JP6837732B2 - Antiviral molding material and its manufacturing method - Google Patents

Description

The present invention relates to an antiviral synthetic resin composition having antiviral properties and a method for producing the same.

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. In recent years, the H5N1 avian influenza virus has spread in Asia and Europe, and there is concern about the emergence of highly virulent influenza mutated based on it. Recently, highly resistant norovirus and Ebola virus, which has a high mortality rate when infected, are rampant, not only preparing for a pandemic (infection explosion) caused by the virus, but also resisting building materials such as interior materials and everyday items. Virus products are becoming more promising.

As a substance that imparts antiviral properties to various building materials, everyday products, etc., Patent Document 1 includes metal oxide powder and hydroxide that enable the generation of hydroxyl radicals that inactivate viruses. The anti-virus material is listed.

Japanese Unexamined Patent Publication No. 2008-37814

However, when the metal oxide powder and the hydroxide are added to the synthetic resin as in Patent Document 1, unless a large amount of the metal oxide powder and the hydroxide are added to the synthetic resin, a short time after contact with the virus In some cases, it was not possible to obtain rapid antiviral performance that would inactivate the resin. On the other hand, when a large amount of metal oxide powder and hydroxide is added to the synthetic resin in order to obtain effective antiviral properties, a large amount of inorganic filler is added to the synthetic resin. As a result, there is a problem that the physical properties of the synthetic resin composition, particularly the mechanical properties, are significantly deteriorated.

Therefore, an object of the present invention is to obtain an antiviral synthetic resin composition that does not significantly deteriorate the physical properties of the synthetic resin composition as a base material even if an antiviral agent is added for the expression of antiviral properties. And.

The means used in the present invention to solve the above-mentioned problems is to add 0 sulfonic acid-based surfactant to 100 parts by weight of at least one synthetic resin selected from polyolefin-based resin, polyester-based resin, and acrylic-based resin. It is an antiviral molding material containing 5 parts by weight or more. Further, the synthetic resin and the sulfonic acid-based surfactant may be melt-kneaded. Further, the sulfonic acid-based surfactant may be an alkylbenzene sulfonic acid-based compound.
The antiviral molding material includes a step of mixing at least one synthetic resin selected from a polyolefin resin, a polyester resin, and an acrylic resin with a sulfonic acid-based surfactant to obtain a synthetic resin mixture, and the above-mentioned step. It can be preferably obtained by a production method including a step of melt-kneading the synthetic resin mixture.

The antiviral synthetic resin composition of the present invention reduces the virus titer in a short time after contact with the virus and inactivates the virus without significantly reducing the physical properties of the synthetic resin composition, particularly the mechanical properties. Can be done.

Hereinafter, the present invention will be described in detail.
The synthetic resin of the present invention may be either a curable resin or a thermoplastic resin, but the thermoplastic resin can be melt-kneaded by heating and the dispersibility of the sulfonic acid-based surfactant can be improved. Is preferable. Examples of the thermoplastic resin include polyvinyl chloride resin, polyolefin resin, polystyrene resin, polyester resin, acrylic resin and the like. Further, as the synthetic resin of the present invention, synthetic rubber such as SBR and NBR may be used.
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.

Further, a synthetic resin obtained by a polymerization method using water as a medium such as emulsion polymerization or suspension polymerization is preferable because the sulfonic acid-based surfactant can be easily dispersed as described later. Examples of such synthetic resins include polyvinyl chloride resins, acrylic resins, and synthetic rubbers such as ABS, SBR, and NBR.

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 copolymerizable 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.

Examples of the sulfonic acid-based surfactant used in the present invention include alkylbenzene sulfonic acid-based compounds, alkyldiphenyl ether disulfonic acid-based compounds, alkylnaphthalene sulfonic acid-based compounds, alkyl sulfate ester-based compounds, polyoxyethylene alkyl sulfate-based compounds, and naphthalene sulfone. Examples thereof include acid 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.

