The present invention relates to restorative materials, in particular to glass-ionomer cements. More particularly, the present invention relates to glass-ionomer cements having particular utility in the repair of human hard tissue, in particular as dental restorative materials and in orthopaedic surgery.
The glass-ionomer cement (GIC) was invented by Wilson and Kent in 1969 (GB 1316129) and is now a well established material with an important role in clinical dentistry and other fields, such as a bone replacement material. It is formed by the combination of a precursor glass in the form of an ion-leachable glass powder and an aqueous solution of a polyalkenoic acid (polyacid). The glass polyalkenoate cement has a combination of clinically attractive characteristics. It can adhere to tooth dentine and enamel as well as to base metals. The cement releases fluoride over a long period of time and this can help to prevent the formation of caries. A particular attraction is that the appearance of the material is similar to that of tooth colour and so can be matched closely with the patient's natural tooth colour. The glass component of a GIC acts as a source of ions for the cement-forming reaction, controls the translucency, setting rate and strength of the cement.
Traditionally, GICs were composed of calcium aluminosilicates but modern GICs replaces the calcium by either strontium or a combination of strontium and lanthanum, which also makes the material radio-opaque. There are a substantial number of potential glasses that could be used to produce GICs, all containing silica, alumina and an alkaline earth or rare earth oxide or fluoride. The two principal glass types are SiO2—Al2O3—CaO and SiO2—Al2O3—CaF2. Many other glasses can be derived from both of these materials.
Calcium fluoride is an essential constituent in fluoride glasses but often cryolite, Na3AlF6, is added to lower the fusion temperature. Apart from lowering the fusion temperature, fluoride improves the handling of the cement paste; increases cement translucency and strength and has a therapeutic quality when used as a dental filling.
In fluoride glasses, the alumina to silica ratio controls the setting time of the cement. Fluoride tends to slow the setting whereas aluminium orthophosphate improves the mixing of the cement. The formation of a GIC requires the complete decomposition of the glass structure so that all of the glass ions are available for release.
It has been observed that as the SiO2:Al2O3 ratio decreases, the compressive strength of the material increases. Setting time also decreases as the SiO2:Al2O3 ratio decreases until phase separation occurs in the glass, which deactivates the glass. As phase separation occurs, the main phase is depleted in calcium and fluoride, which reduces its reactivity. Further acid attack will occur selectively in the remaining phase separated droplets of concentrated calcium and fluoride. It has been reported that phase separated glasses have higher compressive and flexural strengths than clear glasses.
The role of fluoride within GICs is a matter of debate. According to some, in addition to [SiO4] and [AlO4], such glasses contain [SiO3F] or [AlO3F] tetrahedra. The replacement of O2− by F reduces the screening of the central cation and so strengthens the remaining cation-oxygen bonds. However, fluoride is non-bridging and thus structure-breaking. Another view on the role of fluoride suggests that metal fluorides occupy holes in the major glass network.
The polyalkenoic acid is not always present in liquid form. The acid is often supplied in dry form and blended with the glass powder so it can be activated immediately prior to use with water or an aqueous solution of tartaric acid. An increase in concentration of the polyacid increases solution viscosity. This can also lead to higher strengths but at the sacrifice of working time. The molecular weight of the polyacid affects the properties of a GIC. Strength, fracture toughness, and resistance to erosion and wear are all improved as the molecular weight of the polyacid is increased. However, the working time is decreased due to accelerated setting, limiting the maximum practical molecular weight of the polyacid to 75,000.
Reaction-controlling additives are incorporated into the GIC system to give viable setting and working times. Tartaric acid is often added to sharpen the set and increase the hardening rate. It has been shown that strength can also be improved by incorporating additives. Other multifunctional carboxylic additives have been trialled, but none have been shown to be as successful as tartaric acid.
The setting of a glass-ionomer cement occurs in several overlapping stages.
Cement formation with oxide glasses is extremely rapid and the set occurs virtually on contact between the two components making it clinically useless. If tartaric acid is added to the system, a useable cement can be formed. However, other cements are preferred because of their easier manipulation properties. Clinically the most common cements used contain fluoride and (+)-tartaric acid.
The structure of a set glass-ionomer cement can be described as ‘particles of partially degraded glass embedded in a matrix of calcium and aluminium polyalkenoates and sheathed in a layer of siliceous gel’.
