JP2022089142A - Method for removing methicillin-resistant staphylococcus aureus - Google Patents

Abstract

To provide a method for removing methicillin-resistant Staphylococcus aureus (MRSA), particularly a method for removing MRSA from a UV sensitive surface.SOLUTION: The method includes use of bactericidal UV light in a wavelength range of 207 nm-222 nm. The UV light is emitted from a UV lamp 4 having a lamp cover 1 produced from UV-permitted borosilicate glass having a total platinum content of less than 3.5 ppm. There are also disclosed the use of the UV-permitted borosilicate glass and a method for producing the same.SELECTED DRAWING: None

Description

The present invention relates to a method for removing methicillin-resistant Staphylococcus aureus (MRSA), particularly a method for removing MRSA from UV-sensitive surfaces. The method comprises using bactericidal UV light in the wavelength range of 207 nm to 222 nm, wherein the UV light is provided by a UV lamp with a lamp cover made from a particular UV transmissive borosilicate glass. It is released. The present invention includes UV transmissive glass, the use of such UV transmissive glass, and a method for producing the same.

Background of the Invention Methicillin-resistant Staphylococcus aureus (MRSA) refers to a group of Gram-positive bacteria that are genetically different from other strains of Staphylococcus aureus. MRSA is the cause of multiple infectious diseases in humans that are difficult to treat. MRSA is any strain of Staphylococcus aureus that has acquired multidrug resistance to β-lactam antibiotics by horizontal gene transfer and / or natural selection. Beta-lactam antibiotics are a broad spectrum group containing several penams (penicillin derivatives such as methicillin and oxacillin) and cephem, such as cephalosporins.

MRSA is common in hospitals, prisons and nursing homes, and people with open wounds, invasive devices such as catheters, and a weakened immune system are at increased risk of nosocomial infections. Although MRSA started as a nosocomial infection, it has become a livestock infection as well as a community-acquired type.

Recent studies have identified MRSA in many surface waters such as rivers and lakes, where MRSA contaminates drinking water sources such as nurseries, schools, hospitals, special needs homes, elderly homes, and other medical facilities. There are increasing opportunities for easy propagation to all types of areas susceptible to.

This is especially dangerous as common cleaning systems in sewage and sewage treatment plants are not currently equipped with sufficient equipment to filter or remove multidrug resistant bacteria from water.

One of the few countries that has not yet suffered from MRSA is the Netherlands. An important part of the success of the Dutch strategy was an attempt to eliminate MRSA in patients prior to discharge.

Therefore, there is a great need for removal methods that are easy to use and effective against MRSA, especially MRSA present on surfaces that are sensitive to conventional sterility methods.

Methods for removing MRSA with light have been reported in the art. So-called "photosensitizer methods" are widely used in hospitals and other areas with high MRSA risk (or other bacterial contamination). In this method, a photosensitizer, mainly a dye molecule, which is excited when exposed to light is used. When excited by light, these molecules produce reactive oxygen species, which in turn eliminate bacteria.

However, not all reported methods using photosensitizers are sufficient to remove sufficient microorganisms to effectively prevent infection. This is because the photosensitizer may not be sufficiently concentrated to cause significant damage. In addition, many photosensitizers are hydrophobic. For this reason, it is difficult to disperse the photosensitizer in an aqueous environment (eg, biofilm) in which microorganisms normally exist.

Another method in the art is called "ultraviolet germicidal irradiation" (UVGI), which uses short wavelength ultraviolet (UVC) light to destroy nucleic acids and kill microorganisms by destroying their DNA. It kills or inactivates and prevents the inability to perform life-threatening cellular functions. UVGI is used in a variety of applications such as food, air, and water purification.

UVGI devices can generate sufficiently powerful UVC light in an air or water circulation system to create an inhabitable environment for microorganisms such as bacteria, viruses, molds, and other pathogens. UVGI can be combined with a filtration system to disinfect air and water. The use of UVGI for disinfection is a practice that has been accepted since the mid-20th century. It has been used primarily in medical hygiene and sterile work facilities.

Containment facilities are increasingly used for sterilization of drinking and wastewater because they are closed and can be circulated for more reliable UV exposure. In recent years, UVGI has found new uses in air purifiers. The existing UVGI method uses UV light with a wavelength of about 250 nm, for example conventional bactericidal UV lamps based on mercury steam lamps emit at a wavelength of 254 nm.

However, conventional bactericidal UV lamps have been reported to be harmful to the eye, causing UV-associated premutagenic DNA lesions in human skin and being cytotoxic to exposed mammalian skin. There is.

Therefore, due to the risk of harmful effects, including the induction of cancer and even other mutagenic diseases, the general UVGI for the removal of MRSA on mammalian skin, such as patient, health care worker, or livestock skin. The direct use of the law is hindered.

Detailed Description of the Invention In recent years, far UVC light has been effective in killing bacteria regardless of their ability to tolerate drugs, but the effects of skin or eye damage associated with conventional bactericidal UV exposure. Not reported.

However, in a normally transparent cover, the UV absorption of UV light at a wavelength of about 200 nm to about 250 nm is very high. For example, UV light does not penetrate much of conventional glass at wavelengths above 320 nm. Conventional borosilicate glass does not transmit light with wavelengths less than 290 nm. Therefore, these covers require at least a large amount of energy to ensure that they are unacceptable to far UV light or that the treated surface, eg, treated skin, is exposed to sufficient UV. It has the drawback of being This high operating energy also leads to significant energy dissipation, increasing thermal stress not only on the cover but on the entire device. As a result, the life of the device is shortened and the maintenance cost is increased.

Therefore, the challenge in assessing prior art methods is to perform MRSA treatment directly on sensitive surfaces, such as mammalian skin or other UV sensitive materials such as certain gases and / or liquids. It was to provide a novel UVGI method to which UV of far UVC light could be applied for facilitation.

This problem is solved by the method disclosed herein.

The present invention is a method for removing methicillin-resistant Staphylococcus aureus (MRSA), which comprises exposing MRSA to bactericidal UV light in the wavelength range of 207 to 222 nm, wherein the UV light is 3. Irradiated by a UV lamp with a lamp cover made from methicrate glass with a total platinum content of less than 5 ppm. In some embodiments, the glass may further have a low content of iron, titanium, and other heavy metals, each less than 5 ppm.

UV radiation can break organic bonds. Therefore, this is not life-threatening due to the destruction of biological material. In addition, many plastics are damaged by UV light due to haze, embrittlement, and / or disintegration. Therefore, UV light may be harmful to a number of sensitive surfaces or other materials that may be susceptible to UV, such as certain gases and / or liquids.

In humans, excessive exposure to UV radiation can have acute and chronic adverse effects on the folding optics and retina of the eye. The skin, circadian rhythm, and immune system can also be affected. The skin and eyes are most sensitive to UV damage from 265 to 275 nm.

Artificial UVC light with a wavelength of about 250 nm, such as emitted by a conventional UVGI lamp, such as a mercury steam lamp, causes and is exposed to UV-associated premutagenic DNA lesions, for example in a human skin model. It is cytotoxic to mammalian skin. The eye is most sensitive to UV damage in the low UVC band of 265 nm to 275 nm. Radiation of this wavelength is rare in sunlight, but is found in welder arc light and other artificial light sources. Exposure to these can cause "electrical eye inflammation" or "arc eye" (photokeratitis) and can also cause the formation of cataracts, pterygium, and pinguecula.

Therefore, the wavelength applied according to the method of the present invention is in the range of 207 nm to 222 nm. Ultraviolet (UV) light at about 207 nm has antibacterial properties similar to typical bactericidal UV light (254 nm), but is external to higher animals such as amphibians, reptiles, birds, mammals, or human skin. It does not damage the tissue coating. However, in another embodiment, it may be used to remove MRSA from the outer surface of mollusks (shells) and / or arthropods (exoskeletons).

Due to the limited transmission distance of 207 nm light in biological samples (eg, stratum corneum) compared to 254 nm light, treated surfaces, especially mammalian or human skin, such as patient or healthcare worker skin. It is possible to perform selective antibacterial treatment without harming the skin.

With respect to the eye, the most important subject in terms of UV risk is the lens. Since the lens is located distal to the cornea and the cornea is thick enough (500 μm), the transmission of 200 nm light from the cornea to the lens is virtually zero. Considering the effects on the cornea in terms of photokeratitis, the protective device for eye exposure, which is now almost common among surgical staff, is expected to completely protect the cornea from UV exposure at 207 nm. To.

The proposed bactericidal use of 207 nm UV light in the presence of humans is due to the fact that UV light with a wavelength of about 200 nm is very strongly absorbed by proteins (especially via peptide bonds) and other biomolecules. Because it is based, its ability to penetrate biological material is very limited. Thus, for example, the intensity of UV light at 200 nm is reduced by half for a tissue of only about 0.3 mm compared to a much longer distance for about 3 mm and larger UV wavelengths at 250 nm. In contrast, UV light at 200 nm is minimally absorbed by water.

At the cellular level, bacteria are much smaller than almost any human cell. Typical bacterial cell diameters are less than 1 μm, while typical eukaryotic cell diameters range from about 10-25 μm.

Therefore, although 200 nm UV light can penetrate the entire typical bacterial cell, it cannot penetrate significantly beyond the outer periphery of the cytoplasm of a typical eukaryotic cell such as a human cell, and can penetrate the nucleus of a typical eukaryotic cell. Significantly fades before reaching.

In contrast, longer wavelength light from conventional germicidal lamps can reach the human cell nucleus without significant extinction. Based on these biophysical considerations, radiation from conventional UVC lamps is cytotoxic and mutagenic to both bacterial and human cells, while 200 nm UV light is bacterial. It is cytotoxic to human cells but much less cytotoxic or mutagenic to human cells.

However, UV light with wavelengths significantly shorter than 200 nm is not useful as sufficient removal of MRSA can no longer be achieved at these wavelengths. Moreover, at wavelengths below 200 nm, UV reacts with oxygen to form ozone, which is an undesired effect.

UVC light in the range of about 207 to 222 nm effectively removes bacteria regardless of the acquisition of drug resistance, but does not have the skin and eye damage associated with conventional bactericidal UV exposure.

The term "removal" is used herein by ISO 22196: 2011-08-31 for MRSA> 90%,> 95%,> 99%,> 99.9%, or> 99.99% after treatment. Is used for the reduction of.

To achieve such removal, in one embodiment, the present invention has a UV exposure of 2,000 to 8,000 μW · s / cm ² , 2,100-7, for MRSA and / or the surface being treated. It relates to a method in the range of 000 μW · s / cm ² , 2,200 to 5,000 μW · s / cm ² , or 2,300 to 3,000 μW · s / cm ² . In one embodiment, UV exposure of at least about 2,500 μW · s / cm ² results in a 90% reduction in MRSA.

