JP6912165B2 - Antiviral synthetic resin composition to which an antiviral agent is added - Google Patents

Description

An antiviral synthetic resin composition to which an antiviral agent and an antiviral agent are added.

Viral diseases such as severe respiratory tract infection (SARS) virus, avian influenza virus, foot-and-mouth disease virus, and new influenza virus have become social problems one after another. Originally, the host range of the virus is limited, and it is usual that only mammals infect mammals and only birds infect birds. However, since the avian influenza virus has a wide host range that can infect not only birds but also mammals, it may infect humans. At present, the H5N1 avian influenza virus is widespread in Asia and Europe, and there is concern about a pandemic (infection explosion) due to the emergence of highly virulent influenza mutated based on it. Therefore, in order to take measures against pandemics, it is desired to develop a material showing antiviral property and a material capable of imparting antiviral property.

Patent Document 1 discloses a sheet in which an antiviral imparting composition containing regenerated collagen fiber or regenerated collagen powder is mixed with a polyurethane resin and coated on a soft vinyl chloride sheet.

JP-A-2009-127163

The inventors have found that a synthetic resin composition containing a sulfonic acid-based surfactant in a synthetic resin such as a polyvinyl chloride-based resin exhibits high antiviral performance. However, the synthetic resin composition containing a sulfonic acid-based surfactant is likely to be initially colored by being heated during molding, and as a result, the molded product may be discolored.
Therefore, in view of the above circumstances, it is an object of the present invention to provide an antiviral synthetic resin composition which is excellent in antiviral property and has improved discoloration due to molding processing, particularly initial colorability.

Means to which the present invention is used to solve the problems described above, and 100 parts by weight of the thermoplastic resin, an antiviral synthetic resin composition comprising a 2 parts by weight or more antiviral agents, wherein the anti-viral agent It is an antiviral synthetic resin composition in which 33.3 to 100 parts by weight of a sulfonic acid-based surfactant is supported with respect to 100 parts by weight of an inorganic filler. Further, an antiviral synthetic resin composition containing 1.0 part by weight or more of a sulfonic acid-based surfactant with respect to 100 parts by weight of the thermoplastic resin is preferable. Further, an antiviral synthetic resin composition in which the thermoplastic resin is a polyvinyl chloride resin may be used.

The antiviral synthetic resin composition to which the antiviral agent of the present invention is added can reduce the virus titer and inactivate the virus in a short time after contact with the virus. In addition, it is possible to obtain an antiviral synthetic resin composition having improved discoloration due to molding processing, particularly initial colorability.

Hereinafter, the present invention will be described in detail.
The antiviral agent of the present invention is an antiviral agent for adding a synthetic resin in which 3 to 100 parts by weight of a sulfonic acid-based surfactant is carried with respect to 100 parts by weight of the inorganic filler.

Examples of the inorganic filler include calcium carbonate, talc, silica, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, wollastonite, zeolite, zinc oxide, magnesium oxide, carbon black, graphite and glass beads. , Calcium carbonate is preferable from the economical point of view. These inorganic fillers may be used alone, or two or more of them may be used in combination.
The size of the inorganic filler is not particularly limited and can be appropriately set according to the intended use of the final product, but the average particle size is preferably 0.01 to 100 μm, and the dispersibility when added to the synthetic resin is important. From 0.02 to 30 μm, more preferably 0.02 to 10 μm. The average particle size can be measured by, for example, an electron microscope or a laser diffraction type particle size distribution measuring device.
Further, as the inorganic filler, an inorganic filler that has been surface-treated for the purpose of improving compatibility with the synthetic resin may be used. Examples of the surface treatment agent include fatty acids, resin acids, silicic acids, phosphoric acids, and silane coupling agents. Examples of the fatty acid include saturated or unsaturated fatty acids having 6 to 31 carbon atoms, preferably 12 to 28 carbon atoms.

Examples of the sulfonic acid-based surfactant to be supported on the inorganic filler include alkylbenzene sulfonic acid-based compounds, alkyldiphenyl ether disulfonic acid-based compounds, alkylnaphthalene sulfonic acid-based compounds, alkyl sulfate ester-based compounds, and polyoxyethylene alkyl sulfate ester-based compounds. Examples thereof include naphthalene sulfonate formalin condensate compounds. Among these, alkylbenzene sulfonic acid compounds, alkyldiphenyl ether disulfonic acid compounds, and alkylnaphthalene sulfonic acid compounds are preferable from the viewpoint of excellent antiviral properties, and alkylbenzene sulfonic acid compounds having excellent antiviral properties are more preferable.

