Anti-coronavirus agents

Abstract

The purpose of the present invention is: to provide an anti-coronavirus agent; and others. Provided is an anti-coronavirus agent which comprises a polymer containing at least one structural unit (a) selected from a structural unit represented by general formula (1), a structural unit that is a salt of general formula (1) and a structural unit represented by general formula (2). (In general formula (1) and general formula (2), R1, R2 and R3 independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R4 to R8 independently represent a hydrogen atom or an organic group; X represents a bivalent linking group; and Y- represents an anion.)

Description

[Technical field]

[0001] The present invention relates to an anti-coronavirus agent, etc. More specifically, the present invention relates to an anti-coronavirus agent, etc. containing a specific polymer (polymer, copolymer, amino group-containing copolymer). [Background technology]

[0002] Various antiviral agents have been proposed for the prevention of viral infections. For example, Patent Document 1 discloses that a nanostructure composed of a block copolymer containing a specific ammonium moiety can be used as an antiviral agent. For example, Patent Document 2 discloses that a fiber composition composed of a combination of amino acid silver, amino acid zinc, carboxyvinyl polymer, and copper glutamate has antiviral properties against influenza viruses. Furthermore, Non-Patent Document 1 describes that a specific polyamidepolyamine compound has antiviral properties against various viruses. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-011578 [Patent Document 2] JP 2020-012214 A [Non-patent literature]

[0004] [Non-Patent Document 1] Manuela D. et al. P6315-6319 Vol.58 Oct.2014 Antimicrobial Agents and Chemotherapy. Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, antiviral agents containing a specific amino group are known, but there has been a demand for antiviral agents that are also highly effective against coronaviruses, particularly the new coronavirus, etc. An object of the present invention is to provide an antiviral agent that can exert an antiviral effect also against the new coronavirus, etc. [Means for solving the problem]

[0006] The present inventors have conducted various investigations to achieve the above object and have arrived at the present invention.

[0007] That is, the present invention relates to the following inventions. [1] An anti-coronavirus agent (anti-coronavirus composition) comprising a polymer including at least one structural unit (a) selected from a structural unit represented by the following general formula (1), a structural unit which is a salt of the following general formula (1), and a structural unit represented by the following general formula (2): [ka] [ka] (In general formula (1) and general formula (2), R1, R2, and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R4 to R8 each independently represent a hydrogen atom or an organic group, and X represents a divalent linking group. Y - represents an anion.) [2] The polymer further has a Hildebrand solubility parameter of 35 (MPa) 1 / 2 The anti-coronavirus agent according to [1], which comprises a structural unit (b) which is: [3] The anti-coronavirus agent according to [1] or [2], wherein the polymer further contains a structural unit (b) represented by the following general formula (3): [ka] (In general formula (3), R1, R2, and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X represents a divalent linking group, and R9 represents a hydrocarbon group having 2 or more carbon atoms which may have a substituent.) [4] The Hildebrand solubility parameter of the polymer is 8-30 (MPa) 1 / 2 The agent according to any one of [1] to [3], [5] The polymer further has a Hildebrand solubility parameter of 32 (MPa). 1 / 2 The polymer has a Hildebrand solubility parameter of 10 to 25 (MPa). 1 / 2 The agent according to any one of [1] to [4], [6] The agent according to any one of [2] to [5], wherein the structural unit (a) contains a structural unit derived from an N-mono- or dialkylaminoalkyl (meth)acrylate, and the structural unit (b) contains a structural unit derived from an alkyl (meth)acrylate ester. [7] The agent according to any one of [1] to [6], wherein in the polymer, the proportion of the structural unit (a) is 30% by mass or more and the proportion of the structural unit (b) is 1% by mass or more, relative to 100% by mass of all structural units. [8] In the polymer, the proportion of structural units (a) is 50% by mass or more and the proportion of structural units (b) is 5% by mass or more relative to 100% by mass of all structural units, and the Hildebrand solubility parameter of the polymer is 12 to 23 (MPa). 1 / 2 The agent according to any one of [1] to [7], [9] The agent according to any one of [1] to [8], comprising a polymer at a concentration of 0.01% by mass or more.

[10] The agent according to any one of [1] to [9], which is in the form of an aqueous solution containing a polymer [for example, an aqueous solution having a pH of 2 to 11 (for example, 4 to 9)].

[11] A method for inactivating (killing) coronavirus and / or suppressing the proliferation of coronavirus, using an agent (or composition) according to any one of [1] to

[10] .

[0008] Specifically, the present invention may be an anti-coronavirus agent containing a polymer (polymer, copolymer, amino group-containing copolymer) having at least one structural unit (a) [structural unit (a) derived from an amino group-containing monomer] selected from a structural unit represented by the following general formula (1), a structural unit which is a salt of the following general formula (1) (e.g., a salt with an acid), and a structural unit represented by the following general formula (2): In particular, the present invention may be an anti-coronavirus agent comprising a polymer (polymer, copolymer, amino group-containing copolymer) characterized by comprising at least one structural unit (a) [structural unit (a) derived from an amino group-containing monomer] selected from a structural unit represented by the following general formula (1), a structural unit which is a salt of the following general formula (1) (e.g., a salt with an acid), and a structural unit represented by the following general formula (2), and another structural unit (b) [structural unit (b) derived from a monomer containing a hydrocarbon group having two or more carbon atoms] represented by the following general formula (3).

[0009] [ka]

[0010] [ka]

[0011] (In general formula (1) and general formula (2), R1, R2, and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R4 to R8 each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms, and X represents a divalent linking group. Y - represents an anion. However, an asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by general formula (1) or general formula (2) is bonded.)

[0012] [ka]

[0013] (In general formula (3), R1, R2, and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X represents a divalent linking group, and R9 represents a hydrocarbon group having 2 or more carbon atoms which may have a substituent. Here, the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by general formula (3) is bonded.) The present invention includes a method for disinfecting or inactivating (killing a virus) by using (applying and attaching to an application site) the copolymer (anti-coronavirus agent, anti-viral agent) to disinfect or inactivate (kill a virus) a virus (particularly a coronavirus such as the novel coronavirus). Effect of the Invention

[0014] An anti-coronavirus agent containing the polymer (amino group-containing copolymer) of the present disclosure has antiviral properties against coronaviruses, particularly SARS-CoV-2. For example, the polymer (amino group-containing copolymer) of the present disclosure can be used alone or as a composition with other compounds as a product having antiviral properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present disclosure will be described in detail below. In addition, a combination of two or more of the individual preferred embodiments of the present disclosure described below is also a preferred embodiment of the present disclosure.

[0016] [Amino group-containing polymer (copolymer)] The anti-coronavirus agent of the present disclosure includes a polymer having at least a specific structural unit [structural unit (a), a structural unit derived from an amino group-containing monomer]. Such structural units (polymers having such structural units) are likely to act on the coronavirus envelope and therefore are likely to efficiently exert anti-coronavirus functions. In addition, although such structural units (polymers having such structural units) have amino groups or ammonium bases, they are often relatively safe (e.g., less skin irritation and skin sensitization).

[0017] The polymer may have other structural units (structural units different from the structural unit (a)) in addition to the structural unit (a). Typically, in one preferred embodiment, the anti-coronavirus agent includes a copolymer including a structural unit derived from an amino group-containing monomer and a specific structural unit [structural unit (b), a structural unit derived from a hydrophobic monomer (may be referred to as a hydrophobic unit, etc.)]. By incorporating such other structural units in the polymer, the polymer can exhibit even better anti-coronavirus function.

[0018] Incidentally, it has been known that polymers that exhibit antibacterial properties against bacteria exist. On the other hand, viruses are much smaller than bacteria (typical bacteria are 1-2 μm, while coronaviruses are around 0.1 μm), and their outermost structure is a capsid or envelope structure rather than a membrane. Due to these structural differences, it is not believed that antibacterial polymers necessarily have antiviral properties.

