JP7703911B2 - Metal complex ion-bearing polymer, composition, article, and method for producing said polymer - Google Patents

Description

The present disclosure relates to a metal complex ion-carrying polymer, a composition containing the polymer, an article containing the composition, and a method for producing a metal complex ion-carrying polymer.

It has long been known that metal ions, such as silver ions, have antibacterial properties. Recently, metal ions with antiviral properties have also become known. Components (hereinafter referred to as "antibacterial and antiviral agents") that use metal ions and have antibacterial and/or antiviral properties (hereinafter referred to as "antibacterial and antiviral properties") are expected to become increasingly common in the future.

In general, metal ions are supported on the surface and inside of inorganic particle carriers by ion exchange reactions. Examples of inorganic particle carriers that are used are silicates such as zeolite and silica gel, or phosphates such as calcium phosphate and hydroxyapatite. It is believed that the metal ions supported on the inorganic particle carrier are gradually released from inside the inorganic particle carrier, thereby continuously exerting antibacterial and antiviral properties.

However, antibacterial and antiviral agents using such metal ions and inorganic particle carriers have many problems. For example, the following problems (1) to (4) can be mentioned. (1) Since inorganic particle carriers usually have a particle size of about 1 μm, when inorganic particle carriers are included in a coating film, the transparency of the coating film tends to decrease. (2) Since inorganic particle carriers generally tend to aggregate in organic solvents or polymerizable monomers, it is difficult to disperse them uniformly in resin. (3) Silver ions supported on inorganic particle carriers tend to deteriorate or discolor due to the influence of light or heat. (4) In order to obtain a sufficient effect of the antibacterial and antiviral agent, it is necessary to expose the inorganic particle carrier to the surface of the coating film, which causes a decrease in the transparency and scratch resistance of the coating film.

For these reasons, methods of supporting metal ions on organic polymers rather than on inorganic particle carriers are being investigated (see, for example, Patent Documents 1 to 4).

Japanese Patent Application Publication No. 55-038358 Japanese Patent Application Publication No. 04-351672 Japanese Patent Application Publication No. 09-136808 Japanese Patent Application Publication No. 11-158220

The present inventors have investigated a metal ion-supported polymer that includes an organic polymer backbone having a functional group capable of coordinating with a metal ion and a metal ion coordinated by the functional group. As a result, the present inventors have found that such a polymer is prone to aggregation in solution.

The present disclosure aims to provide a metal ion-carrying polymer that is soluble in water or an organic solvent and inhibits aggregation in a solution. It also aims to provide a method for producing such a metal ion-carrying polymer, a composition containing the polymer, and an article containing the composition.

The present inventors have conducted studies to solve the above problems, and as a result, have found that the above problems can be solved by a metal complex ion-supported polymer having the following configuration.
The complex metal ion-bearing polymer of the present disclosure comprises a non-crosslinked organic polymer backbone having a side chain containing a functional group capable of coordinating to a metal ion, and a metal complex ion containing a metal ion and a ligand coordinated to the metal ion, and the metal ion in the complex metal ion is coordinated by the functional group contained in the side chain of the non-crosslinked organic polymer backbone.
The composition of the present disclosure contains the above-mentioned metal complex ion-supporting polymer.
The article of the present disclosure comprises the composition described above.
The method for producing a metal complex ion-supported polymer of the present disclosure includes the steps of: (1) preparing a non-crosslinked organic polymer having a side chain containing a functional group capable of coordinating to a metal ion, a metal salt, and a complexing agent; and (2) dissolving the non-crosslinked organic polymer, the metal salt, and the complexing agent in water to obtain a metal complex ion-supported polymer in which a metal complex ion is supported on the non-crosslinked organic polymer.

According to the present disclosure, it is possible to provide a metal complex ion-carrying polymer that is soluble in water or an organic solvent and suppresses aggregation in a solution. In addition, according to the present disclosure, it is possible to provide a method for producing such a metal complex ion-carrying polymer, a composition containing the polymer, and an article containing the composition.

FIG. 1 is a schematic diagram showing an example of a metal complex ion-supporting polymer according to the present disclosure. FIG. 2 is a flow diagram showing the method for producing the above-mentioned metal complex ion-supported polymer. FIG. 3 is a schematic diagram showing a method for producing the above-mentioned metal complex ion-supported polymer. FIG. 4 is a schematic diagram showing an example of the hydrophobization step.

In this disclosure, "antibacterial" refers to the property of killing or damaging either or both of bacteria and fungi, or the property of persistently inhibiting the growth and proliferation of either or both of bacteria and fungi. Examples of bacteria include Staphylococcus aureus, Escherichia coli, Salmonella enterica, Pseudomonas aeruginosa, Vibrio cholerae, Shigella, Bacillus anthracis, Mycobacterium tuberculosis, Clostridium botulinum, Clostridium tetanus, and Streptococcus. Examples of fungi (or molds) include Trichophyton, Candida, and Aspergillus.

In this disclosure, "antiviral" refers to the property of inactivating a virus by denaturing or damaging the proteins that constitute the viral capsid or envelope. Examples of viruses include norovirus, influenza virus, adenovirus, coronavirus, measles virus, rubella virus, hepatitis virus, herpes virus, and HIV.

[Metal complex ion-supporting polymer]
The metal complex ion-supporting polymer of the present disclosure (hereinafter also referred to as the "polymer of the present disclosure") is
a non-crosslinked organic polymer backbone having side chains that contain functional groups capable of coordinating to metal ions;
The composition comprises a metal ion and a metal complex ion containing a ligand coordinated to the metal ion, and the metal ion in the metal complex ion is coordinated by a functional group contained in a side chain of the non-crosslinked organic polymer skeleton.

The metal complex ion-supported polymer of the present disclosure mainly includes three components: a non-crosslinked organic polymer, a metal ion, and a ligand for the metal ion. The same metal ion is coordinated by a functional group contained in the side chain of the non-crosslinked organic polymer and also by a ligand (low molecular weight compound). The functional group contained in the side chain of the non-crosslinked organic polymer can coordinate to the metal ion. This allows many metal ions to be supported on the non-crosslinked organic polymer. Furthermore, the metal ion supported on the non-crosslinked organic polymer is chemically stabilized by the ligand. This makes the polymer of the present disclosure less susceptible to deterioration or discoloration even when affected by light or heat.
"Coordination" in this disclosure generally means a coordinate bond.

<Non-crosslinked organic polymer backbone>
The polymers of the present disclosure include a non-crosslinked organic polymer backbone. Hereinafter, when the non-crosslinked organic polymer is described as a molecule, it will be referred to simply as a "non-crosslinked polymer," and when described as a component of the polymers of the present disclosure, it will be referred to as a "non-crosslinked polymer backbone."

