Bibliographic data
`
`Title:
`
`MATERIALS AND COMPOSITIONS FOR DENTAL CEMENTS
`AND FILLER MATERIALS
`
`Pub/Pat no:
`
`WO2014140105A1
`
`Pub/Issue Date:
`Inventor(s):
`Applicant(s):
`
`2014-09-18
`BAYERL, THOMAS MARIA
`D2 BIOSCIENCE GROUP LTD| BAYERL THOMAS MARIA
`[GB]
`
`Classification:
`
`AGIRG/O83AI
`
`Application number:9W©2014EP54846 2014-03-12
`
`Priority number:
`
`U$261361780166P 2013-03-13;
`
`Abstract of WO2014140105A1
`
`The invention relates to dental cement or filler material composition comprising graphene and/or
`deuterium oxide or deuterium and their uses in direct or indirect dental restoration. and/or
`
`prevention.
`
`

`

`(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY(PCT)
`(19) World Intellectual Property
`Organization
`International Bureau
`
`(43) International Publication Date
`18 September 2014 (18.09.2014)
`
`WIPO!) PCT
`
`\a
`
`(10) International Publication Number
`WO 2014/140105 Al
`
`(51) International Patent Classification:
`AG6LK 6/083 (2006.01)
`
`(21) International Application Number:
`
`PCT/EP2014/054846
`
`(22) International Filing Date:
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`12 March 2014 (12.03.2014)
`
`English
`
`English
`
`(30) Priority Data:
`61/780, 166
`
`13 March 2013 (13.03.2013)
`
`US
`
`(71) Applicant: D2 BIOSCIENCE GROUP LTD.; 129 Front
`Street, 5th Floor, IIM12, Ilamilton (BM).
`
`Inventor; and
`(72)
`(71) Applicant
`: BAYERL, Thomas Maria [GB/GB]; 55
`Onslow Square, London Greater London SW73LR (GB).
`
`(74) Agents: ETTMAYR, Andreas et al.; Emil-Riedel-StraBe
`18, 80538 Miinchen (DE).
`
`(81)
`
`(84)
`
`Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
`BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
`DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
`HIN, HR, HU,ID,IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,
`KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
`MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI NO, NZ,
`OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,
`SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM,
`TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, 2M,
`ZW.
`
`Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,
`UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
`TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
`EE, ES, FI, FR, GB, GR, HR, HU,IE, IS, IT, LT, LU, LV,
`MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
`TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
`KM,ML, MR, NE, SN, TD, TG).
`
`(54) Title: MATERIALS AND COMPOSITIONS FOR DENTAL CEMENTS AND FILLER MATERIALS
`
`[Continued on next page]
`
`(57) Abstract: The invention relates to dental cementorfiller
`material composition comprising graphene and/or deuterium
`oxide or deuterium andtheir uses in direct or indirect dental
`restoration and/or prevention.
`
`|
`
`FIGURE1
`
`Table A below showsthe results of Example 10:
`
`
`
`SurfacehardnessMH[N/mm].
`
`won 2d £20
`
`
`
`
`265 1 22
`270220000
`255425
`
`KME-G 0.1
`
`GIC
`
`
`
`280423
`
`2081S
`235 + 10
`240216
`5
`KeGo3ie 245812
`
`DKCGO1GIG27020
`
`D-KC-G 0.3
`;
`GIC
`285+15
`KCP oo RMGIC
`135 £20
`KORGRMGIC
`170 #15
`
`N Ces RBC
`175 20
`
`NXB-GRBC
`210420
`cMcic IC
`175.115
`D-omGIc____sGIC
`
`205 +15
`
`
`
`
`
`wo2014/140105A1TIMINMANTIATTNIIMTANATNATUMTMTATAU
`
`

`

`WO 2014/140105 A2 IMTTUIITTNATA TATA TTMTAMARTAIA
`
`Published:
`
`— with international search report (Art. 21(3))
`
`— before the expiration of the time limit for amending the
`claims and to be republished in the event of receipt of
`amendments (Rule 48.2¢h))
`
`

`

`WO 2014/140105
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`PCT/EP2014/054846
`
`Materials and compositions for dental cements andfiller materials
`
`Field of the invention
`
`The field of the invention relates to dental cements orfiller materials for direct or indirect dental
`
`restoration and/or prevention.
