Antiviral composition, antiviral fabric, and antiviral leather

Abstract

To provide an antiviral composition that includes an antiviral agent including a specific quaternary ammonium salt, and a specific binder resin, wherein the antiviral composition has excellent liquid stability and can impart sufficient antiviral properties.SOLUTION: An antiviral composition includes (A) an antiviral agent including a predetermined quaternary ammonium salt, (B) a predetermined aqueous polyurethane resin, and (C) a predetermined nonionic surfactant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present application discloses an antiviral composition, an antiviral fabric, and an antiviral leather. [Background technology]

[0002] In recent years, in connection with increasing awareness of environmental hygiene, quaternary ammonium salt-type antiviral agents and articles to which such antiviral agents are applied have been developed. Various methods have been proposed for immobilizing such quaternary ammonium salt-type antiviral agents on the surface of articles. For example, Patent Document 1 discloses that, in order to immobilize the above-mentioned antiviral agent on synthetic fibers, a binder resin having a carboxyl group is applied to the synthetic fibers prior to the immobilization treatment of the antiviral agent. According to the technology disclosed in Patent Document 1, the antiviral agent can be suitably applied to synthetic fibers such as polyester fibers. Furthermore, Patent Document 2 discloses a method of using a resin having an anionic group as a binder. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2013 / 047642 [Patent Document 2] Patent No. 6482099 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional antiviral compositions are prone to poor liquid stability between the antiviral agent and the binder resin, resulting in problems such as an increase in the viscosity of the treatment bath and the formation of aggregates in a treatment solution containing the composition. In view of these problems, the present application discloses an antiviral composition containing a specific antiviral agent and a specific binder resin, which has good liquid stability between the antiviral agent and the binder resin and can impart sufficient antiviral properties. Furthermore, the present application discloses fabrics and leathers to which an antiviral agent is fixed and which have antiviral properties. [Means for solving the problem]

[0005] The present inventors have conducted research into the above-mentioned problems and found that adding a specific nonionic surfactant to an antiviral composition containing an antiviral agent containing a specific quaternary ammonium salt and an aqueous polyurethane resin having a carboxyl group and / or a carboxylate group improves the liquid stability of the antiviral agent and the aqueous polyurethane resin. Furthermore, they found that when such a composition is used to apply the antiviral agent to various substrates such as fabric substrates and leather substrates, the antiviral agent can be fixed to the substrate in a single process, resulting in an article with good antiviral properties. Specifically, the present application discloses the following antiviral composition, antiviral fabric, and antiviral leather as means for solving the above-mentioned problems.

[0006] The antiviral composition of the present disclosure comprises: (A) an antiviral agent containing at least one of the following quaternary ammonium salts (1a) and (2a); (B) an aqueous polyurethane resin having at least one of a carboxyl group and a carboxylate group; (C) at least one nonionic surfactant selected from the following nonionic surfactants (1c) to (4c) and a polyoxyalkylene sorbitan fatty acid ester having an alkylene oxide polymerization degree of 10 or more and 50 or less; Contains:

[0007] [ka] where R a is a hydrocarbon group having 1 to 3 carbon atoms, and R b is a hydrocarbon group having 1 to 24 carbon atoms, and R c is a hydrocarbon group having 10 to 24 carbon atoms; Y is a q-valent anion, where q is 1 or 2, and p is 1 to 6.

[0008] [ka] where R d is an alkyl group or aryl group having 10 to 20 carbon atoms, and R e is a methyl group, an ethyl group, a propyl group, a butyl group or (AO) x H, AO is an alkylene oxide group having 2 to 4 carbon atoms, x is 1 to 10, and R f is a methyl group, an ethyl group, a benzyl group, or a hydroxyalkyl group having 2 to 4 carbon atoms, r is 1 or 2, s is 1 or 2, r+s is 3, t is 1 or 2, and Z is a monoalkyl phosphate, a dialkyl phosphate, a halogen, a methyl sulfate, an ethyl sulfate, or an aromatic anion.

[0009] [ka] where Ar is an aromatic hydrocarbon group having 6 to 46 carbon atoms, and A 1 O is an alkylene oxide group having 2 to 4 carbon atoms, n1 is 10 to 60, and X 1 is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0010] [ka] where R 1 is a hydrocarbon group having 1 to 30 carbon atoms, and A 2 O is an alkylene oxide group having 2 to 4 carbon atoms, n2 is 5 to 40, and X 2is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0011] [ka] where R 2 is a hydrocarbon group having 1 to 30 carbon atoms, and A 3 O and A 4 O are each independently an alkylene oxide group having 2 to 4 carbon atoms, n3+n4 is 5 to 70, and X 3 and X 4 are each independently at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0012] [ka] where R 3 is a hydrocarbon group having 1 to 30 carbon atoms, and A 5 O is an alkylene oxide group having 2 to 4 carbon atoms, n5 is 5 to 40, and X 5 is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0013] The antiviral fabric of the present disclosure comprises: A method for producing a sterilization product comprising: a fabric substrate; and the antiviral composition of the present disclosure; The antiviral composition is adhered to the fabric substrate.

[0014] The antiviral leather of the present disclosure comprises: A method for treating a leather substrate comprising the antiviral composition of the present disclosure, The antiviral composition is adhered to the leather substrate. [Effects of the Invention]

[0015] The antiviral composition of the present disclosure has better liquid stability when used as a treatment liquid than conventional compositions, and can impart an antiviral agent to various substrates in a single processing run. In other words, a pretreatment step prior to antiviral treatment is not required, and antiviral fabrics, leather, and the like can be produced stably and efficiently at low cost without using special equipment, which is advantageous in terms of production efficiency and cost. Furthermore, the antiviral composition of the present disclosure does not generate resin residue or the like over a long period of time, even when the treatment liquid is prepared by diluting the composition with water or the like and then processed onto a substrate, and the composition has excellent storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0016] 1. Antiviral composition The antiviral composition of the present disclosure comprises: (A) an antiviral agent containing at least one of the following quaternary ammonium salts (1a) and (2a); (B) an aqueous polyurethane resin having at least one of a carboxyl group and a carboxylate group; (C) at least one nonionic surfactant selected from the following nonionic surfactants (1c) to (4c) and a polyoxyalkylene sorbitan fatty acid ester having an alkylene oxide polymerization degree of 10 or more and 50 or less; Contains:

[0017] 1.1 Antiviral Agents (A) The antiviral agent (A) contained in the antiviral agent composition of the present disclosure contains a quaternary ammonium salt. Examples of quaternary ammonium salts include alkoxysilane-based and non-alkoxysilane-based salts. Examples of alkoxysilane-based quaternary ammonium salts include those having an ammonium group and an alkoxysilyl group, each of which has a relatively long-chain hydrocarbon group that exhibits antiviral properties. Specific examples include the following quaternary ammonium salt (1a). On the other hand, examples of non-alkoxysilane-based quaternary ammonium salts include those having an ammonium group with a relatively long-chain hydrocarbon group that exhibits antiviral properties. Specific examples include the following quaternary ammonium salt (2a). In particular, the alkoxysilane-based quaternary ammonium salt (1a) has a highly reactive alkoxysilyl group, which provides strong bonding with the aqueous polyurethane resin (B) described below, and also provides strong bonding with various substrates having sites reactive with the alkoxysilyl group. Therefore, it is believed that excellent antiviral properties are readily exhibited, and that the antiviral effect is likely to be long-lasting.

[0018] 1.1.1 Alkoxysilane-based quaternary ammonium salts (1a) The quaternary ammonium salt (1a) is represented by the following chemical formula:

[0019] [ka] where R a is a hydrocarbon group having 1 to 3 carbon atoms, and R b is a hydrocarbon group having 1 to 24 carbon atoms, and R c is a hydrocarbon group having 10 to 24 carbon atoms, Y is a q-valent anion, q is 1 or 2, and p is 1 or more and 6 or less.

[0020] In the above quaternary ammonium salt (1a), R a may be linear or branched. Examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Among these, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. amay be the same as or different from each other.

[0021] In the above quaternary ammonium salt (1a), two R b may be the same or different. b R can be either linear or branched. b R may contain at least one functional group selected from the group consisting of -O-, -OCO-, and -OH. b The number of carbon atoms is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1.

[0022] In the above quaternary ammonium salt (1a), R c R can be either linear or branched. c The number of carbon atoms in R is preferably 10 to 18, and more preferably 14 to 18. c Examples of such alkyl groups include decyl, isodecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, doeicosyl, trieicosyl, and tetraeicosyl groups.

[0023] In the above quaternary ammonium salt (1a), Y may be a q-valent anion. Examples of Y include halogen ions such as chloride ion and bromide ion; and organic carbonyloxy ions (organic carboxylate ions) such as methylcarbonyloxy ion (acetate ion), ethylcarbonyloxy ion (propionate ion), and phenylcarbonyloxy ion (benzoate ion). Among these, halogen ions such as chloride ion and bromide ion are preferred, with chloride ion being more preferred.

[0024] 1.1.2 Non-alkoxysilane-based quaternary ammonium salts (2a) The quaternary ammonium salt (2a) is represented by the following chemical formula:

[0025] [ka] where R d is an alkyl group or aryl group having 10 to 20 carbon atoms, and R e is a methyl group, an ethyl group, a propyl group, a butyl group or (AO) x H, AO is an alkylene oxide group having 2 to 4 carbon atoms, x is 1 to 10, and R f is a methyl group, an ethyl group, a benzyl group, or a hydroxyalkyl group having 2 to 4 carbon atoms, r is 1 or 2, s is 1 or 2, r+s is 3, t is 1 or 2, and Z is a monoalkyl phosphate, a dialkyl phosphate, a halogen, a methyl sulfate, an ethyl sulfate, or an aromatic anion.

[0026] In the above quaternary ammonium salt (2a), R d is an alkyl group or an aryl group having 10 to 20 carbon atoms. d If the number of carbon atoms is too small or too large, the antiviral activity is likely to decrease. d may have 12 or more carbon atoms or 18 or less carbon atoms.

