Antiviral resin composition and antiviral article

Abstract

To provide an antiviral resin composition that enables the production of an antiviral article with exceptional safety and transparency, and also to provide an antiviral article prepared using the same.SOLUTION: The present invention provides an antiviral resin composition containing an antiviral agent and a resin, wherein the antiviral agent is at least one N-hydroxyethyl-N-[2-hydroxyalkyl]amine selected from the group consisting of (b) to (d), as well as an antiviral article prepared using the antiviral resin composition. (b) 1-[(2-hydroxyethyl)amino]dodecane-2-ol, (c) 1-[(2-hydroxyethyl)amino ]-tetradecane-2-ol, and (d) β-[(hydroxyethyl)amino] alcohol (C=11-14, type 2).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an antiviral agent, an antiviral resin composition, and an antiviral article. [Background technology]

[0002] Antiviral agents are broadly classified into inorganic antiviral agents and organic antiviral agents, for example. When an inorganic antiviral agent is added to a resin, synthetic fiber, paint, etc., the heat resistance and weather resistance of the resulting product are improved. Also, when an organic antiviral agent is added to a resin, synthetic fiber, paint, etc., the mechanical strength of the resulting product is improved.

[0003] As an example of using an inorganic antiviral agent, a resin composition containing inorganic particles including a metal oxide such as iron oxide or aluminum oxide and cuprous oxide particles (Patent Document 1), and a polycarbonate resin composition containing ions of a metal such as silver or zinc (Patent Document 2) have been proposed. Also, as an example of using an organic antiviral agent, a resin composition containing an antiviral agent obtained by supporting a sulfonic acid surfactant on an inorganic filler has been proposed (Patent Document 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-117187 A [Patent Document 2] Patent Publication No. 2021-191831 [Patent Document 3] JP 2017-218516 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, when inorganic antiviral agents are used, there are problems such as a decrease in transparency of the obtained product and a tendency for physical properties such as mechanical strength to deteriorate. Furthermore, since inorganic antiviral agents contain various metal ions, it is necessary to give sufficient consideration to the impact on the ecosystem caused by the accumulation of metals.

[0006] On the other hand, organic antiviral agents do not necessarily have good heat resistance and weather resistance themselves, and also have safety issues such as being prone to leaking from products such as obtained polymer molded articles, etc. Furthermore, depending on the type, organic antiviral agents may tend to reduce the transparency of products such as polymer molded articles and synthetic fibers.

[0007] The present invention has been made in consideration of the problems of the conventional techniques, and an object of the present invention is to provide an antiviral agent having excellent safety, capable of preparing a resin composition capable of producing an antiviral article having excellent transparency, and use thereof. Another object of the present invention is to provide an antiviral resin composition and an antiviral article using the above antiviral agent. [Means for solving the problem]

[0008] That is, according to the present invention, there are provided the following antiviral agents: [1] An antiviral agent comprising N-hydroxyethyl-N-[2-hydroxyalkyl]amine represented by the following general formula (1): RCH(OH)CH 2 NHCH 2 CH 2 OH (1) (In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.) [2] The antiviral agent according to the above [1], wherein the N-hydroxyethyl-N-[2-hydroxyalkyl]amine is at least one compound selected from the group consisting of the following (a) to (d): (a) 2,2'-Iminodiethanol (b) 1-[(2-hydroxyethyl)amino]dodecan-2-ol (c) 1-[(2-hydroxyethyl)amino]-tetradecan-2-ol (d) β-[(hydroxyethyl)amino]alcohol (C=11-14, secondary type)

[0009] The present invention also provides the following antiviral resin composition. [3] An antiviral resin composition comprising the antiviral agent according to [1] or [2] above and a resin. [4] The antiviral resin composition according to [3], wherein the content of the antiviral agent is 0.05 to 10 parts by mass per 100 parts by mass of the resin.

[0010] Furthermore, according to the present invention, there are provided the following antiviral articles. [5] An antiviral article formed from the antiviral resin composition according to [3] or [4] above.

