Antibacterial and antiviral composition, article, and method for manufacturing article

Abstract

To disclose a composition that can give an article antibacterial durability and antiviral durability as well as water absorbing properties.SOLUTION: An antibacterial and antiviral agent composition contains urethane resin and an antibacterial and antiviral agent, the urethane resin having a polyoxyalkylene chain of 30 mass% or more and 94 mass% or less, and the antibacterial and antiviral agent having a quaternary ammonium cation group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present application discloses antibacterial and antiviral compositions, articles, and methods of making articles. [Background technology]

[0002] Patent Document 1 discloses a method for imparting antibacterial properties to synthetic fibers by treating the fibers with a quaternary ammonium salt in the presence of a sulfate surfactant. Patent Document 2 discloses a method for imparting antibacterial properties and water absorbency to cellulosic fibers by treating the fibers with an organosilicone quaternary ammonium salt and a glycidyl ether compound. Patent Document 3 discloses a method for producing antibacterial and antiviral fabrics by treating fabrics with a composition containing an antiviral agent containing a methoxysilane quaternary ammonium salt, an acrylic acid / acrylic acid ester copolymer, a lower alcohol, and water. Patent Document 4 discloses a method for imparting antibacterial properties to an article containing a resin component having carboxyl groups at least on the surface by applying an antibacterial agent containing an ethoxysilane quaternary ammonium salt to the article. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 177284 / 1984 [Patent Document 2] International Publication No. 2012 / 014762 [Patent Document 3] Japanese Patent Application Publication No. 2019-077638 [Patent Document 4] International Publication No. 2013 / 047642 Summary of the Invention [Problem to be solved by the invention]

[0004] In conventional technology, when antibacterial and antiviral articles are washed with water or the like, the antibacterial and antiviral agents tend to come off from the articles. In other words, there is room for improvement in the durable antibacterial and durable antiviral properties of the articles. In particular, sufficient consideration has not been given to durable antiviral properties. Furthermore, in conventional technology, sufficient consideration has not been given to the water absorbency of antibacterial and antiviral articles. A new composition that can impart durable antibacterial, durable antiviral, and water absorbency to articles is needed. [Means for solving the problem]

[0005] As one of the means for solving the above problems, the present application provides: An antibacterial / antiviral agent composition comprising a urethane resin and an antibacterial / antiviral agent, the urethane resin contains 30% by mass or more and 94% by mass or less of polyoxyalkylene chains, The antibacterial and antiviral agent has a quaternary ammonium cation group. Antibacterial and antiviral composition Disclose.

[0006] In the antibacterial and antiviral composition of the present disclosure, The polyoxyalkylene chain may have an alkylene group having 2 to 4 carbon atoms.

[0007] In the antibacterial and antiviral composition of the present disclosure, The urethane resin may have at least a polyoxypropylene chain.

[0008] In the antibacterial and antiviral composition of the present disclosure, The urethane resin may have a structure derived from polyisocyanate, The polyisocyanate may contain at least one of an alkylene diisocyanate having 4 to 10 carbon atoms and an arylene diisocyanate having 6 to 16 carbon atoms.

[0009] The antibacterial and antiviral composition of the present disclosure comprises: The composition may contain a polyester resin in addition to the urethane resin and the antibacterial and antiviral agent, The polyester resin may have a polyoxyalkylene chain and a quaternary ammonium cationic group.

[0010] In the antibacterial and antiviral composition of the present disclosure, The antibacterial and antiviral agent may be a compound represented by the following general formula (1):

[0011] [ka] In formula (1), R1 is an alkyl group having 10 to 22 carbon atoms, R2 is a methyl group, an ethyl group, a propyl group, or a butyl group; R3 is a methyl group, an ethyl group, a propyl group, or a butyl group; R4 is an alkylene group having 2 to 4 carbon atoms, R5 is a methyl group or an ethyl group; R6 is a methyl group or an ethyl group; R7 is a methyl group or an ethyl group; Z1 is a halogen.

[0012] As one of the means for solving the above problems, the present application provides: An article to which the antibacterial and antiviral composition of the present disclosure is attached. Disclose.

[0013] As one of the means for solving the above problems, the present application provides: Adhering the antibacterial and antiviral agent composition of the present disclosure to an object to which antibacterial and antiviral properties are to be imparted, thereby obtaining an article having antibacterial and antiviral properties; A method for manufacturing an article, Disclose. [Effects of the Invention]

[0014] The antibacterial and antiviral agent composition of the present disclosure can impart excellent durable antibacterial and antiviral properties and water absorbency to articles. DETAILED DESCRIPTION OF THE INVENTION

[0015] 1. Antibacterial and antiviral composition The antibacterial and antiviral agent composition of the present disclosure contains a urethane resin and an antibacterial and antiviral agent, wherein the urethane resin has 30% by mass or more and 94% by mass or less of polyoxyalkylene chains, and the antibacterial and antiviral agent has a quaternary ammonium cation group.

[0016] 1.1 Urethane resin The antibacterial and antiviral composition of the present disclosure contains a urethane resin, and the urethane resin has a polyoxyalkylene chain content of 30% by mass or more and 94% by mass or less. In the antibacterial and antiviral composition of the present disclosure, the coexistence of a specific urethane resin with the antibacterial and antiviral agent ensures excellent durable antibacterial and antiviral properties and water absorbency. The urethane resin may be, for example, a hydroxyl-terminated polyurethane resin (hereinafter sometimes referred to as "urethane resin 1") obtained by reacting a polyol having a polyoxyalkylene chain with a polyisocyanate. Alternatively, the urethane resin may be obtained by emulsifying and dispersing an isocyanate-terminated prepolymer obtained by reacting a polyol having a polyoxyalkylene chain with a polyisocyanate in water, followed by a chain extension reaction with a chain extender (hereinafter sometimes referred to as "urethane resin 2"). Both urethane resin 1 and urethane resin 2 may have a polyoxyalkylene chain and a structure derived from the polyisocyanate. In the antibacterial and antiviral composition of the present disclosure, one type of urethane resin may be used alone, or two or more types may be used in combination.

