TW202244112A - Antiviral resin composition comprising hydrophilic polymer, and molded body - Google Patents

Abstract

The purpose of the present invention is to provide an antiviral resin composition that is capable of exhibiting high antiviral properties by itself without adding an additive such as a metal oxide, that is resistant to water, and that can be processed into a molded body such as an injection-molded article, an extrusion-molded article, a film, a fiber, a non-woven fabric or a foam. The present invention pertains to an antiviral resin composition comprising a hydrophilic polymer, characterized by having a contact angle with water of 80 degrees or less, having a water absorption rate of 25% or less, and showing, after 24 hours, an antiviral activity value of 2 or more.

Description

Antiviral resin composition and molded article containing hydrophilic polymer

The present invention relates to an antiviral resin composition and a molded article.

In recent years, since infectious diseases caused by various viruses such as the new coronavirus have threatened human life, countermeasures against them are urgently needed globally. From this point of view, the demand for antiviral materials will only increase, and antiviral properties are required in all products.

Such an antiviral material is reported, for example, as in Patent Document 1 or Patent Document 2, in which a metal oxide composed of silver, copper, zinc, etc. is dispersed in a resin. However, there is a problem of so-called overflow of metal oxides. In addition, there is a problem that the mixed resin is deteriorated by metal oxides.

On the other hand, as in Patent Document 3, polyvinyl alcohol having an amine group has been reported as a polymer compound exhibiting antiviral properties without adding a metal oxide. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2018-172462 [Patent Document 2] Japanese Patent Laid-Open No. 2015-205998 [Patent Document 3] International Publication No. 2017/171066

[Problem to be solved by the invention]

However, polyvinyl alcohol having an amino group, which is a polymer compound of Patent Document 3, is water-soluble, so it has no resistance to water, and also has a problem of moldability, and it is considered that a new material is required.

The object of the present invention is to provide an antiviral resin composition, which can express high antiviral properties by itself without adding additives such as metal oxides, and is resistant to water, and can be processed as a molded product. Injection molded products, extrusion molded products, films, fibers, non-woven fabrics and foams. [Means to solve the problem]

The inventors of the present invention have found that a resin composition containing a hydrophilic polymer and having a water contact angle of 80 degrees or less exhibits antiviral properties by itself without adding additives such as metal oxides. Then, it was found that if the contact angle of water is 80 degrees or less and the water absorption rate is 25% or less, it is resistant to water.

That is, the present invention is an antiviral resin composition characterized by 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 after 24 hours. above. [Effect of Invention]

According to the present invention, it is possible to obtain an antiviral resin composition that exhibits high antiviral properties without spillage of metal oxides or deterioration due to metal oxides, is resistant to water, and has excellent molding processability. excellent.

[Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

The antiviral resin composition of the present invention contains a hydrophilic polymer, has a water contact angle of 80 degrees or less, and a water absorption rate of 25% or less. Because the contact angle of water is less than 80 degrees, it can inhibit virus activity, and because the water absorption rate is less than 25%, it is resistant to water and has excellent molding processability.

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

In the present invention, "antiviral property" means the property of inactivating pathogenic viruses. The antiviral property was evaluated by the antiviral activity value (Mv) after 24 hours or the virus reduction rate (%) after 24 hours as described below.

[Resin composition] The resin composition of the present invention includes a hydrophilic polymer, has a water contact angle of less than 80 degrees, and a water absorption rate of less than 25%. Since the larger the contact area with the virus, the better the contact angle of water is preferably 75 degrees or less. If the water absorption rate exceeds 25%, the swelling of the molded product will increase and the shape stability will deteriorate.

