Antibacterial and antiviral polymer compositions

Abstract

To provide an antibacterial / antiviral polymer composition with a polymer in which glass particles having an antibacterial / antiviral function excellent in antibacterial / antiviral action are dispersed; and to provide an antibacterial / antiviral polymer composition precursor.SOLUTION: Provided is an antibacterial / antiviral polymer composition with a polymer in which glass particles having an antibacterial / antiviral function are dispersed. The glass particles include vanadium oxide, include at least one of phosphorus oxide, tellurium oxide and barium oxide, and further include at least either of silver oxide and copper oxide. A content of the glass particles in the polymer composition is 5 vol.% or more and 50 vol.% or less.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to an antibacterial and antiviral polymer composition containing glass particles with antibacterial and antiviral properties that can inactivate viruses or kill bacteria and suppress or prevent their spread. [Background technology]

[0002] BACKGROUND ART Resin compositions and coating compositions containing materials that exhibit antibacterial or antiviral properties have been developed for the purpose of inhibiting bacterial growth or suppressing viruses in parts of building materials, home appliances, and the like that are likely to be touched by people.

[0003] For example, Patent Document 1 discloses an antibacterial resin composition containing antibacterial silver zeolite, which is made by forming a fluororesin coating on the surface of zeolite carrying antibacterial metal ions, mainly silver ions.

[0004] Patent Document 2 discloses a polyester resin sheet obtained by molding a resin composition containing a polyester resin (a) consisting of specific constituent components, a polyester resin (b) consisting of specific constituent components, a lubricant, and an antibacterial and antifungal agent such as an inorganic silver-based agent.

[0005] Furthermore, Patent Document 3 discloses an antibacterial and antiviral paint capable of forming an antibacterial and antiviral coating film with excellent water resistance, which is made by blending a quaternary ammonium salt and a polycarboxylic acid having a hydrocarbon group with six or more carbon atoms and two or more carboxyl groups into an acrylic-melamine paint. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-045410 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-031586 [Patent Document 3] International Publication No. 2015 / 046372 Summary of the Invention [Problem to be solved by the invention]

[0007] The resin compositions of Patent Documents 1 and 2 are configured to achieve antibacterial properties by adding a general-purpose antibacterial agent to the resin composition. However, the antibacterial agent is essentially an impurity, and increasing the amount of antibacterial agent added improves antibacterial function, but at the same time, the physical properties of the resin composition are reduced. Therefore, the amount of antibacterial agent added to the resin composition is kept low within the range in which antibacterial properties are exhibited. That is, in the resin compositions of Patent Documents 1 and 2, the amount of antibacterial agent added is adjusted near the lower limit of the range in which antibacterial properties are exhibited in order to more stably exhibit antibacterial properties. Furthermore, in Patent Document 3, achieving both antiviral properties and material properties while suppressing costs was a difficult challenge.

[0008] Therefore, an object of the present invention is to provide an antibacterial and antiviral polymer composition in which glass particles having excellent antibacterial and antiviral properties are dispersed in a polymer, and a precursor to the antibacterial and antiviral polymer composition. [Means for solving the problem]

[0009] An example of the present embodiment for solving the above problems is as follows: An antibacterial and antiviral polymer composition in which glass particles having antibacterial and antiviral properties are dispersed in a polymer, wherein the glass particles contain vanadium oxide, one or more of phosphorus oxide, tellurium oxide, and barium oxide, and further one or more of silver oxide and copper oxide, and the content of the glass particles in the polymer composition is 5% by volume or more and 50% by volume or less.

[0010] In the antibacterial and antiviral polymer composition, the vanadium oxide, the phosphorus oxide, the tellurium oxide, the barium oxide, the silver oxide, and the copper oxide contained in the glass particles are each in the following mole % in terms of oxide: 20≦[V2O5]≦40, [P2O5]≦30, [TeO2]≦43, [BaO]≦30, [Ag2O]≦50, [CuO]≦20, 20≦[P2O5]+[TeO2]+[BaO]≦51, 1≦[Ag2O]+[CuO]≦50, [Ag2O]+[CuO]+[BaO]≦2[V2O5] A preferred example is an antibacterial and antiviral polymer composition characterized by:

[0011] In addition, in the antibacterial and antiviral polymer composition, the glass particles further contain one or more of iron oxide, tungsten oxide, and zinc oxide, and the vanadium oxide, barium oxide, silver oxide, copper oxide, iron oxide, tungsten oxide, and zinc oxide are contained in the following mole % in terms of oxide: [Fe2O3]≦15, [WO3]≦15, [ZnO]≦10, 4≦[Fe2O3]+[WO3]+[ZnO]≦33, [Ag2O]+[CuO]+[BaO]+3[Fe2O3]+[ZnO]≦2[V2O5] A preferred example is an antibacterial and antiviral polymer composition characterized by:

[0012] Furthermore, among the antibacterial and antiviral polymer compositions, a preferred example is an antibacterial and antiviral polymer composition characterized by being in the form of a plate.