[0017] 1.1.1 Polyoxyalkylene chain The polyoxyalkylene chain has a polymerized structure of alkylene oxide (-AO-). n(A is an alkylene group, and n is any integer). The number of carbon atoms in the alkylene group in the polyoxyalkylene chain is not particularly limited. For example, the polyoxyalkylene chain may have an alkylene group having 2 to 4 carbon atoms. In the urethane resin, the number of carbon atoms in the alkylene group in one polyoxyalkylene chain may be the same as or different from the number of carbon atoms in the alkylene group in another polyoxyalkylene chain. In addition, one polyoxyalkylene chain may contain alkylene groups with different numbers of carbon atoms.

[0018] Examples of polyols having a polyoxyalkylene chain include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyols formed by block or random copolymerization of alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and tetramethylene oxide. In particular, a urethane resin having a polyoxyalkylene chain with an alkylene group having 2 to 4 carbon atoms can be expected to produce a higher effect, and an even higher effect can be expected when the urethane resin has at least a polyoxypropylene chain. In the urethane resin, the alkylene groups constituting the polyoxyalkylene chain may consist solely of alkylene groups having 2 to 4 carbon atoms. Alternatively, the urethane resin may have only polyoxyethylene chains and polyoxypropylene chains as the polyoxyalkylene chains. When the urethane resin has a polyoxyethylene (POE) chain and a polyoxypropylene (POP) chain, the ratio of the POE chain to the POP chain is not particularly limited. For example, the mass ratio of POP chains to the total of POE chains and POP chains in the urethane resin (POP chains / (POE chains+POP chains)) may be 0.70 or less, 0.65 or less, or 0.60 or less, or may be 0.30 or more, 0.35 or more, or 0.40 or more.

[0019] The number average molecular weight of the polyol having a polyoxyalkylene chain is not particularly limited, but may be, for example, 1,000 or more or 1,200 or more, and 4,000 or less or 3,000 or less.

[0020] In the urethane resin, the proportion of polyoxyalkylene chains is 30% by mass or more and 94% by mass or less. This ensures excellent effects. The lower limit of this proportion may be 40% by mass or more, 50% by mass or more, or 60% by mass or more, and the upper limit may be 93% by mass or less.

[0021] 1.1.2 Structures derived from polyisocyanates In the urethane resin, for example, a urethane bond can be formed by reacting the above-mentioned polyol having a polyoxyalkylene chain with a polyisocyanate. That is, the urethane resin may have a structure derived from a polyisocyanate. The type of polyisocyanate is not particularly limited. For example, the polyisocyanate may contain at least one of an alkylene diisocyanate having 4 to 10 carbon atoms and an arylene diisocyanate having 6 to 16 carbon atoms. Alternatively, the polyisocyanate may consist of only at least one of an alkylene diisocyanate having 4 to 10 carbon atoms and an arylene diisocyanate having 6 to 16 carbon atoms. In particular, a greater effect can be expected when the polyisocyanate contains an alkylene diisocyanate having 4 to 10 carbon atoms. An example of a polyisocyanate is shown below.

[0022] The polyisocyanate may be an aromatic polyisocyanate, an aliphatic polyisocyanate, or an alicyclic polyisocyanate. Examples of aromatic polyisocyanates include toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), and tetramethylxylylene diisocyanate. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate (HDI). Examples of alicyclic polyisocyanates include 1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), and norbornane diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

[0023] Among these polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates can impart non-yellowing properties to articles (particularly, fibers and synthetic leather sheets such as PVC sheets and PU sheets). In particular, the non-yellowing effect is further enhanced when at least one selected from hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane is used.

[0024] In the urethane resin, the proportion of the structure derived from polyisocyanate is not particularly limited, but may be, for example, 5% by mass or more or 6% by mass or more, and 15% by mass or less or 10% by mass or less. Alternatively, the portion of the urethane resin excluding the polyoxyalkylene chain may be composed of a structure derived from polyisocyanate.

[0025] 1.1.3 Supplementary information on structures derived from polyoxyalkylene chains and polyisocyanates When the urethane resin 1 is obtained by reacting the polyol having the polyoxyalkylene chain with the polyisocyanate, the ratio (OH / NCO) of the total number of hydroxyl groups contained in the polyol to the total number of isocyanate groups contained in the polyisocyanate may be 1.0 or more, or 1.1 or more, in terms of molar ratio, and may be 2.5 or less, or 2.0 or less.

[0026] From the viewpoint of expecting even higher effects in terms of durable antibacterial property, durable antiviral property and water absorbency, the urethane resin may have a polyoxyalkylene chain having an alkylene group having 2 to 4 carbon atoms and a structure derived from at least one polyisocyanate selected from alkylene diisocyanates having 4 to 10 carbon atoms and arylene diisocyanates having 6 to 16 carbon atoms, or may have at least a polyoxypropylene chain and at least one polyisocyanate selected from alkylene diisocyanates having 4 to 10 carbon atoms and arylene diisocyanates having 6 to 16 carbon atoms. It may have at least a polyoxypropylene chain and a structure derived from an alkylene diisocyanate having 4 to 10 carbon atoms, it may have a polyoxyethylene chain, a polyoxypropylene chain, and a structure derived from at least one polyisocyanate selected from alkylene diisocyanates having 4 to 10 carbon atoms and arylene diisocyanates having 6 to 16 carbon atoms, or it may have a polyoxyethylene chain, a polyoxypropylene chain, and a structure derived from an alkylene diisocyanate having 4 to 10 carbon atoms.

