Patent Application
20080303181
The present invention relates to single- or multi-colored shaped ceria-stabilized tetragonal zirconia polycrystalline ceramic materials, bodies, blanks and dental shaped parts, a process for their preparation, their use for the preparation of dental restoration shaped parts and also a composition which is particularly suitable for their manufacture.
In the discussion that follows, reference is made to certain structures and/or methods. However, the following references should not be construed as an admission that these structures and/or methods constitute prior art. Applicants expressly reserve the right to demonstrate that such structures and/or methods do not qualify as prior art.
The use of oxide ceramics as a framework material for dental restorations has long been state of the art. This material is characterized by an excellent biocompatibility and outstanding mechanical properties. For many years it has also been widely used as an implant material and for prostheses. In the past few years, ceramics based on partially stabilized ZrO2 ceramics have been used in particular.
The shaping of these ceramics in dental engineering is typically performed by mechanical means. In particular, milling of partially sintered ceramics with CAD/CAM processing units has gained acceptance. The shrinkage which occurs during final densification of shaped bodies, going from a density of approximately 40-60% to a density of more than 95%, is taken into account during the mechanical processing. The quoted density is relative to the theoretical density.
The disadvantages of ZrO2 ceramics are the low translucency and their milky-white color. A non-colored and non-coated restoration or restoration part looks like an unnatural tooth. Coloring the ZrO2 ceramic to match the patient's situation for an aesthetic tooth reconstruction are thus essential.
A particularly great disadvantage of sintered ceramics according to the state of the art is that they do not produce blanks for CAD/CAM processing in open-pored form or in dense-sintered form which are multi-colored or have zones of different colors corresponding to the coloration of a natural tooth.
All that is known from the state of the art is a series of technical solutions for colored, not multi-colored, blanks. However, these solutions have the disadvantage that the natural tooth color, the color gradient, the polychromatism, the graduated translucency and brightness of color were not achieved. These known solutions are described as follows:
The preparation of an open-porous colored and white Y2O3-containing ZrO2 blank is achieved according to EP 1 210 054 from liquids via co-precipitation from chlorides which contain Zr, Y, Al, Ga, Ge, In, Fe, Er and Mn ions. By means of the co-precipitation and subsequent calcination, the prepared powder already contains the coloring ions before shaping. Oxides from the group Fe2O3, Er2O3 and MnO2 are selected as coloring compounds. The disadvantage of this approach is that a very costly and laborious method of the co-precipitation process with subsequent calcination must be carried out in order to obtain a colored powder. This means that this process must be carried out for every single color.
In the following disclosures monolithic ceramics are presented which each allow one specific color, thus polychromatism, is not achieved.
U.S. Pat. No. 5,263,858 (Yoshida et el.) describes the preparation of ivory-colored shaped bodies for dental applications (brackets), wherein during the preparation of the stabilized ZrO2 ceramic coloring compounds in solutions are added before the calcination, or as powdery mixtures of coloring oxides after the calcination. In order to achieve the desired ivory shade, the addition of Fe2O3, Pr6O11 and Er2O3 is necessary. However, this process has the disadvantage that it is a multi-stage process.
It is further known from the state of the art according to FR 2 781 366 to mix the coloring components with the starting powder of the ZrO2, grind and sinter jointly. Fe2O3, CeO2 and Bi2O3 are mentioned as coloring oxides.
EP 0 955 267 mentions contents of 5-49 wt.-% CeO2, whereby coloration is achieved.
For the preparation of completely cubically stabilized zirconium dioxide in an arc-furnace process, according to EP 1 076 036 B1 one or more stabilizing and coloring oxides or their precursors are added to a ZrO2 source. The coloring oxides of the elements Pr, Ce, Sm, Cd, Tb are inserted into the crystal lattice of the ZrO2 after the sintering process.
U.S. Pat. No. 5,656,564 relates to the preparation of zirconium oxide shaped bodies which contain oxides of the rare earths boron oxide, aluminum oxide and/or silicon oxide. The shaped bodies contain zirconium dioxide as a mixed phase of tetragonal and monoclinal ZrO2. Oxides of the elements Pr, Er and Yb are introduced into the sintered ceramic as coloring oxides.
Technical solutions are further known according to the state of the art which allow colored blanks to be obtained by infiltration of liquids. However, these technical solutions have the serious drawback that coloring takes place after the pre-sintering process, and thus liquids are introduced into an open-porous ceramic body. The coloring is not completely homogeneous and also a multi-coloration cannot be achieved.
Unlike sintered ceramics, such as ZrO2 and Al2O3, a process for the preparation of multi-colored glass ceramic blanks is known from DE 197 14 178 C2. However, the preparation of multi-colored ZrO2 blanks is not mentioned in this document.
A disadvantage of the state of the art is that multi-colored sintered ceramic blanks cannot be prepared. Moreover, the solutions according to the state of the art are very costly and quality problems arise. The latter applies to the infiltration technique. Due to the subsequent coloring of a partially sintered blank or of a shaped dental product only the voids (pores) between the partially sintered particles of the starting powder can be occupied by the coloring ions. As a result, only discrete areas of the surface of the particles are colored with a layer of the coloring oxides, a continuous coverage of the surface of the particles of the starting powder not being possible. A further great disadvantage with infiltration is the concentration gradient of the coloring from the outside inwards. If a porous body is introduced into the coloring solution, the starting solution releases part of the dissolved coloring ions, starting from the outside inwards, and thus the coloring solution is “depleted” of some of its coloring substances. The consequence of this is that there is a higher concentration of the coloring ions on oxides outside than in the inside of the shaped body. Furthermore, only a certain depth of penetration can be achieved by means of the infiltration technique.
Ceria-stabilized tetragonal zirconia polycrystalline (Ce-TZP) materials are well known for their considerably higher toughness and resistance to low temperature degradation, i.e, hydrothermal stability or moisture stability, in comparison to yttria-stabilized tetragonal zirconia polycrystalline (Y-TZP), measured under similar environmental conditions. While the fracture toughness of Ce-TZP is indeed considerably greater than that of Y-TZP (maximum fracture toughness (KIC) for Y-TZP is about 10 MPa·m0.5 whereas that for Ce-TZP is about 17 MPa/m2), the attainable flexural strength is lower than the ISO 6872 minimum requirement of 800 MPa for substructures/frameworks used for multi-unit fixed partial dentures (also known as bridges with four or more units). These Class 6 fixed dental prostheses have successfully utilized Y-TZP in many applications.