The methods of the invention can be used to remove MRSA on any type of UV sensitive material that is sensitive to conventional UV radiation with wavelengths above 222 nm. Such a "UV sensitive material" can be any material in which UV with wavelengths above 222 nm, above 250 nm, and / or up to 295 nm can break organic or inorganic bonds. Such UV sensitive materials can include any plastic that is damaged due to haze, embrittlement, and / or disintegration by UV radiation up to 222 nm to 295 nm and / or up to 295 nm.

In another embodiment, the UV sensitive material can be sensitive to crosslinking of the monomers in order to produce a particular polymer by UV radiation above 222 nm, or over 250 nm, and / or up to 295 nm. In yet another embodiment, the UV sensitive material can be a gas or liquid above 222 nm, or above 250 nm, and / or sensitive to UV up to 295 nm.

In yet another embodiment, the UV sensitive material can be a pharmaceutical composition that is more than 222 nm, or more than 250 nm, and / or UV sensitive up to 295 nm.

In yet another embodiment, the UV sensitive material is an insect, invertebrate, vertebrate, mammal or human (eg, arthropod, fish, amphibian, reptile, bird, mammal, and / or human skin, or lobster or insect. It can be a biological tissue surface such as an arthropod-derived chitinous exoskeleton).

Accordingly, the term "biological tissue surface" as defined by the present invention refers to any biological surface that can be harmed by UV radiation above 222 nm, or above 250 nm, and / or up to 295 nm. Include. In one embodiment, the invention is a biological surface that can be harmed by UV radiation outside the wavelength range of 207 to 222 nm, and a biology that is not harmed by UV radiation within the wavelength range of 207 to 222 nm. Including the target surface.

In the present invention, the term "tissue" is used at any cellular tissue level between cells and complete organs. Tissue is a collection of similar cells of the same origin and their extracellular matrix that together perform a particular function. Organs are then formed by functionally grouping together multiple tissues.

Of course, tissue that can be exposed to UV radiation should be included, especially in the MRSA removal method. Most often, these tissues are epithelial tissues formed by cells that line the surface of organs, such as the surface of the skin, the airways, the genital tract, and the inner walls of the gastrointestinal tract. The cells that make up the epithelial layer are connected via tight junctions of the semipermeable membrane. Therefore, this tissue provides a barrier between the organs it covers and the external environment. In addition to this protective function, epithelial tissue may be specialized in functions in secretion, excretion, and absorption. Epithelial tissue helps protect organs from microbes, injuries, and fluid loss.

Therefore, is the method of the present invention preferably applicable to conventional UVGI methods, such as UV treatment of MRSA present on UV sensitive surfaces such as skin tissue or areas where exposure of the eye to UV is unavoidable. Includes methods that may not be appropriate.

The term "mammal" as used herein constitutes a mammary gland, neocortex (region of the brain), fur or hair, which produces milk to feed (lactate) its child in a female. And refers to any vertebrate characterized by the presence of three small and medium ear bones. These characteristics are different from the reptiles and birds that diverged in the Late Triassic, 201 million years ago to 227 million years ago. There are about 5,450 species of mammals. The largest eyes are rodents, bats, and soricomorpha (such as shrews). The next three are primates (apes, monkeys, etc.), Cetartiodactyla (terrestrial whales and artiodactyla), and carnivores (Carnivora) (cats, dogs, lizards, etc.). This definition of mammal also includes humans.

Thus, the term "mammalian skin" refers to any skin of mammals, including livestock skin, and the term "livestock" generally refers to labor and commodities such as cows, goats, horses, pigs, and sheep. For example, it is defined as livestock raised in an agricultural environment to produce meat, eggs, milk, fur, leather, and hair.

In addition, the term "mammalian skin" includes, for example, patients, healthcare workers, people with weak or deficient immune systems (elderly, pediatric, postoperative, post-organ transplant, HIV positive, etc.). It also includes human skin, such as those with high potential exposure to MRSA.

The prior art UV lamp covers are made of sapphire, synthetic quartz, or quartz glass (fused silica glass). However, sapphire is very expensive compared to other permeable materials and cannot be bent, molded, stretched or fused together like glass or metal. In addition, it has very high UV absorption at UVC wavelengths and hardly transmits at wavelengths below 250 nm.

In one embodiment, the glass has a transmittance of at least 50% at 200 nm, better at least 60%, or at least 70%, and / or at least 85% at wavelengths [λ] of 260 nm, 280 nm, and / or 310 nm. Has (measured with a thickness of 1 mm).

Quartz glass and fused silica glass are also expensive to manufacture because of their high melting point, which results in much higher melting and blowing temperatures and labor than other standard glasses. In addition, non-tubular morphology must be sharpened and polished from large blocks. In addition to manufacturing costs, these covers have the drawback of requiring large amounts of energy to ensure sufficient UV exposure of the object, gas, or liquid being processed.

However, the glass of the present invention is suitable for forming rods, sheets, discs, tubes, and bars manufactured by casting, Danner, bellows, and / or downdraw processes.

Furthermore, due to the high operating temperature, the effects of sagging and collapsing may occur over time, especially when the temperature is cycled at high temperatures and surface devitrification becomes apparent. There is. However, this further enhances the weathering effect of the cover, increases UV absorption, and requires even higher operating energy to ensure adequate UV exposure of the treated object, gas, or liquid. This is a vicious circle.

The high operating energy increases thermal stress not only on the cover but on the entire device, which shortens the life of the device and increases maintenance costs.

The glass of the present invention may have excellent optical properties. In one embodiment, the glass has a refractive index nd (λ = _587.6 nm) of 1.40 to 1.58. The refractive index can be less than 1.50.

The glasses described herein have excellent UV permeability. These may have one or more of the following optical properties:
-UV transmittance at 200 nm of at least 60%, at least 62.5% in one embodiment (measured at thickness d = 1 mm);
-UV transmission at 207 nm of at least 65%, at least 67.5% in one embodiment (measured at thickness d = 1 mm);
-UV transmittance at 210 nm of at least 65%, at least 69% in one embodiment (measured at thickness d = 1 mm);
-UV transmission at at least 75%, at least 81% in one embodiment at 230 nm (measured at thickness d = 1 mm); and / or-at least 82.5%, at least 85.2% in one embodiment at 250 nm UV transmittance (measured at thickness d = 1 mm).

In one embodiment, the glass has UV transmission (measured at thickness d = 1 mm) in the wavelength range of 207 nm to 222 nm, ranging from at least 65% at 207 nm to at least 75% at 222 nm. In one embodiment, the UV transmittance ranges from at least 67.9% at 207 nm to at least 76.8% at 222 nm.

The glass and / or glass article preferably has 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%. The transmittance is specifically measured with a sample thickness of 1 mm.

For clarity, the indication that transmittance is measured at a particular wavelength does not mean that the glass is limited to a specified thickness. Instead, the thickness indicates the thickness at which the transmittance can be measured. By specifying the thickness for measurement, the values can be compared reliably. Those skilled in the art will appreciate that any suitable thickness of glass can be used for the glass covers and devices described below. In addition, those skilled in the art will appreciate that transmissions can be measured at thicknesses other than 1 mm and transmission values at 1 mm can be calculated from such measurements.

The present invention utilizes and relates to novel glasses and glass covers (lamp covers, LED cover glasses) that exhibit low UV absorption (ie high UVC transmission), thereby reducing operating energy and lowering operating temperature. Let me. In addition, the novel glass and glass covers of the present invention are relatively inexpensive and easy to manufacture, and can be bent, molded, stretched and fused to ensure a variety of shapes. It can and is resistant to most chemicals, as well as temperature and physical stress.

In one embodiment, the glass has a transmittance of at least 60% (measured at a thickness of 1 mm) over a wavelength range of 207 nm to 222 nm, and the glass has a total platinum content of 3.5 ppm or less. In some embodiments, each has a low iron and titanium content of less than 5 ppm, and the extracted Na ₂ O equivalent in μg units per gram of glass as determined according to ISO 719 is 250 μg / g or less, 200 μg. A borosilicate glass having hydrolysis resistance characterized by being less than / g, less than 180 μg / g, less than 125 μg / g, less than 50 μg / g, less than 40 μg / g, or less than 25 μg / g.

In one embodiment, Pt contamination in glass (ie, Pt ⁰ , Pt ²⁺ , Pt ⁴⁺ , and Pt ⁶⁺ , also referred to as "total platinum content") can reduce UV transmission from 200 nm to about 250 nm. Found. Without being bound by theory, it is believed that platinum contamination in glass can cause phase separation by nucleation within the glass. The glass of the present invention is borosilicate glass with no or very low metal contamination, in particular Pt contamination of less than 3.5 ppm or less than 2.5 ppm. In another embodiment, 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, 0- 0.25 ppm is preferable. In a further embodiment, the glass is free of Pt contamination.

In yet another embodiment, it has been found that TiO ₂ contamination in glass (also referred to as "titanium content") can also further reduce UV transmission from 200 nm to about 250 nm. Therefore, in one embodiment, glass having a TiO ₂ content of 100 ppm or less, preferably 50 ppm or less is preferable. Preferably, the amount of TiO ₂ should be less than 7 ppm, less than 6 ppm, less than 5 ppm, or less than 4 ppm. In another embodiment, the TiO ₂ content can be 0-6.9 ppm, 0-5.8 ppm, 0-4.7 ppm, 0-3.8 ppm, or 0-2.5 ppm. The optional composition preferably has a content of 0 to 1.5 ppm, 0 to 1.0 ppm, 0 to 0.75 ppm, 0 to 0.5 ppm, or 0 to 0.25 ppm. In a further embodiment, the glass is free of TiO ₂ contamination.

In yet another embodiment, it has been found that Fe contamination in glass can also further reduce UV transmission at 200 nm to about 250 nm. In the present specification, the iron content is expressed as parts by weight of Fe ₂ O ₃ in ppm units. This value is well known to those skilled in the art by determining the amount of all iron species present in the glass and assuming that all iron is present as Fe ₂ O ₃ for mass fraction calculations. It can be decided by the method. For example, if 1 mmol of iron is found in the glass, the calculated mass corresponds to 159.70 mg of Fe ₂ O ₃ . This procedure takes into account the fact that the amount of individual iron species in the glass cannot be determined reliably or only with great effort. In some embodiments, the glass comprises Fe ₂ O ₃ less than 100 ppm, particularly less than 50 ppm, or less than 10 ppm. In embodiments where the iron content is particularly low, the Fe ₂ O ₃ content is less than 6 ppm, less than 5 ppm, or less than 4.5 ppm. Optionally, the content of Fe ₂ O ₃ is 0 to 4.4 ppm, 0 to 4.0 ppm, 0 to 3.5 ppm, 0 to 2.0 ppm, or 0 to 1.75 ppm. In some embodiments, the content can be 0-1.5 ppm, or preferably 0-1.25 ppm. In a further embodiment, the glass is free of Fe ₂ O ₃ contamination.