[0027] 1.1.4 Other ingredients The urethane resin may have a structure derived from other components in addition to the structure derived from the polyoxyalkylene chain and polyisocyanate. The urethane resin may have, for example, a polycarbonate polyol, a polyester polyol, or a low-molecular-weight polyhydric alcohol as a copolymerization component. The proportion of the structure derived from other components in the urethane resin may be 0% by mass or more or 0.1% by mass or more, and may be 60% by mass or less or 50% by mass or less. Furthermore, the urethane resin may have various functional groups in addition to the structure derived from the polyoxyalkylene chain and polyisocyanate and the urethane bond.

[0028] Examples of polycarbonate polyols include those obtained by dealcoholization or dephenolization of polyols and carbonates. The polyols may be one or more selected from, for example, 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, ethylene oxide or propylene oxide adducts of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, etc. The carbonates may be one or more selected from diethyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. The polycarbonate polyols may be used singly or in combination of two or more.

[0029] Examples of polyester polyols include those obtained by polycondensation reaction of dibasic acids and polyols. The dibasic acid may be one or more selected from, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, fumaric acid, etc. The polyol may be one or more polyols used in the synthesis of the polycarbonate polyol described above. The polyester polyols may be used alone or in combination of two or more.

[0030] Examples of low molecular weight polyhydric alcohols include ethylene glycol, 1,4-butanediol, hexamethylene glycol, trimethylolpropane, pentaerythritol, sorbitol, etc. The low molecular weight polyhydric alcohols may be used alone or in combination of two or more.

[0031] 1.1.5 Supplementary information about urethane resin 2 The polyol and polyisocyanate used in producing the isocyanate group-terminated prepolymer may be the same as those that can be used in producing the urethane resin 1 described above.

[0032] Examples of chain extenders include low-molecular-weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, hexamethylene glycol, trimethylolpropane, pentaerythritol, and sorbitol, and low-molecular-weight polyamines such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, hydrazine, 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.

[0033] The urethane resin may be, for example, a flame retardant blended urethane resin containing a phosphorus-based compound as a flame retardant component, as disclosed in Japanese Patent Application Laid-Open No. 2006-206839.

[0034] 1.1.6 Urethane resin manufacturing method An example of a method for producing the urethane resin will be described.

[0035] Hydroxyl-terminated polyurethane resins or isocyanate-terminated prepolymers can be produced, for example, by a conventional one-stage (so-called one-shot) method or a multi-stage (isocyanate polyaddition) method. The reaction temperature is preferably 40 to 150°C. An organic solvent that does not react with isocyanate groups 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.

[0036] The residual isocyanate group content in the isocyanate-terminated prepolymer may be 0.2 to 4.0% by mass. Within this range, the polyurethane resin obtained by subsequent chain extension with a polyamine exhibits appropriate flexibility. The residual isocyanate group content in the isocyanate-terminated prepolymer can be determined, for example, as follows: 0.3 g of the obtained prepolymer is placed in an Erlenmeyer flask, and 10 ml of a 0.1 N dibutylamine toluene solution is added and dissolved. Next, a few drops of bromophenol blue solution are added, and the mixture is titrated with a 0.1 N hydrochloric acid methanol solution. The residual isocyanate group content (NCO%) can be determined 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 amount 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.

[0037] To achieve the above-mentioned range of residual isocyanate group content, it is preferable to adjust the molar ratio of hydroxyl groups to isocyanate groups in the raw materials during prepolymer production. Specifically, the ratio of the total number of hydroxyl groups in the raw materials to the total number of isocyanate groups in the raw materials (OH / NCO) is adjusted to a molar ratio of 0.6 to 0.8. By adjusting the molar ratio of hydroxyl groups to isocyanate groups within this range, the viscosity of the isocyanate-terminated prepolymer becomes appropriate, making it easier to emulsify. Furthermore, the texture of articles treated with the antibacterial and antiviral composition (particularly fibers and synthetic leather sheets such as PVC and PU sheets) can be softened, making it easier to prevent whitening when flexed.

[0038] When the urethane resin 1 or the isocyanate-terminated prepolymer contains a structure derived from a diol compound having a carboxyl group and / or a carboxylate group, neutralization of the carboxyl group can be carried out using a known method before, during, or after preparation of the urethane resin 1 or the isocyanate-terminated prepolymer. The compound used to neutralize the carboxyl group is not particularly limited, and examples 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 compounds, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, and tributylamine are particularly preferred.

[0039] The emulsifying equipment used to emulsify and disperse the isocyanate-terminated prepolymer in water is not particularly limited, and examples include a homomixer, a homogenizer, and a disperser. When emulsifying and dispersing the isocyanate-terminated prepolymer in water, it is preferable to emulsify and disperse the isocyanate-terminated prepolymer in water at a temperature ranging from 0 to 40°C to minimize the reaction between the isocyanate group and water. Furthermore, when emulsifying and dispersing in this manner, an emulsifier may be used as needed. A reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, or benzoyl chloride may also be added.