[Hydrophilic polymer] Specific examples of the hydrophilic polymer used in the present invention include hydrophilic polymers such as polyester resins, polyamide resins, polyimide resins, polyether resins, and polyurethane resins. Sexual resin. Among these, polyester-based resins can be preferably used. Preferred examples of polyester-based resins include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyhexamethylene terephthalate. Ester, polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate (polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate), polycyclic In addition to hexane-1,4-dimethylol terephthalate, thermoplastic polyester elastomer, etc., polyethylene isophthalate/terephthalate, polybutylene terephthalate/iso Copolyester of phthalate, polybutylene terephthalate/decane dicarboxylate, etc. Furthermore, "/" here means a copolymer. Among them, thermoplastic polyester elastomers and thermoplastic polyamide elastomers are preferred, and thermoplastic polyester elastomers are more preferred.

In addition, the hydrophilic polymer may be a polymer containing at least one kind of hydrophilic groups such as hydroxyl groups, carbonyl groups, amino groups, and carboxyl groups. Specific examples include polyethylene-based resins and polypropylene-based resins of hydrophobic resins obtained by imparting hydrophilic groups such as hydroxyl groups and carboxyl groups by corona treatment or plasma treatment. Furthermore, the hydrophilic polymer may be obtained by mixing two or more different polymers. As a specific example, a polymer having a water absorption rate of more than 25%, such as polyvinyl alcohol, may be mixed with a hydrophobic resin.

[Thermoplastic polyester elastomer] The thermoplastic polyester elastomer used in the present invention is a copolymer of a high melting point crystalline polymer segment and a low melting point polymer segment.

The high melting point crystalline polymer segment is a polyester formed of an aromatic dicarboxylic acid or its ester-forming derivative, and a diol or its ester-forming derivative.

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, Phenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate, etc. In the present invention, the aforementioned aromatic dicarboxylic acid is mainly used, but a part of the aromatic dicarboxylic acid may be substituted with 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, 4,4'-dicarboxylic acid, Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, or aliphatic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Furthermore, ester-forming derivatives of dicarboxylic acids, such as lower alkyl esters, aryl esters, carbonates, and acid halides, can also be used equally.

In this invention, 2 or more types of said acid components can be used. Examples thereof include combinations of terephthalic acid and isophthalic acid, terephthalic acid and dodecanedioic acid, and terephthalic acid and dimer acid.

Next, as specific examples of diols in the high melting point crystalline polymer segment, diols with a molecular weight of 400 or less are preferred, such as 1,4-butanediol, ethylene glycol, 1,3-propanediol, Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-dimethanol Alicyclic diols such as cyclohexane dimethanol and tricyclodecane dimethanol, and diols, bis (p-hydroxy) diphenyl, bis (p-hydroxy) diphenyl Propane, 2,2'-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]pyridine, 1,1-bis[4-( Aromatic diols such as 2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-p-terphenyl, and 4,4'-dihydroxy-p-quaterphenyl, which are also It can be used in the form of an ester-forming derivative, such as an acetylate, an alkali metal salt, or the like. These dicarboxylic acids, derivatives thereof, diol components and derivatives thereof may be used in combination of two or more.

The low-melting point polymer segment is an aliphatic polyether, but an aliphatic polyester or aliphatic polycarbonate may also be used in combination.

Specific examples of aliphatic polyethers include poly(ethylene oxide) glycol, poly(1,2-propylene oxide) glycol, and poly(propylene oxide) glycol. glycol), poly(1,3-propylene oxide) glycol (poly(trimethylene oxide) glycol), poly(1,4-butylene oxide) glycol (poly(tetramethylene oxide) glycol), poly(1, 6-epoxy hexane) diol (poly(hexamethylene oxide) glycol), poly(1,9-epoxynonane) diol (poly(nonamethylene oxide) glycol), ethylene oxide and 1,2-cyclo Copolymer of propylene oxide, copolymer of 1,4-butylene oxide and 1,6-hexane oxide, copolymer of 1,4-butylene oxide and 1,9-epoxynonane, poly( 1,2-propylene oxide) adducts of ethylene oxide, and copolymers of ethylene oxide and tetrahydrofuran, etc. Among these, ethylene oxide adducts and/or cyclic compounds containing poly(1,4-butylene oxide) diol and/or poly(1,2-propylene oxide) diol are preferred. Copolymer of ethylene oxide and tetrahydrofuran. Among them, ethylene oxide adducts containing poly(1,4-butylene oxide)diol and poly(1,2-propylene oxide)diol are preferred. Furthermore, for example, poly(1,2-propylene oxide) glycol is poly(1,2-propylene oxide) or polypropylene glycol, and poly(1,4-epoxybutylene) glycol is poly(1,4- Butylene oxide) or polytetramethylene ether glycol.