[0019] In this situation, it has been found that the polymer of the present disclosure can unexpectedly exhibit antiviral, particularly anti-coronavirus, functions (particularly excellent anti-coronavirus functions). The reason for this is unclear, but for example, in a polymer having other structural units in addition to the function of the structural unit (a) as described above, the structural unit (a) and the other structural units are clearly separated, and the penetration of the other structural units (hydrophobic portions) into the coronavirus (and further the action and contact of the structural unit (a) with the envelope) is easily and efficiently performed, and further, combined with the high anti-coronavirus function of the structural unit (a) as described above, it is believed that a synergistically excellent anti-coronavirus function can be exhibited. Furthermore, it is believed that by controlling the molecular weight within an appropriate range, the hydrophobic portion can efficiently penetrate the envelope of a minute coronavirus, thereby more efficiently exhibiting the function.

[0020] The above polymer may be referred to as the polymer, copolymer, etc. of the present disclosure.

[0021] <Structural unit (a) (structural unit derived from amino group-containing monomer)> In the present disclosure, the structural unit (a) (structural unit derived from an amino group-containing monomer) is represented by a structural unit of the following general formula (1), a structural unit which is a salt of the following general formula (1) (e.g., a salt with an acid), and / or a structural unit of the following general formula (2).

[0022] [ka]

[0023] [ka]

[0024] In general formula (1) or (2), R1, R2, and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R4 to R8 each independently represent a hydrogen atom or an organic group (e.g., an organic group having 1 to 12 carbon atoms), and X represents a divalent linking group. Y - represents an anion. Here, an asterisk (*) represents an atom contained in a structural unit represented by general formula (1), a structural unit which is a salt of general formula (1), or another structural unit of the same or different type to which a structural unit represented by general formula (2) is bonded. In the present disclosure, "an atom contained in another structural unit of the same type" refers to, for example, a structural unit represented by general formula (1), an atom contained in another structural unit represented by general formula (1), and "an atom contained in another structural unit of a different type" refers to, for example, a structural unit represented by general formula (1), an atom contained in a structural unit other than the structural unit represented by general formula (1).

[0025] The structure derived from the amino group-containing monomer can be formed, for example, by radical polymerization of a monomer having an ethylenically unsaturated group and a primary to tertiary amino group represented by the following general formula (4), or a neutralized product of a primary to tertiary amino group with an acid, or a quaternary ammonium salt group represented by the following general formula (5), but is not limited thereto.

[0026] [ka]

[0027] [ka]

[0028] R4 to R8 in the general formula (4) and the general formula (5) are the same as R4 to R8 in the general formula (1) and the general formula (2).

[0029] In general formula (1) or (2), R1 and R2 may preferably be a hydrogen atom, and R3 may preferably be a hydrogen atom or a methyl group. In the general formulae (1) and (2) (and further (4) and (5)), examples of the organic group include organic groups having 1 to 12 carbon atoms. Examples of the organic group having 1 to 12 carbon atoms include hydrocarbon groups [e.g., alkyl groups (e.g., methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, s-butyl groups, t-butyl groups, etc. 1-12 Alkyl groups, preferably C 1-8 Alkyl groups, more preferably C 1-4 Alkyl groups, alkenyl groups (e.g., vinyl groups, allyl groups, etc.) 2-12 Aliphatic hydrocarbon groups such as alkenyl groups, etc.

[0030] The organic group (hydrocarbon group, etc.) may have a substituent such as a hydroxy group or a halogen atom.

[0031] In formula (1) or (2), R4, R5, R6, R7 and R8 may preferably be a hydrogen atom or a hydrocarbon group (for example, an alkyl group). In addition, R4 and R5 in formula (1), and R6, R7 and R8 in formula (2) may be the same or different, and two of them may be bonded to each other or one of them and X may be bonded to each other to form a ring together with the nitrogen atom (N), or they may not form a ring.

[0032] In the general formula (1) or (2), X, which is a divalent linking group, is, for example, a direct bond, an ether group (or an ether bond, -O-), a thioether group (or a thioether bond, -S-), a group containing a carbonyl group (such as a carbonyl group, an ester group, an amide group, or a urethane group), a hydrocarbon group [for example, an alkylene group or an alkylidene group (such as a methylene group, an ethylene group, a trimethylene group, a propylene group, or a tetramethylene group, etc. 1-20 An alkylene or alkylidene group, preferably C 1-12 An alkylene or alkylidene group, more preferably C 1-8alkylene or alkylidene groups)], and groups in which two or more of these are bonded together {for example, groups in which a hydrocarbon group (an alkylene group or an alkylidene group, etc.) such as a group represented by -C(=O)-OR- [wherein R is a hydrocarbon group (for example, an alkylene group or an alkylidene group such as an ethylene group)] is bonded to another group, etc.}.

[0033] The hydrocarbon group may have a substituent such as a hydroxy group or a halogen atom.

[0034] Incidentally, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, etc. do not usually become X directly, but often become X as a group bonded to a hydrocarbon group, etc. [and further not bonded to the nitrogen atom (N) of formula (1) or (2) (in other words, a hydrocarbon group, etc. is bonded to the nitrogen atom (N) of formula (1) or (2)].

[0035] In particular, X is preferably a group in which a carbonyl group and an alkylene group or an alkylidene group are bonded to each other by an ester bond (-C(=O)-OR-, where R is an alkylene group or an alkylidene group), and -X- preferably contains a structural unit represented by -C(=O)-O-CH2CH2-.

[0036] The polymer may have one or more types of structural units (a).

[0037] The structural unit derived from the amino group-containing monomer is formed, for example, by radical polymerization of the amino group-containing monomer. Specific examples of the amino group-containing monomer include N,N-dialkylamino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, as well as monomers obtained by adding a quaternizing agent to the above monomers, and their hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, etidronic acid, ascorbic acid, neutralized with acids such as carboxylic acid, glutamic acid, and aspartic acid; (meth)acrylamides containing N,N-dialkylamino groups, such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide, and monomers obtained by adding a quaternary agent to the above monomers, or their hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, ethyl acid, Neutralized products with acids such as thrombotic acid, ascorbic acid, glutamic acid, and aspartic acid; monoalkylamino group-containing (meth)acrylates such as monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate, and 2-(tert-butylamino)ethyl (meth)acrylate; and their hydrochloric, acetic, lactic, phosphoric, citric, succinic, malic, etidronic, and aspartic acids. Neutralized products with acids such as corbic acid, glutamic acid, aspartic acid, etc.; monoalkylamino group-containing (meth)acrylamides such as monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide, monoethylaminopropyl (meth)acrylamide, etc., and neutralized products thereof with acids such as hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, etidronic acid, ascorbic acid, glutamic acid, aspartic acid, etc.;Esters of (meth)acrylic acid and alkanolamines, such as 2-aminoethyl (meth)acrylate, and their neutralization products with acids such as hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, etidronic acid, ascorbic acid, glutamic acid, aspartic acid, etc.; N,N-diallylmethylamine and its monomer with a quaternizing agent added thereto, or its neutralization products with acids such as hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, etidronic acid, ascorbic acid, glutamic acid, aspartic acid, etc.; allylamine and its neutralization products with acids such as hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, etidronic acid, ascorbic acid, glutamic acid, aspartic acid, etc.; 1-allyloxy-3-dibutylaminopropan-2-ol, 1-allyloxy- Examples of such monomers include addition reaction products of unsaturated monomers having a cyclic ether-containing group having 2 to 8 carbon atoms, such as 3-diethanolaminopropan-2-ol, with amine compounds having 1 to 24 carbon atoms, and monomers obtained by adding a quaternizing agent thereto, or products neutralized with acids such as hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, etidronic acid, ascorbic acid, glutamic acid, aspartic acid, etc.; alkenyl cyclic amines such as vinylpyrrolidine (1-vinylpyrrolidine, 3-vinylpyrrolidine, etc.), allylpyrrolidine (2-allylpyrrolidine, etc.), vinylpiperidine (2-vinylpiperidine, 3-vinylpiperidine), etc., and products neutralized with acids such as hydrochloric acid, acetic acid, lactic acid, phosphoric acid, citric acid, succinic acid, malic acid, etidronic acid, ascorbic acid, glutamic acid, aspartic acid, etc.;

[0038] The structural unit derived from the amino group-containing monomer is preferably a structural unit derived from an N-substituted aminoalkyl(meth)acrylate, for example, N,N-dimethylaminoethyl(meth)acrylate, represented by the following general formula (6).

[0039] Therefore, the structural unit (a) is an N-substituted aminoalkyl (meth)acrylate [for example, an N-mono- or di-alkylaminoalkyl (meth)acrylate such as N,N-dimethylaminoethyl (meth)acrylate (for example, an N-mono- or di-C 1-4 Alkylamino C1-4 The copolymer may contain structural units derived from alkyl (meth)acrylate.

[0040] [ka]

[0041] R in the above general formula (6) 10 represents a hydrogen atom or a methyl group. However, an asterisk represents an atom contained in another structural unit of the same type or different type to which the structural unit represented by the general formula (6) is bonded. Most preferred is a structural unit derived from N,N-dimethylaminoethyl methacrylate.

[0042] The content of the structural unit (a) (structural unit derived from an amino group monomer) in the polymer (copolymer) of the present disclosure may be, for example, 1% by mass or more (e.g., 2% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more) relative to 100% by mass of all structural units (structural units derived from all monomers constituting the copolymer of the present disclosure), or 100% by mass or less (e.g., less than 100% by mass, 99% by mass or less, 97% by mass or less, 96% by mass or less, 95% by mass or less, 94% by mass or less, 93% by mass or less, 92% by mass or less, 91% by mass or less, 90% by mass or less, 88% by mass or less, 85% by mass or less, 82% by mass or less, 80% by mass or less, etc.).

[0043] The content of the structural unit (a) may be an appropriate range by combining the upper limit and the lower limit, and may be, for example, 1% by mass or more and 99% by mass or less, preferably 10% by mass or more and 97% by mass or less, more preferably 36% by mass or more and 96% by mass or less, and most preferably 50% by mass or more and 95% by mass or less. By being in the above range, the hydrophilic-hydrophobic balance becomes an appropriate range, the ratio of cationic moieties that can act on the surface of the coronavirus and the ratio of hydrophobic moieties that act on the envelope become appropriate, and the water solubility of the copolymer is easily maintained, which tends to improve the anti-coronavirus performance of the anti-coronavirus agent of the present disclosure.

[0044] <Structural unit (b) (structural unit derived from a monomer containing a hydrocarbon group having two or more carbon atoms)> In the present disclosure, the structural unit (b) [structural unit derived from a monomer containing a hydrocarbon group having two or more carbon atoms (for example, in a side chain)] is represented, for example, by a structural unit of the following general formula (3).

[0045] [ka]

[0046] In general formula (3), R1, R2, and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X represents a divalent linking group, and R9 represents a hydrocarbon group having 2 or more carbon atoms which may have a substituent. Here, the asterisk represents an atom contained in another structural unit of the same type or different type to which the structural unit represented by the general formula (3) is bonded. The structure derived from a monomer containing a hydrocarbon group having two or more carbon atoms represents, for example, a structural unit in which a carbon-carbon double bond of a monomer having an ethylenically unsaturated group and a hydrocarbon group having two or more carbon atoms is replaced with a carbon-carbon single bond.

[0047] The hydrocarbon group having 2 or more carbon atoms may usually be a radically polymerizable group (e.g., an ethylenically unsaturated group) or may not be a radically polymerizable group, and may be, for example, a saturated hydrocarbon group, an unsaturated hydrocarbon group (e.g., an alkenyl group), an aromatic hydrocarbon group, or the like, and preferably a saturated hydrocarbon group (e.g., an alkyl group). A monomer containing a hydrocarbon group having 2 or more carbon atoms may have at least one hydrocarbon group having 2 or more carbon atoms, and may have two or more (plural) hydrocarbon groups having 2 or more carbon atoms. When a monomer contains a plurality of hydrocarbon groups having 2 or more carbon atoms, the hydrocarbon groups having 2 or more carbon atoms may be linked via an appropriate linking group (for example, an ether group, a thioether group, an ester group, an amide group, etc.).

[0048] In addition, R9 may form a ring together with X.

[0049] These structural units can be formed, for example, by radical polymerization of the monomer. The structural unit derived from a monomer containing a hydrocarbon group having two or more carbon atoms may have the same structure as a structural unit in which a carbon-carbon double bond is replaced with a carbon-carbon single bond, and may be, for example, a structural unit formed by a post-reaction after polymerization. The structural unit of general formula (3) does not fall under the structural unit (a). Therefore, for example, a monomer containing a hydrocarbon group having 2 or more carbon atoms may have a substituent such as a hydroxyl group or a halogen atom as long as it contains a hydrocarbon group having 2 or more carbon atoms, but usually does not have any of the group represented by formula (4), the salt of the group represented by formula (4) (salt with an acid), and the group represented by formula (5).

[0050] In the general formula (3), X, which is a divalent linking group, is, for example, a direct bond, an ether group (or an ether bond, -O-), a group containing a carbonyl group (an ester group, an amide group, a urethane group, etc.), a group in which these are bonded to a hydrocarbon group {for example, an oxyalkylene group or an oxyalkylidene group [for example, an oxyC group such as an oxymethylene group (-OCH2-) or an oxyethylene group] 1-20An alkylene group or an alkylidene group}. X is preferably an ester group or an amide group, and more preferably, X is an ester group.

[0051] The polymer may have one or more types of structural units (b).

[0052] Examples of the monomer containing a hydrocarbon group having 2 or more carbon atoms include, but are not limited to, esters of (meth)acrylic acid and alcohol which may have a substituent ((meth)acrylate which may have a substituent); aromatic vinyl monomers such as styrene; esters of unsaturated alcohols and carboxylic acids such as vinyl propionate and vinyl butyrate; alkyl vinyl ethers having 2 or more carbon atoms such as ethyl vinyl ether; addition reaction products of unsaturated monomers having a cyclic ether-containing group having 2 to 8 carbon atoms such as 1-allyloxy-3-butoxypropan-2-ol and alcohols having 1 to 20 carbon atoms; alkylene oxide adducts of unsaturated alcohols having 2 to 20 carbon atoms such as ethylene oxide adducts of allyl alcohol, ethylene oxide adducts of methallyl alcohol, and ethylene oxide adducts of isoprenol, and terminal hydrophobically modified products thereof; and cyclic vinyl monomers such as N-vinylpyrrolidone.