[0040] The urethane prepolymer thus 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 urethane prepolymer containing terminal isocyanate groups and the polyamine compound can be completed at a reaction temperature of 20 to 50°C, usually within 30 to 120 minutes.

[0041] When the organic solvent described above is used in producing the isocyanate group-terminated prepolymer, it is desirable to distill off the solvent at 30 to 80°C under reduced pressure after the chain extension reaction or emulsification / dispersion. The urethane resin prepared by such a method can be obtained as an emulsified dispersion of urethane resin 2. The resin solids (non-volatile content) concentration in the emulsified dispersion of the urethane resin is preferably in the range of 20 to 60%. The resin solids concentration in the emulsified dispersion can also be adjusted by adding or distilling off water.

[0042] The urethane resin 1 may also be obtained as an emulsified dispersion, and in this case too, the resin solids concentration in the emulsified dispersion can be adjusted by adding or distilling off water.

[0043] 1.2 Antibacterial and antiviral agents The antibacterial and antiviral composition of the present disclosure contains the above-mentioned urethane resin and an antibacterial and antiviral agent, which has a quaternary ammonium cation group.

[0044] Compounds having a quaternary ammonium cation group can exhibit antibacterial and antiviral properties on the surface of an article. Examples of quaternary ammonium cation groups that have antibacterial and antiviral properties include silane-based ammonium cation groups, polyoxyalkylene alkyl ammonium cation groups, and alkyl ammonium cation groups. The antibacterial and antiviral agent may be a low-molecular-weight compound or a high-molecular-weight compound as long as it has at least one quaternary ammonium cation group. Specific examples of compounds having a quaternary ammonium cation group will be described later.

[0045] The type of anion serving as a counter ion of the quaternary ammonium cation group is not particularly limited. For example, it may be a monoalkyl phosphate, a dialkyl phosphate, a halogen, a methyl sulfate, an ethyl sulfate, or an aromatic anion. Examples of aromatic anions include paratoluenesulfonic acid, xylenesulfonic acid, benzoic acid, and alkylbenzenesulfonic acid.

[0046] The antibacterial and antiviral agent may be at least one compound selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2). In particular, when the antibacterial and antiviral agent is a compound represented by the following general formula (1), a higher effect can be expected.

[0047] [ka]

[0048] [ka]

[0049] In formula (1), R1 is an alkyl group having 10 to 22 carbon atoms, R2 is a methyl group, ethyl group, propyl group, or butyl group, R3 is a methyl group, ethyl group, propyl group, or butyl group, R4 is an alkylene group having 2 to 4 carbon atoms, R5 is a methyl group or ethyl group, R6 is a methyl group or ethyl group, R7 is a methyl group or ethyl group, and Z1 is a halogen.

[0050] Specific examples of R1 include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, doeicosyl, trieicosyl, and tetraeicosyl. R2 and R3 may be the same group. R5 to R7 may be the same group. Z1 may be chlorine, bromine, or another halogen, but particularly high performance can be expected when it is chlorine. The same applies to the halogen in formula (2) and the halogen in formula (3) described below.

[0051] Among the silane-based quaternary ammonium salts represented by formula (1), specific examples of methoxysilane-based quaternary ammonium salts include octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, dodecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, dodecyldiisopropyl(3-trimethoxysilylpropyl)ammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, tetradecyldiethyl(3-trimethoxysilylpropyl)ammonium chloride, tetradecyldi-n-propyl(3-trimethoxysilylpropyl)ammonium chloride, pentadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, Examples of suitable ammonium chlorides include tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, pentadecyldiethyl(3-trimethoxysilylpropyl)ammonium chloride, pentadecyldi-n-propyl(3-trimethoxysilylpropyl)ammonium chloride, hexadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, hexadecyldiethyl(3-trimethoxysilylpropyl)ammonium chloride, hexadecyldi-n-propyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldiethyl(3-trimethoxysilylpropyl)ammonium chloride, and octadecyldi-n-propyl(3-trimethoxysilylpropyl)ammonium chloride. Among these, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride exhibits excellent antibacterial and antiviral properties.

[0052] Among the silane-based quaternary ammonium salts represented by formula (1), specific examples of ethoxysilane-based quaternary ammonium salts include those in which the trimethoxysilyl group in the above-mentioned methoxysilane-based quaternary ammonium salts is substituted with a triethoxysilyl group.

[0053] In formula (2), R8 is an alkyl group or an aryl group having 10 to 20 carbon atoms, and R9 is a methyl group, an ethyl group, a propyl group, a butyl group, or (AO) pH, AO is an alkylene oxide having 2 to 4 carbon atoms, p is an integer of 1 to 10, and R 10 is a methyl group, an ethyl group, a benzyl group, or a hydroxyalkyl group having 2 to 4 carbon atoms, n is 1 or 2, m is 1 or 2, n+m is 3, l is 1 or 2, and Z2 is a monoalkyl phosphate, a dialkyl phosphate, a halogen, a methyl sulfate, an ethyl sulfate, or an aromatic anion.

[0054] In formula (2), if the number of carbon atoms in R8 is too small or too large, the antibacterial and antiviral properties are likely to decrease. The number of carbon atoms in R8 may be 10 or more, or 12 or more, or 20 or less, or 18 or less.

[0055] In formula (2), when R9 is a methyl group, the antibacterial and antiviral properties are even more excellent.

[0056] In equation (2), R 10 When is a hydroxyalkyl group having 2 to 4 carbon atoms, particularly a hydroxyethyl group, the antibacterial and antiviral properties are even more excellent.

[0057] In formula (2), when Z2 is a monoalkyl phosphate or a dialkyl phosphate, the antibacterial and 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.

[0058] In formula (2), specific examples of aromatic anions that can be Z2 include paratoluenesulfonic acid, xylenesulfonic acid, benzoic acid, and alkylbenzenesulfonic acid.

[0059] Specific examples of the compound represented by formula (2) 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, antibacterial and antiviral properties are further improved.

[0060] The antibacterial and antiviral agent may be a polymer compound having a plurality of quaternary ammonium cations. For example, the polymer compound shown in the following formula (3) may be used as the antibacterial and antiviral agent.

[0061] [ka]

[0062] In equation (3), R 11 may be an alkylene group having 1 to 4 carbon atoms, and R 12 may be a methyl group or an ethyl group, and R 13 may be a methyl group or an ethyl group, and R 14 may be an alkylene group having 1 to 4 carbon atoms, and R 15 may be a methyl group or an ethyl group, and R 16 may be a methyl group or an ethyl group, and R 17 may be an alkylene group having 1 to 4 carbon atoms, Z3 may be a halogen, and j may be any natural number. The weight-average molecular weight of the polymer compound represented by formula (5) may be, for example, 2,000 or more or 6,000 or more, and may be 200,000 or less or 80,000 or less.

[0063] 1.3 Composition ratio In the antibacterial and antiviral agent composition of the present disclosure, the ratio of the urethane resin to the antibacterial and antiviral agent is not particularly limited. For example, when the total of the urethane resin and the antibacterial and antiviral agent is taken as 100 mass%, the content of the urethane resin may be 15 mass% or more, or 30 mass% or more, or may be 90 mass% or less, or 80 mass% or less.

[0064] 1.4 Adhesion amount In the antibacterial and antiviral agent composition of the present disclosure, the ratio between the article and the total of the urethane resin and antibacterial and antiviral agent adhered to the article is not particularly limited. For example, the total of the urethane resin and antibacterial and antiviral agent adhered to the article may be 0.1 parts by mass or more, or 5 parts by mass or less, per 100 parts by mass of the article.

[0065] 1.5 Optional components The antibacterial and antiviral composition of the present disclosure may contain other components in addition to the urethane resin and antibacterial and antiviral agent described above. For example, the antibacterial and antiviral composition of the present disclosure may contain a surfactant and water, or a surfactant, an organic solvent, and water. The antibacterial and antiviral composition of the present disclosure may also contain an acid component, an alkali component, a chelating agent, a crosslinking agent, an antifoaming agent, a preservative, etc.

[0066] The antibacterial and antiviral composition of the present disclosure may contain a polyester resin in addition to the urethane resin and antibacterial and antiviral agent. In this case, the polyester resin may have a polyoxyalkylene chain and a quaternary ammonium cation group. When the antibacterial and antiviral composition contains a polyester resin having a polyoxyalkylene chain, the water absorption of the composition is further enhanced. When the antibacterial and antiviral composition contains a polyester resin having a quaternary ammonium cation group, the antibacterial and antiviral properties of the composition are further enhanced. Specific examples of the polyoxyalkylene chain and the quaternary ammonium cation group are the same as those described above. The type of carboxylic acid constituting the polyester resin is also not particularly limited; for example, the dibasic acids described above may be used. In the antibacterial and antiviral composition of the present disclosure, the content of the polyester resin is not particularly limited, but may be, for example, 3% by mass or more or 5% by mass or more, or 30% by mass or less or 15% by mass or less, based on 100% by mass of the total of the urethane resin, the antibacterial and antiviral agent, and the polyester resin.

[0067] 2.Goods An article to which the antibacterial and antiviral composition of the present disclosure is attached has excellent durable antibacterial and antiviral properties, as well as excellent water absorbency.

[0068] The type of article is not particularly limited as long as durable antibacterial and antiviral properties and water absorbency are required. Specific examples of articles include textile products. Alternatively, the antibacterial and antiviral composition of the present disclosure may be applied to articles other than textile products.

[0069] When the article is a textile product, the type of fiber constituting the textile product is not particularly limited and may be natural or chemical. Specific examples of fibers include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite and blended fibers thereof. Examples of polyamides include nylon 6 and nylon 6,6. Examples of polyesters include polyethylene terephthalate, polytrimethylene terephthalate, and polylactic acid. Fibers may take the form of yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, wood, etc. Fibers may be dyed. Fibers may have their surfaces modified in some way.

[0070] 3. Manufacturing method of the article The technology of the present disclosure also has an aspect as a method for producing an article having antibacterial and antiviral properties. That is, the method for producing an article of the present disclosure includes attaching the antibacterial and antiviral agent composition of the present disclosure to an object to which antibacterial and antiviral properties are to be imparted, thereby obtaining an article having antibacterial and antiviral properties. As described above, the object may be a fiber, and the article may be a textile product.

[0071] The method for adhering the antibacterial and antiviral composition to an article is not particularly limited. For example, the method disclosed herein may involve adhering the antibacterial and antiviral composition to an object by bringing the object into contact with a treatment liquid (which may be a dispersion liquid) containing the antibacterial and antiviral composition. The timing of treatment with the treatment liquid is not particularly limited.

[0072] The treatment liquid may contain, for example, the urethane resin and the antibacterial and antiviral agent. The treatment liquid may also contain other components, such as an acid component, an alkali component, a surfactant, a silicone component, an organic solvent, a chelating agent, a softener, an antistatic agent, a crosslinking agent, a penetrating agent, and an antifoaming agent. The pH of the treatment liquid is not particularly limited, but may be, for example, 2 or more and 7 or less. To improve durability, it is preferable to treat the object using a method that includes the steps of applying the treatment liquid to the object and heating it, in addition to the above-mentioned step of treating the object with a treatment liquid containing an antibacterial and antiviral composition, using a crosslinking agent, such as a melamine resin, a glyoxal resin, or a compound having one or more isocyanate groups or blocked isocyanate groups.

[0073] Specific examples of methods for treating an object with a treatment solution include padding, immersion, spraying, and coating. The treatment conditions, such as the concentration of the treatment solution and the heat treatment after application, can be adjusted appropriately, taking into account various factors such as the purpose and performance of the treatment solution. After treating the object with the treatment solution, a cleaning process such as water washing may be performed to remove excess antibacterial and antiviral agent. Furthermore, if the treatment solution contains water, a drying process may be performed to remove the water after applying the treatment solution to the object. The drying method is not particularly limited, and either a dry heat method or a wet heat method may be used. The drying temperature and drying time are also not particularly limited. For example, drying at room temperature to 200°C for 10 seconds to several days may be sufficient. A drying time of 20 seconds to 10 minutes at 40 to 130°C is more preferred. If necessary, a heat treatment at 100 to 190°C for 10 seconds to 5 minutes may be performed after drying. A heating time of 30 seconds to 5 minutes at 130 to 190°C is more preferred.

[0074] 4.Effects As described above, the antibacterial and antiviral agent composition of the present disclosure contains a predetermined urethane resin along with a predetermined antibacterial and antiviral agent, and is therefore able to impart excellent durable antibacterial properties, durable antiviral properties, and water absorbency to articles. [Example]

[0075] The effects of 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.

[0076] 1. Preparation of urethane resin A urethane resin was obtained by reacting a polyol, a polyisocyanate, and optionally a polycarbonate diol in the presence of a catalyst in an alcohol-based solvent at the blending ratio (mass ratio) shown in Table 1 or 2. Specifically, the synthesis was carried out as follows.

[0077] 1.1 Synthesis Example 1 A reaction vessel was charged with 385 parts by mass of polypropylene glycol (molecular weight 2,000), 385 parts by mass of polyethylene glycol (molecular weight 1,540), 60 parts by mass of hexamethylene diisocyanate, and U-catSA603 (manufactured by San-Apro Co., Ltd., catalyst: 1,8-diazabicyclo(5.4.0)undecene formate), and the mixture was reacted at 130°C for 3 hours under a nitrogen atmosphere. The OH / NCO ratio was as shown in Table 1. After cooling, 70 parts by mass of 3-methyl-3-methoxybutanol was added to obtain a urethane resin-containing composition according to Synthesis Example 1 (urethane resin content: 93%).

[0078] 1.2 Synthesis Examples 2 to 12, Comparative Synthesis Examples 1 to 3 A urethane resin-containing composition was obtained in the same manner as in Synthesis Example 1, except that the raw materials shown in Table 1 or 2 below were used in the mass ratios shown in Table 1 or 2 below.

[0079] [Table 1]

[0080] [Table 2]

[0081] 2. Polyester Resin Preparation Polytetramethylene glycol, adipic acid, and methyldiethanolamine were reacted in the blending ratios (mass ratios) shown in Table 3 below to obtain a polyester resin having a polyoxyalkylene chain and a quaternary ammonium cation group. Specifically, 130 parts by mass of polytetramethylene glycol, 12 parts by mass of methyldiethanolamine, 40 parts by mass of adipic acid, and 0.034 parts by mass of zinc acetate were placed in a reaction vessel and reacted at 170°C for 3 hours under a nitrogen atmosphere, followed by a reaction at 240°C for 2 hours. After cooling to 60°C, 10 parts by mass of dimethyl sulfate was added dropwise. After a 2-hour reaction at 60°C, 808 parts by mass of hot water (60°C) was added to obtain a polyester resin-containing composition having a polyoxyalkylene chain and a quaternary ammonium cation group (polyester resin content: 20%).

[0082] [Table 3]

[0083] 3. Antibacterial and Antiviral Preparation The antibacterial and antiviral agents used in this example are as follows:

[0084] Compound A: A compound represented by the following general formula (1), in which R1 is an alkyl group having 14 carbon atoms, R2 is a methyl group, R3 is a methyl group, R4 is a propylene group, R5 is a methyl group, R6 is a methyl group, R7 is a methyl group, and Z1 is chlorine. Compound B: A compound represented by the following general formula (1), in which R1 is an alkyl group having 18 carbon atoms, R2 is a methyl group, R3 is a methyl group, R4 is a propylene group, R5 is a methyl group, R6 is a methyl group, R7 is a methyl group, and Z1 is chlorine.

[0085] [ka]

[0086] The synthesis conditions for compounds A and B were as follows: As is clear from the synthesis conditions below, compounds A and B were used as solutions containing 40% by weight of the compounds.

[0087] 3.1 Synthesis conditions for compound A A reaction vessel was charged with 199 parts by mass of trimethoxysilylpropyl chloride, 240 parts by mass of dimethyltetradecylamine, and 539 parts by mass of triethylene glycol monomethyl ether, and the mixture was reacted at 150°C for 20 hours under a nitrogen atmosphere, yielding 1,100 parts by mass of a solution containing 40% by weight of tetradecyl[3-(trimethoxysilyl)propyl]dimethylammonium chloride.

