JP2022046202A - Resin composition for antiviral floor material and antiviral floor material - Google Patents

Abstract

To provide a polyvinyl chloride resin composition for an antiviral floor material that uses a non-phthalic acid-based plasticizer, prevents the generation of nonyl alcohol and 2-ethyl hexanol, retains an antiviral effect, and does not cause discoloration of resin.SOLUTION: A resin composition for an antiviral floor material contains a polyvinyl chloride resin, at least one plasticizer 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, and an inorganic antiviral agent containing a metal with an average particle size of 2-30 nanometers.SELECTED DRAWING: None

Description

The present invention relates to a resin composition for an antiviral flooring material and an antiviral flooring material, and more specifically, for an antiviral flooring material, which is characterized by not using a phthalate ester as a plasticizing agent and having antiviral properties. It relates to a vinyl chloride resin composition and an antiviral flooring material comprising the above composition.

Vinyl chloride resin is widely used as an interior material for buildings because it has good workability, high mechanical strength and durability, and low flammability as compared with polyolefin.

In order to use vinyl chloride resin as an interior material, phthalates such as bis (2-ethylhexyl) phthalate (DOP) and diisononyl phthalate (DINP) are added for plasticization in order to impart flexibility. It is generally used as a vinyl chloride resin composition.

However, in recent years, the use of general-purpose phthalates such as DOP and DINP has been restricted due to concerns about their effects on the human body.

In addition, when DOP is used for vinyl chloride flooring, it has been pointed out that DOP is hydrolyzed by alkaline base humidity, 2-ethylhexanol is released, pollutes indoor air quality, and emits odor. .. When DINP is used, the same problem arises because the isononyl alcohol is released by hydrolysis.

Examples of the non-phthalic acid-based plasticizer that replaces phthalic acid include cyclohexane-based plasticizers, adipic-based plasticizers, and terephthalic acid-based plasticizers.

In Patent Document 1, diisononylcyclohexane-1,2-dicarboxylate (BaSF's hexamor DINCH (registered trademark)) and di-2-ethylhexyl terephthalate (DOTP manufactured by J-PLUS Co., Ltd.) are used as plasticizers. The vinyl chloride resin composition is disclosed.

Since the above-mentioned DINCH (registered trademark) and DOTP are non-phthalic plasticizers, there is less concern about their effects on the human body, but when used for flooring materials, the plasticizers are hydrolyzed by contact with alkaline undercoat moisture. , And nonyl alcohol and 2-ethylhexanol are generated, which may give off an odor and contaminate the indoor air quality.

In addition, the new coronavirus that occurred in China in 2019 caused the spread of infection all over the world, affecting more than 18 million people and killing about 700,000 people. 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 2 discloses an antiviral chloride resin composition to which a sulfonic acid-based surfactant is added.

Patent Document 3 discloses a plastic obtained by adding a double salt of any oxide of silver, copper, or zinc and a molybdenum oxide to a vinyl chloride resin.

Patent Document 4 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.

Japanese Unexamined Patent Publication No. 2017-115043 JP-A-2015-17078 Japanese Unexamined Patent Publication No. 2018-172462 Japanese Unexamined Patent Publication No. 2019-44096

Since the above-mentioned DINCH (registered trademark) and DOTP are non-phthalic plasticizers, there is less concern about their effects on the human body, but when used for flooring materials, the plasticizers are hydrolyzed by contact with alkaline undercoat moisture. , And nonyl alcohol and 2-ethylhexanol are generated, which may give off an odor and contaminate the indoor air quality.

In addition, in the method of adding a surfactant to the vinyl chloride resin, the surfactant gradually exudes and the amount of the drug decreases, which causes a problem in the sustainability of the antiviral effect, and also adds a metal oxide. The method has a drawback that the resin composition is not suitable for the interior material because the resin is discolored.

The subject of the present invention is that a non-phthalic acid-based plasticizer is used, nonyl alcohol and 2-ethylhexanol are not generated, the antiviral effect is sustained, and the resin is not discolored. It is to provide a vinyl resin composition.

In order to solve the above problems, the first invention of the present invention comprises a vinyl chloride resin, a palmitic acid 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 non-plasticizer. Antiviral flooring resin containing at least one plasticizer selected from the group consisting of linolenic acid esters epoxidized with saturated groups and inorganic antiviral agents containing metals and having an average particle size of 2 to 30 nanometers. It is a composition.
The second invention is an antiviral flooring material comprising the resin composition of the first invention.

