Methods for eradicating pathogens

Abstract

To provide methods for eradication of pathogens, especially methods for eradicating bacteria in confined spaces.SOLUTION: The present invention discloses methods for eradication of pathogens, comprising the use of germicidal UV light at a wavelength of 220 nm, wherein the UV light is emitted by a UV lamp having a lamp cover made of 220 nm-UV-transparent glass; 220 nm-UV-transparent glass; use of such UV-transparent glass; as well as methods for making the same.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for eradicating pathogens, particularly a method for eradicating bacteria in a limited space. The method includes using germicidal UV light at a wavelength of 220 nm, which is emitted by a UV lamp having a lamp cover made of 220 nm UV-transmissive glass. The present invention includes 220 nm UV-transmissive glass, the use of such UV-transmissive glass, and a method for manufacturing the same.

Background Art

[0002] The most relevant pathogens are bacteria and viruses. Pathogens constantly pose a threat to humans and livestock. To remove pathogens, many methods have been developed, including removal using light. The current pandemic of SARS-CoV2 has increased the need for effective and specific means for removing pathogens, particularly viruses.

[0003] Pathogens can be a major problem in hospitals, prisons, and nursing homes, where people with open wounds, those with invasive devices such as catheters, and those with a weakened immune system are at high risk of infection. Regular disinfection and antibiotics / antiviral agents are possible means to address these threats. However, disinfectants can be very aggressive and may cause irritating fumes, which can themselves be harmful or reduce the desire to use these agents effectively, particularly in limited spaces. Antibiotics / antiviral agents can confer resistance to pathogens and may render the agents almost ineffective.

[0004] Therefore, there is a great need for an easy-to-use and effective method for eradicating pathogens, particularly bacteria and viruses, in limited spaces such as hospitals, schools, and nursing homes.

[0005] Methods of eradicating pathogens using light have been reported in the field. So-called "photosensitization" is widely used in hospitals and other areas with high pathogen risk (or other bacterial contamination). This method uses photosensitizers, usually dye molecules, that are excited when exposed to light. Upon light excitation, these molecules generate reactive oxygen species, which then eradicate the pathogens.

[0006] However, not all reported methods using photosensitizers are sufficient to eradicate microorganisms effectively and prevent infection. This is because the photosensitizers may not be sufficiently concentrated to cause significant damage. Furthermore, many photosensitizers are hydrophobic, which makes it difficult to disperse them in aquatic environments where microorganisms typically reside (e.g., biofilms).

[0007] Another method in this field is called "ultraviolet germicidal irradiation" (UVGI), which uses short-wavelength ultraviolet (UVC) light to kill or inactivate microorganisms by destroying nucleic acids and their DNA, preventing them from performing living cellular functions. UVGI is used in a variety of applications, such as food, air, and water purification.

[0008] UVGI devices generate sufficiently strong UVC light in circulating air or water systems, creating an environment unsuitable for microorganisms such as bacteria, viruses, fungi, and other pathogens. UVGI can be combined with filtration systems to sanitize air and water. The application of UVGI for sterilization has been a practice since the mid-20th century. It has primarily been used in medical hygiene and sterilization facilities.

[0009] It is increasingly used to sterilize drinking water and wastewater because the facilities holding it are enclosed and it can be circulated to ensure higher exposure to UV. In recent years, UVGI has found new applications in air purifiers.

[0010] However, conventional germicidal UV lamps are harmful to the eyes, cause pre-mutagenic UV-related DNA lesions in human skin, and have been reported to be cytotoxic to the skin of exposed mammals.

[0011] Therefore, the direct use of conventional UVGI methods for the eradication of pathogens in mammalian skin, such as the skin of patients, healthcare workers, or livestock, is discouraged due to the risk of damaging effects, including the induction of cancer or other mutagenic diseases.

[0012] Recently, it has been reported that far-UVC light efficiently kills bacteria despite their drug-resistant capabilities, without the skin or eye damage associated with conventional germicidal UV exposure.

[0013] However, UV absorption of UV light at wavelengths of approximately 200 nm to 250 nm is very high in otherwise transparent covers. For example, UV light does not transmit well through conventional glass at wavelengths above 320 nm. Conventional glass does not transmit light at wavelengths below 290 nm. Therefore, these covers have the disadvantage of either being unsuitable for far-UV light or requiring at least a large amount of energy to ensure sufficient UV exposure of the surface being treated, such as the skin being treated. [Overview of the project] [Means for solving the problem]

[0014] In one embodiment, the present invention relates to a method for eradicating a pathogen, comprising exposing the pathogen to bactericidal UV light at a wavelength of 222 nm, wherein the UV light is irradiated by a UV lamp having a glass lamp cover, the glass having a transmittance of at least 30% at a wavelength of 220 nm and less than 4% at a wavelength of 200 nm. Optionally, the ozone concentration in the room in which the method is performed is 0.12 mg / m³. 3 It can be less than [amount].

[0015] The lamp cover, placed between the light source and the irradiated space, has the minimum transmittance for UV light at 220 nm, ensuring that sufficient intensity of 220 nm UV light reaches the space to be treated. At 220 nm, many pathogens are particularly vulnerable to light irradiation, while human eyes and skin are less sensitive. Furthermore, the light transmittance of the lamp cover is very low at 200 nm. The decrease in light intensity at approximately 200 nm limits the rate of photodegradation caused by UV irradiation. Photodegradation leads to ozone formation. Ozone can be found at a concentration of 0.12 mg / m³ in confined spaces, such as homes and offices. 3 If present at concentrations exceeding a certain level, it can become problematic. The method disclosed herein reduces ozone formation while protecting the complete eradication of the pathogen.

[0016] In another embodiment, the present invention relates to a method for eradicating a pathogen, comprising exposing the pathogen to bactericidal UV light at a wavelength of 220 nm, wherein the UV light is irradiated by a UV lamp having a glass lamp cover, the glass having a total platinum content of less than 3.5 ppm.

[0017] UV radiation can break down organic bonds, thus becoming hostile to life by destroying biomaterials. Furthermore, many plastics are damaged by UV radiation, resulting in clouding, embrittlement, and / or disintegration. At lower wavelengths, UV light causes photodegradation, which leads to an increase in ozone concentration in the surrounding air.

[0018] In humans, excessive exposure to UV radiation can cause acute and chronic adverse effects on the refractive system and retina of the eye. The skin, circadian system, and immune system can also be affected. The skin and eyes are most sensitive to damage from UV radiation in the 265-275 nm range.

[0019] Therefore, the wavelengths applied by the method of the present invention include 220 nm. Ultraviolet (UV) light at approximately 220 nm has antimicrobial properties similar to typical germicidal UV light (254 nm), but does not cause damage to the outer tissues covering the skin of higher animals, such as amphibians, reptiles, birds, mammals, or humans.

[0020] Compared to 254 nm light, the limited transmission distance of 220 nm light in biological samples (e.g., the stratum corneum) allows for selective antimicrobial treatment without harming mammalian or human skin, such as the skin of a patient or healthcare worker.

[0021] Considering the eyes, the most important target from the perspective of UV risk is the lens. The lens is located distal to the cornea and is thick enough (500 μm) to minimize the transmission of 220 nm light through the cornea to the lens. Even considering the impact on the cornea from the perspective of photokeratitis, any protective equipment against eye splashes that is now almost universal among surgical staff is expected to be sufficient to protect the cornea from 220 nm UV exposure.

[0022] At the cellular level, bacteria are far smaller than almost any human cell. Typical bacterial cells are less than 1 μm in diameter, while typical eukaryotic cells range from approximately 10 to 25 μm in diameter. 220 nm UV light can penetrate throughout a typical bacterial cell, but it cannot penetrate significantly beyond the periphery of the cytoplasm of a typical eukaryotic cell, such as a human cell, and is dramatically attenuated before reaching the nucleus.

[0023] In contrast, higher wavelengths from conventional germicidal lamps can reach human cell nuclei with little attenuation. Based on these biophysical considerations, radiation from conventional UVC lamps is cytotoxic and mutagenic to both bacterial and human cells, while 220nm UV light is cytotoxic to bacteria but less cytotoxic or mutagenic to human cells.

[0024] However, UV light with wavelengths below 200 nm is not useful because sufficient eradication of pathogens can no longer be achieved at those wavelengths. Furthermore, at wavelengths below 200 nm, UV reacts with oxygen to form ozone, and this effect is undesirable.

[0025] UVC light at approximately 222 nm effectively eradicates pathogens despite their drug resistance capabilities, without the skin and eye damage associated with conventional germicidal UV exposure.

[0026] In this application, the term “eradication” is used in accordance with ISO 22196:2011-08-31 to refer to a reduction of more than 90%, more than 95%, more than 99%, more than 99.9%, or more than 99.99% of the pathogen after treatment.

[0027] To achieve such eradication, in one embodiment, the present invention provides a UV exposure of the pathogen and / or the surface to be treated to 2,000-8,000 μW·s / cm². 2 2,100~7,000 μW·s / cm 2 2,200~5,000 μW·s / cm 2 , or 2,300~3,000 μW·s / cm 2 This relates to a method within the range of at least about 2,500 μW·s / cm². In one embodiment, 2 UV exposure results in a 90% reduction in at least one pathogen.