[0027] In the above quaternary ammonium salt (2a), R e is a methyl group, an ethyl group, a propyl group, a butyl group or (AO) x H, AO is an alkylene oxide group having 2 to 4 carbon atoms, and x is 1 to 10. In particular, R e When is a methyl group, the antiviral activity is even better.

[0028] In the above quaternary ammonium salt (2a), R f is a methyl group, an ethyl group, a benzyl group, or a hydroxyalkyl group having 2 to 4 carbon atoms. f When R is a hydroxyalkyl group having 2 to 4 carbon atoms, particularly a hydroxyethyl group, the antiviral properties are even more excellent. f When is a methyl group, the antiviral activity is even more excellent.

[0029] In the above quaternary ammonium salt (2a), examples of aromatic anions that can be Z include paratoluenesulfonic acid, xylenesulfonic acid, benzoic acid, and alkylbenzenesulfonic acid.

[0030] In the above quaternary ammonium salt (2a), when Z is a monoalkyl phosphate and / or a dialkyl phosphate, the antiviral properties are even more excellent. Examples of the alkyl group of the monoalkyl phosphate and dialkyl phosphate include alkyl groups having 1 to 12 carbon atoms. Among these, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 2 to 4 carbon atoms are more preferred. Alternatively, when Z is methyl sulfate or ethyl sulfate, the antiviral properties are also even more excellent.

[0031] Specific examples of the quaternary ammonium salt (2a) include dodecyldimethylhydroxyethylammonium-butyl phosphate salt, tetradecyldimethylhydroxyethylammonium-butyl phosphate salt, dodecyldimethylhydroxyethylammonium-ethyl phosphate salt, tetradecyldimethylhydroxyethylammonium-ethyl phosphate salt, etc. Among these, when dodecyldimethylhydroxyethylammonium-butyl phosphate salt is used, further improved antiviral properties and rust prevention properties can be expected.

[0032] 1.1.3 Other antiviral agents (3a) The antiviral agent contained in the antiviral agent composition of the present disclosure may consist solely of one or more of the above-mentioned quaternary ammonium salts (1a) and (2a), or may be used in combination with other antiviral agents (3a). The other antiviral agents (3a) are not particularly limited. The above-mentioned quaternary ammonium salts (1a) and (2a), particularly the quaternary ammonium salt (1a), have antibacterial (bacteriostatic) effects against gram-positive and gram-negative bacteria, and antiviral effects against enveloped viruses such as influenza virus and measles virus. Furthermore, in addition to the antiviral effect, it is believed that the antiviral agent also has antistatic and deodorizing effects.

[0033] 1.1.4 Antiviral content The concentration of the antiviral agent (A) is not particularly limited as long as it is stably maintained in the composition and an antiviral effect is obtained. For example, the antiviral agent composition of the present disclosure preferably contains 0.01 to 90 mass% of the antiviral agent (A) in an undiluted state before dilution with water or the like, and more preferably contains 0.1 to 75 mass%.

[0034] 1.2 Resin The antiviral agent composition of the present disclosure contains a water-based polyurethane resin (B). The water-based polyurethane resin (B) can function as a binder resin.

[0035] 1.2.1 Water-based polyurethane resin (B) The aqueous polyurethane resin (B) contained in the antiviral agent composition of the present disclosure has at least one of a carboxyl group and a carboxylate group. In this specification, "having at least one of a carboxyl group and a carboxylate group" refers not only to cases where the carboxyl groups present in the composition or on the surface of the fabric are present as undissociated free carboxyl groups (-COOH), but also to cases where terminal hydrogen atoms have been removed to form carboxylate anions, or cases where the carboxylate anions are chemically bonded to antiviral agent molecules, unless otherwise specified.

[0036] The aqueous polyurethane resin (B) may be obtained, for example, by emulsifying and dispersing in water (hereinafter, "dispersion" or "emulsification") a neutralized product of an isocyanate-terminated prepolymer obtained by reacting a polyisocyanate compound, a polyol compound, and a diol compound having at least one of a carboxyl group and a carboxylate group, followed by a chain extension reaction in water using an amine-based chain extender. The term "aqueous polyurethane resin" as used herein refers to a polyurethane resin that is emulsifiable and dispersible in water. Specifically, the term "aqueous polyurethane resin" as used herein refers to a polyurethane resin that exhibits emulsifiable dispersibility in water. Specifically, the term "aqueous polyurethane resin" refers to a polyurethane resin that exhibits no separation or sedimentation even when an emulsified dispersion (solvent: water) containing the polyurethane resin at a concentration of 35% by mass is prepared and then allowed to stand at atmospheric pressure and 20°C for 12 hours.

[0037] The polyisocyanate compound constituting the aqueous polyurethane resin (B) is not particularly limited, and examples thereof include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds. Examples of aromatic polyisocyanate compounds include toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), and tetramethylxylylene diisocyanate. Examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate (HDI). Examples of alicyclic polyisocyanate compounds include 1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), and norbornane diisocyanate. These polyisocyanate compounds can be used alone or in combination of two or more. Among these polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanate compounds can impart non-yellowing properties to substrates. In particular, at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane is preferred.

[0038] The polyol compound constituting the aqueous polyurethane resin (B) is not particularly limited, and examples thereof include polyether polyols, polyester polyols, and polycarbonate polyols. These polyol compounds can be used alone or in combination of two or more. In particular, when polycarbonate polyols are used, the abrasion resistance is improved. The number average molecular weight of the polyol compound is not particularly limited, but may be, for example, from 1,000 to 3,000. When the number average molecular weight is within this range, the appearance quality and abrasion resistance are improved.

[0039] Examples of polyether polyols include polyols that are homoaddition polymers or coaddition polymers (which may be block copolymers or random copolymers) of alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and tetramethylene oxide.

[0040] Examples of polycarbonate polyols include those obtained by dealcoholization reactions or dephenolization reactions between polyols and carbonates. The polyols may be one or more selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, or ethylene oxide or propylene oxide adducts of bisphenol A. The carbonates may be one or more selected from diethyl carbonate, dimethyl carbonate, diphenyl carbonate, and the like. The polycarbonate polyols can be used alone or in combination of two or more.

[0041] Examples of polyester polyols include those obtained by polycondensation reaction of a dibasic acid with the above-mentioned polyols. The dibasic acid may be one or more selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, and fumaric acid. The polyester polyols may be used alone or in combination of two or more.

[0042] Examples of diol compounds having at least one of a carboxyl group and a carboxylate group that constitute the aqueous polyurethane resin (B) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts thereof. Furthermore, polyester polyols having pendant carboxyl groups obtained by reacting a diol compound having a carboxyl group with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or the like can also be used as such diol compounds. The diol compound having a carboxyl group may also be mixed with a diol compound not having a carboxyl group as a diol component and reacted. These diol compounds may be used alone or in combination of two or more.

[0043] The content of at least one of carboxyl groups and carboxylate groups in the aqueous polyurethane resin (B) is not particularly limited. For example, from the viewpoint of the adhesion of the antiviral agent or compatibility with the antiviral agent, the aqueous polyurethane resin (B) may contain at least one of carboxyl groups and carboxylate groups in an amount of 0.4% by mass to 4.0% by mass. Furthermore, when the aqueous polyurethane resin (B) contains both carboxyl groups and carboxylate groups, the total content of the carboxyl groups and carboxylate groups may be 0.4% by mass to 4.0% by mass. The content of the carboxyl groups and carboxylate groups can be determined by calculating the amount of COO per 100 g of polyurethane resin from the amounts of raw materials charged. A content of the carboxyl groups and carboxylate groups of 4.0% by mass or less results in a softer texture and facilitates suppression of the problem of whitening upon bending. Furthermore, when the content of carboxyl groups and carboxylate groups is 0.4% by mass or more, the storage stability of the aqueous polyurethane resin (B) is improved, and more stable processing becomes possible.

[0044] When preparing the above-mentioned isocyanate group-terminated prepolymer, a low molecular weight polyhydric alcohol such as ethylene glycol, 1,4-butanediol, or hexamethylene glycol may be used as the polyol compound.

[0045] Examples of chain extenders include low-molecular-weight polyamines (polyamine compounds containing two or more amino groups of at least one type selected from the group consisting of primary amino groups and secondary amino groups per molecule), such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, norboranediamine, diaminodiphenylmethane, tolylenediamine, xylylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and iminobispropylamine. These chain extenders may be used alone or in combination of two or more.

[0046] The aqueous polyurethane resin (B) may be, for example, a flame retardant-blended urethane resin containing a phosphorus-based compound as a flame retardant component, as disclosed in JP-A-2006-206839.

[0047] Next, a method for producing the aqueous polyurethane resin (B) will be described.

[0048] The specific method for producing the above-mentioned isocyanate-terminated prepolymer is not particularly limited, and can be, for example, a conventionally known single-stage so-called one-shot method or a multi-stage isocyanate polyaddition reaction method. The reaction temperature is preferably 40 to 150°C. An organic solvent that does not react with the isocyanate group may be added during or after the reaction. Examples of such organic solvents include acetone, methyl ethyl ketone, toluene, and tetrahydrofuran. During the reaction, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin di-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine, or bismuth tris(2-ethylhexanoate), or a reaction inhibitor such as phosphoric acid, sodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, or benzoyl chloride may be added as needed.

[0049] The content of residual isocyanate groups in the isocyanate-terminated prepolymer is preferably 0.2 to 4.5% by mass. Within this range, the aqueous polyurethane resin composition obtained by subsequent chain extension with a polyamine exhibits good film-forming properties, and the formed film is soft and exhibits appropriate flexibility. The content of residual isocyanate groups can be determined by the following method.

[0050] 0.3 g of the resulting urethane prepolymer is placed in an Erlenmeyer flask and dissolved in 10 ml of 0.1 N dibutylamine toluene solution. Next, several drops of bromophenol blue solution are added, and the mixture is titrated with 0.1 N hydrochloric acid methanol solution. The free isocyanate group content (NCO%) can be calculated using the following formula: NCO% = (ab) × 0.42 × f / x a: Titration volume of 0.1N hydrochloric acid methanol solution when only 10 ml of 0.1N dibutylamine toluene solution is titrated b: Titration volume of 0.1N hydrochloric acid methanol solution when titrating the composition during reaction f: Factor of 0.1N hydrochloric acid methanol solution x: sampling amount.

