Antimicrobial action of copper in glass

The antimicrobial effect of copper in glass

[0001] Cross reference to related applications

[0002] According to 35U. SC § 119, this application claims priority to the U.S. Provisional Application Serial No. 61/468, 153 filed on March 28, 2011. This application is based on this application and is incorporated by reference in its entirety. this.

[0003] Background of the invention

[0004] Field

[0005] The present invention relates to the production of glass with antimicrobial activity on the surface, and in particular to the production of copper-containing glass surfaces.

The invention also relates to a method for manufacturing the copper-containing glass and its products.

technical background

[0006] There are patents and other published documents on antimicrobial activity, such as the antimicrobial activity of silver in ionic and nanoparticle forms. Although antibacterial activity is desired in different applications for many reasons, there is a clear distinction between antibacterial activity and antiviral activity. The reason for this difference is that the mechanism by which metals such as silver change or kill bacteria may be different from the mechanism by which metals kill viruses. In addition, few mention the antiviral activity of metals other than silver or metal ions. Articles concerning the antiviral activity of copper, copper alloys and copper ions include Inactivation of influenza A virus on copper versus stainless steel surfaces by J. 0. Noyce et al., Appl . Environ. Microbiol Vol. 73 (2007) pages 2748-2750; Cupric and ferric ions inactivate HIV by JL Sagripanti et al. AIDS Res Hum Retroviruses (AIDS Res Hum Retroviruses) Recorded virus) Vol. 12 (1966), pp. 333-337; and Mechanism of copper-mediated inactivation of herpes simplex virus by JL Sagripanti, Antimicrob. Agents Chemother, Vol. 41 (1997), p. Page 12-817. These articles discuss the antiviral properties of copper, and more specifically, discuss Cu⁺²Antiviral activity in solution and metallic copper surface.

[0007] There is a demand for glass with antimicrobial properties in applications such as medical applications where the surface is in contact with the human body.

Summary of the invention

[0008] Embodiments of the present invention relate to glass products incorporating copper ions, metallic copper, and/or colloidal copper (such as copper nanoparticles) in a uniform glass, and a method for preparing the same. The incorporation of copper in the glass product significantly enhances antimicrobial activity, such as antibacterial activity and/or antiviral activity. One advantage of the embodiments described herein is a strong and smooth antiviral glass surface, which can be used in various applications where the antiviral properties are desirable or necessary. The antimicrobial properties are integral to the glass, and are not a coating applied to the surface that will wear or remove. Applications where the anti-viral glass can be used include medicine, health care, laboratory shelves and surfaces, and appliance surfaces where antimicrobial functions will provide benefits.

[0009] One embodiment of the present invention is a copper-containing glass product in which copper is dispersed throughout the glass and the surface of the glass, the copper is selected from: Cu ions, metallic copper, colloidal copper, and combinations thereof; and the glass is antimicrobial nature.

[0010] Another embodiment of the present invention is a method of manufacturing a copper-containing glass article with antimicrobial properties, the

Methods include:

[0011] A batch of batched glass, the glass batch comprising:

[0012] 40-85 Si. ? ;

[0013] 10-40 ofB2O3;

[0014] Α1 of 1T9₂0₃ ；

[0015] 0.1-20 CuO or a selected salt of Cu that can be converted into CuO during the melting process;

[0016] 0-20 Μ?. , Where Μ is Li, Na, K or a combination thereof;

[0017] R0 of 0-25, wherein R is Ca.Sr.Mg or a combination thereof; and

[0018] 0-20 ZnO;

[0019] The batch is melted to form molten glass; and

[0020] The molten glass is shaped to form a copper-containing glass article with antimicrobial properties.

[0021] The additional features and advantages of the present invention are listed in the following detailed description, some of the features and advantages are easy to understand for those skilled in the art from the description, or described by text and its claims And the implementation of the present invention described in the drawings is recognized.

[0022] It should be understood that the foregoing general description and the following detailed description are only examples of the present invention, and are used to provide an overall comment or framework for understanding the nature and characteristics of the claimed invention.

[0023] The included drawings are for further understanding of the present invention, and the drawings are incorporated in and constitute a part of the present invention. The drawings present one or more embodiments of the present invention, and together are used to explain the principle and operation of the present invention.