[0088] 3.2 Synthesis conditions for compound B 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, yielding 1,204 parts by mass of a solution containing 40% by weight of octadecyl[3-(trimethoxysilyl)propyl]dimethylammonium chloride.

[0089] 4. Preparation of treatment solution (antibacterial and antiviral composition) The above urethane resin-containing composition, the above antibacterial and antiviral agent solution, malic acid, and optionally the above polyester resin-containing composition were mixed in the prescribed ratios shown in Tables 4 to 6 below to obtain treatment solutions.

[0090] 5. Adding antibacterial and antiviral properties to items 5.1 Examples 1 to 3, Reference Example 4, Examples 5 and 6, Reference Example 7, Examples 8 and 19. Comparative Examples 4 to 6 Cotton knit (165g / m 2 , manufactured by Irozome Co., Ltd.) or polyester knit (weight 120 g / m 2 (manufactured by Irozome Co., Ltd.) was immersed in the above treatment solution and treated at a wringing rate of 90% (cotton) or 110% (polyester), and then heat-treated at 130°C for 2 minutes to obtain a textile product with antibacterial and antiviral properties.

[0091] 5.2 Comparative Example 1 Treatment was carried out in the same manner as in Example 2, except that no urethane resin was used in preparing the treatment solution, to obtain a textile product with antibacterial and antiviral properties.

[0092] 5.3 Comparative Example 2 Treatment was carried out in the same manner as in Example 1, except that no antibacterial or antiviral agent was used in preparing the treatment solution, to obtain a textile product having antibacterial and antiviral properties.

[0093] 5.4 Comparative Example 3 Treatment was carried out in the same manner as in Example 2, except that polyester resin was used instead of urethane resin in preparing the treatment solution, to obtain a textile product with antibacterial and antiviral properties.

[0094] 5.5 Comparative Example 7 Antibacterial textile products were obtained according to the method described in Patent Document 1 (Japanese Patent Laid-Open Publication No. 62-177284). Specifically, a treatment bath was prepared by adjusting the concentration of compound B solution to 30 g / L and the concentration of sodium sulfate of lauryl alcohol ethylene oxide 3-mol adduct to 5 g / L. Cotton knit or polyester knit was immersed in the treatment bath and treated at a wringing rate of 90% (cotton) or 110% (polyester), followed by heat treatment at 130°C for 2 minutes to obtain fibers with antibacterial and antiviral properties.

[0095] 5.6 Comparative Example 8 Antibacterial textile products were obtained according to the method described in Patent Document 2 (WO 2012 / 014762). Specifically, a treatment bath was prepared by adjusting the treatment solution so that the compound B solution was 30 g / L and the ethylene glycol diglycidyl ether solution was 10 g / L. Cotton knit or polyester knit was immersed in the treatment bath and treated at a wringing rate of 90% (cotton) or 110% (polyester), followed by heat treatment at 130°C for 2 minutes to obtain antibacterial and antiviral textiles.

[0096] 5.7 Comparative Example 9 Antibacterial textile products were obtained according to the method described in Patent Document 3 (JP 2019-077638 A). Specifically, a treatment solution was prepared by adjusting the concentration of compound B solution to 30 g / L and the concentration of acrylic acid / acrylic acid ester copolymer to 30 g / L, and a treatment bath was prepared. Cotton knit or polyester knit was immersed in the treatment bath and treated at a wringing rate of 90% (cotton) or 110% (polyester). Then, heat treatment was performed at 130°C for 2 minutes to obtain antibacterial and antiviral fibers. The acrylic acid / acrylic acid ester copolymer was an aqueous dispersion of an acrylic acid ester copolymer obtained by copolymerizing ethyl acrylate, butyl acrylate, and acrylic acid in molar ratios of 42%, 17%, and 41%, respectively, and had a solids content of 30%.

[0097] 5.8 Comparative Example 10 The cotton knit or polyester knit was used without being immersed in the treatment solution.

[0098] 6. Laundry The textile products were washed according to the JIS L1930 (2014) C4G method. The detergent used was JAFET standard blend detergent (manufactured by the Textile Evaluation Technology Council), with a detergent concentration of 1.33 g / L in the washing liquid. Under the above conditions, the products were washed 10 times.

[0099] 7. Evaluation of durable antibacterial properties Antibacterial activity values ​​were measured using JIS L1902 (2015) quantitative testing (8.2 bacterial liquid absorption method), and the antibacterial performance of textile products was evaluated before and after washing. Staphylococcus aureus NBRC12732 and Klebsiella pneumoniae NBRC13277 were used as the bacteria. The results are shown in Tables 4 to 6 below. The higher the activity values ​​shown in Tables 4 to 6, the better the antibacterial properties.

[0100] 8. Evaluation of durable antiviral activity The antiviral activity value was measured according to JIS L1922 (2016) to evaluate the antiviral performance of textile products. The virus used was influenza A virus (H3N2) ATCC VR-1679. The antiviral activity value was evaluated as log(Va)-log(Vc). The results are shown in Tables 4 to 6 below. As with antibacterial properties, the higher the activity values ​​shown in Tables 4 to 6, the better the antiviral properties. Note that JIS defines an antiviral activity value of 2.0 or higher as effective, but viruses are reduced even with an activity value of 2.0 or less. In this example, an activity value of 1.5 is also considered to be antiviral effective.

[0101] 9.Evaluation of water absorption According to JIS L1907 (2010) 7.11 Drop Method, one drop of water (approximately 12 mg) was dropped onto the test cloth, and the time (seconds) until the reflection from the drop disappeared was measured to evaluate the water absorbency. The smaller the value, the higher the water absorbency. In Tables 4 to 6, "<1" indicates less than 1 second, and "180<" indicates more than 180 seconds.

