JP6246512B2 - Antiviral wallpaper - Google Patents

Description

  The present invention relates to an antiviral wallpaper that inactivates various viruses.

According to the confirmed cases in avian influenza (H5N1) countries and people of the Ministry of Health, Labor and Welfare, highly pathogenic avian influenza has occurred in a wide area such as Asia, Europe, Middle East and Africa since November 2003. Infection of avian influenza has been confirmed not only among poultry, but also from poultry to primates. Especially about humans, more than 600 people have been infected, and more than 350 people have died. . Furthermore, the avian influenza virus poses a risk that it can be mutated and toxicated by crossing with human influenza virus or by itself.
Therefore, there is a craving for technologies and products that can quickly inactivate viruses. In particular, in the interior materials for buildings used in medical facilities that are expected to come into contact with viruses, it is particularly desirable to inactivate viruses. Is big.

For wallpaper, vinyl chloride resins such as vinyl chloride resin and olefin resins are often used. In particular, a vinyl chloride resin has been adopted exclusively because it is inexpensive and excellent in various physical properties, and can be further imparted with design by embossing to form fine irregularities on the surface.

  On the other hand, in Patent Document 1 below, a method using a vinyl-maleic acid copolymer polymer carrying metal ions has been proposed as a method for imparting antiviral properties to fibers. However, it does not show a technique for applying the present invention to wallpaper made of polyvinyl chloride resin.

Japanese Patent No. 4584339

The inventor of the present invention has found that a polyvinyl chloride wallpaper containing a sulfonic acid surfactant can rapidly reduce the virus titer of the virus in contact with the virus and inactivate the virus. However, the present inventors have found an unknown problem that when a sulfonic acid-based surfactant is added at the time of wallpaper production, the dispersibility with the polyvinyl chloride resin is poor, causing appearance defects such as wrinkles on the wallpaper surface.

  That is, an object of the present invention is to provide an antiviral wallpaper having an excellent appearance that rapidly inactivates a virus by rapidly reducing the virus titer of the contacted virus.

As a result of diligent verification of the method for adding the sulfonic acid-based surfactant to the above-mentioned problems, the wallpaper is made using the vinyl chloride resin for paste processing to which the sulfonic acid-based surfactant has been added in advance. It has been found that an antiviral wallpaper can be suitably obtained without any problem.

  The antiviral wallpaper of the present invention is excellent in appearance by reducing the virus titer in a short time after contact with the virus to inactivate the virus.

It is important that the antiviral wallpaper of the present invention comprises a resin layer and a base material layer containing a vinyl chloride resin for paste processing containing 1.2 parts by weight or more of a sulfonic acid surfactant in advance as a resin component. In the wallpaper manufacturing process, there is a process of making sols by mixing vinyl chloride for paste processing with plasticizers, fillers, stabilizers, foaming agents, etc., but sulfonic acid surfactants are insoluble in plasticizers. For this reason, when mixed in this process, the dispersibility in the sol is poor, causing appearance defects such as streaks in the product and deteriorating the appearance.
On the other hand, the sulfonic acid surfactant is water-soluble. Moreover, when producing a vinyl chloride resin for paste processing by emulsion polymerization or seed emulsion polymerization, a latex using water as a solvent is obtained as an intermediate form after polymerization. Therefore, by adding a sulfonic acid surfactant to this latex, the sulfonic acid surfactant is well dispersed in the vinyl chloride resin. Thus, by adding the sulfonic acid surfactant to the latex after polymerization, a paste polyvinyl chloride resin having desired properties can be obtained without affecting the polymerization conditions. By using the vinyl chloride resin for paste processing previously containing a sulfonic acid surfactant obtained by such a technique, a wallpaper can be obtained without impairing the beauty.

  Although it does not restrict | limit especially as a vinyl chloride resin used as the raw material of the vinyl chloride resin for paste processing used for this invention, For example, a polymerization degree 600-3000 can be used suitably.

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, 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 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, as the sulfonic acid surfactant, a sulfonate surfactant is preferable. Specifically, alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as calcium and barium are preferable. Can be used. In particular, sodium dodecylbenzenesulfonate (DBS) is preferred.
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.