Thus, in a preferred embodiment, the total contamination of all contamination with Pt, TiO ₂ , and / or Fe ₂ O ₃ is less than 20 ppm, in another embodiment less than 18.5 ppm, in another embodiment less than 13.5 ppm, separately. In one embodiment, less than 10.5 ppm, and in another embodiment, less than 8.5 ppm glass is preferable. In another embodiment, the sum of all contaminations is 0-8.2 ppm, 0-7.0 ppm, 0-6.0 ppm, 0-5.0 ppm, 0-4.0 ppm, 0-3.0 ppm, 0- Glass having 2.0 ppm, 0 to 1.0 ppm, 0 to 0.5 ppm, and 0 to 0.25 ppm is preferable. In a further embodiment, the glass is free of contamination by at least one, two, or up to all three of the metals selected from Pt, TiO ₂ , and / or Fe ₂ O ₃ .

Also, other contamination with transition elements and / or heavy metals such as lead, rhodium, cadmium, mercury, and hexavalent chromium can be maintained at less than 10 ppm, in another embodiment less than 8.5 ppm. In another embodiment, these contaminations can be maintained at 0-8.2 ppm, 0-7.0 ppm, 0-6.0 ppm, 0-5.0 ppm, or 0-4.0 ppm. In another embodiment, the levels of these contaminations can be 0-3.0 ppm, 0-2.0 ppm, 0-1.0 ppm, 0-0.5 ppm, or 0-0.25 ppm. In a further embodiment, the glass is free of contamination with transition metals and / or heavy metals.

When a chemical element is referred to herein, the description refers to any chemical form, unless otherwise stated in the individual case. For example, the statement that glass has an As content of less than 100 ppm means that the total mass fraction of the existing As species (eg, As ₂ O ₃ , As ₂ O ₅ , etc.) does not exceed the value of 100 ppm. ..

As used herein, the term "ppm" means parts per million on a weight ratio basis (w / w).

In order to produce glass with appropriate UV transmission, it is necessary to avoid metal contamination during the manufacturing process. Therefore, the present invention may also relate to a method for producing glass having a high UV transmittance.

In one embodiment, the glass of the invention is a borosilicate glass with high UV transmittance and the following additional range of physical and chemical parameters.

Unlike quartz, the glasses of the invention have excellent melting properties, such as low transition temperatures and working points. Examples of suitable glass parameters are transition temperatures T _g (ISO 7884-8) below 550 ° C, such as 400 ° C to 500 ° C, 420 ° C to 460 ° C in one embodiment, 450 ° C to 480 ° C in another embodiment. ) Can be selected.

The glass has a T13 temperature of 410 ° C. to 550 ° C., for example, 445 ° C. to 485 ° C. in one embodiment and 490 ° C. to 510 ° C. in another embodiment, that is, a viscosity η (ISO 7884-4) of ^{10 13} _dPa · s. Can have a glass temperature (slow cooling point) in. The glass has a softening point of 650 ° C. to 750 ° C., for example, 690 ° C. to 715 ° C. in one embodiment and 700 ° C. to 725 ° C. in another embodiment, that is, a temperature at which the viscosity becomes ^107.6 dPa · s (softening point). ) (ISO 7884-3). The glass has a working point of 1000 ° C. to 1150 ° C., 1060 ° C. to 1100 ° C. in one embodiment, and 1090 ° C. to 1140 ° C. in another embodiment, that is, a temperature (working point) at which the viscosity becomes ¹⁰⁴ dPa · s. It may have ISO 7884-2). The temperature-viscosity dependence represented by one or more of these parameters accompanies the ability of the glass to be stretched or molded into any desired shape such as other UV lamp covers or UV-LED covers.

Thus, in one embodiment, the glass has a T _g of 420 ° C to 465 ° C: a T ₁₃ of 445 ° C to 485 ° C, a softening point of 690 ° C to 715 ° C, and a working point of 1060 ° C to 1100 ° C.

In another preferred embodiment, the glass has a T _g of 460 ° C to 470 ° C: T ₁₃ of 490 ° C to 510 ° C, a softening point of 700 ° C to 725 ° C, and a working point of 1090 ° C to 1140 ° C.

The glass of the present invention may have a density ρ of 2 to 2.5 gcm ^-3 at 25 ° C. Due to its low density, glass is ideal for portable applications such as portable MRSA removers.

The glass of the present invention can be characterized by a thermal conductivity of 0.8 to 1.2 _Wm ^-1 K ^-1 at 90 ° C., and is therefore most suitable for use as a lamp cover.

UVC glass and UVC glass covers manufactured from it have the following additional features:
The term "solarization" refers to a phenomenon in physics in which the light transmittance changes after a material is exposed to high-energy electromagnetic radiation such as ultraviolet light. Clear glass and many plastics turn amber, green, or other colors when exposed to X-rays, and the glass may turn blue after prolonged sun exposure in the desert. Solarization can permanently degrade the physical or mechanical properties of a material and is one of the mechanisms involved in the decomposition of plastics in the environment.

The glass of the present invention can exhibit very good resistance to "solarization" (see Example section) and is therefore very suitable for use as UV glass. "Solarization" is a decrease in the transmittance of light in various wavelength ranges caused by exposure to short wavelength UV light. Solarization can color the glass or make it completely opaque.

ここで、Ｔ（λ）_０は照射前の透過率であり、Ｔ（λ）_ｉは重水素ランプによってｉ時間照射した後の透過率である。α（λ）が小さいほど、ガラスはソラリゼーションに対してより耐性を有している。耐ソラリゼーション性は、本明細書では波長２００ｎｍについて記述される。耐ソラリゼーション性の規定については、本明細書では約０．７０ｍｍ～０．７５ｍｍのサンプル厚が想定されている。これは、このサンプル厚で測定が行われることを意味する。実用新案登録請求されるガラス物品自体は、異なる厚さを有することができる。照射は重水素ランプを用いて行われる。重水素ランプは、非常に短波のＵＶ範囲まで発光する。本明細書で使用されているランプのカットオフ波長は１１５ｎｍである。重水素ランプの出力は約１Ｗ／ｍ^２とすることができる。以下の重水素ランプ（ＤＵＶ）を使用することができる：１１５ｎｍまでの十分な発光のためのＭｇＦ_２フィルターを備えたHeraeus Noblelight GmbH, Type V04, S-Nr.: V0390 30 W。 Therefore, "solarization resistance" is a characteristic of glass that maintains high transmittance at a specific wavelength even after UV irradiation. This can be explained by calculating the induced absorbance α (λ):

Here, T (λ) ₀ is the transmittance before irradiation, and T (λ) _i is the transmittance after irradiation with a deuterium lamp for i hours. The smaller α (λ), the more resistant the glass is to solarization. Solarization resistance is described herein for a wavelength of 200 nm. Regarding the provision of solarization resistance, a sample thickness of about 0.70 mm to 0.75 mm is assumed in the present specification. This means that measurements are made at this sample thickness. The glass articles themselves for which utility model registration is requested can have different thicknesses. Irradiation is performed using a deuterium lamp. Deuterium lamps emit light up to the very shortwave UV range. The cutoff wavelength of the lamp used herein is 115 nm. The output of the deuterium lamp can be about 1 W / m ² . The following deuterium lamps (DUVs) can be used: Heraeus Noblelight GmbH, Type V04, S-Nr .: V0390 30 W with MgF ₂ filter for sufficient emission up to 115 nm.

The glass used in the present invention also exhibits very good hydrolysis resistance and high airtightness.

The phase separation factor is a measure of the properties of glass that alters hydrolysis resistance as defined in ISO 719 as a result of phase separation. Phase separation occurs when the glass melts due to the effects of temperature. Since it has been proved advantageous to select a glass having a phase separation coefficient as close to 1 as possible, the glass properties of the phase-separated glass are not significantly different from those of the raw glass in terms of hydrolysis resistance. The phase separation coefficient is affected not only by the composition of the glass but also by its thermal history (cooling state).

The phase separation coefficient E is calculated as follows.

Here, _Equiloh and _Equient are the Na ₂ O equivalents of the phase-separated glass and the phase-separated glass, respectively, in μg units per gram determined according to ISO 719: 1989-12. The phase separation factor is a characteristic of glass. This coefficient does not mean that the glass for which utility model registration is requested has undergone phase separation, but when phase separation occurs, the effect on hydrolysis stability is within the range specified by the coefficient. be. All glasses can be analyzed for their phase separation factor. For this purpose, the equivalent of the extracted Na ₂ O is measured on the phase-separated and non-phase-separated test pieces. For measurement purposes, "phase-separated glass" is obtained by holding the glass test strip at a temperature 100 ° C. above the glass transition temperature (T _g ) for 4 hours. This temperature treatment guarantees a constant level of phase separation.

Hydrolysis resistance can be expressed as the amount of Na ₂ O extracted in μg units per 1 g of glass. The Na ₂ O equivalent extracted in μg units per 1 g of glass is determined according to ISO 719: 1989-12. This is a measure of the extractability of basic compounds from glass in water at 98 ° C.

In one embodiment, the glass is 0.1 to 1.65, or 0.2 to 1.65, or 0.35 to 1.65, or 0.40 to 1.65, or 0.65 to 1. It has a phase separation factor of 65, particularly with respect to its hydrolysis resistance, in the range 0.70 to 1.10. In particular, this factor is at least 0.1, or at least 0.2, or at least 0.35, or at least 0.40, or at least 0.70. Preferably, this coefficient is close to 1.00, which corresponds to the case of unchanged hydrolysis resistance after phase separation. In one variant, the phase separation factor is up to 1.40, up to 1.25, or up to 1.10.

In one embodiment, the coefficients are at least 0.70 and up to 1.6. In another variant, the phase separation factor is at least 0.30 and up to 0.5.

Due to the nature of the glass, the UVC glass cover can be hermetically sealed using, for example, laser glass frit sealing. This airtight seal is important because many UVGIs are used in aqueous environments (eg biofilm treatments and water treatments), high humidity environments (eg sewage systems), and / or environments under high gas pressure or vacuum. Is. In addition, the airtight seal allows autoclaving of the final device, eg UVC-LED lamps, for use in hospitals, surgery, laboratories, or other environments where high hygiene standards are required. can do.

This is in contrast to conventional glass, quartz, and / or fused silica glass, which does not have the thermal properties required for laser frit sealing and therefore cannot be hermetically sealed. However, the glasses described herein are suitable for achieving tight, crack-free, close glass frit connections.

The glass of the present invention preferably has a product CTE [° C ^-1 ] x T ₄ [° C.] of up to 0.0055, more preferably up to 0.0053, or up to 0.0051. The product can be at least 0.0044 or at least 0.0045. These glasses have been shown to exhibit favorable properties with respect to melt stress and melt behavior.

"T ₄ " is the temperature at which the glass has a viscosity of ¹⁰⁴ dPa · s. T ₄ can be measured according to methods known to those of skill in the art for determining the viscosity of glass, such as DIN ISO 7884-1: 1998-02. "T ₁₃ " is the temperature at which the glass has a viscosity of 10 ¹³ dPa · s.

