Dental composite with low shrink tensing and high bend stability
Abstract
Dental-Kompositmaterialien auf (Meth)acrylatbasis, wie in Anspruch 1 beschrieben, weisen einen Anteil an TCD-Monomeren in der Gesamtzusammensetzung von 1-15 Gew.% auf, und der der Quotient Biegefestigkeit/Schrumpfspannung beträgt mindestens 35.
Term
1.8 yearsto projected expiry
Projected expiry 14 July 2028, counted from filing; an application has no term until it is granted.
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4 claims: 1 independent, 3 dependent
- 1Dental-Kompositmaterialien mit einem Gesamtfüllstoffgehalt von 70 bis 95 Gew% enthaltend A) in der Füllstoffkomponente 0,5 bis 10 Gew.% nicht-agglomerierte Nanofüller mit Partikelgrößen von 1 bis 50 nm; B) in der Füllstoffkomponente mindestens 60 Gew.% eines Füllstoffgemischs aus 50 bis 90 % grob- und 10 bis 50 % feinteiligen Dentalgläsern, welche ein Größenverhältnis, bezogen auf die mittlere Partikelgröße (d 50 -Wert), von feinteilig zu grobteilig von 1:4 bis 1:30 aufweisen, aufweisen;C) als Monomerkomponente eine Monomermischung aus i. 60 - 80 Gew. % Bis-GMA und einem Mitglied der Gruppe TCD-di-HEMA und TCD-di-HEA, ii. 10 bis 18 Gew. % UDMA , iii. Rest TEDMA und/oder multifunktionelle Vernetzer, D) bis 1 Gew. % Initiator(en) und E) optional in der Füllstoffkomponente mindestens ein weiteres Dentalglas mit sich von den grob- und feinteiligen Dentalgläsern unterscheidender Partikelgröße, dadurch gekennzeichnet, dass der Anteil an TCD-Monomeren in der Gesamtzusammensetzung 1-15 Gew.% beträgt, und dass der Quotient Biegefestigkeit/Schrumpfspannung >/= 35 beträgt.
- 2Dental-Kompositmaterialien nach Anspruch 1, dadurch gekennzeichnet, dass der Anteil an TCD-Monomeren in der Gesamtzusammensetzung 10 - 15 Gew.% beträgt.
- 3Dental-Kompositmaterialien nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Quotient Biegefestigkeit/Schrumpfspannung >/= 40 beträgt.
- 4Dental-Kompositmaterialien nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Quotient Biegefestigkeit/Schrumpfspannung >/= 50 beträgt.
Independent claims4
28 paragraphs, as filed
p0001The invention relates to dental composite materials with low shrinkage stress and high flexural strength.
p0002Light-curing materials based on acrylate / methacrylate undergo a shrinkage in the case of free-radical polymerization because of the molecular distance reducing during the polymerization and the accompanying increase in density. This can be significantly reduced by the addition of inorganic fillers such as, for example, dental glasses or pyrogenic silicas, since a reduced monomer content is obtained per unit volume and the fillers do not shrink during polymerization.
p0003In dental applications, volume shrinkage is of great clinical significance because tensile forces are transmitted to the cavity wall as a result of material shrinkage. If a maximum force is exceeded, this shrinking force can lead to detachment from the cavity wall in the extreme case. Bacteria can penetrate into the resulting marginal gap and subsequently secondary caries develop.
p0004According to <patcit id="pcit0001" dnum="DE102005021332A1"><text>*** "" DE102005021332A1</text></patcit> Light-curing materials based on acrylate / methacrylate have already been presented, which have a reduced shrinking force. This is achieved by various measures: non-agglomerated nanofillers, a filler mixture of coarse and fine-grained dental glasses, predominant substitution of the high-shrinking diluent TEDMA by UDMA (urethane dimethacrylate), use of tricyclodecane derivatives (abbreviated hereinafter TCD) and optionally reduction of the initiator amount . For example, there is only one composition, which contains no TCD.
