JP2019099514A - Anti-virus agent and resin molded article including the same - Google Patents

Abstract

To provide an anti-virus agent that does not comprise Ag and hydrated lime (calcium hydroxide), has high anti-virus properties, and is available at low cost.SOLUTION: The present invention provides an anti-virus agent composed of a glass comprising SiO, and alkali metal oxide and/or alkaline earth metal oxide and having a phase-split structure, and a resin molding containing the anti-virus agent. In the resin molding, a content of the anti-virus agent is 0.01-20 mass%.SELECTED DRAWING: None

Description

  The present invention relates to an antiviral agent exhibiting high antiviral properties, and a resin molded article produced using the same.

  Antibacterial disinfectants and disinfectants are mainly divided into organic and inorganic types. As an inorganic system, for example, an Ag-based antibacterial agent in which Ag ion is supported on a carrier of an inorganic compound is proposed in Patent Document 1. Ag-based antibacterial agents are used in combination with industrial products such as building materials, air filters, masks, clothing, etc., and can impart the effects of sterilization and disinfection to the above-mentioned industrial products.

  The antiviral properties of Ag based antimicrobial agents are considered to be caused by the following mechanism. That is, when the virus is adsorbed on the particle surface of the antibacterial agent, Ag ions enter the DNA / RNA of the virus to form double-stranded bridging. As a result, the function of proliferation is suppressed, causing an inactivation effect of the virus. In addition, for viruses having an envelope (lipid membrane), Ag ions bind to the lipid membrane to block the process of membrane fusion with cells, causing threshing inhibition or replication inhibition.

  Further, Patent Document 2 proposes a fiber using slaked lime (calcium hydroxide) as an antiviral agent. Slaked lime is an antiseptic material frequently used in livestock production because it is inexpensive and can be used even in the presence of organic matter. Recently, the outbreak of highly pathogenic avian influenza (HPAI) has been continued one after another, and is widely used as a preventive measure against it.

  The antiviral properties of slaked lime are believed to be due to its strong alkalization action.

Patent No. 4336937 JP, 2010-209490, A

  Ag-based antibacterial agents have antiviral properties, but in order to obtain effective antiviral properties, it is necessary to increase the concentration of Ag in the antibacterial agents. As a result, there is a problem that the manufacturing cost becomes high and the resin product is discolored.

  Slaked lime, on the other hand, is inexpensive but has insufficient antiviral properties. That is, the inactivation effect of the virus depends on pH, and the higher the pH, the more easily the virus is inactivated. However, since the theoretical pH of the saturated aqueous solution of slaked lime is 12.5, sufficient antiviral property can not be obtained.

Thus, it was an extremely difficult technical task to develop an antiviral agent having both high antiviral ability and low production cost, and the present invention has been made in view of the above circumstances, and is highly antiviral. It is an object of the present invention to provide an antiviral agent which is

  As a result of conducting various studies, the present inventor finds that the above object can be achieved by preparing an antiviral agent using a glass in which an alkali metal component and an alkaline earth metal component are easily eluted, and proposes as the present invention It came to

The antiviral agent of the present invention is characterized in that it comprises SiO ₂ , an alkali metal oxide and / or an alkaline earth metal oxide, and a glass having a phase separation structure.

In the present invention, a glass having a phase separation structure containing SiO ₂ is used. A glass having a phase separated structure containing SiO ₂ generally contains a phase rich in SiO ₂ and having excellent chemical durability, and a phase having SiO ₂ poor and having low chemical durability. When the glass composition contains an alkali metal oxide or an alkaline earth metal oxide, these components are easily contained in the SiO ₂ poor phase. Therefore, when the antiviral agent of the present invention comes in contact with moisture in the environment, the SiO ₂ poor phase (that is, the phase rich in alkali metal oxides and / or alkaline earth metal oxides) to alkali metal components and alkaline earth The metalloid component elutes preferentially. The eluted alkali component and alkaline earth component form hydroxide ions (OH ⁻ ), and the pH rises. When the pH exceeds 12.5, viral membrane proteins begin to be degraded. This effect can inactivate the virus. Furthermore, the glass after elution of the alkali component and the like becomes a porous body in which silanol groups (Si-OH) are formed on the surface. Such a porous body exhibits an action of physically adsorbing viruses, bacteria and molds in pores, and can effectively trap viruses and the like.

  Therefore, the antiviral agent of the present invention exhibits high antiviral properties together with these effects. In addition, the high antiviral property makes it possible to minimize the use of expensive raw materials such as Ag.

