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  • 专利说明
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    • 专利摘要:
    PROCESS FOR PREPARING A GLASS-CERAMIC BODY. The present invention relates to a process for preparing a glass-ceramic body comprising the steps of providing a basic glass body and subjecting the basic glass body to a heat treatment whereby the crystalline phase embedded in a glass matrix is formed. According to the invention, the basic glass body is made of a composition comprising 65 to 72 -% by weight of SiO2, at least 10.1 -% by weight of Li2O and at least 10.1 -% by weight of Al2O3 based on the total weight of the composition, the ratio of Li2O to Al2O3 being from 1:1 to 1.5:1. Heat treatment involves a nucleation step followed by several crystallization steps at different temperatures, whereby two different crystalline phases are formed.
    公开号:BR112013027013B1
    申请号:R112013027013-6
    申请日:2012-04-20
    公开日:2021-05-25
    发明作者:Maria Borczuch-Laczka；Katharzyna Cholewa-Kowalska；Karolina Laczka
    申请人:Straumann Holding Ag；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for preparing a glass-ceramic body, to a glass composition for said process, as well as to a glass-ceramic body that can be obtained by said process and for the use of said glass-ceramic body for dental restoration.
    [0002] Glass-ceramic materials comprise an amorphous phase (glass) and one or more crystalline phases (ceramic) embedded in the amorphous phase. Due to the presence of both an amorphous and a crystalline phase, glass-ceramics share many properties with both glasses and ceramics. They are used in a variety of different technical fields, for example as cooktops, pans and cake tins, as a substrate for magnetic disks or as high-performance reflectors for digital projectors.
    [0003] Glass-ceramics are of particular interest in the field of restorative dentistry, in which the need for dentures, which in terms of functionality and appearance, would perform exactly as their natural equivalents expressed themselves.
    [0004] Conventionally, dental restorations have been prepared according to the method of "porcelain fused to metal" (PFM) in which the metal supporting the framework is used in conjunction with a veneer layer of a ceramic material that forms the color of the prosthesis. The preparation of restorations according to this method involves many preparation steps and is therefore laborious.
    [0005] The PFM method was still developed to replace the metallic structure by a non-metallic inorganic structure. In this regard, a feldspathic glass filled with aluminum particles was proposed. Further development led to the replacement of an opaque ceramic structure with an aluminum-reinforced glass.
    [0006] Dental crowns and bridges are nowadays mostly prepared by CAD/CAM technologies, which are increasingly gaining importance. The manufacturing process comprises two decisive stages: a computer-aided restoration project and its computer-aided shredding. In the crushing stage, the restoration is machined through an empty space.
    [0007] DE-A-19750794 proposed a process for preparing a lithium disilicate glass product suitable for use as a dentifrice product. The process is aimed at high chemical stability, high translucency and good mechanical properties of the product. Due to the high strength and hardening obtained, machining the material, however, results in very high wear of the machining tools and very long processing times. Furthermore, restorations prepared according to this technique show only small strength when their thickness falls within a range of only a few hundred micrometers.
    [0008] US-B-7452836 refers to a process for providing a glass-ceramic that has metastable lithium metasilicate (Li2SiO3) as the main crystalline phase. This lithium metasilicate glass-ceramic has mechanical properties that enable it to be easily machined into even complicated dentifrice restorations without undue tool wear. It can be converted by additional heat treatment into a lithium disilicate glass-ceramic with very good mechanical and translucency properties.
    [0009] Although US-B-7452836 considers making materials having a flexural strength that may be sufficient for the restoration of multiple teeth missing in the front (eg 3-unit bridges), its strength is still not sufficient for posterior bridges or major restorations.
    [00010] Aiming not only an improvement in mechanical properties, but also a highly aesthetic appearance, a material having an internal structure mimicking the structure of a natural tooth would be highly appreciated.
    [00011] Natural teeth consist of a hard, inert and acellular enamel supported by and less mineralized, more resistant and vital hard tissue dentin. Because of its exceptionally high mineral content, enamel is a fragile tissue unable to withstand the forces of chewing without fracturing unless it is supported by stronger dentin.
    [00012] Enamel and dentin not only differ in their mechanical properties, that is their compressive strength, elastic modulus and coefficient of thermal expansion, but also in their appearance. While enamel is translucent and varies in color from pale yellow to gray white, dentin is yellow. In a natural tooth, the thickness of the enamel ranges from a maximum of approximately 2.5 mm to a fraction of it. This variation influences the appearance of the tooth because the underlying dentin is seen through the thinner enamel region, while it gradually weakens towards the thicker ones.
    [00013] In summary, a natural tooth thus has a non-homogeneous structure different from that in the glass-ceramic of US-B-7452835, in which the crystals grow throughout the volume without any spatial order. Unlike a natural tooth, which exhibits a different composition and structure in different parts, be it in the dentin or enamel part, a restoration made of the material according to US-B-7452835 is, in relation to the constitution of the material, quite homogeneous and does not comprise regions of different constitutions as the natural equivalent. A natural tooth may thus not be perfectly imitated by the material according to US-B-7452835.