p0005A composite material is prepared by intimately mixing the following components<tables id="tabl0001" num="0001"><table frame="none"><tgroup cols="4" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="23mm" /><colspec colnum="2" colname="col2" colwidth="51mm" /><colspec colnum="3" colname="col3" colwidth="13mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><tbody><row><entry>Fillers:</entry><entry>Non-agglomerated nanoparticles</entry><entry align="right">6</entry><entry>Parts by weight</entry></row><row><entry>Dental glass 1 μm (silanized)</entry><entry align="right">24</entry><entry>Parts by weight</entry></row><row><entry>Dental glass 8 μm (silanized)</entry><entry align="right">53</entry><entry>Parts by weight</entry></row><row><entry>Monomers:</entry><entry>Bis-GMA (Bowen)</entry><entry align="right">11</entry><entry>Parts by weight</entry></row><row><entry>UDMA</entry><entry align="right">4</entry><entry>Parts by weight</entry></row><row><entry>TEDMA</entry><entry align="right">2</entry><entry>Parts by weight</entry></row><row><entry>Initiator (s):</entry><entry>camphorquinone</entry><entry align="right">0.1</entry><entry>Parts by weight</entry></row><row><entry>sum</entry><entry align="right">100.1</entry><entry>Parts by weight</entry></row></tbody></tgroup></table></tables>
p0006The object of the present invention is to provide a composite material for dental applications with low shrinkage force and high bending strength. In particular, the quotient bending strength / shrinking stress should be optimized.
p0007It has been shown that the in <patcit id="pcit0002" dnum="DE102005021332A1"><text>*** "" DE102005021332A1</text></patcit> Can be significantly improved. Surprisingly, it has been found that the ratio of bending strength to shrinkage stress can be increased when a proportion of TCD monomers is present, of 1-15, particularly preferably above 10% by weight.
p0008The invention thus relates
p0009Dental composite materials having a total filler content of 70 to 95% by weight<ol><li>A) 0.5 to 10% by weight of non-agglomerated nanofillers having particle sizes of 1 to 50 nm in the filler component;</li><li>B) at least 60% by weight of a filler mixture of 50 to 90% coarse and 10 to 50% finely divided dental glasses, which have a size ratio, based on the average particle size (i.e.<sub>50</sub>-Value of Finely divided to coarsely from 1: 4 to 1:30,</li><li>C) as a monomer component a monomer mixture<ol><li>I. 60-80% bis-GMA and one member of the group TCD-di-HEMA or TCD-di-HEA</li><li>Ii. 10 to 18% UDMA</li><li>Iii. Radical TEDMA and / or multifunctional crosslinker</li></ol></li><li>D) to 1% initiator (s) and</li><li>E) optionally at least one further dental glass with a particle size differing from the coarse and fine-particle dental glasses in the filler component.</li></ol>
p0010Non-agglomerated nanofillers are known per se and are described, for example, in <patcit id="pcit0003" dnum="WO0130305A1"><text>WO 0130305 A1</text></patcit> Or the example of SiO<sub>2</sub> in <patcit id="pcit0004" dnum="DE19617931A1"><text>DE 196 17 931 A1</text></patcit> Described. According to the invention, they preferably belong to the group consisting of: SiO<sub>2</sub>, ZrO<sub>2</sub>, TiO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub> And mixtures of at least two of these substances.
p0011You can - as in <patcit id="pcit0005" dnum="DE19617931A1"><text>DE 196 17 931 A1</text></patcit> Described - be dispersed in organic solvents, but also in solvent mixtures containing water or water.
p0012Barium glass powders and / or strontium glass powders are particularly suitable as dental glasses. The average particle size of the coarse-particle dental glasses is preferably 5-10 μm, in particular around 7 μm, and that of the finely divided 0.5 to 2 μm, in particular 1 μm. Optionally existing further dental glasses have, for example, mean particle sizes of 2-5 or 10-50 μm.
p0013The filler component can accordingly have dental glasses with a total of three or more grain fractions. It can also contain further conventional, conventional fillers, such as quartz, glass ceramic or mixtures thereof. In addition, the composites may contain fillers to provide increased x-ray opacity. The average particle size of the radiopaque filler is preferably in the range from 100 to 300 nm, in particular from 180 to 300 nm. Suitable radiopaque fillers are, for example, those described in US Pat<patcit id="pcit0006" dnum="DE3502594A1"><text>DE 35 02 594 A1</text></patcit> Described fluorides of the rare earth metals, ie the trifluorides of elements 57 to 71. A particularly preferred filler is ytterbium fluoride, in particular ytterbium trifluoride with an average particle size of about 300 nm. The amount of the radiopaque filler is preferably from 10 to 50% by weight, in particular Preferably from 20 to 30% by weight, based on the total filler content.
