
[0004] The invention overcomes the problems of the prior art.
[0005] Excavating carie dentin as used herein refers to the removal
of dentin softened by decay by a hand held tool which does not have
a motor.
[0006] Peroxide decay and peroxide decomposing as used herein refer
to break down of peroxide compounds which initiate or facilitate
polymerization to compounds which do not initiate or facilitate
polymerization.
BRIEF DESCRIPTION OF THE INVENTION
[0007] The invention provides dental composition system having
curable liquid which is useful alone as a light curable composition
and which is useful by mixing with a powder in preselected
proportions to form dual cure compositions. The composition system
is useful as cement, liner, base, restorative, pit and fissure
sealants, and/or core build-up material, having improved adhesion
to dentin. A dual cure dental composition includes a powder in
combination with a liquid, which includes polymerizable compounds.
After storing the powder and liquid in separate containers for at
least two weeks, the polymerizable compounds polymerize within 20
minutes of mixing the powder and liquid to form a first polymeric
material having a flexural strength of at least 50 MPa, and an
expansion in water at 37.degree. C. after 90 days of less than 1
percent by volume. More preferably the polymerizable compounds
polymerize within 10 minutes of mixing the powder and liquid to
form a polymeric material having a flexural strength of at least 50
MPa. The liquid is stored in a container for at least two weeks and
a portion of the liquid is exposed to actinic light and polymerizes
within 40 seconds to form a second polymeric material having an
expansion in water at 37.degree. C. after 90 days of less than 1
percent by volume. More preferably the polymerizable compounds
polymerize within 10 minutes of exposing the liquid to liquid to
form a polymeric material having a flexural strength of at least 50
MPa, and an expansion in water at 37.degree. C. after 90 days of
less than 1 percent by volume.
[0008] A storage stable polymerizable liquid composition which
includes a polymerizable phosphoric acid compound and a peroxide
compound. Preferably, while in the liquid composition, the peroxide
compound decomposes within one week at 23.degree. C. by less than
or about equal to the percent of decomposition of TBPO within one
week at 23.degree. C. The liquid polymerizes within 40 seconds from
the moment of exposing the liquid to light (exposure to light is
typically for about 2-10 seconds) to form a polymeric material
having an expansion of less than 1 percent by volume after 90 days
in water at 37.degree. C.
DETAILED DESCRIPTION OF THE INVENTION
[0009] In a preferred embodiment, the invention provides a curable
liquid useful alone and useful with a powder in preselected
proportions to form dental cement, liner, base, restorative, pit
and fissure sealants, and core build-up material. For mixtures, the
ratio preferably used is from 0.5 to 6 parts by weight powder to 1
part by weight liquid. The liquid is cured by exposure to visible
light. The liquid and powder mixtures self cure.
[0010] A preferred embodiment of the invention provides a method of
using a dental composition system having a liquid composition and a
powder composition. The liquid composition is enclosed by a first
container and includes a polymerizable compound, a photoinitiator,
and a first part of a redox polymerization catalyst system. The
powder composition is enclosed by a second container and includes
filler powder and a second part of the polymerization redox
catalyst system. A first tooth surface is cleaned and then a first
portion of the liquid is applied to the first tooth surface. A
second portion of the liquid is mixed with a first portion of the
powder to form a first mixture, which is applied to a second tooth
surface. Preferably the first tooth surface is exposed to light
whereby the liquid composition is cured on the first tooth
surface.
[0011] In a preferred embodiment of the invention, the first tooth
surface is in a first patient's mouth and the second tooth surface
is in a second patient's mouth. The second tooth surface is
preferably treated for example by etching the second tooth enamel
surface, by excavating carie dentin or by drilling into the dentin
thereof. Preferably the second portion of the liquid and the first
portion of the powder are mixed in a weight ratio of between 1 to 5
and 4 to 1. More preferably the second portion of the liquid and
the first portion of the powder are mixed in a weight ratio of
between 1 to 3.4 and 1 to 4.5.
[0012] In a preferred embodiment of the invention a bracket is
applied to the second tooth. Preferably a third portion of the
liquid is mixed with a second portion of the powder to form a
second mixture, which is applied the second mixture to a third
tooth surface. Preferably, the powder includes fluoride elutable
glass.