[0051] To achieve the residual isocyanate group content within the above range, it is preferable to adjust the molar ratio of isocyanate groups to 100 / 80 to 100 / 60 in the raw materials used in producing the prepolymer. By adjusting the molar ratio of isocyanate groups to 100 / 80 to 100 / 60 in this range, the isocyanate-terminated prepolymer has an appropriate viscosity and is easily emulsified. Furthermore, the texture of a structure treated with the antiviral composition can be made softer, and whitening upon bending can be more easily prevented.

[0052] Neutralization of the carboxyl groups of the isocyanate-terminated prepolymer can be carried out using a known method before, during, or after the preparation of the isocyanate-terminated prepolymer. The compound used to neutralize the isocyanate-terminated prepolymer having such a carboxyl group is not particularly limited, and examples thereof include amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N-methyl-diethanolamine, N,N-dimethylmonoethanolamine, N,N-diethylmonoethanolamine, and triethanolamine, potassium hydroxide, sodium hydroxide, and ammonia. Among these, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, and tributylamine are particularly preferred.

[0053] The emulsifying and dispersing equipment used to emulsify and disperse the neutralized isocyanate-terminated prepolymer in water is not particularly limited, and examples include a homomixer, a homogenizer, and a disperser. Furthermore, when emulsifying and dispersing the neutralized isocyanate-terminated prepolymer in water, it is preferable to emulsify and disperse the neutralized isocyanate-terminated prepolymer in water at a temperature range of 0 to 40°C to minimize the reaction between the isocyanate group and water. Furthermore, when emulsifying and dispersing in this manner, a reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, or benzoyl chloride can be added as needed.

[0054] The isocyanate-terminated prepolymer emulsified and dispersed in water may be chain-extended using a polyamine compound containing two or more amino groups of at least one type selected from the group consisting of primary amino groups and secondary amino groups per molecule. The reaction between the isocyanate-terminated prepolymer and the polyamine compound is completed at a reaction temperature of 20 to 50°C, usually within 30 to 120 minutes.

[0055] When the organic solvent described above is used in producing the isocyanate group-terminated prepolymer, it is desirable to distill off the organic solvent at 30 to 80°C under reduced pressure, for example, after the chain extension reaction or emulsion dispersion. An emulsion dispersion of the aqueous polyurethane resin (B) is obtained by such a preparation method. The resin solids (non-volatile content) concentration in the emulsion dispersion of the aqueous polyurethane resin (B) may be, for example, 20% or more and 60% or less. The resin solids concentration can also be adjusted by adding or distilling off water.

[0056] 1.2.2 Other Resins (B') The antiviral composition of the present disclosure may contain, in addition to the aqueous polyurethane resin (B), a resin (B') other than the aqueous polyurethane resin. Examples of the other resin (B') include acrylic resins. The mass ratio of the aqueous polyurethane resin to the acrylic resin is not particularly limited, but may be, for example, 10 parts by mass or more and 100 parts by mass or less of the acrylic resin per 100 parts by mass of the aqueous polyurethane resin (B). Examples of monomers constituting acrylic resins include (meth)acrylic acid derivatives such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene; acrylamides such as acrylamide, diacetone acrylamide, methacrylamide, and maleic acid amide; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl compounds such as vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, and vinylamide; α-olefins such as ethylene and propylene; maleic acid, fumaric acid, itaconic acid, and derivatives thereof. Here, (meth)acrylic acid refers to acrylic acid or methacrylic acid. Such monomers can be used singly or in combination of two or more.

[0057] 1.2.3 Resin content In the antiviral composition of the present disclosure, the content of each of the aqueous polyurethane resin (B) and the acrylic resin (B') is not particularly limited. For example, the antiviral composition of the present disclosure may contain 0.01% by mass or more and 50% by mass or less of the aqueous polyurethane resin. The lower limit may be 0.02% by mass or more, and the upper limit may be 20% by mass or less. Furthermore, when the antiviral composition of the present disclosure is used after dilution with a solvent such as water, the diluted composition may contain 0.001% by mass or more and 20% by mass or less of the aqueous polyurethane resin. The lower limit may be 0.005% by mass or more or 0.01% by mass or more, and the upper limit may be 10% by mass or less.

[0058] Furthermore, in the antiviral agent composition of the present disclosure, the ratio (mass ratio) of the antiviral agent (A) to the aqueous polyurethane resin (B) is not particularly limited. From the viewpoint of further enhancing the antiviral properties and stability effects, for example, the aqueous polyurethane resin (B) is preferably 0.1 parts by mass or more and 50 parts by mass or less per 1 part by mass of the antiviral agent (A). The lower limit is more preferably 0.75 parts by mass or more, and even more preferably 1 part by mass or more, and the upper limit is more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[0059] 1.3 Nonionic surfactants (C) The antiviral agent composition of the present disclosure contains, as the nonionic surfactant (C), at least one of the following nonionic surfactants (1c) to (4c) and a polyoxyalkylene sorbitan fatty acid ester. The nonionic surfactant (C) can function as a dispersant for stably dispersing the antiviral agent (A) and the aqueous polyurethane resin (B) in the same liquid.

[0060] 1.3.1 Nonionic surfactants (1c) The nonionic surfactant (1c) has the following chemical formula:

[0061] [ka] where Ar is an aromatic hydrocarbon group having 6 to 46 carbon atoms, and A 1 O is an alkylene oxide group having 2 to 4 carbon atoms, n1 is 10 to 60, and X 1 is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0062] Ar is not particularly limited as long as it is derived from an aromatic hydrocarbon group and has 6 to 46 carbon atoms. From the viewpoint of further enhancing the effect on liquid stability, the number of carbon atoms in Ar is preferably 6 to 38, and more preferably 10 to 30. Examples of such aromatic hydrocarbon groups include a phenyl group, a naphthyl group, and a 1-5 styrenated phenyl group, with a naphthyl group and a 1-3 styrenated phenyl group being preferred. A 1 O is an alkylene oxide group having 2 to 4 carbon atoms. From the viewpoint of further enhancing the effect on liquid stability, A 1 The number of carbon atoms in O is preferably 2 to 3. n1 is 10 to 60, and preferably 10 to 50 from the viewpoint of further enhancing the effect on liquid stability.

[0063] 1.3.2 Nonionic surfactants (2c) The nonionic surfactant (2c) has the following chemical formula:

[0064] [ka] where R 1 is a hydrocarbon group having 1 to 30 carbon atoms, and A 2 O is an alkylene oxide group having 2 to 4 carbon atoms, n2 is 5 to 40, and X 2 is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0065] R 1 is a hydrocarbon group having 1 to 30 carbon atoms, which may be linear or branched, and may contain an unsaturated bond. From the viewpoint of further enhancing the effect on liquid stability, R 1The number of carbon atoms in A is preferably 8 or more and 22 or less, and more preferably 8 or more and 18 or less. 2 O is an alkylene oxide group having 2 to 4 carbon atoms. 2 The number of carbon atoms in O is preferably 2 or 3. n is 5 or more and 40 or less, and from the viewpoint of further enhancing the effect on liquid stability, it is preferably 5 or more and 30 or less.

[0066] 1.3.3 Nonionic surfactants (3c) The nonionic surfactant (3c) has the following chemical formula:

[0067] [ka] where R 2 is a hydrocarbon group having 1 to 30 carbon atoms, and A 3 O and A 4 O are each independently an alkylene oxide group having 2 to 4 carbon atoms, n3+n4 is 5 to 70, and X 3 and X 4 are each independently at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0068] R 2 is a hydrocarbon group having 1 to 30 carbon atoms, which may be linear or branched, and may contain an unsaturated bond. From the viewpoint of further enhancing the effect on liquid stability, R 2 The number of carbon atoms in A is preferably 8 or more and 22 or less, and more preferably 8 or more and 18 or less. 3 O and A 4 Each O is independently an alkylene oxide group having 2 to 4 carbon atoms. 3 O and A 4 The number of carbon atoms in O is preferably 2 or 3. n3+n4 is 5 or more and 70 or less, and from the viewpoint of further enhancing the effect on liquid stability, it is preferably 8 or more and 60 or less.

[0069] 1.3.4 Nonionic surfactants (4c) The nonionic surfactant (4c) has the following chemical formula:

[0070] [ka] where R 3 is a hydrocarbon group having 1 to 30 carbon atoms, and A 5 O is an alkylene oxide group having 2 to 4 carbon atoms, n5 is 5 to 40, and X 5 is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

[0071] R 3 is a hydrocarbon group having 1 to 30 carbon atoms, which may be linear or branched, and may contain an unsaturated bond. From the viewpoint of further enhancing the effect on liquid stability, R 3 The number of carbon atoms in A is preferably 8 or more and 22 or less, and more preferably 8 or more and 18 or less. 5 O is an alkylene oxide group having 2 to 4 carbon atoms. 5 The number of carbon atoms in O is preferably 2 or 3. n5 is 5 or more and 40 or less, and from the viewpoint of further enhancing the effect on stability, it is preferably 5 or more and 30 or less.

[0072] 1.3.5 Polyoxyalkylene sorbitan fatty acid esters The polyoxyalkylene sorbitan fatty acid ester has a degree of polymerization of the alkylene oxide of 10 or more and 50 or less. If the degree of polymerization of the alkylene oxide is outside this range, it is difficult to obtain the desired liquid stability. The number of carbon atoms of the fatty acid in the polyoxyalkylene sorbitan fatty acid ester is not particularly limited, but is preferably 1 to 22, for example. In particular, those having a fatty acid of 10 to 22 carbon atoms and having a degree of polymerization of the alkylene oxide of 10 or more and 35 or less are more preferred. The number of carbon atoms of the alkylene oxide is preferably 2 or 3, and ethylene oxide is more preferred. Specific examples of polyoxyalkylene sorbitan fatty acid esters include polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan myristate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan isostearate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, and polyoxyethylene sorbitan behenate. "Sorbitan" is obtained by intramolecular dehydration of sorbitol, and specific examples include 1,4-sorbitan, 3,6-sorbitan, 1,5-sorbitan, and its dihydrogenated product, 1,4,3,6-sorbide, or mixtures thereof. Polyoxyethylene sorbitan fatty acid esters may be monoesters, diesters, triesters, tetraesters or higher esters, or mixtures thereof.