In the present invention, the glass constituting the antiviral agent is a composition, in weight percent oxide _equivalent, SiO ₂ 40 to _95%, preferably contains 1~60% Na 2 O + K 2 O + CaO. Here, “Na ₂ O + K ₂ O + CaO” means the total content of Na ₂ O, K ₂ O and CaO.

In the present invention, it is preferable that the glass constituting the antiviral agent further contains B ₂ O ₃ as a composition.

  If the above configuration is adopted, control of phase separation becomes easy, and it becomes easy to optimize the elution amount of the alkali component and the like.

In the present invention, it is preferable that the glass constituting the antiviral agent further contains at least one selected from the group consisting of Ag ₂ O, CuO and ZnO as a composition.

  By adopting the above configuration, the antiviral property can be further improved.

Further, in the present invention, the glass powder constituting the antiviral agent is immersed in 60 ml of pure water at 25 ° C. for 30 minutes, and the pH is measured immediately after the immersion. In the dissolution test in which stirring was performed for 5 seconds immediately before, it is preferable that the pH of the eluate is 12.5 or more. “Density × 4.8 weight parts of glass powder” means, for example, in the case of glass having a density of 2.4 g / cm ³ , it is 2.4 g × 4.8 = 11.52 g worth of glass powder .

  By adopting the above configuration, the antiviral property can be further improved.

  In the present invention, it is preferable that the glass constituting the antiviral agent is in the form of powder.

  If the above configuration is adopted, it becomes easy to produce a resin molded article or the like containing the antiviral agent of the present invention.

  In the present invention, the glass constituting the antiviral agent has an average particle diameter (D50) of 0.1 to 50 μm when the cumulative percentage of particles by laser diffraction particle size distribution measurement is 50%. Is preferred.

  If the above configuration is adopted, it is easy to avoid the situation where the antiviral agent is aggregated or the elution of the alkali component and the like is insufficient.

  The resin molded article of the present invention is characterized by containing the above-mentioned antiviral agent.

  Moreover, in the resin molded product of this invention, it is preferable that content of an antiviral agent is 0.01-20 mass%.

  Hereinafter, the antiviral agent of the present invention will be described in detail.

The glass constituting the antiviral agent in the present invention contains SiO ₂ and an alkali metal oxide and / or an alkaline earth metal oxide. SiO ₂ is a component constituting the skeleton of glass. Alkali metal oxides and alkaline earth metal oxides are components that lower the viscosity of the glass while enhancing the phase separation. Moreover, it is a component which reduces the elution rate of glass. Furthermore, it is a component which forms hydroxide ion (OH < ^- >) in eluate and raises pH. As the alkali metal oxide and alkaline earth metal oxide, Na ₂ O, K ₂ O and CaO are particularly preferable. Although the glass composition range is not limited, for example, a glass containing 40 to 95% of SiO _{2 and} 1 to 60% of Na ₂ O + K ₂ O + CaO in mass% in terms of oxide can be suitably used. The actions of the components constituting the glass and the reasons for defining the contents as described above will be described. In addition, "%" points out the mass% in description of the content range of each component.

SiO ₂ is a main component forming a glass skeleton structure. Moreover, it is a component which raises the viscosity of glass. Furthermore, it is a component which reduces the elution rate of glass. In addition, it is a main component of the remaining glass phase after elution of the alkaline component and the alkaline earth component, and is also a component that exhibits the adsorptivity to viruses. The content of SiO ₂ is preferably 40 to 95%, 55 to 93%, 60 to 90%, 65 to 88%, particularly 68 to 86%. When the content of SiO ₂ is too large, the elution rate of the glass extremely decreases, and it becomes difficult to obtain an antiviral effect. In addition, the melting temperature is increased and the manufacturing cost is increased. When the content of SiO ₂ is too small, the elution rate of the glass is extremely increased, and it is difficult to maintain the antiviral effect.

The content of Na ₂ O + K ₂ O + CaO is preferably 1 to 60%, 3 to 50%, 5 to 40%, 10 to 35%, particularly 12 to 25%. When the content of Na ₂ O + K ₂ O + CaO is too large, the elution rate of the glass extremely increases, and it becomes difficult to maintain the antiviral effect. When the content of Na ₂ O + K ₂ O + CaO is too small, the dissolution rate of the glass is extremely reduced to make it difficult to obtain an antiviral effect. In addition, the melting temperature is increased and the manufacturing cost is increased. The content of Na ₂ O is preferably 1 to 30%, more preferably 5 to 25%, the content of K ₂ O is preferably 0 to 30%, particularly preferably 0 to 20%, and CaO is contained. The amount is preferably 0 to 20%, particularly 0 to 10%.