[0053] The monomer containing a hydrocarbon group having 2 or more carbon atoms preferably contains at least one type of (meth)acrylic acid ester. The (meth)acrylic acid ester is preferably an ester of (meth)acrylic acid and a monoalcohol, the monoalcohol having a hydrocarbon group with 2 to 20 carbon atoms. The hydrocarbon group of the monoalcohol more preferably has 2 to 16 carbon atoms, further preferably has 2 to 12 carbon atoms, and particularly preferably has 2 to 8 carbon atoms. If the carbon number of the hydrocarbon group is 2 to 20, the water solubility and viscosity of the polymer can be within a suitable range, and the polymer is easy to handle. If the carbon number of the hydrocarbon group is 2 to 12, the polymer is easy to produce, and the polymer is excellent in safety in addition to anti-coronavirus properties. Furthermore, if the carbon number of the hydrocarbon group is 2 to 8, the polymer is not only easy to produce, but also excellent in safety, and has increased affinity with the surface protein of coronavirus, resulting in further improved anti-coronavirus properties. The hydrocarbon group is preferably an alkyl group (C 2-20 Alkyl group, C 2-16 Alkyl group, C 2-12 Alkyl group, C 2-8 An alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

[0054] The structural unit (b) (or the hydrophobic unit, for example, the monomer containing a hydrocarbon group having 2 or more carbon atoms) has a solubility parameter (Hildebrand solubility parameter) [solubility parameter in a homopolymer] of 35 (MPa) or less. 1 / 2 Less than (e.g., 33 (MPa) 1 / 2 or less), preferably 32 (MPa) 1 / 2 Less than (e.g., 30.8 (MPa) 1 / 2 or less), more preferably 30 (MPa) 1 / 2 Less than (e.g., 28.7 (MPa) 1 / 2 or less), more preferably 28 (MPa) 1 / 2 Less than (e.g., 26.7 (MPa) 1 / 2 or less), 25 (MPa) 1 / 2 Less than (e.g., 24.6 (MPa) 1 / 2 (see below) etc. The solubility parameter (lower limit value) of the structural unit (b) is not particularly limited, but is, for example, 5 (MPa) 1 / 2 or more (e.g., 8 (MPa) 1 / 2 Above 10(MPa) 1 / 2 Above 10.3(MPa) 1 / 2 or more).

[0055] In addition, when the polymer has two or more types of structural units (b), at least one type of structural unit (b) may have the above-mentioned solubility parameter, or all of the structural units (b) may have the above-mentioned solubility parameter. In addition, when the polymer has two or more kinds of structural units (b), the above-mentioned solubility parameter may be the value (average value) of all the structural units (b). In such a case, the solubility parameter of all the structural units (b) can be calculated, for example, from the solubility parameter of each structural unit (b) (or each monomer) and the volume ratio of each monomer of each structural unit (b) (or each monomer).

[0056] The solubility parameter means the Hildebrand solubility parameter (SP value), and for example, the value calculated by the method described on pages 147 to 154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2) can be referenced.

[0057] The (meth)acrylic acid ester is preferably a (meth)acrylic acid alkyl ester (alkyl (meth)acrylate). Among these, a structural unit derived from ethyl (meth)acrylate and represented by the following general formula (7) is particularly preferred. Therefore, the structural unit (b) is a (meth)acrylic acid alkyl ester [C 1-4 The copolymer may contain structural units derived from alkyl (meth)acrylates (such as ethyl (meth)acrylate).

[0058] [ka]

[0059] In the above general formula (7), R 10represents a hydrogen atom or a methyl group. However, the asterisk represents an atom contained in another structural unit of the same type or different type to which the structural unit represented by the general formula (7) is bonded. Most preferred is a structural unit derived from ethyl methacrylate.

[0060] The content of structural unit (b) (structural unit derived from a hydrophobic monomer) in the polymer (copolymer) of the present disclosure may be, for example, 1% by mass or more (e.g., 2% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more) relative to 100% by mass of all structural units (structural units derived from all monomers constituting the copolymer of the present disclosure), and may be 99% by mass or less (e.g., 97% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, etc.). The content of the structural unit (b) may appropriately range by combining the upper and lower limits, and is, for example, 1 mass% or more and 99 mass% or less, preferably 3 mass% or more and 90 mass% or less, more preferably 4 mass% or more and 70 mass% or less, and most preferably 5 mass% or more and 50 mass% or less. When the content is within this range, the polymer (copolymer) has appropriate hydrophobicity, the anti-coronavirus performance is improved, and the polymer (copolymer) tends to exhibit high anti-viral performance.

[0061] <Other structural units> The polymer (copolymer) of the present disclosure may, if desired, have structural units derived from monomers other than amino group-containing monomers and structural units derived from monomers containing a hydrocarbon group having two or more carbon atoms (also referred to as structural units derived from other monomers). The other monomer is not particularly limited as long as it does not have an amino group and can be copolymerized with the amino group-containing monomer and the monomer containing a hydrocarbon group having 2 or more carbon atoms. As long as the polymer contains the above structural unit (a) and structural unit (b) in an appropriate combination and ratio [for example, a monomer containing a hydrocarbon group having 2 or more carbon atoms is polymerized in a preferred ratio], the function (for example, hydrophobicity) as a copolymer is sufficiently maintained. In the present disclosure, the structural unit derived from another monomer refers to a structural unit in which at least one carbon-carbon double bond of the other monomer is replaced with a carbon-carbon single bond. Note that the structural unit derived from the other monomer may have the same structure as the structure in which at least one carbon-carbon double bond of the other monomer is replaced with a carbon-carbon single bond, and is not limited to a structural unit formed by polymerization of the other monomer, and may be, for example, a structural unit formed by a post-reaction after polymerization.

[0062] Examples of structural units derived from other monomers include, but are not limited to, unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-allyloxyacrylic acid, and salts thereof; olefin monomers such as propylene; vinyl halides such as vinyl chloride; methyl vinyl ether; and the like.

[0063] The polymer may have one or more other structural units.

[0064] The content of structural units derived from other monomers in the polymer (copolymer) of the present disclosure is less than 15% by mass relative to 100% by mass of structural units derived from all monomers constituting the polymer (copolymer) of the present disclosure. More preferably, it is less than 10% by mass, and even more preferably, it is less than 5% by mass. These other monomers may be used alone or in combination of two or more kinds.

[0065] [Physical properties of the amino group-containing polymer (copolymer) of the present disclosure] The polymer (copolymer) of the present disclosure preferably has a weight average molecular weight (Mw) of 4000 or more and 800000 or less, more preferably 6000 or more and 400000 or less, and even more preferably 7000 or more and 80000 or less. By ensuring that the weight average molecular weight is within the above range, the anti-coronavirus performance of the anti-coronavirus agent of the present disclosure is further improved, and the formulation tends to be easy to handle and has excellent water solubility and dispersibility.

[0066] The weight average molecular weight of the polymer (copolymer) of the present disclosure can be measured by a known method, specifically, a GPC method, a viscosity method, or the like. The molecular weight distribution of the polymer (copolymer) of the present disclosure is preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.3 or more, and is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less.

[0067] The solubility parameter (Hildebrand solubility parameter) of the polymer (copolymer) of the present disclosure is, for example, 8 (MPa). 1 / 2 or more (e.g., 10 (MPa) 1 / 2 or more), preferably 12 (MPa) 1 / 2 or more (e.g., 13 (MPa) 1 / 2 or more), more preferably 14 (MPa) 1 / 2 or more (e.g., 14.5 (MPa) 1 / 2 or more), more preferably 15 (MPa) 1 / 2 It may be about the same or higher.

[0068] The solubility parameter (Hildebrand solubility parameter) (upper limit value) of the polymer (copolymer) of the present disclosure is, for example, 30 (MPa). 1 / 2 Less than (e.g., 28 (MPa) 1 / 2 Below, 26 (MPa) 1 / 2 Below, 25 (MPa) 1 / 2 Below, 24 (MPa) 1 / 2 or less), preferably 23 (MPa) 1 / 2 Less than (e.g., 22 (MPa) 1 / 2 or less), more preferably 21 (MPa) 1 / 2 Less than (e.g., 20.5 (MPa)1 / 2 or less), and more preferably 20 (MPa) 1 / 2 It may be the following.

