JP2022046223A - Resin composition for antiviral floor material and antiviral floor material - Google Patents

Abstract

To provide a resin composition for an antiviral floor material that retains antiviral effect and does not cause discoloration of resin, and provide an antiviral floor material.SOLUTION: A resin composition for an antiviral floor material contains a polyvinyl chloride resin and a plasticizer. The plasticizer contains at least one selected from the group consisting of an unsaturated fatty acid and an unsaturated fatty acid ester, and at least one selected from the group consisting of a palmitate, a stearate, an oleate with an epoxidized unsaturated group, a linoleate with an epoxidized unsaturated group, and a linolenate with an epoxidized unsaturated group.SELECTED DRAWING: None

Description

Application for application of Article 30, Paragraph 2 of the Patent Law Japan Architectural Finishing Society 2019 Annual Meeting Academic Lecture / Research Presentation Proceedings Publisher: Japan Architectural Finishing Society 2019 Annual Meeting Academic Lecture Meeting Executive Committee Distribution date: 1st year of Reiwa September 18 [Publications, etc.] Japan Society for Architectural Finishing 2019 Academic Lecture (30th Research Presentation) Date: October 23, 1st year of Reiwa

The present invention relates to a resin composition, in particular, a resin composition characterized by exhibiting antiviral properties that inactivate various viruses, and particularly relates to a vinyl chloride resin composition suitable for flooring materials. The present invention also relates to an antiviral flooring material comprising the resin composition thereof.

The new coronavirus that broke out in China in 2019 has spread worldwide, affecting more than 18 million people and killing about 700,000. Furthermore, the spread of infection is still ongoing, and this number is expected to increase further. At present, there is no effective therapeutic drug or vaccine, so there is a growing interest in technologies and products that contribute to the prevention of infectious diseases.

The virus uses the cells of other organisms to replicate itself and multiply. The basic structure consists of a protein shell (capsid) and internal nucleic acids (DNA, RNA), and has no cells or cell membranes. Nucleic acids are roughly classified into two types depending on whether they are DNA or RNA, and further classified into those in which capsids are covered with an envelope consisting of a lipid bilayer membrane and those in which capsids are not.

Specifically, for example, there is a herpesvirus as a nucleic acid having an envelope with DNA, and an adenovirus as a nucleic acid having no envelope. Influenza virus is the nucleic acid that has an envelope with RNA, and norovirus is the one that does not. The new coronavirus is classified as the same enveloped virus as influenza virus because the nucleic acid has an envelope with RNA.

As an antiviral agent that inactivates the activity of such a virus, sulfonic acid-based surfactants, metal oxides, copper compounds and the like have been conventionally known as those used by adding to vinyl chloride resin.

Patent Document 1 discloses an antiviral chloride resin composition to which a sulfonic acid-based surfactant is added.

Patent Document 2 discloses a plastic in which a double salt of any oxide of silver, copper, or zinc and a molybdenum oxide is added to a vinyl chloride resin.

Patent Document 3 describes a vinyl chloride member containing a monovalent copper compound such as chloride, acetic acid compound, sulfide, and iodide, and a plasticizer such as a phthalate ester-based plasticizer and a trimellitic acid-based plasticizer. It has been disclosed.

JP-A-2015-17078 Japanese Unexamined Patent Publication No. 2018-172462 Japanese Unexamined Patent Publication No. 2019-44096

However, in the method of adding the surfactant to the vinyl chloride resin, the surfactant gradually exudes and the amount of the chemical is reduced, which causes a problem in the sustainability of the effect, and in the method of adding the metal oxide, there is a problem. Since the resin is discolored, there is a drawback that the resin composition is not suitable for the interior material.

An object of the present invention is to provide a resin composition having an antiviral property that maintains an antiviral effect and does not cause discoloration of the resin, and particularly to provide a vinyl chloride resin composition suitable for a floor material. be.