Unfortunately, hydrothermal resistance of Y-TZP ceramics has always been a concern. It has been speculated that incorporation of trivalent Y ions leads to oxygen defects, which are the main cause for hydrothermal instability of the materials. However, incorporation of low amounts of alumina into Y-TZP ceramics has resulted in significant improvement of hydrothermal stability of the Y-TZP ceramics.
The best and most effective method of developing highly resistant, hydrothermally stable ZrO2 ceramics is however incorporation of Ce ions into the lattice of the ZrO2. This incorporation also provides the toughening effect resulting in higher toughness of Ce-TZP ceramics, and simultaneously, no oxygen defects allegedly associated with hydrothermal instability are developed.
U.S. Pat. No. 5,011,403 discloses orthodontic brackets made from ZrO2 having 11 to 20 wt % CeO2, preferably 14 to 17 wt % CeO2. These ceramics however are not sintered to full density and contain nanoporosity.
There are some indications in literature that Ce-TZP can have flexural strength up to about 800 MPa, but it is still not an adequate strength in comparison to Y-TZP materials which commonly exhibit flexural strength above 900 MPa and often above 1000 MPa (up to 1.5 GPa) for better products. It is not surprising that it is Y-TZP materials that have emerged as high-strength framework materials for dental prostheses (single-units up to full arch). However due to the inherent white color of Y-TZP, often the esthetics of the finished restoration are inferior to what is achievable with other all-ceramic systems. It should be noted that Ce-TZP is not pearl-white like Y-TZP and has yellowish, ivory or beige coloration.
Currently there are two predominant commercially available methods that address the stark white color of Y-TZP zirconia. In one method, the color of the zirconia is “hidden” by applying either a layer of stain or liner. The other method entails shading the zirconia by immersion in, or painting with coloring solutions while in the pre-sintered state. Coloring with a stain and/or applying a liner involves an extra fabrication step and lowers translucency. Shading with a coloring solution similarly requires the extra step of dipping or painting, and further requires extra time to dry before sintering. Also, this method is deficient since the color of the final sintered framework often is not uniform.
An alternative method is to use porous zirconia blocks that are preshaded to the desired coloration. Such blocks only need to be fired after any machining, thus eliminating the step of coloring with solutions. As the fully sintered frameworks emerge from the furnace already shaded, the stain/liner step can be eliminated. Additionally, the color of the sintered frameworks is characteristically uniform, which is another advantage over the method of using coloring solutions for shading.
A finished dental restoration should match the color of the patient's teeth, i.e., it should be “tooth colored”. The colors of human teeth appear to range from a light, almost white-tan to a light brown, and occupy a very specific color space. This color space can be described by the commonly used CIE (Commission Internationale de l'Eclariage) L*, a*, b* conventions, which represents colors in a three-dimensional Cartesian coordinate system. L*, or “value”, is a measure of luminance or lightness, and is represented on the vertical axis. The a* and b* coordinates, are a measure of chromaticity and are represented on the horizontal coordinates, with positive a* representing red, negative a* representing green, positive b* representing yellow and negative b* representing blue. U.S. Pat. No. 6,030,209, which is incorporated herein by reference, discusses the CIE L*, a*, b* color coordinates of tooth colors represented by the Vita Lumen® shade guide system manufactured by Vita Zahnfabrik. It provides the color space of tooth colors. Hereinafter, “tooth color” is taken to mean CIE L*, a*, b* color coordinates that fall within or very close to this color space. In terms of coloration, three areas can be distinguished in natural dentition: (a) the incisal area, which is the more translucent; (b) the middle section of the tooth; and (c) the cervical area, which is more chromatic and more intensively colored. Multiplicity of colors of natural dentition exclusive of incisal and cervical areas can be quantitatively described as belonging to color space delineated by L* from about 60 to about 90, a* from about −3 to about +10, and b* from about 12 to about 36.
U.S. Pat. No. 6,713,421, which is hereby incorporated by reference, appears to describe yttria-stabilized zirconia dental milling blanks that are formed with 0-1.9 wt. % coloring oxides from elements of the group Pr, Er, Fe, Co, Ni, Ti, V, Cr, Cu, Mn, with Fe2O3, Er2O3 or MnO2 preferably being used. The composition described therein includes 0.1 to 0.50 wt. % of at least one oxide of aluminum, gallium, germanium and indium for the purpose of lowering the sintering temperature and increasing stability and hydrolytic resistance in the densely sintered state. However, the addition of alumina to zirconia also often results in discrete alumina inclusions distributed throughout the microstructure. This occurs in part due to the low solubility of alumina in zirconia. Further, it presents a particular disadvantage for dental applications because alumina inclusions can lower the translucency of the zirconia since the refractive index of alumina, 1.77, differs considerably from that of tetragonal zirconia, which is 2.16. For example, alumina was added to Ce-TZP in an attempt to strengthen it resulting in very opaceous but strong Ce-TZP-Al2O3 nanocomposite material. Thus, it is desirable that dental zirconia is devoid of any alumina inclusions. A means to achieve this is to minimize, or eliminate, the alumina addition, thereby minimizing the potential for the alumina inclusions in the final microstructure.
In U.S. Pat. No. 6,713,421 the blanks are made from powders or granules that have been doped with the various oxides via a solution followed by a co-precipitation method. The cited advantage of this method is that the various oxides are distributed homogeneously throughout the powder. However, the field of dental restoratives requires many shades (for example, the Lava system offers 7 zirconia core shades and the Vita Classic system offers 16 Vita shades.). Having to prepare so many individually shaded powders or granules can be cost-prohibitive
Another disadvantage of the method set forth in U.S. Pat. No. 6,713,421 is that it requires relatively large amounts of the coloring oxides, iron oxide and erbium oxide. The examples reveal the addition of 0.2 wt. % iron oxide+0.38 erbium oxide (0.58% total) to provide color to 3Y-TZP. Although the patent does not indicate whether this results in a tooth color, it can be inferred from U.S. Pat. No. 5,219,805, which appears to disclose coloration of yttria-stabilized zirconia for dental bracket applications using combinations of Fe2O3, Er2O3, and Pr6O11, that even higher Fe2O3 and Er2O3 concentrations are necessary to achieve tooth coloration. For instance, according to the examples given in U.S. Pat. No. 5,219,805, up to 1.0 mol % Er2O3 (3.0 wt. %) additive is required to achieve dental brackets “having color tone similar to ivory-colored teeth”. Additionally, up to 0.2 mol % Fe2O3 (0.25 wt. %) is required to achieve tooth colors, which although less than the 1 mol % Er2O3 is required, it is still a considerable amount. Such significant quantities can have a negative effect on other properties of the resulting Y-TZP cores, such as on strength, Weibull modulus, hydrolytic resistance, and grain size.