[0028] The method of the present invention can be used to eradicate pathogens in confined spaces, such as homes, hospitals, schools, or nursing homes. Because ozone generation is reduced and the potential harm to human health is limited, this method is ideal for periodic or even continuous use. Optionally, the method can be used to remove pathogens from UV-sensitive materials, such as UV-sensitive surfaces.

[0029] In one embodiment, the UV-sensitive material may be susceptible to crosslinking of monomers that produce a specific polymer upon UV irradiation above 250 nm and / or up to 295 nm. In yet another embodiment, the UV-sensitive material may be a gas or liquid that is sensitive to UV above 250 nm and / or up to 295 nm.

[0030] In yet another embodiment, the UV-sensitive material may be a pharmaceutical composition sensitive to UV wavelengths above 250 nm and / or up to 295 nm.

[0031] In one embodiment, the UV-sensitive material may be the surface of a living tissue, such as the skin of an insect, invertebrate, vertebrate, mammal, or human (e.g., mollusks, fish, amphibians, reptiles, birds, mammals and / or humans), or an arthropod, such as a chitinous exoskeleton from a lobster or insect.

[0032] Accordingly, the term "biological tissue surface" as defined in this invention encompasses all biological surfaces that may be damaged by UV radiation above 250 nm and / or up to 295 nm. In one embodiment, the invention includes biological surfaces that may be damaged by UV radiation outside the wavelength range of 207-220 nm and are not damaged by UV radiation at a wavelength of approximately 220 nm.

[0033] In this invention, the term "tissue" is used to refer to any cellular tissue level between a cell and a complete organ. A tissue is a collection of similar cells and their extracellular matrices from the same origin that together perform specific functions. In this case, an organ is formed by functionally grouping multiple tissues together.

[0034] Naturally, tissues that may be exposed to UV radiation, especially during pathogen eradication methods, should be included. In most cases, these tissues are epithelial tissues, formed by cells that cover the surface of organs, such as the surface of the skin, the respiratory tract, the reproductive organs, and the inner surfaces of the digestive tract. Since the cells containing the epithelial layer are bound together through semipermeable, dense junctions, this tissue provides a barrier between the external environment and the organ it covers. In addition to this protective function, epithelial tissues may also be specialized to function in secretion, excretion, and absorption. Epithelial tissues help protect organs from microorganisms, injuries, and fluid loss.

[0035] Accordingly, the present invention includes methods for UV treatment of pathogens present on surfaces that are sensitive to UV, such as skin tissue, or on areas where eye exposure to UV is unavoidable, in which conventional UVGI methods are not applicable or suitable.

[0036] The term "mammal" in this application refers to any vertebrate that constitutes the classification of the class Mammalia and is characterized in females by the presence of mammary glands that produce milk for nourishing (nurturing) the offspring, a neocortex (region of the brain), fur or hair, and three middle ear bones. These features distinguish them from reptiles and birds, which diverged in the Late Triassic period, 201 to 227 million years ago. There are approximately 5,450 species of mammals. The largest orders are rodents, chiroptera, and soricomorpha (shrews, etc.). The next three are primates (apes, monkeys, etc.), cetartiodactyla (whales and artiodactyla), and carnivora (cats, dogs, seals, etc.). This definition of mammal also includes humans.

[0037] Therefore, the term “mammalian skin” refers to all skin of mammals, including the skin of livestock, while the term “livestock” is generally defined as domesticated animals, such as cattle, goats, horses, pigs, and sheep, that are raised in agricultural settings to provide labor and goods, such as meat, eggs, milk, fur, hides, and wool.

[0038] Furthermore, the term "mammalian skin" also includes the skin of humans, such as patients, healthcare workers, people with weakened or absent immune systems (elderly, children, post-surgery, post-organ transplant, HIV-positive, etc.), and people who are at high risk of exposure to pathogens.

[0039] Prior art UV lamp covers are made of sapphire, synthetic quartz, or quartz glass (fused silica glass). However, sapphire is extremely expensive compared to other transparent materials and cannot be bent, molded, drawn, or melted like glass or metal. Furthermore, it has very high UV absorption at UVC wavelengths and transmits almost no UV light below 250 nm.

[0040] In one embodiment, the glass has a transmittance of at least 30%, at least 35%, at least 40%, or at least 60% at 220 nm (measured at a thickness of 0.71 mm), and / or at least 75% at wavelengths [λ] 260 nm, 280 nm, and / or 310 nm.

[0041] Quartz and fused silica glass have high manufacturing costs due to their high melting points, because the temperatures and labor required for melting and molding are far higher than those for other types of glass. Furthermore, any form other than tubes or sheets must be ground and polished from blocks or ingots. In addition to manufacturing costs, their covers have the disadvantage of requiring a large amount of energy to ensure sufficient UV exposure of the object, gas, or liquid being processed.

[0042] However, the glass disclosed herein is suitable for forming rods, tubes, sheets and bars and is manufactured by casting, Danner, Bellow, redraw and / or downdraw methods.

[0043] The glass of the present invention can have excellent optical properties. In one embodiment, the glass has a refractive index n d(λ=587.6nm) It has a refractive index of 1.48 to 1.58. The refractive index may be 1.50 or higher.

[0044] The glass described herein has excellent UV transmittance at wavelengths significantly above 200 nm. The glass has one or more of the following optical properties: • UV transmittance at 200nm is less than 4.0%, and in one embodiment, less than 3.0%. • UV transmittance at 220nm: at least 20%, in one embodiment at least 30%, at least 40%, at least 50%, or at least 60%. • UV transmittance at 240nm: at least 45%, in one embodiment at least 50%, at least 60%, or at least 70%. • UV transmittance at 260nm: at least 65%, at least 70% in one embodiment, or at least 80%, and / or • UV transmittance at 280nm is at least 72.5%, and in one embodiment at least 85%.

[0045] In one embodiment, the glass has a UV transmittance of at least 40% at 220 nm (measured at a thickness d = 0.71 mm).

[0046] Throughout this disclosure, unless otherwise specified, references to transmittance relate to transmittance at a reference thickness of 0.71 mm. This does not mean that glass, glass articles, or lamp covers have this specific thickness. The aforementioned thickness serves as a reference for determining transmittance. Transmittance can be measured at various thicknesses, and the results can be used to calculate the transmittance value at 0.71 mm.

[0047] Preferably, the glass and / or glass articles have a transmittance of at least 50%, preferably at least 70%, at least 80%, or at least 83% at a wavelength of 254 nm. In one embodiment, the transmittance at 254 nm is up to 99.9%, up to 95%, or up to 90%.

[0048] For purposes of clarification, indicating that the transmittance is measured at a specific wavelength does not mean that the glass is limited to the indicated thickness. Instead, the thickness indicates that the transmittance can be measured at that thickness. By indicating the thickness for the measurement, the values can be reliably compared. One of ordinary skill in the art will understand that any suitable glass thickness can be used in the glass covers and devices described below.

[0049] The present invention uses and relates to glass and glass covers (lamp covers, LED cover glass) that reduce operating energy, lower the operating temperature, and limit photodegradation by exhibiting low UV absorption (i.e., high UVC transmittance) up to a specific wavelength and lower transmittance at lower wavelengths. Further, the glass and cover glass of the present invention are relatively inexpensive and easy to manufacture, can be bent, molded, drawn, melted / fused to ensure a variety of shapes, and are resistant to most chemicals as well as temperature and physics thermal stress.

[0050] In one embodiment, the glass has a transmittance of at least 30% at a wavelength of 220 nm and a transmittance of less than 4.0% at a wavelength of 200 nm, while the glass has a total platinum content of 3.5 ppm or less and, in some embodiments, also has low iron and titanium contents of less than 10 ppm each.

[0051] In one embodiment, Pt contaminants in the glass (i.e., Pt 0 , Pt 2+ , Pt 4+ and Pt 6+The total platinum content (also referred to as "total platinum content") can reduce UV transmittance between 200 nm and approximately 250 nm. While not theoretically bound, platinum contaminants in glass are thought to induce phase separation through nucleation within the glass. The glass of this disclosure may have no or very little metal contamination, and may have less than 3.5 ppm or less than 2.5 ppm of Pt contaminants in particular. In some embodiments, the glass may have more than 0.05 ppm or more than 0.1 ppm of Pt contaminants. In other embodiments, 0-3.5 ppm, 0-2.5 ppm, 0-2.0 ppm, 0-1.5 ppm, 0-1.0 ppm, 0-0.75 ppm, 0-0.5 ppm, and 0-0.25 ppm are preferred. In further embodiments, the glass is free of any Pt contaminants.

[0052] In further embodiments, it has been found that TiO2 contaminants in the glass (also referred to as "titanium content") can further reduce the UV transmittance in the 200 nm to approximately 250 nm range. Therefore, in one embodiment, glass having a TiO2 content of 100 ppm or less, preferably 50 ppm or less, is preferred. Preferably, the amount of TiO2 should be less than 10 ppm, less than 7 ppm, less than 5 ppm, or less than 4 ppm. In other embodiments, the TiO2 content may be 1 to 10 ppm, 1.5 to 9.0 ppm, 2.0 to 8.0 ppm, or 1 to 5 ppm.