[0011] The present invention also provides use of the following compounds as antiviral agents: [6] Use of N-hydroxyethyl-N-[2-hydroxyalkyl]amine represented by the following general formula (1) as an antiviral agent. RCH(OH)CH 2 NHCH 2 CH 2 OH (1) (In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.) Effect of the Invention

[0012] According to the present invention, it is possible to provide an antiviral agent having excellent safety, which can prepare a resin composition capable of producing an antiviral article having excellent transparency, and use thereof. In addition, according to the present invention, it is possible to provide an antiviral resin composition and an antiviral article using the above-mentioned antiviral agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] <Antiviral agents> Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The present inventors found that when N-hydroxyethyl-N-[2-hydroxyalkyl]amine represented by a specific general formula was added to a resin that is a material for various molded articles, fibers, and other products, a resin composition that can produce an article with excellent antiviral properties and transparency without substantially containing metals, metal ions, etc. was obtained, and thus the present invention was completed. That is, the antiviral agent of the present invention is an organic antiviral agent containing N-hydroxyethyl-N-[2-hydroxyalkyl]amine represented by the following general formula (1), and preferably substantially composed of only N-hydroxyethyl-N-[2-hydroxyalkyl]amine. RCH(OH)CH 2 NHCH 2 CH 2 OH (1) (In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.)

[0014] The N-hydroxyethyl-N-[2-hydroxyalkyl]amine is preferably at least one compound selected from the group consisting of the following (a) to (d): (a) 2,2'-Iminodiethanol (b) 1-[(2-hydroxyethyl)amino]dodecan-2-ol (c) 1-[(2-hydroxyethyl)amino]-tetradecan-2-ol (d) β-[(hydroxyethyl)amino]alcohol (C=11-14, secondary type)

[0015] (a) 2,2'-iminodiethanol (hereinafter also referred to as "antiviral agent a") is a compound represented by the following formula (a).

[0016] TIFF0007654151000001.tif27170

[0017] (b) 1-[(2-hydroxyethyl)amino]dodecan-2-ol (hereinafter also referred to as "antiviral agent b") is a compound represented by the following formula (b).

[0018] TIFF0007654151000002.tif33170

[0019] (c) 1-[(2-hydroxyethyl)amino]-tetradecan-2-ol (hereinafter also referred to as "antiviral agent c") is a compound represented by the following formula (c).

[0020] TIFF0007654151000003.tif21170

[0021] (d) β-[(hydroxyethyl)amino]alcohol (C=11-14, secondary type) (hereinafter also referred to as "antiviral agent d") is a mixture of a compound represented by formula (b) (antiviral agent b) and a compound represented by formula (c) (antiviral agent c) (CAS registration number 84836-93-1).

[0022] In acute toxicity tests, the LD50 of antiviral agent d was 2,130 mg / kg for males and 2,700 mg / kg for females, and it is classified as the safest "not applicable" category in the acute toxicity category for health hazards of the United Nations recommendation GHS (Globally Harmonized System of Classification and Labeling of Chemicals). Furthermore, antiviral agent d is listed in Appendix 1, Table 2, serial number 1229 of the Food Sanitation Act and the Positive List System for Food Utensils and Containers and Packaging, which were promulgated on April 28, 2020, and is approved for use in food utensils and containers and packaging applications, making it particularly safe. In addition, the softening point of antiviral agent d is 61.5°C, so it has excellent dispersibility in resins. For this reason, by using antiviral agent d, it is possible to manufacture antiviral resin compositions and various articles with higher transparency.

[0023] By using N-hydroxyethyl-N-[2-hydroxyalkyl]amine as an antiviral agent, it is possible to obtain an antiviral resin composition and various articles which are superior in various properties such as safety, transparency, and mechanical strength, as compared with the case where a conventional antiviral agent is used.

[0024] The antiviral properties of the antiviral agent of the present invention are presumed to be expressed by the following mechanism. First, N-hydroxyethyl-N-[2-hydroxyalkyl]amine, which is a secondary amine, forms a quaternary ammonium salt. The formed quaternary ammonium salt then induces (i) denaturation of the outer shell structure (capsid) of the virus; (ii) denaturation of proteins on the viral envelope required for infection; or (iii) both denaturation of (i) and denaturation of (ii); thus, the antiviral properties are presumed to be expressed.