Additionally, it has been observed that Er2O3 additions to 3Y-zirconia, of 0.2 wt. % or greater, result in sintered bodies that fluoresce to a dark yellow under ultraviolet (UV) lighting. This is inappropriate for a dental framework, which under UV light, ideally, should fluoresce bluish-white to mimic that of natural teeth. Less ideally, the framework should not fluoresce at all in the visible light range. In the latter case, fluorescence is typically imparted to the final restoration by the overlay porcelains. The shortcoming of an inappropriate fluorescence is overcome by the present invention.
The prior art also shows that Cr additions result in green or brown coloration. For example, U.S. Pat. No. 3,984,524 appears to describe olive coloration of cubic zirconia with the addition of 0.1 to 2 wt. % Cr2O3, U.S. Pat. No. 4,742,030 appears to describe green coloration of 5 mol % yttria-stabilized zirconia with the addition of 0.7 wt. % Cr2O3, and brown coloration with addition of 0.2 wt. % Cr2O3, respectively.
U.S. Pat. No. 5,656,564 appears to teach coloration of zirconia for dental bracket applications using combinations of Er2O3 and Pr6O11. The sintered zirconia-based ceramic is produced by a procedure generally including combining constituents in solution, precipitating, calcining, pressing, and sintering.
U.S. Pat. No. 5,011,403 appears to describe coloration of zirconia dental brackets using combinations of one or more of oxides of Fe, Ni and Mn added to a Zr-based powder.
U.S. Pat. No. 6,709,694 appears to describe the use of solutions for coloring of pre-sintered zirconia dental frameworks by immersion, painting or spraying using a metal ion coloring solution or metal complex coloring solution that is applied to a presintered ceramic, followed by sintering to form a translucent, colored dental ceramic. The claimed ions or complexes are of the rare earths elements or subgroups II and VIII, which have an action time of under two hours, and maximum pre-sintered zirconia diameter and height of 10 and 7 mm, respectively. However, this method is not ideal as the color of the final sintered frameworks often are not uniform and the process requires the extra steps of applying the solutions and drying prior to sintering.
The development of pink coloration in zirconia by Er additions is described in (i) P. Duran, P. Recio, J. R. Jurado, C. Pascual and C. Moure, “Preparation, Sintering, and Properties of Translucent Er2O3-Doped Tetragonal Zirconia,” J. Am. Ceram. Soc., vol. 72, no. 11, pp. 2088-93, 1989; and (ii) M. Yashima, T. Nagotome, T. Noma, N. Ishizawa, Y. Suzuki and M. Yoshimura, “Effect of Dopant Species on Tetragonal to Monoclinic Phase Transformation of Arc-Melted ZrO2—RO1.5 (R=Sm, Y, Er, and Sc) in Water at 200° C. and 100 MPa Pressure,” J. Am. Ceram. Soc., no. 78, no. 8, pp. 2229-93, 1989. Additions of CoO, Fe2O3 and Cr2O3 combinations to yttria-stabilized zirconia are known to impart a blue color in the final sintered zirconia bodies, as apparently described in Japanese patent publication 2,145,475. Additions of one or both of the colorants, nickel oxide and cobalt oxide, to yttria-stabilized zirconia have been shown to result in a purplish colored sintered body, as apparently described in U.S. Pat. No. 5,043,316.
Japanese patent publication 3,028,161 appears to describe the preparation of colored zirconia by the steps of: (1) mixing zircon-based pigment with partially stabilized zirconia containing Y2O3, MgO, etc., (2) molding and (3) sintering to provide a colored zirconia sintered product.
Many of the aforementioned coloring additions can negatively affect not only mechanical properties, including strength and fracture toughness, but also isotropic shrinkage and final sintered density. This can happen for a number of reasons including: (1) loss of fracture toughness from a lowering of the “transformation toughening” effect as a result of the over-stabilization of the tetragonal phase by the additive (either chemically, or by grain size reduction) thereby hindering the transformation from the metastable tetragonal phase to monoclinic phase that is necessary for the toughening to happen, (2) loss of strength due to spontaneous microcrack formation that can result if grains grow too large because of the additive, and, (3) loss of strength due to the formation of strength-limiting pores in the microstructure due to the additive. This last reason is what Shah et al. (K. C. Shah, I. Denry and J. A. Holloway, “Physical Properties of Cerium-Doped Tetragonal Zirconia,” Abstract 0080, Journal of Dental Research, Vol. 85, Special Issue A, 2006) attribute the significant loss of strength, down to 275±67 MPa, for 3Y-TZP materials that were colored using Ce salts. Additionally, they observed that strength decreased linearly with the concentration of the coloring additive, Ce.
The problem of formation of coarse pores, along with grain growth, in colored zirconia sintered compacts has also been recently recognized in JP 2005289721.
It is also important to recognize that only certain combinations of coloring agents in certain proportions will enable the matching of the color of a dental article so as to match the desired natural tooth color, e.g., A, B, C, D of the Vita™ classic shade guide and the Chromoscop® universal shade guide.
An object of the invention is to avoid one or more disadvantages of the state of the art described above, and to prepare an oxide powder that contains the coloring compounds uniformly distributed therein and is suitable for further processing to form a dental restoration part from this uniformly colored oxide powder, as well as a shaped body, an open-pored blank and a dental shaped part, which also contain the coloring compounds uniformly distributed therein.
A further object of the invention is to provide single- or multi-colored shaped parts, blanks and dental shaped parts which contain the coloring compounds in a gradient or zones.
The first object of the invention is achieved by processes in which
a) an oxide powder is coated with a coloring substance,
b) the coated powder is optionally graded and optionally filled into a compression mould,
c) the colored powder is compressed to give a shaped body and
d) the compressed shaped body is sintered to produce a blank, and
e) optionally the dental shaped part is formed therefrom.
A further object of the invention is achieved by single- and multi-colored shaped bodies, blanks and dental shaped parts, made from colored oxide ceramic powder or from colored oxide ceramic powder and uncolored oxide ceramic powder, which have a ratio of the oxide ceramic component to the coloring oxide, or of the mixtures of coloring oxides, in parts by weight of 100:0.0001 to 2.0.