In the sulfonic acid-based surfactant used in the present invention, it is assumed that the sulfonic acid group has a high affinity with, for example, the neuroimidase of influenza virus and can exhibit an inhibitory action. In addition, the structure of the functional group has an effect on the approach to neuromiidase, and it is considered that a structure that is not bulky and is not susceptible to steric hindrance is important. In that respect, alkylbenzene sulfonic acid-based surfactants are suitable, and dodecylbenzene sulfonic acid is particularly preferable.
Further, as the above-mentioned sulfonic acid-based surfactant, there are alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium and barium, and the like. Alkali metal salts are preferable in terms of excellent antiviral properties, and sodium dodecylbenzenesulfonate (DBS) is even more preferable.
Further, a plurality of sulfonic acid-based surfactants may be added as long as the antiviral property is not inhibited, and the addition of other types of surfactants is not limited.

The amount of the sulfonic acid-based surfactant to be carried is preferably 3 to 100 parts by weight, more preferably 5 to 70 parts by weight, and 5 to 50 parts by weight with respect to 100 parts by weight of the inorganic filler. Parts by weight are even more preferred. If it is less than 3 parts by weight, the antiviral property becomes poor, and if it is 100 parts by weight or more, it becomes difficult to support it.

As a method for supporting the sulfonic acid-based surfactant on the inorganic filler, a general surface treatment method for the inorganic filler can be used. For example, it may be a wet treatment in which a sulfonic acid-based surfactant is added to an aqueous suspension of the inorganic filler, or it is performed by stirring and mixing the powder of the inorganic filler and the sulfonic acid-based surfactant. It may be a dry treatment.

The synthetic resin may be either a curable resin or a thermoplastic resin, but a thermoplastic resin is preferable because it can be melt-kneaded by heating and the dispersibility of the sulfonic acid-based surfactant can be improved. Examples of the thermoplastic resin include polyvinyl chloride resin, polyolefin resin, polystyrene resin, polyester resin, acrylic resin and the like. Here, from the viewpoint of improving the dispersibility of the sulfonic acid-based surfactant, it is preferable to mix them uniformly before melt-kneading, and for that purpose, the synthetic resin is preferably in the form of powder. Examples of the powdered synthetic resin include polyvinyl chloride-based resin and acrylic-based resin, and these synthetic resins can be preferably used.

When an antiviral agent in which a sulfonic acid-based surfactant is supported on an inorganic filler is added to a synthetic resin, the initial coloration due to processing becomes small. The effect is high in a thermoplastic resin, and a higher effect is particularly seen in a polyvinyl chloride resin.
Generally, a polyvinyl chloride resin is heated at about 150 ° C. to 200 ° C. during processing, and a heat stabilizer is added at that time because it is accompanied by dehydrochloric acid. The coloring of the polyvinyl chloride resin during processing differs depending on the type and combination of heat stabilizers. Here, when the sulfonic acid-based surfactant is added to the polyvinyl chloride resin, it may cause discoloration during processing or plate-out to the processing machine. In this way, it is considered that the sulfonic acid-based surfactant moves in the matrix of the polyvinyl chloride resin and has more chances of contact with additives such as the polyvinyl chloride chain and the stabilizer, so that the yellowing becomes more remarkable. .. Therefore, by adding the sulfonic acid-based surfactant to polyvinyl chloride in a manner of being supported on an inorganic filler, it is possible to suppress the action of the sulfonic acid-based surfactant in a liberated state as described above. It is thought that it can be done.

On the other hand, when an antiviral agent in which a sulfonic acid-based surfactant is supported on the inorganic filler is added to the synthetic resin, a part of the inorganic filler is exposed on the surface of the synthetic resin composition and is supported on the inorganic filler. The sulfonic acid-based surfactant is exposed on the surface and exerts an antiviral effect by coming into contact with an external virus. Such an antiviral effect is a preferred mode of use because the synthetic resin composition is processed into a film or a sheet so that the antiviral agent is more easily exposed.