[0053] In further embodiments, it has been found that Fe contaminants in the glass can further reduce the UV transmittance in the 200 nm to approximately 250 nm range. In this specification, the iron content is expressed in ppm as parts by mass of Fe2O3. This value can be determined, as is well known to those skilled in the art, by identifying the amount of all iron species present in the glass and calculating the mass fraction assuming that all iron exists as Fe2O3. For example, if 2 mmol of iron is found in the glass, the mass assumed for the calculation corresponds to 159.70 mg of Fe2O3. This procedure takes into account the fact that the amount of individual iron species in the glass cannot be reliably determined, or requires considerable effort to determine. In some embodiments, the glass contains less than 100 ppm, particularly less than 50 ppm, or less than 10 ppm of Fe2O3. In one embodiment with a particularly low iron content, the Fe2O3 content is less than 10 ppm, less than 8 ppm, or less than 4.5 ppm. The Fe2O3 content can be any of the following: 0.5–10 ppm, 1–10 ppm, 1.5–9.0 ppm, 2–8.5 ppm, 2.5–8.0 ppm, or 3–7 ppm.

[0054] In the glass of this disclosure, it has been found that reducing conditions during dissolution can increase absorption at approximately 200 nm. Therefore, it is desirable to select reducing dissolution conditions during the production of the glass to the extent that it yields low transmittance at approximately 200 nm. This can be achieved, for example, by adding one or more reducing agents, such as sugars (reducing sugars, such as sucrose), during dissolution, particularly in amounts of 0.1 to 1.0 mass%, for example, 0.2 to 0.6 mass%. However, the above conditions may result in a high proportion of Fe which could adversely affect the transmittance at 220 nm. 2+ To avoid seed formation, it shouldn't be too reducing.

[0055] In one embodiment of the present invention, when a glass molten material is produced by induction heating of the glass to a temperature of 1500°C in a platinum crucible under an argon atmosphere, the partial pressure of oxygen (pO2) in the glass molten material is 0.5 bar or less at 1500°C. The pO2 at 1500°C may be, for example, a maximum of 0.4 bar, a maximum of 0.3 bar, or a maximum of 0.2 bar. In some embodiments, the pO2 may be, for example, at least 0.01 bar, at least 0.02 bar, at least 0.05 bar, or at least 0.1 bar. The pO2 may be, for example, 0.01 bar to 0.5 bar, 0.02 bar to 0.4 bar, 0.05 bar to 0.3 bar, or 0.1 bar to 0.2 bar.

[0056] The pO2 of a glass molten material can be determined, for example, based on the voltage between a reference electrode and a measuring electrode, both of which are placed within the glass molten material. The pO2 can be calculated from the voltage between the electrodes using the Nernst equation. A platinum plate can be used as the measuring electrode. The reference electrode may include a platinum wire placed inside a ZrO2 ceramic tube closed at the tip, the platinum wire in electrically conductive contact with the wall of the ZrO2 tube. The ZrO2 ceramic may be yttrium-stabilized, calcium-stabilized, or magnesium-stabilized (see, for example, European Patent Application Publication No. 1101740 (EP1101740A1), paragraphs 0012, 0013). To measure the pO2 in the glass molten material, pure oxygen is flowed around the platinum wire to ensure a constant pO2 of 1.0 bar is present at the platinum wire inside the reference electrode. ZrO2 is an oxygen conductor and forms a bridge between the platinum inside the reference electrode and the glass molten material, and indirectly between it and the platinum measuring electrode inside the glass molten material. Oxygen ions move through it. The concentration cell "platinum (pO2 = constant = 1.0 bar) / ZrO2 / glass molten material / platinum (pO2 of glass molten material)" generates a voltage. The voltage between the reference electrode and the measuring electrode is proportional to the pO2 in the glass molten material, so it can be converted and the pO2 in the glass molten material can be determined based on the Nernst equation.

[0057] In one embodiment, the Fe2O3 content is 1 ppm to 10 ppm, the TiO2 content is 2 ppm to 30 ppm, and the transmittance at 200 nm is less than 3%.

[0058] Therefore, in a preferred embodiment, glass having a total of less than 20 ppm of all contaminants by Pt, TiO2, and / or Fe2O3 is preferred; in another embodiment, less than 18.5 ppm; in yet another embodiment, less than 13.5 ppm; or less than 10.5 ppm. In yet another embodiment, glass having a total of 1 to 20 ppm, 1.5 to 18.5 ppm, 2.0 to 13.5 ppm; or 2.5 to 12.0 ppm of all contaminants by Pt, TiO2, and / or Fe2O3 is preferred. In a further embodiment, the glass is free from contaminants by at least one of the impurities selected from Pt, TiO2, and / or Fe2O3.

[0059] Other contaminants, such as transition elements and / or heavy metals, e.g., lead, rhodium, cadmium, mercury, and hexavalent chromium, may also be retained at less than 10 ppm, or in other embodiments, less than 8.5 ppm. In other embodiments, these contaminants may be retained at 0-8.2 ppm, 0-7.0 ppm, 0-6.0 ppm, 0-5.0 ppm, or 0-4.0 ppm. In other embodiments, the levels of these contaminants may be 0-3.0 ppm, 0-2.0 ppm, 0-1.0 ppm, 0-0.5 ppm, or 0-0.25 ppm. In further embodiments, the glass is free of any transition metal and / or heavy metal contaminants.

[0060] Where chemical elements are referred to in this application, this description refers to any chemical form unless otherwise specified in each individual case. For example, the statement that glass has an As content of less than 100 ppm means that the sum of the mass fractions of the present As species (e.g., As2O3, As2O5, etc.) does not exceed 100 ppm.

[0061] As used within this application, the term "ppm" means parts per million based on mass versus mass (w / w).

[0062] To manufacture glass with a suitable UV transmittance, metal contamination during the manufacturing process should be avoided. Therefore, the present invention may also relate to a method for manufacturing glass with a high UV transmittance.

[0063] In one embodiment, the glass of the present invention is a glass having high UV transmittance and physical and chemical parameters within the following further range.

[0064] Unlike quartz, the glass of this invention has excellent solubility properties, such as a low transition temperature and working point. An example of a suitable glass parameter is the transition temperature T g (ISO 7884-8) Below 550°C, for example, 400°C to 500°C, which can be selected from 440°C to 480°C in one embodiment and 450°C to 470°C in other embodiments.

[0065] The glass is T 13 Temperature, i.e., viscosity η is 10 13 The glass temperature, with an annealing point (dPa·s) (ISO 7884-4), may range from 410°C to 550°C, for example, 455°C to 495°C in one embodiment and 460°C to 490°C in another embodiment. The glass has a softening point, i.e., a viscosity of 10 7.6 The temperature (softening point) of the glass is dPa·s (ISO 7884-3) 630°C to 720°C, for example, 640°C to 700°C in one embodiment, and 650°C to 690°C in another embodiment. The glass has a working point, i.e., a viscosity of 10 4 The working temperature (dPa·s) (ISO 7884-2) is 900°C to 1150°C, which may be 950°C to 1100°C in one embodiment, and 975°C to 1050°C in another embodiment. The dependence of temperature and viscosity, expressed by one or more of these parameters, is associated with the ability of the glass to be drawn into a desired shape, including UV lamp covers and UV-LED covers, or otherwise molded.

[0066] The glass of the present invention weighs 2.3 to 2.7 g / cm³ at 25°C.-3 , or 2.4~2.6 g·cm -3 For example, 2.55 g·cm -3 It can have a density ρ of less than 1.5. Due to its low density, glass is best suited for mobile applications, such as mobile pathogen eradication devices.

[0067] The glass of the present invention exhibits a temperature of 0.8 to 1.2 W·m at 90°C. -1 ·K -1 , or 0.9~1.1W·m -1 ·K -1 Thermal conductivity λ w It can be characterized in this way, making it most suitable for use as a lamp cover.

[0068] UVC glass and UVC glass covers manufactured from these materials have the following additional characteristics: The glass of the present invention is characterized in particular by its high resistance to solarization. Solarization resistance can be determined by irradiating the glass with a HOK 4 lamp for 144 hours and comparing the transmittance at a wavelength of 220 nm before and after irradiation. The term "HOK 4 lamp" refers to the Phillips high-pressure mercury lamp HOK 4 / 120. The emission spectrum of the HOK 4 lamp is shown in Figure 4. The main emission of the lamp is at a wavelength of 365 nm. The power density at 200-280 nm and a distance of 1 m is 850 μW / cm². 2 For the 144-hour irradiation of the present invention, the distance between the HOK 4 lamp and the sample is selected to be 7 cm.

[0069] The smaller the difference in transmittance before and after irradiation, the higher the solarization resistance. Endurance Solarization is related to low solarization, and vice versa. High solarization is related to high induced extinction. ind It correlates with this.

[0070] Inductive dimming Ext ind This can be determined using the following formula, based on the transmittance before and after 144 hours of irradiation with a HOK 4 lamp and the thickness of the glass sample.

number

[0071] Ext ind This is induced extinction, and T 後 This is the transmittance after 144 hours of irradiation with HOK 4 lamps, T 前 is the transmittance before 144 hours of irradiation with a HOK 4 lamp, d is the thickness of the sample, and ln is the natural logarithm. Unless otherwise specified, the thickness d of the sample is given in cm, so the induced attenuation is given as 1 / cm. Unless otherwise specified, the transmittance before and after irradiation with a HOK 4 lamp is given for a wavelength of 220 nm. Therefore, unless otherwise specified, the induced attenuation described in this disclosure relates to induced attenuation at a wavelength of 220 nm.