[0073] 1.3.6 Nonionic surfactant content In the antiviral composition of the present disclosure, the ratio (mass ratio) of the antiviral agent (A) to the nonionic surfactant (C) is not particularly limited. From the viewpoint of further enhancing the antiviral properties and stability effects, for example, the nonionic surfactant (C) is preferably 0.1 parts by mass or more and 25 parts by mass or less per 1 part by mass of the antiviral agent (A). The lower limit is more preferably 0.25 parts by mass or more, and even more preferably 1 part by mass or more, and the upper limit is more preferably 10 parts by mass or less.

[0074] 1.4 Other ingredients The antiviral composition of the present disclosure may contain various additives, etc. For example, as long as the effects of the above-mentioned components are not hindered, fillers (matt agents), leveling agents (wettability improvers), antifoaming agents, smoothing agents (slippage improvers), antifouling agents, crosslinking agents, emulsifiers, thickeners, preservatives, buffers, pH adjusters, etc. may be contained. When treating leather, it is preferable that the antiviral composition of the present disclosure contain a thickener from the viewpoint of coatability. That is, the coatability of the antiviral composition of the present disclosure can be changed by appropriately adjusting the viscosity using a thickener in combination. Furthermore, as described below, the antiviral composition of the present disclosure may be used after diluting with water, an organic solvent, etc.; in other words, the antiviral composition of the present disclosure may be in the form of a treatment liquid containing water, an organic solvent, etc.

[0075] 2. Antiviral structures The antiviral structure of the present disclosure includes a substrate and a composition. The composition is attached to the surface of the substrate. The composition is the antiviral composition of the present disclosure. Various substrates can be used to form the structure. For example, the substrate may be made of fiber, leather, plastic, glass, metal, or the like.

[0076] The amount of the antiviral agent composition adhered to the substrate is not particularly limited. For example, the amount of the antiviral agent (A) adhered to the substrate is 0.01 g / m 2 or more than 0.02g / m 2 may be 20 g / m or more, 2 Less than or equal to 10g / m 2 The amount of antiviral agent attached may be 0.01 g / m or less. 2 When the amount of antiviral agent adhered is 20 g / m or more, a higher antiviral effect can be obtained. 2 When the amount of the aqueous polyurethane resin (B) adhered to the substrate is 0.01 g / m or less, the occurrence of adhesion due to water droplets can be reduced. 2 or more than 0.06g / m 2 may be 20 g / m or more, 2 Less than or equal to 10g / m2 The amount of the aqueous polyurethane resin (B) attached may be 0.01 g / m or less. 2 When the adhesion amount of the aqueous polyurethane resin (B) is 20 g / m or more, the durability of the antiviral agent is further improved. 2 If it is below this, the texture can be made even softer.

[0077] The antiviral structure may further contain additives, etc. Examples of such additives include colorants, antioxidants, light stabilizers, UV absorbers, flame retardants, softeners, crosslinking agents, other thermoplastic resins, etc. The use of a carbodiimide crosslinking agent in combination can improve abrasion resistance and water resistance.

[0078] Hereinafter, the case where a fabric substrate or a leather substrate is used as the substrate will be described in detail.

[0079] 2.1 Antiviral fabrics The antiviral fabric of the present disclosure comprises a fabric substrate and the antiviral composition of the present disclosure, with the antiviral composition adhered to the fabric substrate. Antiviral agents containing quaternary ammonium salts (1a) and / or (2a) are difficult to immobilize on fabrics that do not have oxygen-containing functional groups on their surfaces, and pretreatment has been required for immobilization. In contrast, the antiviral composition of the present disclosure allows the antiviral agent (A) and the aqueous polyurethane resin (B) to be applied to the fabric substrate in a single treatment, i.e., in the same bath, thereby immobilizing the antiviral agent (A) on the fabric substrate. Furthermore, the antiviral composition of the present disclosure exhibits higher bath stability than conventional same-bath treatments.

[0080] The fabric substrate may be any of woven fabric, knitted fabric, and nonwoven fabric, and can be appropriately selected depending on the application and purpose. The material of the fabric substrate may be natural fiber, chemical fiber, or a combination thereof. Natural fibers include cotton, wool, silk, hemp, etc., and chemical fibers include polyester, polyurethane, polyamide, rayon, acrylic, etc., and a fabric substrate made of these alone or in combination can be selected. Furthermore, from the viewpoint of application and design, other fibers, for example, inorganic fibers such as metal fibers and glass fibers, may be included. Furthermore, these fabric substrates may be subjected to various processes, such as flame retardant processing and stain-resistant processing. For example, polyester-based fabric substrates are mainly selected for vehicle interior applications such as automobile seats.

[0081] Among fabric substrates, the antiviral agent (A) can be relatively easily immobilized on fibers having hydroxyl groups on the surface, such as cotton or wool. Furthermore, when the antiviral agent composition of the present disclosure is used, a fabric having excellent washing durability in which the antiviral agent (A) does not come off even after multiple washings can be obtained with a single treatment.

[0082] The amounts of the antiviral agent (A) and the aqueous polyurethane resin (B) attached to the fabric substrate are not particularly limited as long as the desired effect is achieved. The amount of the antiviral agent (A) attached is, for example, 0.01 to 15 g / m 2 It is preferable that the density is 0.03 to 5 g / m 2 It is more preferable that the amount of the antiviral agent (A) adhered is 0.01 g / m. 2 If it is less than 15g / m, it is difficult to obtain sufficient antiviral effect. 2 If the amount exceeds 100%, there is a risk of deterioration in flammability. In addition, the amount of the aqueous polyurethane resin (B) to be attached is, for example, 0.01 to 15 g / m 2 It is preferable that the density is 0.06 to 5 g / m 2 It is more preferable that the amount of the aqueous polyurethane resin (B) attached is 0.01 g / m 2 If it is less than 15 g / m, the washing durability of the antiviral agent (A) may decrease. 2 If the temperature exceeds this range, the softness of the material may be lost.

[0083] The antiviral fabric may further contain additives, etc. The additives, etc. are as described above.

[0084] 2.2 Antiviral leather The antiviral leather of the present disclosure comprises a leather substrate and the antiviral composition of the present disclosure, with the antiviral composition adhered to the leather substrate. Examples of leather substrates include those with a surface layer made of polyurethane resin (PU), polyvinyl chloride (PVC) leather, pseudo-leather made of polyurethane thermoplastic elastomer (TPU), synthetic leather, artificial leather, and natural leather. Products using such leather substrates include vehicle interior materials, motorcycle seats and grips, shoes, bags, clothing, sanitary products, outdoor tents, furniture, and the like.

[0085] The amounts of the antiviral agent (A) and the aqueous polyurethane resin (B) attached to the leather substrate are not particularly limited as long as the desired effect is achieved. The amount of the antiviral agent (A) attached is, for example, 0.01 to 15 g / m 2 From the viewpoint of efficiency and cost, it is preferably 0.01 to 5 g / m 2 More preferably, it is 0.05 to 2 g / m 2 The amount of the aqueous polyurethane resin (B) attached is, for example, 0.5 to 30 g / m 2 It is preferable that the amount of the aqueous polyurethane resin (B) attached is 0.5 g / m 2 If it is less than 30 g / m, the abrasion resistance of the leather may decrease. 2 If the temperature exceeds this range, the softness and appearance quality of the material may be impaired.

[0086] The antiviral leather may further contain additives, etc. The additives, etc. are as described above.

[0087] 3. Method for producing antiviral construct The method for producing the antiviral structure of the present disclosure includes attaching the antiviral agent composition of the present disclosure to the surface of a substrate.

[0088] The antiviral composition of the present disclosure may be composed of a treatment liquid (dispersion) containing an antiviral agent (A), an aqueous polyurethane resin (B), and a nonionic surfactant (C). In this case, the antiviral composition can be attached to a substrate by contacting the treatment liquid with the substrate. For example, the antiviral agent (A) can be prepared as an aqueous dispersion, a solution of water and / or an organic solvent, or an emulsion having a solids content (nonvolatile content) of 10 to 80% by weight, and the aqueous polyurethane resin (B) can be prepared as an aqueous dispersion or emulsion having a solids content (nonvolatile content) of 10 to 50% by weight. These and the nonionic surfactant (C) can then be diluted with water and / or an organic solvent to a predetermined concentration to produce a treatment liquid for imparting antiviral properties to a substrate. Examples of organic solvents include alcohols (e.g., methanol, ethanol, propanol), acetone, acetonitrile, or mixtures thereof.

[0089] The concentration (active ingredient concentration) of the antiviral agent (A) in the treatment liquid may be, for example, 0.001% by mass or more, 0.002% by mass or more, 0.01% by mass or more, or 0.02% by mass or more, and may be 10% by mass or less, 5% by mass or less, or 4% by mass or less. A concentration of 0.001% by mass or more and 10% by mass or less provides an excellent balance between performance and cost. Furthermore, the concentration (active ingredient concentration) of the aqueous polyurethane resin (B) in the treatment liquid may be, for example, 0.001% by mass or more, 0.005% by mass or more, or 0.1% by mass or more, and may be 50% by mass or less, or 10% by mass or less. A concentration of 0.001% by mass or more and 50% by mass or less provides an excellent balance between performance and cost. Furthermore, the concentration (active ingredient concentration) of the nonionic surfactant (C) in the treatment liquid may be, for example, 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more, and may be 10% by mass or less, or 5% by mass or less. A concentration of 0.001% by mass or more and 10% by mass or less provides an excellent balance between performance and cost.

[0090] In particular, when treating fabrics with an antiviral agent, the concentration of the antiviral agent (A) in the treatment solution (active ingredient concentration) is, for example, preferably 0.01 to 10 mass%, more preferably 0.1 to 5.0 mass%. The concentration of the aqueous polyurethane resin (B) in the treatment solution (active ingredient concentration) is, for example, preferably 0.005 to 1.0 mass%, more preferably 0.01 to 1.0 mass%. The concentration of the nonionic surfactant (C) in the treatment solution (active ingredient concentration) is, for example, preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%.

