Antiviral resin composition and molded body comprising a hydrophilic polymer

Abstract

The present application aims to provide an antiviral resin composition which exhibits high antiviral properties by itself even without the addition of an additive such as a metal oxide, has resistance to water, and can be processed into injection-molded articles, extrusion-molded articles, films, fibers, nonwoven fabrics, and foams. The antiviral resin composition of the present application is characterized by comprising a hydrophilic polymer, having a contact angle of 80 degrees or less with respect to water, having a water absorption rate of 25% or less, and having an antiviral activity value of 2 or more after 24 hours.

Description

Technical Field

[0001] This invention relates to antiviral resin compositions and molded articles. Background Technology

[0002] In recent years, infectious diseases caused by various viruses, such as the novel coronavirus, have threatened human lives, leading to an urgent global demand for countermeasures. From this perspective, the demand for antiviral materials has increased, and antiviral properties are now required in all products.

[0003] As antiviral materials, for example, as described in Patent Documents 1 and 2, materials in which metal oxides formed of silver, copper, zinc, etc., are dispersed in a resin have been reported. However, there is a problem of metal oxide leaching. Furthermore, there is a problem of the resin being mixed being degraded by the metal oxides.

[0004] On the other hand, as in Patent Document 3, polyvinyl alcohol with amino groups has been reported as a polymeric compound that exhibits antiviral activity without the addition of metal oxides.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-172462

[0008] Patent Document 2: Japanese Patent Application Publication No. 2015-205998

[0009] Patent Document 3: International Publication No. 2017 / 171066 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] However, since the amino-containing polyvinyl alcohol, which is the polymer compound in Patent Document 3, is water-soluble, it can be considered to have no resistance to water. In addition, there are problems with its molding and processability, and new materials are required.

[0012] The purpose of this invention is to provide an antiviral resin composition that exhibits high antiviral properties even without the addition of additives such as metal oxides, is water resistant, and can be processed as an injection molded article, extruded article, film, fiber, nonwoven fabric, and foam.

[0013] Methods for solving problems

[0014] The inventors have discovered that resin compositions containing hydrophilic polymers and having a water contact angle of 80 degrees or less exhibit antiviral properties even without the addition of additives such as metal oxides. Furthermore, they have found that if the water contact angle is 80 degrees or less and the water absorption rate is 25% or less, it exhibits water resistance.

[0015] That is, the antiviral resin composition of the present invention is characterized by comprising a hydrophilic polymer, having a water contact angle of less than 80 degrees, a water absorption rate of less than 25%, and an antiviral activity value of more than 2 after 24 hours.

[0016] The effects of the invention

[0017] According to the present invention, an antiviral resin composition can be obtained that does not exhibit metal oxide exudation or deterioration caused by metal oxides, can exhibit high antiviral properties, is water resistant, and has excellent molding and processability. Detailed Implementation

[0018] The present invention will now be described in detail.

[0019] The antiviral resin composition of the present invention comprises a hydrophilic polymer with a water contact angle of 80 degrees or less and a water absorption rate of 25% or less. The water contact angle of 80 degrees or less inhibits viral activity, and the water absorption rate of 25% or less provides water resistance and excellent molding processability.

[0020] The antiviral resin composition of the present invention has an antiviral activity value of 2 or higher after 24 hours in the antiviral test (SARS-CoV-2) described later.

[0021] In this invention, "antiviral activity" refers to the property of inactivating pathogen viruses. Antiviral activity is evaluated by the antiviral activity value (Mv) after 24 hours and the virus reduction rate (%) after 24 hours, as described below.

[0022] [Resin Composition]

[0023] The resin composition of the present invention comprises a hydrophilic polymer with a water contact angle of 80 degrees or less and a water absorption rate of 25% or less. A larger contact area with the virus is better; therefore, a water contact angle of 75 degrees or less is preferred. If the water absorption rate exceeds 25%, the swelling of the molded article increases, and its shape stability deteriorates.