`
`Background of the invention
`
`Dental cements and filler materials can be divided into 3 classes: i) Glass-ionomer cements
`
`(GIC),
`
`ii) resin modified glass ionomer cements (RMGIC) andiii) resin based cements (RBC).
`
`While GIC’s (Naasan MAet al., Am J Dent 11:36-45 , 1998) have advantages regarding their
`
`easy handling, continuing release offlouride ions for prevention of enamel demineralization and
`
`excellent binding to enamel and dentine, RBC’s (Summers A et al., American Journal of
`
`Orthodontics and Dentofacial Orthopedics 126: 200-206, 2004) exhibit better mechanical
`
`parameters (mostly regarding surface hardness, bendingstiffness and compressive strength as
`
`compared to GIC’s) and RMGIC’s (Sidhu SK et al., Am J Dent 8:59-67, 1995) represent the
`
`attempt to have the advantages of the other two classes unified in one dental cementorfiller for
`
`better long term wear and strength. All three classes expose, to a different degree, the feature of
`
`shrinkage during the hardening (curing) process which poses a general problem because of the
`
`possible formation of tiny fissures and mico fractures. Although GiC‘s exhibit, because of their
`
`inorganic nature, several advantages particularly as dentalfilling materials, (flouride release,
`
`dentine binding, colour retention, acid and base resistance), their use is limited because of
`
`inferior mechanical parameters (Zhen Chun Lia et al., Journal of Prosthetic Dentistry 81: 597-
`
`609, 1999). While GIC’s cure in a chemical acid-base reaction without the addition of further
`
`components, RMGIC’s and RBC’s require a source of free radicals for
`
`initiation of the
`
`polymerization of the resin which is either provided by a chemicalinitiator (self-cure) or energy,
`
`preferably in the form of UV-light (light-cure).
`
`If both is used, they are called dual-cure RBC’s
`
`and dual-cure RMGIC’s, respectively.
`
`In the field of dental cements andfiller materials, no material has been devised in the state of the
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`WO 2014/140105
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`PCT/EP2014/054846
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`art which achieve adeqaute reinforcement. The presence of such a material would reduce the
`
`probability of the progression of micro fractures and fissures through the dental cementorfiller
`material during its curing owing to plastic shrinkage and thus contribute to the prevention of
`faults formation and the improvement of mechanical strength.
`
`Summary of the invention
`
`The invention provides materials and compositions for the improvement of the mechanical
`
`parameters,
`
`in particular, without being restricted to these, tensile strength, surface hardness
`
`and compressive strength, of conventional dental cements andfiller materials.
`
`in one aspect, the invention uses graphene(strictly two dimensional single layer carbon sheets
`
`with material parameters which are in virtually all aspects superior to steel) and its chemically
`
`functionalized forms as a material to reinforce dental cements andfiller materials by inclusion of
`
`graphene into the dental cementor filler material matrix, resulting in a composite of higher
`
`mechanical strength.
`
`In another aspect, the invention uses deuterium oxide or deuterium to replace the waterin
`
`conventional glass ionomer dental cement or
`
`filler material preprations to improve the
`
`mechanical parameters of glass ionomer dental cements orfiller materials. According to the
`invention, deuterium oxide or deuterium is used alone or in combination with graphene in the
`
`glass ionomer dental cementor filler material materials.
`
`the invention provides composite glass ionomer dental
`in a further aspect,
`Consequently,
`cementsorfiller materials which include both graphene and deuterium oxide.
`
`the invention provides glass ionomer dental cements (GIC) or filler
`In yet another aspect,
`materials which include either deuterium oxide alone (GIC) or graphene and deuterium oxide
`
`(composite GIC) in combination with one or more water soluble polymers.
