JP2022121199A - Antiviral agent composition, antiviral fabric treated with the composition, antiviral polyurethane sheet, and antiviral polyvinyl chloride sheet - Google Patents

Abstract

To provide an antiviral agent composition which makes it possible to apply an aqueous polyurethane resin and an antiviral agent containing a methoxysilane quaternary ammonium salt in the same bath via one processing step; and also provide an antiviral fabric, a polyurethane sheet, and a polyvinyl chloride sheet, each of which has on its surface a layer formed from the antiviral agent composition.SOLUTION: An antiviral agent composition according to the present invention is a mixture including an antiviral agent that includes a methoxysilane quaternary ammonium salt, and also including, as a binder, an aqueous polyurethane resin that has a carboxyl group and/or a carboxylate group, the composition containing a water-soluble organic polymer (for example, a urethane-modified polyether, etc.) as a dispersant.SELECTED DRAWING: None

Description

The present invention provides a composition containing an antiviral agent, an antiviral fabric treated with the composition, an antiviral polyurethane (PU) sheet surface-coated with the composition, and an antiviral polyvinyl chloride. (PVC) sheet.

In recent years, many antibacterial/antiviral agents and materials to which antibacterial/antiviral agents have been added have been developed in connection with the growing awareness of environmental hygiene. Organosilane compounds containing hydrolyzable groups are known as silicon-containing antibacterial and antiviral agents. Among these, an ethoxysilane-based quaternary ammonium salt is known as an antiviral agent that can be immobilized on the surface of a material (Patent Document 1). This antiviral agent has, in its molecule, an ammonium group having a relatively long-chain alkyl group that exhibits antiviral properties, and an alkoxysilyl group capable of forming a covalent bond with the surface of the material. A silyl group is characterized by reacting with an oxygen-containing functional group such as a hydroxyl group present on the surface of an inorganic material or the like to form a covalent bond, thereby being firmly immobilized on the surface of the material.

On the other hand, when the antiviral agent is immobilized on an article that does not have an oxygen-containing functional group on the surface, such as a synthetic fiber such as polyester fiber or a resin material such as polypropylene, a pretreatment step is required. It had been. Patent Document 1 also discloses that an article is treated with ozone water before applying an antiviral agent in order to impart oxygen-containing functional groups to the surface of the article.

Further, in Patent Document 2, when the antiviral agent is immobilized on a synthetic resin article, plasma treatment is performed prior to immobilization of the antiviral agent, so that the synthetic resin is polymethyl methacrylate resin or polyethylene terephthalate It is disclosed that an antiviral agent can be efficiently immobilized even when it is a resin. Further, Patent Document 3 describes that in addition to ozone water treatment, microwave irradiation is performed in order to immobilize the antiviral agent on the surface of an article. Both ozone water treatment and microwave irradiation are carried out to generate —OH groups, —CHO groups (aldehyde groups), —O— groups, or the like on the surface of articles.

Furthermore, Patent Document 4 discloses that, in order to immobilize the antiviral agent on the synthetic fiber, a binder having a carboxyl group is added to the synthetic fiber prior to immobilization treatment of the antiviral agent. . According to the invention of Patent Document 4, an antiviral agent can be suitably applied to synthetic fibers such as polyester fibers.

In addition, Patent Document 5 discloses a method that can be processed in one step by verifying compatibility between the antiviral agent and a specific acrylic resin component.

JP 2011-98976 A JP 2007-126557 A WO2009/136561 WO2013/047642 Patent No. 6482099

As described above, various methods have been proposed for immobilizing ethoxysilane-based quaternary ammonium salts on the surface of articles, but a plasma processing apparatus is required for plasma processing. In addition, in order to perform ozone water treatment and microwave irradiation, a facility for supplying ozone water and a dedicated facility for generating microwaves are required, respectively.
In Patent Document 4, it is necessary to perform the processing in two stages, first applying the binder and then applying the antiviral agent, which is disadvantageous in terms of production efficiency and cost.
Patent Document 5 discloses a composition containing an antiviral agent whose compatibility is improved by using a specific acrylic resin component, but the compatibility is insufficient and there is room for improvement. rice field.

In view of this situation, the present invention has improved the compatibility between an antiviral agent containing a methoxysilane-based quaternary ammonium salt and a binder (polyurethane resin or a polyurethane resin and an acrylic resin). An object of the present invention is to provide an antiviral agent composition that can be applied in the same bath during processing.
A further object of the present invention is to provide antiviral fabrics, polyurethane sheets, and polyvinyl chloride sheets in which an antiviral agent is immobilized.

The inventors have investigated the above problems, and decided to use an antiviral agent containing a methoxysilane-based quaternary ammonium salt, and as a binder, a water-based polyurethane resin having a carboxyl group and/or a carboxylate group, or A mixture of the polyurethane resin and the acrylic resin was used.
Then, when a water-based polyurethane resin having a carboxyl group and/or a carboxylate group or a mixture of the polyurethane resin and the acrylic resin is used as the binder, a specific water-soluble polymer can be added in advance to form an antiviral agent. Fabrics, polyurethane sheets, and polychlorides that have good binder compatibility, can be fixed to products with antiviral agents in a single process, and have excellent durability and antibacterial and antiviral properties. They found that a vinyl sheet can be obtained, and completed the present invention.

In this specification, "having a carboxyl group and/or a carboxylate group" means that the carboxyl group present in the composition or on the surface of the fabric exists as a free carboxyl group (-COOH) that is not dissociated. In addition to the case where the terminal hydrogen atom is separated to form a carboxylate anion, and the case where the carboxylate anion and the antiviral agent molecule are chemically bonded, unless otherwise specified. shall be taken.

That is, the present invention has the following configurations.
[1] an antiviral agent containing a methoxysilane-based quaternary ammonium salt;
a water-based polyurethane resin having a carboxyl group and/or a carboxylate group as a binder;
and a water-soluble organic polymer as a dispersant.
[2] The antiviral agent composition according to [1], wherein the binder is a mixture of the aqueous polyurethane resin having a carboxyl group and/or a carboxylate group and an acrylic resin.
[3] The antiviral agent composition according to [1] or [2], wherein the methoxysilane-based quaternary ammonium salt is a compound having a structure represented by the following formula (1).

[4] The water-soluble organic polymer is at least one polymer selected from the group consisting of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch, urethane-modified polyether, xanthan gum, and polyvinyl alcohol. The antiviral agent composition according to any one of [1] to [3], characterized in that
[5] The polyurethane resin according to any one of [1] to [4], wherein the content of carboxyl groups and/or carboxylate groups in the polyurethane resin is 0.5 to 4.0% by mass. Antiviral composition.
[6] A layer having antiviral properties is provided on the surface of the fabric base material, and the layer contains an antiviral agent containing a methoxysilane-based quaternary ammonium salt and a carboxyl group and/or a carboxylate group. An antiviral fabric characterized by being a layer containing a water-based polyurethane resin binder.
[7] A layer having antiviral properties is provided on the surface of a sheet made of polyurethane, and the layer comprises an antiviral agent containing a methoxysilane-based quaternary ammonium salt and a carboxyl group and/or a carboxylate group. An antiviral polyurethane sheet characterized by being a layer containing a water-based polyurethane resin binder having
[8] An antiviral layer is provided on the surface of a polyvinyl chloride sheet, and the layer comprises an antiviral agent containing a methoxysilane-based quaternary ammonium salt, a carboxyl group and/or a carboxyl An antiviral polyvinyl chloride sheet characterized by being a layer containing a water-based polyurethane resin binder having a rate group.