[0013] The compositions of the invention preferably contain powder
elute fluoride ion to reduce the solubility of adjacent enamel and
dentin and reduce the incidence of secondary caries.
[0014] Compositions of the present invention which include powder
may be light cured to provide filling materials especially useful
in Class III and Class V restorations. They are also useful as core
build-up materials at high filler solids concentrations with good
strength values and insensitivity to trace interfacial water, the
combination of which is an improvement in this invention.
[0015] The liquid alone is useful as a light curable dental
sealant. The liquid mixed with the powder is useful to provide
consistencies suitable for use as dual cure pit and fissure
sealants. Mixtures of the liquid and powder in ratios of powder to
liquid of from about 3.5 to 1 to about 5 to 1 are useful as dual
cure restoratives and as bases of low solubility and good strength
under other filling materials including conventional composites and
amalgams. The powder containing compositions polymerize rapidly and
preferably elute fluoride ions which can react with hydroxyapatite
of the tooth to form the less acid-soluble fluorapatite structure
to reduce the risk of caries adjacent the filling.
[0016] In accordance with an embodiment of the invention,
intermediate solids concentrations having ratios of powder to
liquid of from about 1.2 to 1 to about 1.8 to 1 are provided for
dual curing adhesive dental cements used under light-transmitting
glass-ceramic inlays, crowns, dental veneers, orthodontic,
brackets, or to fill pits and fissures in teeth according to
current dental practice.
[0017] Dual cure compositions of the invention utilize two catalyst
systems to cause them to harden promptly. Thus for example, for
light curing the catalyst system includes 1) a light sensitizer,
for example (2,4,6-trimethyl benzoyl) phosphine oxide, causes
polymerization to be initiated upon exposure to activating
wavelengths of light; and 2) a reducing compound. Accelerators for
the polymerization, for example metal salts such as copper
acetyl-acetonate, phosphinic acids and phosphinates, may also be
used. A room temperature activating catalyst system comprised of a
redox polymerization system is employed advantageously with the
compositions of the invention by adding, for example, a peroxide
capable of producing free radicals when activated by a reducing
agent at such temperature. Peroxides useful in the invention
include tert-Butyl peroxybenzoate (TBPO). Suitable promoters
include the same reducing agents and accelerators used in light
curing catalyst systems. Preferably dual curable dental
compositions of the invention are comprised of 0.01 to 10 parts by
weight, more preferably 0.02 to 5 parts by weight, and most
preferably 0.03 to 4 parts by weight, of a two catalyst system
ingredients in the polymerizable powder and liquid composition.
[0018] Preferably dual curable dental compositions of the invention
include 1 to 60 percent by weight, more preferably 2 to 50 percent
by weight, most preferably 2 to 40 percent by weight, of an acid
functional polymerizable organic compound in the cured composition.
In accordance with a preferred embodiment of the invention, liquids
contain polymerizable acid functional materials having ethylenic
unsaturation include, among others, organic esters of one or more
acids of phosphorus (hereinafter referred to as phosphorus acid
esters), wherein the organic portion of the ester contains at least
one polymerizable ethylenically unsaturated group. The organic
portion of the ester may be alkenyl, alkenoxy, cycloalkenyl,
aralkenyl, or alkenaryl, and preferably may have from 2 to 40
carbon atoms. The organic portion may be straight chain, branches,
or cyclic, can contain skeletal hetero atoms, i.e., atoms other
than carbon, and can be unsubstituted or substituted with moieties
which do not interfere with the free radical polymerization of the
phosphorus acid esters. Examples of unsaturated phosphorus
containing acid esters which may be used include, but are not
limited to, monomers containing phosphoric acid groups such as
hydroxyethyl methacrylate monophosphate,
2,2,-bis(.alpha.-meth-acryloxy-.beta.-hydroxy-propoxyphenyl)
propane diphosphonate (BIS-GMA diphosphonate), BIS-GMA diphosphate,
methacryloxyethyl phosphate, and glyceryl dimethacrylate phosphate.