[0091] Furthermore, when treating leather with an antiviral agent, the concentration of the antiviral agent (A) in the treatment solution (active ingredient concentration) is, for example, preferably 0.01 to 10 mass%, more preferably 0.1 to 5.0 mass%, and even more preferably 0.1 to 2.5 mass%. The concentration of the aqueous polyurethane resin (B) in the treatment solution (active ingredient concentration) is, for example, preferably 1.0 to 50 mass%, and more preferably 1.0 to 30 mass%. The concentration of the nonionic surfactant (C) in the treatment solution (active ingredient concentration) is, for example, preferably 0.1 to 10 mass%, and more preferably 1.0 to 5.0 mass%.

[0092] In either case, first, the antiviral agent (A), the aqueous polyurethane resin (B), and the nonionic surfactant (C) are diluted with water and / or an organic solvent to a predetermined concentration to prepare a treatment liquid. The treatment liquid is then brought into contact with a substrate to produce an antiviral structure. The method for bringing the treatment liquid into contact with the substrate is not particularly limited and may be determined appropriately depending on the type of substrate, etc.

[0093] Hereinafter, the case where a fabric substrate or a leather substrate is used as the substrate will be described in detail.

[0094] 3.1 Manufacturing method of antiviral fabric The antiviral fabric can be produced by contacting the fabric substrate with the treatment solution. Examples of methods for contacting the fabric substrate with the treatment solution include the Dip-Nip method, the exhaust method, and the coating method.

[0095] When the treatment is performed by the Dip-Nip method, the fabric substrate is first immersed in a treatment solution, squeezed with a mangle or the like, and then heated and dried to adhere the treatment solution to the fabric substrate. Subsequently, a heat-drying treatment is performed to fix the antiviral agent to the fabric substrate. The treatment temperature is not particularly limited and can be within a temperature range including room temperature.

[0096] When treatment is performed by the exhaustion method, a composition (treatment liquid) containing the antiviral agent (A) and the like is heated to 80°C or higher and 140°C or lower, and then a fabric substrate is immersed in the liquid, squeezed with a mangle or the like, and then heated and dried to adhere the antiviral agent to the fabric substrate, thereby allowing the antiviral agent to be fixed.

[0097] When treatment is performed by a coating method, the antiviral agent composition of the present disclosure is adjusted to have an appropriate viscosity, and the composition (treatment liquid) is coated onto a fabric substrate and then dried, thereby immobilizing the antiviral agent on the fabric substrate. The coating method is not particularly limited, and examples thereof include gravure roll processing, spray processing, roll coater processing, jet printing, transfer printing, and screen printing.

[0098] After treating the fabric substrate with the treatment liquid containing the antiviral agent (A), the aqueous polyurethane resin (B), and the nonionic surfactant (C), the fabric substrate may be washed as needed and then air-dried or may be heat-dried. For heat-drying, devices such as a loop dryer, a net dryer, an oven, or a heat setter can be used. The drying / heat treatment temperature for the fabric substrate to which the treatment liquid containing the antiviral agent (A), the aqueous polyurethane resin (B), and the nonionic surfactant (C) has been applied can be 80 to 190°C, and preferably 100 to 160°C. The drying / heat treatment time may be 30 seconds or more or 1 minute or more, and 30 minutes or less or 10 minutes or less.

[0099] 3.2 Manufacturing method for antiviral leather The antiviral leather can be produced by contacting the leather substrate with the above-mentioned treatment solution.

[0100] Examples of methods for contacting the treatment solution with the leather substrate include: applying the treatment solution to the surface of the leather substrate using various coaters such as a gravure coater, a bar coater, a comma coater, a blade coater, and an air knife coater; spraying the treatment solution onto the surface of the leather substrate; and immersing the leather substrate in the treatment solution. Direct coating and reverse coating methods using a gravure coater are particularly preferred. The amount of treatment solution to be applied may be any amount that provides a desired amount of adhesion after drying, and may be, for example, an amount of adhesion after drying of 4 to 40 g / m. 2 The amount is preferably 6 to 30 g / m 2 It is more preferable that the amount be such that

[0101] There are no particular limitations on the method for drying the applied treatment liquid, and for example, drying for 30 seconds to 10 minutes at a temperature in the range of 40 to 160° C. is preferred, and drying for 30 seconds to 2 minutes at a temperature in the range of 80 to 130° C. After drying, aging treatment is preferably carried out at a temperature in the range of 20 to 100° C. for 5 to 72 hours. [Example]

[0102] The technology of the present disclosure will be described in more detail below with reference to examples, but the technology of the present disclosure is not limited to the following examples.

[0103] 1. Antiviral Agents (A) 1.1 Alkoxysilane-based quaternary ammonium salts (1a) A reaction vessel was charged with 199 parts by mass of trimethoxysilylpropyl chloride, 298 parts by mass of dimethyloctadecylamine, and 744 parts by mass of ethanol, and the mixture was reacted at 150°C for 20 hours under a nitrogen atmosphere to obtain 1,241 parts by mass of an ethanol solution containing 40% by mass of an alkoxysilane-based quaternary ammonium salt (1a) as the antiviral agent (A).

[0104] 1.2 Non-alkoxysilane quaternary ammonium salts (2a) A reaction vessel was charged with 143 parts of an alkyl phosphate ester (mono- / di-) in a ratio of approximately 1 / 1, prepared from 3 moles of n-butanol and 1 mole of diphosphorus pentoxide, and 457 parts of water, followed by neutralization with the addition of 260 parts of dodecyldimethylamine. 54 parts of ethylene oxide was added to the neutralized product, and the mixture was reacted at 100°C for 3 hours to obtain 913 parts of a composition containing 50.0% by mass of a non-alkoxysilane quaternary ammonium salt (2a) as the antiviral agent (A).

[0105] 2. Water-based polyurethane resin (B) 2.1 Synthesis example B-1 Into a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 71.7 parts by mass of polycarbonate diol (1,5-pentanediol / 1,6-hexanediol) ("Duranol T5652" manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight 2,000) as a polycarbonate polyol, 0.4 parts by mass of trimethylolpropane as a polyhydric alcohol, 3 parts by mass of 2,2-dimethylolpropionic acid as an anionic hydrophilic group / active hydrogen-containing compound, 0.1 parts by weight of methyl ethyl ketone and 42.2 parts by weight of methyl ethyl ketone were added and mixed uniformly. Then, 23.5 parts by weight of dicyclohexylmethane diisocyanate as an organic polyisocyanate and 0.03 parts by weight of bismuth tris(2-ethylhexanoate) were added and reacted at 80°C for 240 minutes to obtain a methyl ethyl ketone solution of isocyanate-terminated urethane prepolymer with a free isocyanate group content of 2.29% by weight relative to the isocyanate-terminated prepolymer. 2.2 parts by weight of triethylamine was added to this solution and mixed uniformly. 185 parts by weight of water was gradually added to emulsify and disperse the mixture. 1.1 parts by weight of hydrazine monohydrate and 0.4 parts by weight of diethylenetriamine were added as chain extenders to the resulting emulsion and dispersion, and the mixture was stirred for 90 minutes to obtain a polyurethane dispersion. Next, the solvent was removed from this polyurethane dispersion at 40°C under reduced pressure to obtain a stable aqueous polyurethane resin composition containing 35.0% by mass of the aqueous polyurethane resin (B-1).

[0106] 2.2 Synthesis examples B-2~B-7 Stable aqueous polyurethane resin compositions containing 35.0 mass% each of aqueous polyurethane resins (B-2) to (B-7) were obtained in the same manner as in Synthesis Example B-1, except that the types and amounts of organic polyisocyanate, polycarbonate polyol, polyhydric alcohol, anionic hydrophilic group / active hydrogen-containing compound, neutralizing amine, and chain extender shown in Table 1 below were used.

[0107] [Table 1] H12MDI: Dicyclohexylmethane diisocyanate IPDI: Isophorone diisocyanate HDI: Hexamethylene diisocyanate T5652: Duranol T5652 [number average molecular weight 2,000] (manufactured by Asahi Kasei Chemicals Corporation) T5651: Duranol T5651 [number average molecular weight 1,000] (manufactured by Asahi Kasei Chemicals Corporation) C3090: Kuraray Polyol C-3090 [number average molecular weight 3,000] (Kuraray Co., Ltd.) TMP: Trimethylolpropane DMPA: 2,2-dimethylolpropionic acid TEA: Triethylamine DETA: Diethylenetriamine

[0108] 3. Water-based acrylic resin (B') 28 parts of ion-exchanged water was weighed into a reactor equipped with a thermometer, a stirrer, a dropping device, a reflux condenser, and a nitrogen inlet tube. Nitrogen was sealed in and the internal temperature was raised to 80°C. Then, while maintaining that temperature, 2 parts of a 10% ammonium persulfate aqueous solution were added, and immediately, a separately prepared monomer emulsion prepared as described below was continuously added dropwise over 4 hours to perform emulsion polymerization. The monomer emulsion used above was prepared by mixing a monomer mixture of 32 parts of acrylic acid, 45 parts of ethyl acrylate, and 23 parts of butyl acrylate with 4 parts of polyoxyethylene alkyl ether sodium sulfate (manufactured by Kao Corporation, product name: Latemul E-118B) and 30 parts of ion-exchanged water, followed by emulsification. Simultaneously with the dropwise addition of this monomer emulsion, 4 parts of a 5% ammonium persulfate aqueous solution were added dropwise. After completion of the dropwise addition, the mixture was aged at 80°C for 4 hours and then cooled to room temperature. Finally, the mixture was neutralized with aqueous ammonia, and the solid content was adjusted with water to obtain a composition (solid content 60%) containing a water-based acrylic resin (B').

[0109] 4. Nonionic surfactants (C) 4.1 Nonionic surfactants (1c) The following nonionic surfactants (1c-1) to (1c-7) are all represented by the following chemical formula (1c).