[0024] [Hydrophilic polymers]

[0025] Specific examples of the hydrophilic polymers used in this invention include hydrophilic resins such as polyester resins, polyamide resins, polyimide resins, polyether resins, and polyurethane resins. Among these, polyester resins are preferred. Preferred examples of polyester resins include polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate, polyhexanediol terephthalate, polyethylene 1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, polycyclohexane-1,4-dimethylol terephthalate, thermoplastic polyester elastomers, and copolymers such as polyethylene glycol isophthalate / terephthalate, polybutylene glycol terephthalate / isophthalate, and polybutylene glycol terephthalate / decanedicarboxylate. Here, " / " indicates a copolymer. Preferably, it is a thermoplastic polyester elastomer or a thermoplastic polyamide elastomer, and more preferably a thermoplastic polyester elastomer.

[0026] Furthermore, the hydrophilic polymer can be a polymer containing at least one hydrophilic group such as hydroxyl, carbonyl, amino, or carboxyl groups. Specific examples include polyethylene-based resins and polypropylene-based resins, which are hydrophobic resins that have been endowed with hydrophilic groups such as hydroxyl and carboxyl groups through corona treatment or plasma treatment. Further, the hydrophilic polymer can be a mixture of two or more different polymers; specifically, a polymer with a water absorption rate greater than 25%, such as polyvinyl alcohol, can be mixed with a hydrophobic resin.

[0027] [Thermoplastic polyester elastomer]

[0028] The thermoplastic polyester elastomer used in this invention is a copolymer of high-melting-point crystalline polymer segments and low-melting-point polymer segments.

[0029] The high-melting-point crystalline polymer segments are polyesters formed from aromatic dicarboxylic acids or their ester-forming derivatives and diols or their ester-forming derivatives.

[0030] Specific examples of the aforementioned aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. In this invention, the aforementioned aromatic dicarboxylic acids are primarily used, but a portion of these aromatic dicarboxylic acids can be replaced with alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4'-dicyclohexyldicarboxylic acid, as well as aliphatic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanoic acid, and dimer acids. Furthermore, ester-forming derivatives of dicarboxylic acids, such as lower alkyl esters, aryl esters, carbonates, and acyl halides, can also be used equivalently.

[0031] In this invention, two or more of the above-mentioned acid components can be used. Examples include combinations of terephthalic acid and isophthalic acid, terephthalic acid and dodecanoic acid, terephthalic acid and dimer acid, etc.

[0032] Next, as specific examples of diols in high-melting-point crystalline polymer segments, diols with a molecular weight of less than 400 are preferred, such as aliphatic diols like 1,4-butanediol, ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, and 1,10-decanediol; alicyclic diols like 1,1-cyclohexanediethanol, 1,4-dicyclohexanediethanol, and tricyclodecanediethanol; and xylene-2-methyldiethanol, bis(p-hydroxyl)-2-methyldiethanol, etc. Aromatic diols such as 4,2'-dihydroxy-4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-4-terphenyl, and 4,4'-dihydroxy-4-tetraphenyl can also be used as ester-forming derivatives such as acetyl groups and alkali metal salts. These dicarboxylic acids, their derivatives, diol components, and their derivatives can be used in combination of two or more.

[0033] The low-melting-point polymer segment is an aliphatic polyether, but it can be used in combination with aliphatic polyesters and aliphatic polycarbonates.

[0034] Specific examples of aliphatic polyethers include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(oxetane) glycol, poly(tetrahydrofuran) glycol, poly(oxetane) glycol, poly(oxetane) glycol, copolymers of ethylene oxide and propylene oxide, copolymers of oxetane and oxetane, copolymers of oxetane and oxetane, ethylene oxide adducts of poly(propylene oxide) glycol, and copolymers of ethylene oxide and oxetane. Among these, copolymers comprising poly(tetrahydrofuran) glycol and / or ethylene oxide adducts of poly(propylene oxide) glycol and / or copolymers of ethylene oxide and oxetane are preferred. Poly(tetrahydrofuran) glycol and ethylene oxide adducts of poly(propylene oxide) glycol are particularly preferred. Additionally, for example, poly(propylene oxide) glycol is polypropylene oxide or polypropylene glycol, and poly(tetrahydrofuran) glycol is poly(oxacyclopentane) or polytetramethylene ether glycol.