[0013] Furthermore, another example aspect of this embodiment is as follows: An antibacterial and antiviral polymer composition precursor comprising a monomer and glass particles having antibacterial and antiviral functions, wherein the glass particles contain vanadium oxide, and one or more of phosphorus oxide, tellurium oxide, and barium oxide, and further contain one or more of silver oxide and copper oxide, and the content of the glass particles in the polymer composition precursor is 5% by volume or more and 50% by volume or less.

[0014] In addition, in the antibacterial and antiviral polymer composition precursor, the vanadium oxide, the phosphorus oxide, the tellurium oxide, the barium oxide, the silver oxide, and the copper oxide contained in the glass particles are each in the following mole % in terms of oxide: 20≦[V2O5]≦40, [P2O5]≦30, [TeO2]≦43, [BaO]≦30, [Ag2O]≦50, [CuO]≦20, 20≦[P2O5]+[TeO2]+[BaO]≦51, 1≦[Ag2O]+[CuO]≦50, [Ag2O]+[CuO]+[BaO]≦2[V2O5] A preferred example is an antibacterial and antiviral polymer composition precursor characterized by:

[0015] In addition, in the antibacterial and antiviral polymer composition precursor, the glass particles further contain one or more of iron oxide, tungsten oxide, and zinc oxide, and the vanadium oxide, barium oxide, silver oxide, copper oxide, iron oxide, tungsten oxide, and zinc oxide are present in the following mole % in terms of oxide: [Fe2O3]≦15, [WO3]≦15, [ZnO]≦10, 4≦[Fe2O3]+[WO3]+[ZnO]≦33, [Ag2O]+[CuO]+[BaO]+3[Fe2O3]+[ZnO]≦2[V2O5] A preferred example is an antibacterial and antiviral polymer composition precursor characterized by: [Effects of the Invention]

[0016] According to the present invention, it is possible to provide an antibacterial and antiviral polymer composition in which glass particles having antibacterial and antiviral functions, which can store silver or other substances with excellent antibacterial and antiviral properties at high density, are dispersed in a polymer, and a precursor to the antibacterial and antiviral polymer composition. The antibacterial and antiviral polymer composition can achieve both the material properties of the polymer and antibacterial and antiviral properties. [Brief explanation of the drawings]

[0017] [Figure 1] An example of a typical differential thermal analysis (DTA) result of glass is shown below. [Figure 2] 1 shows a schematic diagram of an aluminum alloy plate having a layer formed from a composition containing glass particles and a polymer in an example and a comparative example. [Figure 3] The heating temperature profile of polypropylene (FIG. 3A) and the heating temperature profile of acrylic (FIG. 3B) in the examples and comparative examples are shown. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The following description shows a specific example of the contents of the present invention, and the present invention is not limited to these descriptions. Various changes and modifications can be made by those skilled in the art within the scope of the technical ideas disclosed in this specification. Furthermore, in all drawings used to explain the present invention, parts having the same function are designated by the same reference numerals, and repeated description thereof may be omitted.

[0019] The symbol "to" used herein means that the numerical values ​​before and after it are included as upper and lower limits. In numerical ranges described in stages in this specification, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit described in another stage. The upper or lower limit of a numerical range described herein may be replaced with a value shown in the examples.

[0020] When selecting a material from the group of materials exemplified below, a material may be selected alone or in combination as long as it does not contradict the contents disclosed in this specification. Furthermore, a material other than the group of materials exemplified below may be selected as long as it does not contradict the contents disclosed in this specification.

[0021] The polymer composition of this embodiment is an antibacterial and antiviral polymer composition in which glass particles having antibacterial and antiviral properties are dispersed in a polymer, characterized in that the glass particles contain vanadium oxide, one or more of phosphorus oxide, tellurium oxide, and barium oxide, and further one or more of silver oxide and copper oxide, and the content of the glass particles in the polymer composition is 5% by volume or more and 50% by volume or less.

[0022] Another antibacterial and antiviral polymer composition precursor according to this embodiment, which is different from the polymer composition described above, comprises a monomer and glass particles having antibacterial and antiviral properties, wherein the glass particles contain vanadium oxide, at least one of phosphorus oxide, tellurium oxide, and barium oxide, and at least one of silver oxide and copper oxide, and the content of the glass particles in the polymer composition precursor is 5% by volume or more and 50% by volume or less. The polymer composition may be obtained by polymerizing the monomer in the antibacterial and antiviral polymer composition precursor, or by dispersing the glass particles in a polymer.