Examples of the polyvinyl chloride-based resin include a polyvinyl chloride homopolymer, a copolymer of a vinyl chloride monomer and a monomer having an unsaturated bond capable of copolymerizing with the vinyl chloride monomer, and other than vinyl chloride containing a copolymer. Examples thereof include a graft copolymer obtained by copolymerizing vinyl chloride with the polymer of the above.
These polyvinyl chloride resins may be used alone, or two or more of them may be used in combination. Further, if necessary, the polyvinyl chloride resin may be chlorinated.
The method for chlorinating the polyvinyl chloride resin is not particularly limited, and examples thereof include a photochlorination method and a thermal chlorination method. Further, the degree of polymerization of the polyvinyl chloride resin used in the present invention is not particularly limited.

The amount of the antiviral agent of the present invention added to the synthetic resin is preferably 2 parts by weight or more with respect to 100 parts by weight before the synthetic resin.
If the antiviral agent of the present invention is less than 2 parts by weight, the antiviral property becomes poor. The upper limit is not particularly limited, but is preferably 100 parts by weight or less from the viewpoint of workability.
Further, if the amount of the sulfonic acid-based surfactant is less than 1.0 part by weight, the antiviral property becomes poor. The upper limit is preferably 10 parts by weight or less, preferably 7 parts by weight or less from the processed surface, and more preferably 5 parts by weight or less.
Further, the sulfonic acid-based surfactant is contained in an amount of 1.0 part by weight or more with respect to 100 parts by weight of the synthetic resin, and the sulfonic acid-based surfactant is added in the form of an antiviral agent supported on the inorganic filler. preferable.

The present invention aims to improve antiviral properties, physical properties, processability, etc., in addition to using only the form of an antiviral agent carried on an inorganic filler as the sulfonic acid-based surfactant to be added to the synthetic resin. Antiviral agents can be used in combination with sulfonic acid-based surfactants and other antiviral agents.

In the present invention, as long as the antiviral property is not inhibited with respect to the synthetic resin, a filler, a plasticizer, an ultraviolet absorber, a light stabilizer, an antioxidant, a lubricant, an ultraviolet shield, an antistatic agent, a flame retardant, and a fluorescent substance. Agents, antibacterial agents, fungicides, flame retardants, and flame retardants may be added as appropriate.

The antiviral synthetic resin composition of the present invention can improve the dispersibility of the antiviral agent in the synthetic resin by using the step of mixing the synthetic resin and the antiviral agent of the present invention, and the antiviral agent after molding can be improved. Viral is stable. As a mixing method, there are a container fixed type in which the mixture is mixed by mechanical stirring force and a container rotating type in which the container is rotated and mixed, but either method may be used as long as the antiviral agent is in a good state of dispersion. .. As the container fixed type, there is a Henschel mixer or the like, and as the container rotating type, known equipment such as a container blender can be used.

The antiviral synthetic resin composition of the present invention can improve the dispersibility of the antiviral agent in the synthetic resin by using the step of melt-kneading the synthetic resin and the antiviral agent of the present invention, and after molding, the antiviral synthetic resin composition can be improved. Stable antiviral properties. Any device may be used as long as melt kneading is possible, and known equipment such as a Banbury mixer, a kneader, a double roll machine, and an extruder can be used. It may be molded immediately after melt-mixing, or it may be pelletized once after melt-mixing and then molded.

The antiviral synthetic resin composition of the present invention is a roll molding device, a calendar molding device, a uniaxial or biaxial extrusion device, an inflation molding device, an injection molding device, a thermoforming device, a slush molding device, a paste coater device, a dipping molding device. It is molded by known equipment such as.
When the synthetic resin is a polyvinyl chloride-based resin, it is mainly molded by a roll molding device, a calendar molding device, a uniaxial or biaxial extrusion device, an inflation molding device, an injection molding device, a thermoforming device, or a slash molding device.

The use of the antiviral synthetic resin composition of the present invention is not particularly limited, and examples thereof include sheets, flooring materials, wallpaper, films, clothing fabrics, containers, pipes, toys, and the like.
As other uses, as described in Japanese Patent Application Laid-Open No. 2008-37814, diagnostic equipment, extracorporeal circulation equipment, protective products, clinical examination equipment, hospital equipment, medical consumables, home medical equipment, sanitary materials, etc. It is used in health equipment, hospital buildings, food manufacturing factories, food packaging materials, etc. in a state where the function of inactivating the virus can be exhibited.