The antiviral agent composition of the present invention contains an antiviral agent containing a methoxysilane-based quaternary ammonium salt, a binder, and a water-soluble organic polymer, and is a conventional composition containing an antiviral agent and a binder. The antiviral agent can be imparted in a single process even to synthetic fibers that have better compatibility and do not have hydroxyl groups on the surface. In other words, a pretreatment step prior to antiviral agent treatment becomes unnecessary, and antiviral fabric can be produced stably and efficiently at low cost without using special equipment, and production efficiency and cost can be improved. advantage in terms of Further, the composition of the present invention is excellent in stability without generating resin scum and the like even when a treatment liquid is prepared by diluting it with water or the like and processed into a fabric.
Furthermore, fabrics and synthetic leather sheets (polyurethane sheets, polyvinyl chloride sheets) on which an antiviral layer is formed using the antiviral agent composition of the present invention are also excellent in washing durability. , can maintain its antiviral effect for a long period of time.

FIG. 2 is a schematic diagram showing an example of the production process when producing an antiviral fabric using the antiviral agent composition of the present invention. (a) is a diagram showing an example of the layer structure of an antiviral polyurethane sheet produced using the antiviral agent composition of the present invention, and (b) is an antiviral polyurethane sheet having such a layer structure. It is a process diagram showing an example of the process when manufacturing the. (a) is a diagram showing an example of the layer structure of an antiviral polyvinyl chloride sheet produced using the antiviral agent composition of the present invention, and (b) is an antiviral sheet having such a layer structure. FIG. 2 is a process drawing showing an example of a process for manufacturing a polyvinyl chloride sheet.

[Antiviral agent]
The antiviral agent contained in the antiviral composition of the present invention is an antiviral agent containing a methoxysilane-based quaternary ammonium salt, and the methoxysilane-based quaternary ammonium salt exhibits antiviral properties. It has an ammonium group having a long-chain alkyl group and an alkoxysilyl group capable of forming a covalent bond with the binder on the fabric surface. Specific examples of methoxysilane-based quaternary ammonium salts include compounds represented by the following general formula (2).

（式（２）中、Ｒ^１は炭素原子数１２～２４のアルキル基を示し、Ｒ^２及びＲ^３は同一又は異なっていてもよい炭素原子数１～６の低級アルキル基を示し、Ｘはハロゲンイオン又は有機カルボニルオキシイオン（有機カルボン酸イオン）を示す。）

(In formula (2), R ¹ represents an alkyl group having 12 to 24 carbon atoms, R ² and R ³ represent lower alkyl groups having 1 to 6 carbon atoms which may be the same or different, and X is Halogen ion or organic carbonyloxy ion (organic carboxylate ion).)

X in formula (2) includes halogen ions such as chloride ion and bromide ion, methylcarbonyloxy ion (acetate ion), ethylcarbonyloxyion (propionate ion), phenylcarbonyloxyion (benzoate ion) and the like. An organic carbonyloxy ion (organic carboxylate ion) can be exemplified.

The alkyl group having 12 to 24 carbon atoms for R ¹ in formula (2) includes dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and uneicosyl group. , a doeicosyl group, a trieicosyl group, a tetraeicosyl group, and the like.

Examples of lower alkyl groups having 1 to 6 carbon atoms which may be the same or different for R ² and R ³ in formula (2) include methyl group, ethyl group, propyl group, isopropyl group, butyl group and pentyl. group, hexyl group, cyclohexyl group and the like can be exemplified.

Specific examples of the methoxysilane-based quaternary ammonium salts represented by the general formula (2) 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, pentadecyldiethyl(3-trimethoxysilylpropyl)ammonium chloride, pentadecyldi-n-propyl(3-trimethoxysilylpropyl)ammonium chloride chloride, hexadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, hexadecyldiethyl(3-trimethoxysilylpropyl)ammonium chloride, hexadecyldi-n-propyl(3-trimethoxysilylpropyl)ammonium chloride, octadecyldiethyl (3 -trimethoxysilylpropyl) ammonium chloride, octadecyldi-n-propyl (3-trimethoxysilylpropyl) ammonium chloride, etc. Among these, from the viewpoint of more antiviral properties, octadecyldimethyl (3-trimethoxysilylpropyl) ) ammonium chloride (the following chemical formula (1)) is preferred.

The antiviral agent contained in the antiviral agent composition of the present invention may be one or more of the above methoxysilane-based quaternary ammonium salts, or may be used in combination with other antiviral agents. can also The above-mentioned methoxysilane-based quaternary ammonium salt has an antibacterial (bacteriostatic) effect against Gram-positive and Gram-negative bacteria, and an antiviral effect against enveloped viruses such as influenza virus and measles virus. (Hereinafter, the antibacterial effect and the antiviral effect may be collectively referred to as the antiviral effect.) Furthermore, in addition to the antiviral effect, it is considered to have an antistatic effect and a deodorant effect at the same time.

The concentration of the above antiviral agent is not particularly limited as long as it can be stably maintained in the composition and the effects of the present invention can be obtained. It can be contained in an undiluted state before treatment in an amount of 0.01 to 50% by weight, more preferably 0.02 to 20% by weight. The concentration of the antiviral agent in the treatment liquid when treating the fabric is preferably 0.01 to 1.5% by weight, more preferably 0.02 to 0.45% by weight.

[Water-based polyurethane resin]
The binder (aqueous polyurethane resin) in the antiviral agent composition of the present invention is a neutralization of an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound, a polyol compound, and a diol compound having a carboxyl group and/or a carboxylate group. After emulsifying and dispersing the product in water, chain extension reaction is performed in water using an amine-based chain extension agent. Hereinafter, dispersing or emulsifying is referred to as emulsification dispersion.
Regarding the water-based polyurethane resin, the term "water-based" means that after preparing an emulsified dispersion (solvent: water) in which the concentration of the polyurethane resin in water is 40% by mass, the emulsified dispersion is allowed to stand at 20°C for 12 hours. This means that it is possible to create a state in which no sedimentation or sedimentation is observed.

(Polyisocyanate compound)
The polyisocyanate compound used in the present invention is not particularly limited, and examples thereof include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds. Examples of aromatic polyisocyanate compounds include toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), and tetramethylxylylene diisocyanate. Examples of aliphatic polyisocyanate compounds include hexamethylene diisocyanate (HDI). Examples of alicyclic polyisocyanate compounds include 1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI) and norbornane diisocyanate. These polyisocyanate compounds may be used singly or in combination of two or more. Among such polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanate compounds can be preferably used because they impart non-yellowing properties to fabrics, polyvinyl chloride sheets, and polyurethane sheets. Diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane can be preferably used.