[0102] [Table 4]

[0103] [Table 5]

[0104] [Table 6]

[0105] As is clear from the results shown in Tables 4 to 6, when textile products are treated with a composition containing a predetermined urethane resin and a predetermined antibacterial and antiviral agent, the textile products can maintain high activity values ​​for both antibacterial and antiviral properties before and after washing, and have high durable antibacterial and antiviral properties as well as high water absorbency (Examples 1 to 6). 3, Reference Example 4, Examples 5 and 6, Reference Example 7, Examples 8 and 19).

[0106] On the other hand, when the antibacterial and antiviral composition does not contain a urethane resin, the antiviral properties of the textile product before and after washing are significantly reduced, and water absorbency cannot be ensured (Comparative Examples 1 and 10).

[0107] Furthermore, when the antibacterial and antiviral composition does not contain an antibacterial and antiviral agent, the antibacterial and antiviral properties are not exhibited in the textile product (Comparative Examples 2 and 10).

[0108] Furthermore, when the antibacterial and antiviral composition contains a polyester resin instead of a urethane resin, the antiviral properties of the textile product decrease significantly after washing compared to before washing (Comparative Example 3).

[0109] Furthermore, when the content of polyoxyalkylene chains in the urethane resin contained in the antibacterial and antiviral agent composition is less than 30% by mass or more than 94% by mass, it is difficult to achieve both durable antibacterial properties, durable antiviral properties, and water absorbency, and in particular durable antiviral properties cannot be ensured (Comparative Examples 4 to 6).

[0110] Furthermore, when a sulfate surfactant, a glycidyl ether compound, or a polyacrylic acid / acrylic acid ethyl copolymer is used in combination with an antibacterial / antiviral compound, at least one of durable antibacterial property, durable antiviral property, and water absorbency is not ensured (Comparative Examples 7 to 9).

[0111] From the above, it can be said that an antibacterial and antiviral agent composition that satisfies the following requirements can impart excellent durable antibacterial and antiviral properties and water absorbency to an article. (1) The antibacterial and antiviral composition contains a urethane resin, and the urethane resin has polyoxyalkylene chains in an amount of 30% by mass or more and 94% by mass or less. (2) The antibacterial and antiviral composition contains an antibacterial and antiviral agent having a quaternary ammonium cation group.

Claims

1. A polyester fiber product having an antibacterial and antiviral agent composition attached thereto, the antibacterial and antiviral agent composition contains a urethane resin and an antibacterial and antiviral agent, the urethane resin is a hydroxyl group-terminated polyurethane resin obtained by reacting a polyol having a polyoxyalkylene chain with a polyisocyanate, a ratio (OH / NCO) of the total number of hydroxyl groups contained in the polyol to the total number of isocyanate groups contained in the polyisocyanate is 1.1 or more and 2.5 or less in terms of molar ratio; the urethane resin contains 30% by mass or more and 94% by mass or less of the polyoxyalkylene chain, the polyoxyalkylene chain has a polyoxyethylene chain and a polyoxypropylene chain, The antibacterial / antiviral agent has a quaternary ammonium cation group. Polyester fiber products.

2. The polyisocyanate contains at least one of an alkylene diisocyanate having 4 to 10 carbon atoms and an arylene diisocyanate having 6 to 16 carbon atoms. The polyester fiber product according to claim 1.

3. the antibacterial and antiviral agent composition contains a polyester resin in addition to the urethane resin and the antibacterial and antiviral agent, The polyester resin has a polyoxyalkylene chain and a quaternary ammonium cation group. The polyester fiber product according to claim 1 or 2.

4. The antibacterial and antiviral agent is a compound represented by the following general formula (1): The polyester fiber product according to any one of claims 1 to 3. 【Chemistry 1】 In formula (1), R １ is an alkyl group having 10 to 22 carbon atoms, R ２ is a methyl group, an ethyl group, a propyl group, or a butyl group, R ３ is a methyl group, an ethyl group, a propyl group, or a butyl group, R ４ is an alkylene group having 2 to 4 carbon atoms, R ５ is a methyl group or an ethyl group, R ６ is a methyl group or an ethyl group, R ７ is a methyl group or an ethyl group, Z １ is a halogen.

5. In accordance with JIS L1907 (2010) 7.11 Drop Method, one drop (12 mg) of water is dropped onto a test cloth made of the polyester fiber product, and the time until the reflection from the water drop disappears is measured, and the time is 6 seconds or less. The polyester fiber product according to any one of claims 1 to 4.

6. A method for producing a polyester fiber product, comprising: An antibacterial and antiviral agent composition is attached to a polyester fiber to obtain a polyester fiber product having antibacterial and antiviral properties; Including, the antibacterial and antiviral agent composition contains a urethane resin and an antibacterial and antiviral agent, the urethane resin is a hydroxyl group-terminated polyurethane resin obtained by reacting a polyol having a polyoxyalkylene chain with a polyisocyanate, a ratio (OH / NCO) of the total number of hydroxyl groups contained in the polyol to the total number of isocyanate groups contained in the polyisocyanate is 1.1 or more and 2.5 or less in terms of molar ratio; the urethane resin contains 30% by mass or more and 94% by mass or less of the polyoxyalkylene chain, the polyoxyalkylene chain has a polyoxyethylene chain and a polyoxypropylene chain, The antibacterial / antiviral agent has a quaternary ammonium cation group. Manufacturing method for polyester fiber products.

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