The antiviral synthetic resin composition of the present invention is expected to have antiviral effects on various viruses, but exhibits high antiviral properties particularly on enveloped viruses. Examples of viruses having an envelope include fluenzaviruses such as bird influenza virus, human influenza virus, and pig influenza virus, hepatitis B virus, hepatitis C virus, human immunodeficiency virus, varicella herpes virus, simple herpes virus, and humans. Examples thereof include herpes virus, mumps virus, RS virus, and Ebola virus.

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Antiviral agent]
A sulfonic acid-based surfactant was added to an aqueous suspension of the inorganic filler, stirred, and then dried to obtain an antiviral agent in which the sulfonic acid-based surfactant was carried on the inorganic filler. The amounts of the inorganic filler and the sulfonic acid-based surfactant charged are shown below.
Sulfonic acid-based surfactant B-1: Na alkylbenzene sulfonate (trade name: NANSA (registered trademark) HS90 / S, manufactured by Huntsman Japan)
Inorganic filler A-1: Calcium carbonate Inorganic filler A-2: Silica Antiviral agent E-1: Inorganic filler A-1 Sulfonic acid-based surfactant B-1 6.7 based on 100 parts by weight of calcium carbonate Parts by weight Antiviral agent E-2: Inorganic filler A-1 100 parts by weight of calcium carbonate Sulfonic acid-based surfactant B-1 33.3 parts by weight Antiviral agent E-3: Inorganic filler A-2 50 parts by weight of sulfonic acid-based surfactant B-1 with respect to 100 parts by weight of silica

[Antiviral synthetic resin composition]
Specific substance names of each combination drug used in Examples and Comparative Examples are as follows.
Inorganic filler A-1: Calcium carbonate sulfonic acid-based surfactant B-1: Na alkylbenzene sulfonic acid (trade name: NANSA (registered trademark) HS90 / S, manufactured by Huntsman Japan Co., Ltd.)
(Product name: NANSA (registered trademark) HS90 / S, manufactured by Huntsman Japan)
Polychlorinated Vinyl Chloride Resin C-1: Suspension Vinyl Chloride Resin Average Degree of Polymerization 1000
Polyvinyl chloride resin C-2: Suspension vinyl chloride resin Average degree of polymerization 700
Acrylic resin C-3:
(Product name: Parapet (registered trademark) SA-1000FP manufactured by Kuraray Co., Ltd.)
Acrylic resin C-4:
(Product name: Parapet (registered trademark) GR-F-1000-P manufactured by Kuraray Co., Ltd.)
Olefin resin C-5:
(Product name: Nipolon Hard (registered trademark) 4010A manufactured by Tosoh Corporation)
Olefin resin C-6:
(Product name; Engage (registered trademark) EG8003 manufactured by Dow Chemical Co., Ltd.)
Plasticizer D-1: DOP (di-2-ethylhexyl phthalate)
Plasticant D-2: Polyester-based surfactant Antiviral agent E-1: Inorganic filler A-1 Sulfonic acid-based surfactant B-1 6.7 parts by weight with respect to 100 parts by weight of calcium carbonate Antiviral agent E- 2: Inorganic filler A-1 with respect to 100 parts by weight of calcium carbonate Sulfonic acid-based surfactant B-1 33.3 parts by weight Antiviral agent E-3: Inorganic filler A-2 with respect to 100 parts by weight of silica Sulfonic acid-based surfactant B-1 50 parts by weight <Method for producing sheet-like material>
Stabilizers, plasticizers, strengthening agents, antioxidants, and lubricants were added to the formulations of Examples 1 to 12 shown in Tables 1 and 2 and Comparative Examples 1 to 6 shown in Table 3, and a Henschel mixer was used. Mixing gave a synthetic resin mixture. Then, this synthetic resin mixture was kneaded with a small mixer to obtain an antiviral synthetic resin composition. Immediately after that, a sheet having a thickness of 150 μm was obtained using a double roll machine.

<Antiviral property>
As a test virus, avian influenza virus A / whistling swan / Shimane / 499/83 (H5N3) strain was used. (Hereinafter referred to as H5N3 strain).
The H5N3 strain was diluted with sterile phosphate buffered saline (PBS; pH 7.2) to 1.0 × 10 ⁶ EID _{50 /} 0.1 mL to prepare a test virus solution.