Moreover, it is preferable that the number average molecular weight of these aliphatic polyethers is 300-6000 in the state already copolymerized. The number average molecular weight can be determined using general organic analysis.

Specific examples of the aliphatic polyester include poly(ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and the like. The aliphatic polycarbonate is preferably mainly composed of aliphatic diol residues having 2 to 12 carbon atoms. Examples of such aliphatic diols include 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, 2-methyl-1,8-octanediol, etc.

Regarding the copolymerization ratio of the high melting point crystalline polymer segment and the low melting point polymer segment, the larger the ratio of the low melting point segment is, the more preferable it is. Specifically, the copolymerization ratio of the low-melting point polymer segment 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 It is more than 40%, more preferably more than 45%, more preferably more than 50%.

In addition, the copolymerization ratio of the low-melting-point segment here means the ratio of the low-melting-point segment unit which is a diol component in a low-melting-point segment. That is, it is the ratio of the amount of water molecules formed by the formation of ester bonds from the low melting point segment components of the raw material to the total amount of the copolymer including the low melting point segment, expressed in % by mass. If the composition of the raw material is known, it can be calculated directly. Moreover, it can obtain|require by performing structural analysis of the copolymer containing a low melting point segment by NMR.

The antiviral composition of the present invention is only composed of hydrophilic polymers, and antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, surfactants, lubricants, Additives for dyes, pigments, plasticizers, flame retardants, etc., or talc, mica, glass flakes, calcium carbonate, clay, barium sulfate, glass beads, glass fibers, carbon fibers, cellulose nanofibers, etc. Reinforcement material.

Specific examples of the virus of the present invention include influenza virus, coronavirus, SARS-CoV-2, hepatitis C virus, Japanese encephalitis virus, Zika virus, rubella virus, measles Viruses, 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, cat Feline calicivirus, adenovirus, hepatitis A virus, poliovirus, coxsackievirus, enterovirus, rotavirus, parvovirus, astrovirus, Sapovirus, etc.

The molding system of the present invention is formed by processing the antiviral resin composition of the present invention. Specific forms of the molded article of the present invention include injection molded articles, extrusion molded articles, films, fibers, non-woven fabrics, foams, and the like.

The antiviral resin composition of the present invention can be preferably used for the outer layer of an article to which antiviral properties are to be imparted. That is, it is preferable to provide a method of providing an article having antiviral properties, the aforementioned method including the step of providing an outer layer of the article, and the aforementioned outer layer comprising the antiviral resin composition of the present invention. Here, the outer layer refers to the surface layer of a molded product formed by overlapping two or more layers, or the exposed surface of a single-layer molded product, and examples include film layers of in-mold molded products and two-color molded products. The layer that will be touched by people, the exposed surface of the uncoated mask, etc.

Also, it is preferable to use the antiviral resin composition of the present invention on the outer layer of an article, which is used to impart antiviral properties to the surface of the article.

In addition, the use of the antiviral resin composition of the present invention includes wallpaper, flooring materials, curtains, clothes, trash cans, food packaging materials, bandages, masks, bandages, tableware, furniture, toys, bathroom components , toilet components, kitchen components, home appliances, filters (air filters), bedding (blankets, quilts, sheets), seats for seats (vehicle seats, train seats, airplane seats, home cushions) , hanging rings, handrails, sponges (for cleaning, dishwashing, filter materials), diapers, cleaning tools, pollution diffusion prevention materials, automotive interior materials, etc.