p0014In addition, precipitated mixed oxides, such as, for example, ZrO<sub>2</sub>/ SiO<sub>2</sub>, Can be used as fillers. Preference is given to mixed oxides having a particle size of from 200 to 300 nm and in particular about 200 nm. The mixed oxide particles are preferably spherical and have a uniform size. The mixed oxides preferably have a refractive index of 1.52 to 1.55. Precipitated mixed oxides are preferably used in amounts of 25 to 75% by weight and especially 40 to 75% by weight.
p0015The fillers are preferably silanized to improve the adhesion between the filler and the organic matrix. Suitable as an adhesion promoter is, in particular, α-methacryloxypropyltrimethoxysilane. The amount of the adhesion promoter used depends on the type and BET surface area of the filler.
p0016Suitable multifunctional crosslinkers are, besides TEDMA and UDMA, diethylene glycol di (meth) acrylate, decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and butanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate , 1,12-dodecanediol di (meth) acrylate.
p0017To initiate the polymerization, the composites contain a polymerization initiator, for example an initiator for the radical polymerization. Depending on the type of initiator used, the mixtures can be cold, light-sensitive or heat-polymerizable.
p0018The known peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert.-butylperoctoate or tert.-butyl perbenzoate, but also alpha, alpha'-azobis (isobutyroethyl ester), benzpinacol and 2,2'-dimethylbenzpinacol are suitable as initiators for the hot polymerization .
p0019Suitable photoimitators are, for example, benzoin ketyl ethers or esters, benzilmonoketals, acylphosphine oxides or aliphatic and aromatic 1,2-diketo compounds, such as, for example, 2,2-diethoxyacetophenone 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzene and 4,4 ' Dialkoxybenzil or camphorquinone. Photoinitiators are preferably used together with a reducing agent. Examples of reducing agents are amines such as aliphatic or aromatic tertiary amines, for example N, N-dimethylp-toluidine or triethanolamine, cyanethylmethylaniline, triethylamine, N, N-dimethylaniline, N-methyldiphenylamine, N, N, N-3,5-tetramethylaniline and 4-dimethylaminobenzoic acid ethyl ester or organic phosphites. Common photoinitiator systems are, for example, camphorquinone plus ethyl 4- (N, N-dimethylamino) benzoate, 2- (ethylhexyl) -4- (N, N-dimethylamino) benzoate or N, N-dimethylaminoethyl methacrylate.
p0020An initiator for the polymerization initiated by UV light is especially 2,4,6-trimethylbenzoyldiphenylphosphine oxide. UV photoinitiators can be used alone, in combination with a visible light initiator, an initiator for cold curing and / or an initiator for heat curing.
p0021Radical-forming systems, for example benzoyl or lauroyl peroxide, together with amines such as N, N-dimethyl-sym-xylidine or N, N-dimethyl-p-toluidine, are used as initiators for the cold polymerization.
p0022It is also possible to use dual-curing systems, for example photoinitiators with amines and peroxides.
p0023The initiators are preferably used in amounts of from 0.01 to 1% by weight, based on the total weight of the mixture.
p0024In the case of the cold polymerization, it may be expedient if the composite material is divided into two components which are intended for curing by mixing. It is also possible to provide the material to be cured both by light and by mixing two components.
p0025Composite materials according to the invention as dental materials preferably have a quotient of flexural strength / shrinkage stress of> / = 35, preferably> / = 40, particularly preferably> / = 50.
p0026The following examples illustrate the invention. Parts and percentages are by weight, unless otherwise stated, as in the rest of the description.
