JP2024107447A - Antibacterial/antiviral composition, article, and method for producing article - Google Patents

Abstract

A composition capable of imparting durable antibacterial and antiviral properties and water absorbency to an article is disclosed.
[Solution] An antibacterial and antiviral composition comprising a urethane resin and an antibacterial and antiviral agent, the urethane resin having 30% by mass or more and 94% by mass or less of polyoxyalkylene chains, and the antibacterial and antiviral agent having a quaternary ammonium cation group.
[Selection diagram] None

Description

This application discloses an antibacterial/antiviral composition, an article, and a method for producing the article.

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 organosilicon 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-based 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 at least a carboxyl group on the surface by applying an antibacterial agent containing an ethoxysilane-based quaternary ammonium salt to the article.

Japanese Patent Application Publication No. 177284/1984 International Publication No. 2012/014762 JP 2019-077638 A International Publication No. 2013/047642

In conventional technology, when an antibacterial/antiviral article is washed with water or the like, the antibacterial/antiviral agent is easily removed from the article. In other words, there is room for improvement in the durable antibacterial and durable antiviral properties of the article. 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 properties, durable antiviral properties, and water absorbency to an article is needed.

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 has a polyoxyalkylene chain of 30% by mass or more and 94% by mass or less,
The antibacterial and antiviral agent has a quaternary ammonium cationic 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 a polyisocyanate,
The polyisocyanate may include 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:
In addition to the urethane resin and the antibacterial and antiviral agent, a polyester resin may be contained,
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 to obtain an article having antibacterial/antiviral properties;
A method of manufacturing an article is disclosed, comprising:

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

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.

1.1 Urethane resin The antibacterial and antiviral agent composition of the present disclosure contains a urethane resin, and the urethane resin has a polyoxyalkylene chain of 30% by mass or more and 94% by mass or less. In the antibacterial and antiviral agent composition of the present disclosure, by allowing a specific urethane resin to coexist with the antibacterial and antiviral agent, excellent durable antibacterial properties, durable antiviral properties, and water absorption properties are ensured. The urethane resin may be, for example, a hydroxyl group-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 obtained by emulsifying and dispersing an isocyanate group-terminated prepolymer obtained by reacting a polyol having a polyoxyalkylene chain with a polyisocyanate in water, and then carrying out a chain extension reaction with a chain extender (hereinafter, sometimes referred to as "urethane resin 2"). Both the urethane resin 1 and the urethane resin 2 may have a polyoxyalkylene chain and a structure derived from a polyisocyanate. In the antibacterial and antiviral agent composition of the present disclosure, the urethane resin may be used alone or in combination of two or more kinds.

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 of 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 addition, in the urethane resin, the number of carbon atoms of the alkylene group in one polyoxyalkylene chain and the number of carbon atoms of the alkylene group in another polyoxyalkylene chain may be the same or different from each other. In addition, 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 consisting of 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 higher effect can be expected when the urethane resin has a polyoxyalkylene chain having an alkylene group having 2 to 4 carbon atoms, and even higher effect can be expected when the urethane resin has at least a polyoxypropylene chain. In the urethane resin, the alkylene group constituting the polyoxyalkylene chain may be composed only of alkylene groups having 2 to 4 carbon atoms. In addition, the urethane resin may have only polyoxyethylene chains and polyoxypropylene chains as polyoxyalkylene chains. When the urethane resin has a polyoxyethylene (POE) chain and a polyoxypropylene (POP) chain, the ratio of the POE chain and 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 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 the urethane resin, for example, a urethane bond can be formed by reacting the polyol having the above 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. The polyisocyanate may also be composed 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, when the polyisocyanate contains an alkylene diisocyanate having 4 to 10 carbon atoms, a higher effect can be expected. An example of the polyisocyanate is shown below.

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.

Among these polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates can provide articles (particularly fibers and synthetic leather sheets such as PVC sheets and PU sheets) with non-yellowing properties. 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.

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 urethane resin may be composed of a structure derived from polyisocyanate 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 above-mentioned polyol having a polyoxyalkylene chain with the above-mentioned 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 higher 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 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 an alkylene diisocyanate having 4 to 10 carbon atoms and an arylene diisocyanate 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 the polyisocyanate. The urethane resin may have, for example, polycarbonate polyol, polyester polyol, low molecular weight polyhydric alcohol, etc. as a copolymerization component. The ratio of the structure derived from other components in the urethane resin may be 0 mass% or more or 0.1 mass% or more, and may be 60 mass% or less or 50 mass% or less. In addition to the structure derived from the polyoxyalkylene chain and the polyisocyanate and the urethane bond, the urethane resin may have various functional groups.