(Polyol compound)
Moreover, polyether polyol, polyester polyol, polycarbonate polyol, etc. can be mentioned as a polyol compound. These polyol compounds may be used singly or in combination of two or more. It is desirable to use polycarbonate polyol because it improves the wear resistance of fabrics, polyvinyl chloride sheets, and polyurethane sheets.
Further, the polyol compound preferably has a number average molecular weight of 1,000 to 3,000. When the number average molecular weight is within this range, the appearance quality and abrasion resistance of the fabric, polyvinyl chloride sheet, and polyurethane sheet are improved.

Polyether polyols include, for example, homo-addition polymers or co-addition polymers of alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and tetramethylene oxide (block copolymerization or random copolymerization may be used). A polyol and the like can be mentioned.

Examples of polycarbonate polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol One or more polyols selected from methanol, or ethylene oxide or propylene oxide adducts of bisphenol A; and one or more carbonates selected from diethyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. Those obtained by dealcoholization reaction, dephenolation reaction, etc. with are mentioned. The above polycarbonate polyols can be used singly or in combination of two or more.

Examples of polyester polyols include 1 selected from phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, fumaric acid, and the like. Those obtained by a polycondensation reaction between a seed or two or more dibasic acids and one or two or more polyols used for synthesizing the polycarbonate polyol described above can be mentioned. The above polyester polyols can be used singly or in combination of two or more.

Diol compounds having a carboxyl group and/or a carboxylate group include, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts thereof. Furthermore, as such a diol compound, a polyester polyol having a pendant carboxyl group obtained by reacting a diol compound having a carboxyl group with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or the like can also be used. The diol compound having a carboxyl group may be mixed with a diol compound having no carboxyl group as a diol component and reacted. These diol compounds can be used singly or in combination of two or more.

In the present invention, the content of carboxyl groups in the water-based polyurethane resin is determined from the viewpoint of adhesion of the antiviral agent or compatibility with the antiviral agent. The amount is preferably in the range of 0.5% to 4.0% by weight. The content of carboxyl groups and/or carboxylate groups can be determined by calculating the amount of COO per 100 g of polyurethane resin from the amount of charged raw materials. If the carboxyl group content exceeds 4.0% by mass, the texture of the fabric, polyvinyl chloride sheet, or polyurethane sheet may become hard, and whitening may easily occur when the sheet is bent. On the other hand, if the content is 0.5% by mass or less, the storage stability of the water-based polyurethane resin is lowered, so that stable processing may not be possible.

In the present invention, low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol and hexamethylene glycol can also be used as the polyol compound when preparing the isocyanate group-terminated prepolymer.
(chain extender)
Examples of chain extenders include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, norboranediamine, diaminodiphenylmethane, tri Low molecular weight polyamines such as diamine, xylylenediamine, diethylenetriamine, triethylenetetramine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (at least one selected from the group consisting of primary amino groups and secondary amino groups) polyamine compounds containing two or more of the above amino groups in one molecule). These chain extenders can be used singly or in combination of two or more.

The water-based polyurethane resin contained in the antiviral agent composition of the present invention is, for example, a flame retardant-blended urethane resin containing a phosphorus compound as a flame retardant component disclosed in JP-A-2006-206839. good too.

Next, a method for producing the water-based polyurethane resin will be described.
(Isocyanate group-terminated prepolymer)
In the present invention, the specific method for producing the isocyanate group-terminated prepolymer is not particularly limited. can. The reaction temperature at this time is preferably 40 to 150°C. Also, an organic solvent that does not react with isocyanate groups can be added during or after the reaction. As such an organic solvent, for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, etc. can be used. During the reaction, if necessary, dibutyltin dilaurate, stannous octoate, dibutyltin di-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine, bismath tris (2-ethylhexanoate) or a reaction inhibitor such as phosphoric acid, sodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid and benzoyl chloride.
The content of residual isocyanate groups in the isocyanate group-terminated prepolymer is preferably 0.2 to 4.5% by mass. Within this range, the film formability of the water-based polyurethane resin composition obtained by subsequent chain extension with polyamine is good, and the formed film is soft and exhibits appropriate flexibility.
The residual isocyanate group content can be obtained by the following method.
0.3 g of the resulting urethane prepolymer was placed in an Erlenmeyer flask, mixed with 10 ml of 0.1N dibutylamine toluene solution, and dissolved. Then, several drops of bromophenol blue solution were added, titration was carried out with a 0.1N hydrochloric acid methanol solution, and the free isocyanate group content NCO% was determined by the following formula.
NCO % = (ab) x 0.42 x f/x
a: Titration amount of 0.1N hydrochloric acid methanol solution when only 10 ml of 0.1N dibutylamine toluene solution was 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.
In order to keep the content of residual isocyanate groups within the above range, it is preferable to adjust the molar ratio of isocyanate groups/hydroxyl groups in the starting material to 100/80 to 100/60 when producing the prepolymer. When the isocyanate group/hydroxyl group molar ratio is less than 100/80, the viscosity of the isocyanate group-terminated prepolymer is high, and emulsification and dispersion may become difficult. If it exceeds, the texture of the fabric, polyvinyl chloride sheet, or polyurethane sheet may become hard, and whitening may easily occur when bent.

(neutralization)
Neutralization of the carboxyl groups of the isocyanate group-terminated prepolymer can be carried out using a suitable known method before, during or after the preparation of the isocyanate group-terminated prepolymer. There are no particular restrictions on the compound used for neutralizing the isocyanate group-terminated prepolymer having such a carboxyl group. -dimethylmonoethanolamine, N,N-diethylmonoethanolamine, amines such as triethanolamine, potassium hydroxide, sodium hydroxide, ammonia and the like. Among such compounds, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferred.

(Emulsification dispersion)
In the present invention, the emulsifying and dispersing equipment used for emulsifying and dispersing the neutralized isocyanate group-terminated prepolymer in water is not particularly limited, and examples thereof include homomixers, homogenizers, and dispersers. Further, when emulsifying and dispersing the neutralized product of the isocyanate group-terminated prepolymer in water, the neutralized product of the isocyanate group-terminated prepolymer is emulsified and dispersed in water in a temperature range of 0 to 40 ° C., and the isocyanate group and It is preferable to suppress the reaction with water as much as possible. Furthermore, when emulsifying and dispersing in this manner, reaction inhibitors such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, and benzoyl chloride can be added as necessary. .

(amine extension)
In the present invention, the isocyanate group-terminated prepolymer emulsified and dispersed in water as described above has at least one amino group selected from the group consisting of primary amino groups and secondary amino groups in one molecule. The chain is extended using a polyamine compound containing 1 or more.
The reaction between the isocyanate group-terminated prepolymer and the polyamine compound is completed at a reaction temperature of 20 to 50° C. usually in 30 to 120 minutes.

(solvent removal)
When the aforementioned organic solvent is used in producing the isocyanate group-terminated prepolymer, for example, it is desirable to distill off the solvent at 30 to 80° C. under reduced pressure after the chain extension reaction or emulsification dispersion. By such a preparation method, the polyurethane resin can be obtained as an emulsified dispersion of the polyurethane resin.
The resin solid content (nonvolatile content) concentration in the emulsified dispersion of the polyurethane resin is preferably in the range of 20 to 60%. The resin solid content concentration can also be adjusted by adding or distilling off water.