The non-crosslinked polymer functions as a carrier for metal complex ions. In the present disclosure, the non-crosslinked polymer means a polymer that does not have a three-dimensional crosslinked structure, and is usually a chain polymer such as a linear polymer and a branched polymer. The non-crosslinked polymer does not have a physical or chemical crosslinked structure in, for example, a solvent, and therefore the polymer of the present disclosure that includes a non-crosslinked polymer backbone is soluble in water or a specific organic solvent. Here, "soluble" means that, for example, when 1 g of the polymer is added to 100 mL of a solvent at room temperature (25°C), it does not become cloudy, precipitate, or gel. By using the polymer of the present disclosure that includes a non-crosslinked polymer backbone, a transparent composition can be prepared or a transparent film can be formed.

The non-crosslinked polymer has side chains that contain functional groups capable of coordinating to metal ions.
Examples of the functional group capable of coordinating to a metal ion include a carboxy group, a sulfo group, an amino group, a carbonyl group, a thiol group, a cyanate group, a thiocyanate group, an isothiocyanate group, an imino group, a nitro group, an azide group, a phosphino group, an ether group (ether bond), a thioether group (sulfide bond), and a carbon-carbon double bond.

The functional group capable of coordinating with a metal ion is preferably a chargeable group, more preferably a chargeable group that can be negatively charged (ionized) in water, such as a proton-donating group (Brønsted acid). Examples of such chargeable groups include anionic groups such as carboxy groups and sulfo groups, and carboxy groups are preferred. That is, the non-crosslinked polymer preferably has a side chain containing a chargeable group that can be negatively charged in water. As a result, the molecular chain of the non-crosslinked polymer becomes negatively charged in water, and the entanglement of the molecular chain of the non-crosslinked polymer is untied by electrostatic repulsion, and at the same time, the chargeable group is exposed in water. A metal ion, which will be described later, is bonded to the exposed chargeable group. The chargeable group includes negatively charged (ionized) groups. For example, when the chargeable group is a carboxy group, the chargeable group includes a carboxylate ion.

The side chain may be a charged group itself.

The content of the chargeable group in the non-crosslinked polymer is preferably 0.1 mmol/g or more and 100 mmol/g or less, more preferably 0.5 mmol/g or more and 50 mmol/g or less, and even more preferably 1 mmol/g or more and 20 mmol/g or less. When the content of the chargeable group is within the above range, the entanglement of the molecular chains of the non-crosslinked polymer is sufficiently disentangled in water by electrostatic repulsion, and the non-crosslinked polymer can sufficiently hold the metal complex ions described below by the chargeable group.

It is preferable that the charged groups are uniformly distributed throughout the molecular chain of the non-crosslinked polymer. If the side chains containing the charged groups are unevenly distributed within the molecular chain, the solubility of the non-crosslinked polymer in water may decrease, or the amount of metal ions carried may decrease.

A non-crosslinked polymer having a side chain containing a chargeable group can be obtained, for example, by homopolymerizing or copolymerizing a monomer containing a chargeable group. Examples of non-crosslinked polymers having a side chain containing a chargeable group include vinyl polymers, polysaccharides, and proteins that have a repeating structural unit containing a chargeable group. Among these, vinyl polymers that have a repeating structural unit containing a chargeable group are preferred.

In the above non-crosslinked polymer, the content of the repeating structural unit containing a charged group is preferably 50 mol % or more, more preferably 60 mol % or more, and even more preferably 70 mol % or more of all repeating structural units. In the present disclosure, the content of the above structural units can be determined by NMR.

Examples of vinyl polymers having repeating units containing a chargeable group include homopolymers or copolymers of ethylenically unsaturated monomers containing a chargeable group, and copolymers of ethylenically unsaturated monomers containing a chargeable group and ethylenically unsaturated monomers not containing a chargeable group.

Examples of ethylenically unsaturated monomers containing a charged group include carboxy group-containing monomers such as (meth)acrylic acid, crotonic acid, β-carboxyethyl (meth)acrylate, unsaturated carboxylic acids such as maleic acid, itaconic acid, fumaric acid, and citraconic acid, and anhydrides of unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride; and sulfo group-containing monomers such as vinyl sulfonic acid and p-styrene sulfonic acid.

Examples of ethylenically unsaturated monomers that do not contain a charged group include styrenes, vinyl alkanoates, vinyl esters of aromatic carboxylic acids, and (meth)acrylates.

Examples of styrenes include styrene, methylstyrene, vinyltoluene, vinylethylbenzene, and vinylnaphthalene.
Vinyl alkanoate esters include, for example, vinyl acetate, vinyl propionate, and vinyl butyrate.
An example of the aromatic carboxylic acid vinyl ester is vinyl benzoate.

Examples of (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate; alicyclic or aromatic ring-containing (meth)acrylates such as cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and methylcyclohexyl (meth)acrylate; hydroxyl group-containing (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; and glycidyl group-containing (meth)acrylates such as glycidyl (meth)acrylate.

In a copolymer of an ethylenically unsaturated monomer containing a chargeable group and an ethylenically unsaturated monomer not containing a chargeable group, the content of structural units derived from the ethylenically unsaturated monomer containing a chargeable group is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more of all repeating structural units.

Specific examples of vinyl polymers having repeating units containing charged groups include poly(meth)acrylic acid, polymaleic acid, polyitaconic acid, polyvinylsulfonic acid, polystyrenesulfonic acid, (meth)acrylic acid-maleic acid copolymers, and (meth)acrylic acid-vinylsulfonic acid copolymers, as well as metal salts thereof. Examples of metal salts include sodium salts and potassium salts. Among these, poly(meth)acrylic acid and its metal salts are preferred, and polyacrylic acid and its metal salts are more preferred.

Examples of polysaccharides having repeating units containing charged groups include polysaccharides having repeating units containing carboxy groups, specifically carboxymethyl cellulose, carboxyethyl cellulose, carboxymethyl starch, carboxymethyl dextran, and alginic acid, as well as metal salts thereof. Examples of metal salts include sodium salts and potassium salts.

Among these, carboxymethylcellulose, alginic acid, and metal salts thereof are preferred, and carboxymethylcellulose, sodium carboxymethylcellulose, alginic acid, and sodium alginate are more preferred.

Proteins have repeating building blocks made up of amino acid residues. Examples of amino acids with side chains containing charged groups include acidic amino acids such as aspartic acid and glutamic acid, and basic amino acids such as lysine.

In a protein having amino acid residues with side chains containing charged groups, the proportion (by number) of amino acid residues with side chains containing charged groups is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more of all amino acid residues.

Examples of proteins that have amino acid residues with side chains that contain charged groups include proteins of acidic amino acids such as polyaspartic acid and polyglutamic acid, and proteins of basic amino acids such as poly-L-lysine.

Among non-crosslinked polymers having side chains containing charged groups, poly(meth)acrylic acid is preferred, and polyacrylic acid is more preferred.

As the non-crosslinked polymer having a side chain containing a chargeable group, a commercially available product may be used, or the polymer may be synthesized by polymerizing a monomer by a conventionally known method. After obtaining a non-crosslinked polymer having no chargeable group by polymerizing a monomer not containing a chargeable group, a chargeable group may be introduced into the polymer. For example, carboxymethylcellulose is obtained by substituting some or all of the hydrogen atoms of the hydroxyl groups in the cellulose structure or the hydrogen atoms bonded to the oxygen atoms of the hydroxymethyl groups with carboxymethyl groups. In addition, as the non-crosslinked polymer having a side chain containing a chargeable group, an extract from a natural product such as sodium alginate may be used.

