Dental restorative material.
Abstract
Dental restoration material containing one or more polymerizable (meth) acrylic compounds, polymerization accelerators and / or polymerization initiators and, if appropriate, further additives which are customary in such agents and an inorganic filler mixture, characterized in that the filler mixture is a mixture of at least one optionally silanized amorphous filler, at least one optionally silanized crystalline filler and, possibly in minor amounts, contains a finely divided microfiller.

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4 claims: 4 independent, 0 dependent
- 1Dental restoration material containing one or more polymerizable (meth) acrylic compounds, polymerization accelerators and / or polymerization initiators and, if appropriate, further additives which are customary in such agents and an inorganic filler mixture, characterized in that that it contains, as a filler mixture, a mixture of at least one optionally silanized amorphous filler and at least one optionally silanized crystalline filler and optionally, in minor amounts, a finely divided microfiller. 1. Dentales Restorationsmaterial, enthaltend eine oder mehrere polymerisierbare (Meth)Acrylverbindungen, Polymerisationsbeschleuniger und/oder Polymerisationsinitiatoren und gegebenenfalls weitere in solchen Mitteln an sich übliche Zusätze sowie ein anorganisches Füllstoffgemisch, dadurch gekennzeichnet, daß es als Füllstoffgemisch ein Gemisch aus mindestens einem gegebenenfalls silanisierten amorphen Füllstoff und mindestens einem gegebenenfalls silanisierten kristallinen Füllstoff und gegebenenfalls, in untergeordneten Mengen, einen feinverteilten Mikrofüllstoff enthält.
- 2Dentales Restorationsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß es etwa 60 bis etwa 90 Gew.-% der Gesamtzusammensetzung eines gegebenenfalls silanisierten Füllstoffgemisches enthält, bestehend aus a) etwa 50 bis etwa 90 Gew.-% eines amorphen Füllstoffs undb) etwa 10 bis etwa 50 Gew.-% eines kristallinen Füllstoffs mit jeweils einem mittleren Teilchendurchmesser zwischen etwa 0,3 und etwa 40 Mikron, undc) gegebenenfalls bis zu 10 Gew.-% eines Mikrofüllstoffs mit einem mittleren Teilchendurchmesser von weniger als 0,2 Mikron. 2nd Dental restoration material according to claim 1, characterized in that it contains about 60 to about 90% by weight of the total composition of an optionally silanized filler mixture consisting ofa) about 50 to about 90 wt .-% of an amorphous filler andb) about 10 to about 50% by weight of a crystalline filler each having an average particle diameter between about 0.3 and about 40 microns, andc) optionally up to 10% by weight of a microfiller with an average particle diameter of less than 0.2 microns.
- 3Dentales Restorationsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß es als Füllstoffgemisch ein solches aus etwa 50 bis etwa 75 Gew.-% gegebenenfalls silanisiertem amorphen Lithiumaluminiumsilikat und etwa 25 bis etwa 50 Gew.-% eines gegebenenfalls silanisierten kristallinen AiUminiumsilikats, jeweils mit einem mittleren Teilchendurchmesser zwischen etwa 0,3 und etwa 20 Mikron, und gegebenenfalls bis zu 10 Gew. -% eines gegebenenfalls silanisierten Siliciumdioxids mit.einem mittleren Teilchendurchmesser von weniger als 0,1 Mikron enthält. 3rd Dental restoration material according to claim 1, characterized in that the filler mixture is one of about 50 to about 75% by weight of optionally silanized amorphous lithium aluminum silicate and about 25 to about 50% by weight of an optionally silanized crystalline aluminum silicate, each with an average particle diameter between about 0.3 and about 20 microns, and optionally up to 10 wt. % of an optionally silanized silicon dioxide with an average particle diameter of less than 0.1 micron.
- 4Lichthärtbares dentales Restorationsmaterial, enthaltend eine oder mehrere polymerisierbare (Meth)Acrylverbindungen, Polymerisationsinitiatoren und/oder Polymerisationsbe-:schleuniger, gegebenenfalls weitere in solchen Mitteln übliche Zusätze und etwa 60 bis etwa 90 Gew.-% der Gesamtzusammensetzung eines anorganischen Füllstoffgemisches, dadurch gekennzeichnet, daß das Füllstoffgemisch aus a) 60 bis 75 Gew.-% eines gegebenenfalls silanisierten amorphen Füllstoffs mit einer Teilchengröße zwischen 1 und 20 Mikron,b) 25 bis 40 Gew.-% eines gegebenenfalls silanisierten Füllstoffs mit einer Teilchengröße von 0,5 bis 1 Mikron, undc) gegebenenfalls bis zu 10 Gew.-% eines gegebenenfalls silanisierten feinverteilten Siliciumdioxids mit einer Teilchengröße von weniger als 0,2 Mikron besteht. 4th Light-curable dental restoration material containing one or more polymerizable (meth) acrylic compounds, polymerization initiators and / or polymerization accelerators, optionally further additives customary in such agents and about 60 to about 90% by weight of the total composition of an inorganic filler mixture, characterized in that the filler mixturea) 60 to 75% by weight of an optionally silanized amorphous filler with a particle size between 1 and 20 microns,b) 25 to 40% by weight of an optionally silanized filler with a particle size of 0.5 to 1 micron, andc) optionally up to 10% by weight of an optionally silanized finely divided silicon dioxide with a particle size of less than 0.2 microns.
Independent claims4
59 paragraphs in 1 section, as filed
The present invention relates to a new dental restoration material which contains a special filler mixture.
Dental filling materials based on polymerizable compounds, so-called "composites", contain, in addition to one or more polymerizable monomers, activators, possibly polymerization catalysts and other constituents, a mineral filler.
The type and amount of this filler determine the physical properties of the filling made by the composite. The higher the filler fraction and its particle sizes, the better for the physical properties, but generally the worse the polishability.
Attempts have therefore been made to improve the polishability of such materials by using fillers with small particle sizes between approximately 10 and 300 millimicron; however, this is at the expense of the mechanical properties.
These so-called "microfillers" are used predominantly or almost exclusively in the production of so-called light-curing composites, ie dental restoration materials which are in one phase and contain fillers, polymerizable compounds and a polymerization initiator which forms free radicals under the influence of light.
This is due in particular to the fact that these materials have to have a certain curing depth which is not achieved with most fillers of larger particle sizes, the so-called "MDrofillers".
Other macrofillers that do not have this disadvantage cause discoloration during the polymerization (= curing) of the filling. This applies in particular to the different types of glass which, when used alone, result in a greenish or greyish discoloration during the curing of the filling and, moreover, cannot be polished.
There was therefore a need to develop dental restoration materials, in particular light-curing materials, which do not have these disadvantages, but which can also be easily cured under the influence of light without polymerization catalysts, ie have a satisfactory depth of cure, do not result in discoloration, but have good physical properties, in particular with regard to reduced water absorption, shrinkage, a coefficient of thermal expansion tending towards zero and improved mechanical properties, in particular with regard to hardness and diametric tensile strength.
In addition, it is desirable to achieve at least some degree of polishability.
It has now been found that a dental restoration material having the properties described can be produced if, in such an agent, an inorganic filling material in an amount of from about 60 to about 90% by weight of the total composition is a mixture of at least one optionally silanized amorphous filler , preferably in an amount of about 50 to 90, in particular about 50 to about 75% by weight of the filler mixture, at least one optionally silanized crystalline filler, preferably in an amount of about 10 to 50, in particular about 25 to about 50% by weight of the filler mixture, each with average particle diameters between about 0.3 and about 40 microns, preferably 0.3 and 20 microns used, this mixture to improve the polishability up to about 10% by weight of an optionally silanized microfiller, especially finely divided silicon dioxide with an average particle diameter of up to about 0.2 microns.
Suitable amorphous filling materials are in particular various types of glass such as lithium aluminum silicate glass, powdered quartz, borosilicate glass, barium aluminum silicate, barium aluminum borate silicate or glass ceramic fillers with particle sizes between approximately 0.5 and approximately 40, preferably between 1 and 20 microns. These amorphous fillers as a component of the filler mixture used according to the invention can be X-ray transparent or X-ray opaque. A summary of such suitable filling materials can be found, for example, in RL Bowen, Journal of Dental Research, Vol. 58/5 (May 1979), pp. 1493-1501, in particular pp. 1495-1498.