As the sulfonic acid-based surfactant used in the present invention, a powdery substance or a liquid substance may be used. The powdered product may be powdered by adding an additive to a sulfonic acid-based surfactant. As the liquid material, one dissolved and dispersed in a liquid medium can be used. As a solvent, a sulfonic acid-based surfactant solution, which is an aqueous liquid substance in which a sulfonic acid-based surfactant is dissolved in water, may be used. The powdered sulfonic acid-based surfactant is preferable because it can be easily mixed with a synthetic resin and melt-kneaded and has excellent processability. On the other hand, the liquid sulfonic acid-based surfactant has excellent dispersibility. In particular, a sulfonic acid-based surfactant solution using water as a solvent is excellent in that it can be easily finely dispersed in a synthetic resin polymerized by emulsion polymerization or suspension polymerization.

The sulfonic acid-based surfactant solution using water as a solvent may be added to the synthetic resin in the process of producing the synthetic resin, or may be added when the synthetic resin is melt-kneaded.

Here, when the synthetic resin is polymerized using water as a medium such as emulsion polymerization or suspension polymerization, the sulfonic acid-based surfactant solution can be added in any step of the production of the synthetic resin. For example, a sulfonic acid-based surfactant may be added as an emulsifier used in emulsion polymerization, or a sulfonic acid-based surfactant may be added after the polymerization.

When a sulfonic acid-based surfactant is used as an emulsifier, the behavior of polymerization may change and it may be difficult to obtain a desired synthetic resin. Therefore, it is preferable to add a sulfonic acid-based surfactant after the polymerization in addition to the emulsifier required for the polymerization. When the sulfonic acid-based surfactant is added after the polymerization, it may be added to the latex after the polymerization, or it may be added after the synthetic resin is taken out from the latex. It is preferable to take out the synthetic resin from the lattice after the polymerization, and if there is a washing step after that, add it after the washing step. This is because the sulfonic acid-based surfactant may also be washed away in the water washing step.
Therefore, after polymerization in emulsion polymerization, the solid content (synthetic resin) of the surfactant is separated by a known method such as a spray drying method, an acid addition method, a salt addition method, and a freeze coagulation method, and then dehydration, washing with water, and drying. However, when a synthetic resin is obtained in the form of powder, it is preferable to add the sulfonic acid-based surfactant after washing with water and before drying. The step after the polymerization may be appropriately treated with a desired synthetic resin, and each step may be omitted, the step order may be changed, or another step may be added.
For example, when a synthetic resin is obtained without spray-drying the latex and washing with water, the sulfonic acid-based surfactant can be easily finely dispersed in the synthetic resin by adding a sulfonic acid-based surfactant solution to the latex. it can.

Further, in the polymerization using an aqueous medium such as suspension polymerization, the sulfonic acid-based activator solution can be added by the same method as the emulsion polymerization. For example, the synthetic resin may be separated by a spray drying method or the like after adding a sulfonic acid-based surfactant to the aqueous medium after polymerization, or the sulfonic acid-based surfactant may be separated after the synthetic resin is separated and then washed with water. May be added and dried.

When a sulfonic acid-based surfactant solution using water as a solvent is added at the time of melt-kneading the synthetic resin, it is preferable to add it in the mixing step before the kneading step. When the synthetic resin and the aqueous solution of the sulfonic acid-based surfactant are mixed, it is preferable to provide a drying step after that, but melt-kneading may be performed without drying. Here, in the case of melt-kneading without drying, it is preferable to degas the steam in the kneading step.
When degassing steam in the kneading step, it is preferable to use an open mixer or a roll, and an extruder having a vent can also be used.

The sulfonic acid-based surfactant is preferably finely dispersed in the synthetic resin. The sulfonic acid-based surfactant may reduce the processability of the antiviral synthetic resin composition by heating, and it is preferable to add a lower amount. On the other hand, in order to impart high antiviral properties, it is preferable to add a high amount of the sulfonic acid-based surfactant. Therefore, by finely dispersing the sulfonic acid-based surfactant, a desired antiviral effect can be obtained with a lower addition amount, and deterioration of processability can be prevented.