The weight average molecular weight (Mw) of the non-crosslinked polymer is preferably 1,000 to 1,000,000, more preferably 2,000 to 100,000, and even more preferably 5,000 to 30,000. If Mw is equal to or less than the upper limit, aggregation of the non-crosslinked polymer in the solvent is suppressed, which is preferable. In this disclosure, Mw is the weight average molecular weight in terms of polystyrene, determined by gel permeation chromatography (GPC) in accordance with JIS K7252-1 (2008).

The non-crosslinked polymer backbone constituting the polymer of the present disclosure may have a hydrophobic group bonded to the functional group such as the charged group. That is, the non-crosslinked polymer backbone may have a group in which a hydrophobic group is bonded to the functional group such as the charged group. This increases the solubility of the polymer of the present disclosure in organic solvents and improves the miscibility with other polymers.

In one embodiment, the hydrophobic group is preferably introduced into the non-crosslinked polymer backbone by esterification or amidation of the chargeable group. When the chargeable group is a carboxy group or a sulfo group, examples of the hydrophobic group bonded to the chargeable group include groups represented by -CONHR, -COOR, or _-SO2OR , and when the chargeable group is an amino group, examples of the group represented by -NHCOR, where R is a hydrophobic group.

Examples of hydrophobic groups include hydrocarbon groups such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic ring-containing hydrocarbon groups. The number of carbon atoms in the hydrophobic group is preferably 4 or more and 18 or less. When the polymer of the present disclosure is dissolved in an organic solvent with low polarity (dielectric constant) (toluene, cyclohexane, etc.), it is preferable that many hydrophobic groups with a large number of carbon atoms are bonded to the above-mentioned charged group.

Examples of aliphatic hydrocarbon groups include alkyl groups such as butyl, hexyl, 2-ethylhexyl, octyl, decyl, hexadecyl, and octadecyl; and alkenyl groups such as oleyl. Examples of alicyclic hydrocarbon groups include cycloalkyl groups such as cyclohexyl. Examples of aromatic ring-containing hydrocarbon groups include aralkyl groups such as benzyl.

In the polymer of the present disclosure, the ratio (molar basis) of the groups in which hydrophobic groups are bonded to the charged groups among the charged groups is preferably 0.1% or more and 50% or less, more preferably 0.5% or more and 20% or less, and even more preferably 1% or more and 10% or less. In one embodiment, the above ratio is the ratio of the charged groups that are esterified or amidated by the hydrophobic groups. The above ratio can be measured by nuclear magnetic resonance (NMR) or matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS).

Figure 1 shows a schematic diagram of the polymer of the present disclosure. Figure 1 shows an example in which the non-crosslinked polymer is polyacrylic acid and the metal complex ion is silver ion-thiodiethanol. The metal complex ion-supported polymer 10 includes a non-crosslinked polymer skeleton 11 and a metal complex ion 12 supported on the non-crosslinked polymer skeleton 11. The metal complex ion 12 is composed of a metal ion 13 and a ligand 14. A hydrophobic group 16 (n-octyl group) is bonded to some of the multiple functional groups 15 (carboxy groups) possessed by the non-crosslinked polymer skeleton 11 via an amide bond.

<Metal ions>
The polymers of the present disclosure comprise metal ions supported on the non-crosslinked polymer backbone.
The coordination number to the metal ion is preferably 2. That is, the metal ion is preferably coordinated by both the functional group contained in the non-crosslinked polymer and the ligand.

Examples of metal ions include monovalent cations such as silver ions (Ag ⁺ ), gold ions (Au ⁺ ), and copper ions (Cu ⁺ ), as well as mercury ions (Hg ²⁺ ). By using these metal ions, for example, aggregation or gelation of the polymer in a solution can be suppressed. Among the metal ions, silver ions (Ag ⁺ ) are preferred because of their high antibacterial and antiviral properties.

In the polymer of the present disclosure, the metal ion is characterized in that it is supported on the non-crosslinked polymer in a state in which it forms a complex with a ligand. In the present disclosure, a complex of a metal ion and a ligand coordinated to the metal ion is described as a "metal complex ion." In general, metal complex ions are not easily altered or discolored by the effects of light or heat.

The content (support rate) of metal complex ions in the polymer of the present disclosure is preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 65% by mass or less, and even more preferably 30% by mass or more and 60% by mass or less. If the content is 10% by mass or more, the effects of the metal complex ions (e.g., antibacterial and antiviral properties) are well exhibited. If the content is 70% by mass or less, aggregation of the metal complex ion-supported polymer in the solution is suppressed, and therefore a composition or film with excellent transparency can be obtained.

The metal complex ion content is calculated using the following formula:

In the above formula, "mass of metal complex ion-supported polymer" refers to the mass of solids when the solvent is removed from the obtained metal complex ion-supported polymer. On the other hand, "mass of non-crosslinked polymer" refers to the mass of the non-crosslinked polymer introduced into the reaction system in the metal complex ion support process described below.

<Ligand>
The polymers of the present disclosure include ligands coordinated to metal ions.
The ligand means a compound capable of forming a complex with a metal ion, and is a compound having a functional group capable of coordinating with a metal ion. Examples of functional groups capable of coordinating with a metal ion include monovalent functional groups such as amino groups, hydroxy groups, carboxy groups, and thiol groups; and divalent functional groups such as ether groups (ether bonds) and thioether groups (sulfide bonds). Among these, from the viewpoint of effectively suppressing the aggregation of the metal complex ion-supported polymer in the solution, amino groups, hydroxy groups, ether groups (ether bonds), and thioether groups (sulfide bonds) are preferred. The ligand preferably has at least one functional group selected from amino groups, hydroxy groups, ether groups (ether bonds), and thioether groups (sulfide bonds) as a functional group capable of coordinating with a metal ion. From the viewpoint of effectively suppressing the aggregation of the metal complex ion-supported polymer in the solution, the ligand is preferably not a ligand having a carboxy group or a ligand having a thiol group.

The number of functional groups in the ligand that can be coordinated to a metal ion is preferably 2 or more, more preferably 2 to 6, and even more preferably 2 to 4. With such a number of functional groups, the ligand can be well coordinated to the metal ion.

The ligand is preferably a compound having a molecular weight of 400 or less. The molecular weight of the ligand is more preferably 300 or less, even more preferably 200 or less, and even more preferably 150 or less. With such a molecular weight, the ligand can be well coordinated to the metal ion, and the resulting metal complex ion is well supported on the non-crosslinked polymer.

An example of the ligand is a compound represented by the formula: R ¹ --(R ² ) _n --R ³ .
In the above formula, ^R1 is an amino group or a hydroxy group, and ^R3 is an amino group, a hydroxy group, or a hydrocarbon group, and preferably both ^R1 and ^R3 are amino groups or hydroxy groups. ^R1 and ^R3 may be the same group or different groups.