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, 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, or 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 alone or in combination of two or more.

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 polyols 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.

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.

1.1.5 Supplementary Notes on 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 above urethane resin will be described.

Hydroxyl-terminated polyurethane resin or isocyanate-terminated prepolymer can be produced, for example, by a conventional one-stage so-called one-shot method or a multi-stage isocyanate polyaddition reaction method. The reaction temperature is preferably 40 to 150°C. An organic solvent that does not react with 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, reaction catalysts such as dibutyltin dilaurate, stannous octoate, dibutyltin di-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine, and bismuth tris(2-ethylhexanoate), or reaction inhibitors such as phosphoric acid, sodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, and benzoyl chloride may be added as necessary.

The content of the residual isocyanate group in the isocyanate-terminated prepolymer may be 0.2 to 4.0% by mass. In this range, the polyurethane resin obtained by subsequent chain extension with a polyamine exhibits appropriate flexibility. The content of the residual isocyanate group in the isocyanate-terminated prepolymer can be determined, for example, as follows. That is, 0.3 g of the obtained prepolymer is taken in an Erlenmeyer flask, and 10 ml of a 0.1 N dibutylamine toluene solution is mixed and dissolved. Then, several drops of bromophenol blue solution are added, and titration is performed with a 0.1 N hydrochloric acid methanol solution, and the content of the residual isocyanate group NCO% can be determined by the following formula.
NCO%=(a-b)×0.42×f/x
a: Titration amount of 0.1 N hydrochloric acid methanol solution when only 10 ml of 0.1 N dibutylamine toluene solution was titrated.
b: Titration amount of 0.1 N hydrochloric acid methanol solution when the composition during reaction is titrated.
f: Factor of 0.1N hydrochloric acid in methanol.
x: sampling amount.

In order to set the content of residual isocyanate groups within the above range, it is preferable to adjust the molar ratio of hydroxyl groups/isocyanate groups in the raw material during prepolymer production. Specifically, the ratio (OH/NCO) of the total number of hydroxyl groups in the raw material to the total number of isocyanate groups in the raw material should be adjusted to 0.6 to 0.8 in molar ratio. By adjusting the molar ratio of hydroxyl groups/isocyanate groups within this range, the viscosity of the isocyanate-terminated prepolymer becomes an appropriate range, making it easier to emulsify. In addition, the texture of articles treated with the antibacterial and antiviral agent composition (especially fibers and synthetic leather sheets such as PVC sheets and PU sheets) can be softened, making it easier to prevent whitening when bent.

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, the neutralization of the carboxyl group can be carried out by using a known method before, during, or after the preparation of the urethane resin 1 or the isocyanate-terminated prepolymer. There are no particular limitations on the compound used to neutralize the carboxyl group, and examples of the compound 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 is no particular restriction on the emulsifying equipment used when emulsifying and dispersing the isocyanate-terminated prepolymer in water, and examples of such equipment 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 range of 0 to 40°C to minimize the reaction between the isocyanate group and water. When emulsifying and dispersing in this manner, an emulsifier may be used as necessary. 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 in one 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.

When the aforementioned organic solvent is used in 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 emulsion dispersion. The urethane resin prepared in this manner can be obtained as an emulsion dispersion of urethane resin 2. The resin solids (non-volatile content) concentration in the emulsion dispersion of the urethane resin is preferably in the range of 20 to 60%. The resin solids concentration in the emulsion dispersion can also be adjusted by adding or evaporating water.

The urethane resin 1 may also be obtained as an emulsion dispersion, and in this case too, the resin solids concentration in the emulsion 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-mentioned urethane resin and an antibacterial/antiviral agent. The antibacterial/antiviral agent has a quaternary ammonium cation group.

Compounds having a quaternary ammonium cationic group can exhibit antibacterial and antiviral properties on the surface of an article. Examples of quaternary ammonium cationic groups having antibacterial and antiviral properties include silane-based ammonium cationic groups, polyoxyalkylene alkyl ammonium cationic groups, and alkyl ammonium cationic groups. The antibacterial and antiviral agent only needs to have at least one quaternary ammonium cationic group, and may be a low molecular weight compound or a high molecular weight compound. Specific examples of compounds having a quaternary ammonium cationic group will be described later.

The type of anion that is the counterion 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.

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, when the antibacterial/antiviral agent is a compound represented by the following general formula (1), a higher effect can be expected.