As used herein “layer” means an individual component which produces a single-colored shaped body, blank or dental shaped part. The term “layers” illustrates the course or variation of the color as a color gradient or zones of a multi-colored shaped body, blank or multi-colored dental shaped part.
The invention also relates to the use of the single- or multi-colored shaped body, blank or dental shaped part for the preparation of dental restoration parts.
The invention further relates to a composition based on ZrO2 which can be processed with very small quantities of coloring substances to produce dental restorations closely resembling natural teeth.
It is yet another object of the invention to provide a pre-shaded Ce-TZP material that is formed into uniformly or multi-colored CAD/CAM blanks or dental articles.
It is a further object of the invention to provide a Ce-TZP material that sinters isotropically to full density and yields the required variety of consistent and stable shades useful for dental applications.
It is a still a further object of the invention to provide a Ce-TZP material that exhibits high strength and fracture toughness competitive with Y-TZP materials.
With the processes according to the invention, the coloring of the oxide ceramic takes place before the compression of the blanks and thus before the pre-sintering or sintering process. For the preparation of multi-colored shaped bodies, blanks or dental shaped parts, coating can be carried out with further coloring substances. For this, in a first step a first coloring substance is applied onto an uncolored oxide ceramic powder. In a second step, the next coloring substance is then applied onto further uncolored oxide ceramic powders. Depending on the number of desired colors, in several further steps a further coloring, with further coloring substances may be applied on further uncolored oxide ceramic powders. The result is oxide powder particles containing different color compounds.
Coating with the coloring substances can be carried out in a fluidized-bed reactor. Other coating methods known to a person skilled in the art can also be used according to the invention.
Suitable fluidized-bed methods are known from other fields of the art. These methods have not yet been used for the coloring of oxide ceramic powders which are used in the dental field. A material, loosened by a carrier medium (gas or liquid) of fine-grained solid particles is moved in the fluidized bed (also called fluid bed). For this, a gas flows from bottom to top through a stationary packing comprising oxide ceramic powder with an average grain diameter of the granules of 1 to 100 μm, preferably 30 to 80 μm. At a specific rate of flow (loosening point, fluidizing point) the packing transforms into the fluidized bed. Powders with the given average granule diameter are therefore preferred. Either the bottom spray or the top spray method can be used during the fluidized coating.
As the fluidized bed forms, the weight of the solid particles is neutralized by the oppositely-directed flow force of the carrier medium. The solid then behaves similarly to a liquid, i.e. it can be easily supplied or removed during the operation. A very intensive material and heat exchange takes place in the fluidized bed. Consequently, a coloring of the oxide ceramic powders can be achieved according to the invention by using a fluid which contains coloring substances.
Oxidic sintered ceramics, such as ZrO2 powders, can be used as oxide ceramic powders
As used herein, “sintered ceramics” means products which are produced from crystalline raw materials in a heat treatment process by sintering, wherein the crystal portion is very largely retained and only a small portion, in most cases well below 5 vol-% glass phase portion, forms between the individual crystals.
According to the invention the ZrO2 can also be doped with further metal oxides. For example, doping with CeO2, Y2O3, MgO or CaO is possible. HfO2 and Al2O3 can also be contained in the ZrO2 powder.
The oxides of the d- and f-elements of the periodic table of the elements can be used as coloring oxides. The coloring oxides Pr2O3, Fe2O3, Tb2O3, Er2O3, and/or Cr2O3 and further oxides can be used for this.
Oxides of the elements Mn, V, Ti, Nd, Eu, Dy, Er and/or Yb, in particular oxides of Mn, can be used as further coloring oxides.
In a preferred embodiment, Pr2O3, Fe2O3, Tb2O3, Er2O3, and optionally Mn2O3 are used as coloring oxides according to certain aspects of the present invention.
Aqueous solutions of various salts can be used as coloring substances. Water-soluble salts of d- or f-elements of the periodic table can be utilized. Nitrate or chloride hydrates of these elements are particularly examples. Examples of salts that can be used are Pr(NO3)3.5H2O, Fe(NO3)3.9H2O or Tb(NO3)3.5H2O.
In addition to the coloring substances, suitable water-soluble binders can also be used as compression aids for the powder. The binders can be dissolved with the above-mentioned salts in water and homogenized. Polyvinyl alcohol is one exemplary binder.
According to further embodiments a surfactant can be added to the powder, as this surprisingly improves compressibility. This is shown by a higher compression density at the same pressure. Non-ionic or amphoteric surfactants, such as polyglycol ethers or alkyl sulphonates, can be utilized.
The oxide ceramic powders coated with the coloring substances are preferably graded, e.g. screened using sieves with a mesh width of <90 μm, in a second step. Grading may be performed when there is agglomeration of the powder.
The optionally graded powder is then normally introduced into a compression mold. If the preparation of multi-colored blanks is intended, the first process step described above is carried out several times with other coloring substances or at higher concentrations of the coloring substances, with the result that differently colored powders are produced. In a second step these differently colored powders are poured portion-wise into a compression mold after the grading.
Compression, such as cold isostatic pressing, of a shaped body is carried out at pressures of 50 to 500 MPa, particularly at 70 to 300 MPa, quite particularly at 100 to 200 MPa. According to the invention a uniaxial compression is also possible. In a further process step the obtained shaped body is sintered, in particular pre-sintered. Temperatures of 800 to 1300° C., particularly 1000° C. to 1200° C., quite particularly of 1050° C. to 1150° C., are used for this. A porous blank with a density of at least 30%, particularly 40 to 75% of the theoretical density of the oxide ceramic is obtained by the pre-sintering process. The duration of the pre-sintering at the given temperatures is 1 to 4 hours, particularly 1.5 to 2.5 hours. The complete pre-sintering step including heating and cooling processes usually lasts 38 to 72 hours.
Debindering of the shaped body takes place at the same time during the pre-sintering process. “Debindering” means the burning out of the organic constituents, in particular the binders. However, this debindering can also be carried out in a separate process step.
The obtained single- or multi-colored blank is shaped into a dental shaped part for example in a dental laboratory or dental clinic. This can take place by milling or grinding by means of a CAD/CAM unit. The thus-obtained enlarged preform of a dental shaped part of the dental restoration is then densely-sintered at a temperature of 1200° C. to 1600° C., particularly 1300° C. to 1550° C. and quite particularly 1400° C. to 1500° C. The duration of the dense sintering step lasts 5 minutes and 2 hours, particularly 10 to 30 minutes. The complete dense-sintering process with heating and cooling generally lasts approximately 8 hours. The milling process is carried out such that the dental shaped part displays an excess that takes into account the shrinkage of the shaped part during the dense sintering.