The GIC behaves like a thermoplastic material when initially setting, which makes it very pliable and easy to manipulate—ideal for clinicians. Setting times at 37° C. for thickly mixed cements (for filling purposes) range on average from 2.7 to 4.7 minutes. For more thinly mixed luting agents the setting time can range from 4.5 to 6.3 minutes. Strength develops quickly and after 24 hours the cements can reach very high compressive strength values. Fracture toughness and flexural strength are clinically more significant than compressive strength. The flexural strength of a GIC can reach much higher than that of the original dental silicate cement. In general, GICs exhibit low values for flexural strength and fracture toughness when compared with the values for composite resins or dental amalgams. This makes the GIC less suitable than these materials in load-bearing or high stress situations.
The bond strength of GIC to enamel is far greater than that of GIC to dentine. Bond strength develops quickly and is complete within 15 minutes according to some studies. This property of a GIC is unique as it not only penetrates the pellicle but bonds to the debris, calciferous tooth and smear layer present after drilling.
Although the GIC is the most durable of all dental cements it is still susceptible to attack by aqueous fluids under certain conditions i.e. acid erosion, ion release and water absorption. When fully hardened, the GIC is resistant to erosion provided the solution has a pH of above 4. However, in the initial setting stage, the cement is fully susceptible to acid attack as the cations are in a soluble form, which is why a number of clinicians put varnishes on the surface while the material is maturing. When immature GICs are exposed to neutral solutions such as saliva, they release ions and absorb water. The matrix forming Al3+ (but not Ca2+) can be lost, resulting in permanent damage. Other ions often lost are sodium, fluoride and silicic acid. After storage in water the cements rapidly absorb water. As the cement ages, the absorption of water and loss of aluminium ions ceases. Fluoride and silicic acid continue to be eluted. From this the GIC can be viewed as a device for the sustained release of fluoride. The release of fluoride is biologically important as it is taken up by the adjacent tooth material possibly by the exchange of F for Off in hydroxyapatite. This uptake has the effect of improving the resistance of the tooth material to acid attack. One study showed that fluoride adsorption reduced surface energy making it more difficult for caries-promoting plaque to adhere to the surface. Fluoride release also increases mineralisation of the tooth and decreases the growth of plaque bacteria.
GICs are known for their biocompatibility their ability of the material to perform with appropriate host response in a specific application. For dental applications, glass-ionomers are in contact with hard tissue and close to the pulp. Their low setting exotherm and absence of organic eluants makes them bio compatible in this application. Their ability to release fluoride and an excellent seal are other benefits of these materials. The condition of the seal between the restoration and the tooth is extremely important. It has been shown that if harmful bacteria seep beneath the restoration secondary caries can develop. This occurrence is very high in number with amalgam fillings. The pulpal inflammation caused by a restorative has been shown to be caused by the build up of bacteria and not the chemical toxicity of the restorative. The GIC is well tolerated by living cells, although an important distinction must be made between a freshly mixed cement paste and a set restorative. Fresh cement exhibits an antimicrobial effect but it has been shown that this capacity diminishes with time. It also exhibits some cytotoxicity when freshly mixed but none when set. Both the cytotoxicity and antimicrobial properties are associated with the leachate from the cement. It has been suggested that the cause of this is the low pH and high quantity of fluoride released within the fresh material whereas others suggest the effects are due to the release of metal ions or free polyacrylic acid.
There is almost continuous development of restorative materials to seek to improve their properties. Attempts have therefore frequently been made to try to improve cement strength of GICs, including by carbon fibre or metal reinforcement, in particular by addition of silver-tin alloy to the cement matrix. However, the materials are not aesthetically pleasing. In the 1990s a resin-modified glass-ionomer cement (RMGIC) was developed. Originally developed as a base and liner, it consists of a liquid polyacid, typically poly(acrylic acid), and a photopolymerizable monomer, typically 2-hydroxyethylmethacrylate, HEMA, plus a photoinitiator which react to harden the material when a visible light beam is applied. Once the resin is cured the glass-ionomer maturation reaction continues protected by the cured resin enclosure from moisture and drying out. The addition of the resin component decreases the initial setting time as the light curing process only takes ˜40 seconds. The resin also reduces handling difficulties and substantially increases the wear resistance and physical strength of the cement which makes it a very appealing material to use in the dental industry. This enthusiastic approach to resin modified glass-ionomers has continued up to the present day with many clinical trials and research supporting this type of system.