    [00014] Biocompatible, highly aesthetic and strong materials with an internal structure mimicking that of a natural tooth for a single tooth replacement (crowns) and for a prosthesis formed by one or more crowns (bridges) supported by the modified natural teeth are however , of primordial importance in the field of restorative dentistry. Furthermore, as more dental labs adopt CAD/CAM devices, laboratory-generated CAD/CAM prostheses are expected to rise significantly in the decades ahead. This evolution places an additional requirement of materials for the manufacture of restoration namely. CAD/CAM combine at reasonable costs.
    [00015] A method for preparing prostheses from a void comprising at least one layer of high abrasive strength, at least one layer of high flexural strength and at least one layer of lower hardness and strength is described in US-B-5939211. During the grinding of the restoration, material removal is carried out in such a way that layers with high strength constitute a reinforcing structure.
    [00016] Based on the discovery that so-called functionally graded material can lead to improved resistance to contact damage, US 2008/0213727 proposes a process for providing a functionally graded material including infiltrating ceramic top and bottom surfaces with glass. The resulting structure comprises an outer surface (aesthetic) of residual glass layer, a graduated glass-ceramic layer and a dense inner ceramic.
    [00017] Furthermore, WO 2010/010082 aims at a material imitating the color gradients in a natural tooth and refers to a form-stabilized material comprising a first component and a second component, the second component having a pigmentation different from that of the first and without from that disposed in the first component in such a way that the boundary surface between the components represents a curved spatial surface.
    [00018] In particular in relation to US-B-5939211 and WO 2010/010082, the presence of layers of physically distinct components and thus an interface between different components can have an impact on the stability of the entire dental restoration. Furthermore, the processes according to these documents are relatively laborious.
    [00019] The technique according to US 2008/0213727 enables a gradient of only a very small thickness to be formed. In addition, the gradient is confined to the surface area of the material; the formation of a gradient within the volume of material remote from the surface is not, however, possible according to US 2008/0213727.
    [00020] In general, it would be highly desirable to provide a glass-ceramic body, the properties of which can be adjusted to the current need in a simple and straightforward manner.
    [00021] In particular to perform dental restorations, with both superior mechanical and high aesthetic properties, a glass-ceramic body will be desirable for which different mechanical and optical properties can be obtained in different regions of one and the same body.
    [00022] More particularly and in view of the drawbacks of US 2008/0213727, a glass-ceramic body would be desirable comprising different crystalline phases changing from one region to another in a gradual manner and not being locally limited to specific areas of the material, such so being able to mimic the structure of a natural tooth.
    [00023] The aim of the present invention is thus to provide such a glass-ceramic body in a simple and straightforward way.
    [00024] The objective is solved according to the subject of independent claims 1, 5 and 10. Preferred modalities are given in the dependent claims.
    [00025] According to a first aspect, the present invention relates to a process for preparing a glass-ceramic body comprising the steps of providing a basic glass body and subjecting the basic glass body to a heat treatment in this way a crystalline phase embedded in a glass matrix is formed.
    [00026] According to the process of the invention, the basic glass body is made of a composition comprising 65 to 72 -% by weight of SiO2, at least 10.1 -% by weight of Li2O and at least 10.1 - % by weight of Al2O3 based on the total weight of the composition. Preferably, the ratio of Li2O to Al2O3 is at least 1:1, more preferably about 3:2.
    [00027] According to a specific modality, the ratio of Li2O to Al2O3 is from 1:1 to 1.5:1.
    [00028] The heat treatment involves a nucleation step followed by a first crystallization step in a first temperature range and a second crystallization step in a second temperature range different from the first temperature range. In this way, at least two crystalline phases different from each other are formed.
    [00029] It was surprisingly found that by thermally treating a glass body according to the present invention, not only different crystalline phases can be formed, but that the type of crystalline phases as well as their proportions can be controlled and thereby adjusted to the need current.
    [00030] In particular, different crystalline phases can be formed individually together with application of the heating required for the crystallization steps in a focused manner. In this way, different crystalline phases can be formed in different regions of one and the same body.
    [00031] Consequently, the present invention enables the realization of a structured glass-ceramic body, that is, a glass-ceramic body having crystalline phases differing from region to region. In this regard, the present invention further enables different crystalline phases to be carried out by shifting from one region to another in a gradual manner. This has important implications in particular with regard to the mechanical and optical characteristics of the glass-ceramic body, more particularly in view of a use of the body for a dental restoration, as will be discussed in detail below.
    [00032] As mentioned, the heat treatment according to the process of the invention comprises a nucleation step before the crystallization steps. By the nucleation step, crystallization nuclei are formed. For the nucleation step, the basic glass body, ie the "starting glass", is heated to a temperature of 500°C to 570°C, which is slightly above the glass transition temperature, and a pause up to 3 hours is observed. After this treatment, the nucleated glass shows no significant difference in appearance from the starting glass. Following the nucleation step, the nucleated glass body is heated to higher temperatures and again pauses are observed at specific temperatures (crystallization steps). This treatment leads to differences in both the mechanical properties and appearance of the glass body.