Other suitable polymerizable acid esters are disclosed, for
example, in U.S. Pat. No. 4,499,251 to Omura et al, U.S. Pat. No.
4,222,780 to Shibantani et al, U.S. Pat. No. 4,235,633 to Tomioka,
U.S. Pat. No. 4,259,117 to Yamauchi et al, U.S. Pat. No. 4,368,043
to Yamauchi et al, and Sakashita in U.S. Pat. No. 4,920,188.
[0019] In accordance with a preferred embodiment of this invention,
the liquid contains polymerizable phosphate acid ester monomers
which are reactive with cations eluted from the reactive fillers.
Upon polymerization, alone or in combination with other
polymerizable components, these form polyacids which are also
reactive with cations. Polymerizable phosphates preferred for use
with this invention are adhesive to tooth structure and improve the
adhesion of the compositions.
[0020] In accordance with an embodiment of the invention the liquid
composition preferably includes phosphoric acid esters: 1
[0021] wherein R.sub.1 is hydrogen, lower alkyl of from 1 to 5
carbons, halogen or CN radical; n and m are independently integers
of 1 or greater, Z is an aliphatic, cycloaliphatic or aryl radical
having a carbon chain comprising at least 2 carbon atoms and 0 or
more oxygen or sulfur atoms and having a valency of m+n. In a
preferred embodiment of the invention, the phosphoric acid esters
used are those compositions of Formula I wherein m is 1.
[0022] In accordance with a further embodiment of the invention,
acid esters within the scope of Formula I are partially neutralized
to form phosphoric acid esters of the general Formula II and III as
follows: 2
[0023] wherein M, M.sub.1 and M.sub.2 each is independently a
cation, such as K, Li, Na, NH.sub.4 or an amine. Preferably 20-40
equivalent weight percent of the phosphoric acid ester is
neutralized by reaction with base.
[0024] Preferably the polymerizable liquid composition includes a
polymerizable carboxylic acid compound, such as OEMA to adhere the
polymeric material formed to metal containing substrates for
example brackets and crowns.
[0025] Liquid compositions of the invention preferably include
polymerizable unsaturated substituted aromatic compounds containing
at least one acid moiety. These aromatic compounds are preferably
within the scope of the general formula (I): 3
[0026] wherein
[0027] X, is O, S, 4
[0028] wherein R.sub.1 and R.sub.2 each independently is a
polymerizable unsaturated moiety having from 2 to 13 carbon
atoms,
[0029] R.sub.3, R.sub.4, R.sub.5, and R.sub.6 each independently is
hydrogen, halogen, alkyl having from 1 to 10 carbon atoms or
halogenated alkyl of from 1 to 10 carbon atoms,
[0030] R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13 and R.sub.14
each independently is hydrogen, alkyl having from 1 to 10 carbon
atoms or aryl having from 6 to 10 carbon atoms.
[0031] Z.sub.1 and Z.sub.2 each independently is a moiety including
an acid group or a reactive acid derivative,
[0032] a, m and n each independently is 0 or 1,
[0033] b and p each independently is an integer from 1 to 10.
[0034] In accordance with a preferred embodiment of the invention
R.sub.1 and R.sub.2 each independently is: 5
[0035] wherein R.sub.7 a divalent carbon containing radical and
[0036] R.sub.8 is hydrogen, halogen or alkyl having from 1 to 10
carbon atoms.
[0037] In a preferred embodiment of the invention compounds are
provided within the scope of general formula I wherein n and m are
zero, X is oxygen, sulfonyl or ditrifluoromethyl; Z.sub.1 and
Z.sub.2 are --COO(M) wherein M is hydrogen or an alkali metal,
alkaline-earth metal, amine or amine salt; and R.sub.1 and R.sub.2
are 6
[0038] Most preferably compounds within the scope of general
formula I are those wherein X is oxygen, and M is hydrogen, Li, Na
or K. Appropriate polymerizable unsaturated groups R.sub.1 and
R.sub.2 independently are alkenyl, alkenoxy, cycloalkenyl,
arylalkenyl, and alkenaryl moieties; with vinyl, and styryl
moieties being preferred, and acryl and methacryl moieties that
constitute the polymerizable groups of many monomers in dental
materials being especially preferred.