The average coefficient of linear thermal expansion α (CTE) (20 ° C; 300 ° C, conforming to ISO 7991) is 3.0 to 6.0 × ^10-6K - ¹ in one embodiment. The coefficient of thermal expansion (CTE) can be less than 4.5 x ^10-6 K ^-1 . This is less than 3.5-5 × ^{10-6K -1, more preferably 3.75-4.75 × 10-6K -1 , more} preferably 4.1-4.6 × ^10-6K . It can be in the range of ^-1 , more preferably 4.1 to 4.5 × 10 ^-6 K ^-1 . This allows the thermal expansion characteristics to be matched to the overall thermal expansion characteristics of the UV device, thus preventing tension in the glass cover. In one embodiment, the same or similar CTE is selected for both the UVC glass cover and the underlying UV device (eg UVC-LED package).

Preferably, the glass transition temperature is less than 500 ° C. This can be in the range of 400 ° C. to 550 ° C., more preferably 410 ° C. to 500 ° C., and in another embodiment the range of 420 ° C. to 480 ° C. The processing temperature T ₄ is a temperature at which the viscosity of the glass becomes ¹⁰⁴ dPa · s. The processing temperature T ₄ of the glass of the present invention can be less than 1200 ° C, and in some embodiments less than 1125 ° C. This can be in the range of 1000 ° C to 1200 ° C, more preferably in the range of 1025 ° C to 1175 ° C.

In order to keep the melting properties including T _g and T ₄ within the desired range, the ratio of the content (mol%) of B ₂ O ₃ to the total of SiO ₂ and Al ₂ O ₃ should be narrowed. It may be advantageous to set. In an advantageous embodiment, this ratio is at least 0.15 and / or up to 0.4.

Another important property of glass is the excellent spatial _uniformity of the refractive index nd of the material. Optionally, the change in index of refraction in the glass may correspond to the deformation of the wavefront passing through the glass according to the following equation:
Δs = Δ (nd ^* d) = Δn _d ^* _d + Δd ^* n _d
Here, Δs is the wavefront deviation, d is the thickness of the glass, Δd is the change in thickness (difference between the maximum thickness and the minimum thickness), and Δn _d is the change in the refractive index of the glass (maximum refraction). The difference between the rate and the minimum refractive index). The present invention further includes a glass article having a predetermined wavefront deviation.

The wavefront deviation can be calculated according to the above equation. The refractive index nd (λ = _587.6 nm) and the thickness can be determined at 20 ° C. In one embodiment, the wavefront deviation is determined and / or applied over a surface area of 1 cm ² . The wavefront deviation can be determined for glass with a thickness of 10 mm or less, or glass with a thickness of 1 mm or less. Optionally, the thickness can be at least 200 μm. The wavefront deviation can 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 can be 0.1 μm to 250 μm, or 1 μm to 100 μm, or 2 μm to 85 μm.

Wave surface anomalies can be measured axially, for example in the case of glass tubes, such as those used in discharge lamps, or laterally, for example in the case of rod portions, such as those used in UVC-LED lenses. can do.

The wavefront can also be measured by a wavefront sensor. This is a device that measures the wavefront aberration of a coherent signal to represent the optical quality or lack thereof in an optical system. Without being bound by any particular method, a very common method is to use a Shack-Hartmann small lens array.

Wavefront sensing techniques that replace the Shack-Hartmann system are mathematical techniques such as phase imaging and curvature sensing. These algorithms compute wavefront images from traditional brightfield images at various focal planes without the need for special wavefront optics.

The glass and glass articles according to the present invention may have a low content of wavefront deformation (pulses, bubbles, streaks, etc.) in the glass. In general, it is possible to distinguish between the overall or long range uniformity of the refractive index of a material and the short range deviation from the uniformity of glass. Pulsation is a spatially short range of variation in uniformity in glass. Short range variability is variability over distances from about 0.1 mm up to 2 mm, whereas spatially long range of refractive index overall uniformity is over the entire piece of glass.

In some embodiments, a UV transmission filter can be used, which is a particular unwanted UV wavelength, eg, less than 207 nm, in some embodiments less than 200 nm, and / or more than 222 nm, in some embodiments. The form removes wavelengths above 250 nm.

The glass for a UV cover according to the present invention can allow the formation of a lens for optically forming UV rays, for example for directional focusing of UV light to a target.

Any beam angle from 10 ° to 180 ° is possible. In some embodiments, 10 ° to 20 °, 20 ° to 30 °, 30 ° to 40 °, 40 ° to 50 °, 50 ° to 60 °, 60 ° to 70 °, 70 ° to 80 °, 80. ~ 90 ° can be used. In another embodiment, 15 ° to 35 °, 25 ° to 45 °, 35 ° to 60 °, 45 ° to 90 °, 75 ° to 120 °, 90 ° to 145 °, 120 ° to 180 ° are used. be able to.

In some embodiments, for example, 90 °, 120 °, or even 180 ° when a tube of a particular size or volume or a surface of a particular volume or a particular diameter needs to be decontaminated in a single treatment. A fairly wide beam shape is useful.

In another embodiment, narrow beam shapes such as 10 °, 5 °, and even 1 ° are useful. For example, narrow beam shapes to concentrate UV exposure on the target site and avoid omnidirectional unwanted radiation that would reduce the efficiency of the energy-to-irradiation ratio or the exposure of UV-sensitive surfaces to UV light. Can be used. One example can be limited decontamination of a given area of the eye.

In addition, various lens shapes and beam angles can be used to solve the complex MRSA removal challenges. For example, UV-sensitive surfaces at different levels of sensitivity are adjacent to each other and need to be exposed to UV in a single treatment.

For example, during wound healing and / or surgery where the wound itself is exposed to less UV than the surrounding skin, it may be appropriate to treat the patient's skin in multiple areas with more UV exposure than adjacent areas. be.

The present invention also includes a method of manufacturing an LED package having a cover made of the UVC transmissive glass of the present invention.

The LED package according to the invention may include:
・ LED chip;
-Optional, LED chip-mounted substrates-eg PCBs, polymers, inorganic materials, especially ceramics, metal;
-Base plate (metal, ceramic, glass ceramic, rarely polymer) if it contains an optional feedthrough for the conductor to contact the LED chip;
Frames containing LED chips (metals, ceramics, glass ceramics, rarely polymers) that are attached to or surround the base plate and form some kind of cavity;
The end of the housing (cover), which is at least partially transparent and has the package closed or is manufactured from an entirely transparent material, facing outward from the chip; at least the transparent part of the cover , Made of UVC permeable glass as described herein.

Such windows may be flat or have a shape (ie, lens shape) for altering the path of light.

As mentioned above, UVC-LEDs can be packaged and sealed in some way (eg, laser frit sealing) so that they can be autoclaved, sterilized, and resistant to fluids. Such UVC-LEDs can be used in air and water, surface sterilization; and medical / dental applications.

UVC-LEDs with UVC permeable glass described herein have other advantages over conventional UVGI lamps or devices (such as mercury vapor lamps), for example:
-Immediate on / off function that enables "on-demand disinfection" without wasting energy;
Directive radiation (especially with the use of lenses that allow control of the beam angle), enabling "targeted disinfection" with a simple design;
• Durability of semiconductors for use in rugged and portable devices;
-Low DC power requirements that improve energy efficiency and provide simple and inexpensive electric drives;
-Compact packaging that maximizes design flexibility;
-Environmentally friendly structure by allowing easy disposal without exposure to harmful mercury;
・ High optical performance;
-High radiation output at the specified wavelength;
・ CTE matching with AlN;
・ Relatively low manufacturing price;
-Small size.

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, high-energy-efficiency UV light, such as UVC-LEDs. UV lamps and UV devices based on the present invention have greater energy efficiency compared to conventional UVGI lamps or devices. This is because the glass of the present invention can transmit more than 60% UV light at 200 nm, which greatly improves the ratio between energy input and radiation output.

This becomes important when these glasses are used as covers for UVC-LED lamps. When the energy requirement of a conventional mercury vapor UV lamp is set to 100%, the energy required to generate the same UV radiation with the UVC-LEDs described herein is about 10-30%. In other words, if a conventional UV lamp uses 10 W of energy to emit a particular UV intensity, the devices herein can use only 1-3 W.

As mentioned above, another advantage of the UVC permeable glass described herein is its high thermal conductivity (λ _w ), which is 0.75-1.25 Wm- ¹ at 90 ° C. K ^-1 , and in another embodiment, it can be about 1.0 W · m ^-1 K ^-1 . This excellent thermal conductivity increases the life of the device by allowing excess heat to be easily dissipated before it harms the rest of the device. This is in contrast to quartz glass, which usually has a low optimum thermal conductivity, for example.

Therefore, in one embodiment, the method according to the invention has an energy efficiency index (EEI) of 0.11 or less according to Rule (EU) No. 874/2012 for omnidirectional UV lamps and is directional UV lamp. UV lamps with an energy efficiency index (EEI) of 0.13 or less according to Case Rule (EU) No. 874/2012 may be included.

The methods described herein can be used to remove MRSA from any type of surface, including UV sensitive surfaces, UV sensitive liquids, and / or UV sensitive gases.

Of course, the methods described herein include viruses (eg, influenza or coronaviridae, such as SARS-CoV-2, especially resistant viral variants such as SARS-CoV2-D614G), bacteria (including spores). It can also be used for the removal of other UV-sensitive pathogenic organisms such as pathogenic yeast, mold.

Possible uses include hand disinfectants (eg personal and public toilets), indoor disinfectants in medical environments, MRSA removal during, during or after surgery, wound healing, ophthalmic treatment, food disinfection (eg food manufacturing). Medium and / or supermarket meat, dairy or vegetable counters), disinfection of livestock (especially for intensive animal rearing such as battery laying), pharmaceutical compound production and / or food production process Includes disinfection of UV-sensitive surfaces that often come into contact with storage equipment and / or many different users, such as keyboards, handles, handrails, toothbrushes, hairbrushes, ornaments, touch devices, shaving razors, or children's toys. You can choose from a list of uses.

The UVC devices disclosed in the present invention can also be used in a wide range of applications as "analytical instruments", such as:
HPLC (High Performance Liquid Chromatography): Used in analysis to detect chemicals and compounds in life sciences;
Spectrometer: Used in multiple applications for testing and analysis across biotechnology, life sciences, and environmental monitoring;
-Water quality monitoring sensor: Used to detect chemicals in water (eg, in the process of fracking, for general water safety, or before disposing of treated wastewater).

In another embodiment, the UVC device disclosed in the present invention may include a device for "disinfection of water". In this respect, UVC LEDs have an advantage over conventional mercury lamps that require a long warm-up time (range 50 seconds to 10 minutes) to reach the required sterilization intensity. In addition, frequent on / off cycles can reduce life by 50% or more.

As a result, mercury lamps in these applications need to be maintained all day long, lamps are replaced more frequently, and power consumption increases. In contrast, the immediate on / off performance of UVC LEDs allows for on-demand disinfection, which significantly reduces power consumption.