`
`Within the scope of this invention, the term ,graphene" comprises all types of single layer sp?-
`bonded carbon sheets forming a honeycomb crystal lattice, without or with functional groups
`
`bound to it,
`
`in particular with -OH, -NH2 or -COOH groups or any other, hydrogen bond
`
`formation enabling functional groups bound to its edges. The said honeycombcrystallattice may
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`WO 2014/140105
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`PCT/EP2014/054846
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`have holesin it, resulting in a two-dimensional mesh. Furthermore, the term graphene comprises
`
`both rod like and slab like structures which can be single or fayered on top of each other.
`
`The term “dental cement" as used in this invention comprises all materials which can be used as
`
`a cementin dentistry, in particular resin based cements, resin modified glass ionomer cements
`
`and glass ionomer cements.
`
`The term “filler material* as used in this invention comprises all materials which can be used as a
`
`filler material in dentistry, in particular resin basedfiller materials, resin modified glass ionomer
`
`filler materials and glass ionomerfiller materials.
`
`The term “direct" dental restoration and/or prevention as used in this invention, comprises all
`
`restoration and/or prevention works which are performed onsite, i.e. directly in the mouth of the
`
`patient.
`
`The term “indirect” dental restoration and/or prevention as used in this invention comprisesail
`
`restoration and/or prevention works which are performed off site, i.e. outside the mouth of the
`
`patient, including, but not restricted to, all works to produceinlays, onlays, veneers, bridges and
`
`crowns by both reductive (e.g. milling) and/or additive (e.g. 3-dimensional printing) techniques.
`
`According to the present invention, the terms “dental cement", “cement”, “filler material’, “filler*
`
`and “filler material matrix“ and “filler matrix” are used synonymously.
`
`The term “shrinkage“ or “shrinking* as used in this invention comprises all physical, chemical
`
`and physico-chemical processes which lead to an effective volume reduction of a specimen
`
`made of dental cementor filler material during its curing, including the formation of fractures and
`
`fissures in the specimen.
`
`The term “bulk filling" as used in this invention comprises all methods and/or techniques of direct
`
`dental restoration and/or prevention where a cavity is filled with a suitablefilling material.
`
`The term “one-step bulk filling’ as used in this invention comprises al! methods and/or
`
`techniques of direct dental restoration and/or prevention wherethefilling is performed in a way
`that the total volume of the cavity is filled up completely with thefilling material in one step during
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`WO 2014/140105
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`the setting of the filling material.
`
`The term “deuterium oxide“ as used in this invention comprises deuterium oxide in all possible
`isotopic enrichments above the natural abundance of the deuterium isotope,it further comprises
`all semi-deuterated water molecules (H-O-D) where one hydrogen and one deuterium atom are
`bound to the oxygen atom.
`
`It has a natural abundance in Earth's
`Deuterium is one of two stable isotopes of hydrogen.
`oceans of about one atom in 6,420 of hydrogen. Thus deuterium accounts for approximately
`0.0156% (or on a massbasis: 0.0312%) of all the naturally occurring hydrogen in the oceans,
`while the most commonisotope (hydrogen-1 or protium) accounts for more than 99.98%.
`
`The term “deuterium” comprises all deuterium atoms which originated from deuterium oxide.
`
`According to the invention, the terms “deuterium oxide", “D2O“, “deuterium" and “heavy water,
`are used synonymously and can be replaced by each other.
`
`The term “carbon nanotubes" as usedin this invention is synonymous for single walled and multi
`walled carbon nanotubes.
`
`The term “fibers” as used in this invention, comprises all types of fiber forming materials which
`
`can be included or embeddedinto a cement, such as a portland cement or dental cement, with
`
`the aim of improving the the mechanical stability of said cements.
