JP2016128395A - Antiviral synthetic resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiviral synthetic resin composition which, even when an antiviral agent is added thereto, does not greatly lower physical properties of the substrate synthetic resin composition.SOLUTION: The antiviral synthetic resin composition contains 0.5 pt.wt. or more of a sulfonic acid-based surfactant relative to 100 pts.wt. of a synthetic resin. The antiviral synthetic resin composition can be obtained by melt-kneading the synthetic resin and a powder-type sulfonic acid-based surfactant, where the synthetic resin is preferably a polyvinyl chloride-based resin. Further, the antiviral synthetic resin composition can be suitably obtained by a production method comprising steps of: obtaining a synthetic resin mixture by mixing the synthetic resin and the sulfonic acid-based surfactant; and of melt-kneading the synthetic resin mixture.SELECTED DRAWING: None

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 infection (SARS) virus, avian influenza virus, foot-and-mouth disease virus, and new influenza virus are becoming social problems one after another.
Originally, the host range of viruses is limited, and it is normal that only mammals infect mammals and only birds infect birds. However, since avian influenza virus is a virus with a wide host range that can infect not only birds but also mammals, it may infect humans. In recent years, H5N1 avian influenza virus has spread in Asia and Europe, and there is concern about the emergence of highly toxic influenza mutated based on it. Recently, highly resistant noroviruses and Ebola viruses with high mortality rates when infected are becoming more and more prominent. They are not only prepared for pandemic (infection explosion) caused by viruses, but also resistant to building materials such as interior materials and everyday items. Viral products are expected.

  Patent Document 1 includes metal oxide powders and hydroxides that enable generation of hydroxyl radicals that inactivate viruses as those that impart antiviral properties to various building materials and daily products. Antiviral materials are described.

JP 2008-37814 A

  However, when adding metal oxide powder and hydroxide to the synthetic resin as in Patent Document 1, if a large amount of metal oxide powder and hydroxide is not 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 such as inactivation. On the other hand, when a large amount of metal oxide powder and hydroxide are 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 has been a problem that the physical properties, particularly mechanical properties, of the synthetic resin composition are greatly reduced.

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

The means used by the present invention to solve the above-mentioned problems is to make an antiviral synthetic resin composition containing 0.5 parts by weight or more of a sulfonic acid surfactant with respect to 100 parts by weight of the synthetic resin. In addition, a sulfonic acid surfactant may be added before the synthetic resin kneading step. Furthermore, the sulfonic acid-based surfactant may be added to the synthetic resin in the form of a powder or an aqueous liquid.
The antiviral synthetic resin composition is preferably produced by a production method comprising a step of mixing a synthetic resin and a sulfonic acid surfactant to obtain a synthetic resin mixture, and a step of melt-kneading the synthetic resin mixture. Can be obtained.

  The antiviral synthetic resin composition of the present invention can inactivate the virus by reducing the virus titer in a short time after contact with the virus, without greatly reducing the physical properties, particularly mechanical properties, of the synthetic resin composition. Can do.

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 can be melt-kneaded by heating and can improve the dispersibility of the sulfonic acid surfactant, so that it is a thermoplastic resin. Is preferred. 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 uniformly before melt kneading. For this purpose, the synthetic resin is preferably in the form of powder. Examples of powdered synthetic resins include polyvinyl chloride resins and acrylic resins, and these synthetic resins can be suitably used.

  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 surfactant can be easily dispersed as described later. Examples of such synthetic resins include polyvinyl chloride resins, acrylic resins, ABS, SBR, NBR, and other synthetic rubbers.

Examples of the polyvinyl chloride resin include polyvinyl chloride homopolymers, copolymers of vinyl chloride monomers and monomers having unsaturated bonds copolymerizable with vinyl chloride monomers, and other than vinyl chloride containing copolymers. And a graft copolymer obtained by copolymerizing vinyl chloride with the above polymer.
These polyvinyl chloride resins may be used alone or in combination of two or more. 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. Moreover, the polymerization degree of the polyvinyl chloride resin used in the present invention is not particularly limited.

Examples of the sulfonic acid surfactant used in the present invention include alkylbenzene sulfonic acid compounds, alkyl diphenyl ether disulfonic acid compounds, alkyl naphthalene sulfonic acid compounds, alkyl sulfate esters, polyoxyethylene alkyl sulfate esters, naphthalene sulfones. Examples include acid formalin condensate compounds. Of these, alkylbenzenesulfonic acid compounds, alkyldiphenyl ether disulfonic acid compounds, and alkylnaphthalenesulfonic acid compounds are preferable from the viewpoint of excellent antiviral properties, and alkylbenzenesulfonic acid compounds that are particularly excellent in antiviral properties are more preferable.
In the sulfonic acid surfactant used in the present invention, it is assumed that the sulfonic acid group has a high affinity with, for example, influenza virus neuramidase and can exhibit an inhibitory action. In addition, the structure of the functional group has an influence on the approach to the neuraimidase, and it is considered that a structure that is not bulky and hardly receives steric hindrance is important. In that respect, alkylbenzene sulfonic acid surfactants are preferred, and dodecylbenzene sulfonic acid is particularly preferred.
Furthermore, examples of the sulfonic acid surfactant include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium and barium, and the like. An alkali metal salt is preferable in terms of excellent antiviral properties, and sodium dodecylbenzenesulfonate (DBS) is more preferable.
Further, a plurality of sulfonic acid surfactants may be added as long as antiviral properties are not inhibited, and addition of other types of surfactants is not limited.

  As the sulfonic acid surfactant used in the present invention, a powdery product or a liquid product may be used. The powdery product may be a powdery product obtained by adding an additive to a sulfonic acid surfactant. As the liquid material, those dissolved and dispersed in a liquid medium can be used. A sulfonic acid surfactant solution which is an aqueous liquid in which a sulfonic acid surfactant is dissolved in water may be used as a solvent. Powdered sulfonic acid surfactants are preferred in that they are easy to mix and melt knead with a synthetic resin and are excellent in processability. On the other hand, a liquid sulfonic acid surfactant is excellent in dispersibility. In particular, a sulfonic acid 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 surfactant solution using water as a solvent may be added to the synthetic resin in the synthetic resin production process, 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 surfactant solution can be added in any step of the synthetic resin production. For example, a sulfonic acid surfactant may be added as an emulsifier used in emulsion polymerization, or a sulfonic acid surfactant may be added after polymerization.

When a sulfonic acid surfactant is used as an emulsifier, the polymerization behavior may change, making it difficult to obtain a desired synthetic resin. Accordingly, it is preferable to add a sulfonic acid surfactant separately from the emulsifier necessary for the polymerization after the polymerization. When a sulfonic acid surfactant is added after polymerization, it may be added to the latex after polymerization, or may be added after the synthetic resin is taken out from the latex. It is preferable to take out the synthetic resin from the latex after the polymerization and add it after the water washing step if there is a water washing step thereafter. This is because the sulfonic acid surfactant may be washed away in the water washing step.
Therefore, after polymerization in emulsion polymerization, latex is separated into solids (synthetic resin) by known methods such as spray drying, acid addition, salt addition, freeze coagulation, and then dehydrated, washed with water, and dried. When obtaining a synthetic resin in powder form, the sulfonic acid surfactant is preferably added after washing with water and before drying. In addition, the process after superposition | polymerization should just perform an appropriate process with a desired synthetic resin, each process may be abbreviate | omitted, a process order may be changed, and another process may be added.
For example, when a synthetic resin is obtained without spray drying and washing the latex with water, the sulfonic acid surfactant can be easily finely dispersed in the synthetic resin by adding a sulfonic acid surfactant solution to the latex. it can.

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

When the sulfonic acid surfactant solution using water as a solvent is added during the melt-kneading of the synthetic resin, it is preferably added in the mixing step before the kneading step. When an aqueous solution of a synthetic resin and a sulfonic acid surfactant is mixed, it is preferable to provide a drying step after that, but it may be melt-kneaded without drying. Here, when melt-kneading without drying, it is preferable to degas water vapor in the kneading step.
When water vapor is degassed in the kneading step, it is preferable to use an open mixer or roll, and an extruder having a vent can also be used.

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

  Therefore, it is preferable to add a sulfonic acid surfactant solution containing water as a solvent to the synthetic resin because the sulfonic acid surfactant can be easily finely dispersed in the synthetic resin. On the other hand, when the workability deteriorates due to the influence of moisture, the appearance of the molded article deteriorates or the physical properties deteriorate, it is preferable to add a powdered sulfonic acid surfactant.

  The content of the sulfonic acid surfactant is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the synthetic resin. 1.0-20 weight part is further more preferable. If it is less than 0.5 parts by weight, the antiviral properties are poor.

  In the present invention, the filler, plasticizer, ultraviolet absorber, light stabilizer, antioxidant, lubricant, ultraviolet shielding agent, antistatic agent, flame retardant, fluorescence, as long as antiviral properties are not inhibited against the synthetic resin. Agents, antibacterial agents, antifungal agents, flame retardants, and flame retardants may be added as appropriate.

The antiviral synthetic resin composition of the present invention is a production method comprising a mixing step of mixing a synthetic resin and a sulfonic acid surfactant to obtain a synthetic resin mixture, and a kneading step of melt-kneading the synthetic resin mixture. Can be suitably obtained.
The mixing process may be provided in the synthetic resin manufacturing process, or may be provided as a separate process after the synthetic resin is manufactured. When providing in the manufacturing process of a synthetic resin, as above-mentioned, you may add as an emulsifier in superposition | polymerization and may add after superposition | polymerization.

  The mixing process of mixing a synthetic resin and a sulfonic acid-based surfactant to obtain a synthetic resin mixture includes a container-fixing type that mixes by mechanical stirring force and a container-rotating type that rotates and mixes the containers, but the sulfonic acid-based interface Either method may be used as long as the dispersion of the activator is good. As the container fixing 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 for melt-kneading the synthetic resin mixture, any apparatus may be used as long as melt-kneading is possible, and known equipment such as a Banbury mixer, a kneader, a two-roll machine, and an extruder can be used. After melt mixing, it may be molded immediately, or after melt mixing, it may be once pelletized and then molded. Here, a two-roll machine, an extruder, etc. can serve as a kneading process and a molding process for molding.

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

Although it does not specifically limit as an application of the antiviral synthetic resin composition of this invention, For example, a sheet | seat, a flooring, a wallpaper, a film, cloth for clothes, a container, a pipe, a toy etc. are mentioned.
Other applications include diagnostic equipment, extracorporeal circulation equipment, protective equipment, clinical testing equipment, hospital equipment, medical consumables, home medical equipment, hygiene materials, health hygiene equipment, hospital buildings, food manufacturing plants, food packaging materials For example, it is used in a state where the function of inactivating the virus can be expressed.

  Although the antiviral synthetic resin composition of the present invention is expected to have an antiviral effect in various viruses, it exhibits a high antiviral property particularly against viruses having an envelope. Examples of viruses having an envelope include Ifluenza viruses such as avian influenza virus, human influenza virus and swine influenza virus, hepatitis B virus, hepatitis C virus, human immunodeficiency virus, varicella-zoster virus, herpes simplex virus, human Examples include herpes virus, mumps virus, RS virus, and Ebola virus.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Specific substance names of each compounding agent used in Examples and Comparative Examples are as follows.
Polyvinyl chloride resin A-1: Suspension vinyl chloride resin Average polymerization degree 1000
Polyvinyl 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 Company)
Sulfonic acid surfactant B-1: Alkylbenzenesulfonic acid Na purity 90%
(Product name: NANSA (registered trademark) HS90 / S, manufactured by Huntsman Japan)
Sulfonic acid type surfactant B-2: Alkylbenzenesulfonic acid Na aqueous solution Purity 25%
(Product name: Neoperex (registered trademark) G-25, manufactured by Kao Corporation)
Metal oxide powder and hydroxide C-1: calcined dolomite (trade name; Barriere P-2, manufactured by Mochigase)
Plasticizer D-1: Di-2-ethylhexyl phthalate

The sheet materials of Examples and Comparative Examples were produced by the following manufacturing method.
<Production Method I>
Stabilizers, reinforcing agents, antioxidants, and lubricants are 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 in a Henschel mixer. A synthetic resin mixture was obtained. And this synthetic resin mixture was knead | mixed with the small mixer set to 150 degreeC, and the antiviral synthetic resin composition was obtained. Next, a sheet-like material having a thickness of 150 μm was obtained using a two-roll machine set immediately at 175 ° C. to 190 ° C.
In addition, although the aqueous solution of sodium alkylbenzenesulfonate was added regarding Example 4, the sheet-like material was obtained with the manufacturing method similar to the above.

<Production 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.