[Acrylic resin]
In the antiviral agent composition of the present invention, it is preferable to use an acrylic resin in combination with the water-based polyurethane resin described above as a binder. The weight ratio of the water-based polyurethane resin and the acrylic resin can be selected as appropriate, but is preferably 1:0.1-1.
Examples of acrylic resin monomers contained as binders include methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other (meth)acrylic acid derivatives; styrene, α-methylstyrene, p-methylstyrene and other aromatic vinyl compounds; acrylamide, dye Acrylamides such as acetone acrylamide, methacrylamide, and maleic acid amide; Heterocyclic vinyl compounds such as vinylpyrrolidone; Vinyl compounds such as vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, and vinylamide; α-olefins such as ethylene and propylene; , fumaric acid, itaconic acid and derivatives thereof. Here, (meth)acrylic acid represents acrylic acid or methacrylic acid. Moreover, such a monomer can be used individually by 1 type, or can also be used in combination of 2 or more types.

[Dispersant]
The antiviral agent composition of the present invention contains a water-soluble organic polymer as a dispersant for dispersing the antiviral agent and the polyurethane resin in the same liquid. The is preferably at least one polymer selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch, urethane-modified polyether, xanthan gum and polyvinyl alcohol, particularly urethane-modified poly Ether or xanthan gum are preferred.
In the present invention, the term "water-soluble" means that the substance becomes transparent when dissolved in water at 20°C at a concentration of 0.1% by mass.
The urethane-modified polyether may contain a urethane-modified polyether having a terminal hydrophobic group and a urethane bond in the molecular chain. Urethane-modified polyether containing:

R1-X-(PEG-X-R2-X)m-PEG-X-R1'
(R1, R1′: an alkyl group having 8 to 36 carbon atoms or a hydrocarbon group having an aromatic ring, and R1 and R1′ may be the same or different; R2: a diisocyanate residue having 6 to 36 carbon atoms excluding an NCO group; group, X: urethane bond, PEG: polyethylene glycol residue with a molecular weight of 1,500 to 33,000, m: an integer of 0 or more);

R1-Y-R2-(X-PEG-X-R3)m-X-PEG-X-R2-Y-R1'
(R1, R1': an alkyl group having 8 to 36 carbon atoms or a hydrocarbon group having an aromatic ring, and R1 and R1' may be the same or different; In the diisocyanate residue, R2 and R3 may be the same or different, X: urethane bond, Y: urethane bond or urea bond, PEG: polyethylene glycol residue with a molecular weight of 1,500 to 33,000, m: 0 or more integer);

R1-(OA)p-X-R2-(X-PEG-X-R3)mX-(AO)q-R1'
(R1, R1′: an alkyl group having 8 to 36 carbon atoms or a hydrocarbon group having an aromatic ring, and R1 and R1′ may be the same or different; R2, R3: In the diisocyanate residue, R2 and R3 may be the same or different, X: a urethane bond, A: a hydrocarbon residue containing at least ethylene in a hydrocarbon having 2 to 4 carbon atoms, m: an integer of 0 or more, p, q: an integer of 1 to 200, and p and q may be the same or different);

(R1, R1′, R1″: an alkyl group having 8 to 36 carbon atoms or a hydrocarbon group having an aromatic ring; R1, R1′ and R1″ may be the same or different; functional polyisocyanate residue, A: hydrocarbon residue containing at least ethylene in hydrocarbon having 2 to 4 carbon atoms, X: urethane bond, i, j, k: an integer of 0 or more and (i + j + k) is 3 or more Integer, p, q, r: an integer of 1 to 200, and p, q and r may be the same or different);

(R1, R1′, R1″: an alkyl group having 8 to 36 carbon atoms or a hydrocarbon group having an aromatic ring; R1, R1′ and R1″ may be the same or different; functional polyisocyanate residue, A: a hydrocarbon residue having 2 to 4 carbon atoms and containing at least ethylene, X: a urethane bond, Y: a urethane bond or a urea bond, i, j, k: integers of 0 or more and (i + j + k) is an integer of 3 or more, p, q is an integer of 1 to 200, and p and q may be the same or different);

(R1, R1′, R1″: an alkyl group having 8 to 36 carbon atoms or a hydrocarbon group having an aromatic ring, where R1, R1′ and R1″ may be the same or different; functional polyol or polyamine residue, A: hydrocarbon residue containing at least ethylene with 2 to 4 carbon atoms, X: urethane bond, i, j, k: an integer of 0 or more and (i+j+k) is 3 or more integer, p, q, r: an integer of 1 to 200, and p, q and r may be the same or different);

Compound A having a weight average molecular weight of 10,000 or more and less than 40,000 represented by the following general formula (3) is 20% by mass or more and less than 80% by mass, and a weight average molecular weight of 40,000 or more represented by general formula (4) A composition characterized by containing 20% by mass or more and less than 80% by mass of compound B of less than 140,000 as an essential component:

(Wherein, X1 and X2 are hydrocarbon groups having 15 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR′ and OR″ are C 2 to 4 is an oxyalkylene group, a, b, and d are integers of 1 to 500, and c is an integer of 1 or more.)

(Wherein, X3 and X4 are hydrocarbon groups having 4 to 24 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR′ and OR″ are C 2 to 4 an oxyalkylene group, a, b, and d are integers of 1 to 500, and c is an integer of 1 or more.)
etc.

In addition, the antiviral agent composition of the present invention may contain various additives. For example, emulsifiers, thickeners, preservatives, buffers, pH adjusters and the like may be contained as long as they do not interfere with the effects of the present invention.

[Antiviral fabric]
The present invention also relates to fabrics treated with the antiviral compositions described above. Conventionally, antiviral agents containing methoxysilane-based quaternary ammonium salts are difficult to immobilize on fabrics that do not have oxygen-containing functional groups on the surface, and pretreatment was required when immobilized. However, according to the antiviral agent composition of the present invention, the binder and the antiviral agent can be applied to the fabric in one treatment, that is, in the same bath. In addition, according to the antiviral agent composition of the present invention, resin scum and the like are generated less than in the conventional same-bath treatment.
The fabric may be a woven fabric, a knitted fabric, or a non-woven fabric, and can be appropriately selected depending on the application and purpose. The material of the fabric may be natural fiber, chemical fiber, or a combination thereof. Natural fibers include cotton, wool, silk, hemp, etc., and chemical fibers include polyester, polyurethane, polyamide, rayon, acrylic, etc. It is possible to select a fabric using these alone or in combination. Furthermore, other fibers such as inorganic fibers such as metal fibers and glass fibers may be included from the viewpoint of use and design. Also, these fabrics may be fabrics that have been subjected to various types of processing, such as flame-retardant processing and antifouling processing. For example, polyester-based fabrics are mainly selected for vehicle interior applications such as automobile seats.