[0072] In one embodiment, the induced attenuation at a wavelength of 220 nm is up to 1.0 / cm, up to 0.5 / cm, up to 0.2 / cm, up to 0.1 / cm, up to 0.05 / cm, up to 0.02 / cm, or up to 0.01 / cm. The induced attenuation at a wavelength of 220 nm may be, for example, at least 0.001 / cm, at least 0.002 / cm, or at least 0.005 / cm. The induced attenuation at a wavelength of 220 nm may be, for example, 0.001 / cm to 1.0 / cm, 0.001 / cm to 0.5 / cm, 0.002 / cm to 0.2 / cm, 0.002 / cm to 0.1 / cm, 0.002 / cm to 0.05 / cm, 0.005 / cm to 0.02 / cm, or 0.005 / cm to 0.01 / cm.

[0073] The transmittance at a wavelength of 220 nm (reference thickness 0.71 mm) after 144 hours of irradiation with a HOK 4 lamp may be, for example, at least 30%, at least 35%, at least 40%, or at least 60%.

[0074] The transmittance at a wavelength of 220 nm (reference thickness 0.71 mm) after 144 hours of irradiation with a HOK 4 lamp may be, for example, a maximum of 95.0%, a maximum of 90.0%, a maximum of 85.0%, or a maximum of 80.0%. The transmittance at a wavelength of 220 nm may be in the range of, for example, 30.0% to 95.0%, 35.0% to 90.0%, 40.0% to 85.0%, or 60.0% to 80.0%.

[0075] Due to the properties of glass, UVC glass covers can be hermetically sealed, for example, using laser glass frit sealing. This hermetically sealed seal is important because many UVGI applications are carried out in either aquatic environments (e.g., biofilm treatment or water treatment), humid environments (e.g., sewage systems), and / or environments with increased gas pressure, or under vacuum. Furthermore, the hermetically sealed seal allows the final equipment, such as a UVC-LED lamp, to be autoclaved, and therefore it can be used in hospitals, surgical settings, laboratories, or any other environment where high hygiene standards are required.

[0076] This is in contrast to conventional glass, quartz, and / or fused silica glass, which cannot be hermetically sealed because they do not possess the thermal properties required for laser frit sealing. However, the glass described herein is suitable for achieving crack-free and dense frit connections.

[0077] The glass of the present invention preferably has a CTE [°C] of up to 0.01, more preferably up to 0.0099, or up to 0.0098. -1 The product is ] × T4[°C]. The aforementioned product may be at least 0.0075 or at least 0.0085. These glasses have been shown to exhibit favorable properties with respect to molten stress and melting behavior.

[0078] "T4" is a glass with a viscosity of 10 4This is the temperature at which the viscosity of the glass is dPa·s. T4 can be measured by methods known to those skilled in the art, for example, in accordance with DIN ISO 7884-1: 1998-02, to determine the viscosity of the glass. 13 "The glass has a viscosity of 10 13 This is a temperature with dPa·s.

[0079] The mean linear thermal expansion coefficient α (CTE) (at 20°C; 300°C, according to ISO 7991) is 7.0 to 12.0 × 10 in one embodiment. -6 K -1 The coefficient of thermal expansion (CTE) is 11.5 × 10⁻⁶. -6 K -1 It can be less than 7.5 < 11 × 10 -6 K -1 More preferably 8.75~10.75×10 -6 K -1 , more preferably 9.0~10.0 × 10 -6 K -1 More preferably 9.2 to 9.8 × 10 -6 K -1 This may be within the range of [specify range]. This allows the thermal expansion characteristics to be matched to the overall thermal expansion characteristics of the UV equipment, thus preventing tension within the glass cover. In one embodiment, the same or similar CTE is selected for both the UVC glass cover and the UV equipment underneath (e.g., UVC-LED package).

[0080] Another important property of glass is the refractive index n of the material. d This is due to its excellent spatial homogeneity. Arbitrarily, the variation in refractive index within the glass can correspond to the deformation of the wavefront passing through the glass, according to the following equation: Δs = Δ(n d d) = Δn d ·d+Δd·n d In the above equation, Δs is the wavefront deviation, d is the thickness of the glass, Δd is the thickness variation (the difference between the maximum and minimum thickness), and Δn d This is the variation in refractive index within the glass (the difference between the maximum and minimum refractive indices). The present invention further includes glass articles having the indicated wavefront deviation.

[0081] The wavefront deviation can be calculated according to the above formula. Refractive index n d (λ=587.6nm) and thickness can be specified at 20°C. In one embodiment, the wavefront deviation is given by a surface area of ​​1 cm². 2 The wavefront deviation can be specified for glass with a thickness of 10 mm or less, or for glass with a thickness of 1 mm or less. Optionally, the thickness may be at least 200 μm. The wavefront deviation may be less than ±0.1 mm, less than ±0.08 mm, in a further embodiment less than ±0.035 mm, less than ±25 μm, less than ±15 μm, or less than ±5 μm. Optionally, the wavefront deviation may be between 0.1 μm and 250 μm, or between 1 μm and 100 μm, or between 2 μm and 85 μm.

[0082] Wavefront deviation can be measured axially, for example, in the case of a glass tube used in a discharge lamp, or laterally, for example, in the case of a rod portion used in a lens in a UVC-LED.

[0083] Wavefronts can also be measured by wavefront sensors. These are instruments that measure wavefront aberrations in a coherent signal to describe the optical quality or lack thereof in an optical system. Without being tied to a specific method, a very common method is to use a Shack-Hartmann miniature lens array.

[0084] Alternative wavefront sensing techniques to the Shack-Hartmann system are mathematical techniques such as phase imaging or curvature sensing. These algorithms compute wavefront images at various focal planes from conventional bright-field images without requiring specialized wavefront optics equipment.

[0085] The glass and glass articles according to the present invention may have low concentrations of wavefront deformations (such as striations, bubbles, and streaks) in the glass. Generally, the overall or long-range homogeneity of the refractive index in a material can be distinguished from the short-range deviation from the homogeneity of the glass. Stirring is a spatially short-range variation in homogeneity in the glass. Short-range variation refers to variations over distances of approximately 0.1 mm and up to 2 mm, while spatially long-range overall homogeneity of the refractive index covers the entire glass piece.

[0086] In some embodiments, an ultraviolet transmission filter can be used to filter out certain undesirable UV wavelengths, such as wavelengths above 220 nm.

[0087] The glass for UV covers according to the present invention can be shaped to form a lens, for example, to optically shape a UV beam in order to directionally focus UV light onto a target.

[0088] Any beam angle from 10° to 180° is possible. In some embodiments, angles from 10° to 20°, 20° to 30°, 30° to 40°, 40° to 50°, 50° to 60°, 60° to 70°, 70° to 80°, and 80° to 90° can be used. In other embodiments, angles from 15° to 35°, 25° to 45°, 35° to 60°, 45° to 90°, 75° to 120°, 90° to 145°, and 120° to 180° can be used.

[0089] In some embodiments, for example, when it is necessary to decontaminate a surface of a certain size, a certain volume, or a tube of a certain diameter in a single treatment, a somewhat wider beam shape, such as 90°, 120°, or even 180°, is useful.

[0090] In other embodiments, narrow beam shapes, such as 10°, 5°, or even 1°, are useful. For example, using a narrow beam shape can concentrate UV exposure to a target location, avoiding omnidirectional and undesirable radiation that could result in an inefficient energy-to-emission ratio or exposure of UV-sensitive surfaces to UV light. One example could be limited decontamination of a defined area of ​​an eye.

[0091] Furthermore, various lens shapes and beam angles can be used to solve complex pathogen eradication tasks. For example, when surfaces sensitive to different levels of UV are adjacent to each other and need to be exposed to UV in a single treatment. For instance, during wound treatment and / or surgery, if the wound itself is exposed to lower UV than the surrounding skin, it may be suitable to treat the patient's skin with higher UV exposure in some areas than in adjacent areas.

[0092] The present invention also includes a method for manufacturing an LED package having a cover made of the 220nm UVC-transmitting glass of the present invention.

[0093] The LED package according to the present invention is • LED chip Optionally, a substrate on which the LED chip is mounted, such as a PCB, polymer, inorganic material, especially ceramic, or metal substrate. Optionally, a base plate (metal, ceramic, glass ceramic, polymer) including a feedthrough for a conductor to contact the LED chip. • A frame (metal, ceramic, glass ceramic, polymer) containing the LED chip, which is attached to the base plate or surrounds the base plate and forms several cavities. • A housing (cover) on the opposite side of the chip and distal to the chip, which is at least partially transparent and closes the package, or is made of a material that is transparent as a whole, wherein at least the transparent portion of the cover is made of UVC transparent glass as described herein. It may include.

[0094] Such windows may be flat or have a shape (i.e., a lens shape) that alters the path of light.

[0095] As mentioned earlier, UVC-LEDs can be packaged and sealed (e.g., laser frit sealing) so that they are autoclavable, sterilizable, and resistant to fluids. Such UVC-LEDs can be used for sterilizing air and water, surfaces, and for medical / dental applications.