In order to solve the above problems, the first invention is a resin composition for an antiviral floor material containing a vinyl chloride resin and a plasticizer, wherein the plasticizer is a group consisting of an unsaturated fatty acid and an unsaturated fatty acid ester. A group consisting of at least one selected from, a palmitate ester, a stearic acid ester, an oleic acid ester in which an unsaturated group is epoxidized, a linoleic acid ester in which an unsaturated group is epoxidized, and a linolenic acid ester in which an unsaturated group is epoxidized. It is characterized by containing at least one selected from.
The second invention is an antiviral flooring material comprising the resin composition of the first invention.

The present invention includes the following embodiments.
[1] A resin composition for an antiviral floor material containing a vinyl chloride resin and a plasticizer, wherein the plasticizer is at least one selected from the group consisting of unsaturated fatty acids and unsaturated fatty acid esters, and palmitic acid esters. It is characterized by containing at least one selected from the group consisting of a stearate ester, an oleic acid ester in which an unsaturated group is epoxidized, a linoleic acid ester in which an unsaturated group is epoxidized, and a linolenic acid ester in which an unsaturated group is epoxidized. A resin composition for an antiviral floor material.
[2] The resin composition for an antiviral floor material according to [1], wherein the unsaturated fatty acid is an ω-6 fatty acid and the unsaturated fatty acid ester is an ω-6 fatty acid ester.
[3] The antiviral agent according to [1] or [2], which contains 0.1 to 1.0 part by mass of an inorganic antiviral agent containing a metal and having an average particle size of 2 to 30 nanometers with respect to 100 parts by mass of the resin composition. Resin composition for viral flooring.
[4] The resin composition for an antiviral floor material according to [3], wherein the inorganic antiviral agent contains at least one metal selected from the group consisting of copper, silver and zinc and titanium oxide. thing.
[5] The resin composition for an antiviral floor material according to any one of [1] to [4], which contains 0.5 to 5.0 parts by mass of epoxidized linseed oil with respect to 100 parts by mass of the resin composition.
[6] An antiviral flooring material comprising the resin composition according to any one of [1] to [5].

According to the resin composition of the present invention, a vinyl chloride resin molded body exhibiting antiviral properties can be obtained, and particularly when used as a floor material, the virus on the floor surface of the indoor space can be inactivated.

Hereinafter, the present invention will be described in detail.
The first invention is an antiviral flooring resin composition containing a vinyl chloride resin and a plasticizer, wherein the plasticizer is at least one selected from the group consisting of unsaturated fatty acids and unsaturated fatty acid esters, and palmitin. Includes at least one selected from the group consisting of acid esters, stearic acid esters, oleic acid esters with unsaturated groups epoxidized, linoleic acid esters with unsaturated groups epoxidized and linolenic acid esters with unsaturated groups epoxidized. It is characterized by that.

[Vinyl chloride resin]
The vinyl chloride resin used in the present invention is not particularly limited, and a copolymer of vinyl chloride homopolymer and a copolymer with another copolymerizable monomer can be used. The vinyl chloride resin may be used alone or in combination of two or more. Further, there are no restrictions on the manufacturing method and the degree of polymerization of the vinyl chloride resin.

[Plasticizer]
The plasticizer is at least one selected from the group consisting of unsaturated fatty acids and unsaturated fatty acid esters, as well as palmitic acid esters, stearic acid esters, oleic acid esters with unsaturated groups epoxidized, and linoleic acids with unsaturated groups epoxidized. Includes at least one selected from the group consisting of esters and linolenic acid esters with unsaturated groups epoxidized.