In formula (1), R ₁ is an alkyl group having 10 to 22 carbon atoms, R ₂ is a methyl group, ethyl group, propyl group, or butyl group, R ₃ is a methyl group, ethyl group, propyl group, or 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, and Z ₁ is a halogen.

Specific examples of R ₁ include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, doeicosyl, trieicosyl, and tetraeicosyl. R ₂ and R ₃ may be the same group. R ₅ to R ₇ may be the same group. Z ₁ may be chlorine, bromine, or other halogen, but high performance can be expected especially when it is chlorine. The same applies to the halogen in formula (2) and the halogen in formula (3) described later.

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 the ammonium chloride 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 has good 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 is replaced with a triethoxysilyl group.

In formula (2), R ₈ is an alkyl group or aryl group having 10 to 20 carbon atoms, R ₉ 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, R ₁₀ 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 Z ₂ 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 the formula (2), when R ₉ is a methyl group, the antibacterial and antiviral properties are further improved.

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

Specific examples of the compound represented by formula (2) include dodecyl dimethyl hydroxyethyl ammonium-butyl phosphate salt, tetradecyl dimethyl hydroxyethyl ammonium-butyl phosphate salt, dodecyl dimethyl hydroxyethyl ammonium-ethyl phosphate salt, tetradecyl dimethyl hydroxyethyl ammonium-ethyl phosphate salt, etc. Among these, when dodecyl dimethyl hydroxyethyl ammonium-butyl phosphate salt is used, antibacterial and antiviral properties are further improved.

The antibacterial/antiviral agent may be a polymeric compound having multiple quaternary ammonium cations. For example, a polymeric compound such as that shown in the following formula (3) 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 agent composition of the present disclosure, the ratio of the urethane resin to the antibacterial and antiviral agent is not particularly limited. For example, the content of the urethane resin may be 15% by mass or more or 30% by mass or more, and may be 90% by mass or less or 80% by mass or less, where the total of the urethane resin and the antibacterial and antiviral agent is 100% by mass.

1.4 Amount of Adhesion In the antibacterial and antiviral agent composition of the present disclosure, the ratio between the article and the total of the urethane resin and the antibacterial and antiviral agent adhered to the article is not particularly limited. For example, the total of the urethane resin and the 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 agent composition of the present disclosure may contain other components in addition to the above-mentioned urethane resin and antibacterial and antiviral agent. For example, the antibacterial and antiviral agent composition of the present disclosure may contain a surfactant and water, or may contain a surfactant, an organic solvent, and water. In addition, the antibacterial and antiviral agent composition of the present disclosure may contain an acid component, an alkali component, a chelating agent, a crosslinking agent, an antifoaming agent, a preservative, etc.

In addition, the antibacterial and antiviral agent composition of the present disclosure may contain a polyester resin in addition to the above-mentioned 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 agent composition contains a polyester resin having a polyoxyalkylene chain, the water absorption of the composition is further increased. When the antibacterial and antiviral agent composition contains a polyester resin having a quaternary ammonium cation group, the antibacterial and antiviral properties of the composition are further increased. 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 not particularly limited, and for example, the dibasic acid described above may be used. In the antibacterial and antiviral agent 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, and 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.

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

The type of article is not particularly limited, and may be any article that requires durable antibacterial and antiviral properties and water absorbency. Specific examples of articles include textile products. Alternatively, the antibacterial and antiviral agent 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, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, as well as composite fibers 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. The fibers may take the form of yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, paper, wood, and the like. The fibers may be dyed. The fibers may have a surface that has been subjected to some kind of modification treatment.

3. Method for manufacturing an article The technology of the present disclosure also has an aspect of 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, to obtain 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 of attaching the antibacterial/antiviral composition to an article is not particularly limited. For example, the method disclosed herein may attach the antibacterial/antiviral composition to an object by contacting the object with a treatment liquid (which may be a dispersion liquid) containing the antibacterial/antiviral composition. There is no particular limit to the timing of carrying out the treatment with the treatment liquid.

The treatment liquid may contain, for example, the above-mentioned urethane resin and the above-mentioned 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 to 7. When it is desired to improve durability, it is preferable to treat the object by a method including a step of attaching the treatment liquid to the object and heating it in the above-mentioned step of treating the object with a treatment liquid containing an antibacterial and antiviral agent composition, using a crosslinking agent represented by a melamine resin, a glyoxal resin, or a compound having one or more isocyanate groups or blocked isocyanate groups in combination.

