JP7798965B2 - Antibacterial/antiviral composition, article, and method for manufacturing article - Google Patents

Description

This application discloses antibacterial and antiviral compositions, articles, and methods for manufacturing articles.

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 fabric by treating the fabric 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 its surface by applying an antibacterial agent containing an ethoxysilane quaternary ammonium salt to the article.

Japanese Unexamined Patent Publication No. 177284/1984 International Publication No. 2012/014762 Japanese Patent Application Laid-Open No. 2019-077638 International Publication No. 2013/047642

In conventional technology, when antibacterial/antiviral articles are washed with water or the like, the antibacterial/antiviral agent easily falls off from the article. 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/antiviral articles. A new composition that can impart durable antibacterial, durable antiviral, and water absorbency to articles is needed.

As one of the means for solving the above problems, the present application provides:
An antibacterial/antiviral composition comprising a urethane resin and an antibacterial/antiviral agent,
the urethane resin has a polyoxyalkylene chain content of 30% by mass or more and 94% by mass or less,
The antibacterial and antiviral agent has a quaternary ammonium cation group.
An antibacterial and antiviral composition is disclosed.

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

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

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.

The antibacterial and antiviral composition of the present disclosure comprises:
The antibacterial and antiviral agent 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.

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):

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.

As one of the means for solving the above problems, the present application provides:
An article having the antibacterial and antiviral composition of the present disclosure attached thereto is also disclosed.

As one of the means for solving the above problems, the present application provides:
Adhering the antibacterial/antiviral agent composition of the present disclosure to an object to which antibacterial/antiviral properties are to be imparted, thereby obtaining an article having antibacterial/antiviral properties;
A method of manufacturing an article is disclosed, comprising:

The antibacterial and antiviral composition disclosed herein can impart excellent durable antibacterial and antiviral properties and water absorbency to articles.

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

1.1 Urethane Resin The antibacterial/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/antiviral composition of the present disclosure, the coexistence of a specific urethane resin with the antibacterial/antiviral agent ensures excellent durable antibacterial properties, durable 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 a resin (hereinafter sometimes referred to as "urethane resin 2") 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. 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 agent composition of the present disclosure, one type of urethane resin may be used alone, or two or more types may be used in combination.

1.1.1 Polyoxyalkylene Chain The polyoxyalkylene chain may have a structure (-AO-) _n (A is an alkylene group, and n is any integer) in which alkylene oxide is polymerized. 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. Furthermore, 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. Furthermore, one polyoxyalkylene chain may contain alkylene groups with different numbers of carbon atoms.

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, greater effects can be expected when the urethane resin has a polyoxyalkylene chain containing an alkylene group having 2 to 4 carbon atoms, and even greater effects can be expected when the urethane resin contains 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 contain only polyoxyethylene chains and polyoxypropylene chains as the polyoxyalkylene chain. When the urethane resin has polyoxyethylene (POE) chains and polyoxypropylene (POP) chains, the ratio of POE chains to POP chains 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.

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.

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.

1.1.2 Structure Derived from Polyisocyanate In urethane resins, for example, urethane bonds 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 solely of 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, greater effects can be expected when the polyisocyanate contains an alkylene diisocyanate having 4 to 10 carbon atoms. An example of a polyisocyanate is shown below.

The polyisocyanate may be an aromatic polyisocyanate, an aliphatic polyisocyanate, or a cycloaliphatic 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 cycloaliphatic 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.

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). The non-yellowing effect is particularly enhanced when at least one selected from hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane is used.

The proportion of polyisocyanate-derived structures in the urethane resin 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 urethane resin may be composed of a polyisocyanate-derived structure in the portion excluding the polyoxyalkylene chain.

1.1.3 Supplementary Information Regarding Structures Derived from Polyoxyalkylene Chains and Polyisocyanates When 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, in terms of molar ratio, may be 1.0 or more, or 1.1 or more, and may be 2.5 or less, or 2.0 or less.

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

1.1.4 Other Components 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.

Examples of polycarbonate polyols include those obtained by dealcoholization or dephenolization reactions between polyols and carbonates. The polyols may be one or more selected from the group consisting of 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, and the like. The carbonate may be one or more selected from diethyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. The polycarbonate polyol may be used alone or in combination of two or more.

Polyester polyols include those obtained by the polycondensation reaction of a dibasic acid and a polyol. 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, and fumaric acid. The polyol may be one or more of the polyols used in the synthesis of the polycarbonate polyol described above. The above polyester polyols may be used alone or in combination of two or more.

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

1.1.5 Supplementary Information Regarding Urethane Resin 2 The polyol and polyisocyanate used in producing the isocyanate-terminated prepolymer may be the same as those that can be used in producing the above-mentioned Urethane Resin 1.

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.

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 JP-A-2006-206839.

1.1.6 Method for Producing Urethane Resin An example of a method for producing the urethane resin will be described.

Hydroxyl-terminated polyurethane resins or isocyanate-terminated prepolymers can be produced, for example, by the conventional one-stage so-called one-shot method or the multi-stage isocyanate polyaddition reaction 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. If necessary, 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 during the reaction.