[0069] The δd (dispersion term) in the Hansen solubility parameter of the polymer (copolymer) of the present disclosure is, for example, 10 (MPa) 1 / 2 More than 11 (MPa) is preferable. 1 / 2 More preferably, 12 (MPa) or more 1 / 2 More preferably, 21 (MPa) or more 1 / 2 Less than 20 (MPa) is preferable. 1 / 2 Less than 19 (MPa) is more preferable. 1 / 2 The following is even more preferred:

[0070] The δp (polar term) in the Hansen solubility parameter of the polymer (copolymer) of the present disclosure is, for example, 3.0 (MPa) 1 / 2 More than 4.0 (MPa) is preferable. 1 / 2 More preferably, 5.0 (MPa) or more 1 / 2 More preferably, 11.0 (MPa) or more 1 / 2 The following is preferable: 10.0 (MPa) 1 / 2 Less than 9.0 (MPa) is more preferable. 1 / 2 The following is even more preferred:

[0071] The δh (hydrogen bond term) in the Hansen solubility parameter of the polymer (copolymer) of the present disclosure is, for example, 3.0 (MPa) 1 / 2 More than 4.0 (MPa) is preferable. 1 / 2 More preferably, 5.0 (MPa) or more 1 / 2 More preferably, 11.0 (MPa) or more 1 / 2 The following is preferable: 10.0 (MPa) 1 / 2 Less than 9.0 (MPa) is more preferable. 1 / 2 The following is even more preferred:

[0072] The Hansen solubility parameter is a solubility parameter introduced by Hildebrand, which is divided into three components, the dispersion term δd, the polar term δp, and the hydrogen bond term δh, and expressed in three-dimensional space. The dispersion term δd indicates the effect of nonpolar interactions, the polar term δp indicates the effect of dipole-dipole forces, and the hydrogen bond term δh indicates the effect of hydrogen bonding forces.

[0073] The solubility parameter (Hildebrand solubility parameter, Hansen solubility parameter) of the polymer (copolymer) of the present disclosure can be calculated from the solubility parameters of the monomers [monomers (units derived from) constituting the polymer (copolymer)] used in the polymer (copolymer) and the volume proportion of each monomer.

[0074] As an example of the calculation method, the Hansen solubility parameter of a copolymer obtained by polymerizing 60 parts by mass of N,N-dimethylaminoethyl methacrylate and 40 parts by mass of ethyl methacrylate is mentioned. First, the Hansen solubility parameters of N,N-dimethylaminoethyl methacrylate and ethyl methacrylate are as follows: ·N,N-Dimethylaminoethyl methacrylate (δd=14.3(MPa) 1 / 2 , δp=7.0(MPa) 1 / 2 , δh=7.7(MPa) 1 / 2 ) Ethyl methacrylate (δd=15.8(MPa) 1 / 2 , δp=7.2(MPa) 1 / 2 , δh=7.5(MPa) 1 / 2 ) In addition, when the specific gravity of N,N-dimethylaminoethyl methacrylate is 0.9 and the specific gravity of ethyl methacrylate is 0.9, the volume ratio of N,N-dimethylaminoethyl methacrylate:ethyl methacrylate is 60:40. Then, the Hansen solubility parameters of the copolymer obtained by polymerizing 60 parts by mass of N,N-dimethylaminoethyl methacrylate and 40 parts by mass of ethyl methacrylate are calculated as follows. Copolymer δd = 14.3 x 0.6 + 15.8 x 0.4 = 14.9 (MPa) 1 / 2 Copolymer δp = 7.0 x 0.6 + 7.2 x 0.4 = 7.1 (MPa) 1 / 2 Copolymer δh = 7.7 x 0.6 + 7.5 x 0.4 = 7.6 (MPa) 1 / 2 In the above calculation, the Hansen solubility parameters of each monomer are values ​​extracted from Hansen Solubility Parameters: A User's Handbook.

[0075] The above-mentioned solubility parameter is preferable in that the anti-coronavirus function can be efficiently exhibited.

[0076] The copolymers of the present disclosure may be random copolymers, block copolymers, graft copolymers, and the like.

[0077] [Method for producing amino group-containing polymer (copolymer) of the present disclosure] The method for producing the polymer (copolymer) of the present disclosure is not particularly limited, but it is usually preferable to produce it by polymerizing at least the raw material monomers of the structural unit (a) (for example, an amino group-containing monomer, a monomer containing a hydrocarbon group having 2 or more carbon atoms, and other monomers as necessary). The method for producing the polymer (copolymer) can be, for example, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, living polymerization, graft polymerization, or the like, and is not particularly limited, but solution polymerization is preferable. The solvent used in this case is not particularly limited, but suitable examples include water; monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, and THF (tetrahydrofuran); polyhydric alcohols such as glycerin, (poly)ethylene glycol, propylene glycol, 1,3-butylene glycol, and dipropylene glycol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-heptane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide; and ethers such as diethyl ether and dioxane. These may be used alone or in combination of two or more. Among these, from the viewpoint of the solubility of the monomer components and the resulting polymer (copolymer), it is preferable to use one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. Polymerization may be carried out by adding a polyhydric alcohol solvent such as propylene glycol or ethylene glycol to water. The above-mentioned polyhydric alcohol solvent can increase the solubility of the polymer by using it together with water, and can suppress soap-free polymerization more sufficiently. This can suppress the generation of poorly water-soluble polymer more sufficiently, and can improve the transparency of the solution more. In addition, if the solvent is water, ethyl alcohol, glycerin, 1,3-butanediol, or a combination of two or more of them, it is more suitable in that it can be used directly as a raw material for skin external preparations without carrying out a desolvation process. As described in the section on structural units derived from amino group-containing monomers, the neutralized polymer (copolymer) of the present disclosure can be produced by polymerizing a neutralized monomer, or the neutralized polymer can be produced by polymerizing an unneutralized monomer and then neutralizing it by adding a specified acid.

[0078] [coronavirus] Coronaviruses are enveloped viruses with a single-stranded RNA genome and a nucleocapsid with helical symmetry. Coronaviruses of the present disclosure include coronaviruses that infect humans or non-human animals.

[0079] Coronaviruses that infect humans include human coronavirus 229E, OC43, NL63, HKU-1, severe acute respiratory syndrome (SARS) coronavirus, Middle East respiratory syndrome (MERS) coronavirus, and novel coronavirus (2019-nCoV, SARS-CoV-2).

[0080] Coronaviruses that infect non-humans include porcine epidemic diarrhea virus (PEDV), porcine transmissible gastroenteritis virus (TGEV), feline infectious peritonitis virus (FIPV), canine coronavirus (CCV), bovine coronavirus, equine coronavirus, infectious bronchitis virus (IBV), avian deltacoronavirus, and porcine deltacoronavirus. The coronavirus of the present disclosure may be SARS-CoV-2, which is a virus belonging to the Coronaviridae family and is the causative virus of novel coronavirus disease (COVID-19). In addition, so-called mutant strains (e.g., those with mutations such as N501Y, L452R, E484Q, D614G, P681H, Y145H, A222V, and E484K in the spike protein) are also included in the coronavirus of the present disclosure. Currently known (publicly known) mutant strains include the so-called alpha, beta, gamma, delta, kappa, lambda, mu, and omicron strains, but the target of the anti-coronavirus agent disclosed herein includes not only these known mutant strains, but also currently unknown mutant strains and new mutant strains that will mutate in the future.

[0081] The target for which the anti-coronavirus agent of the present disclosure is used is not particularly limited, and the agent may be used for the purpose of suppressing coronavirus infection in livestock or pets, or may be used in the hope of having antiviral properties against coronaviruses that infect humans. The agent may also be used against SARS coronavirus, MERS coronavirus, or SARS-CoV-2, and in recent years, the agent may be used particularly against SARS-CoV-2, with the expectation of an infection-suppressing effect.

[0082] [Anti-coronavirus agents] The anti-coronavirus agent (composition, anti-coronavirus composition) of the present disclosure essentially contains the polymer (copolymer) of the present disclosure. The content of the polymer (copolymer) of the present disclosure in the anti-coronavirus agent of the present disclosure may be 100% by mass at the upper limit, and the lower limit is not particularly limited, but is preferably 0.01% by mass or more from the viewpoint of effective action of the formulation. The anti-coronavirus agent of the present disclosure may contain a solvent such as water, an antibacterial agent, a preservative, etc. The other components are not particularly limited as long as they do not inhibit the anti-coronavirus performance of the anti-coronavirus agent, and examples thereof include additives such as alkali regulators, anionic surfactants, compatibilizers, stabilizers, and antibacterial agents. Moreover, from the viewpoint of improving the anti-coronavirus activity, the coronavirus agent of the present invention may further contain a metal salt, a metal oxide, a metal hydroxide, etc. The content of the above-mentioned other components is not particularly limited as long as it does not inhibit the anti-coronavirus activity of the anti-coronavirus agent, but is preferably 0 to 20% by mass with respect to 100% by mass of the above-mentioned polymer (copolymer).

[0083] A representative anti-coronavirus agent is in a form containing the polymer (copolymer) of the present disclosure and a solvent [e.g., a solution (particularly an aqueous solution)].

[0084] Examples of the solvent include water and aqueous solvents [eg, alcohols (eg, methanol, ethanol, isopropanol, etc.)], and mixed solvents are also possible.

[0085] In such a form (for example, a solution), the concentration of the polymer (copolymer) may be, for example, about 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.01% by mass or more. It may be diluted as appropriate before use, and the upper limit of the concentration is not particularly limited, but may be, for example, 90% by mass or less, 80% by mass or less, 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, etc.

[0086] In a form containing a solvent (water), the pH (e.g., pH at 25°C) is not particularly limited and may be in the acidic, neutral, or alkaline range. However, depending on the application, application site, application target, etc., the pH may be in a (weakly) acidic to (weakly) alkaline range, for example, 3 to 11, 4 to 10, 5 to 9, 6 to 8, 3 to 8, 3 to 7, 4 to 8, 4.5 to 7.5, 5 to 7, 4 to 6.5, etc. The pH may be, for example, 11 or less, 10 or less, or 9 or less. Such a pH is preferable in that the polymer is likely to exhibit sufficient water solubility and the amount that can effectively act in an aqueous solution is small. The lower limit of the pH may be 2 or more, 3 or more, or 4 or more. Such a lower limit is preferable in that the degree of cationization can be appropriately adjusted and the hydrophobic moiety can efficiently act on the envelope. In addition, such a pH is preferable from the viewpoints of stability when blended into a formulation and irritation when contacted with a living body.

[0087] In addition, the anti-coronavirus agent of the present invention can be blended with additives generally used in pharmaceuticals, quasi-drugs, cosmetics, laundry detergents, miscellaneous goods such as packs and sheet masks, and hygiene products, as necessary, such as oily bases, moisturizers, texture enhancers, surfactants, polymers, thickening / gelling agents, solvents, propellants, antioxidants, reducing agents, oxidizing agents, preservatives and antibacterial agents other than the preservative and antibacterial agent of the present invention, chelating agents, pH adjusters, acids, alkalis, powders, inorganic salts, UV absorbers, whitening agents, vitamins and derivatives thereof, anti-inflammatory agents, anti-inflammatory agents, hair growth agents, blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging agents, tightening agents, cooling agents, warming agents, wound healing promoters, irritation relievers, analgesics, cell activators, plant / animal / microbial extracts, antipruritics, keratin exfoliating / dissolving agents, antiperspirants, cooling agents, astringents, enzymes, nucleic acids, fragrances, dyes, colorants, dyes, pigments, and various types of water. The anti-coronavirus agent of the present disclosure may be used in combination with silver ions, polyalkyleneimines (including derivatives), and the like.

[0088] [Use of anti-coronavirus agents] The anti-coronavirus agent of the present disclosure can be used as an additive for the purpose of imparting anti-viral properties. For example, it can be used in medicines, quasi-drugs, cosmetics, miscellaneous goods such as packs and sheet masks, laundry detergents, sanitary products, etc. When used in these, it can be added according to a formulation method suitable for each application. For example, it can be in the form of a solution dissolved in various solvents, an emulsion, a gel, a foam, a spray, or impregnated into a sheet, etc.

[0089] The anti-coronavirus agent of the present disclosure may be coated on a substrate to form a film having anti-coronavirus properties, forming a laminate having an anti-coronavirus effect. The substrate is not particularly limited in type as long as it plays a role in supporting the anti-coronavirus agent. The substrate may be a part of various devices (for example, a front panel).

[0090] The shape of the substrate is not particularly limited, and examples thereof include a plate, a film, a sheet, a tube, a fiber, and a particle. The form of the substrate surface on which the anti-coronavirus membrane is disposed is not particularly limited, and examples thereof include a flat surface, a concave surface, a convex surface, and a combination thereof.

[0091] The material constituting the substrate is not particularly limited, and examples thereof include wood, metal, glass, ceramics, and plastic (resin). Among these, plastic is preferred from the viewpoint of ease of handling. In other words, a resin substrate is preferred. Examples of methods for applying the anti-coronavirus agent to the surface of a substrate include a spray method, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, an inkjet method, and a die coating method.

[0092] [How to use anti-coronavirus agents] A method of using the anti-coronavirus agent of the present disclosure to suppress the proliferation of coronaviruses or a method of suppressing coronaviruses is a preferred embodiment, and it is particularly preferable to use it against SARS-CoV-2. The antiviral activity value of the anti-coronavirus agent of the present disclosure is preferably 1 or more (particularly more than 1), more preferably 1.5 or more, even more preferably 2 or more, and may be 3 or more. The antiviral activity value of the present disclosure can be calculated by measuring the virus infectivity by the plaque method and using the following formula. formula: Antiviral activity value = Log (virus infectivity of control) - Log (virus infectivity of anti-coronavirus agent) The control can be appropriately selected, and examples thereof include water, saline, and a buffer solution (eg, PBS).

[0093] Such antiviral activity values ​​may be achieved in a relatively short period of time (eg, within 10 minutes, within 20 minutes, within 30 minutes, etc.).

[0094] On the other hand, the above-mentioned antiviral activity value may be maintained for a long period of time, and may be sufficient for a long period of time (e.g., 1 hour or more, 1.5 hours or more, 2 hours or more, 6 hours or more, 12 hours or more, 1 day or more, 3 days or more, 7 days or more, 10 days or more, etc.). EXAMPLES

[0095] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0096] <Method for measuring weight average molecular weight> The weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC) under the following conditions and apparatus: Equipment: Waters e2695 Detector: Differential Refractometer (RI) detector Column: Tosoh TSKgel α-M, α-2500 Column temperature: 40℃ Flow rate: 0.8mL / min Injection volume: 10 μL (eluent preparation solution with a sample concentration of 0.4 wt%) Calibration curve: manufactured by GL Sciences Inc. Polyethylene glycol GPC software: manufactured by Waters Corporation EMPOWER3 Eluent: 0.5 M acetic acid + 0.2 M sodium nitrate / acetonitrile = 50 / 50 (v / v)

[0097] <Method for measuring solid content of polymer> Approximately 1 g of the obtained polymer solution was weighed, dried at 200°C for 15 minutes in a hot air dryer, and the mass of the residue after drying was taken as the solid content, and the ratio to the mass before drying was expressed as a percentage. <pH measurement method> The value at 25°C was measured using a pH meter (F-72 manufactured by Horiba, Ltd.).

[0098] <Production Example 1> 11.1 g of pure water and 100.0 g of 1,3-butanediol (manufactured by Daicel Corporation) were charged into a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90°C with stirring. Subsequently, with stirring, in a polymerization reaction system maintained at 90°C, a monomer solution 1 consisting of 60.0 g of 2-(dimethylamino)ethyl methacrylate (alias: N,N-dimethylaminoethyl methacrylate) (manufactured by Kyoeisha Chemical Co., Ltd., referred to as DAM), a monomer solution 2 consisting of 40.0 g of ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., referred to as EMA), and an initiator aqueous solution consisting of 36.6 g of a 3% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Corporation, referred to as V-50) were each dropped from separate dropping nozzles. Regarding the start time of dropping, the monomer solutions 1 and 2 and the initiator aqueous solution started dropping simultaneously. The monomer solution 1 was dropped for 180 minutes, the monomer solution 2 was dropped for 170 minutes, and the initiator aqueous solution was dropped for 210 minutes. After the completion of all dropping, the reaction solution was further held at 90°C for 30 minutes for aging. After completing the polymerization, 52.5 g of pure water and 200.0 g of 1,3-butanediol were added to obtain copolymer 1. The solid content of the obtained copolymer was 19.8%, pH was 9.0, and weight average molecular weight was 48000. Pure water and citric acid monohydrate were added to the obtained copolymer 1 and stirred to prepare a 2% copolymer aqueous solution with a pH of 6.

[0099] <Production Example 2> Into a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, 11.1 g of pure water and 100.0 g of 1,3-butanediol (manufactured by Daicel Corporation) were placed, and the temperature was raised to 90° C. with stirring. Next, under stirring, into the polymerization reaction system kept at a constant temperature of 90°C, monomer solution 1 consisting of 60.0 g of 2-(dimethylamino)ethyl methacrylate (also known as N,N-dimethylaminoethyl methacrylate) (manufactured by Kyoeisha Chemical Co., Ltd., referred to as DAM), monomer solution 2 consisting of 40.0 g of ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., referred to as EMA), and an initiator aqueous solution consisting of 27.9 g of a 10% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd., referred to as V-50) were each dropped from separate dropping nozzles. Regarding the start time of dropping, the monomer solutions 1 and 2 and the aqueous initiator solution were dropped at the same time, and the monomer solution 1 was dropped for 180 minutes, the monomer solution 2 for 170 minutes, and the aqueous initiator solution for 210 minutes. After the completion of all the dropping, the reaction solution was kept at 90°C for an additional 30 minutes to mature and complete the polymerization, and then 61.1 g of pure water and 200.0 g of 1,3-butanediol were added to obtain copolymer 2. The obtained copolymer had a solid content of 19.8%, a pH of 9.1, and a weight average molecular weight of 20000. Pure water and citric acid monohydrate were added to the obtained copolymer 2 and stirred to prepare a 2% copolymer aqueous solution with a pH of 6.

[0100] <Production Example 3> Into a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, 104.1 g of pure water was placed and heated to 90° C. with stirring. Next, under stirring, into the polymerization reaction system kept at a constant temperature of 90°C, monomer solution 1 consisting of 90.0 g of 2-(dimethylamino)ethyl methacrylate (also known as N,N-dimethylaminoethyl methacrylate) (manufactured by Kyoeisha Chemical Co., Ltd., referred to as DAM), monomer solution 2 consisting of 10.0 g of ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., referred to as EMA), and an initiator aqueous solution consisting of 32.7 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) and 26.4 g of a 2.5% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd., referred to as V-50) were each dropped from separate dropping nozzles. Regarding the start time of dropping, the dropping of the monomer solutions 1 and 2, acetic acid, and the aqueous initiator solution was started at the same time, and the dropping of the monomer solution 1 was started for 180 minutes, the monomer solution 2 for 120 minutes, the acetic acid for 180 minutes, and the aqueous initiator solution for 210 minutes. After the dropping was all completed, the reaction solution was kept at 90°C for another 30 minutes to mature, and the polymerization was completed. Then, 236.7 g of pure water was added to obtain the copolymer 3. The resulting copolymer had a solid content of 20.0%, a pH of 6.4, and a weight average molecular weight of 58000. Pure water was added to the resulting copolymer 3 and stirred to prepare a 2% aqueous copolymer solution.

[0101] <Production Example 4> Into a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, 100.1 g of pure water was placed and heated to 90° C. with stirring. Next, under stirring, into the polymerization reaction system kept at a constant temperature of 90°C, monomer solution 1 consisting of 90.0 g of 2-(dimethylamino)ethyl methacrylate (also known as N,N-dimethylaminoethyl methacrylate) (manufactured by Kyoeisha Chemical Co., Ltd., referred to as DAM), monomer solution 2 consisting of 10.0 g of ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., referred to as EMA), and an initiator aqueous solution consisting of 32.7 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) and 42.4 g of a 5.0% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd., referred to as V-50), were each dropped from separate dropping nozzles. Regarding the start time of dropping, the dropping of the monomer solutions 1 and 2, acetic acid, and the aqueous initiator solution was started at the same time, and the dropping of the monomer solution 1 was started for 180 minutes, the monomer solution 2 for 180 minutes, the acetic acid for 180 minutes, and the aqueous initiator solution for 210 minutes. After the dropping was all completed, the reaction solution was kept at 90°C for another 30 minutes to mature, and the polymerization was completed. Then, 214.2 g of pure water was added to obtain copolymer 4. The resulting copolymer had a solid content of 20.4%, a pH of 5.7, and a weight average molecular weight of 18000. Pure water was added to the resulting copolymer 4 and stirred to prepare a 2% aqueous copolymer solution.

[0102] <Production Example 5> Into a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, 33.3 g of pure water and 77.8 g of 1,3-butanediol (manufactured by Daicel Corporation) were placed, and the temperature was raised to 90° C. with stirring. Next, under stirring, into the polymerization reaction system kept at a constant temperature of 90°C, monomer solution 1 consisting of 80.0 g of 2-(dimethylamino)ethyl methacrylate (also known as N,N-dimethylaminoethyl methacrylate) (manufactured by Kyoeisha Chemical Co., Ltd., referred to as DAM), monomer solution 2 consisting of 20.0 g of ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., referred to as EMA), and an initiator aqueous solution consisting of 34.2 g of a 3% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd., referred to as V-50) were each dropped from separate dropping nozzles. Regarding the start time of dropping, the monomer solutions 1 and 2 and the aqueous initiator solution were dropped at the same time, and the monomer solution 1 was dropped for 180 minutes, the monomer solution 2 for 180 minutes, and the aqueous initiator solution for 210 minutes. After the completion of all the dropping, the reaction solution was kept at 90°C for another 30 minutes to mature and complete the polymerization, and then 66.7 g of pure water and 66.7 g of 1,3-butanediol were added to obtain copolymer 5. The solid content of the obtained copolymer was 26.6%, pH was 9.5, and weight average molecular weight was 52000. Pure water and citric acid monohydrate were added to the obtained copolymer 5 and stirred to prepare a 2% copolymer aqueous solution with a pH of 6.

[0103] <Production Example 6> Into a separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer, 33.3 g of pure water and 77.8 g of 1,3-butanediol (manufactured by Daicel Corporation) were placed, and the temperature was raised to 90° C. with stirring. Next, under stirring, into the polymerization reaction system kept at a constant temperature of 90°C, monomer solution 1 consisting of 80.0 g of 2-(dimethylamino)ethyl methacrylate (also known as N,N-dimethylaminoethyl methacrylate) (manufactured by Kyoeisha Chemical Co., Ltd., referred to as DAM), monomer solution 2 consisting of 20.0 g of ethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., referred to as EMA), and an initiator aqueous solution consisting of 37.7 g of a 10% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd., referred to as V-50) were each dropped from separate dropping nozzles. Regarding the start time of dropping, the monomer solutions 1 and 2 and the aqueous initiator solution were dropped at the same time, and the monomer solution 1 was dropped for 180 minutes, the monomer solution 2 for 180 minutes, and the aqueous initiator solution for 210 minutes. After the completion of all the dropping, the reaction solution was kept at 90°C for another 30 minutes to mature and complete the polymerization, and then 66.7 g of pure water and 66.7 g of 1,3-butanediol were added to obtain copolymer 6. The solid content of the obtained copolymer was 26.3%, pH was 9.2, and weight average molecular weight was 15000. Pure water and citric acid monohydrate were added to the obtained copolymer 6 and stirred to prepare a 2% copolymer aqueous solution with a pH of 6.