`
`The term “reinforcement” as usedin this invention is used synonymouslyfor all suitable methods
`
`and techniques where a substance or material forms microscopic or macroscopic structures of
`
`its own inside a matrix (e.g. a dental cement or filler material) which improve the mechanical
`
`stability of the compound material (e.g. a composite of graphene and dental cementorfiller
`
`material)
`
`The term “composite” as used in the invention relates generally to all materials which are made
`
`of a combination of different substances, in the stricter sense of dental materials it relates to all
`
`kinds of mixtures of materials which can be used tofill a cavity or to glue dental parts and/or
`
`implants.
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`

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`WO 2014/140105
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`The term “setting” of a material, mostly a dental cement or filler material, as used in this
`
`invention, relates to the sum of all physical and chemical processes which are initiated by the
`
`mixing of its components and which result in a change of the physical state of the dental cement
`
`orfiller material, in most cases the transformation to the solid physical state. The “setting time* is
`
`the time span from initial mixing until the material, preferably present in the form of a paste-like
`
`mixture, has becomea solid.
`
`The term “curing” as used in this invention comprises part(s) or all of the setting but includes all
`
`in
`physical, chemical or physico-chemical changes the material undergoes post-setting,
`particular, but not restricted to, the first 100 hours of a material after the initial mixing of its
`
`componentswith theinitiation of a setting reaction.
`
`The term “matrix” as used in this invention relates to all types of host materials (a substance or a
`
`mixtures of several substances) which allow the inclusion or embedding of another material
`
`which is enabled to form structures of its own within the host material and forms a quasi-
`
`continousfluid , semi-fluid or solid phase around the embedded material or structure.
`
`The term “mechanical strength“ as used in this invention relates to all physical parameters which
`can be measured by dedicated techniques to describe qualitatively and quantitatively the
`mechanical state and stability of a material,
`in particular, but not restricted to, tensile strength,
`bendingstiffness, compressive strength and surface hardness.
`
`The term “improvement of mechanical strength" or the term “improvement of mechanical
`parameters" as used in this invention relates to all methods and compositions which improves
`one or several of the physical parameters which describe the mechanical strength of a material
`in the sense that said parameters change by the improvement measurably to give the material
`additional mechanical stability and/or resilience.
`
`The term “glass-ionomer cement" as used in this invention comprises conventional glass
`ionomer cements based on the reaction of silicate glass and polyalkenoic acid or other agents
`suitable for an acid-base reaction which results in a said cement as well as metal reinforced
`glass ionomer cements which additionally comprise a metal componentto release metalions.
`The term “resin based cement as used in this invention relates to all dental cements orfiller
`
`materials based on a hardenable resin which self cures or light cures or dual cures and with the
`resin selected preferably , but not restricted to, from acrylic resin, methacrylic resin, epoxy resin,
`
`

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`WO 2014/140105
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`PCT/EP2014/054846
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`vinyl resin, urethane resin or mixtures of these resins.
`
`The term “resin modified glass ionomer cement" as used in this invention comprisesall glass-
`ionomer cements which contain additionally a resin (such as hydroxymethylmethacrylate) and a
`photoinitiator. It encompasses hybrid ionomer cements, dual-cured and tri-cured glass ionomer
`
`cements.
`
`The term “silane groups“ or “silane chains” as used in this invention relates to all silanating
`agents capable of chemically silanting graphene and include those having at
`least one
`polymerizable double bond and at least one group that easily hydrolyses with water, preferably
`3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropydimethoxy-monochlorosilane,
`3-methacryloxypropidichicromonomethoxysilane, methacryloxypropyltri-chlorosilane,
`
`3-methacryloxypropyldichloromonomethytsilane,
`3-methacryloxypropylmonochlorodimethylsliane, and mixtures thereof.
`
`Brief description of the drawings
`
`The presentinventionis illustrated on the basis of Fig. 1 to 3, although, these do notrestrict the
`
`scope and subject-matters of the invention.
`
`Figure 1
`
`shows a table (Table A) presenting the results from the surface hardness
`
`measurements performed according to Example 10.