[0025] <Antiviral resin composition> The antiviral resin composition of the present invention contains the above-mentioned antiviral agent and resin. The type of resin is not particularly limited. Specific examples of the resin include polyethylene resin, polypropylene resin, polyester resin, polystyrene resin, polyvinyl chloride resin, urethane resin, acrylic resin, polyamide resin, polyvinyl alcohol resin, cellulose resin, phenol resin, and epoxy resin.

[0026] The content of the antiviral agent (N-hydroxyethyl-N-[2-hydroxyalkyl]amine) in the antiviral resin composition is preferably 0.05 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the resin. If the content of the antiviral agent is less than 0.3 parts by mass relative to 100 parts by mass of the resin, the antiviral properties of the resin composition may be difficult to obtain. On the other hand, if the content of the antiviral agent is more than 5 parts by mass relative to 100 parts by mass of the resin, the physical properties of the resin composition may be affected.

[0027] The antiviral resin composition can further contain pigments, various additives, other antiviral agents, and the like, as necessary, within a range that does not impair the effects of the present invention.

[0028] <Anti-viral products> The antiviral article of the present invention is formed from the antiviral resin composition. The type of article is not particularly limited as long as it is formed from the antiviral resin composition. Specific examples of the article include those shown below. Note that the articles shown below may contain various colorants and additives.

[0029] (1) Antiviral molded products The antiviral molded article is an article molded from an antiviral resin composition by injection molding, extrusion molding, blow molding, etc. Specific examples of molded articles include food containers, trash cans, stationery, housings for electrical appliances, cosmetic containers, vehicle interior parts, kitchen utensils, bath products, clothing storage products, etc.

[0030] (2) Antiviral fiber The antiviral fiber is an article in which an antiviral resin composition is fibrous by spinning or the like. The antiviral fiber is also made into a woven or nonwoven fabric. Further specific examples of such articles include clothing and carpets.

[0031] (3) Antiviral paint The antiviral resin composition can be used as a binder and dissolved or dispersed in various solvents to prepare an antiviral paint. EXAMPLES

[0032] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified.

[0033] <Preparing antiviral drugs> The following antiviral agents a to d were prepared. Antiviral agent a: 2,2'-iminodiethanol (CAS registration number 111-42-2, Chemical Substances Control Law Official Gazette Reference Number 2-302, 2-354) Antiviral agent b: 1-[(2-hydroxyethyl)amino]dodecan-2-ol (CAS registration number 2615-84-1, Chemical Substances Control Law Official Gazette Reference Number 2-354) Antiviral agent c: 1-[(2-hydroxyethyl)amino]-tetradecan-2-ol (CAS registration number 56975-13-4, Chemical Substances Control Law Official Gazette Reference Number 2-354) Antiviral agent d: β-[(hydroxyethyl)amino]alcohol (C=11-14, secondary type) (CAS registration number 84836-93-1, Food Sanitation Law, Food utensils, containers and packaging positive list system, Appendix 1, Table 2, serial number 1229)

[0034] <Use and evaluation of antiviral agents> Example 1 Antiviral tests of antiviral agents a to d (technical substances) were conducted using bacteriophage Qβ (non-enveloped virus) and bacteriophage Φ6 (enveloped virus), which are viruses that use bacteria as hosts.

[0035] Bacteriophage Qβ was co-cultured with the host (Escherichia coli) to prepare a bacteriophage stock solution. The prepared stock solution contained 6.7 × 10 6 ~2.6×10 7The test solution was diluted with normal bouillon medium (1 / 500 concentration) to obtain an infectivity titer of pfu / mL (pfu: plaque forming unit). 10 mL of the obtained test solution was placed in a sterile test cup, and antiviral agent A was added to the mixture to obtain 500 ppm. After slowly stirring for 24 hours at 25°C using a shaker, the mixture was appropriately diluted with peptone-added physiological saline. 0.1 mL of E. coli (host) separately cultured in calcium-added LB medium was added to 2.0 mL of calcium-added LB soft agar medium (kept at about 50°C) and stirred well. 1.0 mL of the diluted test solution was further added and stirred well to obtain a mixture containing the virus and E. coli. The obtained mixture was layered on a calcium-added LB agar plate medium, and after the medium solidified, it was cultured at 37°C for 16 to 24 hours. The number of plaques of 30 to 300 pfu that appeared on the medium was counted, and the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated. The virus inhibition rate was calculated using the following formula (the number of digits of the reduced number of plaques (pfu) was used as the number of significant digits). Suppression rate (%) = {(pfu of Comparative Example 1-pfu of Example) / pfu of Comparative Example 1)} x 100

[0036] In addition, the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as above, except that bacteriophage Φ6 was used instead of bacteriophage Qβ, Pseudomonas syringae of the genus Pseudomonas was used as the host, and NB medium was used instead of calcium-supplemented LB medium, and the culture was performed at 25° C. The results are shown in Table 1.