Examples
p0027The results of the measurements (Table II) for the mixtures 312, 349, 357, 363, 307 and 206 listed in the following Table I (comparison, optimized without TCD) show that increases with increasing TCD content of the quotient bending strength / shrinkage stress. TCDs over 10% show values above 50.<tables id="tabl0002" num="0002"><table frame="all"><title>Table I Formulations</title><tgroup cols="7"><colspec colnum="1" colname="col1" colwidth="47mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><colspec colnum="5" colname="col5" colwidth="20mm" colsep="0" /><colspec colnum="6" colname="col6" colwidth="20mm" colsep="0" /><colspec colnum="7" colname="col7" colwidth="21mm" /><thead><row><entry valign="middle">components</entry><entry align="center" valign="top">recipe <b>363</b></entry><entry align="center" valign="top">recipe <b>312</b></entry><entry align="center" valign="top">recipe <b>357</b></entry><entry align="center" valign="top">recipe <b>349</b></entry><entry align="center" valign="top">recipe <b>307</b></entry><entry align="center" valign="top">recipe <b>206</b></entry></row></thead><tbody><row><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>UDMA</entry><entry align="center">4.03</entry><entry align="center">4.02</entry><entry align="center">4.03</entry><entry align="center">2,00</entry><entry align="center">3.92</entry><entry align="center">3.92</entry></row><row><entry>Bis-GMA</entry><entry align="center">10.76</entry><entry align="center">9.15</entry><entry align="center">9.15</entry><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>TEGDMA</entry><entry align="center">1.11</entry><entry align="center">1.11</entry><entry align="center">1.11</entry><entry align="center">2.66</entry><entry align="center">0.95</entry><entry align="center">0.95</entry></row><row><entry>TCDDIHEA</entry><entry align="center" /><entry align="center">1.61</entry><entry align="center">1.61</entry><entry align="center">10.50</entry><entry align="center">12.35</entry><entry align="center">12.35</entry></row><row><entry>Mutifunctional urethane monomer</entry><entry align="center">0.50</entry><entry align="center">0.50</entry><entry align="center">0.50</entry><entry align="center">0.50</entry><entry align="center">1.18</entry><entry align="center">1.18</entry></row><row><entry>BHT</entry><entry align="center">0.04</entry><entry align="center">0.04</entry><entry align="center">0.04</entry><entry align="center">0.04</entry><entry align="center">0.04</entry><entry align="center">0.04</entry></row><row><entry>Nano SiO2 (dispersion)</entry><entry align="center">4,00</entry><entry align="center">4,00</entry><entry align="center">4,00</entry><entry align="center">4,00</entry><entry align="center">4,8</entry><entry align="center">4,8</entry></row><row><entry>Barium aluminosilicate glass filler 0.85 μ silanized</entry><entry align="center">39.50</entry><entry align="center">15.80</entry><entry align="center">39.50</entry><entry align="center">40.00</entry><entry align="center">50.28</entry><entry align="center">50.28</entry></row><row><entry>Barium aluminosilicate glass filler 2 μ silanized</entry><entry align="center" /><entry align="center">23.70</entry><entry align="center" /><entry align="center" /><entry align="center">7.66</entry><entry align="center">7.66</entry></row><row><entry>Barium aluminosilicate glass filler 5 μ silanized</entry><entry align="center">39.50</entry><entry align="center">39.50</entry><entry align="center">39.50</entry><entry align="center">40.00</entry><entry align="center">18.53</entry><entry align="center">18.53</entry></row><row><entry>Light stabilizer 1</entry><entry align="center">0.09</entry><entry align="center">0.09</entry><entry align="center">0.09</entry><entry align="center">0.05</entry><entry align="center">0.07</entry><entry align="center">0.07</entry></row><row><entry>Light stabilizer 2</entry><entry align="center">0.26</entry><entry align="center">0.26</entry><entry align="center">0.26</entry><entry align="center">0.13</entry><entry align="center">0.02</entry><entry align="center">0.02</entry></row><row><entry>DL Campherchinone</entry><entry align="center">0.03</entry><entry align="center">0.03</entry><entry align="center">0.03</entry><entry align="center">0.02</entry><entry align="center">0.02</entry><entry