The sheet 5 cm × 5 cm prepared in the examples shown in Tables 1 and 2 and the comparative example shown in Table 3 was placed on a petri dish, 0.22 ml of the test virus solution was placed on the sheet surface, and 4 cm × was placed on the sheet. The petri dish was covered with a 4 cm polyethylene film, covered with a petri dish, and allowed to stand in an incubator set at 20 ° C. for 1 hour. One hour later, the virus solution on the surface of the sheet was collected, diluted 10-fold with the PBS, and 0.1 mL of the diluted virus solution was inoculated into the allantois cavity of a 10-day-old embryonated chicken egg using an injection needle.

After inoculation, the developed chicken eggs were cultured at 37 ° C. for 2 days, and then the presence or absence of virus growth in the serous membrane cavity was determined by an hemagglutination test, and the virus titer (log ₁₀ EID _{50 /} 0.1 ml) was determined by the method of Red & Muench. Was calculated.
_{Also, as a blank, the virus titer (log 10} EID _{50 /} 0.1 ml) of the test virus solution before the test (before contact with the sheet) was calculated by the above procedure, and the antiviral property of the sheet was that of the virus solution before the test. The evaluation was made by subtracting the virus titer of the virus solution 1 hour after contact with the sheet from the virus titer. The larger this difference is, the stronger the antiviral property of the sheet is.

◯: Difference between virus titer (before test) and virus titer (after 1 hour) is 3 or more High antiviral effect Δ: Difference between virus titer (before test) and virus titer (after 1 hour) is 1 More than 3 Antiviral effect ×: Difference between virus titer (before test) and virus titer (1 hour later) is less than 1 Antiviral effect is low

<Initial coloring by processing>
The initial coloring by processing was visually evaluated for the coloring of the sheets prepared in the examples shown in Tables 1 and 2 and the comparative examples shown in Table 3.

1: Light coloring 2: Slightly colored 3: Large coloring 4: Remarkably colored

Comparing Examples 1 to 12 with Comparative Examples 1 to 5, it can be seen that the synthetic resin composition containing the antiviral agent in the range of the present invention imparts antiviral properties and the initial coloring due to processing is small.
In particular, comparing Examples 1 and 6 with Comparative Examples 1 and 2, by adopting the embodiment of the present invention, even if the amount of the sulfonic acid-based surfactant added is 3 parts by weight or more, the initial coloring due to processing is small and high antiviral property is imparted. It can be seen that the initial coloring due to processing can be suppressed.
Further, looking at Examples 1 and 9, it was found that the effect was obtained regardless of the addition of the plasticizer, and Example 4 in which the filler was further added to Example 2 also had antiviral properties and was antiviral. It can be seen that even if a filler is added in addition to the viral agent, the initial coloring is small and the virus has antiviral properties.
Furthermore, according to Example 5, it can be seen that the effect of the present invention appears even when an antiviral agent in which a sulfonic acid-based surfactant is supported on an inorganic filler and a sulfonic acid-based surfactant are used in combination.
Comparing Examples 6 and 7 with Comparative Example 2, it can be seen that even if the amount of the antiviral agent added in the present invention is increased, the initial coloring during processing does not deteriorate.
In Examples 11 and 12, it can be seen that the effect of the present invention appears even if the type of synthetic resin is changed.

Since the antiviral synthetic resin composition to which the antiviral agent of the present invention is added has the effect of rapidly reducing the virus titer of the contacted virus and inactivating the virus, various everyday products, buildings, vehicles, etc. Sheets, flooring materials, wallpapers, films, clothing fabrics, containers, pipes, toys, diagnostic equipment, extracorporeal circulation equipment, protective products, clinical examination equipment, hospital equipment, medical consumables, home medical equipment Suitable for molded products such as sanitary materials, hygiene equipment, hospital buildings, food manufacturing factories, food packaging materials, etc., especially in hospitals, offices, old-fashioned facilities, public facilities such as schools, buses, trains, etc. It is suitable for places where many people gather and the risk of virus infection is high.

Claims (3)

An anti-viral synthetic resin composition for melt kneading include a thermoplastic resin 100 parts by weight, and the 2 parts by weight or more antiviral agents,
An antiviral synthetic resin composition in which the antiviral agent carries 33.3 to 100 parts by weight of a sulfonic acid-based surfactant with respect to 100 parts by weight of the inorganic filler. The antiviral synthetic resin composition according to claim 1, which contains 1.0 part by weight or more of the sulfonic acid-based surfactant with respect to 100 parts by weight of the thermoplastic resin. The antiviral synthetic resin composition according to claim 1 or 2, wherein the thermoplastic resin is a polyvinyl chloride resin.