[0096] The UVC-LED having UVC-transmitting glass described herein offers further advantages compared to conventional UVGI lamps or equipment (e.g., mercury lamps), for example, • Instant on / off function enables "on-demand disinfection" without wasting energy. • Directional emission that enables "targeted disinfection" with a simple design (especially through the use of lenses that allow control of the beam angle), • Semiconductor durability, enabling use in robust portable devices. • Low DC power requirements, resulting in an energy-efficient, simple, and inexpensive electric drive mechanism. • Compact packaging to maximize design flexibility. • Environmentally friendly design, as it can be easily disposed of without exposure to harmful mercury. • High optical performance, • High radiant output at defined wavelength, • Relatively low manufacturing cost, • Small size It holds.

[0097] Traditionally, both low-pressure and medium-pressure mercury lamps have been used in disinfection systems. However, there is a need to replace these light sources with high-power and energy-efficient UV light, such as UVC-LEDs. The UV lamps and UV devices under the present invention are more energy-efficient than conventional UVGI lamps or devices. This is because the glass can transmit more than 60% of UV light at 220 nm, thus significantly improving the ratio between energy input and radiant output.

[0098] This becomes important when those glasses are used as covers for UVC-LED lamps. If the energy requirement of a conventional mercury UV lamp is set to 100%, the energy required to produce the same UV radiation using the UVC-LEDs described in this application is approximately 10-30%. In other words, if a conventional UV lamp uses 10W of energy to emit a certain UV intensity, the equipment of this application may use only 1-3W.

[0099] As mentioned above, another advantage of the UVC-transmitting glass described in this application is their high thermal conductivity (λ w ) and it is 0.75~1.25W·m at 90℃. -1 ·K -1 In other embodiments, the emission is approximately 1.0 W·m². -1 ·K -1 This can be the case. This excellent thermal conductivity extends the lifespan of the equipment because excess heat can be easily dissipated before it damages other parts of the equipment. This is in contrast to, for example, quartz glass, which usually has a less-than-optimal thermal conductivity.

[0100] Accordingly, in one embodiment, the method according to the present invention may include a UV lamp having an energy efficiency index (EEI) ≤ 0.11 in accordance with Directive (EU) No 874 / 2012 in the case of an omnidirectional UV lamp, and an energy efficiency index (EEI) ≤ 0.13 in accordance with Directive (EU) No 874 / 2012 in the case of a directional UV lamp.

[0101] The methods described herein can be used to eradicate pathogens from any type of surface, including UV-sensitive surfaces, UV-sensitive liquids, and / or UV-sensitive gases.

[0102] Naturally, the methods described herein can also be used to eradicate various UV-sensitive pathogenic organisms, such as viruses (e.g., influenza or coronaviruses, e.g., SARS-CoV-2, especially resistant viral variants, e.g., SARS-CoV-2-D614G), bacteria (including spores), pathogenic yeasts, fungi and their species.

[0103] Possible uses can be selected from a list of uses including hand sanitizers (e.g., in private or public restrooms), room disinfectants in healthcare environments, pathogen eradication during or after surgery, wound treatment, eye treatment, food disinfection (e.g., during food production and / or meat, dairy or vegetable counters in supermarkets), livestock disinfection (especially in intensive livestock farming, such as laying batteries), pharmaceutical compound manufacturing and / or food production processes, storage facilities, and / or disinfection of UV-sensitive surfaces frequently touched by many different users, such as keyboards, handles, handrails, toothbrushes, hairbrushes, ornaments, touch devices, razors or children's toys.

[0104] The UVC instruments disclosed in this invention can also be used for a wide range of "analytical instrument" applications, such as: • HPLC (High-Performance Liquid Chromatography): Used in life sciences for the analysis of chemicals and compounds. • Spectrometers: Used in numerous applications in testing and analysis across biotechnology, life sciences, and environmental monitoring, and • Water quality monitoring sensors: Used to detect chemicals in water (e.g., during hydraulic fracturing, in general water safety cases, or before the disposal of treated wastewater).

[0105] In other embodiments, the UVC equipment disclosed in the present invention may include equipment for “water disinfection.” In this respect, UVC LEDs are advantageous compared to traditional mercury lamps, which require a long warm-up time (somewhere between 50 seconds and 10 minutes) to reach the required germicidal intensity. Furthermore, frequent on / off cycles can reduce the lifespan by more than 50%.

[0106] As a result, mercury lamps in these applications need to be kept on all day, leading to more frequent lamp replacements, increased ozone generation, and higher power consumption. In contrast, the instant on / off capability of UVC LEDs enables on-demand disinfection, which significantly reduces power consumption. Furthermore, frequent on / off cycles do not shorten the lifespan of the LEDs, contributing to lower operating and maintenance costs.

[0107] Further use of the UVC equipment disclosed in this invention is particularly applicable to UV-sensitive surfaces, liquids, or gases. • Protein analysis, i.e., bioinformatics studies of protein structure and function using database searches, sequence comparisons, and structural and functional predictions. • Molecular identification, that is, the process of comparing specific fragments of DNA between organisms. In biotechnology, flow cytometry, based on lasers or impedance, is a biophysical technique used for cell counting, cell sorting, biomarker detection, and protein engineering. It involves suspending cells in a fluid flow and passing them through electrical detection devices. • Biofilm treatment systems, that is, systems that remove organic and inorganic materials from surrounding liquids using bacteria, fungi, algae, and protozoa. • Nitrates and / or NO x This measurement is usually performed at a wavelength of approximately 230 nm. • Skin treatments to improve skin conditions (e.g., psoriasis, vitiligo, itching, neurodermatitis, acne, actinic dermatitis, phototherapy, roseola, etc.) It may include.

[0108] Accordingly, in one embodiment, the use of a UV-LED module may be selected from the group of applications including water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection (e.g., keyboard disinfection, UV sterilizers for escalator handrails), cytometry, molecular identification, protein analysis, biofilm processing, curing, lithography, plant growth, skin treatment, microbial detection, drug discovery, protein analysis, induction of vitamin D3 production in the skin, and / or sterilization.

[0109] Accordingly, in one embodiment, the present invention relates to the use of glass as an hermetically sealed lens cap for UV-LED modules for applications selected from the group of applications including, for example, water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection (e.g., keyboard disinfection, UV sterilizers for escalator handrails), cytometry, molecular identification, protein analysis, biofilm processing, curing, lithography, plant growth, skin treatment (psoriasis, vitiligo, itching, neurodermatitis, acne, actinic dermatitis, phototherapy, roseola), microbial detection, drug discovery, protein analysis, induction of vitamin D3 production in the skin, and / or sterilization.

[0110] The glass is preferably soda-lime glass. In one embodiment, the glass contains the following components (mol %) based on oxides: Ingredient content [mol%] SiO240~85 Al2O30~25 Na2O 0~18 K2O 0-15 MgO 0-10 B2O30.1~4 Li2O 0~10 ZnO 0~5 CaO 0-16 BaO 0~12 ZrO20~5 SnO20~3 SrO 0~4 F - 0-6 Cl - 0-1.

[0111] In another embodiment, the glass comprises the following components (mol %) based on oxides: Ingredient content [mol%] SiO260~84 Al2O30~10 B2O30.5~3.5 Li2O 0~3 Na2O 0~15 K2O 0-12 MgO 0-6 CaO 0-6 SrO 0~4 BaO 0~8 F - 0-6 Cl - 0~0.8 R2O 5~25 RO 0~6.

[0112] Here, "R2O" represents alkali metal oxides Li2O, Na2O, and K2O, and "RO" represents alkaline earth metal oxides MgO, CaO, BaO, and SrO.

[0113] The glass may contain SiO2 in a proportion of at least 40 mol%, or at least 60 mol%. SiO2 contributes to the hydrolysis resistance and permeability of the glass. If the SiO2 content is too high, the melting point of the glass will be too high. Temperatures T4 and T g It also rises sharply. Therefore, the SiO2 content should be limited to a maximum of 78 mol%, or a maximum of 80 mol%, or a maximum of 81 mol%, or a maximum of 82 mol%, or a maximum of 85%.

[0114] Preferably, the SiO2 content is at least 61 mol%, at least 63 mol%, or at least 65 mol%, at least 68 mol%, at least 69 mol%, or at least 70 mol%, or at least 72 mol%, or at least 75 mol%. The content may be limited to a maximum of 84 mol%, or a maximum of 82 mol%, or a maximum of 81 mol%, or a maximum of 80 mol%.

[0115] The glass may contain Al2O3 in a proportion of up to 10 mol%. Al2O3 contributes to the phase separation stability of the glass, but at high proportions it reduces acid resistance. Furthermore, Al2O3 increases the melting point and T4. Therefore, the content of this component should be limited to a maximum of 25 mol%, or a maximum of 9 mol%, or a maximum of 8 mol%, or a maximum of 7 mol%, or a maximum of 5 mol%, or a maximum of 4.5 mol%. In some embodiments, Al2O3 is used in small proportions of at least 0.1 mol%, at least 0.2 mol%, or at least 0.5 mol%, or at least 1.0 mol%. In some embodiments, the glass may be Al2O3-free.

[0116] The glass may contain B2O3 in a proportion of at least 0.5 mol%. B2O3 affects the solubility of the glass. The amount of B2O3 may be limited to 4.0 mol% or less, 3.5 mol% or less, 3.0 mol% or less, 2.5 mol% or less, or 2.0 mol% or less. Limiting the amount of B2O3 is advantageous in order to reduce the transmittance at 200 nm. The B2O3 content may be at least 1.0 mol%, at least 1.2 mol%, or at least 1.5 mol%.