[0024] Brief Description of the Drawings

[0025] The present invention can be better understood only by the following detailed description or together with the accompanying drawings.

[0026] FIG. 1 is an SEM micrograph of a glass with high-density Cu-nanoparticles on the surface and extending into the glass for a distance of about 5um, according to one embodiment.

Detailed ways

[0027] Hereinafter, reference is made in detail to various embodiments of the present invention, and examples of these embodiments are shown in the accompanying drawings. Whenever possible, the same reference numerals are used in all drawings to denote the same or similar parts.

[0028] The term "antimicrobial" as used herein refers to reagents or materials or surfaces containing reagents or materials that can kill or inhibit the growth of at least two different types of microorganisms (bacteria, viruses, and fungi). The term used herein does not mean that it can kill or inhibit the growth of all microbial species in the family, but can kill or inhibit the growth of one or more microbial species from the family. When "antibacterial", "antiviral" or "antifungal" are used to describe an agent, it means that the agent can kill or inhibit the growth of bacteria, viruses or fungi, respectively.

[0029] The term "logarithmic reduction" or "LR" as used herein means Log (Ca/C.), where C_aIs the number of colony forming units (CFU) on the antimicrobial surface containing Cu nanoparticles, C. Is the number of colony forming units (CFU) on the surface of the control glass without Cu nanoparticles. In other words,

[0030] LR=-Log(C_a/C₀）,

[0031] For example, a log reduction equal to 3 means that 99.9% of bacteria or viruses have been killed, and a log reduction equal to 5 means that T 99.999% of bacteria or viruses have been killed.

[0032] The test method used to determine the antibacterial properties of copper-containing glass is an improved version of the JISZ-2801:2000 method,

This is a Japanese industrial standard established for measuring the antibacterial activity of copper-containing glass. The antibacterial activity is quantitatively determined by measuring the viable bacterial cells, which are in close contact with the surface considered to be antibacterial and incubated at 35°C for 24 hours. The cells are then counted and compared with the untreated surface. The improvement of the test is that the incubation time is changed to 6 hours at 37°C. After 6 hours, the sample was taken out of the incubator, and the entire test surface was thoroughly washed with PBS to ensure that all bacteria were removed. Then transfer the cells and the PBS washing solution to the broth agar plate and incubate overnight. Count the bacterial colonies on the agar plate after 16-24 hours. Add 150 μl of a bacterial suspension with a concentration of 1×10° cells/ml to the sample plate. The sample plate 12 can be a copper-containing glass plate or a control (copper-free) plate, and the plate with the bacterial suspension is covered with Parafilm® Plate, form a plate covered with Parafilm®, then incubate the bacteria at 37°C for 6 hours as shown, and finally count the colonies. The samples are tested using (Gram-negative) E. coli.

[0033] One embodiment of the present invention is a copper-containing glass product in which copper is dispersed throughout the glass and the surface of the glass, the copper is selected from: Cu ions, metallic copper, colloidal copper, and combinations thereof; and the glass is antimicrobial nature. Copper (whether as Cu⁺\Cu⁺\Cu nanoparticles in the reduced state can be located on the surface of the glass, part of the copper can be embedded or partly embedded in the glass, and/or the copper can be in any form that can be dispersed throughout the glass product (including the surface). Products and glass can be phosphorus-free, for example without any deliberately added phosphorus.

[0034] In one embodiment, the copper is in a reduced state; the glass article has antimicrobial properties, such as antiviral and/or antibacterial. In one embodiment, the copper is in a reduced state; the glassware has antiviral properties. In one embodiment, the copper is in a reduced state; the glass article has antibacterial properties. The reduced copper can range from the glass surface to a depth of 2-3um. In one embodiment, in the case of reduced copper, copper nanoparticles are on the surface and extend from the glass surface to a depth range of 2-3 μm. In one embodiment, the copper adheres firmly and strongly to the surface, that is, the copper on the surface cannot be removed by wiping or cleaning. The log reduction of the product can be 2 1, such as 2 2, such as 2 3, such as 2 4.

[0035] In one embodiment, the glass has antibacterial properties. The logarithmic reduction of the product can be 2 1, such as 2 2, for example

3, for example 2 4o

[0036] The glass may be strengthened glass, such as ion-exchanged glass.