The dense sintering can also be carried out using microwave energy, which as a rule leads to a shortening of the process times.
The prepared dental shaped part can represent the finished dental restoration, or can be processed further, such as provided with a veneer in order to produce the finished dental restoration.
The dental shaped parts prepared in the way described are characterized, unlike the dental shaped parts previously known from the state of the art, by a high color homogeneity. The coloring ions are present in aqueous phase and are applied homogeneously to the surface of the oxide ceramic powders, in particular in the fluidized bed. Even at very low concentrations of about 0.001 wt.-%, relative to the total amount of powder, a homogeneous coating of the powder is obtained. It is also advantageous according to the invention that mixed colors may be obtained, and blanks can be prepared in multi-colored form.
The invention contemplates the use of multi-colored blanks of the ZrO2 ceramic, that after dense sintering, there is a multi-colored product for restorative dental medicine. This polychromatism is extremely advantageous, quite particularly for multi-span bridges. Thus natural tooth coloration can be perfectly reproduced by such a dental restoration, as the latter does not consist of just one color, but has a color gradient and translucency differences as well as different color brightnesses within the tooth. If a multi-colored bridge according to the invention is now prepared, these aforementioned requirements or properties of a natural tooth can be easily ensured. This ease of preparation of dental shaped parts, e.g. of complicated dental restorations, such as multi-span bridges, is obtainable according to the invention by the fact that the dental technician needs to apply only a few sintered ceramic or sintered glass ceramic veneer layers, or even just one, to the multi-colored ceramic bridge in order to achieve the most natural look. Several layers have to be applied to uncolored ceramics as a veneer and in order to achieve special color effects. Various sinterings are also necessary in case of single-colored ceramics. Operations according to the invention are therefore more effective than according to the state of the art.
A further advantage is that a uniform distribution of pores is not a precondition for coloration. The infiltration technique depends on as uniform as possible a distribution of the pores in order to obtain colorings that are acceptable to at least some extent. Accordingly, wholly different coloring qualities are obtained according to the state of the art because of different roughnesses and inaccessible pores.
It is furthermore advantageous according to the invention that, with the coloring according to the invention of the oxide ceramic powders through the homogeneous distribution of the coloring substances on the surface of the powders or of the agglomerates thereof, no accumulation of the coloring substances occurs. An imperfection in the structure is thereby reliably avoided. If the process described above is carried out with differently colored oxide ceramic powders, the result after the compression, debindering and sintering is a multi-colored blank which has a color gradient which preferably corresponds to that of a natural tooth.
Furthermore, grain growth within the ceramic is not negatively influenced during sintering. The color ion distribution is so favorable that neither color gradients nor accumulations of color ions are visible or analysable with either the human eye or with a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
Finally, a process performed according to the invention in which the blank or the dental shaped part or the dental restoration prepared therefrom contains a composition according to the invention that is described below.
A composition according to the invention is based on ZrO2, and contains the following components:
Pr, calculated as Pr2O3,
Fe, calculated as Fe2O3,
Tb, calculated as Tb2O3, and
Mn, calculated as Mn2O3,
in a total quantity of 0.0001 to 0.75 wt.-%.
Surprisingly, it was shown that such a composition, despite the very small total quantity of coloring components, namely Pr, Fe, Tb and Mn, allows the preparation of blanks, dental shaped parts and finally dental restorations which are intensely colored in the desired way in order to excellently imitate the natural tooth material.
The components Pr, Fe, Tb and Mn can be present in different oxidation stages in the composition, preferably being present in an oxidation stage other than zero.
It is assumed that during the preparation of the composition by the above-given process according to the invention, in particular after pre-sintering or dense-sintering steps have been carried out, an insertion of the components in the form of ions into the crystal lattice of the ZrO2 takes place. For example, it is possible that these ions are inserted into defects of the ZrO2 lattice.
The composition is therefore preferably present in sintered form. In addition it contains the given components preferably homogeneously distributed.
It is further preferred that the composition contains the components in a total quantity of 0.0001 to 0.6 wt. % and in particular 0.0004 to 0.37 wt.-%.
Furthermore, a composition which contains the components in the following quantities has proved particularly effective:
In addition, particular ranges may also exist for the individual components as follows:
Pr, calculated as Pr2O3, in a quantity of 0.0005 to 0.01 wt.-%
Fe, calculated as Fe2O3, in a quantity of 0.005 to 0.4 wt.-%
Tb, calculated as Tb2O3, in a quantity of 0.0001 to 0.075 wt.-%
Mn, calculated as Mn2O3, in a quantity of 0.0001 to 0.075 wt.-%
Finally, it was surprisingly shown that special compositions can be very advantageously used as basic colors in the preparation of dental restorations. Four specific embodiments are described below of the composition according to the invention, giving the contained quantities of the components:
Compositions according to the invention can contain further substances, such as Cr, calculated as Cr2O3, in a quantity of 0.0001 to 0.1 wt.-%.
Furthermore, it is advantageous if the composition includes a stabilizer such as Y2O3. Compositions which contain 4 to 8 wt.-% Y2O3 represent specific embodiments.
Compositions may also contains up to 1 wt.-% Al2O3. This increases the stability of the composition according to the invention under hydrothermal conditions, which is of particular importance when using the composition according to the invention as a dental material. The composition can also contain HfO2.
Compositions which contains more than 95 wt/%, in particular more than 98 wt.-% ZrO2 are contemplated. Compositions in which the ZrO2+HfO2+Y2O3 content of the composition is more than 95 wt.-% are also contemplated.
Compositions according to the invention can be used in particular as dental material. Compositions according to the invention can in particular be prepared by a process in which a powder based on ZrO2 is coated with a source of the components, such as compounds of Pr, Tb, Fe and Mn, in particular by means of fluidized bed coating.
The invention also relates to a shaped body which contains the composition according to the invention and particularly those which have a homogeneous distribution of the components Pr, Tb, Fe and Mn within the whole body and thus an excellent color homogeneity. This shaped body is present in particular as a blank, dental shaped part or dental restoration, i.e. preferably as a sintered shaped body. The shaped body according to the invention can be produced in particular by the above-given process according to the invention for the preparation of blanks and dental shaped parts.