Specific examples of methods for treating an object with a treatment liquid include padding, immersion, spraying, and coating. The treatment conditions, such as the concentration of the treatment liquid and the heat treatment after application, may be adjusted appropriately taking into account various conditions such as the purpose and performance of the treatment liquid. After treating an object with the treatment liquid, a cleaning process such as washing with water may be performed to remove excess antibacterial and antiviral agents. If the treatment liquid contains water, a drying process may be performed to remove water after the treatment liquid is applied to the object. There are no particular limitations on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular limitations on the drying temperature or drying time, and for example, drying may be performed at room temperature to 200°C for 10 seconds to several days. More preferably, 40 to 130°C for 20 seconds to 10 minutes. If necessary, heat treatment may be performed at a temperature of 100 to 190°C for about 10 seconds to 5 minutes after drying. More preferably, 130 to 190°C for 30 seconds to 5 minutes.

4. Effects As described above, the antibacterial and antiviral agent composition of the present disclosure contains a predetermined urethane resin together with a predetermined antibacterial and antiviral agent, and is therefore capable of imparting 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 with reference to examples, but the technology disclosed herein is not limited to the following examples.

1. Preparation of urethane resin In an alcohol-based solvent, in the presence of a catalyst, a polyol, a polyisocyanate, and optionally a polycarbonate diol were reacted in the blending ratio (mass ratio) shown in Table 1 or 2 below to obtain a urethane resin. Specifically, the synthesis was performed as follows.

1.1 Synthesis Example 1
Into a reaction vessel, 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) were placed, and reacted for 3 hours at 130°C under a nitrogen atmosphere. The OH/NCO ratio is 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 ratio shown in Table 1 or 2 below.

2. Preparation of polyester resin Polytetramethylene glycol, adipic acid, and methyldiethanolamine were reacted in the blending ratio (mass ratio) shown in Table 3 below to obtain a polyester resin having a polyoxyalkylene chain and a quaternary ammonium cationic 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, and then reacted at 240°C for 2 hours. After cooling to 60°C, 10 parts by mass of dimethyl sulfate were dropped. 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 (polyester resin content 20%) having a polyoxyalkylene chain and a quaternary ammonium cationic group.

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

Compound A: A compound in which, in the following general formula (1), R ₁ is an alkyl group having 14 carbon atoms, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is a propylene group, R ₅ is a methyl group, R ₆ is a methyl group, R ₇ is a methyl group, and Z ₁ is chlorine.
Compound B: A compound in which, in the following general formula (1), R ₁ is an alkyl group having 18 carbon atoms, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is a propylene group, R ₅ is a methyl group, R ₆ is a methyl group, R ₇ is a methyl group, and Z ₁ 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 199 parts by mass of trimethoxysilylpropyl chloride, 240 parts by mass of dimethyltetradecylamine, and 539 parts by mass of triethylene glycol monomethyl ether were placed in a reaction vessel and reacted at 150° C. for 20 hours under a nitrogen atmosphere to obtain 1,100 parts by mass of a solution containing 40% by weight of tetradecyl[3-(trimethoxysilyl)propyl]dimethylammonium chloride.

3.2 Synthesis Conditions for Compound B 199 parts by mass of trimethoxysilylpropyl chloride, 298 parts by mass of dimethyloctadecylamine, and 744 parts by mass of ethanol were placed in a reaction vessel and reacted at 150° C. for 20 hours under a nitrogen atmosphere to obtain 1,204 parts by mass of a solution containing 40% by weight 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 prescribed 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 19 and Comparative Examples 4 to 6
Cotton knit (basis weight 165 g/ ^m2 , manufactured by Shikisen Co., Ltd.) or polyester knit (basis weight 120 g/ ^m2 , manufactured by Shikisen 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
The treatment was carried out in the same manner as in Example 2, except that no urethane resin was used in the preparation of the treatment liquid, to obtain a textile product having antibacterial and antiviral properties.

5.3 Comparative Example 2
A textile product having antibacterial and antiviral properties was obtained by carrying out treatment in the same manner as in Example 1, except that no antibacterial or antiviral agent was used in preparing the treatment liquid.

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

5.5 Comparative Example 7
According to the method described in Patent Document 1 (JP Patent Publication 62-177284), a textile product having antibacterial properties was obtained. Specifically, a treatment solution was prepared by adjusting the concentration of the solution of compound B to 30 g/L and the concentration of the sodium sulfate of lauryl alcohol ethylene oxide 3 mol adduct to 5 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), and then heat-treated at 130° C. for 2 minutes to obtain a textile product having antibacterial and antiviral properties.