The present invention includes the following embodiments.
[1] It is composed of a vinyl chloride resin, a palmitic acid 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. A resin composition for an antiviral floor material containing at least one plasticizer selected from the group and an inorganic antiviral agent containing a metal and having an average particle size of 2 to 30 nanometers.
[2] The resin composition for an antiviral floor material according to [1], wherein the inorganic antiviral agent contains at least one metal selected from the group consisting of copper, silver and zinc and titanium oxide. thing.
[3] The plasticizer is at least one selected from the group consisting of palmitic acid ester and stearic acid ester, an oleic acid ester in which an unsaturated group is epoxidized, a linolenic acid ester in which an unsaturated group is epoxidized, and an unsaturated group. The resin composition for an antiviral floor material according to [1] or [2], which comprises at least one selected from the group consisting of an epoxidized linolenic acid ester.
[4] The resin composition for an antiviral flooring material according to any one of [1] to [3], which further contains a drying oil.
[5] The resin composition for an antiviral flooring material according to [4], wherein the drying oil is flaxseed oil.
[6] The resin composition for an antiviral flooring material according to any one of [1] to [5], which further contains epoxidized soybean oil.
[7] The resin composition for an antiviral flooring material according to any one of [1] to [6], which further comprises a filler.
[8] The resin composition for an antiviral flooring material according to [7], wherein the filler is calcium carbonate.
[9] The resin composition for an antiviral flooring material according to any one of [1] to [8], which further contains a stabilizer.
[10] An antiviral flooring material comprising the resin composition according to any one of [1] to [9].

According to the resin composition of the present invention, a flexible vinyl chloride resin molded body can be obtained without using a phthalic acid-based plasticizer, and when used as a flooring material, 2-ethylhexanol is released due to the moisture of the base material. Occurs and exhibits antiviral properties.

Hereinafter, the present invention will be described in detail.
The first invention of the present invention is a vinyl chloride resin, a palmitic acid 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 in which an unsaturated group is epoxidized. A resin composition for an antiviral floor material containing at least one plasticizer selected from the group consisting of esters and an inorganic antiviral agent containing a metal and having an average particle size of 2 to 30 nanometers.

[Vinyl chloride resin]
The resin composition for a flooring material of the present invention contains a 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 resin composition for a flooring material of the present invention contains a plasticizer. 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. At least one species selected from the group. Preferred examples of the palmitate ester include methyl palmitate and ethyl palmitate, and preferred examples of the stearic acid ester include methyl stearate and ethyl stearate, which are oleic acid esters in which unsaturated groups are epoxidized. Preferred examples of the above include methyl cis-9,10-epoxyoctadecanoate, ethyl cis-9,10-epoxyoctadecanoate and the like, and preferred examples of the linoleic acid ester in which an unsaturated group is epoxidized include 9, Methyl 10: 12,13-diepoxy octadecanoate, ethyl 9,10: 12,13-diepoxy octadecanoate and the like can be mentioned, and preferred examples of the linolenic acid ester in which an unsaturated group is epoxidized include 9,10 :. Examples thereof include methyl 12,13: 15,16-triepoxy octadecanoate, ethyl 9,10: 12,13: 15,16-triepoxy octadecanoate and the like. These plasticizers may be used alone or in a blend of two or more.

When two or more kinds of plasticizers are blended and used, at least one selected from the group consisting of palmitic acid ester and stearic acid ester, an oleic acid ester in which an unsaturated group is epoxidized, and an unsaturated group in which an unsaturated group is epoxidized. It is particularly preferable to use it in combination with at least one selected from the group consisting of the above-mentioned linoleic acid ester and the epoxidized linolenic acid ester of the unsaturated group.

The content of the plasticizer is preferably 10 to 100 parts by mass, more preferably 30 to 60 parts by mass, still more preferably 40 to 50 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

[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.

[Drying oil]
The resin composition for a flooring material of the present invention preferably contains a drying oil. By including drying oil, stain resistance is improved by forming a film on the surface. Examples of the drying oil include flaxseed oil, castor oil, tung oil and the like, and flaxseed oil is particularly preferable. The content of the drying oil is preferably 0 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

[Epoxyd soybean oil]
The resin composition for flooring of the present invention preferably contains epoxidized soybean oil. The inclusion of epoxidized soybean oil improves the stability of oxidative degradation. The content of the epoxidized soybean oil 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 for a flooring material 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 for a flooring material 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, 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 is an antiviral flooring material comprising the resin composition of the first invention. 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) Alcohol emission from the molded product A 2 mm thick sheet of the vinyl chloride resin composition was cut into 165 mm squares, 2 mL of a 5% NaOH aqueous solution was dropped on one side, and the mixture was left for 24 hours to plasticize the molded product. The agent was hydrolyzed. Then, the dropping solution was wiped off, and the alcohol emission rate (μg / m ² · h) emitted from the molded product was measured according to JIS A1901.

(2) 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.

(3) 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.
◯: Partial discoloration occurs Δ: Overall discoloration occurs.
X: Significant discoloration occurs.