Therefore, it is preferable to add a sulfonic acid-based surfactant solution using water as a solvent to the synthetic resin because the sulfonic acid-based surfactant can be easily finely dispersed in the synthetic resin. On the other hand, when the processability is deteriorated due to the influence of moisture, the appearance of the molded product is deteriorated, or the physical properties are deteriorated, it is preferable to add a powdery sulfonic acid-based surfactant.

The content of the sulfonic acid-based surfactant is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the synthetic resin. More preferably, 1.0 to 20 parts by weight. If it is less than 0.5 parts by weight, the antiviral property becomes poor.

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 comprises a mixing step of mixing a synthetic resin and a sulfonic acid-based surfactant to obtain a synthetic resin mixture, and a kneading step of melt-kneading the synthetic resin mixture. Can be preferably obtained.
The mixing step may be provided in the synthetic resin manufacturing process, or may be provided as a separate step after the synthetic resin is manufactured. When provided in the synthetic resin manufacturing process, it may be added as an emulsifier in polymerization or after polymerization as described above.

As a mixing step of mixing a synthetic resin and a sulfonic acid-based surfactant to obtain a synthetic resin mixture, 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. Either method may be used as long as the dispersion of the activator is in a good state. 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.

As the kneading step of melt-kneading the synthetic resin mixture, 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. Here, the two-roll machine, the extruder, and the like can combine the kneading step and the molding step of molding.

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.
Other uses include diagnostic equipment, extracorporeal circulation equipment, protective products, clinical testing equipment, hospital equipment, medical consumables, home medical equipment, sanitary materials, hygiene equipment, hospital buildings, food manufacturing plants, food packaging materials. It is used in a state where the function of inactivating the virus can be expressed.

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.

Specific substance names of each combination drug used in Examples and Comparative Examples are as follows.
Polychlorinated Vinyl Chloride Resin A-1: Suspension Vinyl Chloride Resin Average Degree of Polymerization 1000
Polychlorinated Vinyl Chloride Resin A-2: Suspension Vinyl Chloride Resin Average Degree of Polymerization 700
Acrylic resin A-3:
(Product name: Parapet (registered trademark) SA-1000FP manufactured by Kuraray Co., Ltd.)
Acrylic resin A-4:
(Product name: Parapet (registered trademark) GR-F-1000-P manufactured by Kuraray Co., Ltd.)
Olefin resin A-5:
(Product name: Nipolon Hard (registered trademark) 4010A manufactured by Tosoh Corporation)
Olefin resin A-6:
(Product name; Engage (registered trademark) EG8003 manufactured by Dow Chemical Co., Ltd.)
Sulfonic acid-based surfactant B-1: Na alkylbenzene sulfonic acid Purity 90%
(Product name: NANSA (registered trademark) HS90 / S, manufactured by Huntsman Japan)
Sulfonic acid-based surfactant B-2: Aqueous solution of sodium alkylbenzene sulfonate Purity 25%
(Product name: Neoperex (registered trademark) G-25, manufactured by Kao Corporation)
Metal oxide powder and hydroxide C-1: calcined dolomite (trade name: Variere P-2, manufactured by Mochigase)
Plasticizer D-1: Di-2-ethylhexyl phthalate

The sheet-like products of Examples and Comparative Examples were prepared by the following production methods.
<Manufacturing method I>
Stabilizers, fortifiers, antioxidants and lubricants were added to the formulations of Examples 1 to 6, 8 and 10 shown in Table 1 and Comparative Examples 1 to 3 shown in Table 2 and mixed with a Henschel mixer. , A synthetic resin mixture was obtained. Then, this synthetic resin mixture was kneaded with a small mixer set at 150 ° C. to obtain an antiviral synthetic resin composition. Immediately after that, a sheet-like product having a thickness of 150 μm was obtained using a double roll machine set at 175 ° C. to 190 ° C.
In Example 4, an aqueous solution of sodium alkylbenzene sulfonate was added, but a sheet-like product was obtained by the same production method as described above.