The above-mentioned hydrocarbon group may be, for example, the hydrocarbon groups exemplified above as the hydrophobic group, and specific examples thereof are the same. The number of carbon atoms in the above-mentioned hydrocarbon group is, for example, 4 or more and 18 or less.

In the above formula, n is 1 when R ³ is an amino group or a hydroxy group, and n is 0 or 1 when R ³ is a hydrocarbon group.

In the above formula, R ² is an alkanediyl group or a substituted alkanediyl group. The substituted alkanediyl group is a group in which an ether bond, a sulfide bond or an -NH- group is inserted between one or more C-C bonds in the alkanediyl group, and/or one or more hydrogen atoms in the alkanediyl group are substituted with at least one group selected from an amino group and a hydroxy group. The substituted alkanediyl group may have one or more substituents. Here, the substituent refers to an ether bond, a sulfide bond, an -NH- group, an amino group and a hydroxy group. The number of carbon atoms in the alkanediyl group and the substituted alkanediyl group is, for example, 1 or more and 10 or less, preferably 2 or more and 8 or less, and more preferably 2 or more and 6 or less.

Examples of ligands include 2,2'-thiodiethanol, ethylenediamine, ethanolamine, diglycolamine, and diethanolamine.

The ligand may have a hydrophobic group. A metal complex ion-carrying polymer having a metal ion coordinated by a ligand having a hydrophobic group has high solubility in an organic solvent. Specific examples of hydrophobic groups are as described above. Examples of ligands having a hydrophobic group include amines having a hydrophobic group. Examples of amines having a hydrophobic group include alkylamines such as n-butylamine, t-butylamine, n-hexylamine, 2-ethylhexylamine, n-octylamine, decylamine, hexadecylamine, and octadecylamine; amines having an aliphatic hydrocarbon group such as alkenylamines such as oleylamine; amines having an alicyclic hydrocarbon group such as cycloalkylamines such as cyclohexylamine; and amines having an aromatic ring-containing hydrocarbon group such as aralkylamines such as benzylamine.

In one embodiment, the ligand is not a small molecule compound containing a carboxyl or thiol group. Examples of small molecule compounds containing a carboxyl or thiol group are sodium citrate, glycine, and L-cysteine. These may cause aggregation of non-crosslinked polymers.

It has been known that functional groups contained in non-crosslinked polymers such as polyacrylic acid form coordinate bonds with metal ions. Surprisingly, the present inventors have discovered for the first time that metal ions coordinated by functional groups contained in non-crosslinked polymers such as polyacrylic acid are also simultaneously coordinated by ligands that are low molecular weight compounds. It is believed that the above-mentioned ligands produce a remarkable stabilizing effect on the metal ions, making them less susceptible to deterioration or discoloration due to the effects of light or heat.

Conventionally, it has been known that an aqueous solution containing, for example, a complex of silver ions (i.e., silver complex ions) is colorless and transparent. Surprisingly, the present inventors have discovered that when the above-mentioned ligand is coordinated to a silver ion coordinated by a functional group contained in a non-crosslinked polymer, a color reaction specific to the ligand is exhibited. In one embodiment, the non-crosslinked polymer is polyacrylic acid, and, for example, when the ligand is 2,2'-thiodiethanol, the color is light yellow, when the ligand is ethylenediamine, the color is orange-yellow, when the ligand is ethanolamine, the color is dark red, and when the ligand is diglycolamine, the color is deep green. In other words, the support of silver complex ions in a non-crosslinked polymer can be confirmed by a color reaction. Below, typical examples (four types) of metal complex ions supported on polyacrylic acid are shown.

For example, in the case of silver ions, as shown in the above chemical formula, it is believed that the sulfur or nitrogen atoms of the ligands (2,2'-thiodiethanol, ethylenediamine, ethanolamine, diglycolamine) and the carboxylate ions in the polyacrylic acid are coordinated on both sides of the silver ion. At this time, if the polyacrylic acid is loosened by the electrostatic repulsion of the carboxylate ions as described above, the silver complex ions will be more likely to come into close proximity to the carboxylate ions in the polyacrylic acid, and the amount of silver complex ions carried will increase.

<Preservation of metal complex ion-supported polymer>
The metal complex ion-supported polymer of the present disclosure is preferably stored in a state dissolved in a solvent. That is, the polymer of the present disclosure is preferably stored in a state of a solution containing the polymer. If the metal complex ion-supported polymer is dried and powdered, it may be difficult to dissolve it again in a solvent.

In one embodiment, a metal complex ion-carrying polymer in which a hydrophobic group is not bonded to the functional group such as the charged group, or in which the amount of hydrophobic group introduced is small, can be stored for a long period of time in water. In one embodiment, a metal complex ion-carrying polymer in which a hydrophobic group is bonded to the functional group such as the charged group, or in which the amount of hydrophobic group introduced is large, can be stored for a long period of time in an organic solvent.

The solvent includes, for example, water and organic solvents.
Examples of the organic solvent include alcohol solvents such as methanol, ethanol, 2-propanol, and 1-butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; hydrocarbon solvents such as n-hexane, cyclohexane, benzene, toluene, and xylene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ether solvents such as tetrahydrofuran; nitrogen-containing solvents such as acetonitrile and N,N-dimethylformamide; and sulfur-containing solvents such as dimethyl sulfoxide.
The solvent may be one type or a mixed solvent of two or more types.

[Method of producing metal complex ion-supported polymer]
The metal complex ion-supported polymer of the present disclosure can be produced, for example, by the following production method.
In one embodiment, the method for producing a metal complex ion-supporting polymer of the present disclosure includes the steps of:
(1) a step of preparing a non-crosslinked organic polymer having a side chain containing a functional group capable of coordinating to a metal ion, a metal salt, and a complexing agent (hereinafter also referred to as "step (1)" or "preparation step");
(2) A step of dissolving a non-crosslinked organic polymer, a metal salt, and a complexing agent in water to obtain a metal complex ion-supported polymer in which a metal complex ion is supported on the non-crosslinked organic polymer (hereinafter also referred to as "step (2)" or "metal complex ion supporting step") (see FIG. 2).

In one embodiment, the method for producing a metal complex ion-supporting polymer of the present disclosure includes the steps of:
(3) A step of bonding a hydrophobic group to the functional group of the non-crosslinked organic polymer (hereinafter also referred to as "step (3)" or "hydrophobization step").
(See FIG. 2 ).

In one embodiment, the manufacturing method includes:
(4) Step of isolating the metal complex ion-supported polymer (hereinafter also referred to as "step (4)" or "polymer isolation step")
(See FIG. 2 ).

<Process (1) (preparation process)>
Step (1) is a step of preparing a non-crosslinked polymer having a side chain containing a functional group capable of coordinating with a metal ion, a metal salt, and a complexing agent. The details of the non-crosslinked polymer have been described above, so they will not be described here. The metal salt and the complexing agent will be described in the following step (2).

<Step (2) (metal complex ion supporting step)>
The step (2) is a step of dissolving the non-crosslinked polymer, the metal salt and the complexing agent in water to obtain a metal complex ion-supported polymer in which the metal complex ion is supported on the non-crosslinked polymer.