[0035] Furthermore, the number average molecular weight of these aliphatic polyethers is preferably 300 to 6000 in the copolymerized state. The number average molecular weight can be determined by general organic analysis.

[0036] Specific examples of aliphatic polyesters include poly(ε-caprolactone), polyheptanolide, polyoctanolide, and polybutylene adipate. Aliphatic polycarbonates are preferably composed primarily of aliphatic diol residues having 2 to 12 carbon atoms. Examples of these aliphatic diols include, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol.

[0037] Regarding the copolymerization ratio of high-melting-point crystalline polymer segments to low-melting-point polymer segments, a higher ratio of low-melting-point segments is preferred. Specifically, the copolymerization ratio of low-melting-point polymer segments is more preferably 9% or more, more preferably 20% or more, more preferably 25% or more, more preferably 30% or more, more preferably 35% or more, more preferably 40% or more, more preferably 45% or more, and more preferably 50% or more.

[0038] Furthermore, the copolymerization ratio of the low-melting-point segments referred to here is the proportion of low-melting-point segment units that are diol components. That is, it is expressed as a percentage by mass (%), representing the amount obtained by subtracting water molecules resulting from ester bond formation from the low-melting-point segment component of the raw material relative to the total amount of the copolymer containing the low-melting-point segments. This can be calculated directly if the composition of the raw material is known. Alternatively, the copolymer containing the low-melting-point segments can be determined through NMR structural analysis.

[0039] The antiviral composition of the present invention may consist of only hydrophilic polymers, and may be supplemented as needed, without compromising the purpose, with the addition of additives such as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, surfactants, lubricants, dyes, pigments, plasticizers, flame retardants, talc, mica, glass flakes, calcium carbonate, clay, barium sulfate, glass beads, glass fibers, carbon fibers, cellulose nanofibers, etc.

[0040] Specific examples of viruses used in this invention include influenza virus, coronavirus, SARS-CoV-2, hepatitis C virus, Japanese encephalitis virus, Zika virus, rubella virus, measles virus, human RS virus, rabies virus, Crimean-Congo hemorrhagic fever virus, Ebola virus, Marburg virus, hepatitis D virus, smallpox virus, hepatitis B virus, human immunodeficiency virus, norovirus, feline calicivirus, adenovirus, hepatitis A virus, poliovirus, Coxsackie virus, enterovirus, rotavirus, parvovirus, astrovirus, and Sapo virus.

[0041] The molded articles of the present invention are processed from the antiviral resin composition of the present invention. Specific forms of the molded articles of the present invention include injection molded articles, extruded molded articles, films, fibers, nonwoven fabrics, and foams.

[0042] The antiviral resin composition of the present invention is preferably used in the outer layer of an article to which antiviral properties are desired. That is, a method for providing an antiviral article preferably includes the step of providing an outer layer of the article, the outer layer comprising the antiviral resin composition of the present invention. Here, "outer layer" refers to the surface portion of a molded body formed by two or more overlapping layers, or the exposed surface of a single-layer molded body. Examples include, for instance, the film layer of an in-mold molded body, the layer in contact with the body of a two-color molded article, and the exposed surface of an uncovered face mask.

[0043] Furthermore, the use of the antiviral resin composition of the present invention for imparting antiviral properties to the surface of articles on the outer layer of articles is preferred.

[0044] Furthermore, examples of uses for the antiviral resin composition of the present invention include wallpaper, flooring materials, curtains, clothing, trash cans, food packaging materials, adhesive plasters, masks, bandages, tableware, furniture, toys, bathroom components, toilet components, kitchen components, home appliances, filters (air purifiers), bedding (blankets, quilts, sheets), seating (car seats, train seats, aircraft seats, family chairs), armrests, handrails, sponges (for cleaning, washing dishes, and filtering), diapers, cleaning tools, pollution diffusion prevention materials, and automotive interior materials.