[Manufacturing Example 1] Production of Plasticizer (P-1) 100 parts by mass of methyl stearate (trade name: methyl stearate 95) manufactured by Nichiyu Co., Ltd. and methyl oleate (trade name: Unistar (registered trademark) M). A plasticizer (P-1) was produced by mixing with 100 parts by mass of the epoxidized product of -182A).

Plasticizer (P-2)
A plasticizer (trade name: JEG3-33) manufactured by JIAAO, which is a mixture of methyl palmitate, methyl stearate, epoxidized oleic acid, epoxidized methyl linoleate, and epoxidized methyl linolenate, is used as a plasticizer (P-2). used.

[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 the plasticizer (P-1) manufactured in Production Example 1, and 100 parts by mass of surface-treated calcium carbonate (Shiraishi calcium stock). Company manufactured, product name: CCR), barium zinc stabilizer (manufactured by ADEKA Co., Ltd., Adecaster (registered trademark) AP-627) by 2 parts by mass and inorganic antiviral agent (manufactured by JGC Catalysts and Chemicals Co., Ltd., product name: ATOMY BALL- (S), composition: Ag / TiO ₂ , average particle size: 5 nm) 0.5 parts by mass were mixed with a Banbury mixer to prepare a resin composition for an antiviral flooring 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 alcohol emission, antiviral property and discoloration property from the molded product. The results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was carried out except that the plasticizer (P-2) was used instead of the plasticizer (P-1), and an antiviral flooring resin composition was prepared and evaluated. 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-2) are used, and a drying oil (manufactured by Nisshin Oillio Group Co., Ltd.) is used. A resin composition for an antiviral flooring material was prepared and evaluated in the same manner as in Example 1 except that 2 parts by mass of flaxseed oil) was added. The results are shown in Table 1.

[Example 4]
A plasticizer (P-2) is used instead of the plasticizer (P-1), and 2 parts by mass of drying oil (linseed oil manufactured by Nisshin Oillio Group Co., Ltd.) and epoxidized soybean oil (manufactured by Nisshin Oil Co., Ltd.) are used. , Trade name: Newsizer (registered trademark) 510R) The same procedure as in Example 1 was carried out except that 5 parts by mass was added, and an antiviral flooring resin composition was prepared and evaluated. The results are shown in Table 1.

[Comparative Example 1]
Similar to Example 1 except that bis (2-ethylhexyl) phthalate (DOP manufactured by J-PLUS Co., Ltd.) was used instead of the plasticizer (P-1) and no inorganic antiviral agent was added. This was carried out to prepare and evaluate an antiviral flooring resin composition. 2-Ethylhexanol was released in the evaluation test of alcohol emission. The results are shown in Table 1.

[Comparative Example 2]
Diisononylcyclohexane-1,2-dicarboxylate (BASF, Hexamole DINCH®) was used instead of the plasticizer (P-1), except that no inorganic antiviral agent was added. , The same procedure as in Example 1 was carried out to prepare and evaluate an antiviral flooring resin composition. Isononyl alcohol was released in the evaluation test of alcohol release. The results are shown in Table 1.

[Comparative Example 3]
The same procedure as in 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) and no inorganic antiviral agent was added. Then, a resin composition for an antiviral floor material was prepared and evaluated. 2-Ethylhexanol was released in the evaluation test of alcohol emission. The results are shown in Table 1.

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 (10)

Select from the group consisting of vinyl chloride resin, 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. A resin composition for an antiviral floor material containing at least one plasticizer and an inorganic antiviral agent having an average particle size of 2 to 30 nanometers containing a metal. The resin composition for an antiviral floor material according to claim 1, wherein the inorganic antiviral agent contains at least one metal selected from the group consisting of copper, silver and zinc and titanium oxide. The plasticizer is at least one selected from the group consisting of palmitic acid ester and 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 an unsaturated group in which an unsaturated group is epoxidized. The resin composition for an antiviral floor material according to claim 1 or 2, which comprises at least one selected from the group consisting of the above-mentioned linolenic acid ester. The resin composition for an antiviral flooring material according to any one of claims 1 to 3, further comprising a drying oil. The resin composition for an antiviral flooring material according to claim 4, wherein the drying oil is flaxseed oil. The resin composition for an antiviral flooring material according to any one of claims 1 to 5, further comprising epoxidized soybean oil. The resin composition for an antiviral flooring material according to any one of claims 1 to 6, further comprising a filler. The resin composition for an antiviral floor material according to claim 7, wherein the filler is calcium carbonate. The resin composition for an antiviral flooring material according to any one of claims 1 to 8, further comprising a stabilizer. An antiviral flooring material comprising the resin composition according to any one of claims 1 to 9.