In the present invention, "antiviral property" means the property of inactivating pathogenic viruses. The antiviral property was evaluated by the antiviral activity value Mv after 24 hours or the virus reduction rate (%) after 24 hours. [Example]

The effect of the present invention is illustrated below by means of examples. Furthermore, % and parts in the examples are all based on mass unless specified. In addition, the physical properties shown in an Example were measured as mentioned later.

[Thermoplastic polyester elastomer (A-1)] Feed 270.0 parts of terephthalic acid, 234.0 parts of 1,4-butanediol, 0.1 part of tetrabutyl titanate, mono-n-butyl-monohydroxide tin 0.1 part, the esterification reaction was started at 160° C. and a reduced pressure of 700 mmHg. Then, while gradually raising the temperature, 59.0 parts of 1,4-butanediol were additionally added continuously. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction, 1.8 parts of tetrabutyl titanate as a polycondensation catalyst and 1.0 part of "IRGANOX" 1330 (manufactured by BASF Corporation) as a stabilizer were added to the esterification reactor. After adding 686.0 parts of poly(1,4-butylene oxide) glycol with an average molecular weight of 1400, the above-mentioned esterification reaction product was moved from the esterification tank to the polycondensation tank. Then, while the reaction system in the polycondensation tank was stirred and polymerized, it took 1 hour from normal pressure to a high vacuum degree below 1 mmHg to gradually make it a decompression system, and at the same time, the temperature was raised to 245° C., On the other hand, polycondensation was carried out at 245° C. and 1 mmHg or less for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-1).

[Thermoplastic polyester elastomer (A-2)] 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-monohydroxide are fed to the esterification tank with rectification tower and mixer. The esterification reaction was started at 160° C. under a reduced pressure of 650 mmHg. Then, while gradually increasing the temperature, further continuously adding 81.0 parts of 1,4-butanediol, the degree of reduced pressure was changed to 500 mmHg from the middle of the reaction. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction, 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 reactor. After adding 354.0 parts of poly(1,4-butylene oxide) diol with an average molecular weight of 1400, the above-mentioned esterification reaction product was moved from the esterification tank to the polycondensation tank. Then, while the reaction system in the polycondensation tank was stirred and polymerized, it took 1 hour from normal pressure to a high vacuum degree below 1 mmHg to gradually make it a decompression system, and at the same time, the temperature was raised to 245° C., On the other hand, polycondensation was carried out at 245° C. and 1 mmHg or less for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-2).