[0045] In this invention, "antiviral activity" refers to the property of inactivating pathogenic viruses. Antiviral activity is evaluated by the antiviral activity value Mv after 24 hours and the virus reduction rate (%) after 24 hours, as described later.

[0046] Example

[0047] The effects of the present invention will be illustrated below through examples. Furthermore, unless otherwise specified, all percentages and parts in the examples refer to mass. Additionally, the physical properties shown in the examples were measured as follows.

[0048] [Thermoplastic polyester elastomer (A-1)]

[0049] 270.0 parts of terephthalic acid, 234.0 parts of 1,4-butanediol, 0.1 parts of tetrabutyl titanate, and 0.1 parts of mono-n-butyl-monohydroxytin oxide were added to an esterification tank equipped with a distillation column and a stirrer, and the esterification reaction was initiated at 160°C and a reduced pressure of 700 mmHg. Then, the temperature was slowly increased, and 59.0 parts of 1,4-butanediol were added continuously. After 3 hours and 40 minutes, a clear reaction product was obtained, and the reaction was terminated. After the esterification reaction was completed, 1.8 parts of tetrabutyl titanate as a polycondensation catalyst and 1.0 part of "IRGANOX" 1330 (manufactured by BASF) as a stabilizer were added to the esterification tank. On the other hand, 686.0 parts of poly(tetrahydrofuran) glycol with a number average molecular weight of 1400 were added to a polycondensation tank, and the above esterification reaction products were transferred from the esterification tank to the polycondensation tank. Subsequently, while stirring and polymerizing the reaction system in the polycondensation tank, a reduced pressure system was slowly formed over 1 hour from atmospheric pressure to a high vacuum of less than 1 mmHg. At the same time, the temperature was raised to 245°C, and polycondensation was carried out at 245°C and less than 1 mmHg for 3 hours and 30 minutes to obtain thermoplastic polyester elastomer (A-1).

[0050] [Thermoplastic polyester elastomer (A-2)]

[0051] 501.0 parts of terephthalic acid, 326.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.2 parts of mono-n-butyl-monohydroxytin oxide were added to an esterification tank equipped with a distillation column and a stirrer. The esterification reaction was initiated at 160°C and a reduced pressure of 650 mmHg. Then, the temperature was slowly increased, and 81.0 parts of 1,4-butanediol were continuously added while the reduced pressure was changed to 500 mmHg midway through the reaction. A clear reaction product was obtained 3 hours and 40 minutes after the start of the reaction, at which point the reaction was considered complete. After the esterification reaction was completed, 2.0 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of IRGANOX 1098 (manufactured by BASF) as a stabilizer were added to the esterification tank. Meanwhile, 354.0 parts of poly(tetrahydrofuran)diol with a number average molecular weight of 1400 were added to the polycondensation tank, and the esterification products were transferred from the esterification tank to the polycondensation tank. Then, while stirring the reaction system in the polycondensation tank, a reduced pressure system was slowly formed from atmospheric pressure to a high vacuum of less than 1 mmHg over 1 hour, while simultaneously raising the temperature to 245°C. Polycondensation was carried out at 245°C and less than 1 mmHg for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-2).

[0052] [Thermoplastic polyester elastomer (A-3)]

[0053] 591.0 parts of terephthalic acid, 385.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.1 parts of mono-n-butyl-monohydroxytin oxide were added to an esterification tank equipped with a distillation column and a stirrer, and the esterification reaction was initiated at 160°C and a reduced pressure of 500 mmHg. Then, the temperature was slowly increased, and 96.0 parts of 1,4-butanediol were added continuously. After 3 hours and 40 minutes, a clear reaction product was obtained, and the reaction was terminated. After the esterification reaction was completed, 1.5 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1098 (manufactured by BASF) as a stabilizer were added to the esterification tank. On the other hand, 231.0 parts of poly(tetrahydrofuran) glycol with a number average molecular weight of 1400 were added to a polycondensation tank, and the above esterification reaction products were transferred from the esterification tank to the polycondensation tank. Subsequently, while stirring and polymerizing the reaction system in the polycondensation tank, a reduced pressure system was slowly formed over 1 hour from atmospheric pressure to a high vacuum of less than 1 mmHg. At the same time, the temperature was raised to 245°C, and polycondensation was carried out at 245°C and less than 1 mmHg for 3 hours and 30 minutes to obtain thermoplastic polyester elastomer (A-3).

[0054] [Thermoplastic polyester elastomer (A-4)]

[0055] 340.0 parts of terephthalic acid, 100 parts of isophthalic acid, 296.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.1 parts of mono-n-butyl-monohydroxytin oxide were added to an esterification tank equipped with a distillation column and a stirrer, and the esterification reaction was initiated at 160°C and a reduced pressure of 500 mmHg. Then, the temperature was slowly increased, and 74.0 parts of 1,4-butanediol were added continuously. After 3 hours and 40 minutes, a clear reaction product was obtained, and the reaction was terminated. After the esterification reaction was completed, 1.9 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1098 (manufactured by BASF) as a stabilizer were added to the esterification tank. On the other hand, 495.0 parts of poly(tetrahydrofuran) glycol with a number average molecular weight of 1400 were added to a polycondensation tank, and the above esterification reaction products were transferred from the esterification tank to the polycondensation tank. Subsequently, while stirring and polymerizing the reaction system in the polycondensation tank, a reduced pressure system was slowly formed over 1 hour from atmospheric pressure to a high vacuum of less than 1 mmHg. At the same time, the temperature was raised to 245°C, and polycondensation was carried out at 245°C and less than 1 mmHg for 3 hours and 30 minutes to obtain thermoplastic polyester elastomer (A-4).

[0056] [Thermoplastic polyester elastomer (A-5)]

[0057] 312 parts of dimethyl terephthalate and 91 parts of dimethyl isophthalate, which will form high-melting-point crystalline polymer segments of crystalline aromatic polyester, 537 parts of an ethylene oxide adduct of poly(propylene oxide) glycol with a number-average molecular weight of 2150, which will form low-melting-point polymer segments of aliphatic polyether units, 167 parts of 1,4-butanediol, and 4 parts of tetrabutoxide titanium were added to a reaction vessel equipped with a ribbon-type stirring blade. The mixture was heated at 190–225°C for 3 hours, and methanol was distilled off the system. Two parts each of IRGANOX 1098 and 1019 (manufactured by BASF) were added to the reaction mixture, and the temperature was raised to 243°C. The pressure in the system was then reduced to 0.2 mmHg after 50 minutes, and polymerization was carried out under these conditions for 3 hours to obtain a thermoplastic polyester elastomer (A-5).

[0058] [Thermoplastic polyester elastomer (A-6)]

[0059] 501.0 parts of terephthalic acid, 326.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, and 0.2 parts of mono-n-butyl-monohydroxytin oxide were added to an esterification tank equipped with a distillation column and a stirrer. The esterification reaction was initiated at 160°C and a reduced pressure of 650 mmHg. Then, the temperature was slowly increased, and 81.0 parts of 1,4-butanediol were continuously added while the reduced pressure was changed to 500 mmHg midway through the reaction. A clear reaction product was obtained 3 hours and 40 minutes after the start of the reaction, at which point the reaction was considered complete. After the esterification reaction was completed, 2.0 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of IRGANOX 1098 (manufactured by BASF) as a stabilizer were added to the esterification tank. Meanwhile, 354.0 parts of a copolymer of oxepane and oxepane with a number average molecular weight of 1400 were added to the polycondensation tank, and the esterification products were transferred from the esterification tank to the polycondensation tank. Then, while stirring the reaction system in the polycondensation tank, a reduced pressure system was slowly formed from atmospheric pressure to a high vacuum of less than 1 mmHg over 1 hour, while simultaneously raising the temperature to 245°C. Polycondensation was carried out at 245°C and less than 1 mmHg for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-6).