[Unsaturated fatty acids]
The unsaturated fatty acids used in the present invention include ω-3 fatty acids linolenic acid, stearidonic acid, eikosatetraenoic acid, eikosapentaenoic acid, and docosapentaenoic acid ((7Z, 10Z, 13Z, 16Z, 19Z) -7. , 10, 13, 16, 19-docosapentaenoic acid), docosapentaenoic acid, linoleic acid which is an ω-6 fatty acid, γ-linolenic acid, arachidonic acid, docosapentaenoic acid, docosapentaenoic acid ((4Z, 7Z,) 10Z, 13Z, 16Z) -4,7,10,13,16-docosapentaenoic acid), palmitoleic acid, which is an ω-7 fatty acid, baxenoic acid, paulic acid, oleic acid, which is an ω-9 fatty acid, and ellaic acid, Elcaic acid, nervonic acid, and sapienoic acid, which is an ω-10 fatty acid, are preferable. Among them, the preferable unsaturated fatty acid is ω-6 fatty acid from the viewpoint of the possibility of producing C6 aldehyde by autoxidation.

[Unsaturated fatty acid ester]
The unsaturated fatty acid ester used in the present invention includes methyl ester of ω-3 fatty acid, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, methyl ester of ω-6 fatty acid, ethyl ester, propyl ester and butyl ester. , Pentyl ester, hexyl ester, ω-7 fatty acid methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, ω-9 fatty acid methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, Hexyl esters, methyl esters of ω-10 fatty acids, ethyl esters, propyl esters, butyl esters, pentyl esters and hexyl esters are preferred. Among them, the preferred unsaturated fatty acid ester is an ω-6 fatty acid ester from the viewpoint of the possibility of producing C6 aldehyde by autoxidation.

[Other plasticizers]
The plasticizer used in the present invention comprises a palmitate ester, a stearic acid ester, an oleic acid ester in which an unsaturated group is epoxidized, a linoleic acid ester in which an unsaturated group is epoxidized, and a linolenic acid ester in which an unsaturated group is epoxidized. Includes at least one selected from the group.
Preferred examples of the palmitic acid ester include methyl palmitate and ethyl palmitate.
Preferred examples of stearic acid ester include methyl stearate and ethyl stearate.
Preferred examples of the oleic acid ester in which an unsaturated group is epoxidized (hereinafter, also referred to as "epoxidized oleic acid ester") are cis-9,10-methyl epoxy octadecanoate and ethyl cis-9,10-epoxy octadecanoate. And so on.
Preferred examples of linoleic acid esters in which unsaturated groups are epoxidized (hereinafter, also referred to as “epoxidized linoleic acid esters”) are 9,10: 12,13-methyl diepoxyoctadecanoate, 9,10: 12,13. -Epoxy octadecanoate ethyl, etc. may be mentioned.
Preferred examples of linolenic acid ester in which unsaturated groups are epoxidized (hereinafter, also referred to as “epoxidized linolenic acid ester”) are 9,10: 12,13,15,16-methyl triepoxyoctadecanoate, 9,10. Examples include: 12,13:15,16-ethyl triepoxy octadecanoate.
These plasticizers may be used alone or in a blend of two or more.
When used as a blend, at least one selected from the group consisting of palmitate and stearic acid esters and oleic acid esters with unsaturated groups epoxidized, linolenic acid esters with unsaturated groups epoxidized and unsaturated groups It is preferably used in combination with at least one selected from the group consisting of linolenic acid esters having an epoxidized group. Further, in order to increase the plasticity, commonly used phthalates, terephthalic acid, trimellitic acid, polyester-based plasticizers and the like may be appropriately added to the extent that the antiviral property is not impaired.

The total amount of the plasticizer added is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and 30 to 60 parts by mass is preferable for flooring materials.
The amount of at least one selected from the group consisting of unsaturated fatty acids and unsaturated fatty acid esters is preferably 15 to 95 parts by mass, and more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. It is more preferably 30 to 60 parts by mass. If this amount is too small, sufficient plasticity cannot be exhibited. If this amount is too large, bleed-out will occur and the surface will become sticky.
At least one selected from the group consisting of palmitic acid ester, stearic acid ester, oleic acid ester with epoxidized unsaturated group, linoleic acid ester with epoxidized unsaturated group and linolenic acid ester with epoxidized unsaturated group. The addition amount is preferably 0.1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and further preferably 1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If this amount is too small, antiviral properties will not be exhibited. If this amount is too large, it will seep out to the resin surface (bleed out), and the surface of the molded product will become sticky, which is not preferable.