In addition, frequent on / off cycles do not shorten the life of the LED, helping to reduce operating and maintenance costs.

Further uses of the UVC devices disclosed in the present invention may include, especially in the case of UV sensitive surfaces, liquids, or gases:
• Bioinformatics studies of protein structure and function using protein analysis, ie database search, sequence comparison, structural and functional prediction.
-Molecular identification, the process of comparing specific DNA fragments between organisms.
• In cytometry, or biotechnology, flow cytometry is used in cell counting, cell sorting, biomarker detection, and protein engineering by suspending cells in a stream of liquid and passing them through an electronic detector. It is a biophysical method based on laser or impedance.
A biofilm treatment system, a system that employs the use of bacteria, fungi, algae, and protozoa to remove organic and inorganic substances from surrounding liquids.
Nitrate and / or NOx measurements, usually performed at wavelengths of approximately 230 nm.
Parasetamol concentration measurements, usually performed at a wavelength of about 245 nm; and / or-Skin treatments to improve skin condition (eg psoriasis, leukoplakia, itching, neurodermatitis, acne, photodermatitis, phototherapy, Rose-colored psoriasis, etc.).

Therefore, in one embodiment, the use of the UV-LED module of the present invention is for water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection (eg keyboard disinfection, escalator). UV sterilizer for handrails), cytometry, molecular identification, protein analysis, biofilm treatment, hardening, lithography, plant growth, skin treatment, bacterial detection, drug discovery, protein analysis, induction of skin vitamin D3 production, and / or sterilization You can choose from the group of.

Therefore, in one aspect, the invention relates to UV-LED modules such as water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection (eg keyboard disinfection, escalator). UV sterilization device for handrails), cytometry, molecular identification, protein analysis, biofilm treatment, hardening, lithography, plant growth, skin treatment (psoriasis, white spots, itching, neurodermatitis, acne, photodermatitis, phototherapy, Use of glass according to the invention as a hermetically sealed lens cap for applications selected from the group of rose-colored rash), bacterial detection, drug discovery, protein analysis, induction of skin vitamin D3 production, and / or sterilization. Regarding.

The glass is preferably borosilicate glass.

In one embodiment, the borosilicate glass comprises the following components (oxide-based mol%):

ここで、「Ｒ_２Ｏ」はアルカリ金属酸化物Ｌｉ_２Ｏ、Ｎａ_２Ｏ、およびＫ_２Ｏを指し、「ＲＯ」はアルカリ土類金属酸化物ＭｇＯ、ＣａＯ、ＢａＯ、およびＳｒＯを指す。 In another embodiment, the borosilicate glass contains the following components (oxide-based mol%):

Here, "R ₂ O" refers to alkali metal oxides Li ₂ O, Na ₂ O, and K ₂ O, and "RO" refers to alkaline earth metal oxides MgO, CaO, BaO, and SrO.

The glass of the present invention may contain SiO ₂ in a proportion of at least 40 mol%, or at least 60 mol%. SiO ₂ contributes to the hydrolysis resistance and permeability of the glass. If the SiO ₂ content is excessively high, the melting point of the glass will be excessively high. Temperatures T ₄ and T _g also increase sharply. Therefore, the content of SiO ₂ should be limited to a maximum of 78 mol% or a maximum of 85%.

Preferably, the content of SiO ₂ 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%. The content can be limited to a maximum of 75 mol%, a maximum of 73 mol%, or a maximum of 72 mol%.

The glass of the present invention contains Al ₂ O ₃ in a proportion of up to 10 mol%. Al ₂ O ₃ contributes to the phase separation stability of the glass, but the acid resistance decreases as the ratio increases. In addition, Al ₂ O ₃ raises the melting temperature and T ₄ . 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, Al ₂ O ₃ is used in low proportions of at least 2 mol%, at least 2.5 mol%, or at least 3 mol%, or at least 3.25 mol%. In some embodiments, the glass does not have to contain Al ₂ O ₃ .

The glass of the present invention may contain B ₂ O ₃ in a proportion of at least 12 mol%. B ₂ O ₃ has a beneficial effect on the melting properties of the glass. In particular, the melting temperature is lowered and the glass can be fused with other materials at a low temperature. However, the amount of B ₂ O ₃ should not be excessively high, otherwise the glass has a strong tendency to phase-separate. In addition, excessive amounts of B ₂ O ₃ adversely affect hydrolysis resistance, and the glass tends to have a large evaporation loss during production, resulting in a knotted glass. Therefore, B ₂ O ₃ should be limited to a maximum of 24 mol%, a maximum of 22 mol%, or a maximum of 20 mol%. The content of B ₂ O ₃ may be at least 5 mol%, at least 12 mol%, or at least 14 mol%.

In a preferred design, the ratio of the total content of B ₂ O ₃ and R ₂ O and RO (mol%) to the total content of SiO ₂ and Al ₂ O ₃ (mol%) is up to 0.4, especially. The maximum is 0.35, more preferably the maximum of 0.34. In one embodiment, this value is at least 0.1, preferably at least 0.2, or at least 0.26. Glasses of the above ratio have excellent properties in terms of hydrolysis resistance and phase separation factor, and show only low degree of induced dimming, especially when used as a UV permeable material. Has the advantage of.

The glass of the present invention may contain Li ₂ O in a proportion of up to 10.0 mol%, or up to 3.0 mol%, or up to 2.8 mol%, or up to 2.5 mol%. Li ₂ O enhances the fusion of the glass and beneficially shifts the UV end to shorter wavelengths. However, lithium oxide tends to evaporate, increasing the tendency for phase separation and increasing the price of the mixture. In a preferred design, the glass contains only a small amount of Li ₂ O, such as 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 is Li. Does not include ₂ O. In certain embodiments, the Li ₂ O content is 1 mol% to 2 mol%.

The glass of the present invention contains Na ₂ O in a proportion of up to 18 mol% or up to 6 mol%. Na ₂ O increases the fusion property of the glass. However, sodium oxide also results in a decrease in UV transmission and an increase in the coefficient of thermal expansion (CTE). The glass may contain Na ₂ O in a proportion of at least 1 mol%, or at least 2 mol%. In one variant, the Na ₂ O content is up to 5 mol%, or up to 4 mol%. In some embodiments, the glass does not have to contain Na ₂ O.

The glass of the present invention contains K2O in a proportion of up to ₄ mol%. _K2O enhances the fusion of the glass and beneficially shifts the UV end to shorter wavelengths. Its content can be at least 0.3 mol%, or at least 0.75 mol%. However, if the potassium oxide content is excessively high, the radioactive properties of its isotope ^40K result in a glass that has a disturbing effect when used in a photomultiplier tube. Therefore, the content of this component should be limited to a maximum of 15 mol%, a maximum of 10 mol%, a maximum of 5 mol%, a maximum of 3 mol%, or a maximum of 2 mol. In some embodiments, the glass does not have to contain _K2O .

In the embodiment of the present invention, the ratio of the content of Na ₂ O to K ₂ O in mol% units is at least 1.5, particularly at least 2. In one embodiment of the invention, the ratio is up to 4, especially up to 3. Both oxides play a role in improving the fusion properties of the glass. However, if too much Na ₂ O is used, the UV transmittance will decrease. If K ₂ O is excessively high, the coefficient of thermal expansion increases. It has been found that the ratios shown achieve the best results, i.e. the UV transmission and coefficient of thermal expansion are in the favorable range. In certain embodiments, the ratio is 1.85-3.

_The amount of R2O in the glass of the present invention is preferably 10 mol% or less, 8 mol% or less, or 7 mol% or less. The glass may contain at least 3.5 mol%, at least 4 mol%, or at _least 4.5 mol% of R2O. Alkali metal oxides increase the fusion of glass, but as mentioned above, higher proportions result in various drawbacks. _In certain embodiments, the R2O content is 4.5 mol% to 6.0 mol%.

The glass of the present invention may contain MgO in a proportion of up to 10 mol%, up to 6 mol%, up to 4 mol%, or up to 2 mol%. Although MgO is advantageous for fusion, it has been found that at high proportions there is a problem with the desired UV transmission and there is a tendency for phase separation. The preferred design does not include MgO.

The glass of the present invention may contain CaO in a proportion of up to 16 mol%, up to 6 mol%, up to 4 mol%, or up to 2 mol%. Although CaO is advantageous for fusion, it has been found that at high proportions it has problems with the desired UV transmission. Preferred forms contain no CaO or only a small amount of CaO, such as at least 0.1 mol%, at least 0.3 mol%, or at least 0.5 mol%.

The glass of the present invention may contain SrO in a proportion of up to 4 mol%, up to 1 mol%, or up to 0.5 mol%. Although SrO is advantageous for fusion, it has been found that at high proportions it has problems with the desired UV transmission. The preferred design does not include SrO.

The glass of the present invention may contain BaO in a proportion of up to 12 mol%, or up to 4 mol%, or up to 2 mol%. BaO improves hydrolysis resistance. However, if the barium oxide content is excessively high, phase separation will occur, resulting in unstable glass. Preferred embodiments include BaO in an amount of at least 0.1 mol%, at least 0.3 mol%, or at least 0.4 mol%. In certain embodiments, the BaO content is 0.3 mol% to 1.5 mol%. In some embodiments, the glass does not have to contain BaO.

Alkaline earth oxide RO has been shown to have a significant effect on the phase separation tendency. Therefore, in some design forms, special attention is paid to the components of these components and their relationship to each other. Therefore, the ratio of BaO in mol% to the total content of MgO, SrO and CaO in mol% should be at least 0.4. Preferably, this value is at least 0.55, or at least 0.7, or at least 1.0. In a particularly preferred embodiment, the value is at least 1.5, even at least 2. BaO offers the greatest advantages in terms of phase separation and hydrolysis resistance compared to other alkaline earth metal oxides. However, the ratio should not exceed 4.0 or 3.0. In an advantageous form, the glass contains at least a small amount of CaO and BaO and does not contain MgO and SrO. In certain embodiments, the ratio is 0.7-2.2.

In particular, advantageous properties can be obtained when the ratio of CaO in the glass to BaO in mol% units is less than 2.0. In particular, this ratio should be less than 1.5 or less than 1.0. In some embodiments, the ratio is even lower, especially less than 0.8, or less than 0.6, and in a preferred design, this ratio is at least 0.3. In certain embodiments, the ratio is 0.4-1.4.

_In one variant, the glass has a ratio of B2O3 to BaO in mol% of at _least 8 and up to 45. Preferably, the ratio is at least 10, or at least 11, and in a preferred design, the ratio is limited to a maximum of 42, or 40, or 39. In another embodiment, the ratio can be limited to a maximum of 15 or 14. In particular, the ratio is 10 or more and 45 or less, or 11 or more and 42 or less in another embodiment, and the ratio is 11 to 16 in a specific embodiment. In another embodiment, the ratio is 35-45.

Glasses with the above ratios show good properties with respect to hydrolysis resistance and phase separation factor, and also show low induced absorbance.

