Solarization stable borosilicate glass and uses thereof
Abstract
The borosilicate glass of the invention is highly resistant to solarization, because it is free of CeO<SUB>2</SUB>. Also it contains 0.01 to 0.05 wt. % of Fe<SUB>2</SUB>O<SUB>3 </SUB>and 0.05 to 0.8 wt. % of TiO<SUB>2</SUB>. This borosilicate glass is especially advantageous for production of flash tubes, gas discharge lamps, and fluorescent tubes for brake lights and display backlights.
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Term ended
Expired 20 February 2022, 4.6 years ago.
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10 claims: 8 independent, 2 dependent
- 1Borosilicatglas mit einer Zusammensetzung (in Gew.-% auf Oxidbasis) von SiO 2 70 - 80 B 2 O 3 13 - 18 Al 2 O 3 0,5 - 4 Li 2 O 0 - 1 Na 2 O 2 - 5 K 2 O 1 - 3 MgO 0 - 1 CaO 0 - 1 BaO 0 - 1 Fe 2 O 3 0,01 - 0,05 TiO 2 0,05 - 0,8 ZrO 2 0 - 1 SnO 2 0 - 0,5 MnO 2 0 - 0,5 Sb 2 O 3 0 - 0,5
- 2Borosilicatglas nach Anspruch 1, gekennzeichnet durch eine Zusammensetzung (in Gew.-% auf Oxidbasis) von SiO 2 70 - 80 B 2 O 3 13 - 18 Al 2 O 3 0,5 - 1 - 3 MgO 0 - 1 CaO 0 - 1 Fe 2 O 3 0,01 - 0,05 TiO 2 0,05 - 0,8 ZrO 2 0 - 1 SnO 2 0 - 0,5 MnO 2 0 - 0,5 Sb 2 O 3 0 - 0,5
- 3Borosilicatglas nach Anspruch 1 oder 2 dadurch gekennzeichnet, daß es wenigstens 0,1 Gew.-%, bevorzugt wenigstens 0,2 Gew.-% TiO 2 enthält.
- 4Borosilicatglas nach wenigstens einem der Ansprüche 1 bis 3 mit einem Transmissionsabfall bei λ = 300 nm von weniger als 5 % nach 15-stündiger HOK-4-Bestrahlung einer 0,2 mm dicken Glasprobe.
- 5Borosilicatglas nach wenigstens einem der Ansprüche 1 bis 4 mit einer Transformationstemperatur Tg < 520 °C, mit einem thermischen Ausdehnungskoeffizienten α 20/300 zwischen 3,7 x 10 -6 /K und 4,2 x 10 -6 /K, einer Transmission τ bei λ ≤ 260 nm von ≤ 30 % (bei 0,2 mm Probendicke).
- 6Borosilicatglas nach wenigstens einem der Ansprüche 1 bis 5 mit einer Transformationstemperatur Tg < 520 °C, mit einem thermischen Ausdehnungskoeffizienten α 20/300 zwischen 3,7 x 10 -6 /K und 4,2 x 10 -6 /K, einer Transmission bei λ ≤ 260 nm von ≤ 0,7 % (bei 0,2 mm Probendicke).
- 7Verwendung eines Glases nach wenigstens einem der Ansprüche 1 bis 4 und 6 für die Herstellung von Leuchtstoffröhren für die Hintergrundbeleuchtungen von Displays.
- 8Verwendung eines Glases nach wenigstens einem der Ansprüche 1 bis 4 und 6 für die Herstellung von Leuchtstoffröhren für Bremslichter von Fahrzeugen.
- 9Verwendung eines Glases nach wenigstens einem der Ansprüche 1 bis 5 für die Herstellung von Blitzlampen.
- 10Verwendung eines Glases nach wenigstens einem der Ansprüche 1 bis 5 für die Herstellung von Gasentladungslampen.
Independent claims10
49 paragraphs in 1 section, as filed
p0001The invention relates to a solarization-stable borosilicate glass and its uses.
p0002BACKGROUND OF THE INVENTION [0002] Background lighting of, for example, displays, for example, of personal computers, laptops, pocket calculators, vehicle navigation systems, use special fluorescent tubes, so-called "backlights".
p0003While conventional fluorescent tubes consist of a soft glass which has a very low degree of solarization stability, solarization-stabilized glasses are required for backlights whose design is basically that of fluorescent tubes in order to ensure long-term functionality.
p0004Due to the construction of the backlights, the glasses used must be vacuum-fusible with tungsten. For this purpose, they must have a thermal expansion adapted to the thermal expansion behavior of W. With the thermal expansion coefficient α<sub>20/300</sub> Of W of 4.4 x 10<sup>-6</sup>/ K are glasses with α<sub>20/300</sub> Between 3.7 x 10<sup>-6</sup>/ K and 4.2 x 10<sup>-6</sup>/ K is suitable. This too is a difference compared to the mentioned soft glasses, which are fused with Fe-Ni alloys.
p0005The glasses are said to have rather low transformation temperatures Tg, ie Tg <520 ° C., so that they can be processed at rather low temperatures.
p0006The transmission process is essential for the glasses. In the visible, as high a light transmittance is required in order to obtain a high light output of the lamp; in the UV range a defined transmission is required according to the application purpose. For example, the influence of harmful UV radiation ≤ 260 nm is to be prevented by correspondingly reducing the UV transmission in order to prevent yellowing and embrittlement of plastics, for example in laptops. Glasses with a UV transmission at λ ≤ 260 nm τ of <0.7%, measured on 0.2 mm thick samples, are suitable for this purpose. For, for example, flashlamps or discharge lamps, transmissions τ at λ ≤ 260 nm range from 30 30% (for 0.2 mm thick samples). The transition from the impermeable to the transmissive wavelength range should be as short as possible, ie the transmission curve should be as steep as possible in this region.
p0007The minimum requirement for the transmission in the visible wavelength range is a transmission of 92% at λ> 400 nm and a sample thickness of 0.2 mm. Therefore, τ (> 400 nm, 0.2 mm) ≥ 92% is required.
p0008A further essential property of glasses for "backlights" is the solarization resistance, which is necessary in order to allow a long service life of the lamps, ie a light output which is as constant as possible. The term "solarization-stable" is understood here to mean glasses which, after irradiation with an Hg high-pressure lamp with a main emission at 365 nm and an irradiation strength of 850 μW / cm, are irradiated after 15 hours of HOK-4 irradiation<sup>2</sup> At 200 to 280 nm at a distance of 1 m, a transmittance drop of less than 5% at 300 nm on a 0.2 mm thick glass sample. The requirements for glasses for flash lamps, for gas discharge lamps and for backlights are very similar. All should have the highest possible solarization stability and have a high transmission in the visible range.
p0009Various publications are already known in the patent literature, which describe more or less solarization-stable glasses, in particular lamp lenses. However, these glasses exhibit the most diverse disadvantages, in particular a lack of solarization resistance which does not meet today's high requirements.
p0010<patcit id="pcit0001" dnum="US5994248A"><text>US 5,994,248</text></patcit> Describes a headlamp lens, made from a glass of a very wide composition range in which SiO.sub.2 is used<sub>2</sub> Component and Al<sub>2</sub>O<sub>3</sub>, B<sub>2</sub>O<sub>3</sub>, Alkaline earth oxides and alkali oxides and small amounts of iron oxides. The K<sub>2</sub>O content can only be between 0 and 1% by weight.
p0011The properties of solar cells which are essential for backlights, flash lamps and gas discharge lamps, such as solarization stability and a thermal expansion that is adapted to tungsten, do not play any role here.
p0012De 195 45 422 A1 relates to a bonding glass for the anodic bonding of silicon components with glass components which is highly Li<sub>2</sub>O-containing and high Fe<sub>2</sub>O<sub>3</sub>/ FeO dopants.
p0013<patcit id="pcit0002" dnum="JP10036135A"><text>JP 10-36135A</text></patcit> Describes glass for electronic imaging. The α-radiation of the glass is as small as possible. For this purpose, the contents of U, Th, Ra <100 ppb in a wide base glass composition and the contents of Fe<sub>2</sub>O<sub>3</sub>, TiO<sub>2</sub>, PbO, ZrO<sub>2</sub> Are <100 ppm.
p0014<patcit id="pcit0003" dnum="EP0735007B1"><text>EP 0 735 007 B1</text></patcit> Describes a concrete lead- and arsenic-free glass with resistance to. Solarization, which has special levels of SnO<sub>2</sub> and CeO<sub>2</sub> , Whereby the solarization stability is increased, but not satisfactorily.
p0015The same applies to CeO<sub>2</sub> and Fe<sub>2</sub>O<sub>3</sub> Containing glass <patcit id="pcit0004" dnum="WO9855413A"><text>WO 98/55413</text></patcit>.
p0016<patcit id="pcit0005" dnum="JP6056467A"><text>JP6056467 A</text></patcit> Describes a UV radiation-absorbing borosilicate glass, which does not lead to negligible amounts of the strongly coloring V<sub>2</sub>O<sub>5</sub> And only relatively small amounts of K<sub>2</sub>O.
p0017This in <patcit id="pcit0006" dnum="JP8012369A"><text>JP 8-12369 A</text></patcit> Described borosilicate glass for discharge lamps contains a total of 0.03 to 3% by weight of at least two of the four components V for UV blocking<sub>2</sub>O<sub>5</sub>, Fe<sub>2</sub>O<sub>3</sub>, TiO<sub>2</sub> and CeO<sub>2</sub>. With these components with high individual parts and their combinations, high transmission and high resistance to solarization are not adjustable.
p0018It is therefore the object of the present invention to provide a solarization-stable, UV (<260 nm) opaque glass with high transmission in the visible region and with a thermal expansion adapted to the expansion behavior of tungsten.
p0019The object is achieved by a borosilicate glass according to the main claim.
p0020A glass having the desired transmission properties preferably consists of a base glass system of 70 to 80% by weight of SiO<sub>2</sub>, 13 to 18% by weight of B<sub>2</sub>O<sub>3</sub>, 0.5 to 4% by weight, preferably 0.5 to <2% by weight of AL<sub>2</sub>O<sub>3</sub>By weight, of alkali metal oxides, preferably from 2 to 5% by weight of Na<sub>2</sub>O and 1 to 3% by weight, preferably> 1 to 3% by weight, K<sub>2</sub>O and 0 to 1% by weight of Li<sub>2</sub>O, preferably Li<sub>2</sub>O-free, and optionally alkaline earth oxides, preferably 0-1% by weight MgO, 0-1% by weight CaO and 0-1% by weight BaO, preferably BaO-free.
p0021Essentially, the simultaneous presence of TiO is essential<sub>2</sub> and Fe<sub>2</sub>O<sub>3</sub> In specific proportions, namely from 0.01 to 0.05% by weight of Fe<sub>2</sub>O<sub>3</sub> And 0.05 to 0.8% by weight of TiO<sub>2</sub>.
p0022The respective minimum contents of both Fe<sub>2</sub>O<sub>3</sub> As well as TiO<sub>2</sub> Are necessary to achieve high solarization resistance. A TiO is preferred<sub>2</sub>Content of at least 0.1% by weight, more preferably a content of at least 0.2% by weight of TiO 2<sub>2</sub>By weight, very particularly preferably at least 0.4% by weight of TiO 2<sub>2</sub>. By the simultaneous presence of these two components in the stated amounts, the UV edge, that is to say the transition between absorption and transmission, is obtained at the desired wavelength.
p0023Higher contents of Fe<sub>2</sub>O<sub>3</sub> As 0.05% by weight would mean a reduction in the transmission in the range from 350 to about 600 nm, which is due to the influence of Fe<sup>3+</sup> Respectively. Higher levels of TiO<sub>2</sub> As 0.8% by weight would, on the other hand, lead to the displacement of the UV edge into the longer-wave visible region and thus to the yellowing of the glasses. In addition, with the increase of both components above the stated maximum contents, ilmenite forms, which leads to the brown coloring of the glass and thus to the reduction of the transmission.
p0024The glass may contain conventional refining agents in conventional amounts, for example evaporation refining agents such as CI<sup>-</sup> and F<sup>-</sup>, But also redox cleansing agents which are effective because of their polyvalent cations, for example SnO<sub>2</sub> and Sb<sub>2</sub>O<sub>3</sub>, Which are preferably present in the glass with in each case 0 to 0.5% by weight. Particular preference is given to a SnO<sub>2</sub>Content between 0 and 0.2% by weight.
p0025As<sub>2</sub>O<sub>3</sub> The glass does not contain any unavoidable impurities since<sub>2</sub>O<sub>3</sub> Would adversely affect solarization resistance.
p0026The same applies to PbO. Therefore, the glass is also PbO-free up to inevitable impurities.
p0027The glass can contain up to 0.5% by weight, preferably up to 0.1% by weight, of MnO<sub>2</sub> contain. In this order of magnitude, it serves as a refining agent and shifts the UV edge into the long-wave region.
p0028The glass may contain from 0 to 1% by weight of ZrO<sub>2</sub> contain. ZrO<sub>2</sub> Is particularly advantageous for the chemical resistance of the glass. Higher levels of ZrO<sub>2</sub> Would have a negative effect on melting, and the processing temperature of the glasses would be too high. There is also the risk that unresolved particulate matter may be left behind. It is preferred to rely on the addition of ZrO<sub>2</sub> , So that the glass is subject to unavoidable contamination by raw materials or by tin corrosion ZrO<sub>2</sub>-free is.
p0029The glass is also free from CeO up to unavoidable impurities<sub>2</sub>. This is of great advantage for the transmission properties, because CeO<sub>2</sub> Has a very negative effect on the solarization resistance.
EXAMPLES:
p0030For the production of the sample glasses and the comparative glasses, customary raw materials were used, ie it is particularly not necessary to use expensive Fe-poor raw materials.
p0031The well-homogenized mixture was melted, refined and homogenized in the laboratory in a Pt crucible at 1,600 ° C. Subsequently, the glass was poured and cooled at 20 K / h.
p0032Table 1 shows a melting example for a 0.5-I melt.<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="19mm" /><colspec colnum="4" colname="col4" colwidth="25mm" /><thead><row><entry align="center" valign="top"><b>oxide</b></entry><entry align="center" valign="top"><b>Wt%</b></entry><entry align="center" valign="top"><b>raw material</b></entry><entry align="center" valign="top"><b>Weight [g]</b></entry></row></thead><tbody><row><entry>SiO<sub>2</sub></entry><entry>74.90</entry><entry>SiO<sub>2</sub></entry><entry>670.51</entry></row><row><entry>B<sub>2</sub>O<sub>3</sub></entry><entry>16.90</entry><entry>H<sub>3</sub>BO<sub>3</sub></entry><entry>145.08</entry></row><row><entry>Al<sub>2</sub>O<sub>3</sub></entry><entry>1.14</entry><entry>Al<sub>2</sub>O<sub>3</sub></entry><entry>7.94</entry></row><row><entry>N / A<sub>2</sub>O</entry><entry>3.73</entry><entry>N / A<sub>2</sub>B<sub>4</sub>O<sub>7</sub></entry><entry>101.04</entry></row><row><entry>K<sub>2</sub>O</entry><entry>1.44</entry><entry>K<sub>2</sub>CO<sub>3</sub></entry><entry>18.65</entry></row><row><entry>CaO</entry><entry>0.60</entry><entry>CaCO<sub>3</sub></entry><entry>0.1727</entry></row><row><entry>MgO</entry><entry>0.42</entry><entry>dolomite</entry><entry>16.38</entry></row><row><entry>NaCl</entry><entry>0.45</entry><entry>NaCl</entry><entry>4.01</entry></row><row><entry>TiO<sub>2</sub></entry><entry>0.40</entry><entry>TiO<sub>2</sub></entry><entry>3.36</entry></row><row><entry>Fe<sub>2</sub>O<sub>3</sub></entry><entry>0.025</entry><entry>Fe<sub>2</sub>O<sub>3</sub></entry><entry>0.0913</entry></row></tbody></tgroup></table></tables>
p0033The properties of the glass thus obtained are given in Table 2, Example A4.
p0034Table 2 shows six examples of glasses according to the invention (A1 to A6) with their compositions (in% by weight based on oxide) and their essential properties.
p0035Table 3 shows the compositions and properties of five comparative glasses (V1 to V5).
p00360.45% by weight of NaCl was added to the glass batches. In the finished glasses, only about 0.29% by weight of NaCl is recovered.
p0037The following properties are given in Tables 2 and 3:<ul><li>The thermal coefficient of expansion a<sub>20/300</sub> [10<sup>-6</sup>/ K]</li><li>The transformation temperature T<sub>G</sub> [° C]</li><li>The solarization resistance, expressed as the difference of transmission at λ = 300 nm between a 0.2 mm thick unirradiated sample and that after 15 hours exposure to a HOK-4 lamp, indicated as Δ<sub>15</sub>Τ (300 nm, 0.2 mm) [%]</li><li>The transmission at λ> 400 nm and a sample thickness of 0.2 mm τ (> 400 nm, 0.2 mm) for the documentation of the high transmission in the visible</li><li>The transmission at λ = 260 nm and a sample thickness of 0.2 mm τ (260 nm, 0.2 mm) for the documentation of transmission in the UV range (UV blocking).</li></ul>
p0038Table 1<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="7"><colspec colnum="1" colname="col1" colwidth="34mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><colspec colnum="3" colname="col3" colwidth="22mm" /><colspec colnum="4" colname="col4" colwidth="22mm" /><colspec colnum="5" colname="col5" colwidth="22mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><colspec colnum="7" colname="col7" colwidth="22mm" /><thead><row><entry namest="col1" nameend="col7" align="left" valign="top">Compositions (% by weight based on oxide) and essential properties of glasses according to the invention (A)</entry></row><row><entry valign="top" /><entry valign="top">A1</entry><entry valign="top">A2</entry><entry valign="top">A3</entry><entry valign="top">A4</entry><entry valign="top">A5</entry><entry valign="top">A6</entry></row></thead><tbody><row><entry>SiO<sub>2</sub></entry><entry>75.17</entry><entry>74.57</entry><entry>74.92</entry><entry>74.90</entry><entry>75.13</entry><entry>75.00</entry></row><row><entry>B<sub>2</sub>O<sub>3</sub></entry><entry>16.96</entry><entry>16.94</entry><entry>16.90</entry><entry>16.90</entry><entry>16.95</entry><entry>16.92</entry></row><row><entry>Al<sub>2</sub>O<sub>3</sub></entry><entry>1.15</entry><entry>1.65</entry><entry>1.14</entry><entry>1.14</entry><entry>1.15</entry><entry>1.15</entry></row><row><entry>N / A<sub>2</sub>O</entry><entry>3.74</entry><entry>3.73</entry><entry>3.73</entry><entry>3.73</entry><entry>3.74</entry><entry>3.73</entry></row><row><entry>K<sub>2</sub>O</entry><entry>1.45</entry><entry>1.45</entry><entry>1.44</entry><entry>1.44</entry><entry>1.45</entry><entry>1.44</entry></row><row><entry>CaO</entry><entry>0.60</entry><entry>0.60</entry><entry>0.60</entry><entry>0.60</entry><entry>0.60</entry><entry>0.60</entry></row><row><entry>MgO</entry><entry>0.42</entry><entry>0.42</entry><entry>0.42</entry><entry>0.42</entry><entry>0.42</entry><entry>0.42</entry></row><row><entry>TiO<sub>2</sub></entry><entry>0.075</entry><entry>0.200</entry><entry>0.400</entry><entry>0.400</entry><entry>0.100</entry><entry>0.100</entry></row><row><entry>SnO<sub>2</sub></entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>0.200</entry></row><row><entry>MnO<sub>2</sub></entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>0.025</entry><entry>-</entry></row><row><entry>Fe<sub>2</sub>O<sub>3</sub></entry><entry>0.013</entry><entry>0.01</entry><entry>0.013</entry><entry>0.025</entry><entry>0.013</entry><entry>0.013</entry></row><row><entry>α<sub>20/300</sub> [10<sup>-6</sup>/ K]</entry><entry>3.84</entry><entry>3.84</entry><entry>3.88</entry><entry>3.80</entry><entry>3.82</entry><entry>3.88</entry></row><row><entry>T<sub>G</sub> [° C]</entry><entry>503</entry><entry>495</entry><entry>511</entry><entry>496</entry><entry>496</entry><entry>504</entry></row><row><entry>Δ<sub>15</sub>Τ (300nm, 0.2mm) [%]</entry><entry>4.4</entry><entry>2.2</entry><entry>2.1</entry><entry>2.4</entry><entry>3,8</entry><entry>4.3</entry></row><row><entry>Τ (260 nm, 0.2 mm) [%]</entry><entry>21</entry><entry>8.7</entry><entry>0.6</entry><entry>0.3</entry><entry>15.7</entry><entry>18.7</entry></row><row><entry>Τ (> 400 nm, 0.2 mm) [%]</entry><entry>> 92</entry><entry>> 92</entry><entry>> 92</entry><entry>> 92</entry><entry>> 92</entry><entry>> 92</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><title>Table 2</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="40mm" /><colspec colnum="2" colname="col2" colwidth="25mm" /><colspec colnum="3" colname="col3" colwidth="23mm" /><colspec colnum="4" colname="col4" colwidth="25mm" /><colspec colnum="5" colname="col5" colwidth="23mm" /><colspec colnum="6" colname="col6" colwidth="25mm" /><thead><row><entry namest="col1" nameend="col6" align="left" valign="top">Compositions (% by weight based on oxide) and essential properties Comparison glasses (V)</entry></row><row><entry valign="top" /><entry valign="top">V1</entry><entry valign="top">V2</entry><entry valign="top">V3</entry><entry valign="top">V4</entry><entry valign="top">V5</entry></row></thead><tbody><row><entry>SiO<sub>2</sub></entry><entry>75.17</entry><entry>75.22</entry><entry>74.57</entry><entry>75.11</entry><entry>75.22</entry></row><row><entry>B<sub>2</sub>O<sub>3</sub></entry><entry>16.96</entry><entry>16.97</entry><entry>16.94</entry><entry>16.95</entry><entry>16.97</entry></row><row><entry>Al<sub>2</sub>O<sub>3</sub></entry><entry>1.15</entry><entry>1.15</entry><entry>1.65</entry><entry>1.15</entry><entry>1.15</entry></row><row><entry>N / A<sub>2</sub>O</entry><entry>3.74</entry><entry>3.74</entry><entry>3.73</entry><entry>3.74</entry><entry>3.74</entry></row><row><entry>K<sub>2</sub>O</entry><entry>1.45</entry><entry>1.45</entry><entry>1.45</entry><entry>1.45</entry><entry>1.45</entry></row><row><entry>CaO</entry><entry>0.60</entry><entry>0.60</entry><entry>0.60</entry><entry>0.60</entry><entry>0.60</entry></row><row><entry>MgO</entry><entry>0.42</entry><entry>0.42</entry><entry>0.42</entry><entry>0.42</entry><entry>0.42</entry></row><row><entry>NaCl</entry><entry>0.45</entry><entry>0.45</entry><entry>0.45</entry><entry>0.45</entry><entry>0.45</entry></row><row><entry>TiO<sub>2</sub></entry><entry>0.075</entry><entry>0.034</entry><entry>0.200</entry><entry>0.100</entry><entry>0.0033</entry></row><row><entry>CeO<sub>2</sub></entry><entry>-</entry><entry>-</entry><entry>-</entry><entry>0.05</entry><entry>-</entry></row><row><entry>Fe<sub>2</sub>O<sub>3</sub></entry><entry>0.0084</entry><entry>0.013</entry><entry>0.0084</entry><entry>0.013</entry><entry>0.0084</entry></row><row><entry>α<sub>20/300</sub> [10<sup>-6</sup>/ K]</entry><entry>nb</entry><entry>3.55</entry><entry>nb</entry><entry>nb</entry><entry>nb</entry></row><row><entry>T<sub>G</sub> [° C]</entry><entry>nb</entry><entry>497</entry><entry>nb</entry><entry>nb</entry><entry>nb</entry></row><row><entry>Δ<sub>15</sub>Τ (300 nm, 0.2 mm) [%]</entry><entry>5.8</entry><entry>5.5</entry><entry>6,7</entry><entry>5.8</entry><entry>7.8</entry></row><row><entry>Τ (260 nm, 0.2 mm)</entry><entry>41.3</entry><entry>39.8</entry><entry>9.6</entry><entry>11</entry><entry>65.8</entry></row><row><entry>Τ (> 400 nm, 0.2 mm)</entry><entry>> 92</entry><entry>> 92</entry><entry>> 92</entry><entry>> 92</entry><entry>> 92</entry></row></tbody></tgroup></table></tables>
p0039FIGS. 1 to 5 show the transmission curves τ against λ (200-400 nm) for some embodiments and comparative examples before (a) and after (b) irradiation.
p0040In detail:<dl id="dl0001"><dt>Fig. 1:</dt><dd>A1 and V1, V5, in each case unirradiated and after 100 hours of irradiation with a HOK-4 lamp (sample thickness: 0.2 mm)</dd><dt>Fig. 2:</dt><dd>A2 and V3, in each case unirradiated and after 100 hours of HOK-4 irradiation (sample thickness: 0.2 mm)</dd><dt>Fig. 3:</dt><dd>A3, A4, respectively unirradiated and after 100 hours of HOK-4 irradiation (0.21 mm sample thickness)</dd><dt>Fig. 4:</dt><dd>A5, A6, in each case unirradiated and after 100 hours of HOK-4 irradiation (test thickness approx. 0.21 mm)</dd><dt>Fig. 5:</dt><dd>A4 and V4, respectively, unirradiated and after 100 hours of HOK-4 irradiation (sample thickness 2 mm)</dd></dl>
p0041The figures show that the desired transmission pattern is determined by the specific contents of TiO<sub>2</sub> and Fe<sub>2</sub>O<sub>3</sub> In particular the comparison with Fe<sub>2</sub>O<sub>3</sub>Examples V1, V5, V3 and the TiO<sub>2</sub>Poor examples V2, V5. Also the importance of CeO<sub>2</sub>-freeness for the transmission is clarified.
p0042The figures as well as the data Δ<sub>15</sub>Τ (300 nm, 0.2 mm) in the tables illustrate the differences in the resistance to solarization between the glasses according to the invention and comparative lenses. Also the negative influence of CeO<sub>2</sub> Is compared, for example, with A5 or A6, but in particular with A1 (see table) or A4 (see FIG <figref idrefs="f0005">Fig. 5</figref>), Clearly.
p0043The glasses according to the invention have a high resistance to solarization, expressed by Δ<sub>15</sub>Τ (> 400 nm, 0.2 mm) 92 92%, and good UV blocking (see FIG. Transmission rate), in particular expressed by τ (≤ 260 nm, 0.2 mm) ≤ 30%.
p0044Furthermore, the glasses have a transformation temperature Tg <520 ° C., which makes them easy to process.
p0045Further, the glasses have a thermal expansion coefficient α<sub>20/300</sub> Between 3.7 x 10<sup>-6</sup>/ K and 4.2 x 10<sup>-6</sup>/ K. They are therefore sufficiently adapted to the thermal expansion behavior of tungsten, ie, they can be fused together with W vacuum.
p0046With these properties, glasses are well suited for the production of lamp bulbs for flash lamps and for gas discharge lamps.
p0047In preferred embodiments with comparatively high TiO<sub>2</sub>The glasses have a particularly good UV blocking, in particular expressed by τ (260 260 nm, 0.2 mm) 0, 0.7%
p0048These glasses are therefore ideally suited for the production of "backlights", for example for background lighting of displays, eg of personal computers, laptops, notebooks, pocket calculators, vehicle navigation systems, scanners, but also mirrors and pictures.
p0049They are also suitable for the production of braking lights of vehicles. In particular, the third additional brake light can preferably be realized by such a special fluorescent tube.
5 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| JPH0656467A | Cites | Japan | Examiner |
| EP1178020A | Cites | European Patent Office (EPO) | – |
| DE4306004A | Cites | Germany | – |
| JP6056467A | Cites | Japan | – |
| PATENT ABSTRACTS OF JAPAN vol. 1996, no. 05, 31. Mai 1996 (1996-05-31) & JP 08 012369 A (TOSHIBA GLASS CO LTD), 16. Januar 1996 (1996-01-16) in der Anmeldung erwähnt | Non-patent | – | – |
| PATENT ABSTRACTS OF JAPAN vol. 1998, no. 06, 30. April 1998 (1998-04-30) & JP 10 036135 A (TOSHIBA GLASS CO LTD), 10. Februar 1998 (1998-02-10) in der Anmeldung erwähnt | Non-patent | – | – |
16 members in 9 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 10108992 | Germany | – | |
| 10108992 | Germany | A | |
| 0201748 | European Patent Office (EPO) | W |
Members16
| Document | Office | Kind | |
|---|---|---|---|
| DE10108992A1 | Germany | A1 | |
| WO02081394A1 | World Intellectual Property Organization (WIPO) | A1 | |
| DE10108992C2 | Germany | C2 | |
| KR20030082603A | Republic of Korea | A | |
| EP1362013A1 | European Patent Office (EPO) | A1 | |
| CN1492844A | China | A | |
| JP2004531445A | Japan | A | |
| CN1243682C | China | C | |
| TWI260311B | Taiwan Province of China | B | |
| US2006205583A1 | United States of America | A1 | |
| US7217673B2 | United States of America | B2 | |
| JP4563649B2 | Japan | B2 | |
| EP1362013B1This record | European Patent Office (EPO) | B1 | |
| AT497487T | Austria | T | |
| ATE497487T1 | Austria | T1 | |
| DE50214893D1 | Germany | D1 |
52 legal events, as 8 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal feeWithdrawnR119 | R119 | DE | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Fee paymentPLFP | PLFP | FR | |
| Fee paymentPLFP | PLFP | FR | |
| Fee paymentPLFP | PLFP | FR | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapse because of not paying annual feesLapsedMM01 | MM01 | AT | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| No opposition filed against granted patent, or epo opposition proceedings concluded without decisionGrantedR097 | R097 | DE | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | EP | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| Be: lapsedLapsedBERE | BERE | EP | |
| European patents designating ireland treated as always having been voidFD4D | FD4D | IE | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Discontinued in the netherlands as no translation has been filedVDEP | VDEP | NL | |
| Dpma publication of mentioned ep patent grantGrantedR096 | R096 | DE | |
| Corresponds to:REF | REF | EP | |
| European patents granted designating irelandGrantedLANGUAGE OF EP DOCUMENT: GERMANFG4D | FG4D | IE | |
| European patent takes effect as a national patent in ch/liEP | EP | CH | |
| Designated contracting statesAK | AK | EP | |
| European patent grantedGrantedNOT ENGLISHFG4D | FG4D | GB | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Grant fee paidORIGINAL CODE: EPIDOSNIGR3GRAS | GRAS | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOSNIGR1GRAP | GRAP | EP | |
| Party data changed (applicant data changed or rights of an application transferred)RAP1 | RAP1 | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Request for extension of the european patentAX | AX | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 1362013
- Application
- 27324441
Titles3
- German
- SOLARISATIONSSTABILES BOROSILICATGLAS UND SEINE VERWENDUNGEN
- English
- SOLARIZATION STABLE BOROSILICATE GLASS AND USES THEREOF
- French
- VERRE BOROSILICATE STABLE A LA SOLARISATION ET SES UTILISATIONS
Classification
- CPC, 1
- C03C3/091
- IPC, 2
- C03C3 091
- H01J61 30
Designated states20
- Contracting states, 20
- Austria
- Belgium
- Switzerland
- Cyprus
- Germany
- Denmark
- Spain
- Finland
- France
- United Kingdom
- Greece
- Ireland
- Italy
- Liechtenstein
- Luxembourg
- Monaco
- Netherlands (Kingdom of the)
- Portugal
- Sweden
- Türkiye