align="center">0.02</entry></row><row><entry>Coinitiator</entry><entry align="center">0.14</entry><entry align="center">0.14</entry><entry align="center">0.14</entry><entry align="center">0.07</entry><entry align="center">0.17</entry><entry align="center">0.17</entry></row><row><entry>PPD</entry><entry align="center">0.02</entry><entry align="center">0.02</entry><entry align="center">0.02</entry><entry align="center">0.01</entry><entry align="center">0.01</entry><entry align="center">0.01</entry></row><row><entry>pigments</entry><entry align="center">0.02</entry><entry align="center">0.03</entry><entry align="center">0.02</entry><entry align="center">0.02</entry><entry align="center" /><entry align="center" /></row><row><entry><b>total</b></entry><entry align="center">100</entry><entry align="center">100</entry><entry align="center">100</entry><entry align="center">100</entry><entry align="center">100</entry><entry align="center">100</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><title>Table II Measurement results</title><tgroup cols="11"><colspec colnum="1" colname="col1" colwidth="31mm" /><colspec colnum="2" colname="col2" colwidth="23mm" /><colspec colnum="3" colname="col3" colwidth="19mm" /><colspec colnum="4" colname="col4" colwidth="21mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><colspec colnum="7" colname="col7" colwidth="22mm" /><colspec colnum="8" colname="col8" colwidth="23mm" /><colspec colnum="9" colname="col9" colwidth="22mm" /><colspec colnum="10" colname="col10" colwidth="19mm" /><colspec colnum="11" colname="col11" colwidth="23mm" /><thead><row><entry align="center" valign="top">material</entry><entry align="center" valign="top">batch</entry><entry namest="col3" nameend="col4" align="center" valign="top">Modulus of elasticity in Mpa</entry><entry align="center" valign="top">TCD monomer</entry><entry namest="col6" nameend="col7" align="center" valign="top">Shrinkage in Mpa<sup>1</sup></entry><entry namest="col8" nameend="col9" align="center" valign="top">3-point bending strength in Mpa</entry><entry morerows="1" align="center" valign="top"><b>quotient</b></entry><entry morerows="1" align="center" valign="top">Std.abw. quotient</entry></row><row><entry valign="top" /><entry align="center" valign="top" /><entry valign="top">E module</entry><entry align="center" valign="top">Std.-abw.</entry><entry valign="top" /><entry align="center" valign="top">24 h MW</entry><entry align="center" valign="top">Std.-abw.</entry><entry align="center" valign="top">Bending strength</entry><entry align="center" valign="top">Std.-abw.</entry></row></thead><tbody><row><entry>Tetric Evo Ceram (Ivoclar Vivadent)</entry><entry align="center"># G 20087</entry><entry>9172</entry><entry align="center">308</entry><entry align="center">3.603</entry><entry align="center">0.158</entry><entry align="center">105.0</entry><entry align="center">5.6</entry><entry align="center"><b>29,14</b></entry><entry align="center">2.0</entry></row><row><entry>Premise (Kerr)</entry><entry align="center"># 438811</entry><entry>7840</entry><entry align="center">239</entry><entry align="center">3,679</entry><entry align="center">0.143</entry><entry align="center">93.0</entry><entry align="center">5.5</entry><entry align="center"><b>25.28</b></entry><entry align="center">1.8</entry></row><row><entry>InTen-S (Ivoclar Vivadent)</entry><entry align="center"># G 02023</entry><entry>9506</entry><entry align="center">690</entry><entry align="center">3,822</entry><entry align="center">0.181</entry><entry align="center">109.0</entry><entry align="center">11.9</entry><entry align="center"><b>28.52</b></entry><entry align="center">3.4</entry></row><row><entry>Filtek Supreme XT (3M aspen)</entry><entry align="center"># 4 AP</entry><entry>6528</entry><entry align="center">374</entry><entry align="center">4,228</entry><entry align="center">0.336</entry><entry align="center">111.0</entry><entry align="center">10.6</entry><entry align="center"><b>26.25</b></entry><entry align="center">3.3</entry></row><row><entry>EsthetX (Dentsply)</entry><entry align="center"># 305000182</entry><entry>11606</entry><entry align="center">585</entry><entry align="center">4,388</entry><entry align="center">0.240</entry><entry align="center">109.0</entry><entry align="center">13.6</entry><entry align="center"><b>24.84</b></entry><entry align="center">3.4</entry></row><row><entry>Herculite XRV (Kerr)</entry><entry align="center"># 06-1262</entry><entry>9585</entry><entry align="center">305</entry><entry align="center">4,636</entry><entry align="center">0.124</entry><entry align="center">138.0</entry><entry align="center">11.9</entry><entry align="center"><b>29.77</b></entry><entry align="center">2.7</entry></row><row><entry>Filtek Z250 (3M aspen)</entry><entry align="center"># 4 LPJ</entry><entry>12174</entry><entry align="center">420</entry><entry align="center">4,887</entry><entry align="center">0.289</entry><entry align="center">153.0</entry><entry align="center">15.3</entry><entry align="center"><b>31.31</b></entry><entry align="center">3.6</entry></row><row><entry>Spectrum TPH (Dentsply)</entry><entry align="center"># 0612001961</entry><entry>10367</entry><entry align="center">334</entry><entry align="center">4,900</entry><entry align="center">0.250</entry><entry align="center">127.0</entry><entry align="center">10.5</entry><entry align="center"><b>25.92</b></entry><entry align="center">2.5</entry></row><row><entry>Xtra Fil (VOCO)</entry><entry align="center"># 530835</entry><entry>16377</entry><entry align="center">669</entry><entry align="center">4,912</entry><entry align="center">0.212</entry><entry align="center">132.0</entry><entry align="center">8,0</entry><entry align="center"><b>26.87</b></entry><entry align="center">2.0</entry></row><row><entry>Quixfil (Dentsply)</entry><entry align="center"># 0404000401</entry><entry>16257. *** "</entry><entry align="center">783</entry><entry align="center">5.041</entry><entry align="center">0.126</entry><entry align="center">130.0</entry><entry align="center">10.5</entry><entry align="center"><b>25.79</b></entry><entry align="center">2.2</entry></row><row><entry>Venus (Heraeus)</entry><entry align="center"># 010119</entry><entry>9160</entry><entry align="center">539</entry><entry align="center">5.180</entry><entry align="center">0.252</entry><entry align="center">120.0</entry><entry align="center">9.6</entry><entry align="center"><b>23,17</b></entry><entry align="center">2.2</entry></row><row><entry>TPH<sup>3</sup> (Dentsply)</entry><entry align="center"># 0409171</entry><entry>9804</entry><entry align="center">330</entry><entry align="center">5.515</entry><entry align="center">0.167</entry><entry align="center">128.0</entry><entry align="center">13.0</entry><entry align="center"><b>23.21</b></entry><entry align="center">2.5</entry></row><row><entry>Grandio (VOCO)</entry><entry align="center"># 441238</entry><entry>16498</entry><entry align="center">544. *** "</entry><entry align="center">5,686</entry><entry align="center">0.202</entry><entry align="center">136.0</entry><entry align="center">13.3</entry><entry align="center"><b>23.92</b></entry><entry align="center">2.5</entry></row><row><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /><entry align="center" /></row><row><entry>Comparative Example 363</entry><entry align="center" /><entry>13658</entry><entry align="center">548</entry><entry>0</entry><entry align="center">3,845</entry><entry align="center">0.193</entry><entry align="center">149.0</entry><entry align="center">6.2</entry><entry align="center"><b>38.75</b></entry><entry align="center">2.5</entry></row><row><entry>Example 312</entry><entry align="center" /><entry>15767</entry><entry align="center">560</entry><entry>1.61</entry><entry align="center">3,250</entry><entry align="center">0.087</entry><entry align="center">130.0</entry><entry align="center">10.4</entry><entry align="center"><b>40.00</b></entry><entry align="center">3.4</entry></row><row><entry>Example 357</entry><entry align="center" /><entry>13727</entry><entry align="center">272</entry><entry>1.61</entry><entry align="center">4,060</entry><entry align="center">0.185</entry><entry align="center">145.0</entry><entry align="center">9.4</entry><entry align="center"><b>35.71</b></entry><entry align="center">2.8</entry></row><row><entry>Example 349</entry><entry align="center" /><entry>14262</entry><entry align="center">661</entry><entry>10.5</entry><entry align="center">3,330</entry><entry align="center">0.143</entry><entry align="center">171.0</entry><entry align="center">7.6</entry><entry align="center"><b>51.35</b></entry><entry align="center">3.2</entry></row><row><entry>Example 206</entry><entry align="center" /><entry>12645</entry><entry align="center">559</entry><entry>12.35</entry><entry align="center">2.796</entry><entry align="center">0.119</entry><entry align="center">169.0</entry><entry align="center">5.0</entry><entry align="center"><b>60.44</b></entry><entry align="center">3.1</entry></row><row><entry>Example 307</entry><entry align="center" /><entry>13836</entry><entry align="center">272</entry><entry>12.35</entry><entry align="center">3.269</entry><entry align="center">0.189</entry><entry align="center">172.0</entry><entry align="center">11.0</entry><entry align="center"><b>52.62</b></entry><entry align="center">4,5</entry></row></tbody></tgroup><tgroup cols="11" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31mm" /><colspec colnum="2" colname="col2" colwidth="23mm" /><colspec colnum="3" colname="col3" colwidth="19mm" /><colspec colnum="4" colname="col4" colwidth="21mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><colspec colnum="7" colname="col7" colwidth="22mm" /><colspec colnum="8" colname="col8" colwidth="23mm" /><colspec colnum="9" colname="col9" colwidth="22mm" /><colspec colnum="10" colname="col10" colwidth="19mm" /><colspec colnum="11" colname="col11" colwidth="23mm" /><tbody><row><entry namest="col1" nameend="col11" align="justify"><sup>1</sup> Measured according to the <nplcit id="ncit0001" npl-type="s"><text>Bonded Disc Method - Dental Materials (2004) 20, 88-95</text></nplcit>) "</entry></row></tbody></tgroup></table></tables>
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| DE102017123006B9 | Cited by | Germany | Applicant |
| WO2011083020A2 | Cited by | World Intellectual Property Organization (WIPO) | Applicant |
| WO2019068611A3 | Cited by | World Intellectual Property Organization (WIPO) | International search |
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| DE102017123006B4 | Cited by | Germany | Search report |
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| DE102017123006B9 | Cited by | Germany | Search report |
| EP2436365A3 | Cited by | European Patent Office (EPO) | Search report |
| EP2436365A2 | Cited by | European Patent Office (EPO) | Applicant |
| DE102017123006B4 | Cited by | Germany | Applicant |
| US11219505B2 | Cited by | United States of America | Applicant |
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| EP2436365A2 | Cited by | European Patent Office (EPO) | Search report |
| EP2193776A3 | Cited by | European Patent Office (EPO) | Search report |
| EP2436366A2 | Cited by | European Patent Office (EPO) | Applicant |
| US9023916B2 | Cited by | United States of America | Applicant |
| US11311357B2 | Cited by | United States of America | Applicant |
| EP2193776A2 | Cited by | European Patent Office (EPO) | Search report |
| WO0130305A1 | Cites | World Intellectual Property Organization (WIPO) | Applicant |
| DE102005002845A1 | Cites | Germany | Search report |
| DE102005021332A1 | Cites | Germany | Applicant |
| DE19617931A1 | Cites | Germany | Applicant |
| DE2816823A1 | Cites | Germany | Search report |
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| DE3703120A1 | Cites | Germany | Search report |
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| EP2016931A2This record | European Patent Office (EPO) | A2 | |
| DE102007034457A1 | Germany | A1 | |
| JP2009024013A | Japan | A | |
| US2009036565A1 | United States of America | A1 | |
| EP2016931A3 | European Patent Office (EPO) | A3 | |
| US2010087565A1 | United States of America | A1 | |
| EP2193776A2 | European Patent Office (EPO) | A2 | |
| EP2193776A3 | European Patent Office (EPO) | A3 | |
| CN101347387B | China | B | |
| JP5483839B2 | Japan | B2 | |
| EP2016931B1 | European Patent Office (EPO) | B1 | |
| ES2528013T3 | Spain | T3 |
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Numbers
- Publication
- 2016931
- Application
- 80126550
Titles3
- German
- Dentalkomposite mit niedriger Schrumpfspannung und hoher Biegefestigkeit
- English
- Dental composite with low shrink tensing and high bend stability
- French
- Composite dentaire doté d'une tension de réduction moindre et d'une haute résistance à la flexion
Classification
- CPC, 2
- A61K6/77
- A61K6/887
- IPC, 4
- A61K6 027
- A61K6 083
- A61K6 884
- A61K6 893
Designated states2
- Contracting states, 1
- Türkiye
- Extension states, 1
- Serbia