[0060] [Thermoplastic polyester elastomer (A-7)]

[0061] 269 ​​parts of dimethyl terephthalate, which will become a high-melting-point crystalline polymer segment formed from crystalline aromatic polyester, 725.0 parts of poly(tetrahydrofuran)diol with a number average molecular weight of 2000, which will become a low-melting-point polymer segment formed from aliphatic polyether units, 92.4 parts of 1,4-butanediol, and 4 parts of tetrabutoxide titanium were added to a reaction vessel equipped with a ribbon-type stirring blade. The mixture was heated at 190–225°C for 3 hours to distill off methanol. After adding 1.5 parts each of IRGANOX 1098 and 1019 (manufactured by BASF) to the reaction mixture, the temperature was raised to 243°C, and then the pressure inside the system was reduced to 0.2 mmHg after 50 minutes. Polymerization was carried out under these conditions for 3 hours to obtain a thermoplastic polyester elastomer (A-7).

[0062] [Thermoplastic Polyester Elastomer (A-8)]

[0063] 595 parts of dimethyl terephthalate (forming high-melting-point crystalline polymer segments of crystalline aromatic polyester), 353.0 parts of poly(tetrahydrofuran)diol (number-average molecular weight 1000) forming low-melting-point polymer segments of aliphatic polyether units, 518 parts of 1,4-butanediol, and 4 parts of titanium tetrabutoxide were added to a reaction vessel equipped with a ribbon-type stirring blade. The mixture was heated at 190–225°C for 3 hours, and methanol was distilled off the system. 1.5 parts each of IRGANOX 1098 and 1019 (manufactured by BASF) were added to the reaction mixture, and the temperature was raised to 243°C. The pressure was then reduced to 0.2 mmHg after 50 minutes, and polymerization was carried out under these conditions for 3 hours to obtain a thermoplastic polyester elastomer (A-7).

[0064] [PBT resin (B)]

[0065] トレコン TM 1100S (manufactured by Higashi Re Co., Ltd.). A polymer of terephthalic acid and 1,4-butanediol.

[0066] [Thermoplastic polyamide elastomer (C)]

[0067] 98.00 parts of 12-aminododecanoic acid and 7.66 parts of adipic acid were added to a pressure vessel. After nitrogen purging, the mixture was slowly heated while supplied with nitrogen and polymerized at 230°C for 4 hours to synthesize an oligomer of nylon 12. 642.5 parts of poly(tetrahydrofuran)diol with a number average molecular weight of 1800, 0.20 parts of tetrabutyl zirconate, and 0.50 parts of the antioxidant "IRGANOX" 1098 (manufactured by BASF) were added to this oligomer. After nitrogen purging, the mixture was slowly heated while supplied with nitrogen and heated at 210°C for 3 hours. Then, the pressure was slowly reduced to 50 Pa over 1 hour, and polymerization was carried out for 2 hours. Finally, the pressure was further increased and reduced over 30 minutes, and polymerization was carried out at 230°C and 30 Pa for 3 hours to obtain a thermoplastic polyamide elastomer (C).

[0068] [Forming of the experimental piece]

[0069] Injection molding was performed using a NEX-1000 injection molding machine manufactured by Nissei Resin Kogyo Co., Ltd., and 80mm × 80mm × 1mm square plate-shaped test pieces were obtained from the granules. Since injection molding can be performed, it can be processed into injection molded products, extruded products, films, fibers, nonwoven fabrics, and foams.

[0070] [Determination of water absorption rate]

[0071] The value is expressed as a percentage by dividing the weight difference of the test piece before and after immersion in water at 23 degrees Celsius after immersion in a square plate-shaped test piece of 80 mm × 80 mm × 1 mm obtained by vacuum drying at 80 °C for 5 hours by the weight of the test piece before treatment.