Among fabrics, fibers having hydroxyl groups on the surface, such as cotton and wool, are relatively easy to immobilize the above antiviral agents. Therefore, it is possible to obtain a fabric excellent in washing durability from which the antiviral agent does not come off even after washing many times.

^The amount of the antiviral agent and binder applied to the fabric is not particularly limited as long as the effect of the present invention is achieved. It is more preferable to be ∼5 g/m ² . If the amount of the antiviral agent is less than 0.03 g/m ² , it is difficult to obtain a sufficient antiviral effect, and if it exceeds 5 g/m ² , there is a risk of reduced combustibility. Also, the amount of the binder attached can be 0.01 to 15 g/m ² , and more preferably 0.06 to 5 g/m ² . If the binder is less than 0.06 g/m ² , the durability of the antiviral agent to washing may deteriorate, and if it exceeds 5 g/m ² , the softness of the material may be impaired.

The fabric may further contain additional additives and the like as long as they have the effects of the present invention. Such additives may include, for example, colorants, antioxidants, light stabilizers, ultraviolet absorbers, flame retardants, softeners, and other thermoplastic resins.

[Method for producing antiviral fabric]
The water-based polyurethane resin having a carboxyl group and/or a carboxylate group, which is a binder contained in the antiviral agent composition of the present invention, can be produced by a conventionally known method. It is available as an aqueous dispersion or emulsion. Also, the antiviral agent contained in the composition of the present invention is available as, for example, an aqueous dispersion, a water/alcohol solution, or an emulsion having a solid content of 40 to 80% by weight. These antiviral agent, binder and dispersant can be diluted with alcohol and/or water to a predetermined concentration and used as a treatment liquid for applying the antiviral agent to fabric.

When treating the fabric with the antiviral agent, the concentration of the antiviral agent in the treatment liquid can be, for example, 0.01 to 1.5% by weight (active ingredient concentration of the antiviral agent), and from the viewpoint of efficiency and cost. from 0.02 to 0.45% by weight. The treatment liquid can use water and/or an organic solvent (eg, ethanol, propanol, acetone, acetonitrile), or a mixture thereof as a solvent. In addition, the concentration of the binder in the treatment liquid can be, for example, 0.005 to 1% by weight (active component concentration of the binder), and from the viewpoint of efficiency and cost, it is 0.01 to 0.2% by weight. is preferred. The concentration of the dispersant in the treatment liquid can be, for example, 0.01 to 10% by weight (concentration of the effective ingredient of the dispersant), and preferably 0.1 to 5% by weight from the viewpoint of efficiency and cost. .

In any case, first, the above antiviral agent, binder and dispersant are diluted with alcohol and/or water to a predetermined concentration to prepare a treatment liquid. Subsequently, the treatment liquid is brought into contact with a fabric to produce a fabric having antiviral properties.

Examples of the method for bringing the treatment liquid into contact with the fabric include a dip-nip method, an exhaustion method, a coating method, and the like. When the Dip-Nip method shown in FIG. 1 is used for treatment, the fabric is first immersed in the treatment liquid, squeezed with a mangle or the like, and then dried by heating to adhere the treatment liquid to the fabric. Subsequently, a heat drying treatment can be performed to immobilize the antiviral agent.

The treatment temperature is not particularly limited, and the treatment can be performed within a temperature range including room temperature. For example, the treatment is performed at 110°C to 180°C. It is believed that the methoxysilane-based quaternary ammonium salt is immobilized on the surface of the article in a relatively short time, and the treatment time is 30 seconds to 10 minutes, preferably 1 minute to 3 minutes. can.

When the treatment is performed by the exhaustion method, a composition (treatment liquid) containing an antiviral agent, a binder and a dispersant is heated to 80° C. to 140° C., and then the fabric is immersed in the liquid and mangled or the like. After squeezing, the antiviral agent can be immobilized on the fabric by heating and drying.

When the treatment is performed by a coating method, the antiviral agent composition of the present invention is adjusted to have an appropriate viscosity, the composition (treatment liquid) is coated on a cloth, and then dried to immobilize the antiviral agent. be able to. The coating method is not particularly limited, and examples thereof include gravure roll processing, spray processing, roll coater processing, jet printing processing, transfer printing processing, screen printing processing and the like.

The drying and heat treatment temperature of the fabric to which the treatment liquid containing the binder, antiviral agent and dispersing agent is applied can be 100 to 190°C, preferably 110 to 160°C.

After treating the fabric with the treatment liquid containing the antiviral agent, the binder and the dispersing agent, the fabric may be washed, if necessary, and dried naturally or dried by heating. In the case of heat-drying, for example, a heat-drying device such as a dryer, a gear oven, or a tenter can be used for drying. In addition, contact between the antiviral agent and the fabric can also be by spraying or coating.

The drying and heat treatment time can be appropriately selected depending on the material, basis weight and application of the fabric to be produced, but it is preferably 1 to 5 minutes. Devices such as loop dryers, net dryers, ovens and heat setters can be used for drying and heat treatment.

[Antiviral polyurethane sheet and its manufacturing method]
The antiviral polyurethane sheet of the present invention produced using the antiviral agent composition has, for example, a layer structure as shown in FIG. Manufactured by
In the process illustrated in FIG. 2(b), the skin resin is first applied to the surface of the release paper (which may be paper with an uneven pattern), dried to form a skin layer, and then the skin An adhesive resin is further applied to the surface of the layer, dried, bonded to a base cloth via the adhesive resin layer, and wound into a roll. After that, the adhesive resin is cured by curing for one day or more in the wound state, the release paper is peeled off to obtain a polyurethane sheet, and finally, the antiviral is applied to the surface of the skin layer formed by the skin resin. The antiviral polyurethane sheet of the present invention can be produced by applying a surface treatment resin solution containing the agent and drying it.
In the present invention, as in the layer structure of FIG. 2(a), a treatment liquid having a composition that does not contain an antiviral agent (methoxysilane-based quaternary ammonium salt) is applied as a surface base treatment layer on the skin layer. An antiviral surface treatment layer may be provided on this layer using a treatment liquid containing an antiviral agent.

[Antiviral polyvinyl chloride sheet and its manufacturing method]
The antiviral polyvinyl chloride sheet of the present invention produced using the antiviral agent composition has, for example, a layer structure as shown in FIG. Manufactured by the process of
In the process illustrated in FIG. 3(b), the skin resin is first applied to the surface of the release paper (which may be paper with an uneven pattern), dried to form a skin layer, and then the skin A foamed resin is further applied to the surface of the layer and dried to form a foamed layer. After that, an adhesive resin is applied to the surface of this layer, bonded to a base fabric through the adhesive resin layer, and dried. After that, the release paper is peeled off to obtain a polyvinyl chloride synthetic leather. Finally, the surface of the skin layer formed by the skin resin is coated with a surface treatment resin solution containing an antiviral agent and dried to produce the antiviral polyvinyl chloride sheet of the present invention.
In addition, in the present invention, as in the layer structure of FIG. 3(a), for the purpose of increasing the adhesion between layers, an acrylic layer without containing an antiviral agent (methoxysilane-based quaternary ammonium salt) is placed on the skin layer. A surface base treatment layer is provided using a treatment liquid having a composition containing a system resin, and on this layer is a surface treatment layer that does not contain an antiviral agent / an antiviral surface treatment layer, or a surface that contains an antiviral agent A treatment layer (antiviral surface treatment layer) may be provided.