`Surface hardness (Martens-hardness, MH) measured according to DIN EN ISO 14577 of
`commercially available dental glass-ionomer cements (KC) and filler materials (KME), resin
`based dental cements (NX3), resin modified glass ionomer cement (KCP) and carbomer —
`modified glass ionomer cement (CMGIC). MH values are shown for the unmodified cements
`(KME, KC, NX3, RXU, CMGIC) and for cements modified by addition of graphene (-G) and/or
`deuterium oxide (D-). The numberin the sample name following the —G represents the graphene
`concentration in wt.%. For example, D-KME-G0.1 denotes deuterium enriched Ketac Molar
`
`Easymix containing 0.1 wt% (% w/w) graphene.
`KC: Ketac Cem® (3M ESPE, Seefeld, Germany); KME: Ketac Molar Easymix® (3M ESPE,
`Seefeld, Germany); KCP: Ketac Cem Plus® (3M ESPE, Seefeld, Germany ); NX3: NX3® dual
`cure resin cement (Kerr Corp. CA, USA).
`
`

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`WO 2014/140105
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`PCT/EP2014/054846
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`Figure 2 shows a table (Table B) presenting the results from the bending stiffness
`
`measurements performed according to Example 11.
`
`Bending stiffness measured according to DIN EN ISO 4049:2009(E) of commercially available
`
`dental glass-ionomer cements (KC) and filler materials (KME), resin based dental cements
`
`(NX3), resin modified glass ionomer cement (KCP) and carbomer —modified glass ionomer
`
`cement (CMGIC). MH values are shown for the unmodified cements (KME, KC, NX3, RXU,
`
`CMGIC) and for cements modified by addition of graphene (-G) and/or deuterium oxide (D-). The
`
`numberin the sample name following the -—G represents the graphene concentration in wt.% (%
`
`wiw). For example, D-KME-G0.1 denotes deuterium enriched Ketac Molar Easymix containing
`
`0.1 wt% (% wiw) graphene.
`KC: Ketac Cem® (3M ESPE, Seefeld, Germany); KME: Ketac Molar Easymix® (3M ESPE,
`Seefeld, Germany); KCP: Ketac Cem Plus® (3M ESPE, Seefeld, Germany ); NX3: NX3® dual
`cure resin cement (Kerr Corp. CA, USA)
`
`Figure 3 shows a table (Table C) presenting the results from the compressive strength
`
`measurements performed according to Example 12.
`
`Compressive strength measured according to DIN EN ISO 9917 of commercially available
`
`dental glass-ionomer cements (KC) and filler materials (KME), resin based dental cements
`
`(NX3}, resin modified giass ionomer cement (KCP) and carbomer —modified glass fonomer
`
`cement (CMGIC). MH values are shown for the unmodified cements (KME, KC, NX3, RXU,
`
`CMGIC) and for cements modified by addition of graphene (-G) and/or deuterium oxide (D-). The
`numberin the sample namefollowing the -G represents the graphene concentration in wt.% (%
`wiw). For example, D-KME-G0.1 denotes deuterium enriched Ketac Molar Easymix containing
`
`0.1 wt% (% wiw) graphene.
`
`KC: Ketac Cem® (3M ESPE, Seefeld, Germany); KME: Ketac Molar Easymix® (3M ESPE,
`Seefeld, Germany); KCP: Ketac Cem Plus® (3M ESPE, Seefeld, Germany ); NX3: NX3® dual
`
`cure resin cement (Kerr Corp. CA, USA)
`
`Detailed description of the invention
`
`The present invention provides means and compositions to improve the essential mechanical
`stability parameters of GIC’s , RMGIC’s and RBC’sby the formation of reinforcement structures
`within the dental cement orfiller material resulting, among other things,
`in the prevention of
`microscopic fractures and fissures during the curing process and improvement of mechanical
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`strength.