<Production Method III>
Acrylic resin A-4 and sulfonic acid surfactant B-2 were uniformly mixed in distilled water and then dried to obtain a mixture of acrylic resin A-4 and sulfonic acid surfactant B-2. . Thereafter, the acrylic resin A-3, the acrylic resin A-4, and the above mixture were adjusted so as to have the composition of Example 9 shown in Table 1, and an antioxidant and a lubricant were added. By mixing, a synthetic resin mixture was obtained. And this synthetic resin mixture was knead | mixed at 150 degreeC with the small mixer, and the antiviral synthetic resin composition was obtained. Subsequently, a sheet-like material having a thickness of 150 μm was obtained immediately using a two-roll machine set at 190 ° C.
In the production methods I to III, the Henschel mixer is the mixing step, and the small mixer and the two rolls are the kneading step.

<Antiviral properties>
The avian influenza virus A / whisling swan / Shimane / 499/83 (H5N3) strain was used as a test virus. (Hereinafter referred to as H5N3 strain).
The test virus solution was prepared by diluting the H5N3 strain with sterile phosphate buffered saline (PBS; pH 7.2) to 1.0 × 10 ⁶ EID ₅₀ /0.1 mL.

  Place the sheet-like material 5 cm × 5 cm prepared in the examples and comparative examples shown in Table 1 on a petri dish, place 0.22 ml of the test virus solution on the surface of the sheet-like material, and place a 4 cm × 4 cm polyethylene film thereon. Covered, covered the petri dish, and allowed to stand for 1 hour in an incubator set at 20 ° C. 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 chorioallantoic cavity of 10-day-old chicken eggs using an injection needle. did.

After inoculation, the embryonated chicken eggs were cultured at 37 ° C. for 2 days, and then the presence or absence of virus growth in the chorioallantoic cavity was determined by the hemagglutination test, and the virus titer (log ₁₀ EID ₅₀ /0.1 ml) was determined by the method of Reed & 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) was calculated as a blank according to the above procedure, and the antiviral property of the sheet-like material was determined before the test. Evaluation was made by subtracting the virus titer of the virus solution one hour after contacting the sheet-like material from the virus titer of the virus solution. The larger this difference, the stronger the antiviral properties of the sheet.

○: The difference between the virus titer (before the test) and the virus titer (after 1 hour) is 3 or more High antiviral effect △: The difference between the virus titer (before the test) and the virus titer (after 1 hour) is 1 Less than 3 Has antiviral effect ×: Difference between virus titer (before test) and virus titer (after 1 hour) is less than 1 Antiviral effect is low

<Impact resistance>
Using the sheet-like materials prepared in the examples and comparative examples described in Table 1, measurement was performed with a film impact tester manufactured by Toyo Seiki Co., Ltd., and the following criteria were evaluated.

○: Not broken.
Δ: Whitening but no breakage.
X: Breaks.

When Examples 1-10 are compared with Comparative Examples 1 and 3, it can be seen that antiviral properties are imparted by containing a sulfonate surfactant within the scope of the present invention. Moreover, when Example 8 and 9 is seen, even if a manufacturing method differs, it turns out that antiviral property is provided.
When Example 3 and Comparative Example 2 are compared, the sulfonate surfactant has anti-viral properties and impact resistance, whereas the metal oxide powder and hydroxide have anti-viral properties but impact resistance. I understand that it is scarce.
Further, when Example 2 and Example 7 having the same composition and different production methods were compared, the sulfonic acid 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, water was evaporated by kneading with a small mixer and two rolls, and the processability and sheet appearance with two rolls were good.
In Example 9, acrylic resin A-4 and sulfonic acid surfactant B-2, which is a sulfonic acid surfactant solution, are mixed in distilled water and then dried. And the sheet appearance was good.

Claims (6)

  An antiviral synthetic resin composition comprising 0.5 parts by weight or more of a sulfonic acid surfactant per 100 parts by weight of a synthetic resin.   The antiviral synthetic resin composition according to claim 1, wherein the sulfonic acid surfactant is added before the synthetic resin kneading step. The antiviral synthetic resin composition according to claim 1 or 2, wherein the sulfonic acid surfactant is added to the synthetic resin in a powder form.   The antiviral synthetic resin composition according to claim 1 or 2, wherein the sulfonic acid surfactant is added to the synthetic resin as an aqueous liquid.   The antiviral synthetic resin composition according to any one of claims 1 to 3, wherein the synthetic resin is a polyvinyl chloride resin. A mixing step of mixing 100 parts by weight of a synthetic resin with 0.5 parts by weight or more of a sulfonic acid surfactant to obtain a synthetic resin mixture;
The manufacturing method which manufactures the antiviral synthetic resin composition of any one of Claims 1-4 provided with the kneading | mixing process which melt-kneads the said synthetic resin mixture.