Metal complex ion-supported polymer, composition, article, and method for producing the polymer

Abstract

To provide a metal ion-carrying polymer that is soluble in water or organic solvent and suppresses aggregation in solution.MEANS FOR SOLVING THE PROBLEM: A metal complex ion-carrying polymer has an uncrosslinked organic polymer backbone having a side chain containing a functional group coordinatable to a metal ion, and a metal complex ion containing a metal ion and a ligand coordinated to the metal ion. The metal ion in the metal complex ion is coordinated by the functional group contained in the side chain of the uncrosslinked organic polymer backbone.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a metal complex ion-supported polymer, a composition containing the polymer, an article containing the composition, and a method for producing a metal complex ion-supported polymer.

Background Art

[0002] It has long been known that metal ions typified by silver ions have antibacterial properties. Recently, metal ions having antiviral properties have also become known. Components having antibacterial and / or antiviral properties (hereinafter also referred to as "antibacterial and antiviral agents") using metal ions are expected to increase more and more in the future.

[0003] Generally, metal ions are supported on the surface and inside of an inorganic particle carrier by an ion exchange reaction. As the inorganic particle carrier, for example, silicates such as zeolite and silica gel, or phosphates such as calcium phosphate and hydroxyapatite are used. The metal ions supported on the inorganic particle carrier are gradually released from the inside of the inorganic particle carrier and are considered to continuously exhibit antibacterial and antiviral properties.

[0004] However, such antibacterial and antiviral agents using metal ions and inorganic particle carriers have many problems. For example, the following problems (1) to (4) can be mentioned. (1) Since the inorganic particle carrier usually has a particle size of about 1 μm, when the inorganic particle carrier is included in a coating film, the transparency of the coating film is likely to decrease. (2) Since the inorganic particle carrier generally tends to aggregate in an organic solvent or a polymerizable monomer, it is difficult to uniformly disperse it in a resin. (3) The silver ions supported on the inorganic particle carrier are likely to be altered or discolored by the influence of light or heat. (4) In order to obtain a sufficient effect by the above antibacterial and antiviral agent, it is necessary to expose the inorganic particle carrier on the coating film surface, which causes a decrease in the transparency and scratch resistance of the coating film.

[0005] For the reasons described above, methods of supporting metal ions on organic polymers rather than inorganic particle carriers have been investigated (see, for example, Patent Documents 1 to 4).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present inventors have studied a metal ion-supported polymer containing an organic polymer skeleton 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 tends to aggregate in solution.

[0008] An object of the present disclosure is to provide a metal ion-supported polymer that is soluble in water or an organic solvent and has suppressed aggregation in solution. Another object of the present disclosure is to provide a method for producing such a metal ion-supported polymer, a composition containing the polymer, and an article containing the composition.

Means for Solving the Problems

[0009] The present inventors have conducted studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by a metal complex ion-supported polymer having the configuration described below. The metal complex ion-supported polymer of the present disclosure includes a non-crosslinked organic polymer backbone having a side chain containing a functional group capable of coordinating with a metal ion, 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 the functional group contained in the side chain of the non-crosslinked organic polymer backbone. The composition of the present disclosure contains the above metal complex ion-supported polymer. The article of the present disclosure includes the above composition. The method for producing the metal complex ion-supported polymer of the present disclosure includes: (1) a step of preparing a non-crosslinked organic polymer having a side chain containing a functional group capable of coordinating with a metal ion, a metal salt, and a complexing agent; and (2) a step of 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 the metal complex ion is supported on the non-crosslinked organic polymer.

Advantages of the Invention

[0010] According to the present disclosure, it is possible to provide a metal complex ion-supported polymer that is soluble in water or an organic solvent and has suppressed aggregation in a solution. Further, according to the present disclosure, it is possible to provide a method for producing such a metal complex ion-supported polymer, a composition containing the polymer, and an article containing the composition.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0012] In the present disclosure, "antibacterial property" refers to the property of killing or damaging either or both of bacteria and fungi, or the property of continuously suppressing the growth and proliferation of either or both of bacteria and fungi. Examples of bacteria include staphylococcus, Escherichia coli, Salmonella, Pseudomonas aeruginosa, Vibrio cholerae, Shigella, Bacillus anthracis, Mycobacterium tuberculosis, Clostridium botulinum, Clostridium tetani, and Streptococcus. Examples of fungi (or molds) include Trichophyton, Candida, and Aspergillus.

[0013] In the present disclosure, "antiviral property" refers to the property of inactivating a virus by denaturing or damaging the protein constituting the capsid or envelope of the virus. Examples of viruses include norovirus, influenza virus, adenovirus, coronavirus, measles virus, rubella virus, hepatitis virus, herpes virus, and HIV.

[0014] [Polymer Supporting Metal Complex Ions] The metal complex ion-supported polymer of the present disclosure (hereinafter also referred to as "the polymer of the present disclosure") comprises a non-crosslinked organic polymer backbone having a side chain containing a functional group capable of coordinating with a metal ion, a metal ion, and a metal complex ion containing a ligand coordinated to the metal ion and is characterized in that the metal ion in the metal complex ion is coordinated by the functional group contained in the side chain of the non-crosslinked organic polymer backbone. This is the characteristic.

[0015] The metal complex ion-supported polymer of the present disclosure mainly comprises three components: a non-crosslinked organic polymer, metal ions, and a ligand for the metal ions. The same metal ions are coordinated by a functional group contained in the side chain of the non-crosslinked organic polymer and at the same time are also coordinated by a ligand (low molecular compound). The functional group contained in the side chain of the non-crosslinked organic polymer can coordinate with metal ions. As a result, many metal ions are supported on the non-crosslinked organic polymer. Furthermore, the metal ions supported on the non-crosslinked organic polymer are chemically stabilized by the ligand. Thus, the polymer of the present disclosure is less likely to be altered or discolored even under the influence of light or heat. In the present disclosure, "coordination" usually means a coordination bond.

[0016] <Non-crosslinked Organic Polymer Skeleton> The polymer of the present disclosure includes a non-crosslinked organic polymer backbone. Hereinafter, when describing the non-crosslinked organic polymer as a molecule, it is simply referred to as a "non-crosslinked polymer", and when describing it as a component of the polymer of the present disclosure, it is referred to as a "non-crosslinked polymer backbone".

[0017] The non-crosslinked polymer functions as a carrier for metal complex ions. In the present disclosure, the non-crosslinked polymer means a polymer having no three-dimensional crosslinked structure, and is usually a chain polymer such as a linear polymer and a branched-chain polymer. The non-crosslinked polymer, for example, has no physical or chemical crosslinked structure in a solvent. Therefore, the polymer of the present disclosure containing a non-crosslinked polymer backbone is soluble in water or a predetermined organic solvent. Here, "soluble" means, for example, that when 1 g of the polymer is added to 100 mL of the solvent at room temperature (25 °C), it does not become cloudy, precipitate, or gelate. By using the polymer of the present disclosure containing a non-crosslinked polymer backbone, a transparent composition can be prepared or a transparent film can be formed.

[0018] The non-crosslinked polymer has a side chain containing a functional group capable of coordinating with metal ions. Examples of functional groups capable of coordinating with metal ions include carboxy groups, sulfo groups, amino groups, carbonyl groups, thiol groups, cyanate groups, thiocyanate groups, isothiocyanate groups, imino groups, nitro groups, azide groups, phosphino groups, ether groups (ether bonds), thioether groups (sulfide bonds), and carbon-carbon double bonds.

[0019] The functional group capable of coordinating with metal ions is preferably a charged group, more preferably a charged group that can be negatively charged (ionized) in water, for example, a proton-donating group (Bronsted acid). Examples of such charged 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 charged group that can be negatively charged in water. Thereby, in water, the molecular chains of the non-crosslinked polymer are negatively charged, and the entanglement of the molecular chains of the non-crosslinked polymer is released by electrostatic repulsion, and at the same time, the charged groups are exposed in water. Metal ions described later are bound to the exposed charged groups. Note that the above-mentioned charged group includes a negatively charged (ionized) group. For example, when the charged group is a carboxy group, the charged group includes carboxylate ions.

[0020] The above side chain may be the charged group itself.

[0021] The content of the charged 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 still more preferably 1 mmol / g or more and 20 mmol / g or less. When the content of the charged group is within the above range, the entanglement of the molecular chains of the non-crosslinked polymer can be sufficiently released by electrostatic repulsion in water, and the non-crosslinked polymer can sufficiently hold the metal complex ions described later by the charged groups.

[0022] The charged groups are preferably uniformly distributed throughout the molecular chain of the non-crosslinked polymer. When 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 supported may decrease.

[0023] The non-crosslinked polymer having a side chain containing a charged group can be obtained, for example, by homopolymerizing or copolymerizing a monomer containing a charged group. Examples of the non-crosslinked polymer having a side chain containing a charged group include vinyl polymers, polysaccharides, and proteins having a repeating structural unit containing a charged group. Among these, vinyl polymers having a repeating structural unit containing a charged group are preferred.

[0024] In the above non-crosslinked polymer, the content ratio of the repeating structural unit containing a charged group is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more in all the repeating structural units. In the present disclosure, the content ratio of the above structural unit can be determined by NMR.

[0025] Examples of the vinyl polymer having a repeating structural unit containing a charged group include homopolymers or copolymers of ethylenically unsaturated monomers containing a charged group, and copolymers of ethylenically unsaturated monomers containing a charged group and ethylenically unsaturated monomers not containing a charged group.

[0026] Examples of the ethylenically unsaturated monomer containing a charged group include carboxy group-containing monomers such as (meth)acrylic acid, crotonic acid, β-carboxyethyl (meth)acrylate, maleic acid, itaconic acid, fumaric acid, and citraconic acid, and anhydrides of unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride; and sulfonic group-containing monomers such as vinylsulfonic acid and p-styrenesulfonic acid.

[0027] Examples of the ethylenically unsaturated monomer that does not contain a charged group include styrenes, vinyl alkanoates, vinyl aromatic carboxylates, and (meth)acrylates.

[0028] Examples of styrenes include styrene, methylstyrene, vinyltoluene, vinyl ethylbenzene, and vinylnaphthalene. Examples of vinyl alkanoates include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of vinyl aromatic carboxylates include vinyl benzoate.

[0029] 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.

[0030] In the copolymer of an ethylenically unsaturated monomer containing a charged group and an ethylenically unsaturated monomer not containing a charged group, the content ratio of the structural unit derived from the ethylenically unsaturated monomer containing a charged group is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more in all the repeating structural units.

[0031] Examples of the vinyl polymer having a repeating structural unit containing a charged group include poly(meth)acrylic acid, polymaleic acid, polyitaconic acid, polyvinylsulfonic acid, polystyrenesulfonic acid, (meth)acrylic acid-maleic acid copolymer, and (meth)acrylic acid-vinylsulfonic acid copolymer, and metal salts thereof. Examples of the metal salts include sodium salts and potassium salts. Among these, poly(meth)acrylic acid and its metal salts are preferable, and polyacrylic acid and its metal salts are more preferable.

[0032] Examples of the polysaccharide having a repeating structural unit containing a charged group include polysaccharides having a repeating structural unit containing a carboxy group, and specifically include carboxymethyl cellulose, carboxyethyl cellulose, carboxymethyl starch, carboxymethyl dextran, and alginic acid, and metal salts thereof. Examples of the metal salts include sodium salts and potassium salts.

[0033] Among these, carboxymethyl cellulose, alginic acid, and metal salts thereof are preferable, and carboxymethyl cellulose, sodium carboxymethyl cellulose, alginic acid, and sodium alginate are more preferable.

[0034] Proteins have repeating structural units composed of amino acid residues. Examples of the amino acids having a side chain containing a charged group include acidic amino acids such as aspartic acid and glutamic acid, and basic amino acids such as lysine.

[0035] In the protein having an amino acid residue having a side chain containing a charged group, the ratio (number basis) of the amino acid residue having a side chain containing a charged group is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more in all amino acid residues.

[0036] Examples of proteins having amino acid residues with side chains containing a charged group include proteins of acidic amino acids such as polyaspartic acid and polyglutamic acid, and proteins of basic amino acids such as poly-L-lysine.

[0037] Among non-crosslinked polymers having a side chain containing a charged group, poly(meth)acrylic acid is preferred, and polyacrylic acid is more preferred.

[0038] As the non-crosslinked polymer having a side chain containing a charged group, a commercially available product may be used, or it may be synthesized by polymerizing a monomer by a conventionally known method. After polymerizing a monomer not containing a charged group to obtain a non-crosslinked polymer not having a charged group, a charged group may be introduced into the polymer. For example, carboxymethyl cellulose can be obtained by substituting part or all of the hydrogen atoms of the hydroxy group in the structure of cellulose or the hydrogen atoms bonded to the oxygen atom of the hydroxymethyl group with carboxymethyl groups. Further, as the non-crosslinked polymer having a side chain containing a charged group, an extract from a natural product such as sodium alginate may be used.

[0039] The weight average molecular weight (Mw) of the non-crosslinked polymer is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 100,000 or less, and still more preferably 5,000 or more and 30,000 or less. When Mw is below the upper limit value, it is preferable because aggregation of the non-crosslinked polymer in a solvent is suppressed. In the present disclosure, Mw is the weight average molecular weight in terms of polystyrene, which is determined by gel permeation chromatography (GPC) in accordance with JIS K7252-1 (2008).

[0040] The non-crosslinked polymer skeleton 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 skeleton may have a group in which a hydrophobic group is bonded to the functional group such as the charged group. Thereby, the solubility of the polymer of the present disclosure in an organic solvent is increased, and the miscibility with other polymers can be improved.

[0041] In one embodiment, the hydrophobic group is preferably introduced into the non-crosslinked polymer backbone by esterification or amidation of the charged group. Examples of the group in which the hydrophobic group is bonded to the charged group include, when the charged group is a carboxy group or a sulfo group, a group represented by -CONHR, -COOR, or -SO2OR, and when the charged group is an amino group, a group represented by -NHCOR. Here, R is a hydrophobic group.

[0042] Examples of the hydrophobic group include hydrocarbon groups such as aliphatic hydrocarbon groups, alicyclic-containing hydrocarbon groups, and aromatic-ring-containing hydrocarbon groups. The number of carbon atoms of the hydrophobic group is preferably 4 or more and 18 or less. When dissolving the polymer of the present disclosure in an organic solvent having a low polarity (dielectric constant) (such as toluene or cyclohexane), it is preferable that a larger number of carbon atoms of the hydrophobic group are bonded to the charged group.

[0043] Examples of the aliphatic hydrocarbon group include alkyl groups such as butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, hexadecyl group, and octadecyl group; and alkenyl groups such as oleyl group. Examples of the alicyclic-containing hydrocarbon group include cycloalkyl groups such as cyclohexyl group. Examples of the aromatic-ring-containing hydrocarbon group include aralkyl groups such as benzyl group.

[0044] In the polymer of the present disclosure, the ratio (molar basis) of the group in which the hydrophobic group is bonded to the charged group 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 still more preferably 1% or more and 10% or less. In one embodiment, the above ratio is the ratio in which the charged group is esterified or amidated by the hydrophobic group. The above ratio can be measured by nuclear magnetic resonance method (NMR) or matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS).

[0045] 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 a 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 consists of a metal ion 13 and a ligand 14. A hydrophobic group 16 (n-octyl group) is bonded to a part of a plurality of functional groups 15 (carboxy groups) of the non-crosslinked polymer skeleton 11 via an amide bond.

[0046] <Metal Ions> The polymer of the present disclosure contains metal ions supported on the non-crosslinked polymer skeleton. The coordination number to the metal ion is preferably 2. That is, it is preferable that the metal ion is coordinated by the functional group contained in the non-crosslinked polymer and the ligand, respectively.

[0047] Examples of the metal ion include monovalent cations such as silver ion (Ag + ), gold ion (Au + ), copper ion (Cu + ), and mercury ion (Hg 2+ ). By using these metal ions, for example, aggregation or gelation in the solution of the polymer can be suppressed. Among these metal ions, silver ion (Ag + ) is preferable because it has high antibacterial and antiviral properties.

[0048] In the polymer of the present disclosure, the metal ion is characterized by being supported on the non-crosslinked polymer in a state of forming 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". Generally, metal complex ions are less likely to undergo alteration or discoloration due to the influence of light or heat.

[0049] The content rate (loading rate) of the 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, still more preferably 30% by mass or more and 60% by mass or less. If the content rate is 10% by mass or more, the effects by the metal complex ions (for example, antibacterial and antiviral properties) are exhibited well. If the content rate is 70% by mass or less, aggregation of the metal complex ion-supported polymer in the solution is suppressed, and thus a composition or a film excellent in transparency can be obtained.

[0050] The content rate of the metal complex ions is calculated using the following calculation formula.

[0051]

Equation

[0052] In the above formula, "the mass of the metal complex ion-supported polymer" represents the solid content mass when the solvent is removed from the obtained metal complex ion-supported polymer. On the other hand, "the mass of the non-crosslinked polymer" represents the mass of the non-crosslinked polymer introduced into the reaction system in the metal complex ion loading step described later.

[0053] <Ligand> The polymer of the present disclosure contains a ligand coordinated to a metal ion. A ligand means a compound capable of forming a complex with a metal ion and is a compound having a functional group capable of coordinating to a metal ion. Examples of the functional group capable of coordinating to a metal ion include monovalent functional groups such as an amino group, a hydroxy group, a carboxy group, and a thiol group; and divalent functional groups such as an ether group (ether bond) and a thioether group (sulfide bond). Among these, from the viewpoint of suppressing the aggregation of the metal complex ion-supported polymer in a solution well, an amino group, a hydroxy group, an ether group (ether bond), and a thioether group (sulfide bond) are preferable. The ligand preferably has at least one functional group selected from an amino group, a hydroxy group, an ether group (ether bond), and a thioether group (sulfide bond) as the functional group capable of coordinating to a metal ion. The ligand is preferably not a ligand having a carboxy group and a ligand having a thiol group from the viewpoint of suppressing the aggregation of the metal complex ion-supported polymer in a solution well.

[0054] The number of functional groups capable of coordinating to a metal ion in the ligand is preferably 2 or more, more preferably 2 or more and 6 or less, and still more preferably 2 or more and 4 or less. With such a number of functional groups, the ligand can coordinate well to the metal ion.

[0055] 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, still more preferably 200 or less, and even more preferably 150 or less. With such a molecular weight, the ligand can coordinate well to the metal ion and the obtained metal complex ion can be supported well on the non-crosslinked polymer.

[0056] Examples of the ligand include a compound represented by the formula: R 1 -(R 2 ) n -R 3 In the above formula, R is an amino group or a hydroxy group, R 1 is an amino group, a hydroxy group, or a hydrocarbon group, and preferably R 3 and R 1 and R3 Each of them is an amino group or a hydroxy group. R 1 and R 3 may be the same group or different groups.

[0057] Examples of the hydrocarbon group include the hydrocarbon groups exemplified as the hydrophobic groups described above, and specific examples thereof are the same. The number of carbon atoms of the hydrocarbon group is, for example, 4 or more and 18 or less.

[0058] In the above formula, when R 3 is an amino group or a hydroxy group, n is 1, and when R 3 is a hydrocarbon group, n is 0 or 1.

[0059] In the above formula, R 2 is an alkanediyl group or a substituted alkanediyl group. The substituted alkanediyl group is a group in which one or more C-C bonds in the alkanediyl group are inserted with an ether bond, a sulfide bond or an -NH- 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 substituent or two 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 of the alkanediyl group and the substituted alkanediyl group is, respectively, for example, 1 or more and 10 or less, preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less.

[0060] Examples of the ligand include 2,2'-thiodiethanol, ethylenediamine, ethanolamine, diglycolamine and diethanolamine.

[0061] The ligand may have a hydrophobic group. A metal complex ion-supported polymer having a metal ion coordinated by a ligand having a hydrophobic group has high solubility in an organic solvent. Specific examples of the hydrophobic group are as described above. Examples of the ligand having a hydrophobic group include amines having a hydrophobic group. Examples of the amine 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.

[0062] In one embodiment, the ligand is not a low molecular weight compound containing a carboxy group or a thiol group. Specific examples of the low molecular weight compound containing a carboxy group or a thiol group are sodium citrate, glycine, and L-cysteine. These may cause aggregation of the non-crosslinked polymer.

[0063] Conventionally, it has been known that a functional group contained in a non-crosslinked polymer such as polyacrylic acid coordinates to a metal ion. Surprisingly, the present inventors have first found that a metal ion coordinated by a functional group contained in a non-crosslinked polymer such as polyacrylic acid is also simultaneously coordinated by a ligand which is a low molecular weight compound. It is considered that the above ligand produces a remarkable stabilizing effect on the metal ion and makes it less likely to be altered or discolored by the influence of light or heat.

[0064] Conventionally, for example, an aqueous solution containing a complex of silver ions (i.e., a silver complex ion) has been known to be colorless and transparent. Surprisingly, the present inventors have found that when a ligand coordinates to silver ions coordinated by a functional group contained in a non-crosslinked polymer, a color reaction characteristic of the ligand is exhibited. In one embodiment, the non-crosslinked polymer is polyacrylic acid. For example, when the ligand is 2,2'-thiodiethanol, it is light yellow; when it is ethylenediamine, it is orange-yellow; when it is ethanolamine, it is dark red; and when it is diglycolamine, it is dark green. In other words, the loading of silver complex ions onto the non-crosslinked polymer can be confirmed by a color reaction. Hereinafter, typical examples (four types) of metal complex ions supported on polyacrylic acid are shown.

[0065]

Chemical formula

[0066] For example, in the case of silver ions, as shown in the above chemical formula, it is considered that the sulfur atom or nitrogen atom of the ligand (2,2'-thiodiethanol, ethylenediamine, ethanolamine, diglycolamine) and the carboxylate ion in polyacrylic acid coordinate to both sides of the silver ion, respectively. At this time, as described above, when polyacrylic acid is loosened by the electrostatic repulsion of carboxylate ions, the silver complex ion is likely to approach the carboxylate ion in polyacrylic acid, so that the loading amount of the silver complex ion increases.

[0067] [Storage of Polymer Supporting Metal Complex Ions] 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. When the metal complex ion-supported polymer is dried into a powder, it may be difficult to redissolve it in a solvent.

[0068] In one embodiment, a metal complex ion-supported polymer in which a hydrophobic group is not bonded to the functional group such as the charged group or the amount of the introduced hydrophobic group is small can be stored in water for a long time. In one embodiment, a metal complex ion-supported polymer in which a hydrophobic group is bonded to the functional group such as the charged group or the amount of the introduced hydrophobic group is large can be stored in an organic solvent for a long time.

[0069] Examples of the solvent include 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 kind or a mixed solvent of two or more kinds.

[0070] [Method for Producing Polymer Supporting Metal Complex Ions] The metal complex ion-supported polymer of the present disclosure can be produced, for example, by the following production method. The production method of the metal complex ion-supported polymer of the present disclosure, in one embodiment, (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 metal complex ions are supported on the non-crosslinked organic polymer (hereinafter also referred to as "step (2)" or "metal complex ion support step") and including (see Fig. 2).

[0071] In one embodiment, the method for producing the metal complex ion-supported polymer of the present disclosure is (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") further including (see Fig. 2).

[0072] In one embodiment, the above production method is (4) A step of isolating the metal complex ion-supported polymer (hereinafter also referred to as "step (4)" or "polymer isolation step") further including (see Fig. 2).

[0073] <Step (1) (Preparation Step)> 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. Since the details of the non-crosslinked polymer have been described above, the description is omitted here. The metal salt and the complexing agent will be described in the following step (2).

[0074] <Step (2) (Step of Supporting Metal Complex Ions)> Step (2) is a step of dissolving the above non-crosslinked polymer, metal salt, and complexing agent in water to obtain a metal complex ion-supported polymer in which metal complex ions are supported on the non-crosslinked polymer.

[0075] When the metal salt and the complexing agent are dissolved in water, metal complex ions are usually formed. Surprisingly, the present inventors have first clarified that when the above non-crosslinked polymer coexists in this system, the metal complex ions are supported on the non-crosslinked polymer. Fig. 3 shows a schematic diagram of the step in which metal complex ions 12 are supported on the non-crosslinked polymer 11.

[0076] The metal salt is not particularly limited as long as it dissolves in water and ionizes. Examples of the metal salt include silver(I) nitrate, gold(I) chloride, copper(I) iodide, and mercury(II) chloride.

[0077] The complexing agent means a compound capable of forming a complex with a metal ion and is a ligand for the metal ion. Since the details of the ligand (a compound having a functional group capable of coordinating to a metal ion) have been described above, the description is omitted here.

[0078] Specifically, step (2) preferably includes a step of preparing an aqueous solution of an uncrosslinked polymer having a side chain containing a functional group capable of coordinating to a metal ion, and a step of adding a metal salt and a complexing agent to the aqueous solution.

[0079] First, the uncrosslinked polymer is dissolved in water. The concentration of the uncrosslinked 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 uncrosslinked polymer is below the upper limit value, the loading efficiency of the metal complex ion is good. When the concentration of the uncrosslinked polymer is above the lower limit value, the production efficiency is good.

[0080] From the viewpoint of promoting the dissolution of the uncrosslinked polymer in water, the aqueous solution may be heated as necessary. For example, the liquid temperature of the aqueous solution is preferably heated to be 50°C or more and 90°C or less, more preferably 60°C or more and 85°C or less.

[0081] In order to charge the charged group preferably contained in the uncrosslinked polymer in water, an acid or a base may be added to the aqueous solution of the uncrosslinked polymer as necessary to adjust the pH. For example, when the charged group is a carboxy group, adjusting the pH of the aqueous solution to the range of 5 or more and 9 or less tends to cause the uncrosslinked polymer to loosen due to electrostatic repulsion and increase the loading amount of the metal complex ion.

[0082] Next, a complexing agent and a metal salt are added to an 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, still more preferably 10 mM or more and 200 mM or less.

[0083] The addition amount of the complexing agent is preferably 1 to 100 times the molar amount of the metal salt, more preferably 1 to 50 times the molar amount, still more preferably 1 to 10 times the molar amount, and particularly preferably 3 to 5 times the molar amount. When the addition amount of the complexing agent is below the upper limit value, it is preferable because the loading amount of the metal complex ions does not decrease. When the addition amount of the complexing agent is above the lower limit value, it is preferable because the solubility of the metal salt in water increases.

[0084] 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 liquid temperature of the aqueous solution is preferably heated to 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.

[0085] The aqueous solution of the metal complex ion-loaded polymer obtained in step (2) may be subjected to a purification step. By the purification step, unreacted substances and impurities can be removed. Examples of the purification method include dialysis and gel filtration chromatography.

[0086] <Step (3) (Hydrophobization Step)> The hydrophobization step is a step of hydrophobizing the functional groups, preferably charged groups, contained in the metal complex ion-loaded polymer. In one embodiment, a hydrophobic group is introduced into the functional groups, preferably charged groups, of the metal complex ion-loaded polymer. For example, a hydrophobic group is introduced by esterifying or amidating the charged group.

[0087] Note that the polymer obtained in the hydrophobization step is also included in the metal complex ion-supported polymer. However, when the polymers before and after the hydrophobization step are described separately, the polymer obtained in the hydrophobization step is described as "metal complex ion-supported hydrophobized polymer". Specific examples of the hydrophobic group are as described above.

[0088] For example, an amide bond is formed by a condensation reaction between a carboxy group in a non-crosslinked polymer backbone supporting a metal complex ion and an amine having a hydrophobic group, and the hydrophobic group is introduced into the polymer backbone. Fig. 4 shows a schematic diagram of the process of introducing an n-octyl group (converting the carboxy group to an n-octylaminocarbonyl group) into the carboxy group of polyacrylic acid supporting a metal complex ion. In the case of a metal complex ion-supported polymer, the hydrophobic group may be introduced by a ligand substitution reaction between the above ligand and an amine having a hydrophobic group.

[0089] Examples of the amine having a hydrophobic group include amines having an aliphatic hydrocarbon group such as alkylamines such as n-butylamine, t-butylamine, n-hexylamine, 2-ethylhexylamine, n-octylamine, decylamine, hexadecylamine, and octadecylamine; 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.

[0090] In order to allow the above condensation reaction to proceed under mild conditions, it is preferable to use a condensing agent. Examples of the condensing agent include carbodiimide-based condensing agents such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), dicyclohexylcarbodiimide, and diisopropylcarbodiimide; triazine-based condensing agents such as 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM); and carbonate-based condensing agents such as carbonyldiimidazole. Among these, EDC·HCl and DMT-MM, which can be used in water, are preferable.

[0091] After converting the carboxy group in the non-crosslinked polymer backbone into an active ester group, an amide bond may be formed. In that case, it is preferable to use N-hydroxysuccinimide (NHS), 1-hydroxybenzotriazole (HOBT), etc. in combination with the above carbodiimide-based condensing agent.

[0092] For example, an ester bond is formed by a condensation reaction between a carboxy group in a non-crosslinked polymer backbone carrying a metal complex ion and an alcohol having a hydrophobic group, and the hydrophobic group is introduced into the above polymer backbone. For example, an amide bond is formed by a condensation reaction between an amino group in a non-crosslinked polymer backbone carrying a metal complex ion and a carboxylic acid having a hydrophobic group, and the hydrophobic group is introduced into the above polymer backbone.

[0093] The above condensation reaction is usually carried out in water. When the miscibility of an amine, alcohol, or carboxylic acid having a hydrophobic group with water is not high, it is preferable to add a necessary amount of alcohol to water. That is, it is preferable to use a mixed solvent of water and alcohol as the reaction solvent. Examples of the alcohol include methanol and ethanol. The mixing ratio of water and alcohol is set so that an alkylamine or the like to be used can be freely miscible with the solvent. For example, octylamine is well miscible with a mixed solvent of equal volumes of water and methanol.

[0094] 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. When the concentration is below the upper limit value, the condensation reaction proceeds well. When the concentration is above the lower limit value, the production efficiency is improved.

[0095] In the hydrophobization step, when the metal complex ion-supported polymer is hydrophobized, an emulsion (aqueous dispersion) of the metal complex ion-supported hydrophobized polymer is usually formed. That is, the emulsion of the metal complex ion-supported polymer is formed simultaneously with the introduction of the hydrophobic group into the non-crosslinked polymer skeleton. When a hydrophobic group is introduced into the metal complex ion-supported polymer, the solubility of the polymer in an aqueous solvent (for example, water and a mixed solvent of water and alcohol) decreases, and part or all of the metal complex ion-supported polymer becomes insoluble in the aqueous solvent and is dispersed in the aqueous solvent as fine droplets. In this way, an O / W type emulsion is formed.

[0096] Hereinafter, an example of hydrophobization using EDC·HCl, NHS, and alkylamine will be described. EDC·HCl and NHS are added to an aqueous solution of the metal complex ion-supported polymer. Their final concentrations are each preferably independently 1 mM or more and 100 mM or less. 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. Thereby, 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 into an active ester group.

[0097] Next, an alkylamine is added to the above aqueous solution. The final concentration of the alkylamine is preferably 10 mM or more and 300 mM or less, more preferably 10 mM or more and 100 mM or less. The reaction temperature is preferably 20°C or more and 50°C or less, and the reaction time is preferably 1 minute or more and 30 minutes or less. Thereby, the active ester group in the non-crosslinked polymer skeleton constituting the metal complex ion-supported polymer reacts with the alkylamine to form an amide bond. In the case of the metal complex ion-supported polymer, a part 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 stabilizes the metal ion as a ligand.

[0098] <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 above emulsion is recovered, for example, by a known method. For example, by allowing the emulsion to stand, it can be separated into two layers: an upper solvent layer and a lower metal complex ion-supported polymer layer. To enhance the separation efficiency, centrifugation or electric field separation may be utilized. For example, after removing the upper solvent, it is preferable to dissolve the metal complex ion-supported polymer remaining at the bottom of the centrifuge tube in an appropriate organic solvent and recover it. Specific examples of the organic solvent are as described above.

[0099] In one embodiment, the isolation of the polymer is carried out by the following procedure. The above 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 treatment.

[0100] [Composition] The composition of the present disclosure contains one or more of the metal complex ion-supported 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 applications.

[0101] The content ratio of the polymer of the present disclosure in the composition of the present disclosure can be arbitrarily selected according to the use of the composition, and in one embodiment, it 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, more preferably 0.1% by mass or more and 5% by mass or less.

[0102] In one embodiment, the composition of the present disclosure contains at least one selected from water and organic solvents. For example, the polymer of the present disclosure is dissolved in at least one selected from water and organic solvents. Examples of the organic solvent include the specific examples described above.

[0103] The content ratio of the solvent in the composition of the present disclosure can be arbitrarily selected according to the use of the composition, and in one embodiment, it 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, more preferably 60% by mass or more and 98% by mass or less.

[0104] 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 organic solvents. Examples of the method for dissolving the polymer of the present disclosure in a solvent include methods using a magnetic stirrer, a motor with a stirring blade, a homogenizer, or an ultrasonic cleaner. In one embodiment, the composition of the present disclosure is provided in forms such as liquid, gel, and spray.

[0105] 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 resins. Since the polymer of the present disclosure has excellent dispersibility in the resin, when the resin has excellent transparency in one embodiment, the transparency of the resin can be maintained.

[0106] Examples of the resin include polyolefins such as polyethylene, polypropylene, and cyclic polyolefin; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; styrenic resins such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and polystyrene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyamide, polyimide, polyamideimide, (meth)acrylic resin, polycarbonate, polyaryl phthalate, polysulfone, polyethersulfone, polyphenylene sulfide, polyurethane, acetal resin, cellulose resin, fluororesin, phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.

[0107] In one embodiment, the polymer of the present disclosure can be used in an amount of 0.1 part by mass or more and 50 parts by mass or less, preferably 0.5 part by mass or more and 40 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the above resin.

[0108] The polymer of the present disclosure and the above resin can be mixed using a known mixing device such as a Henschel mixer, V-type blender, tumbler, roll, and kneader.

[0109] 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 well mixed with the above active energy ray curable resin components. 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.

[0110] The active energy ray curable resin component is a resin component that cures upon irradiation with active energy rays. The resin component may be any of a monomer, an oligomer, and a polymer. Examples of the active energy rays include electromagnetic waves such as ultraviolet rays (UV), X-rays, and γ-rays; and charged particle beams such as electron beams (EB), α-rays, and ion beams.

[0111] As the active energy ray curable resin component, a photocurable resin component is preferable, and a (meth)acrylic photocurable resin component is more preferable. Examples of the (meth)acrylic photocurable resin component include polyfunctional (meth)acrylates [for example, (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, dipentaerythritol hexa(meth)acrylate, etc.], epoxy (meth)acrylates [polyfunctional epoxy (meth)acrylates having 2 or more (meth)acryloyl groups], polyester (meth)acrylates [polyfunctional polyester (meth)acrylates having 2 or more (meth)acryloyl groups], urethane (meth)acrylates [polyfunctional urethane (meth)acrylates having 2 or more (meth)acryloyl groups], silicone (meth)acrylates [polyfunctional silicone (meth)acrylates having 2 or more (meth)acryloyl groups], and (meth)acrylic polymers having a polymerizable group.

[0112] The (meth)acrylic polymer having a polymerizable group may be a polymer in which a polymerizable unsaturated group is introduced into a part of the carboxy groups of the (meth)acrylic polymer. For example, it may be a (meth)acrylic polymer in which the epoxy group of an epoxy group-containing (meth)acrylate is reacted with a part of the carboxy groups of a (meth)acrylic acid-(meth)acrylate copolymer to introduce a polymerizable group (photopolymerizable unsaturated group) into the side chain.

[0113] The polymer of the present disclosure can be used in an amount of 0.1 part by mass or more and 50 parts by mass or less, preferably 0.5 part by mass or more and 40 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the active energy ray-curable resin component.

[0114] When the composition contains a photocurable resin component, the composition preferably contains one or more photoinitiators capable of initiating a curing reaction by light irradiation. Examples of the photoinitiator include alkylphenone compounds, acetophenone compounds, benzoin compounds, acylphosphine oxide compounds, benzophenone compounds, thioxanthone compounds, and aminobenzophenone compounds. The content of the photoinitiator is preferably 0.1 part by mass or more and 15 parts by mass or less, more preferably 0.5 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the photocurable resin component.

[0115] Since the polymer of the present disclosure is excellent in miscibility with the resin and the active energy ray-curable resin component and also excellent in dispersibility, metal complex ions contained in the polymer of the present disclosure can exist at a sufficient density on the surface of the film formed from the composition of the present disclosure. Thereby, in one embodiment, high immediate antibacterial and antiviral properties can be obtained.

[0116] The composition of the present disclosure may contain one or more other antibacterial and antiviral components, such as sodium hypochlorite, aqueous hypochlorous acid, 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 humectant, a thickener, a pH adjuster, and a surfactant, as necessary.

[0117] Using the composition of the present disclosure, various molded articles such as pellets, sheets, films, plates, containers, and pipes can be formed. The composition of the present disclosure may be applied to the surface of a substrate, such as a paint and a coating agent.

[0118] 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, still more preferably 85% or more. The higher the total light transmittance, the more preferable it is in one embodiment, but the upper limit may be, for example, 99%. The total light transmittance is measured in accordance with JIS K7361-1:1997.

[0119] 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, still more preferably 2.0% or less. The lower the haze, the more preferable it is in one embodiment, but the lower limit may be, for example, 0.1%. The haze is measured in accordance with JIS K7136:2000.

[0120] The thickness of the above-mentioned film formed from the composition of the present disclosure is 0.05 μm or more and 200 μm or less in one embodiment, preferably 0.1 μm or more and 10 μm or less, more preferably 0.15 μm or more and 5 μm or less.

[0121] [Article] The article of the present disclosure contains the composition of the present disclosure. In one embodiment, the component formed from the composition of the present disclosure has antibacterial and antiviral properties in the article of the present disclosure. Therefore, the article of the present disclosure is preferably used for at least one of antibacterial and antiviral applications.

[0122] The article of the present disclosure is not particularly limited as long as it contains the composition of the present disclosure. The above article is formed from the composition of the present disclosure or includes a component (for example, 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 includes a layer formed from the composition of the present disclosure, and the layer constitutes at least a part of the surface layer in the article of the present disclosure. Since the article of the present disclosure has excellent antibacterial and antiviral properties in one embodiment, it can be widely used, for example, as an article that a person touches with their hands.

[0123] 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. Further, in the present disclosure, since it is not necessary to contain antibacterial and antiviral particles in the above layer and expose them on the layer surface, a layer excellent in surface smoothness can be formed. Such a layer is excellent in durability.

[0124] In the present disclosure, the antibacterial property of an article is evaluated in accordance with ISO 22196 (JIS Z2801), and the antiviral property of the article is evaluated in accordance with ISO 21702.

[0125] Examples of the above articles include film products for protecting touch panels, face shields, handrails, buttons, switches, windows, etc.; fiber products such as socks, underwear, towels, curtains, and carpets; building materials such as floor materials, wallpapers, tiles, and paints; kitchen supplies such as sponges, cutting boards, film packaging materials, brushes, and lunch boxes; bath and toilet supplies 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; household appliances such as washing machines, vacuum cleaners, and refrigerators; and automotive parts such as steering wheels, shift knobs, air cleaners, and interior materials.

[0126] The present disclosure relates to, for example, the following [1] to

[18] . [1] A metal complex ion-supported polymer comprising a non-crosslinked organic polymer backbone having a side chain containing a functional group capable of coordinating with a metal ion, a metal ion, and a metal complex ion containing a ligand coordinated with the metal ion, wherein the metal ion in the metal complex ion is coordinated by the functional group contained in the side chain of the non-crosslinked organic polymer backbone. [2] The metal complex ion-supported polymer according to the above [1], wherein the functional group is a charged group. [3] The metal complex ion-supported polymer according to the above [2], wherein the charged group is a carboxy group. [4] The metal ion is a silver ion (Ag + ), a gold ion (Au + ), a copper ion (Cu+ ) and mercury ions (Hg 2+ ), and is at least one selected from the group consisting of the metal complex ion-supported polymers according to any one of [1] to [3] above. [5] The metal complex ion-supported polymer according to any one of [1] to [4] above, wherein the content of the metal complex ion is 10% by mass or more and 70% by mass or less. [6] The ligand is a compound having a molecular weight of 400 or less and having at least one functional group selected from an amino group, a hydroxy group, an ether bond, and a sulfide bond, and the metal complex ion-supported polymer according to any one of [1] to [5] above. [7] The metal complex ion-supported polymer according to any one of [1] to [6] above, wherein a hydrophobic group is bonded to a part of a plurality of functional groups of the non-crosslinked organic polymer skeleton. [8] The metal complex ion-supported polymer according to [7] above, wherein the hydrophobic group is a hydrocarbon group having 4 to 18 carbon atoms. [9] A composition containing the metal complex ion-supported polymer according to any one of [1] to [8] above.

[10] The composition according to [9] above, which has antibacterial and / or antiviral properties.

[11] An article containing the composition according to [9] or

[10] above.

[12] A method for producing a metal complex ion-supported polymer, comprising: (1) a step of preparing a non-crosslinked organic polymer having a side chain containing a functional group capable of coordinating with a metal ion, a metal salt, and a complexing agent; and (2) a step of 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 the metal complex ion is supported on the non-crosslinked organic polymer.

[13] The method for producing a metal complex ion-supported polymer according to

[12] above, further comprising (3) a step of bonding a hydrophobic group to a functional group of the non-crosslinked organic polymer.

[14] The method for producing a metal complex ion-supported polymer according to

[13] above, wherein the hydrophobic group is a hydrocarbon group having 4 to 18 carbon atoms.

[15] In step (3), an emulsion of the hydrophobic metal complex ion-supported polymer is formed, and the production method further includes (4) a step of isolating the hydrophobic metal complex ion-supported polymer from the emulsion, the method for producing a metal complex ion-supported polymer according to

[13] or

[14] above.

[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

[12] to

[16] above, wherein the metal salt is at least one selected from silver(I) nitrate, gold(I) chloride, copper(I) iodide, and mercury(II) chloride.

[18] The method for producing a metal complex ion-supported polymer according to any one of

[12] to

[17] above, wherein the complexing agent is a compound having a molecular weight of 400 or less and having at least one functional group selected from an amino group, a hydroxy group, an ether bond, and a sulfide bond.

Examples

[0127] Hereinafter, the polymers and the like of the present disclosure will be described using specific examples. [Antibacterial Test] The antibacterial property of the metal complex ion-supported polymer aqueous solution was evaluated according to the following procedure.

[0128] The polymer (such as a silver complex ion-supported polymer) obtained in the example or comparative example was added to pure water to obtain 10 mL of an aqueous solution (specimen) having a polymer concentration of 0.01% by mass. Escherichia coli (NBRC 3972) used in the test was cultured in a liquid medium at 35 °C for 24 hours for enrichment culture. After the culture, the concentration of Escherichia coli was adjusted to 10 using sterilized normal broth medium (1 / 500 NB medium). 8Adjusted to cfu / mL (cfu: colony forming unit). 0.1 mL of this bacterial solution was inoculated into 10 mL of the above specimen containing the above polymer and left 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 at 30°C for 48 hours, the grown colonies were counted and converted to the number of viable bacteria. As a negative control, PBS without the above polymer was also tested in the same manner. Finally, the antibacterial activity value was calculated using the following formula. When the antibacterial activity value was 3.0 or more, it was determined to be effective.

[0129]

Number

[0130] [Silver Complex Ion Content] According to the formula described above, the content rate of silver complex ions was calculated.

[0131] [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 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 dialysis was performed in pure water. The content rate of silver complex ions in the obtained silver complex ion-supported polymer was 54.9 mass%.

[0132] [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 silver complex ion-supported polymer.

[0133] [Comparative Example 1] When the same procedure as in Example 1 was carried out except that no complexing agent was used, aggregation of the polymer occurred and a white opaque polymer aqueous solution was obtained. This polymer aqueous solution changed color to purple within 1 hour.

[0134] [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 the silver complex ion-supported polymer (4% by mass). 1 mL of an EDC·HCl / NHS aqueous solution (0.1 M each) was added thereto, and the mixture was allowed to stand for 10 minutes. 1 mL of n-octylamine was added thereto, and the mixture was allowed to stand for 3 minutes. Thereby, an emulsion of the silver complex ion-supported hydrophobized polymer was obtained. After centrifuging this emulsion, the supernatant was removed, and the obtained solid content was dissolved in 10 mL of 2-propanol.

[0135] Using the obtained silver complex ion-supported hydrophobized polymers (4 types), a coating agent having the composition shown in Table 2 was prepared. In Table 2, MIBK is methyl isobutyl ketone. After the coating agent was applied to and dried on a polyethylene terephthalate (PET) film (Cosmo Shine (registered trademark) A4100, Toyobo), ultraviolet rays were irradiated. Thereby, a cured film having a thickness of about 150 nm and containing the silver complex ion-supported hydrophobized polymer was formed on the surface of the PET film. In this way, a composite film including the PET film and the cured film was obtained.

[0136] When the optical properties (total light transmittance, haze, chromaticity) of the composite film obtained as described above were evaluated, they were equivalent to those of the untreated PET film (Reference Example 1) (Table 2). That is, the cured film containing the silver complex ion-supported hydrophobized polymer of the present disclosure had very high transparency and no coloring (discoloration) was observed.

[0137] The total light transmittance was measured in accordance with JIS K7361-1, and the haze was measured in accordance with JIS K7136. Chromaticity a * and b * are L standardized by the International Commission on Illumination (CIE) * a * b * in the a * and b *It was measured in accordance with JIS Z8781-4:2013.

[0138] The antibacterial properties of the cured film obtained as described above were evaluated according to ISO 22196 (JIS Z2801). As a result, excellent antibacterial properties were recognized in all cases (Table 2). The negative control was the above PET film not coated with the above coating agent.

[0139]

Table 1

[0140]

Table 2

Explanation of symbols

[0141] 10... Metal complex ion-supported polymer 11... Non-crosslinked polymer (skeleton) 12... Metal complex ion 13... Metal ion 14... Ligand 15... Functional group capable of coordinating to metal ion 16... Hydrophobic group

Claims

1. (1) A step of preparing a non-crosslinked organic polymer having a side chain containing a functional group capable of coordinating with a metal ion, a metal salt, and a complexing agent; (2) A step of 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 metal complex ions are supported on the non-crosslinked organic polymer; (3) A step of bonding a hydrophobic group to the functional group of the non-crosslinked organic polymer The method for producing a metal complex ion-supported polymer according to claim 1, comprising:

2. 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. In the step (3), an emulsion of the hydrophobized metal complex ion-supported polymer is formed, and the production method further includes (4) a step of isolating the hydrophobized metal complex ion-supported polymer from the emulsion. The method for producing a metal complex ion-supported polymer according to claim 1 or 2.

4. The method for producing a metal complex ion-supported polymer according to any one of claims 1 to 3, wherein the functional group is a carboxy group.

5. 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 silver(I) nitrate, gold(I) chloride, copper(I) iodide, and mercury(II) chloride.

6. 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 a molecular weight of 400 or less and having at least one functional group selected from an amino group, a hydroxy group, an ether bond, and a sulfide bond.

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