[Thermoplastic polyester elastomer (A-3)] 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-monohydroxide are fed to the esterification tank with rectification tower and mixer. The esterification reaction was started at 160° C. under a reduced pressure of 500 mmHg. Then, while gradually raising the temperature, 96.0 parts of 1,4-butanediol were additionally added continuously. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction, 1.5 parts of tetrabutyl titanate as a polycondensation catalyst and 0.5 parts of "IRGANOX" 1098 (manufactured by BASF Corporation) as a stabilizer were added to the esterification reactor. After adding 231.0 parts of poly(1,4-butylene oxide) glycol with an average molecular weight of 1400, the above-mentioned esterification reaction product was moved from the esterification tank to the polycondensation tank. Then, while the reaction system in the polycondensation tank was stirred and polymerized, it took 1 hour from normal pressure to a high vacuum degree below 1 mmHg to gradually make it a decompression system, and at the same time, the temperature was raised to 245° C., On the other hand, polycondensation was carried out at 245° C. and 1 mmHg or less for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-3). [Thermoplastic polyester elastomer (A-4)] 340.0 parts of terephthalic acid, 100 parts of isophthalic acid, 296.0 parts of 1,4-butanediol, 0.3 parts of tetrabutyl titanate, mono-n-butyl-mono 0.1 part of tin oxyhydroxide was used, and the esterification reaction was started at 160° C. and a reduced pressure of 500 mmHg. Then, while gradually raising the temperature, 74.0 parts of 1,4-butanediol was additionally added continuously. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction, 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 reactor. After adding 495.0 parts of poly(1,4-butylene oxide) diol with an average molecular weight of 1400, the above-mentioned esterification reaction product was moved from the esterification tank to the polycondensation tank. Then, while the reaction system in the polycondensation tank was stirred and polymerized, it took 1 hour from normal pressure to a high vacuum degree below 1 mmHg to gradually make it a decompression system, and at the same time, the temperature was raised to 245° C., On the other hand, polycondensation was carried out at 245° C. and 1 mmHg or less for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-4). [Thermoplastic polyester elastomer (A-5)] Feed to the reaction vessel equipped with ribbon-type stirring blades is 312 parts of dimethyl terephthalate and 91 parts of dimethyl isophthalate, which are high melting point crystalline polymer segments composed of crystalline aromatic polyester, 537 parts of ethylene oxide adducts of poly(1,2-propylene oxide) diol with a number average molecular weight of 2150 and 1,4 - 167 parts of butanediol and 4 parts of tetrabutoxide titanium (titanium butoxide), heated at 190 to 225° C. for 3 hours to distill methanol out of the system. After adding 2 parts each of "IRGANOX" 1098 and 1019 (manufactured by BASF Corporation) to the reaction mixture, the temperature was raised to 243° C., and the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out for 3 hours under this condition. , to obtain a thermoplastic polyester elastomer (A-5). [Thermoplastic polyester elastomer (A-6)] 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-monohydroxide are fed to the esterification tank with rectification tower and mixer. The esterification reaction was started at 160° C. under a reduced pressure of 650 mmHg. Then, while gradually increasing the temperature, further continuously adding 81.0 parts of 1,4-butanediol, the degree of reduced pressure was changed to 500 mmHg from the middle of the reaction. A transparent reaction product was obtained 3 hours and 40 minutes after the start of the reaction, and the reaction was terminated. After the esterification reaction, 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 reactor. After adding 354.0 parts of a copolymer of 1,4-epoxybutylene and 1,9-epoxynonane with an average molecular weight of 1400, the above-mentioned esterification reaction product was moved from the esterification tank to the polycondensation tank. Then, while the reaction system in the polycondensation tank was stirred and polymerized, it took 1 hour from normal pressure to a high vacuum degree below 1 mmHg to gradually make it a decompression system, and at the same time, the temperature was raised to 245° C., On the other hand, polycondensation was carried out at 245° C. and 1 mmHg or less for 3 hours and 30 minutes to obtain a thermoplastic polyester elastomer (A-6).

[Thermoplastic polyester elastomer (A-7)] 269 parts of dimethyl terephthalate, which is a high-melting crystalline polymer segment composed of crystalline aromatic polyester, and 269 parts of dimethyl terephthalate composed of aliphatic polyether units are fed to a reaction vessel equipped with a ribbon-type stirring blade. 725.0 parts of poly(1,4-butylene oxide) diol, 92.4 parts of 1,4-butanediol, 4 parts of tetrabutoxytitanium, the number average molecular weight of the low-melting point polymer segment is 2000, in The methanol was distilled out of the system by heating at 190-225° C. for 3 hours. After adding 1.5 parts each of "IRGANOX" 1098 and 1019 (manufactured by BASF Corporation) to the reaction mixture, the temperature was raised to 243° C., and the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out for 3 hours under this condition. , to obtain a thermoplastic polyester elastomer (A-7). [Thermoplastic polyester elastomer (A-8)] 595 parts of dimethyl terephthalate, which is a high-melting crystalline polymer segment composed of crystalline aromatic polyester, and 595 parts of dimethyl terephthalate composed of aliphatic polyether units are fed to a reaction vessel equipped with a ribbon-type stirring blade. 353.0 parts of poly(1,4-butylene oxide) diol with a number average molecular weight of 1000 of the low-melting point polymer segment, 518 parts of 1,4-butanediol, 4 parts of tetrabutoxytitanium, in The methanol was distilled out of the system by heating at 190-225° C. for 3 hours. After adding 1.5 parts each of "IRGANOX" 1098 and 1019 (manufactured by BASF Corporation) to the reaction mixture, the temperature was raised to 243° C., and the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out for 3 hours under this condition. , to obtain a thermoplastic polyester elastomer (A-7). [PBT resin (B)] Toraycon™1100S (manufactured by TORAY Co., Ltd.). Polymer of terephthalic acid and 1,4-butanediol.