[0037] The glass as a batch may contain 0.1-20 mol% of copper, such as 1-16 mol%, such as 5-16 mol%, such as 5-15 mol%.

[0038] In one embodiment, the glass as a batch is basically composed of the following components: 47±2 mol% Si0₂, 9 + 1-1. 5 mol% of Α1₂0₃, 27 + 3 mol% of B₂0₃, 7-16 + 1.5 mol% of ZnO, as the copper content increases, Cu is 0.5-10 + 0. 2-1. 5 mol%o

[0039] The glass as an ingredient may contain 10-40 mol% of B₂0₃o The glass used as the ingredient can contain B greater than 1₂O₃/A1₂O₃The proportion, such as greater than 2, such as greater than 3o. In one embodiment, the glass as a batch contains: [0040] 40-85 mol% Si0₂ ；

[0041] 10-40 mol% of B₂0₃ ；

[0042] 1-19 mol% of A1₂0₃ ；

[0043] 0.1-20 mol% of CuO;

[0044] 0-20 mol%]^0, where Μ is Li, Na, K or a combination thereof;

[0045] 0-25 mol% R0, where R is Ca, Sr, Mg or a combination thereof; and

[0046] 0-20 mol% of ZnO.

[0047] The glass as an ingredient may not contain phosphorus.

[0048] In one embodiment, the glass as an ingredient contains:

[0049] 40-70 Si0₂；

[0050] 16-31 of B₂0₃；

[0051] Α1 of 3T5₂0₃；

[0052] CuO of 5T5;

[0053] 0-20 Μ?. , Where Μ is Li, Na, K or a combination thereof;

[0054] R0 of 0-25, wherein R is Ca, Sr, Mg or a combination thereof; and

[0055] 0-17Zn0o

[0056] Another embodiment of the present invention is a method of manufacturing a copper-containing glass article with antimicrobial properties, the method comprising:

[0057] A batch of batched glass, the glass batch comprising:

[0058] 40-85 Si0₂ ；

[0059] 10-40 of B₂0₃ ；

[0060] Α1 of 1-19₂0₃ ；

[0061] 0.1-20 CuO or a selected salt of Cu that can be converted to CuO during the melting process;

[0062] 0-20 Μ?. , Where Μ is Li, Na, K or a combination thereof;

[0063] R0 of 0-25, wherein R is Ca, Sr, Mg or a combination thereof; and

[0064] 0-20 ZnO;

[0065] The batch material is melted to form molten glass; and

[0066] The molten glass is shaped to form a copper-containing glass article with antimicrobial properties.

[0067] According to one embodiment, the method further includes heating the product in a reducing atmosphere at an elevated temperature of 250°C to 475°C, so that the copper ion Cu, which is an oxide or other substance in the glass, is heated⁺²Reduce to metal Cu°_oThe heating may include heating the article for a period of 1-5 hours, for example, 2-5 hours. In one embodiment, the reducing atmosphere includes hydrogen.

[0068] The method may also include strengthening the article after forming. In one embodiment, the strengthening includes exchanging alkali metal ions in the article with alkali metal ions of larger ionic radius.

[0069] Exemplary glass compositions can achieve the incorporation of high concentrations of copper oxide in a uniform glass batch that is easy to form. Examples 1-9 in Table 1 are exemplary glass batches (unit: mol%), excluding all possible compositions across a certain glass category, such as borate glass, aluminoborosilicate glass, and alkaline aluminum boron Silicate glass, soda lime glass. 5-16mol%. As shown in Table 1, the copper in the glass as a batch is determined to be an oxide, and the range is 0.5-16 mol%. The composition in Table 1 is the composition of the ingredients. The composition as described in Table 1 may have, for example: Si. ?For a fluctuation of ±2 mol%, for B2O3, a fluctuation of ±3 mol%, for A1₂0₃In terms of fluctuations of soil 1-1. 5 mol%, ZnO has basically the same activity.