The antiviral agent of the present invention preferably further contains B ₂ O ₃ in the glass composition. B ₂ O ₃ is a component that enhances the phase separation of glass, and makes it easy to control the phase separation. However, if the content of B ₂ O ₃ is too large, the concentration of borate ion B (OH) ^4-in the eluate will increase, and the pH will decrease, making it difficult to obtain an antiviral effect. In addition, the dissolution rate of the glass is extremely increased, making it difficult to maintain the antiviral effect. The content of B ₂ O ₃ is preferably 0 to 25%, 0 to 15%, particularly 0 to 10%.

The antiviral agent of the present invention preferably further contains at least one selected from the group consisting of Ag ₂ O, CuO and ZnO in the glass composition. By introducing Ag ₂ O, CuO and / or ZnO, the antiviral effect can be further enhanced. The total content of these components is preferably 0 to 8%, particularly 0 to 5%, and the content of each component is preferably 0 to 5%, particularly 0 to 2%.

  In the antiviral agent of the present invention, the pH of the eluate is preferably 12.5 or more in the following dissolution test. In this dissolution test, when the pH is 12.5 or less, it becomes difficult to obtain the antiviral property required for the antiviral agent. (1) Classify the glass having a density of 4.8 weight parts constituting the antiviral agent to 130 μm or less. (2) The classified glass powder is immersed in 60 ml of pure water at 25 ° C. for 30 minutes. Stirring is performed for 5 seconds immediately after immersion and immediately before measurement. (3) Measure the pH of the eluate.

  The antiviral agent of the present invention is preferably composed of powdered glass (glass powder). In the case of powdery glass, since it has a large specific surface area, a high antiviral effect can be obtained. Further, kneading with the resin becomes easy, and a resin molded article can be obtained by injection molding or spinning. Such resin molded articles can be used as product members such as cooking utensils, toilet articles, air filters, masks, etc., and can impart antiviral properties to these products.

  The antiviral agent of the present invention preferably has an average particle size (D50) of 0.1 to 50 μm when the cumulative abundance ratio of particles by a laser diffraction type particle size distribution measurement of a glass powder is 50%. When the average particle size (D50) is smaller than 0.1 μm, the glass powders aggregate and it becomes difficult to knead with the resin or the like. Moreover, when it is set as a resin molded product, it may flow out to warm water etc. and it may not be able to contribute to the antimicrobial property of a resin molded product. On the other hand, when the average particle size (D50) is larger than 50 μm, the elution amount per unit mass of the glass powder is reduced, and it becomes difficult to obtain an antiviral effect. The “average particle diameter (D50)” represents a particle diameter of 50% in which the accumulated amount is 50% of the particles accumulated from the smallest particle in the volume-based cumulative particle size distribution curve measured by the laser diffraction method.

  Next, the resin molded product of the present invention will be described.

  The resin molded article of the present invention contains the above-mentioned antiviral agent. The antiviral agent is as described above, and the explanation is omitted here.

  It is preferable that the resin molded product of this invention contains an antiviral agent 0.01 to 20 mass%. When the content of the antiviral agent is less than 0.01% by mass, it becomes difficult to provide the resin molded article with sufficient antiviral performance. On the other hand, when the content of the antiviral agent is more than 20% by mass, it becomes difficult to uniformly disperse in the resin, and it becomes difficult to perform master batch molding.

  In the resin molded article of the present invention, the resin is not particularly limited, and any of thermoplastic resin and thermosetting resin can be used. For example, polyolefin resin, polycarbonate resin, ABS resin, AS resin, polyamide resin, polyurethane resin, polyvinyl alcohol resin, polyester resin, polyethylene terephthalate resin, polyethylene oxide resin, polyphenyl sulfide resin, acrylic resin, melamine resin Phenolic resin, epoxy resin, urea resin, polyimide resin, aliphatic nylon resin, polyvinyl chloride resin, polyvinyl chloride vinylidene resin, vinyl acetate resin, fluorine resin, silicone resin, main engineering It can be used for plastics etc. and these complexes. Moreover, it is applicable also to resin reinforced by glass fiber, boron fiber, and carbon fiber.

  When a thermoplastic resin or thermosetting resin and an antiviral agent are mixed, in order to enhance the dispersibility of the antiviral agent, the antiviral agent surface can be made lipophilic by silane coupling treatment or the like. Examples of the silane coupling agent include aminosilane, epoxysilane, methacrylsilane, ureidosilane and isocyanate silane.

  The resin molded article of the present invention may contain various additives (colloidal silica, zinc oxide, alumina, white carbon, tin oxide, titanium oxide, silicon oxide, etc.) in addition to the antiviral agent.