[0072] [Determination of contact angle]

[0073] The contact angle was measured primarily according to JIS R 3257. Approximately 2 μL of purified water was added dropwise using a syringe to an 80 mm × 80 mm × 1 mm square test piece obtained by vacuum drying at 80 °C for 5 hours, and the contact angle was measured 1 minute after the drop. Furthermore, the contact angle was measured using an FTA188 (manufactured by First Ten Angstrom).

[0074] [Antiviral efficacy test]

[0075] The determination of antiviral activity was basically carried out in accordance with JIS Z2801:2012 Antimicrobial Processed Products Antimicrobial Test.

[0076] The virus used was the SARS-CoV-2 / JP / Hiroshima-46059T / 2020 strain (Pango Lineage: B.1.1), and the cells used for culture were VeroE6 / TMPRSS2 cells (JCRB1819: purchased from the JCRB cell bank). Experiments were conducted at the P3 laboratory facility of the Graduate School of Medicine, Hiroshima University. Other viruses belonging to the SARS-CoV-2 species could also be used for evaluation.

[0077] The test strips were cut into 5cm squares, sterilized by soaking in 80% ethanol, and then dried in a biosafety cabinet while being blown with sterile air through a HEPA filter. 400μl of viral solution was added to the test strips, and a 4cm square ethanol-sterilized paraffin was placed over them to spread the viral solution evenly. The strips were then placed in a 23°C humidified chamber and allowed to react at room temperature for 0 or 24 hours before the viral solution was recovered. "0 hours" refers to recovering the virus within 1 minute of adding the viral solution to the test strip.

[0078] The reacted viral solution was serially diluted 10-fold with DMEM to obtain 10... -1 ~10 -8 The inoculum was diluted 1:1. 50 μl of each dilution was seeded into four wells of a 96-well plate. After 1 hour of adsorption, the inoculum was replaced with 100 μl / well of DMEM. Infection was determined after 3 days based on the appearance of cell degeneration. The 50% tissue culture infection dose (TCID) was calculated using the Behrens-Kraber algorithm. 50 ) / ml, set as the viral infection titer.

[0079] In the table, the viral infection titer is represented by the E designation (JIS X0210:1986).

[0080] [Antiviral test (FCV)]

[0081] The determination of antiviral activity was basically carried out in accordance with JIS Z2801:2012 Antimicrobial Processed Products Antimicrobial Test.

[0082] The virus used was feline calicivirus (FCV) F9 strain (ATCC VR-782), and the cells used for culture were CRFK cells (ATCC CCL-94). The experiments were conducted at the P2 laboratory facility of the Graduate School of Medicine, Hiroshima University.

[0083] The test strips were cut into 5cm squares and sterilized by irradiating the inside and outside with ultraviolet light for 30 minutes each in a biosafety cabinet. 400μl of viral solution was added to each strip, and then a 4cm square of ethanol-sterilized parafilm was placed over it to spread the viral solution evenly. The strips were then placed in a humidified chamber at 23°C and allowed to react at room temperature for 0 or 24 hours before the viral solution was recovered. A 0-hour timeframe means that the virus was recovered within one minute of adding the viral solution to the strip.

[0084] The reacted viral solution was serially diluted 10-fold with DMEM to obtain 10... -1 ~10 -8 The inoculum was diluted 1:1.5 times. 50 μl of each dilution was seeded into four wells of a 96-well plate. After 1 hour of adsorption, the inoculum was replaced with 100 μl / well of DMEM. Infection was determined after 5 days based on the appearance of cell degeneration. The 50% tissue culture infection dose (TCID) was calculated using the Behrens-Kraber algorithm. 50 ) / ml, set as the viral infection titer.

[0085] [Antiviral test (influenza virus)]

[0086] The antiviral activity was determined according to ISO 21702 (2019).