[Inorganic antiviral agent]
As the inorganic antiviral agent used in the present invention, an inorganic antiviral agent containing a metal and having an average particle size of 2 to 30 nanometers is preferably used. As the metal, silver, zinc, copper and the like are preferably used. The inorganic antiviral agent is preferably one in which at least one of those metal ions is supported on any of zeolite, silica gel, and montmorillonite. Inorganic antiviral agents containing titanium oxide are also preferably used. The inorganic antiviral agent more preferably comprises at least one metal selected from the group consisting of copper, silver and zinc and titanium oxide. Specific examples thereof include those in which silver is supported on titanium oxide and those in which zinc is supported on titanium oxide.
The content of the metal ion in the inorganic antiviral agent is not limited as long as it exhibits an antiviral effect, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 20 to 20 to 70% by mass. It is 50% by mass. If the content is too low, sufficient antiviral properties will not be exhibited. If the content is too high, the discoloration property of the resin is lowered.
The average particle size of the inorganic antiviral agent is preferably 2 to 30 nanometers, more preferably 2 to 25 nanometers, and even more preferably 3 to 20 nanometers. If the average particle size is too small, the antiviral property will decrease. If the average particle size is too large, the dispersibility in the plasticizer will decrease.
The average particle size is measured by a dynamic light scattering method.
The amount of the inorganic antiviral agent added is preferably 0.1 to 1.0 part by mass, more preferably 0.3 to 0.9 part by mass, still more preferably, with respect to 100 parts by mass of the vinyl chloride resin. Is 0.2 to 0.8 parts by mass. If this amount is too small, the antiviral property will decrease. If this amount is too large, the dispersibility in the plasticizer will decrease.

[Epoxidized flaxseed oil]
The resin composition for flooring of the present invention preferably contains epoxidized flaxseed oil. By adding epoxidized flaxseed oil, antiviral property and discoloration property are improved. The amount of the epoxidized flaxseed oil added is preferably 0 to 20 parts by mass, more preferably 1 to 10 parts by mass, still more preferably 2 to 7 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

[Filler]
The resin composition of the present invention preferably contains a filler. The inclusion of filler improves dimensional stability and wear resistance. As the filler, an inorganic filler such as calcium carbonate, aluminum hydroxide, zeolite, talc, or silica can be used. Of these, calcium carbonate is preferable. The content of the filler is preferably 10 to 1000 parts by mass, more preferably 30 to 800 parts by mass, still more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

[Stabilizer]
The resin composition of the present invention preferably contains a stabilizer. By including the stabilizer, the discoloration stability during the molding process and the deterioration resistance over time when the molded product is used are improved. As the stabilizer, for example, a stabilizer made by blending a metal such as barium, zinc, calcium and a metal bleach-based stabilizer derived from a fatty acid such as lauric acid and stearic acid, a lubricant, an antioxidant, an auxiliary agent and the like is used. Can be used. The amount of the stabilizer added is not particularly limited, but is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

[Other additives]
In addition, drying oils, pigments, antistatic agents, antibacterial agents, foaming agents and the like can be arbitrarily blended as long as the effects of the present invention are not impaired.

[Manufacturing method of resin composition]
As a method for obtaining the resin composition of the present invention, a known method can be used. For example, it can be obtained by mixing a vinyl chloride resin and a plasticizer, and if necessary, other additives with a Henshell mixer, a Banbury mixer, a ribbon blender, or the like.