Hereinafter, the present invention will be described in more detail based on the present invention and comparative examples, but the present invention is not limited to these.

[Synthesis Example of Aqueous Polyurethane Resin Contained in Antiviral Agent Composition of the Present Invention]
(Synthesis example 1)
251.9 g of 1,6-hexanediol polycarbonate polyol (molecular weight 1,000) and 10.3 g of DMPA (dimethylolpropionic acid) were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blower. , 1,4-BD (butanediol) 3.4 g, and methyl ethyl ketone 114.5 g as a solvent are weighed and mixed uniformly, and then HDI (hexamethylene diisocyanate) 77.0 g is added as a polyisocyanate and heated to 80 ± 5 ° C. for 180 minutes to obtain a methyl ethyl ketone solution of a terminal isocyanate group-containing urethane prepolymer having an isocyanate group content of 1.68% by mass. After that, 7.3 g of triethylamine is added at 60° C. to carry out a neutralization reaction. Next, 643.2 g of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. To this emulsified dispersion, a polyamine aqueous solution prepared by dissolving 9.2 g of hydrazine monohydrate and 1.9 g of diethylenetriamine in 33.1 g of water was added, stirred at 40±5° C. for 90 minutes, and then heated to 40° C. under reduced pressure. The solvent was removed (methyl ethyl ketone was removed) to obtain a water-based polyurethane composition A with a yield of 1 kg and a polyurethane non-volatile content of 35.0%.

(Synthesis example 2)
230.0 g of 1,6-hexanediol polycarbonate polyol (molecular weight 1,000) and 10.3 g of DMPA (dimethylolpropionic acid) were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blower. , 1,4-BD (butanediol) 3.5 g, and methyl ethyl ketone 114.0 g as a solvent are weighed and mixed uniformly, then HDI (hexamethylene diisocyanate) 96.9 g is added as a polyisocyanate and heated to 80 ± 5 ° C. for 180 minutes to obtain a methyl ethyl ketone solution of a terminal isocyanate group-containing urethane prepolymer having an isocyanate group content of 4.26% by mass. After that, 7.4 g of triethylamine is added at 60° C. to carry out a neutralization reaction. Next, 640.2 g of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. A polyamine aqueous solution prepared by dissolving 11.5 g of hydrazine monohydrate and 2.4 g of diethylenetriamine in 41.7 g of water was added to this emulsified dispersion, stirred at 40±5° C. for 90 minutes, and then heated to 40° C. under reduced pressure. The solvent was removed (methyl ethyl ketone was removed) to obtain an aqueous polyurethane composition B with a yield of 1 kg and a polyurethane non-volatile content of 35.0%.

(Synthesis Example 3)
263.2 g of 1,6-hexanediol polycarbonate polyol (molecular weight 1,000) and 5.1 g of DMPA (dimethylolpropionic acid) were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blower. , 1,4-BD (butanediol) 3.4 g, and methyl ethyl ketone 114.4 g as a solvent are weighed and mixed uniformly, then HDI (hexamethylene diisocyanate) 71.4 g is added as a polyisocyanate and heated to 80 ± 5 ° C. for 180 minutes to obtain a methyl ethyl ketone solution of a terminal isocyanate group-containing urethane prepolymer having an isocyanate group content of 1.56% by mass. After that, 3.7 g of triethylamine is added at 60° C. to carry out a neutralization reaction. Next, 639.7 g of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. To this emulsified dispersion, an aqueous polyamine solution prepared by dissolving 8.5 g of hydrazine monohydrate and 1.8 g of diethylenetriamine in 30.7 g of water was added, stirred at 40±5° C. for 90 minutes, and then heated to 40° C. under reduced pressure. The solvent was removed (methyl ethyl ketone was removed) to obtain a water-based polyurethane composition C with a yield of 1 kg and a polyurethane non-volatile content of 35.0%.

(Synthesis Example 4)
287.4 g of 1,6-hexanediol polycarbonate polyol (molecular weight 3,000) and 10.2 g of DMPA (dimethylolpropionic acid) were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blower. , 1,4-BD (butanediol) 3.4 g, and methyl ethyl ketone 115.2 g as a solvent are weighed and mixed uniformly, then HDI (hexamethylene diisocyanate) 44.1 g is added as a polyisocyanate and heated to 80 ± 5 ° C. for 180 minutes to obtain a methyl ethyl ketone solution of a terminal isocyanate group-containing urethane prepolymer having an isocyanate group content of 0.96% by mass. After that, 7.3 g of triethylamine is added at 60° C. to carry out a neutralization reaction. Next, 647.2 g of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. To this emulsified dispersion, an aqueous polyamine solution prepared by dissolving 3.8 g of ethylenediamine and 1.1 g of diethylenetriamine in 14.6 g of water was added, stirred at 40±5° C. for 90 minutes, and then the solvent was removed at 40° C. under reduced pressure ( Removal of methyl ethyl ketone) was carried out to obtain a water-based polyurethane composition D with a yield of 1 kg and a polyurethane non-volatile content of 35.0%.

(Synthesis Example 5)
207.2 g of 1,6-hexanediol polycarbonate polyol (molecular weight 3,000) and 41.6 g of DMPA (dimethylolpropionic acid) were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blower. , 1,4-BD (butanediol) 3.5 g, and methyl ethyl ketone 113.6 g as a solvent are weighed and mixed uniformly, and then HDI (hexamethylene diisocyanate) 88.0 g is added as a polyisocyanate and heated to 80 ± 5 ° C. for 180 minutes to obtain a methyl ethyl ketone solution of a terminal isocyanate group-containing urethane prepolymer having an isocyanate group content of 1.94% by mass. After that, 29.8 g of triethylamine is added at 60° C. to carry out a neutralization reaction. Next, 664.6 g of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. To this emulsified dispersion, a polyamine aqueous solution prepared by dissolving 7.6 g of ethylenediamine and 2.2 g of diethylenetriamine in 29.1 g of water was added, stirred at 40±5° C. for 90 minutes, and then the solvent was removed at 40° C. under reduced pressure ( Removal of methyl ethyl ketone) was carried out to obtain an aqueous polyurethane composition E with a yield of 1 kg and a polyurethane non-volatile content of 35.0%.

(Synthesis Example 6)
170.5 g of 1,6-hexanediol polycarbonate polyol (molecular weight 1,000), 1,6-hexanediol/polyester terephthalic acid were added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen sparge. 80.6 g of polyol (molecular weight 1,000), 10.5 g of DMPA (dimethylolpropionic acid), 3.5 g of 1,4-BD (butanediol), and 114.2 g of methyl ethyl ketone as a solvent were weighed and mixed uniformly. Add 77.5 g of HDI (hexamethylene diisocyanate) as a polyisocyanate and react at 80 ± 5 ° C. for 180 minutes to obtain a methyl ethyl ketone solution of a terminal isocyanate group-containing urethane prepolymer having an isocyanate group content of 1.69% by mass. got After that, 7.5 g of triethylamine is added at 60° C. to carry out a neutralization reaction. Next, 643.2 g of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer. A polyamine aqueous solution prepared by dissolving 9.2 g of hydrazine monohydrate and 1.9 g of diethylenetriamine in 33.3 g of water was added to this emulsified dispersion, stirred at 40±5° C. for 90 minutes, and then heated to 40° C. under reduced pressure. The solvent was removed (methyl ethyl ketone was removed) to obtain a water-based polyurethane composition F with a yield of 1 kg and a polyurethane non-volatile content of 35.0%.