The residual isocyanate group content in the isocyanate group-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 group-terminated prepolymer can be determined, for example, as follows. That is, 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%=(a-b)×0.42×f/x
a: Titration amount 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.

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) should be 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 falls within an appropriate range, 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.

When urethane resin 1 or 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 urethane resin 1 or isocyanate-terminated prepolymer. There are no particular restrictions on the compound used to neutralize the carboxyl group, 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.

There are no particular limitations on the emulsifying equipment used when emulsifying and dispersing the isocyanate-terminated prepolymer in water, and examples include a homomixer, homogenizer, and disperser. Furthermore, 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 range of 0 to 40°C to minimize reaction between the isocyanate groups and water. Furthermore, when emulsifying and dispersing in this manner, an emulsifier may be used as needed. Reaction inhibitors such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, and benzoyl chloride may also be added.

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

If the aforementioned organic solvent is used when producing the isocyanate-terminated prepolymer, it is desirable to evaporate the solvent at 30 to 80°C under reduced pressure after the chain extension reaction or emulsification/dispersion. The urethane resin prepared in this manner can be obtained as an emulsified dispersion of urethane resin 2. The resin solids (non-volatile content) concentration in the emulsified dispersion of 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 evaporating water.

In addition, 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 removing water.

1.2 Antibacterial/Antiviral Agent The antibacterial/antiviral agent composition of the present disclosure contains the above-described urethane resin and an antibacterial/antiviral agent. The antibacterial/antiviral agent has a quaternary ammonium cation group.

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 only needs to have at least one quaternary ammonium cation group, and may be a low molecular weight compound or a high molecular weight compound. Specific examples of compounds having a quaternary ammonium cation group will be described later.

The type of anion that serves as a counterion to 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.

The antibacterial/antiviral agent may be at least one of the compounds represented by the following general formula (1) and the compounds represented by the following general formula (2). In particular, even greater effectiveness can be expected when the antibacterial/antiviral agent is a compound represented by the following general formula (1).

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.

Specific examples of _R1 include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, doeicosyl, trieicosyl, and tetraeicosyl groups. _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.

Specific examples of methoxysilane-based quaternary ammonium salts among the silane-based quaternary ammonium salts represented by formula (1) 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, and 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.

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 has been replaced with a triethoxysilyl group.

In formula (2), _R8 is an alkyl group or aryl group having 10 to 20 carbon atoms, _R9 is a methyl group, ethyl group, propyl group, butyl group, or a group represented by (AO) _pH , where AO is an alkylene oxide having 2 to 4 carbon atoms, p is an integer from 1 to 10, _R10 is a methyl group, ethyl group, 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, 1 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.

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 may be 20 or less or 18 or less.

In formula (2), when R ₉ is a methyl group, the antibacterial and antiviral properties are even more excellent.

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

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.

In formula (2), specific examples of aromatic anions that can be _Z2 include paratoluenesulfonic acid, xylenesulfonic acid, benzoic acid, and alkylbenzenesulfonic acid.

Specific examples of compounds represented by formula (2) include dodecyldimethylhydroxyethylammonium-butyl phosphate salt, tetradecyldimethylhydroxyethylammonium-butyl phosphate salt, dodecyldimethylhydroxyethylammonium-ethyl phosphate salt, and tetradecyldimethylhydroxyethylammonium-ethyl phosphate salt. Among these, dodecyldimethylhydroxyethylammonium-butyl phosphate salt provides even greater antibacterial and antiviral properties.

The antibacterial/antiviral agent may be a polymeric compound having multiple quaternary ammonium cations. For example, a polymeric compound such as that shown in formula (3) below may be used as the antibacterial/antiviral agent.

In formula (3), R ₁₁ may be an alkylene group having 1 to 4 carbon atoms, R ₁₂ may be a methyl group or an ethyl group, R ₁₃ may be a methyl group or an ethyl group, R ₁₄ may be an alkylene group having 1 to 4 carbon atoms, R _{15 may be a methyl group or an ethyl group, R 16 may} be a methyl group or an ethyl group, R ₁₇ may be an alkylene group having 1 to 4 carbon atoms, Z ₃ 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 200,000 or less or 80,000 or less.

1.3 Composition Ratio In the antibacterial and antiviral 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.

1.4 Amount of Adhesion In the antibacterial and antiviral agent composition of the present disclosure, the ratio between the article and the total amount of the urethane resin and antibacterial and antiviral agent adhered to the article is not particularly limited. For example, the total amount 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.

1.5 Optional Components The antibacterial and antiviral composition of the present disclosure may contain other components in addition to the above-described urethane resin and antibacterial and antiviral agent. For example, the antibacterial and antiviral composition of the present disclosure may contain a surfactant and water, or may contain 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, an antiseptic, etc.

The antibacterial/antiviral composition of the present disclosure may also contain a polyester resin in addition to the urethane resin and antibacterial/antiviral agent. In this case, the polyester resin may have a polyoxyalkylene chain and a quaternary ammonium cation group. When the antibacterial/antiviral composition contains a polyester resin having a polyoxyalkylene chain, the water absorption of the composition is further enhanced. When the antibacterial/antiviral composition contains a polyester resin having a quaternary ammonium cation group, the antibacterial/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/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, where the total of the urethane resin, antibacterial/antiviral agent, and polyester resin is 100% by mass.