[Floor material]
The second invention of the present invention is an antiviral flooring material made of the resin composition. Examples of the floor material include floor tiles, floor sheets, carpet tiles and the like. The floor material can be produced by molding the resin composition by a known molding method, for example, injection molding, extrusion molding, calendar molding or the like. Of these, calendar molding is preferable.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to such Examples. The evaluation was performed as follows.
(1) Antiviral property The antiviral property test was evaluated in accordance with ISO 21702. Specifically, a 2 mm-thick sheet of a molded product of a vinyl chloride resin composition was cut into 50 mm squares, and a test virus solution concentration of 2.6 × ¹⁰⁷ PFU / mL was dropped on the surface and covered with a polyethylene film. After 24 hours, the virus solution was washed out with a washout solution and the change in virus concentration was measured for evaluation. Influenza virus (Influenza A virus (H3N2): ATCC VR-1679) and feline calicivirus (ATCC VR-1679) were used as test viruses. When the Antiviral activity is 2.0 or more, it is determined to have antiviral properties.

(2) Discoloration property A sheet having a thickness of 2 mm was cut into 100 mm squares and heated in an oven at 200 ° C. for 1 hour, and the color change on the surface was visually evaluated.
◎: No discoloration.
◯: Discoloration occurs in a very small part.
Δ: Discoloration occurs as a whole.
X: Significant discoloration occurs.

Plasticizer (P-1)
A plasticizer (trade name: E-33) manufactured by JIAAO, which is a mixture of methyl palmitate, methyl stearate, epoxidized methyl oleate, epoxidized methyl linoleate and epoxidized methyl linolenate, is used as a plasticizer (P-1). Used as.

Plasticizer (P-2)
Linoleic acid and docosapentaenoic acid ((4Z, 7Z, 10Z, 13Z, 16Z) -4,7,10,13,16 as ω-6 unsaturated fatty acids in 100 parts by mass of the plasticizer (P-1). -Docosapentaenoic acid) was added in an amount of 5 parts by mass and stirred to obtain a plasticizer (P-2).

Plasticizer (P-3)
Methyl linoleate and methyl docosapentaenoic acid ((4Z, 7Z, 10Z, 13Z, 16Z) -4,7,10, as ω-6 unsaturated fatty acid esters in 100 parts by mass of the plasticizer (P-1). Methyl 13,16-docosapentaenoate) was added in an amount of 5 parts by mass and stirred to obtain a plasticizing agent (P-3).

Plasticizer (P-4)
A plasticizer (P-4) was obtained by adding 10 parts by mass of bis (2-ethylhexyl) phthalate (DOP manufactured by J-PLUS Co., Ltd.) to 100 parts by mass of the plasticizer (P-3) and stirring the mixture.

Plasticizer (P-5)
A plasticizer (P-5) is obtained by adding 50 parts by mass of each of methyl linoleate having an unsaturated group epoxidized and ethyl linoleate having an unsaturated group epoxidized to 100 parts by mass of methyl linoleate and stirring. rice field.

Inorganic antiviral agent JGC Catalysts and Chemicals Co., Ltd.'s inorganic antiviral agent (trade name: ATOMY BALL- (S), composition: Ag / TiO ₂ , average particle size: 5 nm) is used in a small amount as a surfactant (sodium dialkyl sulfosuccinate). It was added to the plasticizer together with the mixture and used with stirring.

[Comparative Example 1]
100 parts by mass of vinyl chloride resin (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: TK-1000), 50 parts by mass of plasticizer (P-1), 100 parts by mass of surface-treated calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: CCR) and barium zinc stabilizer (manufactured by ADEKA Co., Ltd., Adecaster (registered trademark) AP-627) were mixed by 2 parts by mass with a Banbury mixer to prepare a resin composition for a floor material. The prepared resin composition for flooring was processed into a sheet having a thickness of 2 mm with a calendar processing machine, and the obtained sheet was evaluated for antiviral property and discoloration property. The results are shown in Table 1.

[Example 1]
A resin composition for a flooring material was prepared and evaluated in the same manner as in Comparative Example 1 except that the plasticizer (P-2) was used instead of the plasticizer (P-1). The results are shown in Table 1.