[0037] (Examples 2 to 4) Except for using antiviral agents b to d instead of antiviral agent a, the antiviral properties of the antiviral agents were evaluated in the same manner as in Example 1 above. The results are shown in Table 1.

[0038] Comparative Example 1 A test similar to that in Example 1 was carried out, except that no antiviral agent was used. The results are shown in Table 1.

[0039] TIFF0007654151000004.tif77170

[0040] <Production and evaluation of antiviral resin composition and antiviral article (1)> Example 5 100 parts of low-density polyethylene resin and 1.0 part of antiviral agent b were heated and kneaded, and then molded to obtain a transparent sample plate (5 cm x 5 cm). 0.2 mL of the test solution of bacteriophage Qβ prepared in the same manner as in Example 1 was dropped onto the surface of the sample plate. A sterile polyethylene film (4 cm x 4 cm) was placed over the dropped test solution, and the film was pressed lightly to ensure that the test solution was spread over the entire film (film adhesion method). After being kept in an environment of 25°C and a relative humidity of 90% or more for 24 hours, the test solution was washed out with SCDLP medium. The washed-out test solution was appropriately diluted with peptone-added saline, and the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as in Example 1 above. The results are shown in Table 2.

[0041] In addition, the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as above, except that bacteriophage Φ6 was used instead of bacteriophage Qβ, Pseudomonas syringae of the genus Pseudomonas was used as the host, and NB medium was used instead of calcium-supplemented LB medium, and the culture was performed at 25° C. The results are shown in Table 2.

[0042] (Examples 6 and 7) The antiviral properties were evaluated in the same manner as in Example 5 above, except that antiviral agents c and d were used instead of antiviral agent b. The results are shown in Table 2.

[0043] Comparative Example 2 A test similar to that in Example 5 was carried out, except that no antiviral agent was used. The results are shown in Table 2.

[0044] TIFF0007654151000005.tif70170

[0045] <Production and evaluation of antiviral resin compositions and antiviral articles (2)> Example 8 100 parts of polypropylene resin and 2.0 parts of antiviral agent b were heated and kneaded, and then molded to obtain a transparent sample plate (5 cm x 5 cm). 0.2 mL of the test solution of bacteriophage Qβ prepared in the same manner as in Example 1 was dropped onto the surface of the sample plate. A sterile polyethylene film (4 cm x 4 cm) was placed over the dropped test solution, and the film was pressed lightly to ensure that the test solution was spread over the entire film (film adhesion method). After being kept in an environment of 25°C and a relative humidity of 90% or more for 24 hours, the test solution was washed out with SCDLP medium. The washed-out test solution was appropriately diluted with peptone-added saline, and the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as in Example 1 above. The results are shown in Table 3.

[0046] In addition, the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as above, except that bacteriophage Φ6 was used instead of bacteriophage Qβ, Pseudomonas syringae of the genus Pseudomonas was used as the host, and NB medium was used instead of calcium-supplemented LB medium, and the culture was performed at 25° C. The results are shown in Table 3.

[0047] (Examples 9 and 10) Except for using antiviral agents c and d instead of antiviral agent b, the antiviral properties and weather resistance were evaluated in the same manner as in Example 8. The results are shown in Table 3.

[0048] Comparative Example 3 A test similar to that in Example 8 was carried out, except that no antiviral agent was used. The results are shown in Table 3.