Suitable radiopaque fillers are described in particular in US Pat. Nos. 3,801,344, 3,808,170 and 3,975,203 and DE-OS 2,347,591.
Crystalline aluminum silicate, for example from precipitated sodium feldspar, has proven to be a suitable crystalline component of the filler mixture according to the invention. Other suitable crystalline filler components are, for example, lithium aluminum silicate such as beta-eucryptite, synthetic or natural calcium silicate etc., with an average particle size between approximately 0.3 and 40 microns, preferably approximately 0.3 or 0.5 and 20 or 10 microns.
In order to improve the incorporability of the filler mixture according to the invention into the composition and the compatibility with the organic constituents, it is expedient to silanize these fillers with an organosilane. The silanization can be carried out using any suitable organosilane of the general formula<chemistry id="chem0001" num="0001"><img file="EP0091990A2_D0001.tif" /></chemistry>where R, <sub>R</sub><sup>1</sup>, R<sup>2</sup> and R<sup>3</sup> represent the same or different organic radicals with the proviso that at least one radical is an OH group or a radical which can be converted into an OH group, for example by hydrolysis, in particular an alkoxy group. Preferred organosilanes are (meth) acroylpropyldihydroxymethoxysilane, (meth) acroylpropylhydroxyimidoxysilane, (meth) acroylpropyltrimethoxysilane or mixtures thereof; however, vinyl triethoxysilane or vinyl tri (methoxyethoxy) silane, for example, are also suitable silanizing agents.
In order to improve the polishability of the dental restoration material according to the application, a certain proportion of a microfiller, in particular a finely divided silicon dioxide with an average particle diameter below 200 millimicron, can also be present. However, in order not to influence the good physical properties of the cured material, the proportion of this microfiller should not be more than 10% by weight, preferably 4 to 8, in particular approximately 6% by weight, of the total filler content. This microfiller is also preferably silanized. A suitable silanized silica filling material is described in European Patent Application No. 81 102 198.9.
A particularly suitable filler mixture is one that contains about 50 to about 75% by weight. optionally silanized amorphous lithium aluminum silicate with a particle size between about 1 and about 35 microns (average about 5 microns) and about 25 to about 50 wt .-% of an optionally silanized<sup>x)</sup>Contains aluminum silicate with an average particle size between about 0.3 and about 20 microns, in particular 0.5 to 1 micron on average, preferably in a weight ratio of 3: 1.
As already stated, the dental restoration materials according to the invention are particularly suitable for use as light-curing products, ie products which are in one phase and polymerize under the action of light.
Such compositions contain one or more photopolymerization initiators. As such, in particular carbonyl compounds such as benzoin and its derivatives, in particular benzoin methyl ether, benzil and benzene derivatives, for example 4,4-0xidibenzil or other dicarbonyl compounds, e.g. B. diacetyl, 2,3-pentanedione or metal carbonyls, quinones or their derivatives. The proportion of photopolymerization initiator is about 0.01 to about 5% by weight of the total composition.
These light-curable, ie photopolymerizable, preparations preferably also contain so-called polymerization accelerators. These are substances that accelerate the polymerization reaction in the presence of polymerization initiators. Known accelerators are, for example, amines such as p-toluidine, N, N-dimethyl-p-toluidine, N, N-di (hydroxyethyl) -p-toluidine, trialkylamines such as trihexylamine, polyamines such as N, N, N ', N<sup>I-</sup>Tetraalkylalkylenediamines, barbituric acid and dialkylbearbituric acids and sulfimides, preferably in an amount of about 0.01 to about 5% by weight of the total composition. Suitable accelerators are for example from GM Brauer et. al., Journal of Dental Research, Vol. 58 / No. 10 (1979), pp. 1994-2000.