  Hereinafter, the present invention will be described based on examples.

  Table 1 shows Examples (Sample Nos. 1 to 4) and Comparative Examples (Sample Nos. 5 and 6) of the antiviral agent comprising the phase-differentiated glass of the present invention.

  Sample No. in Table 1 1 to 4 were prepared as follows.

  First, various glass raw materials such as natural raw materials and chemical conversion raw materials were weighed and mixed so as to have the glass compositions shown in Table 1, to prepare glass batches. Next, this glass batch was put into a platinum-rhodium alloy crucible, and then heated at 1500 to 1600 ° C. for 4 hours in an indirect heating electric furnace to obtain molten glass. In addition, in order to obtain a homogeneous molten glass, the molten glass was stirred multiple times using a heat resistant stirring rod at the time of heating. Subsequently, the obtained molten glass was poured into a refractory mold, transferred to a heat treatment furnace set at 600 ° C., and gradually cooled to obtain a massive glass sample.

  Subsequently, heat treatment for phase separation was performed on this glass sample. Specifically, the glass sample was put into a heat treatment furnace set at 600 to 750 ° C., and heat treatment was performed for 24 hours to make the glass sample cloudy. When this glass sample was confirmed by a scanning electron microscope, it was confirmed that phase separation occurred.

  The density, the average particle size (D50) and the pH of the eluate were measured for the sample thus obtained. The results are shown in Table 1.

  In addition, sample No. 1 in Table 1 5, 6 were prepared as follows. First, a massive glass sample is obtained from molten glass by the same method as described above, and this sample is used (a state in which heat treatment for phase separation is not performed). Thereafter, when the phase separation state was observed, no phase separation could be confirmed. The density, average particle size (D50) and pH of the eluate were measured for these samples in the same manner as described above. The results are shown in Table 1.

  From Table 1, sample No. 1 which is an example of the present invention. The pH of 1 is 12.7, which is estimated to be excellent antiviral.

  The density was measured by the well-known Archimedes method.

  The average particle size (D50) was determined as follows. First, a glass sample was crushed using a mortar and a pestle, and a glass powder which passed through a 130 μm mesh sieve was collected. Subsequently, the particle size distribution was measured by a laser diffraction type particle size distribution measuring apparatus (SIMADZU SALD-2200), and the particle size at which the cumulative percentage of the particles became 50% from the particle size distribution was defined as the average particle size.

  The pH of the eluate was measured as follows. First, each sample was precisely weighed by density x 4.8 weight. Subsequently, 60 ml of pure water was placed in a 100 ml volume polypropylene container (PP container), the sample was immersed, and a dissolution test was performed under conditions of 25 ° C. for 30 minutes. At that time, the stirring process for 5 seconds was performed immediately after the immersion and immediately before the pH measurement. Agitation was performed by shaking the PP container by hand quickly. Immediately after the completion of the dissolution test, the electrode of the pH meter was immersed in the test solution, and the pH of the eluate was measured. The pH meter used was F-71 manufactured by HORIBA, and the electrode used 9681S-10d.

Claims (9)

1. An antiviral agent comprising SiO ₂ , an alkali metal oxide and / or an alkaline earth metal oxide, and made of a glass having a phase separation structure. Glass, a composition, in weight percent oxide _equivalent, SiO ₂ 40 to _95%, antiviral agent according to claim 1, characterized in that it contains 1~60% Na 2 O + K 2 O + CaO. Glass, antiviral agent according to claim 1 or 2, characterized in that contains B ₂ O ₃ as further composition. Glass, further antiviral agent according to claim 1, characterized in that it contains at least one selected from the group consisting of Ag 2 _O, CuO, ZnO as a composition.   In a dissolution test, the glass powder was classified into a density of 130 μm or less, and the glass powder with a density of 4.8 parts by weight was immersed in 60 ml of pure water at 25 ° C. for 30 minutes and stirred for 5 seconds immediately after immersion and immediately before pH measurement The antiviral agent according to any one of claims 1 to 4, characterized in that the pH of the eluate is higher than 12.5.   The antiviral agent according to any one of claims 1 to 5, which is powdery.   The antiviral agent according to claim 6, wherein the particle diameter (D50) when the cumulative existing ratio of particles by laser diffraction type particle size distribution measurement is 50% is 0.1 to 50 m.   A resin molded article comprising an antiviral agent, wherein the antiviral agent comprises the antiviral agent according to any one of claims 1 to 7.   The resin molded article according to claim 8, wherein the content of the antiviral agent is 0.01 to 20% by mass.