[0117] Optionally, the ratio of the total content (mol%) of B2O3, R2O, and RO to the total content (mol%) of SiO2 and Al2O3 is at most 0.4, at most 0.35, or at most 0.3. In one embodiment, this value is at least 0.1, at least 0.15, or at least 0.2.

[0118] The glass may contain Li2O in amounts of 10.0 mol% or less, 3.0 mol% or less, 2.8 mol% or less, or 2.5 mol% or less. Optionally, the glass may contain only a small amount of Li2O, for example, up to 3.0 mol%, up to 2.8 mol%, up to 2.5 mol%, up to 2.0 mol%, or up to 1.9 mol%, or the glass may be Li2O-free. In a particular embodiment, the Li2O content is 1 mol% to 2 mol%.

[0119] The glass may contain Na2O in amounts of 18 mol% or less, 15 mol% or less, 12 mol% or less, 11 mol% or less, or 10 mol% or less. Na2O increases the fusibility of the glass. Sodium oxide also results in a decrease in UV transmittance and an increase in the coefficient of thermal expansion (CTE). The glass may contain Na2O in amounts of at least 1 mol%, at least 2 mol%, at least 4 mol%, at least 5 mol%, or at least 6 mol%. In one version, the Na2O content is a maximum of 5 mol%, or a maximum of 4 mol%. In some embodiments, the glass may be Na2O-free.

[0120] The glass may contain K2O in a proportion of up to 15 mol%. The proportion may be at least 1 mol%, at least 2 mol%, at least 4 mol%, at least 5 mol%, or at least 6 mol%. The proportion of this component may be limited to a maximum of 15 mol%, at least 12 mol%, at least 10 mol%, at least 9 mol%, or at least 8 mol%. In some embodiments, the glass may be K2O-free.

[0121] In one embodiment, the ratio of the Na2O content to the K2O content in mol% may be at least 1.0, and in particular at least 1.1. In one embodiment of the present invention, the ratio is up to 2, and in particular up to 1.5. Both oxides are useful for improving the fusibility of the glass. In a particular embodiment, the ratio is 1.1 to 1.3.

[0122] The amount of R2O in the glass may be limited to 25 mol% or less, 22 mol% or less, or 20 mol% or less. The glass may contain R2O in an amount of at least 5 mol%, at least 8 mol%, or at least 10 mol%. In certain embodiments, the R2O content is 10 mol% to 20 mol%. R2O may contribute to reducing transmittance at 200 nm.

[0123] The glass may contain MgO in amounts of 10 mol% or less, 6 mol% or less, 4 mol% or less, or 2 mol% or less. While MgO is advantageous for fusibility, high concentrations have been shown to be problematic in terms of desired UV transmittance and phase separation tendencies. A preferred design is MgO-free.

[0124] The glass may contain CaO in amounts of 16 mol% or less, 6 mol% or less, 4 mol% or less, 2 mol% or less, or 1 mol% or less. While CaO is advantageous for fusibility, high proportions have been shown to be problematic with respect to the desired UV transmittance. Preferred forms are CaO-free or contain only a small amount of CaO, e.g., at least 0.1 mol%, at least 0.3 mol%, or at least 0.5 mol%.

[0125] The glass may contain SrO in amounts of 4 mol% or less, 1 mol% or less, or 0.5 mol% or less. While SrO is advantageous for fusibility, it has been shown that high concentrations pose problems with respect to the desired UV transmittance. The preferred design is SrO-free.

[0126] The glass may contain BaO in amounts of 12 mol% or less, 8 mol% or less, 6 mol% or less, 5 mol% or less, or 4 mol% or less. BaO improves hydrolysis resistance. However, excessively high barium oxide content leads to phase separation and, consequently, glass instability. A preferred embodiment contains BaO in amounts of at least 0.5 mol%, at least 1.0 mol%, or at least 1.5 mol%. In certain embodiments, the BaO content is between 1.0 mol% and 4.0 mol%. In some embodiments, the glass may be BaO-free.

[0127] Alkaline earth oxides (ROs) have been shown to have a significant impact on the phase separation tendency. Therefore, in one design configuration, special attention is paid to the content of these components and their relationships to each other. Accordingly, the ratio of BaO in mol% to the total content of MgO, SrO, and CaO in mol% may be at least 2. Optionally, this value may be at least 5, or at least 10, or at least 20. In a particularly preferred configuration, the aforementioned value may be at least 40, or even at least 50. BaO offers the greatest advantage in terms of phase separation and hydrolysis resistance compared to other alkaline earth metal oxides. However, the aforementioned ratio should not exceed 120 or 100. In a favorable configuration, the glass contains at least small amounts of CaO and BaO, and is free of MgO and SrO. In a particular embodiment, the aforementioned ratio is between 50 and 100.

[0128] Favorable properties are obtained particularly when the ratio of the molar percentage of CaO to BaO in the glass is less than 0.2. In particular, this ratio may be less than 0.15 or less than 0.1. In some embodiments, the ratio is even lower, particularly less than 0.08 or less than 0.06, and in preferred designs, this ratio is at least 0.03. In certain embodiments, the ratio is between 0 and 0.1.

[0129] In one version, the glass has a molar ratio of B2O3 to BaO of at least 0.1 and at most 2.0. Preferably, the ratio is at least 0.2 or at least 0.5, and in a preferred design, the ratio is limited to a maximum of 1.8 or 1.5 or 1.2. In other embodiments, the ratio may be limited to a maximum of 1.0 or 0.8. In particular, the ratio is 0.2 or greater and 2.0 or less, or in other embodiments, 0.5 or greater and 1.8 or less, and in specific embodiments, the ratio is 0.2 to 1.0.

[0130] The proportion of RO in the glass of the present invention may be at least 0.3 mol%. Alkaline earth metal oxides are advantageous due to their fusibility, but at high proportions, they have proven problematic with respect to the desired UV transmittance. In one version, the glass contains up to 5 mol% RO. In one embodiment, the proportion of RO is 1 to 5 mol%.

[0131] The total molar content of alkaline earth metal oxides and alkali metal oxides in RO+R2O can be limited to a maximum of 30 mol%. A favorable design may include these components in amounts up to 25 mol%. Preferably, the content of these oxides is at least 5 mol%, at least 10 mol%, or at least 12 mol%. In one embodiment, the proportion of RO+R2O is 12-20 mol%. At excessively high proportions, these components increase the tendency for phase separation and reduce the hydrolysis resistance of the glass.

[0132] The ratio of the B2O3 mol% content to the combined R2O and RO mol% content may be at least 0.01, at least 0.02, or at least 0.05. The ratio may be limited to a maximum of 1.5, a maximum of 1.0, or a maximum of 0.5. In one embodiment, the B2O3 / (RO+R2O) ratio is 0.05 to 0.2. If there is too much alkali or alkaline earth oxide relative to B2O3, alkali or alkaline earth borate may be formed during the phase separation of the glass. It has been proven advantageous to adjust the above ratio.

[0133] T g To ensure that the solubility properties, including T4, are within the desired range, it may be advantageous to set the ratio of the B2O3 content to the total content of SiO2 and Al2O3 in molar percentages within a narrow range. In an advantageous design, this ratio is at least 0.015 and / or at most 0.04. In one embodiment, the B2O3 / (SiO2+Al2O3) ratio is 0.017 to 0.03.

[0134] The ratio of the total alkali metal oxides R2O to the total alkaline earth metal oxides RO in molar percentages is preferably >1, particularly >2 or >4. In the design configuration, this ratio is up to 15, up to 10 or up to 7.5. In one embodiment, the ratio is between 4 and 10.

[0135] The aforementioned glass is F - It may contain in a concentration of 0 to 6 mol%. Preferably, F - The content is a maximum of 4 mol%, or a maximum of 2 mol%. In one design configuration, at least 0.5 mol%, or at least 1 mol%, of this component is used. Component F - This improves the fusibility of the glass and also affects the UV edge towards shorter wavelengths.

[0136] The glass is Cl - It may be contained in a concentration of less than 1 mol%, particularly less than 0.9 mol%, or less than 0.8 mol%. A suitable lower limit is 0.1 mol% or 0.2 mol%.

[0137] The glass may contain ZnO in a concentration of less than 5 mol%, particularly less than 2.5 mol%, or less than 1 mol%. A suitable lower limit is 0.01 mol% or 0.05 mol%. In some embodiments, the glass may be ZnO-free.

[0138] The glass may contain ZrO2 in a content of less than 5 mol%, less than 2.5 mol%, or particularly less than 1 mol%. A suitable lower limit is 0.01 mol% or 0.05 mol%. In some embodiments, the glass may be ZrO2-free.

[0139] The glass may contain SnO2 in a content of less than 3 mol%, particularly less than 2 mol%, or less than 1 mol%. A suitable lower limit is 0.01 mol% or 0.05 mol%. In some embodiments, the glass may be SnO2-free.

[0140] Where this specification states that a glass is free of a certain component or does not contain a particular component, it means that this component may be present at most as an impurity. This means that it is not added in a significant amount. A non-significant amount is less than 0.5 ppm, preferably less than 0.25 ppm, preferably less than 0.125 ppm, and most preferably less than 0.05 ppm.