The brittleness of glass-ionomers has been a significant drawback. The brittle nature of the material means that the distribution of air voids, microcracks and other defects within the cement lowers the strength significantly. The extent of brittleness can also be enhanced by the dehydration the cement undergoes in the oral cavity. It has been shown that low flexural strength limits the clinical use of the GIC as a permanent filling material in the posterior region. It is suggested that the strength of the material is sufficient to withstand moderate occlusal load; provided it is surrounded by tooth structure. The GIC has been deemed ideal for the modern minimal intervention type of conservative operative dentistry because it will have adequate support from the surrounding tooth structure and its inherent brittleness will be of no consequence.
Efforts for improvement have been made in several aspects, involving formation of different kinds of self-cured glass-ionomers, such as acrylic acid-itaconic acid (AA-IA) copolymers and acrylic acid-maleic acid (AA-MA) copolymers, water hardening compositions and dual setting RMGICs.
Even though there are clear improvements in the field, glass-ionomers are still in need of improved surface hardness to enable reliable use in load bearing situations. The present invention seeks to overcome this problem.
The present invention seeks to provide a modified glass-ionomer material which retains the desirable characteristics of conventional glass-ionomer cements (fluoride release, strength, adhesion to human hard tissue, biocompatibility) while improving toughness. Tougher, less brittle materials, are required in order to increase durability within dentistry, and in order to enhance load-bearing ability, notably in the restoration of posterior teeth (molars and premolars), and also in orthopaedics in the repair of bone damaged by trauma or disease.
The present invention also seeks to provide a dental restorative material with enhanced fluoride release, to aid protection of repaired teeth against further damage by dental caries; and to provide a material capable of developing ion-exchange bonding with repaired teeth, with both enamel and dentine.
The present invention also seeks to provide a material for dentistry having inherent anti-microbial properties, in order to reduce the incidence of dental caries adjacent to the repair in the tooth.
The present invention also seeks to provide a material of enhanced biocompatibility, especially for use in bone repair where this property will enhance bone re-growth and the development of a durable and functional interface between the cement and the bone.
In its broadest sense, the present invention provides a glass-ionomer cement composition comprising zinc and phosphate ions.
Zinc phosphate has been used as a dental material since 1879. The material typically comprises zinc oxide powder in which small quantities of magnesium oxide are incorporated. The powder is then reacted with phosphoric acid. The main problem with this type of cement is the setting reaction and the inability to control it. If the reaction is over vigorous, the product becomes a crystalline mass rather than a cement. To moderate the reaction between zinc oxide and phosphoric acid, the zinc oxide can be sintered at between 1000-1350° C., which deactivates and densifies the starting material by reducing the surface area and surface energy. It also alters the composition to make it non-stoichiometric. The addition of magnesium oxide promotes densification and preserves the whiteness of the powder.
The liquid component of zinc phosphate cement is an aqueous solution of phosphoric acid containing aluminium. When the two components, phosphoric acid and zinc oxide, are combined; the cement forms and sets very rapidly. The reaction is strongly exothermic and is greater than with any other dental cement. The excessive heat generated has to be dissipated whilst mixing or the cement will set prematurely. Strength develops very rapidly. It has been reported that approximately half the final strength will be attained within ten minutes of mixing, and 80% after one hour.
It has been shown that the aluminium in the phosphoric acid has a profound effect on the cement. If the aluminium is not added the material formed is a crystalline mass of hopeite with little mechanical strength. On the addition of aluminium an amorphous matrix was formed with a much higher mechanical strength.
Generally, after mixing, the zinc oxide powder is attacked by the acid solution, water acting as the reaction medium. Zinc ions are extracted and the pH at the powder-liquid interface rises. This causes aluminium phosphate or zinc aluminophosphate to precipitate as a gel at the particle surface. This gel coating moderates the reaction. Zinc ions diffuse through this layer and as the pH rises an amorphous gel is precipitated (probably as zinc aluminium phosphate). As the reaction proceeds, the cement matrix becomes more hydrated. The final cement is considered to contain mainly amorphous zinc phosphate with some crystalline hydrated zinc phosphate Zn3(PO4)2.4H2O.
Clinically, zinc phosphate is used as a luting material for the cementation of crowns and bridges. The cement suffers from the lack of the adhesive property but its reliability and speed of set has ensured its place in the dental clinicians' cabinet. Fully hardened cements have brittle characteristics. However, the materials have fairly high compressive strengths.