[0039] In accordance with an embodiment of the composite
composition, phosphoric acid esters useful in the composition
include: 7
[0040] wherein R.sub.1 is hydrogen, lower alkyl of from 1 to 5
carbons,
[0041] halogen or CN radical; n and m are independently integers of
1 or greater, Z is an aliphatic, cycloaliphatic or aryl radical
having a carbon chain comprising at least 2 carbon atoms and 0 or
more oxygen or sulfur atoms and having a valency of m+n.
[0042] In a preferred embodiment of the invention, the phosphoric
acid esters used are those compositions of Formula I wherein m is
1.
[0043] Polymerizable liquid compositions include monomers and/or
prepolymers selected to form, in combination with the other
ingredients of the liquid composition of the invention, a balance
of properties in the liquid prior to polymerization, as well as in
the polymerized product. These include mutual solubility,
stability, viscosity, mechanical strength and physical integrity of
the cured materials, biotolerance, and the like. Monomers useful as
polymerizable monomer in accordance with the invention include
those disclosed in Dentsply's U.S. Pat. Nos. 3,825,518, 3,709,866,
4,553,940, 4,514,342, and 4,657,941. Including ethylene glycol
dimethacrylate, triethylene glycol dimethacrylate, dipropylene
glycol dimethacrylate, BIS-GMA, 1,1,6 trimethyl hexamethylene
urethane dimethacrylate, cyclohexyl methacrylate, hydroxyethyl
methacrylate, glycerol mono-, di- and trimethacrylates. Prepolymers
useful in accordance with the invention include adducts formed by
the reaction of BIS-GMA and 1,1,6 trimethyl hexamethylene
diisocyanate, the adducts formed between polyethers and
diisocyanates end capped with hydroxyethyl methacrylate, the
adducts formed by polyethers or polyalcohols with an isocyanato
methacrylate such as isocyanatoethyl methacrylate. By substituting
the methacrylate function of these monomers and prepolymers with
the corresponding acrylate, fluoroacrylate, or cyanoacrylate
function, additional, polymerizable moieties are provided for use
as monomers or prepolymers in accordance with the invention.
Preferably curable dental compositions of the invention include 1
to 60 parts by weight, more preferably 2 to 50 percent by weight,
most preferably 5 to 40 percent by weight, of polymerizable monomer
and/or prepolymer in the cured composition.
[0044] Preferred reactive fillers for use in accordance with the
invention preferably include elutable cations having a valence of 2
or more, for example, strontium, calcium, zinc, aluminum, iron,
zirconium. Elutable glasses also preferably contain elutable
fluoride ion, for example, finely ground aluminosilicate and
silicate glasses including, for example without limitation, calcium
fluoroaluminosilicate glasses, strontium fluoroalumino-silicates,
strontium-calcium fluoroaluminosilicates and the like. Preferably
curable dental powder compositions of the invention include 10 to
90 percent by weight, more preferably 20 to 90 percent by weight,
most preferably 30 to 90 percent by weight, reactive glass in the
cured composition.
[0045] As used herein, non-reactive fillers are characterized as
those which do not form hardened coherent products within 10 hours
by reaction between the glass filler and a 50% aqueous solution of
the polyacid after being mixed at a ratio of 2 g powder to 1 gram
polyacid solution. Non-reactive fillers are optionally included in
compositions of the invention to include beneficial properties. For
example, fumed silica is a non-reactive filler which is included to
provide viscosity control, and barium alumino-silicate is a
non-reactive filler included to extend the composition, and
increase its strength and radiopacity. Curable dental compositions
in accordance with one embodiment of the invention include
preferably 1 to 60 percent by weight, more preferably 4 to 40
percent by weight, most preferably 4 to 30 percent by weight, of
the non-reactive filler in the cured composition.