5.6 Comparative Example 8
According to the method described in Patent Document 2 (WO 2012/014762), a textile product having antibacterial properties was obtained. Specifically, a treatment solution was prepared by adjusting the concentration of compound B to 30 g/L and ethylene glycol diglycidyl ether to 10 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), and then heat-treated at 130° C. for 2 minutes to obtain antibacterial and antiviral fibers.

5.7 Comparative Example 9
According to the method described in Patent Document 3 (JP 2019-077638 A), a textile product having antibacterial properties was obtained. Specifically, the treatment solution was adjusted so that the solution of compound B was 30 g/L and the acrylic acid/acrylic acid ester copolymer was 30 g/L, and a treatment bath was prepared. Cotton knit or polyester knit was immersed in the treatment bath, treated at a squeeze rate of 90% (cotton) or 110% (polyester), and then heat-treated at 130 ° C. for 2 minutes to obtain a fiber having antibacterial and antiviral properties. The acrylic acid/acrylic acid ester copolymer is an aqueous dispersion of an acrylic acid ester copolymer in which ethyl acrylate, butyl acrylate, and acrylic acid are copolymerized to have a molar ratio of 42%, 17%, and 41%, respectively, and has a solid content of 30%.

5.8 Comparative Example 10
The cotton knit or polyester knit was used as is 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 of the washing liquid was 1.33 g/L. Under the above conditions, the textile products were repeatedly washed 10 times.

7. Evaluation of durable antibacterial properties The antibacterial activity value was measured by JIS L1902 (2015) quantitative test (8.2 bacterial liquid absorption method), and the antibacterial performance of the textile products was evaluated before and after washing. Staphylococcus aureus NBRC12732 and Klebsiella pneumoniae NBRC13277 were used as the bacteria used. 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 the textile product. The influenza A virus (H3N2) ATCC VR-1679 was used as the virus used. 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. In addition, in JIS, an antiviral activity value of 2.0 or more is considered to be effective, but viruses are reduced even if the activity value is 2.0 or less. In this example, it is determined that there is an antiviral effect even if the activity value is 1.5.

9. Evaluation of water absorbency According to JIS L1907 (2010) 7.11 Dropping method, one drop of water (about 12 mg) was dropped onto the test cloth, and the time (seconds) until the reflection by the water 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.

As is clear from the results shown in Tables 4 to 6, when a textile product is treated with a composition containing a specified urethane resin and a specified antibacterial and antiviral agent, the textile product is able to maintain high activity values for both antibacterial and antiviral properties before and after washing, has high durable antibacterial and antiviral properties, and also has high water absorbency (Examples 1 to 19).

On the other hand, when the antibacterial/antiviral composition does not contain a urethane resin, the antiviral properties of the textile product significantly decrease 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).

In addition, when the antibacterial and 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).

In addition, when the content of polyoxyalkylene chains 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 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 property, durable antiviral property and water absorbency to an article.
(1) The antibacterial and antiviral composition contains a urethane resin, and the urethane resin has a polyoxyalkylene chain 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.

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 Shikisen Co., Ltd.) or polyester knit (basis weight 120 g/ ^m2 , manufactured by Shikisen 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.

As is clear from the results shown in Tables 4 to 6, when a textile product is treated with a composition containing a specified urethane resin and a specified antibacterial and antiviral agent, the textile product can maintain high activity values for both antibacterial and antiviral properties before and after washing, and has high durable antibacterial and 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).

Claims (8)

An antibacterial/antiviral agent composition comprising a urethane resin and an antibacterial/antiviral agent,
The urethane resin has a polyoxyalkylene chain of 30% by mass or more and 94% by mass or less,
The antibacterial and antiviral agent has a quaternary ammonium cationic group.
Antibacterial and antiviral compositions. The polyoxyalkylene chain has an alkylene group having 2 to 4 carbon atoms.
The antibacterial and antiviral composition according to claim 1. The urethane resin has at least a polyoxypropylene chain.
The antibacterial and antiviral composition according to claim 1 or 2. The urethane resin has a structure derived from a polyisocyanate,
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 antibacterial and antiviral composition according to any one of claims 1 to 3. The 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 antibacterial and antiviral composition according to any one of claims 1 to 4. The antibacterial and antiviral agent is a compound represented by the following general formula (1):
The antibacterial and antiviral composition according to any one of claims 1 to 5.
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. The antibacterial and antiviral composition according to any one of claims 1 to 6 is attached to the surface of the substrate.
Goods. An antibacterial/antiviral agent composition according to any one of claims 1 to 6 is attached to an object to which antibacterial/antiviral properties are to be imparted, thereby obtaining an article having antibacterial/antiviral properties;
A method for manufacturing an article, comprising: