# Patent

## Title
UV-blocking borosilicate glass, the use of the same, and a fluorescent lamp

## Abstract

The invention relates to a borosilicate glass having the following composition (in wt. % based on oxide content): between 55 and 80 of SiO2; between 8 and 25 of B2O3; between 0.5 and 10 of Al2O3; between 1 and 16 of Li2O+Na2O+K2O; between 0 and 6 of MgO+CaO+SrO+BaO; between 0 and 3 of ZnO; between 0 and 5 of ZrO2; between 0 and 5 of Bi2O3; and between 0 and 3 of MoO3; the sum of the Bi2O3 and MoO3 amounting to between 0.01 and 5. The invention also relates to a fluorescent lamp, especially a miniature fluorescent lamp.

## Background
The invention relates to a UV-blocking borosilicate glass and to the use of the same. The invention also relates to a fluorescent lamp.
Fluorescent lamps, known as backlights, are used as background illumination for, for example, displays, for example of personal computers, laptops, palmtops, vehicle navigation systems.
Typical sizes of miniaturized lamps of this type are an external diameter of between 2 and 5 mm. Typical internal diameters are between 1.8 and 4.8 mm.
Whereas standard fluorescent tubes consist of a soft glass which has a very low solarization stability, glasses which are more solarization-stable are used for backlights, the basic structure of which corresponds to that of fluorescent tubes, in order to ensure long-term functionality.
On account of the structure of the backlights, the glasses used have to be suitable for vacuum-tight fusing to a metal or metal alloy used in lamp manufacture. For this purpose, they have to have a thermal expansion which is matched to the thermal expansion of the metal or metal alloy. For example, if tungsten is used, given the coefficient of thermal expansion α20/300 of W of 4.4×10−6/K, glasses with α20/300 of between 3.4×10−6/K and 4.3×10−6/K are particularly suitable. By way of example, if Kovar, an Fe—Co—Ni alloy, is used, glasses with α20/300 of between 4.3×10−6/K and 6.0×10−6/K are eminently suitable.
The glasses should Lend to have low working points VA, i.e. VA<1200° C., to allow them to be worked at relatively low temperatures. The transformation temperature Tg should be matched to the melting characteristics of the metal or metal alloy to which it is to be fused. For example, in the case of fusing to Kovar, the transformation temperature should preferably be between 440° C. and 530° C. Tg of up to 580° C. is eminently suitable for fusing to tungsten.
The transmission profile is a significant property of glasses. In the visible region, the highest possible light transmission is required, in order to obtain a high light yield from the lamp, whereas in the UV region no transmission or only a low transmission is the aim; in order for the minimum possible amount of the harmful UV radiation to be allowed to pass through. The UV-blocking requirements depend on the uses of the glasses. For example, if they are used as lamp glasses for fluorescent lamps, in particular the Hg line at 253 nm should be blocked.
For example, for backlights, a high UV blocking≦253 nm is desirable in order to ensure that irradiated plastic parts, for example in laptops, do not become yellow and embrittled. This requirement is met by glasses having a UV transmission at λ≦254 nm of τ≦0.1%, measured on specimens which are 0.2 mm thick. For other uses, an UV transmission τ≦0.1% at λ≦240 nm is sufficient. In any event, the transition from the wavelength range which is not transmitted to the wavelength range which is transmitted should be as short as possible, i.e. the transmission curve should be as steep as possible in this region.
The minimum demand imposed on the transmission in the visible wavelength region is, at λ>400 nm and with a specimen thickness of 0.2 mm, a transmission of 90%. Therefore, the requirement is τ (>400 nm; 0.2 mm)≧90%.
A further important property of glasses for fluorescent lamps, in particular for backlights, is the resistance to solarization which is required in order to allow a long lamp service life to be achieved, i.e. a light yield which remains as constant as possible. In the present context, the term “solarization-stable” is to be understood as encompassing glasses which have a drop in transmission of at most 5% at 300 nm after 15 hours' HOK-4 irradiation, i.e. irradiation with an Hg high-pressure lamp with a main emission of 365 nm and an irradiation strength of 850 μW/cm2 at 200 to 280 nm at a distance of 1 m on a glass specimen which is 0.2 mm thick.
The patent literature has already disclosed various documents which describe more or less UV-blocked glasses, in particular lamp glasses. However, these glasses have certain drawbacks, in particular a UV-blocking action which does not comply with the high demands imposed nowadays.
The borosilicate glass for discharge lamps which is described in JP 8-12369 A contains, for UV blocking purposes, a total of from 0.03 to 3% by weight of at least two of the four components V2O5, Fe2O3, TiO2 and CeO2. A high transmission and a high solarization resistance cannot be set using these components, in some cases in high individual proportions, and combinations thereof.
U.S. Pat. No. 5,747,399 describes a glass for miniaturized fluorescent lamps which is supposed to retain its solarization stability and its UV-impermeability by means of TiO2 and/or PbO and/or Sb2O3. However, doping with TiO2, in particular high levels of the latter, leads to discoloration of the class. PbO should also not be used, on account of the associated environmental problems.
Therefore, it is an object of the present invention to provide a glass having a high transmission in the visible region (>400 nm) and a high level of blocking in the UV region (≦240 nm), and also having a thermal expansion which is matched to the expansion of tungsten or Kovar.
The object is achieved by a borosilicate glass in accordance with the main claim.
A glass having the desired transmission properties comprises the base glass system (in % by weight, based on oxide): 55 to 80 SiO2, 8 to 25 B2O3, 0.5 to 10 Al2O3, 1 to 16 Li2O+Na2O+K2O, 0 to 6 MgO+CaO+SrO+BaO, 0 to 3 ZnO and 0 to 5 ZrO2.
The presence of MoO3 and/or Bi2O3, specifically in a total amount of from 0.01 to 5% by weight, with from 0 to 3% of MoO3 and from 0 to 5% of Bi2O3, is crucial to the invention.
The minimum level of MoO3 and/or Bi2O3 is a requirement in order to achieve the high UV blocking. Higher levels of MoO3 and/or Bi2O3 would lead to discoloration of the glass. A minimum total amount of 0.1% by weight is preferred, and a minimum total amount of 0.2% by weight is particularly preferred, as is a maximum total amount of 3% by weight. A minimum MoO3 content of 0.4% by weight or a minimum Bi2O3 content of 1.0% by weight is particularly preferred. Bi2O3 also greatly improves the solarization stability of the glass. In particular in the particularly preferred embodiments, it is possible to achieve UV blocking up to 254 nm, i.e. a τ≦0.1% at τ≦254 nm with a specimen thickness of 0.2 mm. A minimum MoO2 content of 0.6% by weight or a minimum Bi2O3 content of 1.3% by weight is very particularly preferred.
The glass preferably comprises the glass system (in % by weight, based on oxide): SiO2 55-79, B2O3 10-25, Al2O3 0.5-10, Li2O+Na2O+K2O 1-16, MgO+CaO+SrO+BaO 0-6, ZnO 0-3, ZrO2 0-1; Bi2O3 0-5, MoO3 0-3; with BiO2+MoO3 0.1-5.
It is particularly preferred for the glass to comprise the following glass system: SiO2 55-79, B2O3 8-12.5; Al2O3 0.5-10; Li2O+Na2O+K2O 1-16; MgO+CaO+SrO+BaO 0-6; ZnO 0-3; ZrO2 0-3; Bi2O3 0-5; MoO3 0-3; with Bi2O3+MoO3 0.01-5.
It is preferable not to add ZrO2, so that the glass is ZrO2-free, apart from inevitable impurities resulting from raw materials or tank furnace corrosion.
Glasses from the abovementioned composition ranges containing from 70-80% by weight of SiO2 have coefficients of thermal expansion α20/300 of between 3.4×10−6/K and 4.3×10−6/K and are therefore particularly suitable for fusing to tungsten.
Glasses from the composition range (in % by weight, based on oxide) SiO2 73-79, B2O3 12.5-25; Al2O3 0.5-10; Li2O+Na2C+K2O 1-11; MgO+CaO+SrO+BaO 0-6; ZnO 0-3; ZrO2 0-5; Bi2O3 0-5; MoO3 0-3; with Bi2O3+MoO3 0.01-5 are particularly preferred for fusing to tungsten.
Glasses from the abovementioned composition ranges containing from 55-75% by weight of SiO2 have coefficients of thermal expansion of between 4.3×10−6/K and 6.0×10−6/K and are therefore particularly suitable for fusing to Kovar.
Glasses from the composition range (in % by weight, based on oxide) SiO2 55-73; B2O3 15-25; Al2O3 1-10; Li2O+Na2O+K2O 4-16; MgO+CaO+SrO+BaO 0-6; ZnO 0-3; ZrO2 0-5; Bi2O3 0-5; MoO3 0-3; with Bi2O3+MoO3 0.01-5 are particularly preferred for fusing to Kovar.
The glass may contain the usual quantities of standard refining agents, such as for example evaporation refining agents, such as Cl− and F−, but also Redox refining agents, which are active on account of their polyvalent cations, e.g. SnO2 and Sb2O3. It is preferable for the glass to contain 0-1% by weight of Sb2O3, 0-1% by weight of As2O3, 0-1% by weight of SnO2, 0-1% by weight of CeO2, 0-0.5% by weight of Cl, 0-1% by weight of F, 0-0.5 of sulfate, given as SO3.
CeO2 assists with the refining but may have an adverse effect on the solarization stability if it is present in excessive quantity.
Furthermore, the glass may contain 0-5% by weight of TiO2, preferably 0-1% by weight of TiO2, and 0-3% by weight of PbO. TiO2 assists MoO3 and Bi2 O3 by shifting the UV edge, i.e. the transition between absorption and transmission, into the longer-wave range. This makes it possible to achieve UV-blocking actions not only up to 240 nm, but even up to 254 nm and above, even with only the abovementioned low levels of MoO3 and/or Bi2O3. The doping according to the invention, compared to the TiO2 doping of the prior art, makes it possible to dispense altogether with TiO2 or to add it in such small quantities that its disruptive discoloration plays no role.
The glass may contain up to 1% by weight of Fe2O3 without this having any disadvantageous effect. Fe2O3 also contributes to shifting the absorption edge into the longer-wave region.
The glass may also contain small proportions, which have no adverse effect on the glass system, of V2O5, Nb2O5 and WO3.
The total quantity of Fe2O3, CeO2, V2O5, Nb2O5, WO3, TiO2, PbO, As2O3, Sb2O3 should not exceed 5% by weight, since otherwise the glass is excessively discolored in the visible region.


EXEMPLARY EMBODIMENTS
Standard raw materials were used to produce the example glasses and the comparison glasses.
The well-homogenized batch was melted, refined and homogenized in the laboratory in a quartz glass crucible at 1600° C. Then, the glass was cast and cooled at 20 K/h.
The table shows thirteen examples of glasses according to the invention (A1 to A13) and two comparative examples (C1, C2) including their compositions (in % by weight, based on oxide) and their main properties.
The following properties are given in the table:

    
    
        the coefficient of thermal expansion α20/300 [10−6/K]
        the transformation temperature Tg [° C.]
        the working point VA [° C.]
        the softening point EW [° C.]
        the highest wavelength at which τ is at most 0.1% (for a specimen thickness of 0.2 mm) to document the blocking in the UV region (“UV blocking”)
    
    









TABLE





Compositions (in % by weight, based on oxide) and important properties of glasses


according to the invention (A) and of comparison glasses (C)

























C1
C2
A1
A2
A3
A4
A5
A6
A7





SiO2
68.45
67.65
72.6
78.0
72.0
68.0
59.0
69.0
68.25


B2O3
19.0
19.0
14.5
10.8
16.0
12.0
16.0
8.0
19.0


Al2O3
2.65
2.65
2.0
2.0
3.0
1.0
2.0
5.0
2.65


Na2O
0.8
0.8
2.0
2.0
2.0
1.0
1.0
1.0
0.8


K2O
7.7
7.7
—
1.0
1.0
3.0
3.0
3.0
7.7


MgO
—
—
0.5
1.0
1.0
4.0
4.0
4.0
—


CaO
—
—
2.0
0.9
1.9
1.9
3.9
1.9
—


SrO
—
—
1.6
1.0
1.0
1.0
1.0
1.0
—


BaO
—
—
—
—
—
5.0
5.0
2.0
—


Li2O
0.7
0.7
1.0
1.0
1.0
2.0
2.0
2.0
0.7


ZnO
0.6
0.6
2.4
1.0
1.0
1.05
2.0
2.0
0.6


As2O3
0.1
0.1
0.1
—
0.1
—
0.1
0.1
0.1


Sb2O3
—
—
—
0.10
—
—
—
—
—


Cl
—
—
—
—
—
0.05
—
—
—


TiO2
—
0.8
—
—
—
—
0.8
—
—


Bi2O3
—
—
1.30
—
0.80
—
0.2
0.7
0.2


MoO3
—
—
—
1.20
—
0.60
—
0.3
—


α20/300 [10−6/K]
4.68
4.73
3.45
3.42
3.77
5.24
5.78
4.97
4.7


Tg [° C.]
485
491
505
515
502
455
449
487
485


VA [° C.]
1055
1053
1078
1190
1062
872
729
999
1050


EW [° C.]
720
715
761
791
751
626
588
690
720


UV-blocking [nm]
<240
261
254
268
250
254
265
251
242

















A8
A9
A10
A11
A12
A13





SiO2
67.95
66.45
67.65
67.95
67.45
67.85


B2O3
19.0
19.0
19.0
19.0
19.0
19.0


Al2O3
2.65
2.65
2.65
2.65
2.65
2.65


Na2O
0.8
0.8
0.8
0.8
0.8
0.8


K2O
7.7
7.7
7.7
7.7
7.7
7.7


MgO
—
—
—
—
—
—


CaO
—
—
—
—
—
—


SrO
—
—
—
—
—
—


BaO
—
—
—
—
—
—


Li2O
0.7
0.7
0.7
0.7
0.65
0.65


ZnO
0.6
0.6
0.6
0.6
0.60
0.60


As2O3
0.1
0.1
0.1
0.1
0.10
0.10


Sb2O3
—
—
—
—
—
—


Cl
—
—
—
—
—
—


TiO2
—
—
—
—
—
—


Bi2O3
—
2.0
0.8
—
—
0.2


MoO3
0.5
—
—
0.8
1.0
0.4


α20/300 [10−6/K]
4.72
4.81
4.8
4.8
4.86
4.73


Tg [° C.]
485
480
487
485
468
485


VA [° C.]
1050
1040
1053
1050
1051
1050


EW [° C.]
720
720
720
720
710
720


UV-blocking [nm]
248
259
248
255
262
251









Comparative Example C1 has a UV edge at too low a wavelength, i.e. it does not sufficiently block the UV region.
The TiO2-containing Comparative Example C2 has a good UV-blocking action, as is also achieved by the doped glasses without the addition of TiO2 in accordance with the invention.
Exemplary embodiments A1, A3, A7, A9 and A20 show glasses doped purely with Bi2O3. A2, A4, A8, A11 and A12 show glasses doped purely with MoO3. A6 and A13 are examples of mixed doping with Bi2O3 and MoO3. A5 reveals the boosting action of the optional component TiO2 or, compared to C2, the improvement in the blocking achieved by the invention without it being necessary to increase the TiO2 content.
The glasses according to the invention have a high resistance to solarization, expressed by Δ15τ (300 nm; 0.2 mm) of <5%, a high transmission in the visible region, expressed by τ (>400 nm; 0.2 mm)≧90% and a good UV-blocking action, in particular expressed by τ (≦240 nm; 0.2 mm)≦0.1% or by the detail giving the highest wavelength at which τ is at most 0.1% (specimen thickness 0.2 mm). This wavelength is 240 nm or more.
In the preferred embodiments, the glasses have a UV transmission at λ≦254 nm of τ≦0.1%.
Furthermore, the glasses have a working point VA of <1200° C., so that they can be worked successfully.
The glasses have transformation temperatures Tg of between 440° C. and 580° C. They are therefore suitable for fusing to Kovar, for which purpose it is preferable to use the glasses with Tg of between 440° C. and 530° C., or to, tungsten, for which purpose it is preferable to use the glasses with a higher Tg.
Furthermore, the glasses have a coefficient of thermal expansion α20/300 of between 3.4×10−6/K and 6.0×10−6/K. They are therefore sufficiently well matched to the thermal expansion of tungsten or Kovar, i.e. can be fused to one of these materials in a vacuum-tight manner.
With these properties and with τ≦0.1% at λ≦254 nm, the glasses are eminently suitable for the production of fluorescent lamps.
The glasses have a high resistance to crystallization. Consequently, the glasses are eminently suitable for tube drawing, in particular including for the drawing of tubes having the small diameters mentioned above. Therefore, the glasses for fluorescent lamps are also exceedingly well suited to the production of miniaturized fluorescent lamps, for example for the background illumination of displays, e.g. of personal computers, laptops, notebooks, palmtops, vehicle navigation systems, scanners, but also of mirrors and pictures.
The fluorescent lamps produced using the glasses according to the invention, in particular miniaturized fluorescent lamps, satisfy the demands imposed on such lamps.

## Claims

1. A borosilicate glass, having a coefficient of thermal expansion α20/300 of between 3.4×10−6/K and 4.86×10−6/K and a composition, in percent by weight based on oxide content of:
















SiO2
55-80



B2O3
 8-25



Al2O3
0.5-10 



Li2O + Na2O + K2O
 1-16



MgO + CaO + SrO + BaO
0-6



ZnO
0.6-3  



Bi2O3
  0-2.0



MoO3
  0-1.20



with Bi2O3 + MoO3
0.01-2.0; 










and which is free of ZrO2.

2. The borosilicate glass as defined in claim 1, containing from 55-79 percent by weight of said SiO2 and from 10-25 percent by weight of said B2O3.

3. The borosilicate glass as defined in claim 1, containing from 73-79 percent by weight of said SiO2, from 12.5-25 percent by weight of said B2O3, and from 1-11 percent by weight of a total amount of said Li2O+Na2O+K2O.

4. The borosilicate glass as defined in claim 1, containing from 55-73 percent by weight of said SiO2, from 15-25 percent by weight of said B2O3, from 1-10 percent by weight of said Al2O3, and from 4-16 percent by weight of a total amount of said Li2O+Na2O+K2O.

5. The borosilicate glass as defined in claim 1, containing from 55-79 percent by weight of said SiO2 and from 8-12.5 percent by weight of said B2O3.

6. The borosilicate glass as defined in claim 1, containing a total amount of said Bi2O3+MoO3 of from 0.1 to 2.0 percent by weight.

7. The borosilicate glass as defined in claim 6 , wherein said total amount of said Bi2O3+MoO3 is from 0.2 to 2.0 percent by weight.

8. The borosilicate glass as defined in claim 1, additionally containing, in percent by weight based on oxide content:
















Fe2O3
0-1



CeO2
0-1



TiO2
0-5



PbO
0-3



As2O3
0-1



Sb2O3
0-1



with Fe2O3 + CeO2 + TiO2 + PbO +
0-5



As2O3 + Sb2O3 + V2O5 + Nb2O5 + WO3



SnO2
0-1



F
0-1



Cl
  0-0.5



SO3
   0- 0.5.

9. The borosilicate glass as defined in claim 1, having a transformation temperature Tg of between 440° C. and 580° C. and having a transmission τ at λ≦240 nm of ≦0.1% for a specimen thickness of 0.2 mm.

10. The borosilicate glass as defined in claim 1, having a transformation temperature Tg of between 440° C. and 580° C. and having a transmission τ at λ≦254 nm of ≦0.1% for a specimen thickness of 0.2 mm.

11. A fluorescent lamp produced from the borosilicate glass as claimed in claim 10.

12. A miniaturized fluorescent lamp produced from the borosilicate glass as claimed in claim 10.