The proportion of RO in the glass of the present invention can be at least 0.3 mol%. Alkaline earth metal oxides are advantageous for fusion, but at high proportions they have been found to have problems with the desired UV transmission. In one variant, the glass contains up to 3 mol% RO. In one embodiment, the proportion of RO is 1-3 mol%.

The total content of alkaline earth metal oxides and alkali metal oxides in mol% units, RO + R ₂ O, can be limited to a maximum of 10 mol%. An advantageous design can include these components in an amount of up to 9 mol%. Preferably, the content of these oxides is at least 4 mol%, at least 5 mol%, or at least 6 mol%. In one embodiment, the proportion of RO ₊ R2O is 6-8 mol%. These components increase the tendency of phase separation and reduce the hydrolysis resistance of the glass at a very high rate.

The ratio of the content of B ₂ O ₃ in mol% to the total content of R ₂ O and RO in mol% can be at least 1.3, at least 1.5, or at least 1.8. .. The ratio can be limited to a maximum of 6, a maximum of 4.5, or a maximum of 3. In one embodiment, the ratio of B ₂ O ₃ / (RO + R ₂ O) is 1.8-3.5. Excessive presence of alkaline or alkaline earth oxides with respect to B ₂ O ₃ can result in the formation of alkaline or alkaline earth borates during the phase separation of the glass. Adjusting the above ratios proved advantageous.

To ensure that the melting properties, including T _g and T ₄ , are within the desired range, the ratio of the B ₂ O ₃ content to the total SiO ₂ and Al ₂ O ₃ contents in mol% units. It may be advantageous to set it within a narrow range. In a favorable design, this ratio is at least 0.15 and / or up to 0.4. In one embodiment, the ratio of B ₂ O ₃ / (SiO ₂ + Al ₂ O ₃ ) is 0.17 to 0.3.

The ratio of the total alkali metal oxide R2O to the _total alkaline earth metal oxide RO in mol% is preferably more than 1, particularly more than 1.1 or more than 2. In this design form, the ratio is up to 10, up to 7, or up to 5. In one embodiment, the ratio is 2-4.

The glass of the present invention may contain F ⁻ at a content of 0-6 mol%. Preferably, the content of F ⁻ is up to 4 mol%. In some design embodiments, at least 1 mol%, or at least 2 mol% of this component is used. Component F ^- improves the fusion of the glass and affects the UV edge towards shorter wavelengths.

The glass of the present invention may contain Cl ⁻ in a content of less than 1 mol%, particularly less than 0.5 mol% or less than 0.3 mol%. A suitable lower limit is 0.01 mol% or 0.05 mol%.

The glass of the present invention may contain ZnO in a content 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 does not have to contain ZnO.

The glass of the present invention may contain ZrO ₂ 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 does not have to contain ZrO ₂ .

The glass of the present invention may contain SnO ₂ 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 does not have to contain SnO ₂ .

In the present specification, when it is stated that the glass does not contain a component or a specific component, it means that this component can be present only as an impurity at most. do. This means that no significant amount has been added. The non-significant amount is an amount of less than 0.5 ppm, preferably less than 0.25 ppm, preferably less than 0.125 ppm, most preferably less than 0.05 ppm.

In one embodiment, the glass has Fe ₂ O ₃ of less than 10 ppm, particularly less than 5 ppm, or less than 1 ppm. In one embodiment, the glass has less than 10 ppm, especially less than 5 ppm, or less than 1 ppm of TiO ₂ . In one embodiment, the glass has less than 3.5 ppm, especially less than 2.5 ppm, or less than 1.0 ppm arsenic. Glass containing less than 3.5 ppm antimony, less than 2.5 ppm antimony, or less than 1.0 ppm antimony is preferred. Besides adverse effects on UV permeability and solarization, arsenic and antimony in particular are toxic and environmentally dangerous and should be avoided.

In a particularly preferred design, the borosilicate glass contains the following components (oxide-based mol%):

In another particularly preferred form, the glass contains the following mol% components:

In yet another particularly preferred form, the glass contains the following mol% components:

Glass articles can be produced by known stretching processes for glass tubes and glass rods. One of ordinary skill in the art will select appropriate manufacturing processes, such as ingot casting for bars, floating or downdrawing for producing plate-like bodies, depending on the desired shape. Preferably, the cooling of the glass during the process is adjusted to obtain the desired properties.

In one embodiment, the glass article is manufactured using the Danner method or the Bellows method. In the bellows method, the glass melt flows vertically downward (in the direction of gravity) through a forming tool manufactured with an outlet ring and a needle. The forming tool forms a female mold (mold) of the produced cross section of a glass tube or glass rod. In the manufacture of glass tubes, a needle is placed as a molded part in the center of the molding tool.

The difference between the bellows method and the downdraw method is that, firstly, the glass melt of the bellows method deviates horizontally after leaving the forming tool, and secondly, in the bellows method, the passage through which the blown air flows passes. What the needle has. Similar to the Danner method, the blown air prevents the resulting glass tube from collapsing. In the downdraw method, the solidified glass melt is separated without changing the direction in advance. Since there is no change of direction, it is possible to refrain from using the air blown during the manufacture of the glass tube.

In one embodiment, the invention relates to a glass article made from the glass disclosed herein. The thickness of the glass article, especially in the case of a glass tube, can be at least 0.1 mm or at least 0.3 mm. The thickness can be limited to a maximum of 3 mm or a maximum of 2 mm. The outer diameter of the glass article, for example the outer diameter of the glass tube or glass rod, can be up to 50 mm, up to 40 mm, or up to 30 mm. The outer diameter can be, in particular, at least 1 mm, at least 2 mm, or at least 3 mm. In one embodiment, the article has a thickness of at least 3 mm and / or a maximum of 20 mm. Optionally, the thickness is at least 5 mm, at least 6 mm, or at least 8 mm. The thickness may be limited to a maximum of 20 mm, a maximum of 16 mm, a maximum of 14 mm, or a maximum of 12 mm. In one embodiment, the article has a length and a width, in particular the length is greater than the width. The length may be at least 20 mm, at least 40 mm, or at least 60 mm. Optionally, this is up to 1000 mm, up to 600 mm, up to 250 mm, or up to 120 mm. Preferably, the length is 20 mm to 1000 mm, 40 mm to 600 mm, or 60 mm to 250 mm. The width may be at least 10 mm, at least 25 mm, or at least 35 mm. Optionally, the width is up to 575 mm, up to 225 mm, or up to 110 mm. Preferably, the width is 10 mm to 575 mm, 25 mm to 225 mm, or 35 mm to 110 mm.

From the above, the present invention also relates to the following embodiments:
In one aspect, the invention is a method for removing methicillin-resistant Staphylococcus aureus (MRSA), comprising exposing MRSA to bactericidal UV light in the wavelength range of 270 nm to 222 nm. UV light relates to a method in which UV light is emitted by a UV lamp with a lamp cover made of methicrate glass having a total platinum content of less than 3.5 ppm.

In another aspect, the MRSA exposed to bactericidal UV light is present on UV sensitive materials that are sensitive to UV radiation above 222 nm.

In yet another embodiment, the UV sensitive material is the surface of a biological tissue such as the eye or skin of an animal, the animal being selected from insects, invertebrates, vertebrates, mammals, and / or humans.

In yet another embodiment, the removal of MRSA after treatment, according to BS ISO 22196: 2011-08-31, is greater than 99%.

In yet another embodiment, the UV exposure of MRSA is in the range of at least 2,000 to 8,000 microwatt seconds per square centimeter (μW · s / cm ² ).

In yet another aspect, all or part of the UV lamp cover is molded into the shape of a lens.

In another aspect, the invention relates to a glass having a transmittance of at least 60% (measured at a thickness of 1 mm) over a wavelength range of 207 nm to 222 nm, which glass has a total platinum content of 3.5 ppm or less. It is borosilicate glass. In some embodiments, it is 3 ppm or less, 2.5 ppm or less, and 2 ppm or less. The glass also has hydrolysis resistance characterized by an extracted Na ₂ O equivalent of 250 μg / g or less per gram of glass as determined according to ISO 719. In some embodiments, it is 180 μg / g or less, 120 μg / g or less, and 50 μg / g or less.

In yet another embodiment, the glass is at least 40%, at least 50%, at least 55%, at least 60% at 200 nm, and / or at least 55%, at least 60%, at least 65%, and / or 230 nm at 210 nm. It has a transmittance of at least 75%, at least 80%, and at least 85% at wavelengths [λ] of at least 60%, at least 65%, at least 75%, and / or 260 nm, 280 nm, and / or 310 nm (1 mm thickness). Measured with). In one embodiment, the transmittance at 200 nm is up to 95%, up to 85%, or up to 70%.

For many applications, the most uniform transmission possible in the UV range is desired. The glasses of the invention have a ratio of transmittance at 254 nm (measured at a sample thickness of 1 mm each) of at least 1.00 and maximum 2.00, especially maximum 1.65 or maximum 1.50, to transmittance at 200 nm. May have.

In yet another embodiment, the glass comprises less than 10 ppm total content of one or more UV blocking impurities. In some embodiments, it is less than 8 ppm, even less than 5 ppm.

In yet another embodiment, the glass comprises 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 comprises a total platinum content of less than 1.0 ppm.

The wavefront deviation can 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, less than ± 5 μm. Optionally, the wavefront deviation can be 0.1 μm to 250 μm, or 1 μm to 100 μm, or 2 μm to 85 μm.

In yet another embodiment, the glass has a refractive index nd of 1.450 to _1.580 .

In yet another embodiment, the glass comprises the following components (mol%) in the indicated amounts:

In another aspect, the invention relates to UV-LED modules such as water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection (eg keyboard disinfection, escalator handrails). UV sterilizer), cytometry, molecular identification, protein analysis, biofilm treatment, hardening, lithography, plant growth, skin treatment (psoriasis, white spots, itching, neurodermatitis, acne, photodermatitis, phototherapy, roses The use of the glass as a hermetically sealed lens cap in applications selected from the group of color psoriasis), bacterial detection, drug discovery, protein analysis, induction of skin vitamin D3 production, and / or sterilization.

In one aspect, the invention relates to a glass article comprising or comprising 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 end. The polished surface can have a surface roughness Ra of less than 10 nm or less than 5 nm. The chamfered edges are more impact resistant and are more resistant to chipping than the non-chamfered edges.

Thermal and / or Chemical Reinforcement Optionally, the manufacturing process comprises steps to chemically and / or thermally reinforce the glass article. "Tempering" is also called "hardening" or "toughening".