2. Articles Articles to which the antibacterial and antiviral composition of the present disclosure is adhered have excellent durable antibacterial and antiviral properties, as well as excellent water absorbency.

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.

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.

3. Method for Manufacturing an Article The technology of the present disclosure also has an aspect as a method for manufacturing an article having antibacterial and antiviral properties. That is, the method for manufacturing 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.

The method for applying the antibacterial/antiviral composition to an article is not particularly limited. For example, the method disclosed herein may apply the antibacterial/antiviral composition to an object by bringing the object into contact with a treatment liquid (which may be a dispersion liquid) containing the antibacterial/antiviral composition. There is no particular limit to the timing of treatment with the treatment liquid.

The treatment liquid may contain, for example, the urethane resin and the antibacterial/antiviral agent. The treatment liquid may also contain other components, such as an acid component, an alkaline 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 higher and 7 or lower. To improve durability, it is preferable to treat the object using a method that includes applying the treatment liquid to the object and heating it in addition to the above-mentioned process of treating the object with a treatment liquid containing an antibacterial/antiviral composition, and also 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.

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 post-application heat treatment, can be adjusted appropriately, taking into account various factors such as the purpose and performance of the solution. After treating the object with the treatment solution, a cleaning process, such as rinsing with water, 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 is sufficient. A temperature of 40 to 130°C for 20 seconds to 10 minutes 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 temperature of 130 to 190°C for 30 seconds to 5 minutes is even more preferred.

4. Effects As described above, the antibacterial and antiviral 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 an article.

The effects of the technology disclosed herein will be explained in more detail below using examples, but the technology disclosed herein is not limited to the following examples.

1. Preparation of urethane resins In an alcohol-based solvent, in the presence of a catalyst, polyol, polyisocyanate, and optionally polycarbonate diol were reacted in the blending ratios (mass ratios) shown in Tables 1 or 2 below to obtain urethane resins. Specifically, the resins were synthesized as follows.

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-cat SA603 (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%).

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.

2. Preparation of Polyester Resin 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 2 hours at 240°C. After cooling to 60°C, 10 parts by mass of dimethyl sulfate was added dropwise. After reacting at 60°C for 2 hours, 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%).

3. Preparation of Antibacterial and Antiviral Agents The antibacterial and antiviral agents used in this example are as follows.

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.

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.

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 to obtain 1,100 parts by mass of a 40% by weight solution of tetradecyl[3-(trimethoxysilyl)propyl]dimethylammonium chloride.

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 to obtain 1,204 parts by mass of a 40% by weight solution of octadecyl[3-(trimethoxysilyl)propyl]dimethylammonium chloride.

4. Preparation of Treatment Liquid (Antibacterial and Antiviral Agent 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 predetermined ratios shown in Tables 4 to 6 below to obtain treatment liquids.

5. Imparting antibacterial and antiviral properties to articles 5.1 Examples 1 to 3, Reference Example 4, Examples 5 and 6, Reference Example 7, Examples 8 to 19, Comparative Examples 4 to 6
Cotton knit (basis weight 165 g/ ^m2 , manufactured by Irozome Co., Ltd.) or polyester knit (basis weight 120 g/ ^m2 , manufactured by Irozome Co., Ltd.) was immersed in the above treatment solution and treated at a squeezing 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.

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 having antibacterial and antiviral properties.

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.

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

5.5 Comparative Example 7
Antibacterial textile products were obtained according to the method described in Patent Document 1 (JP 62-177284 A). 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, thereby obtaining textiles with antibacterial and antiviral properties.

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 concentration of Compound B solution to 30 g/L and ethylene glycol diglycidyl ether to 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.

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), followed by heat treatment at 130°C for 2 minutes to obtain fibers with antibacterial and antiviral properties. 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%.

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

6. Washing: 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), and the detergent concentration in the washing liquid was 1.33 g/L. Repeated washing was performed 10 times under the above conditions.

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.

8. Evaluation of Durable Antiviral Properties 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 effective as antiviral.

9. Evaluation of Water Absorbency 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 water drop disappeared was measured to evaluate 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.

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

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

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

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

Furthermore, when the polyoxyalkylene chain content in the urethane resin contained in the antibacterial and antiviral 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).

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 properties, durable antiviral properties, and water absorbency is not ensured (Comparative Examples 7 to 9).

From the above, it can be said that an antibacterial and antiviral agent composition that satisfies the following requirements can impart excellent durable antibacterial properties, durable antiviral properties, and water absorbency to an article.
(1) The antibacterial and antiviral composition 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.
(2) The antibacterial and antiviral composition contains an antibacterial and antiviral agent having a quaternary ammonium cation group.

Claims (6)

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. 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. 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. 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.
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. 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 reflection from the water drop disappears is measured; the time is 6 seconds or less.
The polyester fiber product according to any one of claims 1 to 4. 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.