[0070]

<td>example</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td>

<td>Si0₂</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td>

<td>ai₂o₃</td><td>9</td><td>9</td><td>9</td><td>9</td><td>9</td><td>9</td><td>9</td><td>9</td><td>9</td>

<td>S. 3</td><td>27</td><td>27</td><td>27</td><td>27</td><td>27</td><td>27</td><td>27</td><td>27</td><td>27</td>

<td>CuO</td><td>10</td><td>5</td><td>1</td><td>0. 5</td><td>10</td><td>12</td><td>14</td><td>16</td><td>7. 5</td>

<td>ZnO</td><td>7</td><td>12</td><td>16</td><td>16. 5</td><td>7</td><td>5</td><td>3</td><td>1</td><td>9. 5</td>

[0071] Table 1

[0072] After the batch material is melted, it may be employed a conventional glass forming methods such as, but not limited to, the slits pull system, fusion drawing and / or formed float glass. The glass product can be a plate, and in some embodiments, the thickness ranges from 0.3 to 5 mni, and the length and width can be changed. In other embodiments, the glass product can be of any shape, such as an equiangular curved surface or a tube, and in some embodiments, the thickness ranges from 0.3 to 5 μm, and the length and width can be changed. Once the glass product is formed, it can be cut into individual products and processed further, or the entire sheet can be processed further and then cut into products. In either case, the further treatment of the freshly produced copper-containing glass includes treating the glass in a hydrogen atmosphere at a temperature of 450°C for 5 hours, and removing the Cu in the glass.⁺¹And/or Cu⁺²Reduce to Cu°. This process produces high-density metal copper nanoparticles on the surface of the glass, and extends into the glass for example by 5 μm, as shown in the SEM micrograph of FIG. 1. In Figure 1, the glass surface is to the right. The bright pattern represents copper nanoparticles.

[0073] Containing B₂0₃The glass has a tendency to phase separate into a borate-rich phase and a borate-poor phase. Cu may enter the borate-enriched phase, thereby making the Cu concentration locally enriched, which may be beneficial. Join Α1₂0₃Suppresses the tendency of phase separation. Zn also plays the same role. Tables 2 and 3 below show the range of composition (B, A1, Zη).

[0074] Table 2 shows 1% CuO, and A1₂O₃/B₂O₃Exemplary glass batch material changed with SrO, Examples 10-15 (unit: mol%) o

[0075]

<td>example</td><td>10</td><td>11</td><td>12</td><td>13</td><td>14</td><td>15</td>

<td>Si0₂</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td>

<td>Α]2°3</td><td>9</td><td>11</td><td>13</td><td>15</td><td>9</td><td>9</td>

<td>S. 3</td><td>27</td><td>25</td><td>23</td><td>21</td><td>27</td><td>27</td>

<td>CuO</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td><td>1</td>

<td>ZnO</td><td>16</td><td>16</td><td>16</td><td>16</td><td>7</td><td>0</td>

<td>SrO</td><td>0</td><td>0</td><td>0</td><td>0</td><td>9</td><td>16</td>

[0076] Table 2

[0077] Table 3 shows CuO with 5%, and A1₂O₃/B₂O₃Exemplary glass batch with SrO and SrO changed, examples 16-21 (unit: mol%) o

[0078]

<td>example</td><td>16</td><td>17</td><td>18</td><td>19</td><td>20</td><td>21</td>

<td>Si0₂</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td><td>47</td>

<td>People]_2. 3</td><td>9</td><td>11</td><td>13</td><td>15</td><td>9</td><td>9</td>

<td>S. 3</td><td>27</td><td>25</td><td>23</td><td>21</td><td>27</td><td>27</td>

<td>CuO</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td>

<td>ZnO</td><td>12</td><td>12</td><td>12</td><td>12</td><td>6</td><td>0</td>

<td>SrO</td><td>0</td><td>0</td><td>0</td><td>0</td><td>9</td><td>16</td>

[0079] Table 3

[0080] Antibacterial Test

[0081] Use cultured Gram-stain negative Escherichia coli: DH5α-Invitrogen catalog number 18258012, batch number 7672225, which is resistant to kanamycin by PucI9 (Invitrogen) plasmid transformation. Use LB Kan broth (Teknova #L8145) or Typtic soybean broth (Teknova #T1550) to start bacterial culture. Streak about 2 μl of liquid bacterial suspension or a pipette head full of bacteria on the agar plate, and divide it into capped test tubes containing 2-3 ml of broth, and incubate overnight in a shaking incubator at 37°C. The next day the bacterial culture was removed from the incubator and washed twice with PBS. Determine the optical density (0D), dilute the cell culture to about lxlO⁶Final bacterial concentration in CFU/ml. Place the cells on a selected (antimicrobial or non-antimicrobial (control)) glass surface for 6 hours at 37°C. The buffer in each well was collected, and the plate was washed twice with frozen PBS. Mix the buffer and washing solution of each well, and use the surface diffusion plate method to count the colonies.