Preferably, the glass article is fortified at at least one surface, especially thermally and / or chemically fortified. For example, it is possible to chemically strengthen glass articles by ion exchange. In this process, small alkaline ions in the article are usually replaced by large alkaline ions. In many cases, smaller sodium is replaced by potassium. However, it is also possible that very small lithium can be replaced with sodium and / or potassium. Optionally, alkaline ions can be replaced with silver ions. Another possibility is that alkaline earth ions are exchanged with each other according to the same principle as alkaline ions. Preferably, the ion exchange takes place in a molten salt bath between the article surface and the salt bath. Pure molten salts such as molten KNO ₃ can be used for replacement. However, a mixture of salts or a mixture of salts with other ingredients can also be used. If the selectively adjusted compressive stress profile is accumulated in the article, the mechanical resistance of the article can be further enhanced. This can be achieved by a one-step or multi-step ion exchange process.

By replacing small ions with large ions or by thermally strengthening, compressive stress is formed in the corresponding zone, which decreases from the surface of the glass article toward the center. The maximum compressive stress is just below the glass surface and is also called 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 is shown in μm units. Preferably, CS and DoL are measured using Orihara's FSM-60LE appliance.

In one embodiment, CS is greater than 100 MPa. More preferably, the CS is at least 200 MPa, at least 250 MPa, or at least 300 MPa. More preferably, the CS is a maximum of 1,000 MPa, a maximum of 800 MPa, a maximum of 600 MPa, or a maximum of 500 MPa. Preferably, CS is larger than 100 MPa and up to 1,000 MPa, in the range of 200 MPa to 800 MPa, 250 MPa to 600 MPa, or 300 MPa to 500 MPa.

In one embodiment, the glass article is thermally strengthened. Thermal fortification is typically done by quenching the hot glass surface. Thermal reinforcement has the advantage of being able to form a compressive stress layer deeper (larger DoL) than chemical reinforcement. As a result, the thinner the compressive stress layer, the more easily the scratches cannot enter the compressive stress layer, so that the glass is less likely to be scratched.

The glass or glass article can be subjected to, for example, a melting, molding, slow cooling / cooling process, and a heat strengthening process after a low temperature post-treatment step. In this process, the glass body (eg, the aforementioned glass article or pre-product), such as flat glass, is preferably fed horizontally or suspended in an apparatus up to a transition temperature of 150 ° C. above the transition temperature _TG . It is heated rapidly to the temperature. The surface of the glass body is then quenched, for example by blowing cold air through a nozzle system. As a result of quenching of the glass surface, they are frozen in an expanded network, while the interior of the vitreous is slowly cooled and has time to further shrink. As a result, compressive stress is formed in the surface layer, and tensile stress is formed inside. The amount of compressive stress is CTE _glass (coefficient of linear thermal expansion below Tg), CTE _liquid (coefficient of linear thermal expansion above Tg), strain point, softening point, Young's modulus, and between the cooling medium and the glass surface. It depends on various glass parameters such as the amount of heat transfer of the glass, as well as the thickness of the glass body.

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 unreinforced glass. In one embodiment, the glass is heated to a temperature of 750-800 ° C and is rapidly strengthened in a stream of cold air. Optionally, the blowing pressure can be 1-16 kPa. By using the glass or glass articles described herein, compressive stress values of, for example, 50-250 MPa, particularly 75-200 MPa, are achieved with commercially available systems.

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. A 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, a maximum of 200 MPa, a maximum of 160 MPa, or a maximum of 140 MPa. These compressive stress values may be present, especially in heat-strengthened glass articles.

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 certain embodiments, the layer may further be at least 80 μm, at least 100 μm, or at least 150 μm. Optionally, the DoL may be 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, DoL can be 10 μm to 2,000 μm, 20 μm to 1,500 μm, or 30 μm to 1,250 μm. In one embodiment, the glass article is thermally fortified with a DoL of at least 300 μm, at least 400 μm, or at least 500 μm. Optionally, the DoL may be up to 2,000 μm, up to 1,500 μm, or up to 1,250 μm. In one embodiment, the DoL is 300 μm to 2000 μm, 400 μm to 1,500 μm, or 500 μm to 1,250 μm.

Embodiment The present invention relates to a glass having resistance in a plurality of points. Glasses that are particularly resistant are particularly useful when the glass is exposed to special requirements. This is the case, for example, in extreme environments. Extreme environments are areas of application that require special resistance, durability, and safety, such as areas where explosion protection is required.

In one embodiment, the invention relates to a glass article that is particularly suitable for use in extreme environments. The article may be a sheet, disc, tube, rod, ingot, or block. In a preferred embodiment, the article is in the form of a sheet or disc.

Optionally, the glass article consists of glass having a transmittance of at least 60% (measured at a thickness of 1 mm) over a wavelength range of 207 nm to 222 nm, the glass having a total platinum content of 3.5 ppm or less. , A borosilicate glass having a hydrolysis resistance of 250 μg / g or less, represented by the extracted Na _2O equivalent, expressed in μg units per 1 g of glass, as determined according to ISO719, further the glass article is at least. It has a thickness of 0.3 mm, in particular at least 3 mm and / or up to 20 mm.

In extreme environments, thick glass is more mechanically stable than thin glass, so it may be useful to impart a certain minimum thickness to a glass article. However, thicker glass absorbs most of the UV radiation that enters the glass, resulting in heat generation. Large heat generation can be a problem in environments where highly flammable materials are used. Glass articles with low induced dimming at 200 nm and / or 254 nm have the advantage that the transmittance remains high at the wavelength of interest even after long-term use, avoiding extreme heat generation. ..

According to the present invention, glass articles can also be used in UV lamps for disinfecting surfaces in extreme environments. In one embodiment, the glass article is used in a UV lamp (especially as a cover) used to disinfect the site of action. The site of action may be an object that many people touch, such as a handle, especially a door handle. The UV lamp can be positioned, for example, to irradiate the site of action with UV light. In this case, a certain proximity to the site of action is unavoidable. Therefore, at this point, there is a risk that the glass article will be damaged by the impact. Therefore, mechanical resistance is required. Although the mechanical resistance can be improved by thickening the glass article, this reduces the transmittance of the article and significantly increases the heating of the glass during UV lamp operation. Excessive heating should be avoided, which in turn is positively affected by very good transmittance and low induced dimming. Excessive temperatures impair safety due to the risk of burns and explosions to the user. Basically, the risk of burns can be reduced by increasing the distance, but this must be compensated for by higher radiant intensity, with the disadvantage of generating greater heat as well.

The present invention also relates to the use of UV lamps and glass articles in UV lamps, especially for disinfecting in extreme environments, especially for disinfecting sites of action, such as those touched by many people. It has proven advantageous to maintain a minimum distance of 5 cm, especially 7.5 cm or 10 cm, between the surface to be disinfected and the glass article. When using the glass articles described herein, at least 1.0 mW / cm ² , at least 1.5 mW / cm ² , at least 2.5 mW / cm ^{2, at least 3.0 mW / cm 2 ,} or at least at the site of action. The output density can be set to 3.5 W / cm ² . The site of action is the surface to be disinfected. Optionally, the output density is up to 20 mW / cm ² , up to 15 mW / cm ² , or up to 10 mW / cm ² . Specifically, the output density is an output that can be measured at the site of action as UV radiation mediated by a UV lamp, particularly UV-C radiation. Preferably, the site of action is disinfected on a regular basis. This means that the site of action is not irradiated continuously, but only intermittently. For example, the irradiation interval can be triggered by contact, presence, or activation by the user. For example, the irradiation interval may be at least 1 second, at least 5 seconds, at least 10 seconds, or at least 20 seconds. Optionally, the irradiation interval lasts up to 10 minutes, up to 5 minutes, up to 2 minutes, or up to 1 minute.

In one embodiment, the UV lamp and / or the glass article has a heat-optimized structure, and the thickness of the glass article and the UV transmission of the glass article are 70 mm away from the glass article (of the article relative to the light source). The site of action (located on the opposite side) at an ambient temperature of 20 ° C. with a UVC output density of 17.27 mW / cm ² using a medium pressure mercury lamp (eg Philips HOK 4/120) with 120 W / cm and an arc length of 4 cm. The temperature of the surface of the glass article facing the site of action is selected so as not to exceed 45 ° C. when irradiated for 5 seconds. In one embodiment, the radiation passes vertically through the glass article. That is, light enters the glass article substantially perpendicular to the surface facing the light source, and / or light exits the glass article substantially perpendicular to the surface of the glass article facing the site of action. .. In particular, the temperature does not exceed the values of 42.5 ° C, 40 ° C, or 37.5 ° C. In one embodiment, the temperature limit is not exceeded even after irradiation for 10 seconds, 20 seconds, 30 seconds, 45 seconds, 60 seconds, 90 seconds, 120 seconds, 150 seconds, or 180 seconds. This property represents how strongly a glass article is heated when vertically irradiated with a commonly used UV light source. It is realized that UV lamps with lamp covers made from glass articles do not get dangerously hot. UVC output density refers to the output density given by radiation in the UVC range (280-200 nm). Although medium pressure mercury lamps also emit light of other wavelengths, they are not considered herein when considering UVC output densities. The measurement is performed in the surrounding atmosphere. For clarity, the properties described do not limit the use of UV lamps or glass articles to medium pressure mercury lamps.

In one embodiment, the glass article meets the requirements for a fracture pattern according to DIN EN 121501: 2020-07. The entire article or part of the article can be examined and the article can deviate from the specified criteria and be smaller than indicated therein, as long as it is beyond the area considered. Specifically, the region in which the damage pattern is considered can be 40 mm × 40 mm or 25 mm × 25 mm. In one embodiment, the glass article is broken into 25 or more pieces, particularly 30 or more pieces or 40 pieces or more, under the above conditions. It is advantageous for the article to break into many pieces, as smaller pieces have a lower risk of injury if broken. Fracture patterns may be affected, for example, by choice of glass composition, cooling conditions (heat shrinkage), adjustment of glass stress, and / or strengthening of the article.

In one embodiment, the invention relates to a glass article made of glass having a transmittance (measured at a thickness of 1 mm) of at least 60% over a wavelength range of 207 nm to 222 nm, wherein the glass is 3.5 ppm or less. A borosilicate glass having a total platinum content of 250 μg / g or less, characterized by an extracted Na ₂ O equivalent, expressed in μg units per 1 g of glass, as determined according to ISO719. Further the glass article has a thickness of at least 0.3 mm, particularly at least 3 mm and / or up to 20 mm, and the article further has a compressive stress of at least 50 MPa on at least one surface and 40 mm as determined according to DIN EN 121501. It has a fracture pattern characterized in that a region of × 40 mm is broken into 25 pieces or more.

The figure which shows the transmittance curve of "glass no.1" of this invention at a different thickness (1 mm and 0.34 mm) and a different UV wavelength. The figure which shows the possible use of UV transmissive glass in various LED packages a)-f). The figure which shows the possible use of UV transmissive glass in various LED packages a)-e). The figure which shows the transmittance curve of "glass no.1" of this invention. The figure which shows the transmittance curve of "comparison glass 1". The figure which shows the transmittance curve of "comparison glass 2".

Example
Example 1
Both glasses were melted under reducing conditions in a quartz glass crucible and made uniform with a quartz glass stirrer. All melts were placed in a 465 ° C. cooling furnace and cooled to room temperature at a rate of 30 K / h.