[0104] The compositions and solubility parameters [Hildebrand solubility parameters (SP values), Hansen solubility parameters (HSP values, δp, δh, δ)] of the copolymers obtained in Production Examples 1 to 6 are shown in the table below. The Hansen solubility parameters of each monomer were taken from Hansen Solubility Parameters: A User's Handbook.

[0105] [Table 1]

[0106] [Anti-coronavirus test 1] The antiviral test was performed according to ASTM E1052 - Standard test method for evaluating the activity of disinfectants against viruses in suspension. The test virus liquid was a purified version of the novel coronavirus (SARS-CoV-2).

[0107] <Example 1> 0.1 ml of the test virus solution and 0.9 ml of the test solution were mixed and gently shaken at room temperature for a certain period of time. Then, 9.0 ml of SCDLP medium was added to prepare a 10-fold serial dilution, which was then added to the host cells, Vero E6 cells (ATCC CCL-1586), and cultured for 3 days. The virus infectivity after the treatment was determined by the plaque method. The 2% copolymer aqueous solution obtained in Production Example 1 was further diluted with water to a polymer (copolymer) concentration of 0.1% by mass to prepare a test solution, and PBS (phosphate buffered saline) was used as a control. PBS corresponds to 8 g of sodium chloride, 0.2 g of potassium chloride, 1.44 g of disodium hydrogen phosphate, and 0.24 g of potassium dihydrogen phosphate dissolved in water, adjusted to pH 7.4, and made up to 1 L (same below). The antiviral activity value was calculated using the following formula. Antiviral activity value=Log(virus infectivity of control)−Log(virus infectivity of the test solution of Example 1) The virus infectivity and antiviral activity of the test solution of Example 1 are shown in Table 2.

[0108] [Table 2]

[0109] *(E+a) in Table 2 is (×10 a ), for example, (9.50E+06) means (9.50×10 6 ) (hereinafter the same applies to similar descriptions).

[0110] In Example 1 of the present invention, the antiviral activity value reached 2.0 after 1 hour, confirming that the composition has sufficient anti-coronavirus activity. Furthermore, it was found that the anti-coronavirus agent of the present disclosure has an improved anti-viral activity value as time elapses, making it possible to sustain the anti-coronavirus effect.

[0111] [Anti-coronavirus test 2] The antiviral test was carried out according to ASTM E1052 - Standard test method for evaluating the activity of disinfectants against viruses in suspension -. Porcine coronavirus (PED) was used as the test virus liquid.

[0112] <Examples 2 to 7> 1 ml of the test virus solution was mixed with 10 ml of the test solution and gently shaken at room temperature for a certain period of time. After that, it was diluted 10-fold with SCDLP medium, and a 10-fold dilution series was prepared. The solution was then added to the host cells, Vero cells (ATCC CCL-81), and cultured for 5 days. The virus infectivity after the action was determined by the TCID50 method. Each of the 2% copolymer aqueous solutions obtained in Production Examples 1 to 6 was further diluted with water so that the polymer (copolymer) concentration became 0.1% by mass to prepare test solutions (test solutions in Examples 2 to 7, respectively), and PBS (phosphate buffered saline) was used as a control. The antiviral activity value was calculated using the following formula. Antiviral activity value=Log(virus infectivity of control)−Log(virus infectivity of each test solution of Examples 2 to 7)

[0113] The virus infectivity and antiviral activity of each of the test solutions in Examples 2 to 7 are shown in Table 3.

[0114] [Table 3]

[0115] In all of Examples 2 to 7 of the present invention, the antiviral activity value was 1.6 or more after 2 hours, confirming that the compositions had anti-coronavirus activity regardless of molecular weight or composition ratio.

[0116] As described above, all of the copolymers used in Examples 1 to 7 had anti-coronavirus activity, and also had good water solubility, compatibility (ease of blending, dispersibility) with various other ingredients (such as ingredients of cosmetics or cosmetic preparations), and moisturizing properties when applied to the skin. They also had excellent water resistance and stain resistance when applied to the target object (of the coating film formed).

Claims

1. An anti-coronavirus agent comprising a polymer including at least one structural unit (a) selected from a structural unit represented by the following general formula (1), a structural unit which is a salt of the following general formula (1), and a structural unit represented by the following general formula (2), 【Chemistry 1】 【Chemistry 2】 (In general formula (1) and general formula (2), R １ , R ２ , R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ４ From R ８ each independently represents a hydrogen atom or an organic group, and X represents a divalent linking group. － represents an anion.) The polymer further contains a structural unit (b) represented by the following general formula (3): 【Chemistry 3】 (In general formula (3), R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X represents a divalent linking group, and R 9 represents a hydrocarbon group having 2 or more carbon atoms which may have a substituent.) The structural unit (b) contains a structural unit represented by the following general formula (7): 【Chemistry 4】 (In general formula (7), R 10 represents a hydrogen atom or a methyl group.) The content of the structural unit (a) in the polymer is 50% by mass or more based on 100% by mass of all structural units, The content of the structural unit (b) in the polymer is 5% by mass or more based on 100% by mass of all structural units, An anti-coronavirus agent, wherein the weight-average molecular weight of the polymer is 15,000 or more and 800,000 or less.

2. An anti-coronavirus agent comprising a polymer including at least one structural unit (a) selected from a structural unit represented by the following general formula (1), a structural unit which is a salt of the following general formula (1), and a structural unit represented by the following general formula (2), 【Chemistry 5】 【Chemistry 6】 (In general formula (1) and general formula (2), R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 4 to R 8 each independently represent a hydrogen atom or an organic group, X represents a divalent linking group, and Y − represents an anion.) The polymer further contains a structural unit (b) represented by the following general formula (3): 【Chemistry 7】 (In general formula (3), R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X represents a divalent linking group, and R 9 represents a hydrocarbon group having 2 or more carbon atoms which may have a substituent.) The content of the structural unit (a) in the polymer is 50% by mass or more based on 100% by mass of all structural units, The content of the structural unit (b) in the polymer is 30% by mass or more based on 100% by mass of all structural units, An anti-coronavirus agent, wherein the weight-average molecular weight of the polymer is 15,000 or more and 800,000 or less.

3. The Hildebrand solubility parameter of the polymer is 8 to 30 (MPa) １／２ The agent according to claim 1 or 2,

4. The polymer has a Hildebrand solubility parameter of 10 to 25 (MPa). １／２ The agent according to any one of claims 1 to 3,

5. The agent described in any one of claims 1 to 4, wherein the structural unit (a) includes a structural unit derived from an N-mono- or di-alkylaminoalkyl (meth)acrylate.

6. The agent according to any one of claims 2 to 5, wherein the structural unit (a) comprises a structural unit derived from an N-mono- or dialkylaminoalkyl (meth)acrylate, and the structural unit (b) comprises a structural unit derived from an alkyl (meth)acrylate ester.

7. The polymer has a Hildebrand solubility parameter of 12 to 23 (MPa). １／２ The agent according to any one of claims 1 to 6,

8. The agent according to any one of claims 1 to 7, comprising a polymer at a concentration of 0.01% by mass or more.

9. The agent according to claims 1 to 8, which is an additive for imparting antiviral properties to medicines, quasi-drugs, cosmetics, miscellaneous goods, laundry detergents or sanitary products.

10. A method for inactivating coronavirus and / or inhibiting the proliferation of coronavirus using the agent according to any one of claims 1 to 9 (excluding a method for inactivating coronavirus and / or inhibiting the proliferation of coronavirus in humans).

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