[Thermoplastic polyamide elastomer (C)] 98.00 parts of 12-aminododecanoic acid and 7.66 parts of adipic acid were fed to the pressure vessel. After nitrogen substitution, while gradually heating while supplying nitrogen gas, polymerization was carried out at 230° C. for 4 hours to synthesize an oligomer of nylon 12 . To this oligomer, 642.5 parts of poly(1,4-butylene oxide) glycol with an average molecular weight of 1800, 0.20 parts of tetrabutyl zirconate and antioxidant "IRGANOX" 1098 (manufactured by BASF Corporation) were fed into the oligomer. ) 0.50 parts. After nitrogen substitution, gradually heat while supplying nitrogen gas, and heat at 210° C. for 3 hours, then gradually reduce the pressure to 50 Pa over 1 hour, perform polymerization for 2 hours, and then further increase the temperature over 30 minutes. Under reduced pressure, polymerization was carried out at 230° C. and 30 Pa for 3 hours to obtain a thermoplastic polyamide elastomer (C).

[Molding of test piece] Injection molding was performed using an injection molding machine NEX-1000 manufactured by NISSEI PLASTIC INDUSTRIAL CO., LTD., and a square plate-shaped test piece of 80 mm×80 mm×1 mm was obtained from the pellets. Since it can be injection molded, it can be processed into injection molded products, extrusion molded products, films, fibers, nonwoven fabrics, and foams.

[Measurement of water absorption] After immersing the 80mm×80mm×1mm square plate-shaped test piece obtained by vacuum drying at 80°C for 5 hours in 23°C water for 24 hours, divide the weight difference of the test piece before and after immersion by the weight of the test piece before treatment And the value expressed as a percentage.

[Measurement of contact angle] The measurement of the contact angle is basically carried out in accordance with JISR3257. About 2 μL of purified water was dropped using a syringe to a square plate-shaped test piece of 80 mm×80 mm×1 mm obtained by vacuum drying at 80° C. for 5 hours, and the contact angle was measured 1 minute after the drop. In addition, the measurement of a contact angle used FTA188 (made by First Ten Angstrom).

[Antiviral test] The measurement of antiviral activity is basically carried out in accordance with JISZ2801:2012 antibacterial activity test of antibacterial processed products.

SARS-CoV-2/JP/Hiroshima-46059T/2020 strain (Pango Lineage: B.1.1) was used as the virus system, and VeroE6/TMPRSS2 cells (purchased from JCRB1819: JCRB Cell Bank) were used as the cultured cell line. The experiment was carried out at the P3 Experimental Facility of the Graduate School of Medical Sciences, Hiroshima University. Viruses may also be evaluated for other viruses belonging to the species of SARS-CoV-2.

The test piece was cut into 5 cm squares, immersed in 80% ethanol for disinfection, and then dried while blowing sterile air through the HEPA filter in the safety console. 400 μl of the virus liquid was dropped onto the test piece, and covered with ethanol-sterilized parafilm (Parafilm) (4 cm square) from above to spread the virus liquid evenly. Put it into a humid box at 23 degrees, and after allowing it to react at room temperature for 0 or 24 hours, recover the virus liquid. 0 hour means that the virus was recovered within 1 minute after the virus solution was dropped on the test piece.