[0023] The glass composition constituting the glass particles will be described. Generally, the glass composition has a transition temperature T g , yield point M g , softening point T s Strictly speaking, there is a characteristic temperature called the transition point T g , yield point M g and softening point T s is defined by the viscosity of the glass composition, and T g is 10 13.3 poise, M g is 10 11.0 poise, T s is 10 7.65 The lower these characteristic temperatures are, the better the softening and fluidity at low temperatures is. However, on the other hand, the lower these characteristic temperatures are, the more likely the glass is to show poor chemical stability, such as water resistance and saltwater resistance. Among the characteristic temperatures of glass, the softening point T s and crystallization temperature T cry The closer the glass is to the melting point, the greater the tendency for crystallization, making it more likely to crystallize during firing. When glass crystallizes, its softening and fluidity deteriorates, making it difficult to obtain good adhesion and density.

[0024] The glass composition (lead-free low-melting glass composition) that constitutes the glass particles contains, for example, vanadium oxide and phosphorus oxide as main components, and further contains silver oxide or copper oxide for antibacterial and antiviral effects. The structure of this glass composition has a layered structure consisting of VO5 pyramids, with PO4 tetrahedrons and Ag oxide intercalated between the layers. + ions or Cu 2+ It is believed that silver oxide (Ag) is present in the glass particles used in the present invention. The contained phosphorus oxide (P2O5) is a vitrification component for vitrifying vanadium oxide (V2O5). + In the ionic state or copper oxide, Cu 2+ By introducing ions into the glass structure, we found that V2O5-P2O5 based lead-free low-melting glass compositions have antibacterial and antiviral effects.

[0025] In general SiO2-Na2O-based glass compositions and SiO2-B2O3-based glass compositions, Ag+ It is known that Ag can contain hydroxybenzoates and have antibacterial and antiviral properties. + However, the glass particles used in the present invention contain a large amount of Ag. + Ions and Cu 2+ It can contain ions, which is very useful from the viewpoint of antibacterial and antiviral effects.

[0026] The glass composition (lead-free low-melting glass composition) constituting the glass particles may further contain iron oxide (Fe2O3) and / or potassium oxide (K2O). These are believed to be present between the layers of the layered structure. Fe2O3 is effective in improving the water resistance and saltwater resistance of the V2O5-P2O5-based lead-free low-melting glass composition, while K2O is effective in increasing thermal expansion to match the thermal expansion of the glass composition with the substrate. However, if the content is too high, Fe2O3 may increase the tendency for crystallization, resulting in a deterioration in softening fluidity. K2O may also deteriorate the water resistance and saltwater resistance. For example, if barium oxide is included, it may cause barium elution. When the glass composition contains potassium oxide, it is preferable that the mole percent of [K2O], calculated as oxide, is 5≦[K2O]≦20.

[0027] From the above viewpoint, the vanadium oxide, the phosphorus oxide, the tellurium oxide, the barium oxide, the silver oxide, and the copper oxide contained in the glass particles are in the following mole % in terms of oxide: 20≦[V2O5]≦40, [P2O5]≦30, [TeO2]≦43, [BaO]≦30, [Ag2O]≦50, [CuO]≦20, 20≦[P2O5]+[TeO2]+[BaO]≦51, 1≦[Ag2O]+[CuO]≦50, [Ag2O]+[CuO]+[BaO]≦2[V2O5] It is preferable that:

[0028] The glass particles preferably further contain at least one of iron oxide, tungsten oxide, and zinc oxide, wherein the vanadium oxide, barium oxide, silver oxide, copper oxide, iron oxide, tungsten oxide, and zinc oxide are contained in the glass particles in the following mole % of oxide equivalent: [Fe2O3]≦15, [WO3]≦15 (preferably, 1≦[WO3]≦15), [ZnO]≦10, 4≦[Fe2O3]+[WO3]+[ZnO]≦33, [Ag2O]+[CuO]+[BaO]+3[Fe2O3]+[ZnO]≦2[V2O5] It is preferable that:

[0029] The glass particles preferably have an average particle size (D50) of 3 to 50 μm, more preferably 5 to 30 μm. If the particle size is too large, the surface area decreases, and although a long-term effect can be obtained, the antiviral effect decreases, while if the particle size is too small, the effect is high but dispersibility deteriorates. A particle size within the above range is preferable because it provides good dispersibility and high effectiveness.

[0030] The method for producing the glass particles is not particularly limited, and can be based on a conventional method for producing lead-free low-melting glass using vanadium oxide (VO) and phosphorus oxide (PO). For example, oxides containing the respective raw materials, such as VO, PO, AgO, AlPO, FeO, KCO, KVO, TeO, WO, YO, LaO, and CeO, are blended and mixed according to the desired glass particle composition, placed in a container such as a platinum crucible, and heated at 850 to 1300°C for 0.5 to 3.0 hours. The molten material in the container is then stirred appropriately to produce a glass composition in the form of cullets, plates, or the like. The resulting glass composition can then be granulated by a method such as crushing to produce the glass particles.

[0031] The antibacterial and antiviral polymer composition of this embodiment is preferably a composition in which the glass particles are dispersed in a polymer. Because the glass particles have antibacterial and antiviral properties, the antibacterial and antiviral polymer composition can also exhibit antibacterial and antiviral properties.

[0032] The polymer in which the glass particles are dispersed is not particularly limited, and can be a polymer such as a resin or rubber. Examples of the polymer include polyvinyl alcohol, polyvinyl acetal (butyral resin, etc.), celluloses, acrylic urethane resin, acrylic resin, urethane resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, polyethylene terephthalate, polyester resin, polystyrene, polyamide resin, polycarbonate resin, and ABS resin.

[0033] In the antibacterial and antiviral polymer composition of this embodiment, the content (mixing ratio) of the glass particles in the polymer composition is 5% by volume to 50% by volume, preferably 5% by volume to 30% by volume, and more preferably 5% by volume to 20% by volume. Furthermore, in the antibacterial and antiviral polymer composition of this embodiment, the content of the polymer in the polymer composition is 50% by volume to 95% by volume, preferably 70% by volume to 95% by volume, and more preferably 80% by volume to 95% by volume. A content within the above range is preferable because the antibacterial and antiviral effects can be fully exerted.

[0034] The antibacterial and antiviral polymer composition of this embodiment may contain other components. Examples of other components include various additives. Examples of additives include plasticizers, stabilizers, antioxidants, light stabilizers, UV absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, pigments, dyes, and waxes (e.g., natural waxes such as plant-based, animal-based, and mineral-based). One type of additive may be contained alone, or two or more types may be contained.

[0035] The method for producing the antibacterial and antiviral polymer composition is not particularly limited. For example, the antibacterial and antiviral polymer composition can be obtained by mixing the polymer with the glass particles and then softening and molding the mixture. When mixing the polymer with the glass particles, a solvent or dispersion medium capable of dissolving or dispersing the polymer may be used. The solvent or dispersion medium may be either an organic solvent or an aqueous solvent. For example, a glass composition can be obtained by preparing a solution in which a polymer is dissolved in a solvent, mixing the solution with glass particles (glass composition), and then removing the solvent by drying or the like. Alternatively, the antibacterial and antiviral polymer composition can be obtained by mixing a monomer with the glass particles, if necessary in the presence of a solvent, and then polymerizing the monomer in the presence of the glass particles.

[0036] The antibacterial and antiviral polymer composition precursor of this embodiment includes a monomer and the glass particles. Because the glass particles have antibacterial and antiviral properties, the antibacterial and antiviral polymer composition precursor can also exhibit antibacterial and antiviral properties. The antibacterial and antiviral polymer composition precursor is usually used for various purposes as an antibacterial and antiviral polymer composition after polymerizing the monomer. Because the antibacterial and antiviral polymer composition precursor is often in a liquid form, it can also be used as a paint.

[0037] The monomer is not particularly limited, and for example, a monomer that can be polymerized to the above-mentioned polymer can be used. The monomer may also be a macromonomer (a high molecular weight monomer having a polymerizable functional group).

[0038] The antibacterial and antiviral polymer composition precursor has a glass particle content of 5% by volume or more and 50% by volume or less, preferably 5% by volume or more and 30% by volume or less, and more preferably 5% by volume or more and 20% by volume or less. Furthermore, the antibacterial and antiviral polymer composition precursor of this embodiment has a monomer content of 50% by volume or more and 95% by volume or less, preferably 70% by volume or more and 95% by volume or less, and more preferably 80% by volume or more and 95% by volume or less. A content within the above range is preferable because the antibacterial and antiviral effects can be fully exerted.

[0039] The antibacterial and antiviral polymer composition precursor may contain other components. Examples of other components include various additives. Examples of additives include plasticizers, stabilizers, antioxidants, light stabilizers, UV absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, pigments, dyes, and waxes (e.g., natural waxes such as plant-based, animal-based, and mineral-based). One or more types of additives may be contained. Note that when a solvent or dispersion medium is present together with the antibacterial and antiviral polymer composition precursor, the solvent or dispersion medium is not considered a component of the antibacterial and antiviral polymer composition precursor.

[0040] The method for producing the antibacterial and antiviral polymer composition precursor is not particularly limited, and for example, the antibacterial and antiviral polymer composition precursor can be obtained by mixing the monomer and the glass particles, if necessary, in the presence of a solvent. In the antibacterial and antiviral polymer composition precursor, the glass particles are preferably dispersed in the monomer, but the glass particles may also be precipitated.

[0041] The following describes the uses of the antibacterial and antiviral polymer composition of this embodiment and the antibacterial and antiviral polymer composition precursor of this embodiment. The antibacterial and antiviral polymer composition can be used for various applications as an antibacterial and antiviral molded article. The shape of the antibacterial and antiviral polymer composition is not particularly limited, and may be in the form of a plate, sheet, fiber, woven fabric, nonwoven fabric, etc., with a plate being one preferred embodiment. Examples of molded articles of the antibacterial and antiviral polymer composition include plates, sheets, fiber, woven fabric, nonwoven fabric, etc. The antibacterial and antiviral polymer composition precursor may be a paint, as described above. The antibacterial and antiviral polymer composition may be a molded article of a single-layer structure or a multi-layer structure. In the case of a multi-layer structure molded article, at least one layer is formed from the antibacterial and antiviral polymer composition. In the case of a multi-layer structure molded article, it is preferable that at least a portion of the portion that comes into contact with air or a person is formed from the antibacterial and antiviral polymer composition. The paint may be a single-component paint or a multi-component paint in which multiple components are mixed. If the sheet has a single layer structure, its thickness is preferably in the range of 20 to 500 μm, more preferably in the range of 30 to 100 μm. If the sheet has a multilayer structure, it is preferable that each layer have a thickness of 20 μm or more in order to produce a uniform sheet. The molded article may have three or more layers of nonwoven fabric. The fibers may be formed by molding the composition into fibers, mixing the composition with polymer fibers, or attaching the composition to the surface of any fiber, and any thickness may be used. The woven fabric may be applied to clothing or other suitable objects. A molded article having three or more layers of nonwoven fabric may have an inner layer of a nonwoven fabric formed from the antibacterial and antiviral polymer composition of this embodiment. Since nonwoven fabrics are typically air-permeable, antibacterial and antiviral effects can be exhibited even when the inner layer is a nonwoven fabric formed from the antibacterial and antiviral polymer composition. Known nonwoven fabrics can be used for layers other than the inner layer, making it possible to produce, for example, masks.Furthermore, the antibacterial and antiviral polymer composition and the antibacterial and antiviral polymer composition precursor may be used to form a mesh on a molded article. Specific examples of mesh shapes include, but are not limited to, a grid, polka dot, and polygonal shapes. Nonwoven fabrics obtained from the antibacterial and antiviral polymer composition can be laminated with other substrates such as nonwoven fabrics, and / or subjected to various processes such as embossing and pleating, and then suitably used for various applications, such as gas or liquid filtration filters. Examples of applications for the antibacterial and antiviral polymer composition include clothing (medical clothing) (masks, white coats, protective clothing, gloves, etc.); bedding (medical bedding) (futon / pillowcases, curtains, patient amenities, etc.); handrails, doorknobs, touch buttons for elevators and automatic doors, escalator belts, medical device terminals, etc. in hospitals; air conditioning filters in hospitals; tents for temporary medical facilities; mosquito nets for home convalescence; floor wax; hanging rings, handrails, and touch buttons for trains, buses, airplanes, ships, elevators, taxis, etc. These include doorknobs, floors, walls, ceilings, seats, air conditioning filters, etc.; building materials (floors, walls, doors, ceilings), furniture (tables, desks, chairs, curtains, etc.) and air conditioning filters for schools, libraries, companies, supermarkets, detached houses, apartment buildings, etc.; shopping cart grips, shopping basket handles; medical equipment; vehicles; elevators; escalators (belts); home appliances; odor-resistant underwear; socks for preventing athlete's foot; odor-resistant sportswear; odor-resistant shoe insoles; and wet areas (sanitary areas) (kitchens, toilets, baths, sinks, etc.). The antibacterial and antiviral polymer composition of this embodiment can be used as a component that constitutes all or part of these applications. [Example]

[0042] The present embodiment will be described below with reference to examples, but the present disclosure is not limited to these examples.

[0043] [Example 1] In this example, we investigated the influence and effect of the glass composition of the glass particles on the glass properties, and the effect of the antibacterial and antiviral polymer composition. Tables 1 to 6 show the glass compositions and properties of the glass particles (V2O5-P2O5-based lead-free low-melting glass compositions and V2O5-TeO2-based lead-free low-melting glass compositions) used in the examples and comparative examples.

[0044] (Preparation of lead-free low-melting glass composition) Lead-free low-melting glass compositions having the compositions shown in Tables 1 to 6 were prepared by the following method. Powders of V2O5, P2O5, Ag2O, AlPO4, Fe2O3, K2CO3, KVO3, TeO2, WO3, and La2O3 were used as glass raw materials. The raw materials were blended and mixed in the proportions shown in Tables 1 or 4 to a total of approximately 200 g, and then placed in a platinum crucible. The platinum crucible was heated in air in an electric furnace to approximately 900°C at a heating rate of approximately 10°C / min and held for 1 to 2 hours. During this holding period, the molten material in the platinum crucible was stirred with an alumina rod every 20 to 30 minutes to form a uniform glass. After holding, the platinum crucible was removed from the electric furnace, and the molten material in the platinum crucible was poured onto a thick stainless steel plate to obtain glass cullet of the lead-free low-melting glass composition.

[0045] (Evaluation of vitrification state) The obtained glass cullet of the lead-free low-melting glass composition was observed visually and with an optical microscope to check for the presence or absence of surface devitrification, crystallization, phase separation, and undissolved matter, thereby evaluating the vitrification state. Furthermore, when the evaluation was unclear, the glass cullet was crushed and the presence or absence of sharp diffraction peaks was confirmed by powder X-ray diffraction to evaluate the vitrification state. When the obtained glass cullet did not exhibit any of surface devitrification, crystallization, phase separation, or undissolved matter, or when no sharp diffraction peaks were observed by powder X-ray diffraction, it was judged to have a uniform vitrification state and was evaluated as good (◯). On the other hand, when the obtained glass cullet exhibited any of surface devitrification, crystallization, phase separation, or undissolved matter, or when a sharp diffraction peak was observed by powder X-ray diffraction, it was evaluated as not having a uniform vitrification state and as poor (×).

[0046] (Preparation of glass particles) The glass cullet obtained above (production of lead-free low-melting glass composition) was pulverized using a Raikai mill and a jet mill to an average particle size (D50) of about 20 μm to obtain glass particles (glass powder).

[0047] (Measurement of glass characteristic temperature) The characteristic temperatures (transition point, yield point, softening point, etc.) of the glass particles (lead-free low-melting glass composition) were measured by differential thermal analysis (DTA). The glass powder (glass particles) was placed in an aluminum DTA cell and heated in air from room temperature to 550°C at a heating rate of 5°C / min to obtain a DTA curve. Figure 1 shows an example of a typical result of differential thermal analysis (DTA) of glass. As shown in Figure 1, when the glass powder (glass particles) is heated, the transition point T g The endothermic heat begins to be absorbed from the sag point M g The amount of heat absorbed then decreases once and then increases again. The temperature corresponding to the second endothermic peak is the softening point T s When further heated, the crystallization temperature T cry The amount of heat generated increases rapidly from this temperature, reaching an exothermic peak. This exothermic peak is due to the crystallization of glass, and the temperature at which heat generation begins is called the crystallization temperature T cry The temperature at which the exothermic peak reaches its maximum is called the crystallization peak temperature T cry-p Normally, each characteristic temperature is calculated by the tangent method.

[0048] (Evaluation of glass softening fluidity) The softening fluidity of the glass particles (lead-free low-melting glass composition) was evaluated by a button flow test. A powder compact having a diameter of 10 mm and a thickness of 5 mm was obtained as an evaluation sample using the glass powder (glass particles). This powder compact was placed on an aluminum plate and heated in air at a heating rate of 10°C / min until the softening point T sThe softening and flowing state was observed by heating the sample to a temperature 30 to 40°C higher than the reference temperature and holding it for 30 minutes. If good softening and flowing state was obtained, it was evaluated as "Good", and if good softening and flowing state was not obtained due to surface devitrification, crystallization, phase separation, etc., it was evaluated as "Poor".

[0049] (chemical stability) Samples were created by mixing α-terpineol and glass powder on a 50mm x 50mm x 1mm aluminum plate and firing it at 170°C for 30 minutes and 390°C for 30 minutes. The glass-fired aluminum plate was immersed in water and left for at least one day. Samples in which no glass components other than silver were eluted into the solution were marked with an ◯, and samples in which other components were detected were marked with an ×.

[0050] (comprehensive evaluation) The overall evaluation of the glass was that it was not crystallized, and in the chemical stability test, no elution other than silver was found, and the amount of eluted silver was within the required amount (5 × 10 -7 g / cm 3 ) or more was confirmed to be met, and an × was given to items that did not meet the required value in any item.

[0051] (Mixing into polymer (resin material) (production of composition containing glass composition and polymer)) 25 g of the glass particles (lead-free low-melting glass composition) were added to a solution (15 g of polypropylene, 18 g of solvent) prepared by dissolving a resin binder (powdered polypropylene) in a solvent, and the mixture was kneaded for approximately 30 minutes using a mortar and pestle. The paste was applied to an aluminum alloy plate as described below, dried, and the coating state of the resulting film was evaluated by observing it. The volume ratio of the glass varied depending on the glass components used, but the glass particles and polypropylene were used in amounts such that the glass particles accounted for 5 to 30 volume % and the polypropylene for 70 to 95 volume % in the dried composition. α-Terpineol (α-T) was used as the solvent. The mass ratio was 20 to 30 mass % of the total of the glass particles and polypropylene.

[0052] The paste was applied to a 50 × 50 × 2 mm aluminum alloy plate with a thickness of 0.1 mm over a 50 × 50 mm area, as shown in Figure 2. The aluminum alloy plate used was A6501. Furthermore, as shown in the polypropylene heating temperature profile in Figure 3A, the plate was heated in air at a temperature increase rate of 10°C / min, held at 200°C for 1 hour, and then furnace cooled to form a layer made of a composition containing the glass composition and a polymer (polypropylene) on the alloy plate, and a sample was obtained.

[0053] (Mixing with monomer (preparation of composition (paint) containing glass composition and monomer) and curing (production of composition containing glass composition and polymer)) The glass particles (lead-free low-melting-point glass composition) were added to acrylic powder and α-terpineol and kneaded for approximately 30 minutes in a mortar and pestle to prepare a paste. The paste was applied to an aluminum alloy plate as described below, dried, and the coating state of the resulting film was evaluated by observing it. The glass particles and acrylic powder were used in amounts such that, in the paste state (a mixture of glass particles, a composition precursor containing acrylic, and a solvent), the glass particles accounted for 5 to 30 volume % and the acrylic powder for 70 to 95 volume % when the solvent was excluded. The glass particles and acrylic powder were used in amounts such that, in the coating film (a composition containing glass particles and an acrylic resin), the glass particles accounted for 5 to 30 volume % and the cured acrylic (acrylic resin) for 70 to 95 volume %. The mixing ratio of the polymer components was calculated by converting it to weight. The α-terpineol content was 20 to 30 mass % of the total weight of the glass particles and the acrylic powder.

[0054] The paste was applied to a 50 × 50 × 2 mm aluminum alloy plate to a thickness of 0.1 mm over a 50 × 50 mm area, as shown in Figure 2. The aluminum alloy plate used was A6501. Furthermore, as shown in the acrylic heating temperature profile in Figure 3B, the plate was heated in air at a temperature increase rate of 10°C / min, held at 80°C for 3 hours, and then cooled in the furnace. This formed a layer made of a composition containing the glass composition and a polymer (acrylic) on the alloy plate, and a sample was obtained.

[0055] [Table 1]

[0056] [Table 2]

[0057] [Table 3]

[0058] [Table 4]

[0059] [Table 5]

[0060] [Table 6]

[0061] Next, antiviral tests were conducted using the prepared samples. The antiviral tests were conducted based on ISO 21702 (Determination of antiviral activity of plastics and other non-porous surfaces). In this test, enveloped SARS-COV-2 and influenza A viruses were used, and the results are summarized in Table 7 or Table 8. The results took into account the antiviral properties of the material. Note that each test item in Table 7 or Table 8 was measured as follows.

[0062] (Fast effect) Antiviral activity value (R): Indicates the difference in logarithm (R = Ut - At) between the viral infectivity value (Ut) after 2 hours for an untreated test piece (no drug added) and the viral infectivity value (At) after 2 hours for a treated test piece (with antiviral drug added). An R of 2 or higher is considered to be acceptable.

[0063] According to the results shown in Table 7 or Table 8, the test pieces of Examples A-1 to A-33 showed good results against both SARS-COV-2 and influenza A. In contrast, the antiviral activity values ​​(R) of the test pieces of Comparative Examples B-1 to B-4 did not reach the pass value.

[0064] Even if the kneading ratio exceeds 20% by volume, the improvement in effect is small and the cost becomes relatively high, so the kneading ratio is preferably 20% by volume or less. Also, it is thought that no effect was detected in Comparative Example B-1, which had a low kneading ratio.

[0065] [Table 7]

[0066] [Table 8]

[0067] The antibacterial and antiviral polymer composition obtained by blending glass particles into the polymer has antibacterial and antiviral properties and has been shown to be particularly effective against coronaviruses and influenza viruses, but it goes without saying that it can also be applied to all viruses and bacteria for which silver ions and copper ions are effective.

[0068] The present invention is not limited to the above-described embodiments and examples. Anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included within the technical scope of the present invention, and various modifications are included. For example, the above-described embodiments and examples have been described in detail to clearly explain the present invention, and the present invention is not necessarily limited to those that include all of the described configurations. Furthermore, it is possible to replace part of the configuration of one embodiment or example with the configuration of another embodiment or example, and it is also possible to add the configuration of another embodiment or example to the configuration of one embodiment or example. Furthermore, it is possible to add, delete, or replace part of the configuration of each embodiment or example with other configurations.

Claims

1. An antibacterial and antiviral polymer composition in which glass particles having antibacterial and antiviral functions are dispersed in a polymer, the glass particles contain vanadium oxide, at least one of phosphorus oxide, tellurium oxide, and barium oxide, at least one of silver oxide and copper oxide, and at least one of potassium oxide; the content of the glass particles in the polymer composition is 5% by volume or more and 50% by volume or less; The vanadium oxide, the phosphorus oxide, the tellurium oxide, the barium oxide, the silver oxide, the copper oxide, and the potassium oxide contained in the glass particles are expressed in mole % in terms of oxide as follows: 20≦[V 2 O 5 ]≦40, [P 2 O 5 ]≦30, [TeO 2 ]≦43, [BaO]≦30, [Ag2O]≦50, [CuO]≦20, 20≦[P2O5]+[TeO2]+[BaO]≦51, 1≦[Ag 2 O] + [CuO]≦50, [Ag 2 O] + [CuO] + [BaO]≦2[V 2 O 5 ] 2≦[K2O]≦20 1. An antibacterial and antiviral polymer composition comprising:

2. 2. The antibacterial and antiviral polymer composition of claim 1, The glass particles further contain one or more of iron oxide, tungsten oxide, and zinc oxide, and the vanadium oxide, barium oxide, silver oxide, copper oxide, iron oxide, tungsten oxide, and zinc oxide are contained in the following mole % in terms of oxide: [Fe ２ O ３ ]≦15、 [[WO] ３ ]≦15、 [ZnO]≦10, 4≦[Fe ２ O ３ ]+[WO ３ ]+[ZnO]≦33、 [A' ２ O]+[CuO]+[BaO]+3[Fe ２ O ３ ]+[ZnO]≦2[V ２ O ５ ] 1. An antibacterial and antiviral polymer composition comprising:

3. 3. A molded article of the antibacterial and antiviral polymer composition according to claim 1 or 2, characterized in that the molded article is in the shape of a plate.

4. An antibacterial and antiviral polymer composition precursor comprising a monomer and glass particles having antibacterial and antiviral functions, the glass particles contain vanadium oxide, at least one of phosphorus oxide, tellurium oxide, and barium oxide, at least one of silver oxide and copper oxide, and at least one of potassium oxide; the content of the glass particles in the polymer composition precursor is 5% by volume or more and 50% by volume or less; The vanadium oxide, the phosphorus oxide, the tellurium oxide, the barium oxide, the silver oxide, the copper oxide, and the potassium oxide contained in the glass particles are expressed in mole % in terms of oxide as follows: 20≦[V 2 O 5 ]≦40, [P 2 O 5 ]≦30, [TeO 2 ]≦43, [BaO]≦30, [Ag2O]≦50, [CuO]≦20, 20≦[P2O5]+[TeO2]+[BaO]≦51, 1≦[Ag 2 O] + [CuO]≦50, [Ag 2 O] + [CuO] + [BaO]≦2[V 2 O 5 ] 2≦[K2O]≦20 An antibacterial and antiviral polymer composition precursor, characterized in that

5. The antibacterial and antiviral polymer composition precursor according to claim 4, The glass particles further contain one or more of iron oxide, tungsten oxide, and zinc oxide, and the vanadium oxide, barium oxide, silver oxide, copper oxide, iron oxide, tungsten oxide, and zinc oxide are contained in the following mole % in terms of oxide: [Fe ２ O ３ ]≦15、 [[WO] ３ ]≦15、 [ZnO]≦10, 4≦[Fe ２ O ３ ]+[WO ３ ]+[ZnO]≦33、 [A' ２ O]+[CuO]+[BaO]+3[Fe ２ O ３ ]+[ZnO]≦2[V ２ O ５ ] An antibacterial and antiviral polymer composition precursor, characterized in that

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