The melt "Glass No. 1" was melted at 1610 ° C., purified at 1620 ° C. for 60 minutes, then stirred at the same temperature for 30 minutes, and then left at 1620 ° C. for 120 minutes. As a result, the glass had as few bubbles as possible.

After casting, a transparent glass cast block was obtained from a Pt-free form (“Glass No. 1”).

In addition to the chemical analysis of the glass, the transmission curves of the glass were recorded at at least two different locations on the cast block. The index of refraction was also determined as a function of wavelength so that the transmission curve could be calculated for the same sample thickness.

The following table shows the exemplary glass according to the present disclosure in mol%.

Two "comparative glasses" were produced that had the same composition as "Glass No. 1" and contained:
"Comparative Glass 1 (C1)": 7.9 ppm Fe ₂ O ₃ and 8.3 ppm TiO ₂ and 3.5 ppm Pt.
"Comparative Glass 2 (C2)": 3.3 ppm Fe ₂ O ₃ and 20.9 ppm TiO ₂ and 3.8 ppm Pt.

・ Glass No. UV transmittance test using No. 1 Glass No. UV transmission of 1 was tested at various thicknesses and wavelengths. The following transmittances were measured at a thickness of 0.34 mm.
・ 200nm-73.5%
207nm-77.5%
-222nm-83.0%

The following transmittances were measured at a thickness of 1 mm.
・ 200nm-62.2%
207nm-67.5%
222nm-77.0%

After that, the glass No. 1 was compared with comparative glasses C1 and C2. Pt contamination was 3.5 ppm and 3.8 ppm, respectively.

The transmittance at 200 nm is that of glass No. Compared with 1, it decreased from 60 to 65% to about 50% for glass C1 and about 20 to 30% for glass C2. This indicates that not only is the effect of Pt contamination significant, but other contaminants such as iron and titanium affect permeability.

Manufacture of UV Lamps and / or UV-LED Lamps By using glass as a cover for LED packages, UVC transmissive glass No. 1 was used to make a UVC-LED lamp. The package size of the LED package was 3.5 x 3.5 mm.

Other features of LED package:
-Substrate: AlN with a cavity (height about 1.0 mm)
-Window thickness: 0.3 mm (flat)
-Solder material: Au / Sn, Au / Ni

In addition, UVC permeable encapsulation material was used to further protect and cover the LEDs. Such an encapsulation material can be a copolymer of methyl methacrylate and acyloxyimino methacrylate ester. In this example, poly- (methylmethacrylate-co-3-methacryloyl-oxyimimino-2-butanone) was used.

Due to its favorable thermal properties, the glass cover is laser fritted to the package surface to allow the UVC-LED lamp to be autoclaved even at high gas pressures and to be used in environments with high humidity or high gas pressures. Can be sealed.

-Energy efficiency test as a UV-LED cover The LED lamp was compared with the conventional LED lamp. LEDs manufactured using the present invention have been found to have about 30% higher energy efficiency than conventional UV lamps.

-MRSA removal test The surface on which MRSA-CFU (colony forming unit) is present was irradiated with the UVC-LED lamp of the present invention. UVC of 2,500 μW · s / cm ² was irradiated at 200 nm for 10 minutes. After UVC treatment for 10 minutes, the confirmed MRSA-CFU was less than 1%.

Therefore, the glass No. 1 is hydrolysis resistant, characterized by high UV transmission and an equivalent of 20, 25, 30, 50, 100, 180 and / or 250 μg / g or less of Na ₂ O extracted into water at 98 ° C. It is a glass with sex.

Example 2
Other glass compositions of the present invention having high UV permeability and hydrolysis resistance are shown in the table below. The content of the component is described in mol%. Other physical properties of glass are also described.

The following table shows the solarization resistance (induced absorbance) after exposure to deuterium lamps for 48 hours and 96 hours, respectively. The transmittance was measured with a glass thickness of 0.7 to 0.75 mm.

The following table shows the approximate permeation values for some glasses after exposure to deuterium lamps for 48 and 96 hours, respectively.

Detailed Description of the Drawings FIG. 1 shows the transmittance curves of the "glass no. 1" of the present invention at different thicknesses (1 mm and 0.34 mm) and different UV wavelengths.

FIG. 2 shows the possible use of UV permeable glass in various LED packages a) to f). Due to the shape of the glass lens [1], UV light can be focused or dispersed according to a specific application. Further, the cover glass [1] can surround the UV source (eg, UV-LED) [4] so that the UV light is also emitted laterally (see FIGS. 2c-f). The reflective element on the back of the casing [3] can improve the luminous efficiency. As the casing [3], aluminum nitride ceramic (AlN ceramic) having high thermal conductivity can be used. The LED [4] and the glass cover [1] can be metal soldered [2] to the casing [3].

In FIG. 3, instead of metal soldering [2] the glass to the casing [3] (see FIG. 3a), the UV transmissive glass [1] of the present invention may be attached to the casing by laser frit sealing [6]. Yes (see FIGS. 3b) to e)). The LED [4], which can be metal soldered [2] to the casing [3], can be further completely enclosed in the transparent encapsulation material [5]. Such an encapsulation material may be a copolymer of methyl methacrylate and an acyloxyimino methacrylate ester. In the examples, poly- (methylmethacrylate-co-3-methacryloyl-oxyimimino-2-butanone) was used. In that case, the laser frit sealing [6] completely protects the LED elements from environmental influences, resulting in this configuration being a harsh environment, especially with the regular use of strong acid cleaners and / or disinfectants. Optimal for the conditions. Also in this case, aluminum nitride ceramic (AlN ceramic) having high thermal conductivity can be used as the casing [3]. In this case as well, the luminous efficiency can be improved by the reflective element on the back surface of the casing [3].

4 to 6 show the transmittance curves of different glasses. Transmittance at 200 nm decreased from 60-65% (“glass no. 1” of the present invention) to about 50% (“comparative glass no. 1”) and 20-30% (“comparative glass no. 2”). did. This indicates a significant effect on UV transmission by platinum and other contaminants.

FIG. 4 shows a transmittance curve of "Glass no. 1" (manufactured according to Example 1) of the present invention, which does not contain Pt and has a low iron and titanium content. Two measurements were made at different locations on the same glass cast block. The variation in the transmittance measurement of the same glass is due to the non-uniformity of the cast block.

FIG. 5 shows the transmittance curve of "Comparative Glass 1" having a content of 3.5 ppm platinum, 7.9 ppm iron, and 8.3 ppm titanium. Two measurements were made at different locations on the same glass cast block. The variation in the transmittance measurement of the same glass is due to the non-uniformity of the cast block.

FIG. 6 shows the transmittance curve of "Comparative Glass 2" having a content of 3.8 ppm platinum, 3.3 ppm iron, and 20.9 ppm titanium. "Comparative glass 2" was measured three times at different locations on the same glass cast block. The variation in the transmittance measurement of the same glass is due to the non-uniformity of the cast block.

Claims (16)

A method of removing methicillin-resistant Staphylococcus aureus (MRSA), wherein the method comprises exposing the MRSA to bactericidal UV light in the wavelength range of 207 nm to 222 nm, wherein the UV light is 3. A method of being illuminated by a UV lamp with a lamp cover made of borosilicate glass having a total platinum content of less than .5 ppm. The method of claim 1, wherein the exposed MRSA is present on a UV sensitive material that is sensitive to UV radiation above 222 nm. The claim 1 or 2, wherein the UV-sensitive material is a surface of a biological tissue such as an animal's eye or skin, wherein the animal is selected from insects, invertebrates, vertebrates, mammals and / or humans. the method of. The method according to any one of claims 1 to 3, wherein the removal of MRSA after treatment according to BS ISO 22196: 2011-08-31 is more than 99%. The method according to any one of claims 1 to 4, wherein the UV exposure of the MRSA is in the range of at least 2,000 to 8,000 microwatt seconds per square centimeter (μW · s / cm ² ). The method according to any one of claims 1 to 5, wherein all or part of the cover of the UV lamp is molded in the form of a lens. Glass with a transmittance of at least 60% (measured to a thickness of 1 mm) over a wavelength range of 207 nm to 222 nm, with a total platinum content of 3.5 ppm or less and μg units per gram of glass determined according to ISO 719. A glass, which is a borosilicate glass having a hydrolysis resistance characterized by an equivalent Na _2O of 250 μg / g or less. -Has a transmittance of at least 60% at 200 nm and / or a transmittance of at least 85% at wavelengths [λ] of 260 nm, 280 nm and / or 310 nm (measured at a thickness of 1 mm).
7. The glass according to claim 7, which has a wavefront deviation (peak to valley) of less than ± 0.1 mm and / or has a refractive index nd of 1.450 to _1.580 . -The total content of one or more UV blocking impurities is less than 10 ppm.
-The glass of claim 7 or 8, wherein the UV blocking impurities are optionally selected from lead, cadmium, mercury, rhodium, hexavalent chromium, iron, titanium, and any combination thereof. The glass according to any one of claims 7 to 9, wherein the total platinum content is less than 1.0 ppm. The glass contains the following components in the indicated amount (mol%):

The glass according to any one of claims 7 to 10, which is included in. A glass article made of the glass of any one of claims 1 to 11, having a thickness of at least 0.3 mm, particularly at least 3 mm and / or up to 20 mm. 12. The glass article of claim 12, wherein the article is thermally or chemically fortified and has a compressive stress of at least 50 MPa, especially on at least one surface. 12. The glass article according to claim 12 or 13, which has a fracture pattern characterized by a 40 mm × 40 mm region breaking into 25 or more pieces, as determined according to DIN EN 121501. For UV-LED modules, such as water disinfection, analytical instruments (HPLC, spectrometers, water monitoring sensors), air purification, air disinfection, surface disinfection (eg keyboard disinfection, UV sterilizer for escalator handrails), cytometry, Molecular identification, protein analysis, biofilm treatment, hardening, lithography, plant growth, skin treatment (psoriasis, leukoplakia, itching, neurodermatitis, acne, UV dermatitis, phototherapy, rose-colored rash), bacterial detection, Use of the glass according to any one of claims 7 to 14 as an airtight sealed lens cap for applications selected from the group of drug discovery, protein analysis, induction of skin vitamin D3 production, and / or sterilization. .. The use of the glass article according to claim 15 or the glass article according to any one of claims 12 to 14, wherein the thickness of the glass article and the UV transmittance of the glass article are the same with respect to the light source. An ambient temperature of 20 ° C. at a UVC output density of 17.27 mW / cm ² using a medium pressure mercury lamp with 120 W / cm and an arc length of 4 cm at the site of action located on the opposite side of the glass article and 70 mm away from the article. The use of the glass article according to claim 15 or claims 12 to 14, wherein the temperature of the surface of the glass article facing the action site is selected so as not to exceed 45 ° C. when irradiated for 5 seconds. The glass article according to any one of the items.

Images