The reacted virus solution was serially diluted 10-fold with DMEM to obtain a ^10-1 to ^10-8 -fold dilution. Cells in 4 wells of a 96-well plate were inoculated with 50 μl of each dilution, and after 1 hour of adsorption, the inoculum was exchanged with 100 μl/well of DMEM. After 3 days, the appearance of cytopathic effect was used as an index to determine the infection, and the 50% tissue culture infection dose (TCID ₅₀ )/ml was calculated using the Behrens-Kraber algorithm, which was regarded as the infection rate of the virus. In the table, the virus infectivity is expressed in E notation (JIS X0210:1986).

[Antiviral test (FCV)] The measurement of antiviral activity is basically carried out in accordance with JISZ2801:2012 antibacterial activity test of antibacterial processed products.

Feline calicivirus (FCV) F9 strain (ATCC VR-782) was used as the virus system, and CRFK cells (ATCC CCL-94) were used as the cultured cell line. The experiment was carried out at the P2 Experimental Facility of the Graduate School of Medical Sciences, Hiroshima University.

Cut the test piece into 5 cm squares, and irradiate ultraviolet rays for 30 minutes on the inside and outside of the safety console for disinfection. 400 μl of the virus liquid was dropped onto the test piece, and covered with an ethanol-sterilized paraffin film (4 cm square) from above to spread the virus liquid evenly. Put it into a humid box at 23 degrees, and after allowing it to react at room temperature for 0 or 24 hours, recover the virus liquid. 0 hour means that the virus was recovered within 1 minute after the virus solution was dropped on the test piece.

The reacted virus solution was serially diluted 10-fold with DMEM to obtain a ^10-1 to ^10-8 -fold dilution. Cells in 4 wells of a 96-well plate were inoculated with 50 μl of each dilution, and after 1 hour of adsorption, the inoculum was exchanged with 100 μl/well of DMEM. After 5 days, the appearance of cytopathic effect was used as an index to determine the infection, and the 50% tissue culture infection dose (TCID ₅₀ )/ml was calculated using the Behrens-Kraber algorithm, which was regarded as the infection rate of the virus.

[antiviral test (influenza virus)] The determination of antiviral activity is carried out according to ISO21702 (2019).

As virus system, influenza virus (INFLUENZA A VIRUS (H3N2): ATCC VR-1679) was used. The experiment was conducted at the BOKEN Quality Evaluation Institute, a general incorporated foundation in Japan. The intake volume of the test solution was 0.4 mL, and the SCDLP medium was used as the cleaning solution. In addition, 0 hours means that the virus liquid was recovered immediately after inoculation.

[Antiviral activity value] The antiviral activity value (Mv) after 24 hours and the virus reduction rate (%) after 24 hours are to make the virus infection value after 0 hours be Vb, make the virus infection value after 24 hours be Vc, and by the following Find out the formula. Antiviral activity value (Mv)=lg10(Vb)-lg10(Vc) after 24 hours Virus reduction rate (%)=[(Vb-Vc)×100]/Vb after 24 hours.

[Example 1] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-1).

[Example 2] Using the above-mentioned thermoplastic polyester elastomer (A-1), the virus type in Example 1 was changed and evaluated.

[Example 3] Using the above-mentioned thermoplastic polyester elastomer (A-1), the virus type in Example 1 was changed and evaluated.

[Example 4] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-2).

[Example 5] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-3).

[Example 6] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-4).

[Example 7] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-5).

[Example 8] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-6).

[Example 9] Evaluation was performed using the above-mentioned thermoplastic polyamide elastomer (C).

[Example 10] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-7).

[Example 11] Evaluation was performed using the above-mentioned thermoplastic polyester elastomer (A-8).

[Comparative example 1] Evaluation was performed using the above-mentioned PBT resin (B).