  The resin component used in the present invention needs to contain 1.2% by weight or more of a sulfonic acid surfactant, preferably 1.5% by weight or more and 49.9% by weight or less, more preferably 2% by weight. % To 20% by weight. If it is less than 1.2% by weight, the antiviral property is not stably expressed. Here, a more stable antiviral property is expressed by containing 1.5% by weight or more of the sulfonic acid surfactant, and a higher antiviral property is obtained by setting the content to 2% by weight or more. Moreover, it is excellent in the point that workability is more stabilized by setting it as 20 weight% or less.

  As the vinyl chloride resin for paste processing used in the present invention, the vinyl chloride resin for paste processing containing 1.2% by weight or more of the sulfonic acid surfactant in advance may be used alone, or mixed with other vinyl chloride resins. And may be used as a resin component. However, in any case, it is necessary to contain 1.2% by weight or more of the sulfonic acid surfactant with respect to the total amount of the resin component, that is, the vinyl chloride resin, preferably 1.5% by weight or more. It is 9% by weight or less, more preferably 2% by weight or more and 20% by weight or less. If it is less than 1.2% by weight, the antiviral property is not stably expressed.

If necessary, a foaming agent may be used for the antiviral wallpaper of the present invention. In this case, the addition amount is 0.01 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the resin component. It is desirable to limit the amount to not less than 4 parts by weight and more preferably not less than 0.5 parts by weight and not more than 3 parts by weight.
By setting the addition amount of the foaming agent to 0.1 parts by weight or more with respect to 100 parts by weight of the resin component, a wallpaper having a higher foaming ratio can be obtained, and by setting it to 0.5 parts by weight or more, the foaming ratio is further increased. It becomes possible.
On the other hand, in the antiviral wallpaper of the present invention, the sulfonic acid surfactant is present at the interface between the vinyl chloride resin segments, and it is confirmed that the occupied area increases as the content increases. This reduces the adhesion between the vinyl chloride resin segments and causes a decrease in the elastic modulus. When the elastic modulus is lowered, it becomes difficult to hold the foamed cells caused by the decomposition of the foaming agent, and the shrinkage may be caused.
If the addition amount of the foaming agent is 5 parts by weight or less with respect to 100 parts by weight of the resin component, the effect of shrinkage of the foamed cell is almost or slight and the appearance of the wallpaper is not impaired. However, when the amount exceeds 5 parts by weight, the shrinkage of the foamed cells increases, which may cause appearance defects such as discoloration.

One of the preferred embodiments of the present invention is to make the antiviral wallpaper of the present invention substantially free from a foaming agent for the purpose of requiring smoothness and strength.

As the blowing agent used in the present invention, known ones can be used, and examples thereof include azodicarbonamide (ADCA), azobisformamide, oxybenzenesulfonyl hydrazide, paratoluenesulfonyl hydrazide and the like.

  The antiviral wallpaper of the present invention may be provided with a top coat layer on the surface as long as the antiviral property is not inhibited. The topcoat layer can be provided, for example, by applying a resin composition for topcoat as a paint, and acrylic resin, urethane resin, fluorine resin, or the like can be used as the topcoat resin. . Furthermore, if the dynamic friction coefficient of the wallpaper surface can be reduced by the top coat treatment, it becomes possible to have a grade 4 or higher in a test based on the surface-enhanced wallpaper performance regulations. In this case, the coefficient of dynamic friction is preferably set to 0.5 or less, for example, in a test based on ASTM D 1894.

  Here, when the topcoat layer is provided by coating the coating agent, the coating agent is applied in a state having a fine gap in the resin layer. Therefore, since the sulfonic acid surfactant contained in the resin layer can be partially exposed on the surface, it is possible to attack the virus when the virus contacts the wallpaper surface. Thus, even if a top coat layer is provided, antiviral properties are exhibited.

The antiviral wallpaper of the present invention is effective for, for example, an enveloped virus.
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, and RS virus.

  As a method for producing the antiviral wallpaper of the present invention, a step of obtaining a vinyl chloride resin paste sol using a vinyl chloride resin for paste processing containing 1.2% by weight or more of a sulfonic acid surfactant in advance, A step of applying a vinyl chloride resin paste sol to a substrate is characterized. As a specific example, a vinyl chloride resin for paste processing containing 1.2 parts by weight or more of a sulfonic acid surfactant in advance and a plasticizer, a stabilizer, a foaming agent, a filler and the like are stirred to prepare a paste sol, Examples of the production method include drying and solidification after coating on the backing paper. Known methods can be used for stirring and coating methods. In addition to the paste sol composition, various additives such as a coloring agent, a processing aid, an antibacterial agent, an antifungal agent, a flame retardant, a flame retardant, and a defoaming agent may be used as long as the antiviral property is not inhibited. You may add suitably.

The plasticizer is not particularly limited. For example, di-2-ethylhexyl phthalate (DOP), diisononyl phthalate, dibutyl phthalate, dihexyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, trioctyl phthalate, dioctyl adipate, chlorinated fatty acid ester, chlorination Paraffin, epoxidized soybean oil, epoxidized fatty acid ester and the like may be mentioned, and two or more kinds may be used in combination.

The stabilizer is not particularly limited, and examples thereof include a barium (Ba) stabilizer, a calcium stabilizer, a tin stabilizer, a zinc (Zn) stabilizer, a potassium stabilizer, and the like. You may use together.

  Although it does not specifically limit as said filler, For example, calcium carbonate, magnesium carbonate, titanium oxide, magnesium silicate, diatomaceous earth, etc. are mentioned, You may use 2 or more types together.

The backing paper that is the base material layer used in the antiviral wallpaper of the present invention is not particularly limited, and examples thereof include ordinary pulp paper, flame retardant pulp paper, calcium carbonate paper, aluminum hydroxide paper, and fleece paper.

The antiviral wallpaper of the present invention can be provided with a printing layer on the substrate layer as long as the antiviral property is not inhibited. A known method can be used as a method for providing the print layer, and examples include gravure printing, flexographic printing, offset printing, silk screen printing, and the like. Various surface treatment agents may be used in combination for the purpose of improving the coatability of the printed layer and reducing gloss. In addition, when providing the said topcoat layer in addition to a printing layer, it is preferable to provide a topcoat layer on a printing layer.

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

The materials used in the examples and comparative examples are as follows.
Vinyl chloride resin α for paste processing (containing 5.0% by weight of DBS)
Vinyl chloride resin β for paste processing (containing 2.5% by weight of DBS)
Vinyl chloride resin γ for paste processing (1.0% DBS content)
Vinyl chloride resin δ for paste processing (containing 10% by weight of DBS)
DOP (plasticizer)
Ba-Zn stabilizer ADCA (foaming agent)
Calcium carbonate (filler)
DBS (base): powder

  In Example 1, a vinyl chloride resin α for paste processing containing 5.0% by weight of sodium dodecylbenzenesulfonate (DBS) as a sulfonic acid surfactant in a predetermined amount as shown in Table 1, and DBS in advance. Paste containing 1.0% by weight of vinyl chloride resin γ for paste processing, plasticizer (DOP), stabilizer, foaming agent (ADCA), filler (calcium carbonate), diluent, pigment A sol was prepared. Then, this paste sol was applied to a backing paper as a base material layer with a paste coater to provide a resin layer on the base material layer to obtain a wallpaper base. Thereafter, this wallpaper base was foamed at 210 ° C. and mechanically embossed to obtain a test specimen.

The details of Examples 2 to 9 and Comparative Examples 1 and 2 are as shown in Tables 1 and 2, and the production method conformed to Example 1. In Examples 5 and 6, after gelation, a top coat layer was provided with a gravure printing machine and dried at 120 ° C., followed by mechanical embossing.

[Evaluation of wallpaper appearance]
The appearance of the obtained wallpaper was visually evaluated.
○: There is no surface defect and the aesthetic appearance is maintained. Δ: The surface is rough, but it is an acceptable level. ×: There are remarkable surface defects such as streaks.

[Evaluation of antiviral properties]
Antivirus was evaluated as follows.
Avian influenza [A / whisling swan / Shimane / 499/83 (H5N3)] was used as a test virus.
The virus grown in the chorioallantoic cavity of the developing chicken egg was diluted to 1.0 × 10 ⁶ EID ₅₀ /0.1 mL with sterile phosphate buffered saline (PBS) to prepare a virus solution did. 0.22 mL of the virus solution was placed on the test body (5 cm × 5 cm), and it was covered with a polyethylene film (4 cm × 4 cm). The test specimen was placed in a petri dish and allowed to stand for 1 hour in an incubator set at 20 ° C. to bring the specimen into contact with the virus. The virus solution (sample) on the test specimen was collected, diluted 10-fold in steps with PBS, and 0.1 mL was inoculated into the chorioallantoic cavity of 10-day-old chicken eggs. After inoculating and growing chicken eggs at 37 ° C. for 2 days, the presence or absence of virus growth in the chorioallantoic cavity was confirmed by the hemagglutination test, and the virus titer in the sample was calculated by the method of Reed and Muench.
The difference between the “virus titer (after 1 hour)” and the “virus titer (before the test)” represents the strength of the antiviral property, and the larger the difference, the stronger the antiviral property.

[Evaluation of surface strengthenability]
The evaluation was based on a test compliant with the surface-enhanced wallpaper performance regulations established by the Japan Wallcovering Association. Grade 4 or higher is judged to have surface strengthening.
Grade 5: No particular change at first glance Grade 4: Slight surface scratches are observed, but no relatively large surface layer breakage, etc. Grade 3: Surface layer tear is clearly visible Grade 2: Surface Tears and the backing material such as paper is clearly visible (length less than 1cm)
First grade: The surface is torn and the backing material such as paper is clearly visible (length 1cm or more)

[Evaluation results]
In Examples 1 to 6, while maintaining the aesthetic appearance, the virus titer was at least 4.0 or more (about 10 ^−4.0 = 1 / 10,000) at “before virus contact” and “after virus contact 1 hour”. ) Reduced and highly antiviral.
Furthermore, according to Examples 5 and 6, it is also shown that the surface reinforcing property becomes 4th or higher by providing the topcoat layer.

On the other hand, in Comparative Example 1, since the content of the sulfonic acid surfactant relative to the vinyl chloride resin is as small as 1.0% by weight, the virus titer is 2 before “virus contact” and “after virus contact 1 hour”. .5 (10 ^−2.5 = about ^1/100 ), which is a test result indicating that the antiviral property is low as compared with the Examples.
Furthermore, in Comparative Example 2 in which a powdery raw material of DBS was added as a sulfonic acid surfactant at the time of preparing the paste, although the antiviral property was improved, the wallpaper appearance was poor.

[Industrial applicability]
ADVANTAGE OF THE INVENTION According to this invention, the antiviral wallpaper excellent in the external appearance which reduces the virus titer of the virus which contacted rapidly and inactivates a virus can be provided.

Claims (7)

An antiviral wallpaper comprising a resin layer containing, as a resin component, a vinyl chloride resin for paste processing containing 2.5 % by weight or more of a sulfonic acid surfactant in advance, as a resin component.   The resin component contains the vinyl chloride resin for paste processing and another vinyl chloride resin, and further contains 1.2% by weight or more of a sulfonic acid surfactant with respect to the resin component. Antiviral wallpaper described in 1.   The antiviral wallpaper according to claim 1 or 2, wherein the resin layer contains 0.01 to 5 parts by weight of a foaming agent with respect to 100 parts by weight of the resin component. The antiviral wallpaper according to claim 1 or 2, wherein the resin layer contains substantially no foaming agent.   The antiviral wallpaper according to any one of claims 1 to 4, wherein the sulfonic acid surfactant is an alkylbenzene sulfonic acid compound.   6. The resin layer according to any one of claims 1 to 5, wherein the resin layer has a top coat layer on a surface opposite to the base material layer, and has a grade 4 or higher in a test based on a surface-enhanced wallpaper performance specification. Antiviral wallpaper. A method for producing an antiviral wallpaper in which a resin layer containing a vinyl chloride resin for paste processing as a resin component and a base material layer are laminated,
A step of obtaining a vinyl chloride resin paste sol using the vinyl chloride resin for paste processing containing 2.5 % by weight or more of a sulfonic acid surfactant in advance;
And a step of applying the vinyl chloride resin paste sol to the base material layer.