[0110] [ka]

[0111] 4.1.1 Synthesis example 1c-1 47 parts (0.5 mol) of phenol and 0.1 parts of sulfuric acid were charged into a reaction vessel and stirred. Then, 47 parts (0.5 mol) of phenol was charged and heated under a nitrogen gas stream to approximately 80°C. The temperature was further increased to 105-135°C, and 312 parts (3 mol) of styrene monomer was added dropwise. The addition reaction was carried out at 125-135°C for approximately 3 hours, and then cooled to obtain a brown, transparent, viscous tristyrenated phenol. 406 parts (1 mol) of the resulting tristyrenated phenol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C. Then, 836 parts (19 mol) of ethylene oxide were added at 155-165°C and a pressure of 0.39 MPa or less. After the ethylene oxide addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (1c-1). The nonionic surfactant (1c-1) is a surfactant represented by the formula (1c) in which Ar is a tristyrylphenyl having 30 carbon atoms, and A 1 O is ethylene oxide having 2 carbon atoms, n1 is 19, and X 1 is hydrogen.

[0112] 4.1.2 Synthesis example 1c-2 A nonionic surfactant (1c-2) was obtained in the same manner as in Synthesis Example 1c-1, except that 1,320 parts (30 moles) of ethylene oxide was used. The nonionic surfactant (1c-2) is a surfactant represented by the formula (1c) above, in which Ar is a tristyrylphenyl having 30 carbon atoms, and A 1 O is ethylene oxide having 2 carbon atoms, n1 is 30, and X 1 is hydrogen.

[0113] 4.1.3 Synthesis example 1c-3 47 parts (0.5 mol) of phenol and 0.1 parts of sulfuric acid were charged into a reaction vessel and stirred. Then, 47 parts (0.5 mol) of phenol was charged and heated under a nitrogen gas stream to approximately 80°C. The temperature was further increased to 105-135°C, and 208 parts (2 mol) of styrene monomer was added dropwise. An addition reaction was carried out at 125-135°C for approximately 3 hours, followed by cooling to obtain distyrenated phenol. 302 parts (1 mol) of the resulting distyrenated phenol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C. Then, 528 parts (12 mol) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the ethylene oxide addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (1c-3). The nonionic surfactant (1c-3) is a surfactant represented by the formula (1c) in which Ar is a distyrylphenyl having 22 carbon atoms, and A 1 O is ethylene oxide having 2 carbon atoms, n1 is 12, and X 1 is hydrogen.

[0114] 4.1.4 Synthesis example 1c-4 144 parts (1 mole) of 2-naphthalenol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C, after which 572 parts (13 moles) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the ethylene oxide addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (1c-4). Nonionic surfactant (1c-4) is a surfactant represented by the formula (1c) above, where Ar is naphthyl having 10 carbon atoms and A is 1 O is ethylene oxide having 2 carbon atoms, n1 is 13, and X 1 is hydrogen.

[0115] 4.1.5 Synthesis example 1c-5 47 parts (0.5 mol) of phenol and 0.1 parts of sulfuric acid were charged into a reaction vessel and stirred. Then, 47 parts (0.5 mol) of phenol was charged and heated under a nitrogen gas stream to approximately 80°C. The temperature was further increased to 105-135°C, and 312 parts (3 mol) of styrene monomer was added dropwise. An addition reaction was carried out at 125-135°C for approximately 3 hours. The mixture was then cooled to obtain a brown, transparent, viscous tristyrenated phenol. 406 parts (1 mol) of the resulting tristyrenated phenol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C. Then, 174 parts (3 mol) of propylene oxide were reacted at 155-165°C and a pressure of 0.39 MPa or less. Subsequently, 880 parts (20 mol) of ethylene oxide were reacted at 155-165°C and a pressure of 0.39 MPa or less. After the addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (1c-5). Nonionic surfactant (1c-5) is a compound represented by the formula (1c) above, where Ar is a tristyrylphenyl having 30 carbon atoms, and A 1 O is a mixture of ethylene oxide having 2 carbon atoms and propylene oxide having 3 carbon atoms, n1 is 23 (ethylene oxide: 20, propylene oxide: 3), and X 1 is hydrogen.

[0116] 4.1.6 Synthesis example 1c-6 A nonionic surfactant (1c-6) was obtained in the same manner as in Synthesis Example 1c-1, except that 2,200 parts (50 moles) of ethylene oxide was used. The nonionic surfactant (1c-6) is a surfactant represented by the formula (1c) above, in which Ar is a tristyrylphenyl having 30 carbon atoms, and A 1 O is ethylene oxide having 2 carbon atoms, n1 is 50, and X 1 is hydrogen.

[0117] 4.1.7 Synthesis Example 1c-7 (Comparative Example) A nonionic surfactant (1c-7) was obtained in the same manner as in Synthesis Example 1c-1, except that 220 parts (5 moles) of ethylene oxide was used. The nonionic surfactant (1c-7) is a surfactant represented by the formula (1c) above, in which Ar is a tristyrylphenyl having 30 carbon atoms, and A 1O is ethylene oxide having 2 carbon atoms, n1 is 5, and X 1 is hydrogen.

[0118] 4.2 Nonionic surfactants (2c) The following nonionic surfactants (2c-1) to (2c-9) are all represented by the following chemical formula (2c).

[0119] [ka]

[0120] 4.2.1 Nonionic surfactants (2c-1) As the nonionic surfactant (2c-1), a secondary alcohol (having 12 to 14 carbon atoms) ethylene oxide 9 mole adduct (manufactured by Nippon Shokubai Co., Ltd.: Softanol 90) was used. The nonionic surfactant (2c-1) is a compound represented by the formula (2c) above, 1 is a hydrocarbon group having 12-14 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 9, and X 2 is hydrogen.

[0121] 4.2.2 Synthesis example 2c-2 268 parts (1 mole) of oleyl alcohol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C, after which 722 parts (16.4 moles) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the ethylene oxide addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (2c-2). Nonionic surfactant (2c-2) can be obtained by adding R 1 is oleyl with 18 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 16.4, and X 2 is hydrogen.

[0122] 4.2.3 Nonionic surfactants (2c-3) As the nonionic surfactant (2c-3), a decyl alcohol ethylene oxide 8-mol adduct (Noigen XL-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used. The nonionic surfactant (2c-3) is represented by the formula (2c) R 1 is a decyl with 10 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 8, and X 2 is hydrogen.

[0123] 4.2.4 Synthesis example 2c-4 268 parts (1 mole) of oleyl alcohol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C, after which 174 parts (3 moles) of propylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. Subsequently, 792 parts (18 moles) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (2c-4). Nonionic surfactant (2c-4) can be obtained by adding R 1 is oleyl with 18 carbon atoms, and A 2 O is a mixture of ethylene oxide having 2 carbon atoms and propylene oxide having 3 carbon atoms, n2 is 21 (ethylene oxide: 18, propylene oxide: 3), and X 2 is hydrogen.

[0124] 4.2.5 Synthesis example 2c-5 270 parts (1 mole) of stearyl alcohol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C, after which 1100 parts (25 moles) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant 2c-5. Nonionic surfactant (2c-5) is a surfactant represented by the formula (2c) above, where R 1 is stearyl with 18 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 25, and X 2 is hydrogen.

[0125] 4.2.6 Synthesis Example 2c-6 130 parts (1 mole) of 2-ethylhexanol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C, after which 352 parts (8 moles) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (2c-6). Nonionic surfactant (2c-6) is a surfactant represented by the formula (2c) above, where R 1 is 2-ethylhexyl with 8 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 8, and X 2 is hydrogen.

[0126] 4.2.7 Synthesis Example 2c-7 (Comparative Example) 268 parts (1 mole) of oleyl alcohol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C, after which 176 parts (4 moles) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the ethylene oxide addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (2c-7). Nonionic surfactant (2c-7) was obtained by adding R 1 is oleyl with 18 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 4, and X 2 is hydrogen.

[0127] 4.2.8 Nonionic surfactant (2c-8) (comparative example) 2-ethylhexyl glycol was used as the nonionic surfactant (2c-8). The nonionic surfactant (2c-8) is represented by the formula (2c) R 1 is 2-ethylhexyl with 8 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 2, and X 2 is hydrogen.

[0128] 4.2.9 Synthesis Example 2c-9 (Comparative Example) 268 parts (1 mole) of oleyl alcohol and 2.5 parts of caustic soda were charged into an autoclave and heated to approximately 130°C, after which 3828 parts (87 moles) of ethylene oxide were reacted at a temperature of 155-165°C and a pressure of 0.39 MPa or less. After the ethylene oxide addition reaction was completed, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain nonionic surfactant (2c-9). Nonionic surfactant (2c-9) is a surfactant represented by the formula (2c) above, where R 1 is oleyl with 18 carbon atoms, and A 2 O is ethylene oxide having 2 carbon atoms, n2 is 87, and X 2 is hydrogen.

[0129] 4.3 Nonionic surfactants (3c) The following nonionic surfactants (3c-1) to (3c-5) are all represented by the following chemical formula (3c).

[0130] [ka]

[0131] 4.3.1 Synthesis example 3c-1 270 parts (1 mole) of stearylamine was charged into an autoclave and heated to about 130°C, and then 660 parts (15 moles) of ethylene oxide was reacted at a temperature of 155 to 165°C and a pressure of 0.39 MPa or less to obtain a nonionic surfactant (3c-1). The nonionic surfactant (3c-1) was obtained by reacting 270 parts (1 mole) of stearylamine with 660 parts (15 moles) of ethylene oxide at a temperature of 155 to 165°C and a pressure of 0.39 MPa or less. 2 is stearyl with 18 carbon atoms, and A 3 O and A 4 O is ethylene oxide having 2 carbon atoms, n3 + n4 is 15, and X 3 and X 4 is hydrogen.

[0132] 4.3.2 Synthesis example 3c-2 A nonionic surfactant (3c-2) was obtained in the same manner as in Synthesis Example 3c-1, except that 1,320 parts (30 moles) of ethylene oxide was used. The nonionic surfactant (3c-2) was a hydroxy group represented by the formula (3c) R 2 is stearyl with 18 carbon atoms, and A 3 O and A 4 O is ethylene oxide having 2 carbon atoms, n3 + n4 is 30, and X 3 and X 4 is hydrogen.