(Comparative Synthesis Example 1)
244.2 g of 1,6-hexanediol polycarbonate polyol (average molecular weight: 1000), 4.7 g of trimethylolpropane, 0.5 g of dibutyltin dilaurate were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. 099 g and 150 g of methyl ethyl ketone were charged and mixed uniformly, then 97.1 g of H12MDI (dicyclohexylmethane diisocyanate) was added and reacted at 80 ° C. for 300 minutes to obtain a terminal isocyanate group-containing with an isocyanate group content of 1.26% by mass. A methyl ethyl ketone solution of urethane prepolymer was obtained.
The solution was cooled to 30° C. or below, 0.3 g of decyl phosphate and 15.0 g of polyoxyethylene tristyrylphenyl ether (HLB=15) were added, mixed uniformly, and then 638 g of water was added using a disper blade. 7 g was gradually added to effect phase inversion emulsification and dispersion to obtain a dispersion. Then, a polyamine aqueous solution prepared by dissolving 4.8 g of piperazine hexahydrate and 1.9 g of diethylenetriamine in 20.2 g of water was added to the dispersion liquid, and chain elongation reaction was performed for 90 minutes. The solvent was removed to obtain a water-based polyurethane composition G having a yield of 1 kg and a polyurethane non-volatile content of 35.0% by mass.

Table 1 below summarizes the amount of COO groups, the NCO/OH ratio, and the type of polyol in the aqueous polyurethane compositions obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 above.
PCD in the table indicates polycarbonate diol, and PED indicates polyester diol.

(Acrylic composition synthesis example 1)
28 parts of ion-exchanged water was weighed into a reaction apparatus equipped with a thermometer, a stirrer, a dropping device, a reflux condenser, and a nitrogen introduction tube, and nitrogen was sealed therein to raise the internal temperature to 80°C. Then, while maintaining that temperature, 2 parts of a 10% concentration ammonium persulfate aqueous solution was added, and immediately, a separately prepared monomer emulsion prepared as described below was added dropwise continuously for 4 hours. was emulsion polymerized. The monomer emulsion used above is a monomer mixture of 32 parts of acrylic acid, 45 parts of ethyl acrylate, and 23 parts of butyl acrylate, and sodium polyoxyethylene alkyl ether sulfate (manufactured by Kao Corporation, trade name: It was prepared by mixing and emulsifying 4 parts of Latemul E-118B) and 30 parts of deionized water. In parallel with the dropping of the monomer emulsion, 4 parts of a 5% concentration ammonium persulfate aqueous solution was dropped. After completion of dropping, the mixture was aged at 80° C. for 4 hours, and then cooled to room temperature. Finally, the mixture was neutralized with aqueous ammonia, and the solid content was adjusted with water to obtain a water-based acrylic composition a having a solid content of 60%.

(Acrylic composition synthesis example 2)
Water-based acrylic composition b was obtained in the same manner as in Acrylic Composition Synthesis Example 1 except that 25 parts of methyl methacrylate and 75 parts of butyl acrylate were used as the monomer mixture.

(Dispersant Synthesis Example 1)
A polyether monool obtained by adding 500 parts of polyethylene glycol 6000 (molecular weight 6000) and 5 moles of ethylene oxide to n-dodecyl alcohol in a four-necked flask with a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. and dehydrated at 80-90° C. for 3 hours under low pressure (500-1500 Pa) to make the water content of the system 0.03%. After cooling to 70° C., 16.8 parts of hexamethylene diisocyanate was added, reacted at 85 to 90° C. under a stream of nitrogen until the isocyanate content reached 0% (3 hours), and after cooling at room temperature, a pale yellow viscous solid was obtained. of urethane-modified polyether c was obtained.

Each composition shown in Tables 2 to 4 (Examples 1 to 28 and Comparative Examples 1 to 11) was prepared and used as an antiviral agent composition. However, the antiviral agent (methoxysilane-based quaternary ammonium salt) should always be added last in the preparation.

Next, evaluation test results regarding the liquid stability, crispness, coloration, texture, abrasion resistance, and flame retardancy of the prepared antiviral compositions are shown.
Each material used for the evaluation test is as follows.
1. Antiviral agent: methanol solution of 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride

2. Additive:
・ Filler: ACEMATT TS-100 (manufactured by Evonik Industries AG, average particle size: 10 μm)
・Antifoaming agent: Formex 747 (manufactured by Nicca Chemical Co., Ltd.)
・ Leveling agent: Disparon AQ-7120 (manufactured by Kusumoto Kasei Co., Ltd.)

3. Dispersant:
・ Urethane-modified polyether I: Neosticker N (manufactured by Nicca Chemical Co., Ltd.)
・ Urethane-modified polyether II: SN Thickener 603 (manufactured by San Nopco Co., Ltd.)
・ Urethane-modified polyether III: Eleminol N62 (manufactured by Sanyo Chemical Industries, Ltd.)
・Xanthan gum: KELZAN (manufactured by Sansho Co., Ltd.)

[Liquid stability (compatibility) test]
For each composition, the presence or absence of resin scum in the composition after preparation was visually determined. A large amount of resin scum was generated.
The above evaluation results are shown in Tables 2-4.

[Immobilization treatment of antiviral agent]
Regarding the fabric, a polyester base fabric with a mass of 390 g / m ² was dyed, and at the same time, 6% owf of phosphoric acid ester amide was applied as a flame retardant in the bath. % and dried at 150° C. for 2.5 minutes after dip-nip.
As for the polyvinyl chloride sheet (trade name: Lanchar), the surface of the sheet is uniformly coated with 20 g/m ² of polyurethane resin as a surface base treatment layer, and then dried at 120°C for 2 minutes. After that, each composition shown in Tables 2 to 4 was uniformly applied so as to be 20 g/m ² , and dried at 150°C for 2.5 minutes to immobilize the antiviral agent.
Furthermore, for the urethane synthetic leather polyurethane sheet (trade name: Leather Flexeed), each composition shown in Tables 2 to 4 was uniformly applied to the surface of the sheet so as to be 20 g / m ² , and then heated at 150 ° C. After drying for 2.5 minutes, the antiviral agent was immobilized.