[0082] Anti-virus test

[0083] The antiviral test process was carried out using the modified protocol previously described by A. Klibanov et al. (Nature Protocols (2007)). Simply put, dilute adenovirus type 5 to about 10 in phosphate buffered saline (PBS)⁶PFU/mLo apply adenovirus solution (10uL) to the coverslip for 2 hours at room temperature. The virus comes into contact with the coverslip and is then collected by thorough washing with PBS. Then use sterile PBS to dilute the virus-containing washing suspension by 2 times, and use 50 μL of the dilution to infect the HeLa cells, and grow them as a monolayer in a 96-well microplate. Two days later, the virus titer was calculated by counting the infected HeLa cells. As described above (recommended standard test method for disinfectant efficacy on inanimate non-food contact surfaces, EI 153-03, 2010 again Approved) Calculate virus titer reduction. The reduction in% is equal to: [0084] [(Virus survival number on the glass control sample)-(Virus survival number on the sample glass)] Virus survival number on the Ning glass control sample

[0085] Exemplary glasses 1, 2, 6, and 9 of Table 1 were treated with hydrogen at 450° C. for 5 hours and tested with Escherichia coli. JIS

The antibacterial results tested by Z2801 are shown in Table 4 below.

[0086]

<td>example</td><td>CuO</td><td>Log reduction</td>

<td>2</td><td>5%</td><td>log 5</td>

<td>9</td><td>7.50%</td><td>log 4</td>

<td>1</td><td>10%</td><td>log 5</td>

<td>6</td><td>12%</td><td>log5</td>

[0087] Table 4

[0088] Exemplary glasses 2, 5, 6, and 7 of Table 1 were treated with hydrogen at 450° C. for 5 hours and tested with adenovirus. Exemplary glasses 2, 5, 6, and 7 show a log reduction of adenovirus greater than or equal to 5.

[0089] As mentioned above, the exemplary glass used as ingredients 1 and 2 in Table 1 has obvious antibacterial behavior and also has very effective antiviral activity. Compared with the glass control, the virus titer after 2 hours of exposure The reduction reaches 100% (4.5 log reduction). Interestingly, for the same glass that has not been subjected to reducing conditions and Cu exists in the form of ions, the sample does not show significant antiviral activity. However, these same glasses show antiviral activity. These results indicate that the high concentration of nano-sized metallic copper particles on the glass surface is responsible for the strong antiviral activity. In addition, these results suggest that these Cu glass samples have different modes of action when fighting bacteria and viruses. The "killing" mechanism for viruses and bacteria is different.

[0090] Table 5 shows an exemplary glass batch (unit, mol%), Examples 22-27, with CuO added Pyrex® (aluminoborosilicate glass), the basic glass level is 0.25,0.5, 1, 2.5 and 5 mol%.

[0091]

<td>example</td><td>22</td><td>23</td><td>24</td><td>25</td><td>26</td><td>27</td>

<td>Si0₂</td><td>83.27</td><td>83. 27</td><td>83. 27</td><td>83. 27</td><td>83.27</td><td>83. 27</td>

<td>A12O3</td><td>1. 21</td><td>1.21</td><td>1. 21</td><td>1.21</td><td>1. 21</td><td>1.21</td>

<td>S. 3</td><td>11. 53</td><td>11. 53</td><td>11. 53</td><td>11. 53</td><td>11. 53</td><td>11. 53</td>

<td>Na₂0</td><td>3. 99</td><td>3. 99</td><td>3. 99</td><td>3. 99</td><td>3. 99</td><td>3. 99</td>

<td>CuO</td><td>0</td><td>0. 25</td><td>0. 5</td><td>1</td><td>2. 5</td><td>5. 0</td>

<td>R-value</td><td>0. 24</td><td>0. 24</td><td>0. 24</td><td>0. 24</td><td>0. 24</td><td>0. 24</td>

[0092] Table 5

[0093] The exemplary glass was subjected to hydrogen treatment at 450° C. for 5 hours. The antibacterial JIS Z2801 test was performed on exemplary glasses 24 and 27 using Escherichia coli, and the exemplary glasses 24 and 27 had a log reduction greater than one. The log reduction of the exemplary glass 27 is greater than 1.5. Similar results were obtained on unreduced glass.