In a preferred embodiment, the invention contemplates a shaded Ce-TZP ceramic material. It was found that Ce-TZP exhibits strength approaching that of conventionally sintered Y-TZP if Ce-TZP is sintered in a microwave furnace. Such powders can be advantageously used to make uniformly colored or multicoloured CAD/CAM blanks using the methods described herein.
Preferred ranges of coloring agents to Ce-TZP are Fe calculated as Fe2O3: 0.005 to 0.1; Pr calculated as Pr2O3: 0.0001 to 0.05; Tb calculated as Tb2O3: 0.0001 to 0.1 and Er calculated as Er2O3: 0.0001 to 0.5. More preferred ranges include Fe calculated as Fe2O3: 0.005 to 0.06; Pr calculated as Pr2O3: 0.0001 to 0.035; Tb calculated as Tb2O3: 0.0001 to 0.06; and Er calculated as Er2O3: 0.0001 to 0.5. Most preferred ranges include Fe calculated as Fe2O3: 0.005 to 0.03; Pr calculated as Pr2O3: 0.001 to 0.03; Tb calculated as Tb2O3: 0.0001 to 0.03; and Er calculated as Er2O3: 0.0001 to 0.5. Optionally, Mn can be included in an amount of up to 0.005 wt. % (calculated as Mn2O3), but it is better to avoid Mn, to avoid potential greenish effects.
Blanks according to the invention can be provided with a density of 3.0 to 3.5 g/cm3, in particular 3.1 to 3.2 g/cm3.
A shaped body is further preferred which is multi-colored, wherein the polychromatism is brought about in particular by several differently colored layers. Shaped bodies which have at least two differently colored layers and preferably contain up to eight differently colored layers have proved particularly advantageous.
The natural tooth material can be very well imitated by just such a shaped body, such as, e.g., a blank, with at least three differently colored layers. The natural tooth material can be roughly divided into three regions, namely cervical, central and incisal, each having different requirements with regard to visual appearance. Thus the appearance of one layer is preferably matched to the cervical, and the appearance of the other two layers preferably matched to the central and incisal regions of the natural tooth. It has also proved particularly advantageous if at least one layer of the body contains a composition according to the invention and in particular a composition of the above-mentioned four special embodiments of the invention. Moreover, it is also possible that this at least one layer contains a mixture of the above-given four special embodiments and thus the basic colors represented by these embodiments can be modified.
A comparison with conventional colored compositions based on ZrO2 has shown that the special components of the compositions according to the invention, even in very small quantities, allow a desired color intensity to be obtained. The conventional system frequently requires a much greater quantity of coloring components for this, which leads to imperfections in the structure of the bodies produced therefrom. The comparatively small quantities of coloring components used in the case of the compositions according to the invention essentially cause no imperfections in the structure of the bodies produced therefrom, with the result that they and in particular the dental restorations that are finally prepared have excellent physical properties, such as strength and chemical stability.
Finally therefore the invention also relates to the use of the composition according to the invention or of the body according to the invention for the preparation of dental restorations. The dental restoration is in particular a crown and quite particularly preferably a bridge. It is of particular importance in particular with a bridge if the different colors present in the natural teeth that are to be replaced can be imitated as faithfully as possible. However, this is possible in an excellent way with the composition according to the invention and the shaped bodies prepared therefrom, through the provision of correspondingly differently colored regions, such as differently colored layers.
The invention is explained in more detail below by means of the following illustrative, non-limiting examples.
All the optical values L, a and b given within the framework of the examples were determined in accordance with the standards DIN 5033 or DIN 6174, by carrying out a comparison with a white reference sample with the values L*=93.11, a*=0.64 and b*=4.22. The value C represents the vector sum of a and b. Color measurement was carried out by means of a Konica-Minolta CM-3700d spectrometer. The CR value was determined in accordance with the standard BS 5612 and is a measure of opacity.
Partially stabilized ZrO2 powders, e.g. TZ-3Y or TZ-3YSB-C, from the company Tosoh which had the compositions below were used as starting material for compositions according to the invention and shaped bodies, blanks and dental shaped parts prepared therefrom:
An aqueous solution which contained both the coloring ions and a water-soluble binder, such as polyvinyl alcohol (e.g., Optapix PAF2 or PAF35 from the company Zschimmer & Schwarz) was used as a coloring solution for the fluidized-bed coating. The coloring solution can contain one or more coloring ions in order to achieve the desired coloration after the dense sintering. The aqueous coloring solution with about 0.1-2 wt.-% binder (relative to the quantity of powder to be coated) contained the respective coloring ions. This solution was homogenized for approximately half an hour (magnetic stirrer or the like). This coloring solution was then applied completely by means of a fluidized-bed granulator on the uncolored ZrO2 powder. During this step the powder to be coated was kept in suspension (fluidized bed) by means of compressed air (0.15-0.30 bar) and at the same time the coloring solution was sprayed through a nozzle, which was arranged above this fluidized bed, and applied to the powder. The spraying pressure here was between 2 to 6 bar. In addition, the compressed air which was necessary to maintain the fluidized bed was heated to approximately 30 to 80° C., and was thus able to dry the powder at the same time during the process.
ZrO2 powder (TZ-3YSB-C) was coated with an aqueous coloring solution based on Fe(III), Pr, Cr and Tb compounds. The thus-colored powder was introduced into a compression mould and subjected to cold isostatic compression at about 200 MPa. This shaped body was then pre-sintered at a temperature of 1125° C. over a period of about 120 min. to produce a blank and then worked by means of CAD/CAM technology. It was then dense-sintered at about 1500° C. The dental shaped part had a slightly yellowish color after the dense sintering. Square blanks were preferably prepared which preferably had the following measurements:
The preparation of cylindrical blanks was, however, also possible. The crystallite size, analyzed by means of SEM, of the partially sintered blank was about 200 to 400 nm. The crystallite size in the densely sintered restoration was about 400 to 800 nm.
The following TABLE I gives the compositions of differently colored blanks according to Examples 1 to 10 together with the optical values after dense sintering. The levels of the components are expressed as levels of the respective trivalent oxide. ZrO2 powders from Tosoh, Japan, containing 4-8 wt.-% Y2O3 were used as starting material. The powders differed in their primary particle size, specific surface and binder content. These powders were provided as described above with the coloring components.