[Example 2]
A resin composition for a flooring material was prepared and evaluated in the same manner as in Comparative Example 1 except that the plasticizer (P-3) was used instead of the plasticizer (P-1). The results are shown in Table 1.

[Example 3]
Instead of 50 parts by mass of the plasticizer (P-1), 25 parts by mass of the plasticizer (P-1) and 25 parts by mass of the plasticizer (P-4) are used, and further, an inorganic antiviral agent (ATOMY BALL- (S). )) Except for the point that 0.5 parts by mass was added, the same procedure as in Comparative Example 1 was carried out to prepare and evaluate a resin composition for a floor material. The results are shown in Table 1.

[Example 4]
Further, the procedure was carried out in the same manner as in Example 2 except that 0.5 part by mass of an inorganic antiviral agent (ATOMY BALL- (S)) and 5 parts by mass of epoxidized flaxseed oil were added to prepare a resin composition for a floor material. And evaluated. The results are shown in Table 1.

[Example 5]
A resin composition for a flooring material was prepared and evaluated in the same manner as in Comparative Example 1 except that the plasticizer (P-5) was used instead of the plasticizer (P-1). The results are shown in Table 2.

[Comparative Example 2]
The same procedure as in Comparative Example 1 was carried out except that di-2-ethylhexyl terephthalate (DOTP manufactured by J-PLUS Co., Ltd.) was used instead of the plasticizer (P-1) to prepare a resin composition for a flooring material. ,evaluated. The results are shown in Table 2.

[Comparative Example 3]
Similar to Comparative Example 1 except that diisononylcyclohexane-1,2-dicarboxylate (manufactured by BASF, HEXAMOLL (registered trademark) DINCH (registered trademark)) was used instead of the plasticizer (P-1). This was carried out to prepare and evaluate a resin composition for flooring materials. The results are shown in Table 2.

[Comparative Example 4]
The same procedure as in Comparative Example 1 was carried out to prepare a resin composition for a flooring material, except that bis (2-ethylhexyl) phthalate (DOP manufactured by J-PLUS Co., Ltd.) was used instead of the plasticizer (P-1). And evaluated. The results are shown in Table 2.

In systems supplemented with an inorganic antiviral agent, a wide range of nucleic acids, whether DNA or RNA, and whether the capsid is enveloped by a lipid bilayer envelope. Antiviral property was expressed against the virus.

By adding epoxidized flaxseed oil, antiviral property and discoloration property were improved, and good results were obtained as a flooring material.

The resin composition for an antiviral flooring material of the present invention can be suitably used as a material for a flooring material of a building.

Claims (6)

A resin composition for an antiviral floor material containing a vinyl chloride resin and a plasticizer, wherein the plasticizer is at least one selected from the group consisting of unsaturated fatty acids and unsaturated fatty acid esters, as well as palmitic acid esters and stearic acid esters. , An anti-resistant comprising at least one selected from the group consisting of an oleic acid ester in which an unsaturated group is epoxidized, a linoleic acid ester in which an unsaturated group is epoxidized, and a linolenic acid ester in which an unsaturated group is epoxidized. Resin composition for viral flooring. The resin composition for an antiviral floor material according to claim 1, wherein the unsaturated fatty acid is an ω-6 fatty acid and the unsaturated fatty acid ester is an ω-6 fatty acid ester. The antiviral flooring material according to claim 1 or 2, which contains 0.1 to 1.0 part by mass of an inorganic antiviral agent containing a metal and having an average particle size of 2 to 30 nanometers with respect to 100 parts by mass of the resin composition. Resin composition. The resin composition for an antiviral floor material according to claim 3, wherein the inorganic antiviral agent contains at least one metal selected from the group consisting of copper, silver and zinc and titanium oxide. The resin composition for an antiviral floor material according to any one of claims 1 to 4, which contains 0.5 to 5.0 parts by mass of epoxidized flaxseed oil with respect to 100 parts by mass of the resin composition. An antiviral flooring material comprising the resin composition according to any one of claims 1 to 5.