Accordingly, the present invention provides a composition comprising a mixture of a glass ionomer cement and zinc phosphate.
More specifically, the present invention provides a restorative composition comprising a glass ionomer cement and zinc phosphate.
Preferably, the composition comprises from 40 to 95% by weight of glass ionomer cement and from 5 to 60% by weight of zinc phosphate; more preferably, from 60 to 80% by weight of glass ionomer cement and from 20 to 40% by weight of zinc phosphate, even more preferably, from 70 to 80% by weight of glass ionomer cement and from 20 to 30% by weight of zinc phosphate.
Advantageously, the composition comprises about 75% by weight of glass ionomer cement and about 25% by weight of zinc phosphate.
The present invention also provides a composition obtainable by reacting together a glass ionomer cement precursor, a polyalkenoic acid, zinc oxide and phosphoric acid.
The present invention also provides a method of preparing a restorative composition as described above; the method comprising: i) providing a glass ionomer cement precursor glass; ii) providing a deactivated zinc oxide; iii) providing a polyalkenoic acid; and iv) providing a phosphoric acid solution.
Advantageously, the glass ionomer cement precursor glass, zinc oxide and polyalkenoic acid are provided as powdered solids; and the composition is prepared by pre-mixing the powdered solids and then mixing with the phosphoric acid solution.
Alternatively, the glass ionomer cement precursor glass and the zinc oxide are provided as a powdered mixture; the polyalkenoic acid is provided as a solution; and the powdered mixture, polyalkenoic acid solution and phosphoric acid solutions are added to the powdered mixture substantially simultaneously with mixing.
The present invention also provides a kit of parts comprising: a glass ionomer cement precursor glass; ii) deactivated zinc oxide; iii) a polyalkenoic acid; and iv) phosphoric acid solution.
Conveniently, the glass ionomer cement precursor glass and deactivated zinc oxide are provided as a powdered mixture.
The present invention also provides a powdered composition comprising a fluorosilicate glass and deactivated zinc oxide.
Preferably, the composition comprises 40-95% by weight of fluorosilicate glass and 5-60% by weight of zinc oxide.
Advantageously, the glass is a fluoroaluminosilicate glass, preferably a SiO2—Al2O3—CaF2 glass, optionally including one or more of AlPO4, Na3AlF6 and metal oxide or metal fluoride radio-opacifiers.
Preferably, the powdered composition further comprising a polyalkenoic acid, more preferably, in an amount, based on the glass and zinc oxide, of 10-40% by weight.
Suitably, the polyalkenoic acid is a polymer of an ethylenically unsaturated monomer, preferably polyacrylic acid, more preferably in a molar mass range of 5,000-250,000; or a homopolymer of maleic acid, itaconic acid and/or vinyl phosphonic acid or a copolymer thereof with polyacrylic acid; or mixtures of homopolymers thereof.
Preferably, the composition further comprises phosphoric acid, more preferably, in an amount of 5-40% by weight based on the weight of glass and zinc oxide.
Advantageously, the composition further comprises tartaric acid.
Advantageously, the composition further comprises a strengthening additive, preferably a finely divided metal alloy or particulate ceramic.
Suitably, the composition further comprises an additional fluoride-containing compound to enhance fluoride release; preferably, SnF2, NaF and/or sodium mono fluorophosphate.
A composition advantageously further comprises a finely divided bioglass filler.
The compositions are suitable for use, inter alia, as a dental restorative material; as a bone defect repairing material; and as a scaffold material in tissue engineering.
The above and other aspects of the invention will now be described in further detail, by way of example only, with reference to the following examples. The following study was carried out to try to incorporate the adhesive property of a glass-ionomer cement into zinc phosphate with the aim of achieving a material with higher compressive strengths and surface hardness values without compromising the adhesive and biocompatibility of a modem glass-ionomer.
For our studies two different types of cement were used; Fuji IX and zinc phosphate. Fuji IX is a typical GIC and is a strontium-based tooth-coloured glass ionomer luting material of alumino-silicate glass powder which is mixed with 40-45% m/v polyacrylic acid (eg. 0.25 g powder, 0.05 g liquid). Zinc phosphate is formed from a mixture of zinc oxide and phosphoric acid (45-65% m/v; eg. 0.225 g powder and 0.125 g liquid). The characterisation and analytical techniques used in this study were Vickers Hardness, Compressive strength, ICP-OES, Ion Selective Electrode, SEM, EDS and XRD.