[0141] In one embodiment, the glass contains less than 10 ppm, particularly less than 5 ppm, or less than 4 ppm of Fe2O3. In one embodiment, the glass contains less than 10 ppm, particularly less than 5 ppm, or less than 4 ppm of TiO2. In one embodiment, the glass contains less than 3.5 ppm, particularly less than 2.5 ppm, or less than 1.0 ppm of arsenic. Glass containing less than 3.5 ppm of antimony, less than 2.5 ppm, or less than 1.0 ppm of antimony is preferred. In addition to adverse effects on UV transmittance and solarization, arsenic and antimony in particular are toxic and hazardous to the environment and should be avoided.

[0142] Optionally, the glass may contain the following components (mol %) based on oxides: Ingredient content [mol%] SiO268~82 Al2O3 0.1~7 B2O3 1.0~3.0 Li2O 0~3.0 Na2O 1~12 K2O 1-10 CaO 0-4 SrO 0~1 BaO 0.5~6 F - 0-6.

[0143] In another embodiment, the glass comprises the following components (mol%): Ingredient content [mol%] SiO269~81 Al2O3 0.2~5 B2O3 1.2~2.5 Li2O 0~2.5 Na2O 2~11 K2O 2~9 CaO 0~2 SrO 0~0.5 BaO 1.0~5 F - 0.5~4.

[0144] In yet another embodiment, the glass contains the following components (mol%): Ingredient content [mol%] SiO270~80 Al2O3 0.5~4.5 B2O3 1.5~2.0 Li2O 0~2 Na2O 4~10 K2O 4~8 CaO 0~1 SrO 0~0.5 BaO 1.5~4 F - 1-2.

[0145] The present invention also includes glass articles made of glass as described herein. Such glass articles may be manufactured by known drawing methods for glass tubes and rods. Depending on the desired shape, those skilled in the art will select a suitable manufacturing method, for example, ingot casting for bars, or floating or downdrawing for producing sheet glass. Preferably, the cooling of the glass in the method is adjusted to achieve the desired properties.

[0146] In one embodiment, the glass article is manufactured using the Danner process or the Bellow process. In the Bellow process, the molten glass flows vertically downward (in the direction of gravity) through a forming apparatus made of an outlet ring and needles. The forming apparatus forms a negative mold (matrix) of the cross-section from which the glass tube or glass rod is to be produced. In the manufacture of the glass tube, the needles are positioned as a molded part at the center of the forming apparatus.

[0147] The difference between the Bellow process and the downdraw process is, firstly, that in the Bellow process, the glass molten material is deflected horizontally after it leaves the molding apparatus; and secondly, in the Bellow process, the needle has a passage through which air is blown. In the Danner process, the blown air ensures that the resulting glass tube does not collapse. In the downdraw process, the solidified glass molten material is separated without first changing direction. Because it does not change direction, the use of blown air during the production of the glass tube can also be reduced.

[0148] In one embodiment, the present invention relates to a glass article made of glass disclosed herein. The thickness of the glass article, particularly the wall thickness in the case of a glass tube, may be at least 0.1 mm or at least 0.3 mm. The said thickness may be limited to 3 mm or less or 2 mm or less. The outer diameter of the glass article, for example, the outer diameter of a glass tube or glass rod, may be 50 mm or less, 40 mm or less, or 30 mm or less. The said outer diameter may be at least 1 mm, at least 2 mm, or at least 3 mm.

[0149] Therefore, the present invention also relates to the following embodiments: In one embodiment, the present invention relates to a method for eradicating a pathogen, comprising exposing the pathogen to bactericidal UV light having a wavelength of approximately 220 nm, wherein the UV light is irradiated by a UV lamp having a glass lamp cover, and the glass has a total platinum content of less than 3.5 ppm.

[0150] In another embodiment, the pathogen exposed to the germicidal UV light is present on a UV-sensitive material that is sensitive to UV radiation above 222 nm. In yet another embodiment, the UV-sensitive material is a biological tissue surface, such as the eye or skin of an animal, the animal being selected from insects, invertebrates, vertebrates, mammals and / or humans.

[0151] In yet another embodiment, the eradication of the pathogen after treatment is >99% in accordance with BS ISO 22196:2011-08-31.

[0152] In yet another embodiment, the UV exposure of the pathogen is at least 2,000 to 8,000 microwatt-seconds per square centimeter (μWs / cm²). 2 It is within the range of ).

[0153] In yet another embodiment, all or part of the cover of the UV lamp is molded into the shape of a lens.

[0154] In other embodiments, the present invention relates to glass having a transmittance of at least 30% at a wavelength of 220 nm, wherein the glass has a total platinum content of 3.5 ppm or less, and in some embodiments, 3 ppm or less, 2.5 ppm or less, and 2 ppm or less.

[0155] For many applications, a specific transmittance in the aforementioned UV range is desirable. The glass may have a ratio of transmittance at 220 nm to transmittance at 200 nm of at least 20.00 or at least 30.00, particularly up to 100.00 or up to 80.00.

[0156] In yet another embodiment, the glass contains one or more UV-blocking impurities selected from rhodium, lead, cadmium, mercury, hexavalent chromium, iron, titanium, and any combination thereof. In yet another embodiment, the glass has a total platinum content of less than 1.0 ppm.

[0157] The wavefront deviation may be less than ±0.1 mm, less than ±0.08 mm, and in further embodiments, less than ±0.035 mm, less than ±25 μm, less than ±15 μm, or less than ±5 μm. Optionally, the wavefront deviation may be between 0.1 μm and 250 μm, or between 1 μm and 100 μm, or between 2 μm and 85 μm. In yet another embodiment, the glass contains the following components in the indicated amounts (mol%): Ingredient content [mol%] SiO240~85 Al2O30~25 Na2O 0~18 K2O 0-15 MgO 0-10 B2O30.1~4 Li2O 0~10 ZnO 0~5 CaO 0-16 BaO 0~12 ZrO20~5 SnO20~3 SrO 0~4 F - 0-6 Cl - 0-1.

[0158] In other embodiments, the present invention relates to the use of the glass as an hermetically sealed lens cap for UV-LED modules for applications selected from the group of applications including, for example, water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection (e.g., keyboard disinfection, UV sterilizers for escalator handrails), cytometry, molecular identification, protein analysis, biofilm processing, curing, lithography, plant growth, skin treatment (psoriasis, vitiligo, itching, neurodermatitis, acne, actinic dermatitis, phototherapy, roseola), microbial detection, drug discovery, protein analysis, induction of vitamin D3 production in the skin, and / or sterilization.

[0159] In one embodiment, the present invention relates to a glass article comprising or made of the glass described herein. In one embodiment, the glass article has at least one polished surface. Optionally, the glass article has at least one chamfered edge. The polished surface may have a surface roughness Ra of less than 10 nm or less than 5 nm. The chamfered edge is more impact resistant and, in particular, more resistant to chipping than the unchamfered edge.

[0160] Thermal strengthening and / or chemical strengthening Optionally, the manufacturing method includes a step of chemically strengthening and / or thermally strengthening the glass article. The term “tempering” is also referred to as “hardening” or “toughening.”

[0161] Preferably, the glass article is strengthened on at least one surface, particularly thermally and / or chemically. For example, it is possible to chemically strengthen a glass article by ion exchange. In this method, small alkali ions in the article are usually replaced by larger alkali ions. Often, smaller sodium is replaced by potassium. However, it is also possible to replace very small lithium with sodium and / or potassium. Optionally, alkali ions can be replaced with silver ions. Another possibility is to exchange alkaline earth ions with each other according to the same principle as with alkali ions. Preferably, ion exchange takes place in a bath of molten salt, between the article surface and the salt bath. Pure molten salt, such as molten KNO3, can be used for exchange. However, salt mixtures, or mixtures of salt with other components, can also be used. The mechanical resistance of the article can be further increased if a selectively tuned compressive stress profile is constructed within the article. This can be achieved by a one-stage or multi-stage ion exchange process.

[0162] By replacing small ions with larger ions, or through thermal strengthening, compressive stress is created in a corresponding region, which decreases from the surface towards the center of the glass article. The maximum compressive stress is just below the glass surface and is also referred to as CS (compressive stress). CS is a stress and is expressed in units of MPa. The depth of the compressive stress layer is abbreviated as "DoL" and given in units of μm. Preferably, CS and DoL are measured using the FSM-60LE instrument from Orihara Manufacturing Co., Ltd.

[0163] In one embodiment, CS is greater than 100 MPa. More preferably, CS is at least 200 MPa, at least 250 MPa, or at least 300 MPa. More preferably, CS is up to 1,000 MPa, up to 800 MPa, up to 600 MPa, or up to 500 MPa. Preferably, CS is in the range of >100 MPa to 1,000 MPa, 200 MPa to 800 MPa, 250 MPa to 600 MPa, or 300 MPa to 500 MPa.

[0164] In one embodiment, the glass article is thermally strengthened. Thermal strengthening is typically achieved by rapidly cooling a hot glass surface. Thermal strengthening has the advantage of forming a deeper compressive stress layer (greater DoL) than chemical strengthening. This makes the glass more scratch-resistant because its compressive stress layer cannot be easily penetrated by scratches as it can in the case of a thinner compressive stress layer.