[0094] Table 6 shows an exemplary glass batch (unit, mol%), Examples 28-33, with the addition of Vycor® (aluminoborosilicate glass batch) of CuO, the level is 0.25,0.5, 1, 2.5 and 5 mol%.

[0095]

<td>example</td><td>28</td><td>29</td><td>30</td><td>31</td><td>32</td><td>33</td>

<td>Si0₂</td><td>64. 39</td><td>64. 39</td><td>64. 39</td><td>64. 39</td><td>64. 39</td><td>64. 39</td>

<td>A12O3</td><td>1. 55</td><td>1. 55</td><td>1. 55</td><td>1. 55</td><td>1. 55</td><td>1. 55</td>

<td>S. 3</td><td>26. 34</td><td>26. 34</td><td>26. 34</td><td>26. 34</td><td>26. 34</td><td>26. 34</td>

<td>Na₂0</td><td>7. 72</td><td>7. 72</td><td>7. 72</td><td>7. 72</td><td>7. 72</td><td>7. 72</td>

<td>CuO</td><td>0</td><td>0. 25</td><td>0. 5</td><td>1</td><td>2. 5</td><td>5</td>

<td>R-value</td><td>0. 23</td><td>0. 23</td><td>0. 23</td><td>0. 23</td><td>0. 23</td><td>0. 23</td>

[0096] Table 6

[0097] Exemplary glasses 29, 30, and 31 were treated with hydrogen at 450° C. for 5 hours, and the antibacterial test was performed with Escherichia coli using JIS Z2801 test. Exemplary glass 29 has a log reduction of 2.3-5, exemplary glass 30 has a log reduction of 5, and exemplary glass 31 has a log reduction of 3.5. The unreduced glass has similar results.

[0098] Exemplary glass 29 is treated with hydrogen at 450° C. for 1 or 2 hours. In the antiviral test with adenovirus, the log reduction is about 2o

[0099] Table 7 shows exemplary glass batch materials (units, mol%), Examples 34-39, with the addition of borosilicate glass batch materials

The levels of CuO are shown in Table 7.

[0100]

<td>example</td><td>34</td><td>35</td><td>36</td><td>37</td><td>38</td><td>39</td>

<td>Si0₂</td><td>71. 94</td><td>71. 97</td><td>71. 61</td><td>71. 36</td><td>71. 33</td><td>70. 87</td>

<td>A12O3</td><td>0</td><td>0</td><td>3. 3</td><td>5. 47</td><td>5. 61</td><td>7. 79</td>

<td>S. 3</td><td>25. 1</td><td>25. 06</td><td>22. 15</td><td>20. 22</td><td>20. 1</td><td>18. 55</td>

<td>Li₂0</td><td>2. 54</td><td>2. 55</td><td>2. 52</td><td>2. 52</td><td>2. 54</td><td>2. 52</td>

<td>κ₂ο</td><td>0. 42</td><td>0. 42</td><td>0. 42</td><td>0. 42</td><td>0. 42</td><td>0. 42</td>

<td>CuO</td><td>5. 85</td><td>8. 65</td><td>5. 82</td><td>5. 81</td><td>8. 56</td><td>8. 51</td>

<td>R-value</td><td>0. 12</td><td>0. 12</td><td>-0. 02</td><td>-0. 13</td><td>-0. 13</td><td>-0. 26</td>

[0101] Table 7

[0102] Exemplary glass 39 was treated with hydrogen at 450° C. for 5 hours, and an antibacterial test was performed with Escherichia coli. In the JIS Z2801 test result, the logarithm of the exemplary glass 39 is reduced to 5.

[0103] Exemplary glass 36 is treated with hydrogen at 450° C. for 5 hours, and the logarithm of the adenovirus antiviral test is reduced to 5.

[0104] Table 8 shows exemplary glass batches (units, mol%), Examples 40-45, with the addition of aluminoborosilicate glass batches

The levels of CuO are shown in Table 8.