Differently colored powders (different tooth colors) were homogeneously poured successively into a compression mould according to the desired layer thickness and color transition. The powder was subjected to cold isostatic compression at approximately 200 MPa and then pre-sintered at 1125° C. for about 120 min. A preform of a dental shaped part was then produced from the blank and dense-sintered. The dental shaped part was then cut open lengthwise, and a color gradient was seen which cannot be thus prepared by means of the infiltration technique. This natural color gradient, thus the reproduction of the visual properties of the natural tooth, became clear in particular in the case of a 3-span side-tooth bridge. Using the blank according to the invention, it proved possible to reconstruct the natural color transition without an additional coating technique in the dense-sintered dental shaped part. The color transition of a side-tooth bridge according to the invention is characterized in that a higher chroma (a more intense color) is realized in the fissure and at the neck of the tooth than in the area of the cusps of the tooth. A much better aesthetic was obtained compared with the substances and materials of the state of the art. Furthermore, the time spent by the dental technician on the preparation of the completely coated restoration was able to be reduced.
Aqueous systems with soluble ionogenic compounds, preferably chlorides and nitrates, were used as coloring solutions.
Blanks with a color transition comprising, e.g., 2 up to 10 colors, were able to be produced in a large homogeneity as single- and multi-colored blanks with this process.
A 3-span bridge framework was ground from an IPS e.max ZirCAD® bridge block in a CAD/CAM unit (Sirona in Lab®). The shrinkage factor of approximately 20% per space axis was taken into account by a corresponding enlargement ratio during grinding. The grinding process was carried out wet, with the result that the framework had to be dried before the infiltration process. The drying was carried out over 2 hours at about 80° C. under an infrared lamp. The reworked frameworks (removal of handpiece and regrinding of the edges) were infiltrated with the following solutions for the coloring (values in wt.-%), in order to ascertain differences in the color homogeneity:
A bridge framework was immersed for 2 min. in solution 1, infiltration taking place by capillary action. The use of a vacuum or above-atmospheric pressure was dispensed with. After the infiltration the framework was removed from the solution and dabbed dry by means of a paper towel in order to remove the excess coloring solution from the surface. The drying followed under an infrared lamp at 80° C. for approximately 2 hours. Already at this point in time a concentration of the Fe ions at exposed points of the framework (e.g., framework cusps of the masticating surface, high surface curvature) revealed itself. Even after the dense sintering at 1500° C. for 30 min. the color inhomogeneity resulting therefrom was clearly visible. A uniform outer coloring was not realizable.
A further bridge framework was dipped into coloring solution 2 for 2 min. to improve the color homogeneity. Post-treatment took place as described above. It was shown that the disadvantage of the superficial color inhomogeneity was able to be dealt with by the addition of the organic component and thus an increase in the viscosity of the coloring solution. The sintering also took place as described above. However, after the bridge framework was sectioned along the longitudinal axis it was shown that the coloring had taken place only in the outer layer zone of about 0.6 to 1.0 mm and thus there was not homogeneous coloring within the whole framework. This is possibly sufficient for an abutment crown, but there are major doubts in the area of the connectors and of the intermediate section of the bridge. During a subsequent grinding by the dental technician there is the danger that uncolored areas will be partially exposed and the originally intended effect of a coloring will be lost.
The comparative example shows that when infiltration is used as a coloring process only a superficial coloring can be achieved or a complete thorough coloring is achieved with only inhomogeneous coloring varying locally in strength (concentration of the color ions). These disadvantages are avoided according to the invention. A homogeneous coloring of the whole blank is always to be recorded.
It has also proved advantageous if nanoscale ZrO2 powder is used as starting material (primary particle size between 5 and 50 nm and a specific surface of >100 m2/g) for the preparation of the blocks. After working to produce a bridge framework this shows a clearly reduced temperature during the dense sintering. Thus, depending on the materials used, temperatures of below 1250° C. were reached, which allows a dense sintering in customary dental firing furnaces. To prepare colored blocks (single- and multi-colored) the colored powders used above were added as a so-called color concentrate to the nanoscale ZrO2 powder in a proportion of 0.0001 to 2.0 wt.-%. A temperature change during the dense sintering is not necessary.
Further particularly preferred compositions according to the invention were prepared in the manner given above for Examples 1 to 10 and further processed into blanks, dental shaped parts and dental restorations. The portions of the components, calculated as the respective trivalent oxide, and also the total portion of these color components and the presence of an additive possibly present during the compression into shaped bodies are listed in Table III below. The proportions are given as mg of component per kg of the whole composition.
The surfactant was polyglycol ether or alkyl sulphonates.
These compositions and in particular those according to Examples 13 and 17 can be used as typical dental colors. Surprisingly, despite the very small quantities of coloring components, these compositions can be processed into intensely colored dental restorations, such as in particular crowns and bridges.
The optical properties of colored dense-sintered blanks prepared from them are listed in Table IV below.
Commercially available Ce-TZP powders (CEZ-12-1 and CEZ-12-2 grades from Daichikigenso Kagaku Kogyo Co., Ltd.) were used to illustrate the preferred embodiments of the invention. In comparative examples, commercially available Y-TZP powder (TZ-3YB-E grade from TOSOH USA) were used to illustrate higher flexural strength and instability of the selected dopant combinations in conventional Y-TZP zirconia. Both Ce-TZP and Y-TZP powders had specific surface area in the range form 10 to 20 m2/g and were received from the manufacturer in spray-dried condition with a binder (CEZ-12-2) or as a fine powder (CEZ-12-1). The same sintering parameters, using conventional and microwave sintering, were used for both Ce-TZP and Y-TZP doped and undoped powder compacts (blanks). Conventional sintering was carried out in a Deltech furnace at 1450° C. for 2 hours. Microwave sintering was carried out in a Thermwave 1.3 furnace from Ceralink Inc. (Troy, N.Y.), a 1.3 watt single mode microwave with SIC susceptors at 1450° C. 10 to 20 minutes. The best results were obtained using the 10 minute hold.
Zirconia powders were doped with the coloring ions using water-soluble salts of the respective dopants. This entailed (1) first dissolving the appropriate amounts of the required salts in distilled water; (2) thoroughly mixing the solution with TZ-3YB-E (solution:zirconia=25:8 by weight) with a spatula; (3) freeze-drying for at least 12 hours; (4) screening through a 250 mesh (55 micron) nylon screen; and (5) blending for 15 minutes in a Retsch shaker. The salts used for adding Pr (yellow) and Cr (pinkish/mauve/brown) were 99.9% Pr(III) acetate hydrate (Pr(OOCCH3)3.XH2O), and 98% Cr(III) chloride hexahydrate (Cl3Cr.6H2O), respectively. Powders prepared using a solution containing both salts are shaded by a “cocktail” method. Powders made using a solution containing a single salt are referred to as “pigment” powders. To make shades, these powders were blended with white zirconia (TZ-3YB-E) to form the shade equivalent to the above powders using the “cocktail” method.