`
`Preferred candidate material to successfully achieve the task of reinforcing dental cements or
`
`filler materials in accordance with the present invention would possess one or more of the
`
`following characteristics: (i) The material is one (like a rod) or two dimensional (like a sheet, slab
`
`or platelet) and its spatial extension is in the order of micrometers to millimeters in order to span
`
`a distance inside the dental cement orfiller material which is in a reasonable relation to the
`
`external dimensions of the composite.
`
`(ii) The material has superior mechanical parameters
`
`which exceed those of the dental cementor filler material.
`
`(iii) The material exhibits superior
`
`resistance to acids, bases, metal ions and any other liquids and solids (organic and anorganic)
`
`which occur regularly or even temporary in the vicinity of dental cement or filler material
`
`constructs in the mouth. Finally, (iv) the material forms tight bonds with the dental cementorfiller
`
`material matrix in order to truly reinforce the composite rather than forming a
`
`(demixed or
`
`isolated) phase ofits own which would destabilize the composite and to prevent the formation of
`
`miro-fissures or cracks during the curing of the dental cement.
`
`In a first aspect, the present invention provides materials with these characteristics by the first
`
`time introduction of graphene (strictly two dimensional single layer carbon sheets with material
`
`parameters which arein virtually all aspects superior to steel) and its chemically functionalized
`
`forms as a material to reinforce dental cements or filler materials.
`
`lattice,
`Graphene is a single layer sp*-bonded carbon sheet forming a honeycomb crystal
`reportedfirst by Mouras (Mouras,S.et al. , Revue de Chimie Minerale, 1987:24:572) as the two
`
`dimensional (2D) form of graphite.
`
`Grapheneis optically transparent and can be readily produced, amonog other preparation
`
`methods, from graphite by exfoliation techniques (Hernandez,Y. et al., Nature Nanotechnol. 3,
`
`563-568 , 2008) , the resulting graphene platelets have a size of up to 100 um. The edges of
`
`the grapheneplatelets can be modified by -OH, -COOH, -NH2 groups , by Flouride (F) atoms,
`
`or functionalized with silane groups, which allows to dissolve graphen in aqueous and non-
`
`aqueous solutions as well as the controlled modification of its solution properties. This enables
`
`the use of graphene in GIC’s where a hydrophilic graphene is required for the formation of a
`
`composite , but also in RMGIC’s and RBC’s where a hydrophobic graphen is the prerequisite for
`
`its dissolution and binding to the resin matrix.
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`WO 2014/140105
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`According to the present
`invention, graphene is used at a concentration of 0.00001
`weight/weight (% w/w) to 90 % wiw,preferred 0.01 % w/w to 10 % wiw, more preferred 0.01 %
`wiw to 5 %w/w, most preferred 0.05 % w/w to 3 % w/win terms of the dry phase.
`
`In @ second aspect, the invention provides a dental cementorfiller material, preferably a GIC,
`
`comprising of a substance (deuterium oxide or deuterium) to partly or totally replace the waterin
`
`the fluid component of GIC preprations,
`
`to improve the mechanical parameters of dental
`
`cements/filler materials with or without graphene even further.
`
`Deuterium oxide (D20) or heavy wateris a water-like molecule where the two hydrogens bound
`
`to the oxygen atom are replaced by a stable isotope of hydrogen called deuterium. Deuterium
`
`contains an additional neutron in its nucleus and as a result D2O is about 10% heavier than
`
`normal water (H20). This in turn results in a higher density and different vapor pressure. Heavy
`
`water occurs in natural water, roughly every 6000th molecule in natural water is a heavy water
`
`molecule.
`
`It is produced by very energy intensive destillation procedures of natural water and
`
`can be obtained commercially at a very high degree of purity (degree of deuterium enrichment)
`
`of up to 99.9%. Highly enriched deuterium oxide exhibits a approximately 10% higher viscosity
`
`than normal water at the same temperature. Because the setting reaction of a GIC depends,
`
`among other factors, on the viscosity of the fluid phase, the replacement of H2O by 020 in the
`
`fluid component of a GIC provides means of manipulation or modulation of the setting reaction.
`
`This may result in improvements of the mechanicalstability of the cured GIC.