A preferred light-curable dental restoration material contains about 60 to about 90% by weight of the total composition of an inorganic filler mixture, which consists of about 60 to about 75% by weight (calculated on the filler mixture) of an optionally silanized amorphous filler, in particular lithium aluminum silicate a particle size between about 1 and about 20 microns, and about 25 to about 40% by weight of an optionally silanized crystalline filler, especially aluminum silicate, with a particle size of about 0.5 to about 1 micron. If appropriate, this filler mixture can also contain up to 10, preferably up to about 6% by weight of a preferably silanized, finely divided silicon dioxide which has an average particle diameter of less than 0.2 microns. In principle, it is also possible to use the dental restoration materials according to the invention as two-phase preparations, one phase of which contains a polymerization catalyst, for example a peroxide, and the other phase an accelerator for this peroxide, for example an organic amine, the two phases being brought together immediately before filling the teeth and the polymerization takes place in the bored preferably occurs with a relining or a bonding material to be filled cavity.
Suitable peroxides which decompose when the polymerization is initiated to form free radicals are, for example, aryl peroxides such as benzoyl peroxide, cumene hydroperoxide, urea peroxide, tert-butyl hydroperoxide or perbenzoate and silyl peroxides, preferably in amounts of about 0.01 to about 5, in particular about 0.5 up to 2.5% by weight of the total composition.
If one phase of the two-phase agent contains a polymerization initiator, an accelerator of the type described above, preferably an amine or barbituric acid or its derivatives, for example a dialkyl barbituric acid, is advantageously added to the other phase.
In principle, all compounds proposed and suitable for this purpose can be used as polymerizable monomers in the dental restoration materials according to the invention. Here, in particular, the known reaction products of bisphenols, in particular bisphenol A, and glycidyl methacrylate, known under the abbreviation Bis-GMA, the various alkanediol dimethacrylates such as 1,6-hexanediol methacrylate, 1,4-butanediol dimethacrylate, tri- or tetraethylene glycol dimethacrylate, bis (2-methacroylpropyl ) phthalate, isophthalate or terephthalate, trimethylolpropane di and trimethacrylate, and in particular the reaction products from diisocyanates and hydroxyalkyl methacrylates, as described, for example, in DE-OS No. 2,312,559 are described, adducts of (di) isocyanates and 2,2-propane-bis- [3- (4-phenoxy) -1,2-hydroxypropa3-1 - methacrylate according to US Pat. No. 3,629,187 and in particular the adducts of isocyanates and methacroylalkyl ethers, alkoxybenzenes or alkoxycycloalkanes, as described in European Patent Application No. 44 352.
Of course, mixtures of suitable monomers can also be used.
Finally, it is expedient to add UV stabilizers to plastic-based dental filling materials in order to avoid darkening during the aging of the fillings. A particularly suitable UV stabilizer is 2-hydroxy-4-methoxybenzophenone. Another preferred material is 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; however, in principle any physiologically inert UV absorbing agent is suitable for this purpose.
Examples include hydroquinone, p-benzoquinone, p-butylhydroxytoluene and the like. called. The latter compound can also act as an antioxidant in the filling, for example.
An overview of the substances commonly used in dental restorative materials can be found in the previously mentioned article by RL Bowen in the Journal of Dental Research, Vol. 58/5 (May 1979), pp. 1493 to 1503, as well as the related additions to JF Lann, pp. 1504 to 1506.
Composite materials also contain a small amount of dyes or pigments, if necessary, to give the filled tooth surfaces the most natural impression possible.
The following examples serve to explain the invention.
Mixture A
<tables id="tabl0001" num="0001"><img file="EP0091990A2_D0002.tif" /></tables>
Mix B
<tables id="tabl0002" num="0002"><img file="EP0091990A2_D0003.tif" /></tables>
Mixture C
<tables id="tabl0003" num="0003"><img file="EP0091990A2_D0004.tif" /></tables>
EXAMPLES
Examples I to III are compositions not according to the invention.
Example I
<tables id="tabl0004" num="0004"><img file="EP0091990A2_D0005.tif" /></tables>Properties of the hardened material:<tables id="tabl0005" num="0005"><img file="EP0091990A2_D0006.tif" /></tables>
Example II
<tables id="tabl0006" num="0006"><img file="EP0091990A2_D0007.tif" /></tables>Properties of the hardened material:<tables id="tabl0007" num="0007"><img file="EP0091990A2_D0008.tif" /></tables>
Example III
<tables id="tabl0008" num="0008"><img file="EP0091990A2_D0009.tif" /></tables>Properties of the hardened material:<tables id="tabl0009" num="0009"><img file="EP0091990A2_D0010.tif" /></tables>
Examples 1 to 7 are compositions according to the invention.
example 1
<tables id="tabl0010" num="0010"><img file="EP0091990A2_D0011.tif" /></tables>Properties of the hardened material:<tables id="tabl0011" num="0011"><img file="EP0091990A2_D0012.tif" /></tables>
Example 2
<tables id="tabl0012" num="0012"><img file="EP0091990A2_D0013.tif" /></tables>Properties of the hardened material:<tables id="tabl0013" num="0013"><img file="EP0091990A2_D0014.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP0091990A2_D0015.tif" /></tables>
Example 3
<tables id="tabl0015" num="0015"><img file="EP0091990A2_D0016.tif" /></tables>Properties of the hardened material:<tables id="tabl0016" num="0016"><img file="EP0091990A2_D0017.tif" /></tables>
Example 4
<tables id="tabl0017" num="0017"><img file="EP0091990A2_D0018.tif" /></tables>Properties of the hardened material:<tables id="tabl0018" num="0018"><img file="EP0091990A2_D0019.tif" /></tables>
Example 5
<tables id="tabl0019" num="0019"><img file="EP0091990A2_D0020.tif" /></tables>Properties of the hardened material:<tables id="tabl0020" num="0020"><img file="EP0091990A2_D0021.tif" /></tables>
Example 6
<tables id="tabl0021" num="0021"><img file="EP0091990A2_D0022.tif" /></tables>Properties of the hardened material:<tables id="tabl0022" num="0022"><img file="EP0091990A2_D0023.tif" /></tables>
Example 7
<tables id="tabl0023" num="0023"><img file="EP0091990A2_D0024.tif" /></tables>Properties of the hardened material:<tables id="tabl0024" num="0024"><img file="EP0091990A2_D0025.tif" /></tables><tables id="tabl0025" num="0025"><img file="EP0091990A2_D0026.tif" /></tables>
The depth of cure was determined with a curing lamp ("Translux") at an exposure time of 40 seconds. The light-induced discoloration was determined in accordance with ADA specification No. 27.
The results show the superior effect of the compositions according to the invention.
26 sheets
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| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO8503220A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| DE4110612A1 | Cited by | Germany | Search report |
| EP0156105A1 | Cited by | European Patent Office (EPO) | Search report |
| EP0480472A2 | Cited by | European Patent Office (EPO) | Search report |
| EP0449399A2 | Cited by | European Patent Office (EPO) | Search report |
| EP0449399A3 | Cited by | European Patent Office (EPO) | Search report |
| WO9212698A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US5354785A | Cited by | United States of America | Search report |
| EP0480472A3 | Cited by | European Patent Office (EPO) | Search report |
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| US5228907A | Cited by | United States of America | Search report |
| DE3403040A1 | Cited by | Germany | Search report |
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Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 368743 | United States of America | – | |
| 36874382 | United States of America | A | |
| 368743 | – | – | – |
| US19820368743 | – | – | – |
Members8
| Document | Office | Kind | |
|---|---|---|---|
| US4388069A | United States of America | A | |
| EP0091990A2This record | European Patent Office (EPO) | A2 | |
| JPS58189105A | Japan | A | |
| EP0091990A3 | European Patent Office (EPO) | A3 | |
| EP0091990B1 | European Patent Office (EPO) | B1 | |
| AT25926T | Austria | T | |
| DE3275705D1 | Germany | D1 | |
| JPH046162B2 | Japan | B2 |
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Numbers
- Publication
- 0091990
- Publication, DOCDB
- 0091990
- Publication, EPODOC
- EP0091990
- Application
- 82111183
- Application, DOCDB
- 82111183
- Application, EPODOC
- EP19820111183
Titles3
- German
- Dentales Restorationsmaterial
- English
- Dental restorative material
- French
- Matériau pour la restauration des dents
Classification
- CPC, 2
- A61K6/083
- A61K6/887
- IPC, 3
- A61K6 06
- A61K6 083
- A61K6 884
Designated states11
- Contracting states, 11
- Austria
- Belgium
- Switzerland
- Germany
- France
- United Kingdom
- Italy
- Liechtenstein
- Luxembourg
- Netherlands (Kingdom of the)
- Sweden