When a metal salt and a complexing agent are dissolved in water, metal complex ions are usually formed. Surprisingly, the present inventors have clarified for the first time that when the above-mentioned non-crosslinked polymer coexists in this system, the metal complex ions are supported on the non-crosslinked polymer. Figure 3 shows a schematic diagram of the process by which metal complex ions 12 are supported on a non-crosslinked polymer 11.

There are no particular limitations on the metal salt, so long as it dissolves in water and ionizes. Examples of metal salts include silver nitrate (I), gold chloride (I), copper iodide (I), and mercury chloride (II).

A complexing agent is a compound capable of forming a complex with a metal ion, and is a ligand for the metal ion. Details of the ligand (a compound having a functional group capable of coordinating with a metal ion) have been described above, so a detailed explanation will be omitted here.

Specifically, step (2) preferably includes a step of preparing an aqueous solution of a non-crosslinked polymer having a side chain containing a functional group capable of coordinating with a metal ion, and a step of adding a metal salt and a complexing agent to the aqueous solution.

First, the non-crosslinked polymer is dissolved in water. The concentration of the non-crosslinked polymer in the aqueous solution is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% by mass or less. When the concentration of the non-crosslinked polymer is equal to or less than the upper limit, the metal complex ion carrying efficiency is good. When the concentration of the non-crosslinked polymer is equal to or more than the lower limit, the production efficiency is good.

From the viewpoint of accelerating dissolution of the non-crosslinked polymer in water, the aqueous solution may be heated as necessary. For example, the aqueous solution is heated so that the liquid temperature is preferably 50°C or higher and 90°C or lower, more preferably 60°C or higher and 85°C or lower.

In order to charge the chargeable groups preferably contained in the non-crosslinked polymer in water, an acid or base may be added to the aqueous solution of the non-crosslinked polymer as necessary to adjust the pH. For example, when the chargeable groups are carboxy groups, adjusting the pH of the aqueous solution to a range of 5 to 9 tends to loosen the non-crosslinked polymer due to electrostatic repulsion, increasing the amount of metal complex ions carried.

Next, a complexing agent and a metal salt are added to the aqueous solution of the non-crosslinked polymer. The final concentrations of the complexing agent and the metal salt in the aqueous solution are each independently preferably 1 mM or more and 1000 mM or less, more preferably 5 mM or more and 700 mM or less, and even more preferably 10 mM or more and 200 mM or less.

The amount of complexing agent added is preferably 1 to 100 times the amount of metal salt added, more preferably 1 to 50 times, even more preferably 1 to 10 times, and particularly preferably 3 to 5 times. When the amount of complexing agent added is equal to or less than the upper limit, the amount of metal complex ion supported is not reduced, which is preferable. When the amount of complexing agent added is equal to or more than the lower limit, the solubility of the metal salt in water is increased, which is preferable.

From the viewpoint of promoting the loading of metal complex ions onto the non-crosslinked polymer, the aqueous solution may be heated as necessary. For example, the aqueous solution is heated so that the liquid temperature is preferably 50°C or higher and 90°C or lower, more preferably 60°C or higher and 85°C or lower. When heated, the loading of metal complex ions is usually completed within 10 minutes.

The aqueous solution of the metal complex ion-supported polymer obtained in step (2) may be subjected to a purification step. The purification step can remove unreacted substances and impurities. Examples of purification methods include dialysis and gel filtration chromatography.

<Step (3) (hydrophobization step)>
The hydrophobization step is a step of hydrophobizing the functional group, preferably the charged group, contained in the metal complex ion-bearing polymer. In one embodiment, a hydrophobic group is introduced into the functional group, preferably the charged group, of the metal complex ion-bearing polymer. For example, the hydrophobic group is introduced by esterifying or amidating the charged group.

The polymer obtained in the hydrophobization process is also included in the metal complex ion-supported polymer, but when describing the polymer before and after the hydrophobization process with special distinction, the polymer obtained in the hydrophobization process is described as a "metal complex ion-supported hydrophobized polymer."
Specific examples of the hydrophobic group are as described above.

For example, a hydrophobic group is introduced into the polymer skeleton by forming an amide bond through a condensation reaction between a carboxy group in a non-crosslinked polymer skeleton carrying a metal complex ion and an amine having a hydrophobic group. Figure 4 shows a schematic diagram of a process for introducing an n-octyl group into a carboxy group of polyacrylic acid carrying a metal complex ion (converting the carboxy group into an n-octylaminocarbonyl group). In the case of a polymer carrying a metal complex ion, the hydrophobic group may be introduced by a ligand substitution reaction between the ligand and an amine having a hydrophobic group.

Examples of amines having hydrophobic groups include alkylamines such as n-butylamine, t-butylamine, n-hexylamine, 2-ethylhexylamine, n-octylamine, decylamine, hexadecylamine, and octadecylamine; amines having aliphatic hydrocarbon groups such as alkenylamines such as oleylamine; amines having alicyclic hydrocarbon groups such as cycloalkylamines such as cyclohexylamine; and amines having aromatic hydrocarbon groups such as aralkylamines such as benzylamine.

In order to allow the above condensation reaction to proceed under mild conditions, it is preferable to use a condensation agent. Examples of condensation agents include carbodiimide-based condensation agents such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC.HCl), dicyclohexylcarbodiimide, and diisopropylcarbodiimide; triazine-based condensation agents such as 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM); and carbonate-based condensation agents such as carbonyldiimidazole. Among these, EDC.HCl and DMT-MM, which can be used in water, are preferred.

The amide bond may be formed after converting the carboxyl group in the non-crosslinked polymer backbone to an active ester group. In that case, it is preferable to use N-hydroxysuccinimide (NHS) or 1-hydroxybenzotriazole (HOBT) in combination with the carbodiimide-based condensing agent.

For example, a condensation reaction between a carboxy group in a non-crosslinked polymer skeleton carrying a metal complex ion and an alcohol having a hydrophobic group forms an ester bond, and the hydrophobic group is introduced into the polymer skeleton. For example, a condensation reaction between an amino group in a non-crosslinked polymer skeleton carrying a metal complex ion and a carboxylic acid having a hydrophobic group forms an amide bond, and the hydrophobic group is introduced into the polymer skeleton.

The above condensation reaction is usually carried out in water. If the miscibility of the amine, alcohol or carboxylic acid having a hydrophobic group with water is not high, it is preferable to add a required amount of alcohol to the water. In other words, it is preferable to use a mixed solvent of water and alcohol as the reaction solvent. Examples of alcohol include methanol and ethanol. The mixing ratio of water and alcohol is set so that the alkylamine or the like used can be freely mixed with the solvent. For example, octylamine is well miscible in a mixed solvent of equal volumes of water and methanol.

In the above condensation reaction, the concentration of the metal complex ion-supported polymer in the aqueous solution is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less. If the concentration is equal to or less than the upper limit, the condensation reaction proceeds smoothly. If the concentration is equal to or more than the lower limit, the production efficiency is improved.

In the hydrophobization process, the metal complex ion-carrying polymer is hydrophobized, and an emulsion (aqueous dispersion) of the metal complex ion-carrying hydrophobized polymer is usually formed. That is, the emulsion of the metal complex ion-carrying polymer is formed at the same time that the hydrophobic group is introduced into the non-crosslinked polymer backbone. When the hydrophobic group is introduced into the metal complex ion-carrying polymer, the solubility of the polymer in an aqueous solvent (e.g., water and a mixed solvent of water and alcohol) decreases, and part or all of the metal complex ion-carrying polymer cannot be dissolved in the aqueous solvent, and is dispersed in the aqueous solvent as fine droplets. In this way, an O/W type emulsion is formed.

An example of hydrophobization using EDC.HCl, NHS and an alkylamine will be described below.
EDC.HCl and NHS are added to an aqueous solution of a metal complex ion-supported polymer. The final concentrations of these are preferably 1 mM or more and 100 mM or less, respectively. The reaction temperature is preferably 20° C. or more and 60° C. or less, and the reaction time is preferably 1 minute or more and 30 minutes or less. In this way, when a non-crosslinked polymer having a carboxy group is used, the carboxy group in the non-crosslinked polymer skeleton constituting the metal complex ion-supported polymer is converted to an active ester group.

Next, an alkylamine is added to the aqueous solution. The final concentration of the alkylamine is preferably 10 mM to 300 mM, more preferably 10 mM to 100 mM. The reaction temperature is preferably 20°C to 50°C, and the reaction time is preferably 1 minute to 30 minutes. This causes the active ester group in the non-crosslinked polymer skeleton constituting the metal complex ion-supported polymer to react with the alkylamine to form an amide bond. In the case of a metal complex ion-supported polymer, a portion of the alkylamine may undergo a ligand exchange reaction with the ligand coordinated to the metal ion. In this case, the alkylamine is linked to the non-crosslinked polymer and simultaneously stabilizes the metal ion as a ligand.

<Step (4) (Polymer Isolation Step)>
The polymer isolation step is a step of isolating the metal complex ion-supported polymer. The metal complex ion-supported polymer (metal complex ion-supported hydrophobized polymer) in the emulsion is recovered, for example, by a known method. For example, the emulsion can be separated into two layers, an upper solvent layer and a lower metal complex ion-supported polymer layer, by standing still. In order to increase the separation efficiency, centrifugation or electric field separation may be used. For example, it is preferable to remove the upper solvent layer, and then dissolve the lower metal complex ion-supported polymer in a suitable organic solvent and recover it. Specific examples of the organic solvent are as described above.

In one embodiment, the isolation of the polymer is carried out by the following procedure. The emulsion is transferred to a centrifuge tube and centrifuged using a centrifuge. The centrifugal acceleration is preferably 1,000×g or more and 10,000×g or less, and the centrifugation time is preferably 1 minute or more and 30 minutes or less. Next, the supernatant is removed, and the metal complex ion-supported polymer remaining at the bottom of the centrifuge tube is dissolved in an organic solvent such as alcohol. If necessary, ultrasonic treatment is performed during the dissolution process.

[Composition]
The composition of the present disclosure contains one or more of the metal complex ion-supporting polymers of the present disclosure. In one embodiment, the composition of the present disclosure has antibacterial and antiviral properties, and is preferably used for at least one of antibacterial and antiviral purposes.

The content of the polymer of the present disclosure in the composition of the present disclosure can be selected arbitrarily depending on the application of the composition, and in one embodiment is 0.01% by mass or more and 70% by mass or less, preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less.

In one embodiment, the composition of the present disclosure contains at least one selected from water and an organic solvent. For example, the polymer of the present disclosure is dissolved in at least one selected from water and an organic solvent. Examples of the organic solvent include the specific examples described above.

The content of the solvent in the composition of the present disclosure can be selected as desired depending on the application of the composition, and in one embodiment is 30% by mass or more and 99.5% by mass or less, preferably 50% by mass or more and 99% by mass or less, and more preferably 60% by mass or more and 98% by mass or less.

For example, the composition of the present disclosure can be obtained by dissolving the metal complex ion-supported polymer of the present disclosure in at least one solvent selected from water and an organic solvent. Examples of methods for dissolving the polymer of the present disclosure in a solvent include methods using a magnetic stirrer, a motor with stirring blades, a homogenizer, or an ultrasonic cleaner. In one embodiment, the composition of the present disclosure is provided in the form of a liquid, gel, spray, or the like.

In one embodiment, the composition of the present disclosure contains one or more resins other than the polymer of the present disclosure. For example, the polymer of the present disclosure can be well mixed with the above-mentioned resin. Since the polymer of the present disclosure has excellent dispersibility in the resin, in one embodiment, when the resin has excellent transparency, the transparency of the resin can be maintained.

Examples of resins include polyolefins such as polyethylene, polypropylene, and cyclic polyolefins; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; styrene resins such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and polystyrene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacrylonitrile, polyamide, polyimide, polyamideimide, (meth)acrylic resins, polycarbonates, polyarylphthalates, polysulfones, polyethersulfones, polyphenylene sulfides, polyurethanes, acetal resins, cellulose resins, fluororesins, phenolic resins, melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins.

In one embodiment, the polymer of the present disclosure can be used in an amount of 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.5 parts by mass or more and 40 parts by mass or less, and more preferably 1 part by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the resin.

The polymer of the present disclosure and the above resin can be mixed using known mixing devices such as a Henschel mixer, a V-type blender, a tumbler, a roll, and a kneader.

In one embodiment, the composition of the present disclosure contains one or more active energy ray curable resin components. For example, the polymer of the present disclosure can be mixed well with the active energy ray curable resin component. Since the polymer of the present disclosure has excellent dispersibility in the active energy ray curable resin component, in one embodiment, the transparency of the cured product of the active energy ray curable resin component can be maintained.

The active energy ray curable resin component is a resin component that cures when irradiated with active energy rays. The resin component may be any of a monomer, an oligomer, and a polymer. Examples of active energy rays include electromagnetic waves such as ultraviolet rays (UV), X-rays, and gamma rays; and charged particle beams such as electron beams (EB), alpha rays, and ion beams.

As the active energy ray curable resin component, a photocurable resin component is preferred, and a (meth)acrylic photocurable resin component is more preferred. Examples of the (meth)acrylic photocurable resin component include polyfunctional (meth)acrylates [e.g., (meth)acrylates having 2 to 8 polymerizable groups, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate], ethylenediaminetetra(meth)acrylate ... Examples of such polymerizable compounds include epoxy (meth)acrylates [multifunctional epoxy (meth)acrylates having two or more (meth)acryloyl groups], polyester (meth)acrylates [multifunctional polyester (meth)acrylates having two or more (meth)acryloyl groups], urethane (meth)acrylates [multifunctional urethane (meth)acrylates having two or more (meth)acryloyl groups], silicone (meth)acrylates [multifunctional silicone (meth)acrylates having two or more (meth)acryloyl groups], and (meth)acrylic polymers having polymerizable groups.

The (meth)acrylic polymer having a polymerizable group may be a polymer in which a polymerizable unsaturated group has been introduced into some of the carboxy groups of the (meth)acrylic polymer, for example, a (meth)acrylic polymer in which a polymerizable group (photopolymerizable unsaturated group) has been introduced into the side chain by reacting some of the carboxy groups of a (meth)acrylic acid-(meth)acrylic acid ester copolymer with the epoxy groups of an epoxy group-containing (meth)acrylate.

In one embodiment, the polymer of the present disclosure can be used in an amount of 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.5 parts by mass or more and 40 parts by mass or less, and more preferably 1 part by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the active energy ray-curable resin component.

When the composition contains a photocurable resin component, the composition preferably contains one or more photopolymerization initiators capable of initiating a curing reaction by irradiation with light. Examples of photopolymerization initiators include alkylphenone compounds, acetophenone compounds, benzoin compounds, acylphosphine oxide compounds, benzophenone compounds, thioxanthone compounds, and aminobenzophenone compounds. The content of the photopolymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the photocurable resin component.

The polymer of the present disclosure has excellent mixability with resins and active energy ray-curable resin components, and also has excellent dispersibility, so that the metal complex ions contained in the polymer of the present disclosure can be present at a sufficient density on the surface of the film formed from the composition of the present disclosure. This provides, in one embodiment, highly immediate antibacterial and antiviral properties.

The composition of the present disclosure may contain one or more other antibacterial and antiviral components, such as sodium hypochlorite, hypochlorous acid water, and quaternary ammonium salts, as necessary. The composition of the present disclosure may contain at least one selected from the group consisting of a dispersion stabilizer, a moisturizer, a thickener, a pH adjuster, and a surfactant, as necessary.

The compositions of the present disclosure can be used to form various molded articles, such as pellets, sheets, films, plates, containers, and pipes. The compositions of the present disclosure may be applied to the surface of a substrate, such as paints and coatings.

In one embodiment, the total light transmittance of the film formed from the composition of the present disclosure is preferably 75% or more, more preferably 80% or more, and even more preferably 85% or more. In one embodiment, the higher the total light transmittance, the more preferable it is, but the upper limit may be, for example, 99%. The total light transmittance is measured in accordance with JIS K7361-1:1997.

In one embodiment, the haze of the film formed from the composition of the present disclosure is preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 2.0% or less. In one embodiment, the lower the haze, the more preferable it is, but the lower limit may be, for example, 0.1%. Haze is measured in accordance with JIS K7136:2000.

In one embodiment, the thickness of the film formed from the composition of the present disclosure is 0.05 μm or more and 200 μm or less, preferably 0.1 μm or more and 10 μm or less, and more preferably 0.15 μm or more and 5 μm or less.

[Goods]
The article of the present disclosure includes the composition of the present disclosure. In one embodiment, the article of the present disclosure has a component formed from the composition that has antibacterial and antiviral properties. Therefore, the article of the present disclosure is preferably used for at least one of antibacterial and antiviral purposes.

The article of the present disclosure is not particularly limited as long as it contains the composition of the present disclosure. The article is formed from the composition of the present disclosure, or has a component (e.g., a surface layer, a member, or a part) formed from the composition of the present disclosure. In one embodiment, the article of the present disclosure has a layer formed from the composition of the present disclosure, and the layer constitutes at least a part of the surface layer of the article of the present disclosure. In one embodiment, the article of the present disclosure has excellent antibacterial and antiviral properties, and therefore can be widely used, for example, as an article that people touch with their hands.

In one embodiment, the thickness of the layer formed from the composition of the present disclosure is 0.05 μm or more and 200 μm or less, preferably 0.1 μm or more and 10 μm or less, and more preferably 0.15 μm or more and 5 μm or less. In addition, in the present disclosure, since it is not necessary to include antibacterial and antiviral particles in the layer and expose them on the layer surface, a layer with excellent surface smoothness can be formed. Such a layer has excellent durability.

In this disclosure, the antibacterial properties of the article are evaluated in accordance with ISO 22196 (JIS Z2801), and the antiviral properties of the article are evaluated in accordance with ISO 21702.

Examples of the above-mentioned items include film products for protecting touch panels, face shields, handrails, buttons, switches, windows, etc.; textile products such as socks, underwear, towels, curtains, and carpets; building materials such as flooring, wallpaper, tiles, and paint materials; kitchen items such as sponges, cutting boards, film packaging materials, brushes, and lunch boxes; bathroom and toilet items such as bath mats, brushes with toilet cases, and bottles; daily necessities such as toothbrushes, shoe insoles, masks, and antibacterial sprays; toys such as stuffed animals and building blocks; home appliances such as washing machines, vacuum cleaners, and refrigerators; and automotive parts such as steering wheels, shift knobs, air purifiers, and interior materials.

The present disclosure relates to, for example, the following [1] to [18].
[1] A polymer carrying a complex metal ion, comprising: a non-crosslinked organic polymer skeleton having a side chain containing a functional group capable of coordinating to a metal ion; and a metal complex ion containing a metal ion and a ligand coordinated to the metal ion, wherein the metal ion in the complex ion is coordinated by the functional group contained in the side chain of the non-crosslinked organic polymer skeleton.
[2] The metal complex ion-supporting polymer according to the above [1], wherein the functional group is a charged group.
[3] The metal complex ion-supporting polymer according to the above [2], wherein the charged group is a carboxy group.
[4] The metal complex ion-supporting polymer according to any one of the above [1] to [3], wherein the metal ion is at least one selected from the group consisting of silver ions (Ag ⁺ ), gold ions ( ^Au + ), copper ions (Cu ⁺ ) and mercury ions (Hg ²⁺ ).
[5] The polymer carrying a metal complex ion according to any one of the above [1] to [4], wherein the content of the metal complex ion is 10% by mass or more and 70% by mass or less.
[6] The metal complex ion-supported polymer according to any one of the above [1] to [5], wherein the ligand is a compound having at least one functional group selected from an amino group, a hydroxyl group, an ether bond, and a sulfide bond and having a molecular weight of 400 or less.
[7] The metal complex ion-supporting polymer according to any one of the above [1] to [6], wherein a hydrophobic group is bonded to a part of the multiple functional groups possessed by the non-crosslinked organic polymer skeleton.
[8] The metal complex ion-supporting polymer according to the above [7], wherein the hydrophobic group is a hydrocarbon group having 4 to 18 carbon atoms.
[9] A composition comprising the metal complex ion-supporting polymer according to any one of [1] to [8] above.
[10] The composition described in [9] above, which has antibacterial and/or antiviral properties.
[11] An article comprising the composition according to [9] or [10] above.
[12] A method for producing a metal complex ion-supported polymer, comprising: (1) preparing a non-crosslinked organic polymer having a side chain containing a functional group capable of coordinating to a metal ion, a metal salt, and a complexing agent; and (2) dissolving the non-crosslinked organic polymer, the metal salt, and the complexing agent in water to obtain a metal complex ion-supported polymer in which a metal complex ion is supported on the non-crosslinked organic polymer.
[13] (3) The method for producing a metal complex ion-supported polymer according to the above [12], further comprising a step of bonding a hydrophobic group to a functional group possessed by the non-crosslinked organic polymer.
[14] The method for producing a metal complex ion-supported polymer according to the above [13], wherein the hydrophobic group is a hydrocarbon group having 4 to 18 carbon atoms.
[15] The method for producing a polymer carrying a metal complex ion according to the above [13] or [14], further comprising the step of forming an emulsion of a hydrophobized metal complex ion-carrying polymer in the step (3), and isolating the hydrophobized metal complex ion-carrying polymer from the emulsion (4).
[16] The method for producing a metal complex ion-supported polymer according to any one of [12] to [15] above, wherein the functional group is a carboxy group.
[17] The method for producing a metal complex ion-supported polymer according to any one of the above [12] to [16], wherein the metal salt is at least one selected from silver nitrate (I), gold chloride (I), copper iodide (I) and mercury chloride (II).
[18] The method for producing a metal complex ion-supported polymer according to any one of the above [12] to [17], wherein the complexing agent is a compound having at least one functional group selected from an amino group, a hydroxyl group, an ether bond, and a sulfide bond and having a molecular weight of 400 or less.

The polymers and the like of the present disclosure will be described below using specific examples.
[Antibacterial Test]
The antibacterial properties of the aqueous solutions of the metal complex ions-supported polymers were evaluated according to the following procedure.

The polymer (such as a polymer carrying a silver complex ion) obtained in the examples or comparative examples was added to pure water to obtain 10 mL of an aqueous solution (specimen) with a polymer concentration of 0.01% by mass. The E. coli (NBRC 3972) used in the test was cultured in a liquid medium at 35° C. for 24 hours. After the culture, the concentration of the E. coli was adjusted to 10 ⁸ cfu/mL (cfu: colony forming unit) using a sterilized normal bouillon medium (1/500 NB medium). 0.1 mL of this bacterial liquid was inoculated into 10 mL of the specimen containing the polymer and allowed to stand at 25° C. for 24 hours. Then, a 10-fold dilution series of the specimen was prepared using sterilized phosphate buffered saline (PBS). 1 mL was taken from each dilution series and mixed with SCDLP agar medium. After culturing this for 48 hours at 30° C., the grown colonies were counted and converted into viable cell counts. As a negative control, PBS not containing the polymer was also tested in the same manner. Finally, the antibacterial activity value was calculated using the following formula: An antibacterial activity value of 3.0 or more was determined to be effective.

[Silver complex ion content]
The content of silver complex ions was calculated according to the above formula.

[Example 1]
0.6 g of polyacrylic acid (weight average molecular weight 25,000, Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 30 mL of water. 2 mL of thiodiethanol and 0.85 g of silver nitrate were added thereto, and the mixture was stirred at 70 to 80° C. for 10 minutes. As a result, a pale yellow transparent polymer aqueous solution was obtained. The obtained polymer aqueous solution was sealed in a dialysis tube, and dialyzed in pure water. The silver complex ion content of the obtained silver complex ion-supported polymer was 54.9% by mass.

[Examples 2 to 4]
The same procedure as in Example 1 was carried out except that the type and amount of the complexing agent were changed as shown in Table 1, to obtain an aqueous solution of a polymer supporting silver complex ions.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that no complexing agent was used, whereby the polymer flocculated, resulting in a white, opaque aqueous polymer solution, which turned purple within 1 hour.

[Examples 5 to 8]
The silver complex ion-supported polymers obtained in Examples 1 to 4 were hydrophobized according to the following procedure. First, 10 mL of pure water and 20 mL of methanol were added to 10 mL of an aqueous solution of silver complex ions-supported polymer (4 mass%). 1 mL of an aqueous solution of EDC.HCl/NHS (each 0.1 M) was added thereto and allowed to stand for 10 minutes. 1 mL of n-octylamine was added thereto and allowed to stand for 3 minutes. This resulted in an emulsion of a hydrophobized polymer supported with silver complex ions. After centrifuging this emulsion, the supernatant was removed, and the obtained solid content was dissolved in 10 mL of 2-propanol.

Using the obtained silver complex ion-supported hydrophobic polymer (4 types), a coating agent having the composition shown in Table 2 was prepared. In Table 2, MIBK is methyl isobutyl ketone. The coating agent was applied to a polyethylene terephthalate (PET) film (Cosmoshine (registered trademark) A4100, Toyobo) and dried, and then irradiated with ultraviolet light. As a result, a cured film containing silver complex ion-supported hydrophobic polymer and having a thickness of approximately 150 nm was formed on the surface of the PET film. In this way, a composite film comprising a PET film and a cured film was obtained.

The optical properties (total light transmittance, haze, chromaticity) of the composite film obtained as described above were evaluated and found to be equivalent to those of the untreated PET film (Reference Example 1) (Table 2). In other words, the cured film containing the silver complex ion-supported hydrophobic polymer of the present disclosure had very high transparency and no coloring (discoloration) was observed.

The total light transmittance was measured in accordance with JIS K7361-1, and the haze was measured in accordance with JIS K7136. The chromaticity a ^* and b ^* are the a ^* and b ^* of the L ^* a ^* b ^* color system standardized by the International Commission on Illumination (CIE), and were measured in accordance with JIS Z8781-4:2013.

The antibacterial properties of the cured films obtained as described above were evaluated according to ISO 22196 (JIS Z2801). As a result, excellent antibacterial properties were observed in all cases (Table 2). The negative control was the above PET film that was not coated with the above coating agent.

10: Metal complex ion-supporting polymer 11: Non-crosslinked polymer (skeleton)
12: Metal complex ion 13: Metal ion 14: Ligand 15: Functional group capable of coordinating to a metal ion 16: Hydrophobic group

Claims (6)

(1) providing a non-crosslinked organic polymer having a side chain containing a functional group capable of coordinating to a metal ion, a metal salt, and a complexing agent;
(2) dissolving the non-crosslinked organic polymer, a metal salt and a complexing agent in water to obtain a metal complex ion-supported polymer in which a metal complex ion is supported on the non-crosslinked organic polymer ;
(3) binding a hydrophobic group to the functional group of the non-crosslinked organic polymer;
The present invention relates to a method for producing a polymer carrying a metal complex ion, the method comprising the steps of: The method for producing a metal complex ion-supported polymer according to claim 1 , wherein the hydrophobic group is a hydrocarbon group having 4 to 18 carbon atoms. 3. The method for producing a polymer carrying a metal complex ion according to claim 1 or 2, wherein in the step (3), an emulsion of the hydrophobized polymer carrying a metal complex ion is formed, and the production method further comprises a step ( 4 ) of isolating the hydrophobized polymer carrying a metal complex ion from the emulsion. The method for producing a metal complex ion-supported polymer according to claim 1 , wherein the functional group is a carboxy group. The method for producing a metal complex ion-supported polymer according to any one of claims 1 to 4 , wherein the metal salt is at least one selected from the group consisting of silver nitrate (I), gold chloride (I), copper iodide (I) and mercury chloride (II). The method for producing a metal complex ion-supported polymer according to any one of claims 1 to 5 , wherein the complexing agent is a compound having at least one functional group selected from an amino group, a hydroxyl group, an ether bond, and a sulfide bond and having a molecular weight of 400 or less.