[Evaluation of sharpness]
1 ml of distilled water was dropped on the surface of the polyurethane sheet, polyvinyl chloride sheet and fabric which had been subjected to the above fixing treatment, and the roughness after drying was visually evaluated. The above results are shown in Tables 2 to 4, and the evaluation criteria are as follows.
In the liquid stability test described above, compositions that did not have sufficient compatibility were not evaluated for crispiness.
⊚: No sharpness observed ◯: Almost no sharpness observed △: Sharpness observed ×: Remarkable sharpness observed

[Evaluation of coloration]
A cationic color reaction between bromophenol blue and ammonium salt was used to detect the antiviral agent adhered to the fabric. Specifically, a 5 cm × 5 cm sample piece was cut out of the fabric, polyurethane sheet, or polyvinyl chloride sheet after fixing treatment of the antiviral agent, and subjected to a color reaction with bromophenol blue (reactive agent concentration: 0.5 cm). 03% sol, reaction time: 180 seconds), and after drying, the test piece before and after color development was measured with a spectrophotometer (manufactured by Konica Minolta) to calculate ΔE. The measurement and calculation methods conformed to JISZ8781 (2012).
○: ΔE≧10
△: 5 ≤ ΔE < 10
×: ΔE<5
It was set as the pass by (○).

[Evaluation of texture]
3: Flexible texture 2: Slightly flexible texture 1: Hard texture

[Evaluation of wear resistance]
The polyurethane sheet and polyvinyl chloride sheet after fixing treatment of the antiviral agent were worn 10,000 times with a cotton canvas (JIS L 3102 (1954) No. 6) with a load of 0.9 kg using a flat abrasion tester. After carrying out, the state of the test piece was evaluated according to the following criteria.
◎: No damage ○: Slightly damaged ×: Severely damaged

[Evaluation of flame retardancy]
According to FMVSS-302 (US Automobile Safety Standard) JIS D 1201 [established in 1973], the burning rate was measured for 10 fabrics. The average value (arithmetic average value) of the burning speeds of 10 sheets was determined according to the following criteria.
◎: The average value of the burning speed is slower than 50 mm / min, or the burning distance is 50 mm or less and the burning time is within 60 seconds ○: The average value of the burning speed is 50 mm / min or more and less than 100 mm / min ×: Burning speed The average value of 100 mm / min or more

As shown in Table 2 above, in the case of the compositions of Examples 1 to 8 having a composition containing at least one of urethane-modified polyether, which is one type of water-soluble organic polymer, and xanthan gum, as a dispersant, No resin scum was generated, the liquid stability was excellent, and the texture of the treated fabric was good.
On the other hand, in the case of the composition of Comparative Example 1, which contained neither urethane-modified polyether nor xanthan gum as a dispersant, the liquid stability was poor and a large amount of resin scum was observed. Further, in the case of Comparative Example 2 in which an acrylic composition was used instead of the polyurethane composition, resin scum was observed, resulting in poor color development and poor combustibility. In Comparative Example 3 using polyurethane composition G containing no COOH group, there was no resin scum and the liquid stability was good, but the coloration was low.
In the case of Examples 1 to 5 using urethane-modified polyether c, I, II, III and xanthan gum, liquid stability, crispness and color development were all good.
In the case of Examples 1, 6, and 7 containing the polyurethane compositions A, C, and E having COOH% of 0.5, 1.0, and 4.0%, liquid stability, crispness, and color development were all poor. was also good.
In the case of Example 8, which contains polyurethane composition F in which polycarbonate polyol and polyester polyol are used in combination, all of liquid stability, crispness and color development were good.

As shown in Tables 3 and 4 above, the compositions of Examples 9 to 28 having a composition containing at least one of urethane-modified polyether, which is one type of water-soluble organic polymer, and xanthan gum, as a dispersant. In this case, resin scum was not generated and the liquid stability was excellent.
In contrast, the compositions of Comparative Examples 4 and 8, which did not contain the urethane-modified polyether and the xanthan gum as dispersants, exhibited poor liquid stability and a large amount of resin scum. Further, in Comparative Examples 5 and 9, in which the acrylic composition a having a COOH group was used instead of the polyurethane composition, the liquid stability was poor, resin scum was observed, and the color rendition was also poor. In the case of Comparative Examples 6 and 10 using the acrylic resin composition b having no COOH group, although the liquid stability was good, the coloration was poor. In addition, in Comparative Examples 5, 6, 9 and 10, the texture of the polyurethane sheet or polyvinyl chloride sheet was hard and the abrasion resistance was poor. Comparative Examples 7 and 11 using the polyurethane composition G having no COOH group exhibited poor sharpness and color development, and poor wear resistance as a polyurethane sheet or polyvinyl chloride sheet.
In the case of Examples 10 to 13 and 20 to 23 using the urethane-modified polyethers c, I, II and III, all of the liquid stability, crispness and color development were good.
Polyurethane compositions A to E with different COOH % of 0.5, 1.0, 4.0%, NCO/OH ratio of 100/80 to 100/60, or polyol molecular weight of 1000 and 3000, respectively. Examples 10, 14 to 17, 20, and 24 to 27 containing the pigment were excellent in liquid stability, crispness, and color development.
In addition, in the case of Examples 10, 18, 20, and 28 using either urethane-modified polyether or xanthan gum, liquid stability, crispness, and color development were all good, and urethane-modified polyether was used. In the case of Examples 10 and 20, the sharpness was better.

The antiviral agent composition of the present invention can impart an antiviral agent to synthetic fibers or the like that do not have hydroxyl groups on the surface in a single process, and exhibits excellent durable antibacterial and antiviral properties. It is useful for producing fabrics, polyurethane sheets, and polyvinyl chloride sheets with

Claims (8)

an antiviral agent containing a methoxysilane-based quaternary ammonium salt;
a water-based polyurethane resin having a carboxyl group and/or a carboxylate group as a binder;
and a water-soluble organic polymer as a dispersant. 2. The antiviral agent composition according to claim 1, wherein the binder is a mixture of the aqueous polyurethane resin having carboxyl groups and/or carboxylate groups and an acrylic resin. 3. The antiviral agent composition according to claim 1, wherein the methoxysilane-based quaternary ammonium salt is a compound having a structure represented by the following formula (1).

The water-soluble organic polymer is at least one polymer selected from the group consisting of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch, urethane-modified polyether, xanthan gum, and polyvinyl alcohol. The antiviral agent composition according to any one of claims 1 to 3. The antiviral agent composition according to any one of claims 1 to 4, wherein the content of carboxyl groups and/or carboxylate groups in the polyurethane resin is 0.5 to 4.0% by mass. . A layer having antiviral properties is provided on the surface of the fabric base material, and the layer comprises an antiviral agent containing a methoxysilane-based quaternary ammonium salt and a water-based polyurethane having a carboxyl group and/or a carboxylate group. An antiviral fabric characterized by being a layer containing a resin binder. An antiviral layer is provided on the surface of a sheet made of polyurethane, and the layer comprises an antiviral agent containing a methoxysilane-based quaternary ammonium salt and a water-based composition having a carboxyl group and/or a carboxylate group. An antiviral polyurethane sheet characterized by being a layer containing a polyurethane resin binder. An antiviral layer is provided on the surface of a polyvinyl chloride sheet, and the layer contains an antiviral agent containing a methoxysilane-based quaternary ammonium salt and a carboxyl group and/or a carboxylate group. An antiviral polyvinyl chloride sheet characterized by being a layer containing a water-based polyurethane resin binder.

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