[0046] In accordance with a preferred embodiment of the invention
is provided a storage stable polymerizable liquid composition which
includes a polymerizable phosphoric acid compound and a peroxide
compound which decomposes by less than 50 percent within one week
at 23.degree. C. A preferred peroxide is TBPO. Such compositions
are stable for at least 2 weeks and more preferably at least one
month and less preferably at least 6 months. Such liquid
compositions in accordance with the invention preferably polymerize
within 20 minutes and more preferably within 10 minutes of exposure
to actinic light.
[0047] Preferably, both reactive and non-reactive fillers are
included having a coating such as an organic phosphate for
compatibility with the organic components of the compositions. A
suitable organic phosphate is pentaerythritol trimethacrylate
phosphate. Alternative coatings, especially for the non-reactive
fillers, include organic silane, such as gamma methacryloxy propyl
trimethoxy silane applied by procedures well known in the art.
[0048] Preferably, compositions in accordance with the invention
are water tolerant to reduce the effects of surface contamination
by water which may affect adhesion between tooth and restorative.
Preferably, compositions in accordance with the invention more
nearly match the coefficient of thermal expansion than do
conventional composites to permit greater longevity to the adhesive
bond formed. Preferably, compositions in accordance with the
invention are radiopaque through the use of an radiopaque
non-reactive fillers.
EXAMPLE 1
[0049] Powder for use with liquids in accordance with the invention
is formed by adding 96.83 parts by weight strontium
aluminofluorosilicate glass; 1.0 parts by weight benzoyl peroxide;
0.15 parts by weight ascorbyl palmitate FCC concentrate, 0.02 parts
by weight cupric acetylacetonate and 2.0 parts by weight sodium
fluoride.
EXAMPLE 2
[0050] Powder for use with liquids in accordance with the invention
is formed by adding 95.66 parts by weight strontium
aluminofluorosilicate glass; 2.0 parts by weight benzoyl peroxide;
0.3 parts by weight ascorbyl palmitate FCC concentrate, 0.04 parts
by weight cupric acetylacetonate and 2.0 parts by weight sodium
fluoride.
EXAMPLE 3
[0051] Polymerizable liquid prepared by mixing 17.0 parts by weight
of 4,4'-oxydiphenylether-1,1,6,6"-tetracarboxylic acid
1,1'-(methacryloxy) dimethacrylate (OEMA), 1.0 parts by weight of
water, 42.6 parts by weight of bisphenol-A glycidyl dimethacrylate
(Bis GMA); 28.4 parts by weight triethyleneglycol dimethacrylate;
10.0 parts by weight dipentaerythritol pentacrylate phosphoric acid
ester (PENTA); 0.5 parts by weight of tert-Butyl peroxybenzoate
(TBPO) and 0.5 parts by weight diphenyl (2,4,6-trimethyl benzoyl)
phosphine oxide (L-TPO).
EXAMPLE 4
[0052] Polymerizable liquid prepared by mixing 17.0 parts by weight
of 4,4'-oxydiphenylether-1,1,6,6"-tetracarboxylic acid
1,1'-(methacryloxy) dimethacrylate (OEMA), 1.0 parts by weight of
water, 40 parts by weight of bisphenol-A glycidyl dimethacrylate
(Bis GMA); 30.5 parts by weight triethyleneglycol dimethacrylate;
10.0 parts by weight dipentaerythritol pentacrylate phosphoric acid
ester (PENTA); 1.0 parts by weight of tert-Butyl peroxybenzoate
(TBPO) and 0.5 parts by weight diphenyl (2,4,6-trimethyl benzoyl)
phosphine oxide (L-TPO).
EXAMPLE 4A
[0053] The polymerizable liquid prepared in Example 4 is brushed
onto a cleaned tooth and then exposed to light to from a sealant
coating on the tooth.
EXAMPLE 4B
[0054] The polymerizable liquid prepared in Example 3 is brushed
onto a cleaned tooth and then exposed to light to from a sealant
coating on the tooth.
EXAMPLE 5
[0055] A mixture suitable as a dental cement is prepared by mixing
2.5 parts by weight of the powder formed as in Example 2 with 1
part by weight of the polymerizable liquid formed as in Example 4.
Samples are applied to a tooth surface in a patient's mouth and
self polymerizes within 10 minutes to form a cured polymeric
material.
EXAMPLE 6
[0056] A mixture suitable as a dental liner is prepared by mixing
2.5 parts by weight of the powder formed as in Example 2 with 1
part by weight of the polymerizable liquid formed as in Example 4.
Samples are applied to a tooth surface in a patient's mouth and
polymerized by exposing to actinic light using a Caulk MAX curing
light.
EXAMPLE 7
[0057] A mixture suitable as a dental base is prepared by mixing
5.0 parts by weight of the powder formed as in Example 2 with 1
part by weight of the polymerizable liquid formed as in Example 4.
Samples are applied to a tooth surface in a patient's mouth and
polymerized by exposing to actinic light using a Caulk MAX curing
light.
EXAMPLE 8
[0058] A mixture useful as a dental restorative is prepared by
mixing 5.0 parts by weight of the powder formed as in Example 2
with 1 part by weight of the polymerizable liquid of Example 4. The
mixture is applied to a tooth surface in a human patient's mouth
and self polymerizes.
EXAMPLE 9
[0059] A mixture useful as a dental restorative is prepared by
mixing 5.0 parts by weight of the powder formed as in Example 1
with 1 part by weight of the polymerizable liquid of Example 3. The
mixture is applied to a tooth surface in a human patient's mouth
and self polymerizes.
EXAMPLE 10
[0060] A mixture useful as a dental restorative is prepared by
mixing 5.0 parts by weight of the powder formed as in Example 1
with 1 part by weight of the polymerizable liquid of Example 3. The
mixture is applied to a tooth surface in a human patient's mouth,
and is polymerized using light to form a cured polymeric
material.
[0061] The ratios of powder and liquid used in Examples 4A and 5
through 8 are shown in Table 1.
1 TABLE 1 RESTORA- TIVE/ CORE CEMENT LINER BASE BUILD-UP SEALANT
Example 5 6 7 8 4A POWDER/ 2.5/1 2.5/1 5.0/1 5.0/1 LIQUID RATIO
LIQUID 100%
EXAMPLE C1
[0062] This is a comparative example and corresponds exactly with
Example 5 of U. S. Pat. No. 5,367,002 (Case 1627).
EXAMPLE C2
[0063] This is a comparative example and corresponds exactly with
Example 15A of U. S. Pat. No. 5,338,773.
[0064] The polymerizable composition of Examples 4A and C1 are
light cured to form polymeric material having the physical
properties shown in TABLE 2. The polymerizable compositions of
Examples 8, 9 and C2 are self cured to form polymeric material
having the physical properties shown in TABLE 2. Flexural strength
(MPa) is measured by ISO 4049. Bond strength to dentin (psi) is
measured by the Huarg method of Example 4 (column 9, lines 61-68
through column 10, lines 1-22) in U.S. Pat. No. 5,367,002. Linear
expansion (percent) is measured after 7 days in water at 37.degree.
C.
2 TABLE 2 Example 4A 9 8 C1 C2 Flexural 61 71 70 31 31 Strength
(MPa) Bond 1695 839 1631 1097 1522 Strength to Dentin (psi)
Compressive 335 175 206 184 149 Strength (MPa) Linear 0.9 0.16 --
1.7 1.5 expansion in water at 37.degree. C. after 7 days (percent)
Linear -- 0.5 -- -- 3.3 expansion in water at 37.degree. C. after
90 days (percent) Cure Depth more N.A. N.A. 0 N.A. at 2 months than
at 50.degree. C. (mm) 15 * In Table 2 N.A. means Not Applicable
[0065] Preferably the liquid composition includes a polymerizable
compounding having a carboxylic acid containing moiety. An example
of a preferred compound is OEMA.
[0066] Preferably mixtures of powder and liquid form polymerizable
material which polymerizes an adheres to dentin with an adhesion of
at least 700 psi and adheres to metal containing substrates such as
crowns and brackets with an adhesion of at least 500 psi.
[0067] Various alteration and modifications of this invention will
be apparent to those skilled in the art without departing from the
scope and spirit of this invention, and it should be understood
that this invention is not limited to the illustrative embodiments
set forth herein.
* * * * *