It will therefore be understood that this represents, in fact, a four-component mixture of glass and polyacrylic acid and zinc oxide and phosphoric acid in a 50:50 mixture.
A preliminary study was performed on a 50/50 mix of Fuji IX and zinc phosphate.
Three samples were prepared using the same moulds and cure conditions. The surface hardness of the samples was tested after 24 hour storage in an air-tight bag and the results show in Table 1.
This ratio was used to produce a cement which was then subjected to 1 month of storage in water. The hardness of these specimens was tested at 48 h, 1 week and 1 month. The mean data and standard deviations are given in Table 2. Ion release analysis was also carried out on these specimens (Table 3 and illustrated in
From the above results it can be concluded that storage in water reduces the surface hardness of the hybrid material. This may be due to an inappropriate ratio blend resulting in not enough powder reacting when mixed, producing a specimen which is fairly soluble.
Cements comprising 50% Fuji IX and 50% zinc phosphate were used in the initial study and both cement components were made to the manufacturer's instructions and then combined. However, it was apparent that there was excess acid for the required amount of basic powder. An experiment was therefore carried out to determine if the acid type used (either H3PO4 or PAA) made a significant difference (p<0.001) to the surface hardness. 0.3 mL of either acid was incorporated into the powder during mixing and cured at 37° C. for one hour. The samples were then either left in air or distilled water for 24 h after which the surface hardness was tested. This trial was performed in triplicate. The mean data is given in Table 4 with standard deviations in parentheses.
From the results above it appears that by producing a cement using phosphoric acid alone higher surface hardness values are achieved. The cement was very difficult to mix without using polyacrylic acid therefore it was decided to perform another study looking at volume ratios of polyacrylic to phosphoric acid and comparing the resultant surface hardness values.
After further testing it was established that a reduced zinc phosphate content in the material resulted in a higher surface hardness as well as less zinc release. The cement tested (Table 5) had a reduced zinc phosphate content of 25%.
From these results it was established that a ratio of 75% Fuji IX: 25% zinc phosphate and 0.188 mL H3PO4: 0.05 mL PAA was most effective at this stage in terms of surface hardness.
Whilst determining cement ratios and acid volumes, scanning electron micrograph (SEM) images were taken.
The first two trials compare the acid used.
A preliminary EDS study was performed to check that an increasing amount of zinc phosphate was observed on addition to the glass-ionomer. This can be important in ensuring proper mixing when producing the cement.
The spectra show that varying the ratios of glass-ionomer to zinc phosphate can be observed incrementally by EDS, indicating good mixing.
It would be important not to inhibit significantly the release of beneficial fluoride ions from the glass-ionomer component of the hybrid. Table 6 shows fluoride release results from the hybrid mixes above (results are in ppm), with two samples being prepared for each ratio mix (F=Fuji IX).
The results are also plotted graphically in
The results for this study show that after four months the 75%:25% Fuji IX:zinc phosphate has the greatest fluoride release, this is closely followed by the 50:50 mix and then the 100% Fuji IX. These results show that modifying a strontium based glass-ionomer by incorporating zinc phosphate significantly increases the amount of fluoride released compared with GIC alone.
Bioactivity is a beneficial property which developing biomaterials should advantageously possess. Specimens comprising 75% Fuji IX:25% zinc phosphate were prepared, as this composition had exhibited the greatest surface hardness values and greatest fluoride release values. The samples were immersed in simulated body fluid (SBF) for 1 h, 24 h and 1 week to check for bioactivity. The results are shown graphically in
The other hybrids were also immersed in SBF and SEM images were taken and similar bioactivity was confirmed.
From analysis of the above data, it was decided to investigate the properties of compositions having proportions of GIC above the 75% indicated as preferable in the trials so far. It was hypothesised that the compositions may produce increased surface hardness values.
The hardness values are given in Table 8.
The extent of ion release from the hybrids was then assessed using triplicate sets of the hybrid cements. Samples were stored in 10 mL of distilled water at 37° C. for 24 h, 168 h or 1 month. Once the time periods had elapsed the samples were removed and the remaining water was analysed for ion release. The results are shown in Table 9 and illustrated in
Compared with the preliminary studies, the ion release for an 80% GIC: 20% zinc phosphate mixture appears to be reduced at lower zinc phosphate proportions. Even after one month the silicon release from the cement is still under 12 ppm. The early release of zinc from the cement is below 2 ppm and reduces over time.