[0165] The glass or glass article can be subjected to a thermal strengthening process after, for example, a melting, molding, slow cooling / cooling process and a post-treatment step during cold. In this process, the glass body (e.g., the aforementioned glass article or a preliminary product), for example, plate glass, is preferably supplied horizontally or suspended in the apparatus to reach a transition temperature T GThe glass is rapidly heated to temperatures above 150°C. Next, the surface of the glass body is rapidly cooled, for example, by blowing cold air through a nozzle system. As a result of the rapid cooling of the glass surface, they freeze in an extended network, while the interior of the glass body cools slowly, giving it more time to contract. This creates compressive stress in the surface layer and tensile stress in the interior. The amount of compressive stress depends on various glass parameters, such as CTE. ガラス (T g (Average linear thermal expansion coefficient below CTE) 液体 (T g It depends on the mean linear thermal expansion coefficient (above average), strain point, softening point, and Young's modulus, as well as the amount of heat conduction between the cooling medium and the glass surface, and the thickness of the glass body.

[0166] Preferably, a compressive stress of at least 50 MPa is generated. As a result, the bending strength of the glass body can be two to three times that of untempered glass. In one embodiment, the glass is heated to a temperature of 750 to 800°C and rapidly tempered in a stream of cold air. Optionally, the blowing pressure may be 1 to 16 kPa. With the glass or glass articles described herein, compressive stress values ​​of, for example, 50 to 250 MPa, and particularly 75 to 200 MPa, can be achieved in commercially available systems.

[0167] In one embodiment, the glass article has a compressive stress layer having a compressive stress of at least 50 MPa, particularly at least 75 MPa, at least 85 MPa, or at least 100 MPa. The glass article may have a compressive stress layer on one, two, or all of its surfaces. The compressive stress of the compressive stress layer may be limited to a maximum of 250 MPa, 200 MPa, 160 MPa, or 140 MPa. These compressive stress values ​​may be present, particularly in heat-strengthened glass articles.

[0168] In one embodiment, the depth of the compressive stress layer of the glass article is at least 10 μm, at least 20 μm, at least 30 μm, or at least 50 μm. In a particular embodiment, this layer may be further at least 80 μm, at least 100 μm, or at least 150 μm. Optionally, the DoL is limited to a maximum of 2,000 μm, a maximum of 1,500 μm, a maximum of 1,250 μm, or a maximum of 1,000 μm. In particular, the DoL may be between 10 μm and 2,000 μm, 20 μm and 1,500 μm, or 30 μm and 1,250 μm. In one embodiment, the glass article is thermally strengthened with a DoL of at least 300 μm, at least 400 μm, or at least 500 μm. Optionally, the DoL may be a maximum of 2,000 μm, a maximum of 1,500 μm, or a maximum of 1,250 μm. In one embodiment, the DoL is 300 μm to 2,000 μm, 400 μm to 1,500 μm, or 500 μm to 1,250 μm. [Brief explanation of the drawing]

[0169] [Figure 1] This figure shows the use of UV-transmitting glass in various LED packages a) to f). [Figure 2] This figure shows the attachment of the UV-transmitting glass of the present invention to a casing. [Figure 3] This figure shows the transmittance spectra for some of the glasses disclosed herein. [Figure 4] This figure shows the emission spectrum of the HOK 4 lamp. [Examples]

[0170] Alkali-containing silicate glass with the glass composition described in this disclosure was obtained under reducing melting conditions. A sample with a thickness of 0.71 mm was tested for transmittance in the wavelength range of 200 nm to 300 nm before and after irradiation with a HOK 4 lamp. The results are shown in Figure 3.

[0171] In particular, the results obtained for the relevant wavelengths λ=200nm and λ=220nm are summarized in the table below.

[0172] [Table 1]

[0173] The glass exhibits low transmittance at 200 nm and high transmittance at 220 nm. The transmittance at both 200 nm and 220 nm remains substantially unchanged after 144 hours of irradiation with a HOK 4 lamp.

[0174] Detailed description of the drawing Figure 1. Possible uses of UV-transmitting glass in various LED packages a) to f). The shape of the glass lens [1] allows for focusing or dispersing UV light depending on the specific application. Furthermore, a cover glass [1] can surround a UV source (e.g., a UV-LED) [4] so that UV light is also emitted laterally (see Figure 1, c) to f). Reflective elements on the back of the casing [3] can improve luminous efficiency. Aluminum nitride ceramic (AlN ceramic), which has high thermal conductivity, can be used as the casing [3]. The LED [4] and glass cover [1] can be metal-brazed [2] to the casing [3].

[0175] Instead of metal brazing [2] the glass to the casing [3] (see Figure 2, a), the UV-transmitting glass [1] of the present invention can also be attached to the casing via laser frit sealing [6] (see Figure 2, b) to e). The LED [4] can be metal brazed [2] to the casing [3] and further completely sealed within a transparent sealing material [5]. Such a sealing material may be a copolymer of methyl methacrylate and acyloxyminomethacrylate esters. In the above example, poly(methyl methacrylate-co-3-methacryloyl-oxymino-2-butanone) was used. Since the LED element is completely protected from environmental influences based on the laser frit sealing [6], this setup is most suitable for harsh environmental conditions, especially when strong acidic cleaning agents and / or disinfectants are regularly used. Again, aluminum nitride ceramic (AlN ceramic), which has high thermal conductivity, can be used as the casing [3]. Here again, the reflective elements on the back of the casing [3] can improve the luminous efficiency.

[0176] Figure 3 shows the transmittance spectra for some of the glasses according to this disclosure.

[0177] Figure 4 shows the emission spectrum of the HOK 4 lamp.

Claims

1. A method for eradicating a pathogen, comprising exposing the pathogen to germicidal UV light at a wavelength of 220 nm, wherein the germicidal UV light is irradiated by a UV lamp having a glass lamp cover, the glass having a transmittance of at least 30% at a wavelength of 220 nm and less than 4% at a wavelength of 200 nm, the glass having a total platinum content of less than 3.5 ppm, and the glass being composed of the following components: Ingredient content [mol%] Yes 2 40~85 Al 2 O 3 0~25 Na 2 O 0~18 K 2 O 0~15 MgO 0-10 B 2 O 3 0.1~4 Li 2 O 0~10 ZnO 0-5 CaO 0-16 BaO 0-12 ZrO 2 0~5 SnO 2 0~3 SrO 0-4 F - 1~2 Cl - 0~1 A method for eradicating the pathogen, comprising the specified amount (mol%).

2. The method according to claim 1, wherein the pathogen to be exposed is located on a UV-sensitive material that is sensitive to UV radiation above 222 nm, and the UV-sensitive material is the surface of a biological tissue.

3. The method according to claim 2, wherein the UV-sensitive material is the eye or skin of an animal, and the animal is selected from insects, invertebrates, vertebrates, mammals and / or humans.

4. The method according to any one of claims 1 to 3, wherein the eradication of pathogens after treatment exceeds 99% in accordance with BS ISO 22196:2011-08-31.

5. The UV exposure of the pathogen is at least 2,000 to 8,000 microwatt-seconds (μWs / cm²) per square centimeter. 2 The method according to any one of claims 1 to 4, which is within the range of ).

6. The method according to any one of claims 1 to 5, wherein all or part of the cover of the UV lamp is molded into the shape of a lens.

7. It has a transmittance of at least 30% at a wavelength of 220 nm and less than 4.0% at a wavelength of 200 nm, and a total platinum content of less than 3.5 ppm, and consists of the following components: Ingredient content [mol%] Yes 2 40~85 Al 2 O 3 0~25 Na 2 O 0~18 K 2 O 0~15 MgO 0-10 B 2 O 3 0.1~4 Li 2 O 0~10 ZnO 0-5 CaO 0-16 BaO 0-12 ZrO 2 0~5 SnO 2 0~3 SrO 0-4 F - 1~2 Cl - 0~1 Glass containing the indicated amount (mol%).

8. The glass according to claim 7, having a transmittance of at least 30%, at least 35%, at least 40%, or at least 60% at 220 nm, and / or at least 75% at wavelengths [λ] 260 nm, 280 nm, and / or 310 nm.

9. Fe 2 O 3 The glass according to claim 7 or 8, wherein the total content of is 0.5 to 10 ppm.

10. Fe 1 ppm to 10 ppm 2 O 3 TiO content: 2 ppm to 30 ppm 2 The glass according to claim 9, having an amount and having a transmittance of less than 3% at 200 nm.

11. The glass according to any one of claims 7 to 10, wherein the total platinum content is less than 1.0 ppm.

12. The glass according to any one of claims 7 to 11, having a wavefront deviation (peak-valley) of less than ±0.1 mm.

13. The glass has a refractive index n of 1.450 to 1.

580. d A glass according to any one of claims 7 to 12, having the following characteristics.

14. A glass article made of glass according to any one of claims 7 to 13, wherein the glass article is heat-strengthened or chemically strengthened, and in particular has a compressive stress of at least 50 MPa on at least one surface.

15. Use of the glass according to any one of claims 7 to 13 as an hermetically sealed lens cap for a UV-LED module for applications selected from the group of water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection, cytometry, molecular identification, protein analysis, biofilm treatment, curing, lithography, plant growth, skin treatment (psoriasis, vitiligo, itching, neurodermatitis, acne, actinic dermatitis, phototherapy, roseola), microbial detection, drug discovery, protein analysis, induction of vitamin D3 production in the skin, and / or sterilization.

Images