    [00033] In summary, the process of the present invention thus comprises a nucleation step in a first temperature range, after which no significant difference in the mechanical properties and appearance of the basic glass body is observed, followed by at least two crystallization steps, each in a temperature range higher than one of the nucleation step, said crystallization step leading to the formation of at least two different crystalline phases and thus to a glass-ceramic body having properties mechanics in a different appearance than the basic glass body.
    [00034] The crystallization steps thus differ from the nucleation step in that they are carried out at higher temperatures and that they follow with a change in both the mechanical properties and appearance of the material.
    [00035] The heat treatment of the present invention involving two crystallization steps is different from that described in DE 10 2007 011 337 related to surface layer ceramics for dental restorations, the process of the latter comprising merely a crystallization step. The same applies to WO 00/34196, which relates to glass-ceramics useful in the fabrication of single and multiple dental restoration units and which describes a preparation process comprising merely a crystal growth after a nucleation step. Also, US 6,514,890 describes a process comprising a single crystallization step after a nucleation step, said document being - independent of the fact that a different glass composition is used - thereby different from the present invention.
    [00036] Specifically, the basic glass body is heated to a temperature in the range 500°C to 570°C, more specifically 530°C to 570°C, for the nucleation step, followed by at least two steps of crystallization selected from the ranges of 620°C to 680°C, from 800°C to 820°C and from 825°C to 830°C, depending on the desired crystalline phases to be formed in their relative proportions with each other and into the amorphous phase. The duration for any of these steps typically varies in the range of 30 minutes to 10 hours, also depending on the desired crystalline phases to be formed and their proportions.
    [00037] It is known that the process of the present invention may comprise one or more crystallization steps in addition to the first and second crystallization steps mentioned above, leading to three or more crystallization steps.
    [00038] In addition to their temperature ranges, the individual crystallization steps may also differ in their hold times.
    [00039] By carrying out the crystallization steps within the temperature ranges specified above, a glass-ceramic material can be made comprising different crystalline phases, such as lithium disilicate, lithium metasilicate, lithium phosphate, lithium aluminum silicate as a solution solid of beta-spodumene, and cristobalite, and that the respective proportions of the crystalline phases can be adjusted to current needs.
    [00040] As will be shown in detail below, it is particularly preferred that the final glass-ceramic material comprises, as the two main crystalline phases, a lithium disilicate phase and a lithium aluminosilicate phase. As mentioned, the present invention allows to provide various proportions of these phases by adjusting the temperature and duration of the crystallization steps.
    [00041] Regarding the coexistence of a lithium disilicate phase and a lithium aluminosilicate phase, new desirable properties can be realized. In particular, a glass-ceramic body can be made having mechanical properties between the glass-ceramic properties of lithium aluminosilicate having excellent thermal properties and relatively moderate mechanical properties (with a flexural strength of 75 to 150 MPa and a fracture toughness Kic of 1 to 2 MPa^m1/2) and lithium disilicate glass-ceramic having a high strength (with a flexural strength of 350 to 400 MPa and a fracture hardening Klc of 2.3 to 2.9 MPa^ m1/2) and relatively low thermal properties (with a thermal expansion coefficient of 80 to 120^10-7 deg-1).
    [00042] For the particular modality specified in the examples below it has been shown, for example, that the formation of lithium metasilicate and lithium disilicate is favored in the temperature range of 620°C to 820°C and glass-ceramic materials having a flexural strengths of 300 to 400 MPa and a Klc fracture hardening of 2.0 to 2.6 MPa^m1/2 with a thermal expansion coefficient of 60 to 90^10-7 deg-1 can be achieved. In the temperature range of 825°C to 860°C, lithium aluminosilicate crystallization phases are dominant and a glass-ceramic material having a flexural strength of 280 to 330 MPa and a Kic fracture hardening of 2.0 to 2.3 MPa^m1/2 with a thermal expansion coefficient of 40 to 60^10-7 deg-1 can be achieved.
    [00043] Also, the chemical resistance of the final glass-ceramic can be adjusted. In this regard, a high proportion of the lithium disilicate crystalline phase is generally preferable if the high chemical resistance of the final glass-ceramic material is to be achieved.
    [00044] According to a particularly preferred embodiment of the present invention, a first region of the glass body is subjected to the first crystallization step and a second region of the glass body different from the first region is subjected to the second crystallization step in such a way that the proportion of the first crystalline phase (for example lithium disilicate) is higher in the first region than in the second region and the proportion of the second crystalline phase (for example lithium aluminum silicates) is higher in the second region than in the first region .
    [00045] The term "ratio" of the respective crystalline phase is, in the context of the present invention to be understood as -% by volume based on the total volume of the final glass-ceramic body.
    [00046] As for the crystallization steps, the modalities are covered in which the first region is exclusively subjected to the first crystallization step and the second region is exclusively subjected to the second crystallization step. In particular if the second crystallization step is in a higher temperature range, it is also considered that the second region is also subjected to the first crystallization step before being subjected to the second crystallization step.
    [00047] The first temperature range is preferably from 620°C to 820°C. The second temperature range is preferably starting from 825°C, and is more preferably from 825°C to about 1000°C, more preferably from 825°C to about 860°C.
    [00048] More particularly, a crystalline phase of Li2Si2O5 (lithium disilicate) is predominantly formed in the first region, and yet a crystalline phase being selected from the group consisting of LiAlSi2O6, LiAlSiO4, LiAlSi3O8, LiAlSi4O10 (aluminosilicate of lithium) is predominantly formed in the lithium second region, whereby - according to a particularly preferred embodiment - the proportion of crystalline phases changes from one region to another in a gradual manner.
    [00049] This is of particular relevance to preparing a glass-ceramic material to be used for dental restorations, since regions comprising a crystalline phase generally of lithium disilicate are translucent similar to enamel while regions comprising a crystalline phase of Lithium aluminosilicate are opaque similar to dentin. By carrying out a controlled heat treatment, a glass-ceramic body can thus be obtained comprising inhomogeneously distributed crystalline phases attributing to an inhomogeneous color distribution similar to the color distribution of a natural tooth.
    [00050] Also with regard to mechanical properties, the structure of a natural tooth can be accurately imitated by the inhomogeneously distributed crystalline phases, as the lithium disilicate phase confers a greater strength than the lithium aluminosilicate phase corresponding to the situation natural with enamel having greater strength than dentin.
    [00051] Furthermore, the high chemical resistance of the glass-ceramic region of lithium disilicate attributes its viability to an enamel-like region.
    [00052] In view of the CAD/CAM machining of the glass-ceramic body, adjusting the formation of different crystalline phases in different regions of the body still enables a favorable distribution of stresses that strengthens the body and makes it less prone to fracture. In particular, a favorable voltage distribution is obtained if the crystalline phases change from one region to another in a gradual manner. With respect, for example, to the coefficient of thermal expansion, which is different in a lithium disilicate glass-ceramic region than in a lithium aluminosilicate glass-ceramic region, a smooth transition can thus be realized. . This ultimately leads to a body being well suited for CAD/CAM treatment of both single-unit restorations as well as multi-unit bridges. Furthermore, the distribution of the crystalline phases can be adjusted in such a way that the areas to be treated outside the block are preferably predominantly of a softer material than, for example, the areas that will be present in the final restoration.
    [00053] The process of the present invention is not locally confined to the surface area of the body, but enables the selective and controlled formation of different crystalline phases throughout the body and in particular within the body remote from the surface. A spatially confined and controlled heat treatment leading to selective and controlled crystallization can, for example, be performed by laser irradiation, as demonstrated by Kawasaki et al. (Journal of Non-Crystalline Solids 325 (2003) 61 to 69), Honma et al. (Applied Physics Letters 83 (2003), 2796 to 2798), Fujiwara et al. (Chem. Glasses 43C (2002) 213), Gupta et al. (Optical Materials 2005) and others. Other methods enabling a focused and spatially limited heating of the basic glass body, using, for example, electromagnetic radiation or susceptors, are also possible. Furthermore, methods using a coolant paste for hot confinement, ie, protecting certain areas of the basic glass body from being heated, can likewise be carried out.
    [00054] Although the present invention also contains the possibility of forming different crystalline phases in spatially separated regions, the process of the present invention is preferably carried out in such a different way that those crystalline phases changing from one region to another in a gradual manner are formed. This is also of particular relevance regarding the use of the body for a dental restoration as well as in a natural tooth the different structural components change in a gradual manner. Furthermore, any stability issues that may arise at an interface of different materials can be avoided.
    [00055] According to a very simple technique, a temperature gradient can be performed on the basic glass body by properly placing the body in a heating furnace in which such a temperature gradient is present, thereby leading to a gradual change in the composition of the crystalline phase along the gradient.
    [00056] Apart from the process described above, the present invention further relates to a glass composition comprising 65 to 72 -% by weight of SiO2, at least 10.1 -% by weight of Li2O and at least 10.1 -% by weight of Al2O3 based on the total weight of the composition. Preferably, a ratio of Li2O to Al2O3 is at least 1:1, and more preferably it is about 3:2. The term “Li2O to Al2O3 ratio” is understood to mean the ratio of the amount of Li2O to the amount of Al2O3.
    [00057] The glass composition is particularly useful for the process described above. Based on this composition, the desirable glass-ceramic material can be prepared in a simple and straightforward manner, as mentioned above. Particularly, a wide variety of different crystalline phases can be formed.
    [00058] Preferably, the instant invention glass compositions comprise at most 15 -% by weight of Li2O and/or at most 15 -% by weight of Al2O3.
    [00059] According to a specific modality, a ratio of Li2O to Al2O3 is from 1:1 to 1.5:1.
    [00060] According to a preferred embodiment, the composition further comprises 0 to 2 -% by weight of K2O, 1 to 4 -% by weight of Na2O and 0 to 1.5 -% by weight of CeO2. In that regard, the present invention also encompasses a composition essentially consisting of 0 to 2 wt% K2O, 1 to 4 wt% Na2O and 0 to 1.5 wt% CeO2 in addition to SiO2, Li2O and Al2O3.
    [00061] Depending on the final body of glass-ceramic to be made, different crystallizing agents can be used in the glass composition. Typically, the composition thus further comprises 0 to 1.5 -% by weight of CaO, 0 to 1.0 -% by weight of MgO, 0 to 1.5 -% by weight of B2O3, 1 to 5 -% in weight of P2O5, 0 to 3 -% by weight of CaF2, 0 to 2.0 - % by weight of AlF3, 0 to 1.0 - % by weight of Ag, 0 to 5 - % by weight of ZrO2 and 0 to 4 -% by weight of TiO2 based on the total weight of the composition. In this regard, the present invention also encompasses a composition essentially consisting of 0 to 1.5-% by weight of CaO, 0 to 1.0-% by weight of MgO, 0 to 1.5-% by weight of B2O3, 1 to 5 wt% P2O5, 0 to 3 wt% CaF2, 0 to 2.0 wt% AlF3, 0 to 1.0 wt% Ag, 0 to 5 wt% Al weight of ZrO2 and 0 to 4 wt% TiO2 in addition to SiO2, Li2O and Al2O3 and optionally K2O, Na2O and CeO2 in the amounts specified above, whereby preferably a ratio of Li2O to Al2O3 is 1:1 to 1 .5:1. A glass composition being devoid of ZrO2 and TiO2 is particularly preferred to achieve a relatively high content of a lithium disilicate crystalline phase, in particular compared to lithium aluminosilicate phases.
    [00062] According to an alternative preferred embodiment, the glass composition, in addition to SiO2, Li2O and Al2O3, comprises 0 to 2 -% by weight, preferably 0 to 1 -% by weight of K2O, at most 4 -% by weight, preferably at most 2.5 -% by weight of Na2O, 0 to 1.5 -% by weight of CaO, 0 to 1.5 -% by weight of CeO 2 , 1 to 5 -% by weight, preferably 3 to 5 - wt% P2O5, 0 to 0.5 wt%, preferably 0 to 0.1 wt%, most preferably 0 to 0.05 wt% V2O5, 0 to 1 wt% weight of Ag and 0 to 1 -% by weight of ZrO2, the composition being devoid of TiO2, Cu2O, BaO, Sb2O3, Nb2O5, MgO, La2O3 and SnO2. It is therefore particularly preferred that the glass composition essentially consists of 0 to 2 -% by weight, preferably 0 to 1 - % by weight of K 2 O, at most 4 - % by weight, preferably at most 2.5 - % by weight of Na2O, 0 to 1.5 - % by weight of CaO, 0 to 1.5 - % by weight of CeO2 , 1 to 5 - % by weight, preferably 3 to 5 - % by weight of P2O5 , 0 to 0. 5 - % by weight, preferably 0 to 0.1 - % by weight, most preferably 0 to 0.05 - % by weight of V 2 O 5 , 0 to 1 - % by weight, preferably 0 - % by weight of Ag and 0 to 1 - wt% ZrO2 in addition to SiO2, Li2O and Al2O3 in the amounts given above, whereby preferably a ratio of Li2O to Al2O3 is 1:1 to 1.5:1. Furthermore, in this alternative embodiment, the glass composition is preferably devoid of ZrO2 to achieve a relatively high content of a lithium disilicate crystalline phase, in particular compared to lithium aluminosilicate phases.
    [00063] According to another preferred alternative embodiment, the glass composition comprises 65 to 72 -% by weight of SiO2, at least 10.1 -% by weight of Li2O, at least 10.1 -% by weight of Al2O3, whereby preferably a ratio of Li2O to Al2O3 is from 1:1 to 1.5:1, 1 to 5 -% by weight, preferably 3 to 5 -% by weight of P2O5, and optionally 0 to 1.5 -% by weight weight of CeO2, 0 to 0.1 -% by weight, preferably 0 to 0.05 -% by weight of V2O5, 0 to 2 -% by weight, preferably 0 to 1 -% by weight of K2O, at most 4 - % by weight, preferably at most 2.5 - % by weight of Na2O, 0 to 1.5 - % by weight of CaO, 0 to 1 - % by weight of Ag and 0 to 1 - % by weight of ZrO2 , composition being devoid of TiO2, Cu2O, BaO, Sb2O3, Nb2O5, MgO, La2O3 and SnO2. It is therefore particularly preferred that the glass composition essentially consists of 65 72 -% by weight of SiO2, at least 10.1 -% by weight of Li2O, at least 10.1 -% by weight of Al2O3, so preferably a ratio of Li2O to Al2O3 is from 1:1 to 1.5:1, 1 to 5 -% by weight, preferably 3 to 5 -% by weight of P2O5, and optionally 0 to 1.5 -% by weight of CeO2. 0 to 0.1 - wt%, preferably 0 to 0.05 wt% V2O5, 0 to 2 wt%, preferably 0 to 1 wt% K2O, at most 4 wt%, preferably at most 2.5-% by weight of Na2O, 0 to 1.5-% by weight of CaO, 0 to 1-% by weight of Ag and 0 to 1-% by weight of ZrO2. Also in this alternative embodiment, the glass composition is preferably devoid of ZrO2 to achieve a relatively high content of a lithium disilicate crystalline phase, in particular compared to lithium aluminosilicate phases.
    [00064] Typical glass compositions suitable for the purposes of the present invention are as follows: Composition I
    Composition II
    Composition III
    Composition IV
    Composition V


    [00065] All the preferred characteristics of the glass composition mentioned above, and in particular all the specific glass compositions, are similarly preferred with respect to the described process for preparing a glass-ceramic body. They are likewise preferred over the glass-ceramic body itself and for its use for a dental restoration, described below.
    [00066] According to a further aspect, the present invention further relates to a glass-ceramic body comprising at least two crystalline phases selected from the group consisting of Li2SiO3, Li2Si2O5, LiAlSi2O6, LiAlSiO4, LiAlSi3O8, LiAlSi4O10 and Li3PO4.
    [00067] Preferably, the glass-ceramic body comprises five crystalline phases selected from the group consisting of Li2SiO3, Li2Si2O5, LiAlSi2O6, LiAlSiO4, LiAlSi3O8, LiAlSi4O10 and Li3PO4, thereby enabling an almost unlimited adjustment of body properties by appropriately choosing the phases crystalline and a proportion in which they are present.
    [00068] According to a particularly preferred embodiment, the glass-ceramic body comprises
    [00069] a first crystalline phase of Li2Si2O5 (lithium disilicate) and
    [00070] a second crystalline phase selected from the group consisting of LiAlSi2O6, LiAlSiO4, LiAlSi3O8 and LiAlSi4O10.
    [00071] The second crystalline phase is thus a lithium aluminosilicate; among the mentioned groups, LiAlSi2O6 and LiAlSi3O8 are preferred.
    [00072] A particularly preferred combination is LiAlSi2O6, LiAlSi3O8 and Li2Si2O5 further comprising Li3PO4.
    [00073] As mentioned above, the type of crystalline phase as well as its proportion in the glass-ceramic body of the present invention can be controlled by adjusting the temperature profile. For example, a two-phase material having a ratio of lithium aluminosilicate to lithium disilicate ranging from about 30:70 to about 60:40 can be achieved.
    [00074] As also mentioned above, it is preferred that the glass-ceramic body comprises a first region and a second region different from the first region, wherein in the first region a proportion of the first crystalline phase is higher than in the second region and in the second region a proportion of the second crystalline phase is higher than in the first region, thus enabling an inhomogeneous structure of, for example, a natural tooth to be imitated.
    [00075] This includes modalities comprising in the first and second region at least one additional crystalline phase in addition to the first crystalline phase and the second crystalline phase, respectively. In particular, it encompasses modalities comprising in the first region also in the second crystallization phase at a lower ratio than the first crystalline phase and/or in the second region also the first crystalline phase at a lower ratio than the second crystalline phase.
    [00076] In this regard, it is further preferred that the first crystalline phase and the second crystalline phase gradually change from region to region. This covers modalities in which the first crystalline phase gradually decreases with an increase in the second crystalline phase and vice versa, i.e. without a purely amorphous phase disposed between the regions, as well as modalities in which the first crystalline phase decreases towards the second region and the second crystalline phase decreases towards the first region with a purely amorphous phase disposed between the regions.
    [00077] According to a particularly preferred embodiment, the glass-ceramic body is in the form of a dental restoration having an enamel area and a dentin area corresponding to the respective areas of a natural tooth, with the first region being disposed in the enamel area and the second region being placed in the dentin area.
    [00078] Since with regard to color and mechanical properties, the lithium disilicate phase looks like enamel, while the lithium aluminosilicate phase resembles the dentin of a natural tooth, superior restorations can be made appropriate choice of the distribution of these phases. In addition, because lithium aluminosilicate is opaque, a metal brace or implant can be protective from shining through the restoration by properly disposing the lithium aluminosilicate phase within the body.
    [00079] According to a further aspect, the present invention thus also relates to the use of the glass-ceramic body for a dental restoration. Specifically, the present invention relates to the use of the glass-ceramic body for blocks, tooth coating, varnishes, crowns and bridges to multi-unit bridges.
    [00080] In particular, this usage also encompasses the use of the glass-ceramic body as a blank for the CAD/CAM treatment process to prepare a dental restoration. Likewise, the basic glass body can be subjected to the CAD/CAM treatment process before heat treatment involving the crystallization steps, since the change in body volume accompanied by the formation of crystalline phases is negligible.
    [00081] It is understood that the glass-ceramic body of the present invention can likewise be used for other technological areas, in particular areas where a good resistance to hot shock and/or chemical resistance of the material is of relevance.
    [00082] Specifically the glass-ceramic body can be used for cooktops (plates and other elements), cookware and/or kiln oven. A particularly interesting use is in the field of laboratory equipment (chemicals), which is generally subjected to high temperatures as well as harsh chemical conditions.
    [00083] Other areas include apparatus for the generation, distribution and use of energy, in particular power plants. A specific area of interest is use in solar heating collection elements comprising a glass-ceramic center tube.
    [00084] The present invention is further illustrated by means of the following examples in combination with the attached figures, of which
    [00085] Figure 1 shows a graphical representation of a proportion of different phases (-% by volume) in a glass-ceramic material obtained by subjecting the glass composition according to the present invention to different treatment temperatures; and
    [00086] Figure 2 shows a purely schematic representation of a preferred glass-ceramic body according to the present invention to be subjected to a CAD/CAM process to prepare a dental restoration, as well as a fastener to retain the body. Examples
    [00087] The following experiments are based on the following (natural) glass composition:


    [00088] Differential Scanning Calorimetry (DSC) and Differential Thermal Analysis (DTA) of the composition showed three peaks, one at about 655°C, one at about 812°C and one at about 826°C, indicative of three crystallization steps.
    [00089] Based on these findings, a first sample of the glass-composition was - after a nucleation step at 550°C for three hours - subjected to a crystallization step at 660°C for three hours (crystallization step I) . A second and a third sample were subjected to a crystallization step at 815°C for three hours (crystallization step II) followed by crystallization step I and the crystallization step at 830°C for three hours (crystallization step III ) following crystallization step I.
    [00090] X-ray diffraction (XRD) analysis revealed a formation of Li2SiO3 (lithium metasilicate) and lithium aluminosilicate (LAS) in crystallization step I, and a formation of Li2Si2O5 (lithium disilicate) and lithium aluminosilicate in crystallization step II and crystallization step III, with an increased content of lithium aluminosilicate (as spodumene) and a decreased content of lithium disilicate formed in crystallization step III compared to crystallization step II.
    [00091] The content of different phases in the final glass-ceramic in relation to different heat treatments was still determined. In this regard, the crude glass composition - after a nucleation step at 550°C for three hours and the first crystallization step at 660°C for three hours - was subjected to a second crystallization step at an additional temperature by three hours, specifically at a temperature of 760°C (sample 1), 790°C (sample 2), 820°C (sample 3) and 850°C (sample 4). The results are shown in Figure 1.
    [00092] As shown in Figure 1, the content of different phases in the final glass-ceramic material is highly dependent on the temperature of the second crystallization step. For example, a decrease in the amorphous phase with an increase in the temperature of the second crystallization step was detected. For the lithium disilicate phase, the highest content was detected in samples 2 and 3, for which the second crystallization step was at a temperature of 790°C and 820°C, respectively. Lithium aluminum silicate is in sample 1 predominantly present as petalite and in sample 2 almost exclusively present as virgilite. In sample 3 it is present with both virgilite and spodumene, whereas in sample 4 it is present exclusively as spodumene.
    [00093] The results given in Figure 1 illustrate both, that several crystalline phases can be formed in one and the same glass-ceramic material and that the type of crystalline phase and its content can be controlled by adjusting the treatment temperature.
    [00094] It has been shown that different crystalline phases resulting in different mechanical and optical properties can be realized in one and the same glass-ceramic body by applying a temperature gradient for heat treatment. For example, a temperature gradient can be provided in a furnace where the temperature gradually decreases with increasing distance from the furnace heat source (eg located in the middle of the furnace). By properly placing the respective body in the furnace, a temperature gradient is established in the material, leading to crystalline phases gradually changing from one region to another.
    [00095] Specifically, it has been shown that by subjecting the glass composition of the present example to a temperature gradient starting at about 550°C, opalescence starts to form at about 570°C. At about 620°C, a violet shadow in reflectance light and a yellow shadow in transmittance light can be detected, and at about 670°C opalescence is marked. An opaque material is achieved starting at about 700°C.
    [00096] By means of the glass composition of the present example it can thus be shown that the invention not only enables the formation of different crystalline phases in different regions of one and the same body, but also a gradual change of the crystalline phases of a region to another.
    [00097] As schematically shown in Figure 2, the glass-ceramic body 2 of the present invention comprises a first region 4 comprising a high proportion of a first crystalline phase and a second region 6 comprising a high proportion of a second crystalline phase. Depending on the local properties to be achieved in the final restorations 8, the portions to be removed are determined and the body is arranged accordingly. A fastener 10 ensures that the body is held in place during computer-assisted treatment.
    [00098] Giving the distribution of the crystalline phases, a final restoration can be carried out, the surfaces 12 carrying the load having a higher stiffness than, for example, an area of mass 14 of the body 2 to be removed. In this way, a dental restoration with high rigidity on, for example, the pontics, the cusp supporting areas or the edges can be made relatively easily without undue wear of the treatment tools.
    权利要求:
    Claims (7)
    [0001]
    1. Process for preparing a glass-ceramic body (2) comprising the steps of providing a basic glass body and subjecting the basic glass body to a heat treatment in which a crystalline phase embedded in a glass matrix is formed, characterized in that the basic glass body is made of a composition comprising 65 to 72 -% by weight of SiO2, at least 10.1 -% by weight of Li2O and at least 10.1 -% by weight of Al2O3 based in the total weight of the composition, the ratio of Li2O to Al2O3 being from 1:1 to 1.5:1, and the heat treatment involves a nucleation step followed by a first crystallization step in a first temperature range and a second step of crystallization in a second temperature range different from the first temperature range, whereby at least two different crystalline phases are formed.
    [0002]
    2. Process for preparing a glass-ceramic body (2) according to claim 1, characterized in that a first region (4) of the glass body is subjected to a first crystallization step and a second region (6 ) of the glass body other than the first region (4) is subjected to the second crystallization step in such a way that a proportion of the first crystalline phase is higher in the first region (4) than in the second region (6) and a proportion of the the second crystalline phase is higher in the second region (6) than in the first region (4).
    [0003]
    3. Process according to claim 2, characterized in that the regions are heated up to the respective temperature range by means of laser irradiation, electromagnetic radiation and/or susceptors.
    [0004]
    4. Process according to any of the preceding claims, characterized in that the first temperature range is from 620 to 820°C and the second temperature range is from 825°C.
    [0005]
    5. Glass-ceramic body (2) obtained by the process as defined in claim 1, characterized in that it comprises: a) a first crystalline phase of Li2Si2O5 and b) a second crystalline phase selected from the group consisting of LiAlSi2O6, LiAlSiO4, LiAlSi3O8 and LiAlSi4O10, the glass-ceramic body (2) comprising a first region (4) and a second region (6) different from the first region (4), wherein in the first region (4) the proportion of the first crystalline phase is more higher than in the second region (6) and in the second region (6) the proportion of the second crystalline phase is higher than in the first region (4), and the glass-ceramic body (2) being in the form of a restoration dental having an enamel area and a dentin area corresponding to the respective areas of a natural tooth, with the first region (4) being disposed in the enamel area and the second region (6) being disposed in the dentin area.
    [0006]
    6. Glass-ceramic body (2) according to claim 5, characterized in that with respect to the composition of the crystalline phase, the proportion of the first crystalline phase and the second crystalline phase gradually changes from region to region.
    [0007]
    7. Use of a glass-ceramic body (2) characterized in that it is defined in any one of claims 5 to 6, for a dental restoration.
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    同族专利:
    公开号 | 公开日
    AU2012244543A1|2013-11-07|
    JP2014515722A|2014-07-03|
    ES2655173T3|2018-02-19|
    ES2813588T3|2021-03-24|
    CA2833580C|2016-06-28|
    CN107010838A|2017-08-04|
    JP2015231944A|2015-12-24|
    BR112013027013A2|2016-12-27|
    CN107010838B|2020-04-21|
    WO2012143137A1|2012-10-26|
    KR20140005330A|2014-01-14|
    JP2017222564A|2017-12-21|
    US20170267575A1|2017-09-21|
    EP3293157A1|2018-03-14|
    CN103476723A|2013-12-25|
    CA2833580A1|2012-10-26|
    JP6426235B2|2018-11-21|
    US20140141960A1|2014-05-22|
    JP5769873B2|2015-08-26|
    US20160159682A1|2016-06-09|
    CN103476723B|2016-12-07|
    EP2699521A1|2014-02-26|
    US9260342B2|2016-02-16|
    US9688568B2|2017-06-27|
    EP2699521B1|2017-10-18|
    EP3293157B1|2020-06-17|
    US10442726B2|2019-10-15|
    AU2012244543B2|2015-10-01|
    KR101617928B1|2016-05-03|
    JP6220817B2|2017-10-25|
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    法律状态:
    2018-01-16| B07D| Technical examination (opinion) related to article 229 of industrial property law [chapter 7.4 patent gazette]|
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-07-31| B07G| Grant request does not fulfill article 229-c lpi (prior consent of anvisa) [chapter 7.7 patent gazette]|
    2019-11-26| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-24| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11003315|2011-04-20|
    EP11003315.6|2011-04-20|
    PCT/EP2012/001709|WO2012143137A1|2011-04-20|2012-04-20|Process for preparing a glass-ceramic body|
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