[0105]

<td>example</td><td>40</td><td>41</td><td>42</td><td>43</td><td>44</td><td>45</td>

<td>Si0₂</td><td>63. 8</td><td>63. 8</td><td>63. 8</td><td>63. 8</td><td>63. 8</td><td>63. 8</td>

<td>S. 3</td><td>17. 2</td><td>17. 2</td><td>17. 2</td><td>17. 2</td><td>17. 2</td><td>17. 2</td>

[0106]

<td>AI2O3</td><td>6. 1</td><td>6. 1</td><td>6. 1</td><td>6. 1</td><td>6. 1</td><td>6. 1</td>

<td>Na₂0</td><td>1. 8</td><td>1. 8</td><td>1. 8</td><td>1. 8</td><td>1. 8</td><td>1. 8</td>

<td>Li₂0</td><td>4. 16</td><td>4. 16</td><td>4. 16</td><td>4. 16</td><td>4. 16</td><td>4. 16</td>

<td>κ₂ο</td><td>6. 81</td><td>6. 81</td><td>6. 81</td><td>6. 81</td><td>6. 81</td><td>6. 81</td>

<td>CuO</td><td>0</td><td>0. 5</td><td>1</td><td>2. 5</td><td>5</td><td>7. 5</td>

<td>SnO₂</td><td>0. 01</td><td>0. 01</td><td>0. 01</td><td>0. 01</td><td>0. 01</td><td>0. 01</td>

<td>R-value</td><td>0. 39</td><td></td><td></td><td></td><td></td><td></td>

<td>annealing</td><td>485C</td><td></td><td></td><td></td><td></td><td></td>

[0107] Table 8

[0108] Exemplary glass 45 was treated with hydrogen at 450° C. for 5 hours, and an antibacterial test was performed with Escherichia coli. In the test, the logarithm of the exemplary glass 45 was reduced to 5. Unreduced glass 45 has similar results.

[0109] The exemplary glass 45 was tested against virus with adenovirus, and the logarithm was reduced to 2.

[0110] Table 9 shows the antiviral test results of exemplary glasses 2, 6, 7, 33, 36, and 45. Exemplary glasses 7, 2, 6, 36, and 33 have extremely strong and broad antiviral activity. In addition, Exemplary Glass 2 killed 5 logs of HSVo very quickly (5 minutes)

[0111]

<td>Example number</td><td>Mol%. !!!</td><td colspan="2">Antiviral activity (fang</td><td colspan="2">Number reduction/time)</td>

<td></td><td></td><td>Adenovirus</td><td>HIV-1</td><td>Influenza A</td><td>HSV</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>45</td><td>7.5</td><td>2/2 hours</td><td>1.5/1 hour</td><td>NT</td><td>NT</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>7</td><td>3</td><td>5/2 hours</td><td>NT</td><td>TBD</td><td>3.8/1 hour</td>

<td>2</td><td>5</td><td>5/2 hours</td><td>5.32/1 hour</td><td>TBD</td><td>5/5 minutes</td>

<td>6</td><td>10 Or 12</td><td>5/2 hours</td><td>3.92/1 hour</td><td>2.5/30 minutes</td><td>5/1 hour</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>36</td><td>5.8</td><td>5/2 hours</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>33</td><td>5</td><td>4.3/2 hours</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

[0112] Table 9

[0113] In one embodiment, the R-value of the glass used as the ingredient is less than the R-value in the borosilicate glass. The effect is that it can affect the antimicrobial behavior and the ability to precipitate copper nanoparticles in the glass volume. The precipitation on the erased surface is different. The R-value provides an indication of the amount of NBO (non-bridging oxygen) in the glass structure.

[0114] The R-value is defined as the ratio of (total alkali metal-alumina)/boron oxide, molar or cation percentage. It has no meaning in the absence of alkaline oxides.

[0115] The R-value is included where appropriate in the above table. High positive R-values, especially greater than or equal to about 1, seem undesirable.

[0116] Although typical implementations are presented for illustration, the foregoing description should not be considered as limiting the scope of the present or appended claims. Therefore, those skilled in the art can make various changes, modifications and substitutions without departing from the spirit and scope of this or the appended claims.