The silicon release from the 85:15 hybrid (
Similarly to the 80:20 hybrid; the 90:10 hybrid (
All ion release for the 95:5 hybrid (
Bioactivity was then assessed. Triplicate sets of specimens were then prepared, weighed and stored in 10 mL SBF which was prepared using the Kokubo method for either 24 or 168 h. Once this time had elapsed the samples were removed, reweighed and stored for SEM analysis, the remaining SBF was diluted up to 30 mL and then analysed by ICP. The following results were obtained (Tables 13 and 14 and
It is easier to see the general trend of weight gain for the samples stored in SBF for 1 week. The samples containing a higher content of zinc phosphate appear to generally gain more weight. This is a very good indication of bioactivity however the weight gain could also be due simply to the hybrids becoming more hydrated.
Ion-release was then assessed and the results for the various compositions given in Tables 15 to 19 and
It is unclear from the results (
There appears (
Again there appears to be no calcium uptake by the cement in the 95:5 hybrid after 168 hours in SBF (
Fuji IX alone appears (
SEM results for the bioactivity study on the refined specimens are shown in
Fuji IX appears to be unaffected by the storage in SBF for 1 week (
The micrographs of
The 90:10 hybrid cement appears (
Fluoride release studies were then carried out on the further cements. The results are shown in Table 20 and
It can be seen that by incorporating zinc phosphate into a glass-ionomer, elevated levels of fluoride release can be achieved. The results correspond incrementally to the increasing level of zinc phosphate in the cement. In theory as there is no fluoride in zinc phosphate cement there should be less fluoride released the more zinc phosphate that there is in the material. It is clear that the process is not as straightforward as it may first appear as this is not shown by our results.
X-Ray diffraction patterns were obtained to assess the crystallinity within each of the refined materials and it was apparent that incorporating zinc phosphate makes the resulting hybrid more crystalline. There is also evidence that the hybrid may contain zincite and hopeite, as well as the amorphous glass from the glass-ionomer.
A preliminary antimicrobial study was carried out on the compositions. Zone of inhibition studies were carried out using agar plates spread with Bacteroides species. (ATCC 49057) and Actinomyces ordontolyticus (ATCC 17929). Plates contained two specimens and were left in an incubator at 37° C. for 48 h under anaerobic conditions. Zones were observed around both the 80:20 and 85:15 hybrids. There was no zone observed for the 90:10 and 95:5 hybrids. This is most probably due to the small percentage of zinc in these two hybrid materials not diffusing out from the hybrid in a sufficient quantity whereas with the higher percentage zinc-containing hybrids the zinc is more likely to have diffused to the surface of the cement. As no cell count was performed and so the concentration of bacteria was not determined. However, the same concentration was used on all samples and a difference in microbial action determined empirically.
Accordingly, it has been determined by our research that hybrid restorative materials comprising a glass-ionomer cement and zinc phosphate provides advantageous results over the use of either material alone. Fluoride release is enhanced compared with GIC alone as is surface hardness. The low ion (Zn, P, Al, Si, Sr) release in water indicates good entrapment of ions within the matrix and therefore improved maturation of the cement. The SEM results show formation of apatite structures on the surface of the cement at the preferred zinc phosphate compositional levels than is found with pure GIC, indicating enhanced bioactivity and binding clinically to tooth or bone structures. The apatite structures are also more rounded than those formed on zinc phosphate alone. The hybrid material does not lose the antimicrobial properties of zinc phosphate.
The invention comprises a mixture of glass-ionomer and zinc phosphate dental cements. Mixing of these materials leads to the formation of a set cement that has reasonable aesthetics, enhanced fluoride release and enhanced biocompatibility compared with conventional glass ionomers. Mechanically, it is tougher (less brittle) than conventional glass-ionomer cements, and it also has the ability to bond to human hard tissue, especially dentine and enamel.
In the present application, the terms ‘in use’, ‘in situ’ and ‘at the time of use’ are intended to refer to the point in time at which the composition is mixed and then used by the practioner, such as the dentist.
Number | Date | Country | Kind |
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1101170.7 | Jan 2011 | GB | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/GB12/50147 | 1/24/2012 | WO | 00 | 11/8/2013 |