[0133] 4.3.3 Synthesis example 3c-3 A nonionic surfactant (3c-3) was obtained in the same manner as in Synthesis Example 3c-1, except that 2,200 parts (50 moles) of ethylene oxide was used. 2 is stearyl with 18 carbon atoms, and A 3 O and A 4 O is ethylene oxide having 2 carbon atoms, n3 + n4 is 50, and X 3 and X 4 is hydrogen.

[0134] 4.3.4 Synthesis example 3c-4 129 parts (1 mole) of 2-ethylhexylamine was charged into an autoclave and heated to about 130°C, and then 352 parts (8 moles) of ethylene oxide was reacted at a temperature of 155 to 165°C and a pressure of 0.39 MPa or less to obtain a nonionic surfactant (3c-4). The nonionic surfactant (3c-4) was obtained by reacting 129 parts (1 mole) of 2-ethylhexylamine with 352 parts (8 moles) of ethylene oxide at a temperature of 155 to 165°C and a pressure of 0.39 MPa or less. 2 is 2-ethylhexyl with 8 carbon atoms, and A 3 O and A 4 O is ethylene oxide having 2 carbon atoms, n3 + n4 is 8, and X 3 and X 4 is hydrogen.

[0135] 4.3.5 Synthesis example 3c-5 (comparative example) A nonionic surfactant (3c-5) was obtained in the same manner as in Synthesis Example 3c-1, except that 176 parts (4 moles) of ethylene oxide was used. 2 is stearyl with 18 carbon atoms, and A 3 O and A 4 O is ethylene oxide having 2 carbon atoms, n3 + n4 is 4, and X 3 and X 4 is hydrogen.

[0136] 4.4 Nonionic Surfactants (4c) The following nonionic surfactants (4c-1) to (4c-4) are all represented by the following chemical formula (4c): (4c-5) and (4c-6) are represented by the following chemical formula (4c) where R 3 It has hydrogen instead of -C(=O)-.

[0137] [ka]

[0138] 4.4.1 Synthesis example 4c-1 600 parts (1 mole) of polyethylene glycol having a number average molecular weight of 600, 282 parts (1 mole) of oleic acid, and 3 parts of paratoluenesulfonic acid were charged into a reaction vessel and stirred, and then heated under a nitrogen gas flow to 195-205°C for approximately 3 hours to react, and then cooled to obtain nonionic surfactant (4c-1). Nonionic surfactant (4c-1) is a compound represented by the formula (4c) above, where R 3 is an alkenyl group having 17 carbon atoms, and A 5 O is ethylene oxide having 2 carbon atoms, n5 is 13.6, and X 5 is hydrogen.

[0139] 4.4.2 Synthesis example 4c-2 A nonionic surfactant (4c-2) was obtained in the same manner as in Synthesis Example 4c-1, except that 400 parts (1 mole) of polyethylene glycol having a number average molecular weight of 400 was used. The nonionic surfactant (4c-2) was obtained by the procedure shown in Chemical Formula (4c) above. 3 is an alkenyl group having 17 carbon atoms, and A 5 O is ethylene oxide having 2 carbon atoms, n5 is 9.1, and X 5 is hydrogen.

[0140] 4.4.3 Synthesis example 4c-3 A nonionic surfactant (4c-3) was obtained in the same manner as in Synthesis Example 4c-1, except that 1000 parts (1 mole) of polyethylene glycol having a number average molecular weight of 1000 and 565 parts (2 moles) of oleic acid were used. The nonionic surfactant (4c-3) was obtained by the procedure shown in Chemical Formula (4c) above. 3 is an alkenyl group having 17 carbon atoms, and A 5 O is ethylene oxide having 2 carbon atoms, n5 is 22.7, and X 5 This corresponds to oleyl, which has 18 carbon atoms.

[0141] 4.4.4 Synthesis example 4c-4 A nonionic surfactant (4c-4) was obtained in the same manner as in Synthesis Example 4c-1, except that 350 parts (1 mole) of polyethylene glycol having a number average molecular weight of 350 and 144 parts (1 mole) of 2-ethylhexanoic acid were used. The nonionic surfactant (4c-4) was obtained by the procedure shown in Chemical Formula (4c) above. 3 is an alkyl group having 7 carbon atoms, and A 5 O is ethylene oxide having 2 carbon atoms, n5 is 8.0, and X 5 is hydrogen.

[0142] 4.4.5 Nonionic surfactant (4c-5) (Comparative example) As the nonionic surfactant (4c-5), polyethylene glycol (molecular weight 200) (manufactured by Sanyo Chemical Industries, Ltd.: PEG-200) was used.

[0143] 4.4.6 Nonionic surfactant (4c-6) (Comparative Example) As the nonionic surfactant (4c-6), polyethylene glycol (molecular weight 1000) (manufactured by Sanyo Chemical Industries, Ltd.: PEG-1000) was used.

[0144] 4.5 Nonionic Surfactants (5c) 4.5.1 Nonionic surfactants (5c-1) As the nonionic surfactant (5c-1), polyoxyethylene sorbitan monolaurate (20EO) (Kao Corporation: Rheodol TW-L120) was used.

[0145] 4.5.2 Nonionic surfactant (5c-2) (Comparative example) As the nonionic surfactant (5c-2), polyoxyethylene sorbitan monolaurate (6EO) (Kao Corporation: Rheodol TW-L106) was used.

[0146] 4.5.3 Nonionic surfactant (5c-3) (Comparative example) Sorbitan monooleate (Kao Corporation: Rheodol SP-O10V) was used as the nonionic surfactant (5c-3).

[0147] 5. Additives The following additives were used: Filler: ACEMATT TS-100 (manufactured by Evonik Degussa, average particle size: 10 μm) Antifoaming agent: Foamlex 747 (manufactured by Nicca Chemical Co., Ltd.) Leveling agent: Disparlon AQ-7120 (Kusumoto Chemicals Co., Ltd.) Thickener: SN Thickener 612 (manufactured by San Nopco Co., Ltd.) Smoothing agent: KM-862T (Shin-Etsu Chemical Co., Ltd.) Crosslinking agent: Carbodilite SV-02 (Nisshinbo Chemical Co., Ltd.)

[0148] 6. Evaluation conditions 6.1 Liquid stability test The liquid stability was graded as follows: Grade 2 or higher was considered a pass. Grade 1: Aggregates or gelation occurs within 1 hour after preparation Grade 2: No aggregates or gelation were observed 1 hour after preparation, but aggregates or gelation occurred within 6 hours. Grade 3: No aggregates or gelation were observed 6 hours after preparation, but aggregates or gelation occurred within 16 hours. Grade 4: No aggregates or gelation observed 16 hours after preparation

[0149] 6.2 Antiviral Tests Fabrics were tested according to ISO-18184, and leather according to ISO-21702, and the test was graded as follows: A score of 0 or above was considered a pass. ◎: Antiviral activity value of 2 or more 〇: Antiviral activity value 0.5 or more and less than 2 ×: Antiviral activity value less than 0.5

[0150] 7. Preparation of treatment solution and fabrication of antiviral fabric 7.1 Example 1 Mixture 1 was obtained by mixing 5.0 parts of an ethanol solution of quaternary ammonium salt (1a) (non-volatile content 40% by mass) as the antiviral agent (A) with 0.50 parts of a nonionic surfactant (1c-1). Meanwhile, mixed solution 2 was obtained by mixing 0.50 parts of an aqueous polyurethane resin composition (B-1) (non-volatile content 35% by mass) with 94 parts of water. Mixture 1 was added to mixed solution 2 and mixed uniformly to obtain the antiviral agent composition (treatment liquid) of Example 1. The obtained treatment liquid was subjected to the above-described liquid stability test. The results are shown in Table 2 below.

[0151] Mass 390g / m 2 The polyester raw fabric (fabric substrate) was dyed and simultaneously 6% phosphate ester amide was added as a flame retardant in the bath. The fabric was then dipped and nipped in the treatment solution of Example 1 at a pick-up rate of approximately 60%, and then dried at 150°C for 2.5 minutes to obtain a fabric for evaluation. The obtained fabric was subjected to the antiviral test described above. The results are shown in Table 2 below.

[0152] 7.2 Examples 2 to 9 and Comparative Examples 1 to 3 A treatment solution was prepared and a fabric was produced in the same manner as in Example 1, except that the types and contents of the antiviral agent (A), aqueous polyurethane resin (B), and nonionic surfactant (C) in the treatment solution were changed to those shown in Table 2. The results are shown in Table 2.

[0153] 7.3 Examples 10 to 29 and Comparative Examples 4 to 12 The treatment solution was prepared and fabrics were produced in the same manner as in Example 2, except that the type of nonionic surfactant (C) in the treatment solution was changed to that shown in Table 3 below, and the solution stability test and antiviral test were carried out as described above. The results are shown in Table 3 below.

[0154] 7.4 Examples 30 to 37 and Comparative Examples 13 to 20 A treatment solution was prepared and fabrics were produced in the same manner as in Example 9, except that the type of nonionic surfactant (C) in the treatment solution was changed to one shown in Table 4 below, and the solution stability test and antiviral test were carried out as described above. The results are shown in Table 4 below.

[0155] [Table 2]

[0156] [Table 3]

[0157] [Table 4]

[0158] As shown in Table 2 above, when the treatment solution contained a quaternary ammonium salt (1a) as the antiviral agent (A) and a nonionic surfactant (1c-1) (Examples 1 to 8), the solution stability was good and the antiviral properties of the treated fabric were also good. Furthermore, when the treatment solution contained a quaternary ammonium salt (2a) as the antiviral agent (A) and a nonionic surfactant (1c-1) (Example 9), the solution stability was also good and the antiviral properties of the treated fabric were also good. In contrast, when the treatment solution did not contain a nonionic surfactant (Comparative Examples 1 and 2), the solution stability was poor and the treatment bath thickened and gelled within one hour. Furthermore, when the treatment solution did not contain the antiviral agent (A) (Comparative Example 3), sufficient antiviral properties were not obtained in the treated fabric.