<Manufacturing method II>
A stabilizer was added to the formulation of Example 7 shown in Table 1, and a sheet-like product having a thickness of 150 μm was obtained using a two-roll machine set at 185 ° C.

<Manufacturing method III>
Acrylic resin A-4 and sulfonic acid-based surfactant B-2 were uniformly mixed in distilled water and then dried to obtain a mixture of acrylic resin A-4 and sulfonic acid-based surfactant B-2. .. Then, the acrylic resin A-3, the acrylic resin A-4, and the above mixture are adjusted so as to have the composition of Example 9 shown in Table 1, an antioxidant and a lubricant are added, and a Henschel mixer is used. Mixing gave a synthetic resin mixture. Then, this synthetic resin mixture was kneaded at 150 ° C. with a small mixer to obtain an antiviral synthetic resin composition. Immediately after that, a sheet-like product having a thickness of 150 μm was obtained using a double roll machine set at 190 ° C.
In the manufacturing methods I to III, the Henschel mixer is the mixing step, and the small mixer and the two rolls are the kneading steps.

<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-like material 5 cm × 5 cm prepared in the Examples and Comparative Examples shown in Table 1 was placed on a petri dish, 0.22 ml of the test virus solution was placed on the surface of the sheet-like material, and a 4 cm × 4 cm polyethylene film was placed on the sheet-like material. It was covered, the petri dish was covered, and the dish was 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 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. did.

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 allantois 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.
_{In addition, the virus titer (log 10} EID _{50 /} 0.1 ml) of the test virus solution before the test (before contact with the sheet-like material) as a blank was also calculated by the above procedure, and the antiviral property of the sheet-like material was 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 of the virus solution of. The larger this difference is, the stronger the antiviral property of the sheet-like material 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

<Impact resistance>
Using the sheet-like products prepared in Examples and Comparative Examples shown in Table 1, measurements were made with a film impact tester manufactured by Toyo Seiki Co., Ltd. and evaluated according to the following criteria.

◯: Does not break.
Δ: Whitening but not breaking.
X: Breaks.

Comparing Examples 1 to 10 with Comparative Examples 1 and 3, it can be seen that the antiviral property is imparted by containing the sulfonate-based surfactant within the range of the present invention. Further, looking at Examples 8 and 9, it can be seen that antiviral properties are imparted even if the production methods are different.
Comparing Example 3 and Comparative Example 2, the sulfonate-based surfactant has antiviral properties and impact resistance, whereas the metal oxide powder and hydroxide have antiviral properties but impact resistance. It turns out that it is scarce.
Comparing Example 2 and Example 7 with the same composition but different production methods, the sulfonic acid-based surfactant was more finely dispersed by mixing with a Henschel mixer and kneading with a small mixer. It showed a higher antiviral effect.

In Example 4, the water content was evaporated by kneading with a small mixer and two rolls, and the workability and the appearance of the sheet with the two rolls were good.
Further, in Example 9, the acrylic resin A-4 and the sulfonic acid-based surfactant B-2, which is a sulfonic acid-based surfactant solution, are mixed in distilled water and then dried, so that they can be processed with two rolls. And the appearance of the sheet was good.

Claims (4)

An antiviral molding material containing 0.5 parts by weight or more of a sulfonic acid-based surfactant with respect to 100 parts by weight of at least one synthetic resin selected from polyolefin-based resins, polyester-based resins, and acrylic-based resins. The antiviral molding material according to claim 1, wherein the synthetic resin and the sulfonic acid-based surfactant are melt-kneaded. The antiviral molding material according to claim 1 or 2, wherein the sulfonic acid-based surfactant is an alkylbenzene sulfonic acid-based compound. A mixing step of mixing 100 parts by weight of at least one synthetic resin selected from polyolefin-based resin, polyester-based resin, and acrylic-based resin with 0.5 parts by weight or more of a sulfonic acid-based surfactant to obtain a synthetic resin mixture.
The production method for producing an antiviral molding material according to any one of claims 1 to 3, further comprising a kneading step of melt-kneading the synthetic resin mixture.