[0087] The virus used was influenza virus (INFLUENZA A VIRUS (H3N2): ATCC VR-1679). The experiment was conducted at the Boken Quality Evaluation Center. The test solution intake was 0.4 mL, and SCDLP medium was used as the wash solution. The "0 hour" refers to the recovery of the virus solution immediately after inoculation.

[0088] [Antiviral activity value]

[0089] The viral infection titer after 0 hours is set as Vb, and the viral infection titer after 24 hours is set as Vc. The antiviral activity value (Mv) after 24 hours and the viral reduction rate (%) after 24 hours are calculated by the following formula.

[0090] The antiviral activity value (Mv) after 24 hours is calculated as: lg10(Vb) - lg10(Vc).

[0091] Virus reduction rate (%) after 24 hours = [(Vb-Vc)×100] / Vb.

[0092] [Example 1]

[0093] The above-mentioned thermoplastic polyester elastomer (A-1) was used for evaluation.

[0094] [Example 2]

[0095] The virus species of Example 1 was modified using the above-described thermoplastic polyester elastomer (A-1) and evaluated.

[0096] [Example 3]

[0097] The virus species of Example 1 was modified using the above-described thermoplastic polyester elastomer (A-1) and evaluated.

[0098] [Example 4]

[0099] The above-mentioned thermoplastic polyester elastomer (A-2) was used for evaluation.

[0100] [Example 5]

[0101] The above-mentioned thermoplastic polyester elastomer (A-3) was used for evaluation.

[0102] [Example 6]

[0103] The evaluation was conducted using the aforementioned thermoplastic polyester elastomer (A-4).

[0104] [Example 7]

[0105] The above-mentioned thermoplastic polyester elastomer (A-5) was used for evaluation.

[0106] [Example 8]

[0107] The evaluation was conducted using the aforementioned thermoplastic polyester elastomer (A-6).

[0108] [Example 9]

[0109] The above-mentioned thermoplastic polyamide elastomer (C) was used for evaluation.

[0110] [Example 10]

[0111] The evaluation was conducted using the aforementioned thermoplastic polyester elastomer (A-7).

[0112] [Example 11]

[0113] The evaluation was conducted using the aforementioned thermoplastic polyester elastomer (A-8).

[0114] [Comparative Example 1]

[0115] The evaluation was conducted using the aforementioned PBT resin (B).

[0116] [Comparative Example 2]

[0117] Using the above-mentioned PBT resin (B), the virus species of Comparative Example 1 was changed and evaluated.

[0118] The materials, water absorption rate, contact angle, viral infection titers at 0 hours and 24 hours, antiviral activity values ​​after 24 hours, and viral reduction rates after 24 hours for the examples and comparative examples are shown in Tables 1 and 2.

[0119] As can be seen from Examples 1 to 9, thermoplastic polyester elastomers (A-1), (A-2), (A-3), (A-4), (A-5), (A-6), (A-7), (A-8) and thermoplastic polyamide elastomers (C) with contact angles below 80 degrees have a significant virus reduction effect.

[0120] Furthermore, as can be seen from Comparative Examples 1 and 2, the virus reduction effect is small for PBT resin (B) with a contact angle of 81 degrees or more.

[0121] Table 1

[0122]

[0123] Table 2

[0124]

Claims

1. Use of a resin composition comprising a hydrophilic polymer, having a water contact angle of 80 degrees or less, a water absorption rate of 25% or less, and an antiviral activity value of 2 or higher after 24 hours as an antiviral resin composition. The hydrophilic polymer comprises thermoplastic polyester elastomer or thermoplastic polyamide elastomer.

2. The use according to claim 1, characterized in that, The hydrophilic polymer comprises a thermoplastic polyester elastomer.

3. The use of a molded body made from a resin composition containing a hydrophilic polymer, a water contact angle of less than 80 degrees, a water absorption rate of less than 25%, and an antiviral activity value of more than 2 after 24 hours as an antiviral molded body. The hydrophilic polymer comprises thermoplastic polyester elastomer or thermoplastic polyamide elastomer.

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