`
`A salient feature of D2O is its higher strength to bind to other atoms or molecules via so-called
`
`hydrogen bonds. This enables D2O or deuterons in general to bind significantly stronger to
`
`hydrogen bonding sites than hydrogen (or H20)itself.
`
`in GIC formation starting from its two components (an acidic liquid phase
`For example,
`containing water and a solid phase of essentially silicate containing metal ions), hydrogen bonds
`
`play an essential role because water is the medium where the acid base reaction in the setting
`
`process of
`
`the dental cement/filler material
`
`takes place. Hence all water soluble GIC
`
`components (silicate,
`
`ions, acid polymers) will be surrounded by a hydration shell of water
`
`(H20). If H20 is replaced by D20, the increase in (hydrogen) binding strength translates into a
`tighter packing of the components during the settlement process while the higher viscosity of
`
`D20 moduiatesthe diffusion of the components during the setting time. Both processes give rise
`
`to a higher mechanical stability of the settled GIC. Since hydrogen bonds are essential in the
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`setting reaction of GIC’s and their curing, the addition of any water soluble polymers to the GIC
`
`composition which are able to form hydrogen bonds can further improve the mechanical strength
`
`of a GIC under conditions where the H2O is replaced by D2O. Examples for such polymers are
`
`all nonionic, cationic or anionic polymers , in particular acrylic acid based polymers (carbomers),
`
`polyvinyl alcohol based polymers, poly-ethylene oxide polymers and sugar based polymers.
`
`According to the present invention, deuterium oxide or deuterium is used at a concentration of of
`
`3 % vol. to 99,9 % vol., preferred at a concentration of 15 % vol. to 99 % vol., more preferred at
`
`a concentration of 50 % vol. to 99 % vol., even more preferred at a concentration of 70 % val. to
`
`99 % vol., most preferred at a concentration of 80 % vol. to 99 % vol., in terms of the fluid phase
`
`(in solution).
`
`According to the present invention, the water-soluble polymer is used at a concentration of
`0.0001 % wiw to 50 % w/w, more preferred 0.001 % w/w to 25 % w/w and mostpreferred 0.05
`
`% wiw to 5.0 % wiw.
`
`In a third aspect, the present invention further provides for a dual presence of graphene platelets
`(with -OH, -NH2 or -COOH groups or any other, hydrogen bond formation enabled functional
`groups boundto its edges) and of 020 replacing partially or totally the H2O in a dental cement
`orfiller material, preferably a GIC. During curing, this dual presence has an even strongereffect
`regarding the improvement of the resulting mechanical properties of the GIC. This is because
`the deuterons replace the hydrogen atoms at the hydrophilic functional groups attached to the
`graphene edges. The higher (hydrogen) binding strength of the deuterons causes a tighter
`packing of the solid componentsincluding the graphene andits tighter binding to the GIC matrix,
`resulting in improved mechanical strength of the graphene-GIC composite beyond that of just
`
`graphene GIC composites or D2O enriched GIC’s alone.
`
`In RMGIC’s and RBC’s the effect of graphene on the mechanical properties of the composite
`dental cement/filler material is different. Here the embedding of the pristine or flouride —~modified
`
`(hydrophobic) graphene patelets provides essentially a reinforcement of the composite structure
`
`over distances which correlates with the spatial extension of the graphene platelets. The resin
`
`matrix will bind in the setting process to the graphene via the functional groups or directly to the
`
`pristine graphene, because the graphene surface can attract free radicals (induced by an
`initiator molecule (dual cure) of by shining UV light on the mixture (light-cure) which in turn are
`essential for a high degree of polymerization of the resin matrix. As a result, the resin matrix in
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`the vicinity of the graphene platelets exhibits a particularly high polymerization density reinforced
`
`by the underlying graphene platelet and surrounded by the cured resin matrix. This composite
`structure inside the RMGIC’s and RBC,
`respectively,
`significantly improves the overall
`
`mechanical stability of the RMGIC’s and RBC, respectively, and helps to prevent the formation
`
`of fissures during the curing of the RMGIC’s and RBC owing to shrinking of the material.
`
`In general, the reinforcement of dental cements andfilling materials by graphene has important
`
`ramifications for the prevention of shrinking of the materials. The mechanical properties of
`
`graphene boundto the matrix of any dental cementor filling material stabilizes against volume
`loss during the curing of the material, thus preventing the formation of fractures and fissures.
`
`This enables one-step bulk filling techniques for all self curing dentalfilling materials.
`
`The application of all dental cements orfiller materials in patients requires that the color of the
`surrounding tooth is matched by the dental cements orfiller materials to find acceptance with the
`users (dentists) and their patients. The materials/substances used in the present invention
`(graphene and D20) are both optically transparent and thus do not interfere with the coloring
`
`schemeof the the dental cements/filler materials.
`
`The invention relates in its first subject to a dental cement or filler material composition
`
`comprising graphene and/or deuterium oxide or deuterium.
`
`A preferred embodiment relates to an inventive dental cement or filler material, whereby the
`
`dental cementorfiller material is a glass ionomer cementorfiller material or resin based cement
`orfiller material or resin modified glass ionomer cementor filler material.
`
`A further preferred embodiment relates to a dental cement or filler material, whereby the
`grapheneis in its pristine form or with its reactive groups chemically modified, preferably
`modified with hydroxyl, carboxyl, amide or silane functional groups or with the graphene reactive
`
`groups boundto flouride atoms.
`
`Another preferred embodimentrelates to a dental cementoffiller material composition, whereby
`grapheneis comprised at a concentration of 0.00001 % w/w to 90 % wiw, preferred 0.01 % wiw
`to 10 % wiw, more preferred 0.01 % w/w to 5 % w/w, most preferred 0.05 % wi/w to 3 % wiw in
`
`terms of the dry phase.
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`Another preferred embodimentrelates to a dental cementoffiller material composition, whereby
`
`deuterium oxide or deuterium is comprised at a concentration of of 3 % vol. to 99,9 % vol.,
`
`preferred at a concentration of 15 % vol. to 99 % vol., more preferred at a concentration of 50 %
`
`vol.
`
`to 99 % vol., even more preferred at a concentration of 70 % vol.
`
`to 99 % vol., most
`
`preferred at a concentration of 80 % vol. to 99 %vol., in terms of the fluid phase(in solution).
`
`A further preferred embodiment, the dental cementorfiller material, whereby the glass ionomer
`
`cement composition comprises additionally a water soluble polymer, which can form hydrogen
`
`bonds, selected from the group consisting of synthetic or natural polymers being either nonionic,
`cationic or anionic, preferably at neutral pH value, preferably acrylic acid based polymers
`
`(carbomers), polyvinyl alcohol based polymers, poly-ethylene oxide polymers and sugar based
`
`polymers.
`
`A preferred embodiment relates to a dental cement orfiller material for direct or indirect dental
`
`restoration and/or prevention. Another preferred embodiment relates to a dental cementor filler
`
`material for the use in direct or indirect dental restoration and/or prevention.
`
`All conventional state of the art dental cements andfiller materials can be improved according to
`
`the invention regarding their mechanical strength and parameters by the inclusion of graphene
`
`and/or deuterium oxide or deuterium into their matrix prior to the setting/curing process. All
`
`conventional state of the art dental cements and filler materials in well-known compositions and
`
`concentrations can be used to carry out the invention
`
`A preferred embodiment of the invention relates to the inclusion of graphene into dental cements
`
`orfiller materials. The preferred properties of the graphene platelets used for inclusion are single
`layer graphene with the carbons at the edges of the platelets functionalized with chemical
`groups which provide for a optimum binding of the grapheneplatelets with the matrix. For GIC’s
`the most preferred functional groups bound to graphene are hydrophilic and can for hydrogen
`bonds. For RMGIC’s and RBC’s the graphenepreferably used is either pristine or functionalized
`with g