[0159] As shown in Tables 3 and 4 above, when the treatment solution contained nonionic surfactants (1c-1) to (1c-6), (2c-1) to (2c-6), (3c-1) to (3c-4), (4c-1) to (4c-4), or (5c-1) (Examples 2, 9 to 37), the solution stability was excellent and the antiviral properties of the treated fabric were also good. On the other hand, when the treatment solution contained nonionic surfactants (1c-7), (2c-7) to (2c-9), (3c-5), (4c-5), (4c-6), (5c-2), or (5c-3) (Comparative Examples 4 to 20), the solution stability was poor, and the treatment bath thickened and gelled within one hour.

[0160] 8. Preparation of treatment solution and fabrication of antiviral leather 8.1 Preparation of leather substrate A surface layer coating material containing 100 parts by weight of an aqueous polyurethane resin ("Evaphanol HA-68" manufactured by Nicca Chemical Co., Ltd.), 10 parts by weight of an aqueous pigment ("PSM Black C" manufactured by Mikuni Shikiso Co., Ltd.), 1 part by weight of a water-dispersible carbodiimide crosslinker ("NK Assist CI-02" manufactured by Nicca Chemical Co., Ltd.), and 3 parts by weight of an associative thickener ("Neo Sticker S" manufactured by Nicca Chemical Co., Ltd.) was applied to a release paper ("Asahi Release AR-148" manufactured by Asahi Roll Co., Ltd.) at a thickness of 100 μm (wet coating amount). The coating was pre-dried in a dryer at 80 ° C for 2 minutes, and then dried at 120 ° C for 3 minutes to completely evaporate the water, yielding a polyurethane resin film (hereinafter referred to as the "surface layer").

[0161] A polyurethane adhesive liquid mixture containing 100 parts by mass of a two-component aqueous polyurethane resin (Evaphanol HO-38, adhesive base, manufactured by Nicca Chemical Co., Ltd.), 7 parts by mass of an aqueous polyisocyanate curing agent (NK Assist NY-27, manufactured by Nicca Chemical Co., Ltd.), and 5 parts by mass of an associative thickener (Neo Sticker N, manufactured by Nicca Chemical Co., Ltd.) was applied to a thickness of 200 μm (wet application amount) on this surface layer.

[0162] The fabric was then dried at 90°C for 1 minute using a dryer, and immediately after drying, a polyester knit was laminated onto the fabric as a fiber substrate. The fabric was then cured at 120°C for 3 minutes and aged at 40°C for 72 hours. The release paper was then peeled off to obtain a fiber laminate (a leather substrate for evaluation).

[0163] 8.2 Example 38 14 parts of an aqueous polyurethane resin composition (B-1) (non-volatile content 35% by mass), 12.5 parts of an aqueous acrylic resin composition (B') (non-volatile content 60% by mass), 2 parts of a filler (non-volatile content 100% by mass), 0.3 parts of an antifoaming agent (non-volatile content 100% by mass), 1.0 part of a leveling agent (non-volatile content 100% by mass), 5 parts of a smoothing agent (non-volatile content 60% by mass), and 3 parts of a crosslinking agent (non-volatile content 40% by mass). A mixture of 2.9 parts of nonionic surfactant (1c-1) (nonvolatile content 100% by mass) and 1.3 parts of an ethanol solution of quaternary ammonium salt (1a) (nonvolatile content 40% by mass) as the antiviral agent (A) was added to a mixed liquid of 2.5 parts of a thickener (nonvolatile content 40% by mass) and 56 parts of water, and the mixture was mixed uniformly to obtain the antiviral agent composition (treatment liquid) of Example 38. The obtained treatment liquid was subjected to the above-mentioned liquid stability test. The results are shown in Table 5 below.

[0164] The treatment solution of Example 38 was applied to the surface of the leather substrate for evaluation at a rate of 20 g / m 2 After uniformly applying the antiviral agent, the leather was dried at 150°C for 2.5 minutes to fix the antiviral agent. The obtained leather was subjected to the antiviral test described above. The results are shown in Table 5 below.

[0165] 8.3 Examples 39 to 75 and Comparative Examples 21 to 36 The treatment solution was prepared and leather was produced in the same manner as in Example 38, except that the types and contents of the antiviral agent (A), aqueous polyurethane resin (B), and nonionic surfactant (C) in the treatment solution were changed to those shown in Tables 5 to 10, and the solution stability test and antiviral activity test were carried out as described above. The results are shown in Tables 5 to 10.

[0166] [Table 5]

[0167] [Table 6]

[0168] [Table 7]

[0169] [Table 8]

[0170] [Table 9]

[0171] [Table 10]

[0172] As shown in Tables 5 to 7 above, when the antiviral composition contained a quaternary ammonium salt (1a) as the antiviral agent (A), various aqueous polyurethane resins (B), and a nonionic surfactant (1c-1) (Examples 38 to 46), the solution stability was excellent and the antiviral properties of treated leather were also good. Furthermore, when the antiviral composition contained nonionic surfactants (1c-4), (1c-5), (1c-6), (2c-1), (2c-3), (2c-4), (2c-5), (3c-1), (4c-1), and (5c-1) (Examples 47 to 56), the solution stability was also excellent and the antiviral properties of treated leather were also good. In contrast, when the nonionic surfactant (C) was not contained (Comparative Example 21), the solution stability was poor, and the treatment bath thickened and gelled within one hour. Furthermore, when the antiviral agent (A) was not contained (Comparative Example 22), sufficient antiviral properties were not obtained in the treated leather. Furthermore, when (1c-7), (2c-8), (2c-9), (3c-5), (4c-5), and (5c-2) were contained as the nonionic surfactant (C) (Comparative Examples 23 to 28), the liquid stability was poor, and the treatment bath thickened and gelled within one hour.

[0173] As shown in Tables 8 to 10 above, when the antiviral composition contained a quaternary ammonium salt (2a) as the antiviral agent (A), various aqueous polyurethane resins (B), and a nonionic surfactant (1c-1) (Examples 57 to 65), the solution stability was excellent and the antiviral properties of treated leather were also good. Furthermore, when the antiviral composition contained nonionic surfactants (1c-4), (1c-5), (1c-6), (2c-1), (2c-3), (2c-4), (2c-5), (3c-1), (4c-1), and (5c-1) (Examples 66 to 75), the solution stability was also excellent and the antiviral properties of treated leather were also good. In contrast, when the antiviral composition did not contain nonionic surfactant (C) (Comparative Example 29), the solution stability was poor, and the treatment bath thickened and gelled within one hour. Furthermore, when the antiviral agent (A) was not contained (Comparative Example 30), sufficient antiviral properties were not obtained in the treated leather. Furthermore, when (1c-7), (2c-8), (2c-9), (3c-5), (4c-5), and (5c-2) were contained as the nonionic surfactant (C) (Comparative Examples 31 to 36), the liquid stability was poor, and the treatment bath thickened and gelled within one hour.

[0174] 9. Summary From the results of the above examples, it can be said that the following antiviral agent compositions have good liquid stability and can impart sufficient antiviral properties.

[0175] An antiviral composition comprising: (A) an antiviral agent containing at least one of predetermined quaternary ammonium salts (1a) and (2a); (B) an aqueous polyurethane resin having at least one of a carboxyl group and a carboxylate group; (C) at least one nonionic surfactant selected from the group consisting of predetermined nonionic surfactants (1c) to (4c) and polyoxyalkylene sorbitan fatty acid esters having an alkylene oxide polymerization degree of 10 or more and 50 or less; Contains.

Claims

1. (A) an antiviral agent containing at least one of the following quaternary ammonium salts (1a) and (2a); (B) an aqueous polyurethane resin having at least one of a carboxyl group and a carboxylate group; (C) at least one nonionic surfactant selected from the following nonionic surfactants (1c) to (4c) and a polyoxyalkylene sorbitan fatty acid ester having an alkylene oxide polymerization degree of 20 or more and 50 or less; An antiviral composition comprising: 【Chemistry 1】 Here, R ａ is a hydrocarbon group having 1 to 3 carbon atoms, and R ｂ is a hydrocarbon group having 1 to 24 carbon atoms, and R ｃ is a hydrocarbon group having 10 to 24 carbon atoms; Y is a q-valent anion, where q is 1 or 2, and p is 1 to 6. 【Chemistry 2】 Here, R ｄ is an alkyl group or aryl group having 10 to 20 carbon atoms, and R ｅ is a methyl group, an ethyl group, a propyl group, a butyl group, or (AO) ｘ H, AO is an alkylene oxide group having 2 to 4 carbon atoms, x is 1 to 10, and R ｆ is a methyl group, an ethyl group, a benzyl group, or a hydroxyalkyl group having 2 to 4 carbon atoms; r is 1 or 2; s is 1 or 2; r+s is 3; t is 1 or 2; and Z is a monoalkyl phosphate, a dialkyl phosphate, a halogen, a methyl sulfate, an ethyl sulfate, or an aromatic anion. 【Transformation 3】 where Ar is an aromatic hydrocarbon group having 6 to 46 carbon atoms, and A １ O is an alkylene oxide group having 2 to 4 carbon atoms, n1 is 10 to 60, and X １ is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group. 【Chemistry 4】 Here, R １ is a linear or branched hydrocarbon group having 8 to 22 carbon atoms, which may contain an unsaturated bond; A ２ O is an alkylene oxide group having 2 to 4 carbon atoms, n2 is 8 to 40, and X ２ is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group. 【Transformation 5】 Here, R ２ is a hydrocarbon group having 1 to 30 carbon atoms, and A ３ O and A ４ O's are each independently an alkylene oxide group having 2 to 4 carbon atoms, n3+n4 is 8 to 70, and X ３ and X ４ are each independently at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group. 【Transformation 6】 Here, R ３ is a hydrocarbon group having 1 to 30 carbon atoms, and A ５ O is an alkylene oxide group having 2 to 4 carbon atoms, n5 is 8.0 to 40, and X ５ is at least one of a hydrogen atom, an alkanoyl group having 1 to 22 carbon atoms, and an alkenoyl group.

2. A fabric substrate and the antiviral composition according to claim 1, The antiviral composition is attached to the fabric substrate. Antiviral fabric.

3. A method for treating a leather substrate comprising the antiviral composition of claim 1, The antiviral composition is adhered to the leather substrate. Antiviral leather.

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