[0049] TIFF0007654151000006.tif69170

[0050] <Production and evaluation of antiviral resin compositions and antiviral articles (3)> Example 11 100 parts of saturated polyester and 3.0 parts of antiviral agent b were heated and kneaded, and then spun to obtain a transparent sample fiber. 0.4 g of the sample fiber was placed in a vial, and 0.2 mL of a test solution of bacteriophage Qβ prepared in the same manner as in Example 1 was inoculated. After keeping at 25°C for 4 hours, the test solution was washed out with SCDLP medium. The washed-out test solution was appropriately diluted with peptone-added saline, and the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as in Example 1 described above. The results are shown in Table 4.

[0051] In addition, the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as above, except that bacteriophage Φ6 was used instead of bacteriophage Qβ, Pseudomonas syringae of the genus Pseudomonas was used as the host, and NB medium was used instead of calcium-added LB medium, and the culture was performed at 25° C. The results are shown in Table 4.

[0052] (Examples 12 and 13) The antiviral properties were evaluated in the same manner as in Example 11 above, except that antiviral agents of the types shown in Table 4 were used instead of antiviral agent b. The results are shown in Table 4.

[0053] Comparative Example 4 A test similar to that in Example 11 above was carried out, except that no antiviral agent was used. The results are shown in Table 4.

[0054] TIFF0007654151000007.tif69170

[0055] <Production and evaluation of antiviral resin compositions and antiviral articles (4)> Example 14 4.2 parts of antiviral agent a was added to 100.0 parts of a mixed solvent of isopropyl alcohol and water (mass ratio = 1:1), and the mixture was stirred and mixed to obtain a mixed solution. 3.0 parts of the resulting mixed solution was added to 100.0 parts of an acrylic resin binder (trade name "Joncryl HPD-96", manufactured by BASF) prepared to a non-volatile content of 25%, and the mixture was stirred and mixed to obtain a sample. The obtained sample was applied to a corona-treated PET film using a No. 20 bar coater, and then dried to remove isopropyl alcohol and water, forming a transparent coating film in which the amount of antiviral agent a was 0.5 parts relative to 100 parts of non-volatile content of the acrylic resin binder. The formed coating film was cut to a size of 5 cm x 5 cm to prepare a sample plate for antiviral testing. 0.2 mL of a test solution of bacteriophage Qβ prepared in the same manner as in Example 1 was dropped onto the surface of the prepared sample plate. A sterile polyethylene film (4 cm x 4 cm) was placed over the dropped test solution, and the film was pressed lightly to ensure that the test solution was spread over the entire film (film adhesion method). After being kept in an environment of 25°C and a relative humidity of 90% or more for 24 hours, the test solution was washed out with SCDLP medium. The washed-out test solution was appropriately diluted with peptone-added saline, and the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as in Example 1 above. The results are shown in Table 5.

[0056] In addition, the virus infectivity (pfu / mL) and inhibition rate (%) in the test solution were calculated in the same manner as above, except that bacteriophage Φ6 was used instead of bacteriophage Qβ, Pseudomonas syringae of the genus Pseudomonas was used as the host, and NB medium was used instead of calcium-supplemented LB medium, and the culture was performed at 25° C. The results are shown in Table 5.

[0057] Example 15 The antiviral activity was evaluated in the same manner as in Example 14 above, except that antiviral agent d was used instead of antiviral agent a. The results are shown in Table 5.

[0058] Comparative Example 5 A test similar to that in Example 14 above was carried out, except that no antiviral agent was used. The results are shown in Table 5.

[0059] TIFF0007654151000008.tif63170 [Industrial Applicability]

[0060] By using the antiviral agent of the present invention, it is possible to produce antiviral resin compositions and various articles that are excellent in safety and transparency.

Claims

1. Contains an antiviral agent and a resin, The antiviral resin composition, wherein the antiviral agent is at least one N-hydroxyethyl-N-[2-hydroxyalkyl]amine selected from the group consisting of the following (b) to (d): (b) 1-[(2-hydroxyethyl)amino]dodecan-2-ol (c) 1-[(2-hydroxyethyl)amino]-tetradecan-2-ol (d) β-[(hydroxyethyl)amino]alcohol (C=11-14, secondary type)

2. 2. The antiviral resin composition according to claim 1, wherein a content of the antiviral agent per 100 parts by mass of the resin is 0.05 to 10 parts by mass.

3. An antiviral article formed from the antiviral resin composition according to claim 1 or 2.

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