The Pr and Cr dopant levels of pigment powders were determined by X-ray Fluorescence and Inductively Coupled Plasma Optical Emission Spectrometry, respectively. The analyses were done by CoorsTek Analytical Laboratory, Golden, Colo. The measured Cr2O3 and Pr2O3 concentrations were somewhat lower than the calculated values (Cr2O3 about 20% lower, and Pr2O3 29 to 42% lower). The results are set forth in Table V below.
CEZ-12-2 spray dried grade (Daiichi Ce-TZP powder comprising 12 mole % of CeO2) containing 5 wt % acrylic binder was used to make samples. The samples were pressed into the shape of a disc by cold isostatic pressing. After pressing, the samples were debindered and sintered at 1450° C. to achieve full density. Microwave and conventional sintering techniques were used. The size of the sintered samples were about 40 mm in diameter and 4 mm in thickness. The flexural strength was measured on sample sizes in accordance with ISO 6872. The strength of the fully dense CEZ-12-2 samples sintered in a microwave furnace was much higher than the strength of similar samples sintered in conventional furnaces at the same temperature of 1450° C.
Table VI below summarizes the results of strength testing of conventionally sintered and microwave sintered Ce-TZP and Y-TZP having no coloring agents added.
The following Table VII compares color stability of Y-TZP and Ce-TZP samples doped with Pr (0.16 wt % Pr2O3) and subjected to simulated ring burn-out and porcelain pressing cycles.
It should be noted that Ce-TZP doped with Pr was of reddish yellow color and color loss was in the acceptable range (ΔE<3) compared to Y-TZP of yellow color, which had an unacceptable color loss (ΔE≧9).
Fracture toughness was determined as KIC (critical stress intensity factor). Sample preparation was carried out and fracture toughness was measured. Round samples were pressed from raw material and a binder at 125 MPa. The binder was removed by heating the samples at a rate of 0.5-1° C./min up to 1070° C. for two hours. After heating, pregrinding of the samples was conducted using SiC paper (1000 grid). The samples were then sintered in a conventional or microwave furnace. The samples were then ground and polished with different diamond slurries down to 1 mm to obtain parallel surfaces. Fracture toughness was measured with a Zwick Universal Testing Machine ZHUO.2 with a Vickers indenter applying a load of 20 kN. The crack length was measured by an SEM. The fracture toughness was calculated according to the Nihara equation applying the Palmquist crack model.
Fracture toughness of CeTZP is significantly higher than with Y-TZP. The DIN ISO 14577 test used to measure Vickers hardness was followed to determine the crack length produced by the hardness measurement. Samples of Ce-TZP exhibit a yellowish color and the toughness (KIC) is much higher than the white or colored Y-TZP as set forth in Table VIII below.
For a screening of color effect of the different ions in the Ce-TZP matrix, infiltration experiments were conducted. They require only small amounts of zirconium oxide granulate. Using the fluidized bed process requires far less concentrated salt solutions than using the infiltration process. This is due to the fact that in the fluidized bed process, the entire solution is sprayed onto the particles in each case, and thus in contrast to the infiltration process, no excess coloring solution remains. Thus, the fluidized bed process requires less concentrated salt solutions in order to achieve the same color effect. The following non-limited examples illustrate the coloring process of the invention.
For preparation of a 100 gram slip, 60 grams of ZrO2 powder and 40 grams of deionized water were weighed out. Coatex CE158 in the amount of 0.06 wt. % was used as a dispersing agent based on solid content of the suspension. The whole mixture was ground in a ball mill for 24 hours. Subsequently, 2.4 g of PEG 4000 dissolved in water (=0.6 g of solid PEG 4000) was added as binder and 1.2 g of DURAMAX B-1000 (which is liquid) was added as a plastifier to the 100 gram slip. These proportions of binder and plastifier have to be varied depending on the specific surface as well as the resulting pH value of the slip according to the batch of ZrO2 powder used. The binder and the plastifier were prepared separately, and then were added to the slip in order to reduce the risk of rapid polymerization. After the addition of the binder and plastifier, it was imperative that the slip be processed quickly.
The spray conditions of the slip vary with the kind and type of spray dryer used. In order to obtain homogenous, fully filled particles (no hollow balls or donuts), the viscosity had to be adapted. A top spray process was used, even though a bottom spray process is also feasible in this application. The reaction temperature was in the range of about 80 to about 220° C. The spray dried granulate was processed further, adding coloring agents using the fluidized bed technology described herein above. The resultant powder was compressed into shaped bodies. The shaped bodies were debindered, pre-sintered, and sintered by heating from ambient temperature to 300° C. for 5 hours at a rate of 1° C. per minute. The temperature was maintained at 300° C. for five hours. The samples were then heated to 600° C. at a rate of 1° C. per minute. The samples were maintained at 600° C. for five hours. The samples were then heated to 1430° C. at a rate of 5° C. per minute and maintained at 1430° C. for two hours. The samples were cooled down to ambient temperature at 5° C. per minute. The following Table IX sets forth coloring additives for the 100 grams of Ce-TZP samples prepared herein.
The methods and materials described herein provide improved properties for Ce-TZP ceramics useful in the manufacture of dental materials, restoratives and CAD/CAM blocks. Uniformly shaded materials are provide having good color stability and high fracture toughness.
Although the present invention has been described in connection with preferred embodiments thereof, it will be appreciated by those skilled in the art that additions, deletions, modifications, and substitutions not specifically described may be made without department from the spirit and scope of the invention as defined in the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102006024065.0 | May 2006 | DE | national |
| 06120608.2 | Sep 2006 | EP | regional |
| 07004776.6 | Mar 2007 | EP | regional |
This application is a continuation-in-part of U.S. application Ser. No. 11/802,053, filed May 18, 2007, which claims priority pursuant to 35 U.S.C. §119, to German Patent Application No. 10 2006 024 065.0 filed May 23, 2006, and European Patent Application Nos. 06120608.2 filed Sep. 13, 2006, and 07004776.6 filed Mar. 8, 2007, all of which are hereby incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11802053 | May 2007 | US |
| Child | 12138640 | US |