[Comparative example 2] Using the above-mentioned PBT resin (B), the virus species of Comparative Example 1 was changed and evaluated.

Tables 1 and 2 show the materials, water absorption, contact angles, virus infection values at 0 hours and 24 hours, antiviral activity values after 24 hours, and virus reduction rates after 24 hours in Examples and Comparative Examples.

From Examples 1 to 9, it can be seen that the thermoplastic polyester elastomers (A-1), (A-2), (A-3), (A-4), (A-5) with a contact angle of 80 degrees or less , (A-6), (A-7), (A-8) and thermoplastic polyamide elastomer (C), which are highly effective in reducing viruses.

Also, from Comparative Examples 1 and 2, it can be seen that the PBT resin (B) having a contact angle of 81 degrees or more has a small virus reduction effect.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Material Thermoplastic Polyester Elastomer (A-1) 100 100 100 Thermoplastic Polyester Elastomer (A-2) 100 Thermoplastic Polyester Elastomer (A-3) 100 Thermoplastic Polyester Elastomer (A-4) 100 Thermoplastic Polyester Elastomer (A-5) Thermoplastic Polyester Elastomer (A-6) Thermoplastic Polyester Elastomer (A-7) Thermoplastic Polyester Elastomer (A-8) Thermoplastic Polyamide Elastomer (C) PBT resin (B) virus type SARS-CoV-2 Influenza FCV SARS-CoV-2 SARS-CoV-2 SARS-CoV-2 Water absorption (%) 0.7 0.7 0.7 0.4 0.5 0.3 Contact angle (ﾟ) 70 70 70 75 76 75 virus infection price 0 hours (Vb) 2.0E+07 3.3E+05 6.3E+06 6.3E+07 3.6E+07 6.3E+07 24 hours (Vc) 6.3E+02 6.3E+00 3.6E+03 6.3E+04 1.1E+05 6.3E+01 Virus reduction rate after 24 hours (%) 99.9968 99.9981 99.9438 99.9000 99.6838 99.9999 Antiviral activity value (Mv) after 24 hours 4.5 4.7 3.3 3.0 2.5 6.0

[Table 2] Example 7 Example 8 Example 9 Example 10 Example 11 Comparative example 1 Comparative example 2 Material Thermoplastic Polyester Elastomer (A-1) Thermoplastic Polyester Elastomer (A-2) Thermoplastic Polyester Elastomer (A-3) Thermoplastic Polyester Elastomer (A-4) Thermoplastic Polyester Elastomer (A-5) 100 Thermoplastic Polyester Elastomer (A-6) 100 Thermoplastic Polyester Elastomer (A-7) 100 Thermoplastic Polyester Elastomer (A-8) 100 Thermoplastic Polyamide Elastomer (C) 100 PBT resin (B) 100 100 virus type SARS-CoV-2 SARS-CoV-2 SARS-CoV-2 SARS-CoV-2 SARS-CoV-2 SARS-CoV-2 Influenza Water absorption (%) 4.5 0.4 0.4 0.7 0.4 0.1 0.1 Contact angle (ﾟ) 45 75 73 67 74 81 81 virus infection price 0 hours (Vb) 3.6E+07 6.3E+07 2.0E+07 3.6.E+07 3.6.E+07 2.0E+08 4.9E+05 24 hours (Vc) 1.1E+02 2.0E+03 2.0E+03 6.3.E+01 1.1.E+05 2.0E+07 9.5E+04 Virus reduction rate after 24 hours (%) 99.9997 99.9968 99.9900 99.9998 99.6838 90.0000 80.5016 Antiviral activity value (Mv) after 24 hours 5.5 4.5 4.0 5.8 2.5 1.0 0.7

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Claims (3)

An antiviral resin composition characterized by 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 more after 24 hours. The antiviral resin composition according to claim 1, wherein the hydrophilic polymer comprises thermoplastic polyester elastomer. A molded body formed by processing the antiviral resin composition as claimed in claim 1 or 2.